TWI476541B - Image forming method and photohardenable composition - Google Patents
Image forming method and photohardenable composition Download PDFInfo
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- TWI476541B TWI476541B TW099108501A TW99108501A TWI476541B TW I476541 B TWI476541 B TW I476541B TW 099108501 A TW099108501 A TW 099108501A TW 99108501 A TW99108501 A TW 99108501A TW I476541 B TWI476541 B TW I476541B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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Description
本發明係關於影像形成方法及光硬化性組成物。The present invention relates to an image forming method and a photocurable composition.
一般光微影術法之影像形成方法，因微細加工性優異，作業性佳而適合大量生產，被廣泛用於印刷業界或電子學業界。近年，例如在利用於基材上形成反射率不同的影像，使來自發光元件之反射光以受光元件等讀取之編碼器或位移感測器等MEMS(Micro Electro Mechanical Systems)領域等亦有所進展。The image forming method of the general photolithography method is excellent in fine workability and good in workability, and is suitable for mass production, 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.
此般影像形成方法中，由環境負荷降低觀點，以稀鹼水溶液之濕式顯影法，主要用於印刷配線板製造或焊料光阻之形成、進而半導體相關構件之製造等。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.
然而，例如用於MEMS領域時，因需要在晶圓上或鋁配線上圖型化，產生鹼水溶液造成的絕緣劣化、或腐蝕等之問題。因此，不得不利用有機溶劑系之顯影液。However, when used in the field of MEMS, for example, it is necessary to pattern on a wafer or an aluminum wiring to cause problems such as insulation deterioration or corrosion caused by an aqueous alkali solution. Therefore, it is necessary to use an organic solvent-based developer.
另外，作為此般不使用顯影液而形成對比之技術方面，探討利用光硬化與熱熔融之光熱照相術之乾式影像形成方法。該方法與濕式影像形成之情況相異，無廢棄物之問題，故在環境負荷降低觀點亦被期待。Further, as a technique for forming a contrast without using a developing solution as described above, a dry image forming method using photocuring by photohardening and thermal melting is considered. 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.
乾式影像形成方法，例如利用染料之發色的發色型感熱記錄法，且大抵區分為發色性優異的隱色型(leuco form)感熱記錄法與影像安定性優異的二氮型感熱記錄法2大類。然而，在此等之方法，有難以兼顧高對比(高發色性)與影像形成後之品質安定性(影像安定性)之問題。The dry image forming method is, for example, a chromophoric thermosensitive 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 thermosensitive recording method excellent in image stability. 2 major categories. However, in such methods, it is difficult to achieve both the high contrast (high color development) and the quality stability (image stability) after image formation.
對於此，在隱色型感熱記錄法中，揭示例如將電子接受性化合物與電子供給性染料於含有光硬化性組成物之微膠囊中分離、配置，以使影像安定性提升的手法(例如專利文獻1作參照)。然而，即使使微膠囊內之光硬化性組成物充分硬化，亦無法充分抑制硬化部之發色，而有未著色部稍微著色、對比變差之問題。In the leuco-type thermosensitive recording method, for example, a method in which an electron-accepting compound and an electron-donating dye are separated and disposed in a microcapsule containing a photocurable composition to enhance image stability (for example, a patent) is disclosed. Reference 1 is referred to in the literature). However, even if the photocurable composition in the microcapsules is sufficiently cured, the coloration of the cured portion cannot be sufficiently suppressed, and the uncolored portion is slightly colored and the contrast is deteriorated.
又，揭示有層合具酸性基之乙烯基單體與含有光聚合起始劑所成的光聚合性組成物之層與隔離層與電子供給性染料所成的層之手法(例如專利文獻2作參照)。此時，雖變得無未著色部之著色(照相灰霧)，但反而有全體發色度稍減低之問題。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 the color of the uncolored portion (photographing fog) is not obtained, there is a problem that the overall color development is slightly lowered.
對於此，嘗試兼顧未著色部之照相灰霧與低發色度，提案使二成分的一者內包於微膠囊，使另外的成分作為光硬化性組成物之硬化性化合物，或者使另一者的成分同光硬化性組成物一起配置於微膠囊外之手法(例如專利文獻3作參照)。又，提案設置含有內包有電子供給性染料之微膠囊與電子接受性化合物、與含有聚合性乙烯基單體與光聚合起始劑之光硬化性組成物的層之手法(例如專利文獻4作參照)。In view of this, attempts have been made to achieve both photographic fog and low chroma of the uncolored portion, and it is proposed to enclose one of the two components in the microcapsule, to make the other component as 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). In addition, a method of providing a layer containing a microcapsule and an electron-accepting compound containing an electron-donating dye, and a photocurable composition containing a polymerizable vinyl monomer and a photopolymerization initiator is proposed (for example, Patent Document 4) For reference).
雖提案有眾多改善此等影像安定化之手法，但在另一方面卻浮現出發色度降低等之問題。又，此等之手法，因根本地發色部並未硬化，有無法得到硬化物物性之問題。Although there are many suggestions for improving the stability of these images, on the other hand, there are problems such as lowering the chroma. Moreover, in such a method, since the primary coloring portion is not hardened, there is a problem that the physical properties of the cured material cannot be obtained.
如此一來，光熱照相術的影像形成方法中，可用於電子零件等之基板周遭或MEMS感應器等使用環境嚴苛領域之技術尚未確立，目前僅限於感熱記錄紙或防火材等之利用。因此，藉由開發可得到形成對比高的影像且之後影像安定性良好之硬化物性的光硬化性組成物，可期待擴大利用用途。In this way, in the image forming method of photothermography, a technique that can be used for a substrate such as an electronic component or a MEMS sensor or the like in an environment of severe use has not been established, and is currently limited to the use of thermal recording paper or fireproof material. Therefore, it has been expected to expand the use of the photocurable composition which can obtain a cured image having a high contrast and a good image stability afterwards.
[專利文獻1]特開昭52-89915號公報[Patent Document 1] JP-A-52-89915
[專利文獻2]特開昭61-123838號公報[Patent Document 2] JP-A-61-123838
[專利文獻3]特開平3-87827號公報[Patent Document 3] Japanese Patent Laid-Open No. Hei 3-87827
[專利文獻4]特開平4-211252號公報[Patent Document 4] JP-A-4-211252
本發明為有鑑於上述先前技術問題點所成者，目的在於提供除可形成對比高的影像外，且可實現優異影像安定性及良好硬化物性的光硬化性組成物。The present invention has been made in view of the above-mentioned problems of the prior art, and an object of the invention is to provide a photocurable composition which can achieve excellent image stability and good cured physical properties in addition to a highly contrasting image.
根據本發明之一態樣，提供在基板上，形成含有光酸產生劑與電子供給性染料之光硬化性組成物之塗膜，藉由使塗膜在不同波長區域進行多次曝光，而使由著色部與未著色部構成之影像對比形成、固定之影像形成方法。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 subjecting the coating film to multiple exposures in different wavelength regions. A method of forming an image formed by contrast between an image formed by a colored portion and an uncolored portion.
藉由此般構成除可形成對比高的影像外，在所形成影像中，可獲得優異影像安定性及良好硬化物性。In addition to the high contrast image, excellent image stability and good hardenability can be obtained in the formed image.
又，根據本發明之一態樣，提供具備在基板上，形成含有光酸產生劑與電子供給性染料之光硬化性組成物之塗膜的步驟，與在塗膜的特定區域，照射第1波長區域之活性能量線後，形成由著色部與未著色部構成的影像對比之第1曝光步驟，與於塗膜上，照射與第1波長區域不同波長區域且未著色部不發色的第2波長區域之活性能量線後，使影像對比固定的第2曝光步驟之影像形成方法。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.
藉由此般構成，可對光硬化性組成物之塗膜，以與發色用曝光波長不同波長，進行抑制發色而使影像固定之曝光，除可形成對比高的影像外，在所形成影像中，可獲得優異影像安定性及良好硬化物性。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.
又，根據本發明之一態樣，提供於基板上，形成含有光酸產生劑、電子供給性染料、與光硬化性成分之光硬化性組成物的塗膜，藉由照射光酸產生劑的感光波長區域之第1活性能量線於特定區域後，使酸產生，使電子供給性染料發色後，於塗膜形成著色部，並對塗膜照射實質在光酸產生劑的感光波長區域外且為光硬化性成分的感光波長區域之第2活性能量線後，不使塗膜的著色部以外的未著色部實質上發色而將塗膜硬化，形成影像對比之影像形成方法。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.
藉由此般構成，可對光硬化性組成物之塗膜，以與發色用曝光波長不同波長，進行抑制發色而使影像固定之曝光，除可形成對比高的影像外，在所形成影像中，可獲得優異影像安定性及良好硬化物性。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.
本發明之一態樣的影像形成方法中，以經第1活性能量線之照射，進行前述特定區域之硬化為佳。藉由如此地進行硬化，可得到更良好影像安定性。In the image forming method according to an aspect of the present invention, it is preferable that the specific region is hardened by irradiation with the first active energy ray. By hardening in this way, better image stability can be obtained.
又，本發明之一態樣的影像形成方法中，以第1活性能量線之照射後，進行加熱處理為佳。經此般加熱處理，使酸產生劑產生的酸在塗膜內擴散，可促進電子供給性染料之發色，且可得到更高對比的影像。Further, in the image forming method according to an aspect of the present invention, it is preferable to perform heat treatment after irradiation with the first active energy ray. By such heat treatment, the acid generated by the acid generator is diffused in the coating film, and the color development of the electron-donating dye can be promoted, and a higher contrast image can be obtained.
又，本發明之一態樣的影像形成方法中，光硬化性成分以含有下述一般式(I)所表示且在光酸產生劑的感光波長區域外具有感光波長區域之肟酯系光聚合起始劑與含乙烯性不飽和基化合物為佳。Further, in the image forming method according to an aspect of the present invention, the photocurable component is an oxime ester 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.
(式中，R1 為氫原子、碳數1～7之烷基、或苯基，R2 為碳數1～7之烷基、或苯基)(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 a phenyl group)
藉由使用此般光硬化性成分，具有良好光感度，故可得到優異影像安定性及良好硬化物性。By using such a photocurable component, it has a good light sensitivity, so that excellent image stability and good cured physical properties can be obtained.
又，本發明之一態樣的影像形成方法中，光硬化性成分以肟酯系光聚合起始劑為下述式(II)所表示、或下述含有一般式(III)或下述一般式(IV)所表示構造為佳。Further, in the image forming method according to an aspect of the present invention, the photocurable component is represented by the following formula (II) as an oxime ester photopolymerization initiator, or the following general formula (III) or the following The structure represented by the formula (IV) is preferred.
(式中，R3 、R4 各自獨立表示碳數1～12之烷基，R5 、R6 、R7 及R8 各自獨立表示氫原子或碳數1～6之烷基，M為O、S或NH，n為0～5之整數，R9 、R10 為碳數1～12之烷基，R11 為氫原子、碳數1～20之烷基)(wherein R 3 and R 4 each independently represent an alkyl group having 1 to 12 carbon atoms; and R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and M is O; , S or NH, n is an integer of 0 to 5, R 9 and R 10 are an alkyl group having 1 to 12 carbon atoms, and R 11 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms)
藉由使用式(II)所表示肟酯系光聚合起始劑，可以在可見光源廣用的波長405nm進行曝光。又，藉由使用含一般式(III)、(IV)所表示構造之肟酯系光聚合起始劑，即使少量添加亦具有能充分光硬化之高感度，故可形成抑制因搭配光聚合起始劑造成之著色的高透明性的未著色部。By using an oxime ester-based photopolymerization initiator represented by the formula (II), exposure can be carried out at a wavelength of 405 nm which is widely used for a visible light source. 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 formation due to photopolymerization can be suppressed. An uncolored portion having a high transparency which is colored by the initiator.
根據本發明之一態樣，可提供以此等之影像形成方法形成的光硬化影像。藉由此般影像形成方法形成，可獲得對比高且具有優異影像安定性及良好硬化物性之光硬化影像。According to an aspect of the present invention, a photo-cured image formed by such an image forming method can be provided. By the formation of such an image forming method, a photohardenable image having high contrast and excellent image stability and good hardenability can be obtained.
根據本發明之一態樣，提供含有光酸產生劑、電子供給性染料、下述一般式(I)所表示之在前述光酸產生劑的感光波長區域外具有感光波長區域之肟酯系光聚合起始劑、含乙烯性不飽和基化合物為其特徵的光硬化性組成物。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.
(式中，R1 為氫原子、碳數1～7之烷基、或苯基，R2 為碳數1～7之烷基、或苯基)(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 a phenyl group)
藉由此般構成，可對光硬化性組成物之塗膜，以與發色用曝光波長不同波長，進行抑制發色而使影像固定用之曝光，除可形成對比高的影像外，在所形成影像中，可獲得優異影像安定性及良好硬化物性。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 for exposure, and a contrast image can be formed. Excellent image stability and good hardenability are obtained in the image formation.
本發明之一態樣的光硬化性組成物中，肟酯系光聚合起始劑以進而在前述光酸產生劑的感光波長區域亦具有感光波長區域為佳。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.
藉由此般構成，在進行發色用之曝光時，可進行發色領域之硬化。According to this configuration, it is possible to perform hardening in the coloring field when performing exposure for color development.
又，本發明之一態樣的光硬化性組成物中，肟酯系光聚合起始劑以具有下述式(II)所表示、或下述一般式(III)或下述一般式(IV)所表示構造為佳。Further, in the photocurable composition of one aspect of the present invention, the oxime ester photopolymerization initiator has the following formula (II) or the following general formula (III) or the following general formula (IV); The structure shown is good.
(式中，R3 、R4 各自獨立表示碳數1～12之烷基，R5 、R6 、R7 及R8 各自獨立表示氫原子或碳數1～6之烷基，M為O、S或NH，n為0～5之整數，R9 、R10 為碳數1～12之烷基，R11 為氫原子、碳數1～20之烷基)(wherein R 3 and R 4 each independently represent an alkyl group having 1 to 12 carbon atoms; and R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and M is O; , S or NH, n is an integer of 0 to 5, R 9 and R 10 are an alkyl group having 1 to 12 carbon atoms, and R 11 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms)
藉由使用式(II)所表示肟酯系光聚合起始劑，在可見光源廣用的波長405nm進行曝光，可充分使影像固定。By using an oxime ester-based photopolymerization initiator represented by the formula (II), exposure is carried out at a wavelength of 405 nm widely used for a visible light source, whereby the image can be sufficiently fixed.
又，藉由使用含一般式(III)、(IV)所表示構造之肟酯系光聚合起始劑，即使少量添加亦具有能充分光硬化之高感度，故可抑制搭配光聚合起始劑造成的著色，充分利用樹脂的透明性。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 suppressed. The resulting coloring makes full use of the transparency of the resin.
又，根據本發明之一態樣，提供以形成此般光硬化性組成物之塗膜，並藉由照射光酸產生劑的感光波長區域之第1活性能量線於特定區域後，使酸產生，使電子供給性染料發色後，於塗膜形成著色部，對塗膜照射實質在光酸產生劑的感光波長區域外且為光硬化性成分的感光波長區域之第2活性能量線，不使塗膜的著色部以外的未著色部實質上發色而將塗膜硬化得到者為其特徵之硬化物。Further, according to an aspect of the present invention, a coating film for forming a photocurable composition is provided, and an acid is generated by irradiating a first active energy ray of a photosensitive wavelength region of a photoacid generator to a specific region. After the electron-donating dye is colored, a colored portion is formed on the coating film, and the coating film is irradiated with a second active energy ray which is substantially outside the photosensitive wavelength region of the photo-acid generating agent and is a photo-curable component in the photosensitive wavelength region. The uncolored portion other than the colored portion of the coating film is substantially colored, and the cured film is cured by the cured film.
此般硬化物中，除具有良好對比外可得到良好硬化物性。又，使用式(II)所表示肟酯系光聚合起始劑而得之硬化物中，可在可見光源廣用的波長405nm下進行曝光，可簡易地獲得良好硬化物性。又，使用含一般式(III)、(IV)所表示構造的肟酯系光聚合起始劑而得之硬化物中，即使少量添加亦具有能充分光硬化之高感度，故可具有抑制搭配之光聚合起始劑造成的著色之高透明性的未著色部。In such a hardened material, good hardenability can be obtained in addition to good contrast. Further, the cured product obtained by using the oxime ester-based photopolymerization initiator represented by the formula (II) can be exposed to light at a wavelength of 405 nm widely used for a visible light source, and can easily obtain good cured physical properties. Further, the cured product obtained by using the oxime ester-based photopolymerization initiator having the structure represented by the general formulas (III) and (IV) has a high sensitivity capable of sufficiently photocuring even if it is added in a small amount, so that it can suppress the collocation. The uncolored portion of the high transparency which is colored by the photopolymerization initiator.
根據本發明之一態樣的光硬化性組成物及影像形成方法。除可形成對比高的影像，在形成的影像中，變得可得到優異影像安定性及良好硬化物性。A photocurable composition and an image forming method according to an aspect of the present invention. In addition to forming a contrast-high image, excellent image stability and good hardenability are obtained in the formed image.
[實施發明之最佳形態][Best Mode for Carrying Out the Invention]
本發明者們為了解決上述課題，努力研究結果，發現藉由在基板上，形成含有光酸產生劑與電子供給性染料之光硬化性組成物之塗膜，藉由使塗膜在不同波長區域進行多次曝光，而使由著色部與未著色部構成之影像對比形成、固定，可得到高對比影像與優異影像安定性及良好硬化物性。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 using a coating film in different wavelength regions. By performing multiple exposures, the image formed by the colored portion and the uncolored portion is formed and fixed in contrast, and high contrast images, excellent image stability, and good cured physical properties can be obtained.
亦即於含有光酸產生劑與電子供給性染料之光硬化性組成物之塗膜上，設置形成對比的第1曝光步驟，與以光硬化將影像固定的第2曝光步驟之2階段曝光步驟，且分別以不同波長進行曝光。如此一來，在光酸產生劑產生酸之波長下進行第1段曝光，形成期望發色圖型後，在光酸產生劑不產生酸的波長下進行第2段曝光，而在第2段曝光中，可不發色而光硬化。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, the first-stage exposure is performed at a wavelength at which the acid generator generates acid, and after the desired color pattern is formed, 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.
接著，發現含有光酸產生劑、電子供給性染料、下述一般式(I)所表示在前述在光酸產生劑的感光波長區域外具有感光波長區域之肟酯系光聚合起始劑、含乙烯性不飽和基化合物的光硬化性組成物適合於此般2階段曝光步驟，而完成本發明。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.
(式中，R1 為氫原子、碳數1～7之烷基、或苯基，R2 為碳數1～7之烷基、或苯基)(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 a phenyl group)
以下，將本實施形態之影像形成方法詳細說明。Hereinafter, the image forming method of the present embodiment will be described in detail.
首先，於基板上，形成含光酸產生劑與電子供給性染料之光硬化性組成物之塗膜。此時，基板未特別限制，可使用形成有電路之印刷配線板、Si、GaAs、肥粒鐵、玻璃等之晶圓等。又，因本實施形態之影像形成方法為乾式顯影，亦可使用形成有Al配線的基板等、因鹼水溶液而絕緣劣化、腐蝕之基板。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, the image forming method of the present embodiment is dry development, and a substrate such as a substrate on which Al wiring is formed, and a substrate which is deteriorated and corroded by an alkali aqueous solution may be used.
接著，將含有光酸產生劑與電子供給性染料之光硬化性組成物以習知方法，例如網版印刷法、淋塗法、噴塗法、輥塗佈法、旋轉塗佈法等之方法進行塗佈，在60～80℃左右之溫度進行15～60分鐘左右加熱而形成塗膜。又，光硬化性組成物之詳細如後述。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 15 to 60 minutes to form a coating film. Moreover, the details of the photocurable composition will be described later.
接著，藉由使形成的塗膜在不同波長區域進行多次曝光，而使由著色部與未著色部構成之影像對比形成、固定。此時，首先於形成之塗膜上，照射光酸產生劑的感光波長區域之活性能量線，於形成在基板等之塗膜上，形成由著色部與未著色部所成的影像對比(第1曝光步驟)。在此步驟，光酸產生劑及電子供給性染料進行反應。Next, by forming the formed coating film in multiple wavelength regions for a plurality of exposures, the image formed by the colored portion and the uncolored portion is formed and fixed in contrast. At this time, first, the active energy ray of the photosensitive wavelength region of the photo-acid generator is irradiated onto the formed coating film to form an image contrast formed by the colored portion and the uncolored portion on the coating film formed on the substrate or the like (No. 1 exposure step). In this step, the photoacid generator and the electron donating dye are reacted.
亦即第1曝光步驟中，藉由光酸產生劑的感光波長區域之活性能量線之照射，光酸產生劑產生酸。接著，產生的酸與電子供給性染料在塗膜內接觸，產生平衡反應，而使電子供給性染料發色，形成著色部。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. Next, 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 colored portion.
較佳為令照射活性能量線之波長為光硬化性組成物所含之光聚合起始劑、含乙烯性不飽和基化合物等之光硬化性成分的感光波長區域。藉由照射此般波長之活性能量線，光酸產生劑及電子供給性染料與光聚合起始劑、含乙烯性不飽和基化合物進行反應。接著，例如藉由光聚合起始劑產生自由基，而含乙烯性不飽和基化合物進行光聚合、進行硬化。如此一來，著色部之形成同時進行著色部之第一階段硬化。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. In this way, the formation of the colored portion simultaneously performs the first-stage hardening of the colored portion.
在此所用的活性能量線之波長必須為光酸產生劑的感光波長區域。The wavelength of the active energy ray used herein must be the photosensitive wavelength region of the photoacid generator.
具體上，可使用例如紫外光區之i線等之單一波長光或在紫外光區、可見光區、近紅外光區具有廣分光分佈(複數發光譜)之活性能量線，而並未特別限制。接著，作為該光源，可適當利用習知低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、氙氣燈泡、金屬鹵化物燈等。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.
第1曝光步驟中，若優先光聚合，則在發色度上有變得不足之情形，且優先發色度則有光交聯度降低，硬化物性降低之情形。一般光酸產生劑與光聚合起始劑相異，已知不受氧阻礙，具有即使在氧環境下曝光亦安定而可供給酸之優點。因此，此處的曝光方法，因應用途，可適宜地選擇真空密著曝光、近接式曝光、直接成像等。In the first exposure step, when photopolymerization is preferentially performed, the color development degree may be insufficient, and the priority color development may be such that the degree of photocrosslinking is lowered and the cured physical properties are lowered. Generally, 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.
在第1曝光步驟後，使光酸產生劑產生的酸在塗膜內擴散，為更促進電子供給性染料之發色，亦可進行曝光後加熱處理(Post Exposure Bake：PEB)。曝光後加熱處理可使用習知方法、條件。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.
如此一來，形成由著色部與未著色部所成的影像對比後，照射為光酸產生劑的感光波長區域外且為光聚合起始劑等之光硬化性成分的感光波長區域之活性能量線，進行未著色部之硬化及著色部之再硬化(第二階段硬化)(第2曝光步驟)。在此步驟，光聚合起始劑、含乙烯性不飽和基化合物等之光硬化性成分進行反應。亦即、第2曝光步驟中，例如藉由光聚合起始劑產生自由基後，進行含乙烯性不飽和基化合物之光聚合，使塗膜硬化而將影像對比固定。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. In other words, in the second exposure step, for example, a photopolymerization initiator is used to generate a radical, and photopolymerization of the ethylenically unsaturated group-containing compound is carried out to cure the coating film to fix the image.
如此一來，藉由抑制電子供給性染料之發色反應使全面光硬化，固定在第1曝光步驟形成之著色部與未著色部所成的影像對比，而形成具有特定圖型之影像。In this manner, by suppressing the color development reaction of the electron-donating dye to cause total light curing, 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.
在此所用的活性能量線之波長為光酸產生劑的感光波長區域外且為光聚合起始劑等之光硬化性成分的感光波長區域即可。但，為了防止在第二曝光步驟未著色部之照相灰霧，以遠離光酸產生劑的感光波長區域為佳。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 region of a 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.
具體波長因選擇之光酸產生劑而異，除h線、g線之外，亦可利用例如由488nm、512nm、635nm、670nm等各種雷射射出之雷射光、或使此等之出射光以二次諧波元件轉換為半波長者。例如利用後述肟酯系光聚合起始劑為光聚合起始劑時，肟酯系光聚合起始劑可利用具有吸收‧活性波長的h線(405nm)。接著，光源可適宜地選擇使用習知低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、氙氣燈泡、金屬鹵化物燈、雷射等。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 an oxime ester photopolymerization initiator described later is a photopolymerization initiator, an oxime ester photopolymerization initiator can be used as an h line (405 nm) having an absorption wavelength of ‧ active. 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.
此般影像形成方法為可形成對比高的影像且實現優異影像安定性與良好硬化物性者即可，不被此般方法所限定，例如「第1曝光步驟」與「第2曝光步驟」亦可對調。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.
此般影像形成方法中，較宜使用之光硬化性組成物在以下詳細說明。Among the above image forming methods, a photocurable composition which is preferably used is described in detail below.
本實施形態之光硬化性組成物之光酸產生劑對電子供給性染料為具顯色效果之電子接受性化合物，因電子活性能量線之照射產生酸，使後述電子供給性染料發色用。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 electron-active energy ray to cause coloring of an electron-donating dye to be described later.
此般光酸產生劑，例如重氮鎓鹽、碘鎓鹽、溴鎓鹽、氯鎓鹽、鋶鹽、硒鎓鹽、吡喃鎓鹽、噻吡啶鎓鹽、吡啶鎓鹽等之鎓鹽；三(三鹵代甲基)-s-三嗪(例如2,4,6-三(三氯甲基)-s-三嗪)、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-s-三嗪、2-甲基-4,6-雙(三氯甲基)-s-三嗪等之鹵素化化合物；磺酸之2-硝基苄基酯；亞胺基磺酸酯；1-氧代-2-二氮萘醌-4-磺酸酯衍生物；N-羥基醯亞胺=磺酸酯；三(甲烷磺醯基氧基)苯衍生物；雙磺醯基二氮甲烷類；磺醯基羰基烷烴類；磺醯基羰基二氮甲烷類；二磺化合物；鐵丙二烯錯合物等。Such a photoacid generator such as a diazonium salt, an iodonium salt, a bromine sulfonium salt, a chloranium salt, a sulfonium salt, a selenium sulfonium salt, a pyrylium salt, a thiapyridinium salt, a pyridinium salt or 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)- S-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl) Halogenated compound of -s-triazine; 2-nitrobenzyl sulfonate; iminosulfonate; 1-oxo-2-diazonaphthoquinone-4-sulfonate derivative; N - hydroxy quinone imine = sulfonate; tris(methanesulfonyloxy) benzene derivative; bissulfonyl nitromethane; sulfonyl carbonyl alkane; sulfonyl carbonyl diazomethane; a compound; an iron propadiene complex or the like.
此等之光酸產生劑可單獨或2種類以上組合使用。These photoacid generators may be used singly or in combination of two or more kinds.
此般光酸產生劑的搭配量，相對於組成物之固形分100質量份，以5～40質量份為佳。比5質量份少則發色變得不足。又，比40質量份多則影像形成後之影像安定性變差。較佳為10～30質量份。The amount of the photoacid generator to be used 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.
本實施形態之光硬化性組成物之電子供給性染料用於上述光酸產生劑產生的酸造成發色、形成圖型用。The electron-donating dye of the photocurable composition of the present embodiment is used for the coloring of the acid generated by the photo-acid generator to form a pattern.
此般化合物，例如3,3-雙(p-二甲基胺基苯基)-6-甲基胺基鄰苯二甲內酯、3,3-雙(p-二甲基胺基苯基)鄰苯二甲內酯、3-(p-二甲基胺基苯基)-3-(1,2-二甲基吲哚-3-基)鄰苯二甲內酯等之三烯丙基甲烷系化合物、4,4’-雙-二甲基胺基二苯甲基苄基醚、N-鹵代苯基-隱色金黃素、N-2,4,5-三氯苯基隱色金黃素等之二苯基甲烷系化合物、7-二甲基胺基-3-氯螢光黃母體、7-二甲基胺基-3-氯-2-甲基螢光黃母體、2-苯基胺基-3-甲基-6-(N-乙基-N-p-甲苯基胺基)螢光黃母體等之螢光黃母體(fluoran)系化合物、苯甲醯基隱色甲基藍、p-硝基苄基隱色甲基藍等之噻嗪系化合物、3-甲基-螺-二萘並吡喃、3-乙基-螺-二萘並吡喃、3-丙基-螺-二萘並吡喃、3-丙基-螺-二苯並吡喃等之螺系化合物等。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-(1,2-dimethylindol-3-yl)phthalic acid lactone Methane-based compound, 4,4'-bis-dimethylaminobenzhydrylbenzyl ether, N-halophenyl-leucochrome, N-2,4,5-trichlorophenyl Diphenylmethane-based compound such as chromophorin, 7-dimethylamino-3-chlorofluorescent yellow precursor, 7-dimethylamino-3-chloro-2-methylfluorescent yellow matrix, 2 Fluorescent yellow fluoran compound such as phenylamino-3-methyl-6-(N-ethyl-Np-methylphenylamino)fluorescent yellow matrix, benzamidine-based leucomethyl a thiazine compound such as blue, p-nitrobenzyl leucomethyl blue, etc., 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-propyl a spiro compound such as spiro-dinaphthopyran or 3-propyl-spiro-dibenzopyran.
此等之電子供給性染料可單獨或亦可因應必要倂用2種類以上者。又，作為提升影像安定性的習知手段，亦可將電子供給性染料膠囊化後使用。又，於此等之染料可添加提升發色性用的四溴化碳般光氧化劑或防止暗發色之羥基喹啉般添加劑。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 may be encapsulated and used. Further, such a dye may be added with a carbon tetrachloride-like photo oxidizing agent for improving color development or a hydroxyquinoline-like additive for preventing dark color.
此般電子供給性染料之搭配量，相對於光硬化性組成物之固形分100質量份，以3～20質量份為佳。比3質量份少時，發色變得不足。又，比20質量份多時，無法期望有更優異效果。較佳為8～15質量份。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.
本實施形態之光硬化性組成物之光硬化性成分，可例舉如光聚合起始劑、含乙烯性不飽和基化合物等。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.
光聚合起始劑，用於活性能量線之照射產生自由基，使後述含乙烯性不飽和基化合物等聚合。接著，此般光聚合起始劑在光酸產生劑的感光波長區域外必須有感光波長區域。亦即，必須有僅光聚合起始劑有的感光波長區域存在。除光聚合起始劑與光酸產生劑之感光波長區域重疊的波長區域外，必須有僅光聚合起始劑有的感光波長區域存在。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 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 in which only the photopolymerization initiator is present. Except for the wavelength region in which the photopolymerization initiator and the photosensitive wavelength region of the photoacid generator overlap, it is necessary to have only the photosensitive wavelength region of the photopolymerization initiator.
上述光酸產生劑在400nm以下，尤其在紫外光區感光者多。為了不使此般光酸產生劑感光而產生自由基，光聚合起始劑之中更以亦在光酸產生劑的感光波長區域以外具有吸收‧活性者為佳。又，為了抑制搭配光聚合起始劑造成的著色，利用樹脂之透明性，亦以使用少量添加可得到足夠光硬化之高感度光聚合起始劑為佳。The above photoacid generator is more than 400 nm, especially in the ultraviolet region. In order to generate a radical without causing the photoacid generator to be photosensitive, it is preferred that the photopolymerization initiator further has absorption and 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 photohardened by using a small amount of transparency.
此般光聚合起始劑，以肟酯系光聚合起始劑較宜使用。例如下述一般式(I)所表示肟酯系光聚合起始劑，在光酸產生劑的感光波長區域以外亦具有感光波長區域，具特別高光感度者。As such a photopolymerization initiator, an oxime ester photopolymerization initiator is preferably used. 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.
(式中，R1 為氫原子、碳數1～7之烷基、或苯基，R2 為碳數1～7之烷基、或苯基)(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 a phenyl group)
此般肟酯系光聚合起始劑，因在可見光源廣用的405nm具有良好感度，以下述式(II)所表示2-(乙醯基氧基亞胺基甲基)硫黃嘌呤-9-酮為佳。The oxime ester-based photopolymerization initiator has a good sensitivity at 405 nm widely used in a visible light source, and is represented by the following formula (II): 2-(ethylideneoxyiminomethyl)thioxanthine-9 - Ketone is preferred.
又，肟酯系光聚合起始劑，以具有一般式(III)、一般式(IV)所表示構造為佳。Further, the oxime ester photopolymerization initiator is preferably a structure represented by the general formula (III) or the general formula (IV).
(式中，R3 、R4 各自獨立表示碳數1～12之烷基，R5 、R6 、R7 及R8 各自獨立表示氫原子或碳數1～6之烷基，M為O、S或NH，n為0～5之整數，R9 、R10 為碳數1～12之烷基，R11 為氫原子、碳數1～20之烷基)(wherein R 3 and R 4 each independently represent an alkyl group having 1 to 12 carbon atoms; and R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and M is O; , S or NH, n is an integer of 0 to 5, R 9 and R 10 are an alkyl group having 1 to 12 carbon atoms, and R 11 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms)
此般肟酯系光聚合起始劑之中，更以式(II)所表示2-(乙醯基氧基亞胺基甲基)硫黃嘌呤-9-酮特別佳。市售品，可舉例如CGI-325、IRGACURE(登錄商標)OXE01、IRGACUREOXE02(皆Ciba Specialty Chemicals公司製)、N-1919(ADEKA公司製)等。Among the above-mentioned oxime ester-based photopolymerization initiators, 2-(ethylideneoxyiminomethyl)thioxanthene-9-one represented by the formula (II) is particularly preferable. Commercially available products include, for example, CGI-325, IRGACURE (registered trademark) OXE01, IRGACUREOXE02 (all manufactured by Ciba Specialty Chemicals Co., Ltd.), N-1919 (made by Adeka Co., Ltd.), and the like.
此般肟酯系光聚合起始劑可單獨或2種類以上組合使用。The oxime ester-based photopolymerization initiator may be used singly or in combination of two or more kinds.
此般肟酯系光聚合起始劑，相對於後述含乙烯性不飽和基化合物之固形分100質量份，以0.05～10質量份為佳。比0.05質量份少時，光硬化變得不足、影像固定變差。又，比10質量份多時無法期望有更優異效果。較佳為0.5～5質量份。The oxime ester-based photopolymerization initiator is preferably 0.05 to 10 parts 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.
又，肟酯系光聚合起始劑以外的光聚合起始劑，可舉例如二苯甲酮系、乙醯苯系、胺基乙醯苯系、安息香醚系、苄基縮酮系、肟醚系、二茂鈦系等之習知自由基光聚合起始劑。因合倂使用的光酸產生劑而異，以使用可見光區於長波長區域具吸收、活性，且有高感光性之光聚合起始劑特別佳。此等之光聚合起始劑可單獨或2種以上組合使用。In addition, examples of the photopolymerization initiator other than the oxime ester photopolymerization initiator include benzophenone type, acetophenone type, amino acetonide type, benzoin type, benzyl ketal type, and oxime. A conventional radical photopolymerization initiator such as an 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.
又，可將感光波長區域任意設定的起始系，亦可利用例如組合香豆素、花青、方酸等之色素與自由基產生劑的習知2分子複合起始系。已知例如作為自由基產生劑的咪唑二聚物與作為色素之吖啶色素或三嗪系色素之組合、作為自由基產生劑的N-苯基甘胺酸與作為色素之香豆素酮系之組合、作為自由基產生劑的碘鎓鹽與各種色素之組合、作為自由基產生劑的三嗪系化合物與作為色素之芳香族酮衍生物之組合等。又，花青、若丹明、番紅花素等色素之烷基硼酸鹽亦為有效的可見光起始劑，在本實施形態亦可利用此等習知光聚合起始劑系。Further, a starting system in which the photosensitive wavelength region is arbitrarily set may be used, and for example, a conventional two-molecule composite starting system in which a dye such as coumarin, cyanine or squaraine or a radical generating agent is combined 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 pigment. Further, the alkyl borate of a pigment such as cyanine, rhodamine or crocin is also an effective visible light initiator, and such a conventional photopolymerization initiator can also be used in the present embodiment.
又，含乙烯性不飽和基化合物可用於以活性能量線之照射由光聚合起始劑產生自由基而光聚合、使影像固定。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.
此般含乙烯性不飽和基化合物，例如乙二醇、甲氧基四乙二醇、聚乙二醇、丙二醇等之二醇之二丙烯酸酯類；己二醇、三羥甲基丙烷、季戊四醇、二季戊四醇、三-羥基乙基異氰脲酸酯等之多價醇或此等之乙烯氧化物加成物或丙烯氧化物加成物等之多價丙烯酸酯類；苯氧基丙烯酸酯、雙酚A二丙烯酸酯、及此等之酚類之乙烯氧化物加成物或丙烯氧化物加成物等之多價丙烯酸酯類；甘油二縮水甘油基醚、甘油三縮水甘油基醚、三羥甲基丙烷三縮水甘油基醚、三縮水甘油基異氰脲酸酯等之縮水甘油基醚之多價丙烯酸酯類；三聚氰胺丙烯酸酯及/或對應此等丙烯酸酯的各甲基丙烯酸酯類等。The ethylenically unsaturated group-containing compound such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol or the like diol diacrylate; 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; phenoxy acrylate; a polyvalent acrylate such as bisphenol A diacrylate or an ethylene oxide adduct of such a phenol or a propylene oxide adduct; glycerol diglycidyl ether, glycerol triglycidyl ether, three a polyvalent acrylate of a glycidyl ether such as methylolpropane triglycidyl ether or triglycidyl isocyanurate; a melamine acrylate and/or a methacrylate corresponding to the acrylates Wait.
進一步，可舉例如甲酚酚醛清漆型環氧樹脂等之多官能環氧樹脂與丙烯酸反應之環氧基丙烯酸酯樹脂或進而該環氧基丙烯酸酯樹脂之羥基與季戊四醇三丙烯酸酯等之羥基丙烯酸酯與異佛爾酮二異氰酸酯等之二異氰酸酯之half urathane化合物進行反應的環氧基胺基甲酸乙酯丙烯酸酯化合物等。此般環氧基丙烯酸酯系樹脂可不降低指觸乾燥性，且提升光硬化性。Further, for example, an epoxy acrylate resin in which a polyfunctional epoxy resin such as a cresol novolak type epoxy resin and acrylic acid are reacted, or a hydroxyl group of the epoxy acrylate resin and a hydroxy acrylic acid such as pentaerythritol triacrylate may be mentioned. An epoxy hydroxy urethane acrylate compound which reacts 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.
此等含乙烯性不飽和基化合物可1種或2種以上任意組合。These ethylenically unsaturated group-containing compounds may be used alone or in combination of two or more kinds.
此般含乙烯性不飽和基化合物之搭配量，相對於光硬化性組成物之固形分100質量份，以50～95質量份為佳。比50質量份少時，影像的固定變差。又，比95質量份多時，發色度降低。較佳為60～90質量份。The amount of the ethylenically unsaturated group-containing compound to be used is preferably 50 to 95 parts by mass based on 100 parts by mass of the solid content of the photocurable composition. When the amount is less than 50 parts by mass, the fixation of the image is deteriorated. Moreover, when it is more than 95 parts by mass, the color development degree is lowered. It is preferably 60 to 90 parts by mass.
此般光硬化性組成物中，以黏度調整為目的，可因應必要添加有機溶劑。此般有機溶劑，可使用如甲基乙基酮、環己酮等之酮類；甲苯、二甲苯、四甲基苯等之芳香族烴類；溶纖劑、甲基溶纖劑、丁基溶纖劑、卡必醇、甲基卡必醇、丁基卡必醇、丙二醇單甲基醚、二丙二醇單甲基醚、二丙二醇二乙基醚、三丙二醇單甲基醚等之二醇醚類；乙酸乙酯、乙酸丁酯、乳酸丁酯、溶纖劑乙酸酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲基醚乙酸酯、二丙二醇單甲基醚乙酸酯、碳酸丙烯酯等之酯類；辛烷、癸烷等之脂肪族烴類；石油醚、石腦油、溶煤石油精等之石油系溶劑等之習知有機溶劑。此等之有機溶劑，可單獨或二種類以上組合使用。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. Glycol ethers such as carbitol, carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether Ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate An ester such as an ester, a dipropylene glycol monomethyl ether acetate or a propylene carbonate; an aliphatic hydrocarbon such as octane or decane; a petroleum solvent such as petroleum ether, naphtha or petroleum-soluble petroleum spirit; Conventional organic solvents. These organic solvents may be used singly or in combination of two or more kinds.
又，在光硬化性組成物中可因應必要，含有種種添加劑，例如二氧化矽、氧化鋁、滑石、碳酸鈣、硫酸鋇等之無機填料或丙烯小珠或胺基甲酸乙酯小珠等之有機填料等之充填劑、偶合劑、消泡劑、塗平劑等之添加劑等。Further, the photocurable composition may contain various additives such as inorganic fillers such as cerium oxide, aluminum oxide, talc, calcium carbonate, and barium sulfate, or propylene beads or urethane beads, etc., as necessary. Additives such as fillers, coupling agents, antifoaming agents, and coating agents such as organic fillers.
如此一來，經本實施形態之影像形成方法，進而藉由使用適合此影像形成方法的光硬化性組成物，除可形成習知影像形成方法所無法形成的高對比的影像，且可獲得優異影像安定性與良好硬化物性。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.
因此，不僅習知感熱記錄紙或防火材，例如亦可廣泛利用在使用環境嚴苛的電子基板或顯示器相關領域之印記用途或遮光用途。進一步，在濕式影像形成方法無法對應腐蝕問題之鋁配線上亦可形成對比，而可展開於受光元件或位移感測器等、MEMS領域之應用。Therefore, not only the heat sensitive recording paper or the fireproof material but also the imprinting use or the light shielding use in the field of use of an electronic substrate or a display having a severe environment can be widely used. Further, the wet image forming method can also form a contrast on the aluminum wiring which cannot cope with the corrosion problem, and can be developed in the MEMS field, such as a light receiving element or a displacement sensor.
[實施例][Examples]
以下用實施例及比較例將本發明具體說明，但本發明不限於下述實施例。又，以下「份」及「%」若不特別限定時，全部係質量基準。Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples. In addition, the following "parts" and "%" are all based on quality unless otherwise specified.
首先，使用以下之合成例調製樹脂清漆。First, a resin varnish was prepared using the following synthesis example.
於具備攪拌機、溫度計、迴流冷卻管、滴下漏斗及氮導入管的2公升可分離燒杯中，置入甲酚酚醛清漆型環氧樹脂之EPICLON(登錄商標)N-680(DIC公司製、環氧當量=215g/當量)107.5份，加入卡必醇乙酸酯108份、出光石油化學製之Ipzole(登錄商標)#150 108份，進行加熱溶解而得到樹脂溶液。EPICLON (registered trademark) N-680 (made by DIC, epoxy) containing a cresol novolac type epoxy resin in a 2 liter separable beaker equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen inlet tube Equivalent=215 g/eq.) 107.5 parts, 108 parts of carbitol acetate, 108 parts of Ipzole (registered trademark) #150 manufactured by Idemitsu Petrochemical Co., Ltd., and heated and dissolved to obtain a resin solution.
於此樹脂溶液中加入作為聚合禁止劑之對苯二酚0.05份與作為反應觸媒之三苯基膦1.0份。將該混合物於85～95℃加熱，並緩緩滴下丙烯酸36份，進行24小時反應。於得到的環氧基丙烯酸酯中緩緩滴下予先使異佛爾酮二異氰酸酯與季戊四醇三丙烯酸酯以1：1莫耳反應之half urathane 257.5份，並在60～70℃進行4小時反應，而調製樹脂清漆。To the resin solution, 0.05 part of hydroquinone as a polymerization inhibiting agent and 1.0 part of triphenylphosphine as a reaction catalyst were added. The mixture was heated at 85 to 95 ° C, and 36 parts of acrylic acid was gradually dropped, and the reaction was carried out for 24 hours. To the obtained epoxy acrylate, 257.5 parts of half urathane which was previously reacted with isophorone diisocyanate and pentaerythritol triacrylate at 1:1 molar was gradually dropped, and reacted at 60 to 70 ° C for 4 hours. The resin varnish is prepared.
如表1所示，使包含得到的樹脂清漆之種種成分以各比例(質量份)進行搭配，並以攪拌機進行予備混合後，以3滾輪研磨機進行混練，而得到光硬化性組成物1-1～3、2-1～4。As shown in Table 1, various components (including parts by mass) of the obtained resin varnish were mixed, and premixed with a stirrer, and then kneaded by a three-roll mill to obtain a photocurable composition 1- 1 to 3, 2-1 to 4.
註：Note:
＊1：ADEKA(登錄商標)傲普拖碼SP-152(ADEKA公司製)*1: ADEKA (registered trademark) Aopu drag code SP-152 (made by ADEKA)
＊2：S-205(山田化學工業公司製)*2: S-205 (made by Yamada Chemical Industry Co., Ltd.)
＊3：Lucirin(登錄商標)TPO(BASF日本股份公司製)*3: Lucirin (registered trademark) TPO (BASF Japan Stock Co., Ltd.)
＊4：IRGACURE(登錄商標)784(Ciba Specialty Chemicals公司製)*4: IRGACURE (registered trademark) 784 (manufactured by Ciba Specialty Chemicals Co., Ltd.)
＊5：CGI 325(Ciba Specialty Chemicals公司製)*5: CGI 325 (manufactured by Ciba Specialty Chemicals)
＊6：IRGACURE OXE-02(Ciba Specialty Chemicals公司製)*6: IRGACURE OXE-02 (manufactured by Ciba Specialty Chemicals)
＊7：IRGACURE OXE-01(Ciba Specialty Chemicals公司製)*7: IRGACURE OXE-01 (manufactured by Ciba Specialty Chemicals)
＊8：IRGACURE 907(Ciba Specialty Chemicals公司製)*8: IRGACURE 907 (manufactured by Ciba Specialty Chemicals)
＊9：優尼鐵克(登錄商標)R-100(固形分65%)(DIC股份公司製)*9: Unice (registered trademark) R-100 (solid content: 65%) (made by DIC Corporation)
＊10：聶而馬(登錄商標)DA-600(三洋化成工業公司製)*10: Nie Erma (registered trademark) DA-600 (manufactured by Sanyo Chemical Industry Co., Ltd.)
＊11：BYK(登錄商標)-361N(BYK‧日本公司製)*11: BYK (registered trademark) - 361N (BYK‧ Japan company)
＊12：KS-66(信越矽酮公司製)*12: KS-66 (manufactured by Shin-Etsu Chemical Co., Ltd.)
試驗基板之製作：Production of test substrate:
將表1所示之組成物例1～4之光硬化性組成物分別銅箔基板拋光研磨後，以網版印刷法進行全面印刷，藉由80℃×30分乾燥，在基板上形成無色透明塗膜，得到實施例1～3、比較例1～4及參考例之試驗基板。The photocurable compositions of the composition examples 1 to 4 shown in Table 1 were polished and polished, respectively, and then subjected to full-screen printing by screen printing, and dried at 80 ° C × 30 minutes to form a colorless transparent film on the substrate. The test substrates of Examples 1 to 3, Comparative Examples 1 to 4, and Reference Examples were obtained by coating a film.
關於得到的試驗基板，各自以表2條件進行曝光。又，各曝光步驟如以下的條件。The obtained test substrates were each exposed under the conditions of Table 2. Further, each exposure step is as follows.
第1曝光步驟：First exposure step:
透過負遮罩使用金屬鹵化物燈，在全光波長領域以1000J/cm2 進行光照射。之後，在80℃進行10分鐘PEB處理。Light irradiation was performed at 1000 J/cm 2 in the all-optical wavelength region using a metal halide lamp through a negative mask. Thereafter, PEB treatment was carried out for 10 minutes at 80 °C.
第2曝光步驟：The second exposure step:
對經第1曝光步驟的試驗基板，使用振動在光酸產生劑的感光波長區域外且為肟酯系光聚合起始劑之感光波長區域的405nm波長之直描曝光機(PENTAX公司製DI-μ)，使試驗基板上之塗膜全體以300J/cm2 進行光照射。For the test substrate subjected to the first exposure step, a direct exposure machine (a DI-made by PENTAX Corporation) having a wavelength of 405 nm which is outside the photosensitive wavelength region of the photoacid generator and which is a photosensitive wavelength region of an oxime ester photopolymerization initiator is used. μ), the entire coating film on the test substrate was irradiated with light at 300 J/cm 2 .
關於此般實施例1～3、比較例1～4及參考例之試驗基板，如以下所示進行塗膜特性之評估。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.
對比評估：Comparative evaluation:
關於實施例1～3、比較例1～4、參考例之試驗基板，使塗膜的發色以目視確認。評估基準如下。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.
有發色…可見到曝光後之發色Hair color... visible to the color after exposure
無發色…曝光前後無色彩變化No hair color... no color change before and after exposure
黏性評估：Viscosity assessment:
對實施例1～3、比較例1～4及參考例之試驗基板，依曝光前、第1曝光處理後及第2曝光處理後之黏性，進行塗膜(曝光部、未曝光部)之評估。評價基準如下。The test substrates of Examples 1 to 3, Comparative Examples 1 to 4, and Reference Examples were coated (exposed portion, unexposed portion) according to the viscosity before exposure, after the first exposure treatment, and after the second exposure treatment. Evaluation. The evaluation criteria are as follows.
○…指蝕時塗膜表面完全無指跡○...The surface of the coating film is completely free of finger marks when it is etched
×…指蝕時塗膜表面殘留指跡×... finger surface residual fingerprint on the surface of the coating
耐溶劑性評估：Solvent resistance evaluation:
關於實施例1～3、比較例1～4及參考例之試驗基板，為了確認曝光處理後之塗膜(硬化物)之硬化性，著色部‧ 未著色部中各自使用丙二醇單甲基醚乙酸酯(PMA)，進行摩擦試驗10次，將塗膜的溶解‧剝離以目視確認。評估基準如下。In the test substrates of Examples 1 to 3, Comparative Examples 1 to 4, and the reference examples, in order to confirm the curability of the coating film (cured material) after the exposure treatment, propylene glycol monomethyl ether B was used for each of the colored portions and the uncolored portions. The acid ester (PMA) was subjected to a rubbing test 10 times, and the dissolution of the coating film was ‧ peeled off and visually confirmed. The evaluation criteria are as follows.
○…PMA摩擦後，無塗膜的溶解‧剝離○...after PMA friction, no coating dissolution ‧ peeling
△…PMA摩擦後，於塗膜表面有混濁部△... After the PMA is rubbed, there is a turbid part on the surface of the coating film.
×…PMA摩擦後，有塗膜的溶解‧剝離×... After the PMA is rubbed, there is a dissolution of the coating film.
影像安定性(耐候性)評估：Image stability (weatherability) assessment:
關於實施例1～3、比較例1～4及參考例之試驗基板，曝光處理後之塗膜(硬化物)，於螢光燈下1週放置，以目視評估確認照相灰霧。評估基準如下。With respect to the test substrates of Examples 1 to 3, Comparative Examples 1 to 4, and the reference examples, the coating film (cured material) after the exposure treatment was placed under a fluorescent lamp for one week, and the photographic fog was visually evaluated. The evaluation criteria are as follows.
○…即使經一週放置，未見到未著色部之照相灰霧，維持對比狀態○... Even if it is placed for one week, no photographic fog is seen in the uncolored portion, and the contrast state is maintained.
×…經一週放置，可見未著色部之照相灰霧，而無法維持對比之狀態×... After one week of standing, the photographic fog of the uncolored portion is visible, and the state of contrast cannot be maintained.
表2所示般，使用組成物中光酸產生劑的感光波長區域外具有感光域之光聚合起始劑，進行2階段的曝光之實施例1～3中，可兼顧高對比化與優異影像安定性。As shown in Table 2, in Examples 1 to 3 in which two-stage exposure was carried out using a photopolymerization initiator having a photosensitive region outside the photosensitive wavelength region of the photoacid generator in the composition, both high contrast and excellent image were obtained. Stability.
另外，進行習知1階段的曝光的比較例1～4中，雖無法形成對比，但因未著色部未硬化，同樣地維持對比變得困難，無法獲得足夠影像安定性(耐候性)。又，使用組成物中光酸產生劑的感光波長區域外無感光波長區域的光聚合起始劑之參考例中，變得難以維持對比，無法獲得足夠影像安定性(耐候性)。Further, in Comparative Examples 1 to 4 in which the conventional one-stage exposure was performed, although the contrast could not be formed, 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 the contrast, and sufficient image stability (weather resistance) could not be obtained.
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| JP2007059025A (en) * | 2005-08-26 | 2007-03-08 | Fujifilm Corp | Two-photon recording method, two-photon absorption recording material, two-photon absorption recording and reproducing method, optical recording medium, optical recording and reproducing method, three-dimensional volume display and manufacturing method of volume display |
| TW200844652A (en) * | 2006-11-15 | 2008-11-16 | Taiyo Ink Mfg Co Ltd | Process for forming solder resist film and photosensitive composition |
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| EP1602480A1 (en) * | 2004-05-31 | 2005-12-07 | Fuji Photo Film Co., Ltd. | Method for colored image formation |
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