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CN1580953A - Light-sensitive transfer sheet, light-sensitive layers, picture pattern forming method and layout pattern forming method - Google Patents

Light-sensitive transfer sheet, light-sensitive layers, picture pattern forming method and layout pattern forming method Download PDF

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Publication number
CN1580953A
CN1580953A CNA2004100583961A CN200410058396A CN1580953A CN 1580953 A CN1580953 A CN 1580953A CN A2004100583961 A CNA2004100583961 A CN A2004100583961A CN 200410058396 A CN200410058396 A CN 200410058396A CN 1580953 A CN1580953 A CN 1580953A
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CN
China
Prior art keywords
photographic layer
light
layer
sensitive sheet
photographic
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Pending
Application number
CNA2004100583961A
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Chinese (zh)
Inventor
若田裕一
佐藤守正
高岛正伸
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Fujifilm Corp
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Fujifilm Corp
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Publication of CN1580953A publication Critical patent/CN1580953A/en
Pending legal-status Critical Current

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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
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/54—Absorbers, e.g. of opaque materials
    • G03F1/56—Organic absorbers, e.g. of photo-resists
    • 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
    • G03F7/038—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
    • G03F7/06—Silver salts
    • G03F7/07—Silver salts used for diffusion transfer
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Laminated Bodies (AREA)

Abstract

Provided is a light-sensitive sheet and a light-sensitive layers easily forming desired patterns of different thicknesses within an image. In the light-sensitive sheet comprising a support, a first light-sensitive layer and a second light-sensitive layer in this order, wherein each of the first and second light-sensitive layers independently contains a binder, a polymerizable compound and a photopolymerization initiator, sensitivity is regulated so that the sensitivity of the second light-sensitive layer to light is made higher than that of the first light-sensitive layer, and a barrier layer is interposed between the first and second light-sensitive layers. The light-sensitive layers are obtained by stacking the second light-sensitive layer, the barrier layer and the first light-sensitive layer in this order on a substrate.

Description

The formation method of light-sensitive sheet, photosensitive laminated article, image pattern and the formation method of layout pattern
Technical field
The present invention relates to the formation method of light-sensitive sheet, photosensitive laminate, image pattern and the formation method of layout pattern.The present invention be more particularly directed to can be used for making light-sensitive sheet, the duplexer of printed circuit board and use this light-sensitive sheet or the method for duplexer formation printed circuit board layout pattern.
Background technology
Light-sensitive sheet with carrier and photographic layer is widely used as the image pattern formation material that displays such as making printed circuit board, chromatic color filter or columnar material, muscle shape material, distance piece, spaced walls is used with part, printed panel, holograph, microcomputer, general land volt Image forming materials such as (プ Le one Off).
Manufacturing field at printed circuit board; layout pattern is by the offset printing method of taking pictures, and uses the light-sensitive sheet (being also referred to as the transfer printing diaphragm) formed at transparent carrier (such as polyethylene terephthalate) and the photographic layer that forms on this carrier to form.Such as, have in manufacturing under the situation of printed circuit board of reach through hole, go up the formation reach through hole at the substrate (such as attached copper foil plate) that forms printed circuit board, after forming metal cladding on the madial wall of reach through hole, on the substrate surface overlapping bonding on the photographic layer of light-sensitive sheet, in zone that forms layout pattern and the zone that comprises the reach through hole opening portion, allow light shine according to predetermined style, make the photographic layer sclerosis.Then, peel off the carrier of light-sensitive sheet, the harden zone and the unhardened zone dissolving in addition of the harden zone (being called screened film) on the reach through hole opening portion zone that utilize developer solution will form the layout pattern zone are removed, then the metal level that exposes is partly carried out etching processing, by removing the harden zone, on substrate surface, just generated layout pattern again.
Use the method for above-mentioned screened film protection reach through hole metal cladding, be commonly referred to as screen method.And on the printed circuit board of sandwich construction, have sometimes and use the hole between the articulamentum that is called via hole, in this case, when forming layout pattern, be necessary equally to protect via hole with screened film.
In recent years, printed circuit board has been proposed the requirement of very high densification, pursued and have the more light diaphragm of high-resolution.In order to improve the exploring degree of light diaphragm, the thickness of this photographic layer of attenuate is effective.But as mentioned above; the hardened layer that the photographic layer sclerosis forms; play a part reach through hole or via hole that protection forms on printed circuit board; if the thickness of attenuate photographic layer merely; remove in the operation in unhardened district of photosensitive polymer combination and in dissolving and partly to carry out in the operation of etching processing, can produce this screened film the problem destroyed takes place the metal level that exposes.
Up to now, the style that forms high-resolution is possible, has developed the light-sensitive sheet that can form the coverlay that is difficult to destroy widely, and its achievement is as disclosed below.
In patent documentation 1, monomer composition that contains cementing agent composition with carboxyl, specific vinyl urethane compound and specific acrylate compounds and light-sensitive sheet have been narrated with photographic layer of forming by Photoepolymerizationinitiater initiater.
In patent documentation 2, narrated on carrier, be provided with alkali-soluble by the heating can reduce flowability, first photographic layer that active energy curve is had induction, be provided with in the above alkali-soluble by the heating can add large fluidity, can have the light-sensitive sheet with double-deck photographic layer of second photographic layer of induction to activity.In this patent documentation, second photographic layer of light-sensitive sheet is embedded in the reach through hole, therefore can protect the metal level of reach through hole.
In patent documentation 3, narration a kind of photosensitive resin layer composition of knowing clearly, it has first photographic layer and second photographic layer on carrier, and this is two-layer to have the ethylenic copolymer that differs from one another, and on two-layer, containing specific monofunctional monomer, its effect is to have improved cohesiveness and resolution capability.
In patent documentation 4, narrated a kind of method that on carrier, has the light diaphragm of non-adhesive photographic layer and cohesiveness photographic layer and use this light diaphragm manufacturing printed circuit board, its effect is to have improved covering performance and resolution capability.
In patent documentation 5, the two-layer at least photopolymerization layer that on carrier, has photopolymerization speed and differ from one another (thickness 25 μ m～2.5mm) have been narrated, and near the polymerization speed carrier is made the printed circuit board photographic plate faster, can form the bottom embossment shape image wideer than the top on printing surface.
[patent documentation 1] spy opens flat 10-142,789
[patent documentation 2] spy opens flat 8-54,732
[patent documentation 3] spy opens flat 10-111,573
[patent documentation 4] spy opens flat 3-17,650
[patent documentation 5] special public clear 37-1,306
Summary of the invention
The problem that the present invention solves
Problem of the present invention provides a kind of light-sensitive sheet and photosensitive laminated article, can be formed on the different required style of thickness in the image at an easy rate.
Problem of the present invention provides a kind of method, can use light-sensitive sheet or photosensitive laminated article, advantageously generates the different required style of thickness in the image industrial.
Problem of the present invention particularly provides a kind of light-sensitive sheet, can make printed circuit board effectively, can improve the exploring degree owing to accomplished thin layerization, can form the coverlay that is difficult to destroy.
Problem of the present invention also provides a kind of method, can use light-sensitive sheet, at the industrial printed circuit board with holes such as reach through hole and via holes of advantageously making.
Solve the means of problem
In first technical scheme of the present invention, be laminated successively first photographic layer of forming by the photosensitive polymer combination that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater, barrier layer and form by the photosensitive polymer combination that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater and demonstrate the light-sensitive sheet that forms than the second higher photographic layer of the light sensitivity of first photographic layer on carrier.
The preferred example of the invention described above first technical scheme is as follows.
(1) lower alcohol that contains water or carbon number 1～4 of barrier layer demonstrates the resin of compatibility as Main Ingredients and Appearance;
(2) lower alcohol that contains water or carbon number 1～4 of barrier layer has the resin of solubility as Main Ingredients and Appearance;
(3) thickness of barrier layer is in the scope of 0.1～5 μ m;
(4) barrier layer contains polymerizable compound;
(5) barrier layer has photonasty, and the light sensitivity of barrier layer is lower than the light sensitivity of first photographic layer relatively;
(6) contained polymerizable compound is the polymkeric substance with polymerizable group in barrier layer;
(7) polymkeric substance with polymerizable group in above-mentioned (6) has compatibility to the lower alcohol of water or carbon number 1～4;
(8) has the polymkeric substance of polymerizable group in above-mentioned (7), the lower alcohol of water soluble or carbon number 1～4;
(9) under the light sensitivity of first photographic layer was 1 situation, the light sensitivity of second photographic layer was in 2～200 scope;
(10) so that second photographic layer hardens necessary luminous energy A and first photographic layer is hardened ratio that the ratio A/B of necessary luminous energy B represents in 0.005～0.5 scope;
(11) the necessary luminous energy A and make ratio that first photographic layer represents to the ratio C/A of the necessary luminous energy C that begins to harden in 1～10 scope so that second photographic layer hardens;
(12) first photographic layers and second photographic layer all contain sensitizer;
(13) amount of the sensitizer that contains in second photographic layer is more than the amount of sensitizer contained in first photographic layer;
(14) in second photographic layer amount of contained Photoepolymerizationinitiater initiater more than the amount of Photoepolymerizationinitiater initiater contained in first photographic layer;
(15) in second photographic layer amount of contained polymerizable compound more than the amount of polymerizable compound contained in first photographic layer;
(16) first photographic layers are in the scope of absorbance 0.1～1.0 at wavelength 405nm place;
(17) in first photographic layer and/or second photographic layer, contain the compound that has very big absorbing wavelength at 380～430nm;
(18) compound that has a very big absorbing wavelength at 380～430nm in above-mentioned (17) is a sensitizer.
The thickness of (19) first photographic layers is in the scope of 1～100 μ m, and this thickness is greater than the thickness of second photographic layer;
The thickness of (20) second photographic layers is in the scope of 0.1～15 μ m;
(21) carrier is made by synthetic resin, and is transparent;
(22) carrier is the strip carrier;
(23) on second photographic layer, dispose diaphragm;
(24) light-sensitive sheet is a strip, is rolled into web-like;
(25) light-sensitive sheet is used to make printed circuit board.
Second technical scheme of the present invention, second photographic layer, barrier layer of being made up of the photosensitive polymer combination that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater and first photographic layer of being made up of the photosensitive polymer combination that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater and demonstrate the light sensitivity lower than second photographic layer be the laminated photosensitive laminated article that forms on matrix successively.
The preferred example of the invention described above second technical scheme is as follows.
(1) lower alcohol that contains water or carbon number 1～4 of barrier layer demonstrates the resin of compatibility as Main Ingredients and Appearance;
(2) lower alcohol that contains water or carbon number 1～4 of barrier layer has the resin of solubility as Main Ingredients and Appearance;
(3) thickness of barrier layer is in the scope of 0.1～5 μ m;
(4) barrier layer contains polymerizable compound;
(5) barrier layer has photonasty, and the light sensitivity of barrier layer is lower than the light sensitivity of first photographic layer relatively;
(6) contained polymerizable compound has the polymkeric substance of polymerizable group in barrier layer;
(7) polymkeric substance with polymerizable group in above-mentioned (6) demonstrates compatibility to the lower alcohol of water or carbon number 1～4;
(8) have the polymkeric substance water soluble or carbon number 1～4 lower alcohol of polymerizable group in above-mentioned (7);
(9) under the light sensitivity with first photographic layer was 1 situation, the light sensitivity of second photographic layer was in 2～200 scope;
(10) so that second photographic layer hardens necessary luminous energy A and first photographic layer is hardened ratio that the ratio A/B of necessary luminous energy B represents in 0.005～0.5 scope;
(11) the necessary luminous energy A and make ratio that first photographic layer represents to the ratio C/A of the necessary luminous energy C that begins to harden in 1～10 scope so that second photographic layer hardens;
(12) first photographic layers and second photographic layer all contain sensitizer;
(13) amount of the sensitizer that contains in second photographic layer is more than the amount of sensitizer contained in first photographic layer;
(14) in second photographic layer amount of contained Photoepolymerizationinitiater initiater more than the amount of Photoepolymerizationinitiater initiater contained in first photographic layer;
(15) in second photographic layer amount of contained polymerizable compound more than the amount of polymerizable compound contained in first photographic layer;
(16) first photographic layers are in the scope of absorbance 0.1～1.0 at 405nm place;
(17) first photographic layers and/or second photographic layer contain the compound that has very big absorbing wavelength at 380～430nm;
(18) compound that has a very big absorbing wavelength at 380～430nm in above-mentioned (17) is a sensitizer;
The thickness of (19) first photographic layers is in the scope of 1～100 μ m, and this thickness is greater than the thickness of second photographic layer;
The thickness of (20) second photographic layers is in the scope of 0.1～15 μ m;
(21) matrix is to form the substrate that printed circuit board is used;
(22) carrier (especially preferably transparent resin film) that closes on the first photographic layer upper strata;
(23) photosensitive laminated article is a strip, is rolled into web-like;
(24) photosensitive laminated article is to be used to make printed circuit board.
The 3rd technical scheme of the present invention, it is a kind of resin bed that first photographic layer and second photographic layer is hardened together form sclerosis, the image pattern method that formation is made of the zone regional and that do not have hard resin-layer to exist that has these hard resin-layers to exist, this method comprises following operation.
(1) close on the substrate upper strata and state the light-sensitive sheet of the present invention's first technical scheme, obtaining with its second photographic layer is the operation of lamilated body of the position relation of substrate one side;
(2) carry out rayed from the first photographic layer side of lamilated body according to predetermined style, in being subjected to the zone of this illumination, the operation that first photographic layer and second photographic layer are hardened together;
(3) remove the operation of carrier from lamilated body, then
(4) lamilated body is developed, remove the operation of unhardened part in the lamilated body.
The 4th technical scheme of the present invention, be a kind of on substrate, exist to harden together by first photographic layer and second photographic layer form the zone of resin bed, by the zone of the resin bed that exists the sclerosis of second photographic layer to form and do not exist hardening resin regional composing images style form method, this method comprises following operation.
(1) close on the substrate upper strata and state the light-sensitive sheet of the present invention's first technical scheme, obtaining with its second photographic layer is the operation of lamilated body of the position relation of substrate one side;
(2) from first photographic layer, one side of lamilated body, according to the predetermined picture style, light with at least two different irradiation energy levels shines, in the zone that is subjected to the relatively big irradiate light of irradiation energy, first photographic layer and second photographic layer harden together, and being subjected to the irradiation energy less zone that compares, the operation of sclerosis takes place in second photographic layer;
(3) remove the operation of carrier from lamilated body, then
(4) lamilated body is developed, remove the operation of unhardened part in the lamilated body.
In the 3rd technical scheme of the present invention and the 4th technical scheme, preferred example is as follows.
(1) not between operation (2) and operation (4), but between operation (1) and operation (2), carry out the operation of removing carrier from lamilated body of above-mentioned (3);
(2) carry out shining in operation (2) by laser.
The 5th technical scheme of the present invention, be on the substrate that forms printed circuit board, by making first photographic layer and second photographic layer formation hard resin-layer that hardens together, constitute the method that forms of layout pattern by the zone that has covered hard resin-layer and the zone of exposing substrate surface, this method comprises following operation.
(1) close on the substrate upper strata and state the light-sensitive sheet of the present invention's first technical scheme, obtaining with its second photographic layer is the operation of lamilated body of the position relation of substrate one side;
(2) carry out rayed, the operation that first photographic layer and second photographic layer are hardened together from first photographic layer, one side of lamilated body according to predetermined layout pattern;
(3) remove the operation of carrier from lamilated body, then
(4) lamilated body is developed, remove the operation of unhardened part in the lamilated body.
The 6th technical scheme of the present invention, be by on the substrate of formation printed circuit board, making first photographic layer and second photographic layer formation hard resin-layer that hardens together with hole, make this hard resin-layer cover the part in hole, zone that the hard resin-layer that is formed by the sclerosis of second photographic layer covers and the zone of exposing substrate surface constitute the method that forms of layout pattern, and the method comprises following operation.
(1) close on the substrate upper strata and state the light-sensitive sheet of the present invention's first technical scheme, obtaining with its second photographic layer is the operation of lamilated body of the position relation of substrate one side;
(2) from first photographic layer, one side of lamilated body, carry out the big relatively rayed of rayed energy in the part in hole, first photographic layer and second photographic layer are hardened together, and in the zone that forms wiring, carry out the relatively little rayed of rayed energy, make the sclerosis of second photographic layer form the operation of image pattern;
(3) remove the operation of carrier from lamilated body, and
(4) lamilated body is developed, remove the operation of unhardened part in the lamilated body.
Preferred example in the 5th technical scheme of the present invention and the 6th technical scheme is as follows.
(1) not between operation (2) and operation (4), but between operation (1) and operation (2), carries out the operation of removing carrier from lamilated body of above-mentioned (3).
(2) carry out laser radiation in operation (2).
Effect of the present invention
Light-sensitive sheet of the present invention and photosensitive laminated article, by the exposure (also can be referred to as exposure) that changes its light, can arbitrarily the zone in formation different-thickness hardened layer.Therefore, when using light-sensitive sheet of the present invention or photosensitive laminated article to form image, have the hardened layer (can form 3-D view) that can form any thickness, can in required each zone, change light transit dose (can change the concentration of image) in each required zone, can be in required each zone formation demonstrate numerous advantages such as hardened layer of required film strength.Such as,, can add the thickness of heavy case, and, can form the style that makes the thin hardened layer attenuate than higher zone in the film strength of hardened layer in the zone that will improve the exploring degree.
Therefore, light-sensitive sheet of the present invention and photosensitive laminated article, making printed circuit board, particularly have under the situation of printed circuit board in holes such as reach through hole and via hole in manufacturing, can be in forming the zone of layout pattern formation thickness relatively thin, and the exploring degree is than higher hardened layer, and near reach through hole and via hole, it is relatively thick to form thickness, the hardened layer that strength ratio is higher.Therefore, by utilizing the present invention, can make the printed circuit board of high-resolution at the favourable cladding process of industrial usefulness.
Description of drawings
Fig. 1 is the mode chart according to an example section of light-sensitive sheet of the present invention;
Fig. 2 is the mode chart according to another example section of light-sensitive sheet of the present invention;
Fig. 3 is when carrier one side is shone light-sensitive sheet of the present invention, the figure of the light sensitivity curve of the expression quantity of illumination and thin hardened layer relation;
Fig. 4 is the mode chart according to an example section of light-sensitive sheet of the present invention;
Fig. 5 is the mode chart according to another example section of light-sensitive sheet of the present invention;
Fig. 6 is to use the mode chart of the image (hardened layer style) that three layers of light-sensitive sheet according to photographic layer of the present invention can form;
Fig. 7 is the process chart that expression has the printed circuit board operation of reach through hole according to manufacturing of the present invention.
The explanation of symbol
10 light-sensitive sheets
11 carriers
12 first photographic layers
13 barrier layers
14 second photographic layers
15 diaphragms
16 film hardened layers
17 thick film hardened layers
18 stripping films
21 make the used for printed circuit substrate
22 reach through holes
23 metal claddings
24 layout patterns
31 backer rolls
50 light-sensitive sheets
51 carriers
52 first photographic layers
53 barrier layers
54 second photographic layers
55 the 3rd photographic layers
56 diaphragms
Embodiment
As an example of light-sensitive sheet of the present invention, on Fig. 1 and Fig. 2, demonstrate the schematic cross-sectional view of structure with two-layer photographic layer.
In the middle of Fig. 1, light-sensitive sheet 10 is formed with this sequential cascade by carrier 11, first photographic layer 12, barrier layer 13 and second photographic layer 14.Each photosensitive polymer combination that freely contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater of first photographic layer 12 and second photographic layer 14 constitutes, and can harden through illumination.Light-sensitive sheet of the present invention, the principal character that has are that the light sensitivity of its second photographic layer 14 is than first photographic layer, 12 height.At this, so-called light sensitivity, be equivalent to make each photographic layer necessary luminous energy that hardens, so-called light sensitivity height, mean that the exposure that second photographic layer 14 begins to harden is lower than the exposure that makes first photographic layer 12 begin to harden, second photographic layer 14 exposure of finishing sclerosis is lower than the exposure that makes first photographic layer finish sclerosis in other words.
Fig. 2 is the light-sensitive sheet that laminated again upper protective film 15 forms on the light-sensitive sheet of Fig. 1.
First photographic layer, barrier layer and second photographic layer thickness separately can at random be set according to different purposes.But first photographic layer preferably has the thickness of 1～100 mu m range, more preferably has the thickness of 5～80 mu m ranges, especially preferably has the thickness of 10～50 mu m ranges.When the thickness of first photographic layer is thinner than 1 μ m, have the suitably situation of reinforcing membrane intensity, and when thickness surpasses 100 μ m, have the problem on developing such as easy residual development residue.The thickness of first photographic layer is preferably greater than the thickness of second photographic layer.
Barrier layer preferably has the thickness of 0.1～5 mu m range, more preferably has the thickness of 0.5～4 mu m range, especially preferably has the thickness of 1～3 mu m range.When the thickness of barrier layer is thinner than 0.1 μ m, have the situation of abundant barrier of can not conducting electricity, and when the thickness of barrier layer surpasses 5 μ m, the required overlong time of then developing.Second photographic layer preferably has the thickness of 0.1～15 mu m range, more preferably has the thickness of 1～12 mu m range, especially preferably has the thickness of 3～10 mu m ranges.When the thickness of second photographic layer is thinner than 0.1 μ m, when coating, occurs the inhomogeneous of thickness easily, and when thickness surpasses 15 μ m, have problems such as exploring degree reduction.
The layer structure of light-sensitive sheet of the present invention is not limited to the as above layer structure shown in Fig. 1 and Fig. 2, and the layer beyond having as depicted in figs. 1 and 2 also is fine.Such as, between the carrier 11 and first photographic layer 12, between the diaphragm 15 and second photographic layer 14, also can be provided with and regulate carrier and the fissility of substrate and layer, anti-halo layer or the barrier layer etc. of cohesive force.Barrier layer in the case has and prevents or be suppressed at moving of material contained in photographic layer, carrier or the diaphragm, prevents, suppresses effects such as external influence such as oxygen or humidity.
Below with reference to the relation between the hardening capacity of the exposure of Fig. 3 explanation light in light-sensitive sheet of the present invention and photosensitive laminated article and photographic layer.Fig. 3 is illustrated in the light-sensitive sheet of using such as shown in Figure 1; perhaps the light-sensitive sheet shown on Fig. 2 has been peeled off the light-sensitive sheet of diaphragm; under the situation of transfer printing cambium layer zoarium on the substrate; with respect to its lamilated body; with light from a side opposite with substrate; pass through carrier having under the situation of carrier; the photographic layer of perhaps having peeled off carrier as required carries out under light-struck situation, to the exposure of the light of this lamilated body irradiation with at the figure (light sensitivity curve) that concerns between the thin hardened layer by the development treatment generation after this irradiation (exposure).In Fig. 3, transverse axis is represented the exposure of light, and the longitudinal axis is represented to harden by the irradiation of light, carries out development treatment and the thickness of the hardened layer that obtains.The D of the longitudinal axis represents the thickness of the hardened layer that formed by second photographic layer, E represents the summation thickness of the thickness of the thickness of the hardened layer that formed by first photographic layer and barrier layer, and F represents the summation thickness of the thickness of the thickness of thickness, barrier layer of the hardened layer that formed by first photographic layer and the hardened layer that formed by second photographic layer.
As shown in FIG. 3, in the middle of light-sensitive sheet of the present invention, light by the irradiation of carrier one side, having under the situation of carrier, although successively by carrier, first photographic layer, barrier layer and second photographic layer, when luminous energy was fewer, second photographic layer still began sclerosis earlier than first photographic layer.And after second photographic layer all solidified, when increasing luminous energy, first photographic layer just began sclerosis, and when increasing luminous energy again, first photographic layer is with regard to through-hardening.
For the relation between the light sensitivity of the light 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 harden necessary luminous energy C with can be same in order to make the second photographic layer necessary luminous energy A that hardens, but preferred C is greater than luminous energy A.
Have the light-sensitive sheet of light sensitivity curve as mentioned above, Photoepolymerizationinitiater initiater content that can be by making second photographic layer is more than first photographic layer, and perhaps more interpolation sensitizers obtain in second photographic layer.
In photographic layer, add under the situation of sensitizer, absorbance under exposure wavelength (or optical concentration, OD) be important, particularly under the situation of laminated photographic layer, the design of the absorbance on upper strata (being first photographic layer under situation of the present invention) is very important, is described below.
In other words, under the situation that the absorbance of first photographic layer (optical concentration) is high under exposure wavelength, reduce owing to arrive the light quantity of second photographic layer, the sclerosis of second photographic layer is carried out fully inadequately, and the light sensitivity that has strengthened first photographic layer and second photographic layer is poor.Such as, if the absorbance of first photographic layer is 0.3 under exposure wavelength, transmittance is exactly 1/2 so, the exposure on second photographic layer is exactly from 1/2 of the exposure of light source.Equally, under exposure wavelength, if the absorbance of first photographic layer is 0.6, transmittance is exactly 1/4 so, and the exposure that arrives second photographic layer is exactly from 1/4 of the exposure of light source.Particularly, when absorbance surpassed 1.0, transmittance was below 10%, and light does not almost arrive lower floor.
Thus, laminated by photographic layer be in the light-sensitive sheet, in order to keep the light sensitivity of lower floor, the absorbance on upper strata becomes extremely important under exposure wavelength.
In light-sensitive sheet of the present invention, first photographic layer is in the scope of the absorbance under the wavelength 405nm 0.1～1.0.First photographic layer is in the absorbance under the wavelength 405nm more preferably in the scope 0.1～0.8, most preferably in 0.1～0.6 scope.
And second photographic layer is in the absorbance under the wavelength 405nm preferably in the scope 0.1～1.5, more preferably in 0.1～1.0 scope.When absorbance greater than 1.5 the time, transmittance descends, near the sclerosis of photographic layer progress not substrate, the cohesiveness of substrate has the tendency of deterioration.And when absorbance less than 0.1 the time, can not arrive sufficient light sensitivity sometimes.
The absorbance of photographic layer is regulated with the amount that has the compound of absorption usually under exposure wavelength mostly.Regulate the compound of photographic layer light sensitivity, preferably sensitizer.Can in first photographic layer, not use sensitizer yet, if but first photographic layer in the absorbance under the wavelength 405nm in the scope below 0.6, also can add sensitizer.
Sensitizer preferably has the compound of very big absorbing wavelength under 380～430nm.
Light-sensitive sheet of the present invention also can have two-layer above photographic layer.Fig. 4 has just represented the sectional drawing with three layers of photographic layer situation as an one example.Fig. 5 is illustrated in the situation that has diaphragm on the photographic layer of Fig. 4.
In the light-sensitive sheet 50 of Fig. 4 and Fig. 5, represent carrier with 51, on its carrier 51, stacked gradually first photographic layer 52, barrier layer 53, second photographic layer 54, barrier layer 53 and the 3rd photographic layer 55.The light-sensitive sheet that Fig. 5 is illustrated in Fig. 4 is provided with the situation of diaphragm 56.
Under the situation of these three layers of photographic layer structures, to be relatively higher than light sensitivity away from the light sensitivity of the photographic layer of carrier in each photographic layer from the nearer photographic layer of carrier.In other words, the light sensitivity of photographic layer with the 3rd photographic layer for the highest, the second sensitization level height, and the light sensitivity of first photographic layer is minimum.
Use the light-sensitive sheet of structure as shown in Figure 4 and Figure 5, difference according to the essential luminous energy scope of when forming style, using, if only making the luminous energy of the 3rd photographic layer sclerosis is X, the luminous energy that the 3rd photographic layer and second photographic layer are all hardened is Y, make the 3rd photographic layer, the luminous energy of second photographic layer and the first photographic layer through-hardening is Z, when changing the quantity of illumination, as shown in Figure 6, a kind of light-sensitive sheet that forms just can be formed in the style that has three stage different-thickness on the substrate 57, the zone that promptly only has the 3rd photographic layer 55 sclerosis thickness, have the zone of the 3rd photographic layer 55 and second photographic layer, 54 sclerosis thickness, and have the 3rd photographic layer 55, all the harden zone of thickness of second photographic layer 54 and first photographic layer 52.
Have under the situation of N layer (number of plies of photographic layer is N) at photographic layer equally, if its light sensitivity away from carrier layer of light-sensitive sheet of using is relatively higher than the light sensitivity from the nearlyer layer of carrier, just might form a kind of light-sensitive sheet with N stage different-thickness hardened layer style.
In narration up to now, light-sensitive sheet of the present invention, according to its exposure (so-called luminous energy) difference, can obtain the hardened layer of desired thickness by exposure and development treatment, change the style of exposure as required, just can produce from only making, change thickness successively, all harden up to whole photographic layers from the nearest photographic layer sclerosis of substrate.Therefore, use a kind of light-sensitive sheet, give it and can form the different three-dimensional modeling of thickness, perhaps only improve film strength, perhaps only improve the hardening resin image of characteristics such as image concentration in required zone in required zone in the inside of image.
Therefore, using light-sensitive sheet manufacturing printed circuit board of the present invention, particularly make when having the printed circuit board of reach through hole or via hole, just can be at the relative thickness thinning in the zone that forms layout pattern, form the hardened layer of high-resolution, and on reach through hole or via hole, thicken thickness relatively, form high-intensity hardened layer.Thereby the light-sensitive sheet of the application of the invention can form the hardening resin style with enough exploring degree at an easy rate, makes it possible to utilize screen method to have enough screened film intensity, and has high-resolution in required part.
By the present invention as can be seen, can produce light-sensitive sheet, make the light sensitivity of each photographic layer raise successively towards layer away from carrier from one deck near carrier with above-mentioned light sensitivity curve.When this photographic layer has two-layerly or two-layer when above, the method that the light sensitivity of its photographic layer improves successively relatively can be used known ISO technology fully.In other words, the content such as the initiating agent that uses ISO, use sensitizer, increase Photoepolymerizationinitiater initiater and/or sensitizer perhaps improves the content of polymerizable compound in the photographic layer etc.Also can prevent that the ratio of agent from realizing by reducing polymerization inhibitor or polymerization.If particularly having under the situation of two-layer photographic layer, except using initiating agent such as ISO, can be by in second photographic layer, adding sensitizer, making the Photoepolymerizationinitiater initiater in second photographic layer and/or the content of sensitizer be higher than first photographic layer, perhaps make polymerizable compound content in second photographic layer be higher than methods such as first photographic layer and realize.
On carrier of the present invention, first photographic layer, barrier layer that the laminated successively photosensitive polymer combination that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater is formed and the photosensitive polymer combination that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater are formed, and demonstrate second photographic layer that its light sensitivity is relatively higher than first photographic layer, using this light-sensitive sheet to form under the situation of image style (hardening resin style), the luminous energy S that second photographic layer begins to harden 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.And make second photographic layer harden necessary luminous energy A preferably at 0.1～20mJ/cm 2In the scope, more preferably in the scope of 0.2～15mJ/cm, particularly preferably in 0.4～10mJ/cm 2Scope in.
The luminous energy A that second photographic layer sclerosis is required and in order to make the harden ratio (A/B) of necessary luminous energy B of first photographic layer, preferably in 0.005～0.5 scope, more preferably in 0.01～0.4 scope, in 0.02～0.35 scope.And for make second photographic layer harden necessary luminous energy A and make first photographic layer to the ratio (C/A) of the necessary luminous energy C that begins to harden preferably in 1～10 scope, more preferably in 1.1～9 scope, in 1.3～8 scope.This luminous energy C is preferably at 0.1～200mJ/cm 2Scope in, more preferably at 1～100mJ/cm 2Scope in, particularly preferably in 2～50mJ/cm 2Scope in.
The following describes the various materials that in the photographic layer of light-sensitive sheet of the present invention and photosensitive laminated article, use.
[cementing agent]
The cementing agent that uses in each photographic layer preferably can be dissolved in the alkaline aqueous solution, perhaps preferably at least also will have the swelling of alkaline aqueous solution.Example as this type of cementing agent, can utilize the have acidic-group cementing agent of (carboxyl, sulfonic group, phosphate etc.), but the cementing agent with carboxyl be have representational especially, can enumerate such as the ethylenic copolymer that contains carboxyl, the urethane resin that contains carboxyl, polyamic acid resin, modified epoxy etc., but, preferably contain the ethylenic copolymer of carboxyl from the solubleness coating solvent, the dissolubility in alkaline-based developer, suitable aspects such as the physical property consideration of synthesizing and regulating film easily.
The ethylenic copolymer that contains carboxyl can contain the vinyl monomer of carboxyl and (2) by (1) at least and can obtain with the copolymerization of the monomer of its copolymerization.
As the example of the vinyl monomer that contains carboxyl, can enumerate such as (methyl) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid mono alkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer etc.Also can utilize (methyl) acrylic acid 2-hydroxy methacrylate etc. to have addition reaction, list (methyl) acrylic acid ω-carboxyl-polycaprolactam ester of the cyclic acid anhydride of the monomer of hydroxyl and maleic anhydride or fumaric acid anhydride, cyclohexane dicarboxylic acid acid anhydride and so on etc.Also can use the monomer of acid anhydrides such as the maleic anhydride that contains as carboxyl precursor, itaconic anhydride, pyrocitric acid acid anhydride.Wherein from viewpoints such as copolymerization performance and cost, solubility properties, preferred especially (methyl) acrylic acid.
To use when the synthetic above-mentioned multipolymer can copolymerization other monomers have no particular limits, as the example of this type of monomer, the ester class of preferred (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, phenylethylene, (methyl) vinyl cyanide etc.As their example, can enumerate such as following compound.
As the example of (methyl) esters of acrylic acid, can enumerate (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 acetoxyl group ethyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (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 diethylene glycol monomethyl ether ester, (methyl) acrylic acid diethylene glycol monoethyl ether ester, (methyl) acrylic acid diethylene glycol monophenyl ether ester, (methyl) acrylic acid triethylene glycol monomethyl ether ester, (methyl) acrylic acid Triethylene glycol ethyl ether ester, (methyl) polyalkylene glycol acrylate monomethyl ether ester, (methyl) polyalkylene glycol acrylate monoethyl ether ester, acrylic acid beta-phenoxy ethoxy ethyl ester, (methyl) acrylic acid Nonylphenoxy macrogol ester, (methyl) acrylic acid dicyclo pentyl ester, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) acrylic acid dicyclo amylene oxygen base ethyl ester, (methyl) acrylic acid trifluoro ethyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) acrylic acid perfluoro capryl ethyl ester, (methyl) acrylic acid tribromophenyl, (methyl) acrylic acid tribromophenoxy ethyl ester etc.
As the example of crotonates, can enumerate butyl crotonate and the own ester of crotonic acid etc.As the example of vinyl esters, can enumerate vinyl acetate, propionate, vinyl butyrate, Methoxy acetic acid vinyl acetate and vinyl benzoate etc.
As the example of maleic acid diester, can enumerate dimethyl maleate, diethyl maleate and dibutyl maleate etc.As the example of dimethyl ester, can enumerate dimethyl fumarate, DEF and dibutyl fumarate etc.As the example of itaconic acid diester class, can enumerate dimethyl itaconate, diethyl itaconate and dibutyl itaconate etc.
As (methyl) acrylic amide; can enumerate (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, can enumerate 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, by hydroxy styrenes, vinyl benzoic acid methyl esters and the α-Jia Jibenyixi etc. that can be separated group (such as the t-Boc etc.) protection of protection by acidic materials.As the example of vinyl ether, can enumerate methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether and methoxy ethyl vinyl ether etc.
Except above-claimed cpd, can also use heterocyclic group (such as vinylpyridine, vinyl pyrrolidone, vinylcarbazole etc.), N-vinyl formamide, N-vinyl acetamide, N-vinyl imidazole, vinyl caprolactone of (methyl) vinyl cyanide, vinyl substituted etc.
Also can utilize 2-acrylamide-2-methyl propane sulfonic acid, mono phosphoric acid ester (2-acryloxy ethyl ester), mono phosphoric acid ester (1-methyl-2-acryloxy ethyl ester) etc.
Except above-claimed cpd, also can use functional groups' such as having carbamate groups, urea groups, sulfoamido, phenolic group, imide vinyl monomer.As the example of monomer, can be to utilize isocyanates and hydroxyl or the amino synthetic compound of addition reaction that carries out with such carbamate groups or urea groups.Particularly, be can be adapted to pass through the monomer that contains isocyanate groups and contain the compound of a hydroxyl or contain addition reaction between the compound of a primary amine groups or secondary amino group, the perhaps monomer by containing hydroxyl or contain primary amine groups or compound that the addition reaction of the monomer of secondary amino group and monoisocyanates is synthetic.
As the object lesson of the monomer that contains isocyanate groups, can enumerate compound (R as follows 1Expression hydrogen atom or methyl).
[changing 1]
As the object lesson of monoisocyanates, can enumerate such as NSC 87419, n-butyl isocyanate, isocyanic acid methyl phenyl ester, benzyl mustard oil, phenyl isocyanate etc.
As the object lesson of the monomer that contains hydroxyl, can enumerate compound (R as follows 1Expression hydrogen atom or methyl, n represents the integer more than 1).
[changing 2]
Figure A20041005839600211
As the compound that contains a hydroxyl, 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-dodecanol, positive 18 alcohol, cyclopentanol, cyclohexanol, benzylalcohol, phenylethanol etc.), phenols (phenol, cresols, naphthalene alcohol etc.), and as the fluoroethanol that also contains the substituting group alcohols, trifluoroethanol, methyl cellosolve, phenoxetol, chlorophenol, chlorophenesic acid, metoxyphenol, acetoxyl group phenol etc.
As the example of the monomer that contains primary amine groups or secondary amino group, can enumerate vinyl benzylamine etc.
As the object lesson of the compound that contains a primary amine groups or secondary amino group, can enumerate 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), Cycloalkyl amine (cyclopentamine, cyclohexylamine etc.), aralkylamine (benzylamine, phenethyl amine etc.), arylamine (aniline, methylaniline, xylidin, naphthylamines etc.), also have their combination (N-methyl-N-benzylamine etc.) and contain other substituent amine (trifluoro ethamine, the hexafluoro isopropylamine, aminoanisole, methoxy propanamine etc.) etc.
Only a kind of with in the above-claimed cpd still uses two or more to be fine simultaneously.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 be used corresponding separately monomer, according to known method, obtains by the usual way polymerization.Such as utilizing by these monomers are dissolved in the appropriate solvent, the method (solution polymerization process) of adding free radical polymerization initiator polymerization in solution therein obtains.Perhaps, promptly use methods such as emulsion polymerization to carry out polymerization with under the state of above-mentioned monomer in being dispersed in aqueous solvent.
As the example of the appropriate solvent of in solution polymerization process, using, can select arbitrarily according to the dissolubility of the multipolymer of monomer that uses and generation.Can enumerate such as methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, 1-methoxyl-2-propyl alcohol, acetone, MEK, methyl isobutyl ketone, acetic acid methoxyl propyl ester, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl formamide, chloroform, toluene etc.Also can mix these solvents that use two or more.Initiating agent as radical polymerization, can utilize 2,2 '-azoisobutyronitrile (AIBN), 2, the persulfate of superoxide of the azo-compound of 2 '-azo two (2,4 '-methyl pentane nitrile) and so on, benzoyl peroxide and so on and potassium persulfate, ammonium persulfate and so on etc.
In the middle of the ethylenic copolymer that obtains by these monomers, containing ratio from the repetitive of polymerizable compound with carboxyl, be preferably 5～50mol% of whole repetitives in each photographic layer, more preferably 10～40mol% is preferably 15～35mol% especially.When this containing ratio during less than 5mol%, the development deficiency in alkaline aqueous solution sometimes, and when surpassing 50mol%, the developer solution tolerance deficiency of sclerosis part sometimes (image area).
Molecular weight with cementing agent of carboxyl can at random be regulated, but to each photographic layer weight-average molecular weight all preferably 2,000～300,000, preferred especially 4,000～150,000.When weight-average molecular weight less than 2,000 o'clock, film strength is not enough easily, and the tendency that is difficult to stably make is arranged.Surpass at 300,000 o'clock and work as molecular weight, the tendency that reduces development is arranged.
The cementing agent with carboxyl like this can use a kind of or uses two or more simultaneously at each photographic layer.As and with the example of two or more cementing agent situation, can enumerate form by the different copolymer composition two or more cementing agent, different weight-average molecular weight two or more cementing agent and two or more the cementing agent etc. with different dispersion degree.
Cementing agent with carboxyl, its part or all carboxyl can be neutralized by alkaline matter.This cementing agent also can also be used with the resin of different structures such as vibrin, polyamide, urethane resin, epoxy resin, polyvinyl alcohol (PVA), gelatin.
As the example of cementing agent, can enumerate in patent 2,873 resin that dissolves in alkaline aqueous solution of narration in 889.
The content of cementing agent is generally 10～90wt% in each photographic layer, is preferably 20～80wt%, is preferably 40～80wt% especially.When this content with cementing agent (and the high polymer binder that uses simultaneously as required) of carboxyl is crossed when low, reduce easily the alkaline development performance and with form the cohesiveness of printed circuit board with substrate (such as attached copper foil plate), and served as for a long time, reduction is arranged to the stability of development time and the tendency of cured film (screened film) intensity.In order to regulate light sensitivity, in above-mentioned scope, can regulate the containing ratio (improving the containing ratio of polymerizable compound) that makes in second photographic layer containing ratio of contained cementing agent be lower than cementing agent in first photographic layer.
[polymerizable compound]
In photographic layer, use polymerizable compound (so-called monomer), but preferred especially monomer or the oligomer (polyfunctional monomer, multifunctional oligomer) that contains two kinds or two above polymerizable groups that use.As polymerizable group, can enumerate vinyl unsaturated link (such as allyls such as vinyl, allyl ester or allyl ether such as (methyl) acryloyl group, (methyl) acrylamido, styryl, vinyl esters or vinyl ether etc.), polymerisable ring-type ether (such as epoxy radicals, oxa-cyclobutyl) etc.Optimal ethylene class unsaturated link wherein.
As the example of such polyfunctional monomer, can enumerate the ester of unsaturated carboxylic acid (such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid etc.) and aliphatic polyol, the acid amides of unsaturated carboxylic acid and polyamines etc.
As the esters monomer that forms by aliphatic polyol and unsaturated carboxylic acid, its concrete example has, two (methyl) acrylic acid glycol ester as (methyl) acrylate, the ethylidene number is that two (methyl) polyalkylene glycol acrylate ester of 2～18 is (such as two (methyl) acrylic acid binaryglycol ester, two (methyl) acrylic acid triglycol ester, two (methyl) acrylic acid TEG ester, two (methyl) acrylic acid, nine glycol esters, two (methyl) acrylic acid, ten binaryglycol esters, two (methyl) acrylic acid, ten TEG esters etc.), two (methyl) acrylic acid propylene glycol ester, inferior third class number is that two (methyl) acrylic acid polypropylene glycol ester of 2～18 is (such as two (methyl) acrylic acid dipropylene glycol ester, two (methyl) acrylic acid tripropylene glycol ester, two (methyl) acrylic acid, four propylene glycol esters, two (methyl) acrylic acid, ten dipropylene glycol esters etc.), two (methyl) acrylic acid DOPCP, two (methyl) acrylic acid oxygen ethylidene modification DOPCP, the inferior third class modification of two (methyl) acrylic acid oxygen DOPCP, three (methyl) acrylic acid trihydroxymethylpropanyl ester, two (methyl) acrylic acid trihydroxymethylpropanyl ester, trimethylolpropane tris (methyl) acryloyl-oxy propyl ether, three (methyl) acrylic acid trimethylolethane ester, two (methyl) acrylic acid 1, the ammediol ester, two (methyl) acrylic acid 1, the 3-butanediol ester, two (methyl) acrylic acid 1, the 4-butanediol ester, two (methyl) acrylic acid-1,6-hexanediol ester, two (methyl) acrylic acid tetramethylene glycol ester, two (methyl) acrylic acid 1,4-cyclohexane diol ester, three (methyl) acrylic acid 1,2,4-butantriol ester, (methyl) acrylic acid 1, the 5-pentadiol ester, two (methyl) acrylic acid pentaerythritol ester, three (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid pentaerythritol ester, five (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester, three (methyl) acrylic acid sorbitol ester, four (methyl) acrylic acid sorbitol ester, the acid of five (methyl) propylene sorbitol ester, six (methyl) acrylic acid sorbitol ester, two (methyl) acrylic acid dihydroxymethyl dicyclo pentane ester, two (methyl) acrylic acid tristane ester, two (methyl) acrylic acid DOPCP, two (methyl) acrylic acid trihydroxymethylpropanyl ester of neopentyl glycol modification, has two (methyl) acrylic acid alkylene glycol chain ester of each glycol chain/propylene glycol chain (such as the compound of narration in WO 01/98,832) at least, three (methyl) acrylic acid trihydroxymethylpropanyl ester with oxygen ethylidene and/or the inferior third class addition of oxygen, two (methyl) acrylic acid polytetramethylene glycol ester, two (methyl) acrylic acid glyceride, three (methyl) acrylic acid glyceride, two (methyl) acrylic acid dimethyl benzene phenolic ester etc.
In the middle of above-mentioned (methyl) acrylate, as preferred example, viewpoint from easy acquisition, can enumerate two (methyl) acrylic acid glycol ester, two (methyl) polyalkylene glycol acrylate ester, two (methyl) acrylic acid propylene glycol ester, two (methyl) acrylic acid polypropylene glycol ester, has two (methyl) acrylic acid alkylidene diol ester of each glycol chain/propylene glycol chain at least, three (methyl) acrylic acid trihydroxymethylpropanyl ester, four (methyl) acrylic acid pentaerythritol ester, pentaerythritol triacrylate, two (methyl) acrylic acid pentaerythritol ester, five (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester, three (methyl) acrylic acid glyceride, two (methyl) acrylic acid, two glyceride, two (methyl) acrylic acid 1, the ammediol ester, three (methyl) acrylic acid 1,2,4-butantriol ester, two (methyl) acrylic acid 1,4-cyclohexane diol ester, (methyl) acrylic acid 1, the 5-pentadiol ester, two (methyl) acrylic acid DOPCP, three (methyl) acrylic acid trihydroxymethylpropanyl ester of oxyalkylene addition etc.
As form by itaconic acid and aliphatic polyol compound the example of ester class (itaconate), two itaconic acid glycol esters, two itaconic acid propylene glycol esters, two itaconic acids 1 are arranged, 3-butanediol ester, two itaconic acids 1,4-butanediol ester, two itaconic acid tetramethylene glycol esters, two itaconic acid pentaerythritol esters and four itaconic acid sorbitol esters etc.
As the example of crotonic acid and aliphatic polyol ester (crotonates), two crotonic acid glycol esters, two crotonic acid tetramethylene glycol esters, two crotonic acid pentaerythritol esters and four crotonic acid sorbitol esters etc. are arranged.
Example as iso-crotonic acid and aliphatic polyol ester (iso-crotonic acid ester) has two iso-crotonic acid glycol esters, two iso-crotonic acid pentaerythritol esters and four iso-crotonic acid sorbitol esters etc.As the example of maleic acid and aliphatic polyol ester (maleate), two maleic acid glycol esters, two maleic acid triglycol esters, two maleic acid pentaerythritol esters and four maleic acid sorbitol esters etc. are arranged.
And the example of the acid amides that obtains as polyamine compounds and unsaturated carboxylic acid, two (methyl) acryloyl benzylidene amino, two (methyl) acryloyl ethyleneamines, two (methyl) acryloyl 1 are arranged, 6-hexylidene amine, inferior octyl amine, three (methyl) acryloyl of two (methyl) acryloyl diethylene triamine, two (methyl) acryloyl diethylene triamine and two (methyl) acryloyl hexylidene amine etc.
Can also enumerate and have 2 of bis-phenol skeleton, 2-two [4 (3-(methyl) acryloxy-2-hydroxyl propoxyl group) phenyl] propane, 2,2-two [4-((methyl) acryloyl-oxy base oxethyl) phenyl] propane, the substituted oxygen ethylidene of phenol hydroxyl number be 2～20 2,2-two (4-((methyl) acryloxy polyethoxy) phenyl) propane is (such as 2,2-two (4-((methyl) acryloxy diethoxy) phenyl) propane, 2,2-two (4-((methyl) acryloxy tetraethoxy) phenyl) propane, 2,2-two (4-((methyl) acryloxy five ethoxys) phenyl) propane, 2,2-two (4-((methyl) acryloxy ten ethoxys) phenyl) propane, 2,2-two (4-((methyl) acryloxy 15 ethoxys) phenyl) propane etc.), 2,2-two [4-((methyl) acryloxy propoxyl group) phenyl] propane, the substituted oxygen propylidene of phenol hydroxyl number be 2～20 2,2-two (4-((methyl) acryloxy gathers propoxyl group) phenyl) propane is (such as 2,2-two (4-((methyl) acryloxy dipropoxy) phenyl) propane, 2,2-two (4-((methyl) acryloxy four propoxyl group) phenyl) propane, 2,2-two (4-((methyl) acryloxy five propoxyl group) phenyl) propane, 2,2-two (4-((methyl) acryloxy ten propoxyl group) phenyl) propane, 2,2-two (4-((methyl) acryloxy 15 propoxyl group) phenyl) propane etc.) compound (such as the compound of narration in WO 01/98,832 etc.) that contains polyoxyethylene and polyoxy propylidene or in same a part of these compounds as its polyester position simultaneously.Such compound can be as such as BPE-200, BPE-500, BPE-1000 acquisitions such as (Xin Zhong village chemical industry (strain) manufacturings).
The compound that has hydroxyl on end group that obtains with addition product or polymkeric substance as bis-phenol and oxygen ethylidene compound or the inferior third class compound of oxygen etc. is opposite, also can utilize the polymerizable compound that is addition bodily form formula that has with the compound ((methyl) acrylic acid 2-isocyanate group ethyl ester, isocyanic acid α, alpha-alpha-dimethyl-vinyl benzyl ester etc.) of isocyanates polymer-based group with bis-phenol skeleton and carbamate groups.
Also can utilize at linear epoxy resin, butylene glycol-1,4-diglycidyl ether, cyclohexanedimethanol glycidol ether, ethylene glycol diglycidylether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, pentaerythrite four glycidol ethers, bisphenol-A diglycidyl ether, T 55 etc. have contained on the compound of glycidyl addition α, the compound that beta-unsaturated carboxylic acid obtains.
Can also utilize the compound that contains polymerizable group and carbamate groups.Example as such compound, at the public clear 48-41 of spy, 708, the spy opens clear 51-37,193, special fair 5-50,737, special fair 7-7,208, the spy opens 2001-154,346 and Te Kai 2001-356, in 476 grades narration is arranged all, can enumerate such as in a molecule, having the isocyanate compound of two or more polyisocyanate groups (such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, hexylidene diisocyanate, toluene diisocyanate, phenylene vulcabond, the norborene diisocyanate, biphenyl diisocyanate, methyl diphenylene diisocyanate, 3,3 '-dimethyl-4, tripolymers such as the biuret of 4 '-biphenyl diisocyanate and these diisocyanates and isocyanuric acid ester, these diisocyanate and trimethylolpropane, pentaerythrite, polyfunctional alcohols such as glycerine or these oxygen ethylidene compound additions that obtain with addition product polyvalent alcohol etc.) and the vinyl monomer that in molecule, contains hydroxyl (such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, single (methyl) acrylic acid binaryglycol ester, single (methyl) acrylic acid triglycol ester, single (methyl) polyalkylene glycol acrylate ester, single (methyl) acrylic acid dipropylene glycol ester, single (methyl) acrylic acid tripropylene glycol ester, single (methyl) acrylic acid polypropylene glycol ester, two (methyl) acrylic acid trihydroxymethylpropanyl ester, three (methyl) acrylic acid pentaerythritol ester etc.) addition and the vinyl carbamate compound that in a molecule, contains two above polymerism vinyl that obtains.Can also utilize the compound with isocyanuric acid ring of isocyanuric acid three ((methyl) acryloxy ethyl ester), two (methyl) acryloyl group isocyanuric acid ester, oxygen ethylidene modification isocyanuric acid three (methyl) acrylate and so on.
Can also enumerate as open clear 48-64 the spy, 183, special public clear 49-43,191, special public clear 52-30, the polyester acrylate or polyester (methyl) the acrylate oligomer class of narration in the middle of 490 grades, epoxy compound (linear epoxy resin, butylene glycol-1, the 4-diglycidyl ether, the cyclohexanedimethanol glycidol ether, the diethylene glycol 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 (methyl) acrylic acid reaction polyfunctional acrylic ester or the methacrylates such as epoxy acrylate class that obtain.Can also enumerate the ester type compound that obtains by phthalic acid or trimesic acid etc. and the above-mentioned vinyl monomer that in molecule, contains hydroxyl.Also can use at " Japan is association's will then ", vol.20, No.7, photo-hardening monomer and the oligomer introduced in 300～308 pages (1984).
Can also utilize allyl ester (such as diallyl phthalate, diallyl adipate, malonic acid diallyl, diallyl phthalate, trimesic acid triallyl, benzenedisulfonic acid diallyl, isocyanic acid triallyl) and diaryl acid amides (such as acetyl diallylamine etc.).
As polymerizable compound, can use cationically polymerizable divinyl ethers (such as butylene glycol-1, the 4-divinyl ether, the cyclohexanedimethanol divinyl ether, the ethylene glycol bisthioglycolate vinyl ether, the 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 (linear epoxy resin, butylene glycol-1, the 4-diglycidyl ether, the cyclohexanedimethanol glycidol ether, ethylene glycol diglycidylether, the diethylene glycol diglycidyl ether, the dipropylene glycol diglycidyl ether, cyclohexanedimethanodiglycidyl diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, pentaerythrite four glycidol ethers, the bisphenol-A diglycidyl ether, T 55 etc.), oxetanes class (such as 1,4-two [(3-ethyl-3-oxetanes ylmethoxy) methyl] benzene etc.) compound etc.And, can use the compound of narration in 165 as epoxy compound and oxygen heterocycle butane at WO01/22.
Example as vinyl esters, can utilize succinic acid divinyl ester, hexane diacid divinyl ester, phthalic acid divinyl ester, terephthalic acid (TPA) divinyl ester, benzene-1,3-disulfonic acid divinyl ester and butane-1,4-disulfonic acid divinyl ester etc.
As the example of distyryl compound, can enumerate divinylbenzene, 4-allyl styrene and the different acrylonitrile-styrol of 4-etc.
As the compound beyond the above-claimed cpd, can enumerate acrylic acid-N-beta-hydroxyethyl-β-(methacryl amido) ethyl ester, N, N-two (Beta-methyl acrylyl oxy-ethyl) acrylamide, allyl methacrylate etc. have the compound of two or more differing ethylene class unsaturated double-bonds as being suitable for compound of the present invention.
These polyfunctional monomers or oligomer can be separately or two or more be used in combination.
Have again, can use the polymerizable compound (monofunctional monomer) that in molecule, contains a polymerizable group as required simultaneously.Example as monofunctional monomer, can enumerate the compound of being given an example as above-mentioned cementing agent raw material, as open flat 6-236 the spy, monofunctional monomer of list of two alkali shown in 031 ((methyl) acryloyloxyalkyl) single (halogenated hydroxyl Arrcostab) and so on (such as γ-chloro-β-hydroxy propyl-Beta '-methacryloxyethyl-o-phthalic ester etc.) etc. or in patent 2,744,643, WO 00/52,529 and patent 2, compound described in 548,016.
In each photographic layer, the content of monomer of photographic layer is general all in the scope of 5～90wt%, preferably in the scope of 15～60wt%, in the scope particularly preferably in 20～50wt%.When content of monomer was less than above-mentioned scope, the strength degradation of coverlay had served as for a long time, and the edge when preserving merges (fault of extending from the end of volume) and has the tendency of deterioration.The content of polyfunctional monomer that contains two or more polymerizable groups in whole monomers is generally in the scope at 5～100wt%, preferably in the scope of 20～100wt%, more preferably in the scope of 40～100wt%.In order to regulate light sensitivity, in above-mentioned scope, to regulate, the content of monomer that improves second photographic layer also is fine.
[Photoepolymerizationinitiater initiater]
As the Photoepolymerizationinitiater initiater that in light-sensitive sheet of the present invention, uses, so long as have the compound that makes above-mentioned monomer composition begin polymerizing power all is operable, is particularly suitable for using have photosensitive compound from the ultraviolet ray range to the visible light.Photoepolymerizationinitiater initiater preferably contains at least a at about 300～800nm (composition that more preferably has about at least 50 the molecule absorption coefficient of light in 330～500nm) the scope.No matter be the Photoepolymerizationinitiater initiater or the effect of optical excitation sensitizer of producing, so long as the activating agent that generates living radical just can, also can be the initiating agent that begins cationic polymerization according to the difference of monomeric species.
As the Photoepolymerizationinitiater initiater that preferably uses, can enumerate such as halogenated hydrocarbons derivant (such as the compound of the compound with triazine skeleton, Ju You oxadiazole skeleton), Hexaarylbiimidazole, 9 oxime derivate, organic peroxide, sulfhydryl compound, ketonic compound, aromatic series salt, ketoxime ether etc. at photographic layer.From the light sensitivity of photographic layer, retention and with photographic layer and printed circuit board viewpoints such as cohesiveness, wherein preferred especially halogenated hydrocarbon, 9 oxime derivate, six Aryimidazoles, the ketonic compound that use with triazine skeleton with substrate.
As halogenated hydrocarbon compound, can enumerate following compound with triazine skeleton.
At the Bull.Chem.Soc.Japan as if Lin Dengzhu, the compound described in 42,2924 (1969), such as 2-phenyl-4,6-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.
In BrP 1,388, the compound described in 492, such as 2-styryl-4,6-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.
Open clear 53-133 the spy, compound described in 428, such as 2-(4-methoxyl-naphthalene-1-yl)-4,6-two (trichloromethyl)-1,3,5-triazine, 2-(4-ethoxy-naphthalene-1-yl)-4,6-two (trichloromethyl)-1,3,5-triazines, 2-[4-(2-ethoxyethyl group)-naphthalene-1-yl]-4,6-two (trichloromethyl)-1,3,5-triazine, 2-(4,7-dimethoxy-naphthalene-1-yl)-4,6-two (trichloromethyl)-1,3,5-triazine and 2-(acenaphthene-5-yl)-4,6-two (trichloromethyl)-1,3, the 5-triazine.
At Deutsche Bundespatent 3,337, the compound described in 024, such as 2-(4-styryl phenyl)-4,6-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.; The compound of narration in 29,1527 (1964) is such as 2-methyl-4,6-two (trisbromomethyl)-1,3,5-triazines, 2,4,6-three (trisbromomethyl)-1,3,5-triazine, 2,4,6-three (two bromomethyls)-1,3,5-triazine, 2-amino-4-methyl-6-three (bromomethyl)-1,3,5-triazine and 2-methoxyl-4-methyl-6-trichloromethyl-1,3,5-triazines.
Open clear 62-58 the spy, the compound described in 241 is such as 2-(4-phenylacetylene base phenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-naphthyl-1-ethynyl phenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 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)-1,3,5-triazines, 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, the 5-triazine.
Open flat 5-281 the spy, the compound described in 728 is such as 2-(4-trifluoromethyl)-4,6-two (trichloromethyl)-1,3,5-triazines, 2-(2, the 6-difluorophenyl)-4,6-two (trifluoromethyl)-1,3,5-triazine, 2-(2, the 6-dichlorophenyl)-4,6-two (trichloromethyl)-1,3,5-triazine, 2-(2, the 6-dibromo phenyl)-4,6-two (trichloromethyl)-1,3,5-triazines.
Open flat 5-34 the spy, described in 920 2,4-two (trichloromethyl)-6-[4-(N, N-di ethoxy carbonyl methylamino)-3-bromophenyl]-1,3, the 5-triazine, at United States Patent (USP) 4,239, the trihalomethyl group described in 850-s-triaizine compounds, can also enumerate 2,4,6-three (trichloromethyl)-s-triazine, 2-(4-chlorphenyl)-4,6-two (trisbromomethyl)-s-triazine etc.
Can also enumerate at United States Patent (USP) 4,212 the compound described in 976 etc. with 4-oxadiazole skeleton.As compound with 4-oxadiazole skeleton, can enumerate such as 2-trichloromethyl-5-phenyl-1,3, the 4-4-oxadiazole, 2-trichloromethyl-5-(4-chlorphenyl)-1,3, the 4-4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3, the 4-4-oxadiazole, 2-trichloromethyl-5-(2-naphthyl)-1,3, the 4-4-oxadiazole, 2-trisbromomethyl-5-phenyl-1,3, the 4-4-oxadiazole, 2-trisbromomethyl-5-(2-naphthyl)-1,3, the 4-4-oxadiazole, .2-trichloromethyl-5-styryl-1,3, the 4-4-oxadiazole, 2-trichloromethyl-5-(4-chlorostyrene base)-1,3, the 4-4-oxadiazole, 2-trichloromethyl-5-(4-methoxyl-styrene)-1,3, the 4-4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3, the 4-4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxy styryl)-1,3, the 4-4-oxadiazole, 2-trisbromomethyl-5-styryl-1,3,4-4-oxadiazole etc.
As fit for service 9 oxime derivate in the present invention, can also enumerate the compound of representing with following general formula.
[changing 3]
[changing 4]
[changing 5]
[changing 6]
R
(29)n-C 3H 7
(30)n-C 8H 17
(31) camphor
(32)p-CH 3C 6H 4
Figure A20041005839600333
R
(33)nC 3H 7
(34)p-CH 3C 6H 4
As the Hexaarylbiimidazole that can use in the present invention, can enumerate 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (2-fluorophenyl)-4,4 ' 5,5 '-tetraphenyl diimidazole, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (2-chlorphenyl)-4,4 ' 5,5 '-four (3-methoxyphenyl) diimidazole, 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (4-methoxyphenyl) diimidazole, 2,2 '-two (4-methoxyphenyls)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (2-nitrobenzophenone)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (2-aminomethyl phenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-(2-trifluoromethyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, at the compound described in the WO 00/52,529.
Above-mentioned diimidazole compounds can be used in such as Bull.Chem.Soc.Japan, and 33,565 (1960) and J.Org.Chem, the method described in 36 (16) 2262 (1971) is synthetic at an easy rate.
As ketonic compound, can enumerate 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-carbethoxyl group benzophenone, benzophenone tetrabasic carboxylic acid or its tetramethyl ester, 4,4 '-two (dialkyl amido) benzophenone is (such as 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (dicyclohexyl amino) benzophenone, 4,4 '-two (diethylamino) benzophenone, 4,4 '-two (dihydroxy ethyl amino) benzophenone, 4-methoxyl-4 '-dimethylamino benzophenone, 4,4 '-dimethoxy-benzophenone, 4-dimethylamino benzophenone, 4-dimethylaminomethyl Benzophenone, benzyl, anthraquinone, 2-tert-butyl group anthraquinone, 2-methylanthraquinone, phenanthrenequione, xanthone, thioxanthones, the 2-clopenthixal ketone, 2, the 4-diethyl thioxanthone, Fluorenone, 2-benzyl-dimethylamino-1-(4-morpholine and phenyl)-1-butanone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholine also-1-acetone, 2-hydroxy-2-methyl-[4-(1-methyl ethylene) phenyl] propyl alcohol oligomer, benzene idol mattress, benzene idol mattress ethers is (such as benzene idol mattress methyl ether, benzene idol mattress ether, benzene idol mattress propyl ether, benzene idol mattress isopropyl ether, benzene idol mattress phenylate, benzyl dimethyl ketal), acridone, chloro-acridine ketone, N-methylacridine ketone, N-butyl acridone, N-butyl chloride acridone etc.
In addition; can enumerate acridine derivatives (such as the 9-phenylacridine; 1; 7-two (9; 9 '-acridinyl) heptane etc.); N-phenylglycine etc.; polyhalide is (such as phenixin; phenyl tribromo first sulfone; phenyl trichloromethyl ketone etc.); Coumarins is (such as 3-(2-coumarone formoxyl)-7-diethyl amino coumarin; 3-(2-coumarone formoxyl)-7-(1-pyrrolidinyl) cumarin; 3-benzoyl-7-diethyl amino coumarin; 3-(2-methoxybenzoyl base)-7-diethyl amino coumarin; 3-(4-dimethylamino benzoyl)-7-diethyl amino coumarin; 3; 3 '-carbonyl two (5; 7-two positive propoxy cumarins); 3; 3 '-carbonyl two (7-diethyl amino coumarin); 3-benzoyl-ayapanin; 3-(2-furanylcarbonyl)-7-diethyl amino coumarin; 3-(4-diethylamino cinnamoyl)-7-diethyl amino coumarin; 7-methoxyl-3-(3-pyridine carbonyl) cumarin; 3-benzoyl-5; 7-dipropoxy cumarin; 7-benzotriazole-2-basic note legumin etc.; can also enumerate the spy in addition and open flat 5-19; 475; Te Kaiping 7-271; 028; the spy opens 2002-363; 206; the spy opens 2002-363; 207; the spy opens 2002-363; 208; the spy opens 2002-363; the coumarin compound of narration in the middle of 209 grades); amine is (such as 4-dimethylaminobenzoic acid ethyl ester; 4-dimethylaminobenzoic acid butyl ester; 4-dimethylaminobenzoic acid phenethyl ester; 4-dimethylaminobenzoic acid 2-BIDA base ethyl ester; 4-dimethylaminobenzoic acid benzene 2-toluyl oxygen base ethyl ester; pentamethylene two (4-dimethylaminobenzoic acid ester); the phenethyl ester of 3-dimethylaminobenzoic acid and pentamethylene ester; 4-dimethylamino benzaldehyde; 2-chloro-4-dimethylamino benzaldehyde; 4-dimethylamino benzylalcohol; (4-dimethylamino benzoyl) ethyl acetate; 4-piperidines and methyl acetophenone; 4-dimethylamino benzene idol mattress; N; N-dimethyl-4-methylaniline; N; N-diethyl-3-phenetidine; tribenzyl amine; dibenzyl aniline; N-methyl-N-phenyl-benzylamine; 4-bromo-N; accelerine; tridodecylamine; amino Material of Fluoran (ODB; 0BDII etc.); crystal violet rowland lactone; white crystals violet element etc.); the acylphosphine oxide class is (such as two (2; 4; the 6-trimethylbenzoyl)-phenyl phosphine oxide; two (2; 6-dimethoxy benzoyl)-2; 4; 4-trimethyl-benzyl phenyl phosphine oxide; Lucirin TPO etc.); the metallocene class is (such as two (η 5-2; 4-cyclopentadiene-1-yl)-two (2; 6-two fluoro-3-(1H-pyrroles-1-yl)-phenyl) titanium; η 5-cyclopentadienyl group-η 6-cumenyl-iron (1+) hexafluorophosphoric acid (1-) etc.); open clear 53-133 the spy; 428; special public clear 57-1; 819; special public clear 57-6; 096 and United States Patent (USP) 3; disclosed compound in 615,455.
Can also use at United States Patent (USP) 2,367, the disclosed ketal aldehyde compound that connects in 660, United States Patent (USP) 2,448, disclosed even mattress ether compound in 828, United States Patent (USP) 2,722, the aromatic series that on α-hydrocarbon, replaces of narration idol mattress compound in 512, United States Patent (USP) 3,046,127 and 2,951, the multinuclear naphtoquinone compounds of narration in 758, the spy opens 2002-229, the organoboron compound of narration and other the free radical generating agent of giving an example etc. in 194 also have triarylsulfonium salt (with the salt of antimony hexafluoride and hexafluorophosphoric acid), sulfonium salt compounds (being effective as the initiating agent of cationic polymerization) such as (phenyl thienyl) diphenyl sulfonium salt, the salt of narrating among the WO 01/71,428 etc.
Can use a kind of or use two or more Photoepolymerizationinitiater initiater simultaneously.As such combination, can utilize such as at United States Patent (USP) 3,549, the combination of the Hexaarylbiimidazole of narration and 4-aminoketones in 367, special public clear 51-48, the benzothiazole compound of narration and the combination of trihalomethyl group-s-triaizine compounds etc. in 516, perhaps combination, Coumarins and the luxuriant titanium of combination, Hexaarylbiimidazole and the luxuriant titanium of aromatics such as thioxanthene and hydrogen donor (such as the compound that contains dialkyl amido, phenolic compound etc.) and the combination of phenylglycine class etc.
With respect to whole photographic layer compositions of each photographic layer, the consumption of Photoepolymerizationinitiater initiater generally is 0.1～30wt%, preferably in the scope of 0.5～20wt%, in the scope particularly preferably in 0.5～15wt%.Under the situation of the light sensitivity difference of regulating each photographic layer with the content of Photoepolymerizationinitiater initiater, if the amount of the Photoepolymerizationinitiater initiater that contains in second photographic layer is fine more than the amount of the Photoepolymerizationinitiater initiater that contains in first photographic layer.With respect to the amount of Photoepolymerizationinitiater initiater contained in first photographic layer, the amount of contained Photoepolymerizationinitiater initiater is preferably at 1.5～100 times, more preferably at 1.8～50 times, particularly preferably in 2～20 times in second photographic layer.
[sensitizer]
In order when each photographic layer exposes, to regulate light sensitivity or wavelength photoreceptor, can add sensitizer.Using under visible light or ultraviolet ray, the situation of visible light laser as exposure light (active energy ray), sensitizer is can make it to be in excited state by ray by active, interact with other materials (such as free radical generating agent, acid-producing agent etc.) (such as energy move, electronics moves etc.) produce the compound of useful groups such as free radical or acid.
As sensitizer; can utilize known polynuclear aromatic compound class (such as pyrene perylene; benzophenanthrene); the xanthene class is (such as fluorescein; tetrabromofluorescein; erythrosine; rhodamine B; diiodocosin); the cyanine class is (such as indigo carbon cyanine; sulphur carbon cyanine; oxygen carbon cyanine); the merocyanine class is (such as merocyanine; the carbon merocyanine); thiazide is (such as thionine; methylene blue; toluidine blue); acridine is (such as acridine orange; chloroflavin; acridine yellow); anthraquinone class (such as anthraquinone); this storehouse Ali crow nurse (ス Network ア リ ウ system) class (ス Network ア リ ウ system); the acridine ketone is (such as acridone; chloro-acridine ketone; N-methylacridine ketone; N-butyl acridone; N-butyl chloride acridone etc.); Coumarins (can be enumerated such as 3-(2-coumarone formyl)-7-diethyl amino coumarin; 3-(2-coumarone formyl)-7-(1-pyrrolidinyl) cumarin; 3-benzoyl-7-diethyl amino coumarin; 3-(2-methoxybenzoyl base)-7-diethyl amino coumarin; 3-(4-dimethylamino benzoyl)-7-diethyl amino coumarin; 3; 3 '-carbonyl two (5; 7-two positive propoxy cumarins); 3; 3 '-carbonyl two (7-diethyl amino coumarin); 3-benzoyl-ayapanin; 3-(2-furanylcarbonyl)-7-diethyl amino coumarin; 3-(4-diethylamino cinnamoyl)-7-diethyl amino coumarin; 7-methoxyl-3-(3-pyridine carbonyl) cumarin; 3-benzoyl-5; 7-dipropoxy cumarin etc.; can enumerate the spy in addition and open flat 5-19; 475; Te Kaiping 7-271; 028; the spy opens 2002-363; 206; the spy opens 2002-363; 207; the spy opens 2002-363; 208; the spy opens 2002-363, the coumarin compound of narration in 209) etc.
Combination as polymerization initiator and sensitizer, can enumerate such as opening 2001-305 the electronics mobile model initiator system examples such as [(1) power supply subtype initiating agent and sensitizing coloring matter, (2) are subjected to electron type initiating agent and sensitizing coloring matter, (3) power supply subtype initiating agent, sensitizing coloring matter and are subjected to electron type initiating agent (ternary initiator system)] of narration in 734 the spy.
Also can all contain sensitizer at first photographic layer and second photographic layer.With respect to whole compositions of photosensitive polymer combination, the addition of sensitizer is generally in the scope of 0.05～30wt%, preferably in the scope of 0.1～20wt%, in the scope particularly preferably in 0.2～10wt%.When the content of sensitizer is too much, when preserving, can separate out from photographic layer, and when its content is very few, time-consuming in the process of exposure to the susceptibility decline of active energy ray, reduced throughput rate.
Under the situation of the light sensitivity difference of regulating each photographic layer with sensitizer, the amount of the sensitizer that contains in second photographic layer is just passable more than the amount that has contained sensitizer in first photographic layer, amount with respect to sensitizer contained in first photographic layer, the amount of contained sensitizer is preferably 1.5～100 times in second photographic layer, more preferably 1.8～50 times, preferred especially 2～20 times.Also can regulate and make and in first photographic layer, do not contain sensitizer.
[other compositions]
As required, photographic layer can use thermal polymerization inhibitor, plastifier, colour former, colorant simultaneously, can also use and the adhesive accelerant of matrix surface and other auxiliary agent (such as pigment, electroconductive particle, filler, defoamer, fire retardant, levelling agent, peel off promoter, antioxidant, spices, thermal cross-linking agent, surface tension modifier, chain-transferring agent etc.), the performances such as physical property that with this end in view just can regulate the stability of light-sensitive sheet, the performance of taking pictures, color developing, film.Above-mentioned composition can be added in first photographic layer, also can be added in second photographic layer, and its addition can decide according to the purpose of adding, and the addition in each photographic layer can be identical, also can be different.
[thermal polymerization inhibitor]
For the polymerizable compound that prevents photographic layer carries out thermal polymerization or the polymerization along with the process of time, can add the thermal polymerization inhibitor.As the thermal polymerization inhibitor, can enumerate metoxyphenol such as 4-, quinhydrones, the quinhydrones that alkyl or aryl replaces, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, the 2-Viosorb 110,4-methoxyl-2-Viosorb 110, stannous chloride, phenothiazine, chloranil, naphthylamines, betanaphthol, 2,6-two-tert-butyl group-4-cresols, 2,2 '-methylene two (4-methyl-6-tert butyl phenol), pyridine, nitrobenzene, dinitro benzene, picric acid, the 4-methylaniline, methylene blue, the reactant of copper and organic sequestering agent, gaultherolin and phenothiazine, nitroso compound, nitroso compound and Al and sequestrant etc.
With respect to the polymerizable compound of photographic layer, the addition of thermal polymerization inhibitor is preferably in the scope of 0.001～5wt%, more preferably in the scope of 0.005～2wt%, in the scope particularly preferably in 0.01～1wt%.When the addition of thermal polymerization inhibitor surpasses this scope, reduction is arranged to active tendency that can the radiation-sensitive degree, and when being lower than this scope, the tendency that reduces stability when preserving is arranged.
[plastifier]
For the physical property (flexibility) of sense of control photosphere film, can add plastifier.As the example of plastifier, can enumerate phthalates such as repefral, dibutyl phthalate, diisobutyl phthalate, dibutyl phthalate (DHP), dioctyl phthalate, dicyclohexyl phthalate, phthalic acid two (tridecyl) ester, BBP(Butyl Benzyl Phthalate, diisooctyl phthalate, diphenyl phthalate, phthalic acid diaryl, the misery pentyl ester of O-phthalic; Glycol ester classes such as oxalic acid triglycol ester, oxalic acid TEG ester, phthalic acid dimethyl glucose ester, ethyl phthalate ethohexadiol ester, Methyl Benzene-o-dicarboxylate ethohexadiol ester, butyl phthalate butyl glycol ester, triethylene glycol dicaprylate; Phosphoric acid ester such as tricresyl phosphate, triphenyl phosphate; Amide-types such as 4-toluenesulfonamide, benzsulfamide, N-n-butylbenzene sulfonamide, N-normal-butyl acetamide; Aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, dioctyl azelate, dibutyl maleate; Triethyl citrate, tributyl citrate, glycerol triacetate, butyl laurate, 4,5-diepoxy cyclohexane-1, glycolss such as 2-dicarboxylic acid dioctyl ester, polyglycol, polypropylene glycol.
With respect to the whole compositions of photographic layer, the addition of plastifier is preferably in the scope of 0.1～50wt%, more preferably in the scope of 0.5～40wt%, in the scope particularly preferably in 1～30wt%.
[colour former]
In order to give visual image (color developing) in the photographic layer after exposure, can add colour former.As colour former, can enumerate such as three (4-dimethylaminophenyl) methane (clear crystal violet element), three (4-diethylamino phenyl) methane, three (4-dimethylamino-2-aminomethyl phenyl) methane, three (4-diethylamino-2-aminomethyl phenyl) methane, two (4-dibutylamino phenyl)-aminotriaryl methanes classes such as [4-(2-cyanoethyl) methylamino phenyl] methane, two (4-dimethylaminophenyl)-2-quinolyl methane, three (4-dipropyl aminophenyl) methane; 3,6-two (dimethylamino)-9-phenyl yanthine, 3-amino-amino xanthines such as 6-dimethylamino-2-methyl-9-(2-chlorphenyl) xanthine; 3,6-two (diethylamino)-9-(2-ethoxy carbonyl phenyl) thioxanthene, 3, amino thioxanthene classes such as 6-two (dimethylamino) thioxanthene; 3,6-two (diethylamino)-9,10-dihydro-9-phenylacridine, 3,6-two (benzylamino)-9, amino such as 10-dihydro-9-methylacridine-9,10-acridan class; 3,7-two (An Ji Fen oxazine class such as diethylamino) Fen oxazine; 3, amino phenol thiazine ketones such as 7-two (ethylamino) phenothiazine ketone; 3,7-two (diethylamino)-5-hexyl-5, amino dihydrophenazine classes such as 10-dihydro-azophenlyene; Aminophenyl methane classes such as two (4-dimethylaminophenyl) anilino-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. contain the plain acyl derivative of light color of alkaline NH; Three (4-diethylamino-2-tolyl) ethoxy carbonyl terpane (メ Application Application) etc. does not have oxidable hydrogen, but oxidable be the leuco compound of chromophore compound; Colourless indigo pigment; United States Patent (USP) 3,042,515 and 3, the color development type that can be oxidized to organic amine described in 042,517 (such as 4,4 '-ethylene diamine diphenylamine (the original text mistake is divided into two noun-annotations of translation), N, accelerine, 4,4 '-methylene diamine triphenylamine, N-vinylcarbazole).Particularly preferably be the compound of triarylmethane classes such as clear crystal violet element.
Have again, in order to make such shadow color development, known will the combination with halogenide.As halid example, can enumerate halogenated hydrocarbon (such as carbon tetrabromide, iodoform, ethylene dibromide, methylene bromide, amyl bromide, isoamyl bromide, amyl iodide, dibromo-isobutyl alkane, butyl iodide, monobromo 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 trimethylene, hexachlorocyclopentadiene, dibromo-cyclohexane, 1,1,1-three chloro-2,2-two (4-chlorphenyl) ethane etc.); Halogenated alcohols compound (such as 2,2,2-ethapon, ethobrom, 1,3-two chloro-2-propyl alcohol, 1,1, the amino isopropyl alcohol of 1-trichloro-2-propanol, two (hexa-methylene iodine), acetone-bromoform, 2,2,3-three chlorobutanes-1,4-glycol etc.); Halo carbonyl compound (such as 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 compounds (such as 2-bromoethyl methyl ether, 2-bromoethyl ether, two (2-bromoethyl) ether, 1,2-dichloroethyl ether etc.); Halogen ester compounds (such as bromoethyl acetate, ethyl trichloroacetate, trichloroacetic acid trichloro ethyl ester, acrylic acid-2, the homopolymer of 3-dibromo propyl ester and multipolymer, dibromo-propionic acid trichloro ethyl ester, α, β-dichloropropylene acetoacetic ester etc.); The halogen acid amide compounds is (such as chloroacetamide, acetbromamide, dichloro acetamide, trichloroacetamide, tribromoacetamide, three chloroethyl trichloroacetamides, 2-bromine Isopropamide, 2,2,2-trichlorine propionamide, N-chlorine succinamide, N-bromine succinamide etc.); The compound (such as trisbromomethyl phenyl sulfone, 4-nitrobenzophenone trisbromomethyl sulfone, 4-chlorphenyl trisbromomethyl sulfone, tricresyl phosphate (2, the 3-dibromopropyl) ester etc.) that contains sulphur or phosphorus; 2,4-two (trichloromethyl)-6-Phenyltriazole etc.In the middle of organohalogen compounds, preferably on a carbon atom in conjunction with the halogenide of two or more halogen atoms, particularly preferably be the halogenide that on a carbon atom, has three halogen atoms.Organohalogen compounds can use separately, also can two or more be used in combination.Wherein organohalogen compounds are trisbromomethyl phenyl sulfone and 2 especially effectively, 4-two (trichloromethyl)-6-Phenyltriazole.
With respect to whole compositions of photographic layer, the addition of colour former is preferably in the scope of 0.01～20wt%, more preferably in the scope of 0.05～10wt%, in the scope particularly preferably in 0.1～5wt%.With respect to the whole compositions of photographic layer, halid consumption is generally 0.001～5wt%, preferably in the scope of 0.005～1wt%.
[dyestuff]
In order to improve, can use dyestuff to the painted operating performance of photosensitive polymer combination, for the purpose of giving its storage stability.Example as suitable dyestuff, can enumerate bright green (such as its sulfate), tetrabromofluorescein, ethyl violet rowland element, erythrosine B, methyl green, crystal violet rowland element, basic fuchsin, phenolphthalein, 1,3-diphenyl triazine, alizarine lake S, thymolphthalein, the plain 2B of methyl violet rowland, it is red that quinoline is received pyridine, diiodocosin, tropaeoline G, Thymol Blue, xylenol blue, methyl orange, orange IV, diphenyl thyrocarbazone, 2, the 7-dichlorofluorescein, paramethyl red, Congo red, benzopurpurine 4B, α-Nai Hong, Nile blue-A, phenacetarine, methyl violet rowland element, malachite green, paramagenta, 603# oiliness indigo plant [drilling holder (オ リ エ Application ト chemical industry) (strain) manufacturing in the Europe], rhodamine B and rhodamine 6G, Victoria's pure blue B OH etc.As the antithesis negative ion of the dye of positive ion, can be the acid group of organic acid or mineral acid, can enumerate acid group (negative ion) such as bromic acid, acid iodide, sulfuric acid, phosphoric acid, oxalic acid, methane-sulforic acid, toluenesulfonic acid etc.Preferred dyestuff is the dye of positive ion, can enumerate such as malachite green oxalates, malachite green sulfate etc.
With respect to whole compositions of photographic layer, preferred dyestuff addition is in the scope of 0.001～10wt%, more preferably in the scope of 0.01～5wt%, in the scope particularly preferably in 0.1～2wt%.
[adhesion promoters]
For the cohesiveness that improves each interlayer or the cohesiveness of photographic layer transfer printing sheet and matrix, in each layer, can use known so-called adhesion promoters.
As adhesion promoters, can suitably use and open flat 5-11, the adhesion promoters of narration in 439,5-341,532 and 6-43,638 the spy.Specifically can enumerate benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, morpholinyl methyl isophthalic acid-phenyl-triazole-2-thioketones, morpholinyl methyl-5-phenyl-oxazolyls-2-thioketones, 5-amino-morpholinyl methylthiazol-2-thioketones and 2-sulfydryl-5-methyl mercapto thiazole, triazole, tetrazolium, benzotriazole, carboxyl benzotriazole, contain amino benzotriazole, silane coupling agent etc.
With respect to whole compositions of photographic layer, the addition of adhesion promoters is preferably in the scope of 0.001～20wt%, more preferably in the scope of 0.01～10wt%, in the scope particularly preferably in 0.1～5wt%.
Photographic layer can contain such as drawing together at J. organosulfur compound, superoxide, redox compound, azo and two azo-compounds, photo-reduction compound and the organohalogen compound of narrating in " Photosensitive system " the 5th chapter that spreads (コ one サ one) work etc.As the example of organosulfur compound, can enumerate di-n-butyl disulfide, benzyl disulfide thing, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, benzenethiol, trichlorine ethyl methane sulfonate, 2-mercaptobenzimidazole etc.As the example of superoxide, can enumerate di-t-butyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide etc.Redox compound is the combination of superoxide and reductive agent, can enumerate ferrous ion and persulfuric acid ion, ferric ion and superoxide etc.As azo and two azo-compounds, can enumerate α, the azo salt of α '-azoisobutyronitrile, 2-azo two-2-methylbutyronitrile, 4-amino-diphenyl-amine.As the photo-reduction pigment, can enumerate diiodocosin, erythrosine, tetrabromofluorescein, acridine yellow, lactochrome, thionine etc.
[surfactant]
When making light-sensitive sheet,, can add known surfactant in order to improve the unevenness on surface.As the example of surfactant, can suitably select anionic and cationic or non-ionics, amphoteric surfactant, fluorochemical surfactant etc.With respect to the solids content of photosensitive polymer combination, its addition is preferably 0.001～10wt%, and during less than 0.001wt%, the effect of the surface appearance that can not improve when surpassing 10wt%, is easy to generate and reduces close-burning problem.As fluorochemical surfactant, preferably with acrylate with fluorine-containing aliphatic group or methacrylate high molecular surfactant as polymeric composition comprising body, this aliphatic group is the fluorine atom that contains on the chain of 3～20 carbon atoms more than the 40wt%, and has at least 3 hydrogen atoms that combine with carbon atom to be replaced by fluorine atom at the terminal number of combination never.
[barrier layer]
Light-sensitive sheet of the present invention or photosensitive laminated article dispose barrier layer between first photographic layer and second photographic layer.This barrier layer has and prevents or be suppressed at the migration of material contained in photographic layer, carrier, the diaphragm, prevents and suppress to be subjected to the effect of ectocines such as oxygen or humidity.Such as, be provided with barrier layer and move in other layers with regard to having the composition that can prevent in each photographic layer, thus the effect that the emission of the physical property of the light sensitivity of making and film changes.
Barrier layer preferably contains resin, and the lower alcohol that preferably contains water or carbon number 1～4 has the resin of compatibility as Main Ingredients and Appearance.So-called compatibility shows as above-mentioned solvent is had emulsification, dispersion, swelling, is partly dissolved or performance such as infiltration.The lower alcohol that barrier layer also preferably contains water or carbon number 1～4 has the resin of solubility as Main Ingredients and Appearance.
Barrier layer can contain polymerizable compound.This polymerizable compound is the compound with polymerism functional group, adds in the low molecular compound (monomer), also contains macromolecular compound (oligomer, polymkeric substance).Barrier layer can both contain low molecular polymerizable compound, also contained the polymkeric substance (resin) as cementing agent, perhaps preferably contained the high molecular polymerization compound (resin) as cementing agent.
By contained Photoepolymerizationinitiater initiater in first photographic layer or second photographic layer, the perhaps effect of the Photoepolymerizationinitiater initiater that is contained arbitrarily in barrier layer makes that contained polymerizable compound carries out photopolymerization in barrier layer.Contained Photoepolymerizationinitiater initiater in barrier layer when making light-sensitive sheet, can be the part of Photoepolymerizationinitiater initiater contained in first photographic layer or second photographic layer, but shift in the barrier layer.Thereby, barrier layer also be can have photosensitive.But, wish that the light sensitivity of barrier layer is lower than the light sensitivity of first photographic layer (order of light sensitivity is second photographic layer＞first photographic layer＞barrier layer) relatively.
The polymerism functional group of polymerizable compound is ring-opening polymerization group or addition polymerization group preferably, preferred especially addition polymerization group.The addition polymerization group is the ethene unsaturated group especially preferably.
Polymerizable compound preferably has a plurality of polymerism functional group in a molecule.
Low molecular polymerizable compound is same with contained polymerizable compound in above-mentioned photographic layer.But, contained closing property of low molecular weight polycaprolactone compound in barrier layer, preferably the lower alcohol to water or carbon number 1～4 demonstrates compatibility, and preferably the lower alcohol to water or carbon number 1～4 has solubility.
Cementing agent with closing property of low molecular weight polycaprolactone compound uses together preferably demonstrates compatibility to solvent (lower alcohol of water or carbon number 1～4).So-called compatibility means the performance that above-mentioned solvent is had emulsification, dispersion, swelling, dissolving (comprise and being partly dissolved) and soaks into.Contained cementing agent in barrier layer preferably has solubility to solvent (lower alcohol of water or carbon number 1～4).
The quality of closing property of low molecular weight polycaprolactone compound and cementing agent (resin) is than polymerizable compound: cementing agent, and preferably 90: 10～1: 99, be more preferably 70: 30～5: 95, most preferably be 60: 40～5: 95.
Also can use two or more closing property of low molecular weight polycaprolactone compound simultaneously.Also can use closing property of low molecular weight polycaprolactone compound and high molecular polymerization compound (as described below) simultaneously.
As the high molecular polymerization compound (resin) of cementing agent, can obtain by in as the polymkeric substance of cementing agent, importing polymerism functional group.As the example of the polymkeric substance of cementing agent, comprise as described below in photographic layer the example of contained cementing agent.But cementing agent contained in barrier layer is different with cementing agent contained in photographic layer, preferably solvent (lower alcohol of water or carbon number 1～4) is demonstrated compatibility.For compatibility, just as illustrated for the cementing agent that uses with low molecular polymerizable compound.
The molecular weight of high molecular polymerization compound is preferably more than 500, more preferably more than 1000.
The lower alcohol of water or carbon number 1～4 is demonstrated the polymkeric substance of compatibility, and its example comprises polyvinyl alcohol (PVA), modified polyvinylalcohol, polyvinyl pyrrolidone, water soluble polyamide, gelatin, cellulose.The special pure and mild modified polyvinylalcohol of preferably polyethylene.
In order in polymkeric substance, to import polymerizable group, can allow functional group's (such as hydroxyl, amino) to polymkeric substance have active functional group's (such as carboxyl, sulfo group, hydroxyl, carboxylic acid halides, acid anhydride structure, methylol, isocyanate group) and compound with polymerizable group reacts.
Have and the example of the compound of carboxyl (functional group of polymkeric substance being had active functional group, below slightly) polymerizable group, comprise (methyl) acrylic acid, itaconic acid, lauric acid, acrylic acid dimer, vinyl benzoic acid, vinyl oxybenzoic acid etc.
Have can with the compound of the group of sulfo group polymerization, its example comprises 2-acrylamide-2-methyl propane sulfonic acid, styrene sulfonic acid.
Have can with the compound of the group of hydroxyl polymeric, its example comprises (methyl) acrylic acid 2-hydroxy methacrylate.
Have the example of (ring-type) acid anhydrides of polymerizable group, comprise maleic anhydride, itaconic anhydride.Also can use the compound of in other acid anhydrides (such as fumaric acid anhydride, succinic anhydride), introducing the ethene unsaturated group, use as carboxyl with polymerizable group.
Have the compound with the polymerizable group of methylol polymerization, its example comprises methylol (methyl) acrylamide.
Have the compound with isocyanate groups degree of polymerization polymerizable group, its example comprises 2-(methyl) acryloxy ethyl isocyanate, (methyl) acryloyl group isocyanates, 1-(4-ethenylphenyl)-1-methyl ethyl isocyanate, 1-(4-isopropyl phenyl)-1-methyl ethyl isocyanate.
As the high molecular polymerization compound (resin) of cementing agent, also can use water soluble polyurethane resin with polymerizable group (spy opens flat 3-168,209, the spy opens flat 7-25,958 etc.).Glycol and the polyether polyols and the polyisocyanates reaction that will have carboxyl, make resultant of reaction again and have (methyl) acrylate reactions of hydroxyl, the carboxyl in the resin that obtains with the amine neutralization just obtains having the water soluble polyurethane resin of polymerizable group.And polyvalent alcohol and polyisocyanates with quaternary ammonium salt react, and will have (methyl) acrylate and the resultant of reaction reaction of hydroxyl again, also can make the water soluble polyurethane resin with polymerizable group.
Also can use epoxy resin (spy opens flat 4-211,413) as high molecular polymerization compound (resin) with cementing agent function with polymerizable group.Epoxy resin with polymerizable group is by epoxy acrylate and anhydride reaction, obtains with the amine neutralization again.
To have monomer (such as (methyl) acrylate) copolymerization that lower alcohol to water or carbon number 1～4 demonstrates the monomer (such as vinyl pyrrolidone) of the functional group of compatibility and has a plurality of polymerizable groups, will be in latter's monomer contained a part of polymerizable group left behind polymerizable group as polymkeric substance.
With acryloyl morpholine with have the polymkeric substance (spy opens flat 9-146,270) that multipolymer and the methacryl ethyl isocyanate reaction of (methyl) acrylate of hydroxyl obtains and also can be used as high molecular polymerization compound (resin) with cementing agent function.
Also can use two or more high molecular polymerization compound simultaneously.Can also use high molecular polymerization compound and other (not having polymerizable group) polymkeric substance (such as poly-(methyl) acrylate, polyamide, polyester) simultaneously.The preferred polymkeric substance that uses simultaneously also demonstrates compatibility (or solubility) to the lower alcohol of water or carbon number 1～4 equally with the high molecular polymerization compound.
When making above-mentioned barrier layer, can use the cementing agent same with photographic layer, but the layer of preferably forming by the cementing agent different with these.As such polymkeric substance, can use such as various pure dissolubilities, water-soluble polymers, can be scattered in alcohol, be scattered in water, have emulsibility or buck soluble polymer, can enumerate such as polyvinyl alcohol (PVA) (comprising modified polyvinylalcohol), polyvinyl pyrrolidone, water soluble polyamide, gelatin, cellulose etc. and their derivant.These polymkeric substance can use separately, also can two or more use simultaneously.Have again, in the scope of harmless water-soluble and buck dissolubility, also can add various polymkeric substance such as acrylic acid series polymeric compounds, polyamide-based polymkeric substance, polyester based polymer.In barrier layer, also can use in patent 2,794 compound that uses in the thermoplastic resin of narration or the middle layer in 242.
[manufacturing of light-sensitive sheet]
Light-sensitive sheet of the present invention can be according to following order manufacturing.At first, above-mentioned various material dissolves, emulsification be scattered in water or solvent in, be mixed with respectively and make the first photosensitive polymer combination solution that first photographic layer uses and make the second photosensitive polymer combination solution that second photographic layer is used.Also to make and make the solution that barrier layer is used.
As the solvent of the first photosensitive polymer combination solution and the second photosensitive polymer combination solution, can enumerate such as alcohols such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, the tert-butyl alcohol, n-hexyl alcohols; Ketones such as acetone, MEK, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; Ester classes such as ethyl acetate, butyl acetate, n-amyl acetate, Methylsulfate, ethyl propionate, repefral, ethyl benzoate and acetate methoxyl propyl ester; Toluene, dimethylbenzene, benzene, ethylbenzene etc. are aromatic hydrocarbon based; Phenixin, triclene, chloroform, 1,1, halogenated hydrocarbons such as 1-trichloroethanes, ethylene dichloride, Benzene Chloride; Tetrahydrofuran, dimethyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether, 1-methoxyl-ethers such as 2-propyl alcohol; Dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), sulfolane etc.They also can mix use.In the first photosensitive polymer combination solution and the second photosensitive polymer combination solution, also can add known surfactant.
Solvent for the polymer solution of using at the manufacturing barrier layer can use the coating solvent same with photographic layer, also can make the mixed solvent of water or water and solvent.In solvent, can use above-mentioned hydrophilic solvents such as alcohols such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol.It is 10～90% that the consumption of solvent can make the solids content of coating fluid.
Then, the coating first photosensitive polymer combination solution forms first photographic layer by drying on carrier.And then coating forms the coating fluid that barrier layer is used on first photographic layer, and carry out drying.Be coated with the second photographic layer resin combination solution in the above again, form second photographic layer by drying.Coating during multilayer can successively be coated with as mentioned above, also can the while coating multiple.The method of photosensitive resin coating composition solution does not have specific restriction, can adopt and be coated with the whole bag of tricks such as method, woodburytype, line-excellent rubbing method and scraper rubbing method such as spraying process, rolling method, spin-coating method, slot coated method, squeezing and coating method, heavy curtain rubbing method, mould.Drying condition is different because of the ratio of each composition, solvent types, use, usually at temperature drying 30sec～15min of 60～110 ℃.
Photographic layer be than the situation more than 2 layers under, can make required light-sensitive sheet by repeating same operation.When photographic layer two-layer or two-layer when above, the gross thickness of photographic layer can be in the scope of 10 μ m～1mm.
[carrier and diaphragm]
Wish that carrier can peel off photographic layer, and have good light transmittance, have the surface of good planarization simultaneously.Carrier is preferably made with transparent synthetic resin.As the example of carrier, can enumerate polyethylene terephthalate, PEN, polypropylene, tygon, Triafol T, cellulose diacetate, poly-(methyl) alkyl acrylate, poly-(methyl) acrylate copolymer, Polyvinylchloride, polyvinyl alcohol (PVA), polycarbonate, polystyrene, match and cough up various plastic sheetings such as fen, metachloroethylene copolymer, polyamide, polyimide, vinyl chloride-vinyl acetate copolymer, teflon, poly-trifluoro-ethylene, cellulose-based film, nylon film.Also can use two or more compound substance.Preferred especially polyethylene terephthalate in the middle of above-mentioned material.The thickness of carrier is preferably 2～150 μ m, and more preferably 5～100 μ m are preferably 8～50 μ m especially.Carrier is strip preferably.The strip carrier that uses when making light-sensitive sheet of the present invention, its length can arbitrary decisions, are 10～20 such as using length, the carrier of 000m.
Light-sensitive sheet of the present invention can be on second photographic layer configuration protection film.As the example of said protection film, can enumerate the material that in above-mentioned carrier, uses and paper or compound tygon, polyacrylic composite paper etc.Special preferably polyethylene film and polypropylene film.The thickness of diaphragm 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.At this moment, if the cohesive force of photographic layer and carrier as A, and the cohesive force of photographic layer and diaphragm as B, the relation of cohesive force A＞cohesive force B must be arranged.As the example of carrier/diaphragm combination, can enumerate polyethylene terephthalate/polypropylene, polyethylene terephthalate/tygon, Polyvinylchloride/match and cough up fen, polyimide/polypropylene, polyethylene terephthalate/polyethylene terephthalate etc.By at least one side in carrier and the diaphragm is carried out surface treatment, to satisfy the relation of above-mentioned cohesive force.The surface treatment of carrying out carrier is in order to improve the cohesive force with photographic layer, can to enumerate such as painting bottom coating, Corona discharge Treatment, flame treatment, ultraviolet treatment with irradiation, high frequency treatment with irradiation, glow discharge processing, plasma active treatment with irradiation, laser radiation processing etc.Static friction coefficient between carrier and the diaphragm is important.This static friction coefficient is preferably 0.3～1.4, is preferably 0.5～1.2 especially.If less than 0.3 then too sliding, when being rolled into web-like, offset, and under 1.4 the situation of surpassing, be difficult to be rolled into good web-like.
Light-sensitive sheet of the present invention is wound on the volume core cylindraceous, and the row that involves in that is rolled into strip is preserved.The length of this strip can arbitrary decision, such as can be 10～20, selects in the scope of 000m.Can cutting processing be 100～1, the strip of 000m be rolled into web-like to be user-friendly to.This moment preferably carrier rolling in the outside.Above-mentioned web-like light-sensitive sheet also can cut into sheet.When keeping, from protection end face and the viewpoint that prevents that the edge from merging, preferably on end face, place separator (particularly damp proof is wherein put into drying agent), go back the preferred low material bag of moisture-penetrability that uses and tie.
Can carry out surface treatment to diaphragm.This surface treatment is in order to regulate the cohesiveness of diaphragm and photographic layer.Such as on the surface of diaphragm, being coated with the undercoat of forming by polymkeric substance such as polysiloxane, fluorine-containing polyolefin, polyvinyl fluoride and polyvinyl alcohol (PVA).Generally can be after being coated with the coating fluid of above-mentioned polymkeric substance on the diaphragm film, at 30～150 ℃ (particularly 50～120 ℃) thus down dry 1～30min obtains undercoat.Except photographic layer, barrier layer, carrier and diaphragm, can also have cushion, peel ply, tack coat, light absorbing zone, sealer etc.
[matrix]
As the matrix of light-sensitive sheet transfer printing of the present invention, can select from the surface high flatness to any material with concavo-convex surface.Preferred tabular matrix, the promptly so-called substrate of using.Can enumerate substrate that known manufacturing printed circuit board uses, glass plate (soda-lime glass plate etc.), film of synthetic resin, paper, sheet metal etc. specifically.
Second photographic layer of forming by the photosensitive polymer combination that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater on laminated successively on the matrix and form by the photosensitive composite that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater, and its light sensitivity is than the relative first lower photographic layer of second photographic layer, thereby formed photosensitive laminated article.Preferred disposition barrier layer between above-mentioned first photographic layer and second photographic layer is to form photosensitive laminated article.
Light-sensitive sheet of the present invention can be widely used as MATERIALS FOR DISPLAYs such as printed circuit board, chromatic color filter or column material, muscle material, distance piece, spaced walls, holograph, microcomputer, protective materials, P.e.c. style formation material.Wherein be preferably applied to the application of printed circuit board, display part, the application of preferred especially printed circuit board.
[the formation method of style]
Light-sensitive sheet of the present invention can form required style by the method for following formation style, this method comprises following operation: (1) carries out the laminated lamilated body that obtains on substrate, makes the operation of its second photographic layer near substrate one side; (2) rayed of the graphic pattern of being scheduled to from first photographic layer, one side of lamilated body, the operation that first photographic layer that is subjected to light-struck zone and second photographic layer are hardened together; (3) remove the operation of carrier from lamilated body; And (4) develop lamilated body, and the operation that unhardened part in the lamilated body is removed is by the zone of the hardening resin that exists first photographic layer and second photographic layer to harden together to form with there is not the style of the regional composing images of hardening resin.
Light-sensitive sheet of the present invention also can be by the method for following formation image pattern, and form required style: this method comprises: (1) is the laminated lamilated body that obtains on substrate, makes the operation of its second photographic layer near substrate one side; (2) from a side of first photographic layer of lamilated body, zone in the image pattern irradiation light of stipulating, shine at least two light of the energy level that differs from one another, in the bigger zone of the light ray energy of being shone, first photographic layer and second photographic layer harden simultaneously, and, make the operation of second photographic layer sclerosis in the smaller zone of the light ray energy of being shone; (3) remove the operation of carrier from lamilated body; And (4) develop lamilated body, remove the operation of unhardened part in the lamilated body, by on substrate, have first photographic layer and second photographic layer harden simultaneously the resin that forms the zone, have the zone of the resin that forms by the sclerosis of second photographic layer, and by the zone that does not have hardening resin composing images style together.
Yet, in said method, also can be between operation (1) and operation (2), rather than between operation (2) and (4), carry out the operation of removing carrier from lamilated body of (3).
Light source as irradiation light in operation (2), under the situation of shining by carrier, use emission can see through carrier, and the electromagnetic wave of Photoepolymerizationinitiater initiater that can use or sensitizer activation, it is wavelength 300～1,500nm, the light source from the ultraviolet ray to the visible light of preferred 320～800nm scope especially preferably uses the light source in 330～650nm scope.Such as known light sources such as the fluorescent tube that can use (surpassing) high-pressure mercury-vapor lamp, xenon lamp, carbon arc lamp, Halogen lamp LED, used in copy machines etc., light emitting diode, semiconductor lasers.Can use electron ray and X ray in addition.Under the situation of shining, can use same light source from the place of peeling off carrier.Wherein, preferably carry out illumination with laser, Wavelength of Laser is preferably 200～1, and the scope of 500nm is further preferably in the scope of 300～800nm, more preferably in the scope of 370～650nm, most preferably in the scope of 400～450nm.
[manufacture method of printed circuit board]
Light-sensitive sheet of the present invention goes for the manufacturing of printed circuit board, is particularly suitable for making the printed circuit board with reach through hole and via hole.
Light-sensitive sheet of the present invention by the method for following formation layout pattern, can form required style, and this method comprises: (1) carries out the laminated lamilated body that obtains on substrate, makes the operation of its second photographic layer near substrate one side; (2) carry out the illumination of prescribed route style from first photographic layer, one side of lamilated body, make first photographic layer in the zone that is subjected to this illumination and the operation that second photographic layer hardens simultaneously; (3) remove the operation of carrier from lamilated body; And (4) develop lamilated body, remove the operation of unhardened part in the lamilated body, printed circuit board with substrate on, constitute layout pattern by harden the simultaneously zone that the hardening resin that forms covers and the zone of exposing substrate surface of first photographic layer and second photographic layer.
Light-sensitive sheet of the present invention, the layout pattern formation method by following also can form required style, and this method comprises (1) laminated lamilated body that obtains on substrate, makes the operation of its second photographic layer near substrate one side; (2) from first photographic layer, one side of lamilated body, the part bigger irradiate light of illumination energy in the hole, first photographic layer and second photographic layer are hardened simultaneously, and in the zone that forms wiring, with the smaller irradiate light of illumination energy, make the sclerosis of second photographic layer, carry out so light-struck operation of image pattern; (3) remove the operation of carrier from lamilated body; And (4) develop lamilated body, remove the operation of unhardened part in the lamilated body, make the printed circuit board with bore portion with substrate on, form by first photographic layer and second photographic layer harden bore portion that the hardening resin that forms covers simultaneously, the hardening resin covering that formed by the sclerosis of second photographic layer regional and the zone of exposing substrate constituted layout pattern.
In said method, also can be between operation (1) and operation (2), rather than between operation (2) and operation (4), carry out the operation of removing carrier from lamilated body of (3).
As the light source that in operation (2), carries out illumination, to be undertaken by carrier under the situation of illumination, use can see through carrier, and same as mentioned above light source.As light source, more preferably use laser to shine.
Then, on the printed circuit board that obtains, use such as known subtract the type method or add type method (false add type method, entirely add type method) handle the operation of the manufacturing printed circuit board that has formed above-mentioned layout pattern being carried out etching or plating with substrate.In order to make printed circuit board of the present invention with industrial favourable coverage method, the preferred method that subtracts type by etching of using.Can after above-mentioned processing, will remain in the manufacturing printed circuit board and peel off, and under the situation of false add type method, can after peeling off, carry out etching to the copper film portion again, and just can access required printed circuit board with the hardening resin on the substrate.For the printed circuit board of multilayer, also can be with making with the same manufacture method of above-mentioned printed circuit board.
Illustrate that below with reference to Fig. 7 use light-sensitive sheet manufacturing of the present invention has the method for the printed circuit board of reach through hole.Shown in Figure 7, be the situation of the use of light-sensitive sheet shown in Figure 1 or light-sensitive sheet shown in Figure 2.
At first, as shown in Fig. 7 (A), prepare to have the substrate 21 that manufacturing printed circuit board that the surface of reach through hole 22 covered by metal cladding 23 is used.As making printed circuit board, can use attached copper foil plate and on insulating material such as glass-epoxy, be coated with the formed substrate of copper layer, perhaps the laminated film formed copper facing substrate of layer insulation (laminate) on this substrate with substrate 21.
Then; as as shown in Fig. 7 (B), use 10 pressurizations of 31 pairs of light-sensitive sheets of backer roll, its second photographic layer 14 is bonded in makes printed circuit board with on the surface of substrate 21; have under the situation of diaphragm, peel off this diaphragm (laminated operation).Thus, obtained laminated successively and made the lamilated body of printed circuit board with substrate 21, second photographic layer 14, barrier layer 13, first photographic layer 12 and carrier 11 thereof.Laminated to light-sensitive sheet can (30～180 ℃) be carried out under room temperature (15～30 ℃) or heating.Carry out under the heating down particularly preferably in 60～140 ℃.The pressure of hold-down roller is preferably at 1～10kg/cm 2Scope in.The speed of compressing is preferably 1～3m/min.Also can carry out preheating with substrate 21 with making printed circuit board.Can also under reduced pressure carry out laminated.
Also can make printed circuit board with substrate on successively directly coating make the second photosensitive polymer combination solution, barrier layer solution and the first photosensitive polymer combination solution that light-sensitive sheet is used, carry out drying then and replace using light-sensitive sheet, obtained laminated successively thus and made the lamilated body of printed circuit board with substrate, second photographic layer, barrier layer and first photographic layer.
Then, as shown in Fig. 7 (C), the surface rayed from carrier 11 1 sides of lamilated body makes the photographic layer sclerosis.(inferior such as the situation in the light transmission deficiency of carrier) also can peel off carrier earlier and carry out illumination more at this moment, as required.Forming the zone of printed circuit board, shining the light that makes the necessary luminous energy of second photographic layer, 14 sclerosis, forming the hardened layer 16 (wiring portion exposure process) that layout pattern is used according to predetermined style with the layout pattern of substrate 21.Making printed circuit board and on every side with the opening portion of the reach through hole 22 of substrate; irradiation makes first photographic layer 12 and the second photographic layer 14 necessary luminous energy of all hardening, and has formed the zone (bore portion exposure process) of reach through hole protection metal level with hardened layer 17.Wiring portion exposure process and bore portion exposure process can carry out respectively independently, also can walk abreast simultaneously.Exposure is to shine by photomask to carry out, and perhaps uses laser explosure device to be undertaken by laser radiation.Particularly use the latter's laser explosure device, do not use expensive coverage film just can form style, do not have to be suitable for making the goods of a small amount of many kinds owing to the problem of covering on the caused engineering of film.
Undertaken by photomask under the situation of illumination; can only make the luminous energy of second photographic layer sclerosis by the photomask irradiation; the zone of the hardened layer 16 that formation manufacturing layout pattern is used; and use hardened layer 17 zones by the metal level that the photomask irradiation can make second photographic layer and the two-layer luminous energy of all hardening of first photographic layer form the protection reach through hole, can utilize the method for double exposure.Perhaps also can use photomask to carry out single exposure, photomask is made low with the hardened layer 16 regional corresponding part transmittances that form layout pattern, with the metal level hardened layer 17 corresponding part transmittance height of protection reach through hole.Using laser explosure device to carry out under the situation of laser radiation, preferably change the scan exposure of the quantity of illumination as required in addition.
Under the situation of unstripped carrier also, shown in Fig. 7 (D), peel off carrier 11 (carrier stripping process) from lamilated body.
Then; as as shown in Fig. 7 (E); dissolving is removed in the unhardened zone of manufacturing printed circuit board with first photographic layer 12, barrier layer 13 and second photographic layer 14 on the substrate 21 in suitable developer solution; form the style that constitutes layout pattern hardened layer of using 16 and the hardened layer 17 of protecting the reach through hole metal level to use, exposed the metal level 23 (developing procedure) of substrate surface.Developer solution can use alkaline aqueous solution, water system developer solution, organic solvent etc. and the corresponding developer solution of photosensitive polymer combination.As developer solution, preferred weakly alkaline aqueous solution.As the alkali components of this weak alkaline aqueous solution, can enumerate 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.Development is approximately 8～12 with the pH value of weak alkaline aqueous solution, is preferably about 9～11 especially.Specifically can use aqueous sodium carbonate, wet chemical of 0.1～5wt% etc.The temperature of developer solution can be adjusted to the development that is suitable for photographic layer, generally is preferably about 25～40 ℃.The organic solvent (alcohols, ketone, ester class, ethers, amide-type, lactone etc.) that in this developer solution, also can use surfactant, defoamer, organic base (such as ethylenediamine, monoethanolamine, Tetramethylammonium hydroxide, diethylene triamine, triethylene five amine, morpholine, triethanolamine etc.) simultaneously or promote to develop.Developer solution can use water or alkaline aqueous solution are mixed the water system developer solution that organic solvent forms, also can be separately with an organic solvent.
After development, also can handle as required by after-baking or post-exposure, further promote the sclerous reaction of sclerosis part, can use the wet development method to develop as mentioned above, also can use the dry process development method to develop.
Then, as shown in Fig. 7 (F), remove the metal level 23 (etching procedure) that exposes substrate surface with the etching liquid dissolving.Because the opening portion of reach through hole 22 is covered by hardenable resin composition 17 (coverlay), etching liquid can not enter the coat of metal of reach through hole corrosion in reach through hole, and the coat of metal of reach through hole just left behind according to predetermined shape.Just formed layout pattern 24 on substrate 21 at such manufacturing printed circuit board.Under metal level 23 is situation by copper production, can use copper chloride solution, solution of ferrous chloride, alkaline etching solution, hydrogen peroxide etching liquid etc. as etching liquid, wherein from the viewpoint of etching effect, especially preferably use solution of ferrous chloride.
Then, as shown in Fig. 7 (G), in strong alkaline aqueous solution, remove hardened layer 16,17 (removing the hardening thing operation) from making printed circuit board with substrate with the form of stripping film 18.As the alkali composition of strong alkaline aqueous solution, can enumerate NaOH and potassium hydroxide.The pH value of the strong alkaline aqueous solution that uses is approximately 12～14, is preferably about 13～14 especially.Specifically can use sodium hydrate aqueous solution and the potassium hydroxide aqueous solution of 1～10wt%.
Printed circuit board also can be the wiring plate with sandwich construction.Light-sensitive sheet of the present invention not only uses above-mentioned lithographic method, also can use electric plating method.As electric plating method, have such as the copper of copper sulphate plating, cupric pyrophosphate plating etc. electroplate, nickel plating such as scolder plating, water-bath (nickelous sulfate-nickel chloride) plating, nickel sulfamic acid such as Hai Silu (Ha イ ス ロ one) plating scolder, gold-plated firmly, soft gold-plated etc. gold-plated.
[embodiment]
[embodiment 1]
Coating forms the photographic layer (first photographic layer) of 25 μ m by the following solution of forming first photosensitive polymer combination that forms after the drying on the pet film of thickness 20 μ m.
[composition of 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 weight-average molecular weight: 90,000; Tg:70 ℃ of 15 weight portions
Diacrylate ten dimerization propylene glycol esters 6.5 weight portions
Dimethacrylate TEG ester 1.5 weight portions
4,4 '-two (lignocaine) Benzophenone, 0.04 weight portion
Benzophenone 1.0 weight portions
4-toluenesulfonamide 0.5 weight portion
Malachite green oxalates 0.02 weight portion
1,2,4-triazole 0.01 weight portion
Plain 0.2 weight portion of colourless crystallization violet
Trisbromomethyl benzene sulfone 0.1 weight portion
MEK 30 weight portions
Then, coating forms the barrier layer of thickness 1.6 μ m by the following water-soluble polymer solution of forming after the drying on this first photographic layer.
[composition of water-soluble polymer solution]
Polyvinyl alcohol (PVA) (PVA205 Ku Lalei (Network ラ レ) (strain) 13 weight portion manufacturings)
Polyvinyl pyrrolidone 6 weight portions
Water 200 weight portions
Methyl alcohol 180 weight portions
Then, coating forms the photographic layer (second photographic layer) of thickness 5 μ m later on by the following second photosensitive polymer combination solution that forms of forming in drying on this barrier layer.
[composition of 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 weight-average molecular weight: 90,000; Tg:50 ℃ of 15 weight portions
Diacrylate polypropylene glycol ester 6.5 weight portions
Dimethacrylate TEG ester 1.5 weight portions
4,4 '-two (lignocaine) Benzophenone, 0.4 weight portion
Benzophenone 3.0 weight portions
4-toluenesulfonamide 0.5 weight portion
Malachite green oxalates 0.02 weight portion
1,2,4-triazole 0.01 weight portion
Plain 0.2 weight portion of colourless crystallization violet
Trisbromomethyl benzene sulfone 0.1 weight portion
MEK 10 weight portions
1-methoxyl-2-propyl alcohol 20 weight portions
At last, the thick polyethylene film of laminated 12 μ m obtains laminated light-sensitive sheet on second photographic layer.On the volume core, above-mentioned light-sensitive sheet is reeled then, obtain the outside wide 550mm of carrier, the roll of long 200m.Measure the light sensitivity of the light-sensitive sheet that so obtains with the method narrated below, the shortest development time is 30sec, and the second photographic layer necessary luminous energy A that hardens is 4mJ/cm 2, the first photographic layer necessary luminous energy B that hardens is 40mJ/cm 2, to the first photographic layer necessary luminous energy C that begins to harden be 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).Be that the light sensitivity of second photographic layer is exactly 10 under 1 the situation in light sensitivity with first photographic layer.
[embodiment 2]
0.4 weight portion 4 except the second photosensitive polymer combination solution in embodiment 1,4 '-two (diethylamino) Benzophenone, 3.0 weight portion Benzophenones become 0.16 weight portion N-methylacridine ketone, 1.04 weight portions 2,2 '-two (2-chlorphenyls)-4,4 ', 5, beyond 5 '-tetraphenyl diimidazole, obtain light-sensitive sheet similarly to Example 1.The thickness deviation of each layer is in ± 5%.Measure the light sensitivity of the light-sensitive sheet that so obtains with the method narrated below, the shortest development time is 30sec, and the second photographic layer necessary luminous energy A that hardens is 2mJ/cm 2, the first photographic layer necessary luminous energy B that hardens is 40mJ/cm 2, to the first photographic layer necessary luminous energy C that begins to harden be 14mJ/cm 2(the ratio C/A of luminous energy C and luminous energy A is 7, and the ratio A/B of luminous energy A and luminous energy B is 0.05).Be that the light sensitivity of second photographic layer is exactly 20 under 1 the situation in light sensitivity with first photographic layer.
[embodiment 3]
Except the 15 parts by weight of methylmethacrylate/2-EHA/benzyl methacrylate/methacrylic acid copolymer of the second photosensitive polymer combination solution in embodiment 1 changes 13 weight portions into, 6.5 parts by weight of acrylic acid ten dimerization propylene glycol esters change 8.1 weight portions into, 1.5 the dimethacrylate TEG ester of weight portion changes into beyond 1.9 weight portions, obtains light-sensitive sheet similarly to Example 1.The thickness deviation of each layer is in ± 5%.Measure the light sensitivity of the light-sensitive sheet that so obtains with the method narrated below, the shortest development time is 30sec, and the second photographic layer necessary luminous energy A that hardens is 2mJ/cm 2, the first photographic layer necessary luminous energy B that hardens is 40mJ/cm 2, to the first photographic layer necessary luminous energy C that begins to harden be 14mJ/cm 2(the ratio C/A of luminous energy C and luminous energy A is 7, and the ratio A/B of luminous energy A and luminous energy B is 0.05).Be that the light sensitivity of second photographic layer is exactly 20 under 1 the situation in light sensitivity with first photographic layer.
[embodiment 4]
Except in embodiment 3 0.4 weight portion 4 of the second photosensitive polymer combination solution, the Benzophenone of 4 '-two (diethylamino) Benzophenone, 3.0 weight portions is changed into 0.16 weight portion N-methylacridine ketone, 1.04 weight portion 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl diimidazole, again the first photosensitive polymer combination solution is become beyond the following composition, obtain light-sensitive sheet similarly to Example 1.The thickness deviation of each layer is in ± 5%.Measure the light sensitivity of the light-sensitive sheet that so obtains with the method narrated below, the shortest development time is 30sec, and the second photographic layer necessary luminous energy A that hardens is 1mJ/cm 2, the first photographic layer necessary luminous energy B that hardens is 10mJ/cm 2, to the first photographic layer necessary luminous energy C that begins to harden be 3mJ/cm 2(the ratio C/A of luminous energy C and luminous energy A is 3, and the ratio A/B of luminous energy A and luminous energy B is 0.1).Be that the light sensitivity of second photographic layer is exactly 10 under 1 the situation in light sensitivity with first photographic layer.
[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; Weight-average molecular weight: 90,000; Tg:70 ℃) 24 weight portions
Hexamethylene diisocyanate and single (methyl) acrylic acid eight ethylidene esters
1/2 mole of adduct 12 weight portion
N-methylacridine ketone 0.2 weight portion
2,2 '-(Chloro-O-Phenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 0.8 weight portion
2-mercaptobenzimidazole 0.2 weight portion
4-toluenesulfonamide 0.8 weight portion
Malachite green oxalates 0.03 weight portion
1,2,4-triazole 0.03 weight portion
Plain 0.32 weight portion of colourless crystallization violet
Trisbromomethyl benzene sulfone 0.25 weight portion
MEK 55 weight portions
1-methoxyl-2-propyl alcohol 8 weight portions
[comparative example 1]
Except the thickness of first photographic layer among the embodiment 1 is changed into 30 μ m, be not coated with beyond the barrier layer and second photographic layer, obtain light-sensitive sheet similarly to Example 1.Measure the light sensitivity of the light-sensitive sheet that obtains then with method as described below, the shortest development time is 25sec, and making the photographic layer necessary luminous energy B that hardens is 40mJ/cm 2, be 14mJ/cm to the first photographic layer necessary luminous energy C that begins to harden 2
[comparative example 2]
In embodiment 1, be not coated with first photographic layer and barrier layer, only second photographic layer by bed thickness 5 μ m manufactures light-sensitive sheet, measure the light sensitivity of the light-sensitive sheet that obtains with method as described below, the shortest development time is below 10sec, and making the second photographic layer necessary luminous energy B that hardens is 4mJ/cm 2
[assay method of light sensitivity]
(1) assay method of short development time
On passing through the surface of the attached copper foil layer plywood (no reach through hole) of surface grinding, washing and drying; use laminator (model 8B-720-PH; great achievement laminator (strain) is made) second photographic layer and the substrate contacts of the light-sensitive sheet that peels off diaphragm are compressed, manufactured the lamilated body of attached copper foil plate, second photographic layer, barrier layer, first photographic layer and pet film laminated successively.The condition of compressing is 105 ℃ of hold-down roller temperature, hold-down roller pressure 3kg/cm 2, pressing speed 1m/min.Peel off pet film from lamilated body, on whole of the photographic layer on the attached copper foil plate, spray 30 ℃ 1wt% aqueous sodium carbonate with the pressure of 0.15MPa.Mensuration is removed required time of photographic layer on the attached copper foil plate from beginning to spray aqueous sodium carbonate to dissolving, with this as the shortest development time.
(2) mensuration of light sensitivity
The shortest development time is the same with measuring, laminated light-sensitive sheet on substrate.Use has the exposure device of 405nm LASER Light Source, from pet film one side, on the photographic layer of light-sensitive sheet from 0.1mJ/cm 2To 100mJ/cm 2, shine the light of different luminous energies with 2.5 times interval, make the photographic layer sclerosis.After at room temperature leaving standstill 10min, peel off poly terephthalic acid ethylene glycol film from lamilated body.On whole of the one-tenth of the resin combination on the attached copper foil plate, 1wt% aqueous sodium carbonate with 30 ℃ of the pressure injections of 0.15MPa, injecting time is the twice of the shortest development time obtained in (1) in the above, and unhardened resin combination is removed in dissolving, measures the thickness of residual hardened layer.Make the light sensitivity curve that concerns between the quantity of illumination and the thin hardened layer then.Luminous energy (luminous energy C) when luminous energy (luminous energy B) the when luminous energy (luminous energy A) when reading thickness 5 μ m by the light sensitivity curve that so obtains, thin hardened layer 31.6 μ m and thin hardened layer surpass 5 μ m.
[assay method of exploring degree]
Under the condition identical with the evaluation method of the shortest development time of above-mentioned (1), manufactured the lamilated body of attached copper foil plate, second photographic layer, barrier layer, first photographic layer and pet film laminated successively, at room temperature (23 ℃ 55%RH) leave standstill 10min.Use has the exposure device of 405nm LASER Light Source, exposes from pet film one side of the lamilated body that obtains, and the line/interval of the lines of exposure is than being 1/1, and lines are formed the width of 10～50 μ m with the lines of 5 μ m.The exposure of this moment is the luminous energy that makes second photographic layer sclerosis of each light-sensitive sheet.At room temperature leave standstill after the 10min, peel off pet film from lamilated body.On the whole resin combination layer of attached copper foil plate, with the 1wt% aqueous sodium carbonate of 30 ℃ of the pressure injections of 0.15MPa, injecting time is the twice as the shortest time of obtaining previously, and unhardened resin combination is removed in dissolving then.The surface of the attached copper foil plate that has the hardening resin style that so obtains with observation by light microscope, being determined at unusual minimum feature such as does not have to shorten, curl on the lines of hardening resin style, with this as the exploring degree.The numerical value of exploring degree is the smaller the better.
[manufacturing of printed circuit board and evaluation]
Has diameter 3mm; inwall forms the reach through hole of copper plate; on the attached copper foil layer plywood of surface through grinding, washing and drying; peeled off second photographic layer of the light-sensitive sheet of diaphragm on overlapping; produce the lamilated body that has stacked gradually attached copper foil plate, second photographic layer, barrier layer, first photographic layer and pet film as mentioned above; at room temperature (23 ℃ 55%RH) leave standstill 10min.Use has the exposure device of 405nm LASER Light Source, pet film one side from the lamilated body that obtains, shine according to predetermined style in the zone that forms attached copper foil plate layout pattern, its luminous energy can make second photographic layer sclerosis of each light-sensitive sheet, in addition, reach through hole opening portion and peripheral part thereof at attached copper foil plate expose photographic layer, and its luminous energy can make first photographic layer sclerosis of each light-sensitive sheet.After the exposure, peel off pet film from lamilated body, the evaluation method with above-mentioned is the same then, sprays the photographic layer surface with aqueous sodium carbonate, dissolve the unhardened zone of removing first photographic layer and second photographic layer, obtain the embossment style of hardened layer.Examine under a microscope the hardened layer style that obtains, observe forming hardened layer on the layout pattern zone and the hardened layer on the reach through hole opening portion and have or not and peel off or coverlay breakage defectives such as (covering performances).
Measuring the thickness of hardened layer at this moment with laser microscope [VK-9500 agree drill this (キ one エ Application ス) (strain) manufacturing], is 5 μ m at the thickness that forms hardened layer on the layout pattern zone, and the thickness of hardened layer is 31.6 μ m on the reach through hole opening portion.
Then, spray iron chloride etching agent (etching solution that contains iron chloride) on the surface of attached copper foil plate, the copper layer that exposes the zone that is not covered by hardened layer is removed in dissolving.And then the sodium hydrate aqueous solution of injection 2wt%, to remove the hardening thing of embossment shape, obtain having reach through hole, comprised the printed circuit board of layout pattern shape copper layer from the teeth outwards.The printed circuit board that visualization obtains, seeing through the through-hole wall copper plate has no abnormal.
For light-sensitive sheet, relevant exploring degree, hardened layer has or not to be peeled off, and overlayer has or not breakage, and the break-through through-hole plating has N/R evaluation result to be presented in the table 1.
Table 1
It is unusual that exploring degree hardened layer is peeled off the interior copper plate of the damaged reach through hole of overlayer
Embodiment 1 20 μ m nothing
Embodiment 2 20 μ m nothing
Embodiment 3 20 μ m nothing
Embodiment 4 20 μ m nothing
Comparative example 1 40 μ m nothing
Comparative example 2 20 μ m do not have and produce comprehensive breakage (do not have copper residual) arranged
[embodiment 5]
Coating after drying, obtains the photographic layer (first photographic layer) of thickness 20 μ m by the following first photosensitive polymer combination solution of forming on the pet film of 20 μ m thickness
[composition of 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 weight-average molecular weight: 90,000; Tg:70 ℃ of 15 weight portions
Diacrylate ten dimerization propylene glycol esters 6.5 weight portions
Dimethacrylate TEG ester 1.5 weight portions
4,4 '-two (lignocaine) Benzophenone, 0.04 weight portion
Benzophenone 1.0 weight portions
4-toluenesulfonamide 0.5 weight portion
Malachite green oxalates 0.02 weight portion
1,2,4-triazole 0.01 weight portion
Plain 0.2 weight portion of colourless crystallization violet
Trisbromomethyl benzene sulfone 0.1 weight portion
MEK 30 weight portions
Then, on first photographic layer, be coated with by the following water-soluble polymer solution of forming, after drying, the barrier layer of conduction thickness 1.6 μ m.
[composition of water-soluble polymer solution]
Polyvinyl alcohol (PVA) [PVA205 (Ku Lalei) Network ラ レ (strain) 13 weight portions
Make]
Polyvinyl pyrrolidone 6 weight portions
Water 200 weight portions
Methyl alcohol 180 weight portions
Then, coating forms the photographic layer (second photographic layer) of thickness 10 μ m later on by the following second photosensitive polymer combination solution that forms of forming in drying on this barrier layer.
[composition of 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; Weight-average molecular weight: 90,000; Tg:70 ℃) 24 weight portions
Hexamethylene diisocyanate and single (methyl) acrylic acid eight ethylidene esters
1/2 mole of adduct 12 weight portion
N-methylacridine ketone 0.2 weight portion
2,2 '-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 0.8 weight portion
2-mercaptobenzimidazole 0.2 weight portion
4-toluenesulfonamide 0.8 weight portion
Malachite green oxalates 0.03 weight portion
1,2,4-triazole 0.03 weight portion
Plain 0.32 weight portion of colourless crystallization violet
Trisbromomethyl benzene sulfone 0.25 weight portion
MEK 55 weight portions
1-methoxyl-2-propyl alcohol 8 weight portions
Then, coating forms the barrier layer of thickness 1.6 μ m later on by the above-mentioned water-soluble polymer solution of forming in drying on second photographic layer.
On this barrier layer, coating forms the 3rd photographic layer of thickness 5 μ m later on by following the 3rd photosensitive polymer combination solution of forming in drying then.
[composition of 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 weight-average molecular weight: 90,000; Tg:70 ℃ of 13 weight portions
Diacrylate ten dimerization propylene glycol esters 8.1 weight portions
Dimethacrylate TEG ester 1.9 weight portions
N-methylacridine ketone 0.16 weight portion
2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 1.04 weight portions
4-toluenesulfonamide 0.5 weight portion
Malachite green oxalates 0.02 weight portion
1,2,4-triazole 0.01 weight portion
Plain 0.2 weight portion of colourless crystallization violet
Trisbromomethyl benzene sulfone 0.1 weight portion
MEK 10 weight portions
1-methoxyl-2-propyl alcohol 20 weight portions
At last, the polypropylene film (diaphragm) of the thickness 12 μ m that close on the 3rd photographic layer upper strata obtains light-sensitive sheet.The thickness deviation of each tunic is in ± 5%.With the light sensitivity of similarly measuring the light-sensitive sheet that obtains noted earlier, the result, the required luminous energy of the 3rd photographic layer sclerosis is 1mJ/cm 2, the second photographic layer necessary luminous energy of hardening is 8mJ/cm 2, the second photographic layer necessary luminous energy that begins to harden is 3mJ/cm 2, the first photographic layer necessary luminous energy of hardening is 35mJ/cm 2, it is 14mJ/cm that first photographic layer is opened the necessary luminous energy of sclerosis 2, between 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 above-mentioned evaluation condition that the method for short development time is identical under, laminated successively attached copper foil plate, the 3rd photographic layer, barrier layer, second photographic layer, barrier layer, first photographic layer and pet film are made lamilated body, at room temperature (23 ℃ 55%RH) leave standstill 10min.From pet film one side of the lamilated body that obtains, use the exposure device of LASER Light Source with 405nm, when changing exposure, carry out the style irradiation.Then, similarly to Example 1, peel off pet film, carry out development treatment.The result forms the style of different-thickness, and as shown in Figure 10, with the part of low-yield irradiation, thickness is 5 μ m, the part of energy exposure in using, and thickness is 16.6 μ m, with the part of high energy radiation, thickness is 38.2 μ m.
[embodiment 6]
(forming first photographic layer)
The first photosensitive polymer combination solution of the following composition of coating on the thick pet film of 20 μ m, dry then first photographic layer that forms thickness 25 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 weight-average molecular weight: 90,000; Tg:70 ℃ of 15 weight portions
Hexamethylene diisocyanate and eight oxygen ethylidene list (methyl) acrylic acid
1/2 mol ratio adduct, 8 weight portions of ester
4,4 '-two (lignocaine) Benzophenone, 0.04 weight portion
Benzophenone 1.0 weight portions
4-toluenesulfonamide 0.5 weight portion
Malachite green oxalates 0.02 weight portion
1,2,4-triazole 0.01 weight portion
Plain 0.2 weight portion of colourless crystallization violet
Trisbromomethyl benzene sulfone 0.1 weight portion
MEK 30 weight portions
(formation barrier layer)
The water-soluble polymer solution of the following composition of coating on first photographic layer, drying obtains the barrier layer of thickness 1.6 μ m.
Barrier layer solution
Polyvinyl alcohol derivative 13 weight portions of representing with following structural formula
Polyvinyl pyrrolidone 6 weight portions
Water 200 weight portions
Methyl alcohol 180 weight portions
Polyvinyl alcohol derivative
(the importing rate of polymerizable group is 2mol%)
[changing 7]
(forming second photographic layer)
Coating forms the photographic layer of thickness 5 μ m later on by the following second photosensitive polymer combination solution that forms of forming in drying on this barrier layer
The second photographic layer resin combination solution
Methyl methacrylate/2-EHA/benzyl methacrylate/methacrylic acid copolymer (multipolymer is formed (mol ratio)):
40/26.7/4.5/28.8 weight-average molecular weight: 90,000; Tg:50 ℃ of 15 weight portions
Diacrylate polypropylene glycol ester 6.5 weight portions
Dimethacrylate TEG ester 1.5 weight portions
4,4 '-two (lignocaine) Benzophenone, 0.4 weight portion
Benzophenone 3.0 weight portions
4-toluenesulfonamide 0.5 weight portion
Malachite green oxalates 0.02 weight portion
1,2,4-triazole 0.01 weight portion
Plain 0.2 weight portion of colourless crystallization violet
Trisbromomethyl benzene sulfone 0.1 weight portion
MEK 10 weight portions
1-methoxyl-2-propyl alcohol 20 weight portions
(manufacturing light-sensitive sheet)
At last, the thick polypropylene film of laminated 12 μ m obtains laminated light-sensitive sheet on second photographic layer.The thickness deviation of any one deck is all in ± 5%.Measure the light sensitivity of the light-sensitive sheet that so obtains with the method narrated previously, the result who obtains is, the shortest development time is 30sec, and the second photographic layer necessary luminous energy A that hardens is 4mJ/cm 2, the first photographic layer necessary luminous energy B that hardens is 40mJ/cm 2, to the first photographic layer necessary luminous energy C that begins to harden be 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).Be that the light sensitivity of second photographic layer is exactly 10 under 1 the situation in light sensitivity with first photographic layer.
[embodiment 7]
(synthesis example of polyvinyl alcohol derivative)
[PVA205, (Ku Lalei) Network ラ レ (strain) makes] is dissolved in the water of 90 weight portions with 10 weight account polyethylene alcohol.Add therein 2.3 weight portion n-methylolacrylamide are dissolved in the solution that 20.7 weight parts waters obtain, add 0.002 weight portion quinhydrones.Add 0.04 weight portion sulfuric acid therein, react 4h down, obtain on side chain, having the polyvinyl alcohol (PVA) 10 weight % aqueous solution of acrylamide group at 40 ℃.
(manufacturing light-sensitive sheet)
Except will the barrier layer solution among the embodiment 6 change into following, obtain light-sensitive sheet similarly to Example 6.
Barrier layer solution
Synthetic polyvinyl alcohol derivative 10% aqueous solution 130 weight portions
Polyvinyl pyrrolidone 6 weight portions
Water 83 weight portions
Methyl alcohol 180 weight portions
The thickness deviation of any one deck is all in ± 5%.Measure the light sensitivity of the light-sensitive sheet that so obtains with the method narrated previously, the result who obtains is, the shortest development time is 30sec, and the second photographic layer necessary luminous energy A that hardens is 4mJ/cm 2, the first photographic layer necessary luminous energy B that hardens is 40mJ/cm 2, to the first photographic layer necessary luminous energy C that begins to harden be 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 8]
Except will the barrier layer solution among the embodiment 6 change into following, obtain light-sensitive sheet similarly to Example 6.
Barrier layer solution
Polyvinyl alcohol (PVA) [PVA205, (Ku Lalei) Network ラ レ (strain) makes] 13 weight portions
Polyvinyl pyrrolidone 3 weight portions
Diacrylate nine propylene glycol esters 3 weight portions
Water 200 weight portions
Methyl alcohol 180 weight portions
The thickness deviation of any one deck is all in ± 5%.Measure the light sensitivity of the light-sensitive sheet that so obtains with the method narrated previously, the result who obtains is, the shortest development time is 30sec, and the second photographic layer necessary luminous energy A that hardens is 4mJ/cm 2, the first photographic layer necessary luminous energy B that hardens is 40mJ/cm 2, to the first photographic layer necessary luminous energy C that begins to harden be 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).Be that the light sensitivity of second photographic layer is 10 under 1 the situation in the light sensitivity of first photographic layer.
[comparative example 3]
Except the thickness of first photographic layer in embodiment 6 becomes 30 μ m, be not coated with beyond the barrier layer and second photographic layer, make light-sensitive sheet similarly to Example 1.Measure the light sensitivity of the light-sensitive sheet that so obtains with the method narrated previously, the result who obtains is, the shortest development time is 25sec, and making the photographic layer necessary luminous energy B that hardens is 40mJ/cm 2, the first photographic layer necessary luminous energy C that begins to harden is 14mJ/cm 2
[comparative example 4]
In embodiment 6, be not coated with first photographic layer and barrier layer, second photographic layer of coating film thickness 5 μ m is made light-sensitive sheet, measure the light sensitivity of light-sensitive sheet with the method for narrating previously, the result who measures be the shortest development time below 10sec, making the second photographic layer necessary luminous energy B that hardens is 4mJ/cm 2
For the light-sensitive sheet that so obtains, carry out the exploring degree, cover break (part of diameter 3mm and the part of 0.2mm), the copper facing in the reach through hole has no abnormal, storage stability etc. evaluation, the result is presented in the table 2.
Table 2
Photonasty exploring degree covers in the reach through hole that breaks and stores
Transfer printing sheet 3mm 0.2mm copper facing is stable unusually
Embodiment 6 20 μ m do not have good
Embodiment 7 20 μ m do not have good
Embodiment 8 20 μ m do not have good
Comparative example 3 40 μ m nothing-
Comparative example 4 20 μ m break fully break fully have-
(notes)
One: do not have the different photographic layer of light sensitivity, so do not estimate
[embodiment 9]
(forming first photographic layer)
The first photosensitive polymer combination solution of the following composition of coating on the thick pet film of 20 μ m, dry then, just form first photographic layer of thickness 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 weight-average molecular weight: 90,000; Tg:70 ℃ of 15 weight portions
Diacrylate ten dimerization propylene glycol esters 6.5 weight portions
Two (methacrylic acid) TEG ester, 1.5 weight portions
4,4 '-two (lignocaine) Benzophenone, 0.04 weight portion
Benzophenone 1.0 weight portions
4-toluenesulfonamide 0.5 weight portion
Malachite green oxalates 0.02 weight portion
1,2,4-triazole 0.01 weight portion
Plain 0.2 weight portion of colourless crystallization violet
Trisbromomethyl benzene sulfone 0.1 weight portion
MEK 30 weight portions
(formation barrier layer)
The water-soluble polymer solution of the following composition of coating on first photographic layer, drying obtains the barrier layer of thickness 1.6 μ m.
Water-soluble polymer solution
Polyvinyl alcohol derivative 13 weight portions of representing with following structural formula
Polyvinyl pyrrolidone 6 weight portions
Water 200 weight portions
Methyl alcohol 180 weight portions
Polyvinyl alcohol derivative
[changing 8]
(forming second photographic layer)
Coating forms the photographic layer of thickness 10 μ m later on by the following second photosensitive polymer combination solution that forms of forming in drying on this barrier layer
The second photographic layer resin combination solution
Methyl methacrylate/2-EHA/benzyl methacrylate
/ methacrylic acid copolymer (multipolymer is formed (mol ratio)): 24 weight portions
55/11.7/4.5/28.8 weight-average molecular weight: 90,000; Tg:70 ℃
Hexamethylene diisocyanate and eight oxygen ethylidene list (methyl) acrylic acid
1/2 mol ratio adduct, 12 weight portions of ester
N-methylacridine ketone 0.2 weight portion
2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 0.8 weight portion
2-mercaptobenzimidazole 0.2 weight portion
4-toluenesulfonamide 0.8 weight portion
Malachite green oxalates 0.03 weight portion
1,2,4-triazole 0.03 weight portion
Plain 0.32 weight portion of colourless crystallization violet
Trisbromomethyl benzene sulfone 0.25 weight portion
MEK 55 weight portions
1-methoxyl-2-propyl alcohol 8 weight portions
(formation barrier layer)
The water-soluble polymer solution that coating is as above formed on second photographic layer carries out drying, obtains the thick barrier layer of 1.6 μ m.
(forming the 3rd photographic layer)
The 3rd photosensitive polymer combination solution of the following composition of coating carries out drying on barrier layer, forms the 3rd thick photographic layer of 5 μ m.
The 3rd photographic layer resin combination solution
Methyl methacrylate/2-EHA/benzyl methacrylate
/ methacrylic acid copolymer (multipolymer is formed (mol ratio)): 13 weight portions
40/26.7/4.5/28.8 weight-average molecular weight: 90,000; Tg:50 ℃
Diacrylate ten dimerization propylene glycol esters 8.1 weight portions
Two (methacrylic acid) TEG ester, 1.9 weight portions
N-methylacridine ketone 0.16 weight portion
2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 1.04 weight portions
4-toluenesulfonamide 0.5 weight portion
Malachite green oxalates 0.02 weight portion
1,2,4-triazole 0.01 weight portion
Plain 0.2 weight portion of colourless crystallization violet
Trisbromomethyl benzene sulfone 0.1 weight portion
MEK 10 weight portions
1-methoxyl-2-propyl alcohol 20 weight portions
(manufacturing light-sensitive sheet)
The polypropylene film (diaphragm) that laminated 12 μ m are thick on the 3rd photographic layer obtains light-sensitive sheet.The thickness deviation of any one deck is all in ± 5%.Measure the light sensitivity of the light-sensitive sheet that so obtains with the method narrated previously, the result who obtains is, the 3rd photographic layer necessary luminous energy of hardening is 1mJ/cm 2, the second photographic layer necessary luminous energy of hardening is 8mJ/cm 2, making the second photographic layer necessary luminous energy that begins to harden is 3mJ/cm 2, the first photographic layer necessary luminous energy of hardening is 35mJ/cm 2, to the first photographic layer necessary luminous energy that begins to harden be 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 above-mentioned evaluation condition that the method for short development time is identical under, laminated successively attached copper foil plate, the 3rd photographic layer, barrier layer, second photographic layer, barrier layer, first photographic layer and pet film are made lamilated body, at room temperature (23 ℃ 55%RH) leave standstill 10min.From pet film one side of the lamilated body that obtains, use the exposure device of LASER Light Source with 405nm, when changing exposure, carry out the style irradiation.Then, similarly to Example 1, peel off pet film, carry out development treatment.The result forms the style of different-thickness, and as shown in FIG. 6, with the part of low-yield irradiation, thickness is 5 μ m, the part of energy exposure in using, and thickness is 16.6 μ m, with the part of high energy radiation, thickness is 38.2 μ m.
[embodiment 10]
The first photosensitive polymer combination solution of the following composition of coating on the thick pet film of 20 μ m, dry then, just form the photographic layer (first photographic layer) of thickness 20 μ m.First photographic layer is 0.3 in the absorbance at wavelength 405nm place, and transmittance is 50% (reference: the absorbance under wavelength 365nm is less than 0.2).
[composition of 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 weight-average molecular weight: 90,000; Tg:70 ℃ of 15 weight portions
Diacrylate ten dimerization propylene glycol esters 6.5 weight portions
Two (methacrylic acid) TEG ester, 1.5 weight portions
N-methylacridine ketone 0.08 weight portion
Benzophenone 1.0 weight portions
Para toluene sulfonamide 0.5 weight portion
Malachite green oxalates 0.02 weight portion
Morpholinyl methyl isophthalic acid-Phenyltriazole-2-thion (チ オ Application) 0.01 weight portion
Plain 0.2 weight portion of colourless crystallization violet
Trisbromomethyl benzene sulfone 0.1 weight portion
MEK 30 weight portions
Then, the following barrier layer coating fluid of coating on first photographic layer, drying forms the thick barrier layer of 1.6 μ m.
[composition of barrier layer coating fluid]
Polyvinyl alcohol (PVA) [PVA205 Ku Lalei (Network ラ レ) (strain) manufacturing) 13 weight portions
Polyvinyl pyrrolidone (manufacturing of PVPK30:GAF company) 6 weight portions
Water 200 weight portions
Methyl alcohol 180 weight portions
Then, applying implenent is by the following second photosensitive polymer combination solution of forming on barrier layer, and drying forms the thick photographic layer of 5 μ m (second photographic layer), makes light-sensitive sheet.The maximum absorbance of second photographic layer light under wavelength 405nm is 0.3 (reference: the absorbance of wavelength 365nm is less than 0.2).
[composition of 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 weight-average molecular weight: 90,000; Tg:70 ℃ of 15 weight portions
Diacrylate ten dimerization propylene glycol esters 6.5 weight portions
Two (methacrylic acid) TEG ester, 1.5 weight portions
N-methylacridine ketone 0.16 weight portion
Benzophenone 3.0 weight portions
Para toluene sulfonamide 0.5 weight portion
Malachite green oxalates 0.02 weight portion
Morpholinyl methyl isophthalic acid-Phenyltriazole-2-thion (チ オ Application) 0.01 weight portion
Plain 0.2 weight portion of colourless crystallization violet
Trisbromomethyl benzene sulfone 0.1 weight portion
MEK 30 weight portions
[embodiment 11]
Except 0.08 weight portion N-methylacridine ketone in the first photosensitive polymer combination solution of embodiment 10 being become 0.12 weight portion, produce the light-sensitive sheet of embodiment 11 similarly to Example 10.The absorbance of first photographic layer under wavelength 405nm is 0.45, and transmittance is 36%.
[embodiment 12]
Except 0.08 weight portion N-methylacridine ketone in the first photosensitive polymer combination solution of embodiment 10 being become 0.20 weight portion, produce the light-sensitive sheet of embodiment 12 similarly to Example 10.The absorbance of first photographic layer under wavelength 405nm is 0.75, and transmittance is 18%.
[evaluation]
Estimate the light-sensitive sheet of making in embodiment 10～12 as follows, its result is illustrated in the table 3.
[assay method of light sensitivity]
Light-sensitive sheet is pressed on the attached copper foil plate, its second photographic layer is contacted with the surface of attached copper foil plate.Use has the exposure device of 405nm LASER Light Source, from pet film one side, on the photographic layer of light-sensitive sheet from 0.1mJ/cm 2To 100mJ/cm 2, shine the light of different luminous energies with 2.5 times interval, make the photographic layer sclerosis.After at room temperature leaving standstill 10min, peel off the poly terephthalic acid ethylene glycol film of light-sensitive sheet.On become at the resin combination on the attached copper foil plate whole, with the 1wt% aqueous sodium carbonate of 30 ℃ of the pressure injections of 0.15MPa, unhardened resin combination is removed in dissolving, measures the thickness of its hardened layer.Make the light sensitivity curve that concerns between the quantity of illumination and the thin hardened layer then.Luminous energy (luminous energy C) when the luminous energy (luminous energy B) the when luminous energy (luminous energy A) when reading the second photographic layer through-hardening by the light sensitivity curve that so obtains, first photographic layer and second photographic layer harden and first photographic layer begin to harden.
Table 3
First sense, the first sensitization energy luminous energy luminous energy C-A
Photosphere at photosphere at A B C (mJ)
Wavelength wavelength (mJ) is (mJ) (mJ)
Under the 405nm under the 405nm
The light of light
The absorbance transmittance
(1) (%)
Embodiment 10 0.3 50 4 20 10 6
Embodiment 11 0.45 36 5.5 15 8 2.5
Embodiment 12 0.75 18 6 15 82
By the result of table 3 as can be seen, in embodiment 10～12, the light absorbance of first photographic layer under wavelength 405nm is adjusted to below 1.0, in the light-sensitive sheet here, make second photographic layer necessary luminous energy A and the first photographic layer necessary luminous energy C that begins to harden that hardens, their difference C-A strengthens, according to different exposures, make the two-layer sclerosis simultaneously of first photographic layer and second photographic layer, it all is possible still only staying second photographic layer.

Claims (47)

1. light-sensitive sheet, wherein this light-sensitive sheet is laminated successively first photographic layer of being made up of the photosensitive polymer combination that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater, barrier layer and be made up of and its light sensitivity is higher than second photographic layer of first photographic layer the photosensitive polymer combination that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater on carrier.
2. the light-sensitive sheet described in claim 1, wherein the lower alcohol that contains water or carbon number 1～4 of this barrier layer demonstrates the resin of compatibility as Main Ingredients and Appearance.
3. the light-sensitive sheet described in claim 1 or 2, wherein the lower alcohol that contains water or carbon number 1～4 of this barrier layer has the resin of solubility as Main Ingredients and Appearance.
4. as any one light-sensitive sheet in the claim 1～3, wherein the thickness of this barrier layer is in the scope of 0.1～5 μ m.
5. the light-sensitive sheet described in claim 1, wherein this barrier layer contains polymerizable compound.
6. the light-sensitive sheet described in claim 5, wherein barrier layer has photonasty, and the light sensitivity of this barrier layer is lower than the light sensitivity of first photographic layer relatively.
7. the light-sensitive sheet described in claim 5, wherein contained polymerizable compound is the polymkeric substance with polymerizable group in barrier layer.
8. the light-sensitive sheet described in claim 7 wherein has the polymkeric substance of polymerizable group, and the lower alcohol of water or carbon number 1～4 is demonstrated compatibility.
9. the light-sensitive sheet described in claim 8 wherein has the polymkeric substance that the lower alcohol of water or carbon number 1～4 is demonstrated the polymerizable group of compatibility, the lower alcohol of water soluble or carbon number 1～4.
10. as any one described light-sensitive sheet in the claim 1～9, wherein under the light sensitivity with first photographic layer was 1 situation, the light sensitivity of second photographic layer was in 2～200 scope.
11. as any one described light-sensitive sheet in the claim 1～10, wherein ought make the second photographic layer necessary luminous energy of hardening is A, make first photographic layer harden necessary luminous energy when being B, the ratio of representing with A/B is in 0.005～0.5 scope.
12. as the light-sensitive sheet described in the claim 1～11 any one, wherein ought make the second photographic layer necessary luminous energy of hardening is A, make first photographic layer when the necessary luminous energy that begins to harden is C, the ratio of representing with C/A is in 1～10 scope.
13. the light-sensitive sheet as described in the claim 1～12 any one wherein all contains sensitizer in first photographic layer and second photographic layer.
14. the light-sensitive sheet described in claim 13, wherein in second photographic layer amount of contained sensitizer greater than the amount of sensitizer contained in first photographic layer.
15. as the light-sensitive sheet described in the claim 1～14 any one, wherein in second photographic layer amount of contained Photoepolymerizationinitiater initiater greater than the amount of Photoepolymerizationinitiater initiater contained in first photographic layer.
16. as the light-sensitive sheet described in the claim 1～15 any one, wherein in second photographic layer amount of contained polymerizable compound greater than the amount of polymerizable compound contained in first photographic layer.
17. the light-sensitive sheet described in claim 1, wherein first photographic layer is in the scope of absorbance 0.1～1.0 at wavelength 405nm place.
18. the light-sensitive sheet described in claim 1 wherein contains the compound that has very big absorbing wavelength at 380～430nm in first photographic layer and/or second photographic layer.
19. the light-sensitive sheet described in claim 18, wherein, the compound that has very big absorbing wavelength at 380～430nm is a sensitizer.
20. as the light-sensitive sheet described in the claim 1～19 any one, wherein the thickness of first photographic layer is in the scope of 1～100 μ m, and this thickness is greater than the thickness of second photographic layer.
21. as the light-sensitive sheet described in the claim 1～20 any one, wherein the thickness of second photographic layer is in the scope of 0.1～15 μ m.
22. as the light-sensitive sheet described in the claim 1～21 any one, wherein carrier is a synthetic resin, and is transparent.
23. as the light-sensitive sheet described in the claim 1～22 any one, wherein carrier is the carrier of strip.
24. the light-sensitive sheet as described in the claim 1～23 any one wherein is provided with diaphragm on second photographic layer.
25. as the light-sensitive sheet described in the claim 1～24 any one, wherein this transfer printing sheet is a strip, and is rolled into volume.
26. as the light-sensitive sheet described in the claim 1～25 any one, wherein this transfer printing sheet is used for making printed circuit board.
27. a photosensitive laminated article, wherein this lamilated body is second photographic layer be made up of the photosensitive polymer combination that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater on laminated successively on the matrix, barrier layer and is made up of and its light sensitivity is lower than first photographic layer of second photographic layer the photosensitive polymer combination that contains cementing agent, polymerizable compound and Photoepolymerizationinitiater initiater.
28. the photosensitive laminated article described in claim 27, wherein the lower alcohol that contains water or carbon number 1～4 of this barrier layer demonstrates the resin of compatibility as Main Ingredients and Appearance.
29. the photosensitive laminated article described in claim 27 or 28, wherein the lower alcohol that contains water or carbon number 1～4 of this barrier layer has the resin of solubility as Main Ingredients and Appearance.
30. the photosensitive laminated article described in claim 27, barrier layer wherein contains polymerizable compound.
31. the photosensitive laminated article described in claim 30, wherein barrier layer has photonasty, and the light sensitivity of barrier layer is lower than the light sensitivity of first photographic layer relatively.
32. the photosensitive laminated article described in claim 30, wherein contained polymerizable compound is the polymkeric substance with polymerizable group in barrier layer.
33. the photosensitive laminated article described in claim 32, the polymkeric substance that wherein has a polymerizable group demonstrates compatibility for the lower alcohol of water or carbon number 1～4.
34. the photosensitive laminated article described in claim 33 wherein has the polymkeric substance that the lower alcohol of water or carbon number 1～4 is demonstrated the polymerizable group of compatibility, the lower alcohol of water soluble or carbon number 1～4.
35. the photosensitive laminated article described in claim 27, wherein first photographic layer is in the scope of absorbance 0.1～1.0 at wavelength 405nm place.
36. the photosensitive laminated article described in claim 27 wherein contains the compound that has very big absorbing wavelength at 380～430nm in first photographic layer and/or second photographic layer.
37. the photosensitive laminated article described in claim 36, wherein, the compound that has very big absorbing wavelength at 380～430nm is a sensitizer.
38. as any one photosensitive laminated article in the claim 27～37, matrix wherein is to make the printed circuit board substrate.
39. as any one photosensitive laminated article in the claim 27～38, wherein laminated carrier on first photographic layer.
40. by on substrate, exist by first photographic layer and second photographic layer harden simultaneously the hard resin-layer that forms the zone and do not exist hard resin-layer the image pattern that the zone constituted form method, this method comprises following operation:
(1) laminated light-sensitive sheet described in claim 1 on substrate makes its second photographic layer in substrate one side, obtains the operation of lamilated body;
(2) carry out the rayed of predetermined picture style from a side of first photographic layer of lamilated body, the operation that first photographic layer that is subjected to this light-struck zone and second photographic layer are hardened simultaneously;
(3) remove the operation of carrier from lamilated body; Then
(4) lamilated body is developed, remove the operation of unhardened part in the lamilated body.
41. by on substrate, exist by first photographic layer and second photographic layer harden the zone of the hard resin-layer that forms simultaneously, the hard resin-layer that forms by the sclerosis of second photographic layer regional and do not exist hard resin-layer the image pattern that the zone constituted form method, this method comprises following operation:
(1) laminated light-sensitive sheet described in claim 1 on substrate makes its second photographic layer in substrate one side, obtains the operation of lamilated body;
(2) from a side of first photographic layer of lamilated body with at least two kinds of different irradiations can levels light carry out the rayed of specified image style, make to be subjected to rayed energy big relatively light-struck regional first photographic layer and second photographic layer and to harden simultaneously, and be subjected to the operation of second photographic layer sclerosis in the relatively little light-struck zone of rayed energy;
(3) remove the operation of carrier from lamilated body; Then
(4) lamilated body is developed, remove the operation of unhardened part in the lamilated body.
42. the method described in claim 40 or 41 is carried out (3) remove carrier from lamilated body operation wherein between operation (1) and operation (2), rather than between operation (2) and operation (4).
43., wherein carry out rayed in operation (2) by laser radiation as the method described in the claim 40～42 any one.
44. make printed circuit board with substrate on, the layout pattern that the zone constituted that hardens zone that the hard resin-layer that forms covers simultaneously and expose substrate surface by first photographic layer and second photographic layer form method, this method comprises following operation:
(1) laminated light-sensitive sheet described in claim 1 on substrate makes its second photographic layer laminated in substrate one side, obtains the operation of lamilated body;
(2) rayed of the layout pattern of being scheduled to from first photographic layer, one side of lamilated body, the operation that first photographic layer that is subjected to this light-struck zone and second photographic layer are hardened simultaneously;
(3) remove the operation of carrier from lamilated body; Then
(4) lamilated body is developed, remove the operation of unhardened part in the lamilated body.
45. the manufacturing printed circuit board with bore portion with substrate on, by first photographic layer and second photographic layer harden simultaneously bore portion that the hard resin-layer that forms covers, by cover regional of second photographic layer sclerosis formation hard resin-layer and expose substrate surface the layout pattern that the zone constituted form method, this method comprises following operation:
(1) laminated light-sensitive sheet described in claim 1 on substrate makes its second photographic layer laminated in substrate one side, obtains the operation of lamilated body;
(2) carry out the irradiation of image pattern from first photographic layer, one side of lamilated body, make bore portion is carried out the big relatively rayed of illumination energy, first photographic layer and second photographic layer are hardened simultaneously, and in the zone that forms wiring, carry out the relatively little irradiation of illumination energy, make the operation of second photographic layer sclerosis;
(3) remove the operation of carrier from lamilated body; Then
(4) lamilated body is developed, remove the operation of unhardened part in the lamilated body.
46. the method described in claim 44 or 45 is carried out (3) remove carrier from lamilated body operation wherein between operation (1) and operation (2), rather than between operation (2) and operation (4).
47., wherein carry out rayed in the operation (2) by laser radiation as the method described in the claim 44～46 any one.
CNA2004100583961A 2003-08-15 2004-08-13 Light-sensitive transfer sheet, light-sensitive layers, picture pattern forming method and layout pattern forming method Pending CN1580953A (en)

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