TW201106109A - Image forming method and photocurable composition - Google Patents

Abstract

Disclosed is an image forming method which enables the achievement of high contrast, excellent image stability and good curing properties. Also disclosed is a photocurable composition which is used for the image forming method. In the image forming method, a coating film of a photocurable composition that contains a photoacid generator and an electron-donating dye is formed on a substrate, and an image contrast, which is composed of a colored portion and an uncolored portion, is formed and fixed by exposing the coating film a plurality of times using light of different wavelength ranges.

Description

201106109 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an image forming method and a photocurable composition. [Prior Art] The image forming method of the general photolithography method is suitable for mass production because of its excellent micro-machining property and excellent workability, and is widely used in the printing industry or the electronics industry. In recent years, for example, in the field of MEMS (Micro Electro Mechanical Systems), such as an encoder or a displacement sensor, which is formed by using an image having a different reflectance on a substrate and having the reflected light from the light-emitting element read by a light-receiving element or the like, progress. In the image forming method, the wet developing method using a dilute alkali aqueous solution is mainly used for the production of a printed wiring board, the formation of a solder resist, and the manufacture of a semiconductor-related member, from the viewpoint of environmental load reduction. However, for example, in the field of MEMS, problems such as insulation deterioration or corrosion caused by an aqueous alkali solution are caused by patterning on a wafer or an aluminum ruthenium wiring. Therefore, it is necessary to use an organic solvent-based developer. Further, as a technique for forming a contrast without using a developing solution as described above, a dry image forming method using photohardening and photothermal photothermal photography is discussed. This method is different from the case of wet image formation, and there is no problem of waste, so it is expected from the viewpoint of environmental load reduction. The dry image forming method is, for example, a chromogenic heat sensitive recording method using a color development of a dye, and is generally classified into a leuco form thermosensitive recording method excellent in color developability and a diazo type thermal recording method excellent in image stability. -5- 201106109 2 major categories. However, in such methods, there is a problem that it is difficult to achieve both high contrast (high color development) and quality stability (image stability) after image formation. For this, in the leuco type thermal recording method, for example, an electron is disclosed. The method of separating and arranging the accepting compound and the electron-donating dye in the microcapsules containing the photocurable composition to improve the image stability (for example, refer to Patent Document 1). However, even if the photocurable composition in the microcapsules is sufficiently cured, the color development of the cured portion cannot be sufficiently suppressed, and the uncolored portion is slightly colored and the contrast is deteriorated. Further, a method of laminating a layer of a vinyl monomer having an acidic group and a layer of a photopolymerizable composition containing a photopolymerization initiator and a layer formed of a separator and an electron-donating dye is disclosed (for example, Patent Document 2) For reference). At this time, although there is no coloring of the uncolored portion (photographic fog), there is a problem that the overall color development is slightly reduced. In this regard, attempts have been made to achieve both photographic fog and low chroma in the uncolored portion, and it is proposed to encapsulate one of the two components in the microcapsule, to make the other component a curable compound of the photocurable composition, or to make the other A component in which the component is disposed outside the microcapsule together with the photocurable composition (for example, refer to Patent Document 3). Further, it is proposed to provide a method comprising a microcapsule and an electron-accepting compound containing an electron-donating dye, and a layer of a photocurable composition containing a polymerizable vinyl monomer and a photopolymerization initiator (for example, patent document) 4 for reference). Although there are many suggestions for improving the stability of these images, on the other hand, there are problems such as lower chromaticity. Moreover, in such a method, since -6-201106109, the color developing portion is not hardened, and there is a problem that the physical properties of the hardened material cannot be obtained. In this way, in the image forming method of photothermography, it can be used for the periphery of a substrate such as an electronic component or a technology such as a MEMS sensor that is used in an environment with severe environmental conditions, and is currently limited to the use of thermal recording paper or fireproof material. . Therefore, it is expected to expand the use of the photocurable composition which can obtain a high-viscosity image and which has a high image stability after the image is formed. 先前 [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. OBJECTS [Summary of the Invention] 〇 [Problems to be Solved by the Invention] The present invention has been made in view of the above-mentioned problems of the prior art, and aims to provide excellent image stability in addition to images capable of forming contrasts and A photocurable composition having a good cured property. [Means for Solving the Problem] According to an aspect of the present invention, a coating film comprising a photocurable composition containing a photoacid generator and an electron donating dye is formed on a substrate by using the coating film in different wavelength regions. An image forming method in which a plurality of exposures are performed to form and fix an image formed by a colored portion and a color portion of a non-201106109. By this configuration, in addition to the image which can be formed in a high contrast, excellent image stability and good hardenability can be obtained in the formed image. Moreover, according to an aspect of the present invention, there is provided a step of forming a coating film containing a photocurable composition of a photoacid generator and an electron donating dye on a substrate, and irradiating the first region in a specific region of the coating film. After the active energy ray of the wavelength region, a first exposure step of contrasting the image formed by the colored portion and the uncolored portion is formed, and the first coating step is irradiated with a wavelength region different from the first wavelength region and the uncolored portion is not colored. After the active energy ray of the two-wavelength region, the image forming method of the second exposure step of fixing the image contrast is performed. According to this configuration, the coating film of the photocurable composition can be exposed to light at a wavelength different from the exposure wavelength for color development, and the image can be fixed by exposure, and the image can be formed in addition to a high contrast image. Excellent image stability and good hardenability are obtained in the image. Further, according to an aspect of the present invention, a coating film containing a photoacid generator, an electron donating dye, and a photocurable composition of a photocurable component is provided on a substrate, and the photoacid generator is irradiated thereon. After the first active energy ray in the photosensitive wavelength region is in a specific region, an acid is generated, and after the electron-donating dye is colored, a colored portion is formed on the coating film, and the coating film is irradiated substantially outside the photosensitive wavelength region of the photo-acid generator. After the second active energy ray of the photosensitive wavelength region of the photocurable component, the uncolored portion other than the colored portion of the coating film is not colored, and the coating film is cured to form an image contrasting image forming method. According to this configuration, the coating film of the photocurable composition can be exposed to light at a wavelength different from the exposure wavelength of the hair -8 - 201106109 color, and the image can be fixedly exposed, in addition to forming a contrasting image. Excellent image stability and good hardenability can be obtained in the formed image. In the image forming method according to an aspect of the present invention, it is preferred that the specific region is hardened by irradiation with the first active energy line. By hardening in this way, better image stability can be obtained. Further, in the image forming method according to an aspect of the present invention, it is preferable to perform heat treatment after the irradiation of the first active 能量 energy line. By such heat treatment, the acid generated by the acid generator is diffused in the coating film, the color of the electron-donating dye can be promoted, and a higher contrast image can be obtained. Further, in the image forming method according to an aspect of the present invention, the photocurable component is an ester-based photopolymerization which is represented by the following general formula (I) and has a photosensitive wavelength region outside the photosensitive wavelength region of the photoacid generator. The initiator is preferably an ethylenically unsaturated group-containing compound. (I) —C=N-0—C—R2 〇R′ 0 (wherein R 1 is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a phenyl group, and R 2 is an alkyl group having 1 to 7 carbon atoms; Or phenyl) By using such a photocurable component, it has excellent photosensitivity, and thus excellent image stability and good cured physical properties can be obtained. Further, in the image forming method according to one aspect of the invention, the photocurable component is represented by the following formula (II), or the following formula (III) or the following - The structure represented by the general formula (IV) is Jiayi 201106109

(wherein R3 and R4 each independently represent an alkyl group having 1 to 12 carbon atoms; and R5, R6, R7 and R8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and Μ is Ο, 8 or]^11 η is an integer of 〇~5, R9, R1<J is an alkyl group having 1 to 12 carbon atoms, and R11 is a hydrogen atom and an alkyl group having 1 to 20 carbon atoms. By using an oxime ester group represented by the formula (11) The photopolymerization initiator can be exposed at a wavelength of 405 nm widely used for visible light sources. Further, by using an oxime ester photopolymerization initiator having a structure represented by the general formulas (III) and (IV), even if it is added in a small amount, it has a high sensitivity capable of sufficient photohardening, so that formation of a photopolymerization can be suppressed. An uncolored portion having a high transparency which is colored by the initiator. According to an aspect of the present invention, a photo-cured image formed by such an image forming method can be provided. By this image forming method, it is possible to obtain a photohardenable image which is highly contiguous and has excellent image stability and good hardenability. According to an aspect of the present invention, an oxime-based light containing a photoacid generator, an electron-donating dye, and a photosensitive wavelength region outside the photosensitive wavelength region of the photo-acid generator represented by the following general formula (I) is provided. A photocurable composition characterized by a polymerization initiator and an ethylenically unsaturated group-containing compound 〇Ο C=N-0-C-R2 (I) R1 0 (wherein R1 is a hydrogen atom and a carbon number of 1) An alkyl group of ～7 or a phenyl group, and R2 is an alkyl group having 1 to 7 carbon atoms or a phenyl group. The coating film of the photocurable composition can be different from the exposure wavelength for color development. The wavelength is used to suppress the color development and the image is fixed for exposure. In addition to forming a contrasting image, excellent image stability and good hardening properties can be obtained in the formed image. In the photocurable composition of one aspect of the invention, the oxime ester photopolymerization initiator preferably has a photosensitive wavelength region in the photosensitive wavelength region of the photoacid generator. According to this configuration, it is possible to perform hardening in the coloring field when performing exposure for color development. Further, in the photocurable composition of one aspect of the present invention, the 'ester-based photopolymerization initiator is represented by the following formula (II) or the following general formula (III) or the following general formula (IV) The table is not constructed as good. -11 - (II)201106109

C O

hT〇, c'CH;j II II

, H

M

o » . C-C-R3 II N-O-C II 0

(III)

0, c/r10 I

(IV) (wherein R3 and R4 each independently represent an alkyl group having 1 to 12 carbon atoms'. R, R, R7 and R8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M is 0 and η is An integer of 0 to 5, R9 and R1Q are an alkyl group having 1 to 12 carbon atoms, and R11 is a hydrogen atom and an alkyl group having 1 to 20 carbon atoms. By using an oxime ester-based photopolymerization initiator represented by the formula (II) 'Exposure at a wavelength of 40 5 nm widely used in visible light sources can fully fix the image. Further, by using an oxime ester-based photopolymerization initiator having a structure represented by the general formulas (III) and (IV), even if it is added in a small amount, it has a high sensitivity capable of sufficient photocuring, so that the photopolymerization initiator can be inhibited. The resulting coloring 'utilizes the transparency of the resin. Further, according to an aspect of the present invention, a coating film for forming a photocurable composition is provided, and the first active energy ray of -12-201106109 is irradiated by a photosensitive acid region of the photoacid generator in a specific region After the acid is generated and the electron-donating dye is colored, a colored portion is formed on the coating film, and the coating film is irradiated with the second activity in the photosensitive wavelength region which is outside the photosensitive wavelength region of the photo-acid generating agent and is a photocurable component. The energy ray does not cause the uncolored portion other than the colored portion of the coating film to be substantially colored, and the cured film is cured. In this hardened material, good hardenability can be obtained in addition to good contrast. Further, the cured product obtained by using the carboxyl-based photopolymerization initiator represented by the formula (II) can be exposed at a wavelength of 405 nm which is widely used for a visible light source, and can easily obtain good cured physical properties. Further, the cured product obtained by using an oxime ester-based photopolymerization initiator having a structure represented by the general formulas (III) and (IV) has a high sensitivity capable of sufficient photocuring even in a small amount, and thus can suppress the collocation. The uncolored portion of the high transparency which is colored by the photopolymerization initiator. [Effect of the Invention] The photocurable composition and the image forming method according to an aspect of the present invention. In addition to the formation of contrasting images, excellent image stability and good hardenability are obtained in the formed image. [Best Mode for Carrying Out the Invention] In order to solve the above problems, the inventors of the present invention have found that a coating film containing a photocurable composition of a photoacid generator and an electron donating dye is formed on a substrate. By subjecting the coating film to multiple exposures in different wavelength regions, the image formed by the colored portion and the uncolored portion is formed to be -13-201106109 and fixed, and high contrast images, excellent image stability, and good hardened physical properties can be obtained. That is, a first exposure step for forming a contrast and a second exposure step for fixing the image by photohardening are provided on a coating film containing a photocurable composition of a photoacid generator and an electron donating dye. And exposure is performed at different wavelengths. In this way, after performing the first-stage exposure at the wavelength at which the photoacid generator generates acid to form a desired color pattern, the second-stage exposure is performed at a wavelength at which the photo-acid generator does not generate an acid, and in the second stage. In the exposure, the light can be hardened without coloring. Next, it was found that a photoacid generator, an electron-donating dye, and an oxime-based photopolymerization initiator having a photosensitive wavelength region outside the photosensitive wavelength region of the photo-acid generator represented by the following general formula (I), The photocurable composition of the ethylenically unsaturated group compound is suitable for the two-stage exposure step as described above, and the present invention has been completed. —C=N—0—C—R 2 (丨) R1 0 (wherein R 1 is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a phenyl group, and R 2 is an alkyl group having 1 to 7 carbon atoms, or benzene; Base) Hereinafter, the image forming method of the present embodiment will be described in detail. First, a coating film containing a photocurable composition of a photoacid generator and an electron donating dye is formed on a substrate. In this case, the substrate is not particularly limited, and a printed wiring board on which a circuit is formed, a wafer such as Si, GaAs, ferrite, or glass can be used. In addition, since the image forming method of the present embodiment is dry development, a substrate on which an A1 wiring is formed or the like, and a substrate which is deteriorated and corroded by the alkali aqueous solution 201106109 can be used. Next, the photocurable composition containing the photoacid generator and the electron donating dye is subjected to a conventional method such as a screen printing method, a shower coating method, a spray coating method, a roll coating method, a spin coating method, or the like. The coating is heated at a temperature of about 60 to 80 ° C for about 1 to 60 minutes to form a coating film. Further, the details of the photocurable composition will be described later. Then, by subjecting the formed coating film to a plurality of exposures in different wavelength regions, the image formed by the colored portion and the uncolored portion is formed and fixed in contrast. At this time, first, on the formed coating film, the active energy ray of the photosensitive wavelength region of the photo-acid generator is irradiated onto the coating film formed on the substrate or the like to form an image contrast between the colored portion and the uncolored portion. First exposure step). In this step, the photoacid generator and the electron donating dye are reacted. That is, in the first exposure step, the photoacid generator generates an acid by irradiation with an active energy ray of a photosensitive wavelength region of the photoacid generator. Then, the generated acid is brought into contact with the electron-donating dye in the coating film to generate an equilibrium reaction, and the electron-donating dye is colored to form a coloring portion. The wavelength of the irradiation active energy ray is preferably a photosensitive wavelength region of a photopolymerization initiator contained in the photocurable composition or a photocurable component such as an ethylenically unsaturated group-containing compound. The photoacid generator and the electron donating dye are reacted with a photopolymerization initiator and an ethylenically unsaturated group-containing compound by irradiating the active energy ray of such a wavelength. Next, a radical is generated by, for example, a photopolymerization initiator, and the ethylenically unsaturated group-containing compound is photopolymerized and hardened. As a result, the formation of the colored portion simultaneously performs the first-stage hardening of the colored portion. -15- 201106109 The wavelength of the active energy ray used herein must be the photosensitive wavelength region of the photoacid generator. Specifically, a single-wavelength light such as an i-line of an ultraviolet light region or an active energy ray having a broad-spectrum light distribution (complex-emission spectrum) in an ultraviolet light region, a visible light region, and a near-infrared light region can be used without particular limitation. Next, as the light source, a conventional low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon bulb, a metal halide lamp, or the like can be suitably used. In the first exposure step, when photopolymerization is preferentially performed, the color development degree is insufficient, and the preferential color development degree is lowered in the degree of photo-crosslinking, and the cured physical properties are lowered. In general, a photoacid generator is different from a photopolymerization initiator, and it is known that it is not hindered by oxygen, and has an advantage that it can be supplied with an acid even when exposed to an oxygen atmosphere. Therefore, the exposure method herein can be suitably selected for vacuum adhesion exposure, proximity exposure, direct imaging, and the like depending on the application. After the first exposure step, the acid generated by the photo-acid generator is diffused in the coating film to further promote the color development of the electron-donating dye, and post-exposure heat treatment (Post Exposure Bake: PEB) may be performed. Conventional methods and conditions can be used for the post-exposure heat treatment. In this manner, after the image formed by the colored portion and the uncolored portion is formed, the active energy of the photosensitive wavelength region outside the photosensitive wavelength region of the photoacid generator and being a photocurable component such as a photopolymerization initiator is formed. The wire is subjected to hardening of the uncolored portion and re-hardening of the colored portion (second-stage curing) (second exposure step). In this step, a photopolymerization initiator, a photocurable component containing an ethylenically unsaturated group compound or the like is reacted. That is, in the second exposure step, for example, a radical is generated by a photopolymerization initiator, and photopolymerization of an ethylenically unsaturated group-containing compound of B16-201106109 is carried out to deuterate the coating film to fix the image contrast. In this manner, by suppressing the color development reaction of the electron-donating dye, the entire surface is cured, and the image formed by the colored portion formed in the first exposure step and the uncolored portion are compared to form an image having a specific pattern. The wavelength of the active energy ray used herein may be outside the photosensitive wavelength region of the photoacid generator and may be a photosensitive wavelength 〇 region of the photocurable component such as a photopolymerization initiator. However, in order to prevent photographic fogging in the uncolored portion of the second exposure step, it is preferred to leave the photosensitive wavelength region away from the photoacid generator. The specific wavelength varies depending on the photoacid generator to be selected. In addition to the h line and the g line, for example, laser light emitted from various lasers such as 488 nm, 512 nm, 635 nm, and 670 nm may be used, or such light may be emitted. The second harmonic element is converted to a half wavelength. For example, when the oxime ester photopolymerization initiator described later is a photopolymerization initiator, the oxime ester photopolymerization initiator can utilize an h line (4 〇 5 nm) having an absorption/activity wavelength. Next, the light source can be suitably selected from conventional low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, xenon bulbs, metal halide lamps, lasers, and the like. The method for forming an image is such that a high contrast image can be formed and excellent image stability and good hardening properties can be achieved, and is not limited by such methods. For example, the "first exposure step" and the "second exposure step" can also be used. Reversed. Among the above image forming methods, a photocurable composition which is preferably used will be described in detail below. The photoacid generator of the photocurable composition of the present embodiment is an electron-accepting compound having a color-developing effect on an electron-donating dye, and an acid is generated by irradiation of an energy-active -17-201106109 energy line to cause an electron-donating dye to be described later. Hair color. Such photoacid generators, such as diazonium salts, iron iodide salts, bromine gun salts, chlorinated salts, sulfonium salts, selenium salts, pyranium salts, thiapyridine salts, pyridyl salts, and the like; Tris(trihalomethyl)_s_triazine (eg 2,4,6-tris(trichloromethyl)-s-triazine), 2-[2-(5-methylfuran-2-yl) Vinyl]- 4.6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl]-4.6-bis(trichloromethyl)-3-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, etc. Halogenated compound; 2-nitrobenzyl sulfonate; imidosulfonate; 1-oxo-2-diazonaphthoquinone-4-sulfonate derivative; N-hydroxy quinone imine = Sulfonate; tris(methanesulfonyloxy)benzene derivative; bissulfonyldiazomethane; sulfonylcarbonyl alkane; sulfonylcarbonyldiazomethane; disulfonate; iron propadiene Complex and so on. These photoacid generators may be used singly or in combination of two or more kinds. The amount of the photoacid generator to be mixed is preferably 5 to 40 parts by mass based on 100 parts by mass of the solid content of the composition. When the amount is less than 5 parts by mass, the hair color becomes insufficient. Further, when the amount is more than 40 parts by mass, the image stability after image formation is deteriorated. It is preferably 10 to 30 parts by mass. The electron-donating dye of the photocurable composition of the present embodiment is used for coloring and patterning of an acid generated by the photo-acid generator. Such compounds, for example, 3,3-bis(p-dimethylaminophenyl)-6-methylaminophthalic lactone, 3,3-bis(p-dimethylaminophenyl) a phthalic acid ester such as phthalic acid lactone or 3-(p-dimethylaminophenyl)-3-(l,2-dimethylindol-3-yl)phthalic acid lactone Methane-based compound, 4,4'--18- 201106109 bis-dimethylaminobenzhydrylbenzyl ether, N-halophenyl-leucochrome, N-2,4,5-three Diphenylmethane compound such as chlorophenyl leucomycin, 7-dimethylamino-3-chlorofluorescent yellow precursor, 7-dimethylamino-3-chloro-2-methylfluorescence Fluorescent yellow fluoran compound such as yellow mother, 2-phenylamino-3-methyl-6-(N-ethyl-NP-methylphenylamino)fluorescent yellow matrix, benzamidine A thiazine compound such as leucomethyl blue, p-nitrobenzyl leucomethyl blue, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthoquinone A spiro compound such as 3-propyl-spiro-dinaphthopyran or 3-propyl-spiro-dibenzopyran. These electron-donating dyes may be used alone or in combination of two or more types as necessary. Further, as a conventional means for improving image stability, an electron-donating dye can be encapsulated and used. Further, these dyes may be added with a carbon tetrachloride-like photo oxidizing agent for improving color development or a hydroxyquinoline-like additive for preventing dark color. The amount of the electron-donating dye to be used is preferably 3 to 20 parts by mass based on 100 parts by mass of the solid content of the photocurable composition. When the amount is less than 3 parts by mass, the color development becomes insufficient. Moreover, when it is more than 20 parts by mass, a more excellent effect cannot be expected. It is preferably 8 to 15 parts by mass. The photocurable component of the photocurable composition of the present embodiment may, for example, be a photopolymerization initiator or an ethylenically unsaturated group-containing compound. The photopolymerization initiator is used for irradiation of an active energy ray to generate a radical, and to polymerize an ethylenically unsaturated group-containing compound or the like which will be described later. Next, the photopolymerization initiator must have a photosensitive wavelength region outside the photosensitive wavelength region of the photoacid generator. That is, it is necessary to have a photosensitive wavelength region only for the photopolymerization initiator to be present in -19-201106109. Except for the wavelength region in which the photopolymerization initiator and the photo-acid generator overlap the photosensitive wavelength region, it is necessary to have only a photo-sensing wavelength region of the photopolymerization initiator. The above photoacid generator is more than 400 nm, especially in the ultraviolet region. In order to prevent the photoacid generator from being sensitized to generate a radical, it is preferred that the photopolymerization initiator further has an absorption/activity outside the photosensitive wavelength region of the photoacid generator. Further, in order to suppress the coloring caused by the photopolymerization initiator, it is preferred to use a high-sensitivity photopolymerization initiator which is sufficiently photohardenable by using a small amount of the resin. Such a photopolymerization initiator is preferably used as an oxime ester photopolymerization initiator. For example, the oxime ester-based photopolymerization initiator represented by the following general formula (I) has a photosensitive wavelength region in addition to the photosensitive wavelength region of the photoacid generator, and has a particularly high light sensitivity. —C = N-0_C_R2 M, «t ii \l) R1 0 (wherein R1 is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a phenyl group, and R2 is an alkyl group having 1 to 7 carbon atoms, or Phenyl) a phthalate-based photopolymerization initiator, which has a good sensitivity at 4 〇 5 nm widely used in a visible light source, and is represented by the following formula (η): 2-(ethenyloxyiminomethyl)sulfide Astragalus-9-ketone is preferred.

(II) Further oxime ester photopolymerization initiator, having the general formula (ΠΙ) -20- 201106109

The structure represented by the general formula (IV) is preferred.

(IV) (wherein R3 and R4 each independently represent an alkyl group having 1 to 12 carbon atoms, and R5, R, R7 and R8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Μ is 〇, S* NH, η is an integer of 〇~5, R9·, R1. It is a group of carbon number 1 to 12', and R11 is a hydrogen atom and an alkyl group having 1 to 20 carbon atoms. Among them, 2-(ethylideneoxyiminomethyl)thioxanthene-9-one represented by the formula (Π) is particularly preferred. Commercially available products include, for example, CGI-3 25, IRGACURE (registered trademark) OXE01,

G IRGACUREOXE02 (all manufactured by Ciba Specialty Chemicals Co., Ltd.), N-1919 (made by Adeka Co., Ltd.), and the like. The oxime ester-based photopolymerization initiator may be used singly or in combination of two or more kinds. The oxime ester-based photopolymerization initiator is preferably 0.05 to 1 part by mass based on 100 parts by mass of the solid content of the ethylenically unsaturated group-containing compound to be described later. When the amount is less than 0.05 parts by mass, the photocuring is insufficient and the image fixation is deteriorated. Further, when it is more than 10 parts by mass, it is not expected to have a more excellent effect. It is preferably 0.5 to 5 parts by mass. Further, the photopolymerization initiator other than the oxime ester photopolymerization initiator may, for example, be a benzophenone type, an acetophenone type, an amino acetonide type, a benzoin ether type or a benzyl group. A conventional radical photopolymerization initiator such as a ketone system, an oxime ether system or a titanocene system. Depending on the photoacid generator to be used in combination, it is particularly preferable to use a photopolymerization initiator having absorption and activity in a long-wavelength region in the visible light region and having high sensitivity. These photopolymerization initiators may be used singly or in combination of two or more kinds. Further, a starting system in which the photosensitive wavelength region is arbitrarily set may be used, and a conventional 2-molecular complex starting system in which a dye such as coumarin, cyanine or squaraine is combined with a radical generating agent may be used. For example, a combination of an imidazole dimer as a radical generator, a pyridin dye or a triazine dye as a dye, N-phenylglycine as a radical generator, and a coumarin as a pigment are known. The combination, the combination of an iodonium salt as a radical generator, various dyes, a combination of a triazine compound as a radical generator, and an aromatic ketone derivative as a dye. Further, the alkyl borate of a pigment such as cyanine, rhodamine or crocin is also an effective visible light initiator, and in the present embodiment, such a conventional photopolymerization initiator system can be used. Further, the ethylenically unsaturated group-containing compound can be used for photoradical generation of a photopolymerization initiator by irradiation with an active energy ray to photopolymerize and fix an image. Such as an ethylenically unsaturated group-containing compound, such as a glycol diacrylate of ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol or the like; hexanediol, trimethylolpropane, pentaerythritol a polyvalent alcohol such as dipentaerythritol or tris-hydroxyethyl isocyanurate or a polyvalent acrylate such as an ethylene oxide adduct or a propylene oxide adduct; phenoxyacrylic acid-22 - 201106109 Polyester acrylates such as esters, bisphenol A diacrylates, and ethylene oxide adducts or propylene oxide adducts of such phenols; glycerol diglycidyl ether, glycerol triglycidyl a polyvalent acrylate of a glycidyl ether such as a methyl ether, a trimethylolpropane triglycidyl ether or a triglycidyl isocyanurate; a melamine acrylate and/or a corresponding one of the acrylates Acrylates and the like. Further, for example, an epoxy group acrylate resin obtained by reacting a multi-functional epoxy resin such as a cresol novolac type epoxy resin with acrylic acid, or a hydroxyl group of the epoxy acrylate resin and pentaerythritol triacrylate may be mentioned. An epoxy hydroxy urethane acrylate compound obtained by reacting a hydroxy acrylate with a half urathane compound of a diisocyanate such as isophorone diisocyanate. Such an epoxy acrylate-based resin can improve the photocurability without lowering the dryness of the touch. These ethylenically unsaturated group-containing compounds may be used singly or in combination of two or more kinds. The amount of the ethylenically unsaturated group-containing compound is preferably from 5 to 95 parts by mass based on the solid content of the photohardenable composition of 1 〇 0 parts by mass. When the amount is less than 50 parts by mass, the fixation of the image is deteriorated. Further, when it is more than 95 parts by mass, the color development degree is lowered. It is preferably 60 to 90 parts by mass. In the photocurable composition, for the purpose of viscosity adjustment, an organic solvent may be added as necessary. As the organic solvent, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, and butyl cellosolve can be used. Agent, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl-23- 201106109 ether 'dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether, etc. Glycol ethers: ethyl acetate, butyl acetate 'butyl butylate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl Esters such as ether ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate, etc.; aliphatic hydrocarbons such as octane and decane; petroleum petroleum, naphtha, petroleum-soluble petroleum oil, etc. It is a conventional organic solvent such as a solvent. These organic solvents may be used singly or in combination of two or more kinds. Further, 'in the photocurable composition, various additives such as cerium oxide, aluminum oxide, talc, calcium carbonate, barium sulfate, or the like, or propylene beads or urethane beads, etc. may be contained as necessary. Additives such as an antimony agent, a coupling agent, an antifoaming agent, a coating agent, and the like, such as an organic tanning material. In this way, according to the image forming method of the present embodiment, by using the photocurable composition suitable for the image forming method, in addition to the high contrast image which cannot be formed by the conventional image forming method, an excellent image can be obtained. Stability and good hardening properties. Therefore, not only the heat-sensitive recording paper or the fire-retardant material, but also the use of the imprint or the light-shielding use in the field of the use of an electronic substrate or a display having a severe environment can be widely used. Further, in the case where the wet image forming method cannot cope with the corrosion problem, the aluminum wiring can be contrasted, and can be applied to the MEMS field such as a light receiving element or a displacement sensor. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention -24-201106109 is not limited to the following examples. In addition, the following "parts" and "%" are all quality standards unless they are specified. First, a resin varnish was prepared using the following synthesis example. EPICLON (registered trademark) N-680 (made by DIC company, ring volume = 215 g / phenol phenol varnish type resin) was placed in a 2 liter separable beaker equipped with a mixer, a thermometer 'reflux cooling tube, and a dropping funnel introduction tube. Equivalent) 107.5 parts, added carbitol acetate 1 〇 8 parts of Ipzole (registered trademark) #150 of Twilight Petrochemical Co., Ltd. #150 parts of 'heat-dissolved to obtain a resin solution. To the resin solution, a terephthalic solution as a polymerization inhibiting agent and 1.0 part of triphenylphosphine as a reaction catalyst were added. The mixture was heated at 95 ° C, and 36 parts of acrylic acid was gradually dropped, and the epoxy acrylate obtained by the reaction for 24 hours was gradually dropped to give isophorone diester and pentaerythritol triacrylate as 1: 1 molar reaction of urathane 257.5 parts, and reacted at 60 to 70 ° C for 4 hours, while resin varnish. As shown in Table 1, the components (mass parts) of the obtained resin varnish were blended, mixed with a mixer, and kneaded by a 3-roller honing machine to obtain photocurable compositions 1 -, 2- 1^4. In addition to nitrogen and epoxy, when added, add 0.05 85~. In the isocyanide half modulation after each '1~3 -25- 201106109 [Table i] _ Composition 1 2 3 4 "" Photoacid generator · 30.0 30.0 30.0 ------ 30.0 Electron-donor dye *2 20.0 20.0 20.0 —--- 20.0 *3 — — — *4 — _ — Ink polymerization initiator 1 *5 2.0 — — — *6 One 2.0 — *7 — — 2.0 _ *8 — — — 2.0 Acrylate resin varnish β — — — Resin varnish 154.0 154.0 154.0 154.0 Multifunctional acrylate no 50.0 50.0 50.0 50.0 Leveling agent #11 1.0 1.0 1.0 — — 1.0 Anthrone defoamer +12 1.0 1.0 1.0 - 1.0 Total 258.0 258.0 258.0 〜1 ......... 258.0 Note: One * 1 : ADEKA (registered trademark) Aopu drag code SP-152 (made by ADEKA) * 2 : S-205 (made by Yamada Chemical Industry Co., Ltd.) * 3 : Lucirin (registered trademark) TPO (B ASF Japan Co., Ltd.) * 4 : IRGACURE (registered trademark) 784 (manufactured by Ciba Specialty Chemicals Co., Ltd.) * 5 : CGI 325 (manufactured by Ciba Specialty Chemicals) * 6 : IRGACURE OXE -02 (manufactured by Ciba Specialty Chemicals) * 7 : IRGACURE OXE-01 ( Ciba Specialt y Chemicals Co., Ltd.) * 8 : IRGACURE 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) *9: Unitek (registered trademark) R-100 (solid content: 65%) (made by DIC Corporation) *10: Nie Ma ( Registered trademark) DA-600 (manufactured by Sanyo Chemical Industry Co., Ltd.) * 11 : BYK (registered trademark) -361N (BYK. manufactured by Japan) * 12 : KS-66 (manufactured by Shin-Etsu Chemical Co., Ltd.) -26- 201106109 Test substrate Preparation: The photocurable compositions of the composition examples 1 to 4 shown in Table 1 were polished and honed by a copper foil substrate, and then subjected to full-screen printing by screen printing, and dried by 80 ° C x 30 minutes to form on the substrate. As a colorless transparent coating film, the test substrates of Examples 1 to 3, Comparative Examples 1 to 4, and Reference Examples were obtained. The obtained test substrates were each exposed under the conditions of Table 2. Further, each exposure step is as follows. 〇 First exposure step: Use a metal halide lamp through a negative mask to illuminate at 1 000 J/cm2 in the all-optical wavelength range. Thereafter, PEB treatment was carried out for 10 minutes at 80 °C. Second exposure step: For the test substrate subjected to the first exposure step, a direct exposure of a wavelength of 4 〇 5 nm which is outside the photosensitive wavelength region of the photoacid generator and which is a photosensitive wavelength region of the oxime ester photopolymerization initiator is used. Machine (DI-made by PENTAX Co., Ltd.) 〇, the entire coating film on the test substrate was irradiated with light at 300 J/cm 2 . With respect to the test substrates of Examples 1 to 3, Comparative Examples 1 to 4, and Reference Examples, the evaluation of the coating film properties was carried out as follows. Comparative evaluation: With respect to the test substrates of Examples 1 to 3, Comparative Examples 1 to 4, and Reference Examples, the color development of the coating film was visually confirmed. The evaluation criteria are as follows. There is hair color · ·· It can be seen that the hair color after exposure has no hair color.··No color change before and after exposure. Viscosity evaluation: -27- 201106109 Tests of Examples 1 to 3, li, and Examples 1 to 4 and reference examples The substrate was evaluated for the coating film (exposed portion, unexposed portion) according to the viscosity before exposure, after the first exposure treatment, and after the second exposure treatment. The evaluation criteria are as follows. 〇··· When the fingerprint is completely etched, the surface of the coating film is completely free of fingerprints. X···The surface of the coating film remains on the surface of the coating. Solvent resistance evaluation: The test substrates of Examples 1 to 3, Comparative Examples 1 to 4, and Reference Examples In order to confirm the hardenability of the coating film (cured material) after the exposure treatment, propylene glycol monomethyl ether acetate (PMA) was used for each of the colored portion and the uncolored portion, and a rubbing test was performed 1 time to dissolve the coating film. • Peeling is confirmed by visual inspection. The evaluation criteria are as follows. 〇··········································································································· (Evaluation): For the test substrates of Examples 1 to 3, Comparative Examples 1 to 4, and Reference Examples, the coating film (cured material) after the exposure treatment was placed under a fluorescent lamp for one week, and visual observation was confirmed by visual evaluation. . The evaluation criteria are as follows. 〇··· Even if it is placed for one week, no photographic fog is observed in the uncolored portion, and the contrast state is maintained. X···After one week, the photographic fog of the uncolored portion is seen, and the state of contrast cannot be maintained -28-201106109 [Table 2]

EXAMPLES Examples Comparative Examples Comparative Examples Comparative Examples Reference Examples 1 2 3 1 2 3 4 a Products 2-1 2-2 2-3 2-1 2-2 2-3 2-4 2-4 Viscosity before exposure XXXXXXXX Exposure (raJ/cm2) 1000 1000 1000 1000 1000 1000 1000 1000 The first exposure exposure section has some color development, and there are steps to evaluate the viscosity (coloring section) 〇〇〇〇〇〇〇〇 Solvent resistance (colored part) 〇〇〇〇〇〇〇〇 Exposure (mJ/cm2) 300 300 300 — — — 300 2nd exposure exposure part colorless /πτ m No exposure without exposure without coloring Evaluation of viscosity (uncolored part) 〇〇〇XXXXX Solvent resistance (uncolored part) 〇Δ Δ XXXXX After exposure (time) Image stability XXXXX Table 2 shows the use of photoacids in the composition In the examples 1 to 3 in which the photo-sensing region of the agent has a photosensitive region outside the photosensitive wavelength region and in the two-stage exposure, high contrast and excellent image stability can be achieved. Further, in Comparative Examples 1 to 4 in which the conventional one-stage exposure was carried out, although no comparison was made, since the uncolored portion was not cured, it was difficult to maintain the contrast in the same manner, and sufficient image stability (weather resistance) could not be obtained. Further, in the reference example using the photopolymerization initiator having no photosensitive wavelength region outside the photosensitive wavelength region of the photoacid generator in the composition, it was difficult to maintain contrast, and sufficient image stability (weather resistance) could not be obtained. -29-

Claims (1)

201106109 VII. Patent application scope: 1. An image forming method characterized in that the coating film is formed by forming a coating film containing a photo-curable composition of a photoacid generator and an electron-donating dye on a substrate. The wavelength region is subjected to multiple exposures, and the image formed by the colored portion and the uncolored portion is formed and fixed in contrast. 2. A method for forming an image, comprising the steps of: forming a coating film containing a photocurable composition of a photoacid generator and an electron donating dye on a substrate; and forming a specific region of the coating film 0, after irradiating the active energy ray of the first wavelength region, forming a first exposure step of contrasting the image formed by the colored portion and the uncolored portion, and forming a wavelength region different from the first wavelength region on the coating film After irradiating the active energy ray of the second wavelength region where the uncolored portion is not colored, the second exposure step of the image contrast is fixed. 3. An image forming method characterized in that a coating film containing a photoacid generator, an electron supply dye, and a photocurable composition of a photocurable component is formed on a substrate, and D is irradiated to a specific region. After the first active energy ray of the photoacid generator in the photosensitive wavelength region, an acid is generated, and after the electron-donating dye is colored, a colored portion is formed on the coating film, and the coating film is irradiated substantially in the light. After the second active energy ray of the photosensitive wavelength region of the photocurable component is outside the light-receiving wavelength region of the acid-generating agent, the uncoated portion other than the colored portion of the coating film is not colored substantially to form the coating film. Hardens and forms an image contrast. 4. The image forming method according to claim 3, wherein the hardening of the specific region is performed by irradiation with the first active -30-201106109 energy ray. The image forming method according to claim 3, wherein the heat treatment is performed after the irradiation of the first active energy ray. 6. The image forming method of claim 3, wherein the photocurable component contains an oxime ester photopolymerization having a photosensitive wavelength region outside the photosensitive wavelength region of the photoacid generator represented by the following general formula (1) The initiator and the ethylenically unsaturated group-containing compound, 9 = n-〇-c_r2 f η r1 a (1) (wherein R1 is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a phenyl group, and r2 is An alkyl group having 1 to 7 carbon atoms or a phenyl group). 7. The image forming method according to claim 6, wherein the oxime ester photopolymerization initiator is represented by the following formula (II) or contains the following general formula (ΙΠ) or the following general formula (IV); Structure, -31 - (IV) 201106109 (wherein R3 and R4 each independently represent an alkyl group having 1 to 12 carbon atoms'. R5, R, R7 and R8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The elbow is 〇, S_NH, and η is 0. An integer of ~5, R9, R1Q is an alkyl group having a carbon number of 1 to 12' R11 is a hydrogen atom and an alkyl group having 1 to 20 carbon atoms. 8. A photohardening image characterized by the image forming method of any one of claims 1 to 7. A photocurable composition characterized by comprising a photoacid generator' and an electron-donating dye, and a photosensitive wavelength region outside a photosensitive wavelength region represented by the following general formula (I) a phthalocyanine photopolymerization initiator, and an ethylenically unsaturated compound, a C=N-〇-C-R2 R1 〇(1) (wherein R1 is a hydrogen atom, an alkyl group having 7 carbon atoms, or a phenyl group, and R2 is an alkyl group having 1 to 7 carbon atoms or a phenyl group). The photocurable composition of claim 9, wherein the oxime ester photopolymerization initiator is represented by the following formula (II) or comprises the following general formula (ΙΠ) or the following general formula ( IV) the structure represented, -32- (III) 201106109 M ύ R$ R5 C, R « (IV) O ' 6 (wherein R 3 and R 4 each independently represent an alkyl group having 1 to 12 carbon atoms; and R, R, R 7 and R 8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; 'μ is ο, SSNH, η is an integer of 0 to 5, and R9 and R1 are an alkyl group having 1 to 12 carbon atoms, and R11 is a hydrogen atom and an alkyl group having 1 to 20 carbon atoms. A cured product characterized in that a coating film of the photocurable composition of claim 9 is formed on a substrate, and the first active energy ray in the photosensitive wavelength region of the photoacid generator is irradiated to a specific region to cause an acid When the electron-donating dye of the former Q is colored, a colored portion is formed on the coating film, and the coating film is irradiated substantially outside the photosensitive wavelength region of the photo-acid generator, and the photocurable component is After the second active energy ray in the photosensitive wavelength region, the uncolored portion other than the colored portion of the coating film is substantially colored without being colored, and the coating film is cured. 12. The cured product of claim 10, wherein the oxime ester photopolymerization initiator is represented by the following formula (Π) or comprises the following general formula (ΙΠ) or the following general formula (IV) Construction, -33- (II)201106109 M A R6 Rs (III) (IV) (wherein R3 and R4 each independently represent an alkyl group having 1 to 12 carbon atoms, and R5, R6, R7 and R8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and Μ is Ο, S or ΝΗ, η is an integer of 0 to 5, R9 and R1Q are an alkyl group having 1 to 12 carbon atoms, and R11 is a hydrogen atom and an alkyl group having 1 to 20 carbon atoms. -34- 201106109 IV. Designated representative map: (1) The representative representative figure of this case is: no β (2) The symbol of the representative figure is simple: no ❹ -3- 201106109 V. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -4-