CN102770805A - Image formation method and photosensitive composition used in said method - Google Patents
Image formation method and photosensitive composition used in said method Download PDFInfo
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- CN102770805A CN102770805A CN2011800108044A CN201180010804A CN102770805A CN 102770805 A CN102770805 A CN 102770805A CN 2011800108044 A CN2011800108044 A CN 2011800108044A CN 201180010804 A CN201180010804 A CN 201180010804A CN 102770805 A CN102770805 A CN 102770805A
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- wave band
- exposure
- light
- photoacid generator
- image forming
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/675—Compositions containing polyhalogenated compounds as photosensitive substances
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/08—Photoprinting; Processes and means for preventing photoprinting
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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
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
Disclosed is a dry-type image formation method that does not use a liquid developer and produces excellent contrast, coating properties, and in particular, image stability. Also disclosed is a photosensitive composition used in said method. The disclosed image formation method is characterized by the inclusion of: an exposure step (A) which forms an image pattern by partially exposing a film of a photosensitive composition to light with a wavelength less than 280 nm, said photosensitive composition containing a photoacid generator and an electron-donating dye; and an exposure step (B) which fixes the image pattern by exposing the entire surface to light with a wavelength of at least 280 nm.
Description
Technical field
The photosensitive composite that the present invention relates to image forming method and be used for this method; Can take into account high-contrastization and the image forming method of the picture steadiness of excellence and the photosensitive composite that is used for this method in particular to not using the wet developing method.
Background technology
Usually, owing to microfabrication property is excellent, operability well is suitable for a large amount of productions, yet be widely used in printing industry, electronics industry based on photolithographic image forming method now.From reducing the viewpoint of carrying capacity of environment, particularly be widely used in the manufacturing of printed circuit board (PCB), the formation of solder resist and the manufacturing of semiconductor associated components etc. up to now based on the wet developing method of aqueous alkali.
In recent years, this image forming method also extensively is utilized in following various field: the MEMS fields such as manufacturing etc. that for example on base material, form the reflectivity pictures different, read the catoptrical displacement transducer of self-emission device with photo detector etc.When being used in these fields, need be on can wafer, carry out patterning on the mordant aluminium circuit to the aqueous alkali insulation degradation, as image forming method, photoetching process might not be useful.
Now, in these purposes, utilizing the developer solution of organic solvent system mostly, is not preferred from the viewpoint that reduces carrying capacity of environment.Based on such viewpoint, can predict the technology of not using developer solution and forming picture contrast and can promote from now on.
Do not use developer solution and form the technology of image as this, carried out various researchs at present.For example, from reducing the viewpoint of carrying capacity of environment, also can expect dry type image forming method as the problem of no discarded object based on the image forming method of the photosensitive heat display shadow that utilizes photocuring and heat fusing.As based on one of image forming method of this method, can enumerate out the colour developing type thermal sensitive recording method of the colour developing that utilization causes by dyestuff.This method further roughly is divided into the diazonium-type thermal sensitive recording method of utilizing diazo coupling reaction and utilizes leuco dye etc. to give these two kinds of the leuco form thermal sensitive recording methods of electronics property dyestuff.Problem as these methods; Taking into account of quality stability after can enumerating out high-contrast (high-color rendering) and image and forming, or carried out big quantity research (with reference to patent documentation 1,2) about the technology of the high-contrastization of the diazonium-type that on picture steadiness, has superiority at the technology of the stay in gradeization after the image about the leuco form of excellent color reproducing performance formed.
Yet, around substrates such as electronic component, the strict field of environment for use such as MEMS sensor as far as possible the technology of application start do not establish as yet, so far, it utilizes and also only limits in thermal recording paper, the tolerance material fields such as (proof material).
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication sho 52-89915 communique (claims)
Patent documentation 2: japanese kokai publication sho 61-123838 communique (claims)
Summary of the invention
The problem that invention will solve
The present invention has used for reference above-mentioned the problems of the prior art, and its purpose is to provide not to be used developer solution and can realize the dry type image forming method of high comparative and the hi-vision stability and the excellent rerum natura of filming and use the photosensitive composite of this method.
The scheme that is used to deal with problems
Inventors of the present invention etc. are in order to reach above-mentioned purpose; The wave band of the exposure process of the contrast of discovery through will forming image separates with the wave band of the exposure process that carries out photocuring; Carry out multiexposure, multiple exposure, can be respectively with painted and not painted image fixing, and take the lead in having carried out patented claim.
The image forming method of this application is characterised in that; At different-waveband to containing photoacid generator and carrying out multiexposure, multiple exposure for the filming of photosensitive composite of electronics property dyestuff; Thereby carry out forming and photographic fixing respectively by painted and not painted the picture contrast of forming; Preferably, the multiexposure, multiple exposure at different-waveband comprises: form by painted with first exposure process of not painted the picture contrast of forming with carry out at different with the exposure wave band of first exposure process, not painted wave band that does not develop the color whole exposure, will be through photo-crosslinking by second exposure process of painted and not painted the picture contrast photographic fixing of forming.
According to the technical scheme of this application, owing to painted portion, not painted are all carried out photocuring with prior art differently, so the contrast excellent in stability of image after forming, that in technology in the past, can't realize also becomes possibility with taking into account of the rerum natura of filming.
Yet inventor of the present invention etc. observe the image with the said method gained, and the result distinguishes, according to purposes, and deactivating of remaining photoacid generator in the system after image forms and residual as new problem.That is, found following problem: under being exposed to light such as sunshine, in such environment for use, can produce acid, cause unexpected colour developing (painted) reaction by photoacid generator remaining in filming.
Therefore, inventor of the present invention etc. are to the picture steadiness of picture pattern after forming, and are conceived to arrive the ultraviolet composition of the sunshine on ground, through investigating ultraviolet composition to the influence that picture steadiness causes, have solved above-mentioned problem.Promptly; The influence that inventor of the present invention etc. cause picture steadiness for the ultraviolet composition that reduces sunshine; The zone that exposure wavelength is distinguished to this method is furtherd investigate, and the result finds, is set at not enough 280nm, will carries out photocuring and make the exposure wave band of the exposure process B of image fixing be set at the wave band more than the 280nm through the exposure wave band that will carry out the exposure process A that picture pattern forms; Can improve picture steadiness significantly, thereby accomplish the present invention.
Usually as the classification of carrying out according to ultraviolet wavelength, can be divided into the near ultraviolet ray of wavelength 380 ~ 200nm, the far ultraviolet of wavelength 200 ~ 10nm, the extreme ultraviolet line of wavelength 10 ~ 1nm.Comprise in the sunshine UVA (400 ~ 315nm), UVB (315 ~ 280nm), the near ultraviolet ray of the wavelength of UVC (not enough 280nm).Wherein, have only UVA, UVB to arrive the face of land through ozonosphere, the absorption based on material of UVC is obvious, can not pass through atmosphere.
The present invention possesses characteristic aspect following: the characteristic of the UVC from this sunshine, be the phenomenon on the light no show face of land of not enough 280nm; With only under this wavelength the photoacid generator of activate be used for picture pattern and form, the picture steadiness after can improving picture pattern significantly thus and forming.
Promptly; An embodiment according to image forming method of the present invention is characterized in that it comprises following operation: exposure process A; To containing photoacid generator and carrying out the part exposure for the filming of photosensitive composite of electronics property dyestuff, form picture pattern with the light of the wave band of not enough 280nm; With exposure process B, carry out whole exposure with the light of the above wave band of 280nm, with the picture pattern photographic fixing.
At this, the photosensitive composite that is used for image forming method of the present invention preferably contains the acidic photoacid generator of light through the wave band of not enough 280nm, gives electronics property dyestuff, Photoepolymerizationinitiater initiater and contain the ethylenically unsaturated group compound.
In addition, the aforementioned lights polymerization initiator preferably can be through the not acidic wave band of aforementioned lights acid agent, be the light sensation light of the wave band more than the 280nm.
The effect of invention
Find the distinctive effect of following the present invention: according to the present invention; The wavelength of the not enough 280nm of the wave band of the ultraviolet (UV) C of the sunshine through belonging to no show ground forms picture pattern, and the picture steadiness after therefore can be owing to ultraviolet ray contained in the sunshine contrast not formed impacts.Its result; Not only can be used in the past thermal recording paper, tolerance material; Can also extensively be used in for example strict electric substrate, the marking purposes of display association area, the shading purposes of environment for use; And then form image on the aluminium circuit that can in photoetching process, can't handle owing to the problem of corrosion, therefore can expect application extension to MEMS purposes such as photo detector, displacement transducer.
Embodiment
Below, specify image forming method of the present invention.
Image forming method of the present invention is: through filming of photosensitive composite being carried out multiexposure, multiple exposure at different-waveband, carry out respectively by painted and not painted picture pattern of forming (below be also referred to as " picture contrast " etc.) formation and photographic fixing, wherein, said photosensitive composite contains through the acidic photoacid generator of the light of the wave band of not enough 280nm and gives electronics property dyestuff.
In exposure process A, carry out the part exposure with the light of the wave band of not enough 280nm, the photoacid generator of exposure portion produces acid thus, this acid with give reaction of electronics property dyestuff and colour developing, form painted portion.In addition, in exposure process B, carry out whole exposure, suppress chromogenic reaction thus with the light of the wave band more than the not acidic 280nm of photoacid generator, and through photo-crosslinking fixing painted and not painted portion, with the picture contrast photographic fixing.As long as such exposure process A can reach separating of exposure wavelength with B, then order, the number of times to each operation has no particular limits.
The formation image of filming for to photosensitive composite need contain in photosensitive composite to electronics property dyestuff and photoacid generator.Photoacid generator is used by the form of capacitive compound with the electronics of demonstrating as the effect of developer for electronics property dyestuff to the developer in the photosensitive composite.Particularly, photoacid generator be the acid that produces from photoacid generator through when exposure with give the reaction of electronics property dyestuff,, through to electronics property dyestuff and the sour material that develops the color that in filming, contacts.
On the other hand, the influence that picture steadiness is caused for the ultraviolet composition that reduces sunshine separates exposure wavelength in the 280nm place, and the exposure (exposure process A) through not enough 280nm forms by painted and not painted the picture contrast of forming.Therefore, give electronics property dyestuff and the photoacid generator that constitute photosensitive composite of the present invention can use the compound of colour developing under not enough 280nm.
As this electronics property dyestuff of giving, can from known compound, select use at least a according to the tone of expectation is suitable.For example can enumerate out 3; Two (to the dimethylamino phenyl)-6-dimethylamino phthalides, 3 of 3-; Two (to the dimethylamino phenyl) phthalides of 3-, 3-(to dimethylamino phenyl)-3-(1; 2-dimethyl indole-3-yl) triarylmethane based compound, 4 such as phthalide; 4 '-two-dimethylamino benzhydryl benzylic ether, N-halogenophenyl road donaxine (N-halophenyl leucauramine), N-2; 4; Fluorane based compounds such as 5-trichlorophenyl road donaxine diphenyl methane based compounds such as (N-2,4,5-trichlorophenyl leucauramine), 7-dimethylamino-3-chlorine fluorane, 7-dimethylamino-3-chloro-2-methyl fluoran, 2-phenylamino-3-methyl-6-(N-ethyl-N-is to toluidino) fluorane, benzoyl procrypsis methylene blue, to spiro compounds such as thiazine based compounds such as nitrobenzyl procrypsis methylene blue, 3-methyl-spiral shell-dinaphthopyran, 3-ethyl-spiral shell-dinaphthopyran, 3-propyl group-spiral shell-dinaphthopyran, 3-propyl group-spiral shell-dibenzopyrans etc.These can use or make up two or more uses separately for electronics property dyestuff.In addition, as the known means that improve picture steadiness, also can be with using to electronics property dyestuff is encapsulated.In addition, these give in the electronics property dyestuff can also compounding like the photooxidant the carbon tetrabromide that is used to improve colour rendering, adjuvant as the hydroxyquinoline that prevents to show slinkingly look.
As photoacid generator, so long as under the exposure of the wave band of not enough 280nm, produce acid, not acidic known photoacid generator can use under the exposure of the wave band more than the 280nm.
Usually; The intensity of sensitization wave band (light sensitivity) depends on its concentration; Even therefore the edge of the sensitization wave band that photoacid generator had is positioned at the 280nm place; Thereby also can use as not acidic photoacid generator under the exposure of the wave band more than the 280nm through limiting the intensity that its compounding amount reduces 280nm.
As this photoacid generator; For example can enumerate out salt, sulphones, sulphonic acid ester, sulfimide, disulfonyl diazomethane compound and disulfonyl methane compounds etc. such as sulfonium salt, salt compounded of iodine 、 phosphonium salt, diazo salt, ammonium salt, pyridiniujm, ferrocene, can use or make up two or more uses separately.
As a concrete example; Can enumerate out triphenylsulfonium trifluoro-methanyl sulfonate, triphenylsulfonium nine fluorine butane sulphonate, three (4-aminomethyl phenyl) sulfonium trifluoro-methanyl sulfonate, three (4-aminomethyl phenyl) sulfonium hexafluorophosphate, diphenyl-4-aminomethyl phenyl sulfonium trifluoro-methanyl sulfonate, diphenyl-2; 4,6-trimethylphenyl sulfonium tosilate, two (4-tert-butyl-phenyl) iodine hexafluorophosphate, two (4-tert-butyl-phenyl) iodine trifluoro-methanyl sulfonate, two (cyclohexyl sulphonyl) diazomethane, two (tert-butyl group sulphonyl) diazomethane etc.
Among the above-mentioned photoacid generator; From the viewpoint of picture steadiness, better is that the such sensitization wave band of two (cyclohexyl sulphonyl) diazomethanes, two (tert-butyl group sulphonyl) diazomethane is for the wavelength shorter than 280nm, almost less than the photosensitive photoacid generator more than 280nm.
In addition, when using the above-mentioned photoacid generator that receives compounding amount restriction, under the situation that can't fully develop the color, in order to improve colour rendering, compounding produces new acid through the acid that is produced by photoacid generator and makes acid that the acid proliferation generator of chain propagation take place as required.
As this acid proliferation generator, so long as produce acid through the effect of the acid that produced by photoacid generator, and this acid has the material that reaches as the acid strength of the developer effect of giving electronics property dyestuff and just has no particular limits.For example can enumerate out have the tert-butyl group that can use acid dissociation, phenol derivatives of blocking group such as acetal radical, carboxylic acid derivates, sulphonic acid ester, phosphoric acid ester etc.
Exposure wavelength among the exposure process A is not enough 280nm, therefore as its light source, for example can use known light sources such as low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, excimer laser.
In the middle of them, from the viewpoint of contrast formation and subsequent picture steadiness, the nonoverlapping light source of exposure wave band of preferred exposure process A and exposure process B, for example preferred Ar
2Excimer laser (126nm), Kr
2Excimer laser (146nm), F
2Excimer laser (157nm), Xe
2The light source that excimer laser (172nm), ArCl excimer laser (175nm), ArF excimer laser (193nm), KrBr excimer laser (207nm), KrCl excimer laser (223nm), KrF excimer laser (248nm) etc. only have Wavelength distribution at not enough 280nm place.
And then in the middle of them, more preferably ArF excimer laser (193nm), KrBr excimer laser (207nm), KrCl excimer laser (223nm), KrF excimer laser (248nm).
At this moment, state the Photoepolymerizationinitiater initiater sensitization of photosensitive composite after constituting sometimes and produce free radical, cause the photopolymerization that contains the ethylenically unsaturated group compound, this carries out certain photographic fixing when forming painted under kind of situation.
Among the exposure process A, insufficient when when forming painted, carrying out certain photographic fixing in order not occur developing the color, preferably preferentially do not carry out photopolymerization.In this; Because photoacid generator is different with Photoepolymerizationinitiater initiater; Not hindered by oxygen; Therefore, thereby can freely select noncontact Exposure modes such as contact exposure mode, proximity printing, direct imaging mode etc. such as known vacuum driving fit mode even have the advantage that in oxygen atmosphere exposure also can stable supplying acid.Especially the direct imaging mode of utilizing laser that does not more preferably need photomask for the wave band of effective under-utilized 280nm.On the other hand, with after state in the operation of picture contrast photographic fixing, do not reduce the cured coating film rerum natura in order to reduce the photo-crosslinking degree, preferred limit suppresses the chromogenic reaction limit makes the integral light polymerization of filming.
In addition, in the exposure process A of this formation picture contrast, in order to make the acid that produces because of exposure in the interior diffusion of filming, the back heat treated (Post Exposure Bake:PEB) of can making public.As this exposure back heat treated (PEB), but the method for application of known, condition.
Then; In exposure process B; As stated for the picture contrast photographic fixing that will form filming of photosensitive composite through the wave band different with exposure process A, promptly not painted the wave band more than the 280nm that does not develop the color makes public, and utilizes photo-crosslinking to make the integrally curing of filming.
In the present invention; The chromogenic reaction of giving electronics property dyestuff is photoacid generator sensitization and acidic balanced reaction; Therefore in order to ensure the picture steadiness of excellence, preferably must break off the supply source of acid and suppress to film through cross-linking reaction in dyestuff and sour contacting.
Therefore, through the wave band more than the 280nm of not sensitization of photoacid generator, only Photoepolymerizationinitiater initiater sensitization exposure, the photo-crosslinking of integral body that can prevent with the generation of relevant acid that develops the color, only to film, with the picture contrast photographic fixing.In order to carry out this photographic fixing effectively, it is effective especially that the Photoepolymerizationinitiater initiater that constitutes photosensitive composite is selected.Promptly, as Photoepolymerizationinitiater initiater, the preferred use has and the nonoverlapping sensitization wave band of the sensitization wave band of photoacid generator, the i.e. Photoepolymerizationinitiater initiater of the wave band sensitization more than the not acidic 280nm of photoacid generator.
As Photoepolymerizationinitiater initiater, as stated, in the not acidic wave band of above-mentioned photoacid generator, having photosensitive region is requirement, so it selects highly to depend on the combination with photoacid generator.Promptly; As long as the wave band that only has Photoepolymerizationinitiater initiater sensitization and the nonoverlapping sensitization wave band of the acidic wave band of photoacid generator, the sensitization wave band that perhaps except that the overlapping wave band of the wave band of Photoepolymerizationinitiater initiater sensitization and the acidic wave band of photoacid generator, exists Photoepolymerizationinitiater initiater only to have then have no particular limits.In the present invention, because the photoacid generator utilization is acidic photoacid generator under the exposure of the wave band of not enough 280nm, the material that the exposure of the wave band more than the 280nm is produced free radical therefore capable of using is as Photoepolymerizationinitiater initiater.
As this Photoepolymerizationinitiater initiater; Can enumerate out known radical photopolymerization initiating agents such as benzophenone series, acetophenone system, aminoacetophenone system, benzoin ether system, benzil ketals system, acylphosphine oxide system, oxime ether system, oxime ester system, two luxuriant titanium systems; The photoacid generator that preferred especially use is used in combination does not show that the wave band demonstration more than the photoactive 280nm absorbs, photolytic activity, has the Photoepolymerizationinitiater initiater of high photosensitivity at this wave band.These Photoepolymerizationinitiater initiaters can use or make up two or more uses separately.Independent one or more combinations of known photopolymerization promoter such as these Photoepolymerizationinitiater initiaters can be with benzoic acid, tertiary amine system are used.
In addition, as the initiation system that can set the sensitization wave band arbitrarily, the compound initiation of the known bimolecular system that fragrant x legumin, cyanine, side's acid pigments such as (squarylium) and free-radical generating agent are combined for example also capable of using.For example, known have as the imidazole dimer of free radical generating agent with as the acridine pigment of pigment, combination that triazine is pigment, as the N-phenylglycine of free-radical generating agent with as the combination of the coumarin ketone system of pigment, as the combination of the salt compounded of iodine of free-radical generating agent and various pigments, as the triazine based compound of free-radical generating agent with as the combination of the aromatic ketone derivant of pigment etc.In addition, as the also known alkyl borate that cyanine, rhodamine (rhodamine), sarranine pigments such as (safranine) are arranged of effective visible light initiating agent, also can use these known Photoepolymerizationinitiater initiaters to be.
Like this; With the exposure process B of picture contrast photographic fixing only make constitute photosensitive composite contain the ethylenically unsaturated group compound with Photoepolymerizationinitiater initiater reacts, this whole photo-crosslinking of filming of painted (sensitization of the photoacid generator) limit in this operation of limit inhibition.Thus, not painted curing is from needless to say, and painted of sensitization also solidifies again in exposure process A, therefore can obtain the photographic fixing of the excellent image of picture steadiness.
The wave band that utilizes among the exposure process B as stated, the not acidic wave band of photoacid generator in the preferred photosensitive composite.In addition, in order to prevent not painted the atomizing (fogging) of this operation, the wave band that preferably makes exposure is as far as possible away from the acidic wave band of photoacid generator.Be used for photoacid generator of the present invention because in UVC zone, be that the wave band of not enough 280nm produces acid, so as long as this operation is in its long wavelength's one side, injection line, hybrid ray all can.
As the light source of exposure process B,, just can select use aptly so long as can launch the light source that satisfies based on the dynamic rays of the wave band of image fixing this purpose of photo-crosslinking.For example except known low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp or metal halide lamp etc., also can enumerate out known laser instruments such as Argon ion laser, helium-neon laser, helium cadmium laser, pigment laser instrument, semiconductor laser, YAG laser instrument.
Separation method about exposure process B medium wave band; Can use direct separation such as various laser; And then make public across film class such as the filtrator that removes the light below the 300nm, PET, PEN or glass, even the emission wavelength wide exposure source that distributes also can easily carry out the separation of wave band thus.
As described above, in image forming method of the present invention,,, for example preferably comprise above-mentioned Photoepolymerizationinitiater initiater and contain the ethylenically unsaturated group compound so long as sensitization and the composition that carries out photo-crosslinking get final product as the photosensitive composite that uses.
As containing the ethylenically unsaturated group compound, for example can enumerate out the diacrylate class of glycol such as monoethylene glycol, methoxyl TEG, polyglycol, propylene glycol; Polyvalent alcohol or multicomponent methacrylate classes such as their ethylene oxide adduct or propylene oxide adduct such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate; Multicomponent methacrylate classes such as the ethylene oxide adduct of acrylic acid benzene oxygen ester, bisphenol a diacrylate and their phenols or propylene oxide adduct; The multicomponent methacrylate class of glycidol ethers such as glycerin diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester; And each methyl acrylic ester of melamine acrylic ester and/or aforesaid propylene acid esters correspondence etc.
In addition, can enumerate polyfunctional epoxy resins reaction such as the linear phenolic resin varnish type epoxy resin of acrylic acid and cresols of sening as an envoy to and the hydroxyl reaction of the Epocryl that obtains, half carbamate compounds that makes diisocyanate such as hydroxy acrylate such as pentaerythritol triacrylate and IPDI and this Epocryl and the epoxy urethane acrylate compound that obtains etc.This epoxy acrylate is that resin can not make the reduction of dry to touch property and improve photo-curable.This ethylenically unsaturated group compound that contains can use separately or the two or more uses of combination in any according to the purpose purposes.
In addition, in exposure process A,, produce the reduction of the acid generation efficient that causes by exposure sometimes according to the structure of the compound that is used for photosensitive composite.Therefore; For example, the compound with aromatic group can big absorption occur in the somewhere in the zone of not enough 280nm haply, the composition that constitutes through the base resin that uses by non-aromatic system thus; Can improve the transparency, light sensitivity is improved short wavelength's light.
And then, be used for photosensitive composite of the present invention, in order to adjust viscosity, compounding organic solvent as required.As this organic solvent, can use ketones such as MEK, cyclohexanone; Toluene, xylene, tetramethylbenzene etc. are aromatic hydrocarbon based; Glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, BC, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, DPG diethyl ether, tripropylene glycol monomethyl ether; Ester classes such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, BC acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, carbonic allyl ester; Aliphatic hydrocarbon such as octane, decane; Known organic solvents such as oil series solvent such as sherwood oil, naphtha, solvent naphtha.These organic solvents can use or make up two or more uses separately.
In addition; Except that mentioned component; Various adjuvants of compounding as required, coating such as filling agents such as organic filler, coupling agent, foam-breaking agent, levelling agent such as for example inorganic fillers such as silicon dioxide, aluminium oxide, talcum, lime carbonate, barium sulphate, acrylic compounds bead, carbamate bead are with adjuvant etc.
In addition; In the image forming method of the present invention; As filming of the object that forms image, can be to film, for example by what photosensitive composite was processed; On base material, be coated with photosensitive composite with methods such as silk screen print method, heavy curtain rubbing method, spraying process, rolling method, spin-coating methods, the filming of 15 ~ 60 minutes gained of heat drying, or filming of using that the dry film processed by photosensitive composite obtains etc. under 60 ~ 80 ℃ temperature for example.
Embodiment
Embodiment and comparative example below are shown come the present invention is specified, but the present invention does not obviously receive any restriction of following embodiment.Need to prove that following " part " and " % " then are not quality criteria if there is special instruction.
In the various compositions shown in the table 1, ratio (mass parts) cooperate, with after the stirring machine premixed, carry out mixingly with triple-roller mill, obtain composition 1 ~ 7.
[table 1]
* 1:UNIDIC R-100 (solid constituent 65%) (DIC Corporation manufacturing)
* 2:NEOMER DA-600 (Sanyo Chemical Industries, Ltd.'s manufacturing)
* 3:IRGACURE 907 (Xiba Special Chemical Product Co.,Ltd's manufacturing)
* 4:CGI-325 (Xiba Special Chemical Product Co.,Ltd's manufacturing)
* 5:IRGACURE 369 (Xiba Special Chemical Product Co.,Ltd's manufacturing)
* 6:ADEKA OPTOMER SP-066 (ADEKA manufactured)
* 7:TS-01 (SANWA Chemical Co., Ltd. make)
* 8:WPAG-170 (Wako Pure Chemical Industries, Ltd.'s manufacturing)
* 9:ADEKA OPTOMER SP-152 (solid constituent 50%) (ADEKA manufactured)
* 10:KS-66 (SHIN-ETSU HANTOTAI's organosilicon manufactured)
* 11:S-205 (manufacturing of hillside plot chemical industry Co., Ltd.)
The making of＜test substrate＞
On the solid copper substrate that ground of polishing with the photosensitive composite of the composition example 1 ~ 7 of whole respectively printing of serigraphy table 1,80 ℃ of drying 30 minutes, water white filming of formation on substrate thus down.
Such operation is formed the substrate of filming, form image (embodiment 1 ~ 5, comparative example 1 ~ 5), carry out the evaluation of coating characteristics such as picture contrast, viscosity, solvent resistance, picture steadiness with following condition.Evaluation result is shown in table 2.
＜test condition＞
［ exposure process A (picture contrast formation operation) ］
(1) conditions of exposure 1
As exposure process A, light source uses the KrF excimer laser of emission 248nm, to above-mentioned test substrate with 1000mJ/cm
2Carry out patterning.The PEB that under 80 ℃, carried out then 10 minutes handles (exposure back heat treated).
(2) conditions of exposure 2
As exposure process A, light source uses metal halide lamp, across the negative mask of the pattern that is formed with regulation, above-mentioned test substrate is carried out 1000mJ/cm in full optical band
2Rayed.The PEB that under 80 ℃, carried out then 10 minutes handles (exposure back heat treated).
［ exposure process B (picture contrast photographic fixing operation) ］
(3) conditions of exposure 3
As exposure process B, after in exposure process A, finishing to make public,, carry out vacuum driving fit exposure across the PET film with metal halide lamp in order to remove the wavelength below the 300nm, integral body is carried out 1000mJ/cm to filming
2Rayed, obtain having the substrate of filming (image formation substrate) that is formed with image.
(4) conditions of exposure 4
As exposure process B, in exposure process A, finish exposure after, use emission 405nm wavelength directly retouch exposure machine, integral body is carried out 1000mJ/cm to filming
2Rayed, obtain having the substrate of filming (image formation substrate) that is formed with image.
The evaluation of＜coating characteristic＞
(1) picture contrast
Form substrate through visual image and carried out the affirmation of picture contrast embodiment 1 ~ 5, comparative example 1 ~ 5 gained.Metewand is following.
Colour developing is arranged: the colour developing after the visible exposure.
Do not have colour developing: achromatization changes before and after the exposure.
(2) viscosity
The image of embodiment 1 ~ 5, comparative example 1 ~ 5 gained is formed the evaluation of the solid state that substrate carried out filming based on viscosity (referring to the property touched) behind each exposure process.Metewand is following.
Zero: film coated surface residual fingerprint not fully when referring to touch.
*: film coated surface residual fingerprint when referring to touch.
(3) solvent resistance
With acetone the image of embodiment 1 ~ 5, comparative example 1 ~ 5 gained is formed painted and not painted of substrate respectively and carried out friction testing 50 times, the dissolving of filming with Visual Confirmation, peel off, the curable of filming according to this evaluation affirmation.Metewand is following.
Zero: filming behind the friction testing do not have dissolving, peels off.
*: the dissolving of having filmed behind the friction testing, peel off.
(4) picture steadiness
The image of embodiment 1 ~ 5, comparative example 1 ~ 5 gained is formed substrate ultraviolet screener fluorescent light held 1 month,, estimate picture steadiness (photostability) thus with the atomizing of not painted of Visual Confirmation.Metewand is following.
Zero: do not see not painted atomizing after the placement, keep the state of picture contrast.
△: place visible not painted of back atomizing, can differentiate the state of picture contrast.
*: place visible not painted of back atomizing, can not differentiate the state of picture contrast.
[table 2]
Can know by the evaluation result shown in the table 2, in the embodiment 1 ~ 5 that uses the pairing composition 1 ~ 5 of image forming method of the present invention, can form picture contrast, and then picture steadiness thereafter is excellent.
In addition, but know in the comparative example 1 ~ 3 that uses existing image forming method, though can form picture contrast, but because not painted not fully curing, so picture steadiness is poor, can't keep picture contrast.Can know having used the inventor to wait in the comparative example 4 of the image forming method that takes the lead in proposing, can find the tendency of image stabilization property improvement through using the pairing composition 7 of this formation method, but abundant inadequately.In addition, in the comparative example 5 that uses image forming method of the present invention,, therefore can't form picture contrast owing to do not use the pairing composition of image forming method of the present invention.
Claims (7)
1. image forming method is characterized in that it comprises:
Exposure process A to containing photoacid generator and carrying out the part exposure for the filming of photosensitive composite of electronics property dyestuff, forms picture pattern with the light of the wave band of not enough 280nm;
Exposure process B carries out whole exposure with the light of the above wave band of 280nm, with the picture pattern photographic fixing.
2. image forming method according to claim 1 is characterized in that, said photoacid generator is through the acidic photoacid generator of the light of the wave band of not enough 280nm.
3. image forming method according to claim 1 is characterized in that, among the exposure process A, also carries out the photographic fixing based on photo-crosslinking simultaneously.
4. photocuring image, it forms through each the described image forming method in the claim 1 ~ 3.
5. a photosensitive composite is characterized in that, it contains through the acidic photoacid generator of the light of the wave band of not enough 280nm, gives electronics property dyestuff, Photoepolymerizationinitiater initiater and contain the ethylenically unsaturated group compound.
6. photosensitive composite according to claim 5 is characterized in that, said Photoepolymerizationinitiater initiater is through the light sensation light of the above wave band of 280nm.
7. photosensitive composite according to claim 6 is characterized in that, said Photoepolymerizationinitiater initiater also passes through the light sensation light of the wave band of not enough 280nm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2010042259 | 2010-02-26 | ||
| JP2010-042259 | 2010-02-26 | ||
| PCT/JP2011/000572 WO2011105011A1 (en) | 2010-02-26 | 2011-02-02 | Image formation method and photosensitive composition used in said method |
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| CN102770805A true CN102770805A (en) | 2012-11-07 |
| CN102770805B CN102770805B (en) | 2016-10-12 |
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| JP (1) | JP5916600B2 (en) |
| KR (1) | KR101844087B1 (en) |
| CN (1) | CN102770805B (en) |
| WO (1) | WO2011105011A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9568823B2 (en) | 2014-09-12 | 2017-02-14 | Chi Mei Corporation | Photosensitive resin composition for color filter and uses thereof |
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| JP6586958B2 (en) * | 2014-09-29 | 2019-10-09 | 株式会社スリーボンド | Photocurable resin composition |
| JP6504346B2 (en) * | 2015-02-13 | 2019-04-24 | 株式会社スリーボンド | Photocurable resin composition for suppressing short circuit between adjacent electrodes |
| WO2021039841A1 (en) * | 2019-08-27 | 2021-03-04 | 富士フイルム株式会社 | Method for producing cured film, photocurable resin composition, method for producing laminate, and method for producing semiconductor device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3775123A (en) * | 1970-11-05 | 1973-11-27 | Asahi Chemical Ind | PHOTOSENSITIVE MATERIAL CONTAINING A p-PHENYLENEDIAMINE DERIVATIVE COLOR FORMER AND A HALOGENATED HYDROCARBON PHOTOACTIVATOR |
| JPS572034A (en) * | 1980-06-05 | 1982-01-07 | Konishiroku Photo Ind Co Ltd | Mask image forming material and formation of mask image |
| US20050271981A1 (en) * | 2004-05-31 | 2005-12-08 | Hidekazu Oohashi | Method for colored image formation |
| JP2006015740A (en) * | 2004-05-31 | 2006-01-19 | Fuji Photo Film Co Ltd | Color image forming method |
| CN101180577A (en) * | 2005-07-25 | 2008-05-14 | Az电子材料（日本）株式会社 | Photosensitive resin composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5113645B2 (en) * | 1972-05-30 | 1976-05-01 | ||
| JPS5950972B2 (en) * | 1976-05-20 | 1984-12-11 | 日本放送協会 | energy ray recorder |
| JP2700391B2 (en) * | 1988-04-07 | 1998-01-21 | 日本合成化学工業株式会社 | Photosensitive composition |
| JPH0545868A (en) * | 1991-08-09 | 1993-02-26 | Kimoto & Co Ltd | Image forming composition, partial rugged image forming material and partially rugged image forming method |
| JP2005292847A (en) * | 1999-09-17 | 2005-10-20 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element obtained by using the same, process for producing resist pattern, and process for producing printed circuit board |
| JP4705817B2 (en) * | 2004-07-27 | 2011-06-22 | 富士フイルム株式会社 | Planographic printing plate precursor and planographic printing method |
| JP2006088594A (en) * | 2004-09-24 | 2006-04-06 | Fuji Photo Film Co Ltd | Original lithographic printing plate and lithographic printing method using the original plate |
-
2011
- 2011-02-02 JP JP2012501664A patent/JP5916600B2/en active Active
- 2011-02-02 KR KR1020127021921A patent/KR101844087B1/en active IP Right Grant
- 2011-02-02 CN CN201180010804.4A patent/CN102770805B/en active Active
- 2011-02-02 WO PCT/JP2011/000572 patent/WO2011105011A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3775123A (en) * | 1970-11-05 | 1973-11-27 | Asahi Chemical Ind | PHOTOSENSITIVE MATERIAL CONTAINING A p-PHENYLENEDIAMINE DERIVATIVE COLOR FORMER AND A HALOGENATED HYDROCARBON PHOTOACTIVATOR |
| JPS572034A (en) * | 1980-06-05 | 1982-01-07 | Konishiroku Photo Ind Co Ltd | Mask image forming material and formation of mask image |
| US20050271981A1 (en) * | 2004-05-31 | 2005-12-08 | Hidekazu Oohashi | Method for colored image formation |
| JP2006015740A (en) * | 2004-05-31 | 2006-01-19 | Fuji Photo Film Co Ltd | Color image forming method |
| CN101180577A (en) * | 2005-07-25 | 2008-05-14 | Az电子材料（日本）株式会社 | Photosensitive resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9568823B2 (en) | 2014-09-12 | 2017-02-14 | Chi Mei Corporation | Photosensitive resin composition for color filter and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2011105011A1 (en) | 2011-09-01 |
| KR20120120334A (en) | 2012-11-01 |
| KR101844087B1 (en) | 2018-03-30 |
| JPWO2011105011A1 (en) | 2013-06-17 |
| CN102770805B (en) | 2016-10-12 |
| JP5916600B2 (en) | 2016-05-11 |
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