KR101844087B1 - 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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- KR101844087B1 KR101844087B1 KR1020127021921A KR20127021921A KR101844087B1 KR 101844087 B1 KR101844087 B1 KR 101844087B1 KR 1020127021921 A KR1020127021921 A KR 1020127021921A KR 20127021921 A KR20127021921 A KR 20127021921A KR 101844087 B1 KR101844087 B1 KR 101844087B1
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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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Abstract
A dry type image forming method capable of realizing high contrast and excellent coating film properties without using a developing solution, particularly excellent in image stability, and a photosensitive composition for use in the method. The image forming method of the present invention comprises an exposure step A for forming an image pattern by partially exposing a coating film of a photosensitive composition containing a photoacid generator and an electron donating dye to light having a wavelength band of less than 280 nm, and an exposure step B for performing front exposure with light having a wavelength band equal to or greater than 10 nm and fixing the image pattern.
Description
The present invention relates to an image forming method and a photosensitive composition for use in the method, and more particularly to an image forming method capable of achieving both high contrast and excellent image stability without using a wet developing method, ≪ / RTI >
Generally, the image forming method by the photolithography method is excellent in the fine workability and is suitable for mass production because of the advantage of workability, and is widely used in the printing industry and the electronics industry today. Among them, the wet developing method using an aqueous alkali solution has been widely used from the viewpoint of reduction of the environmental load to the production of printed wiring boards, the formation of solder resists, and the production of semiconductor-related members.
In recent years, such an image forming method has been used in various fields such as the manufacture of a displacement sensor that forms an image having a different reflectance on a substrate and reads reflected light from the light emitting element by a light receiving element or the like have. It is not necessarily useful as an image forming method because of the necessity of patterning on a wafer which is insoluble in an alkali aqueous solution and on a corrosive aluminum wiring.
At present, an organic solvent-based developer is often used for these applications, which is not preferable from the viewpoint of environmental load reduction. On the basis of this point, there is a possibility that the technique of forming an image contrast without using a developer will be enlarged in the future.
As a technique for forming an image without using such a developer, various techniques have conventionally been studied. For example, an image forming method by photo thermography using photo-curing and thermal fusing is expected as a dry type image forming method free of waste problems from the viewpoint of environmental load reduction. One of the image forming methods by this method is a color development type thermal recording method using color development by a dye. This method is also largely divided into two methods, diazo type thermal recording method using diazo coupling reaction and leuco type thermal recording method using electron donating dyes such as leuco dyes. Examples of the problems of these methods include high contrast (high coloring property) and quality stability after image formation, and a technique relating to quality stabilization after image formation of a leuco type having excellent color development, or a technique of stabilizing the diazo type Many techniques for contrast enhancement have been studied (see Patent Documents 1 and 2).
However, a technology that can be applied to a field such as an electronic part or the like where a strict use environment such as a MEMS sensor has been established is not established, and thus its use is limited to fields such as a heat sensitive recording and a proof material.
SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art described above, and its object is to provide a dry type image forming method capable of realizing high contrast, high image stability, and excellent coating film properties without using a developer, To provide a photosensitive composition.
The inventors of the present invention have found that the wavelength band of the exposure process for forming the contrast of an image and the wavelength band of the exposure process for photo-curing are separated from each other, and the coloring portion and the uncolored portion are subjected to image exposure , And filed earlier.
The image forming method of this application is a method for forming an image contrast comprising the colored portion and the uncolored portion by fixing the coating film of the photosensitive composition containing the photoacid generator and the electron donating dye plural times in different wavelength bands, A plurality of times of exposure in different wavelength bands preferably includes a first exposure step of forming an image contrast including a colored part and an uncolored part and a second exposure step of forming an image having a different exposure wavelength range from the exposure wavelength band of the first exposure step And a second exposure step of performing front exposure in a wavelength band in which the uncoloured portion is not developed and fixing the image contrast including the colored portion and the uncolored portion by photo-crosslinking.
According to the invention of this application, unlike the prior art, since both the colored portion and the uncolored portion are photo-cured, the contrast stability after the image formation is excellent, and compatibility with the physical properties of the coating film, which can not be achieved by the conventional method, can be achieved .
However, the inventors of the present invention have observed the image obtained by the above method, and it has been found that deactivation of the photoacid generator remaining in the system after image formation remains as a new problem depending on the application. That is, in an environment of use exposed to light such as sunlight, an acid is generated from the photoacid generator remaining in the coating film, causing unintended coloring (coloring) reaction.
Therefore, the inventors of the present invention paid attention to the ultraviolet ray component of sunlight reaching the ground with respect to the image stability after forming the image pattern, and solved the problem by examining the influence of the ultraviolet ray component on the image stability. That is, the inventors of the present invention have made extensive studies on the dispersion band of the exposure wavelength in the present method in order to reduce the influence of the ultraviolet ray component of the sunlight on the image stability. As a result, Is set to less than 280 nm, and the exposure wavelength of the exposure step B, which is subjected to photo-curing and image fixation, is set to a wavelength band of 280 nm or more, the image stability can be remarkably improved and the present invention has been completed .
In general, the ultraviolet rays are divided into ultraviolet rays having a wavelength of 380 to 200 nm, ultraviolet rays having a wavelength of 200 to 10 nm, and extreme ultraviolet rays having a wavelength of 10 to 1 nm. Sunlight contains UVA (400-315 nm), UVB (315-280 nm), and UVC (<280 nm) near-UV. Of these, only UVA and UVB pass through the ozone layer and reach the surface, and UVC is not absorbed by the substance and can not pass through the atmosphere.
The present invention is characterized in that a photoacid generator which is active only at this wavelength is used for forming an image pattern based on the characteristic of UVC in the sunlight, that is, the phenomenon that light of less than 280 nm does not reach the surface, As a result, the image stability after the image pattern formation can be remarkably improved.
That is, according to one embodiment of the image forming method of the present invention, the coating film of the photosensitive composition containing the photoacid generator and the electron donating dye is partially exposed with light having a wavelength band of less than 280 nm to form an image pattern And an exposure step B for performing front exposure with light having a wavelength band of 280 nm or more to fix an image pattern.
Here, the photosensitive composition used in the image forming method of the present invention contains a photoacid generator that generates an acid by light having a wavelength band of less than 280 nm, an electron donating dye, a photopolymerization initiator, and an ethylenically unsaturated group- .
It is also preferable that the photopolymerization initiator is capable of photosensitizing in the wavelength band in which the photoacid generator does not generate acid, that is, in the wavelength band of 280 nm or more.
According to the present invention, since the image pattern is formed at a wavelength of less than 280 nm, which is the wavelength band of UVC, which is the ultraviolet ray of sunlight not reaching the ground, the image pattern is formed by the ultraviolet rays included in the sunlight, The effect unique to the present invention is expressed. As a result, not only can it be used for conventional heat-sensitive recording and proof materials, but also can be widely used for marking applications and light-shielding applications in, for example, electronic substrates and displays related to strict use environments. Further, in photolithography, It is possible to form an image on an aluminum wiring which can not be coped with due to the problem of a light receiving element and a displacement sensor.
Hereinafter, the image forming method of the present invention will be described in detail.
The image forming method of the present invention is a method for forming an image on a coating film of a photosensitive composition containing a photoacid generator and an electron donating dye which generates an acid by light in a wavelength band of less than 280 nm by exposure a plurality of times in different wavelength bands, (Hereinafter also referred to as " image contrast ") including an uncolored portion is formed and fixed.
In the exposure step A, the photoacid generator in the exposed area generates an acid by partially exposing it to light in a wavelength band of less than 280 nm, and the acid reacts with the electron donating dye to develop a colored part. Further, in the exposure step B, the surface of the photoacid generator does not generate acid, and the entire surface is exposed with light having a wavelength band of 280 nm or more, thereby fixing the colored portion and the uncolored portion by photo- do. If the exposure wavelengths are separated from each other in the exposure processes A and B, the order and the number of the processes are not particularly limited.
In order to form an image on the coating film of the photosensitive composition, it is necessary that the electron-accepting dye and the photoacid generator are contained in the photosensitive composition. The photoacid generator is used as an electron-accepting compound exhibiting an effect as a developing agent on an electron donating dye which is a coloring agent in the photosensitive composition. Specifically, the reaction occurs between the acid generated from the photoacid generator and the electron-donating dye upon exposure, that is, the electron-donating dye and the acid are brought into contact with each other in the coating.
On the other hand, in order to reduce the influence of the ultraviolet ray component of sunlight on the image stability, the exposure wavelength is separated at 280 nm, and the image contrast including the colored portion and the uncolored portion is formed by exposure (exposure step A) at less than 280 nm have. Therefore, the electron-donating dye constituting the photosensitive composition of the present invention and the photoacid generator use a compound which develops color at less than 280 nm.
As such electron donating dyes, at least one kind of electron donating dye can be suitably selected from known compounds according to a desired color tone. (P-dimethylaminophenyl) -6-dimethylaminopyrimidine, 3,3-bis (p-dimethylaminophenyl) phthalide, 3- Triarylmethane compounds such as 3- (1,2-dimethylindol-3-yl) phthalide, 4,4'-bis-dimethylaminobenzhydrylbenzyl ether, N-halophenyl leucoamine, N-2 , 4,5-trichlorophenylleucoamine, diphenylmethane compounds such as 7-dimethylamino-3-chlorofluorane, 7-dimethylamino-3-chloro-2-methylfluoran, Fluorine-based compounds such as 3-methyl-6- (N-ethyl-Np-tolylamino) fluorane, thiazine-based compounds such as benzoylated chomomethylene blue and p-nitrobenzyllachomethylene blue, Spiro-based compounds such as dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-propyl-spiro-dinaphthopyran and 3-propyl-spiro-dibenzopyran. These electron donating dyes may be used alone or in combination of two or more. Further, an electron donating dye may be encapsulated and used as a known means for enhancing image stability. These electron-donating dyes may also contain additives such as photo-oxidizing agents such as carbon tetrabromide for improving the coloring property and quinolinol for preventing the coloring of the pigments.
As the photoacid generator, any known photoacid generator that generates an acid by exposure in a wavelength band of less than 280 nm and does not generate an acid in exposure in a wavelength band of 280 nm or more can be used.
Generally, since the intensity (sensitivity) of the photosensitive wavelength band depends on the concentration thereof, even if the end of the photosensitive wavelength band of the photoacid generator occupies 280 nm, by limiting the compounding amount thereof, Or more can be used as a photoacid generator that does not generate an acid.
Examples of such photoacid generators include onium salts such as sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts and ferrocene, sulfone compounds, sulfonic acid esters, sulfonimides, disulfonyldiazo Methane compounds, and disulfonylmethane compounds. These may be used alone or in combination of two or more.
Specific examples thereof include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluorobutanesulfonate, tris (4-methylphenyl) sulfonium trifluoromethanesulfonate, tris (4-methylphenyl) sulfonium hexafluoro Methylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate, bis (4-t-butylphenyl) iodonium hexa Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane and the like can be given .
Among the above-mentioned photoacid generators, from the viewpoint of image stability, the photosensitive wavelength band such as bis (cyclohexylsulfonyl) diazomethane and bis (t-butylsulfonyl) diazomethane has a shorter wavelength than 280 nm, It is more preferable that almost no photosensitivity is observed.
In the case of using a photoacid generator in which the above-mentioned compounding amount is limited, in the case where sufficient coloring is not possible, a new acid is generated by an acid generated from a photoacid generator, An acid proliferating agent capable of proliferating an acid can be added.
Such an acid growth agent is not particularly limited as long as it generates an acid by the action of an acid generated from the photoacid generator and has an acid strength sufficient for the acid to act as a developing agent for the electron donative dye. Examples thereof include phenol derivatives, carboxylic acid derivatives, sulfonic acid esters, and phosphoric acid esters having a protecting group such as a t-butyl group and an acetal group dissociable in acid.
Since the exposure wavelength in the exposure process A is less than 280 nm, known light sources such as low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, and excimer lasers can be used as the light sources.
Among these, a light source in which the exposure bands of the exposure process A and the exposure process B do not overlap is preferable from the viewpoints of contrast formation and image stability thereafter. For example, Ar 2 excimer laser (126 nm), Kr 2 excimer laser ), An F 2 excimer laser (157 nm), a Xe 2 excimer laser (172 nm), an ArCl excimer laser (175 nm), an ArF excimer laser (193 nm), a KrBr excimer laser ), A KrF excimer laser (248 nm), or the like.
Among these, ArF excimer laser (193 nm), KrBr excimer laser (207 nm), KrCl excimer laser (223 nm) and KrF excimer laser (248 nm) are more preferable.
At this time, the photopolymerization initiator constituting the photosensitive composition to be described later is sensitized to generate radicals to initiate photopolymerization of the ethylenically unsaturated group-containing compound. In this case, the fixation is performed at the same time as the formation of the colored portion.
In the case where a fixed fixing is performed simultaneously with the formation of the colored portion in the exposure step A, it is preferable that the light polymerization is not given preference in order not to make the color development insufficient. In this respect, since the photoacid generator does not undergo oxygen inhibition unlike the photopolymerization initiator, there is an advantage that the acid can be stably supplied even in the exposure in the oxygen atmosphere. Therefore, the contact exposure method such as the known vacuum contact method, A non-contact exposure method such as exposure, and a direct imaging method. In particular, in order to effectively utilize the wavelength band of less than 280 nm, a direct imaging method using a laser which does not require a photomask is more preferable. On the other hand, in the step of fixing the image contrast, which will be described later, it is preferable that the entire coating film is photopolymerized while suppressing the color reaction even in the case where the photo-crosslinking degree is lowered and the physical properties of the cured coating film are not lowered.
Further, in the exposure step A for forming such an image contrast, Post Exposure Bake (PEB) may be performed to diffuse the acid generated by the exposure in the coating film. As the post-exposure baking treatment (PEB), known methods and conditions can be applied.
Next, in the exposure step B, in order to fix the image contrast formed on the coated film of the photosensitive composition as described above, exposure is performed in a wavelength band different from that of the exposure step A, that is, in a wavelength band of 280 nm or more, The entire coating is cured by crosslinking.
In the present invention, since the color development reaction of the electron donating dye is an equilibrium reaction with the acid generated by photo-sensitizing the photoacid generator, it is necessary to cut off the supply source of the acid in order to secure excellent image stability, It is preferable to suppress the contact between the dye and the acid in the ink.
It is possible to fix the image contrast by advancing only the photopolymerization of the whole coating film by blocking the generation of an acid related to color development by exposing the photopolymerization initiator in a wavelength band of 280 nm or more without exposure to the photoacid generator. In order to effect such fixation effectively, it is particularly effective to select a photopolymerization initiator constituting the photosensitive composition. That is, it is preferable to use a photopolymerization initiator which sensitizes the photopolymerization initiator in a wavelength band of 280 nm or longer that does not overlap with the photosensitive wavelength band of the photoacid generator, that is, does not generate a photoacid generator acid.
As the photopolymerization initiator, as described above, it is essential that the photoacid generator has a photosensitive band in a wavelength band where no acid is generated. Therefore, the selection depends largely on the combination with the photo acid generator. That is, only a photosensitive wavelength band in which the wavelength band in which the photopolymerization initiator is sensitized and the wavelength band in which the photoacid generator generates the acid do not overlap, or a wavelength band in which the photopolymerization initiator is sensitized and a wavelength band Is not particularly limited as long as the photosensitive wavelength band of only the photopolymerization initiator exists in addition to the overlapping wavelength bands. In the present invention, a photoacid generator that generates an acid by exposure in a wavelength band of less than 280 nm is used, and therefore, a photoacid generator capable of generating a radical for exposure in a wavelength band of 280 nm or more can be used.
Examples of such photopolymerization initiators include known radical photopolymerization initiators such as benzophenone, acetophenone, aminoacetophenone, benzoin ether, benzyl ketal, acylphosphine oxide, oxime ether, oxime ester and titanocene. It is particularly preferable to use a photopolymerization initiator having a photosensitivity exhibiting absorption and photoactivity in a wavelength band of 280 nm or more that does not exhibit photo activity and a high photosensitivity in such a wavelength band. These photopolymerization initiators may be used alone or in combination of two or more. These photopolymerization initiators may be used alone or in combination with two or more kinds of known photopolymerization promoters such as benzoic acid type and tertiary amine type.
Further, as an openable clock capable of arbitrarily setting the photosensitive wavelength band, for example, a known two-molecule complex watch having a combination of a coloring matter such as coumarin, cyanine and squarium with a radical generator may be used. For example, a combination of an imidazole dimer as a radical generator and an acridine dye or a triazine dye as a dye, a combination of N-phenylglycine as a radical generator and a ketokmarine as a dye, iodine as a radical generator A combination of a trivalent compound as a radical generator and an aromatic ketone derivative as a dye are known. Alkyl borates of dyes such as cyanine, rhodamine, and saprinin are also known as effective visible light initiators, and these known photopolymerization initiator systems can also be used.
In the exposure step B for fixing the image contrast as described above, only the ethylenic unsaturated group-containing compound constituting the photosensitive composition and the photopolymerization initiator are allowed to react with each other, thereby suppressing the coloring (sensitization of the photoacid generator) . As a result, not only the curing of the uncolored portion but also the re-curing of the colored portion exposed in the exposure step A progresses, so that it is possible to fix an image excellent in image stability.
As described above, the wavelength band used in the exposure step B is preferably a wavelength band in which the photoacid generator in the photosensitive composition does not generate an acid. Further, in order to prevent fogging of the uncolored portion in the present step, it is preferable to separate the wavelength band of the exposure as far as possible from the wavelength band where the photoacid generator generates acid. Since the photoacid generator used in the present invention generates an acid in the UVC region, that is, in the wavelength band of less than 280 nm, it may be a single line or a mixed line in the present step on the longer wavelength side.
The light source of the exposure process B can be suitably selected and used as long as it can oscillate the active line of the wavelength band according to the purpose of image fixation by photo-crosslinking. For example, there may be used a known lamp such as an argon ion laser, a helium neon laser, a helium cadmium laser, a dye laser, a semiconductor laser, a YAG laser, etc. in addition to known low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, xenon lamps or metal halide lamps Lasers.
With respect to the separation method of the wavelength band in the exposure step B, it is also possible to directly separate them by various kinds of lasers. Furthermore, by exposing the film to a film which cuts light having a wavelength of 300 nm or less or a film such as PET or PEN or a glass, It is possible to easily separate the wavelength band even with an expansive exposure source.
In the image forming method of the present invention as described above, the photosensitive composition to be used should be one capable of photosensitive and photo-crosslinking. For example, it preferably contains the above-mentioned photopolymerization initiator and an ethylenically unsaturated group-containing compound.
Examples of the ethylenically unsaturated group-containing compound include diacrylates of glycols such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol and propylene glycol; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol, and tris-hydroxyethylisocyanurate, or polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts thereof; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; And melamine acrylate, and / or the respective methacrylates corresponding to the acrylate.
In addition, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as cresol novolak type epoxy resin with acrylic acid, a hydroxyl acrylate resin such as pentaerythritol triacrylate, etc., and an isophorone diisocyanate And epoxy urethane acrylate compounds obtained by reacting a half urethane compound of a diisocyanate such as an epoxy urethane acrylate compound. Such an epoxy acrylate resin can improve photo-curability without deteriorating the touch-dry composition. These ethylenically unsaturated group-containing compounds may be used alone or in combination of two or more thereof, depending on the intended use.
Further, depending on the structure of the compound used in the photosensitive composition in the exposure step A, the acid generating efficiency may be lowered by exposure. Thereby, for example, a compound having an aromatic group essentially shows a large absorption in any one of the regions of less than 280 nm, so that the use of a composition composed of a non-aromatic base resin improves the transparency to a short- And the sensitivity can be improved.
An organic solvent may be added to the photosensitive composition for use in the present invention for the purpose of adjusting viscosity, if necessary. Examples of such an organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether And the like; Esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate and propylene carbonate; Aliphatic hydrocarbons such as octane and decane; And petroleum solvents such as petroleum ether, petroleum naphtha and solvent naphtha. These organic solvents may be used alone or in combination of two or more.
In addition to the above components, various additives such as inorganic fillers such as silica, alumina, talc, calcium carbonate and barium sulfate, fillers such as acrylic fillers and organic fillers such as urethane beads, And additives for paints such as paints and the like.
Further, in the image forming method of the present invention, the coating film to be an image to be formed is not particularly limited as long as it includes a photosensitive composition. For example, the photosensitive composition is applied by a screen printing method, a curtain coating method, a spray coating method, Spin coating, or the like, followed by heating and drying at a temperature of, for example, 60 to 80 ° C for 15 to 60 minutes, or those obtained by using a dry film containing a photosensitive composition.
<Examples>
Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but it goes without saying that the present invention is not limited to the following examples. In the following description, "parts" and "%" are based on the entire mass unless otherwise specified.
(Mass parts) shown in Table 1, preliminarily mixed with a stirrer, and kneaded with a three-roll mill to obtain Compositions 1 to 7.
* 1: Unidick R-100 (solid content 65%) (manufactured by DIC)
* 2: NEOMER DA-600 (manufactured by Sanyo Chemical Industries, Ltd.)
* 3: IRGACURE 907 (manufactured by Ciba Specialty Chemicals)
* 4: CGI-325 (manufactured by Ciba Specialty Chemicals)
* 5: Irgacure 369 (manufactured by Ciba Specialty Chemicals)
* 6: Adeka Optomer SP-066 (manufactured by Adeka)
* 7: TS-01 (manufactured by Sanwa Chemical Co., Ltd.)
* 8: WPAG-170 (manufactured by Wako Pure Chemical Industries, Ltd.)
* 9: Adeka Optomer SP-152 (solid content 50%) (manufactured by Adeka Co., Ltd.)
* 10: KS-66 (manufactured by Shin-Etsu Silicone Co., Ltd.)
* 11: S-205 (manufactured by Yamada Chemical Industry Co., Ltd.)
≪ Preparation of test substrate &
The photosensitive compositions of Composition Examples 1 to 7 in Table 1 were each printed on a buffed copper solid substrate by screen printing and dried at 80 DEG C for 30 minutes to form a colorless transparent coating film on the substrate.
An image was formed on the substrate on which the coating film was formed in the manner described below under the following conditions (Examples 1 to 5 and Comparative Examples 1 to 5) to evaluate the coating film characteristics such as image contrast, tack, solvent resistance and image stability . The evaluation results are shown in Table 2.
<Test Conditions>
[Exposure Step A (Image Contrast Forming Step)]
(1) Exposure condition 1
As the exposure process A, the test substrate was patterned at 1000 mJ / cm 2 using a KrF excimer laser oscillating at 248 nm as a light source. Thereafter, PEB treatment (post exposure baking treatment) was performed at 80 캜 for 10 minutes.
(2) Exposure condition 2
As a light exposure step A, a light source was irradiated with light of 1000 mJ / cm 2 in a total light wavelength band through a negative mask having a predetermined pattern formed on the test substrate using a metal halide lamp. Thereafter, PEB treatment (post exposure baking treatment) was performed at 80 캜 for 10 minutes.
[Exposure Step B (Image Contrast Fixing Step)]
(3) Exposure condition 3
After the exposure in the exposure step A as the exposure step B, the entire coating film was irradiated with light at 1000 mJ / cm 2 by using a metal halide lamp over a PET film to cut a wavelength of 300 nm or less, (Image forming substrate) having a coating film formed thereon was obtained.
(4) Exposure condition 4
After the exposure in the exposure step A was completed as the exposure step B, the entire coating film was irradiated with light at 1000 mJ / cm 2 using a direct exposure machine for emitting a wavelength of 405 nm, and a substrate having an image formed thereon ).
<Evaluation of Coating Film Properties>
(1) Image contrast
Image contrast was visually confirmed on the image-formed substrates obtained in Examples 1 to 5 and Comparative Examples 1 to 5. The evaluation criteria are as follows.
In color development ... Appearance of color after exposure
No color development ... No color change before and after exposure
(2) Tacticity
The cured state of the coating film was evaluated on the image-formed substrates obtained in Examples 1 to 5 and Comparative Examples 1 to 5 by the tackiness (retention) after each exposure step. The evaluation criteria are as follows.
○ ... No finger marks remain on the surface of the film during touching
× ... Finger marks remain on the surface of the film during touching
(3) Solvent resistance
The image forming substrate obtained in Examples 1 to 5 and Comparative Examples 1 to 5 was rubbed with acetone 50 times for each of the colored portion and the uncolored portion to visually confirm dissolution and exfoliation of the coating film. And the curability of the coating film was confirmed. The evaluation criteria are as follows.
○ ... Dissolution and no peeling of coating film after rubbing test
× ... Dissolution and peeling of coating film after rubbing test
(4) Image Stability
The image-forming substrates obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were allowed to stand under UV-cut fluorescent lamps for one month, and fogging of uncolored portions was visually confirmed to evaluate image stability (light resistance). The evaluation criteria are as follows.
○ ... The blur of the uncolored portion after being left is not shown, and the image contrast is maintained
△ ... The blur of the uncolored portion after being left is shown, but the determination of the image contrast is possible
× ... The blur of the uncolored portion after being left standing can be seen, and the state in which the image contrast can not be determined
As is apparent from the evaluation results shown in Table 2, in Examples 1 to 5 using the compositions 1 to 5 corresponding to the image forming method of the present invention, it was found that image contrast was able to be formed, .
Further, in Comparative Examples 1 to 3 using the conventional image forming method, image contrast can be formed, but since the uncolored portion is not cured sufficiently, image stability is poor and image contrast can not be maintained. In the comparative example 4 using the image forming method proposed by the present inventors, the image stability tended to be improved by using the composition 7 corresponding to such a forming method, but it was found that it was insufficient. Further, in Comparative Example 5 using the image forming method of the present invention, since the composition corresponding to the image forming method of the present invention was not used, image contrast could not be formed.
Claims (7)
And an exposure step (B) for performing front exposure with light having a wavelength band of 280 nm or more to fix the image pattern.
Wherein the photoacid generator does not generate an acid with light having a wavelength band of 280 nm or more.
Wherein the photoacid generator is selected from the group consisting of triphenylsulfonium trifluoromethanesulfonate, tris (4-methylphenyl) sulfonium trifluoromethanesulfonate, tris (4-methylphenyl) sulfonium hexafluorophosphate, diphenyl- Diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate, bis (cyclohexylsulfonyl) diazomethane and bis (t-butylsulfonyl) diazomethane Or a combination thereof.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010042259 | 2010-02-26 | ||
| JPJP-P-2010-042259 | 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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| KR20120120334A KR20120120334A (en) | 2012-11-01 |
| KR101844087B1 true KR101844087B1 (en) | 2018-03-30 |
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| JP (1) | JP5916600B2 (en) |
| KR (1) | KR101844087B1 (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 |
| CN106715477B (en) * | 2014-09-29 | 2018-10-12 | 三键有限公司 | 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 |
| CN114341731A (en) * | 2019-08-27 | 2022-04-12 | 富士胶片株式会社 | Method for producing cured film, photocurable resin composition, method for producing laminate, and method for producing semiconductor device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| JP2006096027A (en) * | 2004-07-27 | 2006-04-13 | Fuji Photo Film Co Ltd | Lithographic printing original plate and the lithographic printing method |
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| JPS5113569B1 (en) * | 1970-11-05 | 1976-04-30 | ||
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| 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 |
| US7402374B2 (en) * | 2004-05-31 | 2008-07-22 | Fujifilm Corporation | Method for colored image formation |
| JP2006015740A (en) * | 2004-05-31 | 2006-01-19 | Fuji Photo Film Co Ltd | Color image forming method |
| JP4753237B2 (en) * | 2005-07-25 | 2011-08-24 | Ａｚエレクトロニックマテリアルズ株式会社 | Photosensitive resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2006096027A (en) * | 2004-07-27 | 2006-04-13 | Fuji Photo Film Co Ltd | Lithographic printing original plate and the lithographic 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 |
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| Publication number | Publication date |
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| JPWO2011105011A1 (en) | 2013-06-17 |
| WO2011105011A1 (en) | 2011-09-01 |
| KR20120120334A (en) | 2012-11-01 |
| CN102770805A (en) | 2012-11-07 |
| CN102770805B (en) | 2016-10-12 |
| JP5916600B2 (en) | 2016-05-11 |
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