TWI577756B - Color material dispersion liquid, color resin composition for color filters, color filter, and display device - Google Patents
Color material dispersion liquid, color resin composition for color filters, color filter, and display device Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
- C09B67/0066—Aqueous dispersions of pigments containing only dispersing agents
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- 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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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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
本發明係關於一種色材分散液、彩色濾光片用著色樹脂組成物、彩色濾光片及顯示裝置。 The present invention relates to a color material dispersion liquid, a coloring resin composition for a color filter, a color filter, and a display device.
以顯示器等為代表之薄型影像顯示裝置,即所謂平板顯示器,係以較陰極射線管型顯示器薄且於縱深方向上不占空間為特徵,而已大量地上市。其市場價格係隨著生產技術之進化而價格逐年趨於合理,進而需求擴大,生產量亦逐年增加。尤其是彩色液晶電視大致成為TV之主流。又,最近,如藉由自發光而視認性較高之有機EL顯示器般的有機發光顯示裝置,亦作為下一代影像顯示裝置而受到矚目。針對該等影像顯示裝置之性能,強烈期望對比度或色再現性之提高等更進一步之高畫質化、或消耗電力之降低。 A thin image display device typified by a display or the like, which is a so-called flat panel display, is characterized in that it is thinner than a cathode ray tube type display and does not occupy a space in the depth direction, and has been widely marketed. Its market price is steadily increasing year by year with the evolution of production technology, and the demand is expanding, and the production volume is increasing year by year. In particular, color LCD TVs have become the mainstream of TV. In addition, an organic light-emitting display device such as an organic EL display having high visibility from self-luminous light has recently attracted attention as a next-generation image display device. In view of the performance of these image display devices, it is strongly desired to further improve image quality or power consumption, such as improvement in contrast or color reproducibility.
於該等液晶顯示裝置或有機發光顯示裝置中係使用彩色濾光片。例如,於彩色液晶顯示器之情形,以背光源為光源,藉由電驅動液晶而控制光量,該光通過彩色濾光片,藉此進行色表現。因此,對液晶電視之色表現而言,彩色濾光片不可或缺,並負責左右顯示器性能之重要角色。又,有機發光顯示裝置中,有使用彩色濾光片進行畫素之色調整的情況,或對白色發光之有機發光元件使用彩色濾光片而與液晶顯示裝置同樣地形成彩色影像之情形。 Color filters are used in such liquid crystal display devices or organic light emitting display devices. For example, in the case of a color liquid crystal display, a backlight is used as a light source, and the amount of light is controlled by electrically driving the liquid crystal, and the light passes through the color filter, thereby performing color expression. Therefore, color filters are indispensable for the color performance of LCD TVs and are responsible for the important role of left and right display performance. Further, in the organic light-emitting display device, a color filter is used to adjust the color of the pixel, or a color filter is used for the white light-emitting organic light-emitting device, and a color image is formed in the same manner as the liquid crystal display device.
近年來之趨勢,係要求影像顯示裝置之省電力化,且為了提高背光源之利用效率,特別要求彩色濾光片之高亮度化。尤其是於移動式顯示器(行動電話、智慧型手機、平板PC)中成為較大課題。 In recent years, there has been a demand for power saving of video display devices, and in order to improve the utilization efficiency of backlights, high brightness of color filters is particularly required. Especially in mobile displays (mobile phones, smart phones, tablet PCs) has become a big issue.
雖說因技術進化而電池容量變大,但移動式之蓄電量依然有限,另一方面,有隨著畫面尺寸擴大而消耗電力增加之傾向。由於直接關係到移動終端之可使用時間或充電頻度,故包含彩色濾光片之影像顯示裝置將左右移動終端之設計或性能。 Although the battery capacity has increased due to technological evolution, the mobile power storage capacity is still limited. On the other hand, there is a tendency for power consumption to increase as the screen size increases. Since it is directly related to the usable time or charging frequency of the mobile terminal, the image display device including the color filter will design the left or right mobile terminal or the performance.
於此,彩色濾光片通常具有透明基板、形成於透明基板上且包含紅、綠、藍三原色之著色圖案的著色層、與為了劃分各著色圖案而形成於透明基板上的遮光部。 Here, the color filter generally has a transparent substrate, a coloring layer formed on the transparent substrate and including a color pattern of three primary colors of red, green, and blue, and a light shielding portion formed on the transparent substrate to divide each coloring pattern.
於此種著色層之形成方法中,使用耐熱性或耐光性優異之顏料作為色材之顏料分散法被廣泛使用。然而,使用習知顏料之彩色濾光片變得難以達成目前更高亮度化之要求。 In the method of forming such a coloring layer, a pigment dispersion method using a pigment excellent in heat resistance or light resistance as a color material is widely used. However, the use of color filters of conventional pigments has made it difficult to achieve the current higher brightness requirements.
作為用以達成高亮度化之一種手段,已檢討了使用染料之彩色濾光片用感光性樹脂組成物。相較於顏料,染料係通常穿透率較高,可製造高亮度之彩色濾光片,但有耐熱性或耐光性差、於彩色濾光片製造步驟中之高溫加熱時等色度容易變化之問題。又,使用染料之感光性樹脂組成物有於乾燥步驟中容易析出異物之問題。若異物析出於塗膜,則對比度明顯惡化,而難以使用作為著色層。 As a means for achieving high luminance, a photosensitive resin composition for a color filter using a dye has been examined. Compared with pigments, dyes generally have a high transmittance, and can produce high-intensity color filters, but have poor heat resistance or light resistance, and chromaticity is easy to change when heated at high temperatures in the color filter manufacturing step. problem. Further, the photosensitive resin composition using a dye has a problem that foreign matter is easily precipitated in the drying step. When the foreign matter is deposited on the coating film, the contrast is remarkably deteriorated, and it is difficult to use it as a colored layer.
專利文獻1揭示一種特定之著色感光性樹脂組成物,其含有含特定染料與顏料之色材、與特定溶劑。根據專利文獻1,藉由該著色感光性樹脂組成物,可獲得耐熱性高、塗佈不均少 的塗膜。 Patent Document 1 discloses a specific colored photosensitive resin composition containing a color material containing a specific dye and a pigment, and a specific solvent. According to Patent Document 1, it is possible to obtain high heat resistance and low coating unevenness by the colored photosensitive resin composition. Coating film.
又,專利文獻2揭示一種特定之藍色感光性樹脂組成物,其含有特定構造之有機溶劑可溶性染料、與有機顏料作為色材。根據專利文獻2,藉由使用該著色感光性樹脂組成物可獲得高亮度之彩色濾光片。 Further, Patent Document 2 discloses a specific blue photosensitive resin composition containing an organic solvent-soluble dye having a specific structure and an organic pigment as a color material. According to Patent Document 2, a high-intensity color filter can be obtained by using the colored photosensitive resin composition.
專利文獻1及2中之上述特定染料,係溶解於溶劑而使用,耐熱性或耐光性差,且因含有用於使染料溶解之極性溶劑而穩定性惡化。 The specific dyes described in Patent Documents 1 and 2 are used by being dissolved in a solvent, and have poor heat resistance and light resistance, and are deteriorated in stability by containing a polar solvent for dissolving the dye.
專利文獻3揭示一種彩色濾光片用著色樹脂組成物,其含有特定色材,且該色材含有使複數之染料骨架藉由交聯基而交聯的2價以上之陽離子、與2價以上之陰離子。其揭示藉由含有上述色材之彩色濾光片用著色樹脂組成物所形成的著色層為高對比,耐溶劑性及電可靠性優異。 Patent Document 3 discloses a colored resin composition for a color filter, which contains a specific color material, and the color material contains a divalent or higher cation which crosslinks a plurality of dye skeletons by a crosslinking group, and a divalent or higher valence Anion. It is revealed that the coloring layer formed of the colored resin composition for a color filter containing the above color material has high contrast, and is excellent in solvent resistance and electrical reliability.
專利文獻1:日本專利特開2010-211198號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2010-211198
專利文獻2:日本專利特開2010-32999號公報 Patent Document 2: Japanese Patent Laid-Open Publication No. 2010-32999
專利文獻3:國際公開第2012/144521號說明書 Patent Document 3: International Publication No. 2012/144521
專利文獻3記載之含有特定色材的著色樹脂組成物,存在有難以確保黏度穩定性的課題。又,亦要求著色層之進一步耐熱性提升。 The colored resin composition containing a specific color material described in Patent Document 3 has a problem that it is difficult to ensure viscosity stability. Further, further heat resistance of the colored layer is also required to be improved.
本發明係有鑑於上述實際情況而完成者,且目的在於提供經時穩定性優越、並可形成耐熱性提升之塗膜的色材分散液;經時穩定性優越、並可形成耐熱性提升之著色層的彩色濾光片用著色樹脂組成物;使用該著色樹脂組成物之高亮度的彩色濾光片;以及具有該彩色濾光片的顯示裝置。 The present invention has been made in view of the above-described actual circumstances, and an object thereof is to provide a color material dispersion liquid which is excellent in stability over time and which can form a coating film having improved heat resistance; has excellent stability over time and can be improved in heat resistance. A colored resin composition for a color filter of a colored layer; a high-intensity color filter using the colored resin composition; and a display device having the color filter.
本發明之色材分散液係含有下述一般式(I)所示之色材、分散劑、有機酸化合物、與溶劑者;其特徵在於,上述分散劑係至少具有下述一般式(II)所示之構成單位(a),胺價為70mgKOH/g以上且160mgKOH/g以下的嵌段共聚合體;上述溶劑係23℃下之上述色材之溶解度為0.1(g/10ml溶劑)以下的溶劑;在將上述分散劑之上述胺價設為A(mgKOH/g)、將上述色材分散液中所含之上述有機酸化合物之物質量XA(mol)與構成上述色材分散液中所含之上述分散劑的上述構成單位(a)之物質量XB(mol)的比設為X(=XA/XB)時,滿足下式(1)及式(2);在X為未滿1之範圍時,進一步滿足下式(3);X≦1.5 式(1) The color material dispersion liquid of the present invention contains a color material, a dispersant, an organic acid compound, and a solvent represented by the following general formula (I); wherein the dispersant has at least the following general formula (II) The constituent unit (a) shown is a block copolymer having an amine value of 70 mgKOH/g or more and 160 mgKOH/g or less; and the solvent of the above-mentioned solvent system at a temperature of 23 ° C of 0.1 (g/10 ml solvent) or less The above-mentioned amine valence of the dispersant is A (mg KOH / g), and the mass of the organic acid compound X A (mol) contained in the above-mentioned color material dispersion is made up of the above-mentioned color material dispersion. When the ratio of the mass of the constituent unit (a) of the above dispersing agent (X) X B (mol) is X (=X A /X B ), the following formulas (1) and (2) are satisfied; When the range is less than 1, the following formula (3) is further satisfied; X≦1.5 formula (1)
A×X≧40 式(2) A×X≧40 type (2)
A×(1-X)≦42 式(3) A×(1-X)≦42 (3)
[化1]
(一般式(I)中,A係與N直接鍵結之碳原子為不具有π鍵結的a價有機基,該有機基表示至少於與N直接鍵結之末端具有飽和脂肪族烴基的脂肪族烴基、或具有該脂肪族烴基的芳香族基,碳鏈中亦可含有O、S、N;Bc-表示至少含有鎢之c價聚酸陰離子;Ri~Rv分別獨立表示氫原子、亦可具有取代基之烷基或亦可具有取代基之芳基,Rii與Riii、Riv與Rv亦可鍵結形成環構造;Ar1表示亦可具有取代基之2價芳香族基;複數之Ri~Rv及Ar1分別可為相同或相異;a及c表示2以上之整數,b及d表示1以上之整數;e為0或1,在e為0時鍵結不存在;複數之e可為相同或相異);
(一般式(II)中,R1為氫原子或甲基,Q為直接鍵結或2價連結基,R2為碳數1~8之伸烷基、-[CH(R5)-CH(R6)-O]x-CH(R5)-CH(R6)- 或-[(CH2)y-O]z-(CH2)y-所示之2價有機基,R3及R4分別獨立表示亦可被取代之鏈狀或環狀之烴基,或R3及R4彼此鍵結形成環狀構造。R5及R6分別獨立為氫原子或甲基;x表示1~18之整數,y表示1~5之整數,z表示1~18之整數)。 (In general formula (II), R 1 is a hydrogen atom or a methyl group, Q is a direct bond or a divalent linking group, and R 2 is an alkylene group having 1 to 8 carbon atoms, -[CH(R 5 )-CH (R 6 )-O] x -CH(R 5 )-CH(R 6 )- or -[(CH 2 ) y -O] z -(CH 2 ) y - a divalent organic group, R 3 And R 4 each independently represents a chain or cyclic hydrocarbon group which may be substituted, or R 3 and R 4 are bonded to each other to form a cyclic structure. R 5 and R 6 are each independently a hydrogen atom or a methyl group; x represents 1 An integer of ~18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18.)
本發明之色材分散液中,由分散穩定性之觀點而言,較佳係上述有機酸化合物為選自由下述一般式(IV)、及下述一般式(V)所組成之群組的1種以上。 In the color material dispersion liquid of the present invention, it is preferred that the organic acid compound is selected from the group consisting of the following general formula (IV) and the following general formula (V) from the viewpoint of dispersion stability. More than one type.
(式(IV)及式(V)中,Ra及Ra'分別獨立為氫原子、羥基、碳數1~18之烷基、碳數2~18之烯基、芳烷基、芳基、-[CH(Rc)-CH(Rd)-O]s-Re、-[(CH2)t-O]u-Re、或-O-Ra"所示之1價基,Ra及Ra'之任一者含有碳原子;Ra"為碳數1~18之烷基、碳數2~18之烯基、芳烷基、芳基、-[CH(Rc)-CH(Rd)-O]s-Re、-[(CH2)t-O]u-Re所示之1價基;Rb為碳數1~18之烷基、碳數2~18之烯基、芳烷基、芳基、-[CH(Rc)-CH(Rd)-O]s-Re、-[(CH2)t-O]u-Re或-O-Rb'所示之1價基;Rb'為碳數1~18之烷基、碳數2~18之烯基、芳烷基、芳基、-[CH(Rc)-CH(Rd)-O]s-Re、或-[(CH2)t-O]u-Re所示之1價基;Rc及Rd分別獨立為氫原子或甲基,Re為氫原子、或碳數1~18之烷基、碳數2~18之烯基、芳烷基、芳基、-CHO、-CH2CHO、-CO-CH=CH2、-CO-C(CH3)=CH2或-CH2COORf所示之1價基,Rf 為氫原子或碳數1~5之烷基;Ra、Ra'及Rb中,烷基、烯基、芳烷基、芳基分別亦可具有取代基;s表示1~18之整數,t表示1~5之整數,u表示1~18之整數)。 (In the formulae (IV) and (V), R a and R a ' are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group or an aryl group. , -[CH(R c )-CH(R d )-O] s -R e , -[(CH 2 ) t -O] u -R e , or -OR a" , a monovalent group, R Any one of a and R a' contains a carbon atom; R a" is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R c )- CH(R d )-O] s -R e , -[(CH 2 ) t -O] u -R e represents a monovalent group; R b is an alkyl group having 1 to 18 carbon atoms, carbon number 2~ 18 alkenyl, aralkyl, aryl, -[CH(R c )-CH(R d )-O] s -R e , -[(CH 2 ) t -O] u -R e or -OR a monovalent group represented by b' ; R b' is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R c )-CH(R d )-O] s -R e , or -[(CH 2 ) t -O] u -R e represents a monovalent group; R c and R d are each independently a hydrogen atom or a methyl group, and R e is a hydrogen atom Or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH 2 CHO, -CO-CH=CH 2 , -CO-C (CH 3 ) = CH 2 or -CH 2 COOR f is a monovalent group, R f is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and R a , R a ' and R b are an alkyl group or an alkene The group, the aralkyl group and the aryl group may each have a substituent; s represents an integer from 1 to 18, t represents an integer from 1 to 5, and u represents an integer from 1 to 18).
本發明之色材分散液中,由色材分散穩定性優越、進而在作成著色樹脂組成物時抑制影像殘渣發生、並具有高顯影密黏性、溶劑再溶解性優越的觀點而言,較佳係上述分散劑之酸價為1mgKOH/g以上且18mgKOH/g以下,該分散劑之玻璃轉移溫度為30℃以上。 In the color material dispersion liquid of the present invention, it is preferred that the color material has excellent dispersion stability, and further suppresses generation of image residue when the colored resin composition is formed, and has high development adhesiveness and superior solvent resolubility. The acid value of the dispersing agent is 1 mgKOH/g or more and 18 mgKOH/g or less, and the glass transition temperature of the dispersing agent is 30 °C or higher.
本發明之色材分散液係由可調整為所需色調的觀點而言,較佳為進一步含有選自二系色材及系色材的1種以上。 The color material dispersion of the present invention preferably further comprises a second selected from the viewpoint of being adjustable to a desired color tone. Color material and One or more types of color materials are used.
本發明之色材分散液,由耐熱性的觀點而言,較佳係上述系色材為之金屬色澱色材。 The color material dispersion liquid of the present invention is preferably the above from the viewpoint of heat resistance. Color material is Metallic lake color material.
本發明之彩色濾光片用著色樹脂組成物的特徵在於,含有上述本發明之色材分散液、鹼可溶性樹脂、多官能單體、與起始劑。 The colored resin composition for a color filter of the present invention contains the above-described color material dispersion liquid, alkali-soluble resin, polyfunctional monomer, and initiator.
本發明之彩色濾光片用著色樹脂組成物,由提升所得著色層之耐熱性的觀點而言,較佳係上述鹼可溶性樹脂之酸價為80mgKOH/g以上且300mgKOH/g以下。 In the colored resin composition for a color filter of the present invention, the acid value of the alkali-soluble resin is preferably 80 mgKOH/g or more and 300 mgKOH/g or less from the viewpoint of improving the heat resistance of the colored layer.
本發明之彩色濾光片用著色樹脂組成物,由鹼顯影性優越、提升所得著色層之耐熱性的觀點而言,較佳係上述多官能單體具有羧基。 In the colored resin composition for a color filter of the present invention, it is preferred that the polyfunctional monomer has a carboxyl group from the viewpoint of excellent alkali developability and heat resistance of the obtained colored layer.
本發明之彩色濾光片用著色樹脂組成物,由對基板之 密黏性優越、顯影耐性亦優越的觀點而言,較佳係上述鹼可溶性樹脂為具有乙烯性雙鍵的樹脂。 A colored resin composition for a color filter of the present invention, which is composed of a counter substrate From the viewpoint of excellent adhesion and excellent development resistance, it is preferred that the alkali-soluble resin is a resin having an ethylenic double bond.
本發明之彩色濾光片用著色樹脂組成物,由分散穩定性及耐熱性的觀點而言,較佳係上述鹼可溶性樹脂為具有烴環之樹脂。 In the colored resin composition for a color filter of the present invention, the alkali-soluble resin is preferably a resin having a hydrocarbon ring from the viewpoint of dispersion stability and heat resistance.
本發明之彩色濾光片用著色樹脂組成物中,由藉由提升著色層之硬化性而提升耐溶劑性、改善水滲染、且著色層之殘膜率變高的觀點而言,較佳係上述鹼可溶性樹脂所具有之烴環為選自由環戊基、環己基、基、異基、二環戊基、二環戊烯基、金剛烷基、及下述化學式(A)所示取代基所組成之群組的1種以上。 In the colored resin composition for a color filter of the present invention, it is preferred to improve the solvent resistance by improving the curability of the colored layer, to improve water bleeding, and to increase the residual film ratio of the colored layer. The hydrocarbon ring of the above alkali-soluble resin is selected from the group consisting of cyclopentyl, cyclohexyl, Basis One or more groups of the group consisting of a substituent represented by the following formula (A), a dicyclopentyl group, a dicyclopentenyl group, an adamantyl group, and the following formula (A).
本發明之彩色濾光片用著色樹脂組成物中,由藉由提升著色層之硬化性而提升耐溶劑性、改善水滲染、且著色層之殘膜率變高的觀點而言,較佳係上述鹼可溶性樹脂為下述一般式(B)所示化合物。 In the colored resin composition for a color filter of the present invention, it is preferred to improve the solvent resistance by improving the curability of the colored layer, to improve water bleeding, and to increase the residual film ratio of the colored layer. The above alkali-soluble resin is a compound represented by the following general formula (B).
(其中,上述一般式(B)中,X表示下述一般式(D)所示之基,Y分別獨立表示多元羧酸或其酸酐之殘基,Ri表示下述一般式(C)所示之基,j為0~4之整數,k為0~3之整數,n為1以上之整數。) (In the above general formula (B), X represents a group represented by the following general formula (D), and Y each independently represents a residue of a polyvalent carboxylic acid or an anhydride thereof, and R i represents a general formula (C) below. The base of the graph, j is an integer from 0 to 4, k is an integer from 0 to 3, and n is an integer of 1 or more.)
(其中,上述一般式(C)中,Rii為氫原子或甲基,Riii分別獨立表示氫原子或甲基。) (In the above general formula (C), R ii is a hydrogen atom or a methyl group, and R iii each independently represents a hydrogen atom or a methyl group.)
(其中,上述一般式(D)中,Riv分別獨立表示氫原子、碳數1~5之烷基、苯基、或鹵原子,Rv表示-O-或-OCH2CH2O-。) (In the above general formula (D), R iv each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom, and R v represents -O- or -OCH 2 CH 2 O-. )
本發明之彩色濾光片用著色樹脂組成物中,由抑制水滲染、耐溶劑性及感度優越的觀點而言,較佳係上述起始劑為肟酯系光聚合起始劑。 In the colored resin composition for a color filter of the present invention, the initiator is preferably an oxime ester photopolymerization initiator from the viewpoint of suppressing water permeation, solvent resistance, and sensitivity.
本發明之彩色濾光片用著色樹脂組成物,由著色樹脂組成物對基板之密黏性的經時穩定性優越的觀點而言,較佳係矽烷偶合劑之含有比例係相對於著色樹脂組成物中之總固形份為1質量%以下。 In the colored resin composition for a color filter of the present invention, it is preferable that the content ratio of the decane coupling agent is relative to the coloring resin from the viewpoint that the coloring resin composition has excellent stability with respect to the adhesion of the substrate. The total solid content in the substance is 1% by mass or less.
本發明之彩色濾光片係至少具備透明基板、與設置於 該透明基板上之著色層者,其特徵為,該著色層之至少一層係具有使上述本發明之彩色濾光片用著色樹脂組成物硬化而形成之著色層。 The color filter of the present invention has at least a transparent substrate and is disposed on The coloring layer on the transparent substrate is characterized in that at least one layer of the colored layer has a coloring layer formed by curing the coloring resin composition of the color filter of the present invention.
本發明之顯示裝置的特徵在於,具有上述本發明之彩色濾光片。 The display device of the present invention is characterized by having the above-described color filter of the present invention.
根據本發明,可提供經時穩定性優越、並可形成耐熱性提升之塗膜的色材分散液;經時穩定性優越、並可形成耐熱性提升之著色層的彩色濾光片用著色樹脂組成物;使用該著色樹脂組成物之高亮度的彩色濾光片;以及具有該彩色濾光片的顯示裝置。 According to the present invention, it is possible to provide a color material dispersion liquid which is excellent in stability over time and which can form a coating film having improved heat resistance; a coloring resin for a color filter which is excellent in stability over time and can form a coloring layer having improved heat resistance a composition; a high-intensity color filter using the colored resin composition; and a display device having the color filter.
1‧‧‧透明基板 1‧‧‧Transparent substrate
2‧‧‧遮光部 2‧‧‧Lighting Department
3‧‧‧著色層 3‧‧‧Colored layer
10‧‧‧彩色濾光片 10‧‧‧Color filters
20‧‧‧對向基板 20‧‧‧ opposite substrate
30‧‧‧液晶層 30‧‧‧Liquid layer
40‧‧‧液晶顯示裝置 40‧‧‧Liquid crystal display device
50‧‧‧有機保護層 50‧‧‧Organic protective layer
60‧‧‧有機氧化膜 60‧‧‧Organic oxide film
71‧‧‧透明陽極 71‧‧‧Transparent anode
72‧‧‧電洞注入層 72‧‧‧ hole injection layer
73‧‧‧電洞輸送層 73‧‧‧ hole transport layer
74‧‧‧發光層 74‧‧‧Lighting layer
75‧‧‧電子注入層 75‧‧‧Electronic injection layer
76‧‧‧陰極 76‧‧‧ cathode
80‧‧‧有機發光體 80‧‧‧Organic emitters
100‧‧‧有機發光顯示裝置 100‧‧‧Organic light-emitting display device
201‧‧‧2價以上之陽離子 Cations above 201‧‧‧2
202‧‧‧2價以上之陰離子 Anions above 202‧‧‧2
203‧‧‧離子鍵 203‧‧‧ ion bond
210‧‧‧分子締合體 210‧‧‧Molecular association
圖1為表示本發明之彩色濾光片之一例的概略剖面圖。 Fig. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention.
圖2為表示本發明之顯示裝置之一例的概略剖面圖。 Fig. 2 is a schematic cross-sectional view showing an example of a display device of the present invention.
圖3為表示本發明之顯示裝置之另一例的概略剖面圖。 Fig. 3 is a schematic cross-sectional view showing another example of the display device of the present invention.
圖4為表示一般式(I)所示色材之分子締合狀態的模式圖。 Fig. 4 is a schematic view showing a state of molecular association of the color material represented by the general formula (I).
圖5為表示實施例1~22及比較例1~16之色材分散液之A與X間之關係的X-A平面圖。 Fig. 5 is a plan view showing the relationship between A and X of the color material dispersion liquids of Examples 1 to 22 and Comparative Examples 1 to 16.
以下,依序說明本發明之色材分散液、彩色濾光片用著色樹脂組成物、彩色濾光片及顯示裝置。 Hereinafter, the color material dispersion liquid, the coloring resin composition for color filters, the color filter, and the display device of the present invention will be described in order.
尚且,於本發明中,光包括可見及非可見區域之波長之電磁波,進而包括放射線,放射線係包括例如微波、電子束。具體而言,係指波長5μm以下之電磁波、及電子束。 Still, in the present invention, the light includes electromagnetic waves of wavelengths of visible and non-visible regions, and further includes radiation, and the radiation system includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
本發明中所謂(甲基)丙烯酸,係表示各丙烯酸及甲基丙烯酸;所謂(甲基)丙烯酸酯,係表示各丙烯酸酯及甲基丙烯酸酯。 In the present invention, (meth)acrylic acid means each acrylic acid and methacrylic acid; and the (meth)acrylic acid ester means each acrylate and methacrylate.
本發明中所謂有機基,係指具有1個以上碳原子之基。 The term "organic group" as used in the present invention means a group having one or more carbon atoms.
又,本發明中所謂固形份,係指構成著色樹脂組成物之溶劑以外的所有成分,即使是液狀單體亦視為涵括於該固形份中。 Moreover, the solid content in the present invention means all components other than the solvent constituting the coloring resin composition, and even a liquid monomer is considered to be included in the solid content.
本發明之色材分散液係含有下述一般式(I)所示之色材、分散劑、有機酸化合物、與溶劑者;其特徵在於,上述分散劑係至少具有下述一般式(II)所示之構成單位(a),胺價為70mgKOH/g以上且160mgKOH/g以下的嵌段共聚合體;上述溶劑係23℃下之上述色材之溶解度為0.1(g/10ml溶劑)以下的溶劑;在將上述分散劑之上述胺價設為A(mgKOH/g)、將上述色材分散液中所含之上述有機酸化合物之物質量XA(mol)與構成上述色材分散液中所含之上述分散劑的上述構成單位(a)之物質量XB(mol)的比設為X(=XA/XB)時,滿足下式(1)及式(2);在X為未滿1之範圍時,進一步滿足下式(3);X≦1.5 式(1) The color material dispersion liquid of the present invention contains a color material, a dispersant, an organic acid compound, and a solvent represented by the following general formula (I); wherein the dispersant has at least the following general formula (II) The constituent unit (a) shown is a block copolymer having an amine value of 70 mgKOH/g or more and 160 mgKOH/g or less; and the solvent of the above-mentioned solvent system at a temperature of 23 ° C of 0.1 (g/10 ml solvent) or less The above-mentioned amine valence of the dispersant is A (mg KOH / g), and the mass of the organic acid compound X A (mol) contained in the above-mentioned color material dispersion is made up of the above-mentioned color material dispersion. When the ratio of the mass of the constituent unit (a) of the above dispersing agent (X) X B (mol) is X (=X A /X B ), the following formulas (1) and (2) are satisfied; When the range is less than 1, the following formula (3) is further satisfied; X≦1.5 formula (1)
A×X≧40 式(2) A×X≧40 type (2)
A×(1-X)≦42 式(3) A×(1-X)≦42 (3)
[化8]
(一般式(I)中,A係與N直接鍵結之碳原子為不具有π鍵結的a價有機基,該有機基表示至少於與N直接鍵結之末端具有飽和脂肪族烴基的脂肪族烴基、或具有該脂肪族烴基的芳香族基,碳鏈中亦可含有O、S、N;Bc-表示至少含有鎢之c價聚酸陰離子;Ri~Rv分別獨立表示氫原子、亦可具有取代基之烷基或亦可具有取代基之芳基,Rii與Riii、Riv與Rv亦可鍵結形成環構造;Ar1表示亦可具有取代基之2價芳香族基;複數之Ri~Rv及Ar1分別可為相同或相異;a及c表示2以上之整數,b及d表示1以上之整數;e為0或1,在e為0時鍵結不存在;複數之e可為相同或相異;) (In the general formula (I), the carbon atom directly bonded to the A system and N is an a-valent organic group having no π bond, and the organic group means a fat having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N. a hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group may further contain O, S, and N in the carbon chain; B c- represents a c-valent polyacid anion containing at least tungsten; and R i to R v each independently represent a hydrogen atom And an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ii and R iii , R iv and R v may also bond to form a ring structure; Ar 1 represents a divalent aromatic group which may also have a substituent. Family basis; R i ~ R v and Ar 1 of the plural number may be the same or different; a and c represent an integer of 2 or more, b and d represent an integer of 1 or more; e is 0 or 1, when e is 0 The bond does not exist; the plural e can be the same or different;)
(一般式(II)中,R1為氫原子或甲基,Q為直接鍵結或2價連結基,R2為碳數1~8之伸烷基、-[CH(R5)-CH(R6)-O]x-CH(R5)-CH(R6)- 或-[(CH2)y-O]z-(CH2)y-所示之2價有機基,R3及R4分別獨立表示亦可被取代之鏈狀或環狀之烴基,或R3及R4彼此鍵結形成環狀構造。R5及R6分別獨立為氫原子或甲基;x表示1~18之整數,y表示1~5之整數,z表示1~18之整數。) (In general formula (II), R 1 is a hydrogen atom or a methyl group, Q is a direct bond or a divalent linking group, and R 2 is an alkylene group having 1 to 8 carbon atoms, -[CH(R 5 )-CH (R 6 )-O] x -CH(R 5 )-CH(R 6 )- or -[(CH 2 ) y -O] z -(CH 2 ) y - a divalent organic group, R 3 And R 4 each independently represents a chain or cyclic hydrocarbon group which may be substituted, or R 3 and R 4 are bonded to each other to form a cyclic structure. R 5 and R 6 are each independently a hydrogen atom or a methyl group; x represents 1 An integer of ~18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18.)
上述本發明之色材分散液由於具有上述特定色材、上述特定分散劑、有機酸化合物、特定溶劑,故該色材分散液之經時穩定性優越,可獲得耐熱性提升之塗膜。 Since the color material dispersion liquid of the present invention has the specific color material, the specific dispersant, the organic acid compound, and the specific solvent, the color material dispersion liquid is excellent in stability over time, and a coating film having improved heat resistance can be obtained.
藉由上述特定之組合而可發揮如上述般之效果的作用,雖仍有未闡明之部分,但可推判如下。 The effect of the above-described effects can be exerted by the specific combination described above, and there are still unexplained parts, but the following can be inferred.
一般式(I)所示之色材係如圖4所示般,含有2價以上之陰離子202、與2價以上之陽離子201,故於該色材之凝集體中,陰離子與陽離子並非單純地依1分子對1分子進行離子鍵結,推判係經由離子鍵203而形成複數分子締合的分子締合體210。因此,一般式(I)所示之色材的表觀分子量相較於習知色澱色材之分子量格外增大。由此種分子締合體之形成推判固體狀態下之凝集力更加提高、使熱運動降低,可抑制離子對的解離或陽離子部的分離、提升耐熱性。 As shown in FIG. 4, the color material represented by the general formula (I) contains a divalent or higher anion 202 and a divalent or higher cation 201. Therefore, in the aggregate of the color material, the anion and the cation are not simply One molecule is ion-bonded to one molecule, and it is estimated that a molecular association body 210 in which a plurality of molecules are associated is formed via the ionic bond 203. Therefore, the apparent molecular weight of the color material represented by the general formula (I) is particularly increased as compared with the molecular weight of the conventional lake color material. The formation of the molecular association body is used to determine that the cohesive force in the solid state is further improved and the thermal motion is lowered, and the dissociation of the ion pair or the separation of the cation portion and the improvement of the heat resistance can be suppressed.
本發明之色材分散液係將此種一般式(I)所示之色材,於特定溶劑中,使用有機酸化合物、作為分散劑之具有於側鏈具胺基的構成單位(a)且胺價為70mgKOH/g以上且160mgKOH/g以下的嵌段共聚合體予以分散。該分散劑中,構成單位(a)所具有之胺基係對一般式(I)所示之色材具有親和性,故吸附於上述一般式(I)所示之色材,推判可使該色材依分子締合之狀態予以分散。藉由使用胺價為70mgKOH/g以上且160mgKOH/g以下的嵌段共聚合體,則對於色 材之親和性部位、與對於溶劑之親和性部位的比例變得適當而分散性優越。又,藉由使用如上述般之對色材之親和性部位依嵌段存在的嵌段共聚合體,可有效率地吸附於具有分子締合狀態之上述色材,分散穩定性優越。 In the color material dispersion liquid of the present invention, the color material represented by the general formula (I) is an organic acid compound and a constituent unit (a) having an amine group in a side chain as a dispersing agent in a specific solvent. The block copolymer having an amine value of 70 mgKOH/g or more and 160 mgKOH/g or less is dispersed. In the dispersant, the amine group of the constituent unit (a) has an affinity for the color material represented by the general formula (I), so that it can be adsorbed to the color material represented by the above general formula (I), and the estimation can be made. The color material is dispersed in a state of molecular association. By using a block copolymer having an amine value of 70 mgKOH/g or more and 160 mgKOH/g or less, for color The ratio of the affinity portion of the material to the affinity portion for the solvent is appropriate and the dispersibility is excellent. Further, by using the block copolymer which is present in the affinity portion of the color material as described above, it can be efficiently adsorbed to the color material having the molecular association state, and the dispersion stability is excellent.
上述分散劑所具有之胺基係在進一步與上述有機酸化合物形成鹽的狀態時,推判可更加提升對上述特定色材之親和性。因此,推判若使經鹽形成之胺基吸附於上述一般式(I)所示之色材,則使該色材之分子締合狀態穩定化,提升分散穩定性。其結果,抑制黏度之經時變化。又,由於上述色材之分子締合狀態穩定化,故即使在所得之著色層中,仍維持分子締合狀態,而成為耐熱性優越者,即使在經過加熱步驟後仍可保持高亮度。 When the amine group of the dispersant further forms a salt with the organic acid compound, it is estimated that the affinity for the specific color material can be further improved. Therefore, it is estimated that when the amine group formed by the salt is adsorbed to the color material represented by the above general formula (I), the molecular association state of the color material is stabilized, and the dispersion stability is improved. As a result, the change in viscosity with time is suppressed. Further, since the molecular association state of the color material is stabilized, even in the obtained coloring layer, the molecular association state is maintained, and the heat resistance is superior, and high luminance can be maintained even after the heating step.
本發明者等人經潛心研究的結果,獲得下述見解:在將上述分散劑之上述胺價設為A(mgKOH/g)、將上述色材分散液中所含之上述有機酸化合物之物質量XA(mol)與構成上述色材分散液中所含之上述分散劑的上述構成單位(a)之物質量XB(mol)的比設為X(=XA/XB)時, 藉由依滿足A×X≧40之關係的方式選擇上述分散劑,且具有上述有機酸化合物,則對色材之親和性成為適合於分散的值,故分散穩定性特別提升,抑制經時之黏度變化。 As a result of intensive studies, the inventors of the present invention have obtained the following findings: the above-mentioned amine valence of the dispersing agent is A (mg KOH / g), and the organic acid compound contained in the color material dispersion is contained. When the ratio of the amount X A (mol) to the mass of the constituent unit (a) X B (mol) constituting the dispersing agent contained in the color material dispersion is X (=X A /X B ), When the dispersant is selected in such a manner that the relationship of A×X≧40 is satisfied, and the organic acid compound is present, the affinity for the color material becomes a value suitable for dispersion, so that the dispersion stability is particularly improved, and the viscosity over time is suppressed. Variety.
又,獲得下述見解:在X未滿1時,藉由依滿足A×(1-X)≦42之關係的方式選擇上述分散劑,且調配上述有機酸化合物,則使未進行鹽形成之胺基的量減少,故於分散步驟中,可穩定地保持色材之分子締合狀態,可形成耐熱性特別優越的塗膜。 Further, it has been found that when X is less than 1, the dispersant is selected in such a manner that the relationship of A × (1-X) ≦ 42 is satisfied, and the organic acid compound is blended to form an amine which is not subjected to salt formation. Since the amount of the base is reduced, in the dispersion step, the molecular association state of the color material can be stably maintained, and a coating film having particularly excellent heat resistance can be formed.
尚且,推判在依分散劑之構成單位(a)大多未進行鹽形狀之狀態 下進行了分散步驟的情況,於使形成上述分子締合狀態之一般式(I)所示之色材經分散時,於分散步驟及燒成過程中,分散劑之胺基與一般式(I)所示之色材中之陽離子進行鹽交換,色材之分子締合狀態一部分被破壞,其結果,有耐熱性惡化的情形。 In addition, it is presumed that the constituent units of the dispersant (a) are mostly not in the shape of a salt. In the case where the dispersion step is carried out, when the color material represented by the general formula (I) which forms the above-mentioned molecular association state is dispersed, the amine group of the dispersant and the general formula (I) are dispersed during the dispersion step and the firing process. The cations in the color material shown are subjected to salt exchange, and a part of the molecular association state of the color material is partially destroyed, and as a result, heat resistance is deteriorated.
又,在X超過1的範圍,即有機酸化合物相對於構成單位(a)依過剩量存在的情況,由於平衡更偏向鹽形成方向,故未進行鹽形成之胺基更減少,色材之分子締合狀態難以被破壞。因此,即使在所得之著色層中,仍維持分子締合狀態,故成為耐熱性優越者。 Further, when X is more than 1, that is, when the organic acid compound is present in excess of the constituent unit (a), since the equilibrium is more toward the salt formation direction, the amine group which is not subjected to salt formation is further reduced, and the molecule of the color material is further reduced. The state of association is difficult to destroy. Therefore, even in the obtained coloring layer, since the molecular association state is maintained, it is excellent in heat resistance.
若X為1.5以下,即相對於上述分散劑所具有之構成單位(a)而上述有機酸化合物為1.5莫耳當量以下,則未進行鹽形成而存在之有機酸化合物有助於分子締合狀態的穩定化,故分散穩定性優越,且由於其比例較少因而有機酸化合物不析出。又,推判相對於分散劑所具有之1個胺基,1個有機酸化合物進行鹽形成,A與X之關係係不論有機酸化合物之價數均為相同。 When X is 1.5 or less, that is, the organic acid compound is 1.5 mole equivalent or less with respect to the constituent unit (a) of the dispersant, the organic acid compound which is not formed by salt formation contributes to the molecular association state. Since it is stabilized, the dispersion stability is excellent, and since the proportion thereof is small, the organic acid compound does not precipitate. Further, it is estimated that one organic acid compound is formed into a salt with respect to one amine group of the dispersing agent, and the relationship between A and X is the same regardless of the valence of the organic acid compound.
如此,本發明之色材分散液由於依滿足A×X≧40之關係、及A×(1-X)≦42之關係的任一者,選擇使用上述特定之分散劑與有機酸化合物,故該色材分散液之經時穩定性優越,可獲得耐熱性提升的塗膜。 As described above, the color material dispersion liquid of the present invention selectively uses the above-mentioned specific dispersant and organic acid compound because it satisfies the relationship of A×X≧40 and the relationship of A×(1-X)≦42. The color material dispersion has excellent stability over time, and a coating film having improved heat resistance can be obtained.
本發明之色材分散液係至少含有一般式(I)所示之色材、有機酸化合物、與溶劑者,在不損及本發明效果之前提下,視需要亦可進一步含有其他成分。 The color material dispersion liquid of the present invention contains at least the color material, the organic acid compound, and the solvent represented by the general formula (I), and is added before the effect of the present invention is not impaired, and may further contain other components as necessary.
以下,依序詳細說明此種本發明之色材分散液的各成分。 Hereinafter, each component of the color material dispersion of the present invention will be described in detail in order.
本發明之色材分散液係含有下述一般式(I)所示之色材。 The color material dispersion liquid of the present invention contains the color material represented by the following general formula (I).
(一般式(I)中,A係與N直接鍵結之碳原子為不具有π鍵結的a價有機基,該有機基表示至少於與N直接鍵結之末端具有飽和脂肪族烴基的脂肪族烴基、或具有該脂肪族烴基的芳香族基,碳鏈中亦可含有O、S、N;Bc-表示至少含有鎢之c價聚酸陰離子;Ri~Rv分別獨立表示氫原子、亦可具有取代基之烷基或亦可具有取代基之芳基,Rii與Riii、Riv與Rv亦可鍵結形成環構造;Ar1表示亦可具有取代基之2價芳香族基;複數之Ri~Rv及Ar1分別可為相同或相異;a及c表示2以上之整數,b及d表示1以上之整數;e為0或1,在e為0時鍵結不存在;複數之e可為相同或相異。) (In the general formula (I), the carbon atom directly bonded to the A system and N is an a-valent organic group having no π bond, and the organic group means a fat having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N. a hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group may further contain O, S, and N in the carbon chain; B c- represents a c-valent polyacid anion containing at least tungsten; and R i to R v each independently represent a hydrogen atom And an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ii and R iii , R iv and R v may also bond to form a ring structure; Ar 1 represents a divalent aromatic group which may also have a substituent. Family basis; R i ~ R v and Ar 1 of the plural number may be the same or different; a and c represent an integer of 2 or more, b and d represent an integer of 1 or more; e is 0 or 1, when e is 0 The bond does not exist; the complex e can be the same or different.)
作為一般式(I)所示之色材並無特別限定,可由例如國際公開第2012/144520號說明書記載之一般式(I)所示之化合物中適當選擇使用,可單獨使用1種或組合2種以上使用。 The coloring material represented by the general formula (I) is not particularly limited, and may be appropriately selected from the compounds represented by the general formula (I) described in the specification of International Publication No. 2012/144520, and may be used alone or in combination 2 More than one kind.
尚且,一般式(I)所示之色材亦可涵括於後述之色澱色材中,但在符合一般式(I)所示之色材之前提下,本發明中,係將其視為符合 一般式(I)所示之色材。 Further, the color material represented by the general formula (I) may be included in the color lake material described later, but is taken up before the color material shown in the general formula (I), and in the present invention, it is regarded as For compliance The color material shown by the general formula (I).
一般式(I)所示之色材的製造方法並無特別限定。可藉由例如國際公開第2012/144520號說明書記載之製造方法而獲得。 The method for producing the color material represented by the general formula (I) is not particularly limited. It can be obtained, for example, by the production method described in the specification of International Publication No. 2012/144520.
本發明之色材分散液係在不損及本發明效果的範圍內,以色調控制為目的,亦可進一步含有其他色材。作為其他色材,可列舉公知之顏料及染料,可使用1種或2種以上。 The color material dispersion liquid of the present invention may further contain other color materials for the purpose of color tone control within a range that does not impair the effects of the present invention. As the other coloring material, a known pigment and a dye can be used, and one type or two or more types can be used.
由獲得所需色調的觀點而言,較佳係進一步含有選自二系色材、及系色材的1種以上作為其他色材。作為較佳之二顏料的具體例,可列舉顏料紫23等。又,作為較佳之系色材的具體例,可列舉酸性紅51、52、87、92、94、289、388;C.I.酸性紫9、30、102;磺酸玫瑰紅G、磺酸玫瑰紅B、磺酸玫瑰紅101、磺酸玫瑰紅640等;日本專利特開2010-32999號公報、日本專利特開2010-211198號公報、日本專利第4492760號公報等記載之染料等;進而亦可為後述之系色澱色材。本發明中,由兼具亮度及耐熱性的觀點而言,較佳係使用系色澱色材。 From the viewpoint of obtaining a desired color tone, the preferred system further comprises a second selected from the group consisting of Color material, and One or more types of color materials are used as other color materials. As the better second Specific examples of the pigment include Pigment Violet 23 and the like. Also, as a better Specific examples of the coloring material include acid red 51, 52, 87, 92, 94, 289, 388; CI acid violet 9, 30, 102; sulfonic acid rose red G, sulfonic acid rose red B, sulfonic acid rose red 101, sulfonic acid rose 640, etc.; Japanese Patent Laid-Open No. 2010-32999, Japanese Patent Laid-Open No. 2010-211198, Japanese Patent No. 4492760, and the like. Dyes, etc.; furthermore, may be described later It is a color lake material. In the present invention, it is preferably used from the viewpoint of having both brightness and heat resistance. It is a color lake material.
本發明中所謂色澱色材,係指對溶劑具可溶性之色材與對離子進行鹽形成而呈不溶化的色材。色澱色材通常可藉由將後述色材、與後述色澱化劑於溶劑中混合而獲得。作為上述對溶劑具可溶性之色材,由彩色濾光片之高亮度化的觀點而言,較佳係使用穿透率高的染料。該染料可視所需色調而適當選擇,可為偶氮系染料、蒽醌系染料、三芳基甲烷系染料、系染料、花菁系染料、靛系染料等具有任一種基本骨架(發色部位)的染料。又,上述染料 亦可為具有陰離子性取代基之酸性染料、或具有陽離子性取代基之鹼性染料等分類為任一種的染料。 In the present invention, the term "color-separating color material" means a color material which is soluble in a solvent and which is formed by salt formation and insolubilization. The lake color material can be usually obtained by mixing a color material described later with a coloring agent described later in a solvent. As the color material which is soluble in the solvent, it is preferable to use a dye having a high transmittance from the viewpoint of increasing the luminance of the color filter. The dye may be appropriately selected depending on the desired color tone, and may be an azo dye, an anthraquinone dye, or a triarylmethane dye. A dye having any one of a basic skeleton (chromophoric moiety) such as a dye, a cyanine dye, or an anthraquinone dye. Further, the dye may be a dye classified into any one of an acid dye having an anionic substituent or a basic dye having a cationic substituent.
作為酸性染料,可列舉例如C.I.酸性紫29、31、33、34、36、36:1、39、41、42、43、47、51、63、76、103、118、126、C.I.酸性藍2、8、14、25、27、35、37、40、41、41:1、41:2、43、45、46、47、49、50、51、51、53、54、55、56、57、58、62、62:1、63、64、65、68、69、70、78、79、80、81、96、111、124、127、127:1、129、137、138、143、145、150、175、176、183、198、203、204、205、208、215、220、221、225、226、227、230、231、232、233、235、239、245、247、253、257、258、260、261、264、266、270、271、272、273、274、277、277:1、278、280、281、282、286、287、288、289、290、291、292、293、294、295、298、301、302、304、305、306、307、313、316、318、322、324、327、331、333、336、339、340、343、344、350、C.I.酸性綠10、17、25、25:1、27、36、37、38、40、41、42、44、54、59、69、71、81、84、95、101、110、117等之蒽醌系酸性染料;C.I.酸性紫15、16、17、19、21、23、24、25、38、49、72、C.I.酸性藍1、3、5、7、9、19、22、83、90、93、100、103、104、109、C.I.酸性綠3、5、6、7、8、9、11、13、14、15、16、18、22、50、50:1等之三芳基甲烷系酸性染料;C.I.酸性紅50、51、52、87、92、94、289、388、C.I.酸性紫9、30、102、磺酸玫瑰紅G、磺酸玫瑰紅B、磺酸玫瑰紅101、磺酸玫瑰紅640等之系酸性染料等。系酸性染料中,較佳為C.I.酸性紅50、C.I.酸性紅52、C.I.酸性紅289、C.I.酸性紫9、C.I.酸性紫30、C.I.酸性藍19等之玫瑰 紅系酸性染料。 Examples of the acid dye include CI Acid Violet 29, 31, 33, 34, 36, 36:1, 39, 41, 42, 43, 47, 51, 63, 76, 103, 118, 126, CI Acid Blue 2 , 8, 14, 25, 27, 35, 37, 40, 41, 41:1, 41:2, 43,45,46,47,49,50,51,51,53,54,55,56,57 , 58, 62, 62: 1, 63, 64, 65, 68, 69, 70, 78, 79, 80, 81, 96, 111, 124, 127, 127: 1, 129, 137, 138, 143, 145 , 150, 175, 176, 183, 198, 203, 204, 205, 208, 215, 220, 221, 225, 226, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257 , 258, 260, 261, 264, 266, 270, 271, 272, 273, 274, 277, 277: 1, 278, 280, 281, 282, 286, 287, 288, 289, 290, 291, 292, 293 , 294, 295, 298, 301, 302, 304, 305, 306, 307, 313, 316, 318, 322, 324, 327, 331, 333, 336, 339, 340, 343, 344, 350, CI Acid Green 10, 17, 25, 25: 1, 27, 36, 37, 38, 40, 41, 42, 44, 54, 59, 69, 71, 81, 84, 95, 101, 110, 117, etc. Acid dye; C I Acid Violet 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72, CI Acid Blue 1, 3, 5, 7, 9, 19, 22, 83, 90, 93, 100, 103,104,109, CI acid green 3,5,6,7,8,9,11,13,14,15,16,18,22,50, 50:1 triarylmethane acid dye; CI Acid red 50, 51, 52, 87, 92, 94, 289, 388, CI acid violet 9, 30, 102, sulfonic acid rose red G, sulfonic acid rose red B, sulfonic acid rose red 101, sulfonic acid rose red 640 Wait for It is an acid dye or the like. Among the acid dyes, preferred are rose red acid dyes such as CI Acid Red 50, CI Acid Red 52, CI Acid Red 289, CI Acid Violet 9, CI Acid Violet 30, and CI Acid Blue 19.
又,作為市售之鹼性染料,可列舉例如C.I.鹼性紫1、3、14、C.I.鹼低藍1、5、7、8、11、26、C.I.鹼性綠1、4等之三芳基甲烷系鹼性染料;C.I.鹼性黃13、C.I.鹼性紅14等之花菁系鹼性染料;C.I.鹼性紅29等之偶氮系鹼性染料;C.I.鹼性紫11等之系鹼性染料等。此等染料可單獨使用1種或組合2種以上使用。 Moreover, as a commercially available basic dye, for example, CI basic violet 1, 3, 14, CI alkali low blue 1, 5, 7, 8, 11, 26, CI basic green 1, 4, etc. Methane-based basic dye; CI basic yellow 13, CI basic red 14 and other cyanine-based basic dyes; CI basic red 29 and other azo-based basic dyes; CI alkaline purple 11 etc. It is a basic dye or the like. These dyes may be used alone or in combination of two or more.
本發明中,由作為著色層而容易獲得所需色調而言,其中,較佳係使用選自上述系酸性染料及上述系鹼性染料的1種以上染料。 In the present invention, in view of easily obtaining a desired color tone as a colored layer, it is preferred to use one selected from the above. Acid dye and above One or more dyes which are basic dyes.
色澱色材中,對離子係視上述染料種類而異,酸性染料之對離子為陽離子,鹼性染料之對離子為陰離子。因此,上述色澱化劑係配合上述染料而適當選擇使用。亦即,在將上述酸性染料進行不溶化的情況,係使用產生該染料之對陽離子的化合物作為色澱化劑;在將上述鹼性染料進行不溶化的情況,係使用產生該染料之對陰離子的化合物作為色澱化劑。 In the lake coloring material, the ion system varies depending on the type of the dye, the counter ion of the acid dye is a cation, and the counter ion of the basic dye is an anion. Therefore, the above-mentioned laking agent is appropriately selected and used in combination with the above dye. That is, in the case where the above acid dye is insolubilized, a compound which produces a cation of the dye is used as a lake forming agent; and in the case where the above basic dye is insolubilized, a compound which produces an anion of the dye is used. As a lake former.
作為酸性染料之對陽離子,除了銨陽離子之外,可列舉金屬陽離子、或無機聚合物等。 Examples of the counter cation of the acid dye include a metal cation or an inorganic polymer in addition to the ammonium cation.
作為產生銨陽離子之色澱化劑,適當者可列舉例如1級胺化合物、2級胺化合物、3級胺化合物等;其中,由耐熱性及耐光性優越的觀點而言,較佳係使用2級胺化合物或3級胺化合物。 As a coloring agent which produces an ammonium cation, a 1st grade amine compound, a 2nd grade amine compound, a tertiary amine compound, etc. are mentioned, for example, and it is preferable to use 2 from a viewpoint of the outstanding heat resistance and light resistance. Amine compound or a tertiary amine compound.
又,作為產生金屬陽離子之色澱化劑,可由具有所需金屬離子之金屬鹽中適當選擇。 Further, as the coloring agent for producing metal cations, it may be appropriately selected from metal salts having a desired metal ion.
酸性染料之對陽離子可單獨使用1種、或組合2種以上使用。 The cation of the acid dye may be used singly or in combination of two or more.
另一方面,作為無機陰離子,可列舉例如含氧酸的陰 離子(磷酸離子、硫酸離子、鉻酸離子、鎢酸離子(WO4 2-)、鉬酸離子(MoO4 2-)等)、或使複數之含氧酸經縮合的聚酸陰離子等之無機陰離子或其混合物。 On the other hand, examples of the inorganic anion include an anion of an oxo acid (phosphoric acid ion, sulfate ion, chromic acid ion, tungstic acid ion (WO 4 2- ), molybdate ion (MoO 4 2- ), etc.), or An inorganic anion or the like of a polyacid anion or the like obtained by condensing a plurality of oxyacids.
本發明中色澱色材由耐熱性及耐光性的觀點而言,其中,較佳為包含鹼性染料與無機陰離子的色澱色材,更佳係包含鹼性染料與聚酸陰離子的色澱色材。 The lake color material in the present invention is preferably a lake coloring material containing a basic dye and an inorganic anion, more preferably a lake comprising a basic dye and a polyacid anion, from the viewpoint of heat resistance and light resistance. Color material.
本發明中,較佳係組合系染料之金屬色澱色材作為其他色材,其中,較佳係系酸性染料之金屬色澱色材。 In the present invention, a preferred combination Dye-based metal lake color material as other color materials, among which, preferred It is a metal lake color material of acid dye.
作為該色澱色材中之系酸性染料,其中,較佳係下述一般式(VI)所示化合物,具有玫瑰紅系酸性染料者。 As the color lake material The acid dye is preferably a compound represented by the following general formula (VI) and having a rosin-based acid dye.
(一般式(VI)中,R10~R13分別獨立表示氫原子、烷基、芳基、或雜芳基,R10與R12、R11與R13亦可鍵結形成環構造。R14表示酸性基,X表示鹵原子。m表示0~5之整數。一般式(VI)係具有1個以上酸性基者,n為0以上之整數。) (In the general formula (VI), R 10 to R 13 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and R 10 and R 12 , R 11 and R 13 may be bonded to each other to form a ring structure. 14 represents an acidic group, and X represents a halogen atom. m represents an integer of 0 to 5. The general formula (VI) has one or more acidic groups, and n is an integer of 0 or more.
R10~R13中之烷基並無特別限定。可列舉例如亦可具有取代基之碳數1~20之直鏈或分枝狀烷基等,其中,較佳為碳數1~8之直鏈或分枝的烷基、更佳係碳數1~5之直鏈或分枝的烷基。作為烷基亦可具有之取代基,並無特別限定,可列舉例如芳基、鹵 原子、羥基等,作為被取代之烷基,可列舉苄基等,進而亦可具有鹵原子或酸性基作為取代基。 The alkyl group in R 10 to R 13 is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent may, for example, be a linear or branched alkyl group having a carbon number of 1 to 8, preferably a carbon number. A linear or branched alkyl group of 1 to 5. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group. The substituted alkyl group may, for example, be a benzyl group or the like, or may have a halogen atom or an acidic group. Substituent.
R10~R13中之芳基並無特別限定。可列舉例如碳數6~20之亦可具有取代基的芳基,其中,較佳為苯基、萘基等。R10~R13中之雜芳基,可列舉碳數5~20之亦可具有取代基的雜芳基,較佳係含有氮原子、氧原子、硫原子作為雜原子者。 The aryl group in R 10 to R 13 is not particularly limited. For example, an aryl group having a carbon number of 6 to 20 and having a substituent may be mentioned, and among them, a phenyl group, a naphthyl group or the like is preferable. Examples of the heteroaryl group in R 10 to R 13 include a heteroaryl group having 5 to 20 carbon atoms which may have a substituent, and preferably a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom.
作為芳基或雜芳基亦可具有之取代基,可列舉例如碳數1~5之烷基、鹵原子、酸性基、羥基、烷氧基、胺甲醯基、羧酸酯基等。 The aryl group or the heteroaryl group may have a substituent, and examples thereof include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an acidic group, a hydroxyl group, an alkoxy group, an aminomethyl group, and a carboxylate group.
尚且,R10~R13可為相同或相異。 Further, R 10 to R 13 may be the same or different.
作為酸性基或其鹽之具體例,可列舉羧基(-COOH)、羧根基(-COO-)、羧酸鹽基(-COOM,於此M表示金屬原子)、磺酸根基(-SO3 -)、磺酸基(-SO3H)、磺酸鹽基(-SO3M,於此M表示金屬原子)等;其中,較佳係具有磺酸根基(-SO3 -)、磺酸基(-SO3H)、或磺酸鹽基(-SO3M)之至少1種。尚且,作為金屬原子M,可列舉鈉原子、鉀原子等。 Specific examples of the acidic group or a salt thereof include a carboxyl group (-COOH), a carboxyl group (-COO - ), a carboxylate group (-COOM, wherein M represents a metal atom), and a sulfonate group (-SO 3 -). a sulfonic acid group (-SO 3 H), a sulfonate group (-SO 3 M, wherein M represents a metal atom), and the like; wherein, preferably, a sulfonate group (-SO 3 - ), a sulfonic acid group At least one of (-SO 3 H) or a sulfonate group (-SO 3 M). Further, examples of the metal atom M include a sodium atom and a potassium atom.
作為一般式(VI)所示化合物,由高亮度化之觀點而言,其中,較佳為酸性紅50、酸性紅52、酸性紅289、酸性紫9、酸性紫30、酸性藍19等。 From the viewpoint of increasing the luminance, the compound represented by the general formula (VI) is preferably acid red 50, acid red 52, acid red 289, acid violet 9, acid violet 30, acid blue 19 or the like.
又,由耐熱性的觀點而言,一般式(VI)中,較佳係m=1且n=0之具有甜菜鹼構造的化合物。 Further, from the viewpoint of heat resistance, in the general formula (VI), a compound having a betaine structure of m = 1 and n = 0 is preferred.
上述系酸性染料之金屬色澱色材,係使用含有金屬原子者作為色澱化劑。藉由使用含金屬原子之色澱化劑,使色材之耐熱性變高。作為此種色澱化劑,較佳係含有成為2價以上金屬陽離子之金屬原子的色澱化劑。 Above A metal lake coloring material which is an acid dye, which uses a metal atom as a lake former. The heat resistance of the color material is made high by using a metal atom-containing coloring agent. As such a lake-forming agent, a lake-forming agent containing a metal atom of a metal cation of two or more valences is preferable.
在上述色澱色材中組合其他色材使用的情況,色材之調配比例係依獲得所需色調之方式予以適當調整即可。由耐熱性及耐光性優越的觀點而言,其中,相對於合併了色澱色材與其他色材之色材總量100質量份,上述色澱色材較佳為30~100質量份、更佳為60~99質量份、再更佳為70~98質量份。 In the case where the other color materials are used in combination with the above-mentioned lake color materials, the blending ratio of the color materials may be appropriately adjusted in such a manner as to obtain a desired color tone. From the viewpoint of superior heat resistance and light resistance, the above-mentioned lake color material is preferably 30 to 100 parts by mass, more preferably 100 parts by mass based on the total amount of the color materials incorporating the lake color material and the other color materials. Preferably, it is 60 to 99 parts by mass, and more preferably 70 to 98 parts by mass.
本發明之色材分散液,係使用至少具有下述一般式(II)所示之構成單位(a),且胺價為70mgKOH/g以上且160mgKOH/g以下的嵌段共聚合體作為分散劑。 In the color material dispersion liquid of the present invention, a block copolymer having at least the structural unit (a) represented by the following general formula (II) and having an amine value of 70 mgKOH/g or more and 160 mgKOH/g or less is used as a dispersing agent.
(一般式(II)中,R1為氫原子或甲基,Q為2價連結基,R2為碳數1~8之伸烷基、-[CH(R5)-CH(R6)-O]x-CH(R5)-CH(R6)-或-[(CH2)y-O]z-(CH2)y-所示之2價有機基,R3及R4分別獨立表示亦可被取代之鏈狀或環狀之烴基,或R3及R4彼此鍵結形成環狀構造。R5及R6分別獨立為氫原子或甲基。 (In general formula (II), R 1 is a hydrogen atom or a methyl group, Q is a divalent linking group, R 2 is an alkylene group having 1 to 8 carbon atoms, -[CH(R 5 )-CH(R 6 ) -O] x -CH(R 5 )-CH(R 6 )- or -[(CH 2 ) y -O] z -(CH 2 ) y - the divalent organic group, R 3 and R 4 respectively Independently, a chain or cyclic hydrocarbon group which may be substituted, or R 3 and R 4 are bonded to each other to form a cyclic structure, and R 5 and R 6 are each independently a hydrogen atom or a methyl group.
x表示1~18之整數,y表示1~5之整數,z表示1~18之整數。) x represents an integer from 1 to 18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18. )
上述一般式(II)所示之構成單位(a)所具有之胺基,係 對上述一般式(I)所示之色材具有親和性,藉由吸附於該色材,可使該色材依分子締合狀態進行分散。又,本發明中一般式(II)所示之構成單位(a)係即使於分散液中,與後述之有機酸化合物進行鹽形成的情況,仍被視為涵括於上述一般式(II)所示之構成單位者。 The amine group of the constituent unit (a) represented by the above general formula (II) is The color material shown in the above general formula (I) has an affinity, and by adsorbing the color material, the color material can be dispersed in a molecular association state. In addition, the structural unit (a) represented by the general formula (II) in the present invention is considered to be included in the above general formula (II) even when it is formed into a salt with an organic acid compound to be described later in the dispersion liquid. The constituent units shown.
作為上述一般式(II)之2價連結基Q,可列舉例如碳數1~10之伸烷基、伸芳基、-CONH-基、-COO-基、碳數1~10之醚基(-R'-OR"-:R'及R"分別獨立為伸烷基)及此等之組合等。其中,由所得之聚合物的耐熱性或對適合使用作為溶劑之丙二醇單甲基醚醋酸酯(PGMEA)之溶解性、或屬於相對較廉價之材料的觀點而言,Q較佳為-COO-基。 Examples of the divalent linking group Q of the above general formula (II) include an alkylene group having 1 to 10 carbon atoms, an extended aryl group, a -CONH- group, a -COO- group, and an ether group having 1 to 10 carbon atoms ( -R'-OR"-: R' and R" are each independently an alkylene group) and combinations thereof. Among them, Q is preferably -COO- from the viewpoint of heat resistance of the obtained polymer or solubility in the use of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, or a relatively inexpensive material. base.
上述一般式(II)之2價有機基R2為碳數1~8之伸烷基、-[CH(R5)-CH(R6)-O]x-CH(R5)-CH(R6)-或-[(CH2)y-O]z-(CH2)y。上述碳數1~8之伸烷基,可為直鏈狀、分枝狀之任一種,例如亞甲基、伸乙基、三亞甲基、伸丙基、各種伸丁基、各種伸戊基、各種伸己基、各種伸辛基等。 The above-mentioned divalent organic group R 2 of the general formula (II) is an alkylene group having 1 to 8 carbon atoms, -[CH(R 5 )-CH(R 6 )-O] x -CH(R 5 )-CH ( R 6 )- or -[(CH 2 ) y -O] z -(CH 2 ) y . The above alkyl group having 1 to 8 carbon atoms may be any of linear or branched, such as methylene, ethyl, trimethylene, propyl, various butyl, and various pentyl groups. , a variety of extensions, a variety of extensions and so on.
R5及R6分別獨立為氫原子或甲基。 R 5 and R 6 are each independently a hydrogen atom or a methyl group.
作為上述R2,由分散性之觀點而言,較佳為碳數1~8之伸烷基,其中,R2更佳為亞甲基、伸乙基、伸丙基、伸丁基,再更佳為亞甲基及伸乙基。 As the above R 2 , from the viewpoint of dispersibility, an alkylene group having 1 to 8 carbon atoms is preferable, and among them, R 2 is more preferably a methylene group, an ethyl group, a propyl group or a butyl group. More preferably, it is a methylene group and an ethyl group.
作為上述一般式(II)之R3、R4彼此鍵結形成的環狀構造,可列舉例如5~7員環之含氮雜環單環或此等為2個縮合而成的縮合環。該含氮雜環較佳為不具有芳香性者,更佳為飽和環。 Examples of the cyclic structure in which R 3 and R 4 in the above general formula (II) are bonded to each other include a nitrogen-containing heterocyclic monocyclic ring having 5 to 7 membered rings or a condensed ring in which these two are condensed. The nitrogen-containing hetero ring is preferably one which does not have aromaticity, more preferably a saturated ring.
作為上述一般式(II)所示之構成單位(a),可列舉由(甲基)丙烯醯氧基丙基二甲基胺、(甲基)丙烯醯氧基乙基二甲基胺、(甲 基)丙烯醯氧基丙基二乙基胺、(甲基)丙烯醯氧基乙基二乙基胺等所衍生的構成單位等,但並不定於此等。 Examples of the structural unit (a) represented by the above general formula (II) include (meth)acryloxypropyldimethylamine and (meth)acryloxyethyl dimethylamine ( A The constituent unit derived from acryloxypropyldiethylamine, (meth)acryloxyethyldiethylamine or the like is not limited thereto.
上述分散劑中,一般式(II)所示之構成單位(a)較佳係藉由含有3個以上而形成色材親和性之嵌段部。由分散性及分散穩定性優越、抑制經時之黏度變化、耐熱性優越的觀點而言,該色材親和性之嵌段部較佳係含有上述一般式(II)所示之構成單位(a)3~50個、更佳係含有6~40個、再更佳係含有10~30個。 In the above dispersing agent, the constituent unit (a) represented by the general formula (II) is preferably a block portion containing three or more kinds of coloring material affinity. The block portion of the color material affinity preferably contains the constituent unit represented by the above general formula (II) from the viewpoints of excellent dispersibility and dispersion stability, suppression of viscosity change over time, and excellent heat resistance. 3~50, more preferably 6~40, and even better 10~30.
一般式(II)所示之構成單位(a)可為包含1種者,亦可為含有2種以上之構成單位者。 The constituent unit (a) represented by the general formula (II) may be one type or two or more constituent units.
上述嵌段共聚合體,由分散性的觀點而言,較佳係具有具上述一般式(II)所示之構成單位的色材親和性嵌段部(以下有時記載為A嵌段),與不具上述一般式(II)所示之構成單位(a)、且具有可與上述一般式(II)進行共聚合之構成單位的溶劑親和性嵌段部(以下有時記載為B嵌段)。本發明中,嵌段共聚合體之各嵌段的配置並無特別限定,可設為例如AB嵌段共聚合體、ABA嵌段共聚合體、BAB嵌段共聚合體等。其中,由分散性優越的觀點而言,較佳為AB嵌段共聚合體、或ABA嵌段共聚合體。 The block copolymer is preferably a color material affinity block portion (hereinafter sometimes referred to as an A block) having a constituent unit represented by the above general formula (II) from the viewpoint of dispersibility, and A solvent affinity block portion (hereinafter sometimes referred to as a B block) having a constituent unit (a) represented by the above general formula (II) and having a constituent unit copolymerizable with the above general formula (II). In the present invention, the arrangement of the respective blocks of the block copolymer is not particularly limited, and examples thereof include an AB block copolymer, an ABA block copolymer, and a BAB block copolymer. Among them, from the viewpoint of superior dispersibility, an AB block copolymer or an ABA block copolymer is preferred.
作為可與上述一般式(II)進行共聚合之構成單位,由提升一般式(I)所示之色材之分散性及分散穩定性、並亦提升耐熱性的觀點而言,較佳係由下述一般式(III)所示之構成單位。 As a constituent unit which can be copolymerized with the above general formula (II), it is preferred from the viewpoint of improving the dispersibility and dispersion stability of the color material represented by the general formula (I) and also improving heat resistance. The constituent unit shown by the following general formula (III).
[化13]
(一般式(III)中,R7表示氫原子或甲基;A表示直接鍵結或2價連結基;R8為碳數1~18之烷基、碳數2~18之伸烷基、芳烷基、芳基、-[CH(R9)-CH(R10)-O]x-R11-或-[(CH2)y-O]z-R11所示之1價基;R9及R10分別獨立為氫原子或甲基,R11為氫原子、或碳數1~18之烷基、碳數2~18之烯基、芳烷基、芳基、-CHO、-CH2CHO、或-CH2COOR12所示之1價基,R12為為氫原子或碳數1~5之直鏈狀、分枝狀、或環狀之烷基。x表示1~18之整數,y表示1~5之整數,z表示1~18之整數。m表示3~200之整數,n表示10~200之整數。) (In the general formula (III), R 7 represents a hydrogen atom or a methyl group; A represents a direct bond or a divalent linking group; and R 8 is an alkyl group having 1 to 18 carbon atoms; an alkylene group having 2 to 18 carbon atoms; An aralkyl group, an aryl group, a monovalent group represented by -[CH(R 9 )-CH(R 10 )-O] x -R 11 - or -[(CH 2 ) y -O] z -R 11 ; R 9 and R 10 are each independently a hydrogen atom or a methyl group, and R 11 is a hydrogen atom, or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, - a monovalent group represented by CH 2 CHO or -CH 2 COOR 12 , and R 12 is a linear, branched or cyclic alkyl group having a hydrogen atom or a carbon number of 1 to 5. x represents 1 to 18 The integer, y represents an integer from 1 to 5, z represents an integer from 1 to 18. m represents an integer from 3 to 200, and n represents an integer from 10 to 200.)
作為上述一般式(III)之2價連結基A,可設為與上述一般式(II)中之Q相同者,由所得之聚合物的耐熱性或對適合使用作為溶劑之丙二醇單甲基醚醋酸酯(PGMEA)之溶解性、或屬於相對較廉價之材料的觀點而言,A較佳為-COO-基。 The divalent linking group A of the above general formula (III) can be the same as the Q in the above general formula (II), and the heat resistance of the obtained polymer or the use of propylene glycol monomethyl ether as a solvent can be suitably used. From the viewpoint of the solubility of acetate (PGMEA) or a relatively inexpensive material, A is preferably a -COO- group.
R8中,上述碳數1~18之烷基可為直鏈狀、分枝狀、環狀之任一種,可列舉例如甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、各種戊基、各種己基、各種辛基、各種癸基、各種十二基、各種十四基、各種十六基、各種十八基、環戊基、環己基、環辛基、環十二基、基、異基、二環戊基、金剛烷基、低級烷基取代金剛烷基等。 In R 8 , the alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and an n-butyl group. Isobutyl, t-butyl, tert-butyl, various pentyl, various hexyl groups, various octyl groups, various fluorenyl groups, various dodecyl groups, various tetradecyl groups, various hexadecanyl groups, various octadecyl groups, rings Pentyl, cyclohexyl, cyclooctyl, cyclododeyl, Basis A group, a dicyclopentyl group, an adamantyl group, a lower alkyl group substituted adamantyl group or the like.
上述碳數2~18之烯基可為直鏈狀、分枝狀、環狀之任一種。作為此種烯基,可列舉例如乙烯基、烯丙基、丙烯基、各種丁烯基、 各種己烯基、各種辛烯基、各種癸烯基、各種十二烯基、各種十四烯基、各種十六烯基、各種十八烯基、環戊烯基、環己烯基、環辛烯基等。 The alkenyl group having 2 to 18 carbon atoms may be any of a linear chain, a branched chain, and a cyclic chain. Examples of such an alkenyl group include a vinyl group, an allyl group, a propenyl group, and various butenyl groups. Various hexenyl groups, various octenyl groups, various decenensyl groups, various dodecenyl groups, various tetradecenyl groups, various hexadecenyl groups, various octadecyl groups, cyclopentenyl groups, cyclohexenyl groups, rings Octenyl and the like.
其中,由分散性、基板密黏性的觀點而言,R8較佳為甲基、各種丁基、各種己基、苄基、環己基、羥乙基。 Among them, R 8 is preferably a methyl group, various butyl groups, various hexyl groups, benzyl groups, cyclohexyl groups, or hydroxyethyl groups from the viewpoint of dispersibility and substrate adhesion.
作為亦可具有取代基之芳基,可列舉苯基、聯苯基、萘基、甲苯基、二甲苯基等。芳基之碳數較佳為6~24、更佳為6~12。 Examples of the aryl group which may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The carbon number of the aryl group is preferably from 6 to 24, more preferably from 6 to 12.
作為亦可具有取代基之芳烷基,可列舉苄基、苯乙基、萘甲基、聯苯基甲基等。芳烷基之碳數較佳為7~20、更佳為7~14。 Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like. The carbon number of the aralkyl group is preferably from 7 to 20, more preferably from 7 to 14.
作為芳基或芳烷基等之芳香環的取代基,除了碳數1~4之直鏈狀、分枝狀的烷基之外,可列舉烯基、硝基、鹵原子等。 Examples of the substituent of the aromatic ring such as an aryl group or an aralkyl group include an alkyl group, a nitro group, and a halogen atom, in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.
又,上述R11為氫原子或亦可具有取代基之碳數1~18之烷基、碳數2~18之烯基、芳烷基、芳基、-CHO、-CH2CHO、或-CH2COOR12所示之1價基,R12為氫原子或碳數1~5之直鏈狀、分枝狀、或環狀之烷基。 Further, the above R 11 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms which may have a substituent, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH 2 CHO, or - A monovalent group represented by CH 2 COOR 12 , and R 12 is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms.
上述R11所示之1價基中,作為亦可具有的取代基,可列舉例如碳數1~4之直鏈狀、分枝狀或環狀的烷基、F、Cl、Br等之鹵原子等。 The monovalent group represented by the above R 11 may, for example, be a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, or a halogen such as F, Cl or Br. Atoms, etc.
上述R11中之碳數1~18之烷基、及碳數2~18之烯基、芳烷基、芳基,係如上述R8所示。 The alkyl group having 1 to 18 carbon atoms and the alkenyl group, aralkyl group and aryl group having 2 to 18 carbon atoms in the above R 11 are as shown in the above R 8 .
上述R8中,x、y及z係與上述一般式(II)中之R2相同。 In the above R 8 , x, y and z are the same as R 2 in the above general formula (II).
本發明中,上述嵌段共聚合體之溶劑親和性嵌段部的玻璃轉移溫度(Tg)係適當選擇即可。由耐熱性的觀點而言,其中,溶劑親和性嵌段部之玻璃轉移溫度(Tg)較佳為80℃以上、更佳為 100℃以上。 In the present invention, the glass transition temperature (Tg) of the solvent affinity block portion of the block copolymer may be appropriately selected. From the viewpoint of heat resistance, the glass transition temperature (Tg) of the solvent affinity block portion is preferably 80 ° C or higher, more preferably Above 100 °C.
本發明中之溶劑親和性嵌段部之玻璃轉移溫度(Tg)可藉由下式計算,且同樣地亦可計算色材親和性嵌段部及嵌段共聚合體之玻璃轉移溫度。 The glass transition temperature (Tg) of the solvent affinity block portion in the present invention can be calculated by the following formula, and the glass transition temperature of the color material affinity block portion and the block copolymer can also be calculated in the same manner.
1/Tg=Σ(Xi/Tgi) 1/Tg=Σ(Xi/Tgi)
於此,溶劑親和性嵌段部係設為自i=1至n為止之n個單體成分進行共聚合。Xi為第i個單體之重量分率(ΣXi=1),Tgi為第i個單體之均聚物之玻璃轉移溫度(絕對溫度)。其中,Σ取自i=1至n之和。再者,各單體之均聚物玻璃轉移溫度之值(Tgi)可採用Polymer Handbook(3rd Edition)(J.Brandrup,E.H.Immergut著(Wiley-Interscience,1989))之值。 Here, the solvent affinity block portion is a copolymerization of n monomer components from i=1 to n. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. Among them, the sum from i=1 to n is taken. Further, the value of the homopolymer glass transition temperature (Tgi) of each monomer can be a value of Polymer Handbook (3rd Edition) (J. Brandrup, E.H. Immergut (Wiley-Interscience, 1989)).
構成溶劑親和性嵌段部之構成單位的數量,若依分散劑之胺價成為70mgKOH/g以上且160mgKOH/g以下的範圍適當調整即可。其中,由溶劑親和性部位與色材親和性部位有效地作用、提升色材分散性的觀點而言,構成溶劑親和性嵌段部之構成單位的數量較佳為10~200、更佳為10~100、再更佳為10~70。 The number of constituent units constituting the solvent affinity block portion may be appropriately adjusted depending on the range in which the amine value of the dispersant is 70 mgKOH/g or more and 160 mgKOH/g or less. In particular, the number of constituent units constituting the solvent affinity block portion is preferably from 10 to 200, more preferably 10, from the viewpoint that the solvent affinity portion and the color material affinity portion effectively act to enhance the dispersibility of the color material. ~100, more preferably 10~70.
溶劑親和性嵌段部若依具有作為溶劑親和性部位之機能的方式選擇即可,構成溶劑親和性嵌段部的重複單位可為包含1種者,亦可含有2種以上之重複單位。 The solvent affinity block portion may be selected so as to function as a solvent affinity portion, and the repeating unit constituting the solvent affinity block portion may be one type or two or more types of repeat units.
於使用作為本發明分散劑之嵌段共聚合體中,作為一般式(II)所示之構成單位之單位數m、與構成溶劑親和性嵌段部之單位數n的比率m/n,較佳為0.01~1之範圍內,由色材之分散性、分散穩定性的觀點而言,更佳為0.05~0.7之範圍內。 In the block copolymer of the dispersant of the present invention, the ratio of the unit number m of the constituent unit represented by the general formula (II) to the unit number n of the solvent affinity block portion is preferably m/n. In the range of 0.01 to 1, it is preferably in the range of 0.05 to 0.7 from the viewpoint of dispersibility and dispersion stability of the color material.
本發明中,分散劑係選擇使用胺價為70mgKOH/g以 上且160mgKOH/g以下者。藉由胺價為上述範圍內,則黏度之經時穩定性或耐熱性優越,同時鹼顯影性或溶劑再溶解性亦優越。本發明中,由分散性及分散穩定性的觀點而言,分散劑之胺價較佳係80mgKOH/g以上、更佳係90mgKOH/g以上。另一方面,由溶劑再溶解性的觀點而言,分散劑之胺價較佳為120mgKOH/g以下、更佳為105mgKOH/g以下。 In the present invention, the dispersant is selected to have an amine price of 70 mgKOH/g. Above and 160mgKOH / g or less. When the amine value is within the above range, the viscosity stability or heat resistance is excellent, and alkali developability or solvent resolubility is also excellent. In the present invention, the amine valence of the dispersing agent is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more, from the viewpoint of dispersibility and dispersion stability. On the other hand, from the viewpoint of solvent resolubility, the amine value of the dispersing agent is preferably 120 mgKOH/g or less, more preferably 105 mgKOH/g or less.
胺價係指與中和試料1g中所含胺成分所需的過氯酸等值的氫氧化鉀的mg數,可藉由JIS-K7237所定義的方法進行測定。在藉該方法進行測定時,與分散劑中之有機酸化合物進行鹽形成的胺基中,通常該有機酸化合物發生解離,故可測定使用作為分散劑之嵌段共聚合體本身的胺價。 The amine value is the number of mg of potassium hydroxide equivalent to the perchloric acid required for neutralizing the amine component contained in 1 g of the sample, and can be measured by a method defined in JIS-K7237. In the amine group formed by salting with the organic acid compound in the dispersing agent, the organic acid compound is usually dissociated, and the amine valence of the block copolymer itself as a dispersing agent can be measured.
本發明所使用之分散劑的酸價,由表現顯影殘渣之抑制效果的觀點而言,下限較佳為1mgKOH/g以上。其中,由顯影殘渣之抑制效果更優越的觀點而言,分散劑之酸價更佳為2mgKOH/g以上。又,本發明所使用之分散劑的酸價,由可防止顯影密黏性之惡化或溶劑再溶解性之惡化的觀點而言,上限較佳為18mgKOH/g以下。其中,由顯影密黏性及溶解再溶解性良好的觀點而言,分散劑之酸價更佳為16mgKOH/g以下、再更佳為14mgKOH/g以下。 The acid value of the dispersing agent used in the present invention is preferably 1 mgKOH/g or more from the viewpoint of the effect of suppressing the development residue. Among them, the acid value of the dispersing agent is more preferably 2 mgKOH/g or more from the viewpoint of further suppressing the effect of the development residue. Moreover, the acid value of the dispersing agent used in the present invention is preferably 18 mgKOH/g or less from the viewpoint of preventing deterioration of development adhesiveness or deterioration of solvent resolubility. In particular, the acid value of the dispersing agent is preferably 16 mgKOH/g or less, and more preferably 14 mgKOH/g or less from the viewpoint of good development adhesiveness and dissolution resolubility.
又,本發明中,分散劑之玻璃轉移溫度,由提升顯影密黏性的觀點而言,較佳為30℃以上。若分散劑之玻璃轉移溫度較低,則尤其接近顯影液溫度(通常為23℃左右),有顯影密黏性降低之虞。此理由可推判係:若該玻璃轉移溫度接近顯影液溫度,則顯影時分散劑之運動變大,其結果,顯影密黏性惡化。藉由玻璃轉移溫度為30℃以上,可抑制顯影時之分散劑的分子運動,故推判可抑 制顯影密黏性的降低。 Further, in the present invention, the glass transition temperature of the dispersant is preferably 30 ° C or higher from the viewpoint of improving the development adhesiveness. If the glass transition temperature of the dispersant is low, it is particularly close to the developer temperature (usually about 23 ° C), and the development adhesiveness is lowered. For this reason, it can be inferred that if the glass transition temperature is close to the developer temperature, the movement of the dispersant during development becomes large, and as a result, the development adhesiveness is deteriorated. By the glass transition temperature of 30 ° C or more, the molecular motion of the dispersant during development can be suppressed, so the suppression can be suppressed. The development of the adhesive density is reduced.
分散劑之玻璃轉移溫度,由顯影密黏性的觀點而言,其中,較佳為32℃以上、更佳為35℃以上。另一方面,由容易精秤等使用時之操作性的觀點而言,較佳為200℃以下。 The glass transition temperature of the dispersant is preferably 32 ° C or higher, more preferably 35 ° C or higher, from the viewpoint of developing adhesion. On the other hand, from the viewpoint of ease of handling when used in a fine scale or the like, it is preferably 200 ° C or lower.
本發明之分散劑的玻璃轉移溫度可根據JIS K7121、藉由示差掃描熱量測定(DSC)進行測定而求得。 The glass transition temperature of the dispersant of the present invention can be determined by measuring by differential scanning calorimetry (DSC) according to JIS K7121.
又,本發明中,由色材分散穩定性優越、在作為著色樹脂組成物時抑制顯影殘渣發生、且溶劑再溶解性優越、進而具有高顯影密黏性的觀點而言,上述分散劑之酸價較佳為1mgKOH/g以上且18mgKOH/g以下,玻璃轉移溫度為30℃以上。 Further, in the present invention, the dispersing agent is excellent in the viewpoint of excellent dispersion stability of the color material, suppression of development residue when the colored resin composition is formed, superior solvent resolubility, and high development-adhesiveness. The price is preferably 1 mgKOH/g or more and 18 mgKOH/g or less, and the glass transition temperature is 30 °C or more.
若提高色材濃度、增加分散劑含量,則由於黏結劑量相對減少,故著色樹脂層於顯影時容易由基底基板剝離。藉由使分散劑含有包含來自含羧基單體之構成單位的B嵌段,並具有上述特定之酸價及玻璃轉移溫度,則提升顯影密黏性。然而,酸價過高時,推判雖然顯影性優越,但極性過高而於顯影時容易發生剝離。 When the concentration of the color material is increased and the content of the dispersant is increased, the amount of the binder is relatively reduced, so that the colored resin layer is easily peeled off from the base substrate during development. When the dispersant contains a B block containing a constituent unit derived from a carboxyl group-containing monomer and has the above specific acid value and glass transition temperature, the development adhesiveness is improved. However, when the acid value is too high, it is presumed that although the developability is excellent, the polarity is too high and peeling easily occurs during development.
作為上述含羧基單體,可使用可與具有一般式(II)所示之構成單位的單體進行共聚合、並含有不飽和雙鍵與羧基的單體。作為此種單體,可列舉例如(甲基)丙烯酸、乙烯基安息香酸、順丁烯二酸、順丁烯二酸單烷基酯、反丁烯二酸、伊康酸、丁烯酸、桂皮酸、丙烯酸二聚物等。又,亦可利用2-羥乙基(甲基)丙烯酸酯等之具有羥基的單體與如順丁烯二酸酐或酞酸酐、環己烷二羧酸酐般之環狀酐的加成反應物,ω-羧基-聚己內酯單(甲基)丙烯酸酯等。又,亦可使用順丁烯二酸酐、伊康酸酐、檸康酸酐等之含酸酐基單體作為羧基前驅物。其中,由共聚合性或成本、溶解性、玻璃轉移 溫度等的觀點而言,特佳為(甲基)丙烯酸。 As the carboxyl group-containing monomer, a monomer which can be copolymerized with a monomer having a structural unit represented by the general formula (II) and contains an unsaturated double bond and a carboxyl group can be used. Examples of such a monomer include (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, and the like. Cinnamic acid, acrylic acid dimer, and the like. Further, an addition reactant of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride or decanoic anhydride or cyclohexane dicarboxylic anhydride may be used. , ω-carboxy-polycaprolactone mono (meth) acrylate, and the like. Further, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used as the carboxyl precursor. Among them, by copolymerization or cost, solubility, glass transfer From the viewpoint of temperature and the like, (meth)acrylic acid is particularly preferred.
上述嵌段共聚合體中,來自含羧基單體之構成單位的含有比例,係依嵌段共聚合體之酸價成為上述特定酸價範圍內的方式適當設定即可,並無特別限定,相對於嵌段共聚合體之總構成單位的合計質量,較佳為0.05~4.5質量%、更佳為0.07~3.7質量%。 In the block copolymer, the content ratio of the constituent unit derived from the carboxyl group-containing monomer is appropriately set so that the acid value of the block copolymer is within the specific acid value range, and is not particularly limited. The total mass of the total constituent units of the segment copolymer is preferably from 0.05 to 4.5% by mass, more preferably from 0.07 to 3.7% by mass.
藉由使來自含羧基單體之構成單位的含有比例為上述下限值以上,可表現顯影殘渣之抑制效果,藉由為上述上限值以下,可防止顯影密黏性之惡化或溶劑再溶解性之惡化。 When the content ratio of the constituent unit derived from the carboxyl group-containing monomer is at least the above lower limit value, the effect of suppressing the development residue can be exhibited, and if it is at most the above upper limit value, deterioration of development adhesiveness or solvent redissolution can be prevented. Sexual deterioration.
尚且,來自含羧基單體之構成單位若為上述特定之酸價即可,可為包含1種者,亦可含有2種以上之構成單位。 In addition, the constituent unit derived from the carboxyl group-containing monomer may be one or more kinds of constituent units, and may be contained in two or more constituent units.
又,將本發明所使用之分散劑的玻璃轉移溫度設為特定值以上,由提升顯影密黏性的觀點而言,單體之均聚物之玻璃轉移溫度之值(Tgi)為10℃以上的單體較佳係依合計計於B嵌段中設為75質量%以上、更佳為85質量%以上。 Moreover, the glass transition temperature of the dispersing agent used in the present invention is set to a specific value or more, and the value of the glass transition temperature (Tgi) of the monomer homopolymer is 10 ° C or more from the viewpoint of improving the developing adhesiveness. The amount of the monomer is preferably 75% by mass or more, and more preferably 85% by mass or more based on the total amount of the B block.
上述嵌段共聚合體中,作為上述A嵌段之構成單位之單位數m、與上述B嵌段之構成單位之單位數n的比率m/n,較佳為0.05~1.5之範圍內,由色材之分散性、分散穩定性的觀點而言,更佳為0.1~1.0之範圍內。 In the block copolymer, the ratio m/n of the unit number m of the constituent units of the A block and the unit number n of the constituent units of the B block is preferably in the range of 0.05 to 1.5. From the viewpoint of dispersibility and dispersion stability of the material, it is more preferably in the range of 0.1 to 1.0.
上述嵌段共聚合體之重量平均分子量Mw並無特別限定,由作為色材分散性及分散穩定性良好者的觀點而言,較佳為1000~20000、更佳為2000~15000、再更佳為3000~12000。 The weight average molecular weight Mw of the above-mentioned block copolymer is not particularly limited, and is preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, even more preferably from the viewpoint of good dispersibility and dispersion stability of the color material. 3000~12000.
其中,重量平均分子量(Mw)係藉由凝膠滲透層析法(GPC),以標準聚苯乙烯換算值的形式求得。 Here, the weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) in the form of a standard polystyrene equivalent.
上述嵌段共聚合體之製造方法並無特別限定。可藉由 公知方法製造嵌段共聚合體,其中,較佳係以活性聚合法進行製造。其理由係,由於難以發生鏈移動或失活,可製造分子量均勻之共聚合體,可提升分散性等所致。作為活性聚合法,可列舉活性自由基聚合法、基轉移聚合法等之活性陰離子聚合法、活性陽離子聚合法等。利用此等方法使單體依序聚合,藉此可製造共聚合體。例如,先製造A嵌段,使構成B嵌段之構成單位對A嵌段進行聚合,藉此可製造嵌段共聚合體。又,上述製造方法中,亦可使A嵌段與B嵌段之聚合順序為相反。又,亦可分別製造A嵌段與B嵌段,其後,使A嵌段與B嵌段進行偶合。 The method for producing the above block copolymer is not particularly limited. By A block copolymer is produced by a known method, and among them, it is preferably produced by a living polymerization method. The reason for this is that it is difficult to cause chain movement or deactivation, and a copolymer having a uniform molecular weight can be produced, which can improve dispersibility and the like. Examples of the living polymerization method include a living anionic polymerization method such as a living radical polymerization method and a base transfer polymerization method, and a living cationic polymerization method. The monomers are sequentially polymerized by these methods, whereby a copolymer can be produced. For example, the block A is first produced, and the constituent unit constituting the B block is polymerized to the A block, whereby a block copolymer can be produced. Further, in the above production method, the polymerization order of the A block and the B block may be reversed. Further, the A block and the B block may be separately produced, and then the A block and the B block may be coupled.
本發明之色材分散液中,使用具有上述一般式(II)所示之構成單位的聚合體的至少一種作為分散劑,其含量係視所使用之色材種類、進而後述之彩色濾光片用感光性著色樹脂組成物中之固形份濃度等而適當選定。 In the color material dispersion liquid of the present invention, at least one of the polymer having the constituent unit represented by the above general formula (II) is used as a dispersing agent, and the content thereof depends on the type of the color material to be used, and further, a color filter to be described later. The concentration of the solid content in the photosensitive colored resin composition is appropriately selected.
分散劑之含量,由分散性及分散穩定性的觀點而言,相對於色材分散液中之總固形份100質量份,較佳為依3~45質量份、更佳為依5~35質量份的比例調配。 The content of the dispersant is preferably from 3 to 45 parts by mass, more preferably from 5 to 35 parts by mass, based on 100 parts by mass of the total solid content in the color material dispersion liquid, from the viewpoint of dispersibility and dispersion stability. Proportion of proportions.
尤其是在形成色材濃度高之塗膜或著色層時,分散劑之含量係相對於色材分散液中之總固形份100質量份,較佳為依3~25質量份、更佳為依5~20質量份的比例調配。 In particular, when a coating film or a colored layer having a high color material concentration is formed, the content of the dispersing agent is preferably from 3 to 25 parts by mass, more preferably, based on 100 parts by mass of the total solid content in the color material dispersion. 5 to 20 parts by mass ratio.
尚且,本發明中,固形份係上述溶劑以外者之全部,亦包括溶解於溶劑中之單體等。 Further, in the present invention, the solid portion is all other than the above solvent, and includes a monomer dissolved in a solvent or the like.
本發明之色材分散液係含有有機酸化合物。本發明中有機酸化 合物若為可與上述使用作為分散劑之嵌段共聚合體所具有之胺基形成鹽者即可,可適當選擇使用。本發明中,藉由使用上述有機酸化合物,則色材之分散性及分散穩定性優越,可得到耐熱性優越的塗膜,進而由於鹽形成部位對於鹼顯影時之鹼水溶液具有高親和性,故可作為鹼顯影性優越者。 The color material dispersion of the present invention contains an organic acid compound. Organic acidification in the present invention The compound may be a salt which can form a salt with the amine group which is used as the above-mentioned block copolymer as a dispersing agent, and can be suitably used. In the present invention, by using the organic acid compound, the dispersibility and dispersion stability of the color material are excellent, and a coating film having excellent heat resistance can be obtained, and the salt forming portion has high affinity for the alkali aqueous solution during alkali development. Therefore, it can be used as an alkali developability.
有機酸化合物係在與上述一般式(II)所示之構成單位(a)所具有之胺基形成鹽的情況,成為一般式(II')所示之構造。 When the organic acid compound forms a salt with the amine group of the structural unit (a) represented by the above general formula (II), it has a structure represented by the general formula (II').
(一般式(II')中,A-為來自有機酸化合物之陰離子,其他符號係與上述一般式(II)相同。) (In the general formula (II'), A - is an anion derived from an organic acid compound, and the other symbols are the same as the above general formula (II).)
本發明中,有機酸化合物若為具有1個以上之碳原子、與酸性基的化合物即可,並無特別限定。作為有機酸化合物所具有之酸性基,可列舉羧基、磺酸基、磷酸基等,由分散性、分散穩定性、耐熱性及鹼顯影性的觀點而言,較佳為磺酸基或磷酸基。又,由鹼顯影性的觀點而言,較佳為具有磷酸基。 In the present invention, the organic acid compound is not particularly limited as long as it is a compound having one or more carbon atoms and an acidic group. The acidic group of the organic acid compound may, for example, be a carboxyl group, a sulfonic acid group or a phosphoric acid group. From the viewpoints of dispersibility, dispersion stability, heat resistance and alkali developability, a sulfonic acid group or a phosphoric acid group is preferred. . Further, from the viewpoint of alkali developability, it is preferred to have a phosphate group.
有機酸化合物1分子中所含之酸性基的數量並無特別限定,由分散性、分散穩定性、耐熱性及鹼顯影性的觀點而言,1分子中之酸性基較佳為1~3個、更佳為1~2個。又,酸性基之價數並無特別限定,由分散穩定性、耐熱性及顯影性的觀點而言,較佳為1~3價 之酸、更佳為1~2價之酸。 The amount of the acidic group contained in the molecule of the organic acid compound is not particularly limited, and the acid group in one molecule is preferably from 1 to 3 from the viewpoints of dispersibility, dispersion stability, heat resistance and alkali developability. More preferably, it is 1~2. Further, the valence of the acidic group is not particularly limited, and is preferably from 1 to 3 in terms of dispersion stability, heat resistance and developability. The acid is more preferably an acid of 1 to 2 valence.
本發明中,有機酸化合物,由容易與分散劑所具有之胺基進行鹽形成的觀點而言,分子量較佳為5000以下、更佳為100以上且1000以下、再更佳為150以上且500以下。 In the present invention, the organic acid compound is preferably 5,000 or less, more preferably 100 or more and 1,000 or less, still more preferably 150 or more and 500, from the viewpoint of easy salt formation with the amine group of the dispersing agent. the following.
本發明中,由分散性、分散穩定性、耐熱性及鹼顯影性優越的觀點而言,有機酸化合物較佳為選自由下述一般式(IV)、及下述一般式(V)所組成之群組的1種以上。 In the present invention, the organic acid compound is preferably selected from the group consisting of the following general formula (IV) and the following general formula (V) from the viewpoint of superior dispersibility, dispersion stability, heat resistance and alkali developability. One or more of the groups.
(式(IV)及式(V)中,Ra及Ra'分別獨立為氫原子、羥基、碳數1~18之烷基、碳數2~18之烯基、芳烷基、芳基、-[CH(Rc)-CH(Rd)-O]s-Re、-[(CH2)t-O]u-Re、或-O-Ra"所示之1價基,Ra及Ra'之任一者含有碳原子;Ra"為碳數1~18之烷基、碳數2~18之烯基、芳烷基、芳基、-[CH(Rc)-CH(Rd)-O]s-Re、-[(CH2)t-O]u-Re所示之1價基;Rb為碳數1~18之烷基、碳數2~18之烯基、芳烷基、芳基、-[CH(Rc)-CH(Rd)-O]s-Re、-[(CH2)t-O]u-Re或-O-Rb'所示之1價基;Rb'為碳數1~18之烷基、碳數2~18之烯基、芳烷基、芳基、-[CH(Rc)-CH(Rd)-O]s-Re、或-[(CH2)t-O]u-Re所示之1價基;Rc及Rd分別獨立為氫原子或甲基,Re為氫原子、或碳數1~18之烷基、碳數2~18之烯基、芳烷基、芳基、-CHO、-CH2CHO、-CO-CH=CH2、-CO-C(CH3)=CH2或-CH2COORf所示之1價基,Rf 為氫原子或碳數1~5之烷基;Ra、Ra'及Rb中,烷基、烯基、芳烷基、芳基分別亦可具有取代基;s表示1~18之整數,t表示1~5之整數,u表示1~18之整數。) (In the formulae (IV) and (V), R a and R a ' are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group or an aryl group. , -[CH(R c )-CH(R d )-O] s -R e , -[(CH 2 ) t -O] u -R e , or -OR a" , a monovalent group, R Any one of a and R a' contains a carbon atom; R a" is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R c )- CH(R d )-O] s -R e , -[(CH 2 ) t -O] u -R e represents a monovalent group; R b is an alkyl group having 1 to 18 carbon atoms, carbon number 2~ 18 alkenyl, aralkyl, aryl, -[CH(R c )-CH(R d )-O] s -R e , -[(CH 2 ) t -O] u -R e or -OR a monovalent group represented by b' ; R b' is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R c )-CH(R d )-O] s -R e , or -[(CH 2 ) t -O] u -R e represents a monovalent group; R c and R d are each independently a hydrogen atom or a methyl group, and R e is a hydrogen atom Or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH 2 CHO, -CO-CH=CH 2 , -CO-C (CH 3 ) = CH 2 or -CH 2 COOR f is a monovalent group, R f is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and R a , R a ' and R b are an alkyl group or an alkene The group, the aralkyl group, and the aryl group may each have a substituent; s represents an integer from 1 to 18, t represents an integer from 1 to 5, and u represents an integer from 1 to 18.
上述一般式(IV)中,於Ra及Ra'具有芳香環之情形,該芳香環上亦可具有適當之取代基,例如碳數1~4之直鏈狀、分枝狀之烷基等。 In the above general formula (IV), in the case where R a and R a ' have an aromatic ring, the aromatic ring may have a suitable substituent such as a linear or branched alkyl group having 1 to 4 carbon atoms. Wait.
上述碳數1~18之烷基、芳烷基、芳基可設為與上述分散劑中之R8相同者。 The alkyl group, the aralkyl group or the aryl group having 1 to 18 carbon atoms may be the same as R 8 in the above dispersant.
在Ra及/或Ra'為-O-Ra"時,成為酸性磷酸酯。 When R a and/or R a ' is -OR a" , it becomes an acidic phosphate.
尚且,在Ra"具有芳香環的情況,該芳香環上亦可具有適當之取代基,例如碳數1~4之直鏈狀、分枝狀之烷基等。 Further, in the case where R a " has an aromatic ring, the aromatic ring may have an appropriate substituent such as a linear or branched alkyl group having 1 to 4 carbon atoms.
於上述Re所表示之1價基中,作為亦可具有之取代基,可列舉例如碳數1~4之直鏈狀、分枝狀或環狀之烷基、F、Cl、Br等鹵原子等。 The monovalent group represented by the above R e may, for example, be a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, or a halogen such as F, Cl or Br. Atoms, etc.
上述Re中碳數1~18之烷基係如上述R8所示;碳數2~18之烯基係如上述Ra及Ra'所示。 The alkyl group having 1 to 18 carbon atoms in the above R e is represented by the above R 8 ; and the alkenyl group having 2 to 18 carbon atoms is represented by the above R a and R a ' .
於Ra、Ra'及Ra"中,s為1~18之整數,t為1~5之整數,u為1~18之整數。s較佳為1~4之整數、更佳為1~2之整數;t較佳為1~4之整數、更佳為2或3。u較佳為1~4之整數、更佳為1~2之整數。 In R a , R a ' and R a" , s is an integer from 1 to 18, t is an integer from 1 to 5, and u is an integer from 1 to 18. s is preferably an integer from 1 to 4, more preferably An integer of 1 to 2; t is preferably an integer of 1 to 4, more preferably 2 or 3. u is preferably an integer of 1 to 4, more preferably an integer of 1 to 2.
上述一般式(V)中,於Rb具有芳香環之情形,該芳香環上亦可具有適當之取代基,例如碳數1~4之直鏈狀、分枝狀之烷基等。 In the above general formula (V), in the case where R b has an aromatic ring, the aromatic ring may have an appropriate substituent such as a linear or branched alkyl group having 1 to 4 carbon atoms.
在Rb為-O-Rb'時,成為酸性硫酸酯。上述Rb'為碳數1~18之烷基、碳數2~18之烯基、芳烷基、芳基、-[CH(Rc)-CH(Rd)-O]s-Re、或-[(CH2)t-O]u-Re所示之1價基。 When R b is -OR b' , it becomes an acidic sulfate. The above R b ' is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R c )-CH(R d )-O] s -R e Or a 1-valent group represented by -[(CH 2 ) t -O] u -R e .
上述碳數1~18之烷基、芳烷基、芳基係如上述R8所示;碳數2~18之烯基係如上述Ra及Ra'所示。尚且,在Rb'具有芳香環的情況,該芳香環上亦可具有適當之取代基,例如碳數1~4之直鏈狀、分枝狀之烷基等。 The alkyl group having 1 to 18 carbon atoms, the aralkyl group and the aryl group are represented by the above R 8 ; and the alkenyl group having 2 to 18 carbon atoms is represented by the above R a and R a ' . Further, in the case where R b ' has an aromatic ring, the aromatic ring may have an appropriate substituent such as a linear or branched alkyl group having 1 to 4 carbon atoms.
上述Rc、Rd及Re係與上述相同。 The above R c , R d and R e are the same as described above.
於上述Rb及Rb'中,s為1~18之整數,t為1~5之整數,u為1~18之整數。較佳之s、t、u係與上述Ra、Ra'及Ra"相同。 In the above R b and R b ' , s is an integer from 1 to 18, t is an integer from 1 to 5, and u is an integer from 1 to 18. Preferably, s, t, and u are the same as R a , R a ' and R a ' .
作為上述一般式(IV)所示之有機酸化合物,由提升色材之分散性、且所獲得之著色層之對比度較高、且耐熱性優異的觀點而言,較佳係上述一般式(IV)中之Ra及Ra'分別獨立為氫原子、羥基、甲基、乙基、亦可具有取代基之芳基或芳烷基、乙烯基、烯丙基、-[CH(Rc)-CH(Rd)-O]s-Re、或-[(CH2)t-O]u-Re、或-O-Ra"所示之1價基,Ra及Ra"之任一者包含碳原子,且Ra"為甲基、乙基、亦可具有取代基之芳基或芳烷基、乙烯基、烯丙基、-[CH(Rc)-CH(Rd)-O]s-Re、或-[(CH2)t-O]u-Re,Rc及Rd分別獨立為氫原子或甲基,更佳係Ra為羥基,且Ra'為亦可具有取代基之芳基。 The organic acid compound represented by the above general formula (IV) is preferably a general formula (IV) from the viewpoint of improving the dispersibility of the color material and having a high contrast ratio of the obtained coloring layer and excellent heat resistance. Wherein R a and R a ' are each independently a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, an aryl group or an aralkyl group which may have a substituent, a vinyl group, an allyl group, -[CH(R c ) -CH(R d )-O] s -R e , or -[(CH 2 ) t -O] u -R e , or a -valent group represented by -OR a" , R a and R a" One containing a carbon atom, and R a" is a methyl group, an ethyl group, an aryl group or an aralkyl group which may have a substituent, a vinyl group, an allyl group, -[CH(R c )-CH(R d ) -O] s -R e , or -[(CH 2 ) t -O] u -R e , R c and R d are each independently a hydrogen atom or a methyl group, more preferably R a is a hydroxyl group, and R a ' It is an aryl group which may also have a substituent.
又,作為一般式(V)所示之有機酸化合物,由提升色材之分散性、且所獲得之著色層之對比度較高、且耐熱性優異的觀點而言,較佳係一般式(V)中之Rb為甲基、乙基、亦可具有取代基之芳基或芳烷基、乙烯基、烯丙基、-[CH(Rc)-CH(Rd)-O]s-Re、或-[(CH2)t-O]u-Re、或-O-Rb'所示之1價基,Rb'為甲基、乙基、亦可具 有取代基之芳基或芳烷基、乙烯基、烯丙基、-[CH(Rc)-CH(Rd)-O]s-Re、或-[(CH2)t-O]u-Re,Rc及Rd分別獨立為氫原子或甲基,更佳係Rb為亦可具有取代基之芳基。 Further, the organic acid compound represented by the general formula (V) is preferably a general formula (V) from the viewpoint of improving the dispersibility of the color material and having a high contrast ratio of the obtained coloring layer and excellent heat resistance. R b is methyl, ethyl, aryl or aralkyl which may also have a substituent, vinyl, allyl, -[CH(R c )-CH(R d )-O] s - R e , or -[(CH 2 ) t -O] u -R e , or a monovalent group represented by -OR b' , wherein R b ' is a methyl group, an ethyl group, an aryl group which may have a substituent or Aralkyl, vinyl, allyl, -[CH(R c )-CH(R d )-O] s -R e , or -[(CH 2 ) t -O] u -R e ,R c And R d are each independently a hydrogen atom or a methyl group, and more preferably R b is an aryl group which may have a substituent.
其中,上述一般式(IV)及一般式(V)所示之有機酸化合物,由提升色材之分散性、且所獲得之著色層之對比度較高、且耐熱性優異之觀點而言,較佳係Ra、Ra'及/或Ra"、及/或Rb及/或Rb'具有芳香環。由色材分散性之觀點而言,較佳為Ra、Ra'及Ra"之至少1個、或者Rb或Rb'為亦可具有取代基之芳基或芳烷基,更具體而言為苄基、苯基、甲苯基、萘基、聯苯基。於上述一般式(IV)中,於Ra及Ra'之一者具有芳香環時,Ra及Ra'之另一者亦可適當地使用氫原子或羥基者。 Among them, the organic acid compound represented by the above general formula (IV) and general formula (V) is improved from the viewpoint of improving the dispersibility of the color material, the contrast of the obtained coloring layer is high, and the heat resistance is excellent. Preferably, R a , R a ' and/or R a" , and/or R b and/or R b' have an aromatic ring. From the viewpoint of dispersibility of the color material, R a , R a ' and At least one of R a " or R b or R b ' is an aryl or aralkyl group which may have a substituent, more specifically a benzyl group, a phenyl group, a tolyl group, a naphthyl group, or a biphenyl group. In the above general formula (IV), when one of R a and R a ' has an aromatic ring, the other of R a and R a ' may suitably use a hydrogen atom or a hydroxyl group.
又,由耐熱性或耐藥品性、尤其是耐鹼性的觀點而言,作為上述一般式(IV)及一般式(V)所示之有機酸化合物,較佳係碳原子直接鍵結於磷(P)或硫(S)的化合物,較佳係Ra及Ra'分別獨立為氫原子、羥基、碳數1~18之烷基、碳數2~18之烯基、芳烷基、芳基、-[CH(Rc)-CH(Rd)-O]s-Re、-[(CH2)t-O]u-Re所示之1價基,Ra及Ra'之任一者包含碳原子。又,較佳為Rb為碳數1~18之烷基、碳數2~18之烯基、芳烷基、芳基、-[CH(Rc)-CH(Rd)-O]s-Re、-[(CH2)t-O]u-Re所示之1價基。 Further, from the viewpoint of heat resistance, chemical resistance, and particularly alkali resistance, the organic acid compound represented by the above general formula (IV) and general formula (V) is preferably bonded directly to phosphorus. (P) or a compound of sulfur (S), preferably R a and R a ' are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, An aryl group, -[CH(R c )-CH(R d )-O] s -R e , -[(CH 2 ) t -O] u -R e represents a monovalent group, R a and R a ' Either contains a carbon atom. Further, R b is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R c )-CH(R d )-O] s a monovalent group represented by -R e and -[(CH 2 ) t -O] u -R e .
本發明中,由分散性、耐熱性方面而言,有機酸化合物較佳為苯磺酸、對甲苯磺酸、單丁基磷酸、二丁基磷酸、甲基磷酸、二苄基磷酸、二苯基磷酸、苯基膦酸等;其中,更佳為對甲苯磺酸、苯基膦酸。又,有機酸化合物亦可使用如對甲苯磷酸一水合物般之水合物。 In the present invention, the organic acid compound is preferably benzenesulfonic acid, p-toluenesulfonic acid, monobutylphosphoric acid, dibutylphosphoric acid, methylphosphoric acid, dibenzylphosphoric acid or diphenyl, in terms of dispersibility and heat resistance. Phosphoric acid, phenylphosphonic acid, etc.; among them, p-toluenesulfonic acid and phenylphosphonic acid are more preferable. Further, as the organic acid compound, a hydrate such as p-toluene phosphate monohydrate can also be used.
本發明中,有機酸化合物可單獨使用1種、或組合2種以上使用。 In the present invention, the organic acid compound may be used singly or in combination of two or more.
本發明中,分散劑及有機酸化合物之合計含量並無特別限定,由分散性及分散穩定性的觀點而言,相對於色材100質量份,分散劑及有機酸化合物之合計含量較佳為10~120質量份、更佳為20~100質量份、再更佳為30~80質量份。 In the present invention, the total content of the dispersing agent and the organic acid compound is not particularly limited, and from the viewpoint of dispersibility and dispersion stability, the total content of the dispersing agent and the organic acid compound is preferably 100 parts by mass of the color material. 10 to 120 parts by mass, more preferably 20 to 100 parts by mass, still more preferably 30 to 80 parts by mass.
本發明之色材分散液,係藉由依下述方法組合使用分散劑與有機酸化合物,而使色材分散液之色材分散性及分散穩定性優越,可得到耐熱性優越的塗膜,進而由於鹽形成部位對鹼顯影時之鹼水溶液具有高溶解性,故可作成為鹼顯影性優越者。亦即,在將上述分散劑之上述胺價設為A(mgKOH/g)、將上述色材分散液中所含之上述有機酸化合物之物質量XA(mol)與構成上述色材分散液中所含之上述分散劑的上述構成單位(a)之物質量XB(mol)的比設為X(=XA/XB)時,滿足下式(1)及式(2);在X為未滿1之範圍內,進一步滿足下式(3);X≦1.5 式(1) In the color material dispersion liquid of the present invention, by using a dispersing agent and an organic acid compound in combination as described below, the dispersibility and dispersion stability of the color material dispersion liquid are excellent, and a coating film excellent in heat resistance can be obtained. Since the salt-forming portion has high solubility in the aqueous alkali solution at the time of alkali development, it is excellent in alkali developability. In other words, the amine value of the dispersant is A (mgKOH/g), and the mass of the organic acid compound contained in the color material dispersion X A (mol) and the color material dispersion are formed. When the ratio of the mass of the constituent unit (a) X B (mol) of the dispersing agent contained in the above-mentioned dispersing agent is X (=X A /X B ), the following formulas (1) and (2) are satisfied; X is in the range of less than 1, further satisfying the following formula (3); X≦1.5 (1)
A×X≧40 式(2) A×X≧40 type (2)
A×(1-X)≦42 式(3) A×(1-X)≦42 (3)
上式(1)表示相對於上述分散劑所具有之胺基,上述有機酸化合物為1.5莫耳當量以下。若有機酸化合物為1.5莫耳當量以下,則未進行鹽形成而存在之有機酸化合物的比例少,色材之分散穩定性優越,有機酸化合物不析出。尚且,未進行鹽形成而存在 之有機酸化合物具有提升塗膜之耐熱性與鹼顯影性的效果。本發明中,較佳係X≦1.3、更佳係0.7≦X≦1.2。 The above formula (1) represents an amine group which is contained in the above dispersant, and the organic acid compound is 1.5 mol equivalent or less. When the organic acid compound is 1.5 mol equivalent or less, the ratio of the organic acid compound which is not formed by salt formation is small, the dispersion stability of the color material is excellent, and the organic acid compound does not precipitate. Still, there is no salt formation The organic acid compound has an effect of improving the heat resistance and alkali developability of the coating film. In the present invention, it is preferably X≦1.3, more preferably 0.7≦X≦1.2.
上式(2)表示在假設為所添加之有機酸與分散劑之胺基依1:1進行100%鹽形成時,於分散劑所具有之胺基中相當於用於鹽形成之部分的胺價。又,在X超過1的範圍時,推判由於過剩之有機酸化合物使化合物(I)之色澱構造穩定化,故耐熱性更加提升。滿足上式(2)之色材分散液由於對色材之親和性適合於分散,故分散穩定性優越。 The above formula (2) represents an amine equivalent to a portion for salt formation in the amine group of the dispersing agent, assuming that the organic acid to be added and the amine group of the dispersing agent are formed by 100% salt in a ratio of 1:1. price. Further, when X is in the range of more than 1, it is estimated that the excessively-organic organic acid compound stabilizes the lake structure of the compound (I), so that heat resistance is further improved. The color material dispersion liquid satisfying the above formula (2) is suitable for dispersion because of its affinity for the color material, so that the dispersion stability is excellent.
又,近年來隨著彩色濾光片之高精細化,而要求彩色濾光片之著色層減薄。為了使著色層減薄,必須相對於著色樹脂組成物中之固形份提高顏料濃度,分散劑之顯影性亦造成大幅影響。 Further, in recent years, as the color filter is made finer, the color layer of the color filter is required to be thinned. In order to reduce the thickness of the colored layer, it is necessary to increase the pigment concentration with respect to the solid content in the colored resin composition, and the developability of the dispersant is also greatly affected.
即使在顏料濃度高之著色樹脂組成物中,為了實現充分之顯影性,較佳係鹽形成部較多,亦即有機酸較多;A×X≧60、更佳係A×X≧80。 Even in the colored resin composition having a high pigment concentration, in order to achieve sufficient developability, it is preferred that the salt forming portion is large, that is, a large amount of organic acid; A × X ≧ 60, more preferably A × X ≧ 80.
由對溶劑之再溶解性的觀點而言,較佳係鹽形成部較少,亦即有機酸較少;A×X≦130、更佳係A×X≦110。 From the viewpoint of resolubility to the solvent, it is preferred that the salt forming portion is small, that is, the organic acid is less; A × X ≦ 130, more preferably A × X ≦ 110.
又,上式(2)表示在假設為所添加之有機酸與分散劑之胺基依1:1進行100%鹽形成時,於分散劑所具有之胺基中相當於用於鹽形成之部分的胺價。滿足上式(2)之色材分散液由於未進行鹽形成之胺基較少,故色材之分子締合狀態難以被破壞。因此,使用滿足上式(2)之色材分散液所製作的著色樹脂組成物係黏度穩定性優越,於藉此著色樹脂組成物所形成之著色層中,亦由於維持著分子締合狀態,故耐熱性優越。又,在X為1以上的範圍時,由於未進行鹽形成之胺基較少,故與X未滿1且滿足上式(2)之情況同樣 地,耐熱性優越。 Further, the above formula (2) indicates that when the organic acid to be added and the amine group of the dispersing agent are formed into a 100% salt by 1:1, the amine group contained in the dispersing agent corresponds to the portion for salt formation. The price of the amine. Since the color material dispersion liquid satisfying the above formula (2) has less amine groups which are not subjected to salt formation, the molecular association state of the color material is hard to be broken. Therefore, the coloring resin composition produced by using the color material dispersion liquid satisfying the above formula (2) is excellent in viscosity stability, and in the coloring layer formed by the colored resin composition, the molecular association state is maintained. Therefore, the heat resistance is excellent. In addition, when X is in the range of 1 or more, since the number of amine groups which are not salt-formed is small, it is the same as the case where X is less than 1 and the above formula (2) is satisfied. Ground, excellent heat resistance.
尚且,本發明中,XA係有機酸化合物之物質量,設為並不包括色澱色材所含有之對陰離子、或鹼可溶性樹脂。 Further, in the present invention, the mass of the X A- based organic acid compound is such that it does not include a counter anion or an alkali-soluble resin contained in the lake color material.
本發明中作為溶劑,係使用上述一般式(I)所示之色材於23℃下之溶解度為0.1(g/10ml溶劑)以下的溶劑。藉由使用對色材實質上不溶解的此種溶劑或難溶性的溶劑,本發明之色材分散液可使上述一般式(I)所示之色材於溶劑中依分子締合狀態分散而使用。本發明中所使用之溶劑,由分散性、耐熱性優越、可得到高亮度之塗膜的觀點而言,較佳係於23℃下之上述一般式(I)所示之色材的溶解度為0.05(g/10ml溶劑)以下的溶劑。 In the present invention, as the solvent, a solvent having a solubility in a coloring matter represented by the above general formula (I) at 23 ° C of 0.1 (g/10 ml of solvent) or less is used. By using such a solvent or a poorly soluble solvent which is substantially insoluble in the color material, the color material dispersion liquid of the present invention can disperse the color material represented by the above general formula (I) in a solvent in a molecular association state. use. In the solvent used in the present invention, the solubility of the coloring material represented by the above general formula (I) at 23 ° C is preferably from the viewpoint of obtaining a coating film having high dispersibility and heat resistance and obtaining high brightness. 0.05 (g/10 ml solvent) or less of the solvent.
尚且,本發明中,於23℃下之上述色材及上述系染料的溶解度為0.1(g/10ml溶劑)以下的溶劑,可藉由以下評價方法而簡易判定。 Further, in the present invention, the above color material at 23 ° C and the above The solvent having a solubility of the dye of 0.1 (g/10 ml solvent) or less can be easily determined by the following evaluation method.
首先,藉下述方法,可判斷是否為上述一般式(I)所示之色材實質上不溶解的溶劑。 First, it is possible to judge whether or not the coloring material represented by the above general formula (I) is substantially insoluble in the solvent by the following method.
於20mL樣本管瓶中,投入欲判斷溶解性之色材0.1g,使用10ml全量吸量管投入溶劑S,進一步加蓋後以超音波處理3分鐘。所得液係於23℃水浴中靜置保管60分鐘。將其上清液5ml藉PTFE5μm薄膜過濾器進行過濾,再以0.25μm薄膜過濾器進行過濾,去除不溶物。以紫外可見分光光度計(例如島津製作所公司製UV-2500PC)使用1cm槽測定所得液之吸光光譜。求得各色材之極大吸收波長中之吸光度(abs)。此時,若吸光度(abs)未滿測定上限值之40%(於島 津製作所公司製UV-2500PC的情況,吸光度(abs)為未滿2),則該溶劑可評價為上述色材實質上不溶解的溶劑。此時,吸光度(abs)為測定上限值之40%以上時,係進一步藉由下述評價方法求得溶解度。 In a 20 mL sample vial, 0.1 g of the color material to be judged for solubility was placed, and the solvent S was placed in a 10 ml full pipette, further capped, and ultrasonically treated for 3 minutes. The obtained liquid was stored in a water bath at 23 ° C for 60 minutes. 5 ml of the supernatant was filtered through a PTFE 5 μm membrane filter, and then filtered through a 0.25 μm membrane filter to remove insoluble matter. The absorption spectrum of the obtained liquid was measured using a 1 cm tank using an ultraviolet-visible spectrophotometer (for example, UV-2500PC manufactured by Shimadzu Corporation). The absorbance (abs) in the maximum absorption wavelength of each color material was obtained. At this time, if the absorbance (abs) is less than 40% of the upper limit of the measurement (on the island) In the case of UV-2500PC manufactured by Tsuzuki Seisakusho Co., Ltd., if the absorbance (abs) is less than 2), the solvent can be evaluated as a solvent in which the color material is substantially insoluble. In this case, when the absorbance (abs) is 40% or more of the upper limit of the measurement, the solubility is further determined by the following evaluation method.
首先,取代上述溶劑S,使用欲判斷溶解性之色材的良溶劑(例如甲醇等之醇),同樣地製得濾液,製作色材溶液,其後適當稀釋為10000倍~100000倍左右,同樣地測定色材之極大吸收波長中的吸光度。由上述溶劑S之色材溶液與良溶劑之色材溶液的吸光度與稀釋倍率,算出色材對上述溶劑S的溶解度。 First, in place of the solvent S, a good solvent (for example, an alcohol such as methanol) for determining the solubility of the color material is used, and a filtrate is prepared in the same manner to prepare a color material solution, which is then appropriately diluted to about 10,000 times to 100,000 times. The absorbance in the maximum absorption wavelength of the color material is measured. The solubility of the color material in the solvent S is calculated from the absorbance and the dilution ratio of the color material solution of the solvent S and the color material solution of the good solvent.
其結果,上述色材之溶解度為0.1(g/10ml溶劑)以下的溶劑,判斷為本發明中可使用之色材為難溶性的溶劑。 As a result, the solubility of the color material is 0.1 or less (g/10 ml of solvent) or less, and it is judged that the coloring material usable in the present invention is a solvent which is poorly soluble.
上述色材之溶解度為0.1(g/10ml溶劑)以下的溶劑,由提升色材分散液之分散穩定性的觀點而言,較佳為於色材分散液之總溶劑中含有95質量%以上、更佳為含有98質量%以上、最佳為含有100質量%。 The solvent having a solubility of the color material of 0.1 or less (g/10 ml of the solvent) is preferably 95% by mass or more in the total solvent of the color material dispersion, from the viewpoint of improving the dispersion stability of the color material dispersion. More preferably, it is 98% by mass or more, and most preferably 100% by mass.
本發明之色材分散液中,由分散安定性的觀點而言,較佳係由酯系溶劑中適當選擇使用。 In the color material dispersion liquid of the present invention, it is preferably selected from the ester solvent as appropriate from the viewpoint of dispersion stability.
作為酯系溶劑,可列舉例如醋酸乙酯、醋酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、乳酸乙酯、甲氧基醋酸乙酯、丙二醇單甲基醚醋酸酯、3-甲氧基-3-甲基-1-醋酸丁酯、3-甲氧基醋酸丁酯、甲氧基醋酸丁酯、乙氧基醋酸乙酯、乙基賽璐蘇醋酸酯、二丙二醇甲基醚醋酸酯、丙二醇二醋酸酯、1,3-丁二醇二醋酸酯、環己醇醋酸酯、1,6-己二醇二醋酸酯、二乙二醇單乙基醚醋酸酯、二乙二醇單丁基醚醋酸酯等。 Examples of the ester solvent include ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, ethyl methoxyacetate, and propylene glycol monomethyl ether acetate. , 3-methoxy-3-methyl-1-acetic acid butyl ester, 3-methoxyacetic acid butyl ester, butyl methoxyacetate, ethoxyethyl acetate, ethyl cyproterone acetate, two Propylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, 1,6-hexanediol diacetate, diethylene glycol monoethyl ether acetate , diethylene glycol monobutyl ether acetate, and the like.
其中,由對人體的危險性低、於室溫附近之揮發性低但加熱乾 燥性佳的觀點而言,較佳為使用丙二醇單甲基醚醋酸酯(PGMEA)。於此情況下,尚具有在與習知使用了PGMEA之著色樹脂組成物轉換時不需要特別洗淨步驟的優點。 Among them, the risk to the human body is low, the volatility near the room temperature is low, but the heat is dry From the viewpoint of good dryness, propylene glycol monomethyl ether acetate (PGMEA) is preferably used. In this case, there is an advantage that a special washing step is not required in the conversion with the conventional colored resin composition using PGMEA.
作為本發明所使用之溶劑,較佳為丙二醇單甲基醚醋酸酯於總溶劑中含有50質量%以上、更佳為含有70質量%以上、再更佳為含有90質量%以上。 The solvent to be used in the present invention is preferably propylene glycol monomethyl ether acetate in an amount of 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more in the total solvent.
此等溶劑可單獨或組合2種以上而使用。 These solvents may be used alone or in combination of two or more.
本發明之色材分散液,係相對於含有該溶劑之色材分散液之總量,依如上述般之溶劑通常為50~95質量%、較佳為60~85質量%的比例使用而調製。若溶劑過少,則黏度上升、分散性容易降低。又,若溶劑過少,則色材濃度降低,有在調製彩色濾光片用著色樹脂組成物後難以達成目標之色度座標的情形。 The color material dispersion liquid of the present invention is prepared by using a solvent in a ratio of 50 to 95% by mass, preferably 60 to 85% by mass, based on the total amount of the color material dispersion liquid containing the solvent. . When the amount of the solvent is too small, the viscosity increases and the dispersibility is liable to lower. In addition, when the amount of the solvent is too small, the color material concentration is lowered, and it is difficult to achieve the target chromaticity coordinate after the coloring resin composition for a color filter is prepared.
本發明之色材分散液中,在不損及本發明效果之前提下,視需要亦可進一步調配分散輔助樹脂、其他成分。 In the color material dispersion liquid of the present invention, the dispersion auxiliary resin and other components may be further prepared as needed without impairing the effects of the present invention.
作為分散輔助樹脂,可列舉例如後述之彩色濾光片用著色樹脂組成物所例示的鹼可溶性樹脂。藉由鹼可溶性樹脂之立體阻礙使色材彼此難以接觸,有分散穩定化或因該分散穩定化效果而減少分散劑之效果的情形。作為鹼可溶性樹脂,由分散穩定性及耐熱性的觀點而言,較佳係使用具有烴環之樹脂;由色材之分子締合狀態穩定化、提升耐熱性的觀點而言,較佳係使用酸價高的樹脂。 The dispersing auxiliary resin may, for example, be an alkali-soluble resin exemplified as a colored resin composition for a color filter to be described later. The color materials are hardly contacted with each other by the steric hindrance of the alkali-soluble resin, and there is a case where the dispersion is stabilized or the effect of the dispersion is reduced by the effect of the dispersion stabilization. The alkali-soluble resin is preferably a resin having a hydrocarbon ring from the viewpoint of dispersion stability and heat resistance, and is preferably used from the viewpoint of stabilizing the molecular association state of the color material and improving heat resistance. A resin with a high acid value.
另外,作為其他成分,可列舉例如用於提升濕潤性的界面活性劑、消泡劑、防收縮劑、抗氧化劑、抗凝集劑、紫外線吸收劑等。 Further, examples of the other component include a surfactant, an antifoaming agent, an anti-shrinking agent, an antioxidant, an anti-aggregating agent, and an ultraviolet absorber for improving wettability.
本發明之色材分散液,係使用作為用於調製後述彩色濾光片用著色樹脂組成物的預備調製物。亦即,所謂色材分散液,係於調製後述著色樹脂組成物的前階段中,預備調製之(組成物中之色材成分)/(組成物中之色材成分以外的固形份)比(質量比)較高的色材分散液。具體而言,(組成物中之色材成分)/(組成物中之色材成分以外的固形份)比(質量比)通常為1.0以上。例如,藉由將色材分散液與至少感光性黏結劑成分混合,可調製分散性優越的著色樹脂組成物。 The color material dispersion liquid of the present invention is used as a preliminary preparation for preparing a colored resin composition for a color filter to be described later. In other words, the color material dispersion liquid is a ratio of (a color component in the composition)/(a solid content other than the color material component in the composition) prepared in the pre-stage of preparing the colored resin composition described later ( A color material dispersion with a higher mass ratio). Specifically, the ratio (mass ratio) of the (color component in the composition) / (solid content other than the color component in the composition) is usually 1.0 or more. For example, by mixing the color material dispersion with at least the photosensitive binder component, a colored resin composition having excellent dispersibility can be prepared.
本發明中,色材分散液之製造方法若為將上述一般式(I)所示色材藉由分散劑,分散於溶劑中而得到色材分散液的方法,並無特別限定,例如:(1)事先將分散劑混合、攪拌於溶劑中,調製分散劑溶液,接著混合有機酸化合物使分散劑所具有之胺基與有機酸化合物進行鹽形成。將此與一般式(I)所示之色材與視需要之其他成分混合,使用公知攪拌機或分散機予以分散的方法;(2)將分散劑混合、攪拌於溶劑中,調製分散劑溶液,接著混合一般式(I)所示之色材及有機酸化合物、與視需要之其他成分,使用公知攪拌機或分散機予以分散的方法;(3)將分散劑混合、攪拌於溶劑中,調製分散劑溶液,接著混合一般式(I)所示之色材及視需要之其他成分,使用公知攪拌機或分散機作成分散液後,添加有機酸化合物的方法等。 In the present invention, the method for producing a color material dispersion liquid is not particularly limited as long as the color material shown in the above formula (I) is dispersed in a solvent by a dispersant to obtain a color material dispersion liquid, for example: 1) The dispersant is previously mixed and stirred in a solvent to prepare a dispersant solution, and then the organic acid compound is mixed to form a salt of the amine group and the organic acid compound which the dispersant has. Mixing the color material represented by the general formula (I) with other components as needed, and dispersing it by using a known mixer or disperser; (2) mixing and stirring the dispersant in a solvent to prepare a dispersant solution, Next, the color material and the organic acid compound represented by the general formula (I), and other components as necessary, are mixed by a known agitator or a disperser; (3) the dispersant is mixed and stirred in a solvent to prepare a dispersion. The agent solution is then mixed with a color material represented by the general formula (I) and optionally other components, and a method of adding an organic acid compound by using a known mixer or disperser to form a dispersion.
本發明中,由色材之分散穩定性的觀點而言,較佳係設為上述(1)之方法。 In the present invention, from the viewpoint of dispersion stability of the color material, the method of the above (1) is preferred.
作為用於進行分散處理之分散機,可列舉雙輥、三輥 等輥磨機、球磨機、振動球磨機等球磨機、塗料調和器、連續盤型珠磨機、連續環型珠磨機等珠磨機。作為珠磨機之較佳分散條件,所使用之珠徑較佳為0.03~2.00mm,更佳為0.10~1.0mm。 As the dispersing machine for performing the dispersion treatment, a double roll or a triple roll can be cited. Ball mills such as ball mills, ball mills, vibrating ball mills, paint blenders, continuous disc bead mills, continuous loop bead mills, etc. As a preferred dispersion condition of the bead mill, the bead diameter to be used is preferably from 0.03 to 2.00 mm, more preferably from 0.10 to 1.0 mm.
具體而言,可列舉,藉由珠徑為相對較大之2mm氧化鋯珠進行預備分散,再以珠徑為相對較小之0.1mm氧化鋯珠進行本分散。又,分散後,較佳係藉由0.5~0.1μm之薄膜過濾器進行過濾。 Specifically, the dispersion is carried out by a 2 mm zirconia bead having a relatively large bead diameter, and the dispersion is carried out by using a relatively small 0.1 mm zirconia bead having a bead diameter. Further, after dispersion, it is preferably filtered by a membrane filter of 0.5 to 0.1 μm.
本發明之彩色濾光片用著色樹脂組成物之特徵在於,含有上述本發明之色材分散液、鹼可溶性樹脂、多官能單體、與起始劑。 The colored resin composition for a color filter of the present invention is characterized by comprising the above-described color material dispersion liquid, alkali-soluble resin, polyfunctional monomer, and initiator.
本發明之彩色濾光片用著色樹脂組成物由於含有上述本發明之色材分散液,故經時穩定性優越、可形成耐熱性提升的著色層,鹼顯影性亦優越。 Since the colored resin composition for a color filter of the present invention contains the above-described color material dispersion liquid of the present invention, it has excellent stability over time, and can form a coloring layer having improved heat resistance, and is excellent in alkali developability.
本發明之彩色濾光片用著色樹脂組成物係至少含有一般式(I)所示之色材、分散劑、有機酸化合物、鹼可溶性樹脂、多官能單體、起始劑、與溶劑者;在不損及本發明效果之前提下,視需要亦可進一步含有其他成分。 The colored resin composition for a color filter of the present invention contains at least a color material, a dispersant, an organic acid compound, an alkali-soluble resin, a polyfunctional monomer, a starter, and a solvent represented by the general formula (I); It may be further provided without further impairing the effects of the present invention, and may further contain other components as needed.
以下,依序詳細說明此種本發明之彩色濾光片用著色樹脂組成物的各成分,但關於色材、分散劑、有機酸化合物、及溶劑,由於可設為與上述本發明之色材分散液相同者,故於此省略其說明。 Hereinafter, each component of the colored resin composition for a color filter of the present invention will be described in detail. However, the color material, the dispersant, the organic acid compound, and the solvent can be used as the color material of the present invention. Since the dispersion is the same, the description thereof is omitted here.
本發明中之鹼可溶性樹脂係通常具有羧基者,在具有作為黏結 劑樹脂之作用,且對形成圖案時所使用之顯影液、特佳為對鹼顯影液具有可溶性的前提下,則可適當選擇使用。又,鹼可溶性樹脂亦可涵括於有機酸化合物中,但本發明中鹼可溶性樹脂係視為與有機酸化合物為不同物。 The alkali-soluble resin in the present invention usually has a carboxyl group and has a bond as a binder. The action of the resin may be appropriately selected and used on the premise that the developer used for pattern formation is particularly soluble in the alkali developer. Further, the alkali-soluble resin may be included in the organic acid compound, but the alkali-soluble resin in the present invention is considered to be different from the organic acid compound.
本發明中鹼可溶性樹脂之酸價並無特別限定。由提升分散穩定性等之經時穩定性、提升由該樹脂組成物所得之著色層之耐熱性的觀點而言,作為鹼可溶性樹脂較佳係使用酸價為80mgKOH/g以上且300mgKOH/g以下的樹脂。酸價為80mgKOH/g以上之樹脂係酸性基相對較多,使上述一般式(I)所示之色材之分子締合體、與上述分散劑所具有之胺基間的相互作用穩定化,推判可提升分散穩定性等之經時穩定性,提升由該樹脂組成物所得之著色層的耐熱性。 The acid value of the alkali-soluble resin in the present invention is not particularly limited. From the viewpoint of improving the stability over time of dispersion stability and the like and improving the heat resistance of the coloring layer obtained from the resin composition, it is preferable to use an acid value of 80 mgKOH/g or more and 300 mgKOH/g or less as the alkali-soluble resin. Resin. The acid-based acid group having an acid value of 80 mg KOH/g or more is relatively large, and the interaction between the molecular association of the color material represented by the above general formula (I) and the amine group of the dispersant is stabilized. It is judged that the stability over time of dispersion stability and the like can be improved, and the heat resistance of the coloring layer obtained from the resin composition can be improved.
尚且,本發明中酸價係表示用於中和固形份1g所需要之KOH的質量(mg),根據JIS K 0070,藉電位差滴定法所求得之值。 Further, the acid value in the present invention means the mass (mg) of KOH required for neutralizing 1 g of the solid fraction, and the value obtained by potentiometric titration according to JIS K 0070.
酸價為80mgKOH/g以上之鹼可溶性樹脂由於為具有相對較多之酸性基的樹脂,故容易與存在於上述一般式(I)所示之色材之分子締合體表面附近的陰離子所具有之鹼性基相互作用,其結果,推判鹼可溶性樹脂容易吸附於上述分子締合體表面。由於該鹼可溶性樹脂之酸價相對較高,故一旦經吸附,則即使於高溫加熱下亦難以解離,可更加抑制色材之分解等,推判可抑制亮度降低,格外提升耐熱性。又,藉由使用酸價為80mgKOH/g以上的鹼可溶性樹脂,該酸性基有助於與基板間之密黏性,即使未使用習知用於改善與基板間之密黏性的矽烷偶合劑,仍提升與基板間之密黏性。 Since the alkali-soluble resin having an acid value of 80 mgKOH/g or more is a resin having a relatively large amount of acidic groups, it is easy to have an anion existing in the vicinity of the surface of the molecular association body of the color material represented by the above general formula (I). The basic group interacts, and as a result, it is estimated that the alkali-soluble resin is easily adsorbed on the surface of the above-mentioned molecular complex. Since the acid-soluble valence of the alkali-soluble resin is relatively high, it is difficult to dissociate even when heated under high temperature, and the decomposition of the color material can be further suppressed, and the decrease in brightness can be suppressed, and the heat resistance can be particularly improved. Further, by using an alkali-soluble resin having an acid value of 80 mgKOH/g or more, the acidic group contributes to the adhesion to the substrate even if a conventional decane coupling agent for improving the adhesion to the substrate is not used. , still improve the adhesion between the substrate and the substrate.
本發明中之較佳鹼可溶性樹脂,具體而言,可列舉具 有羧基之丙烯酸系共聚合體、具有羧基之環氧基(甲基)丙烯酸酯樹脂等。該等之中,特佳為於側鏈具有羧基、且進而於側鏈具有乙烯性不飽和基等的光聚合性官能基者。其原因在於,藉由含有光聚合性官能基所形成之硬化膜之膜強度提高。又,該等丙烯酸系共聚合體、及環氧基丙烯酸酯樹脂可混合2種以上使用。 Preferred alkali-soluble resins in the present invention, specifically, An acrylic copolymer having a carboxyl group, an epoxy (meth)acrylate resin having a carboxyl group, or the like. Among these, a photopolymerizable functional group having a carboxyl group in a side chain and an ethylenically unsaturated group in a side chain is particularly preferable. This is because the film strength of the cured film formed by the photopolymerizable functional group is improved. Further, these acrylic copolymers and epoxy acrylate resins may be used in combination of two or more kinds.
具有具羧基之構成單位的丙烯酸系共聚合體,係例如使含羧基之乙烯性不飽和單體、及視需要之可共聚合的其他單體,藉公知方法進行(共)聚合而獲得的(共)聚合體。 The acrylic copolymer having a constituent unit having a carboxyl group is obtained by, for example, (co)polymerizing a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, another monomer copolymerizable by a known method. ) Polymer.
作為含羧基之乙烯性不飽和單體,可列舉例如(甲基)丙烯酸、乙烯基安息香酸、順丁烯二酸、順丁烯二酸單烷基酯、反丁烯二酸、伊康酸、丁烯酸、桂皮酸、丙烯酸二聚物等。又,亦可利用2-羥乙基(甲基)丙烯酸酯等之具有羥基的單體與如順丁烯二酸酐或酞酸酐、環己烷二羧酸酐般之環狀酐的加成反應物,ω-羧基-聚己內酯單(甲基)丙烯酸酯等。又,亦可使用順丁烯二酸酐、伊康酸酐、檸康酸酐等之含酐單體作為羧基前驅物。其中,由共聚合性或成本、溶解性、玻璃轉移溫度等的觀點而言,特佳為(甲基)丙烯酸。 Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, and itaconic acid. , butenoic acid, cinnamic acid, acrylic acid dimer, and the like. Further, an addition reactant of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride or decanoic anhydride or cyclohexane dicarboxylic anhydride may be used. , ω-carboxy-polycaprolactone mono (meth) acrylate, and the like. Further, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used as the carboxyl precursor. Among them, (meth)acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature and the like.
鹼可溶性樹脂,由著色層之密黏性優越的觀點而言,較佳係進一步具有烴環。藉由於鹼可溶性樹脂中具有屬於巨大基團的烴環,可抑制硬化時之收縮,緩和與基板間之剝離,提升基板密黏性。又,本發明者等人發現,藉由使用具有烴環之鹼可溶性樹脂,可抑制所得著色層之耐溶劑性,尤其是可抑制著色層的膨潤。關於其作用尚未闡明,但推判藉由於著色層內含有巨大之烴環,而抑制著色層內之分子動作,結果使塗膜強度變高而抑制溶劑所造成之膨潤。 The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. By having a hydrocarbon ring belonging to a large group among the alkali-soluble resins, shrinkage at the time of curing can be suppressed, the peeling from the substrate can be alleviated, and the substrate adhesion can be improved. Moreover, the inventors of the present invention have found that by using an alkali-soluble resin having a hydrocarbon ring, the solvent resistance of the obtained colored layer can be suppressed, and in particular, swelling of the colored layer can be suppressed. Although the effect has not yet been elucidated, it is presumed that the molecular action in the colored layer is suppressed by the inclusion of a large hydrocarbon ring in the colored layer, and as a result, the strength of the coating film is increased to suppress the swelling caused by the solvent.
作為此種烴環,可列舉亦可具有取代基之環狀脂肪族烴環、亦可具有取代基之芳香族環、及此等之組合;烴環亦可具有羰基、羧基、氧羰基、醯胺基等之取代基。其中,在含有脂肪族環時,可提升著色層之耐熱性或密黏性,同時可提升所得著色層的亮度。 Examples of such a hydrocarbon ring include a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and combinations thereof; and the hydrocarbon ring may have a carbonyl group, a carboxyl group, an oxycarbonyl group, or a hydrazine group; a substituent such as an amine group. Among them, when the aliphatic ring is contained, the heat resistance or the adhesion of the colored layer can be improved, and the brightness of the resulting colored layer can be improved.
作為烴環之具體例,可列舉環丙烷、環丁烷、環戊烷、環己烷、降烷、三環[5.2.1.0(2,6)]癸烷(二環戊烷)、金剛烷等之脂肪族烴環;苯、萘、蒽、菲、茀等芳香族環;聯苯、三聯苯、二苯基甲烷、三苯基甲烷、茋等之鏈狀多環;或下述化學式(A)所示之cardo構造等。 Specific examples of the hydrocarbon ring include cyclopropane, cyclobutane, cyclopentane, cyclohexane, and descending. An aliphatic hydrocarbon ring of an alkane, a tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), an adamantane or the like; an aromatic ring such as benzene, naphthalene, anthracene, phenanthrene or anthracene; biphenyl, triple a chain polycyclic ring such as benzene, diphenylmethane, triphenylmethane or hydrazine; or a cardo structure represented by the following chemical formula (A).
作為烴環,在含有脂肪族環時,由提升著色層之耐熱性或密黏性、同時提升所得著色層之亮度的觀點而言為特佳。 As the hydrocarbon ring, when the aliphatic ring is contained, it is particularly preferable from the viewpoint of improving the heat resistance or adhesion of the colored layer and simultaneously increasing the brightness of the obtained colored layer.
又,在含有上述化學式(A)所示cardo構造的情況,由提升著色層之硬化性、提升耐溶劑性(NMP膨潤抑制)的觀點而言為較佳。 Moreover, in the case of containing the cardo structure represented by the above chemical formula (A), it is preferable from the viewpoint of improving the hardenability of the colored layer and improving the solvent resistance (NMP swelling inhibition).
本發明所使用之鹼可溶性樹脂中,由容易調整各構成單位量、增加上述具烴環之構成單位量而容易提升該構成單位所具有之機能的觀點而言,較佳係除了具羧基之構成單位之外,另外使用具有上述具烴環之構成單位的丙烯酸系共聚合體。 In the alkali-soluble resin used in the present invention, it is preferred to have a carboxyl group from the viewpoint of easily adjusting the respective constituent unit amounts and increasing the constituent unit amount of the hydrocarbon ring to easily improve the function of the constituent unit. In addition to the unit, an acrylic copolymer having the above constituent unit having a hydrocarbon ring is additionally used.
具羧基之構成單位、與上述具烴環之丙烯酸系共聚合體,可藉由使用具烴環之乙烯性不飽和單體作為上述「可共聚合之其他單 體」而調製。 The constituent unit having a carboxyl group and the above-mentioned acrylic copolymer having a hydrocarbon ring can be used as the above-mentioned "copolymerizable other monomer" by using an ethylenically unsaturated monomer having a hydrocarbon ring. Modulated by the body.
作為具烴環之乙烯性不飽和單體,可列舉例如(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸異酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯等。 Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and (meth)acrylic acid. Ester, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and the like.
本發明之鹼可溶性樹脂,由提升硬化膜之膜強度而提升顯影耐性、且抑制硬化膜之熱收縮而與基板間之密黏性優越的觀點而言,較佳係具有乙烯性雙鍵。在具有乙烯性雙鍵的情況,於彩色濾光片製造時之樹脂組成物的硬化步驟中,該鹼可溶性樹脂彼此、或該鹼可溶性樹脂與多官能單體等可形成交聯鍵結。其結果,推判可提升著色層之硬化膜的膜強度,抑制硬化膜之熱收縮而與基板間之密黏性優越。藉由選擇使用具有乙烯性雙鍵之鹼可溶性樹脂,並藉由本發明之彩色濾光片用著色樹脂組成物所形成的著色層,係即使在相對於著色樹脂組成物之總固形份將後述矽烷偶合劑設為1質量份以下的情況,基板密黏性仍優越。 The alkali-soluble resin of the present invention preferably has an ethylenic double bond from the viewpoint of improving the development resistance of the cured film and improving the heat shrinkage of the cured film and being excellent in adhesion to the substrate. In the case of having an ethylenic double bond, in the hardening step of the resin composition at the time of production of the color filter, the alkali-soluble resins or the alkali-soluble resin and the polyfunctional monomer may form a cross-linking bond. As a result, it is estimated that the film strength of the cured film of the colored layer can be improved, and the heat shrinkage of the cured film can be suppressed to be excellent in adhesion to the substrate. By selecting an alkali-soluble resin having an ethylenic double bond and using the coloring layer formed of the colored resin composition for a color filter of the present invention, the decane will be described later even with respect to the total solid content of the colored resin composition. When the coupling agent is used in an amount of 1 part by mass or less, the substrate adhesion is still excellent.
於鹼可溶性樹脂中導入乙烯性雙鍵的方法,係由習知公知方法適當選擇即可。例如,對鹼可溶性樹脂所具有之羧基,加成分子內兼具有環氧基與乙烯性雙鍵之化合物,例如(甲基)丙烯酸環氧丙酯等,而於側鏈導入乙烯性雙鍵的方法;或在將具有羥基之構成單位導入至共聚合體時,於分子內加成具備異氰酸酯基與乙烯性雙鍵的化合物,而於側鏈導入乙烯性雙鍵的方法等。 The method of introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected by a conventionally known method. For example, a compound having an epoxy group and an ethylenic double bond in a component, such as a carboxyl group having an epoxy group and an ethylenic double bond, may be added to the side chain to introduce an ethylenic double bond. Or a method in which a compound having a hydroxyl group is introduced into a copolymer, a compound having an isocyanate group and an ethylenic double bond is added to the molecule, and a vinyl double bond is introduced into the side chain.
本發明之鹼可溶性樹脂亦可進一步含有(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯等具有酯基之構成單位等的其他構成單位。具有酯基之構成單元不僅作為抑制彩色濾光片用著色樹脂組成物之鹼可溶性的成分而發揮功能,亦作為提高溶劑之溶解性、甚至 溶劑再溶解性之成分而發揮功能。 The alkali-soluble resin of the present invention may further contain other constituent units such as a constituent unit having an ester group such as methyl (meth)acrylate or ethyl (meth)acrylate. The constituent unit having an ester group functions not only as an alkali-soluble component for suppressing the coloring resin composition for a color filter, but also as a solvent to improve solubility and even It functions as a component of solvent resolubility.
本發明中之鹼可溶性樹脂,較佳係具有具羧基之構成單位、與具烴環之構成單位的丙烯酸系共聚合體;更佳係具有具羧基之構成單位、具烴環之構成單位、與具乙烯性雙鍵之構成單位的丙烯酸系共聚合體。 The alkali-soluble resin in the present invention preferably has an acrylic copolymer having a carboxyl group and a constituent unit having a hydrocarbon ring; more preferably, it has a constituent unit having a carboxyl group, a constituent unit having a hydrocarbon ring, and An acrylic copolymer of a constituent unit of an ethylenic double bond.
作為本發明之鹼可溶性樹脂,較佳可使用上述含有cardo構造之具羧基之環氧基(甲基)丙烯酸酯樹脂(以下稱為cardo樹脂)。 As the alkali-soluble resin of the present invention, an epoxy group-containing (meth) acrylate resin (hereinafter referred to as cardo resin) having a carboxyl group structure as described above can be preferably used.
上述含有cardo構造之具羧基之環氧基(甲基)丙烯酸酯樹脂(以下稱為cardo樹脂)的正確機制尚未闡明,但由於茀骨格含有π共軛系,故可認為對自由基呈高感度。藉由將後述肟酯系光聚合起始劑與cardo樹脂組合,可進一步提升溶劑耐性、水滲染、感度等之要求性能。 The correct mechanism of the carboxyl group-containing epoxy (meth) acrylate resin (hereinafter referred to as cardo resin) containing the cardo structure has not been elucidated, but since the tibia lattice contains a π-conjugated system, it is considered to be highly sensitive to free radicals. . By combining an oxime ester photopolymerization initiator described later with a cardo resin, the required properties such as solvent resistance, water bleeding, and sensitivity can be further improved.
作為cardo樹脂,較佳可列舉例如日本專利特開2007-119720號公報記載之下述一般式(B)所示的聚合性化合物、及日本專利特開2006-308698號公報記載的具茀骨架之環氧基(甲基)丙烯酸酯與多元酸的反應物(聚縮合物)等。 The cardo resin is preferably a polymerizable compound represented by the following general formula (B) described in JP-A-2007-119720, and a ruthenium skeleton described in JP-A-2006-308698. A reaction product (polycondensate) of an epoxy group (meth) acrylate with a polybasic acid or the like.
(其中,上述一般式(B)中,X表示下述一般式(D)所示之基,Y分別獨立表示多元羧酸或其酸酐之殘基,Ri表示下述一般式(C)所 示之基,j為0~4之整數,k為0~3之整數,n為1以上之整數。) (In the above general formula (B), X represents a group represented by the following general formula (D), and Y each independently represents a residue of a polyvalent carboxylic acid or an anhydride thereof, and R i represents a general formula (C) below. The base of the graph, j is an integer from 0 to 4, k is an integer from 0 to 3, and n is an integer of 1 or more.)
(其中,上述一般式(C)中,Rii表示氫原子或甲基,Riii分別獨立表示氫原子或甲基。) (In the above general formula (C), R ii represents a hydrogen atom or a methyl group, and R iii each independently represents a hydrogen atom or a methyl group.)
(其中,上述一般式(D)中,Riv分別獨立表示氫原子、碳數1~5之烷基、苯基、或鹵原子,Rv表示-O-或-OCH2CH2O-。) (In the above general formula (D), R iv each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom, and R v represents -O- or -OCH 2 CH 2 O-. )
本發明所使用之cardo樹脂,係例如可藉由將茀雙酚化合物進行環氧化而作成茀雙酚化合物之環氧化合物,對其使(甲基)丙烯酸反應而作成環氧基(甲基)丙烯酸酯,對此環氧基(甲基)丙烯酸酯使與多元羧酸或其酸酐反應而獲得。 The cardo resin used in the present invention can be obtained by, for example, epoxidizing a bismuth bisphenol compound to form an epoxy compound of a bisphenol compound, and reacting the (meth)acrylic acid to form an epoxy group (methyl). An acrylate obtained by reacting the epoxy (meth) acrylate with a polyvalent carboxylic acid or an anhydride thereof.
作為茀雙酚化合物,較佳可列舉上述一般式(D)中,Rv為-O-,且此-O-成為-OH者。 The bisphenol compound preferably has the above formula (D), and R v is -O-, and this -O- is -OH.
作為茀雙酚化合物,可列舉9,9-雙(4-羥苯基)茀、9,9-雙(4-羥基-3-甲基苯基)茀、9,9-雙(4-羥基-3-甲氧基苯基)茀、9,9-雙(4-羥基-3,5-二甲基苯基)茀、9,9-雙(4-羥基-3-氟苯基)茀、9,9-雙(4-羥基-3-氯苯基)茀、9,9-雙(4-羥基-3-溴苯基)茀、9,9-雙(4-羥基-3,5-二氯苯基)茀、9,9-雙(4-羥基-3,5-二溴苯基)茀等之雙酚化合物、及此等之混合 物。 Examples of the quinone bisphenol compound include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and 9,9-bis(4-hydroxyl). 3-methoxyphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9,9-bis(4-hydroxy-3-fluorophenyl)anthracene 9,9-bis(4-hydroxy-3-chlorophenyl)indole, 9,9-bis(4-hydroxy-3-bromophenyl)anthracene, 9,9-bis(4-hydroxy-3,5 a bisphenol compound such as -dichlorophenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)anthracene, and the like Things.
作為上述具有茀骨架之環氧基(甲基)丙烯酸酯樹脂的反應中所使用的多元羧酸及其酸酐,可列舉順丁烯二酸、琥珀酸、伊康酸、酞酸、四氫酞酸、六氫酞酸、甲基四氫酞酸、甲基內亞甲基四氫酞酸、氯橋酸、甲基四氫酞酸、戊二酸等之二羧酸或此等之酸酐;聯苯基四羧酸、二苯基酮四羧酸、聯苯基醚四羧酸、聯苯碸四羧酸、4-(1,2-二羧乙基)-1,2,3,4-四氫萘-1,2-二羧酸、丁烷四羧酸、焦蜜石酸等之四羧酸或此等之酸二酐;偏苯三甲酸或其酸酐等之三羧酸或此等之酸酐等。該等可單獨使用,亦可併用2種以上。 Examples of the polyvalent carboxylic acid and an acid anhydride used in the reaction of the epoxy group (meth) acrylate resin having an anthracene skeleton include maleic acid, succinic acid, itaconic acid, citric acid, and tetrahydroanthracene. a dicarboxylic acid such as acid, hexahydrophthalic acid, methyltetrahydrofurfuric acid, methyl endomethylenetetrahydrofurfuric acid, chlorohydrin, methyltetrahydrofurfuric acid, glutaric acid or the like; or an acid anhydride thereof; Biphenyltetracarboxylic acid, diphenylketonetetracarboxylic acid, biphenyl ether tetracarboxylic acid, biphenyl fluorene tetracarboxylic acid, 4-(1,2-dicarboxyethyl)-1,2,3,4 a tetracarboxylic acid such as tetrahydronaphthalene-1,2-dicarboxylic acid, butanetetracarboxylic acid or pyromic acid or an acid dianhydride thereof; a tricarboxylic acid such as trimellitic acid or an anhydride thereof or the like Such as acid anhydride and the like. These may be used alone or in combination of two or more.
作為本發明所使用之cardo樹脂,較佳可列舉屬於茀環氧基(甲基)丙烯酸酯衍生物與二羧酸酐及/或四羧酸二酐間之加成生成物的具有茀骨架之環氧基(甲基)丙烯酸酯加成物。 The cardo resin used in the present invention is preferably a ring having an anthracene skeleton which is an addition product of an anthracene epoxy (meth) acrylate derivative and a dicarboxylic anhydride and/or a tetracarboxylic dianhydride. An oxy (meth) acrylate adduct.
作為本發明可使用之cardo樹脂的市售物商品名,可列舉INR-16M(Nagase ChemteX(股)製)、商品名V259ME(新日鐵住金化學(股)製)等。 The commercially available product name of the cardo resin which can be used in the present invention includes INR-16M (manufactured by Nagase ChemteX Co., Ltd.) and trade name V259ME (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.).
具有羧基之環氧基(甲基)丙烯酸酯樹脂可分別單獨使用1種,亦可併用2種以上。 The epoxy group (meth) acrylate resin having a carboxyl group may be used alone or in combination of two or more.
彩色濾光片用著色樹脂組成物中所使用之鹼可溶性樹脂,可單獨使用1種,亦可組合2種以上使用,其含量並無特別限制,相對於彩色濾光片用著色樹脂組成物之固形份總量,鹼可溶性樹脂較佳為5~60質量%、更佳為10~40質量%之範圍內。若鹼可溶性樹脂之含量少於上述下限值,則有無法得到充分之鹼顯影性的情形;又,若鹼可溶性樹脂之含量多於上述上限值,則有顯影時發生膜粗糙或圖案缺陷之情形。尚且,本發明中,固形份係指上述溶 劑以外之所有者,亦包括液狀之多官能單體等。 The alkali-soluble resin to be used in the coloring resin composition may be used singly or in combination of two or more kinds, and the content thereof is not particularly limited, and the coloring resin composition for a color filter is used. The total amount of the solid content, the alkali-soluble resin is preferably in the range of 5 to 60% by mass, more preferably 10 to 40% by mass. If the content of the alkali-soluble resin is less than the above lower limit, sufficient alkali developability may not be obtained. Further, if the content of the alkali-soluble resin is more than the above upper limit, film roughness or pattern defect may occur during development. The situation. Further, in the present invention, the solid portion means the above dissolution The owner other than the agent also includes liquid polyfunctional monomers and the like.
鹼可溶性樹脂係藉由適當調整各構成單位的填裝量,而可作成為具有所需性能的鹼可溶性樹脂。 The alkali-soluble resin can be used as an alkali-soluble resin having desired properties by appropriately adjusting the amount of each constituent unit.
含羧基之乙烯性不飽和單體之填裝量,係相對於單體總量,較佳為5~50質量%、更佳為10~40質量%。 The amount of the carboxyl group-containing ethylenically unsaturated monomer to be charged is preferably 5 to 50% by mass, more preferably 10 to 40% by mass based on the total amount of the monomers.
含羧基之乙烯性不飽和單體的比例未滿5質量%時,則所獲得之塗膜對鹼顯影液之溶解性降低,圖案形成變得困難。又,若含羧基之乙烯性不飽和單體的比例超過50質量%,則有於藉由鹼顯影液進行顯影時,容易導致所形成之圖案自基板上脫落或圖案表面之膜粗糙的傾向。 When the ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the obtained coating film to the alkali developing solution is lowered, and pattern formation becomes difficult. In addition, when the ratio of the carboxyl group-containing ethylenically unsaturated monomer exceeds 50% by mass, when the image is developed by an alkali developer, the formed pattern tends to fall off from the substrate or the film on the pattern surface tends to be rough.
又,在可較佳使用作為鹼可溶性樹脂之具有具羧基之構成單位、與具烴環之構成單位的丙烯酸系共聚合體中,含羧基之乙烯性不飽和單體的填裝量係相對於單體總量,較佳為5~50質量%、更佳為10~40質量%。又,於該丙烯酸系共聚合體中,含烴環之乙烯性不飽和單體之填裝量係相對於單體總量,較佳為30~80質量%、更佳為40~75質量%。 Further, in the acrylic copolymer having a carboxyl group and a constituent unit having a hydrocarbon ring as an alkali-soluble resin, the amount of the carboxyl group-containing ethylenically unsaturated monomer is relatively small. The total amount of the body is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. Further, in the acrylic copolymer, the amount of the hydrocarbon-containing ring-containing ethylenically unsaturated monomer is preferably from 30 to 80% by mass, and more preferably from 40 to 75% by mass based on the total amount of the monomers.
又,在可較佳使用作為鹼可溶性樹脂之具有具羧基之構成單位、具烴環之構成單位、與具乙烯性雙鍵之構成單位的丙烯酸系共聚合體中,在對含羧基之乙烯性不飽和單體於分子內加成兼具有環氧基與乙烯性雙鍵之化合物,而導入乙烯性雙鍵的情況,含羧基之乙烯性不飽和單體的填裝量係相對於單體總量,較佳為5~50質量%、更佳為10~40質量%。於該丙烯酸系共聚合體中,含烴環之乙烯性不飽和單體之填裝量係相對於單體總量,較佳為30~80質量%、更佳為40~75質量%。又,於該丙烯酸系共聚合體中,兼具 有環氧基與乙烯性雙鍵之化合物係相對於含羧基之乙烯性不飽和單體之填裝量,較佳為10~95質量%、更佳為15~90質量%。 Further, in the acrylic copolymer having a carboxyl group, a constituent unit having a hydrocarbon ring, and a constituent unit having an ethylenic double bond, which is an alkali-soluble resin, the ethyl group having no carboxyl group is preferably used. A saturated monomer is added to a compound having an epoxy group and an ethylenic double bond in a molecule, and when an ethylenic double bond is introduced, a carboxyl group-containing ethylenically unsaturated monomer is charged in a total amount relative to the monomer. The amount is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. In the acrylic copolymer, the amount of the hydrocarbon-containing ring-containing ethylenically unsaturated monomer is preferably from 30 to 80% by mass, more preferably from 40 to 75% by mass, based on the total amount of the monomers. Moreover, in the acrylic copolymer, both The compound having an epoxy group and an ethylenic double bond is preferably 10 to 95% by mass, more preferably 15 to 90% by mass based on the amount of the carboxyl group-containing ethylenically unsaturated monomer.
在丙烯酸系共聚合體為具有具羧基與烴環之構成單位時,該構成單位係視為包含於各具羧基之構成單位、具烴環之構成單位中。 When the acrylic copolymer has a constituent unit having a carboxyl group and a hydrocarbon ring, the constituent unit is considered to be contained in a constituent unit having a carboxyl group and a constituent unit having a hydrocarbon ring.
本發明之鹼可溶性樹脂中,具羧基之構成單位、具烴環之構成單位、及具乙烯性雙鍵之構成單位以外所含的其他構成單位,係於總構成單位中較佳為0~30質量%、更佳為0~20質量%。 In the alkali-soluble resin of the present invention, the constituent unit having a carboxyl group, the constituent unit having a hydrocarbon ring, and other constituent units other than the constituent unit having an ethylenic double bond are preferably 0 to 30 in the total constituent unit. The mass %, more preferably 0 to 20 mass%.
上述鹼可溶性樹脂,由對顯影液所使用之鹼水溶液的顯影性(溶解性)的觀點、以及提升著色層之耐熱性的觀點而言,係選擇使用酸價為80mgKOH/g以上且300mgKOH/g以下者。其中,較佳為90mgKOH/g以上且280mgKOH/g以下、更佳為100mgKOH/g以上且250mgKOH/g以下。酸價為100mgKOH/g以上之鹼可溶性樹脂,由提升亮度及耐熱性及密黏性的觀點而言為較佳。又,在將一般式(I)所示之色材、與酸性染料之金屬色澱色材組合使用時,由提升耐熱性的觀點而言,較佳係使用酸價為90mgKOH/g以上的鹼可溶性樹脂。 The alkali-soluble resin is selected from the viewpoints of developability (solubility) of the aqueous alkali solution used for the developer and the heat resistance of the colored layer. The acid value is preferably 80 mgKOH/g or more and 300 mgKOH/g. The following. Among them, it is preferably 90 mgKOH/g or more and 280 mgKOH/g or less, more preferably 100 mgKOH/g or more and 250 mgKOH/g or less. The alkali-soluble resin having an acid value of 100 mgKOH/g or more is preferable from the viewpoint of improving brightness, heat resistance and adhesion. Further, when the color material represented by the general formula (I) and the metal lake color material of the acid dye are used in combination, it is preferred to use a base having an acid value of 90 mgKOH/g or more from the viewpoint of improving heat resistance. Soluble resin.
酸價為上述下限值以上之鹼可溶性樹脂,容易與存在於上述一般式(I)所示之色材之分子締合體表面附近的陰離子所具有之鹼性基相互作用,其結果,推判鹼可溶性樹脂容易吸附於上述分子締合體表面。由於該鹼可溶性樹脂之酸價相對較高,故一旦經吸附,則即使於高溫加熱下亦難以解離,可更加抑制色材之分解等,推判可抑制亮度降低,格外提升耐熱性。 The alkali-soluble resin having an acid value of not less than the above lower limit is likely to interact with the basic group of an anion existing in the vicinity of the surface of the molecular association body of the color material represented by the above general formula (I). The alkali-soluble resin is easily adsorbed on the surface of the above-mentioned molecular association body. Since the acid-soluble valence of the alkali-soluble resin is relatively high, it is difficult to dissociate even when heated under high temperature, and the decomposition of the color material can be further suppressed, and the decrease in brightness can be suppressed, and the heat resistance can be particularly improved.
在鹼可溶性樹脂之側鏈具有乙烯性不飽和基的情況下,乙烯性不飽和鍵結當量較佳為100~2000之範圍、特佳為 140~1500之範圍。該乙烯性不飽和鍵結當量若為2000以下,則顯影耐性或密黏性優越。又,若為100以上,由於可使上述具羧基之構成單位、或具烴環之構成單位等之其他構成單位的比例相對增加,故顯影性或耐熱性優越。 In the case where the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the ethylenically unsaturated bond equivalent is preferably in the range of from 100 to 2,000, particularly preferably The range of 140~1500. When the ethylenically unsaturated bond equivalent is 2,000 or less, development resistance or adhesion is excellent. In addition, when the ratio is 100 or more, the ratio of the constituent unit having the carboxyl group or the other constituent unit having the constituent unit of the hydrocarbon ring can be relatively increased, so that the developability or heat resistance is excellent.
於此,所謂乙烯性不飽和鍵結當量,係指上述鹼可溶性樹脂中之乙烯性不飽和鍵結每1莫耳的重量平均分子量,由下述數式(4)所示。 Here, the ethylenically unsaturated bond equivalent is a weight average molecular weight per one mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (4).
(數式(4)中,W表示鹼可溶性樹脂之質量(g),M表示鹼可溶性樹脂W(g)中所含之乙烯性雙鍵之莫耳數(mol)。) (In the formula (4), W represents the mass (g) of the alkali-soluble resin, and M represents the molar number (mol) of the ethylenic double bond contained in the alkali-soluble resin W (g).)
上述乙烯性不飽和鍵結當量,例如可根據JIS K 0070:1992記載之碘價之試驗方法而算出。 The ethylenically unsaturated bond equivalent can be calculated, for example, according to the test method of the iodine value described in JIS K 0070:1992.
又,上述乙烯性不飽和鍵結當量亦可藉由將數式(1)中之W設為構成鹼可溶性樹脂之單體及化合物的合計質量(g),將M設為藉下述數式(5)所算出之鹼可溶性樹脂中之乙烯性雙鍵之莫耳數(mol),而藉由鹼可溶性樹脂之合成時之調配量簡易地算出。 Further, the ethylenically unsaturated bond equivalent can be obtained by setting the W in the formula (1) to the total mass (g) of the monomer and the compound constituting the alkali-soluble resin, and setting M to the following formula. (5) The molar number (mol) of the ethylenic double bond in the calculated alkali-soluble resin, and the amount of the mixture in the synthesis of the alkali-soluble resin is simply calculated.
本發明之著色樹脂組成物中,在不損及本發明效果之範圍內,亦可進一步含有其他樹脂。作為其他樹脂之具體例,可列舉例如聚碳酸酯樹脂、聚乙烯醇樹脂、聚乙烯吡咯啶酮樹脂、羥乙基纖維素樹脂、羧甲基纖維素樹脂、聚氯乙烯樹脂、三聚氰胺樹脂、酚樹脂、 醇酸樹脂、環氧樹脂、聚胺基甲酸酯樹脂、聚酯樹脂、順丁烯二酸樹脂、聚醯胺樹脂、聚醯亞胺樹脂等;其中,由耐熱性的觀點而言,較佳為聚醯胺樹脂、或聚醯亞胺樹脂,更佳為具有環狀構造之聚醯胺樹脂、或具有環狀構成之聚醯亞胺樹脂。此等樹脂可為具有鹼可溶性者,亦可為不具有鹼可溶性者。又,此等樹脂可組合1種或2種以上。 The colored resin composition of the present invention may further contain other resins insofar as the effects of the present invention are not impaired. Specific examples of the other resin include polycarbonate resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin, hydroxyethyl cellulose resin, carboxymethyl cellulose resin, polyvinyl chloride resin, melamine resin, and phenol. Resin, An alkyd resin, an epoxy resin, a polyurethane resin, a polyester resin, a maleic acid resin, a polyamide resin, a polyimide resin, or the like; wherein, from the viewpoint of heat resistance, The polyamine resin or the polyimine resin is preferably a polyamine resin having a cyclic structure or a polyimide resin having a cyclic structure. These resins may be those having an alkali solubility or those having no alkali solubility. Further, these resins may be used alone or in combination of two or more.
鹼可溶性樹脂之重量平均分子量並無特別限定。其中,較佳為1,000~500,000之範圍、更佳為3,000~200,000。未滿1,000時,硬化後之黏結劑機能明顯降低;若超過500,000,則藉由鹼顯影液進行顯影時,有圖案形成變得困難的情形。 The weight average molecular weight of the alkali-soluble resin is not particularly limited. Among them, it is preferably in the range of 1,000 to 500,000, more preferably in the range of 3,000 to 200,000. When it is less than 1,000, the function of the binder after hardening is remarkably lowered. When it exceeds 500,000, when patterning is performed by an alkali developer, pattern formation becomes difficult.
本發明之彩色濾光片用著色樹脂組成物中所使用的鹼可溶性樹脂,可單獨使用1種,亦可組合2種以上使用;其含量係相對於著色樹脂組成物所含之色材100質量份,通常為10~1000質量份的範圍內、較佳為20~500質量份的範圍內。若鹼可溶性樹脂之含量過少,則有無法得到充分之鹼顯影性的情形;又,若鹼可溶性樹脂之含量過多,則色材之比例相對變低,有無法得到充分之著色濃度的情形。 The alkali-soluble resin to be used in the colored resin composition for a color filter of the present invention may be used singly or in combination of two or more kinds thereof; the content thereof is based on the mass of the color material 100 contained in the colored resin composition. The portion is usually in the range of 10 to 1000 parts by mass, preferably 20 to 500 parts by mass. When the content of the alkali-soluble resin is too small, sufficient alkali developability may not be obtained. Further, when the content of the alkali-soluble resin is too large, the ratio of the color material is relatively low, and a sufficient coloring concentration may not be obtained.
本發明之彩色濾光片用著色樹脂組成物中所使用之多官能單體,只要為可藉由後述起始劑進行聚合者即可,並無特別限定,通常使用具有2個以上之乙烯性不飽和雙鍵之化合物,特佳為具有2個以上之丙烯醯基或甲基丙烯醯基之多官能(甲基)丙烯酸酯,更佳為三官能以上之多官能(甲基)丙烯酸酯。 The polyfunctional monomer to be used in the coloring resin composition for a color filter of the present invention is not particularly limited as long as it can be polymerized by a starting agent to be described later, and usually has two or more kinds of ethylenicity. The compound having an unsaturated double bond is particularly preferably a polyfunctional (meth) acrylate having two or more acryl fluorenyl groups or methacryl fluorenyl groups, more preferably a trifunctional or higher polyfunctional (meth) acrylate.
多官能(甲基)丙烯酸酯中,作為三官能以上之多官能(甲基)丙烯酸酯,可列舉例如三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、烷基改質二季戊四醇三(甲基)丙烯酸酯、琥珀酸酐改季戊四醇四(甲基)丙烯酸酯、磷酸三(甲基)丙烯酸酯、參(丙烯醯氧基乙基)異三聚氰酸酯、參(甲基丙烯醯氧基乙基)異三聚氰酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二(三羥甲基丙烷)四丙烯酸酯、烷基改質二季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、烷基改質二季戊四醇五(甲基)丙烯酸酯、羧酸改質二季戊四醇五(甲基)丙烯酸酯、琥珀酸酐改質二季戊四醇五(甲基)丙烯酸酯、胺基甲酸乙酯三(甲基)丙烯酸酯、酯三(甲基)丙烯酸酯、胺基甲酸乙酯六(甲基)丙烯酸酯、酯六(甲基)丙烯酸酯等。 In the polyfunctional (meth) acrylate, examples of the trifunctional or higher polyfunctional (meth) acrylate include trimethylolpropane tri(meth)acrylate and trimethylolethane tris(methyl). Acrylate, tris(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkyl modified dipentaerythritol tri(meth)acrylate, succinic anhydride modified pentaerythritol IV (meth) acrylate, tris(meth) acrylate, propylene (propylene oxy oxy) isomeric cyanurate, stilbene (methacryloxyethyl) isomeric cyanurate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, bis(trimethylolpropane)tetraacrylate, alkyl modified dipentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxy five (Meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, carboxylic acid modified dipentaerythritol Acrylate, succinic anhydride modified dipentaerythritol penta (methyl) propyl Ester, urethane tri (meth) acrylate, an ester tri (meth) acrylate, urethane hexa (meth) acrylate ester hexa (meth) acrylate.
本發明中,由提升光硬化性(高感度)之觀點而言,多官能單體較佳係具有3個(三官能以上)以上可聚合之雙鍵者;可適當列舉例如3元以上之多元醇之聚(甲基)丙烯酸酯類。又,本發明中,由提升鹼顯影性的觀點而言,多官能單體較佳為具有羧基。作為具羧基之多官能單體,可列舉例如上述多元醇之聚(甲基)丙烯酸酯類的羧酸改質物等。 In the present invention, the polyfunctional monomer preferably has three (trifunctional or higher) or more polymerizable double bonds from the viewpoint of enhancing photocurability (high sensitivity); for example, a polyvalent amount of three or more may be appropriately cited. Poly(meth)acrylates of alcohols. Further, in the present invention, the polyfunctional monomer preferably has a carboxyl group from the viewpoint of improving alkali developability. Examples of the polyfunctional monomer having a carboxyl group include a polycarboxylic acid modified product of a poly(meth)acrylate of the above polyol.
作為多元醇之聚(甲基)丙烯酸酯類的具體例,可列舉三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等。 Specific examples of the poly(meth)acrylates of the polyhydric alcohols include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.
又,作為多元醇之聚(甲基)丙烯酸酯類的羧酸改質物,可列舉季戊四醇三(甲基)丙烯酸酯的琥珀酸改質物、二季戊四醇五(甲基)丙烯酸酯的琥珀酸改質物等。 Further, examples of the carboxylic acid modified product of the poly(meth)acrylate of the polyhydric alcohol include a succinic acid modified product of pentaerythritol tri(meth)acrylate and a succinic acid modified product of dipentaerythritol penta (meth)acrylate. Wait.
此等多官能單體可單獨使用1種,亦可組合2種以上使用。例如,亦可將具羧基之多官能單體、與不具羧基之多官能單體組合使用。由提升耐熱性及密黏性的觀點而言,較佳係具有羧基之季戊四醇三(甲基)丙烯酸酯的琥珀酸改質物、二季戊四醇五(甲基)丙烯酸酯之琥珀酸改質物。 These polyfunctional monomers may be used alone or in combination of two or more. For example, a polyfunctional monomer having a carboxyl group may be used in combination with a polyfunctional monomer having no carboxyl group. From the viewpoint of improving heat resistance and adhesion, a succinic acid modified product of a pentaerythritol tri(meth)acrylate having a carboxyl group and a succinic acid modified product of dipentaerythritol penta (meth) acrylate are preferable.
此種多官能單體亦可適當使用市售物,例如作為含有二季戊四醇五(甲基)丙烯酸酯之琥珀酸改質物的市售物,可列舉商品名M-520D、TO-2371(東亞合成(股)公司製)等。 Commercially available products such as a succinic acid modified product containing dipentaerythritol penta (meth) acrylate may be suitably used as such a polyfunctional monomer, and may be exemplified by trade names M-520D and TO-2371 (East Asia Synthesis). (share) company system) and so on.
本發明之彩色濾光片用著色樹脂組成物中所使用之上述多官能單體的含量並無特別限制,相對於著色樹脂組成物之固形份總量,多官能單體的含量較佳為5~60質量%、更佳為10~40質量%。若多官能單體之含量少於上述範圍,則光硬化無法充分進行,有曝光部分溶出之情形;又,若多官能單體之含量多於上述範圍,則有鹼顯影性降低之虞。 The content of the above polyfunctional monomer used in the colored resin composition for a color filter of the present invention is not particularly limited, and the content of the polyfunctional monomer is preferably 5 based on the total amount of the solid content of the colored resin composition. ~60% by mass, more preferably 10 to 40% by mass. When the content of the polyfunctional monomer is less than the above range, the photocuring is not sufficiently performed, and the exposed portion is eluted. Further, when the content of the polyfunctional monomer is more than the above range, the alkali developability is lowered.
作為本發明之彩色濾光片用著色樹脂組成物中所使用之起始劑,並無特別限制,可由習知所知悉之各種起始劑中組合1種或2種以上使用。 The initiator used in the coloring resin composition for a color filter of the present invention is not particularly limited, and one or two or more kinds of the various initiators known in the art can be used in combination.
作為起始劑,可列舉芳香族酮類、苯偶姻醚類、鹵甲基二唑化合物、α-胺基酮、聯咪唑類、N,N-二甲基胺基二苯基酮、 鹵甲基-S-三系化合物、9-氧硫等。作為起始劑之具體例,可列舉二苯基酮、4,4'-雙二乙基胺基二苯基酮、4-甲氧基-4'-二甲基胺基二苯基酮等之芳香族酮類;苯偶姻甲基醚等之苯偶姻醚類;乙基苯偶姻等之苯偶姻;2-(鄰氯苯基)-4,5-苯基咪唑二聚物等之聯咪唑類;2-三氯甲基-5-(對甲氧基苯乙烯基)-1,3,4-二唑等之鹵甲基二唑化合物;2-(4-丁氧基-萘-1-基)-4,6-雙-三氯甲基-S-三等之鹵甲基-S-三系化合物;2,2-二甲氧基-1,2-二苯基乙烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-啉丙酮、1,2-苄基-2-二甲基胺基-1-(4-啉基苯基)-丁酮-1,1-羥基-環己基-苯基酮、苄基、苯甲醯基安息香酸、苯甲醯基安息香酸甲酯、4-苯甲醯基-4'-甲基二苯基硫、苄基甲基縮酮、二甲基胺基苯甲酸酯、對二甲基胺基安息香酸異戊酯、2-正丁氧基乙基-4-二甲基胺基苯甲酸酯、2-氯-9-氧硫、2,4-二乙基-9-氧硫、2,4-二甲基-9-氧硫、異丙基-9-氧硫、4-苯甲醯基-甲基二苯基硫、1-羥基-環己基-苯基酮、2-苄基-2-(二甲基胺基)-1-[4-(4-啉基)苯基]-1-丁酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-啉基)苯基]-1-丁酮、α-二甲氧基-α-苯基苯乙酮、苯基雙(2,4,6-三甲基苯甲醯基)氧化膦、2-甲基-1-[4-(甲硫基)苯基]-2-(4-啉基)-1-丙酮等。 Examples of the initiator include aromatic ketones, benzoin ethers, and halomethyl groups. Diazole compound, α-amino ketone, biimidazole, N,N-dimethylaminodiphenyl ketone, halomethyl-S-three Compound, 9-oxosulfur Wait. Specific examples of the initiator include diphenyl ketone, 4,4'-bisdiethylaminodiphenyl ketone, and 4-methoxy-4'-dimethylaminodiphenyl ketone. Aromatic ketones; benzoin ethers such as benzoin methyl ether; benzoin such as ethyl benzoin; 2-(o-chlorophenyl)-4,5-phenylimidazole dimer Ethylene imidazole; 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4- Halomethyl group such as oxadiazole Diazole compound; 2-(4-butoxy-naphthalen-1-yl)-4,6-bis-trichloromethyl-S-three Halomethyl-S-three Compound; 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2- Phenanthroline, 1,2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzamidine benzoic acid, benzamidine benzoic acid methyl ester, 4-benzylidene-4' -methyldiphenylsulfide, benzylmethylketal, dimethylaminobenzoate, p-dimethylamino benzoic acid isoamyl ester, 2-n-butoxyethyl-4-dimethyl Amino benzoate, 2-chloro-9-oxo 2,4-diethyl-9-oxosulfur 2,4-dimethyl-9-oxosulfur Isopropyl-9-oxosulfur , 4-benzylidene-methyldiphenylsulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4- Phenyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzylidene)phosphine oxide, 2- Methyl-1-[4-(methylthio)phenyl]-2-(4- Polinyl)-1-propanone and the like.
其中,較佳為使用2-甲基-1-[4-(甲硫基)苯基]-2-啉基丙烷-1-酮、2-芾基-2-(二甲基胺基)-1-(4-啉基苯基)-1-丁酮、4,4'-雙(二乙基胺基)二苯基酮、二乙基-9-氧硫。由調整感度、抑制水滲染、提升顯影耐性之觀點而言,更佳係組合如2-甲基-1-[4-(甲硫基)苯基]-2-啉基丙烷-1-酮般之α-胺基苯乙酮系起始劑與如二乙基-9-氧硫般之9-氧硫系起始劑。 Among them, 2-methyl-1-[4-(methylthio)phenyl]-2- is preferably used. Lolinylpropan-1-one, 2-mercapto-2-(dimethylamino)-1-(4- Polinylphenyl)-1-butanone, 4,4'-bis(diethylamino)diphenyl ketone, diethyl-9-oxosulfur . From the viewpoint of adjusting sensitivity, inhibiting water bleeding, and improving development resistance, a more preferable combination such as 2-methyl-1-[4-(methylthio)phenyl]-2- 啉-ylpropan-1-one-like α-aminoacetophenone-based initiator and, for example, diethyl-9-oxosulfur 9-oxygen sulfur Is the initiator.
α-胺基苯乙酮系起始劑與9-氧硫系起始劑的含量,係相對於著色樹脂組成物之固形份總量,較佳為5~15質量%。若起始劑量為15質量%以下,則製造製程中之昇華物減低,故較佳。若起始劑為5質量%以上,則水滲染等顯影耐性提升。 α-Aminoacetophenone-based initiator and 9-oxosulfur The content of the initiator is preferably from 5 to 15% by mass based on the total amount of the solid content of the colored resin composition. If the starting dose is 15% by mass or less, the sublimate in the manufacturing process is reduced, which is preferable. When the amount of the initiator is 5% by mass or more, development resistance such as water bleeding is improved.
本發明中,由水滲染抑制效果高的觀點而言,起始劑中較佳為含有肟酯系光起始劑。又,所謂水滲染,係指鹼顯影後,在以純水潤洗後,發生如水滲染般之痕跡的現象。此種水滲染在預烘烤後消失,故作為製品並無問題,但在顯影後於圖案化面之外觀檢查時,被檢測出為不均勻異常,而有無法區別正常品與異常品的問題發生。因此,若外觀檢查時檢查裝置之檢查感度降低,則結果引起最終之彩色濾光片製品的產率下降,而造成問題。 In the present invention, from the viewpoint of high water permeation inhibiting effect, it is preferred that the initiator contains an oxime ester photoinitiator. Further, the term "water infiltration" refers to a phenomenon in which, after aging with pure water, a trace such as water infiltration occurs. Since such water permeation disappears after prebaking, there is no problem as a product, but when the appearance of the patterned surface is examined after development, it is detected as an unevenness abnormality, and there is a possibility that the normal product and the abnormal product cannot be distinguished. The problem has occurred. Therefore, if the inspection sensitivity of the inspection apparatus is lowered at the time of visual inspection, the result is that the yield of the final color filter article is lowered, causing a problem.
作為該肟酯系光起始劑,由減低因分解物造成之彩色濾光片用著色樹脂組成物之污染或裝置污染的觀點而言,較佳係具有芳香環者,更佳為具有含芳香環之縮合環者;再更佳為具有含苯環與雜環之縮合環者。 The oxime ester-based photoinitiator preferably has an aromatic ring, and more preferably has a fragrance, from the viewpoint of reducing contamination by a colored resin composition for a color filter due to decomposition products or contamination of a device. The condensed ring of the ring; more preferably, it has a condensed ring containing a benzene ring and a hetero ring.
作為肟酯系光起始劑,可由1,2-辛二酮-1-[4-(苯硫基)-、2-(鄰苯甲醯基肟)]、1-(鄰乙醯基肟)1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-乙酮、日本專利特開2000-80068號公報、特開2001-233842號公報、特表2010-527339、特表2010-527338、特開2013-041153等記載的肟酯系光起始劑中適當選擇。作為市售物,亦可使用IRGACURE OXE-01、IRGACURE OXE-02、IRGACURE OXE-03(以上為BASF公司製)、ADEKA OPT-N-1919、ADEKA ARKLS NCI-930、ADEKA ARKLS NCI-831(以上為ADEKA公司製)、TR-PBG-304、TR-PBG-326、TR-PBG-345、TR-PBG-3057(以上為常 州強力電子新材料公司製)等。 As the oxime ester photoinitiator, 1,2-octanedione-1-[4-(phenylthio)-, 2-(o-benzylidene fluorenyl)], 1-(o-ethylindenyl) can be used. 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone, Japanese Patent Laid-Open No. 2000-80068, JP-A-2001-233842 The oxime ester photoinitiator described in the above-mentioned Japanese Patent Publication No. 2010-527339, No. 2010-527338, and JP-A-2013-041153 is appropriately selected. As a commercially available product, IRGACURE OXE-01, IRGACURE OXE-02, IRGACURE OXE-03 (above, BASF), ADEKA OPT-N-1919, ADEKA ARKLS NCI-930, ADEKA ARKLS NCI-831 (above) ADEKA company), TR-PBG-304, TR-PBG-326, TR-PBG-345, TR-PBG-3057 (above State Strong Electronic New Materials Co., Ltd.).
作為本發明所使用之該肟酯系光起始劑,由耐溶劑性、顯影耐性、圖案缺陷發生之抑制效果、以及水滲染發生抑制效果優越的觀點而言,其中,較佳為使用產生芳基自由基、尤其是產生苯基自由基的肟酯系光起始劑,更佳為使用產生烷基自由基、尤其是產生甲基自由基的肟酯系光起始劑。此推判係相較於芳基自由基,烷基自由基的自由基移動容易活性化所致。作為產生烷基自由基之肟酯系光起始劑,可列舉1-(鄰乙醯基肟)1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-乙酮(商品名:IRGACURE OXE-02,BASF製)、(2,4,6-三甲基苯基)[8-[[(乙醯基氧基]亞胺基][2-(2,2,3,3-四氟丙氧基)苯基]甲基]-11-(2-乙基己基)-11H-苯并[a]咔唑-5-基]-甲酮(商品名:IRGACURE OXE-03,BASF製)、1-(鄰乙醯基肟)1-[9-乙基-6-(1,3-二氧戊環,4-(2-甲氧基苯氧基)-9H-咔唑-3-基]-乙酮(商品名:ADEKA OPT-N-1919,ADEKA公司製)、鄰乙醯基肟(9-乙基-6-硝基-9H-咔唑-3-基)[4-(2-甲氧基-1-甲基乙氧基-2-甲基苯基)]-甲酮(商品名:ADEKA ARKLS NCI-831,ADEKA公司製)、1-(鄰乙醯基肟)3-環戊基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-1-丙酮(商品名:TR-PBG-304,常州強力電子新材料公司製)、1-(鄰乙醯基肟)3-環戊基-1-[2-(2-嘧啶基硫基)-9H-咔唑-3-基]-1-丙烷(商品名:TR-PBG-314,常州強力電子新材料公司製)、1-(鄰乙醯基肟)2-環己基-1-[2-(2-嘧啶基氧基)-9H-咔唑-3-基]-乙酮(商品名:TR-PBG-326,常州強力電子新材料公司製)、1-(鄰乙醯基肟)2-環己基-1-[2-(2-嘧啶基硫基)-9H-咔唑-3-基]-乙酮(商品名:TR-PBG-331,常州強力電子新材料公司製)、1-(鄰乙醯基 肟)1-[4-[3-[1-[(乙醯基氧基)亞胺基]乙基]-6-[4-[(4,6-二甲基-2-嘧啶基)硫基]-2-甲基苯甲醯基]-9H-咔唑-9-基]苯基]-1-辛酮(商品名:EXTA-9,UNION CHEMICAL製)等。 The oxime ester-based photoinitiator used in the present invention is preferably produced by the use of solvent resistance, development resistance, suppression effect of pattern defects, and water permeation suppression effect. An aryl radical, especially an oxime ester photoinitiator which produces a phenyl radical, more preferably an oxime ester photoinitiator which produces an alkyl radical, in particular a methyl radical. This reasoning is that the radical movement of the alkyl radical is easily activated compared to the aryl radical. As the oxime ester photoinitiator which produces an alkyl radical, 1-(o-ethylindenyl) 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indole is exemplified. Zyridin-3-yl]-ethanone (trade name: IRGACURE OXE-02, manufactured by BASF), (2,4,6-trimethylphenyl)[8-[[(ethylideneoxy)imino) ][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]oxazol-5-yl] -Methyl ketone (trade name: IRGACURE OXE-03, manufactured by BASF), 1-(o-ethyl fluorenyl) 1-[9-ethyl-6-(1,3-dioxolan, 4-(2- Methoxyphenoxy)-9H-indazol-3-yl]-ethanone (trade name: ADEKA OPT-N-1919, manufactured by ADEKA), o-acetyl hydrazine (9-ethyl-6-nitrate) -9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl)]-methanone (trade name: ADEKA ARKLS NCI-831, ADEKA company, 1-(o-ethylindenyl) 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzimidyl)-9H-indazol-3-yl] 1-acetone (trade name: TR-PBG-304, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1-(o-ethenylhydrazine) 3-cyclopentyl-1-[2-(2-pyrimidinylthio) )-9H-carbazol-3-yl]-1-propane (trade name: TR-PBG-314, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1- (oight) Ethyl hydrazide) 2-cyclohexyl-1-[2-(2-pyrimidinyloxy)-9H-indazol-3-yl]-ethanone (trade name: TR-PBG-326, Changzhou Power Electronics) Manufactured by Material Co., Ltd., 1-(o-ethylindenyl) 2-cyclohexyl-1-[2-(2-pyrimidinylthio)-9H-indazol-3-yl]-ethanone (trade name: TR -PBG-331, manufactured by Changzhou Power Electronic Materials Co., Ltd.), 1-(o-ethylidene) 肟) 1-[4-[3-[1-[(Ethyloxy)imino]ethyl]-6-[4-[(4,6-dimethyl-2-pyrimidinyl)sulfide ]]-2-methylbenzylidene]-9H-carbazol-9-yl]phenyl]-1-octanone (trade name: EXTA-9, manufactured by UNION CHEMICAL).
又,由提升感度之觀點而言,較佳係於肟酯系光起始劑中組合具有3級胺構造的光起始劑使用。其理由係,具有3級胺構造之光起始劑,由於在分子內具有屬於氧淬滅劑的3級胺構造,故由起始劑所產生之自由基難以藉由氧使其失活,可提高感度所致。上述具有3級胺構造之光起始劑的市售物,可列舉例如2-甲基-1-(4-甲硫基苯基)-2-啉基丙烷-1-酮(例如IRGACURE 907,BASF公司製)、2-苄基-2-(二甲基胺基)-1-(4-啉基苯基)-1-丁酮(例如IRGACURE 369,BASF公司製)、4,4'-雙(二乙基胺基)二苯基酮(例如HICURE ABP,川口藥品製)等。 Further, from the viewpoint of enhancing the sensitivity, it is preferred to use a photoinitiator having a tertiary amine structure in combination with an oxime ester photoinitiator. The reason is that a photoinitiator having a tertiary amine structure has a tertiary amine structure belonging to an oxygen quencher in the molecule, so that a radical generated by the initiator is difficult to be deactivated by oxygen. Can increase the sensitivity. A commercially available product of the above-mentioned photoinitiator having a tertiary amine structure may, for example, be 2-methyl-1-(4-methylthiophenyl)-2- Lolinylpropan-1-one (for example, IRGACURE 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4- Polinylphenyl)-1-butanone (for example, IRGACURE 369, manufactured by BASF Corporation), 4,4'-bis(diethylamino)diphenyl ketone (for example, HICURE ABP, manufactured by Kawaguchi Pharmaceutical Co., Ltd.), and the like.
本發明中,起始劑較佳為使用肟酯系光起始劑,其中,更佳為含有烷基自由基系肟酯化合物。 In the present invention, the initiator is preferably an oxime ester photoinitiator, and more preferably an alkyl radical oxime ester compound.
在組合了烷基自由基系肟酯化合物、與α-胺基烷基苯酮系起始劑的情況,可得到水滲染抑制效果優越的塗膜,感度之調節亦變得容易。 When an alkyl radical oxime ester compound and an α-aminoalkylphenone-based initiator are combined, a coating film having an excellent water permeation inhibiting effect can be obtained, and the sensitivity can be easily adjusted.
又,在組合烷基自由基系肟酯化合物、與芳基自由基系肟酯化合物使用的情況,可依較少起始劑量而得到耐溶劑性與水滲染抑制特別優越的塗膜,感度調節亦變得容易。 Further, when an alkyl radical oxime ester compound or an aryl radical oxime ester compound is used in combination, a coating film which is particularly excellent in solvent resistance and water permeation suppression can be obtained with a small initial dose, and sensitivity Adjustment is also easy.
烷基自由基系肟酯化合物的量,係相對於著色樹脂組成物之固形份總量,較佳為2~7質量%。若起始劑量未滿7質量%,由於對於遮罩開口,圖案不致過粗,故較佳。若起始劑量為2質量%以上,則耐溶劑性變得良好。 The amount of the alkyl radical oxime ester compound is preferably from 2 to 7% by mass based on the total amount of the solid content of the colored resin composition. If the starting dose is less than 7% by mass, since the pattern is not too thick for the mask opening, it is preferable. When the starting dose is 2% by mass or more, the solvent resistance becomes good.
本發明之著色樹脂組成物中所使用之起始劑的含量,並無特別限制,相對於著色樹脂組成物之固形份總量,較佳為1~40質量%、更佳為2~30質量%、特佳為3~20質量%。若其含量少於上述範圍,則無法產生充分之聚合反應,故有無法作成為著色層之硬度充足者的情形;另一方面,若多於上述範圍,則著色樹脂組成物之固形份中之色材等的含量相對變少,有無法得到充分之著色濃度的情形。 The content of the initiator used in the colored resin composition of the present invention is not particularly limited, and is preferably from 1 to 40% by mass, more preferably from 2 to 30% by mass based on the total amount of the solid content of the colored resin composition. %, particularly preferably 3 to 20% by mass. If the content is less than the above range, a sufficient polymerization reaction cannot be produced, so that the hardness of the colored layer may not be sufficient. On the other hand, if it is more than the above range, the solid content of the colored resin composition is The content of the color material or the like is relatively small, and there is a case where a sufficient coloring density cannot be obtained.
於本發明之著色樹脂組成物中,在不損及本發明目的之範圍內,視需要亦可含有各種添加劑。作為添加劑,可列舉例如抗氧化劑、聚合停止劑、鏈移動劑、均染劑、可塑劑、界面活性劑、消泡劑、矽烷偶合劑、紫外線吸收劑、密黏促進劑等。 In the colored resin composition of the present invention, various additives may be contained as needed within the range not impairing the object of the present invention. Examples of the additive include an antioxidant, a polymerization stopper, a chain shifting agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a decane coupling agent, an ultraviolet absorber, a dense adhesion promoter, and the like.
本發明中,為了提升與基板間之密黏性,亦可使用矽烷偶合劑。本發明中所謂矽烷偶合劑,係表示具有1個以上選自矽醇基及烷氧基矽基之基的化合物。 In the present invention, a decane coupling agent may be used in order to improve the adhesion to the substrate. In the present invention, the decane coupling agent is a compound having one or more groups selected from the group consisting of a decyl group and an alkoxy group.
矽烷偶合劑,由密黏性的觀點而言,通常相對於著色樹脂組成物之總固形份而使用2質量%以上。對此,本發明者等人發現,在將矽烷偶合劑、與上述一般式(I)所示之色材組合使用時,該矽烷偶合劑發生經時變化。因此,由即使在長期間保管後對基板之密黏性仍不降低、且抑制感度變化而可得到如設計般之圖案狀著色層的觀點而言,較佳係相對於著色樹脂組成物之固形份,將矽烷偶合劑設 為1質量%以下;更佳係相對於著色樹脂組成物之總固形份,設為0.5質量%以下;再更佳為實質上不含有。 The decane coupling agent is usually used in an amount of 2% by mass or more based on the total solid content of the colored resin composition from the viewpoint of adhesion. On the other hand, the inventors of the present invention have found that when a decane coupling agent is used in combination with the coloring matter represented by the above general formula (I), the decane coupling agent changes over time. Therefore, from the viewpoint of obtaining a pattern-like colored layer as designed, even if the adhesion to the substrate after storage for a long period of time is not lowered and the sensitivity change is suppressed, it is preferable to form a solid layer with respect to the colored resin composition. Part, the decane coupling agent is set It is 1% by mass or less; more preferably, it is 0.5% by mass or less based on the total solid content of the colored resin composition; more preferably, it is substantially not contained.
作為矽烷偶合劑之具體例,可列舉乙烯基參(β-甲氧基乙氧基)矽烷、乙烯基乙氧基矽烷、乙烯基三甲氧基矽烷等之乙烯基矽烷類;γ-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷等之(甲基)丙烯酸矽烷類;β-(3,4-環氧基環己基)乙基三甲氧基矽烷、β-(3,4-環氧基環己基)甲基三甲氧基矽烷、β-(3,4-環氧基環己基)乙基三乙氧基矽烷、β-(3,4-環氧基環己基)甲基三乙氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷等之環氧基矽烷類;N-β(胺基乙基)γ-胺基丙基三甲氧基矽烷、N-β(胺基乙基)γ-胺基丙基三乙氧基矽烷、N-β(胺基乙基)γ-胺基丙基甲基二乙氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、N-苯基-γ-胺基丙基三乙氧基矽烷等之胺基矽烷類;γ-巰基丙基三甲氧基矽烷、γ-巰基丙基三乙氧基矽烷等之硫基矽烷類等之矽烷偶合劑;其中,由與基板間之密黏性的觀點而言,較佳為3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷。 Specific examples of the decane coupling agent include vinyl decane such as vinyl gin (β-methoxyethoxy) decane, vinyl ethoxy decane, and vinyl trimethoxy decane; γ-methyl propylene; a (meth)acrylic acid decane such as methoxypropyltrimethoxydecane or 3-methylpropenyloxypropyltrimethoxydecane; β-(3,4-epoxycyclohexyl)ethyltrimethyl Oxydecane, β-(3,4-epoxycyclohexyl)methyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltriethoxydecane, β-(3, Epoxy decane such as 4-epoxycyclohexyl)methyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N-β(aminoethyl)γ-aminopropyltriethoxydecane, N-β (amino group B) Γ-aminopropylmethyldiethoxydecane, γ-aminopropyltriethoxydecane, γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyl Amino decane such as trimethoxy decane, N-phenyl-γ-aminopropyltriethoxy decane; γ-mercaptopropyl A decane coupling agent such as a thiodecane such as methoxy decane or γ-mercaptopropyltriethoxy decane; and among them, 3-methyl propylene is preferred from the viewpoint of adhesion to a substrate. Methoxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methyl Acryloxypropyltriethoxydecane.
本發明之著色樹脂組成物,由耐熱性及耐光性的觀點而言,較佳係含有抗氧化劑。抗氧化劑可由習知公知者中適當選擇。作為抗氧化劑之具體例,可列舉例如受阻酚系抗氧化劑、胺系抗氧化劑、 磷系抗氧化劑、硫系抗氧化劑、肼系抗氧化劑等,由耐熱性及耐光性的觀點而言,較佳為使用受阻酚系抗氧化劑。 The colored resin composition of the present invention preferably contains an antioxidant from the viewpoint of heat resistance and light resistance. The antioxidant can be appropriately selected from those well-known by those skilled in the art. Specific examples of the antioxidant include hindered phenol-based antioxidants and amine-based antioxidants. A phosphorus-based antioxidant, a sulfur-based antioxidant, an antimony-based antioxidant, or the like is preferably a hindered phenol-based antioxidant from the viewpoint of heat resistance and light resistance.
作為受阻酚系抗氧化劑,可列舉例如季戊四醇肆[3-(3,5-二第三丁基-4-羥苯基)丙酸酯](商品名:IRGANOX 1010,BASF公司製)、1,3,5-參(3,5-二第三丁基-4-羥苄基)三聚異氰酸酯(商品名:IRGANOX 3114,BASF公司製)、2,4,6-參(4-羥基-3,5-二第三丁基苄基)1,3,5-三甲苯(商品名:IRGANOX 1330,BASF公司製)、2,2'-亞甲基雙(6-第三丁基-4-甲基酚)(商品名:Sumilizer MDP-S,住友化學製)、6,6'-硫雙(2-第三丁基-4-甲基酚)(商品名:IRGANOX 1081,BASF公司製)、3,5-二第三丁基-4-羥苄基磺酸二乙酯(商品名:IRGAMOD 195,BASF公司製)等。其中,由耐熱性及耐光性的觀點而言,較佳為季戊四醇肆[3-(3,5-二第三丁基-4-羥苯基)丙酸酯](商品名:IRGANOX 1010,BASF公司製)。 The hindered phenol-based antioxidant is, for example, pentaerythritol 肆 [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF Corporation), 1, 3,5-gin(3,5-di-t-butyl-4-hydroxybenzyl)-trimeric isocyanate (trade name: IRGANOX 3114, manufactured by BASF Corporation), 2,4,6-gin (4-hydroxy-3) ,5-di-t-butylbenzyl) 1,3,5-trimethylbenzene (trade name: IRGANOX 1330, manufactured by BASF Corporation), 2,2'-methylenebis(6-tert-butyl-4- Methylphenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical Co., Ltd.), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: IRGANOX 1081, manufactured by BASF Corporation) 3,5-di-tert-butyl-4-hydroxybenzylsulfonate (trade name: IRGAMOD 195, manufactured by BASF Corporation). Among them, from the viewpoint of heat resistance and light resistance, pentaerythritol 肆 [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, BASF) is preferred. Company system).
於使用抗氧化劑時,其調配量若為不損及本發明效果之範圍,則無特別限定。作為抗氧化劑之調配量,相對於著色樹脂組成物中之總固形份100質量份,抗氧化劑較佳為0.1~5.0質量份、更佳為0.5~4.0質量份。若為上述下限值以上,則耐熱性及耐光性優越。另一方面,若為上述上限值以下,則可將本發明之著色樹脂組成物作成為高感度的感光性樹脂組成物。 When the antioxidant is used, the amount thereof is not particularly limited as long as it does not impair the effects of the present invention. The amount of the antioxidant is preferably 0.1 to 5.0 parts by mass, more preferably 0.5 to 4.0 parts by mass, per 100 parts by mass of the total solid content in the colored resin composition. When it is more than the above lower limit, heat resistance and light resistance are excellent. On the other hand, when it is at most the above upper limit value, the colored resin composition of the present invention can be used as a highly sensitive photosensitive resin composition.
又,作為上述界面活性劑,可列舉例如聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、山梨醇酐脂肪酸酯類、脂肪酸改質聚酯類、3級胺改質聚胺基甲酸酯類等。又,其他亦可使用氟系界面活性劑。 Further, examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene nonyl phenyl ether. Polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and the like. Further, a fluorine-based surfactant may also be used.
再者,作為可塑劑,可列舉例如酞酸二丁酯、酞酸二辛酯、三甲苯酚等。作為消泡劑、均染劑,可列舉例如矽系、氟系、丙烯酸系之化合物等。 Further, examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and trimethyl phenol. Examples of the antifoaming agent and the leveling agent include a quinone-based, fluorine-based, and acrylic-based compound.
作為鏈移動劑,較佳為例如單官能硫醇化合物、多官能硫醇化合物,其中更佳為多官能硫醇化合物。 As the chain shifting agent, for example, a monofunctional thiol compound or a polyfunctional thiol compound is preferable, and among them, a polyfunctional thiol compound is more preferable.
作為單官能硫醇化合物,可列舉2-巰基苯并噻唑、2-巰基苯并咪唑、2-巰基苯并唑、2-巰基甲基苯并咪唑、2-巰基甲基苯并唑、2-巰基甲基苯并噻唑等。其中,由使光聚合起始劑所產生之自由基進行鏈移動、提升硬化性的觀點而言,單官能硫醇化合物較佳為2-巰基甲基苯并噻唑。 Examples of the monofunctional thiol compound include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoene. Oxazole, 2-mercaptomethylbenzimidazole, 2-mercaptomethylbenzo Oxazole, 2-mercaptomethylbenzothiazole and the like. Among them, the monofunctional thiol compound is preferably 2-mercaptomethylbenzothiazole from the viewpoint of chain-shifting the radical generated by the photopolymerization initiator and improving the hardenability.
作為多官能硫醇化合物,並無特別限定,可使用各種化合物。多官能硫醇化合物可列舉例如1,2-乙二硫醇、1,3-丙二硫醇、1,4-丁二硫醇、1,6-己二硫醇、1,8-辛二硫醇、1,2-環己二硫醇、癸二硫醇、乙二醇雙硫基乙醇酸酯、乙二醇雙(3-巰基丙酸酯)、乙二醇雙硫基乙醇酸酯、1,4-丁二醇二硫基乙醇酸酯、1,4-丁二醇雙(3-巰基丙酸酯)、三羥甲基丙烷參硫基乙醇酸酯、三羥甲基丙烷參(3-巰基丙酸酯)、季戊四醇肆硫基乙醇酸酯、季戊四醇肆(3-巰基丙酸酯)、二季戊四醇六(3-巰基丙酸酯)、其他各種多元醇與硫基乙醇酸、巰基丙酸等之含硫醇基羧酸的酯。 The polyfunctional thiol compound is not particularly limited, and various compounds can be used. The polyfunctional thiol compound may, for example, be 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octane Mercaptan, 1,2-cyclohexanedithiol, decanedithiol, ethylene glycol dithioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol dithioglycolate , 1,4-butanediol dithioglycolate, 1,4-butanediol bis(3-mercaptopropionate), trimethylolpropane thioglycolate, trimethylolpropane (3-mercaptopropionate), pentaerythritol thioglycolate, pentaerythritol ruthenium (3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), various other polyols and thioglycolic acid, An ester of a thiol-containing carboxylic acid such as mercaptopropionic acid.
又,作為多官能硫醇化合物,可列舉三巰基丙酸參(2-羥乙基)三聚異氰酸酯、1,4-二甲基巰基苯、2,4,6-三巰基-s-三、2-(N,N-二丁基胺基)-4,6-二巰基-s-三等。又,多官能硫醇化合物 可列舉2,5-己二硫醇、2,9-癸二硫醇、1,4-雙(1-巰基乙基)苯、酞酸二(1-巰基乙酯)、酞酸二(2-巰基丙酯)、酞酸二(3-巰基丁酯)、酞酸二(3-巰基異丁酯)等之相對於硫醇基於α位及/或β位之碳原子具有取代基的多官能硫醇化合物;乙二醇雙(3-巰基丁酸酯)、丙二醇雙(3-巰基丁酸酯)、二乙二醇雙(3-巰基丁酸酯)、丁二醇雙(3-巰基丁酸酯)、辛二醇雙(3-巰基丁酸酯)、三羥甲基丙烷參(3-巰基丁酸酯)、季戊四醇肆(3-巰基丁酸酯)、二季戊四醇陸(3-巰基丁酸酯)、乙二醇雙(2-巰基丙酸酯)、丙二醇雙(2-巰基丙酸酯)、二乙二醇雙(2-巰基丙酸酯)、丁二醇雙(2-巰基丙酸酯)、辛二醇雙(2-巰基丙酸酯)、三羥甲基丙烷參(2-巰基丙酸酯)、季戊四醇肆(2-巰基丙酸酯)、二季戊四醇陸(2-巰基丙酸酯)、乙二醇雙(3-巰基異丁酸酯)、丙二醇雙(3-巰基異丁酸酯)、二乙二醇雙(3-巰基異丁酸酯)、丁二醇雙(3-巰基異丁酸酯)、辛二醇雙(3-巰基異丁酸酯)、三羥甲基丙烷參(3-巰基異丁酸酯)、季戊四醇肆(3-巰基異丁酸酯)、二季戊四醇陸(3-巰基異丁酸酯)、乙二醇雙(2-巰基異丁酸酯)、丙二醇雙(2-巰基異丁酸酯)、二乙二醇雙(2-巰基異丁酸酯)、丁二醇雙(2-巰基異丁酸酯)、辛二醇雙(2-巰基異丁酸酯)、三羥甲基丙烷參(2-巰基異丁酸酯)、季戊四醇肆(2-巰基異丁酸酯)、二季戊四醇陸(2-巰基異丁酸酯)、乙二醇雙(4-巰基戊酸酯)、丙二醇雙(4-巰基異戊酸酯)、二乙二醇雙(4-巰基戊酸酯)、丁二醇雙(4-巰基戊酸酯)、辛二醇雙(4-巰基戊酸酯)、三羥甲基丙烷參(4-巰基戊酸酯)、季戊四醇肆(4-巰基戊酸酯)、二季戊四醇陸(4-巰基戊酸酯)、乙二醇雙(3-巰基戊酸酯)、丙二醇雙(3-巰基戊酸酯)、二乙二醇雙(3-巰基戊酸酯)、丙二醇雙(3-巰基戊酸酯)、辛二醇雙(3-巰基戊酸酯)、三羥甲基丙烷參(3-巰基戊酸酯)、季戊四醇 肆(3-巰基戊酸酯)、二季戊四醇陸(3-巰基戊酸酯)等。 Further, examples of the polyfunctional thiol compound include trisylpropionate (2-hydroxyethyl)trimeric isocyanate, 1,4-dimethylnonylbenzene, and 2,4,6-trimethyl-s-trid. , 2-(N,N-dibutylamino)-4,6-dimercapto-s-three Wait. Further, examples of the polyfunctional thiol compound include 2,5-hexanedithiol, 2,9-nonanedithiol, 1,4-bis(1-mercaptoethyl)benzene, and di(1-decylethyl) phthalate. ), bis(2-mercaptopropyl phthalate), bis(3-mercaptobutyl phthalate), bis(3-mercaptoisobutyl phthalate), etc. based on the alpha and/or beta positions relative to the thiol a polyfunctional thiol compound having a substituent of a carbon atom; ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), Butanediol bis(3-mercaptobutyrate), octanediol bis(3-mercaptobutyrate), trimethylolpropane ginseng (3-mercaptobutyrate), pentaerythritol bismuth (3-mercaptobutyrate) , dipentaerythritol tert-(3-mercaptobutyrate), ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate) ), butanediol bis(2-mercaptopropionate), octanediol bis(2-mercaptopropionate), trimethylolpropane ginseng (2-mercaptopropionate), pentaerythritol bismuth (2-mercaptopropionate) Acid ester), dipentaerythritol tert-(2-mercaptopropionate), ethylene glycol bis(3-mercaptoisobutyrate), propylene glycol bis(3-mercaptoisobutyrate), diethylene glycol bis (3-巯Isobutyrate), butanediol bis(3-mercaptoisobutyrate), octanediol bis(3-mercaptoisobutyrate), trimethylolpropane ginseng (3-mercaptoisobutyrate) , pentaerythritol bismuth (3-mercaptoisobutyrate), dipentaerythritol ter (3-mercaptoisobutyrate), ethylene glycol bis(2-mercaptoisobutyrate), propylene glycol bis(2-mercaptoisobutyrate) , diethylene glycol bis(2-mercaptoisobutyrate), butanediol bis(2-mercaptoisobutyrate), octanediol bis(2-mercaptoisobutyrate), trimethylolpropane Reference (2-mercaptoisobutyrate), pentaerythritol bismuth (2-mercaptoisobutyrate), dipentaerythritol tert-(2-mercaptoisobutyrate), ethylene glycol bis(4-mercaptovalerate), propylene glycol Bis(4-mercaptoisovalerate), diethylene glycol bis(4-mercaptovalerate), butanediol bis(4-mercaptovalerate), octanediol bis(4-mercaptovalerate) , trimethylolpropane ginseng (4-mercapto valerate), pentaerythritol bismuth (4-mercapto valerate), dipentaerythritol tert-(mercapto valerate), ethylene glycol bis(3-mercaptovalerate) ), propylene glycol bis(3-mercaptovalerate), diethylene glycol bis(3-mercaptovalerate), propylene glycol bis(3-mercaptovalerate), octanediol bis(3-mercapto pentane) Ester), trimethylolpropane reference (3-mercaptovalerate), pentaerythritol tetrakis (3-mercapto-valerate), dipentaerythritol land (3-mercaptovalerate) and the like.
本發明中,上述多官能硫醇化合物中較佳為季戊四醇肆(3-巰基丁酸酯)。 In the present invention, among the above polyfunctional thiol compounds, decyl pentaerythritol (3-mercaptobutyrate) is preferred.
作為製品,可列舉季戊四醇肆(3-巰基丁酸酯)(PTMP;昭和電工公司製「Karenz MT(商標)PE1」)。 The product is exemplified by pentaerythritol strontium (3-mercaptobutyrate) (PTMP; "Karenz MT (trademark) PE1" manufactured by Showa Denko Co., Ltd.).
一般式(I)所示之色材及其他色材之合計含量,係相對於著色樹脂組成物之固形份總量,較佳為以3~65質量%、更佳為以4~55質量%之比例進行調配。若為上述下限值以上,則在將著色樹脂組成物塗佈成既定膜厚(通常為1.0~5.0μm)時之著色層具有充分色濃度。又,若為上述上限值以下,則分散性及分散安定性優越,且可得到具有充分硬度、或與基板之密黏性的著色層。再者,於本發明中,固形份為除了上述溶劑以外之所有者,亦包括液狀之多官能性單體等。 The total content of the color material and other color materials represented by the general formula (I) is preferably from 3 to 65% by mass, more preferably from 4 to 55% by mass, based on the total amount of the solid content of the colored resin composition. The ratio is adjusted. When it is more than the above lower limit value, the colored layer has a sufficient color density when the colored resin composition is applied to a predetermined film thickness (usually 1.0 to 5.0 μm). Moreover, when it is at most the above upper limit value, dispersibility and dispersion stability are excellent, and a coloring layer having sufficient hardness or adhesion to a substrate can be obtained. Further, in the present invention, the solid content is an owner other than the above solvent, and includes a liquid polyfunctional monomer or the like.
另外,作為分散劑之含量,若為可使一般式(I)所示之色材均勻地分散者,則並無特別限定,例如相對於著色樹脂組成物之固形份總量,可使用3~40質量%。進而,相對於著色樹脂組成物之固形份總量,較佳為5~35質量%、特佳為5~25質量%。若為上述下限值以上,則一般式(I)所示之色材之分散性及分散安定性優越、黏度之經時穩定性優越。又,若為上述上限值以下,則可成為著色層之亮度良好者。 In addition, the content of the dispersing agent is not particularly limited as long as the coloring material represented by the general formula (I) can be uniformly dispersed. For example, the total amount of the solid content of the colored resin composition can be used. 40% by mass. Further, the total amount of the solid content of the colored resin composition is preferably 5 to 35% by mass, particularly preferably 5 to 25% by mass. When it is more than the above lower limit value, the color material shown by the general formula (I) is excellent in dispersibility and dispersion stability, and the viscosity stability over time is excellent. Moreover, when it is below the said upper limit, the brightness of a colored layer can be favorable.
鹼可溶性樹脂與多官能單體、與起始劑之合計含量,係相對於著色樹脂組成物之固形份總量,較佳為以10~92質量%、更佳為以 15~87質量%之比例進行調配。若為上述下限值以上,則可得到具有充分硬度、或與基板間之密黏性的著色層。又,若為上述上限值以下,則因熱收縮所造成之微小皺紋的發生亦被抑制。 The total content of the alkali-soluble resin, the polyfunctional monomer, and the starter is preferably from 10 to 92% by mass, more preferably from 10 to 92% by mass based on the total amount of the solid content of the colored resin composition. The ratio is 15~87% by mass. When it is at least the above lower limit value, a coloring layer having sufficient hardness or adhesion to the substrate can be obtained. Moreover, if it is less than the above upper limit, the occurrence of minute wrinkles due to heat shrinkage is also suppressed.
又,溶劑之含量係可於能精度良好地形成著色層的範圍內適當設定。相對於包含該溶劑之上述著色樹脂組成物之總量,通常為55~95質量%之範圍內,其中,更佳為65~88質量%之範圍內。藉由使上述溶劑之含量為上述範圍內,可作成為塗佈性優越者。 Further, the content of the solvent can be appropriately set within a range in which the coloring layer can be formed with high precision. The total amount of the above colored resin composition containing the solvent is usually in the range of 55 to 95% by mass, and more preferably in the range of 65 to 88% by mass. When the content of the above solvent is within the above range, it is possible to obtain a coating property superior.
本發明之彩色濾光片用著色樹脂組成物之製造方法,若為含有上述本發明之色材分散液與鹼可溶性樹脂、多官能單體、起始劑、溶劑與視所需而使用之各種添加成分,可使色材藉分散劑均勻分散於溶劑中的方法即可,可使用公知之混合手段進行混合而調製。 The method for producing a colored resin composition for a color filter of the present invention is a mixture containing the above-described color material dispersion liquid of the present invention, an alkali-soluble resin, a polyfunctional monomer, a starter, a solvent, and the like. The component may be added, and the color material may be uniformly dispersed in a solvent by a dispersing agent, and may be prepared by mixing using a known mixing means.
作為該樹脂組成物之調製方法,可列舉例如:(1)於上述本發明之色材分散液中,混合鹼可溶性樹脂、多官能單體、起始劑與視所需而使用之各種添加成分的方法;(2)於溶劑中,同時投入色材、分散劑、鹼可溶性樹脂、多官能單體、起始劑與視所需而使用之各種添加成分,並予以混合的方法;(3)於溶劑中,添加、混合分散劑、鹼可溶性樹脂、多官能單體、起始劑與視所需而使用之各種添加成分後,加入色材並予以分散的方法;(4)於溶劑中,添加色材、分散劑與鹼可溶性樹脂而調製分散液,於該分散液中,進而添加、混合鹼可溶性樹脂、多官能單體、起始劑與視所需而使用之各種添加成分的方法等。 Examples of the method for preparing the resin composition include (1) mixing the alkali-soluble resin, the polyfunctional monomer, the initiator, and various additives to be used as needed in the color material dispersion of the present invention. (2) a method of simultaneously adding a coloring material, a dispersing agent, an alkali-soluble resin, a polyfunctional monomer, an initiator, and various additives as required in a solvent, and mixing them in a solvent; (3) a method of adding and mixing a dispersing agent, an alkali-soluble resin, a polyfunctional monomer, an initiator, and various additives to be used as needed, and then adding a coloring material and dispersing it in a solvent; (4) in a solvent, A coloring material, a dispersing agent, and an alkali-soluble resin are added to prepare a dispersion liquid, and an alkali-soluble resin, a polyfunctional monomer, an initiator, and various additives to be used as needed are added and mixed in the dispersion. .
此等方法中,由有效防止色材之凝集、使其均勻分散的觀點而 言,較佳係上述(4)之方法。 Among these methods, from the viewpoint of effectively preventing aggregation of the color material and uniformly dispersing it In other words, the method of the above (4) is preferred.
本發明之彩色濾光片係至少具備透明基板、與設於該透明基板上之著色層者,該著色層之至少一者具有使上述本發明之著色樹脂組成物硬化而形成的著色層。 The color filter of the present invention includes at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers has a colored layer formed by curing the colored resin composition of the present invention.
針對此種本發明之彩色濾光片,參照圖式進行說明。圖1為表示本發明之彩色濾光片之一例的概略剖面圖。根據圖1,本發明之彩色濾光片10具有透明基板1、遮光部2、及著色層3。 The color filter of the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light shielding portion 2, and a coloring layer 3.
本發明之彩色濾光片所使用之著色層,其至少一者為使上述本發明之彩色濾光片用著色樹脂組成物硬化而形成的著色層。 At least one of the coloring layers used in the color filter of the present invention is a coloring layer formed by curing the coloring resin composition of the color filter of the present invention.
著色層通常形成於後述透明基板上之遮光部之開口部,通常由3色以上之著色圖案所構成。 The colored layer is usually formed on the opening of the light-shielding portion on the transparent substrate to be described later, and is usually composed of three or more colored patterns.
另外,作為該著色層之配列,並無特別限定,例如可設為條紋型、馬賽克型、三角型、4像素配置型等一般配列。又,著色層之寬、面積等可任意設定。 In addition, the arrangement of the colored layer is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangular type, or a four-pixel arrangement type. Further, the width, area, and the like of the colored layer can be arbitrarily set.
該著色層之厚度可藉由調整塗佈方法、著色樹脂組成物之固形份濃度或黏度等而適當控制,通常較佳為1~5μm之範圍。 The thickness of the colored layer can be appropriately controlled by adjusting the coating method, the solid content concentration or viscosity of the colored resin composition, and the like, and is usually preferably in the range of 1 to 5 μm.
例如,於著色樹脂組成物為感光性樹脂組成物時,該著色層可藉由下述方法而形成。 For example, when the colored resin composition is a photosensitive resin composition, the colored layer can be formed by the following method.
首先,使用噴塗法、浸塗法、棒塗法、輥塗法、旋塗法、模塗法等塗佈手段將上述本發明之彩色濾光片用著色樹脂組成物塗佈 於後述透明基板上,使濕塗膜形成。 First, the coloring resin composition for a color filter of the present invention is coated by a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. A wet coating film is formed on a transparent substrate to be described later.
接著,使用加熱板或烘箱等使該濕塗膜乾燥後,於其上經由既定圖案之遮罩進行曝光,使鹼可溶性樹脂及多官能單體等進行光聚合反應,作成感光性之塗膜。作為曝光所使用之光源,可列舉例如:低壓水銀燈、高壓水銀燈、金屬鹵化物燈等紫外線、電子束等。曝光量係根據所使用之光源或塗膜之厚度等而適當調整。 Then, the wet coating film is dried by a hot plate or an oven, and then exposed to a mask of a predetermined pattern, and an alkali-soluble resin, a polyfunctional monomer, or the like is photopolymerized to form a photosensitive coating film. Examples of the light source used for the exposure include ultraviolet rays such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the thickness of the light source or coating film to be used and the like.
又,於曝光後,為了促進聚合反應,亦可進行加熱處理。加熱條件係根據所使用之著色樹脂組成物中之各成分之調配比例、或塗膜之厚度等而適當選擇。 Further, after the exposure, in order to promote the polymerization reaction, heat treatment may be performed. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition to be used, the thickness of the coating film, and the like.
接著,使用顯影液進行顯影處理,溶解、除去未曝光部分,藉此依所需圖案形成塗膜。作為顯影液,通常使用於水或水溶性溶劑中使鹼溶解的溶液。於該鹼性溶液中,亦可適量添加界面活性劑等。又,顯影方法可採用一般方法。 Next, development processing is carried out using a developing solution to dissolve and remove the unexposed portion, thereby forming a coating film in a desired pattern. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. In the alkaline solution, a surfactant or the like may be added in an appropriate amount. Further, the development method can employ a general method.
顯影處理後,通常進行顯影液之清洗、著色樹脂組成物之硬化塗膜之乾燥,形成著色層。再者,顯影處理後,為了使塗膜充分硬化,亦可進行加熱處理。加熱條件並無特別限定,可根據塗膜之用途而適當選擇。 After the development treatment, the developer is usually washed and the cured coating film of the colored resin composition is dried to form a colored layer. Further, after the development treatment, heat treatment may be performed in order to sufficiently cure the coating film. The heating conditions are not particularly limited and may be appropriately selected depending on the use of the coating film.
本發明之彩色濾光片中之遮光部,係於後述透明基板上形成為圖案狀者,可設為與一般彩色濾光片中使用作為遮光部者相同。 The light-shielding portion of the color filter of the present invention is formed into a pattern on a transparent substrate to be described later, and can be used as a light-shielding portion in a general color filter.
該遮光部之圖案形狀,並無特別限定,可列舉例如條紋狀、矩陣狀等之形狀。作為該遮光部,可列舉例如使黑色顏料分散或溶解於黏結劑樹脂中而成者,或鉻、氧化鉻等之金屬薄膜等。該金屬薄 膜可為CrOx膜(x為任意之數)及Cr膜之2層積層而成者;又,亦可為進一步降低反射率之CrOx膜(x為任意之數)、CrNy膜(y為任意之數)及Cr膜之3層積層而成者。 The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. Examples of the light-shielding portion include a black pigment dispersed or dissolved in a binder resin, or a metal film such as chromium or chromium oxide. The metal thin film may be a CrO x film (x is an arbitrary number) and a two-layer layer of a Cr film; or a CrO x film (x is an arbitrary number) or a CrN y film which further reduces the reflectance. (y is an arbitrary number) and three layers of the Cr film are laminated.
於該遮光部為使黑色色材分散或溶解於黏結劑樹脂中而成者時,作為該遮光部之形成方法,若為可對遮光部進行圖案化之方法即可,並無特別限定,可列舉例如使用遮光部用著色樹脂組成物之光微影法、印刷法、噴墨法等。 When the light-shielding portion is formed by dispersing or dissolving the black color material in the binder resin, the method of forming the light-shielding portion may be a method of patterning the light-shielding portion, and is not particularly limited. For example, a photolithography method using a colored resin composition for a light-shielding portion, a printing method, an inkjet method, or the like is exemplified.
圖案狀之遮光部係例如可依與上述著色層之形成相同的方法予以形成。 The patterned light-shielding portion can be formed, for example, in the same manner as the formation of the colored layer described above.
遮光部之膜厚,於金屬薄膜時,係設為0.2~0.4μm左右,於使黑色色材分散或溶解於黏結劑樹脂中而成者時,係設為0.5~2μm左右。 The film thickness of the light-shielding portion is about 0.2 to 0.4 μm in the case of a metal thin film, and is about 0.5 to 2 μm when the black color material is dispersed or dissolved in the binder resin.
彩色濾光片之著色層的色度,可配合光源等而適當調整,並無特別限定,例如在藍色著色層時,於C光源下之色度(x、y)時,較佳係x為0.12~0.27、y為0.04~0.18之範圍內。 The chromaticity of the color layer of the color filter can be appropriately adjusted in accordance with a light source or the like, and is not particularly limited. For example, in the case of a blue colored layer, when the chromaticity (x, y) under the C light source is preferable, x is preferable. It is in the range of 0.12 to 0.27 and y is in the range of 0.04 to 0.18.
作為本發明之彩色濾光片中之透明基板,若為對可見光呈透明之基材即可,並無特別限定,可使用一般之彩色濾光片所使用的透明基板。具體而言,可列舉石英玻璃、無鹼玻璃、合成石英板等無可撓性之透明剛性材;或透明樹脂薄膜、光學用樹脂板、可撓玻璃等具有可撓性之透明軟性材。 The transparent substrate in the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples thereof include a flexible transparent rigid material such as quartz glass, an alkali-free glass, or a synthetic quartz plate, or a flexible transparent material such as a transparent resin film, an optical resin plate, or a flexible glass.
該透明基板之厚度並無特別限定,根據本發明之彩色濾光片的用途,例如可使用100μm~1mm左右者。 The thickness of the transparent substrate is not particularly limited, and for the use of the color filter of the present invention, for example, about 100 μm to 1 mm can be used.
再者,本發明之彩色濾光片係除了上述透明基板、遮光部及著色層以外,例如亦可為形成保護層或透明電極層、進而配向膜或配向突起、柱狀間隔件等者。 Further, the color filter of the present invention may be, for example, a protective layer or a transparent electrode layer, an alignment film, an alignment protrusion, a columnar spacer, or the like in addition to the transparent substrate, the light shielding portion, and the coloring layer.
本發明之顯示裝置的特徵在於,具有上述本發明之彩色濾光片。本發明中,顯示裝置之構成並無特別限定,可由習知公知之顯示裝置中適當選擇,可列舉例如液晶顯示裝置、或有機發光顯示裝置等。 The display device of the present invention is characterized by having the above-described color filter of the present invention. In the present invention, the configuration of the display device is not particularly limited, and may be appropriately selected from known display devices, and examples thereof include a liquid crystal display device and an organic light-emitting display device.
液晶顯示裝置的特徵為,具有上述本發明之彩色濾光片、對向基板、及形成於上述彩色濾光片與上述對向基板之間的液晶層。 The liquid crystal display device is characterized by comprising the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
針對此種本發明之液晶顯示裝置,參照圖式進行說明。圖2為表示液晶顯示裝置之一例的概略圖。如圖2所示,液晶顯示裝置40具有彩色濾光片10、具有TFT陣列基板等之對向基板20、及形成於上述彩色濾光片10與上述對向基板20間之液晶層30。 The liquid crystal display device of the present invention will be described with reference to the drawings. 2 is a schematic view showing an example of a liquid crystal display device. As shown in FIG. 2, the liquid crystal display device 40 includes a color filter 10, an opposite substrate 20 having a TFT array substrate, and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20.
再者,本發明之液晶顯示裝置並不限定於此圖2所示之構成,可設為一般作為彩色濾光片所使用之液晶顯示裝置的公知構成。 Further, the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and can be generally configured as a liquid crystal display device used for a color filter.
作為本發明之液晶顯示裝置之驅動方式,並無特別限定,可採用一般液晶顯示裝置所使用之驅動方式。作為此種驅動方式,可列舉例如:TN方式、IPS方式、OCB方式、及MVA方式等。於本發明中,可適當使用該等之任一方式。 The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method used in a general liquid crystal display device can be employed. Examples of such a driving method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be suitably used.
另外,作為對向基板,可根據本發明之液晶顯示裝置之驅動方 式等而適當選擇使用。 Further, as the counter substrate, the driving side of the liquid crystal display device according to the present invention can be used. Select the appropriate use.
再者,作為構成液晶層之液晶,係根據本發明之液晶顯示裝置之驅動方式等,可使用介電異向性相異之各種液晶、及此等之混合物。 In addition, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and a mixture thereof can be used according to the driving method of the liquid crystal display device of the present invention.
作為液晶層之形成方法,可使用一般使用作為液晶單元之製作方法的方法,可列舉例如真空注入方式或液晶滴下方式等。 As a method of forming the liquid crystal layer, a method generally used as a method for producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
有機發光顯示裝置的特徵在於,具有上述本發明之彩色濾光片、與有機發光體。 The organic light-emitting display device is characterized by comprising the above-described color filter of the present invention and an organic light-emitting body.
針對此種有機發光顯示裝置,參照圖式進行說明。圖3為表示有機發光顯示裝置之一例的概略剖面圖。如圖3所示,本發明之有機發光顯示裝置100具有彩色濾光片10、及有機發光體80。於彩色濾光片10、與有機發光體80之間亦可具有有機保護層50或無機氧化膜60。 Such an organic light-emitting display device will be described with reference to the drawings. 3 is a schematic cross-sectional view showing an example of an organic light emitting display device. As shown in FIG. 3, the organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting body 80.
作為有機發光體80之積層方法,可列舉例如於彩色濾光片上面逐次形成透明陽極71、電洞注入層72、電洞輸送層73、發光層74、電子注入層75、及陰極76之方法,或將形成於另一基板上之有機發光體80貼合於無機氧化膜60上之方法等。有機發光體80中之透明陽極71、電洞注入層72、電洞輸送層73、發光層74、電子注入層75、及陰極76、其他之構成,可適當使用公知者。如此所製作之有機發光顯示裝置100亦可應用於例如被動驅動方式之有機EL顯示器或主動驅動方式之有機EL顯示器中。 As a method of laminating the organic light-emitting body 80, for example, a method of sequentially forming the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 on the color filter may be mentioned. Or a method of bonding the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60 or the like. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 in the organic light-emitting body 80, and other configurations can be suitably used. The organic light-emitting display device 100 thus fabricated can also be applied to, for example, a passively driven organic EL display or an active driving organic EL display.
再者,本發明之有機發光顯示裝置並不限定於此圖3所示之構成,可設為一般作為彩色濾光片所使用之有機發光顯示裝置的公知構成。 Further, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and can be generally configured as an organic light-emitting display device used for a color filter.
以下針對本發明,例示實施例進行具體說明。本發明並不限制於此等記載。 Hereinafter, the embodiments will be specifically described with reference to the present invention. The invention is not limited to the description.
尚且,本發明中鹼性共聚合體之重量平均分子量Mw,係藉由GPC(凝膠滲透層析法)依標準聚苯乙烯換算值的形式求得。測定係使用東曹(股)製之HLC-8120GPC,以添加了0.01莫耳/公升之溴化鋰的N-甲基吡咯啶酮作為洗提溶劑,將校正曲線用聚苯乙烯標準設為Mw377400、210500、96000、50400、20650、10850、5460、2930、1300、580(以上為Polymer Laboratories公司製Easi PS-2系列)及Mw1090000(東曹(股)製),以TSK-GEL ALPHA-M×二根(東曹(股)製)作為測定管柱而進行。又,對於成為鹼性共聚合體之原料的巨單體或接枝共聚合體,亦依上述條件進行。 Further, the weight average molecular weight Mw of the basic copolymer in the present invention is determined by GPC (gel permeation chromatography) in terms of a standard polystyrene conversion value. For the measurement, HLC-8120GPC manufactured by Tosoh Corporation was used, N-methylpyrrolidone with 0.01 mol/liter lithium bromide was added as the elution solvent, and the calibration curve was set to Mw377400 and 210500 using the polystyrene standard. , 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (above is Easi PS-2 series made by Polymer Laboratories) and Mw1090000 (made by Tosoh Co., Ltd.), with TSK-GEL ALPHA-M×2 (Tosoh Co., Ltd.) was carried out as a measuring column. Further, the macromonomer or the graft copolymer which is a raw material of the basic copolymer is also subjected to the above conditions.
又,酸價(mgKOH/g)係根據JIS K 0070,藉由電位差滴定法所求得之值。 Further, the acid value (mgKOH/g) is a value obtained by a potentiometric titration method in accordance with JIS K 0070.
使和光純藥(股)製1-碘萘15.2g(60mmol)、三井化學(股)製降烷二胺(NBDA)(CAS No.56602-77-8)4.63g(30mmol)、第三丁氧鈉8.07g(84mmol)、Aldrich製2-二環己基膦基-2',6'-二甲氧基聯苯0.09g(0.2mmol)、和光純藥(股)製醋酸鈀0.021g(0.1mmol)分散於二甲苯30mL,以130-135℃反應48小時。反應結束後,冷卻至室溫 加水進行萃取。接著以硫酸鎂乾燥,進行濃縮,藉此得到8.5g(產率70%)下述化學式(1)所示之中間體1。 The production of 1-iodonaphthalene 15.2g (60mmol) and Mitsui Chemicals Co., Ltd. Alkyldiamine (NBDA) (CAS No. 56602-77-8) 4.63 g (30 mmol), sodium butoxide sodium 8.07 g (84 mmol), 2-dicyclohexylphosphino-2', 6'-di, manufactured by Aldrich 0.09 g (0.2 mmol) of methoxybiphenyl and 0.021 g (0.1 mmol) of palladium acetate produced by Wako Pure Chemical Industries Co., Ltd. were dispersed in 30 mL of xylene, and reacted at 130-135 ° C for 48 hours. After completion of the reaction, the mixture was cooled to room temperature and added with water for extraction. Then, the mixture was dried over magnesium sulfate and concentrated to give 8.5 g (yield: 70%) of Intermediate 1 of the formula (1) below.
所得之化合物係藉下述分析結果確認為目標化合物。 The obtained compound was confirmed to be the target compound by the following analysis.
‧MS(ESI)(m/z):407(M+H) ‧MS(ESI)(m/z):407(M+H)
‧元素分析值:CHN實測值(85.47%、8.02%、6.72%);理論值(85.26%、8.11%、6.63%) ‧ Elemental analysis values: CHN measured values (85.47%, 8.02%, 6.72%); theoretical values (85.26%, 8.11%, 6.63%)
裝入8.46g(20.8mmol)之中間體1、東京化成工業製4,4'-雙(二甲基胺基)二苯基酮13.5g(41.6mmol)、甲苯60mL,以45-50℃進行攪拌。滴下和光純藥工業製磷醯氯6.38g(51.5mmol),迴流2小時並冷卻。反應結束後,傾析甲苯。對樹脂狀析出物加入氯仿40mL、水40mL、濃鹽酸進行溶解,分液出氯仿層。將氯仿層以水洗淨,以硫酸鎂進行乾燥、濃縮。對濃縮物加入醋酸乙酯65mL並迴流。冷卻後過濾析出物,得到15.9g(產率70%)下述化學式(2)所示之中間體2(BB7-Nb-dimer)。 8.46 g (20.8 mmol) of Intermediate 1, Tokyo Chemical Industry Co., Ltd. 4,4'-bis(dimethylamino)diphenyl ketone 13.5 g (41.6 mmol), toluene 60 mL, and 45-50 ° C Stir. 6.38 g (51.5 mmol) of phosphonium chloride was prepared by the Wako Pure Chemical Industries, and refluxed for 2 hours and cooled. After the reaction was completed, toluene was decanted. To the resinous precipitate, 40 mL of chloroform, 40 mL of water, and concentrated hydrochloric acid were added to dissolve, and a chloroform layer was separated. The chloroform layer was washed with water, dried over magnesium sulfate and concentrated. 65 mL of ethyl acetate was added to the concentrate and refluxed. After cooling, the precipitate was filtered to obtain 15.9 g (yield: 70%) of the intermediate 2 (BB7-Nb-dimer) represented by the following chemical formula (2).
所得之化合物係藉由下述分析結果確認為目標化合物。 The obtained compound was confirmed to be the target compound by the following analysis.
‧MS(ESI)(m/z):511(+)、2價 ‧MS(ESI)(m/z): 511(+), 2 price
‧元素分析值:CHN實測值(78.13%、7.48%、7.78%);理論值(78.06%、7.75%、7.69%) ‧ Elemental analysis values: CHN measured values (78.13%, 7.48%, 7.78%); theoretical values (78.06%, 7.75%, 7.69%)
將5.00g(4.58mmol)之中間體2加入至水300ml中,以90℃使其溶解作成中間體2溶液。接著將日本無機化學工業製磷鎢酸‧n水合物H3[PW12O40]‧nH2O(n=30)10.44g(3.05mmol)置入於水100mL中,以90℃攪拌,調製磷鎢酸水溶液。於先前之中間體2溶液中以90℃混合磷鎢酸水溶液,濾取生成之沉澱物,以水洗淨。將所得之濾餅乾燥,得到13.25g(產率98%)下述化學式(3)所示之色材A。 5.00 g (4.58 mmol) of the intermediate 2 was added to 300 ml of water, and dissolved at 90 ° C to prepare an intermediate 2 solution. Then, 10.4 g (3.05 mmol) of phosphotungstic acid ‧n hydrate H 3 [PW 12 O 40 ]‧nH 2 O (n=30) manufactured by Nippon Chemical Industry Co., Ltd. was placed in 100 mL of water, and stirred at 90 ° C to prepare An aqueous solution of phosphotungstic acid. The aqueous solution of phosphotungstic acid was mixed at 90 ° C in the previous intermediate 2 solution, and the resulting precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 g (yield 98%) of a color material A represented by the following chemical formula (3).
所得之化合物係藉由下述分析結果確認為目標化合物。(莫耳比W/Mo=100/0) The obtained compound was confirmed to be the target compound by the following analysis. (Morby W/Mo=100/0)
‧MS(ESI)(m/z):510(+)、2價 ‧MS(ESI)(m/z): 510(+), 2 price
‧元素分析值:CHN實測值(41.55%、5.34%、4.32%);理論值(41.66%、5.17%、4.11%) ‧ Elemental analysis values: CHN measured values (41.55%, 5.34%, 4.32%); theoretical values (41.66%, 5.17%, 4.11%)
又,藉由31P-NMR確認到磷鎢酸之聚酸構造係在成為色材A後仍保持著。 Further, it was confirmed by 31 P-NMR that the polyacid structure of the phosphotungstic acid remained after the coloring material A.
將500ml之四口分離燒瓶減壓乾燥後,予以置換為Ar(氬)。於Ar氣流下,加入脫水THF100g、甲基三甲基矽基二甲基烯酮縮醛1.6g、四丁基銨-3-氯苯甲酸酯(TBACB)之1M乙腈溶液0.15ml、1,3,5-三甲苯0.2g。對其使用滴下漏斗,歷時45分鐘滴下甲基丙烯酸甲酯40g。由於反應進行時發熱,故藉由冰冷將溫度保持為未滿40℃。1小時後,歷時15分鐘滴下甲基丙烯酸二甲基胺基乙酯10g。反應1小時後,加入甲醇5g使反應停止。將溶劑減壓去除,得到 嵌段共聚合體I。藉GPC測定(NMP LiBr10mM)所求得之重量平均分子量Mw為7.600,胺價為70mgKOH/g。 The 500-ml four-necked flask was dried under reduced pressure and then replaced with Ar (argon). Under a stream of Ar, 100 g of dehydrated THF, 1.6 g of methyltrimethyldecyl dimethyl ketene acetal, and 1 M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB) were added, and 1,5 ml, 3,5-trimethylbenzene 0.2 g. Using a dropping funnel, 40 g of methyl methacrylate was dropped over 45 minutes. Since the reaction was heated, the temperature was kept below 40 ° C by ice cooling. After 1 hour, 10 g of dimethylaminoethyl methacrylate was dropped over 15 minutes. After reacting for 1 hour, 5 g of methanol was added to stop the reaction. The solvent is removed under reduced pressure to obtain Block copolymer I. The weight average molecular weight Mw determined by GPC measurement (NMP LiBr 10 mM) was 7.600, and the amine value was 70 mgKOH/g.
將所得之嵌段共聚合體I溶解於PGMEA,製作60wt%溶液。 The obtained block copolymer I was dissolved in PGMEA to prepare a 60 wt% solution.
於合成例4中,除了變更為甲基丙烯酸甲酯37g、甲基丙烯酸二甲基胺基乙酯13g以外,其餘與合成例4同樣的方式進行,得到嵌段共聚合體II。重量平均分子量Mw為7.600,胺價為90mgKOH/g。 In the same manner as in Synthesis Example 4 except that 37 g of methyl methacrylate and 13 g of dimethylaminoethyl methacrylate were changed to the synthesis example 4, the block copolymer II was obtained. The weight average molecular weight Mw was 7.600, and the amine value was 90 mgKOH/g.
於合成例4中,除了變更為甲基丙烯酸甲酯35g、甲基丙烯酸二甲基胺基乙酯15g以外,其餘與合成例4同樣的方式進行,得到嵌段共聚合體III。重量平均分子量Mw為7.600,胺價為105mgKOH/g。 In the same manner as in Synthesis Example 4 except that 35 g of methyl methacrylate and 15 g of dimethylaminoethyl methacrylate were changed to the synthesis example 4, the block copolymer III was obtained. The weight average molecular weight Mw was 7.600, and the amine value was 105 mgKOH/g.
於合成例4中,除了變更為甲基丙烯酸甲酯33g、甲基丙烯酸二甲基胺基乙酯17g以外,其餘與合成例4同樣的方式進行,得到嵌段共聚合體IV。重量平均分子量Mw為7.600,胺價為120mgKOH/g。 In the same manner as in Synthesis Example 4 except that 33 g of methyl methacrylate and 17 g of dimethylaminoethyl methacrylate were changed to the synthesis example 4, the block copolymer IV was obtained. The weight average molecular weight Mw was 7.600, and the amine value was 120 mgKOH/g.
於合成例4中,除了變更為甲基丙烯酸甲酯30g、甲基丙烯酸二甲基胺基乙酯20g以外,其餘與合成例4同樣的方式進行,得到 嵌段共聚合體V。重量平均分子量Mw為7.600,胺價為140mgKOH/g。 In the same manner as in Synthesis Example 4 except that 30 g of methyl methacrylate and 20 g of dimethylaminoethyl methacrylate were changed in Synthesis Example 4, Block copolymer V. The weight average molecular weight Mw was 7.600, and the amine value was 140 mgKOH/g.
於合成例4中,除了變更為甲基丙烯酸甲酯27.5g、甲基丙烯酸二甲基胺基乙酯22.5g以外,其餘與合成例4同樣的方式進行,得到嵌段共聚合體VI。重量平均分子量Mw為7.600,胺價為160mgKOH/g。 In the same manner as in Synthesis Example 4 except that 27.5 g of methyl methacrylate and 22.5 g of dimethylaminoethyl methacrylate were changed to Synthesis Example 4, a block copolymer VI was obtained. The weight average molecular weight Mw was 7.600, and the amine value was 160 mgKOH/g.
於合成例4中,除了變更為甲基丙烯酸甲酯41.5g、甲基丙烯酸二甲基胺基乙酯8.5g以外,其餘與合成例4同樣的方式進行,得到嵌段共聚合體VII。重量平均分子量Mw為7.600,胺價為60mgKOH/g。 In the same manner as in Synthesis Example 4 except that 41.5 g of methyl methacrylate and 8.5 g of dimethylaminoethyl methacrylate were changed, the block copolymer VII was obtained. The weight average molecular weight Mw was 7.600, and the amine value was 60 mgKOH/g.
於合成例4中,除了變更為甲基丙烯酸甲酯26g、甲基丙烯酸二甲基胺基乙酯24g以外,其餘與合成例4同樣的方式進行,得到嵌段共聚合體VIII。重量平均分子量Mw為7.600,胺價為170mgKOH/g。 In the same manner as in Synthesis Example 4 except that 26 g of methyl methacrylate and 24 g of dimethylaminoethyl methacrylate were changed to the synthesis example 4, the block copolymer VIII was obtained. The weight average molecular weight Mw was 7.600, and the amine value was 170 mgKOH/g.
將所得之嵌段共聚合體VIII溶解於PGMEA,製作60wt%溶液。 The obtained block copolymer VIII was dissolved in PGMEA to prepare a 60 wt% solution.
於具備冷卻管、添加用漏斗、氮氣用進氣口、機械攪拌機、數位溫度計之反應器中加入丙二醇甲醚乙酸酯(簡稱PGMEA)80.0質量份,一邊於氮氣流下進行攪拌,一邊加溫至溫度90℃。歷時1.5小時滴下甲基丙烯酸甲酯50.0質量份、甲基丙烯酸正丁酯30.0質量份、甲基丙烯酸苄酯20.0質量份、巰基乙醇4.0質量份、PGMEA 30質量份、α,α'-偶氮二異丁腈(簡稱AIBN)1.0質量份之混合溶液,進而反應3小時。接著,停止氮氣流,將該反應溶液冷卻至80℃,加入Karenz MOI(昭和電工(股)公司製造)8.74質量份、二月桂酸二丁基錫0.125g、對甲氧基苯酚0.125質量份、及PGMEA 10質量份並攪拌3小時,藉此獲得巨單體I之49.5%溶液。所得巨單體I之GPC測定結果係重量平均分子量(Mw)為4010,數量平均分子量(Mn)為1910,分子量分佈(Mw/Mn)為2.10。 80.0 parts by mass of propylene glycol methyl ether acetate (PGMEA) was added to a reactor equipped with a cooling tube, an addition funnel, a nitrogen gas inlet, a mechanical stirrer, and a digital thermometer, and the mixture was heated while stirring under a nitrogen stream. Temperature 90 ° C. 50.0 parts by mass of methyl methacrylate, 30.0 parts by mass of n-butyl methacrylate, 20.0 parts by mass of benzyl methacrylate, 4.0 parts by mass of mercaptoethanol, 30 parts by mass of PGMEA, and α,α'-azo were dropped over 1.5 hours. A mixed solution of 1.0 part by mass of diisobutyronitrile (abbreviated as AIBN) was further reacted for 3 hours. Then, the nitrogen gas flow was stopped, and the reaction solution was cooled to 80 ° C, and 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko Co., Ltd.), 0.125 g of dibutyltin dilaurate, 0.125 parts by mass of p-methoxyphenol, and PGMEA were added. 10 parts by mass and stirred for 3 hours, thereby obtaining a 49.5% solution of macromonomer I. The GPC measurement result of the obtained macromonomer I was 4010, the weight average molecular weight (Mn) was 1910, and the molecular weight distribution (Mw/Mn) was 2.10.
於具備冷卻管、添加用漏斗、氮氣用進氣口、機械攪拌機、數位溫度計之反應器中加入PGMEA 80.0質量份,一邊於氮氣流下進行攪拌,一邊加溫至溫度85℃。歷時1.5小時滴下上述(1)之巨單體I溶液75.76質量份(有效固形份49.5質量份)、甲基丙烯酸二甲基胺基乙酯(簡稱DMMA)12.5質量份、正十二硫醇1.24質量份、PGMEA 20.0質量份、AIBN 0.5質量份之混合溶液,加熱攪拌3小時後,歷時10分鐘滴下AIBN 0.10質量份、PGMEA 10.0質量份之混合液,進而於相同溫度下進行1小時熟成,藉此獲得接枝共聚合體I之25.4%溶液。所得之接枝共聚合體I之GPC測定之結果,重量平均分子量(Mw)為11480,數量平均分子量(Mn)為4650,分子量 分佈(Mw/Mn)為2.47。又,胺價為89mgKOH/g。 80.0 parts by mass of PGMEA was placed in a reactor equipped with a cooling tube, an addition funnel, a nitrogen gas inlet, a mechanical stirrer, and a digital thermometer, and the mixture was heated to a temperature of 85 ° C while stirring under a nitrogen stream. 75.76 parts by mass of the macromonomer I solution of the above (1) (49.5 parts by mass of the solid content), 12.5 parts by mass of dimethylaminoethyl methacrylate (DMMA), and n-dodecyl alcohol 1.24 were added dropwise over 1.5 hours. A mixed solution of a mass fraction, PGMEA 20.0 parts by mass, and AIBN 0.5 parts by mass, and after heating and stirring for 3 hours, a mixture of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was dropped over 10 minutes, and further aged at the same temperature for 1 hour. This gave a 25.4% solution of graft copolymer I. As a result of GPC measurement of the obtained graft copolymer I, the weight average molecular weight (Mw) was 11,480, and the number average molecular weight (Mn) was 4,650. The distribution (Mw/Mn) was 2.47. Further, the amine value was 89 mgKOH/g.
於聚合槽中填裝PGMEA150質量份,於氮環境下升溫為100℃後,將甲基丙烯酸(MAA)22質量份、甲基丙烯酸環己酯(CHMA)64質量份及PERBUTYL O(日油股份有限公司製)6質量份、鏈移動劑(正十二硫醇)2質量份歷時1.5小時連續滴下。其後,保持100℃持續反應,在上述主鏈形成用混合物之滴下結束經2小時後,添加對甲氧基苯酚0.1質量份作為聚合抑制劑而停止聚合。 150 parts by mass of PGMEA was placed in a polymerization tank, and after heating to 100 ° C in a nitrogen atmosphere, 22 parts by mass of methacrylic acid (MAA), 64 parts by mass of cyclohexyl methacrylate (CHMA), and PERBUTYL O (Nippon Oil Co., Ltd.) were added. 6 parts by mass of a chain shifting agent (n-dodecylmercaptan), 2 parts by mass, continuously dripped for 1.5 hours. Thereafter, the reaction was continued at 100 ° C, and after completion of the dropwise addition of the above-mentioned main chain-forming mixture for 2 hours, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization.
接著,一邊吹入空氣,一邊添加甲基丙烯酸環氧丙酯(GMA)14質量份作為含環氧基化合物,升溫為110℃後,添加三乙基胺0.8質量份並依110℃進行加成反應15小時,得到鹼可溶性樹脂A溶液(重量平均分子量(Mw)9,000,酸價90mgKOH/g,固形份40質量%)。 Next, 14 parts by mass of glycidyl methacrylate (GMA) was added as an epoxy group-containing compound while blowing air, and the temperature was raised to 110 ° C, and 0.8 parts by mass of triethylamine was added thereto, and the mixture was added at 110 ° C. After reacting for 15 hours, an alkali-soluble resin A solution (weight average molecular weight (Mw) 9,000, acid value: 90 mgKOH/g, solid content: 40% by mass) was obtained.
又,上述重量平均分子量係以聚苯乙烯作為標準物質,以THF作為洗提液,藉由Shodex GPC System-21H進行測定。又,酸價之測定方法係根據JIS K 0070所測定。以下鹼可溶性樹脂B~E亦依同樣方法測定重量平均分子量、酸價。 Further, the above weight average molecular weight was measured by using Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent. Further, the method for measuring the acid value is measured in accordance with JIS K 0070. The following alkali-soluble resins B to E were also subjected to the same method to measure a weight average molecular weight and an acid value.
於製造例1中,除了將甲基丙烯酸(MAA)設為26.5質量份、甲基丙烯酸環己酯(CHMA)設為59.5質量份以外,其餘與製造例1同樣的方式進行,得到鹼可溶性樹脂B之PGMEA溶液(固形份40質量%)。鹼可溶性樹脂B之重量平均分子量為9,000,酸價為 120mgKOH/g。 In the same manner as in Production Example 1, except that the methacrylic acid (MAA) was 26.5 parts by mass and the cyclohexyl methacrylate (CHMA) was 59.5 parts by mass, the alkali-soluble resin was obtained. PPGMEA solution of B (solid content 40% by mass). The alkali-soluble resin B has a weight average molecular weight of 9,000 and an acid value of 120 mg KOH / g.
於製造例1中,除了將甲基丙烯酸(MAA)設為29.5質量份、甲基丙烯酸環己酯(CHMA)設為56.5質量份以外,其餘與製造例1同樣的方式進行,得到鹼可溶性樹脂C之PGMEA溶液(固形份40質量%)。鹼可溶性樹脂C之重量平均分子量為9,000,酸價為140mgKOH/g。 In the same manner as in Production Example 1, except that the methacrylic acid (MAA) was 29.5 parts by mass and the cyclohexyl methacrylate (CHMA) was 56.5 parts by mass, the alkali-soluble resin was obtained. PPGMEA solution of C (solid content 40% by mass). The alkali-soluble resin C had a weight average molecular weight of 9,000 and an acid value of 140 mgKOH/g.
於製造例1中,除了將甲基丙烯酸(MAA)設為18.5質量份、甲基丙烯酸環己酯(CHMA)設為67.5質量份以外,其餘與製造例1同樣的方式進行,得到鹼可溶性樹脂D之PGMEA溶液(固形份40質量%)。鹼可溶性樹脂D之重量平均分子量為9,000,酸價為70mgKOH/g。 In the same manner as in Production Example 1, except that the methacrylic acid (MAA) was 18.5 parts by mass and the cyclohexyl methacrylate (CHMA) was 67.5 parts by mass, the alkali-soluble resin was obtained. DPGMEA solution (solid content 40% by mass). The alkali-soluble resin D had a weight average molecular weight of 9,000 and an acid value of 70 mgKOH/g.
於聚合槽中填裝PGMEA129質量份,於氮環境下升溫為100℃後,將甲基丙烯酸(MAA)5.8質量份、甲基丙烯酸甲酯(MMA)20.4質量份、甲基丙烯酸環氧丙酯(BzMA)59.8質量份及PERBUTYL O(日油股份有限公司製)6質量份、鏈移動劑(正十二硫醇)2質量份歷時1.5小時連續滴下。其後,保持100℃持續反應,在上述主鏈形成用混合物之滴下結束經2小時後,添加對甲氧基苯酚0.1質量份作為聚合抑制劑而停止聚合,得到鹼可溶性樹脂E溶液(重量平 均分子量(Mw)9,000,酸價70mgKOH/g,固形份40質量%)。 129 parts by mass of PGMEA was placed in a polymerization tank, and after heating to 100 ° C in a nitrogen atmosphere, 5.8 parts by mass of methacrylic acid (MAA), 20.4 parts by mass of methyl methacrylate (MMA), and glycidyl methacrylate were added. (BzMA) 59.8 parts by mass and 6 parts by mass of PERBUTYL O (manufactured by Nippon Oil Co., Ltd.) and 2 parts by mass of a chain shifting agent (n-dodecylmercaptan) were continuously dropped over 1.5 hours. Thereafter, the reaction was continued at 100 ° C, and after completion of the dropwise addition of the above-mentioned main chain-forming mixture for 2 hours, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor, and polymerization was stopped to obtain an alkali-soluble resin E solution (weight-flat The average molecular weight (Mw) was 9,000, the acid value was 70 mgKOH/g, and the solid content was 40% by mass.
對製造例1所得之鹼可溶性樹脂A溶液(固形份40質量%)31.4質量份,添加作為多官能單體之二季戊四醇六丙烯酸酯(DPHA)(ARONIX M402(東亞合成製))18.8質量份、作為起始劑之IRGACURE 907(BASF製)5.9質量份、KAYACURE-DETX-S(日本化藥製)2.0質量份、抗氧化劑IRGANOX 1010(BASF製)0.8質量份、PGMEA41.2質量份,得到感光性黏結劑成分CR-1。 To 31.4 parts by mass of the alkali-soluble resin A solution (solid content: 40% by mass) obtained in Production Example 1, 18.8 parts by mass of dipentaerythritol hexaacrylate (DPHA) (ARONIX M402 (manufactured by Toagosei Co., Ltd.)) as a polyfunctional monomer was added. 5.9 parts by mass of IRGACURE 907 (manufactured by BASF), 2.0 parts by mass of KAYACURE-DETX-S (manufactured by Nippon Kasei Co., Ltd.), 0.8 parts by mass of antioxidant IRGANOX 1010 (manufactured by BASF), and 41.2 parts by mass of PGMEA were obtained as a starter. The adhesive component CR-1.
於調製例1中,除了取代鹼可溶性樹脂A溶液(固形份40質量%),而分別使用製造例2~3之鹼可溶性樹脂B~C溶液(固形份40質量%)以外,其餘與調製例1同樣的方式進行,得到感光性黏結劑成分CR-2~CR-3。 In the preparation example 1, except for the alkali-soluble resin A solution (solid content: 40% by mass), the alkali-soluble resin B-C solution (solid content: 40% by mass) of Production Examples 2 to 3 was used, and the other examples were prepared. 1 In the same manner, photosensitive adhesive components CR-2 to CR-3 were obtained.
對製造例2所得之鹼可溶性樹脂B溶液(固形份40質量%)31.4質量份,添加作為多官能單體之多元酸改質丙烯酸寡聚物(ARONIX M520(東亞合成製))18.8質量份、作為起始劑之IRGACURE 907(BASF製)5.9質量份、KAYACURE-DETX-S(日本化藥製)2.0質量份、抗氧化劑IRGANOX 1010(BASF製)0.8質量份、PGMEA41.2質量份,得到感光性黏結劑成分CR-4。 To 31.4 parts by mass of the alkali-soluble resin B solution (solid content: 40% by mass) obtained in Production Example 2, 18.8 parts by mass of a polybasic acid-modified acrylic oligomer (ARONIX M520 (manufactured by Toagosei Co., Ltd.)) as a polyfunctional monomer was added. 5.9 parts by mass of IRGACURE 907 (manufactured by BASF), 2.0 parts by mass of KAYACURE-DETX-S (manufactured by Nippon Kasei Co., Ltd.), 0.8 parts by mass of antioxidant IRGANOX 1010 (manufactured by BASF), and 41.2 parts by mass of PGMEA were obtained as a starter. The adhesive component CR-4.
於調製例1中,除了取代鹼可溶性樹脂A溶液(固形份40質量%),而使用製造例4之鹼可溶性樹脂D溶液(固形份40質量%)以外,其餘與調製例1同樣的方式進行,得到感光性黏結劑成分CR-5。 In the same manner as in Preparation Example 1, except that the alkali-soluble resin A solution (solid content: 40% by mass) was used instead of the alkali-soluble resin A solution (solid content: 40% by mass) of the production example 1 was used. The photosensitive adhesive component CR-5 was obtained.
於225mL美乃滋瓶中,加入PGMEA65.1質量份、鹼可溶性樹脂E溶液(固形份40質量%)14.6質量份、合成例4之嵌段共聚合體(固形份60質量%)6.8質量份並攪拌。於其中加入苯膦酸(商品名:PPA,日產化學公司製)0.48質量份(相對於嵌段共聚合體之3級胺基為0.6莫耳當量),於室溫攪拌30分鐘。 65.2 parts by mass of PGMEA, 14.6 parts by mass of an alkali-soluble resin E solution (solid content: 40% by mass), and 6.8 parts by mass of a block copolymer (solid content: 60% by mass) of Synthesis Example 4 were stirred and stirred in a 225 mL mayon bottle. . To this was added 0.48 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) (0.6 molar equivalent to the tertiary amine group of the block copolymer), and the mixture was stirred at room temperature for 30 minutes.
裝入合成例3之色材A 13.0質量份、粒徑2.0mm氧化鋯珠100質量份,藉塗料振盪器(淺田鐵工公司製)振盪1小時作為預備解碎,接著變更為粒徑0.1mm氧化鋯珠200份藉塗料振盪器進行4小時分散作為正式解碎,得到色材分散液A-1。 1 part by mass of the color material A of the synthesis example 3 and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were shaken by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as a preliminary pulverization, and then changed to a particle diameter of 0.1 mm. 200 parts of zirconia beads were dispersed by a coating shaker for 4 hours to form a solid dispersion, and a color material dispersion A-1 was obtained.
於實施例1中,除了將嵌段共聚合體的固形份與有機酸化合物的合計質量份設為固定,如表1般變更嵌段共聚合體之種類、與苯膦酸的調配比率以外,其餘與實施例1同樣的方式進行,得到色材分散液A-2~A-3、B-1~B-6、C-1~C-2、D-1~D-4、E-1~E-2、F-1~F-2。 In the first embodiment, the total mass of the block copolymer and the total mass of the organic acid compound were fixed, and the type of the block copolymer and the blending ratio with the phenylphosphonic acid were changed as shown in Table 1. In the same manner as in Example 1, the color material dispersions A-2 to A-3, B-1 to B-6, C-1 to C-2, D-1 to D-4, and E-1 to E were obtained. -2, F-1~F-2.
於實施例1中,除了將嵌段共聚合體的固形份與有機酸化合物的合計質量份設為固定,如表1般變更嵌段共聚合體之種類、與苯膦酸的調配比率以外,其餘與實施例1同樣的方式進行,得到色材分散液A-4、B-7~B-8、C-3~C-4、D-5~D-7、E-3~E-4、F-3~F-5、G、H。 In the first embodiment, the total mass of the block copolymer and the total mass of the organic acid compound were fixed, and the type of the block copolymer and the blending ratio with the phenylphosphonic acid were changed as shown in Table 1. In the same manner as in Example 1, the color material dispersions A-4, B-7~B-8, C-3~C-4, D-5~D-7, E-3~E-4, F were obtained. -3~F-5, G, H.
於225mL美乃滋瓶中,加入PGMEA65.3質量份、鹼可溶性樹脂E溶液(固形份40質量%)14.6質量份、Disperbyk LPN6919(BYK Chemie公司製,丙烯酸分散劑,固形份60質量%)(胺價120mgKOH/g,固形份60質量%)6.3質量份並攪拌。於其中加入苯膦酸(商品名:PPA,日產化學公司製)0.77質量份(相對於LPN6919之3級胺基為0.6莫耳當量),於室溫攪拌30分鐘。 65.3 parts by mass of PGMEA, 14.3 parts by mass of an alkali-soluble resin E solution (solid content: 40% by mass), Disperbyk LPN6919 (acrylic dispersant made by BYK Chemie Co., Ltd., 60 parts by mass of solid content) (amine) in a 225 mL mayon bottle The price was 120 mgKOH/g, and the solid content was 60% by mass) of 6.3 parts by mass and stirred. 0.77 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) was added thereto (0.6 molar equivalent to the amine group of LPN6919), and the mixture was stirred at room temperature for 30 minutes.
裝入合成例3之色材A 13.0質量份、粒徑2.0mm氧化鋯珠100質量份,藉塗料振盪器(淺田鐵工公司製)振盪1小時作為預備解碎,接著變更為粒徑0.1mm氧化鋯珠200份藉塗料振盪器進行4小時分散作為正式解碎,得到色材分散液I。 1 part by mass of the color material A of the synthesis example 3 and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were shaken by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as a preliminary pulverization, and then changed to a particle diameter of 0.1 mm. 200 parts of zirconia beads were dispersed by a coating shaker for 4 hours to form a solid dispersion, and a color material dispersion I was obtained.
於225mL美乃滋瓶中,加入PGMEA57.6質量份、鹼可溶性樹脂E溶液(固形份40質量%)14.6質量份、比較合成例4之接枝共聚合體I(胺價89mgKOH/g,固形份25.4質量%)13.7質量份並攪拌。於其中加入磷酸二甲基丙烯酸氧基乙酯(商品名:P-2M,共榮社化 學製)1.07質量份(相對於接枝共聚合體I之3級胺基為0.6莫耳當量),於室溫攪拌30分鐘。 To 225 mL of a cannabis bottle, 57.6 parts by mass of PGMEA and 14.6 parts by mass of an alkali-soluble resin E solution (solid content: 40% by mass) were added, and the graft copolymer I of Comparative Synthesis Example 4 was compared (amine price: 89 mgKOH/g, solid content: 25.4) Mass%) 13.7 parts by mass and stirred. Ethyl oxyethyl methacrylate was added thereto (trade name: P-2M, Gongrong Shehua 1.07 parts by mass (0.6 molar equivalents relative to the amine group of the graft copolymer I), and stirred at room temperature for 30 minutes.
裝入合成例3之色材A 13.0質量份、粒徑2.0mm氧化鋯珠100質量份,藉塗料振盪器(淺田鐵工公司製)振盪1小時作為預備解碎,接著變更為粒徑0.1mm氧化鋯珠200份藉塗料振盪器進行4小時分散作為正式解碎,得到色材分散液J。 1 part by mass of the color material A of the synthesis example 3 and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were shaken by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as a preliminary pulverization, and then changed to a particle diameter of 0.1 mm. 200 parts of zirconia beads were dispersed by a coating shaker for 4 hours to form a solid dispersion, and a color material dispersion J was obtained.
將實施例及比較例之色材分散液分別於室溫(25℃)保管,在調製經1日後及保管1個月後,分別測定黏度。黏度係使用振動式黏度計(SEKONIC製VM-200T2),於25.0±1.0℃下進行測定,採用測定開始30秒後之值。 The color material dispersion liquids of the examples and the comparative examples were each stored at room temperature (25 ° C), and the viscosity was measured after one day of preparation and one month after storage. The viscosity was measured at 25.0 ± 1.0 ° C using a vibrating viscometer (VM-200T2 manufactured by SEKONIC), and the value was 30 seconds after the start of the measurement.
比較分散1日後之黏度、與保存1個月後之黏度,將黏度變化為10%以內者設為A,將黏度變化超過10%者設為B。將結果示於表1。若黏度變化為10%以內,則分散穩定性優越,評價為實用範圍。 The viscosity after 1 day of dispersion was compared with the viscosity after 1 month of storage. The viscosity was changed to 10% or less, and the viscosity was changed to 10%. The results are shown in Table 1. When the viscosity change is within 10%, the dispersion stability is excellent, and the evaluation is a practical range.
混合實施例1之色材分散液A-1 30.5質量份、調製例1之感光性黏結劑成分CR-1 26.9質量份、界面活性劑MEGAFAC R08MH(DIC製)0.01質量份、PGMEA42.5質量份,得到實施例20之著色樹脂組成物。 30.5 parts by mass of the color material dispersion liquid A-1 of Example 1, 26.9 parts by mass of the photosensitive adhesive component CR-1 of Preparation Example 1, 0.01 parts by mass of the surfactant MEGAFAC R08MH (manufactured by DIC), and 42.5 parts by mass of PGMEA The colored resin composition of Example 20 was obtained.
於實施例20中,除了取代色材分散液A-1而分別變更為下表2記載之色材分散液以外,其餘與實施例20同樣的方式進行,得到實施例21~38之著色樹脂組成物。 In the same manner as in Example 20, except that the color material dispersion liquid A-1 was replaced with the color material dispersion liquid described in Table 2 below, the coloring resin compositions of Examples 21 to 38 were obtained. Things.
於實施例20中,除了取代色材分散液A-1而使用色材分散液D-1,取代感光性黏結劑成分CR-1而分別使用感光性黏結劑成分CR-2~CR-5以外,其餘與實施例20同樣的方式進行,得到實施例39~42之著色樹脂組成物。 In the example 20, the color material dispersion liquid D-1 was used instead of the color material dispersion liquid A-1, and the photosensitive adhesive agent component CR-1 was used instead of the photosensitive adhesive component CR-2 to CR-5. The rest was carried out in the same manner as in Example 20 to give the colored resin compositions of Examples 39 to 42.
於實施例20中,除了將色材分散液及感光性黏結劑成分分別變更為下表2之組合以外,其餘與實施例20同樣的方式進行,得到比較例18~34之著色樹脂組成物。 In the same manner as in Example 20 except that the color material dispersion liquid and the photosensitive binder component were changed to the combination of the following Table 2, the colored resin compositions of Comparative Examples 18 to 34 were obtained.
對實施例及比較例之著色樹脂組成物,使用與色材分散液之分散穩定性評價相同的方法進行測定。 The colored resin compositions of the examples and the comparative examples were measured by the same method as the evaluation of the dispersion stability of the color material dispersion.
比較調製1日後之黏度、與保存1個月後之黏度,將黏度變化為3%以內者設為A,將黏度變化超過3%且5%以內者設為B,將超過5%者設為C。將結果示於表2。若黏度變化為5%以內,則穩定性優越,評價為實用範圍。 Comparing the viscosity after 1 day of preparation and the viscosity after 1 month of storage, the viscosity is changed to 3% or less, and the viscosity is changed to more than 3% and within 5%, B is set, and more than 5% is set. C. The results are shown in Table 2. If the viscosity change is within 5%, the stability is excellent, and the evaluation is a practical range.
將實施例及比較例之著色樹脂組成物分別使用旋塗器塗佈於厚0.7mm之玻璃基板(NH TECHNO GLASS(股)製,「NA35」)上。其後,於80℃加熱板上進行加熱乾燥3分鐘。未經由光罩而使用超高壓水銀燈照射60mJ/cm2之紫外線,藉此得到硬化膜(藍色著色膜)。該硬化膜之膜厚(T;μm)係依後述後烘烤後之色度成為y=0.090的方式調整。測定此著色膜之色度(L0、a0、b0),其後,將形成了著色膜之玻璃板以230℃之無塵爐進行後烘烤25分鐘,再次測定所得著色膜之色度(L1、a1、b1)。 Each of the colored resin compositions of the examples and the comparative examples was applied onto a glass substrate (manufactured by NH TECHNO GLASS, "NA35") having a thickness of 0.7 mm using a spin coater. Thereafter, the film was dried by heating on a hot plate at 80 ° C for 3 minutes. A cured film (blue colored film) was obtained by irradiating ultraviolet rays of 60 mJ/cm 2 with an ultrahigh pressure mercury lamp without using a photomask. The film thickness (T; μm) of the cured film was adjusted so that the chromaticity after post-baking was y=0.090. The chromaticity (L 0 , a 0 , b 0 ) of the colored film was measured, and thereafter, the glass plate on which the colored film was formed was post-baked in a dust-free oven at 230 ° C for 25 minutes, and the color of the obtained colored film was measured again. Degree (L 1 , a 1 , b 1 ).
又,著色膜之色度係使用Olympus(股)公司製「顯微分光測定裝置OSP-SP200」進行測定。 In addition, the chromaticity of the colored film was measured using the "microscopic spectroscopic measuring device OSP-SP200" manufactured by Olympus Co., Ltd.
藉下式,評價後烘烤前後之著色膜的色度變化。將結果示於表2。 The chromaticity change of the color film before and after baking was evaluated by the following formula. The results are shown in Table 2.
△Eab={(L1-L0)2+(a1-a0)2+(b1-b0)2}1/2 △Eab={(L 1 -L 0 ) 2 +(a 1 -a 0 ) 2 +(b 1 -b 0 ) 2 } 1/2
將△Eab為3以下者設為A,將△Eab超過3且5以下者設為B,將△Eab超過5且6以下者設為C,將△Eab超過6者設為D。若△Eab為5以下,則耐熱性優越,評價為實用範圍。 When ΔEab is 3 or less, A is set, ΔEab is more than 3 and 5 or less is B, ΔEab is more than 5 and 6 or less is C, and ΔEab is more than 6 is D. When ΔEab is 5 or less, heat resistance is excellent, and it is evaluated as a practical range.
將實施例、及比較例中黏度穩定性評價為B之比較例之著色樹脂組成物分別使用旋塗器塗佈於厚0.7mm之玻璃基板(NH TECHNO GLASS(股)製,「NA35」)上。膜厚調整為2.5μm。其後,於80℃加熱板上進行加熱乾燥3分鐘後,經由光罩圖案而使用超高壓水銀燈照射60mJ/cm2之紫外線。其後,對形成了著色層之玻璃板,使用0.05質量%氫氧化鉀水溶液作為鹼顯影液進行淋浴顯影,測定光罩圖案完全出現為止的時間。將結果示於表2。 The colored resin compositions of the comparative examples in which the viscosity stability was evaluated as B in the examples and the comparative examples were each applied to a glass substrate (manufactured by NH TECHNO GLASS, "NA35") having a thickness of 0.7 mm using a spin coater. . The film thickness was adjusted to 2.5 μm. Thereafter, the film was dried by heating on a hot plate at 80 ° C for 3 minutes, and then irradiated with ultraviolet rays of 60 mJ/cm 2 through a mask pattern using an ultrahigh pressure mercury lamp. Thereafter, the glass plate on which the colored layer was formed was subjected to shower development using a 0.05 mass% potassium hydroxide aqueous solution as an alkali developing solution, and the time until the mask pattern was completely formed was measured. The results are shown in Table 2.
僅準備所評價之著色樹脂組成物之數量的玻璃棒,將前端分別浸漬於實施例、及比較例中黏度穩定性評價為B之比較例之著色樹脂組成物中3cm左右而使其附著,於溫度23℃、濕度70%之環境下乾燥30分鐘。其後,將附著了著色樹脂組成物之玻璃棒之前端浸漬於PGMEA中,攪拌15秒。將攪拌後1分鐘內附著於玻璃棒之著色樹脂組成物全部溶解者設為A,未全部溶解而殘存剝離片者設為B。將結果示於表2。 Only the glass rods in which the number of the colored resin compositions evaluated were prepared were immersed in the colored resin composition of the comparative example in which the viscosity stability was evaluated as B in the examples and the comparative examples, and were adhered to each other. It was dried for 30 minutes in an environment of a temperature of 23 ° C and a humidity of 70%. Thereafter, the front end of the glass rod to which the colored resin composition was attached was immersed in PGMEA and stirred for 15 seconds. When the colored resin composition adhering to the glass rod within 1 minute after the stirring was all dissolved, it was set to A, and if it was not completely dissolved, the peeling sheet remained as B. The results are shown in Table 2.
可知,具有一般式(I)所示之色材、分散劑、有機酸化合物,且分散劑與有機酸化合物滿足上述式(1)~式(3)的實施例1~19的色材分散液,即使在保管1個月後黏度變化仍為10%以內,分散穩定性優越。 It is understood that the color material dispersion liquid of Examples 1 to 19 having the general formula (I), the dispersant, and the organic acid compound, and the dispersant and the organic acid compound satisfy the above formulas (1) to (3) Even after the storage for 1 month, the viscosity change is still within 10%, and the dispersion stability is excellent.
又,可知,使用該實施例1~19之色材分散液所調製的實施例20~42的著色樹脂組成物,係分散穩定性優越,可形成耐熱性提升的塗膜。 Moreover, it is understood that the colored resin compositions of Examples 20 to 42 prepared by using the color material dispersion liquids of Examples 1 to 19 are excellent in dispersion stability, and can form a coating film having improved heat resistance.
又,可知,X為0.9以上之實施例21、22、25~28、30、32~34、36及38之著色樹脂組成物;使用了酸價高之鹼可溶性樹脂的實施例39及40;以及使用了具羧基之多官能單體的實施例41的著色樹脂組成物,具有特別優越的耐熱性。 Further, it is understood that X is a colored resin composition of Examples 21, 22, 25-28, 30, 32-34, 36, and 38 of 0.9 or more; Examples 39 and 40 using an alkali-soluble resin having a high acid value; Further, the colored resin composition of Example 41 using a polyfunctional monomer having a carboxyl group has particularly excellent heat resistance.
參照圖5說明實施例及比較例之結果。圖5為表示實施例1~22及比較例1~15之色材分散液的A與X之關係的X-A平面圖。又,圖5中,表示A×X=40、A×(1-X)=42、A=160、A=70、X=1.5的圖表。圖5中,將滿足A×X≧40、A×(1-X)≦42、A≦160、A≧70、X≦1.5的區域設為區域I;將滿足A×X≧40、A×(1-X)>42及A≦160的區域設為區域II;將滿足A×X<40、A×(1-X)≦42及A≧70的區域設為區域III;將滿足A×X<40、A×(1-X)>42、A≦160、A≧70的區域設為區域IV。 The results of the examples and comparative examples will be described with reference to Fig. 5 . Fig. 5 is a plan view showing the relationship between A and X of the color material dispersion liquids of Examples 1 to 22 and Comparative Examples 1 to 15. Further, in Fig. 5, graphs showing A × X = 40, A × (1-X) = 42, A = 160, A = 70, and X = 1.5 are shown. In Fig. 5, a region satisfying A × X ≧ 40, A × (1-X) ≦ 42, A ≦ 160, A ≧ 70, and X ≦ 1.5 is referred to as region I; A × X ≧ 40, A × will be satisfied. The area of (1-X)>42 and A≦160 is set to area II; the area satisfying A×X<40, A×(1-X)≦42 and A≧70 is set as area III; A region where X<40, A×(1-X)>42, A≦160, and A≧70 is set as the region IV.
區域I中,包括實施例1~實施例19之色材分散液。區域II中包括比較例3、5、7、8、10、12及13之色材分散液。區域III中包括比較例1之色材分散液。又,區域IV中包括比較例2、4、6、 9及11之色材分散液。 In the region I, the color material dispersion liquids of Examples 1 to 19 were included. The color material dispersion of Comparative Examples 3, 5, 7, 8, 10, 12 and 13 was included in the area II. The color material dispersion of Comparative Example 1 was included in the region III. Also, Region IV includes Comparative Examples 2, 4, and 6. 9 and 11 color material dispersion.
如上表1之結果所示,區域I及II所包括之實施例及比較例的色材分散液,係分散穩定性優越。尤其是由實施例1、比較例3、5、7、10及12的色材分散液、與比較例1、2、4、6、9及11的色材分散液的比較可知,在A×X=40成為境界線、滿足A×X≧40(式2)的情況,色材分散液的分散穩定性優越。 As shown in the results of the above Table 1, the color material dispersion liquids of the examples and the comparative examples included in the regions I and II were excellent in dispersion stability. In particular, comparison of the color material dispersion liquids of Examples 1, Comparative Examples 3, 5, 7, 10, and 12 with the color material dispersion liquids of Comparative Examples 1, 2, 4, 6, 9, and 11 shows that at A × When X=40 is a boundary line and A×X≧40 (Formula 2) is satisfied, the dispersion stability of the color material dispersion liquid is excellent.
另一方面,如表2之結果所示,可知,使用含有於區域I及III所包括之色材分散液的實施例20~42及比較例18的著色樹脂組成物所形成的著色膜,係耐熱性評價為A或B,耐熱性優越。尤其是由使用了在A×(1-X)=42上之點的實施例4、10、12、16及18的實施例23、29、31、35及37的結果可知,在A×(1-X)=42成為境界線、滿足A×(1-X)≦42(式3)的情況,著色膜之耐熱性優越。 On the other hand, as shown in the results of Table 2, it was found that the coloring film formed of the colored resin compositions of Examples 20 to 42 and Comparative Example 18 contained in the color material dispersion liquids included in the regions I and III was used. The heat resistance was evaluated as A or B, and the heat resistance was excellent. In particular, from the results of Examples 23, 29, 31, 35 and 37 of Examples 4, 10, 12, 16 and 18 using the point at A × (1-X) = 42, it is known that at A × ( 1-X)=42 is a boundary line and satisfies A×(1-X)≦42 (Formula 3), and the heat resistance of the colored film is excellent.
於實施例1~19中,除了取代PPA而分別使用等莫耳量之對甲苯磺酸一水合物(東京化成工業股份有限公司製)以外,其餘與實施例1~19同樣的方式進行,得到實施例43~61之色材分散液(依序為K-1~K-3、L-1~L-6、M-1~M-2、N-1~N-4、O-1~O-2、P-1~P-2)。 In the same manner as in Examples 1 to 19, except that the molar amount of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of PPA, each of Examples 1 to 19 was obtained. The color material dispersions of Examples 43 to 61 (in the order of K-1~K-3, L-1~L-6, M-1~M-2, N-1~N-4, O-1~) O-2, P-1~P-2).
於比較例1~13中,除了取代PPA而使用分別等莫耳量之對甲苯磺酸一水合物(東京化成工業股份有限公司製)以外,其餘與比較例1~13同樣的方式進行,得到比較例35~47之色材分散液(依序為K-4、L-7~L-8、M-3~M-4、N-5~N-7、O-3~O-4、P-3~P-4)。 In Comparative Examples 1 to 13, except that each of the molar amounts of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of PPA, the same procedure as in Comparative Examples 1 to 13 was carried out. The color material dispersions of Comparative Examples 35 to 47 (in the order of K-4, L-7~L-8, M-3~M-4, N-5~N-7, O-3~O-4, P-3~P-4).
對實施例43~61及比較例35~47的色材分散液,依與上述色材分散液之分散穩定性評價相同的方法,評價色材分散液之分散穩定性。將結果示於表3。 With respect to the color material dispersion liquids of Examples 43 to 61 and Comparative Examples 35 to 47, the dispersion stability of the color material dispersion liquid was evaluated in the same manner as the dispersion stability evaluation of the above color material dispersion liquid. The results are shown in Table 3.
於實施例20中,除了將色材分散液及感光性黏結劑成分變更為下表4之組合以外,其餘與實施例20同樣的方式進行,得到實施例62~80之著色樹脂組成物。 In the same manner as in Example 20 except that the color material dispersion liquid and the photosensitive binder component were changed to the combination of the following Table 4, the colored resin compositions of Examples 62 to 80 were obtained.
於實施例20中,除了將色材分散液及感光性黏結劑成分變更為下表4之組合以外,其餘與實施例20同樣的方式進行,得到比較例48~60之著色樹脂組成物。 In the same manner as in Example 20 except that the color material dispersion liquid and the photosensitive binder component were changed to the combination of the following Table 4, the colored resin compositions of Comparative Examples 48 to 60 were obtained.
對實施例62~80及比較例48~60的著色樹脂組成物,分別依與上述著色樹脂組成物之黏度穩定性評價、耐熱性評價、顯影時間之評價、及溶劑再溶解性之評價相同的方法,進行評價。將結果示於表4。 The colored resin compositions of Examples 62 to 80 and Comparative Examples 48 to 60 were the same as the evaluation of the viscosity stability, the evaluation of the heat resistance, the evaluation of the development time, and the evaluation of the solvent resolubility of the colored resin composition, respectively. Method, evaluation. The results are shown in Table 4.
可知,具有一般式(I)所示之色材、分散劑、有機酸化合物,且分散劑與有機酸化合物滿足上述式(1)~式(3)的實施例43~61的色材分散液,即使在保管1個月後黏度變化仍為10%以內,分散穩定性優越。 It is understood that the color material dispersion liquid of the examples 43 to 61 of the above formulas (1) to (3) is obtained by the color material, the dispersant, and the organic acid compound represented by the general formula (I), and the dispersant and the organic acid compound satisfy the above formulas (1) to (3). Even after the storage for 1 month, the viscosity change is still within 10%, and the dispersion stability is excellent.
又,可知,使用該實施例43~61之色材分散液所調製的實施例62~80的著色樹脂組成物,係分散穩定性優越,可形成耐熱性提升的塗膜。 Further, it was found that the colored resin compositions of Examples 62 to 80 prepared by using the color material dispersion liquids of Examples 43 to 61 were excellent in dispersion stability and formed a coating film having improved heat resistance.
由表2與表4之比較,使用了屬於2價有機酸化合物之苯膦酸的實施例20~42、及比較例18~30之著色樹脂組成物;與除了使用了1價有機酸化合物之對甲苯磺酸以外、其餘分別對應於上述著色樹脂組成物的實施例62~80、及比較例48~60的著色樹脂組成物,係著色樹脂組成物之黏度穩定性評價、耐熱性評價、顯影時間之評價、及溶劑再溶解性之評價均得到與相對應之著色樹脂組成物同樣的結果。由此可知,不論有機酸化合物之價數,式(1)~式(3)仍成立。其結果可推測,嵌段共聚合體所具有一般(II)所示之構成單位(a)、及有機酸化合物係不論有機酸化合物之價數而均依1對1進行鹽形成所致。 From the comparison of Table 2 and Table 4, the colored resin compositions of Examples 20 to 42 and Comparative Examples 18 to 30 which are phenylphosphonic acids belonging to the divalent organic acid compound were used; and in addition to the use of the monovalent organic acid compound The colored resin compositions of Examples 62 to 80 and Comparative Examples 48 to 60, which correspond to the above-mentioned colored resin composition, other than p-toluenesulfonic acid, were evaluated for viscosity stability, heat resistance evaluation, and development of the colored resin composition. Both the evaluation of the time and the evaluation of the solvent resolubility gave the same results as the corresponding colored resin composition. From this, it is understood that the formula (1) to the formula (3) are satisfied regardless of the valence of the organic acid compound. As a result, it is presumed that the block copolymer has a constituent unit (a) represented by the general formula (II) and an organic acid compound which is formed by salt formation in a one-to-one manner regardless of the valence of the organic acid compound.
於合成例4中,除了變更為甲基丙烯酸甲酯36.5g、甲基丙烯酸二甲基胺基乙酯13.5g以外,其餘與合成例4同樣的方式進行,得到嵌段共聚合體IX。重量平均分子量Mw為7,600,胺價為 95mgKOH/g。 In the same manner as in Synthesis Example 4 except that 36.5 g of methyl methacrylate and 13.5 g of dimethylaminoethyl methacrylate were changed, the block copolymer IX was obtained. The weight average molecular weight Mw is 7,600, and the amine price is 95 mg KOH / g.
於具備冷卻管、添加用漏斗、氮氣用進氣口、機械攪拌機、數位溫度計之500mL圓底四口分離燒瓶中加入THF250質量份、氯化鋰0.6質量份,充分進行氮置換。將反應燒瓶冷卻至-60℃後,使用注射筒注入丁基鋰4.9質量份(15質量%己烷溶液)、二異丙胺1.1質量份、異丁酸甲酯1.0質量份。將B嵌段用單體之甲基丙烯酸1-乙氧基乙酯(EEMA)2.2質量份、甲基丙烯酸2-(三甲基矽氧基)乙酯(TMSMA)29.1質量份、甲基丙烯酸2-乙基己酯(EHMA)12.8質量份、甲基丙烯酸正丁酯(BMA)13.7質量份、甲基丙烯酸苄酯(BzMA)9.5質量份、甲基丙烯酸甲酯(MMA)17.5質量份,使用添加用漏斗歷時60分鐘滴下。30分鐘後,將A嵌段用單體之甲基丙烯酸二甲基胺基乙酯(DMMA)26.7質量份歷時20分鐘滴下。反應30分鐘後,加入甲醇1.5質量份使反應停止。所得之前驅物嵌段共聚合體THF溶液係於己烷中進行再沉澱,藉過濾、真空乾燥進行精製,以PGMEA稀釋作成固形份30質量%溶液。加入水32.5質量份,升溫為100℃反應7小時,將來自EEMA之構成單位進行脫保護而作成來自甲基丙烯酸(MAA)的構成單位,將來自TMSMA之構成單位進行脫保護而作成來自甲基丙烯酸2-羥乙酯(HEMA)的構成單位。使所得之嵌段共聚合體PGMEA溶液於己烷中再沉澱,藉過濾、真空乾燥進行精製,得到嵌段共聚合體X(酸價8mgKOH/g,Tg38℃)。以GPC(凝膠滲透層析法)確認如此所得之嵌段共聚合體X,結果重量平均分子量Mw為7730。又胺價為95mgKOH/g。 To a 500 mL round bottom four-neck separation flask equipped with a cooling tube, an addition funnel, a nitrogen gas inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added, and nitrogen substitution was sufficiently performed. After cooling the reaction flask to -60 ° C, 4.9 parts by mass of butyllithium (15 mass% hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA) of the B block, 29.1 parts by mass of 2-(trimethyldecyloxy)ethyl methacrylate (TMSMA), methacrylic acid 12.8 parts by mass of 2-ethylhexyl ester (EHMA), 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA). Use the addition funnel to drip for 60 minutes. After 30 minutes, the A block was dropped with 26.7 parts by mass of a monomeric dimethylaminoethyl methacrylate (DMMA) over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to prepare a 30% by mass solid solution. 32.5 parts by mass of water was added, and the temperature was raised to 100 ° C for 7 hours. The constituent unit derived from EEMA was deprotected to form a constituent unit derived from methacrylic acid (MAA), and the constituent unit derived from TMSMA was deprotected to prepare a methyl group. The constituent unit of 2-hydroxyethyl acrylate (HEMA). The obtained block copolymer PGMEA solution was reprecipitated in hexane, and purified by filtration and vacuum drying to obtain a block copolymer X (acid value: 8 mg KOH / g, Tg 38 ° C). The block copolymer X thus obtained was confirmed by GPC (gel permeation chromatography), and the weight average molecular weight Mw was 7730. The amine value was also 95 mgKOH/g.
於合成例11中,除了依單體比率成為表5所示之方式變更填裝比率以外,其餘與合成例11同樣的方式進行,得到嵌段共聚合體XI~XIV。 In the synthesis example 11, the block copolymers XI to XIV were obtained in the same manner as in the synthesis example 11 except that the monomer ratio was changed as shown in Table 5.
表中之簡稱係如以下。 The abbreviations in the table are as follows.
PME-200:甲氧基聚乙二醇單甲基丙烯酸酯(商品名:PME-200,日油股份有限公司製,BLEMMER-PME-200,伸乙氧基重複數=4) PME-200: methoxypolyethylene glycol monomethacrylate (trade name: PME-200, manufactured by Nippon Oil Co., Ltd., BLEMMER-PME-200, ethoxylated repeat number = 4)
對製造例1所得之鹼可溶性樹脂A溶液(固形份40質量%)36.9質量份,添加作為多官能單體之二季戊四醇六丙烯酸酯(DPHA)(ARONIX M402(東亞合成製))22.1質量份、作為起始劑之IRGACURE 907(BASF製)1.8質量份、KAYACURE-DETX-S(日本化藥製)0.6質量份、抗氧化劑IRGANOX 1010(BASF製)0.8質量份、PGMEA37.9質量份,得到感光性黏結劑成分CR-6。 36.9 parts by mass of dibasic pentaerythritol hexaacrylate (DPHA) (ARONIX M402 (manufactured by Toagosei Co., Ltd.)), which is a polyfunctional monomer, was added to 36.9 parts by mass of the alkali-soluble resin A solution (solid content: 40% by mass) obtained in Production Example 1, 1.8 parts by mass of IRGACURE 907 (manufactured by BASF), 0.6 parts by mass of KAYACURE-DETX-S (manufactured by Nippon Kasei Co., Ltd.), 0.8 parts by mass of antioxidant IRGANOX 1010 (manufactured by BASF), and 37.9 parts by mass of PGMEA were obtained as a starter. The adhesive component CR-6.
於調製例6中,除了將起始劑之種類及調配量變更為表8之實施例96~101之欄記載的組合以外,其餘與調製例6同樣的方式進行,得到感光性黏結劑成分CR-7~12。 In the same manner as in Preparation Example 6, except that the type of the initiator and the amount of the preparation were changed to the combinations described in the columns of Examples 96 to 101 of Table 8, the photosensitive adhesive component CR was obtained. -7~12.
又,表8中之起始劑之簡稱係如以下。 Further, the abbreviations of the initiators in Table 8 are as follows.
IRG907:IRGACURE 907(BASF製) IRG907: IRGACURE 907 (made by BASF)
DETX:KAYACURE-DETX-S(日本化藥製) DETX: KAYACURE-DETX-S (made by Nippon Kasei Co., Ltd.)
OXE01:IRGACURE OXE01(BASF製) OXE01: IRGACURE OXE01 (made by BASF)
OXE02:IRGACURE OXE02(BASF製) OXE02: IRGACURE OXE02 (manufactured by BASF)
NCI930:ADEKA ARKLS NCI-930(ADEKA製,肟酯系光起始劑) NCI930: ADEKA ARKLS NCI-930 (made by ADEKA, oxime-based photoinitiator)
PBG304:TR-PBG-304(常州強力電子新材料公司製,肟酯系光起始劑) PBG304: TR-PBG-304 (made by Changzhou Power Electronic New Material Co., Ltd., oxime ester photoinitiator)
除了取代鹼可溶性樹脂A溶液(固形份40質量%),變更為鹼可溶性樹脂F溶液(含有cardo構造之具羧基之環氧基(甲基)丙烯酸酯樹脂,型號INR-16M Nagase ChemteX(股)製,固形份54.5%),並依固形份成為相同質量份的方式調整使用量以外,其餘與調製例6~12同樣的方式進行,得到感光性黏結劑成分CR-13~19。 In addition to replacing the alkali-soluble resin A solution (solid content 40% by mass), it was changed to an alkali-soluble resin F solution (carboxy-containing epoxy (meth) acrylate resin containing cardo structure, model number INR-16M Nagase ChemteX (share) In the same manner as in Preparation Examples 6 to 12, the photosensitive adhesive components CR-13 to 19 were obtained, except that the amount of the solid content was adjusted to 54.5%.
除了取代鹼可溶性樹脂A溶液(固形份40質量%),變更為鹼可溶性樹脂G溶液(具有茀骨架之丙烯酸環氧酯的酸酐聚縮合物的丙二醇單甲基醚醋酸酯溶液,商品名V259ME,新日鐵住金化學(股)製,固形份55.8質量%),並依固形份成為相同質量份的方式調整使用量以外,其餘與調製例6~12同樣的方式進行,得到感光性黏結劑成分CR-20~26。 In place of the alkali-soluble resin A solution (solid content: 40% by mass), the solution was changed to an alkali-soluble resin G solution (a propylene glycol monomethyl ether acetate solution having an anhydride polycondensate of an epoxy acrylate having an anthracene skeleton, trade name V259ME, In the same manner as in the preparation examples 6 to 12, a photosensitive adhesive component was obtained, except that the amount of the solid portion was adjusted to be the same by the amount of the solid portion, which was 55.8 mass%). CR-20~26.
對鹼可溶性樹脂G溶液(固形份55.8質量%)26.4質量份,添加作為多官能單體之季戊四醇四丙烯酸酯(PETA)(ARONIX M305(東亞合成製))22.1質量份、作為起始劑之IRGACURE OXE01(BASF製)1.2質量份、IRGACURE OXE02(BASF藥製)1.2質量份、抗氧化劑IRGANOX 1010(BASF製)0.8質量份、PGMEA37.9質量份,得 到感光性黏結劑成分CR-27。 To 26.4 parts by mass of the alkali-soluble resin G solution (solid content: 55.8 mass%), 22.1 parts by mass of pentaerythritol tetraacrylate (PETA) (ARONIX M305 (manufactured by Toagosei Co., Ltd.)) as a polyfunctional monomer was added, and IRGACURE as a starter was added. 1.2 parts by mass of OXE01 (manufactured by BASF), 1.2 parts by mass of IRGACURE OXE02 (manufactured by BASF Pharmaceutical Co., Ltd.), 0.8 parts by mass of antioxidant IRGANOX 1010 (manufactured by BASF), and 37.9 parts by mass of PGMEA. To the photosensitive adhesive component CR-27.
對鹼可溶性樹脂G溶液(固形份55.8質量%)26.4質量份,添加作為多官能單體之多元酸改質丙烯酸寡聚物(ARONIX M520(東亞合成製))22.1質量份、作為起始劑之IRGACURE OXE01(BASF製)1.2質量份、IRGACURE OXE02(BASF製)1.2質量份、抗氧化劑IRGANOX 1010(BASF製)0.8質量份、PGMEA37.9質量份,得到感光性黏結劑成分CR-28。 To 26.4 parts by mass of the alkali-soluble resin G solution (solid content: 55.8 mass%), 22.1 parts by mass of a polybasic acid-modified acrylic oligomer (ARONIX M520 (manufactured by Toagosei Co., Ltd.)) as a polyfunctional monomer was added as a starter. 1.2 parts by mass of IRGACURE OXE01 (manufactured by BASF), 1.2 parts by mass of IRGACURE OXE02 (manufactured by BASF), 0.8 parts by mass of an antioxidant IRGANOX 1010 (manufactured by BASF), and 37.9 parts by mass of PGMEA, a photosensitive binder component CR-28 was obtained.
於225mL美乃滋瓶中,加入PGMEA63.3質量份、鹼可溶性樹脂E溶液(固形份40質量%)13.0質量份、合成例10之嵌段共聚合體IX溶液(胺價95mgKOH/g,固形份45質量%)10.0質量份並攪拌。於其中加入苯膦酸(商品名:PPA,日產化學公司製)0.72質量份(相對於嵌段共聚合體之3級胺基為0.6莫耳當量),於室溫攪拌30分鐘。 63.3 parts by mass of PGMEA, 13.0 parts by mass of an alkali-soluble resin E solution (solid content: 40% by mass), and a block copolymer IX solution of Synthesis Example 10 (amine price 95 mgKOH/g, solid content 45) were added to a 225 mL mayon bottle. Mass%) 10.0 parts by mass and stirred. To this was added 0.72 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) (0.6 molar equivalent to the tertiary amine group of the block copolymer), and the mixture was stirred at room temperature for 30 minutes.
裝入合成例3之色材A 13.0質量份、粒徑2.0mm氧化鋯珠100質量份,藉塗料振盪器(淺田鐵工公司製)振盪1小時作為預備解碎,接著變更為粒徑0.1mm氧化鋯珠200份藉塗料振盪器進行4小時分散作為正式解碎,得到色材分散液Q。 1 part by mass of the color material A of the synthesis example 3 and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were shaken by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as a preliminary pulverization, and then changed to a particle diameter of 0.1 mm. 200 parts of zirconia beads were dispersed by a coating shaker for 4 hours to form a solid dispersion, and a color material dispersion liquid Q was obtained.
於實施例81中,除了取代嵌段共聚合體IX溶液,分別變更為 合成例11~15之嵌段共聚合體X~XIV溶液以外,其餘與實施例81同樣的方式進行,得到實施例82~87之色材分散液R~W。 In Example 81, except for the substituted block copolymer IX solution, it was changed to The coloring material dispersions R to W of Examples 82 to 87 were obtained in the same manner as in Example 81 except for the block copolymer X to XIV solutions of Synthesis Examples 11 to 15.
對於實施例81~87之色材分散液,依與上述色材分散液之分散穩定性評價同樣的方法,評價色材分散液之分散穩定性。將結果示於表6。 With respect to the color material dispersion liquids of Examples 81 to 87, the dispersion stability of the color material dispersion liquid was evaluated in the same manner as the dispersion stability evaluation of the above color material dispersion liquid. The results are shown in Table 6.
混合實施例81之色材分散液Q 27.4質量份、調製例1之感光性黏結劑成分CR-1 23.5質量份、季戊四醇肆(3-巰基丁酸酯)(PTMP;昭和電工公司製「Karenz MT(商標)PE1」)0.47質量份、界面活性劑MEGAFAC R08MH(DIC製)0.01質量份、PGMEA48.6質量份,得到實施例88之著色樹脂組成物。 27.4 parts by mass of the color material dispersion liquid of Example 81, 23.5 parts by mass of the photosensitive adhesive component CR-1 of Preparation Example 1, and pentacene tetradecanoate (3-mercaptobutyrate) (PTMP; "Karenz MT" by Showa Denko Co., Ltd. (Trademark) PE1") 0.47 parts by mass, surfactant MEGAFAC R08MH (manufactured by DIC) 0.01 parts by mass, and PGMEA 48.6 parts by mass, the colored resin composition of Example 88 was obtained.
於實施例88中,除了取代色材分散液Q,分別變更為色材分散液R~W以外,其餘與實施例88同樣的方式進行,得到實施例89~94之著色樹脂組成物。 In the same manner as in Example 88 except that the color material dispersion liquid Q was changed to the color material dispersion liquid R to W, the colored resin compositions of Examples 89 to 94 were obtained.
對實施例88~94的著色樹脂組成物,分別依與上述著色樹脂組成物之黏度穩定性評價、耐熱性評價、顯影時間之評價、及溶劑再溶解性之評價相同的方法,進行評價。將結果示於表7。 The colored resin compositions of Examples 88 to 94 were evaluated in the same manner as the evaluation of the viscosity stability of the colored resin composition, the evaluation of heat resistance, the evaluation of development time, and the evaluation of solvent resolubility. The results are shown in Table 7.
於實施例88中,除了取代感光性黏結劑成分CR-1,分別變更為感光性黏結劑成分CR-6~28以外,其餘與實施例88同樣的方式進行,得到實施例95~117之著色樹脂組成物。 In Example 88, the coloring of Examples 95 to 117 was carried out in the same manner as in Example 88 except that the photosensitive adhesive component CR-1 was replaced with the photosensitive adhesive component CR-6 to 28, respectively. Resin composition.
混合實施例82之色材分散液R 27.4質量份、調製例6之感光性黏結劑成分CR-6 23.5質量份、季戊四醇肆(3-巰基丁酸酯)(PTMP;昭和電工公司製「Karenz MT(商標)PE1」)0.47質量份、界面活性劑MEGAFAC R08MH(DIC製)0.01質量份、PGMEA48.6質量份,得到實施例118之著色樹脂組成物。 27.4 parts by mass of the color material dispersion R of Example 82, 23.5 parts by mass of the photosensitive adhesive component CR-6 of Preparation Example 6, and quinone tetradecanoate (3-mercaptobutyrate) (PTMP; "Karenz MT, manufactured by Showa Denko" (Trademark) PE1") 0.47 parts by mass, surfactant MEGAFAC R08MH (manufactured by DIC) 0.01 parts by mass, and PGMEA 48.6 parts by mass, the colored resin composition of Example 118 was obtained.
於實施例118中,除了取代感光性黏結劑成分CR-6,分別變更為感光性黏結劑成分CR-7~26以外,其餘與實施例118同樣的方式進行,得到實施例119~140之著色樹脂組成物。 In the same manner as in Example 118 except that the photosensitive adhesive component CR-6 was replaced by the photosensitive adhesive component CR-6, the coloring of Examples 119 to 140 was obtained. Resin composition.
於實施例118中,除了變更為表所示之色材分散液與感光性黏結劑成分以外,其餘與實施例118同樣的方式進行,得到實施例141~150之著色樹脂組成物。 In the same manner as in Example 118 except that the color material dispersion liquid and the photosensitive binder component shown in the table were changed, the colored resin compositions of Examples 141 to 150 were obtained.
將實施例之著色樹脂組成物分別使用旋塗器依後烘烤後之膜厚成為2.5μm左右的方式塗佈於厚0.7mm、100mm×100mm之玻璃基板(NH TECHNO GLASS(股)製,「NA35」)上。其後,於80℃加熱板上進行加熱乾燥3分鐘。未經由光罩而使用超高壓水銀燈照射40mJ/cm2之紫外線,以220℃之無塵爐進行後烘烤30分鐘,藉此得到硬化膜(藍色著色膜)。 The colored resin composition of the example was applied to a glass substrate having a thickness of 0.7 mm and 100 mm × 100 mm by a spin coater and a film thickness of about 2.5 μm after baking (NH TECHNO GLASS, Ltd., "NA35"). Thereafter, the film was dried by heating on a hot plate at 80 ° C for 3 minutes. The ultraviolet rays of 40 mJ/cm 2 were irradiated with an ultrahigh pressure mercury lamp without using a photomask, and post-baking was performed for 30 minutes in a dust-free furnace at 220 ° C to obtain a cured film (blue colored film).
測定所得硬化膜之膜厚並作為T1。其後,將此膜浸漬於25℃N-甲基吡咯啶酮中60分鐘,測定剛取出後之膜厚並作為T2。計算T2/T1×100(%),將未滿103%之情況設為AA,103%以上且未滿105%之情況設為A,105%以上且未滿110%之情況設為B,110%以上且未滿115%之情況設為C,115%以上之情況設為D。將結果示於表8~10。若上述評價基準為AA、A、B或C,則可供於實用,但若評價結果為B、進而A,則效果更加優越。 The film thickness of the obtained cured film was measured and referred to as T1. Thereafter, the film was immersed in 25° C-methylpyrrolidone for 60 minutes, and the film thickness immediately after the extraction was measured to obtain T2. Calculate T2/T1×100 (%), set the case of less than 103% to AA, 103% or more and less than 105%, and set it to A, 105% or more and less than 110%. When it is more than % and less than 115%, it is set to C, and 115% or more is set to D. The results are shown in Tables 8 to 10. If the above evaluation criteria are AA, A, B or C, it is practical, but if the evaluation result is B and further A, the effect is further superior.
將實施例之著色樹脂組成物分別使用旋塗器塗佈於厚0.7mm、100mm×100mm之玻璃基板(NH TECHNO GLASS(股)製,「NA35」)上後,使用加熱板於80℃進行乾燥3分鐘,藉此形成厚3.0μm之著色層。將上述形成了著色層之玻璃板,使用0.05質量%氫氧化鉀水溶液作為鹼顯影液進行淋浴顯影60秒。以目視觀察上述著色層形成後之玻璃基板的未曝光部(50mm×50mm)後,藉含有乙醇之透鏡清潔布(東麗公司製,商品名TORAYSEE MK清潔布)充分擦拭,以目視觀察其透鏡清潔布之著色程度。將結果示於表8~10。 Each of the colored resin compositions of the examples was applied onto a glass substrate (manufactured by NH TECHNO GLASS, "NA35") having a thickness of 0.7 mm and 100 mm × 100 mm by a spin coater, and then dried at 80 ° C using a hot plate. 3 minutes, thereby forming a coloring layer having a thickness of 3.0 μm. The glass plate on which the colored layer was formed was subjected to shower development using a 0.05% by mass aqueous potassium hydroxide solution as an alkali developing solution for 60 seconds. The unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer was visually observed, and then thoroughly wiped with a lens cleaning cloth (trade name: TORAYSEE MK cleaning cloth, manufactured by Toray Industries, Inc.) containing ethanol to visually observe the lens. The degree of coloring of the cleaning cloth. The results are shown in Tables 8 to 10.
A:以目視未確認到顯影殘渣,透鏡清潔布完全無著色。 A: The development residue was not visually confirmed, and the lens cleaning cloth was completely free from coloration.
B:以目視未確認到顯影殘渣,確認到透鏡清潔布之稍微著色。 B: The development residue was not visually observed, and it was confirmed that the lens cleaning cloth was slightly colored.
C:以目視確認到稍微之顯影殘渣,並確認到透鏡清潔布之著色。 C: A slight development residue was visually confirmed, and the color of the lens cleaning cloth was confirmed.
D:以目視確認到顯影殘渣,並確認到透鏡清潔布之著色。 D: The development residue was visually confirmed, and the color of the lens cleaning cloth was confirmed.
若為上述評價基準A、B或C,則可供於實用;但若評價結果為B、進而A,則效果更加優越。將結果示於表8~10。 If it is the above evaluation criteria A, B or C, it is practical, but if the evaluation result is B and further A, the effect is more excellent. The results are shown in Tables 8 to 10.
將實施例之著色樹脂組成物分別使用旋塗器塗佈於厚0.7mm、100mm×100mm之玻璃基板(NH TECHNO GLASS(股)製,「NA35」)上後,使用加熱板於80℃進行乾燥3分鐘,藉此形成厚3.0μm之著色層。其後,未經由光罩而使用超高壓水銀燈全面照射40mJ/cm2之紫外線。接著,以0.05wt%氫氧化鉀(KOH)作為顯影液進行旋轉顯影,使其與顯影液接液60秒後以純水洗淨而進行顯影處理,將洗淨後之基板旋轉10秒以離心去除水後,立刻如下述般測定純水之接觸角,評價水滲染。 Each of the colored resin compositions of the examples was applied onto a glass substrate (manufactured by NH TECHNO GLASS, "NA35") having a thickness of 0.7 mm and 100 mm × 100 mm by a spin coater, and then dried at 80 ° C using a hot plate. 3 minutes, thereby forming a coloring layer having a thickness of 3.0 μm. Thereafter, ultraviolet rays of 40 mJ/cm 2 were completely irradiated with an ultrahigh pressure mercury lamp without passing through a photomask. Next, the mixture was rotated and developed with 0.05 wt% of potassium hydroxide (KOH) as a developing solution, and the solution was liquid-contacted with the developing solution for 60 seconds, and then washed with pure water to carry out development treatment, and the washed substrate was rotated for 10 seconds to be centrifuged. Immediately after the water was removed, the contact angle of the pure water was measured as described below, and the water bleeding was evaluated.
純水之接觸角的測定,係對上述剛離心去除了水後的著色層表面,滴下純水1.0μL之液滴,依θ/2法計測著滴10秒後之靜態接觸角。測定裝置係使用協和界面科學公司製之接觸角計DM 500進行測定。將結果示於表8~10。 The contact angle of pure water was measured on the surface of the colored layer immediately after the water was removed by centrifugation, and a droplet of 1.0 μL of pure water was dropped, and the static contact angle after the dropping for 10 seconds was measured by the θ/2 method. The measurement apparatus was measured using a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Tables 8 to 10.
A:接觸角80度以上 A: The contact angle is 80 degrees or more
B:接觸角65度以上且未滿80度 B: The contact angle is 65 degrees or more and less than 80 degrees.
C:接觸角50度以上且未滿65度 C: contact angle of 50 degrees or more and less than 65 degrees
D:接觸角未滿50度 D: The contact angle is less than 50 degrees
若水滲染評價基準為A或B,則可供於實用;但若評價結果為A,則效果更加優越。 If the water infiltration evaluation standard is A or B, it is available for practical use; but if the evaluation result is A, the effect is more superior.
將實施例及比較例所得之彩色濾光片用感光性著色樹脂組成物分別使用旋塗器塗佈於厚0.7mm、100mm×100mm之玻璃基板(NH TECHNO GLASS(股)製,「NA35」)上後,使用加熱板於60℃進行乾燥3分鐘,藉此形成厚2.5μm之著色層。對此著色層經由具有2~80μm遮罩開口寬之光罩而使用超高壓水銀燈照射60mJ/cm2之紫外線。對上述形成了著色層之玻璃板,使用0.05質量%氫氧化鉀水溶液作為鹼顯影液進行淋浴顯影60秒。以光學顯微鏡觀察顯影後之基板,觀察有無相對於遮罩開口線寬的著色層。將結果示於表8~10。 Each of the photosensitive colored resin compositions obtained in the examples and the comparative examples was applied to a glass substrate having a thickness of 0.7 mm and 100 mm × 100 mm using a spin coater (NH TECHNO GLASS, "NA35"). After the above, drying was performed at 60 ° C for 3 minutes using a hot plate, thereby forming a coloring layer having a thickness of 2.5 μm. The colored layer was irradiated with ultraviolet rays of 60 mJ/cm 2 using an ultrahigh pressure mercury lamp through a mask having a mask opening width of 2 to 80 μm. The glass plate on which the colored layer was formed was subjected to shower development using a 0.05% by mass aqueous potassium hydroxide solution as an alkali developing solution for 60 seconds. The developed substrate was observed with an optical microscope to observe the presence or absence of a colored layer with respect to the opening line width of the mask. The results are shown in Tables 8 to 10.
A:於遮罩開口線寬未滿10μm之部分觀察到著色層。 A: A colored layer was observed in a portion of the mask opening line width of less than 10 μm.
B:於遮罩開口線寬10μm以上且未滿20μm之部分觀察到著色層。 B: A colored layer was observed in a portion of the mask opening line width of 10 μm or more and less than 20 μm.
C:於遮罩開口線寬20μm以上且未滿50μm之部分觀察到著色層。 C: A colored layer was observed in a portion of the mask opening line having a width of 20 μm or more and less than 50 μm.
D:於遮罩開口線寬50μm以上且未滿80μm之部分觀察到著色層。 D: A colored layer was observed in a portion of the mask opening line width of 50 μm or more and less than 80 μm.
E:於遮罩開口線寬80μm以下之部分未觀察到著色層。 E: No colored layer was observed in a portion of the mask opening line width of 80 μm or less.
若上述評價基準為A、B或C,則可供於實用;但若評價結果為B、進而A,則彩色濾光片用感光性著色樹脂組成物係適合於更高精細化。 When the evaluation criteria are A, B or C, it is practical. However, when the evaluation result is B and further A, the photosensitive colored resin composition for a color filter is suitable for higher definition.
可知,使用了酸價為1mgKOH/g以上且18mgKOH/g以下、玻璃轉移溫度為30℃以上之分散劑的著色樹脂組成物,顯影殘渣、基板密黏性、顯影密黏性特別優越。 It is understood that a colored resin composition having a dispersant having an acid value of 1 mgKOH/g or more and 18 mgKOH/g or less and a glass transition temperature of 30 ° C or more is used, and development residue, substrate adhesion, and development adhesion are particularly excellent.
可知,使用了一般式(B)所示之鹼可溶性樹脂的著色樹脂組成物,係更加抑制NMP所造成的膨潤、耐溶劑性優越。 It is understood that the colored resin composition using the alkali-soluble resin represented by the general formula (B) is more excellent in suppressing swelling and solvent resistance by NMP.
又,可知,使用了肟酯系起始劑之實施例係耐溶劑性(NMP膨潤抑制)優越,更加抑制水滲染的發生。 Moreover, it is understood that the examples using the oxime ester-based initiator are superior in solvent resistance (NMP swelling inhibition) and further suppress the occurrence of water bleeding.
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JP7059009B2 (en) * | 2016-03-31 | 2022-04-25 | 株式会社Dnpファインケミカル | Photosensitive colored resin composition, color filter and its manufacturing method, and display device |
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JP2018097128A (en) * | 2016-12-13 | 2018-06-21 | 東洋インキScホールディングス株式会社 | Color filter coloring composition and color filters |
CN110249263B (en) * | 2017-03-31 | 2023-12-08 | Dnp精细化工股份有限公司 | Photosensitive coloring resin composition, cured product thereof, color filter and display device |
TWI766941B (en) * | 2017-03-31 | 2022-06-11 | 南韓商東友精細化工有限公司 | Blue photosensitive resin composition and color filter and image display device manufactured using the same |
KR101928489B1 (en) * | 2017-05-02 | 2018-12-12 | 주식회사 엘지화학 | Coloring agent compound and coloring composition comprising the same |
JP7017867B2 (en) * | 2017-05-19 | 2022-02-09 | 東友ファインケム株式会社 | Color curable resin composition, color filter and display device |
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JP6555490B2 (en) * | 2017-10-24 | 2019-08-07 | 東洋インキScホールディングス株式会社 | Photosensitive composition for color filter and color filter |
CN110007560B (en) * | 2017-12-04 | 2022-03-15 | 东友精细化工有限公司 | Colored photosensitive resin composition, color filter and display device |
CN109976093B (en) * | 2017-12-04 | 2021-11-16 | 东友精细化工有限公司 | Colored photosensitive resin composition, color filter and display device |
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