CN102770805B - Image forming method and the photosensitive composite for the method - Google Patents
Image forming method and the photosensitive composite for the method Download PDFInfo
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- CN102770805B CN102770805B CN201180010804.4A CN201180010804A CN102770805B CN 102770805 B CN102770805 B CN 102770805B CN 201180010804 A CN201180010804 A CN 201180010804A CN 102770805 B CN102770805 B CN 102770805B
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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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- 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
Thering is provided a kind of can not use developer solution to realize high comparative and the dry type image forming method of excellent Physical properties of coating film, particularly picture steadiness excellence and the photosensitive composite for the method.The image forming method of the present invention is characterised by, comprising: exposure process A, with the light of the wave band less than 280nm, the film containing photoacid generator and the photosensitive composite giving electro dyestuff is carried out Partial exposure, forms picture pattern；Exposure process B, carries out whole exposure with the light of the wave band of more than 280nm, and picture pattern is fixing.
Description
Technical field
The present invention relates to image forming method and the photosensitive composition for the method
Thing, can take into account high-contrast in particular to not using wet developing method
With the image forming method of excellent picture steadiness and for the photonasty of the method
Compositions.
Background technology
Generally, based on photolithographic image forming method owing to microfabrication is excellent,
Operability is good and is suitable to produce in a large number, be the most also also widely used for printing industry,
Electronics industry.From the viewpoint of reducing carrying capacity of environment, it is based particularly on aqueous alkali
Wet developing method be widely used in the manufacture of printed circuit board (PCB), welding resistance up to now
The formation of agent and the manufacture etc. of quasiconductor associated components.
In recent years, this image forming method is also widely used in following various fields:
Such as formed on base material the different image of reflectance, with photo detector etc. read from
The MEMS fields etc. such as the manufacture of the displacement transducer of the reflection light of light-emitting component.Work as profit
When these fields, need can on the wafer of aqueous alkali insulation degradation, have
Patterning on corrosive aluminum circuit, as image forming method, photoetching process is also
It is not necessarily useful.
Now, these purposes utilize the developer solution of organic solvent system mostly, from subtracting
It is undesirable from the viewpoint of few carrying capacity of environment.Based on the insight that, can be pre-
See and do not use developer solution and form the technology of picture contrast and can promote from now on.
Do not use developer solution to form the technology of image as this, carried out each at present
Plant research.Such as, from the viewpoint of reducing carrying capacity of environment, based on utilizing photocuring
Also can expect as without garbage with the image forming method of the photothermography of heat fusing
The dry type image forming method of problem.As image forming method based on the method
One of, the colour developing type thermal sensitive recording method utilizing the colour developing caused by dyestuff can be listed.
The method is roughly divided into further and utilizes the diazonium-type sensible heat of diazo coupling reaction to remember
Record method and utilize leuco dye etc. to the leuco form thermal sensitive recording method of electro dyestuff this two
Kind.As the problem of these methods, can list high-contrast (high-color rendering) with
Image formed after the taking into account, to the leuco form about excellent color reproducing performance of quality stability
Image formed after stay in grade technology or about in picture steadiness
The technology of the high-contrast of the diazonium-type having superiority has carried out numerous studies (with reference to specially
Profit document 1,2).
But, around the substrates such as electronic component, MEMS sensor etc. use environment
The technology of strict field application start as far as possible is not yet established, and so far, it utilizes also
It is only limitted in the field such as thermal recording paper, enduring material (proof material).
Prior art literature
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 52-89915 publication (claims)
Patent documentation 2: Japanese Laid-Open Patent Publication 61-123838 publication (claims)
Summary of the invention
The problem that invention is to be solved
The present invention has used for reference above-mentioned the problems of the prior art, its object is to provide not
Use developer solution can realize high comparative and hi-vision stability and the painting of excellence
The dry type image forming method of film physical property and the photosensitive composite of use the method.
For solving the scheme of problem
The present inventor etc., in order to reach above-mentioned purpose, find by formation being schemed
The wave band of the wave band of the exposure process of the contrast of picture and the exposure process carrying out photocuring
Separately, carry out multiexposure, multiple exposure, can respectively by fixing to colored portion and non-colored portion image,
And take the lead in having carried out patent application.
The image forming method of this application is characterised by, at different-waveband to containing light
Acid agent and the film to the photosensitive composite of electro dyestuff carry out multiexposure, multiple exposure,
Thus the picture contrast carrying out respectively being made up of colored portion and non-colored portion formed and
Fixing, it is preferred that the multiexposure, multiple exposure at different-waveband includes: to be formed by colored portion
Non-colored portion composition picture contrast the first exposure process and with first expose
The wave band that wave band is different, that non-colored portion does not develops the color that exposes of light operation carries out whole exposure
Light, by photo-crosslinking by fixing for the picture contrast being made up of colored portion and non-colored portion
The second exposure process.
According to the technical scheme of this application, due to unlike the prior art to colored portion,
Non-colored portion all carries out photocuring, the contrast excellent in stability after therefore image is formed,
Cannot realize in conventional technique is also possibly realized with taking into account of Physical properties of coating film.
But, the present inventor etc. observes the image of gained in aforementioned manners, knot
Fruit is distinguished, according to purposes, image formed after system in the going of photoacid generator of remaining
Activation remains as new problem.I.e., it was found that following problem: be exposed to the sun
Under the light such as light in such use environment, can be produced by the photoacid generator of remaining in film
Acid, causes unexpected colour developing (coloring) reaction.
Therefore, the image stabilization after the present inventor etc. are formed for picture pattern
Property, it is conceived to arrive the UV-shares of the sunlight on ground, by investigating ultraviolet
The impact that picture steadiness is caused by composition, solves above-mentioned problem.That is, the present invention
Inventor wait in order to reduce what picture steadiness was caused by the UV-shares of sunlight
Impact, conducts in-depth research the region made a distinction by exposure wavelength of this method,
It was found that the exposure wave band of the exposure process A by picture pattern formation will be carried out
It is set as less than 280nm, makes the fixing exposure process B of image by carrying out photocuring
Exposure wave band be set as the wave band of more than 280nm, image can be significantly improved steady
Qualitative, thus complete the present invention.
The classification carried out usually used as the wavelength according to ultraviolet, can be divided into wavelength
The nearultraviolet rays of 380 ~ 200nm, the far ultraviolet rays of wavelength 200 ~ 10nm, wavelength
The extreme ultraviolet line of 10 ~ 1nm.Sunlight includes UVA(400 ~ 315nm), UVB
(315 ~ 280nm), UVC(are less than 280nm) the nearultraviolet rays of wavelength.Wherein,
Only UVA, UVB can arrive earth's surface, the suction based on material of UVC by ozone layer
Receive substantially, it is impossible to pass through air.
The present invention possesses feature at following aspect: the spy of the UVC from this sunlight
Property, i.e. light less than 280nm do not arrive the phenomenon on earth's surface and set out, and will only be in this wavelength
The photoacid generator of lower activation is formed for picture pattern, thus can significantly improve
Picture pattern formed after picture steadiness.
That is, according to an embodiment of the image forming method of the present invention, its feature
Being, it includes following operation: exposure process A, with the light of the wave band less than 280nm
Film containing photoacid generator and the photosensitive composite giving electro dyestuff is carried out portion
Divide exposure, form picture pattern；With exposure process B, with the wave band of more than 280nm
Light carries out whole exposure, and picture pattern is fixing.
Here, the photosensitive composite for the image forming method of the present invention preferably contains
Have and produce the photoacid generator of acid by the light of the wave band less than 280nm, to electro dye
Material, Photoepolymerizationinitiater initiater and the compound Han ethylenically unsaturated group.
It addition, foregoing photo-polymerization initiator preferably can not produced by aforementioned photoacid generator
Sour wave band, the i.e. light of the wave band of more than 280nm are photosensitive.
The effect of invention
Find the distinctive effect of the following present invention: according to the present invention, by belonging to
The wavelength less than 280nm of the wave band reaching the ultraviolet (UV) C of the sunlight on ground is formed
Picture pattern, thus without due to ultraviolet contained in sunlight to contrast shape
Picture steadiness after one-tenth impacts.Its result, is possible not only to be used in conventional
Thermal recording paper, enduring material, it is also possible to be extensively used in and such as use environment strict
Electric substrate, the marking purposes of display association area, shading purposes, Jin Erneng
Formation figure on enough aluminum circuit that cannot process due to the problem of corrosion in photolithography
Picture, therefore can expect application extension to the MEMS such as photo detector, displacement transducer
In purposes.
Detailed description of the invention
Hereinafter, the image forming method of the present invention is described in detail.
The image forming method of the present invention is: by different-waveband to photosensitive composition
The film of thing carries out multiexposure, multiple exposure, carries out respectively being made up of colored portion and non-colored portion
Picture pattern is (hereinafter also referred to " picture contrast " etc..) formation and fixing, its
In, described photosensitive composite contains the light generation acid by the wave band less than 280nm
Photoacid generator and give electro dyestuff.
In exposure process A, carry out Partial exposure with the light of the wave band less than 280nm,
Thus exposure portion photoacid generator produce acid, this acid with react to electro dyestuff and show
Color, forms colored portion.It addition, in exposure process B, do not produce with photoacid generator
The light of the wave band of more than the 280nm of acid carries out whole exposure, thus suppresses chromogenic reaction,
And by photo-crosslinking fixed coloring portion and non-colored portion, picture contrast is fixing.This
As long as exposure process A and B of sample can reach the separation of exposure wavelength, then to each operation
Sequentially, number of times has no particular limits.
In order to the film of photosensitive composite is formed image, need at photosensitive composition
Containing to electro dyestuff and photoacid generator in thing.Photoacid generator is with to photosensitive composition
The electronics demonstrating the effect as developer to electro dyestuff of the developer in thing
Used by the form of capacitive compound.Specifically, when photoacid generator is by exposure
From photoacid generator produce acid with react to electro dyestuff, i.e., by electro
The material that dyestuff contacts in film with acid and develops the color.
On the other hand, picture steadiness is made in order to reduce the UV-shares of sunlight
The impact become, separates exposure wavelength, by the exposure less than 280nm at 280nm
(exposure process A) forms the picture contrast being made up of colored portion and non-colored portion.
Therefore, constitute the present invention photosensitive composite to electro dyestuff and photoacid generator
The compound of colour developing under less than 280nm can be used.
As this to electro dyestuff, can be according to desired from known compound
Tone suitably selects to use at least one.Include, for example out 3,3-double (to diformazan ammonia
Base phenyl)-6-dimethylamino Phthalide, double (to the dimethylamino phenyl) Phthalide of 3,3-,
3-(is to dimethylamino phenyl)-3-(1,2-dimethyl indole-3-base) Phthalide etc. three virtue
Methylmethane based compound, 4,4 '-bis--dimethylamino benzhydryl benzylic ether, N-halogeno-benzene
Base road donaxine (N-halophenyl leucauramine), N-2,4,5-trichlorophenyl road gram
The diphenylmethanes such as amine (N-2,4,5-trichlorophenyl leucauramine)
Compound, 7-dimethylamino-3-chlorine fluorane, 7-dimethylamino-3-chloro-2-methyl fluorane,
2-phenylamino-3-methyl-6-(N-ethyl-N-p-totuidine base) the fluorane system such as fluorane
Compound, benzoyl leuco methylene blue, to thiazines such as nitrobenzyl leuco methylene blue
Based compound, 3-methyl-spiral shell-dinaphthopyran, 3-ethyl-spiral shell-dinaphthopyran, 3-
The spiro compounds such as propyl group-spiral shell-dinaphthopyran, 3-propyl group-spiral shell-dibenzopyrans
Deng.These can be used alone or be used in combination of two or more to electro dyestuff.Separately
Outward, as the known means improving picture steadiness, it is also possible to will be to electro dye
Expect encapsulated use.It addition, can also be compounded such as in these give electro dyestuff
For improving the such photooxidant of the carbon tetrabromide of color rendering properties, as prevented from showing slinkingly color
The such additive of hydroxyquinoline.
As photoacid generator, as long as produce under the exposure less than the wave band of 280nm
Acid, does not produce the known photoacid generator of acid under the exposure of the wave band of more than 280nm
Can use.
Generally, the intensity (light sensitivitys) of photosensitive wave band depends on its concentration, is therefore
The edge making the photosensitive wave band that photoacid generator had is positioned at 280nm, it is possible to pass through
Limit its compounding amount thus reduce the intensity of 280nm, as the wave band at more than 280nm
Exposure under do not produce acid photoacid generator and use.
As this photoacid generator, include, for example out sulfonium salt, iodine salt, salt,
The salt such as diazol, ammonium salt, pyridiniujm, ferrocene, sulphones, sulphonic acid ester,
Sulfimide, disulfonyl diazomethane compound and disulfonyl methane compounds etc.,
May be used alone or in combination two or more use.
As a concrete example, can list triphenylsulfonium triflate alkyl sulfonate,
Triphenylsulfonium nine fluorine butane sulfonate, three (4-aminomethyl phenyl) sulfonium trifluoromethayl sulfonic acid
Salt, three (4-aminomethyl phenyl) sulfonium hexafluorophosphate, diphenyl-4-aminomethyl phenyl sulfonium three
Fluoromethane sulfonate, diphenyl-2,4,6-trimethylphenyl sulfonium tosilate, double
(4-tert-butyl-phenyl) iodine hexafluorophosphate, double (4-tert-butyl-phenyl) iodine
Trifluoro-methanyl sulfonate, double (cyclohexylsulfonyl) Azimethylene., double (tert-butyl group sulphur
Acyl) Azimethylene. etc..
Among above-mentioned photoacid generator, from the viewpoint of picture steadiness, more preferably
Be double (cyclohexylsulfonyl) Azimethylene., double (tert-butyl group sulphonyl) Azimethylene. this
The photosensitive wave band of sample is the wavelength shorter than 280nm, almost without the sense at more than 280nm
The photoacid generator of photosensitiveness.
During additionally, use the above-mentioned photoacid generator limited by compounding amount, cannot be abundant
In the case of colour developing, in order to improve color rendering properties, can be compounded as required by being produced by light
The acid that acid agent produces produces new acid and makes acid that the acid proliferation generator of chain propagation to occur.
As this acid proliferation generator, as long as the work of the acid by being produced by photoacid generator
With producing acid, and this acid has and reaches as to the developer effect of electro dyestuff
The material of acid strength just has no particular limits.Include, for example out to have and can use acid
The phenol derivatives of blocking group such as the tert-butyl group that dissociates, acetal radical, carboxylic acid derivates,
Sulphonic acid ester, phosphoric acid ester etc..
Exposure wavelength in exposure process A is less than 280nm, therefore as its light source,
Such as can use low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, excimer laser etc.
Known light source.
In the middle of them, formed from contrast and subsequent the viewpoint of picture steadiness is come
See, preferably the nonoverlapping light source of exposure wave band of exposure process A and exposure process B, example
Such as preferred Ar2Excimer laser (126nm), Kr2Excimer laser (146nm),
F2Excimer laser (157nm), Xe2Excimer laser (172nm), ArCl
Excimer laser (175nm), ArF excimer laser (193nm), KrBr are accurate
Molecular laser (207nm), KrCl excimer laser (223nm), KrF standard are divided
Sub-laser instrument (248nm) etc. are only less than the light source at 280nm with Wavelength distribution.
And then in the middle of them, more preferably ArF excimer laser (193nm), KrBr
Excimer laser (207nm), KrCl excimer laser (223nm), KrF are accurate
Molecular laser (248nm).
Now, the Photoepolymerizationinitiater initiater sometimes constituting aftermentioned photosensitive composite photosensitive and
Producing free radical, cause the photopolymerization containing ethylenically unsaturated group compound, this is planting
In the case of, formed carry out while colored portion certain fixing.
In exposure process A, formed carry out while colored portion certain fixing time,
Insufficient in order to occur without colour developing, the most preferentially carry out photopolymerization.In this,
Owing to photoacid generator is different from Photoepolymerizationinitiater initiater, do not hindered by oxygen, therefore have i.e.
Make in oxygen atmosphere exposure can also the advantage of stable supplying acid, thus can freely select
Select the noncontacts such as contact exposure mode, proximity printing such as the known closely sealed mode of vacuum
Exposure mode, direct imaging mode etc..Especially for the most under-utilized 280nm
Wave band and more preferably need not the direct imaging mode utilizing laser of photomask.Separately
On the one hand, by operation fixing for aftermentioned picture contrast, in order to reduce photo-crosslinking
Spending and do not reduce cured coating film physical property, preferably limit suppression chromogenic reaction limit makes film overall
Photopolymerization.
Additionally, in the exposure process A of this formation picture contrast, in order to make because of
The acid exposed and produce, at film internal diffusion, can be exposed post-heating and process (Post
Exposure Bake:PEB).Process (PEB) as this exposure post-heating, can answer
By known method, condition.
Then, in exposure process B, as mentioned above in order to will be to photosensitive composite
Film formed picture contrast fixing and by the ripple different from exposure process A
The wave band of more than the 280nm that section, the most non-colored portion do not develop the color is exposed, and utilizes light
Crosslinking makes film integrally curing.
In the present invention, the chromogenic reaction to electro dyestuff be photoacid generator photosensitive and
Produce the balancing response of acid, therefore to guarantee the picture steadiness of excellence, preferably must
The supply source of acid must be broken off and by the dyestuff in cross-linking reaction suppression film and acid
Contact.
Therefore, by the most photosensitive at photoacid generator, only Photoepolymerizationinitiater initiater is photosensitive
The wave band exposure of more than 280nm, can prevent the generation to the relevant acid that develops the color, only enter
The overall photo-crosslinking of row film, picture contrast is fixing.In order to effectively carry out this
Fixing, carrying out selected to the Photoepolymerizationinitiater initiater constituting photosensitive composite is to have especially
Effect.I.e., as Photoepolymerizationinitiater initiater, the sense that have with photoacid generator is preferably used
The nonoverlapping photosensitive wave band of optical band, i.e. photoacid generator do not produce acid 280nm with
On the photosensitive Photoepolymerizationinitiater initiater of wave band.
As Photoepolymerizationinitiater initiater, as it has been described above, do not produce acid at above-mentioned photoacid generator
Wave band in have photosensitive region be requirement, therefore its select to be highly dependent on
The combination of photoacid generator.As long as that is, only exist the photosensitive wave band of Photoepolymerizationinitiater initiater with
Photoacid generator produces the nonoverlapping photosensitive wave band of wave band of acid or except photopolymerization causes
The photosensitive wave band of agent produces with photoacid generator and only exists beyond the wave band that the wave band of acid is overlapping
The photosensitive wave band that Photoepolymerizationinitiater initiater has, then have no particular limits.In the present invention
In, due to photoacid generator utilization is to produce under the exposure less than the wave band of 280nm
The photoacid generator of acid, therefore the available exposure to the wave band of more than 280nm is produced from
By the material of base as Photoepolymerizationinitiater initiater.
As this Photoepolymerizationinitiater initiater, can list benzophenone series, 1-Phenylethanone. system,
Aminoacetophenone system, benzoin ether system, benzil ketals system, acylphosphine oxide system,
The known radical photopolymerization initiators such as oxime ether system, oxime ester system, titanocenes system, special
It is not preferably used in the photoacid generator being applied in combination and does not show photoactive more than 280nm
Wave band display absorb, photolytic activity, the photopolymerization at this wave band with high photosensitivity is drawn
Send out agent.These Photoepolymerizationinitiater initiaters may be used alone or in combination two or more use.This
A little Photoepolymerizationinitiater initiaters can photopolymerization promoter known with benzoic acid system, tertiary amine system etc.
Independent one or more be applied in combination.
It addition, as can arbitrarily set the initiation system of photosensitive wave band, be such as also with
By pigment and free-radical generating agent such as perfume x legumin, cyanine, side'ss acid (squarylium)
The known bimolecular combined is compound causes system.For example, as it is known that have as freedom
The imidazole dimer of base propellant and as the acridine pigment of pigment, triazine system pigment
Combination, the N-phenylglycine as free-radical generating agent and the coumarin as pigment
The combination of ketone system, as the iodine salt of free-radical generating agent and the combination of various pigment,
Triazine based compound as free-radical generating agent and the aromatic ketone as pigment derive
The combination etc. of thing.It addition, as effective visible light initiator it is known that cyanine,
The alkyl borate of the pigments such as rhodamine (rhodamine), sarranine (safranine),
It is used as Photoepolymerizationinitiater initiater system known to these.
So, exposure process B fixing for picture contrast is only made composition photonasty group
Reacting containing ethylenically unsaturated group compound and Photoepolymerizationinitiater initiater of compound, limit
This is overall to suppress the coloring in this operation (photoacid generator photosensitive) limit to carry out film
Photo-crosslinking.Thus, the solidification of non-colored portion is from needless to say, in exposure process A
Photosensitive colored portion is also carried out resolidification, therefore can get the figure that picture steadiness is excellent
Picture fixing.
The wave band utilized in exposure process B is as described above, it is preferred in photosensitive composite
Photoacid generator do not produce acid wave band.It addition, in order to prevent not colouring of this operation
The atomization (fogging) in portion, preferably makes the wave band of exposure produce away from photoacid generator as far as possible
The wave band of raw acid.For the present invention photoacid generator due in UVC region, i.e. not enough
The wave band of 280nm produces acid, as long as therefore this operation is in its long wavelength side, single
Ray, hybrid ray.
As the light source of exposure process B, as long as can launch satisfied based on photo-crosslinking
The light source of the dynamic rays of the wave band of the fixing this purpose of image, it is possible to select aptly
Select use.Such as except known low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, surpass
Beyond high voltage mercury lamp, xenon lamp or metal halide lamp etc., also can list argon ion and swash
Light device, helium neon laser, helium cadmium laser, pigment laser device, semiconductor laser,
The known laser instrument such as YAG laser.
About the separation method of exposure process B medium wave band, can be straight with various laser etc.
Connect separation, and then across the filter of the light removing below 300nm, PET, PEN etc.
Thin film class or glass are exposed, even thus launching the exposure that Wavelength distribution is wide
Source also is able to easily carry out the separation of wave band.
As described above, in the image forming method of the present invention, as the sense used
Photosensitiveness compositions, as long as photosensitive and carry out the compositions of photo-crosslinking, the most excellent
Choosing comprises above-mentioned Photoepolymerizationinitiater initiater and the compound Han ethylenically unsaturated group.
As containing ethylenically unsaturated group compound, include, for example out ethylene glycol, first
The diacrylate esters of the glycol such as epoxide TEG, Polyethylene Glycol, propylene glycol；Oneself
Glycol, trimethylolpropane, tetramethylolmethane, dipentaerythritol, trihydroxyethyl isocyanide
The polyhydric alcohol such as urea acid esters or their ethylene oxide adduct or propylene oxide adduct etc.
Multicomponent methacrylate class；Acrylic acid benzene oxygen ester, bisphenol a diacrylate and they
The ethylene oxide adduct of phenols or the multicomponent methacrylate such as propylene oxide adduct
Class；Glycerin diglycidyl ether, T 55, trimethylolpropane tris
Polynary the third of the glycidyl ethers such as glycidyl ether, triglycidyl group isocyanuric acid ester
Olefin(e) acid esters；And melamine acrylate and/or aforesaid propylene acid esters corresponding
Each methyl acrylic ester etc..
It addition, send as an envoy to acrylic acid and cresol novolac type epoxy resin can be enumerated
Deng polyfunctional epoxy resin reaction and obtain Epocryl, make Ji Wusi
Two isocyanides such as the hydroxy acrylates such as alcohol triacrylate and isophorone diisocyanate
Half carbamate compounds of acid esters and the hydroxyl reaction of this Epocryl
And the epoxy amino formic acid esters acrylate compounds etc. obtained.This epoxy acrylic
Ester system resin can not make dry to touch reduce and improve photo-curable.This containing olefinic
Unsaturated group compound can be used alone or combination in any two kinds according to purpose purposes
Used above.
It addition, in exposure process A, according to the compound for photosensitive composite
Structure, produce the reduction of the sour generation efficiency caused by exposure sometimes.Therefore,
Such as, the compound with aromatic group generally can be in the region less than 280nm
Somewhere big absorption occurs, from there through using by the base resin of non-aromatic family
The compositions constituted, can improve the transparency of the light to short wavelength, make light sensitivitys carry
High.
And then, in the photosensitive composite of the present invention, in order to adjust viscosity,
Organic solvent can be compounded as required.As this organic solvent, can use butanone,
The ketones such as Ketohexamethylene；Toluene, dimethylbenzene, durol etc. are aromatic hydrocarbon；Molten fibre
Agent, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl card
Must alcohol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, three
The glycol ethers such as propylene glycol monomethyl ether；Ethyl acetate, butyl acetate, butyl lactate,
Cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl card must
Alcohol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, carbon
The esters such as acid propylene ester；The aliphatic hydrocarbon such as octane, decane；Petroleum ether, Petroleum,
The known organic solvent such as the petroleum solvents such as solvent naphtha.These organic solvents can
To be used alone or to be used in combination of two or more.
It addition, in addition to mentioned component, various additive, example can be compounded as required
As the inorganic fillers such as silicon dioxide, aluminium oxide, Talcum, calcium carbonate, barium sulfate, third
The filleies such as organic filler such as olefin(e) acid class beadlet, carbamate beadlet, coupling agent,
The additive for coatings such as defoamer, levelling agent etc..
Additionally, in the image forming method of the present invention, as the object forming image
Film, the film can being made up of photosensitive composite, such as, use silk screen printing
The methods such as method, heavy curtain rubbing method, spraying process, rolling method, spin-coating method are coated with on base material
Cloth photosensitive composite, heat drying 15 ~ 60 minutes at a temperature of such as 60 ~ 80 DEG C
The film that the dry film that the film of gained or use are made up of photosensitive composite obtains
Deng.
Embodiment
The present invention is specifically described by embodiment described below and comparative example, but this
Invention is not obviously by any restriction of following embodiment.It should be noted that following
" part " and " % " is the most then quality criteria.
In the various compositions shown in table 1, ratio (mass parts) coordinate, pre-with blender
After mixing, carry out mixing with triple-roller mill, obtain compositions 1 ~ 7.
[table 1]
* 1:UNIDIC R-100(solid constituent 65%) (DIC Corporation manufacture)
* 2:NEOMER DA-600(Sanyo Chemical Industries, Ltd. manufactures)
* 3:IRGACURE 907(Xiba Special Chemical Product Co., Ltd manufactures)
* 4:CGI-325(Xiba Special Chemical Product Co., Ltd manufactures)
* 5:IRGACURE 369(Xiba Special Chemical Product Co., Ltd manufactures)
* 6:ADEKA OPTOMER SP-066(ADEKA company manufactures)
* 7:TS-01(SANWA Chemical Co., Ltd. manufacture)
* 8:WPAG-170(Wako Pure Chemical Industries, Ltd. manufactures)
* 9:ADEKA OPTOMER SP-152(solid constituent 50%) (ADEKA
Company manufactures)
* organosilicon company of 10:KS-66(SHIN-ETSU HANTOTAI manufactures)
* 11:S-205(hillside plot chemical industry Co., Ltd. manufactures)
The making ＞ of ＜ test substrate
With silk screen printing whole printing table respectively on the solid copper substrate that polishing is ground
The photosensitive composite of the compositions example 1 ~ 7 of 1, at 80 DEG C be dried 30 minutes, thus
Substrate is formed water white film.
So operation is formed the substrate of film, forms image by following condition (real
Execute example 1 ~ 5, comparative example 1 ~ 5), carry out picture contrast, viscosity, solvent resistance,
The evaluation of the coating characteristics such as picture steadiness.Evaluation result is shown in table 2.
＜ experimental condition ＞
Exposure process A(picture contrast formation process) ］
(1) conditions of exposure 1
As exposure process A, light source uses the KrF excimer laser launching 248nm
Device, to above-mentioned test substrate with 1000mJ/cm2Pattern.Then at 80 DEG C
Carry out the PEB process (exposure post-heating processes) of 10 minutes.
(2) conditions of exposure 2
As exposure process A, light source uses metal halide lamp, across being formed with rule
The negative mask of fixed pattern, is carried out in full optical band above-mentioned test substrate
1000mJ/cm2Light irradiate.Then the PEB process carried out at 80 DEG C 10 minutes (exposes
Light post-heating processes).
The fixing operation of exposure process B(picture contrast) ］
(3) conditions of exposure 3
As exposure process B, after terminating exposure in exposure process A, in order to remove
The wavelength of below 300nm, carries out vacuum with metal halide lamp across PET film closely sealed
Exposure, carries out 1000mJ/cm to film entirety2Light irradiate, obtain having and be formed
The substrate (image formation substrate) of the film of image.
(4) conditions of exposure 4
As exposure process B, after terminating exposure in exposure process A, use and launch
The wavelength of 405nm directly retouch exposure machine, film entirety is carried out 1000mJ/cm2Light
Irradiate, obtain the substrate (image formation substrate) with the film being formed with image.
The evaluation ＞ of ＜ coating characteristic
(1) picture contrast
By visually the image formation substrate of embodiment 1 ~ 5, comparative example 1 ~ 5 gained being entered
Go the confirmation of picture contrast.Metewand is as follows.
There is a colour developing: the colour developing after visible exposure.
Without colour developing: achromatization change before and after exposure.
(2) viscosity
Based on viscosity after each exposure process (the finger property touched) to embodiment 1 ~ 5, comparative example
The image of 1 ~ 5 gained forms the evaluation that substrate has carried out the solid state of film.Evaluate
Benchmark is as follows.
Zero: film coated surface when touch the most not residual fingerprint.
×: film coated surface residual fingerprint when touch.
(3) solvent resistance
With acetone, the image of embodiment 1 ~ 5, comparative example 1 ~ 5 gained is formed substrate respectively
Colored portion and non-colored portion carried out 50 friction testings, to be visually confirmed to be film
Dissolve, peel off, confirm the curable of film according to this evaluation.Metewand is as follows.
Zero: the film after friction testing is without dissolving, peeling off.
×: the film after friction testing has dissolving, peeling.
(4) picture steadiness
The image of embodiment 1 ~ 5, comparative example 1 ~ 5 gained is formed substrate at ultraviolet screen
Cover and place 1 month under fluorescent lamp, to be visually confirmed to be the atomization of non-colored portion, thus evaluate
Picture steadiness (light resistance).Metewand is as follows.
Zero: have no the atomization of non-colored portion after placement, maintain the state of picture contrast.
△: the atomization of non-colored portion seen from after placement, picture contrast can be differentiated
State.
×: the atomization of non-colored portion seen from after placement, picture contrast can not be differentiated
State.
[table 2]
Evaluation result as shown in Table 2 understands, at the image forming method using the present invention
In the embodiment 1 ~ 5 of corresponding compositions 1 ~ 5, picture contrast can be formed, and then
Thereafter picture steadiness is excellent.
Additionally, understand in the comparative example 1 ~ 3 using existing image forming method,
Although picture contrast can be formed, but owing to non-colored portion is not sufficiently cured, therefore scheme
As poor stability, it is unable to maintain that picture contrast.Understand and employing the present inventor etc.
Take the lead in propose image forming method comparative example 4 in, by using this forming method institute
Corresponding compositions 7 is it appeared that the tendency improved of picture steadiness, but the most abundant.
It addition, in using the comparative example 5 of image forming method of the present invention, owing to not using
Compositions corresponding to the image forming method of the present invention, therefore cannot form image pair
Degree of ratio.
Claims (5)
1. not using a dry type image forming method for wet developing method, its feature exists
In, comprising:
Exposure process A, with only less than having the light source of Wavelength distribution at 280nm to containing
There is photoacid generator and to electro dyestuff and the photosensitive composite of Photoepolymerizationinitiater initiater
Film carry out Partial exposure, form picture pattern；
Exposure process B, the light source being separated off with the wave band of below 300nm carries out whole
Exposure, picture pattern is fixing,
Described photoacid generator be by the light of the wave band less than 280nm produce acid and
The photoacid generator of acid is not produced under the light of more than 280nm,
Described Photoepolymerizationinitiater initiater is photosensitive by the light of the wave band of more than 280nm.
Image forming method the most according to claim 1, it is characterised in that expose
In light operation A, carry out based on photo-crosslinking fixing the most simultaneously.
3. a photocuring image, it is formed by the image described in claim 1 or 2
Method is formed.
4. a photosensitive composite, it is characterised in that it contains by deficiency
The light of the wave band of 280nm produces acid and does not produce acid under the light of more than 280nm
Photoacid generator, to electro dyestuff, Photoepolymerizationinitiater initiater and the unsaturated group Han olefinic
Dough compound, described Photoepolymerizationinitiater initiater is photosensitive by the light of the wave band of more than 280nm.
Photosensitive composite the most according to claim 4, it is characterised in that institute
State Photoepolymerizationinitiater initiater photosensitive also by the light of the wave band less than 280nm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2010-042259 | 2010-02-26 | ||
| JP2010042259 | 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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| Publication Number | Publication Date |
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| CN102770805A CN102770805A (en) | 2012-11-07 |
| CN102770805B true CN102770805B (en) | 2016-10-12 |
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| CN201180010804.4A Active CN102770805B (en) | 2010-02-26 | 2011-02-02 | Image forming method and the photosensitive composite for the method |
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| JP (1) | JP5916600B2 (en) |
| KR (1) | KR101844087B1 (en) |
| CN (1) | CN102770805B (en) |
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| TWI531860B (en) | 2014-09-12 | 2016-05-01 | Chi Mei Corp | Photosensitive resin composition for color filter and its application |
| KR102311319B1 (en) * | 2014-09-29 | 2021-10-08 | 가부시끼가이샤 쓰리본드 | 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 |
| KR102648552B1 (en) * | 2019-08-27 | 2024-03-18 | 후지필름 가부시키가이샤 | Method for producing a cured film, a photocurable resin composition, a method for producing a laminate, and a method for producing a semiconductor device |
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| 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 |
| CN101180577A (en) * | 2005-07-25 | 2008-05-14 | Az电子材料（日本）株式会社 | Photosensitive resin composition |
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|---|---|---|---|---|
| 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 |
| JPS572034A (en) * | 1980-06-05 | 1982-01-07 | Konishiroku Photo Ind Co Ltd | Mask image forming material and formation of mask image |
| 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 |
| JP2006015740A (en) * | 2004-05-31 | 2006-01-19 | Fuji Photo Film Co Ltd | Color image forming method |
| US7402374B2 (en) * | 2004-05-31 | 2008-07-22 | Fujifilm Corporation | Method for colored image formation |
| 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 KR KR1020127021921A patent/KR101844087B1/en active IP Right Grant
- 2011-02-02 JP JP2012501664A patent/JP5916600B2/en active Active
- 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 (2)
| 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 |
| CN101180577A (en) * | 2005-07-25 | 2008-05-14 | Az电子材料（日本）株式会社 | Photosensitive resin composition |
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| KR20120120334A (en) | 2012-11-01 |
| KR101844087B1 (en) | 2018-03-30 |
| JP5916600B2 (en) | 2016-05-11 |
| CN102770805A (en) | 2012-11-07 |
| JPWO2011105011A1 (en) | 2013-06-17 |
| WO2011105011A1 (en) | 2011-09-01 |
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