TWI437284B - Color filter and method for manufacturing the same - Google Patents

Color filter and method for manufacturing the same Download PDF

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TWI437284B
TWI437284B TW097137025A TW97137025A TWI437284B TW I437284 B TWI437284 B TW I437284B TW 097137025 A TW097137025 A TW 097137025A TW 97137025 A TW97137025 A TW 97137025A TW I437284 B TWI437284 B TW I437284B
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pigment
group
acid
ring
polymer
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TW200928458A (en
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Mikio Nakagawa
Shigetomo Tsujihata
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Fujifilm Corp
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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
    • G03F7/0005—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Description

彩色濾光片及其製法Color filter and its preparation method

本發明係關於彩色濾光片及該彩色濾光片之製法，詳而言之，係關於對比優異之彩色濾光片及其製造方法。The present invention relates to a color filter and a method of producing the color filter, and more particularly to a color filter excellent in contrast and a method of manufacturing the same.

彩色濾光片係含有使有機顔料或無機顔料分散之顔料分散組成物、多官能單體、光聚合起始劑、鹼可溶性樹脂及其他成分做為著色感光性組成物，且可使用彼等藉由光刻法(photolithography method)等形成著色圖案而可製造。The color filter contains a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a photopolymerization initiator, an alkali-soluble resin, and other components as a coloring photosensitive composition, and can be used by them. It can be produced by forming a colored pattern by a photolithography method or the like.

近年來，彩色濾光片在液晶顯示裝置(Liquid Crystal Display：LCD)用途方面，不僅是螢幕而且在電視(television：TV)的用途上係有擴大的傾向，伴隨著該用途擴大的傾向，在色度、對比(contrast)等中會非常要求高度的顏色特性。特別是由於對比係對於顯示裝置中的畫質賦予重大的影響，而特別受到注目。In recent years, the use of a color filter in liquid crystal display (LCD) is not only a screen but also a tendency to expand in the use of television (television: TV), and it tends to expand as the use expands. High color characteristics are highly desirable in chromaticity, contrast, and the like. In particular, since the contrast system has a significant influence on the image quality in the display device, it is particularly noticed.

相對於上述的要求，係有在更微細的狀態分散顔料(良好的分散性)、在安定的狀態下進行分散(良好的分散安定性)的要求。分散性為不充分之情形中，係在所形成之著色光阻膜產生不規則邊紋(fringe：indentations at edge portions，在邊緣部分的鋸齒狀)或表面凹凸，會使得所製造之彩色濾光片的色度或尺寸精度下降，而會有所謂對比顯著變差的問題。In response to the above-mentioned requirements, there is a demand for dispersing a pigment in a finer state (good dispersibility) and dispersing in a stable state (good dispersion stability). In the case where the dispersibility is insufficient, the formed colored photoresist film is formed with irregular fringe (fringe: indentations at edge portions) or surface irregularities, which causes the color filter to be manufactured. The chromaticity or dimensional accuracy of the sheet is degraded, and there is a problem that the contrast is significantly deteriorated.

對比降低的要因係可舉例如由於組成物中因顔料粒子之背光(back light)所引起的散射，而在偏光板交叉配置時的漏光。為此，由於考慮到彩色濾光片的高對比化，所以著色組成物中的平均粒徑越小者為佳。The reason for the contrast reduction is, for example, light leakage at the time of cross-arrangement of the polarizing plates due to scattering due to back light of the pigment particles in the composition. For this reason, since the high contrast of the color filter is considered, the smaller the average particle diameter in the colored composition is, the better.

選擇顔料粒子以提昇對比之技術已揭示有使用平均粒徑為100~300nm顔料之方法(例如，參照特開2003-248115號)，或使用超音波衰減型粒度分布測定裝置測定平均粒徑，以選擇規定範圍的粒子、具體上係使用D84 為1.0μm以下、D50 為0.5μm以下、D16 為0.3μm以下、最大峰值為0.5μm以下之顔料粒子之方法(例如，參照特開2005-165307)等。然而，由於微細化顔料的粒徑時顔料粒子的表面積會變大，所以顔料粒子間的凝集力增強，而變得大多難以高度的水準兼具分散性與分散安定性，即使根據前述技術，現狀係實用上滿足水準的高對比化尚未被達成，進一步的高對比化係為所期望的。The technique of selecting pigment particles to enhance contrast has revealed a method of using a pigment having an average particle diameter of 100 to 300 nm (for example, refer to JP-A-2003-248115), or measuring an average particle diameter using an ultrasonic attenuation type particle size distribution analyzer. Specifically, a method of selecting a particle having a predetermined range, and using a pigment particle having a D 84 of 1.0 μm or less, a D 50 of 0.5 μm or less, a D 16 of 0.3 μm or less, and a maximum peak of 0.5 μm or less is used (for example, refer to the special opening 2005- 165307) and so on. However, since the surface area of the pigment particles is increased when the particle diameter of the pigment is refined, the cohesive force between the pigment particles is enhanced, and it is often difficult to achieve a high level of dispersibility and dispersion stability, even according to the aforementioned technique. A high contrast that is practically satisfactory has not been achieved, and further high contrast is desirable.

本發明係有鑑於前述以往技術的問題點中已完成者，而達成以下的目的。The present invention has been achieved in view of the above problems of the prior art.

亦即，本發明係提供能得到高對比之彩色濾光片、及這樣的彩色濾光片之製法。That is, the present invention provides a color filter capable of obtaining high contrast, and a method of producing such a color filter.

本發明人等專心一意檢討的結果，發現在所形成之著色圖案皮膜中，藉由將顔料2次粒子的占有率控制在規定之值以下，可解決前述課題，而完成本發明。As a result of intensive review, the present inventors have found that the above problem can be solved by controlling the occupancy rate of the pigment secondary particles to a predetermined value or less in the formed color pattern film, and the present invention has been completed.

亦即，前述解決課題之手段係如下所示。That is, the means for solving the above problems are as follows.

<1>一種彩色濾光片，其特徵係包含將含有平均粒徑為15~150nm的顔料之光硬化性組成物賦予至基板上所形成之著色圖案，且該著色圖案表面在AFM(Atomic Force Microscope：原子間力顯微鏡)的觀察結果所得之畫像中的2次粒子的占有率為40%以下。<1> A color filter comprising a colored pattern formed by imparting a photocurable composition containing a pigment having an average particle diameter of 15 to 150 nm to a substrate, and the surface of the colored pattern is at AFM (Atomic Force) In the image obtained by the observation of the Microscope: atomic force microscope, the occupancy rate of the secondary particles is 40% or less.

<2>如<1>中所記載之彩色濾光片，其中前述光硬化性組成物係含有有機溶媒、平均粒徑為15~150nm的顔料、含有來自下述通式(1)所示單體之共聚合單位的聚合物、光聚合性化合物、與光聚合起始劑。(2) The color filter according to the above aspect, wherein the photocurable composition contains an organic solvent, a pigment having an average particle diameter of 15 to 150 nm, and a single crystal derived from the following formula (1) A polymer of a copolymerization unit, a photopolymerizable compound, and a photopolymerization initiator.

[在通式(1)中，R1 表示氫原子、或取代或無取代的烷基。R2 表示伸烷基。W表示-CO-、-C(=O)O-、-CONH-、-OC(=O)-、或伸苯基。X表示-O-、-S-、-C(=O)O-、-CONH-、-C(=O)S-、-NHCONH-、-NHC(=O)O-、-NHC(=O)S-、-OC(=O)-、-OCONH-、或-NHCO-。Y表示-NR3 -、-O-、-S-、或-N=，且透過與其相鄰接之原子團而與N原子連結可形成環狀構造。R3 表示氫原子、烷基、或芳基。m及n係各自獨立地表示0或1]。[In the formula (1), R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group. R 2 represents an alkylene group. W represents -CO-, -C(=O)O-, -CONH-, -OC(=O)-, or a phenyl group. X represents -O-, -S-, -C(=O)O-, -CONH-, -C(=O)S-, -NHCONH-, -NHC(=O)O-, -NHC(=O ) S-, -OC(=O)-, -OCONH-, or -NHCO-. Y represents -NR 3 -, -O-, -S-, or -N=, and is bonded to the N atom through the atomic group adjacent thereto to form a ring structure. R 3 represents a hydrogen atom, an alkyl group, or an aryl group. The m and n systems each independently represent 0 or 1].

<3>如<2>中所記載之彩色濾光片，其中在前述通式(1)中，Y係透過相鄰接之原子團而與N原子連結所形成之環狀構造為縮合環構造。<3> The color filter according to <2>, wherein in the above formula (1), the ring structure in which Y is transmitted through the adjacent atomic group and is bonded to the N atom is a condensed ring structure.

<4>如<2>或<3>中所記載之彩色濾光片，其中前述聚合物係更含有來自末端具有乙烯性不飽和鍵的聚合性低聚物之共聚合單位的接枝共聚物。<4> The color filter according to <2> or <3> wherein the polymer further contains a graft copolymer of a copolymerizable unit derived from a polymerizable oligomer having an ethylenically unsaturated bond at the terminal. .

<5>如<2>~<4>項中任一項之彩色濾光片，其中前述聚合物係更含有來自具有酸基之單體的共聚合單位之聚合物。The color filter according to any one of <2> to <4> wherein the polymer further contains a polymer derived from a copolymerization unit of a monomer having an acid group.

<6>如<2>~<5>項中任一項之彩色濾光片，其中前述光硬化性組成物係更含有鹼可溶性樹脂。The color filter of any one of <2> to <5>, wherein the photocurable composition further contains an alkali-soluble resin.

<7>一種彩色濾光片之製法，其特徵係包含感光性膜形成步驟，其係藉由將含有有機溶媒、平均粒徑為15~150nm的顔料、含有來自下述通式(1)所示單體之共聚合單位的聚合物、光聚合性化合物、與光聚合起始劑之光硬化性組成物直接或透過其他之層賦予至基板上，以形成感光性膜之感光性膜形成步驟；著色圖案形成步驟，其係藉由對所形成之該感光性膜依序進行圖案曝光及顯像，以形成在原子間力顯微鏡的觀察結果所得之畫像中的2次粒子的占有率為40%以下之著色圖案的著色圖案形成步驟，<7> A method for producing a color filter, comprising the step of forming a photosensitive film by using a pigment containing an organic solvent having an average particle diameter of 15 to 150 nm and containing a formula (1) A photosensitive film forming step of forming a photopolymerizable unit polymer, a photopolymerizable compound, and a photocurable composition of a photopolymerization initiator directly or through another layer to form a photosensitive film a coloring pattern forming step of patterning exposure and development of the formed photosensitive film in order to form a quadratic particle occupation ratio of 40 in an image obtained by observation of an atomic force microscope a color pattern forming step of the color pattern below %,

[在通式(1)中，R1 表示氫原子、或取代或無取代的烷基。R2 表示伸烷基。W表示-CO-、-C(=O)O-、-CONH-、-OC(=O)-、或伸苯基。X表示-O-、-S-、-C(=O)O-、-CONH-、-C(=O)S-、-NHCONH-、-NHC(=O)O-、-NHC(=O)S-、-OC(=O)-、-OCONH-、或-NHCO-。Y表示-NR3 -、-O-、-S-、或-N=，且透過與其相鄰接之原子團而與N原子連結可形成環狀構造。R3 表示氫原子、烷基、或芳基。m及n係各自獨立地表示0或1]。[In the formula (1), R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group. R 2 represents an alkylene group. W represents -CO-, -C(=O)O-, -CONH-, -OC(=O)-, or a phenyl group. X represents -O-, -S-, -C(=O)O-, -CONH-, -C(=O)S-, -NHCONH-, -NHC(=O)O-, -NHC(=O ) S-, -OC(=O)-, -OCONH-, or -NHCO-. Y represents -NR 3 -, -O-, -S-, or -N=, and is bonded to the N atom through the atomic group adjacent thereto to form a ring structure. R 3 represents a hydrogen atom, an alkyl group, or an aryl group. The m and n systems each independently represent 0 or 1].

本發明的較佳態様之一，可舉例如在即使使用微細粒徑之顔料的情形中，藉由將使用具有高顔料分散性與分散安定性之顔料分散組成物的硬化性組成物使用於著色圖案的形成，能得到光透射性與對比優異之彩色濾光片的態様。In one of the preferred embodiments of the present invention, for example, in the case of using a pigment having a fine particle diameter, a curable composition using a pigment dispersion composition having high pigment dispersibility and dispersion stability is used for coloring. With the formation of the pattern, the state of the color filter excellent in light transmittance and contrast can be obtained.

根據本發明，可提供能得到高對比之彩色濾光片、及製造這樣的彩色濾光片之製法。According to the present invention, it is possible to provide a color filter capable of obtaining high contrast and a method of manufacturing such a color filter.

實施發明之最佳形態Best form for implementing the invention

以下，針對本發明的顔料分散組成物、光硬化性組成物、彩色濾光片及其製造方法加以詳細說明。Hereinafter, the pigment dispersion composition, the photocurable composition, the color filter, and the method for producing the same according to the present invention will be described in detail.

本發明的彩色濾光片係以具備塗布含有平均粒徑為15~150nm的顔料之光硬化性組成物所形成之著色圖案，且該著色圖案表面在AFM的觀察結果所得之畫像中的2次粒子的占有率為40%以下為其特徵。2次粒子的占有率需要為40%以下，較佳為25%以下，更佳為10%以下。The color filter of the present invention has a coloring pattern formed by applying a photocurable composition containing a pigment having an average particle diameter of 15 to 150 nm, and the surface of the colored pattern is twice in the image obtained by the observation of the AFM. The particle occupancy rate is 40% or less. The occupancy rate of the secondary particles needs to be 40% or less, preferably 25% or less, more preferably 10% or less.

此處，顔料的1次粒徑係可藉由電子顯微鏡(Hitachi High-Technologies Corporation(股)製S-4800)，以倍率10萬倍、n=100以上而進行測定的。Here, the primary particle diameter of the pigment can be measured by an electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation) at a magnification of 100,000 times and n=100 or more.

顔料的平均粒徑係能使用動態光散射型粒度分布測定裝置(日機裝(股)製Microtrack UPA-150)，並視需要以分散媒進行稀釋而可測定。The average particle diameter of the pigment can be measured by using a dynamic light scattering type particle size distribution measuring apparatus (Microtrack UPA-150, manufactured by Nikkiso Co., Ltd.), and if necessary, diluted with a dispersion medium.

在本發明中所謂2次粒子的占有率，係在AFM(原子間力顯微鏡)的膜表面之觀察畫像中施加除去雜訊、或微粒子等之處理後的畫像中，算出對於畫像全面之2次粒子的面積分率者，本發明係採用依照以下的方法所測定之值。In the present invention, the occupancy rate of the secondary particles is calculated by applying a treatment for removing noise or fine particles to the observation image on the surface of the film of the AFM (atomic force microscope), and calculating the total number of times for the portrait. In the case of the area fraction of particles, the present invention employs values measured in accordance with the following methods.

<顔料2次粒子的占有率><Occupation rate of pigment secondary particles>

所形成之著色圖案的膜表面係以AFM(Veeco Instruments製NanoScope IIIa,TappingMode)觀察，以得到表面的觀察畫像。The film surface of the formed color pattern was observed by AFM (NopeScope IIIa, Tapping Mode, manufactured by Veeco Instruments) to obtain an observed image of the surface.

此處，當評價使用特定的顔料分散組成物之著色圖案時，可將在0.7mm玻璃基板上以乾燥膜厚為2.0μm之條件進行塗布、乾燥所形成之皮膜(著色圖案)當作被檢體。Here, when the coloring pattern using a specific pigment dispersion composition is evaluated, a film (coloring pattern) formed by coating and drying on a 0.7 mm glass substrate under conditions of a dry film thickness of 2.0 μm can be regarded as a test. body.

接著，關於所得之像，使用美國國立衛生研究所製的畫像處理程式「Image J」並依照以下的順序進行畫像的處理，以求得畫像中的2次粒子的占有率。Then, the image processing program "Image J" manufactured by the National Institutes of Health of the United States was used to process the image in the following order to obtain the occupancy rate of the secondary particles in the image.

1.在灰階(gray scale)變換、電平(level)校正之後，消去畫像的雜訊(noise)與波紋，依照判別分析法而予以2值化。1. After the gray scale conversion and the level correction, the noise and the ripple of the image are erased, and the noise is binarized according to the discriminant analysis method.

2.藉由Watershed法分割相接的粒子。2. The adjacent particles are separated by the Watershed method.

3.萃取50nm以上的粒子並算出占有率。3. Extract particles of 50 nm or more and calculate the occupancy rate.

在該條件下測定2次粒子的占有率時，超過40%的占有率與例如占有率為42~45%的具有該著色圖案之彩色濾光片做對比的話，可確認在實用上難謂有充分的狀態。When the occupancy rate of the secondary particles is measured under these conditions, if the occupancy ratio of more than 40% is compared with, for example, a color filter having the coloring pattern of 42 to 45%, it is confirmed that it is practically difficult to Full state.

像這樣的條件、亦即在含有平均粒徑為15~150nm的顔料之著色圖案中，以上述條件所測定之畫像中的2次粒子的占有率為40%以下之手段，係可舉例如當形成著色圖案之際，使用能控制顔料凝集之硬化性組成物，並同時控制在皮膜形成時於塗膜中的乾燥凝集，具體的手段係可舉例如使用微細顔料的分散性及其安定性優異之光硬化性組成物以形成著色圖案之手段等。In such a condition, that is, in a coloring pattern containing a pigment having an average particle diameter of 15 to 150 nm, the ratio of the secondary particles in the image measured by the above conditions is 40% or less, for example, when When a colored pattern is formed, a curable composition capable of controlling the aggregation of the pigment is used, and at the same time, dry aggregation in the coating film at the time of film formation is controlled, and specific means are, for example, excellent dispersibility and stability of the fine pigment. The photocurable composition is a means for forming a colored pattern or the like.

以下，具體說明使用微細顔料的分散性及其安定性優異之光硬化性組成物以形成著色圖案之手段。Hereinafter, a means for forming a colored pattern using a photocurable composition excellent in dispersibility of a fine pigment and excellent stability can be specifically described.

<顔料分散組成物><Pigment Dispersion Composition>

本發明中，使微細的顔料為均勻地且不用擔心經過長時間所引起的凝集而可安定分散的手段之一，係採用將含有來自下述通式(1)所示單體之共聚合單位的聚合物做為顔料分散樹脂使用之方法。In the present invention, one of the means for allowing the fine pigment to be uniformly dispersed without fear of agglomeration caused by a long period of time is a copolymerization unit containing a monomer derived from the following formula (1). The polymer is used as a method of using a pigment dispersion resin.

[含有來自通式(1)所示單體之共聚合單位的聚合物]形成本發明的著色圖案之光硬化性組成物中，較佳係含有來自下述通式(1)所示單體之共聚合單位的聚合物。[Polymer containing a copolymerization unit derived from a monomer represented by the general formula (1)] The photocurable composition forming the colored pattern of the present invention preferably contains a monomer derived from the following general formula (1) The copolymerized unit of the polymer.

在本發明有關之光硬化性組成物中，特定聚合物係具有做為顔料分散劑之機能者。以下的說明中，「含有來自通式(1)所示單體之共聚合單位的聚合物」係有適宜稱為「特定顔料分散劑」而說明之情形。In the photocurable composition according to the present invention, the specific polymer has a function as a pigment dispersant. In the following description, the "polymer containing a copolymerization unit derived from a monomer represented by the general formula (1)" is appropriately described as a "specific pigment dispersant".

在通式(1)中，R1 表示氫原子、或取代或無取代的烷基。R2表示伸烷基。W表示-CO-、-C(=O)O-、-CONH-、-OC(=O)-、或伸苯基。X表示-O-、-S-、-C(=O)O-、-CONH-、-C(=O)S-、-NHCONH-、-NHC(=O)O-、-NHC(=O)S-、-OC(=O)-、-OCONH-、或-NHCO-。Y表示-NR3 -、-O-、-S-、或-N=，且透過與其相鄰接之原子團而與N原子連結可形成環狀構造。R3 表示氫原子、烷基、或芳基。m及n係各自獨立地表示0或1。In the formula (1), R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group. R2 represents an alkylene group. W represents -CO-, -C(=O)O-, -CONH-, -OC(=O)-, or a phenyl group. X represents -O-, -S-, -C(=O)O-, -CONH-, -C(=O)S-, -NHCONH-, -NHC(=O)O-, -NHC(=O ) S-, -OC(=O)-, -OCONH-, or -NHCO-. Y represents -NR 3 -, -O-, -S-, or -N=, and is bonded to the N atom through the atomic group adjacent thereto to form a ring structure. R 3 represents a hydrogen atom, an alkyl group, or an aryl group. The m and n lines each independently represent 0 or 1.

以下，詳細說明本發明的重要成分、即在特定聚合物中為必要共聚合單位的通式(1)所表示之單體。Hereinafter, the important component of the present invention, that is, the monomer represented by the formula (1) which is a necessary copolymerization unit in a specific polymer, will be described in detail.

在通式(1)中，R1 表示氫原子、或取代或無取代的烷基。In the formula (1), R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group.

R1 所表示之烷基係以碳數1~12的烷基為佳、碳數1~8的烷基為較佳、碳數1~4的烷基為特佳。The alkyl group represented by R 1 is preferably an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

R1 所表示之烷基為取代烷基之情形中，可導入的取代基係可舉例如羥基、烷氧基、芳氧基、醯氧基、鹵素基、等。In the case where the alkyl group represented by R 1 is a substituted alkyl group, examples of the substituent which can be introduced include a hydroxyl group, an alkoxy group, an aryloxy group, a decyloxy group, a halogen group, and the like.

R1 所表示之較佳烷基，具體而言可舉例如甲基、乙基、丙基、正丁基、異丁基、第三丁基、正己基、環己基、2-羥基乙基、3-羥基丙基、2-羥基丙基、2-甲氧基乙基、等。Preferred alkyl groups represented by R 1 include, for example, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxyethyl, and the like.

R2 表示伸烷基。R 2 represents an alkylene group.

R2 所表示之伸烷基係以碳數1~12的伸烷基為佳、碳數1~8的伸烷基為較佳、碳數1~4的伸烷基為特佳。The alkylene group represented by R 2 is preferably an alkylene group having 1 to 12 carbon atoms, an alkylene group having 1 to 8 carbon atoms being preferred, and an alkylene group having 1 to 4 carbon atoms being particularly preferred.

R2 所表示之伸烷基當可導入之情形，亦可具有取代基，該取代基係可舉例如羥基、烷氧基、芳氧基、醯氧基、等。The alkylene group represented by R 2 may have a substituent when it can be introduced, and examples of the substituent include a hydroxyl group, an alkoxy group, an aryloxy group, a decyloxy group, and the like.

R2 所表示之較佳伸烷基，具體而言，可舉例如亞甲基、伸乙基、伸丙基、三亞甲基、四亞甲基等。The preferred alkylene group represented by R 2 may, for example, be a methylene group, an ethylidene group, a stretched propyl group, a trimethylene group or a tetramethylene group.

W表示-CO-、-C(=O)O-、-CONH-、-OC(=O)-、或伸苯基，較佳為-C(=O)O-或-CONH-。W represents -CO-, -C(=O)O-, -CONH-, -OC(=O)-, or a phenyl group, preferably -C(=O)O- or -CONH-.

Y表示-NR3 -、-O-、-S-、或-N=，且透過與其相鄰接之原子團而與N原子連結可形成環狀構造。Y represents -NR 3 -, -O-, -S-, or -N=, and is bonded to the N atom through the atomic group adjacent thereto to form a ring structure.

R3 表示氫原子、烷基、或芳基，較佳為氫原子或甲基。R 3 represents a hydrogen atom, an alkyl group, or an aryl group, preferably a hydrogen atom or a methyl group.

Y係特佳為-S-、-NH-、或-N=。The Y system is particularly preferably -S-, -NH-, or -N=.

Y係透過與其相鄰接之原子團而與N原子連結所形成之環狀構造，可舉例如咪唑環、嘧啶環、***環、四唑環、噻唑環、唑環、等的單環構造、及、苯并咪唑環、苯并噻唑環、苯并唑環、嘌呤環、喹唑啉環、萘嵌間二氮雜苯環、等的縮合環構造，從與顔料的親和性之點，較佳為縮合環構造。縮合環構造之中，可舉例如苯并咪唑環、苯并噻唑環、及苯并唑環為特佳。The ring structure in which Y is bonded to the N atom through the atomic group adjacent thereto, and examples thereof include an imidazole ring, a pyrimidine ring, a triazole ring, a tetrazole ring, and a thiazole ring. Monocyclic structure of azole ring, etc., and benzimidazole ring, benzothiazole ring, benzo The condensed ring structure of the azole ring, the anthracene ring, the quinazoline ring, the naphthalene diazabenzene ring, or the like is preferably a condensed ring structure from the point of affinity with the pigment. Among the condensed ring structures, for example, a benzimidazole ring, a benzothiazole ring, and a benzo The azole ring is particularly good.

X表示-O-、-S-、-C(=O)O-、-CONH-、-C(=O)S-、-NHCONH-、-NHC(=O)O-、-NHC(=O)S-、-OC(=O)-、-OCONH-、或-NHCO-。X係以-O-、-S-、-CONH-、-NHCONH-、及-NHC(=O)S-為特佳。X represents -O-, -S-, -C(=O)O-, -CONH-, -C(=O)S-, -NHCONH-, -NHC(=O)O-, -NHC(=O ) S-, -OC(=O)-, -OCONH-, or -NHCO-. The X system is particularly preferably -O-, -S-, -CONH-, -NHCONH-, and -NHC(=O)S-.

m及n係各自獨立地表示0或1，m及n特佳係均為1。The m and n series each independently represent 0 or 1, and both m and n are all 1.

通式(1)所示單體之較佳具體例(單體M-1~單體M-18)係係如以下所列舉，惟本發明不受此等所限制。Preferred specific examples of the monomer represented by the formula (1) (monomer M-1 to monomer M-18) are as follows, but the present invention is not limited thereto.

在本發明的特定聚合物，從賦予顔料的分散安定性之觀點，係含有來自前述通式(1)所示單體之共聚合單位，同時更含有來自末端具有乙烯性不飽和鍵之聚合性低聚物的共聚合單位之接枝共聚物為特佳。The specific polymer of the present invention contains a copolymerization unit derived from the monomer represented by the above formula (1) from the viewpoint of imparting dispersion stability to the pigment, and further contains a polymerizable group having an ethylenically unsaturated bond from the terminal. The graft copolymer of the copolymerization unit of the oligomer is particularly preferred.

像這樣的於末端具有乙烯性不飽和鍵之聚合性低聚物，由於為具有規定的分子量之化合物，所以亦稱為大分子單體。以下的說明中，在本發明的「於末端具有乙烯性不飽和鍵之聚合性低聚物」係有適宜稱為「聚合性低聚物」或「大分子單體」之情形。Such a polymerizable oligomer having an ethylenically unsaturated bond at its terminal is also called a macromonomer because it is a compound having a predetermined molecular weight. In the following description, the "polymerizable oligomer having an ethylenically unsaturated bond at the terminal" of the present invention is suitably referred to as "polymerizable oligomer" or "macromonomer".

於本發明中根據所望所使用的聚合性低聚物，係由聚合物鏈部分與其末端具有乙烯性不飽和雙鍵之可聚合官能基的部分所構成的。具有像這樣的乙烯性不飽和雙鍵之基係僅在聚合物鏈的一末端具有，從能得到所期望的接枝聚合物之觀點而言為佳。具有乙烯性不飽和雙鍵之基係以(甲基)丙烯醯基、乙烯基為佳，特佳為(甲基)丙烯醯基。The polymerizable oligomer used in the present invention is composed of a polymer chain functional moiety having a polymerizable functional group having an ethylenically unsaturated double bond at its terminal. The group having such an ethylenically unsaturated double bond is only present at one end of the polymer chain, and is preferably from the viewpoint of obtaining a desired graft polymer. The group having an ethylenically unsaturated double bond is preferably a (meth) acrylonitrile group or a vinyl group, and particularly preferably a (meth) acryl fluorenyl group.

又，該大分子單體係聚苯乙烯換算的數量平均分子量(Mn)為1000~10000的範圍為佳、特佳係在2000~9000的範圍。Further, the macromolecular single-system polystyrene-equivalent number average molecular weight (Mn) is preferably in the range of 1,000 to 10,000, and particularly preferably in the range of from 2,000 to 9000.

上述聚合物鏈的部分一般係由(甲基)丙烯酸烷酯、苯乙烯及其衍生物、丙烯腈、乙酸乙烯基及丁二烯所構成之群選出的至少一種單體所形成之單獨聚合物或共聚物、或聚環氧乙烷、聚環氧丙烷、聚己內酯。The polymer chain portion is generally a single polymer formed from at least one monomer selected from the group consisting of alkyl (meth)acrylate, styrene and its derivatives, acrylonitrile, vinyl acetate and butadiene. Or a copolymer, or polyethylene oxide, polypropylene oxide, polycaprolactone.

上述聚合性低聚物較佳係下述通式(2)所表示之低聚物。The polymerizable oligomer is preferably an oligomer represented by the following formula (2).

通式(2)中，R11 及R13 係各自獨立地表示氫原子或甲基。In the formula (2), R 11 and R 13 each independently represent a hydrogen atom or a methyl group.

R12 係表示含有碳原子數1~12的伸烷基之連結基，該連結基係亦可為碳原子數1~12的伸烷基，複數個的該伸烷基亦可透過酯鍵、醚鍵、醯胺鍵等而鍵結者。R12 係較佳為碳原子數1~4的伸烷基、或碳數1~4的伸烷基係解開酯鍵所鍵結之基。表示R12 之伸烷基係可具有取代基(例如，羥基)。R 12 represents a linking group containing an alkylene group having 1 to 12 carbon atoms, and the linking group may also be an alkylene group having 1 to 12 carbon atoms, and a plurality of alkylene groups may also pass through an ester bond. The bond is bonded by an ether bond, a guanamine bond or the like. R 12 is preferably a group in which an alkylene group having 1 to 4 carbon atoms or a stretching alkyl group having 1 to 4 carbon atoms is bonded to an ester bond. The alkylene group representing R 12 may have a substituent (for example, a hydroxyl group).

Y表示不具有取代基之苯基、具有1個碳原子數1~4烷基之苯基或-COOR14 。此處，R14 表示碳原子數1~6的烷基、苯基或碳原子數7~10的芳基烷基。Y係較佳為苯基或-COOR14 ，此處，但是R14 表示碳原子數1~12的烷基。Y represents a phenyl group having no substituent, a phenyl group having 1 to 4 carbon atoms, or -COOR 14 . Here, R 14 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group or an arylalkyl group having 7 to 10 carbon atoms. Y is preferably a phenyl group or -COOR 14 , and R 14 represents an alkyl group having 1 to 12 carbon atoms.

Q表示20~200的整數。Q represents an integer from 20 to 200.

在本發明中使用於特定顔料分散劑合成之聚合性低聚物(大分子單體)的較佳例，可舉例如聚(甲基)丙烯酸甲酯、聚正(甲基)丙烯酸丁酯及聚(甲基)丙烯酸異丁酯、(甲基)丙烯醯基與聚苯乙烯分子末端的一個結合之聚合物。市場可取得的此等聚合性低聚物係可舉例如片末端甲基丙烯醯基化聚苯乙烯低聚物(Mn=6000、商品名：AS-6、東亞合成化學工業(股)製)、片末端甲基丙烯醯基化聚甲基丙烯酸甲酯低聚物(Mn=6000、商品名：AA-6、東亞合成化學工業(股)製)及片末端甲基丙烯醯基化聚正丁基丙烯酸酯低聚物(Mn=6000、商品名：AB-6、東亞合成化學工業(股)製)。Preferred examples of the polymerizable oligomer (macromonomer) used in the synthesis of a specific pigment dispersant in the present invention include, for example, poly(methyl) acrylate, poly-n-butyl (meth) acrylate, and A polymer of poly(meth)acrylate isobutyl ester, (meth)acrylonitrile group and a polystyrene molecule end. The polymerizable oligomer which can be obtained in the market is, for example, a sheet-end methacryl-fluorenylated polystyrene oligomer (Mn=6000, trade name: AS-6, manufactured by Toagosei Chemical Co., Ltd.) , end-end methacryl-methylated polymethyl methacrylate oligomer (Mn=6000, trade name: AA-6, manufactured by East Asia Synthetic Chemical Industry Co., Ltd.) and terminal methacryloyl thiolated poly-positive Butyl acrylate oligomer (Mn = 6000, trade name: AB-6, manufactured by East Asia Synthetic Chemical Industry Co., Ltd.).

本發明有關之特定顔料分散劑較佳係更含有來自酸基之單體的共聚合單位。特定顔料分散劑係藉由更含有來自酸基之單體的共聚合單位，例如，當本發明的顔料分散組成物應用於光刻法之圖案形成時，可使圖案形成性更為提昇。The specific pigment dispersant of the present invention is preferably a copolymerization unit further containing a monomer derived from an acid group. The specific pigment dispersant is further improved in pattern formation by, for example, a copolymerization unit containing a monomer derived from an acid group, for example, when the pigment dispersion composition of the present invention is applied to pattern formation by photolithography.

具有酸基之單體係可舉例如丙烯酸、甲基丙烯酸、巴豆酸、α-氯基丙烯酸、內桂酸(cinnamic acid)等的不飽和單羧酸類；順丁烯二酸、順丁烯二酸酐、反丁烯二酸、衣康酸、衣康酸酐、檸康酸、檸康酸酐、中康酸等的不飽和二羧酸或其酸酐類；3價以上的不飽和多元羧酸或其酸酐類；琥珀酸單(2-丙烯醯氧基乙基)酯、琥珀酸單(2-甲基丙烯醯氧基乙基)酯、酞酸單(2-丙烯醯氧基乙基)酯、酞酸單(2-甲基丙烯醯氧基乙基)酯等的2價以上之多元羧酸的單[(甲基)丙烯醯氧基烷基)酯類；ω-羧基-聚己內酯單丙烯酸酯、ω-羧基-聚己內酯單甲基丙烯酸酯等的兩末端羧基聚合物的單(甲基)丙烯酸酯類等。The single system having an acid group may, for example, be an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid or cinnamic acid; maleic acid or maleic acid; An unsaturated dicarboxylic acid or an anhydride thereof such as an acid anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride or mesaconic acid; or an unsaturated polycarboxylic acid having a valence of 3 or more or Anhydrides; succinic acid mono(2-propenyloxyethyl) ester, succinic acid mono(2-methylpropenyloxyethyl) ester, decanoic acid mono(2-propenyloxyethyl) ester, Mono[(meth)acryloxyalkyl)esters of divalent or higher polycarboxylic acids such as citric acid mono(2-methylpropenyloxyethyl) ester; ω-carboxy-polycaprolactone A mono(meth)acrylate such as a mono- carboxy polymer such as monoacrylate or ω-carboxy-polycaprolactone monomethacrylate.

本發明有關之特定顔料分散劑係在不損及效果之範圍內，亦可更含有可共聚合之乙烯基單體做為共聚合成分。The specific pigment dispersant according to the present invention may further contain a copolymerizable vinyl monomer as a copolymerization component within a range not impairing the effect.

這裡可使用的乙烯基單體係沒有特別地限制，較佳為(甲基)丙烯酸酯類、巴豆酸酯類、乙烯酯類、順丁烯二酸二酯類、反丁烯二酸二酯類、衣康酸二酯類、(甲基)丙烯醯胺類、乙烯基醚類、乙烯醇的酯類、苯乙烯類、(甲基)丙烯腈等。像這樣的乙烯基單體之具體例係可舉例如以下的化合物。The vinyl single system which can be used herein is not particularly limited, and is preferably a (meth) acrylate, a crotonate, a vinyl ester, a maleic acid diester, or a fumaric acid diester. Classes, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth)acrylonitrile, and the like. Specific examples of the vinyl monomer as described above include, for example, the following compounds.

(甲基)丙烯酸酯類之例子可舉例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸第三辛酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸十八烷酯、(甲基)丙烯酸乙醯氧基乙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-(2-甲氧基乙氧基)乙酯、(甲基)丙烯酸3-苯氧基-2-羥基丙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸二甘醇單甲基醚、(甲基)丙烯酸二甘醇單乙基醚、(甲基)丙烯酸三乙二醇單甲基醚、(甲基)丙烯酸三乙二醇單乙基醚、(甲基)丙烯酸聚乙二醇單甲基醚、(甲基)丙烯酸聚乙二醇單乙基醚、(甲基)丙烯酸β-苯氧基乙氧基乙酯、(甲基)丙烯酸壬基苯氧基聚乙二醇、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯基羥乙酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸八氟戊酯、(甲基)丙烯酸全氟辛基乙酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸三溴基苯酯、(甲基)丙烯酸三溴基苯基羥乙酯等。Examples of the (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (methyl). N-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butyl (meth)acrylate Cyclohexyl ester, 2-ethylhexyl (meth)acrylate, third octyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, (methyl) Ethyloxyethyl acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxy (meth) acrylate Ethyl ester, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, (A) Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl (meth)acrylate Ether, (meth)acrylic acid polyethylene glycol monomethyl ether, (meth)acrylic acid poly Glycol monoethyl ether, β-phenoxyethoxyethyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, dicyclopentenyl (meth)acrylate, ( Dicyclopentenyl hydroxyethyl methyl methacrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, (meth) acrylate Dicyclopentyl ester, tribromophenyl (meth)acrylate, tribromophenyl hydroxyethyl (meth)acrylate, and the like.

此外，在本說明書中「丙烯基、甲基丙烯基」表示任一者或是雙方時係記載為「(甲基)丙烯基」。In the present specification, "acryloyl group or methacryl group" means "(meth)acrylyl group" when it indicates either or both.

巴豆酸酯類之例子可舉例如巴豆酸丁酯、及巴豆酸己酯等。Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.

乙烯酯類之例子可舉例如乙烯基乙酸酯、乙烯基丙酸酯、乙烯基丁酸酯、乙烯基甲氧基乙酸酯、及安息香酸乙烯酯等。Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, and vinyl benzoate.

順丁烯二酸二酯類之例子可舉例如順丁烯二酸二甲酯、順丁烯二酸二乙酯、及順丁烯二酸二丁酯等。Examples of the maleic acid diesters include, for example, dimethyl maleate, diethyl maleate, and dibutyl maleate.

反丁烯二酸二酯類之例子可舉例如反丁烯二酸二甲酯、反丁烯二酸二乙酯、及反丁烯二酸二丁酯等。Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

衣康酸二酯類之例子可舉例如衣康酸二甲酯、衣康酸二乙酯、及衣康酸二丁酯等。Examples of the itaconic acid diesters include, for example, dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

(甲基)丙烯醯胺類係可舉例如(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-丙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N正丁基(甲基)丙烯醯胺、N-第三丁基(甲基)丙烯醯胺、N-環己基(甲基)丙烯醯胺、N-(2-甲氧基乙基)(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-苯基(甲基)丙烯醯胺、N-苄基(甲基)丙烯醯胺、(甲基)丙烯醯基味啉、雙丙酮丙烯醯胺等。Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-propyl (A). Base) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-cyclohexyl ( Methyl) acrylamide, N-(2-methoxyethyl)(methyl) acrylamide, N,N-dimethyl(meth) decylamine, N,N-diethyl (A Base) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) propylene sulfhydryl, diacetone acrylamide, and the like.

苯乙烯類之例子可舉例如苯乙烯、甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、羥基苯乙烯、甲氧基苯乙烯、丁氧基苯乙烯、乙醯氧基苯乙烯、氯基苯乙烯、二氯基苯乙烯、溴基苯乙烯、氯基甲基苯乙烯、藉由酸性物質可脫保護之基(例如t-Boc等)所保護的羥基苯乙烯、乙烯基安息香酸甲酯、及α-甲基苯乙烯等。Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethylstyrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxystyrene, and methoxy. Styrene, butoxystyrene, ethoxylated styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, deprotectable groups by acidic substances ( For example, t-Boc or the like is protected by hydroxystyrene, methyl benzoic acid methyl ester, and α-methylstyrene.

乙烯基醚類之例子可舉例如甲基乙烯基醚、丁基乙烯基醚、己基乙烯基醚、及甲氧基乙基乙烯基醚等。Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

本發明有關的特定顔料分散劑之較佳態様，較佳係舉例如包含含有2~50質量%之來自前述通式(1)所示單體之共聚合單位，以及含有10~90質量%的來自於末端具有乙烯性不飽和鍵之聚合性低聚物的共聚合單位、含有1~30質量%的來自具有酸基之單體的共聚合單位、含有0~20質量%的來自乙烯基單體之共聚合單位的共聚物。The preferred state of the specific pigment dispersant according to the present invention is preferably, for example, a copolymerization unit containing 2 to 50% by mass of the monomer represented by the above formula (1), and 10 to 90% by mass. a copolymerization unit derived from a polymerizable oligomer having an ethylenically unsaturated bond at the terminal, a copolymerization unit containing 1 to 30% by mass of a monomer derived from an acid group, and a 0 to 20% by mass derived from a vinyl group Copolymerized unit copolymer.

本發明有關的特定顔料分散劑之較佳分子量，係以重量平均分子量(Mw)為15000~200000、以數量平均分子量(Mn)為8000~100000為佳。此外，分子量係可按照凝膠滲透層析法(GPC，Gel Permeation Chromatography)來測定。The preferred molecular weight of the specific pigment dispersant according to the present invention is preferably from 15,000 to 200,000 by weight average molecular weight (Mw) and from 8,000 to 100,000 by number average molecular weight (Mn). Further, the molecular weight can be measured by gel permeation chromatography (GPC, Gel Permeation Chromatography).

以下，係列舉本發明有關的光硬化性組成物中能適宜使用的特定顔料分散劑之具體例[例示化合物1~例示化合物16]以及其重量平均分子量，惟本發明係並不受限於此等。In the following, specific examples of the specific pigment dispersant which can be suitably used in the photocurable composition according to the present invention [exemplary compound 1 to exemplary compound 16] and the weight average molecular weight thereof are listed, but the present invention is not limited thereto. Wait.

例示化合物(1)：前述單體M-2/末端甲基丙烯醯基化聚甲基丙烯酸甲酯共聚物(10/90質量%、重量平均分子量50000)Illustrative compound (1): the aforementioned monomer M-2/terminal methacryl oxime-based polymethyl methacrylate copolymer (10/90% by mass, weight average molecular weight 50000)

例示化合物(2)：前述單體M-2/甲基丙烯酸/末端甲基丙烯醯基化聚甲基丙烯酸甲酯共聚物(10/15/75質量%、重量平均分子量25000)Illustrative compound (2): the aforementioned monomer M-2/methacrylic acid/terminal methacryl oxime-based polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 25000)

例示化合物(3)：前述單體M-3/甲基丙烯酸2-羥乙酯/末端甲基丙烯醯基化聚甲基丙烯酸甲酯共聚物(5/10/85質量%、重量平均分子量40000)Illustrative compound (3): the aforementioned monomer M-3 / 2-hydroxyethyl methacrylate / terminal methacryl oxime polymethyl methacrylate copolymer (5/10/85 mass%, weight average molecular weight 40,000 )

例示化合物(4)：前述單體M-3/甲基丙烯酸/甲基丙烯酸苄酯共聚物/末端甲基丙烯醯基化聚甲基丙烯酸甲酯共聚物(15/5/10/65質量%、重量平均分子量60000)Illustrative compound (4): the aforementioned monomer M-3/methacrylic acid/benzyl methacrylate copolymer/terminal methacryl oxime-based polymethyl methacrylate copolymer (15/5/10/65 mass%) , weight average molecular weight 60000)

例示化合物(5)：前述單體M-4/末端甲基丙烯醯基化聚甲基丙烯酸甲酯共聚物(10/90質量%、重量平均分子量80000)Illustrative compound (5): the aforementioned monomer M-4/terminal methacryl oxime polymethyl methacrylate copolymer (10/90% by mass, weight average molecular weight: 80000)

例示化合物(6)：前述單體M-4/甲基丙烯酸/末端甲基丙烯醯基化聚甲基丙烯酸甲酯共聚物(10/15/75質量%、重量平均分子量30000)Illustrative compound (6): the aforementioned monomer M-4/methacrylic acid/terminal methacryl oxime-based polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 30000)

例示化合物(7)：前述單體M-5/丙烯酸/末端甲基丙烯醯基化聚甲基丙烯酸甲酯共聚物(25/15/60質量%、重量平均分子量60000)Illustrative Compound (7): the aforementioned monomer M-5/acrylic acid/terminal methacryl oxime-based polymethyl methacrylate copolymer (25/15/60% by mass, weight average molecular weight 60000)

例示化合物(8)：前述單體M-5/末端甲基丙烯醯基化聚丙烯酸丁酯共聚物(15/85質量%、重量平均分子量40000)Illustrative compound (8): the aforementioned monomer M-5/terminal methacryl oxime polybutyl acrylate copolymer (15/85 mass%, weight average molecular weight 40,000)

例示化合物(9)：前述單體M-6/甲基丙烯酸2-羥乙酯/末端甲基丙烯醯基化聚甲基丙烯酸甲酯共聚物(15/10/75質量%、重量平均分子量80000)Illustrative compound (9): the aforementioned monomer M-6 / 2-hydroxyethyl methacrylate / terminal methacryl oxime polymethyl methacrylate copolymer (15/10/75 mass%, weight average molecular weight 80000 )

例示化合物(10)：前述單體M-6/末端甲基丙烯醯基化聚甲基丙烯酸甲酯共聚物(12/88質量%、重量平均分子量50000)Illustrative Compound (10): the aforementioned monomer M-6/terminal methacryl oxime polymethyl methacrylate copolymer (12/88% by mass, weight average molecular weight 50,000)

例示化合物(11)：前述單體M-7/甲基丙烯酸/末端甲基丙烯醯基化聚甲基丙烯酸甲酯共聚物(10/15/75質量%、重量平均分子量25000)Illustrative compound (11): the aforementioned monomer M-7/methacrylic acid/terminal methacryl oxime-based polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 25000)

例示化合物(12)：前述單體M-7/甲基丙烯酸/甲基丙烯酸苄酯/甲氧基聚乙二醇甲基丙烯酸酯共聚物(10/10/50/30質量%、重量平均分子量40000)Illustrative compound (12): the aforementioned monomer M-7/methacrylic acid/benzyl methacrylate/methoxy polyethylene glycol methacrylate copolymer (10/10/50/30% by mass, weight average molecular weight) 40000)

例示化合物(13)：前述單體M-10/甲基丙烯酸2-羥乙酯/末端甲基丙烯醯基化聚苯乙烯共聚物(5/10/85質量%、重量平均分子量20000)Illustrative compound (13): the above-mentioned monomer M-10 / 2-hydroxyethyl methacrylate / terminal methacryl oxime polystyrene copolymer (5/10/85 mass%, weight average molecular weight 20000)

例示化合物(14)：前述單體M-10/甲基丙烯酸/末端甲基丙烯醯基化聚甲基丙烯酸甲酯共聚物(10/15/75質量%、重量平均分子量25000)Illustrative compound (14): the aforementioned monomer M-10/methacrylic acid/terminal methacryl oxime-based polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 25000)

例示化合物(15)：前述單體M-10/甲氧基聚乙二醇甲基丙烯酸酯共聚物(15：85質量%、重量平均分子量15000)Illustrative compound (15): the aforementioned monomer M-10/methoxy polyethylene glycol methacrylate copolymer (15:85 mass%, weight average molecular weight 15000)

例示化合物(16)：前述單體M-13/甲基丙烯酸/末端甲基丙烯醯基化聚甲基丙烯酸甲酯共聚物(10/15/75質量%、重量平均分子量20000)Illustrative compound (16): the aforementioned monomer M-13/methacrylic acid/terminal methacryl oxime-based polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 20000)

在本發明的特定顔料分散劑、如上述的共聚物係可藉由將前述通式(1)所表示之單體、按照所望所併用之聚合性低聚物、或其他單體，於溶媒中進行自由基聚合而可得到。自由基聚合起始劑係可使用眾所周知的化合物，可適宜使用偶氮系起始劑(例如，二甲基-2,2’-偶氮雙(2-甲基丙酸酯)dimethyl-2,2'-Azobis(2-methylpropionate)、偶氮二異丁腈(azobisisobutyronitrile)、2,2’-偶氮雙(2-脒基丙烷)2鹽酸鹽(2,2'-Azobis(2-amidinopropane)dihydrochloride)等)、過氧化物(過氧化苯甲醯基(benzoyl peroxide)、過硫酸鉀(potassium persulfate)等)。除了起始劑以外，亦可添加鏈移動劑(例如，2-氫硫基乙醇(2-mercaptoethanol)、3-氫硫基丙酸(3-Mercaptopropionic acid)、2-氫硫基乙酸(2-Mercaptoacetic acid)、十二烷基硫醇(dodecyl mercaptan))而合成。The specific pigment dispersant of the present invention, such as the above-mentioned copolymer, can be used in the solvent by using the monomer represented by the above formula (1), the polymerizable oligomer used in combination, or other monomer. It can be obtained by radical polymerization. As the radical polymerization initiator, a well-known compound can be used, and an azo initiator (for example, dimethyl-2,2'-azobis(2-methylpropionate)dimethyl-2 can be suitably used. 2'-Azobis(2-methylpropionate), azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) 2 hydrochloride (2,2'-Azobis(2-amidinopropane) Dihydrochloride), peroxide (benzoyl peroxide, potassium persulfate, etc.). In addition to the starter, a chain shifting agent (for example, 2-mercaptoethanol, 3-Mercaptopropionic acid, 2-hydrothioacetic acid (2-) may be added. Mercaptoacetic acid), synthesized from dodecyl mercaptan.

此外，關於具體的合成例係如後述。Further, specific synthesis examples will be described later.

特定顔料分散劑在顔料分散組成物中的含量，相對於後述之顔料的質量，以0.5~100質量%為佳、3~70質量%為更佳。顔料分散劑的量在該範圍内時，能得到充分的顔料分散效果。此外，顔料分散劑即使加入多於100質量%，亦無法期待顔料分散效果的進一步提昇效果。The content of the specific pigment dispersant in the pigment dispersion composition is preferably from 0.5 to 100% by mass, more preferably from 3 to 70% by mass, based on the mass of the pigment to be described later. When the amount of the pigment dispersant is within this range, a sufficient pigment dispersion effect can be obtained. Further, even if the pigment dispersant is added in an amount of more than 100% by mass, the effect of further enhancing the pigment dispersion effect cannot be expected.

本發明的顔料分散組成物係在有機溶媒中，含有顔料、與特定顔料分散劑者，可視需要使用樹脂成分等的其他成分來構成。The pigment dispersion composition of the present invention is composed of a pigment and a specific pigment dispersant in an organic solvent, and may be formed by using other components such as a resin component as needed.

該顔料分散組成物由於含有特定顔料分散劑，所以在有機溶媒中顔料的分散狀態係為良好，得到良好的色特性的同時，例如在構成彩色濾光片時能得到高的對比。特別是能發揮有機顔料優異的分散效果。Since the pigment dispersion composition contains a specific pigment dispersant, the dispersion state of the pigment in the organic solvent is good, and good color characteristics are obtained, and high contrast can be obtained, for example, when constituting a color filter. In particular, it is possible to exhibit an excellent dispersion effect of an organic pigment.

[平均粒徑為15~150nm的顔料][Pigments with an average particle size of 15 to 150 nm]

在本發明，彩色濾光片著色圖案中為達成高對比係必要含有平均粒徑為15~150nm的顔料，但是只要能滿足該粒徑，顔料係可適宜選擇以往眾所周知的各種無機顔料或有機顔料來使用。In the color filter coloring pattern of the present invention, it is necessary to contain a pigment having an average particle diameter of 15 to 150 nm in order to achieve a high contrast ratio. However, as long as the particle diameter can be satisfied, the pigment system can appropriately select various inorganic pigments or organic pigments which have been conventionally known. To use.

顔料係可為無機顔料、有機顔料，考慮到高透射率為佳時，儘可能使用粒子尺寸小者為佳，惟考慮到處理(handling)性時，做為顔料的平均粒徑亦必須在上述範圍，較佳係在15~50nm的範圍。The pigment system may be an inorganic pigment or an organic pigment. When the high transmittance is good, it is preferable to use a particle size as small as possible, but in consideration of handling, the average particle diameter of the pigment must also be as described above. The range is preferably in the range of 15 to 50 nm.

此處，所謂的顔料的平均粒徑係表示2次粒子的平均粒徑，具體而言，可以上述的方法來進行測定。Here, the average particle diameter of the pigment means the average particle diameter of the secondary particles, and specifically, the measurement can be carried out by the above method.

前述無機顔料係可舉例如以金屬氧化物、金屬錯鹽等所表示之金屬化合物。具體而言，可舉例如鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、鋅、銻等的金屬氧化物、及前述金屬的複合氧化物等。The inorganic pigment may, for example, be a metal compound represented by a metal oxide or a metal salt. Specific examples thereof include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

前述有機顔料係可舉例如以下者。The above organic pigments may, for example, be as follows.

C.I.顏料黃11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199；C.I.顏料橙36,38,43,71；C.I.顏料紅81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270；C.I.顏料紫19,23,32,37,39；C.I.顏料藍1,2,15,15：1,15：3,15：6,16,22,60,66；C.I.顏料綠7,36,37；C.I.顏料棕25,28；C.I.顏料黑1,7；在本發明的顔料係沒有特別地限制，惟較佳為下述的顔料。CI Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199; CI Pigment Orange 36, 38, 43, 71; CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270; CI Pigment Violet 19, 23, 32, 37, 39; CI Pigment Blue 1 , 2,15,15:1,15:3,15:6,16,22,60,66; CI Pigment Green 7,36,37; CI Pigment Brown 25,28; CI Pigment Black 1,7; The pigment of the invention is not particularly limited, but is preferably a pigment as described below.

C.I.顏料黃11,24,108,109,110,138,139,150,151,154,167,180,185,C.I.顏料橙36,71,C.I.顏料紅122,150,171,175,177,209,224,242,254,255,264,C.I.顏料紫19,23,37,C.I.顏料藍15：1,15：3,15：6,16,22,60,66,C.I.顏料綠7,36；C.I.顏料黑7CI Pigment Yellow 11,24,108,109,110,138,139,150,151,154,167,180,185,CI Pigment Orange 36,71,CI Pigment Red 122,150,171,175,177,209,224,242,254,255,264,CI Pigment Violet 19,23,37,CI Pigment Blue 15:1,15:3,15:6,16,22,60,66 , CI Pigment Green 7,36; CI Pigment Black 7

此等有機顔料係可單獨使用、或為了提昇色純度而使用各種組合。組合的具體例係如以下所示。These organic pigments can be used singly or in various combinations in order to improve color purity. Specific examples of the combination are as follows.

例如，紅色顔料係可使用蒽醌系顔料、苝系顔料、二酮基吡咯并吡咯(diketo pyrrolo pyrrole)系顔料單獨或彼等之至少一種與雙偶氮系黃色顔料、異吲哚啉系黃色顔料、喹酞酮系黃色顔料或苝系紅色顔料的混合等。例如，蒽醌系顔料係可舉例如C.I.顏料紅177，苝系顔料係可舉例如C.I.顏料紅155、C.I.顏料紅224，二酮基吡咯并吡咯系顔料係可舉例如C.I.顏料紅254，從色再現性之點係以與C.I.顏料黃139的混合為佳。又，紅色顔料與黃色顔料之質量比係以100：5~100：50為佳。低於100：5的話，難以抑制400nm~500nm的光透射率，且會有難以提昇色純度之情形。又，超過100：50時，主波長會變得比短波長要短，會有變的比NTSC(National Television Standards Committee，美國國家電視標準委員會)所定目標色相的偏差要大的情形。特別是前述質量比係以100：10~100：30的範圍為最適宜。此外，組合紅色顔料彼此的情形，可與色度一併進行調整。For example, the red pigment may be an anthraquinone pigment, an anthraquinone pigment, a diketo pyrrolo pyrrole pigment alone or at least one of them, and a disazo yellow pigment, an isoporphyrin yellow. Mixing of pigments, quinophthalone yellow pigments or fluorene red pigments. For example, the ruthenium pigment may be, for example, CI Pigment Red 177, and the ruthenium pigment may, for example, CI Pigment Red 155 or CI Pigment Red 224, and the diketopyrrolopyrrole pigment may be, for example, CI Pigment Red 254. The point of color reproducibility is preferably a mixture with CI Pigment Yellow 139. Moreover, the mass ratio of the red pigment to the yellow pigment is preferably from 100:5 to 100:50. When it is less than 100:5, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and it may be difficult to improve the color purity. Further, when the ratio exceeds 100:50, the dominant wavelength becomes shorter than the short wavelength, and the variation is larger than the target hue of the NTSC (National Television Standards Committee). In particular, the aforementioned mass ratio is most preferably in the range of 100:10 to 100:30. Further, the case where the red pigments are combined with each other can be adjusted together with the chromaticity.

又，綠色顔料係可鹵化酞菁系顔料單獨使用、或可使用其與雙偶氮系黃色顔料、喹酞酮系黃色顔料、甲亞胺系黃色顔料或是異吲哚啉系黃色顔料的混合。例如，像這樣的例係以C.I.顏料綠7、36、37與C.I.顏料黃83、C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、C.I.顏料黃180或C.I.顏料黃185的混合為佳。綠色顔料與黃色顔料的質量比係以100：5~100：150為佳。質量比低於100：5的話，難以抑制400nm~450nm的光透射率，且會有無法提昇色純度之情形。又，超過100：150時，主波長會變的比長波長要長，且會有比NTSC目標色相所定的偏差要大的情形。質量比係以100：30~100：120的範圍為特佳。Further, the green pigment-based halogenated phthalocyanine-based pigment may be used alone or in combination with a disazo-based yellow pigment, a quinacridone-based yellow pigment, a azomethine-based yellow pigment or an iso-porphyrin-based yellow pigment. . For example, such an example is preferably a mixture of CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or CI Pigment Yellow 185. . The mass ratio of the green pigment to the yellow pigment is preferably from 100:5 to 100:150. When the mass ratio is less than 100:5, it is difficult to suppress the light transmittance of 400 nm to 450 nm, and the color purity may not be improved. Moreover, when it exceeds 100:150, the dominant wavelength becomes longer than the long wavelength, and there is a case where the deviation from the NTSC target hue is larger. The mass ratio is particularly good in the range of 100:30 to 100:120.

藍色顏料係可酞菁系顔料單獨使用、或是使用其與二(dioxazine)系紫色顔料的混合。例如，C.I.顏料藍15：6與C.I.顏料紫23的混合為佳。藍色顔料與紫色顔料的質量比係以100：0~100：50為佳、更佳為100：5~100： 30。Blue pigment can be used alone or in combination with phthalocyanine pigments (dioxazine) is a blend of purple pigments. For example, a mixture of CI Pigment Blue 15:6 and CI Pigment Violet 23 is preferred. The mass ratio of the blue pigment to the purple pigment is preferably from 100:0 to 100:50, more preferably from 100:5 to 100 : 30.

又，黑色矩陣用的顔料係可舉例如碳黑、鈦黑(black titanium oxide)、氧化鐵、氧化鈦單獨或此等之混合，較佳為碳黑與鈦黑之組合。又，碳黑與鈦黑的質量比係以100：0~100：60的範圍為佳。超過100：60時，會有分散安定性降低之情形。Further, the pigment for the black matrix may, for example, be carbon black, black titanium oxide, iron oxide or titanium oxide alone or in combination, and is preferably a combination of carbon black and titanium black. Further, the mass ratio of carbon black to titanium black is preferably in the range of 100:0 to 100:60. When it exceeds 100:60, there is a case where the dispersion stability is lowered.

製造本發明有關的光硬化性組成物，較佳係得到該顔料為預先分散於溶劑中而成之顔料分散組成物，在像這樣的顔料分散組成物中顔料的含量係相對於該組成物的總固體成分(質量)，以40~90質量%為佳、50~80質量%為更佳。顔料的含量在前述範圍内時，色濃度係為充分且能有效地確保優異之色特性。In the production of the photocurable composition according to the present invention, it is preferred to obtain a pigment dispersion composition in which the pigment is dispersed in a solvent in advance, and the pigment content in the pigment dispersion composition like this is relative to the composition. The total solid content (mass) is preferably 40 to 90% by mass, more preferably 50 to 80% by mass. When the content of the pigment is within the above range, the color density is sufficient and excellent color characteristics can be effectively ensured.

[有機溶媒][organic solvent]

在本發明中用以調製顔料分散組成物或光硬化性組成物之有機溶媒，可舉例如1-甲氧基-2-丙基乙酸酯、1-甲氧基-2-丙醇、乙二醇單甲基醚、二甘醇單甲基醚、乙酸乙基、乙酸丁酯、乳酸乙基、丙酮、甲基乙基酮、甲基異丁基酮、環己酮、正丙醇、2-丙醇、正丁醇、環己醇、乙二醇、二甘醇、甲苯、二甲苯等。In the present invention, an organic solvent for preparing a pigment dispersion composition or a photocurable composition may, for example, be 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol or B. Glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene, and the like.

又，有機溶媒的添加量係可根據顔料分散組成物的用途等而做適宜選擇，在本發明從用於調製後述的光硬化性組成物、操作性之觀點，含有顔料及顔料分散劑之固體成分濃度係可添加成5~50質量%。In addition, the amount of the organic solvent to be added can be appropriately selected depending on the use of the pigment dispersion composition, etc., and the solid of the pigment and the pigment dispersant is contained in the present invention from the viewpoint of preparation of a photocurable composition to be described later and workability. The component concentration can be added in an amount of 5 to 50% by mass.

顔料分散組成物的調製方法係沒有特別地限制，例如，可藉由使用顔料、顔料分散劑與溶劑，且使用縱型或橫型的砂磨機(sand grinder)、鋼針研磨機(pin mil)、狹縫研磨機(slit mil)、超音波分散機等，以0.01~1mm粒徑的玻璃、氧化鋯等能以珠粒來進行微分散處理而可得到。The preparation method of the pigment dispersion composition is not particularly limited, and for example, by using a pigment, a pigment dispersant and a solvent, and using a vertical or horizontal sand grinder, a steel needle grinder (pin mil) ), a slit mil, an ultrasonic disperser, etc., which can be obtained by finely dispersing a glass having a particle diameter of 0.01 to 1 mm, zirconia, or the like by beads.

又，於進行珠粒分散之前，亦可使用二輥、三輥、球磨機、滾筒研磨機trom mel(rotary sieve)、分散機、捏和機、捏和擠壓機、勻化器、攪拌機、單軸或雙軸的擠壓機等，一邊給予強力的剪斷力、一邊進行混煉分散處理。Further, before the bead dispersion, a two-roll, a three-roller, a ball mill, a trummel mill (rotary sieve), a disperser, a kneader, a kneading extruder, a homogenizer, a mixer, and a single can also be used. A shaft or a biaxial extruder or the like is subjected to a kneading dispersion treatment while giving a strong shearing force.

此外，關於混煉、分散的詳細係記載於T.C.Patton著”Paint Flow and Pigment Dispersion”(1964年JohnWiley and Sons社刊)等。Further, the details of the kneading and dispersion are described in "Paint Flow and Pigment Dispersion" by T.C. Patton (John Wiley and Sons, 1964).

本發明有關的顔料分散組成物由於係用於彩色濾光片形成用的光硬化性組成物的調製，所以較佳為可溶於鹼性水溶液。The pigment dispersion composition according to the present invention is preferably soluble in an alkaline aqueous solution because it is used for preparation of a photocurable composition for color filter formation.

<光硬化性組成物><Photocurable composition>

形成著色圖案之光硬化性組成物係含有已述之顔料分散組成物、光聚合性化合物、光聚合起始劑，更含有鹼可溶性樹脂為佳，亦可視需要含有其他成分。The photocurable composition forming the colored pattern contains the pigment dispersion composition, the photopolymerizable compound, and the photopolymerization initiator described above, and further preferably contains an alkali-soluble resin, and may contain other components as necessary.

該光硬化性組成物由於含有已述之特定顔料分散劑，所以在組成物中顔料能以良好的分散狀態保持，得到良好的色特性的同時，構成彩色濾光片的話可以控制在膜中的顔料的凝集，所以可得到高的對比。Since the photocurable composition contains the specific pigment dispersant described above, the pigment can be held in a good dispersed state in the composition, and good color characteristics can be obtained, and the color filter can be controlled in the film. The agglutination of the pigment gives a high contrast.

以下，針對關於本發明的光硬化性組成物中所含有的各成分加以詳述。Hereinafter, each component contained in the photocurable composition of the present invention will be described in detail.

[顔料分散組成物][Pigment Dispersion Composition]

著色圖案形成用的光硬化性組成物係使用前述顔料分散組成物的至少一種所構成者。關於構成光硬化性組成物之本發明的顔料分散組成物的詳細內容，係如上所述。The photocurable composition for forming a colored pattern is formed by using at least one of the above-described pigment dispersion compositions. The details of the pigment dispersion composition of the present invention constituting the photocurable composition are as described above.

在光硬化性組成物中顔料分散組成物的含量係相對於光硬化性組成物的總固體成分(質量)，以顔料的含量在5~70質量%範圍之量為佳、在15~60質量%範圍之量為更佳。顔料分散組成物的含量在該範圍内時，色濃度係為充分且可有效確保優異之色特性。The content of the pigment dispersion composition in the photocurable composition is preferably from 5 to 70% by mass, and from 15 to 60% by mass based on the total solid content (mass) of the photocurable composition. The amount of % range is better. When the content of the pigment dispersion composition is within this range, the color density is sufficient and excellent color characteristics can be effectively ensured.

[鹼可溶性樹脂][alkali soluble resin]

本發明的光硬化性組成物較佳係含有鹼可溶性樹脂之至少一種。藉由於光硬化性組成物中含有鹼可溶性樹脂，在將該光硬化性組成物應用於由光刻法所成的圖案形成之際，可使得圖案形成性更為提昇。The photocurable composition of the present invention preferably contains at least one of alkali-soluble resins. When the photocurable composition contains an alkali-soluble resin, the patterning property can be further improved when the photocurable composition is applied to a pattern formed by photolithography.

鹼可溶性樹脂係線狀有機高分子聚合物，可從分子(較佳係以丙烯酸系共聚物、苯乙烯系共聚物為主鏈之分子)中具有至少1個能促進鹼可溶性之基(例如羧基、磷酸基、磺酸基等)的鹼可溶性樹脂之中做適宜選擇。其中，更佳係可溶於有機溶劑且可藉由弱鹼性水溶液顯像者。The alkali-soluble resin-based linear organic high molecular polymer may have at least one base capable of promoting alkali solubility (for example, a carboxyl group) from a molecule (preferably an acrylic copolymer or a styrene copolymer-based molecule). An alkali-soluble resin such as a phosphate group or a sulfonic acid group is suitably selected. Among them, it is more preferably soluble in an organic solvent and can be imaged by a weakly alkaline aqueous solution.

鹼可溶性樹脂的製造中，可適用例如基於眾所周知的自由基聚合法之方法。利用自由基聚合法來製造鹼可溶性樹脂之際的溫度、壓力、自由基起始劑的種類及其量、溶媒的種類等等的聚合條件，係可為熟悉該項技術之業者所能情意設定的，亦可設定為實驗性的條件。In the production of an alkali-soluble resin, for example, a method based on a well-known radical polymerization method can be applied. The polymerization conditions for the temperature, the pressure, the type and amount of the radical initiator, the type of the solvent, and the like by the radical polymerization method for the production of the alkali-soluble resin can be set for the person familiar with the technology. It can also be set as an experimental condition.

上述的線狀有機高分子聚合物較佳係在側鏈具有羧酸之聚合物。例如，可舉例在特開昭59-44615號、特公昭54-34327號、特公昭58-12577號、特公昭54-25957號、特開昭59-53836號、特開昭59-71048號的各公報中所記載的甲基丙烯酸共聚物、丙烯酸共聚物、衣康酸共聚物、巴豆酸共聚物、順丁烯二酸共聚物、部分酯化順丁烯二酸共聚物等、以及於側鏈具有羧酸之酸性纖維素衍生物、於具有羥基之聚合物附加酸酐者等，以及可舉例於側鏈具有(甲基)丙烯醯基之高分子聚合物亦為較佳。The above linear organic high molecular polymer is preferably a polymer having a carboxylic acid in a side chain. For example, it can be exemplified in JP-A-59-44615, JP-A-54-34327, JP-A-58-12577, JP-A-54-25957, JP-A-59-53836, JP-A-59-71048 a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, etc., as described in each of the publications, and on the side It is also preferred that the chain has an acidic cellulose derivative of a carboxylic acid, a polymer anhydride having a hydroxyl group, and the like, and a polymer having a (meth) acrylonitrile group in the side chain.

此等之中，特別是以由(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、或(甲基)丙烯酸苄酯/(甲基)丙烯酸/其他單體所構成之多元共聚物為適宜。Among these, a multicomponent copolymer composed of a benzyl (meth) acrylate/(meth)acrylic acid copolymer or a benzyl (meth) acrylate/(meth)acrylic acid/other monomer is used. suitable.

除此之外，可舉例如共聚合甲基丙烯酸2-羥乙酯者等亦為有用者。該聚合物係可以任意之量混合使用。Other than this, it is also useful, for example, to copolymerize 2-hydroxyethyl methacrylate. The polymer can be used in any combination.

除上述以外，可舉例如特開平7-140654號公報中所記載之(甲基)丙烯酸2-羥基丙酯/聚苯乙烯大分子單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物、丙烯酸2-羥基-3-苯氧基丙酯/聚甲基丙烯酸甲酯大分子單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物、甲基丙烯酸2-羥乙酯/聚苯乙烯大分子單體/甲基丙烯酸甲酯/甲基丙烯酸共聚物、甲基丙烯酸2-羥乙酯/聚苯乙烯大分子單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物等。In addition to the above, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer and acrylic acid described in JP-A-7-140654, for example, may be mentioned. 2-Hydroxy-3-phenoxypropyl ester/polymethyl methacrylate macromer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer Molecular/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and the like.

關於鹼可溶性樹脂之具體的構成單位，特別是以(甲基)丙烯酸、及可與其共聚合之其他單體的共聚物為適宜。The specific constituent unit of the alkali-soluble resin is particularly preferably a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith.

可與前述(甲基)丙烯酸共聚合之其他單體係可舉例如(甲基)丙烯酸烷酯、(甲基)丙烯酸芳酯、乙烯系化合物等。此處，烷基及芳基的氫原子亦可以取代基來取代。Other single systems which can be copolymerized with the above (meth)acrylic acid include, for example, alkyl (meth)acrylate, aryl (meth)acrylate, and a vinyl compound. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.

前述(甲基)丙烯酸烷酯及(甲基)丙烯酸芳酯之具體例係可舉例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸苄酯、丙烯酸苄酯、丙烯酸甲苯酯、丙烯酸萘酯、丙烯酸環己酯等。Specific examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl). ) butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, benzyl (meth)acrylate, benzyl acrylate, Toluene acrylate, naphthalene acrylate, cyclohexyl acrylate, and the like.

又，前述乙烯系化合物係可舉例如苯乙烯、α-甲基苯乙烯、乙烯基甲苯、甲基丙烯酸縮水甘油酯、丙烯腈、乙烯基乙酸酯、N-乙烯基吡咯啶酮、甲基丙烯酸四氫糠酯、聚苯乙烯大分子單體、聚甲基丙烯酸甲酯大分子單體、CH2 =CR4 R5 [此處，R4 表示氫原子或碳數1~5的烷基，R5 表示碳數6~10的芳香族烴環]、CH2 =C(R4 )(COOR6 )[此處，R4 表示氫原子或碳數1~5的烷基，R6 表示碳數1~8的烷基或碳數6~12的芳烷基]等。Further, examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, and methyl group. Tetrahydrofurfuryl acrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH 2 =CR 4 R 5 [wherein R 4 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms R 5 represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms], and CH 2 = C(R 4 )(COOR 6 ) [wherein R 4 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 6 represents An alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms.

此等可共聚合之其他單體係可單獨1種、或組合2種以上使用。家的可共聚合之其他單體係選自於CH2 =CR4 R5 、CH2 =C(R4 )(COOR6 )、(甲基)丙烯酸苄酯、(甲基)丙烯酸苄酯及苯乙烯中的至少1種，特佳為CH2 =CR4 R5 及/或CH2 =C(R4 )(COOR6 )。此等之R4 、R5 及R6 係分別與前述者同義。These other single systems which can be copolymerized may be used alone or in combination of two or more. Other copolymerizable single systems of the family are selected from CH 2 =CR 4 R 5 , CH 2 =C(R 4 )(COOR 6 ), benzyl (meth)acrylate, benzyl (meth)acrylate, and At least one of styrene is particularly preferably CH 2 =CR 4 R 5 and/or CH 2 =C(R 4 )(COOR 6 ). These R 4 , R 5 and R 6 systems are each synonymous with the foregoing.

在光硬化性組成物中鹼可溶性樹脂的含量係相對於該組成物的總固體成分，以1~20質量%為佳、更佳為2~15質量%，特佳為3~12質量%。The content of the alkali-soluble resin in the photocurable composition is preferably from 1 to 20% by mass, more preferably from 2 to 15% by mass, even more preferably from 3 to 12% by mass, based on the total solid content of the composition.

[光聚合性化合物][Photopolymerizable compound]

本發明有關的光硬化性組成物係含有光聚合性化合物的至少一種。The photocurable composition according to the present invention contains at least one of photopolymerizable compounds.

可使用於本發明之光聚合性化合物，可選自於具有至少一個乙烯性不飽和雙鍵之加成聚合性化合物，具有至少1個、較佳為2個以上之末端乙烯性不飽和鍵的化合物。像這樣的化合物群係為該產業領域中所普遍知悉的，在本發明此等係可沒有特別限定的使用。此等係具有例如單體、預聚物、亦即二聚體、三聚體及低聚物、或彼等之混合物以及彼等之共聚物等的化學形態。單體及其共聚物的例係可舉例如不飽和羧酸(例如，丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、異巴豆酸、順丁烯二酸等)、或其酯類、醯胺類，較佳係使用不飽和羧酸與脂肪族多元醇化合物之酯、不飽和羧酸與脂肪族多價胺化合物之醯胺類。又，具有羥基或胺基、氫硫基等的求核性取代基之不飽和羧酸酯或是醯胺類與單官能或是多官能異氰酸酯類或是環氧類的加成反應物、及單官能或是多官能的羧酸之脫水縮合反應物等係亦為適宜使用。又，具有異氰酸酯基、或環氧基等的親電子性取代基之不飽和羧酸酯或是醯胺類與單官能或是多官能的醇類、胺類、硫醇類的加成反應物、以及具有鹵素基、或甲苯磺醯氧基等的脫離性取代基之不飽和羧酸酯或是醯胺類與單官能或是多官能的醇類、胺類、硫醇類之取代反應物亦為適宜。又，其他的例子亦可使用將上述的不飽和羧酸取代為不飽和膦酸、苯乙烯、乙烯基醚等之化合物群脂肪族多元醇化合物與不飽和羧酸之酯的單體之具體例，丙烯酸酯係可舉例如乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、1,3-丁二醇二丙烯酸酯、四亞甲基二醇二丙烯酸酯、丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三(丙烯醯氧基丙基)醚、三羥甲基乙烷三丙烯酸酯、己二醇二丙烯酸酯、1,4-環己二醇二丙烯酸酯、四乙二醇二丙烯酸酯、新戊四醇二丙烯酸酯、新戊四醇三丙烯酸酯、新戊四醇四丙烯酸酯、二新戊四醇二丙烯酸酯、二新戊四醇六丙烯酸酯、山梨糖醇三丙烯酸酯、山梨糖醇四丙烯酸酯、山梨糖醇五丙烯酸酯、山梨糖醇六丙烯酸酯、三(丙烯醯氧基乙基)異三聚氰酸酯、聚酯丙烯酸酯低聚物、異三聚氰酸EO改質三丙烯酸酯等。The photopolymerizable compound which can be used in the present invention can be selected from an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one, preferably two or more terminal ethylenically unsaturated bonds. Compound. Such a compound group is generally known in the industrial field, and the present invention can be used without particular limitation. These are chemical forms such as monomers, prepolymers, i.e., dimers, trimers, and oligomers, or mixtures thereof, and copolymers thereof. Examples of the monomer and the copolymer thereof include, for example, an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), or an ester thereof, or an anthracene. The amine is preferably an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound. Further, an unsaturated carboxylic acid ester having a core-requiring substituent such as a hydroxyl group, an amine group or a thiol group; or an addition reaction product of a guanamine and a monofunctional or polyfunctional isocyanate or an epoxy; A dehydration condensation reaction product of a monofunctional or polyfunctional carboxylic acid or the like is also suitably used. Further, an unsaturated carboxylic acid ester having an isocyanate group or an electrophilic substituent such as an epoxy group or an addition reactant of a guanamine and a monofunctional or polyfunctional alcohol, an amine or a thiol And an unsaturated carboxylic acid ester having a derivatizing substituent such as a halogen group or a tosyloxy group, or a substituted reactant of a decylamine and a monofunctional or polyfunctional alcohol, an amine or a thiol. Also suitable. Further, as another example, a specific example of a monomer in which the above unsaturated carboxylic acid is substituted with a compound aliphatic aliphatic polyol compound such as unsaturated phosphonic acid, styrene or vinyl ether and an ester of an unsaturated carboxylic acid may be used. Examples of the acrylates include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, and neopentyl Diol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene methoxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1, 4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, neopentyl alcohol diacrylate, neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate, dipentaerythritol diacrylate , dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(propylene methoxyethyl) heterotrimerization Cyanate ester, polyester acrylate oligomer, EO change of iso-cyanuric acid Triacrylate.

甲基丙烯酸酯係可舉例如四亞甲基二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、新戊二醇二甲基丙烯酸酯、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、乙二醇二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、己二醇二甲基丙烯酸酯、新戊四醇二甲基丙烯酸酯、新戊四醇三甲基丙烯酸酯、新戊四醇四甲基丙烯酸酯、二新戊四醇二甲基丙烯酸酯、二新戊四醇六甲基丙烯酸酯、山梨糖醇三甲基丙烯酸酯、山梨糖醇四甲基丙烯酸酯、貳[p-(3-甲基丙烯醯氧基-2-羥基丙氧基)苯基]二甲基甲烷、貳-[p-(甲基丙烯醯氧基乙氧基)苯基]二甲基甲烷等。Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethylolpropane trimethacrylate. , trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, hexanediol dimethacrylate, neopentyl glycol Acrylate, neopentyl alcohol trimethacrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol three Methacrylate, sorbitol tetramethacrylate, 贰[p-(3-methylpropenyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, 贰-[p-(甲Acryloxyethoxy)phenyl]dimethylmethane or the like.

衣康酸酯係可舉例如乙二醇二衣康酸酯、丙二醇二衣康酸酯、1,3-丁二醇二衣康酸酯、1,4-丁二醇二衣康酸酯、四亞甲基二醇二衣康酸酯、新戊四醇二衣康酸酯、山梨糖醇四衣康酸酯等。巴豆酸酯係可舉例如乙二醇二巴豆酸酯、四亞甲基二醇二巴豆酸酯、新戊四醇二巴豆酸酯、山梨糖醇四二巴豆酸酯等。異巴豆酸酯係可舉例如乙二醇二異巴豆酸酯、新戊四醇二異巴豆酸酯、山梨糖醇四異巴豆酸酯等。順丁烯二酸酯係可舉例如乙二醇二蘋果酸酯、三乙二醇二蘋果酸酯、新戊四醇二蘋果酸酯、山梨糖醇四蘋果酸酯等。The itaconate ester may, for example, be ethylene glycol pentylene acetate, propylene glycol conjugated acid ester, 1,3-butylene glycol isaconate, 1,4-butanediol conjugated acid ester, Tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetraconate, and the like. Examples of the crotonate include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradodetoic acid ester. Examples of the isocrotonate include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of the maleic acid ester include ethylene glycol di malate, triethylene glycol di malate, neopentyl glycol dimalate, and sorbitol tetramalate.

其他的酯的例子，例如於特公昭51-47334、特開昭57-196231記載的脂肪族醇系酯類、或具有特開昭59-5240、特開昭59-5241、特開平2-226149記載的芳香族系骨架者、含有特開平1-165613記載之胺基者等亦為適宜使用。再者，前述的酯單體係亦可做為混合物使用。Examples of the other esters include, for example, the aliphatic alcohol esters described in Japanese Patent Publication No. Sho 51-47334, JP-A-57-196231, or JP-A-59-5240, JP-A-59-5241, JP-A-2-226149 The aromatic skeleton described above and the amine group described in JP-A-1-156613 are also suitably used. Furthermore, the aforementioned ester monolithic system can also be used as a mixture.

又，脂肪族多價胺化合物與不飽和羧酸之醯胺的單體之具體例係可舉例如亞甲基貳-丙烯醯胺、亞甲基貳-甲基丙烯醯胺、1,6-六亞甲基貳。丙烯醯胺、1,6-六亞甲基貳-甲基丙烯醯胺、二乙三胺參丙烯醯胺、苯二甲基貳丙烯醯胺、苯二甲基貳甲基丙烯醯胺等。其他的較佳醯胺系單體之例子可舉例如具有特公昭54-21726記載的環己烯構造者。Further, specific examples of the monomer of the aliphatic polyvalent amine compound and the decylamine of the unsaturated carboxylic acid include, for example, methylene hydrazine-acrylamide, methylene hydrazine-methacrylamide, 1,6- Hexamethylene hydrazine. Acrylamide, 1,6-hexamethylene fluorene-methacrylamide, diethylenetriamine propylene amide, phenyldimethyl decyl decylamine, benzodimethyl methacrylamide, and the like. Other examples of the preferred amide-based monomer include those having the cyclohexene structure described in JP-A-54-21726.

又，使用異氰酸酯與羥基的加成反應所製造之胺甲酸酯系加成聚合性化合物亦為適宜，像這樣的具體例係可舉例如特公昭48-41708號公報中所記載的在1分子內具有2個以上異氰酸酯基之聚異氰酸酯化合物中，附加含有下述通式(A)所示羥基之乙烯基單體的、於1分子中含有2個以上聚合性乙烯基之乙烯基胺甲酸酯化合物等。In addition, a urethane-based addition polymerizable compound produced by an addition reaction of an isocyanate and a hydroxy group is also suitable, and a specific example thereof is exemplified in JP-A-48-41708. In the polyisocyanate compound having two or more isocyanate groups, a vinylamine containing at least two polymerizable vinyl groups in one molecule is added to a vinyl monomer having a hydroxyl group represented by the following formula (A). Ester compound and the like.

CH2 =C(R34 )COOCH2 CH(R35 )OH(A)CH 2 =C(R 34 )COOCH 2 CH(R 35 )OH(A)

(但是，R34 及R35 係表示H或CH3 )(However, R 34 and R 35 represent H or CH 3 )

又，如特開昭51-37193號、特公平2-32293號、特公平2-16765號中所記載的胺甲酸酯丙烯酸酯類、或具有如特公昭58-49860號、特公昭56-17654號、特公昭62-39417號、特公昭62-39418號記載的環氧乙烷系骨架之胺甲酸酯化合物類亦為適宜。再者，藉由使用特開昭63-277653號、特開昭63-260909號、特開平1-105238號中所記載、於分子内具有胺基構造或硫化物構造之加成聚合性化合物類的話，可得到感光速度非常優異之光聚合性組成物。Further, the urethane acrylates described in JP-A-51-37193, JP-A No. 2-32293, and JP-A No. 2-16765, or JP-A-58-49860, JP-A-56- A urethane compound of an ethylene oxide-based skeleton described in JP-A-62-39417 and JP-A-62-39418 is also suitable. In addition, an addition polymerizable compound having an amine structure or a sulfide structure in a molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-10-15238, is used. In this case, a photopolymerizable composition having a very excellent photospeed can be obtained.

其他之例係可舉例如特開昭48-64183號、特公昭49-43191號、特公昭52-30490號、各公報中所記載的聚酯丙烯酸酯類、環氧樹脂與(甲基)丙烯酸反應之環氧丙烯酸酯類等的多官能丙烯酸酯或甲基丙烯酸酯。又，亦可舉例如特公昭46-43946號、特公平1-40337號、特公平1-40336號記載的特定不飽和化合物、或特開平2-25493號記載的乙烯基膦酸系化合物等。又，某些情形中，使用含有特開昭61-22048號記載的全氟烷基之構造為適宜。再者，亦可使用在日本黏著協會誌vol.20、No.7、第300~308頁(1984年)中做為光硬化性單體及低聚物所介紹者。Other examples include polyester acrylates, epoxy resins, and (meth)acrylic acid described in JP-A-48-64183, JP-A-49-43191, JP-A-52-30490, and each of the publications. A multifunctional acrylate or methacrylate such as an epoxy acrylate which is reacted. In addition, a specific unsaturated compound described in JP-A-46-43946, JP-A No. 1-40337, JP-A No. 1-40336, or a vinylphosphonic acid-based compound described in JP-A No. 2-25493, may be mentioned. Further, in some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is suitable. Further, it can also be used as a photocurable monomer and oligomer in the Japanese Adhesive Society vol. 20, No. 7, pp. 300-308 (1984).

關於此等之加成聚合性化合物，其構造係可單獨使用或併用，添加量等的使用方法的詳細內容，可配合最終的光硬化性組成物的性能設計做任意地設定。例如，可由下述之觀點來做選擇。With respect to these addition polymerizable compounds, the structure can be used singly or in combination, and the details of the method of use such as the amount of addition can be arbitrarily set in accordance with the performance design of the final photocurable composition. For example, the choice can be made from the following points of view.

感度之觀點中，較佳係每1分子之不飽和基含量多的構造，較多時以2官能以上為佳。又，為提高硬化膜的強度，較佳係3官能以上者，再者，藉由併用不同的官能數、不同的聚合性基(例如丙烯酸酯、甲基丙烯酸酯、苯乙烯系化合物、乙烯基醚系化合物)者，以調整感度與強度兩者之方法亦為有效。In the viewpoint of sensitivity, it is preferred that the structure has a large content of unsaturated groups per molecule, and more preferably two or more functional groups. Further, in order to increase the strength of the cured film, it is preferably a trifunctional or higher functional group, and further, different functional groups and different polymerizable groups (for example, acrylate, methacrylate, styrene compound, vinyl) are used in combination. In the case of an ether compound, it is also effective to adjust both sensitivity and strength.

又，對於與光硬化性組成物之中的其他成分(例如，鹼可溶性樹脂等的黏結劑聚合物、光聚合起始劑、著色劑(顔料)的相溶性、分散性，加成聚合化合物的選擇．使用法亦為重要的要因，例如低純度化合物的使用、或藉由併用2種以上可使得相溶性提昇。In addition, compatibility with other components (for example, a binder polymer such as an alkali-soluble resin, a photopolymerization initiator, a colorant (pigment), and dispersibility of the photocurable composition, addition polymerization compound The method of use is also an important factor, for example, the use of a low-purity compound or the combination of two or more can improve the compatibility.

又，以提昇與基板等的黏附性為目的，亦可選擇特定的構造。Moreover, it is also possible to select a specific structure for the purpose of improving adhesion to a substrate or the like.

加成聚合性化合物係相對於光硬化性組成物中的不揮發性成分，較佳在5~70質量%、更佳在10~60質量%的範圍使用。又，此等係可單獨使用、亦可2種以上合併使用。除此之外，加成聚合性化合物的使用法，從對於氧之聚合阻礙大小、解像度、泛白性、折射率變化、表面黏著性等的觀點，可任意選擇適合的構造、配合、添加量。The addition polymerizable compound is preferably used in an amount of from 5 to 70% by mass, more preferably from 10 to 60% by mass, based on the nonvolatile component in the photocurable composition. Further, these may be used singly or in combination of two or more. In addition, the method of using the addition polymerizable compound can arbitrarily select an appropriate structure, blending, and addition amount from the viewpoints of inhibition of oxygen polymerization, size, resolution, whitening property, refractive index change, surface adhesion, and the like. .

[光聚合起始劑][Photopolymerization initiator]

本發明有關的光硬化性組成物係含有光聚合起始劑之至少一種。The photocurable composition according to the present invention contains at least one of photopolymerization initiators.

光聚合起始劑係可舉例如特開平57-6096號公報中所記載之鹵甲基二唑(halomethyl oxadiazole)、特公昭59-1281號公報、特開昭53-133428號公報等中所記載之鹵甲基-s-三等活性鹵化合物、美國專利USP-4318791、歐洲專利公開EP-88050A等的各說明書中所記載之縮酮、乙縮醛、或苯偶姻烷基醚類等的芳香族羰基化合物、美國專利USP-4199420說明書中所記載之二苯基酮類等的芳香族酮化合物、Fr-2456741說明書中所記載之(9-氧雜) 類或吖啶系化合物、特開平10-62986號公報中所記載之香豆素系或聯二咪唑系等的化合物、特開平8-015521號公報等的鎏有機硼素錯體等等。The photopolymerization initiator may, for example, be a halomethyl group described in JP-A-57-6096. Halomethyl-s-three described in halomethyl oxadiazole, JP-A-59-1281, and JP-A-53-133428 An aromatic carbonyl compound such as a ketal, an acetal or a benzoin alkyl ether described in each of the specifications of the active halogen compound, the US Patent No. US-A-4318791, and the European Patent Publication No. EP-88050A, USP -4199420, an aromatic ketone compound such as a diphenyl ketone or a (9-oxa) described in the specification of Fr-2456741 A compound such as a coumarin-based compound or a biimidazole-based compound described in JP-A-10-62986, or a bismuth organoboron conjugate such as JP-A-8-015521.

其中，光聚合起始劑係較佳為苯乙酮系、縮酮系、二苯基酮系、苯偶姻系、苯甲醯系、酮系、活性鹵化合物(三系、鹵甲基二唑系、香豆素系)、吖啶系、聯二咪唑系、肟酯系等。Among them, the photopolymerization initiator is preferably an acetophenone-based, a ketal-based, a diphenylketone-based, a benzoin-based system, or a benzamidine-based system. Ketone system, active halogen compound (three Halomethyl An oxadiazole system, a coumarin system, an acridine system, a biimidazole system, an oxime ester system, and the like.

前述苯乙酮系的光聚合起始劑係可適宜舉例如2,2-二乙氧基苯乙酮、p-二甲基胺基苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、p-二甲基胺基苯乙酮、4’-異丙基-2-羥基-2-甲基-苯丙酮、1-羥基-環己基-苯基-酮、2-苄基-2-二甲基胺基-1-(4-啉基苯基)-丁酮-1、2-甲苯基-2-二甲基胺基-1-(4-啉基苯基)-丁酮-1、2-甲基-1-[4-(甲硫基)苯基]-2-啉基丙酮-1等。The acetophenone-based photopolymerization initiator may, for example, be 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone or 2-hydroxy-2-methyl-1- Phenyl-propan-1-one, p-dimethylaminoacetophenone, 4'-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-one 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)-butanone-1, 2-tolyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2- Orolinic acetone-1 and the like.

前述縮酮系的光聚合起始劑係可適宜舉例如苄基二甲基縮酮、苄基-β-甲氧基乙基乙縮醛等。The ketal-based photopolymerization initiator may, for example, be benzyl dimethyl ketal or benzyl-β-methoxyethyl acetal.

前述二苯基酮系的光聚合起始劑係可適宜舉例如二苯基酮、4,4’-(雙二甲基胺基)二苯基酮、4,4’-(雙二乙基胺基)二苯基酮、4,4’-二氯基二苯基酮等。The diphenyl ketone-based photopolymerization initiator may, for example, be diphenyl ketone, 4,4'-(bisdimethylamino)diphenyl ketone or 4,4'-(bisdiethyl). Amino)diphenyl ketone, 4,4'-dichlorodiphenyl ketone, and the like.

前述苯偶姻系或苯甲醯系的光聚合起始劑係可適宜舉例如苯偶姻異丙基醚、苯偶姻異丁基醚、苯偶姻甲基醚、甲基o-苯甲醯基苯甲酸酯等。The photopolymerization initiator of the above benzoin or benzamidine type may, for example, be benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether or methyl o-benzoic acid. Mercaptobenzoic acid ester and the like.

前述酮系的光聚合起始劑係可適宜舉例如二乙硫基酮、二異丙硫基酮、單異丙硫基酮、氯硫基酮、等。The foregoing A ketone-based photopolymerization initiator may suitably be, for example, a diethylthio group. Ketone, diisopropylthio Ketone, monoisopropylthio Ketone, chlorothio Ketone, etc.

前述活性鹵素光聚合起始劑(三系，二唑系，香豆素系)的光聚合起始劑係可適宜舉例如2,4-貳(三氯基甲基)-6-p-甲氧基苯基-s-三、2,4-貳(三氯基甲基)-6-p-甲氧基苯乙烯基-s-三、2，4-貳(三氯基甲基)-6-(1-p-二甲基胺基苯基)-1,3-丁二烯基-s-三、2,4-貳(三氯基甲基)-6-聯苯-s-三、2，4-貳(三氯基甲基)-6-(p-甲基聯苯)-s-三、p-羥基乙氧基苯乙烯基-2,6-二(三氯基甲基)-s-三、甲氧基苯乙烯基-2,6-二(三氯基甲基)-s-三、3,4-二甲氧基苯乙烯基-2,6-二(三氯基甲基)-s-三、4-苯并氧雜環戊烷-2,6-二(三氯基甲基)-s-三、4-(o-溴基-p-N,N-(二乙氧基羰基胺基)-苯基)-2,6-二(氯基甲基)-s-三、4-(p-N,N-(二乙氧基羰基胺基)-苯基)-2,6-二(氯基甲基)-s-三、2-三氯基甲基-5-苯乙烯基-1,3,4-二唑、2-三氯基甲基-5-(氰基苯乙烯基)-1,3,4-二唑、2-三氯基甲基-5-(萘甲醯-1-基)-1,3,4-二唑、2-三氯基甲基-5-(4-苯乙烯基)苯乙烯基-1,3,4-二唑,3-甲基-5-胺基-((s-三-2-基)胺基)-3-苯基香豆素、3-氯基-5-二乙基胺基-((s-三-2-基)胺基)-3-苯基香豆素、3-丁基-5-二甲基胺基-((s-三-2-基)胺基)-3-苯基香豆素等。The aforementioned reactive halogen photopolymerization initiator (three system, The photopolymerization initiator of the oxadiazole system and the coumarin system may suitably be, for example, 2,4-indole (trichloromethyl)-6-p-methoxyphenyl-s-three. 2,4-贰(trichloromethyl)-6-p-methoxystyryl-s-three 2,4-贰(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3-butadienyl-s-three 2,4-贰(trichloromethyl)-6-biphenyl-s-three 2,4-贰(trichloromethyl)-6-(p-methylbiphenyl)-s-three , p-hydroxyethoxystyryl-2,6-di(trichloromethyl)-s-three Methoxystyryl-2,6-di(trichloromethyl)-s-three 3,4-dimethoxystyryl-2,6-di(trichloromethyl)-s-three 4-benzooxol-2,6-di(trichloromethyl)-s-three 4-(o-bromo-pN,N-(diethoxycarbonylamino)-phenyl)-2,6-di(chloromethyl)-s-three , 4-(pN,N-(diethoxycarbonylamino)-phenyl)-2,6-di(chloromethyl)-s-three 2-trichloromethyl-5-styryl-1,3,4- Diazole, 2-trichloromethyl-5-(cyanostyryl)-1,3,4- Diazole, 2-trichloromethyl-5-(naphthoquinone-1-yl)-1,3,4- Diazole, 2-trichloromethyl-5-(4-styryl)styryl-1,3,4- Diazole, 3-methyl-5-amino-((s-three) -2-yl)amino)-3-phenylcoumarin, 3-chloro-5-diethylamino-((s-three) -2-yl)amino)-3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-three) -2-yl)amino)-3-phenylcoumarin.

前述吖啶類系的光聚合起始劑係可適宜舉例如9-苯基吖啶、1,7-貳(9-吖啶基)庚烷等。The acridine-based photopolymerization initiator may, for example, be, for example, 9-phenyl acridine or 1,7-fluorene (9-acridinyl) heptane.

前述聯二咪唑系的光聚合起始劑係可適宜舉例如2-(o-氯基苯基)-4,5-二苯基咪唑二聚物、2-(o-甲氧基苯基)-4,5-二苯基咪唑二聚物、2-(2,4-二甲氧基苯基)-4,5-二苯基咪唑二聚物等。The bisimidazole-based photopolymerization initiator may, for example, be 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer or 2-(o-methoxyphenyl). -4,5-diphenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer, and the like.

除上述以外，可舉例如1-苯基-1,2-丙二酮-2-(o-乙氧基羰基)肟、o-苯甲醯基-4’-(苯并氫硫基)苯甲醯基-己基-酮肟、2,4,6-三甲基苯基羰基-二苯基磷氧化物、六氟膦酸基-三烷基苯基鏻鹽等。In addition to the above, for example, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)anthracene, o-benzimidyl-4'-(benzohydrothio)benzene Mercapto-hexyl-ketooxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphine oxide, hexafluorophosphonic acid-trialkylphenyl phosphonium salt, and the like.

本發明中所使用的光聚合起始劑係不限定於以上的光聚合起始劑，亦可使用其他眾所周知者。例如，可舉例美國專利第2,367,660號說明書中所記載之連位聚酮醇醛醇化合物、美國專利第2,367,661號及第2,367,670號說明書中所記載之α-羰基化合物、美國專利第2,448,828號說明書中所記載之偶因醚、美國專利第2,722,512號說明書中所記載之α-烴經取代之芳香族偶因化合物、美國專利第3,046,127號及第2,951,758號說明書中所記載之多核醌化合物、美國專利第3,549,367號說明書中所記載之三烯丙基咪唑二聚物/p-胺基苯基酮的組合、特公昭51-48516號公報中所記載之苯并噻唑系化合物/三鹵甲基-s-三系化合物等。The photopolymerization initiator used in the present invention is not limited to the above photopolymerization initiator, and other known ones may be used. For example, the vicinal polyaldol alcohol compound described in the specification of U.S. Patent No. 2,367,660, the α-carbonyl compound described in the specification of U.S. Patent Nos. 2,367,661 and 2,367,670, and the specification of U.S. Patent No. 2,448,828. The polyether cation compound described in the specification of U.S. Patent No. 2,722, 512, and the polynuclear ruthenium compound described in the specification of U.S. Patent Nos. 3,046,127 and 2,951,758, U.S. Patent No. 3,549,367. The combination of the triallyl imidazole dimer/p-aminophenyl ketone described in the specification, the benzothiazole compound/trihalomethyl-s-three described in Japanese Patent Publication No. Sho 51-48516 A compound or the like.

又，亦可併用此等之光聚合起始劑。Further, such photopolymerization initiators may be used in combination.

在光硬化性組成物中光聚合起始劑的含量係相對於該組成物的總固體成分，以0.1~15.0質量%為佳、更佳為0.5~10.0質量%。光聚合起始劑的含量在該範圍内時，聚合反應係能良好地進行且可形成強度良好的膜。The content of the photopolymerization initiator in the photocurable composition is preferably from 0.1 to 15.0% by mass, more preferably from 0.5 to 10.0% by mass, based on the total solid content of the composition. When the content of the photopolymerization initiator is within this range, the polymerization reaction proceeds well and a film having good strength can be formed.

本發明有關的光硬化性組成物若以提高光聚合起始劑(自由基起始劑)的自由基發生效率、感光波長的長波長化為目的的話，亦可含有增感劑。The photocurable composition according to the present invention may contain a sensitizer for the purpose of increasing the radical generating efficiency of the photopolymerization initiator (radical initiator) and increasing the wavelength of the photosensitive wavelength.

可使用於本發明之增感劑係對於自由基起始劑，能以電子移動機構或能量移動機構增感者為佳。It is preferred that the sensitizer used in the present invention is sensitized to an electron-transporting mechanism or an energy-moving mechanism for a radical initiator.

可使用於本發明之增感劑係屬於以下所列舉之化合物類，且可舉例如在300nm~450nm的波長領域具有吸收波長者。The sensitizer to be used in the present invention belongs to the following compounds, and may, for example, have an absorption wavelength in the wavelength range of 300 nm to 450 nm.

較佳的增感劑之例子可舉例如屬於以下的化合物類，且在330nm至450nm領域具有吸收波長者。Examples of preferred sensitizers include, for example, the following compounds and those having an absorption wavelength in the field of 330 nm to 450 nm.

例如，可舉例多核芳香族類(例如，菲、蒽、芘、苝、三鄰亞苯、9,10-二烷氧基蒽)、 類(例如，螢光素(Fluorescein)、曙紅(Eosin)、赤蘚紅鈉鹽、若丹明B、玫瑰紅)、硫酮類(異丙硫基酮、二乙硫基酮、氯硫基酮)、花青類(例如硫羰花青、氧雜羰花青)、部花青類(例如，部花青、羰部花青)、酞菁類、噻類(例如，硫堇、亞甲藍、甲苯胺藍)、吖啶類(例如，吖啶橙、氯基黃素、吖啶黃素)、蒽醌類(例如，蒽醌)、方形鎓類(squaryliums)(例如，方形)、吖啶橙、香豆素類(例如，7-二乙基胺基-4-甲基香豆素)、酮香豆素、啡噻類、啡類、苯乙烯基苯類、偶氮化合物、二苯基甲烷、三苯基甲烷、二苯乙烯基苯類、咔唑類、卟啉、螺環化合物、喹吖啶酮、靛藍、苯乙烯基、吡喃鎓化合物、亞甲吡咯化合物、吡唑啉***化合物、苯并噻唑化合物、巴比妥酸衍生物、硫代巴比妥酸衍生物、苯乙酮、二苯基酮、硫酮、米其勒酮等的芳香族酮化合物、N-芳基唑烷酮等的雜環化合物等。For example, polynuclear aromatics (for example, phenanthrene, anthracene, anthracene, anthracene, tri-o-phenylene, 9,10-dialkoxyfluorene), Classes (eg, Fluorescein, Eosin, Erythrosin sodium, Rhodamine B, Rose Red), Sulfur Ketones Ketone, diethylthio Ketone, chlorothio Ketones, cyanines (eg, thiocarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbocyanine), phthalocyanines, thiophenes Classes (eg, thioindigo, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acridine flavin), terpenoids (eg, guanidine), square steroids (squaryliums) (for example, square ), acridine orange, coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarin, thiophene Class, brown , styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, oxazoles, porphyrins, spiro compounds, quinacridones, indigo, styryl , pyrylium compound, methylene pyrrole compound, pyrazoline triazole compound, benzothiazole compound, barbituric acid derivative, thiobarbituric acid derivative, acetophenone, diphenyl ketone, sulfur Aromatic ketone compounds such as ketones and miscules, N-aryl groups a heterocyclic compound such as an oxazolidinone or the like.

本發明有關的光硬化性組成物係亦可含有共增感劑。在本發明光硬化性組成物的共增感劑係具有能使對於增感色素或起始劑之活性放射線的感度更一層的提昇、或能抑制因為氧所引起的聚合性化合物之聚合阻礙等的作用。The photocurable composition according to the present invention may further contain a co-sensitizer. The co-sensitizer of the photocurable composition of the present invention has an effect of improving the sensitivity of the active radiation to the sensitizing dye or the initiator, or suppressing polymerization inhibition of the polymerizable compound due to oxygen. The role.

像這樣的共增感劑之例子可舉例如胺類、例如M.R.sander等人著「Journal of Polymer Society」第10巻3173頁(1972)、特公昭44-20189號公報、特開昭51-82102號公報、特開昭52-134692號公報、特開昭59-138205號公報、特開昭60-84305號公報、特開昭62-18537號公報、特開昭64-33104號公報、Research Disclosure 33825號記載的化合物等，具體而言，可舉例如三乙醇胺、p-二甲基胺基安息香酸乙酯、p-甲醯基二甲基苯胺、p-甲硫基二甲基苯胺等。Examples of such a co-sensitizer include, for example, an amine, for example, MRsander, et al., "Journal of Polymer Society", pp. 10, pp. 3173 (1972), Japanese Patent Publication No. 44-20189, and JP-A-51-82102. Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Specific examples of the compound and the like described in No. 33,825 include triethanolamine, p-dimethylamino benzoic acid ethyl ester, p-methylmercaptodimethylaniline, p-methylthiodimethylaniline, and the like.

共增感劑之其他例子係可舉例如硫醇及硫化物類、例如，特開昭53-702號公報、特公昭55-500806號公報、特開平5-142772號公報記載的硫醇化合物、特開昭56-75643號公報的二硫化物化合物等，具體而言，可舉例如2-氫硫基苯并噻唑、2-氫硫基苯并唑、2-氫硫基苯并咪唑、2-氫硫基-4(3H)-喹唑啉、β-氫硫基萘等。Other examples of the co-sensitizers include, for example, a thiol compound, and a thiol compound described in JP-A-53-500806 The disulfide compound or the like of JP-A-56-75643, specifically, for example, 2-hydrothiobenzothiazole or 2-hydrothiobenzophenone Oxazole, 2-hydrothiobenzimidazole, 2-hydrothio-4(3H)-quinazoline, β-hydrothionaphthalene, and the like.

又，其他例子係可舉例如胺基氧化合物(例如：N-苯基甘胺酸等)、特公昭48-42965號公報記載的有機金屬化合物(例如：三丁基錫乙酸酯等)、特公昭55-34414號公報記載的氫供與體、特開平6-308727號公報記載的硫磺化合物(例如：三聚甲硫醛等)等。In addition, other examples include an organometallic compound (for example, N-phenylglycine), an organometallic compound (for example, tributyltin acetate, etc.) described in JP-A-48-42965, and a special public. A sulfur-containing compound (for example, trimeric methyl mercapaldehyde or the like) described in JP-A-H05-344727, and the like.

此等共增感劑的含量係從由於聚合成長速度與鏈移動的平衡會使硬化速度提昇之觀點，相對於光硬化性組成物的總固體成分質量，以0.1~30質量%的範圍為佳、1~25質量%的範圍為較佳、0.5~20質量%的範圍為更佳。The content of the co-sensitizer is preferably from 0.1 to 30% by mass based on the total solid content of the photocurable composition from the viewpoint of increasing the curing rate due to the balance between the polymerization growth rate and the chain shift. The range of 1 to 25% by mass is preferably in the range of 0.5 to 20% by mass.

接著，說明上述以外之成分。Next, components other than the above will be described.

[溶劑][solvent]

本發明有關的光硬化性組成物一般係可使用上述成分以及溶劑而適宜地調製。The photocurable composition according to the present invention can be suitably prepared by using the above components and a solvent.

做為溶劑者，酯類係可舉例如乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、烷酯類、乳酸甲酯、乳酸乙酯、羥乙酸甲酯、羥乙酸乙酯、羥乙酸丁酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、以及、3-羥丙酸甲酯及3-羥丙酸乙酯等的3-羥丙酸烷酯類(例如，3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯)、以及2-羥丙酸甲酯、2-羥丙酸乙酯、及2-羥丙酸丙酯等的2-羥丙酸烷酯類(例如，2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-氧基-2-甲基丙酸甲酯、2-氧基-2-甲基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯)、以及丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-丁酮酸甲酯、2-丁酮酸乙酯等；As the solvent, the ester may, for example, be ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate or isopropyl butyrate. Ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl glycolate, ethyl hydroxyacetate, butyl glycolate, methyl methoxyacetate, ethyl methoxyacetate , 3-hydroxypropionic acid alkyl esters such as butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate ( For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and 2-hydroxypropionic acid An alkyl 2-hydroxypropionate such as an ester, ethyl 2-hydroxypropionate or propyl 2-hydroxypropionate (for example, methyl 2-methoxypropionate or ethyl 2-methoxypropionate) , propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropanoate, 2-oxy- Ethyl 2-methylpropionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, and methyl pyruvate, Ketone, ethyl pyruvate, propyl pyruvate, acetyl methyl acetate, ethyl acetyl, 2-butanone, methyl, and ethyl 2-butanone;

醚類係可舉例如二甘醇二甲基醚、四氫呋喃、乙二醇單甲基醚、乙二醇單乙基醚、甲基乙二醇***乙酸酯、乙基乙二醇***乙酸酯、二甘醇單甲基醚、二甘醇單乙基醚、二甘醇單丁基醚、丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯、丙二醇丙基醚乙酸酯等；Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl glycol diethyl ether acetate, and ethyl glycol diethyl ether acetate. Ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc. ;

酮類係可舉例如甲基乙基酮、環己酮、2-庚酮、3-庚酮等；Examples of the ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like;

芳香族烴類係可舉例如甲苯、二甲苯等。Examples of the aromatic hydrocarbons include toluene and xylene.

此等之中，較佳係3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙基乙二醇***乙酸酯、乳酸乙酯、二甘醇二甲基醚、乙酸丁酯、3-甲氧基丙酸甲酯、2-庚酮、環己酮、乙基二甘醇一***乙酸酯、丁基二甘醇一***乙酸酯、丙二醇甲基醚乙酸酯等。Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl glycol ethyl ether acetate, ethyl lactate, diethylene glycol dimethyl ether, Butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl diglycol monoethyl ether acetate, butyl diglycol monoethyl ether acetate, propylene glycol methyl ether Acid esters, etc.

溶劑係除了單獨使用以外，亦可組合2種以上使用。The solvent may be used alone or in combination of two or more.

[其他成分][Other ingredients]

本發明有關的光硬化性組成物中，可視需要含有氟系有機化合物、熱聚合抑制劑、填充劑、特定顔料分散劑及前述鹼可溶性樹脂以外的高分子化合物、界面活性劑、黏附促進劑、抗氧化劑、紫外線吸收劑、凝集抑制劑等的各種添加物。The photocurable composition according to the present invention may optionally contain a fluorine-based organic compound, a thermal polymerization inhibitor, a filler, a specific pigment dispersant, and a polymer compound other than the alkali-soluble resin, a surfactant, an adhesion promoter, and Various additives such as antioxidants, ultraviolet absorbers, and aggregation inhibitors.

<氟系有機化合物><Fluorine organic compound>

藉由含有氟系有機化合物，可改善做為塗布液時的液體特性(特別是流動性)，且可改善塗布厚度的均一性或省液性。亦即，由於基板與塗布液的界面張力降低且對基板的濕潤性係為改善、對基板的塗布性係為提昇之故，所以從即使在以少量的液量形成數μm左右之薄膜的情形，亦可形成厚度不均小且均一厚度的膜之點而言係為有效。By containing a fluorine-based organic compound, liquid characteristics (especially fluidity) when used as a coating liquid can be improved, and uniformity of coating thickness or liquid-saving property can be improved. In other words, since the interfacial tension between the substrate and the coating liquid is lowered, the wettability to the substrate is improved, and the coating property to the substrate is improved, the film is formed from a film having a small amount of liquid by a small amount of liquid. It is also effective in forming a film having a small thickness unevenness and a uniform thickness.

氟系有機化合物的氟含有率係較佳為3~40質量%，更佳為5~30質量%，特佳為7~25質量%。氟含有率在該範圍内時，從塗布厚度均一性或省液性之點而言為有效的，且於組成物中的溶解性亦為良好。The fluorine content of the fluorine-based organic compound is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, particularly preferably from 7 to 25% by mass. When the fluorine content is within this range, it is effective from the viewpoint of coating thickness uniformity or liquid-saving property, and the solubility in the composition is also good.

氟系有機化合物係可舉例如Megaface F171、同F172、同F173、同F177、同F141、同F142、同F143、同F144、同R30、同F437(以上，DIC Corporation製)、Fluorad FC430、同FC431、同FC171(以上，住友3M(股)製)、surfron S-382、同SC-101、同SC-103、同SC-104、同SC-105、同SC1068、同SC-381、同SC-383、同S393、同KH-40(以上，旭硝子(股)製)等。Examples of the fluorine-based organic compound include Megaface F171, F172, F173, F177, F141, F142, F143, F144, R30, F437 (above, DIC Corporation), Fluorad FC430, and FC431. With FC171 (above, Sumitomo 3M (share) system), surfron S-382, same SC-101, same SC-103, same SC-104, same SC-105, same SC1068, same SC-381, same SC- 383, with S393, with KH-40 (above, Asahi Glass Co., Ltd.).

氟系有機化合物係特別是在例如塗布形成之塗布膜太薄時，防止塗布不均或厚度不均上為有效的。又，即使在容易引起液切之狹縫塗布中亦為有效的。The fluorine-based organic compound is particularly effective in preventing coating unevenness or thickness unevenness, for example, when the coating film formed by coating is too thin. Moreover, it is effective even in the slit coating which is easy to cause liquid cutting.

氟系有機化合物的添加量係相對於顔料分散組成物或光硬化性組成物的總質量，以0.001~2.0質量%為佳、更佳為0.005~1.0質量%。The amount of the fluorine-based organic compound to be added is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the pigment dispersion composition or the photocurable composition.

<熱聚合起始劑><Thermal polymerization initiator>

本發明有關的光硬化性組成物中含有熱聚合起始劑亦為有效。熱聚合起始劑係可舉例如各種的偶氮系化合物、過氧化物系化合物，前述偶氮系化合物係可舉例如偶氮雙系化合物，前述過氧化物系化合物係可舉例如酮過氧化物、過氧化縮酮、氫過氧化物、二烷基過氧化物、二醯基過氧化物、過氧化酯、過氧化二碳酸酯等。It is also effective to contain a thermal polymerization initiator in the photocurable composition according to the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds, and examples of the azo compound include azobis compounds, and examples of the peroxide compounds include ketone peroxidation. , peroxy ketal, hydroperoxide, dialkyl peroxide, dimercapto peroxide, peroxyester, peroxydicarbonate, and the like.

<界面活性劑><Surfactant>

本發明有關的光硬化性組成物中，從改善塗布性之觀點，較佳係使用各種的界面活性劑而構成的，且可使用非離子系、陽離子系、陰離子系的各種界面活性劑。其中，尤以非離子系界面活性劑中具有全氟基烷基之氟系界面活性劑為佳。In the photocurable composition according to the present invention, various surfactants are preferably used from the viewpoint of improving coatability, and various surfactants of nonionic, cationic or anionic type can be used. Among them, a fluorine-based surfactant having a perfluoroalkyl group in the nonionic surfactant is particularly preferred.

氟系界面活性劑之具體例係可舉例如DIC Corporation製的Megaface(註冊商標)系列、3M公司製的F1uorad(註冊商標)系列等。Specific examples of the fluorine-based surfactant include, for example, the Megaface (registered trademark) series manufactured by DIC Corporation, and the F1uorad (registered trademark) series manufactured by 3M Company.

除上述以外，光硬化性組成物中，添加物的具體例可舉例如玻璃、氧化鋁等的填充劑；衣康酸共聚物、巴豆酸共聚物、順丁烯二酸共聚物、部分酯化順丁烯二酸共聚物、酸性纖維素衍生物、於具有羥基之聚合物附加酸酐者、醇可溶性耐綸、由雙酚A與環氧氯丙烷所形成之苯氧基樹脂等的鹼可溶樹脂；非離子系、陽離子系、陰離子系等的界面活性劑，具體上可舉例如酞菁衍生物(市售品EFKA-745(森下產業公司製))；有機矽氧烷聚合物KP341(信越化學工業公司製)、(甲基)丙烯酸系(共)聚合物Polyflow No.75、No.90、No.95(共榮社油脂化學工業公司製)、W001(裕商公司製)等的陽離子系界面活性劑；In addition to the above, specific examples of the additive in the photocurable composition include a filler such as glass or alumina; an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification. An acid soluble in a maleic acid copolymer, an acidic cellulose derivative, a polymer anhydride having a hydroxyl group, an alcohol-soluble nylon, a phenoxy resin formed from bisphenol A and epichlorohydrin In particular, a surfactant such as a nonionic, a cationic or an anionic surfactant, for example, a phthalocyanine derivative (commercial product EFKA-745 (manufactured by Morishita Sangyo Co., Ltd.)); an organic siloxane polymer KP341 (Shin-Etsu Catalysts of Chemical Industry Co., Ltd., (meth)acrylic (co)polymers Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoei Oil & Fat Chemicals Co., Ltd.), W001 (manufactured by Yusei Co., Ltd.) System surfactant;

其他添加物等之例係可舉例如聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油烯基醚、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、山梨糖醇酐脂肪酸酯(BASF公司製的Pluronic L10、L31、L61、L62、10R5、17R2、25R2、Tetronic 304、701、704、901、904、150R1等的非離子系界面活性劑；W004、W005、W017(裕商公司製)等的陰離子系界面活性劑；EFKA-46、EFKA-47、EFKA-47EA、EFKA聚合物100、EFKA聚合物400、EFKA聚合物401、EFKA聚合物450(以上森下產業公司製)、Disperse aid 6、Disperse aid 8、Disperse aid15、Disperse aid9100(San Nopco Limited製)等的高分子分散劑；Solsperse 3000、5000、9000、12000、13240、13940、17000、24000、26000、28000等的各種Solsperse分散劑(Zeneca公司製)；Adeka Pluronic L31,F38,L42,L44,L61,L64,F68,L72,P95,F77,P84,F87、P94,L101,P103,F108、L121、P-123(旭電化公司製)及Isonet S-20(三洋化成公司製)；2-(3-第三丁基-5-甲基-2-羥基苯基)-5-氯基苯并***、烷氧基二苯基酮等的紫外線吸收劑；及聚丙烯酸鈉等的凝集抑制劑。Examples of other additives and the like include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether. , polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, manufactured by BASF Corporation) Nonionic surfactants such as 701, 704, 901, 904, and 150R1; anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer dispersion of polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse aid 6, Disperse aid 8, Disperse aid 15, Disperse aid 9100 (manufactured by San Nopco Limited) Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc., various Solsperse dispersants (manufactured by Zeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (made by Asahi Kasei Co., Ltd.) and Iso Net S-20 (manufactured by Sanyo Chemical Co., Ltd.); 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, alkoxydiphenyl ketone, etc. A UV absorber; and an agglutination inhibitor such as sodium polyacrylate.

又，謀求促進未硬化部的鹼溶解性、使光硬化性組成物的顯像性能更為提昇之情形中，可在光硬化性組成物中進行有機羧酸、較佳為分子量1000以下之低分子量有機羧酸的添加。具體而言，可舉例如甲酸、乙酸、丙酸、丁酸、戊酸、新戊酸、己酸、二乙基乙酸、庚酸、辛酸等的脂肪族單羧酸；草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、巴西二酸、甲基丙二酸、乙基丙二酸、二甲基丙二酸、甲基琥珀酸、四甲基琥珀酸、檸康酸等的脂肪族二羧酸；丙三羧酸、烏頭酸、樟腦三酸等的脂肪族三羧酸；安息香酸、苯乙酸、茴香甲酸、2,3-二甲基苯甲酸、3,5-二甲基苯甲酸等的芳香族單羧酸；酞酸、異酞酸、對酞酸、偏苯三酸、均苯三甲酸、偏苯四甲酸、均苯四甲酸等的芳香族聚羧酸；苯基乙酸、氫化阿托酸、氫化肉桂酸、扁桃酸、苯基琥珀酸、阿托酸、肉桂酸、肉桂酸甲酯、肉桂酸苄酯、伸肉桂基乙酸、香豆酸、傘形酸等的其他的羧酸。Further, in the case where the alkali solubility of the uncured portion is promoted and the development performance of the photocurable composition is further improved, the organic carboxylic acid can be formed in the photocurable composition, preferably having a molecular weight of 1,000 or less. Addition of molecular weight organic carboxylic acids. Specific examples thereof include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid, and caprylic acid; oxalic acid, malonic acid, and the like. Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, An aliphatic dicarboxylic acid such as methyl succinic acid, tetramethyl succinic acid or citraconic acid; an aliphatic tricarboxylic acid such as glycerin tricarboxylic acid, aconitic acid or camphoric acid; benzoic acid, phenylacetic acid, anisic acid, An aromatic monocarboxylic acid such as 2,3-dimethylbenzoic acid or 3,5-dimethylbenzoic acid; citric acid, isophthalic acid, p-citric acid, trimellitic acid, trimesic acid, and benzene An aromatic polycarboxylic acid such as tetracarboxylic acid or pyromellitic acid; phenylacetic acid, hydrogenated atropic acid, hydrogenated cinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, cinnamic acid Other carboxylic acids such as benzyl ester, cinnamyl acetic acid, coumaric acid, and umbrella acid.

<熱聚合抑制劑><thermal polymerization inhibitor>

本發明的光硬化性組成物中，較佳係更添加熱聚合抑制劑，例如以氫醌、p-甲氧基酚、二-第三丁基-p-甲酚、焦棓酚、第三丁基鄰苯二酚、苯醌、4,4’-硫貳(3-甲基-6-第三丁基酚)、2,2’-亞甲基貳(4-甲基-6-第三丁基酚)、2-氫硫基苯并咪唑等為有用。In the photocurable composition of the present invention, it is preferred to further add a thermal polymerization inhibitor such as hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, and third. Butyl catechol, benzoquinone, 4,4'-thiopurine (3-methyl-6-tert-butylphenol), 2,2'-methylene hydrazine (4-methyl-6- Tributylphenol), 2-hydrothiobenzimidazole, and the like are useful.

本發明有關的光硬化性組成物係可藉由在已述之顔料分散組成物中含有鹼可溶性樹脂、光聚合性化合物、及光聚合起始劑(較佳係與溶劑一起)，且於其中混合視需要的界面活性劑等的添加劑而調製。The photocurable composition according to the present invention may comprise an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator (preferably together with a solvent) in the pigment dispersion composition described above, and The mixture is prepared by mixing an additive such as a surfactant.

<彩色濾光片及其製造方法><Color filter and method of manufacturing the same>

本發明的彩色濾光片係可藉由使用已述之本發明有關的光硬化性組成物，在玻璃等的基板上形成經著色之膜(著色圖案)而製作者。The color filter of the present invention can be produced by forming a colored film (colored pattern) on a substrate such as glass by using the photocurable composition according to the present invention.

具體而言，前述光硬化性組成物係藉由直接或透過其他之層賦予(較佳係藉由回轉塗布、狹縫塗布、流延塗布、軋輥塗布等的塗布方法來塗布)至基板上以形成感光性膜，並在所形成之感光性膜上，透過規定之遮罩圖案進行曝光，且在曝光後以顯像液顯像除去未硬化部，藉以形成各色(例如3色或4色)的著色圖案(例如著色像素)，而最適於製造彩色濾光片。Specifically, the photocurable composition is applied directly or through another layer (preferably by a coating method such as spin coating, slit coating, cast coating, roll coating, etc.) onto the substrate. Forming a photosensitive film, exposing through a predetermined mask pattern on the formed photosensitive film, and removing the uncured portion by developing with a developing liquid after exposure, thereby forming respective colors (for example, three colors or four colors) The color pattern (such as colored pixels) is best suited for the manufacture of color filters.

藉此，液晶顯示裝置或固體攝像元件中所使用的彩色濾光片係可以製程上困難性少、高品質且低成本的方式製作。Thereby, the color filter used in the liquid crystal display device or the solid-state image sensor can be produced in a manner that is less difficult in process, high in quality, and low in cost.

此時，用於曝光之放射線係特別是以g線、h線、i線、j線等的紫外線為佳。In this case, the radiation system for exposure is preferably ultraviolet rays such as g-line, h-line, i-line, or j-line.

由賦予(較佳為塗布)至基板上的本發明光硬化性組成物而成之膜的乾燥(預烘烤(pre-bake))，係可使用加熱板、烘箱等且在50~140℃的溫度範圍、以10~300秒的條件下來進行。Drying (pre-bake) of a film obtained by imparting (preferably coating) to the photocurable composition of the present invention on a substrate can be carried out using a hot plate, an oven or the like at 50 to 140 ° C. The temperature range is 10 to 300 seconds.

所謂的顯像係使曝光後的未硬化部於顯像液中溶出，僅殘留硬化部。顯像溫度係通常為20~30℃，顯像時間係通常為20~90秒。In the so-called development system, the unhardened portion after exposure is eluted in the developing liquid, and only the hardened portion remains. The development temperature is usually 20 to 30 ° C, and the development time is usually 20 to 90 seconds.

顯像液只要是只溶解未硬化部中光硬化性組成物之膜，而沒有溶解硬化部者即可，無論哪一種均可使用。具體而言，可使用各種有機溶劑的組合或鹼性的水溶液。The developing solution may be used as long as it dissolves only the film of the photocurable composition in the unhardened portion, and does not dissolve or harden the film. Specifically, a combination of various organic solvents or an aqueous alkaline solution can be used.

前述有機溶劑係可舉例如在調製前述光硬化性組成物之際所使用的、做為己述之有機溶媒或是溶劑所列舉者。The organic solvent may, for example, be used as an organic solvent or a solvent as described above when preparing the photocurable composition.

前述鹼性的水溶液係可舉例如將氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、矽酸鈉、偏矽酸鈉、氨水、乙基胺、二乙基胺、二甲基乙醇胺、氫氧化四甲基銨、氫氧化四乙基銨、膽碱、吡咯、吡啶、1,8-二氮雜雙環-[5,4,0]-7-十一碳醯等的鹼性化合物，溶解成濃度為0.001~10質量%、較佳為0.01~1質量%之鹼性水溶液。The alkaline aqueous solution may, for example, be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine or dimethylethanolamine. a basic compound such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, pyridine, 1,8-diazabicyclo-[5,4,0]-7-undecene, It is dissolved in an alkaline aqueous solution having a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass.

此外，鹼性水溶液做為顯像液使用之情形中，一般係在顯像後用水進行洗淨(沖洗(rinse))。Further, in the case where the alkaline aqueous solution is used as a developing liquid, it is usually washed with water (rinse) after development.

顯像後係洗淨除去剩餘的顯像液，且施加乾燥之後，一般係在100~240℃的溫度下實施加熱處理(後烘烤(post-bake))。After the development, the remaining developing liquid is removed by washing, and after drying is applied, heat treatment (post-bake) is generally carried out at a temperature of 100 to 240 °C.

前述的後烘烤係為了使硬化為完全的顯像後的加熱，通常係在約200℃～250℃進行加熱(烤硬(hard-bake))。該後烘烤處理係可將顯像後的塗布膜，以成為上述條件的方式使用加熱板或對流式烘箱(熱風循環式乾燥機)、高頻加熱機等的加熱手段，以連續式或分批(batch)式來進行。The above-mentioned post-baking is usually performed by heating at about 200 ° C to 250 ° C in order to heat the film to complete heating (hard-bake). In the post-baking treatment, the coating film after development can be used in a continuous manner or in a heating means such as a hot plate or a convection oven (hot air circulation dryer) or a high-frequency heating device to achieve the above conditions. Batch type is used.

以上的操作係可藉由配合所期望的色相數、各色各依序進行，而可製作形成複數色著色之硬化膜而成的彩色濾光片。The above operation can be carried out by mixing the desired number of hue and each color in order, and a color filter formed by forming a cured film of a plurality of colored colors can be produced.

將本發明有關的光硬化性組成物賦予至基板上以形成膜之情形中，膜的乾燥厚度係一般為0.3~5.0μm，較佳為0.5~3.5μm，最好是1.0~2.5μm。In the case where the photocurable composition according to the present invention is applied to a substrate to form a film, the dry thickness of the film is generally from 0.3 to 5.0 μm, preferably from 0.5 to 3.5 μm, more preferably from 1.0 to 2.5 μm.

於像這樣的基板上所形成之著色圖案，由於微細粒徑的顔料係均勻且安定地分散的，所以在皮膜表面中由AFM的觀察結果所得之畫像中的2次粒子的占有率，可達成40%以下。In the colored pattern formed on the substrate as described above, since the pigment having a fine particle diameter is uniformly and stably dispersed, the occupancy rate of the secondary particles in the image obtained by the observation of the AFM on the surface of the film can be achieved. 40% or less.

彩色濾光片中所使用的基板係可舉例如液晶顯示裝置The substrate used in the color filter may be, for example, a liquid crystal display device.

等中所使用的無鹼玻璃、鈉鈣玻璃、PYREX(註冊商標)玻璃、石英玻璃、及於此等上附著透明導電膜者、載固體攝像元件等中所使用的光電變換元件基板、例如矽基板等、以及塑膠基板。此等之基板上係通常形成有隔離各像素之黑條(black stripe)。An alkali-free glass, a soda-lime glass, a PYREX (registered trademark) glass, a quartz glass, a photoelectric conversion element substrate used in a solid-state image sensor or the like, and the like, for example, ruthenium. A substrate or the like, and a plastic substrate. These substrates are typically formed with black stripe that isolates each pixel.

塑膠基板較佳係在其表面具有氣體障壁(gas barrier)層及/或耐溶劑性層。The plastic substrate preferably has a gas barrier layer and/or a solvent resistant layer on its surface.

透過其他之層附著光硬化性組成物於基板上時的其他之層，可舉例如氣體障壁層、耐溶劑性層、等。The other layer when the photocurable composition is attached to the substrate through another layer may, for example, be a gas barrier layer or a solvent resistant layer.

上述，主要是重點說明彩色濾光片的著色圖案用途，惟即使在構成隔離彩色濾光片的各著色像素之黑色矩陣的形成中，亦能同樣適用本發明的手段。The above is mainly directed to the use of the coloring pattern of the color filter, but the means of the present invention can be equally applied even in the formation of the black matrix of each of the colored pixels constituting the isolated color filter.

黑色矩陣係藉由使用做為顔料之碳黑、鈦黑等的黑色顔料之本發明光硬化性組成物(顔料分散組成物)並進行圖案曝光、顯像，然後可視需要更進行後烘烤以促進膜的硬化而可形成。The black matrix is subjected to pattern exposure, development, and post-baking as needed by using a photocurable composition (pigment dispersion composition) of the present invention as a black pigment of carbon black or titanium black as a pigment. It can be formed by promoting hardening of the film.

實施例Example

以下，根據實施例來更具體地說明本發明，惟本發明只要在不超過其主旨之範圍，並不受限於以下的實施例。此外，特別是沒有事先限定的話，「份」表示「質量份」。Hereinafter, the present invention will be more specifically described based on the examples, but the present invention is not limited to the following examples as long as it does not exceed the scope of the gist of the invention. In addition, "parts" means "parts by mass" unless otherwise specified.

[合成例1][Synthesis Example 1]

(單體1的合成)(synthesis of monomer 1)

使9.51份的2-胺基嘧啶溶解於30份的吡啶中，並加熱至45℃。於其中滴下17.1份的2-丙烯醯基羥乙基異氰酸酯，於50℃中更進行加熱攪拌5小時。一邊攪拌該反應液、一邊倒入200份的蒸餾水，藉由過濾、洗淨所得之析出物，以得到23.8份的單體1。9.51 parts of 2-aminopyrimidine was dissolved in 30 parts of pyridine and heated to 45 °C. 17.1 parts of 2-propenylhydroxyethyl isocyanate was added dropwise thereto, and the mixture was further stirred under heating at 50 ° C for 5 hours. While stirring the reaction liquid, 200 parts of distilled water was poured, and the obtained precipitate was filtered and washed to obtain 23.8 parts of monomer 1.

(聚合物1的合成)(Synthesis of Polymer 1)

將5.0份的前述單體1、37.5份的於末端具有甲基丙烯醯基之聚甲基丙烯酸甲酯(AA-6：東亞合成公司製)、7.5份的甲基丙烯酸、及167質量份的甲氧基丙二醇，導入經氮取代之三頸燒瓶中，以攪拌機(新東科學(股)製：Three one motor)攪拌，一邊使氮氣流入燒瓶内、一邊加熱並昇溫至78℃。於其中加入0.1份的二甲基-2,2’-偶氮雙(2-甲基丙酸酯)(和光純藥(股)製：V-601)，於78℃下進行加熱攪拌2小時。2小時後，更加入0.1份的V-601並加熱攪拌3小時，以得到聚合物1(前述之例示化合物(2))的30%溶液。5.0 parts of the above-mentioned monomers 1 and 37.5 parts of polymethyl methacrylate (AA-6: manufactured by Toagosei Co., Ltd.) having a methacryl oxime group at the terminal, 7.5 parts of methacrylic acid, and 167 parts by mass The methoxypropanediol was introduced into a three-necked flask which was replaced with nitrogen, and stirred with a stirrer (manufactured by Shinto Scientific Co., Ltd.: Three one motor), and while allowing nitrogen gas to flow into the flask, the mixture was heated and heated to 78 °C. 0.1 part of dimethyl-2,2'-azobis(2-methylpropionate) (Wako Pure Chemical Co., Ltd.: V-601) was added thereto, and the mixture was stirred under heating at 78 ° C for 2 hours. . After 2 hours, 0.1 part of V-601 was further added and stirred under heating for 3 hours to obtain a 30% solution of the polymer 1 (the aforementioned exemplified compound (2)).

[合成例2][Synthesis Example 2]

除了將合成例1之單體1的合成中所使用的9.51份的2-胺基嘧啶，變更為13.3份的2-胺基苯并咪唑以外，藉由與合成例1同様的方法，得到聚合物2(前述之例示化合物(6))的30%溶液。Polymerization was carried out by the same method as in Synthesis Example 1, except that 9.51 parts of 2-aminopyrimidine used in the synthesis of the monomer 1 of Synthesis Example 1 was changed to 13.3 parts of 2-aminobenzimidazole. A 30% solution of the substance 2 (the aforementioned exemplified compound (6)).

[合成例3][Synthesis Example 3]

(單體3的合成)(synthesis of monomer 3)

使13.3份的2-氫硫基苯并咪唑及13.3份的碳酸鉀溶解於30份的二甲亞碸中，並加熱至45℃。於其中滴下22.9份的氯基甲基苯乙烯，於50℃下更進行加熱攪拌5小時。一邊攪拌該反應液、一邊將蒸餾水200份倒入，過濾、洗淨所得之析出物，藉以得到25.6份的單體3。13.3 parts of 2-hydrothiobenzimidazole and 13.3 parts of potassium carbonate were dissolved in 30 parts of dimethyl hydrazine and heated to 45 °C. 22.9 parts of chloromethylstyrene was added dropwise thereto, and the mixture was further stirred under heating at 50 ° C for 5 hours. While stirring the reaction liquid, 200 parts of distilled water was poured, and the resulting precipitate was filtered and washed to obtain 25.6 parts of the monomer 3.

(聚合物3的合成)除了將合成例1的單體1變更為單體3以外，藉由與合成例1同様的方法，以得到聚合物3(前述之例示化合物(14))的30%溶液。(Synthesis of Polymer 3) In the same manner as in Synthesis Example 1, except that the monomer 1 of Synthesis Example 1 was changed to the monomer 3, 30% of the polymer 3 (the aforementioned exemplified compound (14)) was obtained. Solution.

[實施例1][Example 1]

<顔料分散組成物的調製><Preparation of pigment dispersion composition>

(組成(1)](composition (1)]

．1次粒徑為28nm之紅色顔料(C.I.顏料紅254)10份. 1 time red pigment (C.I. Pigment Red 254) with a particle size of 28 nm

．聚合物1的30%溶液(特定顔料分散劑)　26.6份. 30% solution of polymer 1 (specific pigment dispersant) 26.6 parts

．丙二醇單甲基醚乙酸酯　63.4份. Propylene glycol monomethyl ether acetate 63.4 parts

於組成(1)中加入0.3mm的氧化鋯珠粒，以珠粒研磨機分散4小時，以得到顔料分散液(著色糊)(1)。所得到顔料分散液中顔料的平均粒徑係以粒度分布計(日機裝(股)製：Microtrac)測定時為50nm。0.3 mm of zirconia beads were added to the composition (1), and dispersed in a bead mill for 4 hours to obtain a pigment dispersion (coloring paste) (1). The average particle diameter of the pigment in the obtained pigment dispersion liquid was 50 nm as measured by a particle size distribution meter (manufactured by Nikkiso Co., Ltd.: Microtrac).

此外，紅色顔料的1次粒子的平均粒徑係藉由電子顯微鏡(Hitachi High-Technologies Corporation(股)製：S-4800)來測定。Further, the average particle diameter of the primary particles of the red pigment was measured by an electron microscope (manufactured by Hitachi High-Technologies Corporation: S-4800).

<光硬化性組成物的調製><Modulation of Photocurable Composition>

混合下述組成，以調製彩色濾光片製作用的光硬化性組成物(1)。The following composition was mixed to prepare a photocurable composition (1) for producing a color filter.

．顔料分散液(1)　48.0份. Pigment dispersion (1) 48.0 parts

．甲基丙烯酸/甲基丙烯酸苄酯共聚物　3.3份. Methacrylic acid / benzyl methacrylate copolymer 3.3 parts

(莫耳比30/70、重量平均分子量10000、45%丙二醇單甲基醚乙酸酯溶液)(Morby 30/70, weight average molecular weight 10000, 45% propylene glycol monomethyl ether acetate solution)

．二新戊四醇六丙烯酸酯　2.9g. Dipentaerythritol hexaacrylate 2.9g

．Irgacure 369(Ciba Specialty Chemicals製)　0.2g. Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.2g

．氫醌單甲基醚　0.01g. Hydroquinone monomethyl ether 0.01g

．丙二醇單甲基醚乙酸酯　45g. Propylene glycol monomethyl ether acetate 45g

<著色圖案的製作><Production of coloring pattern>

將根據前述方法所得之光硬化性組成物(1)塗布於0.7mm玻璃基板上，並以100mJ/cm2 (照度20mW/cm2 )的條件使其，以形成厚度2.0μm的紅色光硬化性組成物層(著色圖案)。The photocurable composition (1) obtained by the above method was applied onto a 0.7 mm glass substrate and allowed to stand at a condition of 100 mJ/cm 2 (illuminance of 20 mW/cm 2 ) to form a red photocurable layer having a thickness of 2.0 μm. Composition layer (coloring pattern).

<2次粒子的占有率測定><Measurement of occupancy rate of secondary particles>

所形成之著色圖案的膜表面係以AFM(Veeco Instruments製Nanoscope IIIa,TappingMode)進行觀察，以得到表面的觀察畫像。The film surface of the formed color pattern was observed by AFM (Nanoscope IIIa, Tapping Mode, manufactured by Veeco Instruments) to obtain an observed image of the surface.

接著，關於所得之像係使用畫像處理程式「Image J」，按照以下的順序來進行畫像的處理，以求得畫像中的2次粒子的占有率。Then, the image processing program "Image J" is used for the obtained image system, and the image processing is performed in the following order to obtain the occupancy rate of the secondary particles in the image.

1.進行灰階變換、電平校正之後，消去畫像的雜訊與波紋，按照判別分析法使其2值化。1. After performing gray scale conversion and level correction, the noise and ripple of the image are erased and binarized according to the discriminant analysis method.

2.按照Watershed法分割相接的粒子。2. Divide the adjacent particles according to the Watershed method.

3.萃取50nm以上的粒子並算出占有率。3. Extract particles of 50 nm or more and calculate the occupancy rate.

根據上述的方法，算出於實施例1所得之分散液的2次粒子的占有率時為22%。According to the above method, when the occupancy rate of the secondary particles of the dispersion obtained in Example 1 was calculated, it was 22%.

[實施例2][Embodiment 2]

<顔料分散組成物的調製><Preparation of pigment dispersion composition>

[組成(2)][Composition (2)]

．1次粒徑為20nm之綠色顔料(C.I.顏料綠36)14.0份. 14.0 parts of green pigment (C.I. Pigment Green 36) with a particle size of 20 nm

．聚合物1的30%溶液(特定顔料分散劑)　37.3份. 30% solution of polymer 1 (specific pigment dispersant) 37.3 parts

．丙二醇單甲基醚乙酸酯　48.7份. Propylene glycol monomethyl ether acetate 48.7 parts

於組成(2)中加入0.3mm的氧化鋯珠粒，以珠粒研磨機分散5小時，以得到顔料分散液(著色糊(paste))(2)。所得到顔料分散液中顔料的平均粒徑係以粒度分布計測定時，其結果為55nm。0.3 mm of zirconia beads were added to the composition (2), and dispersed in a bead mill for 5 hours to obtain a pigment dispersion (paste) (2). When the average particle diameter of the pigment in the obtained pigment dispersion liquid was measured by a particle size distribution meter, the result was 55 nm.

<光硬化性組成物的調製><Modulation of Photocurable Composition>

混合下述組成，以調製彩色濾光片製作用的光硬化性組成物(2)。The following composition was mixed to prepare a photocurable composition (2) for color filter production.

．顔料分散液(2)　48.0份. Pigment dispersion (2) 48.0 parts

．甲基丙烯酸/甲基丙烯酸苄酯共聚物　4.0份. Methacrylic acid / benzyl methacrylate copolymer 4.0 parts

(莫耳比30/70、重量平均分子量10000、45%丙二醇單甲基醚乙酸酯溶液)(Morby 30/70, weight average molecular weight 10000, 45% propylene glycol monomethyl ether acetate solution)

．二新戊四醇六丙烯酸酯　3.5g. Dipentaerythritol hexaacrylate 3.5g

．Irgacure369(Ciba Specialty Chemicals製)　0.2g. Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.2 g

.氫醌單甲基醚　0.01gHydroquinone monomethyl ether 0.01g

.丙二醇單甲基醚乙酸酯　44gPropylene glycol monomethyl ether acetate 44g

<著色圖案的製作><Production of coloring pattern>

除了變更為光硬化性組成物(2)以外，以與實施例1同樣的方法得到著色圖案。A colored pattern was obtained in the same manner as in Example 1 except that the photocurable composition (2) was changed.

<2次粒子的占有率測定><Measurement of occupancy rate of secondary particles>

以與實施例1同樣的方法，算出2次粒子的占有率時為28%。In the same manner as in Example 1, when the occupancy rate of the secondary particles was calculated, it was 28%.

[實施例3][Example 3]

<顔料分散組成物的調製><Preparation of pigment dispersion composition>

[組成(3)][Composition (3)]

．1次粒徑為25nm之藍色顔料(C.I.顏料藍15：6)　10.0份. 1st blue pigment with a particle size of 25nm (C.I. Pigment Blue 15:6) 10.0 parts

．聚合物1的30%溶液(特定顔料分散劑)　23.3份. 30% solution of polymer 1 (specific pigment dispersant) 23.3 parts

．丙二醇單甲基醚乙酸酯　66.6份. Propylene glycol monomethyl ether acetate 66.6 parts

於組成(3)中加入0.3mm的氧化鋯珠粒，以珠粒研磨機分散6小時，以得到顔料分散液(著色糊)(3)。所得到的顔料分散液中顔料的平均粒徑係以粒度分布計測定時，其結果為46nm。0.3 mm of zirconia beads were added to the composition (3), and dispersed in a bead mill for 6 hours to obtain a pigment dispersion (coloring paste) (3). When the average particle diameter of the pigment in the obtained pigment dispersion liquid was measured by a particle size distribution meter, the result was 46 nm.

<光硬化性組成物的調製><Modulation of Photocurable Composition>

除了將顔料分散液(1)變更為顔料分散液(3)以外，係全部以與實施例1同樣的方法，以調製光硬化性組成物(3)。The photocurable composition (3) was prepared in the same manner as in Example 1 except that the pigment dispersion liquid (1) was changed to the pigment dispersion liquid (3).

<著色圖案的製作><Production of coloring pattern>

除了將光硬化性組成物(1)變更為光硬化性組成物(3)以外，以與實施例1同樣的方法得到著色圖案。A colored pattern was obtained in the same manner as in Example 1 except that the photocurable composition (1) was changed to the photocurable composition (3).

<2次粒子的占有率測定><Measurement of occupancy rate of secondary particles>

以與實施例1同樣的方法，算出2次粒子的占有率時為38%。In the same manner as in Example 1, when the occupancy rate of the secondary particles was calculated, it was 38%.

[實施例4][Example 4]

除了將聚合物1變更為聚合物2以外，係全部以與實施例1同樣的方法，以得到顔料分散液(4)、光硬化性組成物(4)及著色圖案。A pigment dispersion liquid (4), a photocurable composition (4), and a coloring pattern were obtained in the same manner as in Example 1 except that the polymer 1 was changed to the polymer 2.

[實施例5][Example 5]

除了將聚合物1變更為聚合物2以外，係全部以與實施例2同樣的方法，以得到顔料分散液(5)、光硬化性組成物A pigment dispersion liquid (5) and a photocurable composition were obtained in the same manner as in Example 2 except that the polymer 1 was changed to the polymer 2.

(5)及著色圖案。(5) and color pattern.

[實施例6][Embodiment 6]

除了將聚合物1變更為聚合物2以外，係全部以與實施例3同樣的方法，以得到顔料分散液(6)、光硬化性組成物(6)及著色圖案。A pigment dispersion liquid (6), a photocurable composition (6), and a coloring pattern were obtained in the same manner as in Example 3 except that the polymer 1 was changed to the polymer 2.

[實施例7][Embodiment 7]

除了將聚合物1變更為聚合物3以外，係全部以與實施例1同樣的方法，以得到顔料分散液(7)、光硬化性組成物(7)及著色圖案。The pigment dispersion liquid (7), the photocurable composition (7), and the coloring pattern were obtained in the same manner as in Example 1 except that the polymer 1 was changed to the polymer 3.

[實施例8][Embodiment 8]

除了將聚合物1變更為聚合物3以外，係全部以與實施例2同樣的方法，以得到顔料分散液(8)、光硬化性組成物(8)及著色圖案。A pigment dispersion liquid (8), a photocurable composition (8), and a coloring pattern were obtained in the same manner as in Example 2 except that the polymer 1 was changed to the polymer 3.

[實施例9][Embodiment 9]

除了將聚合物1變更為聚合物3以外，係全部以與實施例3同樣的方法，以得到顔料分散液(9)、光硬化性組成物(9)及著色圖案。A pigment dispersion liquid (9), a photocurable composition (9), and a coloring pattern were obtained in the same manner as in Example 3 except that the polymer 1 was changed to the polymer 3.

[比較例1)[Comparative Example 1]

<顔料分散組成物的調製><Preparation of pigment dispersion composition>

[組成(10)][Composition (10)]

‧1次粒徑為28nm紅色顔料(C.I.顏料紅254)10.0份‧1 time particle size 28nm red pigment (C.I. Pigment Red 254) 10.0 parts

‧分散劑(BYK-Chemie GmbH製BYK-161)(比較顔料分散劑)　6.0份‧Dispersant (BYK-161 by BYK-Chemie GmbH) (Comparative Pigment Dispersant) 6.0 parts

‧丙二醇單甲基醚乙酸酯　84.0份於組成(10)中加入0.3mm的氧化鋯珠粒，以珠粒研磨機分散2小時，以得到顔料分散液(著色糊)(10)。所得到的顔料分散液中顔料的平均粒徑係以粒度分布計測定時，其結果為90nm。‧ Propylene glycol monomethyl ether acetate 84.0 parts of 0.3 mm of zirconia beads were added to the composition (10), and dispersed in a bead mill for 2 hours to obtain a pigment dispersion (coloring paste) (10). When the average particle diameter of the pigment in the obtained pigment dispersion liquid was measured by a particle size distribution meter, the result was 90 nm.

<光硬化性組成物的調製><Modulation of Photocurable Composition>

除了變更為顔料分散液(10)以外，係全部以與實施例1同樣的方法，以調製光硬化性組成物(10)。The photocurable composition (10) was prepared in the same manner as in Example 1 except that the pigment dispersion liquid (10) was changed.

<著色圖案的製作><Production of coloring pattern>

除了變更為光硬化性組成物(10)以外，以與實施例1同樣的方法得到著色圖案。A colored pattern was obtained in the same manner as in Example 1 except that the photocurable composition (10) was changed.

<2次粒子的占有率測定><Measurement of occupancy rate of secondary particles>

以與實施例1同様的方法，算出2次粒子的占有率時為49%。In the same manner as in Example 1, the occupancy rate of the secondary particles was 49%.

[比較例2][Comparative Example 2]

<顔料分散組成物的調製><Preparation of pigment dispersion composition>

[組成(11)][Composition (11)]

‧1次粒徑為20nm之綠色顔料(C.I.顏料綠36)14.0份‧1 green pigment (C.I. Pigment Green 36) with a particle size of 20 nm 14.0 parts

‧分散劑(BYK-Chemie GmbH製BYK-161)(比較顏料分散劑)　8.4份‧Dispersant (BYK-161 by BYK-Chemie GmbH) (Comparative Pigment Dispersant) 8.4 parts

‧丙二醇單甲基醚乙酸酯　77.6份‧ Propylene glycol monomethyl ether acetate 77.6 parts

於組成(11)中加入0.3mm的氧化鋯珠粒，以珠粒研磨機分散2小時，以得到顔料分散液(著色糊)(11)。所得到的顔料分散液中顔料的平均粒徑係以粒度分布計測定時，其結果為81nm。0.3 mm of zirconia beads were added to the composition (11), and dispersed by a bead mill for 2 hours to obtain a pigment dispersion (coloring paste) (11). When the average particle diameter of the pigment in the obtained pigment dispersion liquid was measured by a particle size distribution meter, the result was 81 nm.

<光硬化性組成物的調製><Modulation of Photocurable Composition>

除了變更為顔料分散液(11)以外，係全部以與實施例1同樣的方法，以調製光硬化性組成物(11)。The photocurable composition (11) was prepared in the same manner as in Example 1 except that the pigment dispersion liquid (11) was changed.

<著色圖案的製作><Production of coloring pattern>

除了變更為光硬化性組成物(11)以外，以與實施例1同樣的方法得到著色圖案。A colored pattern was obtained in the same manner as in Example 1 except that the photocurable composition (11) was changed.

<2次粒子的占有率測定><Measurement of occupancy rate of secondary particles>

以與實施例1同様的方法，算出2次粒子的占有率為55%。In the same manner as in Example 1, the occupancy rate of the secondary particles was calculated to be 55%.

[比較例3][Comparative Example 3]

<顔料分散組成物的調製><Preparation of pigment dispersion composition>

[組成(12)][Composition (12)]

‧1次粒徑為25nm之藍色顔料(C.I.顏料藍15：6)10.0份‧1 blue pigment with a particle size of 25 nm (C.I. Pigment Blue 15:6) 10.0 parts

‧分散劑(BYK-ChemieGmbH製BYK-161)(比較顔料分散劑)　6.0份‧ Dispersant (BYK-ChemieGmbH BYK-161) (Comparative Pigment Dispersant) 6.0 parts

‧丙二醇單甲基醚乙酸酯　84.0份‧ Propylene glycol monomethyl ether acetate 84.0 parts

於組成(12)中加入0.3mm氧化鋯珠粒，以珠粒研磨機分散2小時，以得到顔料分散液(著色糊)(12)。所得到的顔料分散液中顔料的平均粒徑係以粒度分布計測定時，其結果為97nm。0.3 mm of zirconia beads were added to the composition (12), and dispersed in a bead mill for 2 hours to obtain a pigment dispersion (coloring paste) (12). When the average particle diameter of the pigment in the obtained pigment dispersion liquid was measured by a particle size distribution meter, the result was 97 nm.

<光硬化性組成物的調製><Modulation of Photocurable Composition>

除了變更為顔料分散液(12)以外，係全部以與實施例1同樣的方法，以調製光硬化性組成物(12)。The photocurable composition (12) was prepared in the same manner as in Example 1 except that the pigment dispersion liquid (12) was changed.

<著色圖案的製作><Production of coloring pattern>

除了變更為光硬化性組成物(12)以外，以與實施例1同樣的方法得到著色圖案。A colored pattern was obtained in the same manner as in Example 1 except that the photocurable composition (12) was changed.

<2次粒子的占有率測定><Measurement of occupancy rate of secondary particles>

以與實施例1同樣的方法，算出2次粒子的占有率為60%。In the same manner as in Example 1, the occupancy rate of the secondary particles was calculated to be 60%.

<對比的測定><Measurement of comparison>

對比係將前述實施例及比較例中所作成之彩色濾光片，設置於2片偏光板之間，於一方設置光源、其相反側設置亮度計(TOPCON公司製BM-5A)，以進行亮度(透射光強度)的測定。由偏光軸成平行時的亮度、與成垂直時的亮度之比來算出對比。結果係表示於下述表1。In contrast, the color filters prepared in the above-described examples and comparative examples were placed between two polarizing plates, and a light source was provided on one side, and a luminance meter (BM-5A manufactured by TOPCON Co., Ltd.) was provided on the opposite side to perform brightness. (Measurement of transmitted light intensity). The contrast was calculated from the ratio of the luminance when the polarization axes were parallel and the luminance when the polarization axes were parallel. The results are shown in Table 1 below.

由表1，可知若根據本發明的彩色濾光片用著色圖案可實現高對比。From Table 1, it is understood that high contrast can be achieved with the colored pattern for a color filter according to the present invention.

<使用光硬化性組成物之彩色濾光片的調製><Modulation of Color Filter Using Photocurable Composition>

在100mm×100mm的玻璃基板(1737、Corning Inc.製)上，塗布黑色光硬化性組成物CK-9910L(FUJIFILM Electronic Materials Co.,Ltd.製)，在120℃的加熱板乾燥120秒鐘(預烘烤)。然後，透過光罩以100mJ/cm2 (照度20mW/cm2 )進行曝光，並以鹼性顯像液CDK-1(FUJIFILM Electronic Materials Co.,Ltd.製)的1%水溶液覆蓋曝光後的塗膜，靜止60秒鐘。静止後，淋浴狀散布純水並洗去流出顯像液。而且，將如上述般施加曝光及顯像之塗膜於220℃的烘箱中加熱處理(後烘烤)1小時，在玻璃基板上形成彩色濾光片用BM圖案。On a 100 mm × 100 mm glass substrate (manufactured by Corning Inc.), a black photocurable composition CK-9910L (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied and dried on a hot plate at 120 ° C for 120 seconds ( Pre-bake). Then, the film was exposed to light at 100 mJ/cm 2 (illuminance: 20 mW/cm 2 ) through a photomask, and the exposed coating was covered with a 1% aqueous solution of an alkaline developing solution CDK-1 (manufactured by FUJIFILM Electronic Materials Co., Ltd.). Membrane, resting for 60 seconds. After standing still, spray the pure water in the shower and wash away the developing liquid. Further, the coating film subjected to exposure and development as described above was heat-treated (post-baking) in an oven at 220 ° C for 1 hour to form a BM pattern for a color filter on a glass substrate.

接著，將光硬化性組成物(1)塗布成膜厚2.0um，並在90℃的加熱板乾燥60秒鐘。然後，透過光罩以100mJ/cm2 (照度20mW/cm2 )進行曝光，並以鹼性顯像液CDK-1的1%水溶液覆蓋曝光後的塗膜，靜止60秒鐘。静止後，淋浴狀散布純水並洗淨流出顯像液。而且，將如上述般施加曝光及顯像之塗膜於220℃的烘箱中加熱處理(後烘烤)1小時，在玻璃基板上形成彩色濾光片用的紅色圖案(著色樹脂被膜)。使用光硬化性組成物(2)、(3)並以與上述同様的方法，於玻璃基板上形成彩色濾光片用的著色圖案(著色樹脂被膜)，以製作著色濾光片基板(彩色濾光片)A。Next, the photocurable composition (1) was applied to a film thickness of 2.0 μm, and dried on a hot plate at 90° C. for 60 seconds. Then, the film was exposed to light at 100 mJ/cm 2 (illuminance: 20 mW/cm 2 ) through a photomask, and the exposed coating film was covered with a 1% aqueous solution of an alkaline developing solution CDK-1, and allowed to stand for 60 seconds. After standing still, spray pure water in a shower and wash out the developing solution. Then, the coating film subjected to exposure and development as described above was heat-treated (post-baked) in an oven at 220 ° C for 1 hour to form a red pattern (colored resin film) for a color filter on a glass substrate. Using the photocurable compositions (2) and (3), a colored pattern (colored resin film) for a color filter is formed on a glass substrate by the same method as described above to prepare a colored filter substrate (color filter) Light film) A.

又，除了將光硬化性組成物變更為(4)、(5)、(6)以外，全部同樣地製作彩色濾光片B。又，除了將光硬化性組成物變更為(7)、(8)、(9)以外，全部同樣地製作彩色濾光片C。又，除了將光硬化性組成物變更為(10)、(11)、(12)以外，全部同樣地製作彩色濾光片D。In addition, the color filter B was produced in the same manner except that the photocurable composition was changed to (4), (5), and (6). In addition, the color filter C was produced in the same manner except that the photocurable composition was changed to (7), (8), and (9). In addition, the color filter D was produced in the same manner except that the photocurable composition was changed to (10), (11), and (12).

<彩色濾光片的評價><Evaluation of Color Filters>

針對所製作的著色濾光片基板(彩色濾光片)，進行如以下所述的評價。結果表示於下述表2。The evaluation was performed as described below with respect to the produced color filter substrate (color filter). The results are shown in Table 2 below.

(3)對比(3) Comparison

在著色濾光片基板的著色樹脂被膜上設置偏光板並***著色樹脂被膜，使用Topcon公司製的BM-5A測定來測定偏光板為平行時的亮度與直交時的亮度，並將平行時的亮度除以直交時的亮度所得之值(=平行時的亮度/直交時的亮度)做為評價對比用的指標。值越大時，顯示為高對比。A polarizing plate was placed on the colored resin film of the colored filter substrate, and a colored resin film was inserted, and the brightness at the time when the polarizing plates were parallel and the brightness at the time of the orthogonality were measured using a BM-5A measurement manufactured by Topcon Co., Ltd., and the brightness in parallel was measured. The value obtained by dividing the brightness at the time of the intersection (= brightness in parallel/brightness in orthogonal) is used as an index for evaluation comparison. The higher the value, the higher the contrast.

Claims (6)

一種彩色濾光片，其特徵係包含將含有平均粒徑為15~150nm且選自包含C.I.顏料黃11,24,108,109,110,138,139,150,151,154,167,180,185,C.I.顏料橙36,71,C.I.顏料紅122,150,171,175,177,209,224,242,254,255,264,C.I.顏料紫19,23,37,C.I.顏料藍15：1,15：3,15：6,16,22,60,66,C.I.顏料綠7及36之群組之至少一種的顏料、有機溶媒、含有來自下述通式(1)所示單體之共聚合單位的聚合物、光聚合性化合物、與光聚合起始劑之光硬化性組成物塗布至基板上所形成之著色圖案，該著色圖案表面在原子間力顯微鏡的觀察結果所得之畫像中的2次粒子的占有率為40%以下； [在通式(1)中，R1 表示氫原子、或無取代的烷基，R2 表示碳數1~4的伸烷基，W表示-C(=O)O-、-CONH-、或伸苯基，X表示-S-、-NHCONH-、或-NHC(=O)S-，Y表示-NR3 -、-O-、-S-、或-N=，且透過與其相鄰接之原子團而與N原子連結可形成選自咪唑環、嘧啶環、***環、四唑環、噻唑環、唑環、苯并咪唑環、苯并噻唑環、苯并唑環、嘌呤環、喹唑啉環、萘嵌間二氮雜苯環之 環狀構造，R3 表示氫原子、或甲基，m及n係表示1]。A color filter characterized by comprising an average particle size of 15 to 150 nm and selected from the group consisting of CI Pigment Yellow 11,24,108,109,110,138,139,150,151,154,167,180,185, CI Pigment Orange 36,71, CI Pigment Red 122,150,171,175,177,209,224,242,254,255,264, CI Pigment Violet 19,23,37 , CI Pigment Blue 15:1, 15:3, 15:6, 16, 22, 60, 66, at least one of the group of CI Pigment Greens 7 and 36, an organic solvent containing the following formula (1) a coloring pattern formed by coating a polymer of a monomer unit, a photopolymerizable compound, and a photocurable composition of a photopolymerization initiator onto a substrate, the surface of the coloring pattern being examined by an atomic force microscope The occupancy rate of the secondary particles in the image obtained by the observation is 40% or less; [In the formula (1), R 1 represents a hydrogen atom or an unsubstituted alkyl group, R 2 represents an alkylene group having 1 to 4 carbon atoms, and W represents -C(=O)O-, -CONH-, Or phenyl, X represents -S-, -NHCONH-, or -NHC(=O)S-, Y represents -NR 3 -, -O-, -S-, or -N=, and is adjacent thereto The atomic group is bonded to the N atom to form an imidazole ring, a pyrimidine ring, a triazole ring, a tetrazole ring, a thiazole ring, Oxazole ring, benzimidazole ring, benzothiazole ring, benzo a ring structure of an azole ring, an anthracene ring, a quinazoline ring, or a naphthene diazabenzene ring, R 3 represents a hydrogen atom or a methyl group, and m and n represent 1]. 如申請專利範圍第1項之彩色濾光片，其中前述聚合物係更含有來自末端具有乙烯性不飽和鍵的聚合性低聚物之共聚合單位的接枝共聚物。 The color filter of claim 1, wherein the polymer further contains a graft copolymer derived from a copolymerization unit of a polymerizable oligomer having an ethylenically unsaturated bond at its terminal. 如申請專利範圍第1項之彩色濾光片，其中前述聚合物係更含有來自具有酸基之單體的共聚合單位之聚合物。 A color filter according to claim 1, wherein the polymer further contains a polymer derived from a copolymerization unit of a monomer having an acid group. 如申請專利範圍第1項之彩色濾光片，其中前述聚合物係更含有來自末端具有乙烯性不飽和鍵的聚合性低聚物之共聚合單位的接枝共聚物，及前述聚合物係更含有來自具有酸基之單體的共聚合單位之聚合物。 The color filter of claim 1, wherein the polymer further comprises a graft copolymer derived from a copolymerization unit of a polymerizable oligomer having an ethylenically unsaturated bond at the terminal, and the polymer system A polymer containing a copolymerized unit derived from a monomer having an acid group. 如申請專利範圍第1至4項中任一項之彩色濾光片，其中前述光硬化性組成物係更含有鹼可溶性樹脂。 The color filter according to any one of claims 1 to 4, wherein the photocurable composition further contains an alkali-soluble resin. 一種彩色濾光片之製法，其特徵係包含感光性膜形成步驟，其係藉由將含有有機溶媒、平均粒徑為15~150nm的顏料、含有來自下述通式(1)所示單體之共聚合單位的聚合物、光聚合性化合物、與光聚合起始劑之光硬化性組成物直接或透過其他之層賦予至基板上，以形成感光性膜之感光性膜形成步驟；著色圖案形成步驟，其係藉由對所形成之該感光性膜依序進行圖案曝光及顯像，以形成在原子間力顯微鏡的觀察結果所得之畫像中的2次粒子的占有率為40%以下之著色圖案的著色圖案形成步驟， [在通式(1)中，R1 表示氫原子、或取代或無取代的烷基，R2 表示伸烷基，W表示-CO-、-C(=O)O-、-CONH-、-OC(=O)-、或伸苯基，X表示-O-、-S-、-C(=O)O-、-CONH-、-C(=O)S-、-NHCONH-、-NHC(=O)O-、-NHC(=O)S-、-OC(=O)-、-OCONH-、或-NHCO-，Y表示-NR3 -、-O-、-S-、或-N=，且透過與其相鄰接之原子團而與N原子連結可形成環狀構造，R3 表示氫原子、烷基、或芳基，m及n係各自獨立地表示0或1]。A method for producing a color filter, comprising the step of forming a photosensitive film by using a pigment containing an organic solvent having an average particle diameter of 15 to 150 nm and containing a monomer derived from the following formula (1) The photopolymerization unit polymer, the photopolymerizable compound, and the photocurable composition of the photopolymerization initiator are applied to the substrate directly or through other layers to form a photosensitive film forming step of the photosensitive film; a step of forming a pattern of exposure and development of the photosensitive film formed in order to form a second-order particle occupancy ratio of 40% or less in an image obtained by observation of an atomic force microscope a coloring pattern forming step of the colored pattern, [In the formula (1), R 1 represents a hydrogen atom, or a substituted or unsubstituted alkyl group, R 2 represents an alkylene group, and W represents -CO-, -C(=O)O-, -CONH-, -OC(=O)-, or phenyl, X represents -O-, -S-, -C(=O)O-, -CONH-, -C(=O)S-, -NHCONH-,- NHC(=O)O-, -NHC(=O)S-, -OC(=O)-, -OCONH-, or -NHCO-, Y represents -NR 3 -, -O-, -S-, or -N=, and is bonded to the N atom through an atomic group adjacent thereto to form a cyclic structure, R 3 represents a hydrogen atom, an alkyl group, or an aryl group, and m and n each independently represent 0 or 1].
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JP5455344B2 (en) 2014-03-26
KR20090033089A (en) 2009-04-01

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