CN1641481A - Light-sensitive transfer sheet, light-sensitive layers, method for forming image pattern and method for distribution pattern - Google Patents

Light-sensitive transfer sheet, light-sensitive layers, method for forming image pattern and method for distribution pattern Download PDF

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Publication number
CN1641481A
CN1641481A CNA2004101006745A CN200410100674A CN1641481A CN 1641481 A CN1641481 A CN 1641481A CN A2004101006745 A CNA2004101006745 A CN A2004101006745A CN 200410100674 A CN200410100674 A CN 200410100674A CN 1641481 A CN1641481 A CN 1641481A
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China
Prior art keywords
photographic layer
light
transfer sheet
methyl
sensitive transfer
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Chinese (zh)
Inventor
若田裕一
佐藤守正
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Fujifilm Corp
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Fujifilm Corp
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Publication of CN1641481A publication Critical patent/CN1641481A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • G03F7/027—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
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70216—Mask projection systems
    • G03F7/70283—Mask effects on the imaging process
    • G03F7/70291—Addressable masks, e.g. spatial light modulators [SLMs], digital micro-mirror devices [DMDs] or liquid crystal display [LCD] patterning devices

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to a photosensitive transfer sheet, a photosensitive laminated body, a method for forming image patterns, a method for forming wiring patterns. The invention uses the photosensitive transfer sheet which comprises a first photosensitive layer including binder, polymerization compound and polymerization initiator, a barrier layer comprising polymerization compound and a second photosensitive layer including binder, polymerization compound and polymerization initiator and having a relatively higher photo sensibility than that of the first photosensitive layer which overlay in sequence on a support body. In addition, the invention forms an image by the photosensitive laminated body comprising a second photosensitive layer including binder, polymerization compound and polymerization initiator, a barrier layer comprising polymerization compound and a first photosensitive layer including binder, polymerization compound and polymerization initiator and having a relatively lower photo sensibility than that of the second photosensitive layer which overlay in sequence on a substrate. Expected patterns with different thickness can be easily formed in images according to the invention.

Description

The method of light-sensitive transfer sheet, light-sensitive layers body, the method that forms picture pattern, formation Wiring pattern
Technical field
The present invention relates to the formation method of light-sensitive transfer sheet, light-sensitive layers body, picture pattern and the formation method of Wiring pattern.The present invention be more particularly directed to as useful light-sensitive transfer sheet, the laminated body of manufacturing distributing board, and use this light-sensitive transfer sheet or laminated body to form the method for the Wiring pattern of printed circuit board (PCB).
Background technology
Light-sensitive transfer sheet with supporter and photographic layer just is being widely used in making printed circuit board (PCB), color filter and post material, band muscle material, dividing plate (spacer), next door etc. and is showing that the picture pattern with parts, galley, holograph, micromachine, proof various Image forming materials such as (proof) etc. forms material.
In the manufacturing field of printed circuit board (PCB), Wiring pattern forms by the photoetching technique of using the light-sensitive transfer sheet of being made up of transparent supporting body (for example polyethylene terephthalate) and the photographic layer that forms (being also referred to as the dry film erosion resistant) on its supporter.For example have under the situation of printed circuit board (PCB) of through hole in manufacturing, go up the formation through hole in printed circuit board (PCB) formation with substrate (for example copper plating film laminated plate), after the through hole madial wall partly forms the coat of metal, make the overlapping and driving fit of photographic layer of substrate surface and light-sensitive transfer sheet, form zone and the zone difference pattern form irradiates light according to the rules that comprises via openings portion at Wiring pattern, make photographic layer solidify.Then strip the supporter of light-sensitive transfer sheet, after using developing solution dissolution to remove Wiring pattern to form consolidation zone and consolidation zone (being called masked film) the uncured zone in addition on the via openings portion zone on the zone, the metal level part that etch processes is exposed, by removing consolidation zone, on substrate surface, generate Wiring pattern then.
Use the method for the metal cladding of above-mentioned masked film (tent) protection through hole, be commonly referred to as covering method (tenting).In the printed circuit board (PCB) of sandwich construction, the hole of using between the articulamentum that is called via the hole is set also sometimes in addition, in the case equally need be when forming Wiring pattern by the masked film protection via bore portion.
Densification to printed circuit board (PCB) in recent years requires improving constantly, and needing can more high-resolution photoetching film.In order to improve the resolution of photoetching film, make that the thickness attenuation of its photographic layer is effective.Yet as mentioned above; the through hole that the existing protection of cured layer that photographic layer solidifies forms on printed circuit board (PCB) or via the function in hole; if but made the thickness attenuation of photographic layer simply, then could appear at dissolving and remove the problem that this masked film is broken in the operation of the operation in uncured zone of photosensitive polymer combination and the metal level part that etch processes is exposed.
Exploitation also in vogue up to now can form high resolution design and can form the light-sensitive transfer sheet of the masked film that is difficult to break, and its achievement discloses as follows.
In patent documentation 1, put down in writing light-sensitive transfer sheet with photographic layer of forming by the cementing agent composition that contains carboxyl, the monomer component that contains special ethylene aminocarbamic acid ethyl ester compound and specific acrylate compounds and Photoepolymerizationinitiater initiater.
In patent documentation 2, put down in writing light-sensitive transfer sheet with two layers of photographic layer, this light-sensitive transfer sheet be alkali-soluble is set on supporter, by adding first photographic layer of the little and induction active energy ray of thermal fluidity, and alkali-soluble be set in the above, form by adding big and second photographic layer induction active energy ray of thermal fluidity.Having described in this patent documentation can be by imbedding the metal level of protecting through hole in the through hole with second photographic layer of light-sensitive transfer sheet.
In patent documentation 3, put down in writing the photoresist laminated body that on supporter, has first photographic layer and second photographic layer, described two layers have different mutually ethylenic copolymers and contain specific monofunctional monomer on two-layer, as its effect, put down in writing and to have improved driving fit and explanation.
In patent documentation 4, put down in writing the photoresist that on supporter, has non-adhesive photographic layer and cohesiveness photographic layer and used its method that forms printed circuit board (PCB),, put down in writing and to have improved covering and explanation property as its effect.
In patent documentation 5, disclose at least two layers of optical polymerism layer on base material, having photopolymerization speed and differ from one another (thickness is 25 μ m～2.5mm), near the photographic plate of the fast printing embossment manufacturing usefulness of the polymerization speed of base material one side, put down in writing the example of the base portion that the forms printing surface matrix wideer than the top.
[patent documentation 1] spy opens flat 10-142789 communique
[patent documentation 2] spy opens flat 8-54732 communique
[patent documentation 3] spy opens flat 10-111573 communique
[patent documentation 4] spy opens flat 3-17650 communique
[patent documentation 5] special public clear 37-1306 communique
Summary of the invention
Problem of the present invention is to provide the light-sensitive transfer sheet and the light-sensitive layers body that can form the different desired pattern of thickness easily in image.
Problem of the present invention also is to provide use light-sensitive transfer sheet or light-sensitive layers body, the industrial advantageously different desired method of patterning of formation thickness in image.
Problem of the present invention is particularly in the light-sensitive transfer sheet that provides effective for the printed circuit board (PCB) manufacturing, can also can form the masked film that is difficult to break by thin layer realization high resolving powerization.
Problem of the present invention also is to provide uses light-sensitive transfer sheet or light-sensitive layers body, and industrial can advantageously the manufacturing has through hole and via the method for the printed circuit board (PCB) of hole portions such as hole.
The present invention first relates to stacked in order first photographic layer that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater on supporter, and the restraining barrier of containing polymerizable compound with contain cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater and have the light-sensitive transfer sheet of the second high photographic layer of the light sensitivity of relative first photographic layer.
The preferred implementation of above-mentioned first invention is as described below.
(1) restraining barrier has photonasty, and the light sensitivity of relative first photographic layer of the light sensitivity on restraining barrier is low.
(2) polymerizable compound that contains in the restraining barrier is the polymkeric substance that contains polymerizable group.
(3) polymkeric substance that contains polymerizable group in above-mentioned (2) is that 1～4 lower alcohol shows compatibility for water or carbon number.
(4) polymkeric substance that contains polymerizable group in above-mentioned (3) is that 1～4 lower alcohol is solvable for water or carbon number.
(5) also to contain for water or carbon number be the polymkeric substance that 1～4 lower alcohol shows compatibility on the restraining barrier.
(6) polymkeric substance in above-mentioned (5) is that 1～4 lower alcohol is solvable for water or carbon number.
(7) restraining barrier has the thickness of 0.1～5 mu m range.
(8) under the light sensitivity of first photographic layer was 1 situation, the light sensitivity of second photographic layer was in 2～200 scope.
(9) be used to solidify the needed luminous energy A of second photographic layer and being used to and solidify the ratio of representing with A/B of the needed luminous energy B of first photographic layer in 0.005～0.5 scope.
(10) be used to solidify the needed luminous energy A of second photographic layer and begin to solidify in the scope of ratio of representing with C/A of needed luminous energy C 1～10 until first photographic layer.
The amount of the Photoepolymerizationinitiater initiater that contains in (11) second photographic layers is more than the amount of the Photoepolymerizationinitiater initiater that contains in first photographic layer.
The amount of the polymerizable compound that contains in (12) second photographic layers is more than the amount of the polymerizable compound that contains in first photographic layer.
(13) first photographic layers have the thickness of 1～100 mu m range, and its thickness is bigger than the thickness of second photographic layer.
(14) second photographic layers have the thickness of 0.1～15 mu m range.
(15) supporter is by synthetic resin manufacturing and transparent.
(16) supporter is microscler supporter.
(17) on second photographic layer, dispose protective film.
(18) be longitudinal bodies, be rolled into the roller shape.
(19) the printed circuit board (PCB) manufacturing is used.
The present invention second relates to stacked in order second photographic layer that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater on matrix, the restraining barrier of containing polymerizable compound with contain cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater and have the light-sensitive layers body of the first low photographic layer of the light sensitivity of relative second photographic layer.
The preferred implementation of above-mentioned second invention is as described below.
(1) restraining barrier has photonasty, and the light sensitivity of relative first photographic layer of the light sensitivity on restraining barrier is low.
(2) polymerizable compound that contains in the restraining barrier is the polymkeric substance that contains polymerizable group.
(3) polymkeric substance that contains polymerizable group in above-mentioned (2) is that 1～4 lower alcohol shows compatibility for water or carbon number.
(4) polymkeric substance that contains polymerizable group in above-mentioned (3) is that 1～4 lower alcohol is solvable for water or carbon number.
(5) also to contain for water or carbon number be the polymkeric substance that 1～4 lower alcohol shows compatibility on the restraining barrier.
(6) polymkeric substance in above-mentioned (5) is that 1～4 lower alcohol is solvable for water or carbon number.
(7) restraining barrier has the thickness of 0.1～5 mu m range.
(8) under the light sensitivity of first photographic layer was 1 situation, the light sensitivity of second photographic layer was in 2～200 scope.
(9) be used to solidify the needed luminous energy A of second photographic layer and being used to and solidify the ratio of representing with A/B of the needed luminous energy B of first photographic layer in 0.005～0.5 scope.
(10) be used to solidify the needed luminous energy A of second photographic layer and begin to solidify in the scope of ratio of representing with C/A of needed luminous energy C 1～10 until first photographic layer.
The amount of the Photoepolymerizationinitiater initiater that contains in (11) second photographic layers is more than the amount of the Photoepolymerizationinitiater initiater that contains in first photographic layer.
The amount of the polymerizable compound that contains in (12) second photographic layers is more than the amount of the polymerizable compound that contains in first photographic layer.
(13) first photographic layers have the thickness of 1～100 mu m range, and its thickness is bigger than the thickness of second photographic layer.
(14) second photographic layers have the thickness of 0.1～15 mu m range.
(15) matrix is a printed circuit board (PCB) formation substrate.
(16) on first photographic layer, be laminated with supporter (being preferably transparent resin film especially).
(17) the printed circuit board (PCB) manufacturing is used.
The present invention the 3rd relate to contain following operation, on substrate, form method by the picture pattern that constitutes with lower area, promptly should the zone, be the zone that exists by the curing resin layer that is solidified to form jointly by first photographic layer and second photographic layer and do not exist the zone of curing resin layer to constitute.
(1) position that becomes substrate-side according to its second photographic layer on substrate concerns the light-sensitive transfer sheet of stacked above-mentioned first invention, obtains the operation of laminated body;
(2) the first photographic layer side picture pattern according to the rules from laminated body carries out rayed, feasible first photographic layer and the common operation of solidifying of second photographic layer of accepting its light-struck zone;
(3) remove the operation of supporter from laminated body; And
(4) laminated body is developed and remove the operation of uncured portion in the laminated body.
The present invention the 4th relate to contain following operation, on substrate, form method by the picture pattern that constitutes with lower area, promptly should the zone, be the zone that exists by the resin bed that is solidified to form jointly by first photographic layer and second photographic layer, the zone that exists of the resin bed that is solidified to form by second photographic layer and do not exist the zone of curing resin layer to constitute.
(1) position that becomes substrate-side according to its second photographic layer on substrate concerns the light-sensitive transfer sheet of stacked above-mentioned first invention, obtains the operation of laminated body;
(2) to shining the zone of the different mutually irradiation energy of secondary at least light, first photographic layer side picture pattern according to the rules by laminated body carries out rayed, make first photographic layer and second photographic layer of accepting the big relatively light-struck zone of rayed energy solidify jointly, and the feasible operation of accepting second photographic layer curing in the relatively little light-struck zone of rayed energy;
(3) remove the operation of supporter from laminated body; And
(4) laminated body is developed and remove the operation of uncured portion in the laminated body.
Preferred scheme is as follows in the 3rd invention of the present invention and the 4th invention.
(3) operation of removing supporter by the laminated body of above-mentioned (3) is not to carry out between operation (2) and operation (4), but carries out between operation (1) and operation (2).
(4) rayed in the operation (2) is undertaken by laser radiation.
The present invention the 5th relate to contain following operation, on printed circuit board (PCB) forms with substrate, form method by the picture pattern that constitutes with lower area, promptly should the zone, be to constitute by the zone of exposing by the zone that curing resin layer covered that is solidified to form jointly by first photographic layer and second photographic layer and substrate surface.
(1) position that becomes substrate-side according to its second photographic layer on substrate concerns the light-sensitive transfer sheet of stacked above-mentioned first invention, obtains the operation of laminated body;
(2) rayed of the Wiring pattern of stipulating from first photographic layer, one side of laminated body makes first photographic layer and the common operation of solidifying of second photographic layer of accepting its light-struck zone;
(3) remove the operation of supporter from laminated body; And
(4) laminated body is developed and remove the operation of uncured portion in the laminated body.
The present invention the 6th relate to contain following operation, on the printed circuit board (PCB) that contains porose portion forms with substrate, form method by the Wiring pattern that constitutes with lower area, this zone is by constituting by the hole portion that curing resin layer covered that is solidified to form jointly by first photographic layer and second photographic layer with by the zone that the zone that curing resin layer covered that is solidified to form by second photographic layer and substrate surface expose.
(1) position that becomes substrate-side according to its second photographic layer on substrate concerns the light-sensitive transfer sheet of stacked above-mentioned first invention, obtains the operation of laminated body;
(2) carry out light-struck operation of following such picture pattern, promptly, give hole portion rayed energy big relatively rayed by the first photographic layer side of laminated body, win photographic layer and second photographic layer are solidified jointly, and form the zone at distribution and give the rayed energy relatively little rayed, make second photographic layer solidify;
(3) remove the operation of supporter from laminated body; And
(4) laminated body is developed and remove the operation of the uncured portion in the laminated body.
Preferred scheme is as follows in the 5th invention of the present invention and the 6th invention.
(3) operation of removing supporter by the laminated body of above-mentioned (3) is not to carry out between operation (2) and operation (4), but carries out between operation (1) and operation (2).
(4) rayed in the operation (2) is undertaken by laser radiation.
Light-sensitive transfer sheet of the present invention can form the different cured layer of thickness by changing the exposure (being also referred to as exposure) of its light.Therefore can be only in the thickness (formation 3 d image) of desirable area change film, the transit dose (changing the concentration of image) that changes light, change film strength etc.Therefore also can form the so-called thickness thickening that for example makes the cured layer of the part of wanting reinforcing membrane intensity, make the pattern of thickness attenuation of the cured layer of the part of wanting to improve resolution.Thereby, if light-sensitive transfer sheet of the present invention is used for the printed circuit board (PCB) manufacturing, particularly has a through hole and during via the manufacturing of the printed circuit board (PCB) of hole portions such as hole, can form the cured layer of the height explanation that forms the thickness relative thin in the zone at Wiring pattern, form the thick relatively high-intensity cured layer of thickness at through hole or in via the hole.
Have again by between first photographic layer and second photographic layer, the restraining barrier being set, can prevent the mixing of interlayer of first photographic layer and second photographic layer and moving of material, light-sensitive transfer sheet easy to manufacture, the change of sensitivity is few when preserving in addition.Moreover because this restraining barrier also has polymerism, therefore in the development of first photographic layer and the common part (part that the thickness of cured film is thick) of solidifying of second photographic layer etc. being handled, can prevent floating and fault (particularly in little zone, through hole footpath etc., taking place easily) etc. such as peel off on first photographic layer/restraining barrier/arbitrary interface of second photographic layer.Can use industrial favourable covering method to make high-resolution printed circuit board (PCB) for this reason.
Description of drawings
The one routine mode sectional drawing of [Fig. 1] light-sensitive transfer sheet of the present invention.
The mode sectional drawing of other examples of [Fig. 2] light-sensitive transfer sheet of the present invention.
[Fig. 3] expression is rayed amount during by supporter one side irradiates light and the curve of sensitivity diagrammatic sketch of cured layer thickness relationship to light-sensitive transfer sheet of the present invention.
The mode sectional drawing of one example of [Fig. 4] light-sensitive transfer sheet of the present invention.
The mode sectional drawing of other examples of [Fig. 5] light-sensitive transfer sheet of the present invention.
It is the mode chart of three layers the light-sensitive transfer sheet image example (cured layer pattern) that can form that photographic layer of the present invention is used in [Fig. 6] expression.
[Fig. 7] represents the artwork with printed circuit board (PCB) manufacturing process of through hole of the present invention.
Embodiment
[restraining barrier]
The restraining barrier can be provided with between first photographic layer and second photographic layer.The restraining barrier has and prevents or control the function that the composition that contains in two photographic layers moves.The restraining barrier also has for the composition that contains in photographic layer and supporter and other random layers (for example protective film) and prevents or control mobile function.Can prevent because composition moves the variation of the sensitivity that causes photographic layer and each layer rerum natura by the restraining barrier.The restraining barrier can also have the function that moves of exterior materials of preventing (for example oxygen) and relax because the function of the influence that the variation of external condition (for example humidity) produces.
Polymerizable compound is contained on the restraining barrier.Polymerizable compound is the compound that contains polymerism functional group, also comprises macromolecular compound (oligomer, polymkeric substance) except low molecular compound (monomer).Polymkeric substance (resin) both sides that the restraining barrier is preferably contained low molecular polymerizable compound and played the cementing agent effect are perhaps contained the high molecular polymerizable compound (resin) that plays the cementing agent effect.
The polymerizable compound that contains in the restraining barrier carries out photopolymerization by the effect of Photoepolymerizationinitiater initiater that contains in first photographic layer or second photographic layer or the Photoepolymerizationinitiater initiater that contains arbitrarily in the restraining barrier.The Photoepolymerizationinitiater initiater that contains in the restraining barrier also can be that the part of the Photoepolymerizationinitiater initiater that contains in first photographic layer or second photographic layer moves to the Photoepolymerizationinitiater initiater on restraining barrier when making light-sensitive transfer sheet.Thereby the restraining barrier also can have photonasty.But, hope be the light sensitivity low (order of sensitivity is second photographic layer＞first photographic layer＞restraining barrier) of relative first photographic layer of light sensitivity on restraining barrier.
The polymerism functional group of polymerizable compound is ring-opening polymerization group or addition polymerization group preferably, is more preferably the addition polymerization group.The addition polymerization group is the ethene unsaturated group especially preferably.
Preferably has a plurality of polymerism functional group in a part of polymerizable compound.
The polymerizable compound that contains in low molecular polymerizable compound and the aftermentioned photographic layer is same.But closing property of the low molecular weight polycaprolactone compound that contains in the restraining barrier is that 1～4 lower alcohol shows compatibility with respect to water or carbon number preferably, is that 1～4 lower alcohol is solvable with respect to water or carbon number more preferably.
The cementing agent that uses simultaneously with closing property of low molecular weight polycaprolactone compound preferably shows compatibility with respect to solvent (water or carbon number are 1～4 lower alcohol).So-called compatibility is meant for above-mentioned solvent to have emulsification, dispersion, expansion, dissolving (comprise and be partly dissolved), wetting state.The cementing agent that contains in the restraining barrier is more preferably solvable with respect to solvent (water or carbon number are 1～4 lower alcohol).
The mass ratio of closing property of low molecular weight polycaprolactone compound and cementing agent (resin) is polymerizable compound preferably: cementing agent is 90: 10～1: 99, more preferably 70: 30～5: 95, and most preferably 60: 40～5: 95.
Also can use closing property of the low molecular weight polycaprolactone compound more than two kinds simultaneously.Also can use low molecular polymerizable compound and high molecular polymerizable compound (following) simultaneously.
The high molecular polymerization compound (resin) that plays the cementing agent function can obtain by import polymerism functional group in the polymkeric substance that plays the cementing agent function.The example that plays the polymkeric substance of cementing agent function comprises the example of the cementing agent that contains in the aftermentioned photographic layer.But the cementing agent that contains in the cementing agent that contains in the restraining barrier and the photographic layer is different, preferably shows compatibility with respect to solvent (water or carbon number are 1～4 lower alcohol).About compatibility as describing for the cementing agent that uses simultaneously with closing property of low molecular weight polycaprolactone compound.
The molecular weight of high molecular polymerization compound is preferably more than 500, more preferably more than 1000.
With respect to water or carbon number is that 1～4 lower alcohol shows that the example of the polymkeric substance of compatibility comprises polyvinyl alcohol (PVA), modified polyvinylalcohol, polyvinyl pyrrolidone, water soluble polyamide, gelatin, cellulose.Particularly preferably be polyvinyl alcohol (PVA) and modified polyvinylalcohol.
In order in polymkeric substance, to import polymerizable group, can make it to have the compound reaction of reactive functional group (for example carboxyl, sulfo group, hydroxyl, acid halide, acid anhydride structure, methylol, isocyanate group) and polymerizable group with the functional group of containing relative polymkeric substance (for example hydroxyl, amino).
(functional group with respect to polymkeric substance has reactive functional group to contain carboxyl, below omit) and the example of the compound of polymerizable group, (methyl) acrylic acid, itaconic acid, cinnamic acid, acrylic acid dimer, vinyl benzoic acid, vinyl oxygen benzoic acid comprised.
The example that contains the compound of sulfo group and polymerizable group comprises 2-acrylamide-2-methyl propane sulfonic acid, styrene sulfonic acid.
The example that contains the compound of hydroxyl and polymerizable group comprises 2-hydroxyethyl (methyl) acrylate.
The example that contains (ring-type) acid anhydrides of polymerizable group comprises maleic anhydride and itaconic anhydride.Other compounds that import the ethene unsaturated group in acid anhydrides (for example phthalic anhydride, succinic anhydride) also can be as the carboxyl that contains polymerizable group.
The example that contains the compound of methylol and polymerizable group comprises methylol (methyl) acrylamide.
The example that contains the compound of isocyanate group and polymerizable group comprises 2-(methyl) acryloxy ethyl isocyanate, (methyl) acryloyl group isocyanates, 1-(4-ethenylphenyl)-1-Methylethyl isocyanates, 1-(4-isopropenyl phenyl)-1-Methylethyl isocyanates.
As the high molecular polymerization compound (resin) that plays the cementing agent function, can use the water soluble polyurethane resin that contains polymerizable group (spy open flat 3-168209 number, with each communique record of 7-25958 number).The water soluble polyurethane resin that contains polymerizable group can be by making two pure and mild polyoxyalkylene glycols and the polyisocyanate reaction that contains carboxyl, make again resultant of reaction with contain (methyl) acrylate reactions of hydroxyl, the carboxyl in the resin that obtains obtains with the amine neutralization.In addition, also can be by making polyvalent alcohol and the polyisocyanate reaction contain quaternary ammonium salt, make resultant of reaction and (methyl) acrylate reactions that contains hydroxyl again, make the water soluble polyurethane resin that contains polymerizable group.
The epoxy resin (spy opens in the flat 4-211413 communique and puts down in writing) that contains polymerizable group also can be as the high molecular polymerization compound (resin) that plays the cementing agent function.Contain polymerizable group epoxy resin can by make epoxy acrylate and anhydride reaction, obtain with amine neutralization.
Make that contain with respect to water or carbon number is that 1～4 lower alcohol shows the monomer (for example vinyl pyrrolidone) of compatibility functional group and contains monomer (for example (methyl) allyl acrylate) copolymerization of a plurality of polymerizable groups, the polymerizable group that the part of the polymerizable group that contains in the back monomer can be used as polymkeric substance is remaining.
By making that multipolymer of acryloyl morpholine and (methyl) acrylate that contains hydroxyl and the polymkeric substance that the reaction of methacryl ethyl isocyanate obtains (spy opens flat 9-146270 communique record) also can be as the high molecular polymerization compounds (resin) that plays the cementing agent function.
Also can use the high molecular polymerization compound more than two kinds simultaneously.The high molecular polymerization compound also can and other (not containing polymerizable group) polymkeric substance (for example poly-(methyl) acrylate, polyamide, polyester) use simultaneously.Polymkeric substance of Shi Yonging and high molecular polymerization compound are same simultaneously, are that 1～4 lower alcohol shows compatibility (perhaps solubility) with respect to water or carbon number preferably.
The composition (for example Photoepolymerizationinitiater initiater, sensitizer, thermal polymerization inhibitor, plastifier, colour former, colorant, pigment, electroconductive particle, filling agent, defoamer, fire retardant, levelling agent, peel off promoter, antioxidant, spices, thermal cross-linking agent, surface tension modifier, chain-transferring agent) of photographic layer described later can be contained in the restraining barrier.These any compositions are that 1～4 lower alcohol shows compatibility (perhaps solubility) with respect to water or carbon number preferably also.Thermoplastic resin (No. 2794242 communique record of patent) also can be contained in the restraining barrier.
The thickness on restraining barrier is preferably the scope of 0.1～5 μ m.Restraining barrier more than two layers can be set.
[basic structure of light-sensitive transfer sheet and light-sensitive layers body]
As an example of light-sensitive transfer sheet of the present invention, the mode sectional drawing with two layers of photographic layer structure is as shown in Fig. 1 and Fig. 2.
In Fig. 1, light-sensitive transfer sheet 10 is according to the sequential cascade of supporter 11, first photographic layer 12, restraining barrier 13, second photographic layer 14.First photographic layer 12 and second photographic layer 14 are made up of the photosensitive polymer combination that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater respectively, solidify by rayed.The principal character of light-sensitive transfer sheet of the present invention is that second photographic layer 14 wants high with respect to first photographic layer, 12 light sensitivity.Here so-called light sensitivity, being equivalent to separately, photographic layer solidifies needed luminous energy, so-called light sensitivity height is meant that the curing of second photographic layer 14 begins with the rayed amount of lacking than first photographic layer 12, and perhaps the curing of second photographic layer 14 finishes with the rayed amount of lacking than first photographic layer 12.
Fig. 2 is stacked guard film 15 and the light-sensitive transfer sheet that obtains again on the light-sensitive transfer sheet of Fig. 1.
The thickness of first photographic layer, restraining barrier and second photographic layer can at random be set according to purpose respectively.But the thickness of first photographic layer is preferably the scope of 1～100 μ m, and the scope of 5～80 μ m more preferably is preferably the scope of 10～50 μ m especially.If the thickness of first photographic layer is thinner than 1 μ m, then improper sometimes for reinforcing membrane intensity, if thickness surpasses 100 μ m, the easy residual problem that waits on developing of development residue then appears sometimes.The thickness of the first photographic layer preferably thickness than second photographic layer is big.
The thickness on restraining barrier is preferably the scope of 0.1～5 μ m, and the scope of 0.5～4 μ m more preferably is preferably the scope of 1～3 μ m especially.If the thickness on restraining barrier is thinner than 0.1 μ m, then can not get sufficient block sometimes, the needs that develop if thickness surpasses 5 μ m are long-time.The thickness of second photographic layer is preferably the scope of 0.1～15 μ m, and the scope of 1～12 μ m more preferably is preferably the scope of 3～10 μ m especially.If the thickness of second photographic layer is thinner than 0.1 μ m, thickness becomes inhomogeneous easily when then applying, if thickness surpasses 15 μ m, problems such as resolution reduction then can occur.
The layer structure of light-sensitive transfer sheet of the present invention is not limited to the layer structure shown in above-mentioned Fig. 1 and Fig. 2, also can contain the layer layer in addition shown in Fig. 1 and Fig. 2.For example can layer, anti-halo layer or restraining barrier etc. that adjust supporter and strippable substrate and closing force be set between the supporter 11 and first photographic layer 12 and between the protective film 15 and second photographic layer 14.At this moment restraining barrier has preventing or the moving and the function of external actions such as oxygen and humidity etc. of the material that suppresses to contain in photographic layer, supporter or the protective film.
The relation of the curing amount of the exposure of light in light-sensitive transfer sheet of the present invention and the light-sensitive layers body and photographic layer then on one side is described on one side with reference to Fig. 3.Fig. 3 for example represents the light-sensitive transfer sheet after transfer printing on the substrate is peeled off protective film from the light-sensitive transfer sheet shown in the light-sensitive transfer sheet shown in Fig. 1 or Fig. 2 and forms under the situation of laminated body; has under the situation of supporter by a side opposite by supporter or peel off supporter as required and with rayed on photographic layer the time rayed amount and by this irradiation (exposure) then figure (light sensitivity curve) of the thickness relationship of the cured layer of development treatment generation then with substrate for this laminated body.Transverse axis is represented the exposure of light in Fig. 3, and the longitudinal axis represents to solidify and carry out by rayed the thickness of the cured layer that obtains after the development treatment.The D of the longitudinal axis represents the thickness of the cured layer that formed by second photographic layer, E represents the thickness that the thickness on the thickness of the cured layer that formed by first photographic layer and restraining barrier adds up to, and F represents the thickness of the thickness total of the thickness on thickness, restraining barrier of the cured layer that formed by first photographic layer and the cured layer that formed by second photographic layer.
As shown in Figure 3, the light that in light-sensitive transfer sheet of the present invention, shines from supporter one side, though containing under the situation of supporter according to supporter, first photographic layer, the restraining barrier sequential advancement of second photographic layer then, but curing ratio first photographic layer of second photographic layer is wanted to begin with less luminous energy earlier.After whole second photographic layer solidified, if increase luminous energy, then the curing of first photographic layer began then, if increase luminous energy again, then whole first photographic layer solidifies.
Relation for the sensitivity of the sensitivity of first photographic layer and second photographic layer, be under 1 the situation in the light sensitivity of first photographic layer, the light sensitivity of second photographic layer is preferably in 2～200 scope, more preferably in 2.5～100 scope, in 3～50 scope.
First photographic layer begin to solidify needed luminous energy C can with for solidify the needed luminous energy A of second photographic layer with the amount, but preferably big than luminous energy A.
Also have light-sensitive transfer sheet as shown in fig. 1 such, thickness E when between first photographic layer and second photographic layer, having the restraining barrier, the thickness of the cured layer that expression is formed by first photographic layer and the cured layer thickness that forms by second photographic layer and the gross thickness of barrier layer thickness.
Light-sensitive transfer sheet of the present invention in addition also can have the photographic layer more than two layers.As the one example, the sectional view when photographic layer is three layers as shown in Figure 4.The situation that has protective film in addition on the photographic layer of Fig. 4 as shown in Figure 5.
In the light-sensitive transfer sheet 50 of Fig. 4 and Fig. 5, supporter is represented with 51, stacked in order first photographic layer 52, restraining barrier 53, second photographic layer 54, restraining barrier 53 and the 3rd photographic layer 55 on its supporter 51.Fig. 5 is illustrated in the structure that protective film 56 is set on the light-sensitive transfer sheet of Fig. 4.
Even under the situation of these three layers of photographic layer structures, for each photographic layer, compare with near the sensitivity of the side photographic layer supporter, become high relatively away from the sensitivity of the photographic layer of supporter one side.Promptly for the sensitivity of photographic layer, the 3rd photographic layer is the highest, next second sensitization floor height, and the sensitivity of first photographic layer is minimum.
Use the light-sensitive transfer sheet of structure shown in Fig. 4 and Fig. 5, according to the zone that is used to form the needed luminous energy of pattern, by changing the luminous energy X that the 3rd photographic layer is solidified, the luminous energy Y that the 3rd photographic layer and second photographic layer are solidified, make the 3rd photographic layer, luminous energy Z and rayed amount that second photographic layer and first photographic layer all solidify, as shown in Figure 6, the pattern that will have three stage different-thickness, promptly, to have the only zone of the thickness of the 3rd photographic layer curing, have the zone of the thickness that the 3rd photographic layer and second photographic layer solidify and have the 3rd photographic layer, the zone of the thickness that second photographic layer and first photographic layer all solidify can form with a kind of light-sensitive transfer sheet.
If same in addition usability photosphere be N layer (the sensitization number of plies is N), with supporter near the sensitivity of a side photographic layer compare the relative high light-sensitive transfer sheet of sensitivity away from the photographic layer of supporter one side, the cured layer pattern with N stage different-thickness can be with a kind of light-sensitive transfer sheet formation.
As putting down in writing so far, light-sensitive transfer sheet of the present invention is according to its exposure (so-called luminous energy), can make the thickness of the cured layer that obtains by exposure and development treatment is desirable thickness, as required by changing the pattern of exposure, can make zone that the photographic layer near substrate is solidified, changing thickness until zones that making is all solidified photographic layer successively.Thereby, can be formed on the different three-dimensional structure of image inner thickness and give the cured resin image that only improves desired regional film strength or only improve characteristics such as desired area image concentration etc. with a kind of light-sensitive transfer sheet.
Thereby, if light-sensitive transfer sheet of the present invention is used for the printed circuit board (PCB) manufacturing, especially for having through hole and during via the manufacturing of the printed circuit board (PCB) in hole, can form the cured layer of the height explanation that forms the thickness relative thin in the zone at Wiring pattern, form the thick relatively high-intensity cured layer of thickness at through hole or in via the hole.Thereby the light-sensitive transfer sheet of the application of the invention, have the abundant masked film intensity that can be used as the covering method utilization, and be easy to form the solidified resin pattern of abundant resolution in the high-resolution part of needs.
According to the present invention, can judge that the light-sensitive transfer sheet with above-mentioned curve of sensitivity can be by from realizing away from the sensitivity that supporter one side improves each photographic layer successively relatively near supporter one side direction.This photographic layer is more than two layers and the method that improves the sensitivity of those photographic layers successively can all be used known high sensitivity technology.Initiating agent that promptly can be by for example using high sensitivity, use sensitizer, increase the content of Photoepolymerizationinitiater initiater and/or sensitizer or increase polymerizable compound in the photographic layer containing ratio, reduce methods such as polymerization inhibitor or polymerization inhibitor ratio and obtain.Particularly under photographic layer is two layers situation, except by the initiating agent that uses high sensitivity, also can the method acquisition such as Duo than first photographic layer by the containing ratio that in second photographic layer, adds sensitizer, the content of Photoepolymerizationinitiater initiater in second photographic layer and/or sensitizer is Duoed than first photographic layer or make polymerizable compound in second photographic layer.
On supporter of the present invention, use stacked in order first photographic layer of forming by the photosensitive composite that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater, the restraining barrier, and form and show second photographic layer of the light sensitivity that light sensitivity than first photographic layer is high relatively and the light-sensitive transfer sheet that obtains by the photosensitive composite that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater, form under picture pattern (solidified resin pattern) situation, the luminous energy S that second photographic layer begins to solidify is preferably at 0.05～10mJ/cm 2Scope in, more preferably at 0.1～5mJ/cm 2Scope in, particularly preferably in 0.15～2.5mJ/cm 2Scope in.In addition in order to make second photographic layer solidify needed luminous energy A preferably at 0.1～20mJ/cm 2Scope in, more preferably at 0.2～15mJ/cm 2Scope in, particularly preferably in 0.4～10mJ/cm 2Scope in.
Be used to solidify the needed luminous energy A of second photographic layer and be used to solidify the ratio (A/B) of the needed luminous energy B of first photographic layer preferably in 0.005～0.5 scope, more preferably in 0.0 1～0.4 scope, in 0.02～0.35 scope.And be used to solidify the needed luminous energy A of second photographic layer and until ratio (C/A) that first photographic layer begins to solidify needed luminous energy C preferably in the scope 1～10, more preferably in 1.1～9 scope, in 1.3～8 scope.This luminous energy C is preferably at 0.1～200mJ/cm in addition 2Scope in, more preferably at 1～100mJ/cm 2Scope in, particularly preferably in 2～50mJ/cm 2Scope in.
Secondly the various materials that use in the photographic layer for light-sensitive transfer sheet of the present invention and light-sensitive layers body describe.
[cementing agent]
The cementing agent that uses in each photographic layer is preferably solvable or have swelling property at least in alkaline aqueous solution.Example as such cementing agent, can use the have acidic-group cementing agent of (carboxyl, sulfonic group, phosphate etc.), specifiable especially is to be the ethylenic copolymer that for example contains carboxyl of representative, the urethane resin that contains carboxyl, polyamic acid resin, modified epoxy etc. with the cementing agent that contains carboxyl, owing to be adjusted in the dissolubility that applies in the solvent, the dissolubility in the alkaline-based developer, synthetic adaptability, film rerum natura etc. easily, therefore preferably contain the ethylenic copolymer of carboxyl.
Contain carboxyl ethylenic copolymer can by will be at least (1) contain the vinyl monomer of carboxyl and (2) can obtain with the monomer copolymerization of its copolymerization.
As the example of the vinyl monomer that contains carboxyl, specifiable is (methyl) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid one Arrcostab, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer etc.Also can use 2-hydroxyethyl (methyl) acrylate etc. to contain addition compound product, ω-carboxyl polycaprolactone one (methyl) acrylate of the monomer of hydroxyl and maleic anhydride or phthalic anhydride, cyclohexane dicarboxylic acid acid anhydride and so on cyclic anhydride etc. in addition.In addition, the precursor as carboxyl also can use maleic anhydride, itaconic anhydride, citraconic anhydride etc. to contain the monomer of acid anhydride.Also have in the middle of these, from viewpoints such as copolymerization and cost, dissolubilities, preferred especially (methyl) acrylic acid.
As being used for the monomer that synthetic other of above-mentioned multipolymer can copolymerization, not restriction especially, example as such monomer is preferably ester class, phenylethylene, (methyl) vinyl cyanide of (methyl) esters of acrylic acid, crotonates class, vinyl ester, maleic acid diester class, dimethyl ester class, itaconic acid diester class, (methyl) acrylic amide, vinyl ethers, vinyl alcohol etc.Specifiable as such example is for example following such compound.
As the example of (methyl) esters of acrylic acid, specifiable is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate, (methyl) acrylic acid tert-butyl group cyclohexyl, (methyl) 2-EHA, (methyl) acrylic acid uncle monooctyl ester, (methyl) dodecylacrylate, (methyl) acrylic acid stearyl, (methyl) acrylic acid acetyl 2-ethoxyethyl acetate, (methyl) phenyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-methoxyl ethyl ester, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) acrylic acid 3-phenoxy group-2-hydroxy propyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid diglycol monomethyl ether-ether, (methyl) acrylic acid diglycol monoethyl ether ester, (methyl) acrylic acid diglycol one phenyl ether-ether, (methyl) acrylic acid triethylene glycol monomethyl ether-ether, (methyl) acrylic acid triethylene glycol monoethyl ether ester, (methyl) polyalkylene glycol acrylate monomethyl ether-ether, (methyl) polyalkylene glycol acrylate monoethyl ether ester, propenoic acid beta-propoxyl group ethoxy ethyl ester, (methyl) acrylic acid Nonylphenoxy macrogol ester, (methyl) acrylic acid two cyclopentane esters, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid two cyclopentene 2-ethoxyethyl acetates, (methyl) acrylic acid trifluoro ethyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) acrylic acid perfluoro capryl ethyl ester, (methyl) acrylic acid tribromo phenylester, (methyl) acrylic acid tribromo phenyl 2-ethoxyethyl acetate etc.
As the example of crotonates class, specifiable is butyl crotonate and the own ester of crotonic acid etc.As the example of vinyl ester, specifiable is vinylacetate, vinyl propionic ester, vinyl butyrate, vinyl methoxyacetic acid ester and benzoic acid vinyl esters etc.
As the example of maleic acid diester class, specifiable is dimethyl maleate, diethyl maleate and dibutyl maleate etc.As the example of dimethyl ester class, specifiable is dimethyl fumarate, DEF and dibutyl fumarate etc.As the example of itaconic acid diester class, specifiable is dimethyl itaconate, diethyl itaconate and dibutyl itaconate etc.
As (methyl) acrylic amide; specifiable is (methyl) acrylamide; N-methyl (methyl) acrylamide; N-ethyl (methyl) acrylamide; N-propyl group (methyl) acrylamide; N-isopropyl (methyl) acrylamide; N-normal-butyl (methyl) acrylamide; the N-tert-butyl group (methyl) acrylamide; N-cyclohexyl (methyl) acrylamide; N-(2-methoxy ethyl) (methyl) acrylamide; N; N-dimethyl (methyl) acrylamide; N, N-diethyl (methyl) acrylamide; N-phenyl (methyl) acrylamide; N-benzyl (methyl) acrylamide; (methyl) acryloyl morpholine; diacetone acrylamide etc.
As the example of phenylethylene, specifiable is hydroxy styrenes, vinyl benzoic acid methyl esters and the α-Jia Jibenyixi etc. of the group that styrene, methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, cumene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chlorostyrene, dichlorostyrene, bromstyrol, 1-chloro-4-methyl-benzene, employing can be by the acidic materials deprotections (for example t-Boc etc.) protection.As the example of vinyl ethers, specifiable is methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether and methoxy ethyl vinyl ether etc.
Except above-claimed cpd, also can use heterocyclic group (for example vinylpyridine, vinyl pyrrolidone, vinylcarbazole etc.), N-vinyl formamide, N-vinyl acetamide, N-vinyl imidazole, vinyl caprolactone of (methyl) vinyl cyanide, vinyl substituted etc.
In addition, also can use 2-acrylamide-2-methyl propane sulfonic acid, phosphoric acid one (2-acryloxy ethyl ester), phosphoric acid one (1-methyl-2-acryloxy ethyl ester) etc.
Except above-claimed cpd, also can use the vinyl monomer of functional groups such as for example containing carbamic acid base, urea groups, sulfoamido, phenolic group, imide.As the monomer that contains carbamic acid base or urea groups like this, can utilize for example isocyanate group and hydroxyl or amino addition reaction synthetic.Concretely, monomer that can be by containing isocyanate group with contain the compound of 1 hydroxyl or contain the addition reaction of the compound of 1 uncle or secondary amino group, perhaps contain the monomer of hydroxyl or contain uncle or the monomer of secondary amino group and the addition reaction of monoisocyanates etc. are synthesized.
As the object lesson of the monomer that contains isocyanate group, can enumerate for example following compound (R1 represents hydrogen atom or methyl).
[changing 1]
Figure A20041010067400231
As the object lesson of monoisocyanates, can enumerate for example NSC 87419, n-butyl isocyanate, TI, benzyl mustard oil, phenyl isocyanate etc.
As the object lesson that contains carboxylic monomer, can enumerate for example following compound (R 1Expression hydrogen atom or methyl, n represents the integer more than 1).
[changing 2]
As the compound that contains 1 hydroxyl, also can enumerate alcohols (methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, sec-butyl alcohol, the tert-butyl alcohol, n-hexyl alcohol, 2-Ethylhexyl Alcohol, Decanol, n-dodecane alcohol, n-octadecane alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, phenethyl alcohol etc.), phenols (phenol, cresols, naphthols etc.), contain substituent in addition as fluoroethanol, trifluoroethanol, methyl cellosolve, phenoxetol, chlorophenol, two chlorophenols, metoxyphenol, acetoxyl group phenol etc.
As the example that contains the uncle or the monomer of secondary amino group, for example can enumerate vinyl benzylamine etc.
Object lesson as the compound that contains 1 uncle or secondary amino group, specifiable is alkyl amine (methylamine, ethamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, hexylamine, 2 ethyl hexylamine, decyl amine, lauryl amine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkyl amine (cyclopentamine, cyclohexylamine etc.), aralkylamine (benzylamine, phenyl ethylamine etc.), arylamine (aniline, tolyl amine, dimethylaniline, naphthylamines etc.), also have these combination (N-methyl-N-benzyl amine etc.), contain substituent amine (trifluoro ethamine in addition, the hexafluoro isopropylamine, aminoanisole, methoxy propanamine etc.) etc.
Above-claimed cpd can only use a kind of, perhaps uses simultaneously more than two kinds.The example of particularly preferred other monomers is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) benzyl acrylate, (methyl) 2-EHA, styrene, chlorostyrene, bromstyrol and hydroxy styrenes etc.
Such ethylenic copolymer can make corresponding separately monomer copolymerization obtain according to conventional method by adopting known method.For example can use and these monomers are dissolved in the appropriate solvent and obtain to wherein adding the method (solution polymerization process) that radical polymerization initiator makes it polymerization in solution.Carry out the polymerization of so-called emulsion polymerization etc. under the state that also can in aqueous medium, make above-mentioned monomer disperse in addition.
As the example of the appropriate solvent that uses in the solution polymerization process, can select arbitrarily according to the dissolubility of the multipolymer of used monomer and generation.Specifiable is for example methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, 1-methoxyl-2-propyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxy propyl yl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl formamide, chloroform, toluene.These solvents can mix use more than two kinds.In addition, can use 2 as radical polymerization initiator, 2 '-azo two (isobutyronotriles) (AIBN), 2,2 '-azo two (2,4 '-methyl pentane nitrile) and so on azo-compound, the persulfate of superoxide of benzoyl peroxide and so on and potassium persulfate, ammonium persulfate and so on etc.
The containing ratio that contains the repetitive in the polymerizable compound of carboxyl in the ethylenic copolymer that comes free these monomers to obtain, preferably be 5～50 moles of % in all repetitives of multipolymer at each photographic layer, more preferably 10～40 moles of % are preferably 15～35 moles of % especially.If 5 moles of % of this containing ratio less than, then the development in the alkaline water is not enough sometimes, if surpass 50 moles of % then the developer solution patience of cured portion (image section) is not enough sometimes.
The molecular weight that contains the cementing agent of carboxyl can be adjusted arbitrarily, but at each photographic layer, the quality mean molecular weight all is preferably 2000～300000, is preferably 4000～150000 especially.If quality mean molecular weight less than 2000, then film strength is not enough easily, has in addition to be difficult to the stable trend of making.If molecular weight surpasses 300000 in addition, then development property has a declining tendency.
These contain the cementing agent of carboxyl in addition, all can use a kind ofly at each photographic layer, also can use the cementing agent more than two kinds simultaneously.As the example that uses the situation of cementing agent more than 2 kinds simultaneously, specifiable is the cementing agent more than 2 kinds that is become to be grouped into by different copolymer, the cementing agent more than 2 kinds of different quality mean molecular weight, the cementing agent more than 2 kinds of different dispersion degree etc.
The cementing agent that contains carboxyl, part or all of its carboxyl can neutralize with alkaline matter.Cementing agent can also use the different resins of structure such as vibrin, polyamide, urethane resin, epoxy resin, polyvinyl alcohol (PVA), gelatin simultaneously.
In addition as the example of cementing agent, also can enumerate the soluble resin in alkaline aqueous solution put down in writing in No. 2873889 grades of special permission etc.
The content of the cementing agent in the photographic layer all is generally 10～90 quality % at each photographic layer, is preferably 20～80 quality %, is preferably 40～80 quality % especially.This contain carboxyl cementing agent (and the macromolecule bond that uses simultaneously as required) if content few, alkali development and descend easily with adaptation that printed circuit board (PCB) forms with substrate (for example copper plating film laminated plate) then is if mistake has a declining tendency with respect to the stability of development time and the intensity of cured film (masked film) at most.In addition in order to regulate sensitivity, also can in above-mentioned scope, carry out the adjustment of following such grade, that is, make the containing ratio of the cementing agent that contains in second photographic layer than the containing ratio low (improving the containing ratio of polymerizable compound) of the cementing agent that contains in first photographic layer.
[polymerizable compound]
In photographic layer, use polymerizable compound (so-called monomer), preferred especially monomer or the oligomer (polyfunctional monomer, multifunctional oligomer) that contains 2 above polymerizable groups that use.As polymerizable group; specifiable be ethene unsaturated link (for example vinyl such as (methyl) acryloyl group, (methyl) acrylamido, styryl, vinyl esters and vinyl ether, allyls such as allyl ether and allyl ester etc.), can polymerization ring-type ether (for example epoxy radicals, oxetanyl etc.) etc.Optimal ethylene unsaturated link in the middle of these.
As the example of such polyfunctional monomer, specifiable is the acid amides etc. of ester, unsaturated carboxylic acid and the multivalence amines of unsaturated carboxylic acid (for example acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid etc.) and aliphatic polyol compound.
Object lesson as the monomer of the ester of aliphatic polyol compound and unsaturated carboxylic acid, as (methyl) acrylate ethylene glycol bisthioglycolate (methyl) acrylate is arranged, the ethene radix is 2～18 polyglycol two (methyl) acrylate (diglycol two (methyl) acrylate for example, triethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, nine glycol two (methyl) acrylate, ten diglycol two (methyl) acrylate, tetradecaethylene glycol two (methyl) acrylate etc.), propylene glycol two (methyl) acrylate, the propylene radix is 2～18 polypropylene glycol two (methyl) acrylate (dipropylene glycol two (methyl) acrylate for example, tripropylene glycol two (methyl) acrylate, four propylene glycol two (methyl) acrylate, ten dipropylene glycol two (methyl) acrylate etc.), neopentyl glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate of oxirane modification, neopentyl glycol two (methyl) acrylate of epoxy pronane modification, trimethylolpropane tris (methyl) acrylate, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris ((methyl) acryloxy propyl group) ether, trimethylolethane trimethacrylate (methyl) acrylate, 1, ammediol two (methyl) acrylate, 1,3-butylene glycol two (methyl) acrylate, 1,4-butylene glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, tetramethyl glycol two (methyl) acrylate, 1,4-cyclohexanediol two (methyl) acrylate, 1,2,4-butantriol three (methyl) acrylate, 1,5-pentanediol two (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, D-sorbite three (methyl) acrylate, D-sorbite four (methyl) acrylate, D-sorbite five (methyl) acrylate, D-sorbite six (methyl) acrylate, dihydroxymethyl two cyclopentane two (methyl) acrylate, tristane two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane two (methyl) acrylate of neopentyl glycol modification, at least respectively two (methyl) acrylate (for example compound of putting down in writing in the WO01/98832 communique etc.) that contains the alkene glycol chains of a glycol chain/propylene glycol chain, addition three (methyl) acrylate of trimethylolpropane of oxirane and/or epoxypropane, polytetramethylene glycol two (methyl) acrylate, glycerine two (methyl) acrylate, glycerine three (methyl) acrylate, xylenols two (methyl) acrylate etc.
As preferred example in above-mentioned (methyl) esters of acrylic acid, from its angle that obtains easily, specifiable is ethylene glycol bisthioglycolate (methyl) acrylate, polyglycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, at least respectively two (methyl) acrylate that contains the alkene glycol chains of a glycol chain/propylene glycol chain, trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythritol triacrylate, pentaerythrite two (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, glycerine three (methyl) acrylate, two glycerine two (methyl) acrylate, 1, ammediol two (methyl) acrylate, 1,2,4-butantriol three (methyl) acrylate, 1,4-cyclohexanediol two (methyl) acrylate, 1,5-pentanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, three (methyl) acrylate of the trimethylolpropane of oxirane addition etc.
Example as the ester (itaconate) of itaconic acid and aliphatic polyol compound, ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1 are arranged, 3-butylene glycol diitaconate, 1,4-butylene glycol diitaconate, tetramethyl glycol diitaconate, pentaerythrite diitaconate and D-sorbite four itaconates etc.
Example as the ester (crotonates) of crotonic acid and aliphatic polyol compound has ethylene glycol bisthioglycolate crotonates, tetramethyl glycol two crotonatess, pentaerythrite two crotonatess and D-sorbite four or two crotonatess etc.
Example as the ester (iso-crotonic acid ester) of iso-crotonic acid and aliphatic polyol compound has ethylene glycol bisthioglycolate iso-crotonic acid ester, pentaerythrite two iso-crotonic acid esters and D-sorbite four iso-crotonic acid esters etc.Example as the ester (maleate) of maleic acid and aliphatic polyol compound has ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate and D-sorbite four maleates etc.
In addition as the example of the acid amides of deriving by multivalence amines and unsaturated carboxylic acid class, methylene two (methyl) acrylamide, ethylene (methyl) acrylamide, 1 are arranged, 6-hexylidene two (methyl) acrylamide, Ya Xinji two (methyl) acrylamide, diethylene triamine three (methyl) acrylamide, diethylene triamine two (methyl) acrylamide and dimethylbenzene two (methyl) acrylamide etc.
What can also enumerate in addition is to contain 2 of bis-phenol skeleton, two [4-(3-(methyl) propylene oxygen-2-hydroxyl propoxyl group) phenyl] propane of 2-, 2, two [4-(4-(methyl) the propylene oxygen ethoxy) phenyl] propane of 2-, the substituted ethylene oxy radix of the OH of 1 phenol base be 2～20 2, two (4-((methyl) acryloxy polyethoxy) phenyl) propane of 2-(for example 2, two (4-((methyl) acryloxy diethoxy) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy tetraethoxy) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy five ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy ten ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy 15 ethoxys) phenyl) propane of 2-etc.), 2, two [4-((methyl) propylene oxygen propoxyl group) phenyl] propane of 2-, the substituted propenyloxy group number of the OH of 1 phenol base be 2～20 2, two (4-((methyl) acryloxy gathers propoxyl group) phenyl) propane of 2-(for example 2, two (4-((methyl) acryloxy dipropoxy) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy four propoxyl group) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy five propoxyl group) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy ten propoxyl group) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy 15 propoxyl group) phenyl) propane of 2-etc.) and in a part, contain the compound etc. (for example the compound of putting down in writing in the WO01/98832 communique etc.) of polyoxyethylene skeleton and polyoxypropylene skeleton simultaneously as the polyethers position of these compounds.These compounds can be used as for example BPE-200, BPE-500, BPE-1000 acquisitions such as (Xin Zhong village chemical industry (strain) manufacturings).
In addition, also can use as for as the addition product of bis-phenol and oxirane or epoxypropane etc., addition polymer and the end that obtains contains compound (2-isocyanates ethyl (methyl) acrylate, the α that the compound of hydroxyl has isocyanate group and polymer-based group, alpha-alpha-dimethyl one vinyl benzyl based isocyanate etc.) to add adult such, contain the polymerizable compound of bis-phenol skeleton and carbamic acid base.
In addition, also can use at phenolic resin varnish type epoxy resin, butylene glycol-1,4-diglycidyl ether, cyclohexanedimethanol glycidol ether, ethylene glycol diglycidylether, diglycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, pentaerythrite four glycidol ethers, bisphenol A diglycidyl ether, glycerine triglycidyl group ether etc. contain addition α in the glycidyl compound, the compound that beta-unsaturated carboxylic acid obtains.
Also can use the compound that contains polymerizable group and carbamic acid base in addition.Example as such compound, specifiable is at the public clear 48-41708 of spy, the spy opens clear 51-37193, special fair 5-50737, special fair 7-7208, the spy opens 2001-154346, the spy opens record in the 2001-356476 communique etc., for example by containing the polyisocyanate compounds (for example 1 of 2 above isocyanate group in 1 molecule, hexamethylene-diisocyanate, trimethyl 1, hexamethylene-diisocyanate, isophorone diisocyanate, Xylene Diisocyanate, toluene diisocyanate, phenylene vulcabond, the norborene diisocyanate, diphenyl diisocyanate, methyl diphenylene diisocyanate, 3,3 '-dimethyl-4, the trimer of the biuret body of 4 '-diphenyl diisocyanate and these diisocyanate and isocyanuric acid ester etc., these diisocyanates and trimethylolpropane, pentaerythrite, polyfunctional alcohols such as glycerine or the polyfunctional alcohol that obtained by these ethylene oxide adducts etc. add adult etc.) and molecule in contain vinyl monomer (2-hydroxyethyl (methyl) acrylate for example of hydroxyl, 2-hydroxypropyl (methyl) acrylate, 4-hydroxyl butyl (methyl) acrylate, diglycol one (methyl) acrylate, triethylene glycol one (methyl) acrylate, polyglycol one (methyl) acrylate, dipropylene glycol one (methyl) acrylate, tripropylene glycol one (methyl) acrylate, polypropylene glycol one (methyl) acrylate, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate etc.) contain the vinyl urethane compounds etc. of 2 above polymerism vinyl in 1 molecule that addition obtains.Also can use the compound that contains isocyanurate ring three (methyl) acrylate as the cyamelide of three ((methyl) acryloxy ethyl) isocyanuric acid ester, two (methyl) propylene isocyanuric acid ester, oxirane modification etc. in addition.
What can enumerate in addition is that the spy opens clear 48-64183 number, the spy opens clear 49-43191 number, polyester acrylate and polyester (methyl) the acrylate oligomer class put down in writing in special public clear 52-30490 number each communique, make epoxy compound (phenolic resin varnish type epoxy resin, butylene glycol-1, the 4-diglycidyl ether, the cyclohexanedimethanol glycidol ether, the diglycol diglycidyl ether, the dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, pentaerythrite four glycidol ethers, bisphenol A diglycidyl ether, T 55 etc.) and the polyfunctional acrylic ester and the methacrylates such as epoxy acrylate class of (methyl) acrylic acid reaction.What also can enumerate in addition is carboxylate that is obtained by the vinyl monomer that contains hydroxyl in phthalic acid or trimellitic acid etc. and the above-mentioned molecule etc.Can also use in the bonding association of Japan magazine 20 the 7th phases of volume the 300th～308 page (1984) material of introducing as photo-curable monomer and oligomer.
Also can use allyl ester (for example phthalic acid diallyl ester, hexane diacid diallyl ester, malonic acid diallyl ester, phthalic acid diallyl ester, trimellitic acid triallyl ester, benzenedisulfonic acid diallyl ester, triallyl isourea acid esters etc.) in addition; And diallyl acid amides (for example diallyl acetamide etc.).
In addition as polymerizable compound, also can use the divinyl ethers (butylene glycol-1 for example of cationically polymerizable, the 4-divinyl ether, the cyclohexanedimethanol divinyl ether, the ethylene glycol bisthioglycolate vinyl ether, diethylene glycol divinyl ether, the dipropylene glycol divinyl ether, the hexanediol divinyl ether, the trimethylolpropane tris vinyl ether, pentaerythrite tetrem alkene ether, the bisphenol-A divinyl ether, glycerine trivinyl ether etc.), epoxy compound (phenolic resin varnish type epoxy resin, butylene glycol-1, the 4-diglycidyl ether, cyclohexanedimethanodiglycidyl diglycidyl ether, ethylene glycol diglycidylether, the diglycol diglycidyl ether, the dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, pentaerythrite four glycidol ethers, bisphenol A diglycidyl ether, T 55 etc.), oxetanes class (for example 1, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] benzene of 4-etc.).As epoxy compound, oxetanes class, also can use the compound of putting down in writing among the WO01/22165 in addition.
As the example of vinyl acetate, also can use succinic acid divinyl ester, hexane diacid divinyl ester, phthalic acid divinyl ester, terephthalic acid (TPA) divinyl ester, divinylbenzene-1,3-disulfonate and divinyl butane-1,4-disulfonate etc.
As the example of distyryl compound, what can enumerate is divinylbenzene, 4-allyl styrene and 4-isopropene styrene etc.
Also have as the compound beyond the above-claimed cpd, N-beta-hydroxyethyl-β-(methacryl amido) ethyl propylene acid esters, N, N-two (Beta-methyl propylene oxygen ethyl) acrylamide, allyl methacrylate etc. contain the compound of 2 above differing ethylene unsaturated double-bonds, can enumerate the compound that uses among the present invention as being fit to.
These polyfunctional monomers, oligomer can separately or make up more than 2 kinds and use.
Also can use molecule to contain the polymerizable compound (monofunctional monomer) of 1 polymerizable group in addition as required simultaneously.As the example of monofunctional monomer, the specifiable compound of opening record in the such monofunctional monomer of disclosed 2 yuan-((methyl) acryloyloxyalkyl)-(halo hydroxy alkyl ester) in the flat 6-236031 communique (for example γ-chloro-β-hydroxy propyl-Beta '-methacryloxyethyl-phthalic ester etc.) etc. and No. 2744643, patent, WO00/52529 number, No. 2548016 communiques of patent etc. as the illustrated compound of above-mentioned cementing agent raw material, spy.
The content of monomer in the photographic layer is all general in the scope of 5～90 quality %, preferably in the scope of 15～60 quality %, in the scope particularly preferably in 20～50 quality % at each photographic layer.Hide film strength if the content of monomer is lower than above-mentioned scope and reduce, if the trend that when preserving, has edge-melting (fault of oozing out from reel ends) to worsen at most.Contain the content of the polyfunctional monomer of 2 above polymerizable groups in whole in addition monomers, general in the scope of 5～100 quality %, preferably in the scope of 20～100 quality %, more preferably in the scope of 40～100 quality %.In addition in order to adjust sensitivity, also can in above-mentioned scope, improve monomer containing ratio one side's etc. of second photographic layer adjustment.
[Photoepolymerizationinitiater initiater]
As the Photoepolymerizationinitiater initiater that is used for light-sensitive transfer sheet of the present invention, having the compound that causes above-mentioned monomer component polymerizing power can all use, and is particularly suitable for using having photosensitive material for ultraviolet range～visible light ray.Photoepolymerizationinitiater initiater preferably contains and at least aly (more preferably has the composition at least about 50 molecule absorptivity in 330～500nm) scopes at about 300～800nm.Photoepolymerizationinitiater initiater both can be with light activated sensitizer the activating agent that certain effect generates living radical to take place in addition, also can be to cause the such initiating agent of cationic polymerization according to monomeric species.
As the preferred Photoepolymerizationinitiater initiater that uses in the photographic layer, specifiable is for example halogenated hydrocarbons derivant (material that for example has the triazine skeleton, the material of Ju You oxadiazole skeleton), hexa-aryl bi-imidazole, 9 oxime derivate, organic peroxide, thio-compounds, ketonic compound, aromatic series salt, ketoxime ether etc.Wherein the viewpoints such as adaptation of particularly using substrate from sensitivity, keeping quality and photographic layer and the printed circuit board (PCB) formation of photographic layer are preferably used halogenated hydrocarbons, 9 oxime derivate, hexa-aryl bi-imidazole, the ketonic compound that contains the triazine skeleton.
As the halogenated hydrocarbon compound that contains the triazine skeleton, specifiable is following compound.
If work Bull.Chem.Soc.Japan such as woods, the compound of 42,2924 (1969) records, 2-phenyl-4 for example, 6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-chlorphenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-tolyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-methoxyphenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(2, the 4-dichlorophenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2,4,6-three (trichloromethyl)-1,3,5-triazines, 2-methyl-4,6-two (trichloromethyl)-1,3,5-triazines, 2-n-nonyl-4,6-two (trichloromethyl)-1,3,5-triazines and 2-(α, α, β-three chloroethyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine.
The compound of No. 1388492 instructionss of BrP record, 2-styryl-4 for example, 6-two (trichloromethyl)-1,3,5-triazine, 2-(4-methyl styrene base)-4,6-two (trichloromethyl)-1,3,5-triazine, 2-(4-methoxyl-styrene)-4,6-two (trichloromethyl)-1,3,5-triazines and 2-(4-methoxyl-styrene)-4-amino-6-trichloromethyl-1,3, the 5-triazine.
The compound of special public clear 53-133428 communique record, 2-(4-methoxyl-naphthoyl-1-yl)-4 for example, 6-two (trichloromethyl)-1,3,5-triazine, 2-(4-ethoxy-naphthoyl-1-yl)-4,6-two (trichloromethyl)-1,3,5-triazine, 2-[4-(2-ethoxyethyl group)-naphthoyl-1-yl]-4,6-two (trichloromethyl)-1,3,5-triazine, 2-(4,7-dimethoxy-naphthoyl-1-yl)-4,6-two (trichloromethyl)-1,3,5-triazine and 2-(acenaphthene acyl-5-yl)-4,6-two (trichloromethyl)-1,3,5-triazines.
The compound of No. 3337024 instructionss of Deutsche Bundespatent record, 2-(4-styryl phenyl)-4 for example, 6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-(4-methoxyl-styrene) phenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(1-naphthyl ethenylidene phenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-chlorostyrene base phenyl-4,6-two (trichloromethyl)-1,3,5-triazines, 2-(4-thiophene-2-ethenylidene phenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-thiophene-3-ethenylidene phenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-furans-2-ethenylidene phenyl)-4,6-two (trichloromethyl)-1,3,5-triazine and 2-(4-coumarone-2-ethenylidene phenyl)-4,6-two (trichloromethyl)-1,3,5-triazines.
People such as F.C.Schaefer are at J.Org.Chem.; 29, the compounds of record in 1527 (1964), 2-methyl-4 for example, 6-two (trisbromomethyl)-1,3,5-triazine, 2,4,6-three (trisbromomethyl)-1,3,5-triazines, 2,4,6-three (two bromomethyls)-1,3,5-triazine, 2-amino-4-methyl-6-three (bromomethyl)-1,3,5-triazines and 2-methoxyl-4-methyl-6-trichloromethyl-1,3, the 5-triazine.
The spy opens the compound of clear 62-58241 communique record, 2-(4-phenylacetylene base phenyl)-4 for example, 6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-naphthyl-1-ethynyl phenyl)-4,6-two (trichloromethyl)-1,3,5-triazines, 2-(4-(4-tolyl ethinyl) phenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-(4-methoxyphenyl) ethynyl phenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-(4-isopropyl phenyl ethinyl) phenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-(4-ethylphenyl ethinyl) phenyl)-4,6-two (trichloromethyl)-1,3,5-triazines.
The compound of Te Kaiping 5-281728 communique record, 2-(4-trifluoromethyl)-4 for example, 6-two (trichloromethyl)-1,3,5-triazine, 2-(2, the 6-difluorophenyl)-4,6-two (trichloromethyl)-1,3,5-triazines, 2-(2, the 6-dichlorophenyl)-4,6-two (trichloromethyl)-1,3,5-triazine, 2-(2, the 6-dibromo phenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine.
2 of Te Kaiping 5-34920 communique record, 4-two (trichloromethyl)-6-[4-(N, N-di ethoxy carbonyl methylamino)-and the 3-bromophenyl]-1,3, trihalomethyl group-s-triaizine compounds of putting down in writing in 5-triazine, No. 4239850 instructions of United States Patent (USP), also having specifiable is 2,4,6-three (trichloromethyl)-s-triazine, 2-(4-chlorphenyl)-4,6-two (trisbromomethyl)-s-triazine etc.
What also can enumerate in addition is the compound etc. of the Han You oxadiazole skeleton of record in No. 4212976 instructions of United States Patent (USP) etc.As the compound of Han You oxadiazole skeleton, specifiable is 2-trichloromethyl-5-phenyl-1,3 for example, 4-oxadiazole, 2-trichloromethyl-5-(4-yl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4 diazole, 2-trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-three bromo-5-phenyl-1,3,4-oxadiazole, 2-trisbromomethyl-5-(2-naphthyl)-1 ,-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-three chloro-5-(4-chlorostyrene base)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4 oxygen base styryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl) 3,4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxy styryl)-1 ,-oxadiazole, 2-trisbromomethyl-5-styryl-1,3,4-oxadiazole etc.
As the 9 oxime derivate that is fit among the present invention use, specifiable is the thing that following general formula is represented.
[changing 3]
Figure A20041010067400351
[changing 4]
[changing 5]
Figure A20041010067400371
[changing 6]
Figure A20041010067400381
R (29) n-C 3H 7(30) n-C 8H 17(31) camphyl (32) p-CH 3C 6H 4
Figure A20041010067400382
R(33)n-C 3H 7(34)p-CH 3C 6H 4
As operable hexa-aryl bi-imidazole among the present invention, specifiable is 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2-chlorphenyl)-4,4 ', the two imidazoles of 5,5 '-four (3-methoxyphenyls), 2,2 '-two (2-chlorphenyls)-4,4 ', the two imidazoles of 5,5 '-four (4-methoxyphenyls), 2,2 '-two (4-methoxyphenyls)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2-nitrobenzophenones)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2-aminomethyl phenyls)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2-trifluoromethyls)-4,4 ', 5,5 '-tetraphenyl double imidazole, the compound of putting down in writing in the WO00/52529 communique etc.
The above-mentioned pair of imidazoles can be by for example Bull.Chem.Soc.Japan, and disclosed methods are easy to synthesize in 33,565 (1960) and J.Org.Chem, 36 (16) 2262 (1971).
As ketonic compound, specifiable is benzophenone, 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, the 4-methoxy benzophenone, the 2-chlorobenzophenone, the 4-chlorobenzophenone, 4-bromine benzophenone, the 2-carboxyl benzophenone, 2-ethoxy carbonyl benzophenone, benzophenone tetrabasic carboxylic acid or its tetramethyl ester, 4,4 '-two (dialkyl amido) benzophenone (for example 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (dicyclohexyl amino) benzophenone, 4,4 '-two (lignocaine) benzophenone, 4,4 '-two (dihydroxy ethyl amino) benzophenone, 4-methoxyl-4 '-dimethylamino benzophenone, 4,4 '-dimethoxy-benzophenone, 4-dimethylamino benzophenone, 4-dimethylamino acetophenone, the benzyl anthraquinone, 2-tert-butyl group anthraquinone, 2-methylanthraquinone, phenanthrenequione, xanthone, thioxanthones, 2-chloro-thioxanthones, 2, the 4-diethyl thioxanthone, Fluorenone, 2-benzyl-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholine-1-acetone, 2-hydroxy-2-methyl-[4-(1-methyl ethylene) phenyl] propyl alcohol oligomer, benzoin, benzoin ethers (benzoin methylether for example, benzoin ethyl ether, the benzoin propyl ether, benzoin iso-propylether, the benzoin phenylate, benzyl dimethyl ketal), acridone, chloro-acridine ketone, N-methylacridine ketone, N-butyl acridone, N-butyl-chloro-acridine ketone etc.
In addition; what can also enumerate in addition is acridine derivatives (9-phenylacridine for example; 1; 7-two (9; 9 '-acridinyl) heptane etc.); N-phenylacridine etc.; multi-halogenated compounds (carbon tetrabromide for example; phenyl tribromo first sulfone; phenyl trichloromethyl ketone etc.); Coumarins (3-(2-coumarone formoxyl)-7-lignocaine cumarin for example; 3-(2-coumarone formoxyl)-7-(1-pyrrolidinyl) cumarin; 3-benzoyl-7-lignocaine cumarin; 3-(2-methoxybenzoyl base)-7-lignocaine cumarin; 3-(4-dimethylamino benzoyl)-7-lignocaine cumarin; 3; 3 '-carbonyl two (5; 7-two positive propoxy cumarins); 3; 3 '-carbonyl two (7-lignocaine cumarin); 3-benzoyl-ayapanin; 3-(2-furanylcarbonyl)-7-lignocaine cumarin; 3-(4-lignocaine cinnamyl)-7-lignocaine cumarin; 7-methoxyl-3-(3-pyridine radicals carbonyl) cumarin; 3-benzoyl-5; 7-dipropoxy cumarin; 7-benzotriazole-2-basic note legumin etc.; other specifiable spies of being open flat 5-19475 number; Te Kaiping 7-271028 number; the spy opens 2002-363206 number; the spy opens 2002-363207 number; the spy opens 2002-363208 number; the spy opens the middle coumarin compounds of putting down in writing such as 2002-363209 communique); amine (ethyl 4-dimethy laminobenzoate for example; the positive butyl ester of 4-dimethylamino benzoic acid; 4-dimethylamino benzoic acid phenethyl ester; 4-dimethylamino benzoic acid 2-phthaloyl imino ethyl ester; 4-dimethylamino benzoic acid 2-methacryloxy ethyl ester; pentamethylene two (4-dimethylaminobenzoic acid ester); the phenethyl ester of 3-dimethylamino benzoic acid and pentylidene ester; the 4-dimethylaminobenzaldehyde; 2-chloro-4-dimethylaminobenzaldehyde; 4-dimethylamino benzylalcohol; (4-dimethylamino benzoyl) ethyl acetate; 4-sends pyridine subbase acetophenone; 4-dimethylamino benzoin; N; N-dimethyl-4-toluidine; N; N-diethyl-3-phenetidine; tribenzyl amine; the dibenzyl phenyl amine; N-methyl-N-phenylbenzyl amine; 4-bromo-N; accelerine; tridecyl amine; amino glimmering hydro carbons (ODB; ODBII etc.); the gentian violet lactone; procrypsis gentian violet etc.); acylphosphine oxide class (for example two (2; 4; the 6-trimethylbenzoyl)-phenyl phosphine oxide; two (2; 6-dimethoxy benzoyl)-2; 4; 4-trimethyl-amyl group phenyl phosphine oxide; LucirinTPO etc.); class of metallocenes (two (η 5-2 for example; 4-cyclopentadiene-1-yl)-two (2,6-two chloro-3-(1H-pyrroles-1-yl) phenyl) titanium; η 5-cyclopentadienyl group-η 6-cumenyl one iron (1+)-hexafluoro phosphite (1-) etc.); special public clear 53-133428 communique; special public clear 57-1819 communique; with disclosed compound in 57-6096 communique and No. 3615455 instructions of United States Patent (USP) etc.
Moreover also can use the disclosed polyketone aldehyde compound that connects in No. 2367660 instructions of United States Patent (USP), the acyloin ether compound of putting down in writing in No. 2448828 instructions of United States Patent (USP), the aromatic series acyloin compound of putting down in writing in No. 2722512 instructions of United States Patent (USP) that is replaced by α-hydrocarbon, the multinuclear naphtoquinone compounds of putting down in writing in No. 3046127 instructions of United States Patent (USP) and same No. 2951758 instructions, the spy opens the organoboron compound put down in writing in the 2002-229194 communique and other illustrative free radical generating agents etc., also has triarylsulfonium salt (salt of antimony hexafluoride and hexafluorophosphoric acid), (phenyl sulfur phenenyl) diphenyl sulfonium salt etc. and so on De phosphonium salt compound (effectively as cationic polymerization initiators), the salt compound of WO01/71428 communique record etc.
Photoepolymerizationinitiater initiater can use a kind of or use simultaneously more than two kinds.As such combination, can use the benzothiazole compound put down in writing in the hexa-aryl bi-imidazole put down in writing in No. 3549367 instructions of United States Patent (USP) for example and the combination of 4-aminoketones, the special public clear 51-48516 communique and the combination of trihalomethyl group-s-triaizine compounds etc., also can use aromatic ketone compound such as thioxanthene and hydrogen to supply with combination, Coumarins and the cyclopentadienyltitanium of combination, hexa-aryl bi-imidazole and cyclopentadienyltitanium of body (for example containing dialkyl amino based compound, oxybenzene compound etc.) and the combination of phenylglycine class in addition.
The consumption of Photoepolymerizationinitiater initiater, at each photographic layer all with respect to photographic layer whole compositions generally in the scope of 0.1～30 quality %, preferably in the scope of 0.5～20 quality %, in the scope particularly preferably in 0.5～15 quality %.Regulate under the situation of sensitivity difference of each photographic layer at the content that uses Photoepolymerizationinitiater initiater in addition, the amount of the Photoepolymerizationinitiater initiater that contains in second photographic layer more than the amount of the optical polymerism initiating agent that contains in first photographic layer more and gets final product.Photoepolymerizationinitiater initiater content is preferably 1.5～100 times amount with respect to the content of the Photoepolymerizationinitiater initiater of first photographic layer in second photographic layer, and more preferably 1.8～50 times amount is preferably 2～20 times amount especially.
[sensitizer]
In order to regulate sensitivity and wavelength photoreceptor in each photographic layer exposure, can add sensitizer.Use luminous ray and ultraviolet light visible light laser as the light (active energy ray) of exposure etc. under the situation, sensitizer becomes excited state by active energy ray, interact with other materials (for example free radical generating agent, acid-producing agent etc.) (for example energy moves, electronics moves etc.), can produce useful groups such as free radical and acid.
As sensitizer; also can use the known polynuclear aromatic same clan (pyrene perylene for example; three adjacent inferior benzene); xanthenes class (fluorescein for example; eosin; erythrosine; rhodamine B; rose-red); cyanines class (indoles carbonyl cyanines for example; sulfo-carbonyl cyanines; oxo carbonyl cyanines); part cyanines class (part cyanines for example; carbonyl part cyanines); thiazide (thionine for example; methylenum careuleum; toluidine blue); acridine (acridine orange for example; chloroflavin; acridine yellow); anthraquinone class (for example anthraquinone); squarilium class (for example squarilium); acridine ketone (acridone for example; the chloro acridone; N-methylacridine ketone; N-butyl acridone; N-butyl-chloro acridone etc.); (specifiable be 3-(2-coumarone formoxyl)-7-lignocaine cumarin for example to Coumarins; 3-(2-coumarone formoxyl)-7-(1-pyrrolidinyl) cumarin; 3-benzoyl-7-lignocaine cumarin; 3-(2-methoxybenzoyl base)-7-lignocaine cumarin; 3-(4-dimethylamino benzoyl)-7-lignocaine cumarin; 3; 3 '-carbonyl two (5; 7-two positive propoxy cumarins); 3; 3 '-carbonyl two (7-lignocaine cumarin); 3-benzoyl-ayapanin; 3-(2-furanylcarbonyl)-7-lignocaine cumarin; 3-(4-lignocaine cinnamyl)-7-lignocaine cumarin; 7-methoxyl-3-(3-pyridine carbonyl) cumarin; 3-benzoyl 1; 7-dipropoxy cumarin etc., the in addition specifiable spy of being opens flat 5-19475 number; Te Kaiping 7-271028 number; the spy opens 2002-363206 number; the spy opens 2002-363207 number; the spy opens 2002-363208 number; the spy opens 2002-363209 number and waits the coumarin compound of putting down in writing in each communique) etc.
As the combination of polymerization initiator and sensitizer, specifiable is for example special example that the electronics mobile model initiator system of putting down in writing in the 2001-305734 communique [(1) electronics supply-type initiating agent and sensitizing coloring matter, (2) electronics acceptance type initiating agent and sensitizing coloring matter, (3) electronics supply-type initiating agent, sensitizing coloring matter and electronics acceptance type initiating agent (ternary initiator system)] puts down in writing in waiting etc. of opening.
First photographic layer and second photographic layer can contain sensitizer separately.The addition of sensitizer is with respect to the whole compositions of photosensitive polymer combination, and is general in the scope of 0.05～30 quality %, preferably in the scope in the scope of 0.1～20 quality %, particularly preferably in 0.2～10 quality %.If the addition of sensitizer is separated out from photographic layer at most,, thereby in exposure technology, can reduce productivity by spended time if very little then reduce for the sensitivity of active energy ray when preserving.
Using sensitizer to regulate under the situation of sensitivity difference of each photographic layer, the amount that the amount of the sensitizer that contains in second photographic layer cans be compared to the sensitizer that contains in first photographic layer most is the most.Sensitizer content is preferably 1.5～100 times amount with respect to the content of the sensitizer of first photographic layer in second photographic layer, and more preferably 1.8～50 times amount is preferably 2～20 times amount especially.Can not regulate in addition so that do not contain sensitizer in first photographic layer yet.
[other compositions]
Photographic layer also can use thermal polymerization inhibitor, plastifier, colour former, colorant to also have and the driving fit promoter of matrix surface and other auxiliary agent classes (for example pigment, electroconductive particle, filling agent, defoamer, fire retardant, levelling agent, peel off promoter, antioxidant, spices, thermal cross-linking agent, surface tension modifier, chain-transferring agent etc.) as required simultaneously, can regulate character such as stability as the light-sensitive transfer sheet of target, photography property, printing, film rerum natura thus.Mentioned component can be added in any one deck in first photographic layer and second photographic layer, and its addition determines according to purpose, both can be the same or different to the addition of photographic layer separately in addition.
[thermal polymerization inhibitor]
Thermal polymerization inhibitor for the thermal polymerization of the polymerizable compound that prevents photographic layer or through the time polymerization and adding.As thermal polymerization inhibitor, specifiable is 4-metoxyphenol for example, quinhydrones, the quinhydrones that alkyl or aryl replace, tert-butyl catechol, pyrogallol, the 2-dihydroxy benaophenonel, 4-methoxyl-2-dihydroxy benaophenonel, stannous chloride, phenothiazine, chloranil, naphthylamines, betanaphthol, 2,6-di-t-butyl-4-cresols, 2,2 '-methylene two (4-methyl-6-tert butyl phenol), pyridine, nitrobenzene, dinitro benzene, picric acid, the 4-toluidine, methylenum careuleum, copper and organic sequestering agent reactant, gaultherolin and phenothiazine, nitroso compound, the chelate of nitroso compound and A1 etc.
The addition of thermal polymerization inhibitor is with respect to the polymerizable compound of photographic layer, preferably in the scope of 0.001～5 quality %, more preferably in the scope of 0.005～2 quality %, in the scope particularly preferably in 0.01～1 quality %.Become many if the addition of thermal polymerization inhibitor exceeds this scope, the trend of reduction is then arranged for the sensitivity of active energy ray, if exceed that this scope tails off then stability when preserving has the trend of reduction.
[plastifier]
Plastifier is to add for the film rerum natura (flexibility) of sense of control photosphere.As the example of plastifier, specifiable is phthalates such as repefral, dibutyl phthalate, diisobutyl phthalate, dibutyl phthalate (DHP), dioctyl phthalate, dicyclohexyl phthalate, phthalic acid tricosyl ester, butyl benzyl phthalate, diisooctyl phthalate, diphenyl phthalate, diallyl phthalate, dioctyl phthalate; Diol-lipids such as triethylene-glycol diacetate, tetraethylene glycol diacetate esters, dimethyl glycol phthalate, monoethyl phthalate, methyl phthallyl ethyl glycollate, BPBG, triethylene glycol dieaprylate; Phosphoric acid esters such as three cresyl phosphates, triphenyl; Amide-types such as 4-toluenesulfonamide, benzsulfamide, N-n-butylbenzene sulfonamide, N-normal-butyl acetamide; Fatty acid dibasic acid ester classes such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, dioctyl azelate, dibutyl maleate; Triethyl citrate, tributyl citrate, glycerine triacetyl ester, butyl laurate, 4,5-diepoxy hexamethylene-1,2-dicarboxylic acid dioctyl ester etc., glycolss such as polyglycol, polypropylene glycol.
The addition of plastifier with respect to whole compositions of photographic layer preferably in the scope of 0.1～50 quality %, more preferably in the scope of 0.5～40 quality %, in the scope particularly preferably in 1～30 quality %.
[colour former]
Colour former adds in order to give exposure back photographic layer visual picture (printing function).Specifiable as colour former is three (4-dimethylamino phenyl) methane (procrypsis gentian violet), three (4-lignocaine phenyl) methane, three (4-dimethylamino-2-aminomethyl phenyl) methane, three (4-lignocaine-2-aminomethyl phenyl) methane, two (4-dibutylamino phenyl)-aminotriaryl methanes classes such as [4-(2-cyano ethyl) methylamino phenyl] methane, two (4-dimethylamino phenyl)-2-quinolyl methane, three (4-dipropyl aminophenyl) methane for example; 3,6-two (dimethylamino)-9-phenyl yanthine, 3-amino-amino xanthines such as 6-dimethylamino-2-methyl-9-(2-chlorphenyl) xanthine; 3,6-two (lignocaine)-9-(2-ethoxy carbonyl phenyl) thioxanthene, 3, amino thioxanthene classes such as 6-two (dimethylamino) thioxanthene; 3,6-two (lignocaine)-9,10-dihydro-9-phenylacridine, 3,6-two (benzyl amino)-9, amino such as 10-dihydro-9-methylacridine-9,10-acridan class; 3,7-two (amino phenoxazine class such as lignocaine) phenoxazine; 3, amino phenothiazines such as 7-two (ethylamino) phenthiazone; 3,7-two (lignocaine)-5-hexyl-5, amino dihydrophenazine classes such as 10-dihydrophenazine; Aminophenyl methane classes such as two (4-dimethylamino phenyl) phenylamino methane; 4-amino-4 '-dimethylamino diphenylamine, 4-amino-α, β-amino hydrogen cinnamic acids such as dicyano hydrogen methyl cinnamate; 1-(2-naphthyl)-hydrazine classes such as 2-phenyl hydrazine; 1,4-two (ethylamino)-2, the amino-2 of 3-dihydroanthracene quinones, 3-dihydroanthracene quinones; N, N-diethyl-phenethyl phenyl aminess such as 4-phenethyl aniline; 10-acetyl group-3,7-two (dimethylamino) phenothiazine etc. contains the acyl derivative of the procrypsis pigment of alkaline NH; But three (4-lignocaine-2-tolyl) ethoxy carbonyl terpane etc. does not have hydrogen that can oxidation can be oxidized to the procrypsis compound of chromophore compound; Procrypsis indigo pigment; No. 3042515, United States Patent (USP) and with the organic amine that can be oxidized to the color development shape of record in No. 3042517 (for example 4,4 '-ethylenediamine, diphenylamine, N, accelerine, 4,4 '-methylene diamine triphenylamine, N-vinylcarbazole).Particularly preferably be triarylmethane compounds such as procrypsis gentian violet.
Moreover make up in order to make these leuco compound color developments, to be known that with halogenated compound.Example as halogenated compound, specifiable is halogenated hydrocarbons (for example carbon tetrabromide, iodoform, ethylene dibromide, methylene bromide, bromo pentane, bromo isopentane, iodo-pentane, isobutane bromide, butyl iodide, bromo diphenyl methane, carbon trichloride, 1,2-ethylene dibromide, 1,1,2,2-tetrabromoethane, 1,2-two bromo-1,1,2-trichloroethanes, 1,2,3-tribromopropane, 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachloro cyclopropylene, hexachlorocyclopentadiene, dibromo-cyclohexane, 1,1,1-three chloro-2,2-two (4-chlorphenyl) ethane etc.); Halohydrin compound (for example 2,2,2-ethapon, ethobrom, 1,3-two chloro-2-propyl alcohol, 1,1, the amino isopropyl alcohol of 1-trichloro-2-propanol, two (iodine hexylidene), tribromo tert-butyl group alcohol, 2,2,3-three chlorobutanes-1,4-glycol etc.); Halo carbonyl compound (for example 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, perbrome-acetone, 1,1,3,3-tetrachloroacetone, 1,1,1-trichloroacetone, 3,4-two bromo-2-butanone, 1,4-two chloro-2-butanone-dibromo cyclohexanone etc.); Halogen ether compound (for example 2-bromo-ethyl-methyl ether, 2-bromoethyl ethylether, two (2-bromoethyl) ether, 1,2-Dichloroethyl ethylether etc.); Halogen ester compound (for example bromoethyl acetate, ethyl trichloroacetate, trichloroacetic acid trichloro ethyl ester, 2, the homopolymer of 3-dibromopropyl acrylate and multipolymer, dibromo-propionic acid trichloro ethyl ester, α, β-dichloropropylene acetoacetic ester etc.); Halogen acid amide compound (for example chloroacetamide, acetbromamide, dichloro acetamide, trichloroacetamide, tribromoacetamide, three chloroethyl trichloroacetamides, 2-bromine Isopropamide, 2,2,2-trichlorine propionamide, N-chloro-succinimide, N-bromine succinimide etc.); The compound (for example trisbromomethyl phenyl sulfone, 4-nitrobenzophenone trisbromomethyl sulfone, 4-chlorphenyl trisbromomethyl sulfone, three (2, the 3-dibromopropyl) phosphate etc.), 2 that contains sulphur or phosphorus, 4-two (trichloromethyl)-6-Phenyltriazole etc.Preferably have the halogenide that is attached to 2 above halogen atoms on the same carbon atom in the halogenated organic compound, particularly preferably in the halogenide that has 3 halogen atoms on 1 carbon atom.Organohalogen compounds both can use separately, also can use simultaneously more than 2 kinds.Wherein particularly preferred organohalogen compounds are trisbromomethyl phenyl sulfones, 2,4-two (trichloromethyl)-6-Phenyltriazole.
The addition of colour former is with respect to whole compositions of photographic layer, preferably in the scope of 0.01～20 quality %, more preferably in the scope of 0.05～10 quality %, in the scope particularly preferably in 0.1～5 quality %.Halid in addition amount is with respect to whole compositions of photographic layer, and is general in the scope of 0.001～5 quality %, is preferably 0.005～1 quality %.
[dyestuff]
In photographic layer, in order to improve operability that photosensitive polymer combination is painted, and can use dyestuff in order to give storage stability.Example as suitable dyestuff, specifiable is bright green (for example its sulfate), eosin, ethyl violet, Erythrosin B, methyl green, gentian violet, basic fuchsin, phenolphthalein, 1,3-diphenyl triazine, alizarin red S, thymolphthalein, methyl violet 2B, quinaldine red, rose-red, rice tower Neil Huang, the yellow phthalein of Thymol, xylenol blue, methyl orange, orange IV, diphenylthiocarbazone, 2, the 7-dichlorofluorescein, paramethyl red, Congo red, this assistant purple 4B, Alpha-Naphthyl is red, Nile blue A, phenacetolin, methyl violet, peacock green, paramagenta, oil blue #603 (オ リ エ Application ト chemical industry (strain) manufacturing), rhodamine B and rhodamine 6G, Victoria's pure blue B OH etc.As the corresponding negative ion of the dye of positive ion, the residue of organic acid or mineral acid preferably, specifiable is the residue (negative ion) of bromic acid, acid iodide, sulfuric acid, phosphoric acid, oxalic acid, methane-sulforic acid, toluenesulfonic acid etc. for example.Preferred dyestuff is the dye of positive ion, and specifiable is for example malachite green oxalates, malachite green sulfate etc.
The preferred addition of dyestuff is the amount of the scope of 0.001～10 quality % with respect to whole compositions of photographic layer, more preferably in the scope of 0.01～5 quality %, in the scope particularly preferably in 0.1～2 quality %.
[driving fit promoter]
For the adaptation that improves each interlayer or the adaptation between light-sensitive transfer sheet and the matrix, can use known so-called driving fit promoter in each layer.
As driving fit promoter, the suitable spy of use opens flat 5-11439 communique, the spy opens flat 5-341532 communique and the spy opens the middle driving fit promoter of putting down in writing such as flat 6-43638 communique.Specifiable concretely be benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2 one mercaptobenzoxazoles, 2-mercaptobenzothiazole, 3-morpholine methyl-1-phenyl-triazole-2-thioketones, 3-morpholine methyl-1-phenyl-oxadiazoles-2-thioketones, 5-amino-3-morpholine methyl-thiadiazoles-2-thioketones and 2-sulfydryl-5-methyl mercapto thiadiazoles, triazole, tetrazolium, benzotriazole, carboxyl benzotriazole, contain amino benzotriazole, silane coupling agent etc.
The preferred addition of driving fit promoter is the scope of 0.001 quality～20 quality % with respect to whole compositions of photographic layer, more preferably in the scope of 0.01～10 quality %, in the scope particularly preferably in 0.1 quality %～5 quality %.
Photographic layer also can contain organosulfur compound, superoxide, redox compounds, azo and two azo-compounds, photo-reduction pigment and the organohalogen compounds of putting down in writing in J. コ-サ-work " ラ イ ト セ Application シ テ イ Block シ ス テ system ズ " the 5th chapter for example etc.As the example of organosulfur compound, specifiable be di-n-butyl disulfide, benzyl disulfide thing,, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, benzenethiol, trichlorine ethyl methane sulfonate, 2-mercaptobenzimidazole etc.As the example of superoxide, specifiable is di-tert-butyl peroxide, benzoyl peroxide base, methyl-ethyl-ketone peroxide.Redox compound is the material that is combined to form by superoxide and reductive agent, and specifiable is ferrous ion and persulfuric acid ion, ferric ion and superoxide etc.As azo and two azo-compounds, specifiable is α, the phenodiazine class of α '-azoisobutyronitrile, 2-azo two-2-methylbutyronitrile, 4-amino-diphenyl-amine.As the photo-reduction pigment, specifiable is rose-red, erythrosine, eosin, acridine yellow, lactochrome, thionine.
[surfactant]
In order to improve when making light-sensitive transfer sheet, produce planar inhomogeneous, can add known surfactant.As the example of surfactant, can suitably be selected from anionic species and cationic surfactant and nonionic class surfactant, amphoteric surfactant, fluorochemical surfactant etc.Addition is preferably 0.001～10 quality % with respect to solid constituent in the photosensitive polymer combination, if less than 0.001 quality % then can not get the effect of planar improvement, if would surpass 10 quality % then be easy to generate the problem that so-called adaptation descends.As fluorine class surfactant, what also preferably have the fluorinated aliphatic group that contains the above fluorine atom of 40 quality % and replaced by fluorine by at least 3 hydrogen atoms that combine with carbon atom of the terminal number of nonbonding on 3～20 carbochains is the high molecular surfactant etc. of copolymer composition with acrylate or methacrylate.
[manufacturing of light-sensitive transfer sheet]
Light-sensitive transfer sheet of the present invention can be by for example following method manufacturing.At first, make above-mentioned various material dissolves, emulsification or be dispersed in water or solvent in, modulation forms the first photosensitive polymer combination solution that first photographic layer uses and forms the second photosensitive polymer combination solution that second photographic layer is used respectively.Modulation forms the solution that the restraining barrier is used in addition.
As the solvent of the first photosensitive polymer combination solution and the second photosensitive polymer combination solution, specifiable is alcohols such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, sec-butyl alcohol, n-hexyl alcohol for example; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; Ester classes such as ethyl acetate, butyl acetate, n-Amyl acetate, Methylsulfate, ethyl propionate, repefral, ethyl benzoate and methoxy-propyl acetate; Toluene, dimethylbenzene, benzene, ethylbenzene etc. are aromatic hydrocarbon based; Phenixin, triclene, chloroform, 1,1, halogenated hydrocarbons such as 1-trichloroethanes, methylene chloride, monochloro-benzene; Tetrahydrofuran, Anaesthetie Ether, glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxyl-ethers such as 2-propyl alcohol; Dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, sulfone etc., these also can mix use.In the first photosensitive polymer combination solution and the second photosensitive polymer combination solution, can add known surfactant.
The solvent that forms the polymer solution of using on the restraining barrier also can use the coating solvent same with photographic layer, can make the mixed solvent of water or water and solvent.Solvent can use above-mentioned hydrophilic solvents such as alcohols such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol etc.Using of solvent preferably makes solid constituent be 10%～90% of coating liquid.
Secondly on supporter, apply the first photosensitive polymer combination solution, form first photographic layer by drying.Then on first photographic layer, apply and form the coating liquid that the restraining barrier is used, drying.By applying the second photosensitive polymer combination solution and dry in the above, form second photographic layer.Coating during multilayer both can apply as mentioned above in order, also can be simultaneously with multiple coating.The painting method of photosensitive polymer combination solution limits especially, for example can adopt that gunite, rolling method, spin-coating method, slit are coated with method, squeezes extrusion method, curtain coating method, dip coating, gravure are coated with method, the coiling rod is coated with the whole bag of tricks such as method and knife coating.As drying condition, according to each composition, solvent types, usage ratio etc. and different, but be 30 second～15 minute usually under 60～110 ℃ temperature.
Even photographic layer more than 2 layers situation under, also can make desirable light-sensitive transfer sheet by repeating same operation.By making that photographic layer is more than two layers, the thickness summation of photographic layer also may be in the scope of 10 μ m～1mm.
[supporter and protective film]
It is good that supporter wishes to peel off the permeability of photographic layer and light, and Biao Mian flatness is good in addition.Supporter is preferably with synthetic resin manufacturing and transparent.As the example of supporter, specifiable is various plastic sheetings such as polyethylene terephthalate, Polyethylene Naphthalate, polypropylene, tygon, cellulose triacetate, cellulose diacetate ester, poly-(methyl) alkyl acrylate, poly-(methyl) acrylate copolymer, Polyvinylchloride, polyvinyl alcohol (PVA), polycarbonate, polystyrene, viscose paper, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride vinyl acetate co-polymer, politef, poly-triclene, cellulose family film, nylon film.Also can use by the compound substance of forming more than two kinds in these in addition.Preferred especially polyethylene terephthalate in above-mentioned.The thickness of supporter is preferably 2～150 μ m, and more preferably 5～100 μ m are preferably 8～50 μ m especially.Supporter is preferably rectangular supporter.The length of the rectangular supporter that uses when making light-sensitive transfer sheet of the present invention can arbitrary decision, for example can use the length of 10m～20000m.
Light-sensitive transfer sheet of the present invention can be on second photographic layer configuration protection film.As the example of above-mentioned protective film, specifiable is the material that uses in the above-mentioned supporter and paper or laminated polyethylene, polyacrylic paper etc.Particularly preferably be polyethylene film, polypropylene film.The thickness of protective film is preferably in the scope of 5～100 μ m, more preferably in the scope of 8～50 μ m, in the scope particularly preferably in 10～30 μ m.The cohesive force B of the cohesive force A of photographic layer and supporter and photographic layer and protective film need satisfy the relation of cohesive force A＞cohesive force B at that time.As the example of the combination of supporter/protective film, specifiable is polyethylene terephthalate/polypropylene, polyethylene terephthalate/polyethylene, Polyvinylchloride/viscose paper, polyimide/polypropylene, polyethylene terephthalate/polyethylene terephthalate etc.In addition, carry out surface treatment, can satisfy the relation of above-mentioned cohesive force by at least one side to supporter and protective film.The surface treatment of supporter can be in order to improve the cohesive force with photographic layer, and specifiable is for example being coated with of undercoat, Corona discharge Treatment, flame treatment, ultraviolet treatment with irradiation, high-frequency treatment with irradiation, glow discharge treatment with irradiation, plasma active treatment with irradiation, laser light irradiation processing etc.The coefficient of static friction of supporter and protective film also is important in addition.These coefficient of static friction are preferably 0.3～1.4, are preferably 0.5～1.2 especially.If less than 0.3, then because sliding excessively, generation misplaces when making the roller shape.When surpassing 1.4, be difficult to be rolled into good roller shape in addition.
Light-sensitive transfer sheet of the present invention for example is wound on volume core cylindraceous, and is rolled into the roller shape with elongate body and takes care of.The length of this elongate body can arbitrary decision, for example can select in the scope of 10m～20000m.For the user uses easily, also can carry out rip cutting processing, in the scope of 100m～1000m, make elongate body roller shape.At this moment preferably make supporter become outermost in addition by coiling.Also the light-sensitive transfer sheet of above-mentioned roller shape can be cut into sheet in addition.In when keeping, from the end face protection, prevent the viewpoint of edge-melting, preferably dividing plate (moisture resistance is particularly put into the dividing plate of drying agent) is set at end face, packing is also preferably used the low material of moisture-penetrability in addition.
Protective film also can carry out surface treatment.Surface treatment is carried out for the cohesiveness of regulating protective film and photographic layer.The undercoat of being made up of polymkeric substance such as polysiloxane, fluorinated polyolefin, polyvinyl fluoride and polyvinyl alcohol (PVA) for example is set on the surface of protective film.The formation of undercoat generally by after applying the coating liquid of above-mentioned polymkeric substance on the surface of protective film, was carried out down at 30～150 ℃ (particularly 50～120 ℃) in dry 1～30 minute.Except photographic layer, restraining barrier, supporter, protective film, also can have layers such as cushion, peel ply, tack coat, light absorbing zone, sealer in addition.
[matrix]
As the matrix of transfer printing light-sensitive transfer sheet of the present invention, can to material, select arbitrarily from the high material of surface smoothing with convex-concave surface.Preferably using tabular matrix is substrate.Specifiable concretely is the film, paper, sheet metal etc. of substrate, glass plate (soda-lime glass plate etc.), the synthetic resin of known printed circuit board (PCB) manufacturing usefulness.
Stacked in order by cementing agent, polymerizable compound with contain second photographic layer that the photosensitive polymer combination of Photoepolymerizationinitiater initiater is formed on matrix, and form and demonstrate first photographic layer low with respect to the light sensitivity of second photographic layer by cementing agent, polymerizable compound and the photosensitive polymer combination that contains Photoepolymerizationinitiater initiater, form the light-sensitive layers body.Also have, be preferably formed in the light-sensitive layers body that forms the configuration restraining barrier between above-mentioned first photographic layer and second photographic layer.
Light-sensitive transfer sheet of the present invention can be widely used as printed circuit board (PCB), color filter and post material, band muscle material, dividing plate, next door etc. and show with parts, holograph, micro computer, proof various Image forming materials such as (proof), pattern formation material.Wherein be preferably applied to printed circuit board (PCB), display unit, be preferably applied to printed circuit board (PCB) especially.
[pattern formation method]
Light-sensitive transfer sheet of the present invention can be by comprising (1) becomes substrate-side according to its second photographic layer on substrate the stacked operation that obtains laminated body of position relation, (2) carry out the rayed of specified image pattern by first photographic layer, one side of laminated body, feasible first photographic layer and the common operation of solidifying of second photographic layer of accepting its rayed zone, (3) remove the operation of supporter from laminated body, and (4) develop laminated body, remove the operation of uncured portion in the laminated body, on substrate, form the method for the picture pattern that constitutes by existing zone of cured resin that is solidified to form jointly by first photographic layer and second photographic layer and the non-existent zone of cured resin, form desirable pattern.
In addition, light-sensitive transfer sheet of the present invention also can be by comprising (1) becomes substrate-side according to its second photographic layer on substrate the stacked operation that obtains laminated body of position relation, (2) by first photographic layer, the one side picture pattern according to the rules of laminated body rayed is carried out in the zone of the light that shines the different mutually irradiation energies of two-stage at least, make first photographic layer and second photographic layer of accepting the big relatively light-struck zone of rayed energy solidify jointly, and the operation that feasible second photographic layer of accepting the relatively little light-struck zone of rayed energy solidifies, (3) remove the operation of supporter from laminated body, and (4) develop laminated body, remove the operation of uncured portion in the laminated body, on substrate, form the existing zone of resin that is solidified to form jointly by first photographic layer and second photographic layer, the zone that the resin that second photographic layer is solidified to form exists, and the method for the picture pattern of the non-existent zone of cured resin formation, form desirable pattern.
But in said method, the operation that (3) remove supporter from laminated body can not carried out between operation (2) and operation (4) yet, and carries out between operation (1) and operation (2).
As light-struck light source in the operation (2), can use to be created in the electromagnetic wave that sees through supporter when carrying out rayed and make used Photoepolymerizationinitiater initiater and sensitizer activate, wavelength light source, especially preferably use the light source of 330nm～650nm scope at the ultraviolet～luminous ray of the preferred 320～800nm scope of 300～1500nm by supporter.For example can use the known light source such as fluorescent tube, LED, semiconductor laser of (surpassing) high-pressure mercury-vapor lamp, xenon lamp, carbon arc lamp, Halogen lamp LED, used in copy machines etc.In addition also can use electronics line or X line etc.Also can use same light source even after peeling off supporter, carry out in addition under light-struck situation.Wherein rayed preferably adopts the irradiation of laser beam to carry out, and Wavelength of Laser is preferably in the scope of 200～1500nm, more preferably in the scope of 300～800nm, particularly preferably in the scope of 370nm～650nm, most preferably in the scope of 400nm～450nm.
[manufacture method of printed circuit board (PCB)]
Light-sensitive transfer sheet of the present invention is suitable for the manufacturing of printed circuit board (PCB), particularly has through hole or via the manufacturing of the printed circuit board (PCB) of hole portions such as hole.
Light-sensitive transfer sheet of the present invention can to become the position relation of substrate-side according to its second photographic layer on substrate stacked by comprising (1), obtain the operation of laminated body, (2) carry out the rayed of regulation Wiring pattern by first photographic layer, one side of laminated body, feasible first photographic layer and the common operation of solidifying of second photographic layer of accepting its light-struck zone, (3) remove the operation of supporter from laminated body, and (4) develop laminated body, remove the operation of uncured portion in the laminated body, on printed circuit board (PCB) forms with substrate, form the method for the Wiring pattern that the zone of being exposed by zone that cured resin covered that is solidified to form jointly by first photographic layer and second photographic layer and substrate surface constitutes, form desirable pattern.
In addition, light-sensitive transfer sheet of the present invention also can be by comprising (1) becomes substrate-side according to its second photographic layer on substrate the stacked operation that obtains laminated body of position relation, (2) carry out rayed from first photographic layer, one side of laminated body, form the operation of picture pattern, promptly hole portion being carried out the big relatively rayed of rayed energy solidifies win photographic layer and second photographic layer jointly, and distribution is formed the zone to carry out the relatively little rayed of rayed energy and makes second photographic layer solidify, (3) remove the operation of supporter from laminated body, and (4) develop laminated body, remove the operation of uncured portion in the laminated body, on forming with substrate, the printed circuit board (PCB) with hole portion forms the hole portion that cured resin covered that is solidified to form jointly by by first photographic layer and second photographic layer, the zone that cured resin covered that is solidified to form by second photographic layer, and the method for the Wiring pattern that constitutes of the substrate surface zone of exposing, form desirable pattern.
In said method, the operation that (3) remove supporter from laminated body can not carried out between operation (2) and operation (4) yet, and carries out between operation (1) and operation (2).
As light-struck light source in the operation (2), can use undertaken by supporter under light-struck situation seeing through supporter and with above-mentioned same light source.As light source, preferably undertaken by the irradiation of laser beam.
Then, in order to make printed circuit board (PCB), preferably adopt for example known subtraction of the method for carrying out etching or plating operation or addition (half add, full addition) to handle with substrate for the printed circuit board (PCB) formation that has formed above-mentioned Wiring pattern.The present invention forms printed circuit board (PCB) in order to adopt industrial favourable covering method, preferably uses by etched subtraction.Printed circuit board (PCB) forms and can peel off with cured resin remaining in the substrate after the above-mentioned processing, peels off a laggard step etching copper film section in addition and get final product under the situation of half add, can form desirable printed circuit board (PCB).Multilayer board also can be made equally with the manufacture method of above-mentioned printed circuit board (PCB) in addition.
Secondly at using light-sensitive transfer sheet manufacturing of the present invention to have the method for the printed circuit board (PCB) of through hole, describe with reference to accompanying drawing 7.Fig. 7 shows the light-sensitive transfer sheet shown in Fig. 1 or the situation of the light-sensitive transfer sheet shown in Fig. 2 used.
At first shown in Fig. 7 (A), preparation has through hole 22 and forms with substrate 21 at the printed circuit board (PCB) of the surface coverage coat of metal 23.Form with substrate 21 as printed circuit board (PCB), can use the copper plating film laminated base plate and on insulating substrates such as glass one epoxy, form the substrate of copper plate or dielectric film forms copper plate between these substrate top laminate substrate (laminated base plate).
Then as Fig. 7 (B) shown in, use backer roll 31 crimping light-sensitive transfer sheets 10, peel off this protective film under the situation of protective film containing, make its second photographic layer 14 and printed circuit board (PCB) formation with the surface of substrate 21 join (stacked operation).Obtain stacked in order printed circuit board (PCB) thus and form the laminated body of using substrate 21, second photographic layer 14, restraining barrier 13, first photographic layer 12 and supporter.The stacked of light-sensitive transfer sheet can carry out under (30～180 ℃) under room temperature (15～30 ℃) or the heating.Particularly preferably in carrying out under 60～140 ℃ the heating.The roll-in of crimping quinone is preferably at 1～10kg/cm 2Scope in.Crimping speed is preferably 1～3m/ minute.Also can heat printed circuit board (PCB) in addition in advance forms with substrate 21.Also can under reduced pressure carry out stacked in addition.
Do not use light-sensitive transfer sheet, but directly apply the second photosensitive polymer combination solution, barrier layer solution, the first photosensitive polymer combination solution and dry of making light-sensitive transfer sheet and using in order by the surface that forms at printed circuit board (PCB) with substrate, can obtain by printed circuit board (PCB) formation with substrate, second photographic layer, restraining barrier, be the laminated body of the such sequential cascade of first photographic layer then.
Then as Fig. 7 (C) shown in, make photographic layer curing from the face irradiates light of supporter 11 sides of laminated body.Also having at this moment can be as required (for example the inadequate situation of photopermeability of supporter etc.), carries out rayed while peel off supporter.The Wiring pattern that forms with substrate 21 at printed circuit board (PCB) forms in the zone, and pattern form irradiation according to the rules is used to solidify the light of second photographic layer, 14 needed luminous energies, forms the zone (wiring part exposure process) that Wiring pattern forms the cured layer 16 of usefulness.Form with the peristome of the through hole 22 of substrate and on every side at printed circuit board (PCB); irradiation is used for solidifying respectively the light of first photographic layer 12 and second photographic layer, 14 needed luminous energies, forms the zone (through-hole section exposure process) of the metal level protection of through hole with cured layer 17.Wiring part exposure process and through-hole section exposure process can independently carry out respectively, but preferably carry out simultaneously.Exposure is preferred by the photomask irradiation light, perhaps uses laser explosure device irradiating laser light.Particularly the method for the latter's use laser explosure device owing to the mask that does not use high price just can form pattern, thereby can not produce because therefore the problem on the operation that mask causes is applicable to the manufacturing of a small amount of many kinds goods.
Passing through under the situation of photomask irradiates light; also can use the method for 2 exposures; promptly the cured layer 16 regional photomasks that form usefulness by Wiring pattern formation usefulness shine the luminous energy that only makes that second photographic layer solidifies, and protect the cured layer 17 regional photomasks that form usefulness of usefulness to shine the luminous energy that makes second photographic layer and the two-layer curing of first photographic layer by the metal level of through hole.Perhaps also can use corresponding to Wiring pattern and form the light transmission rate of cured layer 16 area parts of usefulness photomask low, that make corresponding to the light transmission rate of cured layer 17 area parts of the metal level protection usefulness of through hole is high, carry out single exposure.On the other hand, under the situation of using laser explosure device irradiating laser light, Yi Bian preferably change the rayed amount in the zone that needs separately, Yi Bian carry out scan exposure.
Under the situation of unstripped supporter also, shown in Fig. 7 (D), peel off supporter 11 (supporter stripping process) from laminated body.
Secondly shown in Fig. 7 (E); use suitable developing solution dissolution to remove printed circuit board (PCB) and form the uncured zone of using first photographic layer 12, restraining barrier 13 and second photographic layer 14 on the substrate 21; the cured layer 16 of formation Wiring pattern formation usefulness and the metal level protection of through hole make the coat of metal 23 of substrate surface expose (developing procedure) with the pattern of cured layer 17.Developer solution preferably uses the developer solution corresponding to photosensitive polymer combination such as alkaline aqueous solution, water class developer solution, organic solvent.As developer solution, preferred weak alkaline aqueous solution.As the alkali composition of this weak alkaline aqueous solution, specifiable is lithium hydroxide, NaOH, potassium hydroxide, lithium carbonate, sodium carbonate, sal tartari, lithium bicarbonate, sodium bicarbonate, saleratus, sodium phosphate, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, borax etc.The pH of the weak alkaline aqueous solution that uses in developing in addition is preferably 9～11 especially for about 8～12.Can use aqueous sodium carbonate, wet chemical of 0.1～5 quality % etc. concretely.The temperature of developer solution can be adjusted in conjunction with the development of photographic layer in addition, but generally is preferably about 25 ℃～40 ℃.The organic solvent (alcohols, ketone, ester class, ethers, amide-type, lactone etc.) that also can use surfactant, defoamer, organic base (for example ethylenediamine, monoethanolamine, tetramethyl ammonium hydroxide, diethylene triamine, triethylene five amine, morpholine, triethanolamine etc.) in addition in this developer solution simultaneously and be used to promote develop.Developer solution both can use the water class developer solution of mixed water or alkaline aqueous solution and organic solvent, also can be separately with an organic solvent.
In addition, after development, can handle by back heat treated and post-exposure as required, implement further to promote the processing of the curing reaction of solidified portion.Developing both can be above-mentioned wet development method, also can adopt dried development method to carry out.
Then shown in Fig. 7 (F), adopt the etching solution dissolving to remove the coat of metal 23 (etching work procedure) that exposes at substrate surface.The peristome of through hole 22 is because the resin combination (masked film) 17 of being cured covers, so etching solution can not enter the coat of metal in the through hole internal corrosion through hole, and the coat of metal of through hole is residual with the shape of regulation.Form with forming Wiring pattern 24 on the substrate 21 at printed circuit board (PCB) thus.Under the situation that the coat of metal 23 forms with copper, can use copper chloride solution, ferric chloride solution, alkaline etch solution, hydroperoxide kind etching solution etc. as etching solution.Preferred especially ferric chloride solution wherein from etching factor aspect.
Secondly shown in Fig. 7 (G), adopt strong alkaline aqueous solution, as stripping film 18, remove (solidfied material is removed operation) with substrate from printed circuit board (PCB) formation with cured layer 16,17.As the alkali composition of strong alkaline aqueous solution, specifiable is NaOH, potassium hydroxide etc.It is about 12～14 that the pH of used in addition strong alkaline aqueous solution is preferably, and is preferably about 13～14 especially.Can use sodium hydrate aqueous solution, potassium hydroxide aqueous solution of 1～10 quality % etc. concretely.
Printed circuit board (PCB) can be the printed circuit board (PCB) of sandwich construction in addition.Light-sensitive transfer sheet of the present invention in addition not only is used for above-mentioned etch process, also can be used for shikishima plating process.As the plating method, for example copper facing such as copper sulphate plating, cupric pyrophosphate plating is arranged, soft solder plating such as soft solder plating, watt is bathed (nickelous sulfate monochlor(in)ate nickel) plating, nickel plating such as nickel sulfamic acid plating, the hard gold of plating, the soft gold of plating etc. are gold-plated.
[embodiment 1]
(formation of first photographic layer)
On the thick polyethylene terephthalate thin film of 20 μ m, apply the first photosensitive polymer combination solution and the drying formed by following component, form the first thick photographic layer of 25 μ m.
The first photosensitive polymer combination solution
(multipolymer is formed (mol ratio) to methyl methacrylate/2-EHA/benzyl methacrylate/methacrylic acid copolymer: 15 mass parts 55/11.7/4.5/28.8 quality mean molecular weight: 90,000, Tg:70 ℃)
1/2 mol ratio addition product, 8 mass parts of hexamethylene diisocyanate and eight oxirane one (methyl) acrylate
4,4 '-two (lignocaine) benzophenone, 0.04 mass parts
Benzophenone 1.0 mass parts
4-toluenesulfonamide 0.5 mass parts
Peacock green oxalates 0.02 mass parts
1,2,4-triazole 0.01 mass parts
Procrypsis gentian violet 0.2 mass parts
Trisbromomethyl phenyl sulfone 0.1 mass parts
Methyl ethyl ketone 30 mass parts
(formation on restraining barrier)
On first photographic layer, apply water-soluble polymer solution and the drying formed by following component, form the thick restraining barrier of 1.6 μ m.
Barrier layer solution
Polyvinyl alcohol derivative 13 mass parts that following structural formula is represented
Polyvinylpyrrolidone 6 mass parts
Water 200 mass parts
Methyl alcohol 180 mass parts
Polyvinyl alcohol derivative
(the importing rate of polymerizable group is 2 moles of %)
[changing 7]
Figure A20041010067400561
(formation of second photographic layer)
On the restraining barrier, apply the second photosensitive polymer combination solution and the drying formed by following component, form the second thick photographic layer of 5 μ m.
The second photosensitive polymer combination solution
Methyl methacrylate/2-EHA/benzyl methacrylate/methacrylic acid copolymer (multipolymer is formed (mol ratio): 40/26.7/4.5/28.8, quality mean molecular weight: 90,000, Tg:50 ℃) 15 mass parts
Polypropyleneglycol diacrylate 6.5 mass parts
Tetraethylene glycol dimethacrylate 1.5 mass parts
4,4 '-two (lignocaine) benzophenone, 0.4 mass parts
Benzophenone 3.0 mass parts
4-toluenesulfonamide 0.5 mass parts
Peacock green oxalates 0.02 mass parts
1,2,4-triazole 0.01 mass parts
Procrypsis gentian violet 0.2 mass parts
Trisbromomethyl phenyl sulfone 0.1 mass parts
Methyl ethyl ketone 10 mass parts
1-methoxyl-2-propyl alcohol 20 mass parts
(making of light-sensitive transfer sheet)
The thick polypropylene film of stacked 12 μ m on second photographic layer obtains light-sensitive transfer sheet at last.The thickness deviation of any one deck is all in ± 5%.Measure the sensitivity of the light-sensitive transfer sheet obtain thus by the aftermentioned method, the shortest development time of result is 30 seconds, and being used to solidify the required luminous energy A of second photographic layer is 4mJ/cm 2, being used to solidify the required luminous energy B of first photographic layer is 40mJ/cm 2, beginning to solidify required luminous energy C until first photographic layer is 14mJ/cm 2(the ratio C/A of luminous energy C and luminous energy A is 3.5, and the ratio A/B of luminous energy A and luminous energy B is 0.1).Under the light sensitivity of first photographic layer was 1 situation, the light sensitivity of second photographic layer was 10 in addition.
[embodiment 2]
(synthesis example of polyvinyl alcohol derivative)
10 mass parts polyvinyl alcohol (PVA) (PVA205 Network ラ レ (strain) manufacturing) are dissolved in the 90 mass parts water.The solution and the 0.002 mass parts quinhydrones of dissolving 2.3 mass parts n-methylolacrylamide in wherein being added on 20.7 mass parts water.Again to wherein adding 0.04 mass parts sulfuric acid and making it, obtain containing on the side chain 10 quality % aqueous solution of the polyvinyl alcohol (PVA) of acrylamido 40 ℃ of down reactions 4 hours.
(making of light-sensitive transfer sheet)
Except the barrier layer solution among the embodiment 1 is become following, obtain light-sensitive transfer sheet similarly to Example 1.
Barrier layer solution
10% aqueous solution, 130 mass parts of synthetic polyvinyl alcohol derivative
Polyvinylpyrrolidone 6 mass parts
Water 83 mass parts
Methyl alcohol 180 mass parts
The thickness deviation of any one deck is all in ± 5%.Measure the sensitivity of the light-sensitive transfer sheet obtain thus by the aftermentioned method, the shortest development time of result is 30 seconds, and being used to solidify the required luminous energy A of second photographic layer is 4mJ/cm 2, being used to solidify the required luminous energy B of first photographic layer is 40mJ/cm 2, beginning to solidify required luminous energy C until first photographic layer is 14mJ/cm 2(the ratio C/A of luminous energy C and luminous energy A is 3.5, and the ratio A/B of luminous energy A and luminous energy B is 0.1).
[embodiment 3]
(making of light-sensitive transfer sheet)
Except the barrier layer solution among the embodiment 1 is become following, obtain light-sensitive transfer sheet similarly to Example 1.
Barrier layer solution
Polyvinyl alcohol (PVA) (PVA205, Network ラ レ (strain) make) 13 mass parts
Polyvinylpyrrolidone 3 mass parts
Nine propylene glycol diacrylates, 3 mass parts
Water 200 mass parts
Methyl alcohol 180 mass parts
The thickness deviation of any one deck is all in ± 5%.Measure the sensitivity of the light-sensitive transfer sheet obtain thus by the aftermentioned method, the shortest development time of result is 30 seconds, and being used to solidify the required luminous energy A of second photographic layer is 4mJ/cm 2, being used to solidify the required luminous energy B of first photographic layer is 40mJ/cm 2, beginning to solidify required luminous energy C until first photographic layer is 14mJ/cm 2(the ratio C/A of luminous energy C and luminous energy A is 3.5, and the ratio A/B of luminous energy A and luminous energy B is 0.1).Under the light sensitivity of first photographic layer was 1 situation, the light sensitivity of second photographic layer was 10 in addition.
[comparative example 1]
Except the thickness with first photographic layer among the embodiment 1 becomes 30 μ m, do not apply the restraining barrier and second photographic layer, make light-sensitive transfer sheet similarly to Example 1.Measure the sensitivity of the light-sensitive transfer sheet obtain thus by the aftermentioned method, the shortest development time of result is 25 seconds, and being used to solidify the required luminous energy B of photographic layer is 40mJ/cm 2, beginning to solidify required luminous energy C until first photographic layer is 14mJ/cm 2
[comparative example 2]
Do not apply first photographic layer, restraining barrier among the embodiment 1, only make the light-sensitive transfer sheet that second photographic layer by thickness 5 μ m constitutes, measure the sensitivity of the light-sensitive transfer sheet that obtains thus by the aftermentioned method, the shortest development time of result is below 10 seconds, and being used to solidify the required luminous energy B of second photographic layer is 4mJ/cm 2
[assay method of sensitivity]
(1) assay method of short development time
The limit peels the protective film of light-sensitive transfer sheet; the limit uses laminating machine (MODEL 8B-720-PH, great achievement ラ ミ ネ--(strain) are made) joins light-sensitive transfer sheet according to second photographic layer and the substrate of light-sensitive transfer sheet mode to be crimped onto on the surface through the copper plating film laminated plate (not having through hole) of surface grinding, washing and drying, makes the laminated body by the such sequential cascade of copper plating film laminated plate, second photographic layer, restraining barrier, first photographic layer, polyethylene terephthalate thin film.The crimping condition is: 105 ℃ of crimping roller temperature, crimping roller pressure 3kg/cm 2, 1 meter/minute of crimping speed.Peel polyethylene terephthalate film from laminated body, on the whole surface of the photographic layer on the copper plating film laminated plate, spray 30 ℃ 1 quality % aqueous sodium carbonate with the expulsion pressure of 0.15MPa.Mensuration is removed the needed time to the photographic layer on the copper plating film laminated plate is dissolved from beginning to spray aqueous sodium carbonate, with this time as the shortest time of developing.
(2) mensuration of sensitivity
Same with the mensuration of the shortest development time, stacked light-sensitive transfer sheet on substrate.On the photographic layer of light-sensitive transfer sheet, use exposure device by polyethylene terephthalate thin film one side, from 0.1mJ/cm with 405nm LASER Light Source 2With 2 1/2Doubly at interval until 100mJ/cm 2, the light that the irradiates light energy is different makes photographic layer solidify.After at room temperature leaving standstill 10 minutes, peel off polyethylene terephthalate thin film from laminated body.On the whole surface of the resin combination layer on the copper plating film laminated plate, adopt the injection of 0.15Mpa to press, the time that the shortest development time of trying to achieve with above-mentioned (1) is 2 times is sprayed 30 ℃ of 1 quality % aqueous sodium carbonate, and uncured resin combination is removed in dissolving, measures the thickness of residual cured layer.Then draw the relation of rayed amount and cured layer thickness, obtain curve of sensitivity.Luminous energy (luminous energy C) when luminous energy (luminous energy B) when luminous energy (luminous energy A), the cured layer thickness when the curve of sensitivity that obtains thus reads cured layer thickness and is 5 μ m is 31.6 μ m and cured layer thickness surpass 5 μ m.
[assay method of resolution]
Under the condition identical with above-mentioned (1) the shortest development time evaluation method, by stacked copper plating film laminated plate, second photographic layer, restraining barrier, first photographic layer, polyethylene terephthalate thin film in order, make laminated body, room temperature (23 ℃ left standstill 10 minutes under 55%RH).From the polyethylene terephthalate thin film top of the laminated body that obtains, use exposure device with 405nm LASER Light Source, according to line/spacing=1/1, until 50 μ m, carry out the exposure of each live width with 5 μ m classifications by live width 10 μ m.At this moment exposure is the luminous energy that second photographic layer of each light-sensitive transfer sheet solidifies.After at room temperature leaving standstill 10 minutes, peel off polyethylene terephthalate thin film from laminated body.To the whole surface of the resin combination layer on the copper plating film laminated plate, adopt the injection of 0.15Mpa to press, with 30 ℃ of 1 quality % aqueous sodium carbonate of time injection of 2 times of above-mentioned the shortest development times of trying to achieve, uncured resin combination is removed in dissolving.The surface of the copper plating film laminated plate that has solidified resin pattern that obtains like this with observation by light microscope, measuring on the line of solidified resin pattern does not have unusual minimum feature such as shortening, fold, with it as resolution.Resolution sizes is more little then good more.
[manufacturing of printed circuit board (PCB) and evaluation]
Have respectively 200 have copper plate, diameter 3mm and 0.2mm through hole at inwall; and the surface is by on the copper plating film laminated plate of grinding, washing and drying; overlapping second photographic layer of peeling off the light-sensitive transfer sheet of protective film; lamination; with above-mentioned stacked equally in order copper plating film laminated plate, second photographic layer, restraining barrier, first photographic layer, polyethylene terephthalate thin film; make laminated body, room temperature (23 ℃ left standstill 10 minutes under 55%RH).Polyethylene terephthalate thin film top from the laminated body that obtains, use has the exposure device of 405nm LASER Light Source, form in the zone light of luminous energy that according to the rules pattern form irradiation is used to solidify second photographic layer of each light-sensitive transfer sheet at the Wiring pattern of copper plating film laminated plate, on the other hand in the via openings portion and the peripheral region thereof of copper plating film laminated plate, irradiation is used to solidify the light of luminous energy of first photographic layer of each light-sensitive transfer sheet, and photographic layer is exposed.After the exposure, peel off polyethylene terephthalate thin film from laminated body, then on the photographic layer surface, spray aqueous sodium carbonate equally with above-mentioned evaluation method, the uncured zone that first photographic layer, restraining barrier and second photographic layer are removed in dissolving, obtain the embossment (Wiring pattern portion only is that second photographic layer solidifies, and the peristome of through hole and peripheral region thereof are that first photographic layer, restraining barrier and second photographic layer solidify) of cured layer.The cured layer pattern that obtains with microscopic examination, the masked film of observing cured layer in the via openings portion of diameter 3mm and the diameter 0.2mm number of (covering) of breaking.
Also have when measuring the thickness of cured layer at this moment with laser microscope (VK-9500, キ-エ Application ス (strain) manufacturing), it is 5 μ m that Wiring pattern forms the regional thickness of going up cured layer, and the thickness of cured layer is 31.2 μ m (being 30 μ m in the comparative example 1) in the via openings portion.
Then spray iron chloride エ Star チ ヤ Application ト (etching solution that contains iron chloride) on the surface of copper plating film laminated plate, the copper layer that exposes the zone that does not cover with cured layer is removed in dissolving.Then spray the sodium hydrate aqueous solution of 2 quality %, remove the solidfied material embossment, obtain having through hole, have the printed circuit board (PCB) of Wiring pattern shape copper layer on the surface.Whether that the copper plate of the printed circuit board through-hole inwall that visualization obtains has is no abnormal (remaining copper facing).
[evaluation of storage stability]
Light-sensitive transfer sheet was preserved 1 day under 40 ℃, the environment of 60%RH.Estimate equally with above-mentioned sensitivity degree assay method then.The result, can form with preserve before equally only make that according to exposure being evaluated as of pattern that the cured film thickness of part that second photographic layer solidifies and common part of solidifying first photographic layer/second photographic layer is different is good, it is bad to form being evaluated as of such pattern (the sensitivity difference between photographic layer reduces or do not have the sensitivity poor).
At the light-sensitive transfer sheet that obtains like this, evaluation resolution, masked film are broken (diameter 3mm part and 0.2mm part), the interior copper facing of through hole has no abnormal, storage stability, and the result is as shown in table 1.
Table 1
Photonasty resolution Masked film is brokenPlating is preserved stable in the through hole
The abnormality of transfer paper 3mm 0.2mm copper
Embodiment 1 20 μ m do not have good
Embodiment 2 20 μ m do not have good
Embodiment 3 20 μ m do not have good
Comparative example 1 40 μ m nothing-
Comparative example 2 20 μ m all break all break have-
(notes)
-: owing to do not have the different photographic layer of sensitivity, therefore do not estimate
[embodiment 4]
(formation of first photographic layer)
On the thick polyethylene terephthalate thin film of 20 μ m, apply the first photosensitive polymer combination solution and the drying formed by following component, form the first thick photographic layer of 20 μ m.
The first photosensitive polymer combination solution
Methyl methacrylate/2-EHA/benzyl methacrylate/methacrylic acid copolymer (multipolymer is formed (mol ratio): 55/11.7/4.5/28.8, quality mean molecular weight: 90,000, Tg:70 ℃) 15 mass parts
12 polypropyleneglycol diacrylates, 6.5 mass parts
Tetraethylene glycol dimethacrylate 1.5 mass parts
4,4 '-two (lignocaine) benzophenone, 0.04 mass parts
Benzophenone 1.0 mass parts
4-toluenesulfonamide 0.5 mass parts
Peacock green oxalates 0.02 mass parts
1,2,4-triazole 0.01 mass parts
Procrypsis gentian violet 0.2 mass parts
Trisbromomethyl phenyl sulfone 0.1 mass parts
Methyl ethyl ketone 30 mass parts
(formation on restraining barrier)
On first photographic layer, apply water-soluble polymer solution and the drying formed by following component, form the thick restraining barrier of 1.6 μ m.
Water-soluble polymer solution
Polyvinyl alcohol derivative 13 mass parts that following structural formula is represented
Polyvinylpyrrolidone 6 mass parts
Water 200 mass parts
Methyl alcohol 180 mass parts
Polyvinyl alcohol derivative
[changing 8]
Figure A20041010067400631
(formation of second photographic layer)
On the restraining barrier, apply the second photosensitive polymer combination solution and the drying formed by following component, form the second thick photographic layer of 10 μ m.
The second photosensitive polymer combination solution
Methyl methacrylate/2-EHA/benzyl methacrylate/methacrylic acid copolymer (multipolymer is formed (mol ratio): 55/11.7/4.5/28.8, quality mean molecular weight: 90,000, Tg:70 ℃) 24 mass parts
1/2 mol ratio addition product, 12 mass parts of hexamethylene diisocyanate and eight oxirane one (methyl) acrylate
N-methylacridine ketone 0.2 mass parts
2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 0.8 mass parts
2-mercaptobenzimidazole 0.2 mass parts
4-toluenesulfonamide 0.8 mass parts
Peacock green oxalates 0.03 mass parts
1,2,4-triazole 0.03 mass parts
Procrypsis gentian violet 0.32 mass parts
Trisbromomethyl phenyl sulfone 0.25 mass parts
Methyl ethyl ketone 55 mass parts
1-methoxyl-2-propyl alcohol 8 mass parts
(formation on restraining barrier)
On second photographic layer, apply water-soluble polymer solution and the drying formed by said components, form the thick restraining barrier of 1.6 μ m.
(formation of the 3rd photographic layer)
On the restraining barrier, apply the 3rd photosensitive polymer combination solution and the drying formed by following component, form the 3rd thick photographic layer of 5 μ m.
The 3rd photosensitive polymer combination solution
Methyl methacrylate/2-EHA/benzyl methacrylate/methacrylic acid copolymer (multipolymer is formed (mol ratio): 40/26.7/4.5/28.8, quality mean molecular weight: 90,000, Tg:50 ℃) 13 mass parts
12 polypropyleneglycol diacrylates, 8.1 mass parts
Tetraethylene glycol dimethacrylate 1.9 mass parts
N-methylacridine ketone 0.16 mass parts
2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl, two miaows, 1.04 mass parts
4-toluenesulfonamide 0.5 mass parts
Peacock green oxalates 0.02 mass parts
1,2,4-triazole 0.01 mass parts
Procrypsis gentian violet 0.2 mass parts
Trisbromomethyl phenyl sulfone 0.1 mass parts
Methyl ethyl ketone 10 mass parts
1-methoxyl-2-propyl alcohol 20 mass parts
(making of light-sensitive transfer sheet)
The thick polypropylene film (protective film) of stacked 12 μ m obtains light-sensitive transfer sheet on the 3rd photographic layer.The thickness deviation of any one deck is all in ± 5%.The sensitivity of the light-sensitive transfer sheet that obtains thus with the same mensuration of said method, it is 1mJ/cm that the result is used to solidify the required luminous energy of the 3rd photographic layer 2, being used to solidify the required luminous energy of second photographic layer is 8mJ/cm 2, beginning to solidify required luminous energy until second photographic layer is 3mJ/cm 2, being used to solidify the required luminous energy of first photographic layer is 35mJ/cm 2, beginning to solidify required luminous energy until first photographic layer is 14mJ/cm 2Between the 3rd photographic layer and second photographic layer, C/A=8/3, A/B=3/14, between second photographic layer and first photographic layer, C/A=1.75, A/B=8/35.
With the same condition of the shortest above-mentioned development time evaluation method under, stacked in order copper plating film laminated plate, the 3rd photographic layer, restraining barrier, second photographic layer, restraining barrier, first photographic layer, polyethylene terephthalate thin film, make laminated body, room temperature (23 ℃ left standstill 10 minutes under 55%RH).By the polyethylene terephthalate thin film top of the laminated body that obtains, use to have the exposure device of 405nm LASER Light Source, carry out patterned illumination while change exposure.Peel off polyethylene terephthalate thin film then similarly to Example 1, carry out development treatment.As a result, can form as shown in Figure 10 segment thickness with low-yield irradiation be 5 μ m, with in the segment thickness of energy exposure be 16.6 μ m, be the pattern of the different-thickness of 38.2 μ m with the segment thickness of high energy radiation.

Claims (38)

1. light-sensitive transfer sheet, on supporter, be laminated with first photographic layer that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater in order, with the restraining barrier of containing polymerizable compound, and contain cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater and have second photographic layer than the relative high light sensitivity of the light sensitivity of first photographic layer.
2. according to the light-sensitive transfer sheet of claim 1 record, wherein the restraining barrier has photonasty, and the light sensitivity of relative first photographic layer of the light sensitivity on restraining barrier is low.
3. according to the light-sensitive transfer sheet of claim 1 record, wherein the polymerizable compound that contains in the restraining barrier is the polymkeric substance that contains polymerizable group.
4. according to the light-sensitive transfer sheet of claim 3 record, the polymkeric substance that wherein contains polymerizable group is 1～4 lower alcohol demonstration compatibility for water or carbon number.
5. according to the light-sensitive transfer sheet of claim 4 record, be 1～4 the lower alcohol polymkeric substance that contains polymerizable group that shows compatibility for water or carbon number wherein be that 1～4 lower alcohol is solvable for water or carbon number.
6. according to the light-sensitive transfer sheet of claim 1 record, wherein also to contain for water or carbon number be the polymkeric substance that 1～4 lower alcohol shows compatibility on the restraining barrier.
7. according to the light-sensitive transfer sheet of claim 6 record, be the polymkeric substance that 1～4 lower alcohol shows compatibility wherein for water or carbon number, for water or carbon number 1～4 lower alcohol solubility.
8. the light-sensitive transfer sheet of putting down in writing in each according to claim 1～7, wherein the restraining barrier has the thickness of 0.1～5 mu m range.
9. the light-sensitive transfer sheet of putting down in writing in each according to claim 1～8, wherein under the light sensitivity of first photographic layer was 1 situation, the light sensitivity of second photographic layer was in 2～200 scope.
10. the light-sensitive transfer sheet of putting down in writing in each according to claim 1～9, the ratio of representing with A/B that wherein is used to solidify the needed luminous energy A of second photographic layer and is used to solidify the needed luminous energy B of first photographic layer is in 0.005～0.5 scope.
11., wherein be used to solidify the needed luminous energy A of second photographic layer and begin to solidify in the scope of ratio of representing with C/A of needed luminous energy C 1～10 until first photographic layer according to the light-sensitive transfer sheet that claim 1～10 is put down in writing in each.
12. according to the light-sensitive transfer sheet that claim 1～11 is put down in writing in each, wherein the amount of the Photoepolymerizationinitiater initiater that contains in second photographic layer is more than the amount of the Photoepolymerizationinitiater initiater that contains in first photographic layer.
13. according to the light-sensitive transfer sheet that claim 1～12 is put down in writing in each, wherein the amount of the polymerizable compound that contains in second photographic layer is more than the amount of the polymerizable compound that contains in first photographic layer.
14. according to the light-sensitive transfer sheet that claim 1～13 is put down in writing in each, wherein first photographic layer has the thickness of 1～100 mu m range, and its thickness is bigger than the thickness of second photographic layer.
15. according to the light-sensitive transfer sheet that claim 1～14 is put down in writing in each, wherein second photographic layer has the thickness of 0.1～15 mu m range.
16. according to the light-sensitive transfer sheet that claim 1～15 is put down in writing in each, wherein supporter is a synthetic resin system and transparent.
17. according to the light-sensitive transfer sheet that claim 1～16 is put down in writing in each, wherein supporter is rectangular supporter.
18. the light-sensitive transfer sheet according to claim 1～17 is put down in writing in each wherein disposes protective film on second photographic layer.
19. according to the light-sensitive transfer sheet that claim 1～18 is put down in writing in each, it is an elongate body, is rolled into the roller shape.
20. according to the light-sensitive transfer sheet that claim 1～19 is put down in writing in each, it is used to make printing distributing board.
21. light-sensitive layers body, on matrix, be laminated with second photographic layer that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater in order, with the restraining barrier of containing polymerizable compound, and contain cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater and have first photographic layer than the relative low light sensitivity of the light sensitivity of second photographic layer.
22. according to the light-sensitive layers body of claim 21 record, wherein the restraining barrier has photonasty, the light sensitivity of relative first photographic layer of the light sensitivity on restraining barrier is low.
23. according to the light-sensitive layers body of claim 21 record, wherein the polymerizable compound that contains in the restraining barrier is the polymkeric substance that contains polymerizable group.
24. according to the light-sensitive layers body of claim 23 record, the polymkeric substance that wherein contains polymerizable group is 1～4 lower alcohol demonstration compatibility for water or carbon number.
25., be that 1～4 lower alcohol shows that the polymkeric substance that contains polymerizable group of compatibility is 1～4 lower alcohol solubility for water or carbon number wherein for water or carbon number according to the light-sensitive layers body of claim 24 record.
26. according to the light-sensitive layers body of claim 21 record, wherein also to contain for water or carbon number be the polymkeric substance that 1～4 lower alcohol shows compatibility on the restraining barrier.
27., be the polymkeric substance that 1～4 lower alcohol shows compatibility wherein, for water or carbon number 1～4 lower alcohol solubility for water or carbon number according to the light-sensitive layers body of claim 26 record.
28. power requires 21～27 light-sensitive layers bodies of putting down in writing in each according to profit, wherein the restraining barrier has the thickness of 0.1～5 mu m range.
29. the light-sensitive layers body of putting down in writing in each according to claim 21～28, wherein matrix is that printing distributing board forms and uses substrate.
30. the light-sensitive layers body according to claim 21 or 29 records wherein is laminated with supporter on first photographic layer.
31. method that forms picture pattern, comprising following operation, is to form the zone of the curing resin layer existence that is solidified to form jointly by first photographic layer and second photographic layer and the method for the picture pattern that the non-existent zone of curing resin layer is constituted on substrate:
(1) position that becomes substrate-side according to its second photographic layer on substrate concerns the light-sensitive transfer sheet of stacked claim 1 record, obtains the operation of laminated body;
(2) the first photographic layer side picture pattern according to the rules from laminated body carries out rayed, feasible first photographic layer and the common operation of solidifying of second photographic layer of accepting its light-struck zone;
(3) remove the operation of supporter by laminated body; And
(4) laminated body is developed and remove the operation of uncured portion in the laminated body.
32. method that forms picture pattern, comprise following operation, it is the zone that on substrate, forms the resin bed existence that is solidified to form jointly by first photographic layer and second photographic layer, the method of the picture pattern that zone that exists with the resin bed that is solidified to form by second photographic layer and the non-existent zone of curing resin layer are constituted:
(1) position that becomes substrate-side according to its second photographic layer on substrate concerns the light-sensitive transfer sheet of stacked claim 1 record, obtains the operation of laminated body;
(2) by first photographic layer, the one side picture pattern rayed according to the rules of the laminated body zone of the different irradiation energy of secondary at least light mutually, make first photographic layer and second photographic layer of accepting the big relatively light-struck zone of rayed energy solidify jointly, and the feasible operation of accepting second photographic layer curing in the relatively little light-struck zone of rayed energy;
(1) removes the operation of supporter by laminated body; And
(2) laminated body is developed and remove the operation of uncured portion in the laminated body.
33. according to the methods of claim 31 or 32 records, wherein the operation of removing supporter from laminated body of (3) is not to carry out between operation (2) and operation (4), but carries out between operation (1) and operation (2).
34. according to the method that claim 31～33 is put down in writing in each, wherein the rayed in the operation (2) is to be undertaken by laser radiation.
35. method that forms Wiring pattern, comprising following operation, is to form on printing distributing board forms with substrate by the zone of the curing resin layer covering that is solidified to form jointly with first photographic layer and second photographic layer and the method for the Wiring pattern that the zone was constituted that substrate surface exposes:
(1) position that becomes substrate-side according to its second photographic layer on substrate concerns the light-sensitive transfer sheet of stacked claim 1 record, obtains the operation of laminated body;
(2) rayed of the Wiring pattern of stipulating from first photographic layer, one side of laminated body makes first photographic layer and the common operation of solidifying of second photographic layer of accepting its light-struck zone;
(3) remove the operation of supporter from laminated body; And
(4) laminated body is developed and remove the operation of uncured portion in the laminated body.
36. method that forms Wiring pattern, comprising following operation, is to form the hole portion that covered by the curing resin layer that is solidified to form jointly with first photographic layer and second photographic layer and the method for the Wiring pattern that the zone was constituted that the zone that covers with the curing resin layer that second photographic layer is solidified to form and substrate surface expose on the printing distributing board that contains porose portion forms with substrate:
(1) position that becomes substrate-side according to its second photographic layer on substrate concerns the light-sensitive transfer sheet of stacked claim 1 record, obtains the operation of laminated body;
(2) give hole portion rayed energy big relatively rayed from first photographic layer, one side of laminated body, win photographic layer and second photographic layer are solidified jointly, and form the zone at distribution and give the rayed energy relatively little rayed, what make that second photographic layer solidifies carries out the light-struck operation of picture pattern;
(1) removes the operation of supporter from laminated body; And
(2) laminated body is developed and remove the operation of uncured portion in the laminated body.
37. according to the methods of claim 35 or 36 records, wherein the operation of removing supporter from laminated body of (3) is not to carry out between operation (2) and operation (4), but carries out between operation (1) and operation (2).
38. according to the method that claim 35～37 is put down in writing in each, wherein the rayed in the operation (2) is to be undertaken by laser radiation.
CNA2004101006745A 2004-01-14 2004-12-08 Light-sensitive transfer sheet, light-sensitive layers, method for forming image pattern and method for distribution pattern Pending CN1641481A (en)

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