TW201527443A - Pigment composition and manufacturing method thereof, water-soluble organic solvent for grinding and kneading, and pigment composition for color filter - Google Patents
Pigment composition and manufacturing method thereof, water-soluble organic solvent for grinding and kneading, and pigment composition for color filter Download PDFInfo
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- TW201527443A TW201527443A TW103142134A TW103142134A TW201527443A TW 201527443 A TW201527443 A TW 201527443A TW 103142134 A TW103142134 A TW 103142134A TW 103142134 A TW103142134 A TW 103142134A TW 201527443 A TW201527443 A TW 201527443A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0002—Grinding; Milling with solid grinding or milling assistants
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0022—Wet grinding of pigments
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/008—Preparations of disperse dyes or solvent dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
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Abstract
Description
本發明是有關於一種含有經微細化的顏料的顏料組成物及其製造方法。另外，本發明是有關於一種適於製造所述顏料組成物的磨碎混練用的水溶性有機溶劑。進而，本發明是有關於一種含有所述顏料組成物的彩色濾光片用顏料組成物。 The present invention relates to a pigment composition containing a finely divided pigment and a method for producing the same. Further, the present invention relates to a water-soluble organic solvent for grinding and kneading which is suitable for producing the pigment composition. Further, the present invention relates to a pigment composition for a color filter containing the pigment composition.
顏料多被用作以塗料、油墨(ink)、塑膠用著有色材料等為代表的各種產業資材的有色材料。為了將顏料用作有色材料，而對粗顏料進行多次加工處理。例如，於粗顏料中添加水溶性有機溶劑、水溶性無機鹽及樹脂來進行磨碎混練步驟。其後經過純化步驟，進行乾燥粉碎步驟而獲得粉體。亦存在將顏料以粉體的形式直接使用的用途，但通常是分散於溶劑、樹脂等分散介質中而使用。作為其他方法，亦提出有於純化步驟後省略乾燥粉碎步驟而獲得顏料組成物的方法(專利文獻1)。 Many pigments are used as colored materials for various industrial materials such as paints, inks, and plastic materials. In order to use the pigment as a colored material, the coarse pigment is processed a plurality of times. For example, a water-soluble organic solvent, a water-soluble inorganic salt, and a resin are added to the crude pigment to carry out a grinding and kneading step. Thereafter, after the purification step, a dry pulverization step is carried out to obtain a powder. There is also a use of the pigment in the form of a powder, but it is usually used by dispersing it in a dispersion medium such as a solvent or a resin. As another method, a method of obtaining a pigment composition by omitting the drying and pulverizing step after the purification step is also proposed (Patent Document 1).
為了獲得優異的有色材料，確保顏料於分散介質中的分 散性良好變得特別重要。若顏料的分散性差，則存在以下問題：於製造步驟中無法自分散機中取出組成物，或產品的黏度穩定性差，或於保存中發生凝膠化等。另外，亦存在展色物(drawndown object)表面的光澤性降低、發生勻化(leveling)不良等問題。 In order to obtain excellent colored materials, ensure the pigment in the dispersion medium Good dispersion is especially important. If the dispersibility of the pigment is poor, there is a problem in that the composition cannot be taken out from the dispersing machine in the production step, or the viscosity stability of the product is poor, or gelation occurs during storage. In addition, there is also a problem that the glossiness of the surface of the drawn object is lowered and the leveling is poor.
因此，為了控制加工顏料的分散性，迄今為止正在全力 地進行研究開發。例如，正在進行對顏料的表面進行改質而提高分散性的技術、用以確保分散狀態良好的分散劑的開發等(例如專利文獻2)。 Therefore, in order to control the dispersibility of processed pigments, we are doing our best so far. Research and development. For example, a technique of modifying the surface of a pigment to improve dispersibility, and development of a dispersant for ensuring a good dispersion state are being carried out (for example, Patent Document 2).
[專利文獻1]日本專利特開2010-106260號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-106260
[專利文獻2]國際公開第2008/007776號 [Patent Document 2] International Publication No. 2008/007776
於高精細化的要求變嚴格的趨勢下，將彩色濾光片用顏料組成物、彩色濾光片用感光性顏料組成物、噴墨油墨或電子方式顯影劑等顏料組成物中的顏料加以微細化變得重要。然而，若進行顏料的微細化處理，則產生以下問題：顏料彼此容易凝聚，故分散性降低，或黏度穩定性劣化等。 In the tendency of the high-definition demand to be strict, the color filter is finely pigmented in a pigment composition such as a pigment composition, a photosensitive pigment composition for a color filter, an inkjet ink, or an electronic developer. It becomes important. However, when the pigment is refined, the following problems occur: the pigments are easily aggregated with each other, so that the dispersibility is lowered, or the viscosity stability is deteriorated.
本發明是鑒於所述背景而成，其目的在於提供一種經微細化的顏料的分散性能優異、且生產效率高的經微細化的顏料組成物及其製造方法，磨碎混練用的水溶性有機溶劑，以及彩色濾 光片用顏料組成物。 The present invention has been made in view of the above-described background, and an object of the invention is to provide a fine pigment composition which is excellent in dispersibility of a finely pigmented pigment and has high production efficiency, and a method for producing the same, and a water-soluble organic compound for grinding and kneading. Solvent, and color filter A pigment composition for a light sheet.
本發明者等人為了解決所述課題而反覆進行了努力研究，結果令人驚訝地發現，於使用滿足(i)~(iv)全部的水溶性有機溶劑來進行製造的以下態樣中，可解決本申請案發明的課題，從而完成了本發明。 The inventors of the present invention have repeatedly conducted intensive studies to solve the above problems, and as a result, surprisingly, it has been found that the following aspects can be produced by using a water-soluble organic solvent satisfying all of (i) to (iv). The present invention has been accomplished by solving the problems of the invention of the present application.
[1]一種顏料組成物的製造方法，具備：步驟(a)，於顏料中至少添加水溶性無機鹽及水溶性有機溶劑，藉由磨碎混練將所述顏料加以微細化；步驟(b)，於步驟(a)之後投入水而獲得懸浮液；步驟(c)，於步驟(b)之後去除所述水溶性無機鹽，且以滿足以下的(A)的方式去除所述水溶性有機溶劑；以及步驟(d)，於步驟(c)之後去除水，並且所述水溶性有機溶劑滿足以下的(i)~(iv)，(A)相對於所述顏料組成物中所含的所述顏料100質量份，所述水溶性有機溶劑以0.005質量份~0.5質量份的範圍而殘留；(i)分子量為100~350、更佳為130~350；(ii)具有合計2個以上的包含羥基及/或酯基的官能基(F)；(iii)60℃下的黏度為2mPa．s~140mPa．s；(iv)不含醚鍵。 [1] A method for producing a pigment composition, comprising: step (a), adding at least a water-soluble inorganic salt and a water-soluble organic solvent to the pigment, and miniaturizing the pigment by grinding and kneading; and step (b) After the step (a), water is added to obtain a suspension; in step (c), the water-soluble inorganic salt is removed after the step (b), and the water-soluble organic solvent is removed in a manner satisfying the following (A). And step (d), removing water after the step (c), and the water-soluble organic solvent satisfies the following (i) to (iv), wherein (A) is relative to the pigment composition 100 parts by mass of the pigment, the water-soluble organic solvent remaining in the range of 0.005 parts by mass to 0.5 parts by mass; (i) molecular weight of 100 to 350, more preferably 130 to 350; (ii) total of two or more inclusions a hydroxyl group and/or an ester group functional group (F); (iii) a viscosity at 60 ° C of 2 mPa. s~140mPa. s; (iv) does not contain an ether bond.
[2]如[1]所記載的顏料組成物的製造方法，其中所述水溶性有機溶劑為選自2-乙基-1,3-己二醇、2,4-二乙基-1,5-戊二醇、單乙酸甘油酯(monoacetin)、二乙酸甘油酯(diacetin)、三乙酸甘油 酯(triacetin)、三丙酸甘油酯(tripropionin)、三丁酸甘油酯(tributyrin)、2-甲基戊烷-2,4-二醇、2-丁基-2-乙基-1,3-丙二醇、1,5-戊二醇、1,6-己二醇及1,2,6-己三醇中的至少一種。 [2] The method for producing a pigment composition according to [1], wherein the water-soluble organic solvent is selected from the group consisting of 2-ethyl-1,3-hexanediol and 2,4-diethyl-1. 5-pentanediol, monoacetin, diacetin, triacetin Triacetin, tripropionin, tributyrin, 2-methylpentane-2,4-diol, 2-butyl-2-ethyl-1,3 At least one of propylene glycol, 1,5-pentanediol, 1,6-hexanediol, and 1,2,6-hexanetriol.
[3]如[1]或[2]所記載的顏料組成物的製造方法，其中於步驟(a)中更含有樹脂。 [3] The method for producing a pigment composition according to [1] or [2], wherein the resin is further contained in the step (a).
[4]如[1]至[3]中任一項所記載的顏料組成物的製造方法，其中所述顏料為選自染色色澱系顏料(dyed lake pigments)、偶氮系顏料、酞菁系顏料及縮合多環系顏料中的至少一種。 [4] The method for producing a pigment composition according to any one of [1] to [3] wherein the pigment is selected from the group consisting of dyed lake pigments, azo pigments, and phthalocyanines. At least one of a pigment and a condensed polycyclic pigment.
[5]如[1]至[4]中任一項所記載的顏料組成物的製造方法，其中於步驟(c)之後且步驟(d)之前，進行添加分散溶劑並進行混合攪拌的步驟(e)。 [5] The method for producing a pigment composition according to any one of [1] to [4] wherein, after the step (c) and before the step (d), a step of adding a dispersion solvent and performing mixing and stirring is carried out ( e).
[6]一種顏料組成物，含有平均一次粒徑在5nm~1,000nm的範圍內的經微細化的顏料，並且相對於所述顏料組成物中所含的所述顏料100質量份，滿足以下的(i)~(iv)的水溶性有機溶劑以0.005質量份~0.5質量份的範圍而殘留；(i)分子量為100~350、更佳為130~350；(ii)具有合計2個以上的包含羥基及/或酯基的官能基(F)；(iii)60℃下的黏度為2mPa．s~140mPa．s；(iv)不含醚鍵。 [6] A pigment composition containing a fine pigment having an average primary particle diameter in the range of 5 nm to 1,000 nm, and satisfying the following with respect to 100 parts by mass of the pigment contained in the pigment composition; The water-soluble organic solvent of (i) to (iv) remains in the range of 0.005 parts by mass to 0.5 parts by mass; (i) the molecular weight is 100 to 350, more preferably 130 to 350; (ii) the total of two or more a functional group (F) comprising a hydroxyl group and/or an ester group; (iii) a viscosity at 60 ° C of 2 mPa. s~140mPa. s; (iv) does not contain an ether bond.
[7]一種磨碎混練用的水溶性有機溶劑，其用於製造含有平均一次粒徑在5nm~1,000nm的範圍內的經微細化的顏料的顏料組 成物，並且所述磨碎混練用的水溶性有機溶劑滿足以下的(i)~(iv)，(i)分子量為100~350、更佳為130~350；(ii)具有合計2個以上的包含羥基及/或酯基的官能基；(iii)60℃下的黏度為2mPa．s~140mPa．s；(iv)不含醚鍵。 [7] A water-soluble organic solvent for grinding and kneading, which is used for producing a pigment group containing a fine pigment having an average primary particle diameter in the range of 5 nm to 1,000 nm a product, and the water-soluble organic solvent for the grinding and kneading satisfies the following (i) to (iv), (i) a molecular weight of 100 to 350, more preferably 130 to 350; (ii) a total of two or more a functional group containing a hydroxyl group and/or an ester group; (iii) a viscosity at 60 ° C of 2 mPa. s~140mPa. s; (iv) does not contain an ether bond.
[8]如[7]所記載的磨碎混練用的水溶性有機溶劑，其中所述水溶性有機溶劑為選自2-乙基-1,3-己二醇、2,4-二乙基-1,5-戊二醇、單乙酸甘油酯、二乙酸甘油酯、三乙酸甘油酯、三丙酸甘油酯、三丁酸甘油酯、2-甲基戊烷-2,4-二醇、2-丁基-2-乙基-1,3-丙二醇、1,5-戊二醇、1,6-己二醇中的至少一種。 [8] The water-soluble organic solvent for grinding and kneading as described in [7], wherein the water-soluble organic solvent is selected from the group consisting of 2-ethyl-1,3-hexanediol and 2,4-diethyl. -1,5-pentanediol, monoacetin, diacetin, triacetin, tripropionate, tributyrin, 2-methylpentane-2,4-diol, At least one of 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, and 1,6-hexanediol.
[9]一種彩色濾光片用顏料組成物，含有如[6]所記載的顏料組成物。 [9] A pigment composition for a color filter, comprising the pigment composition according to [6].
根據本發明，具有以下效果：可提供一種經微細化的顏料的分散性能優異、且生產效率高的經微細化的顏料組成物及其製造方法，磨碎混練用的水溶性有機溶劑，以及彩色濾光片用顏料組成物。 According to the present invention, it is possible to provide a fine pigment composition excellent in dispersibility of a finely pigmented pigment and high in production efficiency, a method for producing the same, a water-soluble organic solvent for grinding and kneading, and color The pigment composition for the filter.
圖1為用以說明實施形態的顏料組成物的製造步驟的流程圖。 Fig. 1 is a flow chart for explaining a manufacturing procedure of a pigment composition of an embodiment.
圖2為用以說明實施形態的顏料組成物的製造步驟的流程圖。 Fig. 2 is a flow chart for explaining the steps of producing the pigment composition of the embodiment.
以下，對應用本發明的實施形態的一例加以說明。再者，其他實施形態只要符合本發明的主旨，則亦當然包括在本發明的範疇內。另外，本說明書中，「任意的數A~任意的數B」的記載於該範圍內包括數A作為下限值，包括數B作為上限值。 Hereinafter, an example of an embodiment to which the present invention is applied will be described. Furthermore, other embodiments are of course included in the scope of the present invention as long as they conform to the gist of the present invention. In the present specification, the description of "arbitrary number A to arbitrary number B" includes the number A as the lower limit value and the number B as the upper limit value in the range.
本發明的顏料組成物可藉由至少實施圖1所示的以下的步驟(a)~步驟(d)而獲得。 The pigment composition of the present invention can be obtained by performing at least the following steps (a) to (d) shown in Fig. 1 .
<步驟(a)>於步驟(a)中，於顏料中至少添加水溶性無機鹽及水溶性有機溶劑，藉由磨碎混練來將顏料加以微細化。利用磨碎混練的顏料的微細化方法並無特別限定，可應用任意的方法，較佳為利用所謂鹽磨(salt milling)處理的磨碎混練步驟等。進行微細化的顏料的平均一次粒徑可根據用途而變動，通常為5nm~1,000nm。此處所用的顏料通常可使用未經處理的粗顏料，但亦可使用經過某些處理步驟的顏料。另外，所使用的顏料可為單獨一種亦可為多種。 <Step (a)> In the step (a), at least a water-soluble inorganic salt and a water-soluble organic solvent are added to the pigment, and the pigment is finely pulverized by grinding and kneading. The method of miniaturizing the pigment by the kneading and kneading is not particularly limited, and any method can be applied, and a grinding and kneading step by a so-called salt milling treatment or the like is preferable. The average primary particle diameter of the pigment to be refined may vary depending on the application, and is usually 5 nm to 1,000 nm. The pigments used herein can generally be used as untreated coarse pigments, but pigments which have undergone certain processing steps can also be used. Further, the pigments used may be either single or plural.
關於磨碎混練方法，可使用捏合機、二輥磨機、三輥磨機、球磨機、研磨機(attritor)、臥式砂磨機、立式砂磨機或/及環型珠磨機等混練機，對至少含有顏料、水溶性無機鹽及水溶性有機溶劑的混合物進行磨碎混練。只要根據顏料的種類或所需求的微細化的程度等來適當調整處理條件等即可。較佳為於機械混練時進行加熱。水溶性無機鹽作為破碎助劑(crushing assistant)而發揮功能，於鹽磨時利用水溶性無機鹽的高硬度使顏料破碎。藉 由使鹽磨處理時的條件最適化，可獲得一次粒徑非常微細，另外，分佈的幅度窄而具有狹窄(sharp)的粒度分佈的顏料。 For the grinding and kneading method, a kneading machine, a two-roll mill, a three-roll mill, a ball mill, an attritor, a horizontal sand mill, a vertical sand mill, or a ring bead mill can be used for kneading. A mixture of at least a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is ground and kneaded. The treatment conditions and the like may be appropriately adjusted depending on the type of the pigment, the degree of miniaturization required, and the like. It is preferred to perform heating during mechanical kneading. The water-soluble inorganic salt functions as a crushing assistant, and the pigment is broken by the high hardness of the water-soluble inorganic salt during salt milling. borrow By optimizing the conditions for the salt milling treatment, it is possible to obtain a pigment having a very small primary particle diameter and a narrow distribution width and a sharp particle size distribution.
顏料只要為不偏離本發明的主旨的範圍，則並無特別限 定，可應用有機顏料及無機顏料。較佳的顏料可例示：選自染色色澱系顏料、偶氮系顏料、酞菁系顏料及縮合多環系顏料中的至少一種有機顏料。偶氮系顏料可為可溶性偶氮顏料、不溶性偶氮顏料的任一種。所述顏料的較佳具體例可列舉以下顏料。 The pigment is not particularly limited as long as it does not deviate from the gist of the present invention. Organic pigments and inorganic pigments can be applied. A preferred pigment is exemplified by at least one organic pigment selected from the group consisting of a dyed lake pigment, an azo pigment, a phthalocyanine pigment, and a condensed polycyclic pigment. The azo pigment may be any of a soluble azo pigment and an insoluble azo pigment. Preferred examples of the pigment include the following pigments.
染色色澱顏料可列舉：顏料黃(以下簡稱為PY)18、PY100、PY104、顏料橙(以下簡稱為PO)39、顏料紅(以下簡稱為PR)81、PR83、PR90、PR169、PR172、PR173、PR174、PR193、顏料紫(以下簡稱為PV)1、PV2、PV3、PV4、PV12、PV27、PV39、顏料藍(以下簡稱為PB)1、PB2、PB14、PB62、顏料綠(以下簡稱為PG)1、PG2、PG3、PG4、PG45、顏料棕(PBr)3等。 Examples of the dyed lake pigment include pigment yellow (hereinafter abbreviated as PY) 18, PY100, PY104, pigment orange (hereinafter abbreviated as PO) 39, pigment red (hereinafter abbreviated as PR) 81, PR83, PR90, PR169, PR172, PR173. , PR174, PR193, Pigment Violet (hereinafter abbreviated as PV) 1, PV2, PV3, PV4, PV12, PV27, PV39, Pigment Blue (hereinafter referred to as PB) 1, PB2, PB14, PB62, Pigment Green (hereinafter referred to as PG) 1, PG2, PG3, PG4, PG45, pigment brown (PBr) 3, and the like.
偶氮系顏料可列舉：PR53、PR50、PR49、PR57：1、PR48：1、PR52：1等可溶性偶氮顏料，PR1、PR3、PO5、PR21、PR114、PR5、PR146、PR170、PO38、PR187、PY1、PY3、PY167、PY154、PO36、PY12、PY13、PY14等不溶性偶氮顏料，PR144、PR166、PR214、PR242、PY93、PY94、PY95等縮合偶氮顏料等。 Examples of the azo-based pigments include soluble azo pigments such as PR53, PR50, PR49, PR57:1, PR48:1, and PR52:1, PR1, PR3, PO5, PR21, PR114, PR5, PR146, PR170, PO38, and PR187. Insoluble azo pigments such as PY1, PY3, PY167, PY154, PO36, PY12, PY13, and PY14, and condensed azo pigments such as PR144, PR166, PR214, PR242, PY93, PY94, and PY95.
酞菁系顏料可列舉：PB16、PB15：1、PB15：2、PB15：3、PB15：4、PB15：5、PB15：6、PG7、PG36、PG58、鋁酞菁等。 Examples of the phthalocyanine-based pigment include PB16, PB15:1, PB15:2, PB15:3, PB15:4, PB15:5, PB15:6, PG7, PG36, PG58, and aluminum phthalocyanine.
縮合多環系顏料可列舉：PY24、PY108、PO51、PR168、PR177、PB60等、PY38、PR88、PO43、PR194、PR178、PR179、PY138、 PV23、PV19、PR122、PY109、PY110、PY150、PY139、PR254、PR255、PR272、PO71、二溴二酮基吡咯并吡咯等。 Examples of the condensed polycyclic pigments include PY24, PY108, PO51, PR168, PR177, PB60, etc., PY38, PR88, PO43, PR194, PR178, PR179, PY138, PV23, PV19, PR122, PY109, PY110, PY150, PY139, PR254, PR255, PR272, PO71, dibromodionepyrrolopyrrole and the like.
水溶性有機溶劑發揮使顏料及水溶性無機鹽濕潤的作用，必須溶解(混合)於水中，且實質上不溶解所使用的水溶性無機鹽。進而，本發明的水溶性有機溶劑滿足以下的(i)~(iv)。即，滿足以下所有條件：(i)分子量為100~350、更佳為130~350，(ii)具有合計2個以上的包含羥基(OH基)及/或酯基(-COO-基)的官能基(F)，且(iii)60℃下的黏度為2mPa．s~140mPa．s，(iv)不含醚鍵。 The water-soluble organic solvent acts to wet the pigment and the water-soluble inorganic salt, and must be dissolved (mixed) in water and substantially does not dissolve the water-soluble inorganic salt used. Further, the water-soluble organic solvent of the present invention satisfies the following (i) to (iv). That is, all of the following conditions are satisfied: (i) a molecular weight of 100 to 350, more preferably 130 to 350, and (ii) a total of two or more hydroxyl groups (OH groups) and/or ester groups (-COO groups). Functional group (F), and (iii) viscosity at 60 ° C is 2 mPa. s~140mPa. s, (iv) does not contain an ether bond.
本發明的水溶性有機溶劑可使用單獨一種亦可併用多種。滿足該些(i)~(iv)的水溶性有機溶劑(以下亦稱為本發明的水溶性有機溶劑)適合作為磨碎混練用的溶劑。再者，於不偏離本發明的主旨的範圍內，不排除使用本發明的水溶性有機溶劑以外的溶劑(包括不滿足所述(i)~(iv)的任一個以上的水溶性有機溶劑)。然而，就有效地提高經微細化的顏料的分散性的觀點而言，較佳為實質上使用本發明的水溶性有機溶劑。以下，對本發明的水溶性有機溶劑加以說明。 The water-soluble organic solvent of the present invention may be used alone or in combination of two or more. The water-soluble organic solvent (hereinafter also referred to as the water-soluble organic solvent of the present invention) which satisfies the above (i) to (iv) is suitable as a solvent for the kneading and kneading. Further, a solvent other than the water-soluble organic solvent of the present invention (including a water-soluble organic solvent that does not satisfy any one of the above (i) to (iv)) is not excluded within the scope of the gist of the present invention. . However, from the viewpoint of effectively improving the dispersibility of the finely divided pigment, it is preferred to substantially use the water-soluble organic solvent of the present invention. Hereinafter, the water-soluble organic solvent of the present invention will be described.
所謂(ii)的具有合計2個以上的包含羥基及/或酯基的官能基(F)，包括a)含有2個以上的羥基且不含酯基的溶劑、b)含有2個以上的酯基且不含羥基的溶劑、及c)含有羥基與酯基兩 者且兩者合計成為2個以上的情況三種態樣。(iii)的黏度為於60℃的溫度下單獨測定水溶性有機溶劑時的黏度。本申請案說明書的水溶性有機溶劑的黏度為依據日本工業標準(Japanese Industrial Standards，JIS)Z 8803的規定並使用圓錐平板型旋轉黏度計(東機產業公司製造的黏度測定器：TVE-20L)測定的值。另外，如(iv)所指定，水溶性有機溶劑於其分子中不含醚鍵。 The functional group (F) having two or more hydroxyl groups and/or ester groups in total (ii) includes a) a solvent containing two or more hydroxyl groups and no ester group, and b) two or more esters. a solvent that does not contain a hydroxyl group, and c) contains a hydroxyl group and an ester group In the case where the total of the two is two or more, the three aspects are the same. The viscosity of (iii) is the viscosity when the water-soluble organic solvent is separately measured at a temperature of 60 °C. The viscosity of the water-soluble organic solvent in the specification of the present application is in accordance with Japanese Industrial Standards (JIS) Z 8803 and a conical plate type rotary viscometer (a viscosity measuring device manufactured by Toki Sangyo Co., Ltd.: TVE-20L) is used. Measured value. Further, as specified in (iv), the water-soluble organic solvent does not contain an ether bond in its molecule.
藉由使用滿足(i)~(iv)全部的水溶性有機溶劑，可 改善經微細化的顏料的分散性。其理由雖尚在推測範圍內，但可認為，本發明的水溶性有機溶劑與顏料的相互作用帶來了良好的結果。另外可認為，藉由相對於顏料使本發明的水溶性有機溶劑以特定的範圍殘留，而有可抑制經微細化的顏料的凝聚的效果。 By using all of the water-soluble organic solvents that satisfy (i) to (iv), The dispersibility of the finely divided pigment is improved. Although the reason is still within the estimated range, it is considered that the interaction between the water-soluble organic solvent of the present invention and the pigment brings about good results. In addition, it is considered that the water-soluble organic solvent of the present invention remains in a specific range with respect to the pigment, and the effect of suppressing aggregation of the finely pigmented pigment can be suppressed.
步驟(a)中所用的水溶性有機溶劑只要滿足所述(i) ~(iv)全部，則並無特別限定，較佳例可列舉：選自2-乙基-1,3-己二醇(16.6mPa．s)、2,4-二乙基-1,5-戊二醇(67.2mPa．s)、單乙酸甘油酯(13.7mPa．s)、二乙酸甘油酯(8.2mPa．s)、三乙酸甘油酯(4.1mPa．s)、三丙酸甘油酯(2.7mPa．s)、三丁酸甘油酯(3.3mPa．s)、2-甲基戊烷-2,4-二醇(5.8mPa．s)、2-丁基-2-乙基-1,3-丙二醇(43.7mPa．s)、1,5-戊二醇(20.9mPa．s)、1,6-己二醇(25.2mPa．s)及1,2,6-己三醇(137.6mPa．s)中的至少一種。 The water-soluble organic solvent used in the step (a) is only required to satisfy the above (i) All of (iv) is not particularly limited, and preferred examples thereof are selected from the group consisting of 2-ethyl-1,3-hexanediol (16.6 mPa.s) and 2,4-diethyl-1,5. - pentanediol (67.2 mPa.s), monoacetin (13.7 mPa.s), diacetin (8.2 mPa.s), triacetin (4.1 mPa.s), tripropionate ( 2.7 mPa.s), tributyrin (3.3 mPa.s), 2-methylpentane-2,4-diol (5.8 mPa.s), 2-butyl-2-ethyl-1, 3-propanediol (43.7 mPa.s), 1,5-pentanediol (20.9 mPa.s), 1,6-hexanediol (25.2 mPa.s) and 1,2,6-hexanetriol (137.6 mPa) At least one of .s).
本發明的水溶性有機溶劑的添加量並無特別限定，相對 於顏料100質量份，較佳為使用5質量份~1,000質量份，更佳為使用50質量份~500質量份。水溶性有機溶劑可使用一種亦可併 用多種。 The amount of the water-soluble organic solvent to be added of the present invention is not particularly limited, and The amount of the pigment is preferably from 5 parts by mass to 1,000 parts by mass, more preferably from 50 parts by mass to 500 parts by mass, per 100 parts by mass of the pigment. A water-soluble organic solvent can be used in one type. Use a variety.
步驟(a)中所用的水溶性無機鹽只要為如其名稱般顯示出水溶性的無機鹽即可，於不偏離本發明的主旨的範圍內並無限定。較佳例可列舉氯化鈉、氯化鋇、氯化鉀、硫酸鈉等。就價格的方面而言，較佳為使用氯化鈉(食鹽)。就處理效率與生產效率兩方面而言，相對於顏料100質量份，水溶性無機鹽較佳為使用50質量份~2,000質量份，更佳為使用300質量份~1,000質量份。 The water-soluble inorganic salt used in the step (a) is not particularly limited as long as it is a water-soluble inorganic salt as the name of the present invention. Preferable examples thereof include sodium chloride, cesium chloride, potassium chloride, and sodium sulfate. In terms of price, sodium chloride (salt) is preferably used. In terms of both the treatment efficiency and the production efficiency, the water-soluble inorganic salt is preferably used in an amount of from 50 parts by mass to 2,000 parts by mass, more preferably from 300 parts by mass to 1,000 parts by mass, per 100 parts by mass of the pigment.
於步驟(a)中，亦可進一步添加分散劑、色素衍生物等添加劑。分散劑可列舉樹脂及/或低分子量的界面活性劑等。 In the step (a), an additive such as a dispersant or a dye derivative may be further added. Examples of the dispersant include a resin and/or a low molecular weight surfactant.
用作分散劑的樹脂的種類並無特別限定，可使用天然樹脂、改質天然樹脂、合成樹脂、經天然樹脂改質的合成樹脂等。該樹脂於室溫下為固體，較佳為水不溶性，且更佳為可溶於所述本發明的水溶性有機溶劑中。相對於顏料100質量份，樹脂的使用量較佳為5質量份~100質量份的範圍。於實施樹脂處理的情形時使用本發明的水溶性有機溶劑的優點之一在於使樹脂溶解。可認為藉由使用本發明的水溶性有機溶劑，可使樹脂均勻地被覆於顏料上，即便於顏料經乾燥的情形時，被覆樹脂亦抑制顏料彼此的凝聚，有助於提高分散性。 The type of the resin to be used as the dispersing agent is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin is a solid at room temperature, preferably water-insoluble, and more preferably soluble in the water-soluble organic solvent of the present invention. The amount of the resin used is preferably in the range of 5 parts by mass to 100 parts by mass based on 100 parts by mass of the pigment. One of the advantages of using the water-soluble organic solvent of the present invention in the case of carrying out the resin treatment is to dissolve the resin. It is considered that by using the water-soluble organic solvent of the present invention, the resin can be uniformly coated on the pigment, and even when the pigment is dried, the coating resin suppresses aggregation of the pigments and contributes to improvement of dispersibility.
用作分散劑的樹脂的較佳例可列舉：聚胺基甲酸酯、聚酯、不飽和聚醯胺、磷酸酯、多羧酸及其胺鹽/銨鹽/烷基胺鹽、多羧酸酯、含羥基的多羧酸酯、聚矽氧烷、改質聚丙烯酸酯等油性 分散劑，(甲基)丙烯酸-(甲基)丙烯酸酯共聚物、(甲基)丙烯酸-苯乙烯共聚物、苯乙烯-馬來酸共聚物等水溶性樹脂或水溶性高分子化合物。樹脂型的分散劑可單獨使用一種亦可混合使用兩種以上。樹脂型的分散劑的質量平均分子量較佳為1,000~30,000左右。 Preferable examples of the resin used as the dispersing agent include polyurethanes, polyesters, unsaturated polyamines, phosphates, polycarboxylic acids and amine/ammonium salts/alkylamine salts thereof, and polycarboxylates. Oil properties such as acid esters, hydroxyl-containing polycarboxylates, polyoxyalkylene oxides, modified polyacrylates, etc. A dispersing agent, a water-soluble resin such as a (meth)acrylic acid-(meth)acrylate copolymer, a (meth)acrylic acid-styrene copolymer, or a styrene-maleic acid copolymer, or a water-soluble polymer compound. The resin type dispersant may be used alone or in combination of two or more. The resin type dispersant preferably has a mass average molecular weight of about 1,000 to 30,000.
具體可列舉：索努帕斯(SOLSPERSE)3000、索努帕斯(SOLSPERSE)13240、索努帕斯(SOLSPERSE)13940、索努帕斯(SOLSPERSE)16000、索努帕斯(SOLSPERSE)17000、索努帕斯(SOLSPERSE)18000、索努帕斯(SOLSPERSE)20000、索努帕斯(SOLSPERSE)21000、索努帕斯(SOLSPERSE)24000SC、索努帕斯(SOLSPERSE)24000GR、索努帕斯(SOLSPERSE)26000、索努帕斯(SOLSPERSE)27000、索努帕斯(SOLSPERSE)28000、索努帕斯(SOLSPERSE)31845、索努帕斯(SOLSPERSE)32000、索努帕斯(SOLSPERSE)32500、索努帕斯(SOLSPERSE)32550、索努帕斯(SOLSPERSE)34750、索努帕斯(SOLSPERSE)35100、索努帕斯(SOLSPERSE)35200、索努帕斯(SOLSPERSE)36000、索努帕斯(SOLSPERSE)36600、索努帕斯(SOLSPERSE)37500、索努帕斯(SOLSPERSE)38500、索努帕斯(SOLSPERSE)39000、索努帕斯(SOLSPERSE)41000(以上為日本路博潤(Lubrizol Japan)公司製造)；迪斯帕畢克(DISPERBYK)-101、迪斯帕畢克(DISPERBYK)-102、迪斯帕畢克(DISPERBYK)-106、迪斯帕畢克(DISPERBYK)-108、迪斯帕畢克(DISPERBYK)-109、迪斯帕畢克(DISPERBYK)-110、迪斯帕畢克(DISPERBYK)-111、 迪斯帕畢克(DISPERBYK)-112、迪斯帕畢克(DISPERBYK)-116、迪斯帕畢克(DISPERBYK)-130、迪斯帕畢克(DISPERBYK)-140、迪斯帕畢克(DISPERBYK)-142、迪斯帕畢克(DISPERBYK)-145、迪斯帕畢克(DISPERBYK)-161、迪斯帕畢克(DISPERBYK)-162、迪斯帕畢克(DISPERBYK)-163、迪斯帕畢克(DISPERBYK)-164、迪斯帕畢克(DISPERBYK)-166、迪斯帕畢克(DISPERBYK)-167、迪斯帕畢克(DISPERBYK)-168、迪斯帕畢克(DISPERBYK)-170、迪斯帕畢克(DISPERBYK)-171、迪斯帕畢克(DISPERBYK)-174、迪斯帕畢克(DISPERBYK)-180、迪斯帕畢克(DISPERBYK)-182、迪斯帕畢克(DISPERBYK)-183、迪斯帕畢克(DISPERBYK)-184、迪斯帕畢克(DISPERBYK)-185、迪斯帕畢克(DISPERBYK)-2000、迪斯帕畢克(DISPERBYK)-2001、迪斯帕畢克(DISPERBYK)-2008、迪斯帕畢克(DISPERBYK)-2009、迪斯帕畢克(DISPERBYK)-2022、迪斯帕畢克(DISPERBYK)-2025、迪斯帕畢克(DISPERBYK)-2050、迪斯帕畢克(DISPERBYK)-2070、迪斯帕畢克(DISPERBYK)-2096、迪斯帕畢克(DISPERBYK)-2150、迪斯帕畢克(DISPERBYK)-2155、迪斯帕畢克(DISPERBYK)-2163、迪斯帕畢克(DISPERBYK)-2164(以上為日本畢克化學(BYK Chemie Japan)公司製造)；畢克(BYK)-P104、畢克(BYK)-P104S、畢克(BYK)-P105、畢克(BYK)-9076、畢克(BYK)-9077、畢克(BYK)-220S(以上為日本畢克化學(BYK Chemie Japan)公司製造)；埃夫卡 (EFKA)4008、埃夫卡(EFKA)4009、埃夫卡(EFKA)4010、埃夫卡(EFKA)4015、埃夫卡(EFKA)4046、埃夫卡(EFKA)4047、埃夫卡(EFKA)4010、埃夫卡(EFKA)4015、埃夫卡(EFKA)4020、埃夫卡(EFKA)4050、埃夫卡(EFKA)4055、埃夫卡(EFKA)4060、埃夫卡(EFKA)4080、埃夫卡(EFKA)4300、埃夫卡(EFKA)4330、埃夫卡(EFKA)4400、埃夫卡(EFKA)4401、埃夫卡(EFKA)4402、埃夫卡(EFKA)4403、埃夫卡(EFKA)4406、埃夫卡(EFKA)4800、埃夫卡(EFKA)5010、埃夫卡(EFKA)5044、埃夫卡(EFKA)5207、埃夫卡(EFKA)5244、埃夫卡(EFKA)5054、埃夫卡(EFKA)5055、埃夫卡(EFKA)5063、埃夫卡(EFKA)5064、埃夫卡(EFKA)5065、埃夫卡(EFKA)5066、埃夫卡(EFKA)5070(以上為日本巴斯夫(BASF Japan)公司製造)；阿吉斯帕(Ajisper)PB821(F)、阿吉斯帕(Ajisper)PB822、阿吉斯帕(Ajisper)PB880、阿吉斯帕(Ajisper)PB881、阿吉斯帕(Ajisper)PN-411、阿吉斯帕(Ajisper)PA-111(以上為味之素精密技術(Ajinomoto Fine-techno)公司製造)；海諾特(Hinoact)(川研精化公司製造)；迪斯帕隆(DISPARLON)KS-860、迪斯帕隆(DISPARLON)KS-873N、迪斯帕隆(DISPARLON)7004、迪斯帕隆(DISPARLON)1831、迪斯帕隆(DISPARLON)1850、迪斯帕隆(DISPARLON)1860、迪斯帕隆(DISPARLON)DA-7301、迪斯帕隆(DISPARLON)DA-325、迪斯帕隆(DISPARLON)DA-375、迪斯帕隆(DISPARLON)DA-234、迪斯帕隆(DISPARLON)PW-36(以上為楠本化成公司 製造)等。 Specific examples are: SOSOLERS 3000, SOLSPERS 13340, SOLSPERS 13940, SOLSPERS 16000, SOSOLERS 17000, cable SOLSPERSE 18000, SOSOLPERSE 20000, SOLSPERS 21000, SOLSPERSE 24000SC, SOSOLERS 24000GR, SONOSPERSE 26000, SONOSPERSE 27000, SONOSPERSE 28000, SOLSPERS 31845, SOLSPERS 32000, SOLSPERS 32500, Sonour SOLSPERSE 32550, SOLSPPERSE 34750, SOLSPERS 35100, SOLSPERS 35200, SOLSPERS 36000, SOLSPERS 36600, SOLSPERSE 37500, SOSOLPERSE 38500, SOSOLERS 39000, SOLSPERS 41000 (above is manufactured by Lubrizol Japan) ); DISPERBYK-101, DISPERBYK-102, DISPERBYK-106, DISPARK (DISP) ERBYK)-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPARK ( DISPERBYK)-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DIS DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK )-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISC DISPERBYK-183, DISPERBYK-184, DISPERBYK-185, DISPERBYK-2000, DISPERBYK -2001, DISPERBYK-2008, DISPERBYK-2009, DISPERBYK-2022, DISPERBYK-2025, DISPA DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164 (above is Japan's BYK Chemical ( BYK Chemie Japan); BYK-P104, BYK-P104S, BYK-P105, BYK-9076, BYK-9077, BYK (BYK)-220S (above is made by BYK Chemie Japan); Evka (EFKA) 4008, EFKA 4009, EFKA 4010, EFKA 4015, EFKA 4046, EFKA 4047, EFKA 4010, EFKA 4015, EFKA 4020, EFKA 4050, EFKA 4055, EFKA 4060, EFKA 4080 , EFKA 4300, EFKA 4330, EFKA 4400, EFKA 4401, EFKA 4402, EFKA 4403, 埃EFKA 4406, EFKA 4800, EFKA 5010, EFKA 5044, EFKA 5207, EFKA 5244, Evka (EFKA) 5054, EFKA 5055, EFKA 5063, EFKA 5064, EFKA 5065, EFKA 5066, EFKA ) 5070 (above is BASF Japan); Ajisper PB821 (F), Ajisper PB822, Ajisper PB880, Ajispa ( Ajisper) PB881, Ajisper PN-411, Ajisper PA-111 (above Ajinomoto Fine-techno); Heinert (Hinoact) (made by Chuanyan Refinery Co., Ltd.); DISPARLON KS-860, DISPARLON KS-873N, DISPARLON 7004, DISPARLON 1831, DISPARLON 1850, DISPARLON 1860, DISPARLON DA-7301, DISPARLON DA-325, DISPARLON DA -375, DISPARLON DA-234, DISPARLON PW-36 (above is Nanben Chemical Company) Manufacturing) and so on.
用作分散劑的界面活性劑的較佳例可列舉：萘磺酸福馬 林縮合物鹽、芳香族磺酸福馬林縮合物、聚氧伸乙基烷基磷酸酯等陰離子活性劑；聚氧伸乙基烷基醚等非離子活性劑，烷基胺鹽、四級銨鹽等陽離子活性劑等。 Preferred examples of the surfactant used as the dispersing agent include: naphthalenesulfonic acid Anionic active agent such as condensate salt, aromatic sulfonic acid famarin condensate, polyoxyalkylene alkyl phosphate; nonionic active agent such as polyoxyethylene ethyl ether, alkylamine salt, quaternary ammonium A cationic active agent such as a salt.
具體可列舉：德莫耳(Demol)N、德莫耳(Demol)RN、德莫耳(Demol)MS、德莫耳(Demol)SN-B；愛慕根(Emulgen)120、愛慕根(Emulgen)430；阿塞他命(Acetamin)24、阿塞他命(Acetamin)86；擴特命(Quartamin)24P(以上為花王公司製造)；普萊薩福(Prisurf)AL、普萊薩福(Prisurf)A208F(以上為第一工業製藥公司製造)；阿卡德(Arcard)C-50、阿卡德(Arcard)T-28、阿卡德(Arcard)T-50(以上為獅王(Lion)公司製造)等。 Specific examples include: Demol N, Demol RN, Demol MS, Demol SN-B, Emulgen 120, Emulgen 430; Acetamin 24, Acetamin 86; Quartamin 24P (above is made by Kao); Prisurf AL, Prisurf A208F (above the first industrial pharmaceutical company); Arcard C-50, Arcard T-28, Arcard T-50 (above Lion) Manufacturing) and so on.
用作分散劑的有機顏料的衍生物較佳為以有機顏料作 為基本骨架、且於分子內導入有賦予酸性的取代基或賦予鹼性的取代基的化合物。可認為藉由添加有機顏料的衍生物，其吸附於成為分散對象的顏料上而賦予極性，藉此由與分散劑或樹脂的相互作用來賦予分散效果。另外，可期待有助於顏料的結晶穩定化、或分散穩定化的效果。 The derivative of the organic pigment used as the dispersing agent is preferably made of an organic pigment A compound which is a basic skeleton and introduces a substituent which imparts an acid or a substituent which gives a basicity into a molecule. It is considered that by adding a derivative of an organic pigment, it is adsorbed on a pigment to be dispersed to impart polarity, thereby imparting a dispersion effect by interaction with a dispersant or a resin. Further, an effect of contributing to the stabilization of the crystallization of the pigment or the stabilization of the dispersion can be expected.
具體而言，除了山陽色素公司製造的合成品以外，市售品的例子可列舉：埃夫卡(EFKA)-6745、埃夫卡(EFKA)-6750(埃夫卡添加劑(EFKA Additive)公司製造)，畢克-增效劑(BYK-Synergist)2100(日本畢克化學(BYK Chemie Japan)公 司製造)，索努帕斯(SOLSPERSE)5000、索努帕斯(SOLSPERSE)12000、索努帕斯(SOLSPERSE)22000(以上為日本路博潤(Lubrizol Japan)公司製造)等。 Specifically, in addition to the synthetic products manufactured by Sanyo Pigment Co., Ltd., examples of commercial products include Efka (EFKA)-6745 and EFKA-6750 (EFKA Additive). ), BYK-Synergist 2100 (BYK Chemie Japan) Manufactured by the company), SOSOLERSE 5000, SOLSPERSE 12000, SOSOLERS 22000 (above is Lubrizol Japan).
另外，纖維素衍生物、橡膠衍生物或/及蛋白衍生物亦可依據合成樹脂而選擇使用具有相同性能者。該些合成樹脂尤其可較佳地使用環氧樹脂及(甲基)丙烯酸系樹脂。其原因在於：通用性廣，透明性高，另外製成彩色濾光片時的各種耐性亦優異。 Further, the cellulose derivative, the rubber derivative or/and the protein derivative may be selected to have the same properties depending on the synthetic resin. As the synthetic resin, an epoxy resin and a (meth)acrylic resin are particularly preferably used. The reason for this is that it has wide versatility and high transparency, and is excellent in various resistances when a color filter is produced.
所述環氧樹脂是指於分子中含有1個以上的環氧基的環氧化物(epoxide)，本發明中較佳為未經硬化劑交聯而具有溶解性者。 環氧化物可列舉：雙酚系、酚醛清漆系、烷基苯酚系、間苯二酚系、聚二醇系、酯系、N-縮水甘油胺等縮水甘油基型、或環狀脂肪族環氧化物等。 The epoxy resin refers to an epoxide containing one or more epoxy groups in the molecule. In the present invention, it is preferred to have a solubility without cross-linking with a curing agent. Examples of the epoxide include a glycidyl group such as a bisphenol system, a novolak system, an alkylphenol system, a resorcinol system, a polyglycol system, an ester system, and an N-glycidylamine, or a cyclic aliphatic ring. Oxide, etc.
所述(甲基)丙烯酸系樹脂為選自丙烯酸、甲基丙烯酸及該些酸的酯的單體中的單體或混合物的共聚物，該等亦可為進一步與苯乙烯、乙酸乙烯酯、馬來酸酐等自由基聚合性單體的共聚物。 The (meth)acrylic resin is a copolymer of a monomer or a mixture of monomers selected from the group consisting of acrylic acid, methacrylic acid, and esters of the acid, which may further be combined with styrene, vinyl acetate, A copolymer of a radically polymerizable monomer such as maleic anhydride.
添加至顏料中的水溶性有機溶劑、水溶性無機鹽、分散 劑等的各使用量只要在可進行顏料的微細化處理的範圍內，則並無限定，對於微細化處理而言，重要的是具有如下黏度、硬度：可賦予藉由水溶性無機鹽將顏料有效地磨碎的剪切力的黏度、硬度。 Water-soluble organic solvent, water-soluble inorganic salt, dispersion added to the pigment The amount of each of the agents and the like is not limited as long as it can be subjected to the refining treatment of the pigment. For the refining treatment, it is important to have the following viscosity and hardness: the pigment can be imparted by the water-soluble inorganic salt. The viscosity and hardness of the shear force that is effectively ground.
<步驟(b)>進行步驟(a)之後，於其中投入水而獲 得懸浮液(圖1)。較佳為於步驟(a)結束後，自磨碎混練機中取 出顏料分散體，投入水並進行攪拌，獲得懸浮液。所添加的水的分量只要為足以獲得懸浮液的量即可，並無特別限定。視需要亦可加溫。例如，添加步驟(a)的質量的10倍~10,000倍的質量的水來進行混合攪拌。此時的混合攪拌條件並無特別限定，例如可於溫度25℃~90℃下進行。 <Step (b)> After performing step (a), water is added thereto A suspension was obtained (Fig. 1). Preferably, after the end of step (a), taking from the grinding and kneading machine The pigment dispersion was discharged, and water was poured and stirred to obtain a suspension. The amount of water to be added is not particularly limited as long as it is an amount sufficient to obtain a suspension. Warm up as needed. For example, mixing and stirring is carried out by adding water having a mass of 10 times to 10,000 times the mass of the step (a). The mixing and stirring conditions at this time are not particularly limited, and can be carried out, for example, at a temperature of from 25 ° C to 90 ° C.
<步驟(c)>於步驟(b)的處理後，將水溶性無機鹽去除，且將滿足以下的(A)的水溶性有機溶劑去除(圖1)。 <Step (c)> After the treatment of the step (b), the water-soluble inorganic salt is removed, and the water-soluble organic solvent satisfying the following (A) is removed (Fig. 1).
(A)相對於顏料組成物中所含的顏料100質量份，以0.005質量份~0.5質量份的範圍而殘留水溶性有機溶劑。 (A) The water-soluble organic solvent remains in the range of 0.005 parts by mass to 0.5 parts by mass based on 100 parts by mass of the pigment contained in the pigment composition.
關於使水溶性有機溶劑殘留於所述特定範圍內的方法，可藉由控制去除條件(例如清洗條件、乾燥條件、過濾條件)而容易地調整。只要可達成所述目的，則處理步驟不限，簡便的是藉由過濾來去除濾液的方法。 The method of leaving the water-soluble organic solvent in the specific range can be easily adjusted by controlling the removal conditions (for example, washing conditions, drying conditions, and filtration conditions). As long as the object can be achieved, the processing steps are not limited, and the method of removing the filtrate by filtration is simple.
關於相對於顏料組成物中所含的顏料100質量份的殘留溶劑，可藉由測定來求出顏料組成物中的總固體成分中的本發明的水溶性有機溶劑的殘留溶劑，並根據固體成分中的顏料的比例而算出。此處，所謂固體成分中的顏料的比例，是設定為顏料的添加量相對於最終獲得的顏料組成物中的總固體成分量之比例。再者，實際上有時於步驟(b)等中稍許損耗顏料，但本說明書中的固體成分中的顏料的比例是如上所述般設定。 With respect to 100 parts by mass of the residual solvent of the pigment contained in the pigment composition, the residual solvent of the water-soluble organic solvent of the present invention in the total solid content in the pigment composition can be determined by measurement, and based on the solid content Calculated by the ratio of the pigment in the middle. Here, the ratio of the pigment in the solid content is set as a ratio of the amount of the pigment added to the total solid content in the finally obtained pigment composition. Further, in some cases, the pigment may be slightly lost in the step (b) or the like, but the ratio of the pigment in the solid content in the present specification is set as described above.
<步驟(d)>於步驟(c)之後將水去除(圖1)。去除水的方法並無限定，較佳方法可列舉進行乾燥處理的方法。關於 步驟(d)的乾燥條件，例如可例示：於常壓下、於80℃~120℃的範圍內進行12小時~48小時左右的乾燥的方法；於減壓下、於25℃~80℃的範圍內進行12小時~60小時左右的乾燥的方法；於-60℃~-5℃的範圍內經冷凍後，於減壓下、於25℃~80℃的範圍內進行12小時~60小時左右的乾燥的方法。乾燥處理並無特別限定，可例示利用噴霧乾燥(spray dry)裝置的方法。亦可與乾燥處理同時或於乾燥處理後進行粉碎處理。 <Step (d)> The water was removed after the step (c) (Fig. 1). The method of removing water is not limited, and a preferable method is a method of performing a drying process. on The drying condition of the step (d) is, for example, a method of drying in a range of from 80 ° C to 120 ° C under normal pressure for about 12 hours to 48 hours; and under reduced pressure at 25 ° C to 80 ° C. Drying in the range of 12 hours to 60 hours; after freezing in the range of -60 ° C ~ -5 ° C, under reduced pressure, in the range of 25 ° C ~ 80 ° C for 12 hours to 60 hours Dry method. The drying treatment is not particularly limited, and a method using a spray drying apparatus can be exemplified. The pulverization treatment may be carried out simultaneously with the drying treatment or after the drying treatment.
藉由使用本發明的水溶性有機溶劑，可獲得體密度高的 粉末狀的顏料組成物。即，若以定性的表述換言之，則藉由使用本發明的水溶性有機溶劑，可獲得含有柔軟且蓬鬆的粉末狀的經微細化的顏料的顏料組成物。較佳的體密度可根據用途而變動，但較佳為設定為0.4g/mL以下。 By using the water-soluble organic solvent of the present invention, high bulk density can be obtained A powdery pigment composition. In other words, in the case of qualitative expression, a pigment composition containing a soft and fluffy powdery fine pigment can be obtained by using the water-soluble organic solvent of the present invention. The preferred bulk density may vary depending on the application, but is preferably set to 0.4 g/mL or less.
於圖2中，對本發明的顏料組成物的製造方法的較佳實 施態樣的一例加以說明。較佳態樣可例示圖2所示的路徑r1~路徑r3的步驟。 In Fig. 2, the method for producing the pigment composition of the present invention is better. An example of a mode is described. The preferred embodiment can exemplify the steps of the path r1 to the path r3 shown in FIG. 2.
除了進行步驟(a)~步驟(d)而獲得粉體的路徑r1以外，可列舉：於步驟(d)之後進行步驟(e)的路徑r2；於步驟(c)之後進行步驟(e)，其後進行步驟(d)的路徑r3。藉由路徑r1所得的顏料組成物為粉末狀，藉由路徑r2、路徑r3所得的顏料組成物為分散於分散溶劑中的例如清漆狀者。再者，本發明的顏料組成物只要包括步驟(a)~步驟(d)即可，可任意地添加步驟(e)。另外，亦可於不偏離本發明的主旨的範圍內任意添加其他 步驟。 In addition to the step (a) to the step (d) of obtaining the powder path r1, the step r2 of the step (e) is performed after the step (d); and the step (e) is performed after the step (c), Thereafter, the path r3 of the step (d) is performed. The pigment composition obtained by the path r1 is in the form of a powder, and the pigment composition obtained by the path r2 and the path r3 is, for example, a varnish dispersed in a dispersion solvent. Further, the pigment composition of the present invention may include any of the steps (a) to (d), and the step (e) may be arbitrarily added. In addition, it is also possible to arbitrarily add other components within the scope of the gist of the invention. step.
較佳的製造方法可根據產品的種類或根據需求(needs) 而變動，就製造步驟的簡便性的觀點而言，較佳為如圖2的路徑r3般直接獲得分散溶劑的方法。另外，就製造步驟的簡便性的觀點而言，以粉體的形式取出的方法較佳為路徑r1。另外，就進一步提高所得的顏料組成物的分散性的觀點而言，較佳為於路徑r1、路徑r2的步驟(d)中，於去除水時進行乾燥粉碎處理。 The preferred manufacturing method can be based on the type of product or on demand (needs) Further, from the viewpoint of the simplicity of the production step, a method of directly obtaining a dispersion solvent as in the path r3 of Fig. 2 is preferable. Further, from the viewpoint of the simplicity of the production steps, the method of taking out in the form of a powder is preferably the path r1. Moreover, from the viewpoint of further improving the dispersibility of the obtained pigment composition, it is preferred to carry out the drying and pulverizing treatment in the step (d) of the path r1 and the path r2 when water is removed.
<步驟(e)>經過步驟(d)後，於其中添加分散溶劑 並進行混合攪拌(參照圖2)。混合攪拌方法只要為可均勻地分散的方法，則並無特別限制。例如可列舉葉輪(impeller)、溶解器(dissolver)、均質攪拌機(homomixer)、超音波均質機等。此種處理亦可將兩種以上組合進行。於步驟(e)中，亦可除了分散溶劑以外添加分散助劑或其他添加劑。例如可添加黏合劑樹脂、色素衍生物、界面活性劑、其他色素等。該些添加劑只要不妨礙顏料的分散性即可，並無特別限定，較佳為溶解於分散溶劑中。藉由使用分散助劑，可提高顏料的分散性，更有效地防止分散後的顏料的再凝聚。 <Step (e)> After the step (d), a dispersing solvent is added thereto Mix and stir (see Figure 2). The mixing and stirring method is not particularly limited as long as it is a method capable of uniformly dispersing. For example, an impeller, a dissolver, a homomixer, an ultrasonic homogenizer, etc. are mentioned. This treatment can also be carried out in combination of two or more. In the step (e), a dispersing aid or other additives may be added in addition to the dispersing solvent. For example, a binder resin, a dye derivative, a surfactant, other pigments, or the like can be added. These additives are not particularly limited as long as they do not interfere with the dispersibility of the pigment, and are preferably dissolved in a dispersion solvent. By using a dispersing aid, the dispersibility of the pigment can be improved, and the re-agglomeration of the pigment after dispersion can be more effectively prevented.
(分散溶劑)步驟(e)中所用的分散溶劑只要不妨礙 顏料的分散性即可，並無特別限定。較佳例可列舉：1,2,3-三氯丙烷、2-庚酮、3,5,5-三甲基-2-環己烯-1-酮、3,3,5-三甲基環己酮、3-乙氧基丙酸乙酯、3-甲氧基-3-甲基丁基乙酸酯、3-甲氧基丁基乙酸酯、4-庚酮、間二甲苯、間二乙基苯、間二氯苯、正丁基苯、 乙酸正丙酯、鄰二甲苯、鄰氯甲苯、鄰二乙基苯、鄰二氯苯、對氯甲苯、對二乙基苯、第二丁基苯、第三丁基苯、γ-丁內酯、異佛爾酮、乙二醇二***、乙二醇二丁醚、乙二醇單異丙醚、乙二醇單***、乙二醇單***乙酸酯、乙二醇單第三丁醚、乙二醇單丁醚、乙二醇單丁醚乙酸酯、乙二醇單丙醚、乙二醇單己醚、乙二醇單甲醚、乙二醇單甲醚乙酸酯、二異丁基酮、二乙二醇二***、二乙二醇二甲醚、二乙二醇單異丙醚、二乙二醇單***乙酸酯、二乙二醇單丁醚、二乙二醇單丁醚乙酸酯、二乙二醇單甲醚、環己醇、環己醇乙酸酯、環己酮、二丙二醇二甲醚、二丙二醇甲基醚乙酸酯、二丙二醇單***、二丙二醇單丁醚、二丙二醇單丙醚、二丙二醇單甲醚、二丙酮醇、2-乙基-1,3-己二醇、2,4-二乙基-1,5-戊二醇、單乙酸甘油酯、二乙酸甘油酯、三乙酸甘油酯、三丙酸甘油酯、三丁酸甘油酯、2-甲基戊烷-2,4-二醇、2-丁基-2-乙基-1,3-丙二醇、1,5-戊二醇、1,6-己二醇、三丙二醇單丁醚、三丙二醇單甲醚、丙二醇二乙酸酯、丙二醇苯醚、丙二醇單***、丙二醇單***乙酸酯、丙二醇單丁醚、丙二醇單丙醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單甲醚丙酸酯、苄醇、甲基異丁基酮、甲基環己醇、乙酸正戊酯、乙酸正丁酯、乙酸異戊酯、乙酸異丁酯、乙酸丙酯、二元酸酯等。另外可列舉：乳酸乙酯、1,3-丁二醇(1,3-butanediol)、1,3-丁二醇(1,3-butylene glycol)、1,3-丁二醇二乙酸酯、1,4-二噁烷、2-甲基-1,3-丙二醇、3-甲基-1,3-丁二醇、3-甲氧基-3-甲基-1-丁醇、3-甲氧基丁醇、N,N-二甲基乙醯胺、N,N- 二甲基甲醯胺、正丁醇等。 (dispersing solvent) the dispersing solvent used in the step (e) as long as it does not interfere The dispersibility of the pigment is not particularly limited. Preferred examples thereof include 1,2,3-trichloropropane, 2-heptanone, 3,5,5-trimethyl-2-cyclohexen-1-one, and 3,3,5-trimethyl. Cyclohexanone, ethyl 3-ethoxypropionate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, 4-heptanone, m-xylene, Meta-diethylbenzene, m-dichlorobenzene, n-butylbenzene, N-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, t-butylbenzene, t-butylbenzene, γ-butane Ester, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol single third Ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, Diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethyl Glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol single Ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, 2-ethyl-1,3-hexanediol, 2,4-diethyl-1,5-pentyl Glycol, monoacetin, diacetin, triacetin Ester, tripropionate, tributyrin, 2-methylpentane-2,4-diol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentane Alcohol, 1,6-hexanediol, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol single Propyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-pentyl acetate, n-butyl acetate, Isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, and the like. Further, there may be mentioned ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, and 1,3-butylene glycol diacetate. , 1,4-dioxane, 2-methyl-1,3-propanediol, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3 -methoxybutanol, N,N-dimethylacetamide, N,N- Dimethylformamide, n-butanol, and the like.
該些分散溶劑中，就顏料組成物各成分的溶解性及塗佈 性良好的方面而言，較佳為使用乳酸乙酯，丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯等二醇乙酸酯類，苄醇等芳香族醇類或環己酮等酮類。 Solubility and coating of each component of the pigment composition among the dispersion solvents In terms of good properties, it is preferred to use ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. Alcohol acetates, aromatic alcohols such as benzyl alcohol or ketones such as cyclohexanone.
該些分散溶劑可單獨使用或混合使用。另外，分散溶劑 可根據所使用的用途而適當設定，就將顏料組成物調節為適當的黏度而可形成作為目標的均勻膜厚的濾波節(fliter segment)的方面而言，較佳為以顏料的總質量為基準(100質量%)而以500質量%~4,000質量%的量使用。於路徑r3的情況下，因於步驟(d)之後包括將水去除的步驟，故分散溶劑更佳為使用非水溶性有機溶劑。 These dispersion solvents may be used singly or in combination. In addition, the dispersion solvent It can be appropriately set according to the use to be used, and in terms of adjusting the pigment composition to an appropriate viscosity to form a fliter segment having a uniform film thickness as a target, it is preferable to use the total mass of the pigment as The standard (100% by mass) is used in an amount of 500% by mass to 4,000% by mass. In the case of the path r3, since the step of removing water after the step (d) is included, it is more preferable to use a water-insoluble organic solvent as the dispersion solvent.
(黏合劑樹脂)步驟(e)中所用的黏合劑樹脂可使用 以前公知的熱塑性樹脂或熱硬化性樹脂等。黏合劑樹脂較佳為樹脂型分散劑，該樹脂型分散劑含有具有吸附於添加顏料的性質的顏料親和性部位、及與顏料載體具有相容性的部位，且發揮吸附於添加顏料上而使於顏料載體中的分散變穩定的作用。黏合劑樹脂可單獨使用或混合使用兩種以上。 (Binder resin) The adhesive resin used in the step (e) can be used. A thermoplastic resin or a thermosetting resin or the like which has been conventionally known. The binder resin is preferably a resin type dispersant containing a pigment affinity site having a property of adsorbing to the added pigment and a site compatible with the pigment carrier, and exhibiting adsorption to the added pigment. The dispersion in the pigment carrier becomes stable. The binder resin may be used singly or in combination of two or more.
所述熱塑性樹脂例如可列舉：丙烯酸系樹脂、縮丁醛樹 脂、苯乙烯-馬來酸共聚物、氯化聚乙烯、氯化聚丙烯、聚氯乙烯、氯乙烯-乙酸乙烯酯共聚物、聚乙酸乙烯酯、聚胺基甲酸酯系樹脂、聚酯樹脂、乙烯系樹脂、醇酸樹脂、聚苯乙烯樹脂、聚醯胺 樹脂、橡膠系樹脂、環化橡膠系樹脂、纖維素類、聚乙烯(高密度聚乙烯(High Density Polyethylene，HDPE)、低密度聚乙烯(Low Density Polyethylene，LDPE))、聚丁二烯及聚醯亞胺樹脂等。 Examples of the thermoplastic resin include acrylic resin and butyral tree. Fat, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester Resin, vinyl resin, alkyd resin, polystyrene resin, polyamine Resin, rubber-based resin, cyclized rubber-based resin, cellulose, polyethylene (High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE)), polybutadiene, and poly醯 imine resin and the like.
構成熱塑性樹脂的單體的較佳例可列舉以下單體。例如可列舉：(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-2-乙基己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、苯氧基二乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯或乙氧基聚乙二醇(甲基)丙烯酸酯等(甲基)丙烯酸酯類，或(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-異丙基(甲基)丙烯醯胺、二丙酮(甲基)丙烯醯胺或丙烯醯基嗎啉等(甲基)丙烯醯胺類，苯乙烯或α-甲基苯乙烯等苯乙烯類，乙基乙烯醚、正丙基乙烯醚、異丙基乙烯醚、正丁基乙烯醚或異丁基乙烯醚等乙烯醚類，乙酸乙烯酯或丙酸乙烯酯等脂肪酸乙烯酯類。 Preferred examples of the monomer constituting the thermoplastic resin include the following monomers. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (methyl) ) isobutyl acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, (methyl) ) lauryl acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate a (meth) acrylate such as phenoxy diethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate or ethoxy polyethylene glycol (meth) acrylate, or (Meth) acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide (meth) acrylamide such as diacetone (meth) acrylamide or acryl hydrazinomorph, styrene such as styrene or α-methyl styrene, ethyl vinyl ether, n-propyl vinyl ether , isopropyl vinyl ether, n-butyl vinyl ether or isobutyl Enol ethers and other vinyl ethers, vinyl acetate or vinyl propionate and other vinyl esters of fatty acids.
另外可列舉：環己基馬來醯亞胺、苯基馬來醯亞胺、甲基馬來醯亞胺、乙基馬來醯亞胺、1,2-雙馬來醯亞胺乙烷、1,6-雙馬來醯亞胺己烷、3-馬來醯亞胺丙酸、6,7-亞甲基二氧基-4-甲基-3-馬來醯亞胺香豆素、4,4'-雙馬來醯亞胺二苯基甲烷、雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷、N,N'-1,3-伸苯基二馬來醯亞胺、 N,N'-1,4-伸苯基二馬來醯亞胺、N-(1-芘基)馬來醯亞胺、N-(2,4,6-三氯苯基)馬來醯亞胺、N-(4-胺基苯基)馬來醯亞胺、N-(4-硝基苯基)馬來醯亞胺、N-苄基馬來醯亞胺、N-溴甲基-2,3-二氯馬來醯亞胺、N-琥珀醯亞胺基-3-馬來醯亞胺苯甲酸酯、N-琥珀醯亞胺基-3-馬來醯亞胺丙酸酯、N-琥珀醯亞胺基-4-馬來醯亞胺丁酸酯、N-琥珀醯亞胺基-6-馬來醯亞胺己酸酯、N-[4-(2-苯并咪唑基)苯基]馬來醯亞胺、9-馬來醯亞胺吖啶等N-取代馬來醯亞胺類。 Further, there may be mentioned cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane, 1 , 6-Bismaleimide hexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4 , 4'-Bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylene Base two maleimide, N,N'-1,4-phenylene dimaleimide, N-(1-indenyl)maleimide, N-(2,4,6-trichlorophenyl)maleide Imine, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl -2,3-dichloromaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-3-maleimide propionic acid Ester, N-succinimide-4-merineimine butyrate, N-succinimide-6-maleimide caproate, N-[4-(2-benzo N-substituted maleimide such as imidazolyl)phenyl]maleimide or 9-maleimine acridine.
所述熱硬化性樹脂例如可列舉：環氧樹脂、苯并胍胺樹 脂、松香改質馬來酸樹脂、松香改質富馬酸樹脂、三聚氰胺樹脂、脲樹脂及酚樹脂等。其中，就提高耐熱性的觀點而言，可更佳地使用環氧樹脂、三聚氰胺樹脂。 Examples of the thermosetting resin include an epoxy resin and a benzoguanamine tree. Fat, rosin modified maleic acid resin, rosin modified fumaric acid resin, melamine resin, urea resin and phenol resin. Among them, an epoxy resin or a melamine resin can be more preferably used from the viewpoint of improving heat resistance.
另外，樹脂型分散劑的較佳例可例示：聚胺基甲酸酯、 聚丙烯酸酯等多羧酸酯、不飽和聚醯胺、多羧酸、多羧酸(部分)胺鹽、多羧酸銨鹽、多羧酸烷基胺鹽、聚矽氧烷、長鏈聚胺基醯胺磷酸鹽、含羥基的多羧酸酯或該等的改質物、藉由聚(低級伸烷基亞胺)與具有游離羧基的聚酯的反應所形成的醯胺或其鹽等油性分散劑，(甲基)丙烯酸-苯乙烯共聚物、(甲基)丙烯酸-(甲基)丙烯酸酯共聚物、苯乙烯-馬來酸共聚物、聚乙烯醇、聚乙烯基吡咯啶酮等水溶性樹脂或水溶性高分子化合物、聚酯系、改質聚丙烯酸酯系、環氧乙烷/環氧丙烷加成化合物、磷酸酯系等。 Further, preferred examples of the resin type dispersant are exemplified by polyurethane, Polycarboxylates such as polyacrylates, unsaturated polyamines, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polyoxyalkylene oxides, long chain polycondensation An amine decylamine phosphate, a hydroxyl group-containing polycarboxylate or the like, a guanamine or a salt thereof formed by a reaction of a poly(lower alkylene imine) with a polyester having a free carboxyl group Oily dispersant, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resin, water-soluble polymer compound, polyester-based, modified polyacrylate-based, ethylene oxide/propylene oxide addition compound, phosphate ester, and the like.
就藉由少量的添加量而顏料組成物的黏度變低、顯示出 高的分光透射率的理由而言，所述樹脂型分散劑較佳為具有鹼性 官能基的高分子分散劑，較佳為含氮原子的接枝共聚物或於側鏈上具有三級胺基、四級銨鹽基、含有含氮雜環等的官能基的且含氮原子的丙烯酸系嵌段共聚物及胺基甲酸酯系高分子分散劑等。 樹脂型分散劑較佳為以顏料的總量為基準(100質量%)而使用5質量%~200質量%左右，就成膜性的觀點而言，更佳為使用10質量%~100質量%左右。 The viscosity of the pigment composition is lowered by a small amount of addition, and it is shown For the reason of high spectral transmittance, the resin type dispersant is preferably alkaline The functional polymer dispersant is preferably a nitrogen atom-containing graft copolymer or a nitrogen atom having a tertiary amino group, a quaternary ammonium salt group, a functional group containing a nitrogen-containing heterocyclic ring or the like in a side chain. Acrylic block copolymer and urethane polymer dispersant. The resin-type dispersant is preferably used in an amount of from 5% by mass to about 200% by mass based on the total amount of the pigment (100% by mass), and more preferably from 10% by mass to 100% by mass in terms of film formability. about.
市售的樹脂型分散劑可列舉：日本畢克化學(BYK Chemie Japan)公司製造的迪斯帕畢克(Disperbyk)-101、迪斯帕畢克(Disperbyk)-103、迪斯帕畢克(Disperbyk)-107、迪斯帕畢克(Disperbyk)-108、迪斯帕畢克(Disperbyk)-110、迪斯帕畢克(Disperbyk)-111、迪斯帕畢克(Disperbyk)-116、迪斯帕畢克(Disperbyk)-130、迪斯帕畢克(Disperbyk)-140、迪斯帕畢克(Disperbyk)-154、迪斯帕畢克(Disperbyk)-161、迪斯帕畢克(Disperbyk)-162、迪斯帕畢克(Disperbyk)-163、迪斯帕畢克(Disperbyk)-164、迪斯帕畢克(Disperbyk)-165、迪斯帕畢克(Disperbyk)-166、迪斯帕畢克(Disperbyk)-170、迪斯帕畢克(Disperbyk)-171、迪斯帕畢克(Disperbyk)-174、迪斯帕畢克(Disperbyk)-180、迪斯帕畢克(Disperbyk)-181、迪斯帕畢克(Disperbyk)-182、迪斯帕畢克(Disperbyk)-183、迪斯帕畢克(Disperbyk)-184、迪斯帕畢克(Disperbyk)-185、迪斯帕畢克(Disperbyk)-190、迪斯帕畢克(Disperbyk)-2000、迪斯帕畢克(Disperbyk)-2001、迪斯帕畢克(Disperbyk)-2020、迪斯 帕畢克(Disperbyk)-2025、迪斯帕畢克(Disperbyk)-2050、迪斯帕畢克(Disperbyk)-2070、迪斯帕畢克(Disperbyk)-2095、迪斯帕畢克(Disperbyk)-2150、迪斯帕畢克(Disperbyk)-2155或安泰拉(Anti-Terra)-U、安泰拉(Anti-Terra)-203、安泰拉(Anti-Terra)-204或畢克(BYK)-P104、畢克(BYK)-P104S、畢克(BYK)-220S、畢克(BYK)-6919或拉提門(Lactimon)、拉提門(Lactimon)-WS或畢庫曼(Bykumen)等；日本路博潤(Lubrizol Japan)公司製造的索努帕斯(SOLSPERSE)-3000、索努帕斯(SOLSPERSE)-9000、索努帕斯(SOLSPERSE)-13000、索努帕斯(SOLSPERSE)-13240、索努帕斯(SOLSPERSE)-13650、索努帕斯(SOLSPERSE)-13940、索努帕斯(SOLSPERSE)-16000、索努帕斯(SOLSPERSE)-17000、索努帕斯(SOLSPERSE)-18000、索努帕斯(SOLSPERSE)-20000、索努帕斯(SOLSPERSE)-21000、索努帕斯(SOLSPERSE)-24000、索努帕斯(SOLSPERSE)-26000、索努帕斯(SOLSPERSE)-27000、索努帕斯(SOLSPERSE)-28000、索努帕斯(SOLSPERSE)-31845、索努帕斯(SOLSPERSE)-32000、索努帕斯(SOLSPERSE)-32500、索努帕斯(SOLSPERSE)-32550、索努帕斯(SOLSPERSE)-33500、索努帕斯(SOLSPERSE)-32600、索努帕斯(SOLSPERSE)-34750、索努帕斯(SOLSPERSE)-35100、索努帕斯(SOLSPERSE)-36600、索努帕斯(SOLSPERSE)-38500、索努帕斯(SOLSPERSE)-41000、索努帕斯(SOLSPERSE)-41090、索努帕斯(SOLSPERSE)-53095、索努帕斯(SOLSPERSE)-55000、 索努帕斯(SOLSPERSE)-76500等；巴斯夫(BASF)公司製造的埃夫卡(EFKA)-46、埃夫卡(EFKA)-47、埃夫卡(EFKA)-48、埃夫卡(EFKA)-452、埃夫卡(EFKA)-4008、埃夫卡(EFKA)-4009、埃夫卡(EFKA)-4010、埃夫卡(EFKA)-4015、埃夫卡(EFKA)-4020、埃夫卡(EFKA)-4047、埃夫卡(EFKA)-4050、埃夫卡(EFKA)-4055、埃夫卡(EFKA)-4060、埃夫卡(EFKA)-4080、埃夫卡(EFKA)-4400、埃夫卡(EFKA)-4401、埃夫卡(EFKA)-4402、埃夫卡(EFKA)-4403、埃夫卡(EFKA)-4406、埃夫卡(EFKA)-4408、埃夫卡(EFKA)-4300、埃夫卡(EFKA)-4310、埃夫卡(EFKA)-4320、埃夫卡(EFKA)-4330、埃夫卡(EFKA)-4340、埃夫卡(EFKA)-450、埃夫卡(EFKA)-451、埃夫卡(EFKA)-453、埃夫卡(EFKA)-4540、埃夫卡(EFKA)-4550、埃夫卡(EFKA)-4560、埃夫卡(EFKA)-4800、埃夫卡(EFKA)-5010、埃夫卡(EFKA)-5065、埃夫卡(EFKA)-5066、埃夫卡(EFKA)-5070、埃夫卡(EFKA)-7500、埃夫卡(EFKA)-7554、埃夫卡(EFKA)-1101、埃夫卡(EFKA)-120、埃夫卡(EFKA)-150、埃夫卡(EFKA)-1501、埃夫卡(EFKA)-1502、埃夫卡(EFKA)-1503等；味之素精密技術(Ajinomoto Fine-techno)公司製造的阿吉斯帕(Ajisper)PA111、阿吉斯帕(Ajisper)PB711、阿吉斯帕(Ajisper)PB821、阿吉斯帕(Ajisper)PB822、阿吉斯帕(Ajisper)PB824等。 Commercially available resin type dispersants can be cited as: BYK Chemical (BYK) Chemie Japan) Disperbyk-101, Disperbyk-103, Disperbyk-107, Disperbyk-108, Disperbyk-110, Disperbyk-111, Disperbyk-116, Disperbyk-130, Despabike ( Disperbyk)-140, Disperbyk-154, Disperbyk-161, Disperbyk-162, Disperbyk-163, Di Disperbyk-164, Disperbyk-165, Disperbyk-166, Disperbyk-170, Disperbyk ) -171, Disperbyk-174, Disperbyk-180, Disperbyk-181, Disperbyk-182, Diss Disperbyk-183, Disperbyk-184, Disperbyk-185, Disperbyk-190, Disperbyk -2000, Disperbyk-2001, Disperbyk-2020, Diss Disperbyk-2025, Disperbyk-2050, Disperbyk-2070, Disperbyk-2095, Disperbyk -2150, Disperbyk-2155 or Anti-Terra-U, Anti-Terra-203, Anti-Terra-204 or BYK- P104, BYK-P104S, BYK-220S, BYK-6919 or Lactimon, Lactimon-WS or Bykumen; Japan's Lubrizol Japan's SOSOLPERSE-3000, SOSOLERSE-9000, SOSOLERSE-13000, SOSOLERSE-13240 , SOSOLERSE - 13650, SOSOLERSE - 13940, SOSOLERSE - 16000, SOSOLERSE - 17,000, SOSOLERS - 18000 , SOSOPERS-20000, SOLSPERS-21000, SOLSPERS-24000, SOLSPERS-26000, SOLSPERS-27000 , SOSOPERS-28000, SOLSPERS-31845, Sonupas (SOL SPERSE)-32000, SOLSPERS-32500, SOLSPERS-32550, SOLSPERS-33500, SOSOLERS-32600, Sonupas (Sourse) SOLSPERSE)-34750, SOSOLERS-35100, SOLSPERS-36600, SOLSPERS-38500, SOSOLERS-41000, Sonupas SOLSPERSE)-41090, SOSOLERS-53095, SOSOLERS-55000, SOSOLERSE-76500, etc.; EFKA-46, EFKA-47, EFKA-48, EFKA manufactured by BASF ) -452, EFKA-4008, EFKA-4009, EFKA-4010, EFKA-4015, EFKA-4020, angstrom EFKA-4047, EFKA-4050, EFKA-4055, EFKA-4060, EFKA-4080, EFKA -4400, EFKA-4401, EFKA-4402, EFKA-4403, EFKA-4406, EFKA-4408, Eve Card (EFKA)-4300, EFKA-4310, EFKA-4320, EFKA-4330, EFKA-4340, EFKA - 450, EFKA-451, EFKA-453, EFKA-4540, EFKA-4550, EFKA-4560, Evka (EFKA)-4800, EFKA-5010, EFKA-5065, EFKA-5066, EFKA-5070, EFKA-7500 , EFKA-7554, EFKA-1101, EFKA-120, EFKA-150, angstrom Card (EFKA)-1501, EFKA-1502, EFKA-1503, etc.; Ajisper PA111, manufactured by Ajinomoto Fine-techno Ajisper PB711, Ajisper PB821, Ajisper PB822, Ajisper PB824, and the like.
為了使顏料良好地分散，黏合劑樹脂的質量平均分子量 (Mw)較佳為5,000~80,000的範圍，更佳為7,000~50,000的範 圍。另外，數量平均分子量(Mn)較佳為2,500~40,000的範圍，Mw/Mn的值較佳為10以下。 In order to disperse the pigment well, the mass average molecular weight of the binder resin (Mw) is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000. Wai. Further, the number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw/Mn is preferably 10 or less.
此處，質量平均分子量(Mw)、數量平均分子量(Mn) 為於東曹(Tosoh)公司製造的凝膠滲透層析儀「HLC-8120GPC」中，將東曹(Tosoh)公司製造的「TSK-GEL SUPER H5000」、「TSK-GEL SUPER H4000」、「TSK-GEL SUPER H3000」及「TSK-GEL SUPER H2000」串列連結作為分離管柱，移動相使用四氫呋喃，於40℃下測定的以聚苯乙烯作為標準物質的換算分子量。黏合劑樹脂的添加量並無特別限定，若考慮到成膜性或耐候性、顏色特性，則較佳為以顏料的總質量為基準(100質量%)而以20質量%~500質量%的量使用。 Here, mass average molecular weight (Mw), number average molecular weight (Mn) "TSK-GEL SUPER H5000", "TSK-GEL SUPER H4000", "TSK" manufactured by Tosoh Corporation for the gel permeation chromatography "HLC-8120GPC" manufactured by Tosoh Corporation -GEL SUPER H3000" and "TSK-GEL SUPER H2000" were connected in series as a separation column, and the mobile phase was converted to a molecular weight of polystyrene as a standard material measured at 40 ° C using tetrahydrofuran. The amount of the binder resin to be added is not particularly limited, and in view of film formability, weather resistance, and color characteristics, it is preferably 20% by mass to 500% by mass based on the total mass of the pigment (100% by mass). The amount is used.
於用於彩色濾光片用途的情形時，黏合劑樹脂較佳為於 可見光範圍的400nm~700nm的整個波長範圍內，分光透射率較佳為80%以上、更佳為95%以上的樹脂。另外，於以鹼顯影型著色抗蝕劑的形態使用的情形時，較佳為使用將含酸性基的乙烯性不飽和單體共聚合而成的鹼可溶性乙烯系樹脂。另外，為了進一步提高光感度，亦可使用具有乙烯性不飽和活性雙鍵的能量線硬化性樹脂。 For use in color filter applications, the binder resin is preferably The resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more, in the entire wavelength range of 400 nm to 700 nm in the visible light range. When it is used in the form of an alkali-developing type coloring resist, it is preferred to use an alkali-soluble vinyl resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer. Further, in order to further improve the light sensitivity, an energy ray-curable resin having an ethylenically unsaturated active double bond may also be used.
將含酸性基的乙烯性不飽和單體共聚合而成的鹼可溶 性樹脂例如可列舉具有羧基、碸基等酸性基的樹脂。鹼可溶性樹脂的具體例可列舉：具有酸性基的丙烯酸系樹脂、α-烯烴/馬來酸 (酐)共聚物、苯乙烯/苯乙烯磺酸共聚物、乙烯/(甲基)丙烯酸共聚物或異丁烯/馬來酸(酐)共聚物等。其中，選自具有酸性基的丙烯酸系樹脂及苯乙烯/苯乙烯磺酸共聚物中的至少一種樹脂、特別是具有酸性基的丙烯酸系樹脂由於耐熱性、透明性高，故可較佳地使用。 Alkali soluble by copolymerization of an acidic group-containing ethylenically unsaturated monomer The resin is, for example, a resin having an acidic group such as a carboxyl group or a fluorenyl group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, and an α-olefin/maleic acid. (Anhydride) copolymer, styrene/styrenesulfonic acid copolymer, ethylene/(meth)acrylic acid copolymer or isobutylene/maleic acid (anhydride) copolymer, and the like. Among them, at least one selected from the group consisting of an acrylic resin having an acidic group and a styrene/styrenesulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency. .
具有乙烯性不飽和活性雙鍵的能量線硬化性樹脂可使 用：使具有異氰酸酯基、醛基、環氧基等反應性取代基的(甲基)丙烯酸系化合物或肉桂酸與具有羥基、羧基、胺基等反應性取代基的高分子反應，將(甲基)丙烯醯基、苯乙烯基等光交聯性基導入至該高分子中而成的樹脂。另外，較佳為藉由(甲基)丙烯酸羥基烷基酯等具有羥基的(甲基)丙烯酸系化合物將苯乙烯-馬來酸酐共聚物或α-烯烴-馬來酸酐共聚物等含有酸酐的高分子加以半酯化而成者。作為彩色濾光片用途，兼具鹼可溶性能與能量線硬化性能的熱塑性樹脂亦較佳。 An energy ray-curable resin having an ethylenically unsaturated active double bond can By reacting a (meth)acrylic compound or a cinnamic acid having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group with a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amine group, A resin obtained by introducing a photocrosslinkable group such as an acrylonitrile group or a styryl group into the polymer. Further, it is preferred that the styrene-maleic anhydride copolymer or the α-olefin-maleic anhydride copolymer or the like contains an acid anhydride by a (meth)acrylic compound having a hydroxyl group such as a hydroxyalkyl (meth)acrylate. The polymer is semi-esterified. As a color filter, a thermoplastic resin having both alkali solubility and energy ray hardening properties is also preferable.
(色素衍生物)色素衍生物可列舉：於有機顏料、蒽醌、 吖啶酮或三嗪中導入有鹼性取代基、酸性取代基或可具有取代基的鄰苯二甲醯亞胺甲基而成的化合物，例如可使用日本專利特開昭63-305173號公報、日本專利特公昭57-15620號公報、日本專利特公昭59-40172號公報、日本專利特公昭63-17102號公報、日本專利特公平5-9469號公報等中記載的化合物，該些化合物可單獨使用或混合使用兩種以上。於使用色素衍生物的情形時，就明度、分散性的觀點而言，較佳為具有偶氮骨架、萘酚偶氮骨架、 二酮基吡咯并吡咯(diketopyrrolopyrrole)骨架、蒽醌骨架(anthraquinone)、喹酞酮(quinophthalone)骨架及苝(perylene)骨架的化合物。 (Pigment Derivative) The pigment derivative is exemplified by organic pigments, hydrazine, A compound obtained by introducing a basic substituent, an acidic substituent or a phthalimidomethyl group which may have a substituent to an acridone or a triazine, for example, Japanese Patent Laid-Open Publication No. SHO63-305173 a compound described in Japanese Patent Publication No. Sho 57-15620, Japanese Patent Publication No. Sho 59-40172, Japanese Patent Publication No. Sho 63-17102, Japanese Patent Publication No. Hei 5-9469, and the like. Use two or more types alone or in combination. In the case of using a dye derivative, it is preferred to have an azo skeleton, a naphthol azo skeleton, from the viewpoint of lightness and dispersibility. A compound of a diketopyrrolopyrrole skeleton, an anthraquinone, a quinophthalone skeleton, and a perylene skeleton.
就提高添加顏料的分散性的觀點而言，以添加顏料的總 量為基準(100質量%)，色素衍生物的調配量較佳為0.5質量%以上，更佳為1質量%以上，進而佳為3質量%以上。另外，就耐熱性、耐光性的觀點而言，以添加顏料的總量為基準(100質量%)，較佳為40質量%以下，更佳為35質量%以下。 From the viewpoint of improving the dispersibility of the added pigment, the total amount of added pigment The amount of the pigment derivative to be added is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 3% by mass or more. In addition, from the viewpoint of heat resistance and light resistance, based on the total amount of the added pigment (100% by mass), it is preferably 40% by mass or less, and more preferably 35% by mass or less.
(界面活性劑)界面活性劑的較佳一例可列舉：月桂基 硫酸鈉、聚氧伸乙基烷基醚硫酸鹽、十二烷基苯磺酸鈉、苯乙烯-丙烯酸共聚物的鹼鹽、硬脂酸鈉、烷基萘磺酸鈉、烷基二苯基醚二磺酸鈉、月桂基硫酸單乙醇胺、月桂基硫酸三乙醇胺、月桂基硫酸銨、硬脂酸單乙醇胺、苯乙烯-丙烯酸共聚物的單乙醇胺、聚氧伸乙基烷基醚磷酸酯等陰離子性界面活性劑；聚氧伸乙基油基醚、聚氧伸乙基月桂基醚、聚氧伸乙基壬基苯基醚、聚氧伸乙基烷基醚磷酸酯、聚氧伸乙基山梨糖醇酐單硬脂酸酯、聚乙二醇單月桂酸酯等非離子性界面活性劑；烷基四級銨鹽或該等的環氧乙烷加成物等陽離子性界面活性劑；烷基二甲基胺基乙酸甜菜鹼等烷基甜菜鹼、烷基咪唑啉等兩性界面活性劑。界面活性劑可單獨使用或混合使用。 A preferred example of the (surfactant) surfactant is: lauryl Sodium sulfate, polyoxyethylene ethyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalene sulfonate, alkyl diphenyl Sodium ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene ethyl ether phosphate, etc. Anionic surfactant; polyoxyethylene ethyl oleyl ether, polyoxyethylene ethyl lauryl ether, polyoxyethyl phenyl ether, polyoxyethylene ethyl ether phosphate, polyoxyethylene a nonionic surfactant such as sorbitan monostearate or polyethylene glycol monolaurate; a cationic surfactant such as an alkyl quaternary ammonium salt or such an ethylene oxide adduct An amphoteric surfactant such as an alkylbetaine or an alkylimidazoline such as an alkyldimethylaminoacetic acid betaine. The surfactants may be used singly or in combination.
關於添加樹脂型分散劑或/及界面活性劑的情形的調配 量，以添加顏料的總量為基準(100質量%)，所述調配量較佳為 0.1質量%~55質量%，更佳為0.1質量%~45質量%。於樹脂型分散劑或/及界面活性劑的調配量小於0.1質量%的情形時，難以獲得添加效果，若調配量多於55質量%，則有時由過剩的分散劑對分散造成不良影響。 Formulation of the case of adding a resin type dispersant or/and a surfactant The amount is based on the total amount of the added pigment (100% by mass), and the blending amount is preferably 0.1% by mass to 55% by mass, more preferably 0.1% by mass to 45% by mass. When the amount of the resin-type dispersant or/and the surfactant is less than 0.1% by mass, it is difficult to obtain an effect of addition, and if the amount is more than 55% by mass, the excessive dispersant may adversely affect the dispersion.
經過所述步驟，可獲得本發明的顏料組成物。本發明的 顏料組成物大多情況下是分散於分散溶劑中而使用，但藉由在路徑r1中預先獲得粉末狀的顏料組成物，可於即將使用之前或產品製造時，根據用途或需求來選定分散溶劑的種類或調配比進行調和(路徑r2)。 Through the steps, the pigment composition of the present invention can be obtained. The invention In many cases, the pigment composition is used by being dispersed in a dispersion solvent, but by previously obtaining a powdery pigment composition in the path r1, the dispersion solvent can be selected depending on the use or demand immediately before use or at the time of product manufacture. The type or blend ratio is blended (path r2).
於該情形時，亦可確保長期保存性，或減少運輸費等。根據路徑r1，藉由以粉末狀獲得，亦可應對粉末的需求。另一方面，根據路徑r3，因省略乾燥粉碎處理步驟，故可簡化製造步驟。 In this case, long-term preservation, or reduction of transportation costs, etc., can also be ensured. According to the path r1, the powder can also be obtained in a powder form. On the other hand, according to the path r3, since the dry pulverization processing step is omitted, the manufacturing steps can be simplified.
根據本發明的顏料組成物的製造方法，藉由使用滿足(i)~(iv)的水溶性有機溶劑，所得的顏料組成物的分散性變優異。考察其原因在於：藉由使用水溶性有機溶劑來進行步驟(a)~步驟(d)，與使用以前所用的溶劑的情形相比較，可獲得體密度更高的顏料組成物。 According to the method for producing a pigment composition of the present invention, the dispersibility of the obtained pigment composition is excellent by using a water-soluble organic solvent satisfying (i) to (iv). The reason for this is that the steps (a) to (d) are carried out by using a water-soluble organic solvent, and a pigment composition having a higher bulk density can be obtained as compared with the case of using a solvent used previously.
經過本發明的步驟(e)所得的使經微細化的顏料分散於分散溶劑中而成的顏料組成物亦可進一步添加光聚合性單體而用作感光性顏料組成物。可添加至感光性顏料組成物中的光聚合性單體中，包括藉由紫外線或熱等進行硬化而生成透明樹脂的單體或低聚物。 The pigment composition obtained by dispersing the finely divided pigment in the dispersion solvent obtained in the step (e) of the present invention may be further used as a photosensitive pigment composition by further adding a photopolymerizable monomer. The photopolymerizable monomer which can be added to the photosensitive pigment composition includes a monomer or oligomer which is cured by ultraviolet rays or heat to form a transparent resin.
藉由紫外線或熱等進行硬化而生成透明樹脂的單體、低 聚物例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸-β-羧基乙酯、聚乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、1,6-己二醇二縮水甘油醚二(甲基)丙烯酸酯、雙酚A二縮水甘油醚二(甲基)丙烯酸酯、新戊二醇二縮水甘油醚二(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、(甲基)丙烯酸三環癸酯、酯丙烯酸酯、羥甲基化三聚氰胺的(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、丙烯酸胺基甲酸酯等各種丙烯酸酯及甲基丙烯酸酯，(甲基)丙烯酸、苯乙烯、乙酸乙烯酯、羥基乙基乙烯醚、乙二醇二乙烯醚、季戊四醇三乙烯醚、(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、N-乙烯基甲醯胺、丙烯腈等，但未必限定於該些化合物。光聚合性化合物可單獨使用或混合使用兩種以上。 A monomer which is formed by curing by ultraviolet rays or heat to form a transparent resin. Examples of the polymer include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (methyl). Cyclohexyl acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di Methyl) acrylate, tripropylene glycol di(meth) acrylate, trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6 - hexanediol diglycidyl ether di(meth) acrylate, bisphenol A diglycidyl ether di(meth) acrylate, neopentyl glycol diglycidyl ether di(meth) acrylate, dipentaerythritol (Meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecyl (meth) acrylate, ester acrylate, (meth) acrylate of methylolated melamine, epoxy (methyl) Various acrylates and methacrylates such as acrylates and urethane acrylates, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether Ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinyl methamine, acrylonitrile, etc., but not necessarily limited thereto Some compounds. The photopolymerizable compound may be used singly or in combination of two or more.
於使用聚合性單體作為感光性顏料組成物的情形時，視 需要可添加適當的光聚合起始劑、增感劑、胺系化合物、勻化劑(leveling agent)、硬化劑、硬化促進劑、用以使經時黏度穩定的儲存穩定劑、或/及用以提高與透明基板的密接性的矽烷偶合劑等密接改良劑。例如，為了藉由紫外線照射使顏料組成物硬化並藉由光微影法來形成濾波節，能以溶劑顯影型或鹼顯影型感光性顏料組成物的形態來製備。 When a polymerizable monomer is used as a photosensitive pigment composition, It is necessary to add a suitable photopolymerization initiator, a sensitizer, an amine compound, a leveling agent, a hardener, a hardening accelerator, a storage stabilizer for stabilizing the viscosity over time, and/or The adhesion improving agent is added to a decane coupling agent or the like which improves the adhesion to the transparent substrate. For example, in order to cure the pigment composition by ultraviolet irradiation and form a filter segment by photolithography, it can be prepared in the form of a solvent development type or an alkali development type photosensitive pigment composition.
所述光聚合起始劑可使用：4-苯氧基二氯苯乙酮、4-第 三丁基-二氯苯乙酮、二乙氧基苯乙酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮或2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮等苯乙酮系化合物；安息香、安息香甲醚、安息香***、安息香異丙醚或苯偶醯二甲基縮酮等安息香系化合物；二苯甲酮、苯甲醯基苯甲酸、苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、羥基二苯甲酮、丙烯酸化二苯甲酮、4-苯甲醯基-4'-甲基二苯基硫醚或3,3',4,4'-四(第三丁基過氧化羰基)二苯甲酮等二苯甲酮系化合物；硫雜蒽酮、2-氯硫雜蒽酮、2-甲基硫雜蒽酮、異丙基硫雜蒽酮、2,4-二異丙基硫雜蒽酮或2,4-二乙基硫雜蒽酮等硫雜蒽酮系化合物；2,4,6-三氯均三嗪、2-苯基-4,6-雙(三氯甲基)均三嗪、2-(對甲氧基苯基)-4,6-雙(三氯甲基)均三嗪、2-(對甲苯基)-4,6-雙(三氯甲基)均三嗪、2-向日葵基-4,6-雙(三氯甲基)均三嗪、2,4-雙(三氯甲基)-6-苯乙烯基均三嗪、2-(萘-1-基)-4,6-雙(三氯甲基)均三嗪、2-(4-甲氧基-萘-1-基)-4,6-雙(三氯甲基)均三嗪、2,4-三氯甲基-(向日葵基)-6-三嗪或2,4-三氯甲基-(4'-甲氧基苯乙烯基)-6-三嗪等三嗪系化合物；1,2-辛二酮-1-[4-(苯硫基)-2-(O-苯甲醯基肟)]或O-(乙醯基)-N-(1-苯基-2-氧代-2-(4'-甲氧基-萘基)亞乙基)羥基胺等肟酯系化合物；雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物或2,4,6-三甲基苯甲醯基二苯基膦氧化物等膦系化合物；9,10- 菲醌、樟腦醌、乙基蒽醌等醌系化合物；硼酸酯系化合物；咔唑系化合物；咪唑系化合物；或二茂鈦系化合物等。光聚合起始劑可使用一種或混合使用兩種以上。 The photopolymerization initiator can be used: 4-phenoxydichloroacetophenone, 4-di Tributyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylbenzene Ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-(dimethylamino)-2-[(4-A Phenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone or 2-benzyl-2-dimethylamino-1-(4-morpholinyl) An acetophenone compound such as phenyl)-butan-1-one; a benzoin compound such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin dimethyl ketal; benzophenone, benzene Methyl benzoic acid, methyl benzyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, benzoated benzophenone, 4-benzylidene-4'-methyl a benzophenone compound such as phenyl sulfide or 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone; thioxanthone or 2-chlorothiazepinone; a thioxanthone compound such as 2-methylthiazinone, isopropyl thioxanthone, 2,4-diisopropylthiaxanone or 2,4-diethylthiaxanone; , 4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxy Phenyl)-4,6-bis(trichloromethyl)s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)s-triazine, 2-sunyl-4,6 - bis(trichloromethyl)s-triazine, 2,4-bis(trichloromethyl)-6-styryl-triazine, 2-(naphthalen-1-yl)-4,6-bis (three Chloromethyl)s-triazine, 2-(4-methoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl)s-triazine, 2,4-trichloromethyl-(sunflower a triazine-based compound such as 6-triazine or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione-1-[ 4-(phenylthio)-2-(O-benzylidenehydrazide)] or O-(ethinyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy) Anthracene ester compound such as hydroxy-naphthyl)ethylidene hydroxyamine; bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide or 2,4,6-trimethylbenzene a phosphine compound such as mercapto diphenylphosphine oxide; 9,10- An anthraquinone compound such as phenanthrenequinone, camphorquinone or ethylhydrazine; a borate ester compound; an oxazole compound; an imidazole compound; or a titanocene compound. The photopolymerization initiator may be used alone or in combination of two or more.
所述增感劑可列舉：查耳酮(chalcone)衍生物、二亞 苄基丙酮(dibenzalacetone)等所代表的不飽和酮類、苯偶醯或樟腦醌等所代表的1,2-二酮衍生物、安息香衍生物、茀衍生物、萘醌衍生物、蒽醌衍生物、氧雜蒽衍生物、硫雜蒽衍生物、氧雜蒽酮衍生物、硫雜蒽酮衍生物、香豆素衍生物、酮基香豆素衍生物、花青衍生物、部花青衍生物、氧雜菁(oxonol)衍生物等聚次甲基色素、吖啶衍生物、吖嗪衍生物、噻嗪衍生物、噁嗪衍生物、吲哚啉衍生物、薁衍生物、薁鎓(azlenium)衍生物、方酸內鎓鹽衍生物、卟啉衍生物、四苯基卟啉衍生物、三芳基甲烷衍生物、四苯并卟啉衍生物、四吡嗪並紫菜嗪(tetrapyrazinoporphyrazine)衍生物、酞菁衍生物、四氮雜紫菜嗪(tetraazaporphyrazine)衍生物、四喹噁啉並紫菜嗪衍生物、萘酞菁衍生物、亞酞菁(sub phthalocyanine)衍生物、吡喃鎓衍生物、噻喃鎓衍生物、四菲林(tetraphyrin)衍生物、輪烯(annulene)衍生物、螺吡喃衍生物、螺噁嗪衍生物、硫代螺吡喃衍生物、金屬芳烴錯合物、有機釕錯合物或米其勒酮衍生物、α-醯氧基酯、醯基膦氧化物、苯甲醯甲酸甲酯、苯偶醯、9,10-菲醌、樟腦醌、乙基蒽醌、4,4'-二乙基間二苯鄰苯二甲內酯(4,4'-diethyl isophthalophenone)、3,3'或4,4'-四(第三丁基過氧化羰基)二苯甲酮、4,4'-二乙基胺基二苯甲酮等。 增感劑可使用一種或混合使用兩種以上。 The sensitizer may be exemplified by chalcone derivatives and two substances. 1,2-dione derivatives, benzoin derivatives, anthracene derivatives, naphthoquinone derivatives, anthracene derivatives represented by unsaturated ketones, benzophenone or camphorquinone represented by dibenzalacetone or the like , oxanthene derivative, thioxanthene derivative, xanthone derivative, thioxanthone derivative, coumarin derivative, keto coumarin derivative, cyanine derivative, merocyanine a polymethine dye, an acridine derivative, a pyridazine derivative, a thiazine derivative, an oxazine derivative, a porphyrin derivative, an anthracene derivative, or an anthracene such as a derivative or an oxonol derivative. (azlenium) derivative, squaric acid ylide derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine Derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaline and laverazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyranthene derivatives , thiamidine derivatives, tetraphyrin derivatives, annulene a derivative, a spiropyran derivative, a spirooxazine derivative, a thiospiropyran derivative, a metal aromatic hydrocarbon complex, an organic ruthenium complex or a Michelin derivative, an α-decyloxy ester, Mercaptophosphine oxide, methyl benzoic acid methyl ester, benzoin, 9,10-phenanthrenequinone, camphorquinone, ethylhydrazine, 4,4'-diethyl metabenzolone ( 4,4'-diethyl isophthalophenone), 3,3' or 4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone, and the like. The sensitizer may be used alone or in combination of two or more.
進而，增感劑可列舉：大河原信等人編著的「色素手冊」 (1986年，講談社)、大河原信等人編著的「功能性色素的化學」(1981年，CMC)、及池森忠三朗等人編著的「特殊功能材料」(1986年，CMC)中記載的增感劑，但不限定於該些增感劑。另外，除此以外，亦可含有對紫外至近紅外範圍的光顯示出吸收的增感劑。 Further, the sensitizer is exemplified by the "Pigment Handbook" edited by Okawa Shinto et al. (In 1986, Kodansha), "Chemistry of Functional Pigments" (CMC, 1981), and "Special Functional Materials" (1986, CMC), edited by Chishiro-Sara, et al. Sensible, but not limited to these sensitizers. Further, in addition to this, a sensitizer which exhibits absorption of light in the ultraviolet to near-infrared range may be contained.
所述胺系化合物可列舉：三乙醇胺、甲基二乙醇胺、三 異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸2-二甲基胺基乙酯、4-二甲基胺基苯甲酸2-乙基己酯及N,N-二甲基對甲苯胺等。 The amine compound may, for example, be triethanolamine, methyldiethanolamine or the like. Isopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylamine benzoate Ethyl ethyl ester, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.
所述勻化劑較佳為主鏈中具有聚醚結構或聚酯結構的二甲基矽氧烷。主鏈中具有聚醚結構的二甲基矽氧烷的具體例可列舉：東麗道康寧(Toray-Dow corning)公司製造的FZ-2122、畢克化學(BYK Chemie)公司製造的畢克(BYK)-333等。主鏈中具有聚酯結構的二甲基矽氧烷的具體例可列舉畢克化學(BYK Chemie)公司製造的畢克(BYK)-310、畢克(BYK)-370等。主鏈中具有聚醚結構的二甲基矽氧烷與主鏈中具有聚酯結構的二甲基矽氧烷亦可併用。關於勻化劑的含量，通常較佳為以感光性顏料組成物的總質量為基準(100質量%)而使用0.003質量%~0.5質量%。 The homogenizing agent is preferably dimethyloxane having a polyether structure or a polyester structure in the main chain. Specific examples of the dimethyl siloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray-Dow Corning Co., Ltd., BYK manufactured by BYK Chemie Co., Ltd. (BYK) )-333 and so on. Specific examples of the dimethyloxane having a polyester structure in the main chain include BYK-310, BYK-370, and the like manufactured by BYK Chemie. A dimethyl methoxy olefin having a polyether structure in the main chain and a dimethyl methoxy olefin having a polyester structure in the main chain may be used in combination. The content of the leveling agent is usually preferably from 0.003% by mass to 0.5% by mass based on the total mass of the photosensitive pigment composition (100% by mass).
作為勻化劑而尤佳者為於分子內具有疏水基與親水基 的所謂界面活性劑的一種，且具有以下特徵：即便具有親水基亦 於水中的溶解性小，於添加至感光性顏料組成物中的情形時，其降低表面張力的能力低，進而儘管降低表面張力的能力低但對玻璃板的濡濕性良好者有用，可較佳地使用能以不出現由起泡所致的塗膜缺陷的添加量來充分抑制帶電性者。具有此種較佳特性的勻化劑可較佳地使用具有聚環氧烷單元的二甲基聚矽氧烷。聚環氧烷單元有聚環氧乙烷單元、聚環氧丙烷單元，二甲基聚矽氧烷亦可一併具有聚環氧乙烷單元與聚環氧丙烷單元。 Particularly preferred as a leveling agent is a hydrophobic group and a hydrophilic group in the molecule. One of the so-called surfactants, and has the following characteristics: even with a hydrophilic group The solubility in water is small, and when it is added to the photosensitive pigment composition, the ability to lower the surface tension is low, and although the ability to lower the surface tension is low, it is useful for the glass sheet to have good wettability, and is preferably used. The use of the coating can sufficiently suppress the chargeability without the addition amount of the coating film defect caused by foaming. As the leveling agent having such a preferred property, dimethylpolyoxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit has a polyethylene oxide unit and a polypropylene oxide unit, and the dimethyl polyoxyalkylene may have a polyethylene oxide unit and a polypropylene oxide unit.
另外，聚環氧烷單元與二甲基聚矽氧烷的鍵結形態可為 聚環氧烷單元鍵結於二甲基聚矽氧烷的重複單元中的懸垂(pendant)型、鍵結於二甲基聚矽氧烷的末端的末端改質型、與二甲基聚矽氧烷交替重複鍵結的直鏈狀的嵌段共聚物型的任一種。具有聚環氧烷單元的二甲基聚矽氧烷是由東麗道康寧(Toray-Dow corning)公司製造並市售，例如可列舉FZ-2110、FZ-2122、FZ-2130、FZ-2166、FZ-2191、FZ-2203、FZ-2207，但不限定於該些化合物。 In addition, the bonding form of the polyalkylene oxide unit and the dimethyl polyoxyalkylene may be a pendant type in which a polyalkylene oxide unit is bonded to a repeating unit of dimethyl polyoxyalkylene, a terminal modified type bonded to a terminal of dimethyl polyoxyalkylene, and a dimethyl polyfluorene The oxane alternately repeats any of the linear block copolymer types bonded. The dimethyl polyoxyalkylene having a polyalkylene oxide unit is manufactured by Toray-Dow Corning Co., Ltd. and is commercially available, and examples thereof include FZ-2110, FZ-2122, FZ-2130, and FZ-2166. FZ-2191, FZ-2203, and FZ-2207 are not limited to these compounds.
勻化劑中，亦可輔助添加陰離子性、陽離子性、非離子性或兩性的界面活性劑。界面活性劑亦可混合使用兩種以上。 In the homogenizing agent, an anionic, cationic, nonionic or amphoteric surfactant may also be added. The surfactant may also be used in combination of two or more.
輔助添加至勻化劑中的陰離子性界面活性劑可列舉：聚氧伸乙基烷基醚硫酸鹽、十二烷基苯磺酸鈉、苯乙烯-丙烯酸共聚物的鹼鹽、烷基萘磺酸鈉、烷基二苯基醚二磺酸鈉、月桂基硫酸單乙醇胺、月桂基硫酸三乙醇胺、月桂基硫酸銨、硬脂酸單乙醇胺、硬脂酸鈉、月桂基硫酸鈉、苯乙烯-丙烯酸共聚物的單乙醇胺、 聚氧伸乙基烷基醚磷酸酯等。 The anionic surfactant added to the leveling agent may be exemplified by polyoxyethylene ethyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, alkylnaphthalenesulfonate. Sodium, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, styrene - Monoethanolamine of acrylic copolymer, Polyoxyethylene ethyl ether phosphate and the like.
輔助添加至勻化劑中的陽離子性界面活性劑可列舉烷 基四級銨鹽或該等的環氧乙烷加成物。輔助添加至勻化劑中的非離子性界面活性劑可列舉：聚氧伸乙基油基醚、聚氧伸乙基月桂基醚、聚氧伸乙基壬基苯基醚、聚氧伸乙基烷基醚磷酸酯、聚氧伸乙基山梨糖醇酐單硬脂酸酯、聚乙二醇單月桂酸酯等兩性界面活性劑，烷基二甲基胺基乙酸甜菜鹼等烷基甜菜鹼、烷基咪唑啉等兩性界面活性劑，另外可列舉氟系或矽酮系的界面活性劑。 The cationic surfactant added to the leveling agent can be exemplified by an alkane a quaternary ammonium salt or such an ethylene oxide adduct. The nonionic surfactant added to the homogenizing agent may be exemplified by polyoxyethylene ethyl oleyl ether, polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl phenyl ether, polyoxyethylene Amphoteric surfactants such as alkyl alkyl ether phosphate, polyoxyethylene ethyl sorbitan monostearate, polyethylene glycol monolaurate, alkyl beets such as alkyl dimethyl amino acetic acid betaine Examples of the amphoteric surfactant such as a base or an alkyl imidazoline include a fluorine-based or an anthrone-based surfactant.
作為所述硬化劑，酚系樹脂、胺系化合物、酸酐、活性 酯、羧酸系化合物、磺酸系化合物等有效，但不特別限定於該些化合物，只要可與熱硬化性樹脂反應，則可使用任意的硬化劑。 另外，該些硬化劑中，較佳為於一分子內具有2個以上的酚性羥基的化合物、胺系硬化劑。所述硬化促進劑例如可使用：胺化合物(例如二氰二醯胺、苄基二甲基胺、4-(二甲基胺基)-N,N-二甲基苄基胺、4-甲氧基-N,N-二甲基苄基胺、4-甲基-N,N-二甲基苄基胺等)、四級銨鹽化合物(例如氯化三乙基苄基銨等)、封閉異氰酸酯化合物(例如二甲基胺等)、咪唑衍生物二環式脒化合物及其鹽(例如咪唑、2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、4-苯基咪唑、1-氰基乙基-2-苯基咪唑、1-(2-氰基乙基)-2-乙基-4-甲基咪唑等)、磷化合物(例如三苯基膦等)、胍胺化合物(例如三聚氰胺、胍胺、乙醯胍胺、苯并胍胺等)、均三嗪衍生物(例如2,4-二胺基-6-甲基丙烯醯氧基乙基均三嗪、2-乙烯基-2,4- 二胺基均三嗪、2-乙烯基-4,6-二胺基均三嗪-異氰脲酸加成物、2,4-二胺基-6-甲基丙烯醯氧基乙基均三嗪-異氰脲酸加成物等)等。該些化合物可單獨使用一種，亦可併用兩種以上。相對於熱硬化性樹脂100質量份，所述硬化促進劑的含量較佳為0.01質量份~15質量份。 As the curing agent, a phenol resin, an amine compound, an acid anhydride, and an activity The ester, the carboxylic acid compound, the sulfonic acid compound, and the like are effective, but are not particularly limited to these compounds, and any curing agent can be used as long as it can react with the thermosetting resin. Further, among these curing agents, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. As the hardening accelerator, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methyl can be used. Oxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compound (for example, triethylbenzylammonium chloride, etc.), Blocking isocyanate compounds (such as dimethylamine, etc.), imidazole derivatives, bicyclic guanidine compounds and salts thereof (such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., phosphorus a compound (for example, triphenylphosphine or the like), a guanamine compound (for example, melamine, guanamine, acetamide, benzoguanamine, etc.), a s-triazine derivative (for example, 2,4-diamino-6-A) Acryloxyethyl s-triazine, 2-vinyl-2,4- Diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine-isocyanuric acid adduct, 2,4-diamino-6-methylpropenyloxyethyl Triazine-isocyanuric acid adducts, etc.). These compounds may be used alone or in combination of two or more. The content of the hardening accelerator is preferably from 0.01 part by mass to 15 parts by mass per 100 parts by mass of the thermosetting resin.
所述儲存穩定劑例如可列舉：苄基三甲基氯化物、二乙 基羥基胺等氯化四級銨，乳酸、草酸等有機酸及其甲醚，第三丁基鄰苯二酚，四乙基膦、四苯基膦等有機膦，亞磷酸鹽等。相對於著色劑100質量份，儲存穩定劑能以0.1質量份~10質量份的量使用。 The storage stabilizer may, for example, be benzyltrimethyl chloride or diethyl A quaternary ammonium chloride such as hydroxyamine, an organic acid such as lactic acid or oxalic acid and a methyl ether thereof, a tert-butyl catechol, an organic phosphine such as tetraethylphosphine or tetraphenylphosphine, or a phosphite. The storage stabilizer can be used in an amount of 0.1 part by mass to 10 parts by mass relative to 100 parts by mass of the colorant.
所述密接改良劑可列舉：乙烯基三(β-甲氧基乙氧基)矽 烷、乙烯基乙氧基矽烷、乙烯基三甲氧基矽烷等乙烯基矽烷類，γ-甲基丙烯醯氧基丙基三甲氧基矽烷等(甲基)丙烯酸矽烷類，β-(3,4-環氧環己基)乙基三甲氧基矽烷、β-(3,4-環氧環己基)甲基三甲氧基矽烷、β-(3,4-環氧環己基)乙基三乙氧基矽烷、β-(3,4-環氧環己基)甲基三乙氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷等環氧矽烷類，N-β-(胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基三乙氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基甲基二乙氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、N-苯基-γ-胺基丙基三乙氧基矽烷等胺基矽烷類，γ-巰基丙基三甲氧基矽烷、γ-巰基丙基三乙氧基矽烷等硫矽烷類等矽烷偶合 劑。相對於感光性顏料組成物中的著色劑100質量份，密接改良劑能以0.01質量份~10質量份、較佳為0.05質量份~5質量份的量而使用。 The adhesion improving agent may be exemplified by vinyl tris(β-methoxyethoxy) fluorene. Vinyl decane such as alkane, vinyl ethoxy decane or vinyl trimethoxy decane, methacrylic acid decane such as γ-methyl propylene methoxy propyl trimethoxy decane, β-(3, 4 -Epoxycyclohexyl)ethyltrimethoxydecane, β-(3,4-epoxycyclohexyl)methyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltriethoxy Rings such as decane, β-(3,4-epoxycyclohexyl)methyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane Oxanes, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, N-β-(aminoethyl)-γ-aminopropyltriethoxydecane, N -β-(Aminoethyl)-γ-aminopropylmethyldiethoxydecane, γ-aminopropyltriethoxydecane, γ-aminopropyltrimethoxydecane, N-benzene Amino decanes such as γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltriethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-mercaptopropyl Decane coupling such as thiononane such as triethoxy decane Agent. The adhesion improving agent can be used in an amount of from 0.01 part by mass to 10 parts by mass, preferably from 0.05 part by mass to 5 parts by mass, per 100 parts by mass of the coloring agent in the photosensitive pigment composition.
本發明的顏料組成物較佳為藉由離心分離、利用燒結過 濾器或膜濾器的過濾等方法，將5μm以上的粗大粒子、較佳為1μm以上的粗大粒子、更佳為0.5μm以上的粗大粒子及所混入的灰塵去除。顏料組成物較佳為實質上不含0.5μm以上的粒子。更佳為以0.3μm以下為宜。 The pigment composition of the present invention is preferably obtained by centrifugation and sintering. A method of filtering the filter or the membrane filter or the like removes coarse particles of 5 μm or more, coarse particles of preferably 1 μm or more, coarse particles of 0.5 μm or more, and dust mixed therein. The pigment composition preferably contains substantially no particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.
(彩色濾光片)繼而，對將本發明的顏料組成物應用於 彩色濾光片的情形加以說明。使用本發明的顏料組成物所形成的彩色濾光片例如可用作紅色濾波節、綠色濾波節及藍色濾波節。 (Color filter) Next, applying the pigment composition of the present invention The case of a color filter will be described. The color filter formed using the pigment composition of the present invention can be used, for example, as a red filter section, a green filter section, and a blue filter section.
綠色濾波節可使用含有綠色顏料及顏料載體的通常的 綠色顏料組成物來形成。綠色顏料例如可使用顏色索引(Color Index，C.I.)顏料綠7、C.I.顏料綠10、C.I.顏料綠36、C.I.顏料綠37、C.I.顏料綠58等。另外，亦可使用鋁酞菁等藍色顏料。 The green filter section can use the usual green pigment and pigment carrier. A green pigment composition is formed. As the green pigment, for example, Color Index (C.I.) Pigment Green 7, C.I. Pigment Green 10, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Green 58, and the like can be used. Further, a blue pigment such as aluminum phthalocyanine can also be used.
另外，綠色顏料組成物中亦可併用黃色顏料。可併用的 黃色顏料可列舉：C.I.顏料黃1、C.I.顏料黃2、C.I.顏料黃3、C.I.顏料黃4、C.I.顏料黃5、C.I.顏料黃6、C.I.顏料黃10、C.I.顏料黃12、C.I.顏料黃13、C.I.顏料黃14、C.I.顏料黃15、C.I.顏料黃16、C.I.顏料黃17、C.I.顏料黃18、C.I.顏料黃24、C.I.顏料黃31、C.I.顏料黃32、C.I.顏料黃34、C.I.顏料黃35、C.I.顏料黃35：1、C.I.顏料黃36、C.I.顏料黃36：1、C.I.顏料黃37、C.I.顏料黃37：1、C.I. 顏料黃40、C.I.顏料黃42、C.I.顏料黃43、C.I.顏料黃53、C.I.顏料黃55、C.I.顏料黃60、C.I.顏料黃61、C.I.顏料黃62、C.I.顏料黃63、C.I.顏料黃65、C.I.顏料黃73、C.I.顏料黃74、C.I.顏料黃77、C.I.顏料黃81、C.I.顏料黃83、C.I.顏料黃93、C.I.顏料黃94、C.I.顏料黃95、C.I.顏料黃97、C.I.顏料黃98、C.I.顏料黃100、C.I.顏料黃101、C.I.顏料黃104、C.I.顏料黃106、C.I.顏料黃108、C.I.顏料黃109、C.I.顏料黃110、C.I.顏料黃113、C.I.顏料黃114、C.I.顏料黃115、C.I.顏料黃116、C.I.顏料黃117、C.I.顏料黃118、C.I.顏料黃119、C.I.顏料黃120、C.I.顏料黃123、C.I.顏料黃126、C.I.顏料黃127、C.I.顏料黃128、C.I.顏料黃129、C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃147、C.I.顏料黃150、C.I.顏料黃151、C.I.顏料黃152、C.I.顏料黃153、C.I.顏料黃154、C.I.顏料黃155、C.I.顏料黃156、C.I.顏料黃161、C.I.顏料黃162、C.I.顏料黃164、C.I.顏料黃166、C.I.顏料黃167、C.I.顏料黃168、C.I.顏料黃169、C.I.顏料黃170、C.I.顏料黃171、C.I.顏料黃172、C.I.顏料黃173、C.I.顏料黃174、C.I.顏料黃175、C.I.顏料黃176、C.I.顏料黃177、C.I.顏料黃179、C.I.顏料黃180、C.I.顏料黃181、C.I.顏料黃182、C.I.顏料黃185、C.I.顏料黃187、C.I.顏料黃188、C.I.顏料黃193、C.I.顏料黃194、C.I.顏料黃198、C.I.顏料黃199、C.I.顏料黃213、C.I.顏料黃214、C.I.顏料黃218、C.I.顏料黃219、C.I.顏料黃220或C.I.顏料黃221等黃色顏料。另外，亦可併用呈黃色的鹼性染料、酸性染料的成鹽化合物。 Further, a yellow pigment may be used in combination with the green pigment composition. Can be used together The yellow pigments may be listed as: CI Pigment Yellow 1, CI Pigment Yellow 2, CI Pigment Yellow 3, CI Pigment Yellow 4, CI Pigment Yellow 5, CI Pigment Yellow 6, CI Pigment Yellow 10, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 18, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 32, CI Pigment Yellow 34, CI Pigment Yellow 35, CI Pigment Yellow 35:1, CI Pigment Yellow 36, CI Pigment Yellow 36:1, CI Pigment Yellow 37, CI Pigment Yellow 37:1, CI Pigment Yellow 40, CI Pigment Yellow 42, CI Pigment Yellow 43, CI Pigment Yellow 53, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 62, CI Pigment Yellow 63, CI Pigment Yellow 65, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 77, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 115, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 118, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 123, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 161, CI Pigment Yellow 162, CI Pigment Yellow 164, CI Pigment Yellow 166 CI Pigment Yellow 167, CI Pigment Yellow 168, CI Pigment Yellow 169, CI Pigment Yellow 170, CI Pigment Yellow 171, CI Pigment Yellow 172, CI Pigment Yellow 173, CI Pigment Yellow 174, CI Pigment Yellow 175, CI Pigment Yellow 176, CI Pigment Yellow 177, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 181, CI Pigment Yellow 182, CI Pigment Yellow 185, CI Pigment Yellow 187, CI Pigment Yellow 188, CI Pigment Yellow 193, CI Pigment Yellow 194, A yellow pigment such as CI Pigment Yellow 198, CI Pigment Yellow 199, CI Pigment Yellow 213, CI Pigment Yellow 214, CI Pigment Yellow 218, CI Pigment Yellow 219, CI Pigment Yellow 220 or CI Pigment Yellow 221. Further, a salt-forming compound which is a yellow basic dye or an acid dye may be used in combination.
藍色濾波節可使用含有藍色顏料及顏料載體的通常的 藍色顏料組成物來形成。藍色顏料例如可使用：C.I.顏料藍15、C.I.顏料藍15：1、C.I.顏料藍15：2、C.I.顏料藍15：3、C.I.顏料藍15：4、C.I.顏料藍15：6、C.I.顏料藍16、C.I.顏料藍22、C.I.顏料藍60、C.I.顏料藍64等。另外，藍色顏料組成物中可併用紫色顏料。 可併用的紫色顏料可列舉：C.I.顏料紫1、C.I.顏料紫19、C.I.顏料紫23、C.I.顏料紫27、C.I.顏料紫29、C.I.顏料紫30、C.I.顏料紫32、C.I.顏料紫37、C.I.顏料紫40、C.I.顏料紫42、C.I.顏料紫50等紫色顏料。另外，亦可使用呈藍色或紫色的鹼性染料、酸性染料的成鹽化合物。於使用染料的情形時，就耐熱性及明度的方面而言，較佳為氧雜蒽系染料。 The blue filter section can use the usual blue pigment and pigment carrier. A blue pigment composition is formed. Blue pigments can be used, for example: CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 16. CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and the like. Further, a purple pigment may be used in combination in the blue pigment composition. The purple pigments which can be used together are: CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 27, CI Pigment Violet 29, CI Pigment Violet 30, CI Pigment Violet 32, CI Pigment Violet 37, CI Pigment Purple pigments such as Violet 40, CI Pigment Violet 42, and CI Pigment Violet 50. Further, a salt-forming compound which is a blue or violet basic dye or an acid dye can also be used. In the case of using a dye, a xanthene-based dye is preferred in terms of heat resistance and lightness.
(彩色濾光片的製造方法)彩色濾光片可使用本發明的顏料組成物藉由印刷法或光微影法而製造。 (Manufacturing Method of Color Filter) The color filter can be produced by a printing method or a photolithography method using the pigment composition of the present invention.
關於利用印刷法的濾波節的形成，僅重複進行作為印刷油墨而製備的顏料組成物的印刷與乾燥便可實現圖案化，因此成本低且量產性優異。進而，由於印刷技術的發展，可進行具有高的尺寸精度及平滑度的微細圖案的印刷。為了進行印刷，較佳為設定為於印刷版上或於膠毯(blanket)上油墨不會乾燥、固化般的組成。另外，印刷機上的油墨的流動性的控制亦重要，亦可藉由分散劑或體質顏料來調整油墨黏度。 In the formation of the filter segment by the printing method, patterning can be realized only by printing and drying the pigment composition prepared as the printing ink, and the cost is low and the mass productivity is excellent. Further, due to the development of printing technology, it is possible to perform printing of a fine pattern having high dimensional accuracy and smoothness. For printing, it is preferable to set the composition so that the ink does not dry and solidify on the printing plate or on the blanket. In addition, the control of the fluidity of the ink on the printing press is also important, and the viscosity of the ink can also be adjusted by a dispersing agent or an extender pigment.
於藉由光微影法來形成濾波節的情形時，藉由噴霧塗佈、旋轉塗佈、狹縫塗佈、輥式塗佈等塗佈方法，將作為所述溶 劑顯影型或鹼顯影型著色抗蝕劑材料而製備的顏料組成物以乾燥膜厚成為0.2μm~5μm的方式塗佈於透明基板上。對於視需要而經乾燥的膜，經由以與該膜接觸或不接觸的狀態而設置的具有既定圖案的遮罩來進行紫外線曝光。其後，浸漬於溶劑或鹼顯影液中，或者藉由噴霧等來噴霧顯影液，將未硬化部去除而形成所需的圖案後，對其他顏色重複進行同樣的操作而可製造彩色濾光片。進而，為了促進著色抗蝕劑材料的聚合，視需要亦可實施加熱。根據光微影法，可製造精度較所述印刷法更高的彩色濾光片。 When a filter segment is formed by photolithography, it is applied as a solution by a coating method such as spray coating, spin coating, slit coating, or roll coating. The pigment composition prepared by the developer-developing type or the alkali-developing type coloring resist material is applied onto a transparent substrate so that the dry film thickness is 0.2 μm to 5 μm. For a film that is dried as needed, ultraviolet exposure is performed via a mask having a predetermined pattern provided in a state of being in contact with or not in contact with the film. Thereafter, the film is immersed in a solvent or an alkali developing solution, or the developing solution is sprayed by spraying or the like, and the uncured portion is removed to form a desired pattern, and then the same operation is repeated for the other colors to manufacture a color filter. . Further, in order to promote polymerization of the colored resist material, heating may be carried out as needed. According to the photolithography method, a color filter having a higher precision than the printing method can be manufactured.
顯影時，可使用碳酸鈉、氫氧化鈉等的水溶液作為鹼顯 影液。另外，亦可使用二甲基苄基胺、三乙醇胺等有機鹼。另外，亦可於顯影液中添加消泡劑或界面活性劑。再者，為了提高紫外線曝光感度，亦可於將所述著色抗蝕劑塗佈乾燥後，將水溶性或鹼水溶性樹脂、例如聚乙烯醇或水溶性丙烯酸系樹脂等塗佈乾燥，形成用來防止因氧抑制聚合的膜後，進行紫外線曝光。 When developing, an aqueous solution of sodium carbonate, sodium hydroxide or the like can be used as a base. Shadow liquid. Further, an organic base such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant may be added to the developer. Further, in order to increase the ultraviolet exposure sensitivity, the colored resist may be applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied and dried to form a coating. After preventing the polymerization of the film by oxygen, ultraviolet exposure is performed.
除了所述方法以外，彩色濾光片可藉由電沈積法、轉印 法等來製造，本發明的顏料組成物可用於任一方法中。再者，電沈積法為利用形成於基板上的透明導電膜，藉由膠體粒子的電泳而於透明導電膜上電沈積形成各色濾波節，由此製造彩色濾光片的方法。另外，轉印法為於剝離性的轉印基片(base sheet)的表面上預先形成濾波節，並將該濾波節轉印至所需基板上的方法。 In addition to the method, the color filter can be transferred by electrodeposition, transfer The pigment composition of the present invention can be used in any method. Further, the electrodeposition method is a method of manufacturing a color filter by electrodepositing a transparent conductive film formed on a substrate by electrophoresis of colloidal particles to form respective color filter segments on the transparent conductive film. Further, the transfer method is a method of previously forming a filter segment on the surface of a peelable transfer base sheet and transferring the filter segment onto a desired substrate.
可於在透明基板或反射基板上形成各色濾波節之前，預 先形成黑色矩陣。黑色矩陣可使用鉻或鉻/氧化鉻的多層膜、氮化 鈦等的無機膜或分散有遮光劑的樹脂膜，但不限定於該些膜。另外，亦可於所述透明基板或反射基板上預先形成薄膜電晶體(Thin Film Transistor，TFT)，其後形成各色濾波節。另外，於使用本發明的顏料組成物所得的彩色濾光片上，視需要而形成外塗膜或透明導電膜等。 Before the color filter segments are formed on the transparent substrate or the reflective substrate, A black matrix is formed first. Black matrix can use chrome or chrome / chrome oxide multilayer film, nitride An inorganic film such as titanium or a resin film in which a light shielding agent is dispersed is not limited to the films. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then color filter segments may be formed. Further, on the color filter obtained by using the pigment composition of the present invention, an overcoat film, a transparent conductive film, or the like is formed as needed.
根據本發明的顏料組成物的製造方法，如上文所述，藉由使用本發明的水溶性有機溶劑進行步驟(a)~步驟(d)的處理，可提供一種經微細化的顏料的分散性能優異的顏料組成物。進而可提供一種生產效率高的顏料組成物。另外，根據本發明，可提供一種經微細化的顏料的分散性能優異、且生產效率高的磨碎混練用的水溶性有機溶劑。 According to the method for producing a pigment composition of the present invention, as described above, by performing the treatment of the steps (a) to (d) using the water-soluble organic solvent of the present invention, the dispersion property of the finely pigmented pigment can be provided. Excellent pigment composition. Further, a pigment composition having high production efficiency can be provided. Further, according to the present invention, it is possible to provide a water-soluble organic solvent for grinding and kneading which is excellent in dispersibility of a finely pigmented pigment and has high production efficiency.
以下，根據實施例對本發明加以說明，但本發明不限定於此。再者，實施例及比較例中，所謂「份」是指「質量份」。首先，對實施例及比較例中所用的樹脂、顏料、色素衍生物及溶劑加以說明。 Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, the "parts" means "parts by mass". First, the resins, pigments, dye derivatives and solvents used in the examples and comparative examples will be described.
(合成例1：樹脂A)於具備氣體導入管、溫度計、冷凝器及攪拌機的反應容器(以下將具備該些構件的反應容器簡稱為「反應容器A」)中，添加甲基丙烯酸正丁酯60份及甲基丙烯酸苄酯140份，以氮氣進行置換。將反應容器內加熱至80℃，添加溶解有3-巰基-1,2-丙二醇12份及2,2'-偶氮雙異丁腈0.1份的溶液，反 應10小時，藉由固體成分測定確認95%已反應。繼而，追加均苯四甲酸二酐19份、環己酮231份及作為觸媒的1,8-二氮雜雙環-[5.4.0]-7-十一烯0.40份，於120℃下反應7小時。藉由酸值的測定確認98%以上的酸酐經半酯化，獲得樹脂A。 (Synthesis Example 1: Resin A) n-butyl methacrylate was added to a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer (hereinafter, a reaction vessel having such members is simply referred to as "reaction vessel A") 60 parts and 140 parts of benzyl methacrylate were replaced with nitrogen. The reaction vessel was heated to 80 ° C, and a solution in which 12 parts of 3-mercapto-1,2-propanediol and 0.1 parts of 2,2'-azobisisobutyronitrile were dissolved was added. It should be confirmed by solid content measurement that 95% has been reacted for 10 hours. Then, 19 parts of pyromellitic dianhydride, 231 parts of cyclohexanone, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 120 ° C. 7 hours. It was confirmed by the measurement of the acid value that 98% or more of the acid anhydride was half-esterified to obtain the resin A.
(合成例2：樹脂B)於反應容器A中添加1-十二醇62.6 份、ε-己內酯287.4份及作為觸媒的氧化單丁基錫(IV)0.1份，以氮氣進行置換後，於120℃下加熱4小時，進行攪拌。藉由固體成分測定確認98%已反應後，添加均苯四甲酸二酐73.3份，於120℃下反應2小時。藉由酸值的測定確認98%以上的酸酐經半酯化，獲得樹脂B。 (Synthesis Example 2: Resin B) Addition of 1-dodecanol to the reaction vessel A 62.6 28 parts of ε-caprolactone and 0.1 part of monobutyltin oxide (IV) as a catalyst were replaced with nitrogen, and then heated at 120 ° C for 4 hours, followed by stirring. After 98% of the reaction was confirmed by solid content measurement, 73.3 parts of pyromellitic dianhydride was added, and the mixture was reacted at 120 ° C for 2 hours. It was confirmed by the measurement of the acid value that 98% or more of the acid anhydride was half-esterified to obtain the resin B.
(合成例3：樹脂C)於反應容器A中添加丙烯酸正丁 酯160份、甲基丙烯酸2-([1'-甲基亞丙基胺基]羧基胺基)乙酯(昭和電工公司製造)40份，以氮氣進行置換。將反應容器內加熱至80℃，添加3-巰基-1,2-丙二醇12份，反應12小時。藉由固體成分測定確認95%已反應。繼而，追加均苯四甲酸二酐19份、環己酮231份及作為觸媒的1,8-二氮雜雙環-[5.4.0]-7-十一烯0.40份，於100℃下反應7小時。藉由酸值的測定確認98%以上的酸酐經半酯化，獲得樹脂C。 (Synthesis Example 3: Resin C) Adding n-butyl acrylate to the reaction vessel A Forty-six parts of ester and 2-([1'-methylpropyleneamino]carboxylamino) methacrylate (manufactured by Showa Denko Co., Ltd.) 40 parts were replaced with nitrogen. The inside of the reaction vessel was heated to 80 ° C, and 12 parts of 3-mercapto-1,2-propanediol was added, and the reaction was carried out for 12 hours. It was confirmed by solid content measurement that 95% had reacted. Then, 19 parts of pyromellitic dianhydride, 231 parts of cyclohexanone, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100 ° C. 7 hours. It was confirmed by the measurement of the acid value that 98% or more of the acid anhydride was half-esterified to obtain the resin C.
(合成例4：樹脂D)於反應容器A中添加酸值為200 且分子量為5,000的苯乙烯-丙烯酸樹脂20份、對甲氧基苯酚0.2份、氯化十二烷基三甲基銨0.2份及丙二醇單甲醚乙酸酯40份，以氮氣進行置換。滴加甲基丙烯酸-(3,4-環氧環己基)甲酯7.7份， 於100℃的溫度下反應30小時。使反應液於水中再沈澱並加以乾燥，藉此獲得樹脂D。 (Synthesis Example 4: Resin D) An acid value of 200 was added to the reaction vessel A. Further, 20 parts of a styrene-acrylic resin having a molecular weight of 5,000, 0.2 parts of p-methoxyphenol, 0.2 parts of dodecyltrimethylammonium chloride, and 40 parts of propylene glycol monomethyl ether acetate were replaced with nitrogen. 7.7 parts of (3,4-epoxycyclohexyl)methyl methacrylate was added dropwise. The reaction was carried out at a temperature of 100 ° C for 30 hours. The reaction liquid was reprecipitated in water and dried, whereby Resin D was obtained.
(合成例5：樹脂E)於反應容器A中添加甲基丙烯酸 甲酯15.0份、末端經甲基丙烯醯化的聚甲基丙烯酸甲酯[樹脂東亞合成公司製造的「AA-6」]70.0份、甲基丙烯酸15.0份及1-甲氧基-2-丙醇334.0份，以氮氣進行置換。將反應容器內加熱至90℃，添加2,2'-偶氮雙(2,4-二甲基戊腈)(和光純藥公司製造的「V-65」)0.5份，於90℃下進行2小時加熱攪拌。進而添加0.5份的V-65，進行3小時加熱攪拌而獲得樹脂E。 (Synthesis Example 5: Resin E) Adding methacrylic acid to the reaction vessel A 15.0 parts of methyl ester, polymethyl methacrylate deuterated by methacrylic acid ("AA-6" by Resin East Asia Synthetic Co., Ltd.] 70.0 parts, 15.0 parts of methacrylic acid, and 1-methoxy-2-propene 334.0 parts of alcohol was replaced with nitrogen. The inside of the reaction vessel was heated to 90 ° C, and 0.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) ("V-65" manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was carried out at 90 ° C. Stir and heat for 2 hours. Further, 0.5 part of V-65 was added, and the mixture was heated and stirred for 3 hours to obtain a resin E.
(合成例6：樹脂F)於反應容器A中添加甲基丙烯酸 甲酯45.0份、甲基丙烯酸15.0份及丙烯酸乙酯40.0份，以氮氣進行置換。將反應容器內加熱至80℃，添加3-巰基-1,2-丙二醇6.0份、及使2,2'-偶氮雙異丁腈0.1份溶解於環己酮45.3份中所得的溶液，反應10小時。藉由固體成分測定確認95%已反應後，追加1,2,3,4-丁烷四羧酸二酐(新日本理化公司製造的「理化德(Rikacid)BT-100」)8.8份、環己酮69.2份及作為觸媒的1,8-二氮雜雙環-[5.4.0]-7-十一烯0.2份，於120℃下反應7小時。藉由酸值的測定確認98%以上的酸酐經半酯化，獲得樹脂F。 (Synthesis Example 6: Resin F) Adding methacrylic acid to the reaction vessel A 45.0 parts of methyl ester, 15.0 parts of methacrylic acid, and 40.0 parts of ethyl acrylate were replaced with nitrogen. The reaction vessel was heated to 80 ° C, and 6.0 parts of 3-mercapto-1,2-propanediol was added, and a solution obtained by dissolving 0.1 part of 2,2'-azobisisobutyronitrile in 45.3 parts of cyclohexanone was reacted. 10 hours. After confirming 95% of the reaction by solid content measurement, 8.8 parts of 1,2,3,4-butanetetracarboxylic dianhydride ("Rikacid BT-100" manufactured by Nippon Chemical and Chemical Co., Ltd.) was added. 69.2 parts of hexanone and 0.2 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were reacted at 120 ° C for 7 hours. It was confirmed by the measurement of the acid value that 98% or more of the acid anhydride was half-esterified to obtain the resin F.
(合成例7：樹脂G)於反應容器A中添加甲基丙烯酸 5.0份、甲基丙烯酸甲酯15.0份及丙烯酸-2-甲氧基乙酯60.0份，以氮氣進行置換。將反應容器內加熱至80℃，添加3-巰基-1,2-丙二醇6.0份、及將2,2'-偶氮雙異丁腈0.1份溶解於丙二醇單甲醚乙 酸酯45.4份中所得的溶液，反應10小時。藉由固體成分測定確認95%已反應。繼而，追加均苯四甲酸二酐(大賽璐(Daicel)化學工業公司製造)9.7份、丙二醇單甲醚乙酸酯31.7份及作為觸媒的1,8-二氮雜雙環-[5.4.0]-7-十一烯0.2份，於120℃下反應7小時。藉由酸值的測定確認98%以上的酸酐經半酯化，獲得樹脂G。 (Synthesis Example 7: Resin G) Adding methacrylic acid to Reaction Vessel A 5.0 parts, 15.0 parts of methyl methacrylate and 60.0 parts of 2-methoxyethyl acrylate were replaced with nitrogen. The reaction vessel was heated to 80 ° C, 6.0 parts of 3-mercapto-1,2-propanediol was added, and 0.1 part of 2,2'-azobisisobutyronitrile was dissolved in propylene glycol monomethyl ether B. The solution obtained in 45.4 parts of the acid ester was reacted for 10 hours. It was confirmed by solid content measurement that 95% had reacted. Then, 9.7 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industry Co., Ltd.), 31.7 parts of propylene glycol monomethyl ether acetate, and 1,8-diazabicyclo-[5.4.0 as a catalyst were added. 0.2 parts of 7-undecene was reacted at 120 ° C for 7 hours. It was confirmed by the measurement of the acid value that 98% or more of the acid anhydride was half-esterified to obtain the resin G.
(合成例8：樹脂H)於反應容器A中添加丙烯酸羥基乙酯83份、ε-己內酯821份、氧化單丁基錫0.009份及甲基對苯二酚0.93份，於100℃下反應10小時直至殘存的ε-己內酯成為1%以下為止。於經調整為60℃的反應液中，一面攪拌一面添加聚乙烯亞胺(日本觸媒公司製造的「SP200」)100份進行反應。藉由質子核磁共振(Nuclear Magnetic Resonance，NMR)確認丙烯酸基已消失，獲得樹脂H。 (Synthesis Example 8: Resin H) 83 parts of hydroxyethyl acrylate, 821 parts of ε-caprolactone, 0.009 parts of monobutyltin oxide, and 0.93 parts of methyl hydroquinone were added to the reaction vessel A, and the reaction was carried out at 100 ° C. The time until the remaining ε-caprolactone becomes 1% or less. In the reaction liquid adjusted to 60 ° C, 100 parts of polyethyleneimine ("SP200" manufactured by Nippon Shokubai Co., Ltd.) was added thereto while stirring. It was confirmed by proton nuclear magnetic resonance (NMR) that the acrylic group had disappeared, and the resin H was obtained.
(合成例9：樹脂I)於反應容器A中添加丙烯酸羥基乙酯60.3份、ε-己內酯889份、氧化單丁基錫0.042份及甲基對苯二酚0.94份，於100℃下反應10小時直至殘存的ε-己內酯成為1%以下為止。於經調整為60℃的反應液中添加聚乙烯亞胺(SP200：日本觸媒公司製造)50份進行反應。藉由質子NMR確認丙烯酸基已消失，獲得樹脂I。 (Synthesis Example 9: Resin I) 60.3 parts of hydroxyethyl acrylate, 889 parts of ε-caprolactone, 0.042 parts of monobutyltin oxide, and 0.94 parts of methyl hydroquinone were added to the reaction vessel A, and the reaction was carried out at 100 ° C. The time until the remaining ε-caprolactone becomes 1% or less. 50 parts of polyethyleneimine (SP200: manufactured by Nippon Shokubai Co., Ltd.) was added to the reaction liquid adjusted to 60 ° C to carry out a reaction. It was confirmed by proton NMR that the acrylic group had disappeared, and Resin I was obtained.
(合成例10：樹脂J)於反應容器A中添加具有異氰酸酯基的碳二亞胺當量為316的聚碳二亞胺化合物57.0份及甲基二乙醇胺16.0份，於約100℃下保持2小時，使異氰酸酯基與羥基反應。繼而添加丙二醇單甲醚乙酸酯97.7份後，添加末端具有羧 基的分子量為1,000的12-羥基硬脂酸自縮合物178.7份，於約90℃下保持，使碳二亞胺基與羧基反應。其後，添加丙二醇單甲醚乙酸酯97.7份而獲得樹脂J。 (Synthesis Example 10: Resin J) 57.0 parts of a polycarbodiimide compound having an isocyanate group having a carbodiimide equivalent of 316 and 16.0 parts of methyldiethanolamine were added to the reaction vessel A, and kept at about 100 ° C for 2 hours. The isocyanate group is reacted with a hydroxyl group. Then, after adding 97.7 parts of propylene glycol monomethyl ether acetate, the terminal has a carboxyl group. The base of the 12-hydroxystearic acid self-condensate having a molecular weight of 1,000 was 178.7 parts, and it was kept at about 90 ° C to react the carbodiimide group with a carboxyl group. Thereafter, 97.7 parts of propylene glycol monomethyl ether acetate was added to obtain a resin J.
(合成例11：樹脂K)於反應容器A中添加N,N-二甲 基甲醯胺50份、甲基丙烯酸甲酯50份及胺基乙硫醇鹽酸鹽1.14份，升溫至80℃為止。添加2,2'-偶氮雙(異丁腈)0.082份，於氮氣流下一面攪拌一面於80℃下加熱。反應5.5小時後，添加二環己基碳二亞胺2.5份，於80℃下進一步加熱4小時。反應結束後，將燒瓶內的溶液冷卻至室溫為止，於0.5%碳酸鉀水溶液1,000份中再沈澱，獲得白色粉末的樹脂K。 (Synthesis Example 11: Resin K) Addition of N,N-dimethyl to reaction vessel A 50 parts of carbamide, 50 parts of methyl methacrylate and 1.14 parts of amino ethanethiol hydrochloride were heated to 80 °C. 0.082 parts of 2,2'-azobis(isobutyronitrile) was added, and the mixture was heated at 80 ° C while stirring under a nitrogen stream. After reacting for 5.5 hours, 2.5 parts of dicyclohexylcarbodiimide was added, and further heating was carried out at 80 ° C for 4 hours. After completion of the reaction, the solution in the flask was cooled to room temperature, and reprecipitated in 1,000 parts of a 0.5% potassium carbonate aqueous solution to obtain a white powder of resin K.
(合成例12：樹脂L)於四口燒瓶中添加月桂醇(新日 本理化公司製造的「卡爾醇(Kalcol)2098」)150.0份及28%的甲氧化鈉甲醇溶液(川研精化公司製造的「SM-28」)2.63份，於減壓下於90℃下反應50分鐘。繼而將反應混合物的總量添加至高壓釜(autoclave)中，升溫至110℃後，以高壓釜的內壓成為0.2MPa~0.4MPa的方式用3小時添加環氧乙烷351.9份進行反應。將所得的反應物400.0份及113.9份的SM-28添加至四口燒瓶中，於減壓下於80℃下攪拌3.5小時，合成烷氧化物。於該四口燒瓶中進一步添加甲苯200.0份及單氯乙酸鈉77.27份，於110℃下攪拌14小時。將所得的反應混合物冷卻至80℃，於其中投入水244.8份及75%的硫酸水溶液74.93份，將該混合物於80℃下攪拌30分鐘，靜置30分鐘後，進行分液而收集反應產物的甲苯溶液。其後，對 該所收集的反應產物的甲苯溶液中進一步實施2次利用10%的硫酸鈉水溶液244.8份的清洗。將反應產物的甲苯溶液濃縮後，藉由過濾將析出的鹽去除，獲得416.5份的醚羧酸化合物。 (Synthesis Example 12: Resin L) Adding lauryl alcohol to a four-necked flask (New Day) 2.63 parts of "Kalcol 2098" manufactured by the Physicochemical Co., Ltd. and 2.63 parts of a 28% sodium methoxide methanol solution ("SM-28" manufactured by Kasei Seiki Co., Ltd.), under reduced pressure at 90 ° C Reaction for 50 minutes. Then, the total amount of the reaction mixture was added to an autoclave, and the temperature was raised to 110° C., and then the reaction was carried out by adding 351.9 parts of ethylene oxide for 3 hours so that the internal pressure of the autoclave became 0.2 MPa to 0.4 MPa. 400.0 parts of the obtained reaction product and 113.9 parts of SM-28 were placed in a four-necked flask, and the mixture was stirred at 80 ° C for 3.5 hours under reduced pressure to synthesize an alkoxide. Further, 200.0 parts of toluene and 77.27 parts of sodium monochloroacetate were further added to the four-necked flask, and the mixture was stirred at 110 ° C for 14 hours. The obtained reaction mixture was cooled to 80 ° C, and 244.8 parts of water and 74.93 parts of a 75% sulfuric acid aqueous solution were added thereto, and the mixture was stirred at 80 ° C for 30 minutes, and allowed to stand for 30 minutes, and then liquid separation was carried out to collect the reaction product. Toluene solution. Later, right The toluene solution of the collected reaction product was further washed twice with 244.8 parts of a 10% aqueous sodium sulfate solution. After the toluene solution of the reaction product was concentrated, the precipitated salt was removed by filtration to obtain 416.5 parts of an ether carboxylic acid compound.
繼而，於反應容器A中添加聚烯丙胺15.0%水溶液(PAA-01：日東紡績公司製造)100.0份及所述醚羧酸化合物55.5份，以氮氣進行置換。將該混合物於減壓下於100℃下脫水後，將其溫度升溫至150℃，於壓力1.3kPa下反應2小時，獲得樹脂L。 Then, 100.0 parts of a polyallylamine 15.0% aqueous solution (PAA-01: manufactured by Nitto Bose Co., Ltd.) and 55.5 parts of the ether carboxylic acid compound were added to the reaction vessel A, and the mixture was replaced with nitrogen. The mixture was dehydrated at 100 ° C under reduced pressure, and the temperature was raised to 150 ° C, and the mixture was reacted at a pressure of 1.3 kPa for 2 hours to obtain a resin L.
(合成例13：樹脂M)將聚乙烯亞胺(數量平均分子量為600)50份及粉末狀的氫氧化鈉1.0份添加至高壓釜中，加熱至80℃。其後，進行3次氮氣置換，加熱至170℃。繼而，以不超過0.5MPa的方式用5小時添加共計500份的環氧乙烷，其後加熱2小時。冷卻至80℃後，於氮氣流下攪拌1小時，將未反應的環氧乙烷去除至反應體系外。繼而，冷卻至室溫為止，獲得540份的樹脂M。 (Synthesis Example 13: Resin M) 50 parts of polyethyleneimine (number average molecular weight: 600) and 1.0 part of powdered sodium hydroxide were placed in an autoclave and heated to 80 °C. Thereafter, nitrogen substitution was performed three times, and the mixture was heated to 170 °C. Then, a total of 500 parts of ethylene oxide was added over 5 hours in a manner not exceeding 0.5 MPa, followed by heating for 2 hours. After cooling to 80 ° C, the mixture was stirred under a nitrogen stream for 1 hour to remove unreacted ethylene oxide to the outside of the reaction system. Then, after cooling to room temperature, 540 parts of Resin M was obtained.
(合成例14：樹脂N)於反應容器A中添加甲基丙烯酸二甲基胺基乙酯50.0份、甲基丙烯酸甲酯50.0份及1-甲氧基-2-丙醇233.3份，以氮氣進行置換後，進行加熱而升溫至90℃為止。於其中添加2,2'-偶氮雙(2,4-二甲基戊腈)(和光純藥公司製造的「V-65」)6.0份，於90℃下進行2小時加熱攪拌。進而添加6.0份的V-65，進行3小時加熱攪拌，藉此獲得樹脂N。 (Synthesis Example 14: Resin N) 50.0 parts of dimethylaminoethyl methacrylate, 50.0 parts of methyl methacrylate and 233.3 parts of 1-methoxy-2-propanol were added to the reaction vessel A, and nitrogen gas was used. After the replacement, the mixture was heated and heated to 90 °C. To this was added 6.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) ("V-65" manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C for 2 hours. Further, 6.0 parts of V-65 was added, and heating and stirring were carried out for 3 hours, whereby Resin N was obtained.
(合成例15：樹脂O)於反應容器A中製備胺基苯并咪唑酮14.9份、甲基丙烯酸-2-異氰酸基乙酯21.2份及乙酸乙酯 150份的混合溶液，於其中添加二乙酸二丁基錫0.96份，一面攪拌一面於50℃下反應7.5小時。將反應溶液冷卻至室溫為止，滴加至己烷1,000份中，結果固體析出。將所析出的固體過濾後加以風乾，藉此獲得含有苯并咪唑酮的單體26.0份。 (Synthesis Example 15: Resin O) 14.9 parts of an aminobenzimidazolone, 21.2 parts of 2-isocyanatoethyl methacrylate, and ethyl acetate were prepared in the reaction vessel A. To 150 parts of the mixed solution, 0.96 part of dibutyltin diacetate was added thereto, and the mixture was reacted at 50 ° C for 7.5 hours while stirring. The reaction solution was cooled to room temperature, and added dropwise to 1,000 parts of hexane, whereby a solid precipitated. The precipitated solid was filtered and air-dried to obtain 26.0 parts of a benzimidazolone-containing monomer.
於另一反應容器A中添加二甲基亞碸40.0份及單末端經甲基丙烯醯化的聚甲基丙烯酸甲酯(AA-6：東亞合成公司製造)32.0份，以氮氣進行置換後，進行加熱而升溫至78℃為止。用2小時將另行製備的下述單體溶液與起始劑溶液同時滴加至反應容器A中。 40.0 parts of dimethyl hydrazine and 32.0 parts of polymethyl methacrylate (AA-6: manufactured by Toagosei Co., Ltd.) which was methacrylized at the single terminal were added to another reaction vessel A, and after replacing with nitrogen gas, Heating was carried out until the temperature was raised to 78 °C. The following monomer solution prepared separately and the starter solution were simultaneously added dropwise to the reaction vessel A over 2 hours.
所述含苯并咪唑酮的單體：2.00份 The benzimidazolone-containing monomer: 2.00 parts
甲基丙烯酸：6.00份 Methacrylic acid: 6.00 parts
二甲基亞碸：43.3份 Dimethyl hydrazine: 43.3 parts
2,2'-偶氮雙(2,4-二甲基戊腈)(和光純藥公司製造的「V-65」)：0.101份 2,2'-azobis(2,4-dimethylvaleronitrile) ("V-65" manufactured by Wako Pure Chemical Industries, Ltd.): 0.101 parts
二甲基亞碸：10.0份 Dimethyl hydrazine: 10.0 parts
滴加後攪拌1小時，添加0.202份的V-65，進而將內溫於78℃下保持2小時，其後進行加熱並於90℃下保持30分鐘。繼而，將反應溶液冷卻至室溫為止，使溶液於水3,000份中再沈澱並進行真空乾燥，藉此獲得樹脂O。 After the dropwise addition, the mixture was stirred for 1 hour, 0.202 parts of V-65 was added, and the internal temperature was maintained at 78 ° C for 2 hours, followed by heating and maintaining at 90 ° C for 30 minutes. Then, the reaction solution was cooled to room temperature, and the solution was reprecipitated in 3,000 parts of water and vacuum dried, whereby Resin O was obtained.
(合成例16：樹脂P)於反應容器A中添加甲基丙烯酸 -2-羥基乙酯58.5份、甲基丙烯酸甲酯54.0份及硫代乙醇酸4.77份，一面於氮氣流下攪拌，一面加溫至溫度80℃。添加2,2'-偶氮雙異丁腈0.147份反應2小時，進而添加四氫呋喃30份反應3小時。冷卻後，利用乙酸乙酯200份將反應溶液稀釋，以己烷3,000份進行再沈澱，獲得白色粉末105.5份。繼而，於該白色粉末90份中添加二甲苯200份、甲基丙烯酸縮水甘油酯13.5份、N,N-二甲基十二烷基胺0.142份及對苯二酚0.1份，於150℃下攪拌3小時。冷卻後，利用己烷3,000份使該反應溶液再沈澱，獲得白色粉末88份。進而，一面攪拌所得的白色粉末80份、琥珀酸酐31.0份及1-甲氧基-2-丙基乙酸酯160份的混合溶液，一面使之於90℃下反應6小時。利用乙酸乙酯200份將反應溶液稀釋，利用己烷3,000份進行再沈澱，獲得70份作為白色粉末的具有含羧基的重複單元的巨單體(MM-1)。 (Synthesis Example 16: Resin P) Adding methacrylic acid to the reaction vessel A 58.5 parts of 2-hydroxyethyl ester, 54.0 parts of methyl methacrylate, and 4.77 parts of thioglycolic acid were stirred while stirring under a nitrogen stream to a temperature of 80 °C. 0.147 parts of 2,2'-azobisisobutyronitrile was added and reacted for 2 hours, and further 30 parts of tetrahydrofuran was added and reacted for 3 hours. After cooling, the reaction solution was diluted with 200 parts of ethyl acetate, and reprecipitated with 3,000 parts of hexane to obtain 105.5 parts of a white powder. Then, 200 parts of xylene, 13.5 parts of glycidyl methacrylate, 0.142 parts of N,N-dimethyldodecylamine, and 0.1 part of hydroquinone were added to 90 parts of the white powder at 150 ° C. Stir for 3 hours. After cooling, the reaction solution was reprecipitated with 3,000 parts of hexane to obtain 88 parts of a white powder. Further, while stirring a mixed solution of 80 parts of the obtained white powder, 31.0 parts of succinic anhydride, and 160 parts of 1-methoxy-2-propyl acetate, the mixture was reacted at 90 ° C for 6 hours. The reaction solution was diluted with 200 parts of ethyl acetate, and reprecipitated with 3,000 parts of hexane to obtain 70 parts of a macromonomer (MM-1) having a carboxyl group-containing repeating unit as a white powder.
關於以後的步驟，除了對合成例15的調配組成將甲基丙烯酸的添加量變更為0份、將單末端經甲基丙烯醯化的聚甲基丙烯酸甲酯的添加量變更為14.0份、進而添加24.0份的所述MM-1以外，與合成例15同樣地進行操作，獲得樹脂P。 In the subsequent steps, the addition amount of methacrylic acid was changed to 0 part, and the amount of polymethyl methacrylate which was mono-terminally methacrylate-diminated was changed to 14.0 parts, and further, The resin P was obtained in the same manner as in Synthesis Example 15 except that 24.0 parts of the above MM-1 was added.
(合成例17：樹脂Q)於反應容器A中添加甲基丙烯 酸-2-羥基乙酯32.5份、甲基丙烯酸甲酯75.1份及硫代乙醇酸2.65份，一面於氮氣流下攪拌，一面加溫至溫度80℃。添加2,2'-偶氮雙異丁腈0.082份反應2小時，進而添加四氫呋喃30份反應3小時。冷卻後，利用乙酸乙酯200份將反應溶液稀釋，利用己烷3,000 份進行再沈澱，獲得白色粉末99.2份。繼而，於該白色粉末90份中添加二甲苯200份、甲基丙烯酸縮水甘油酯13.5份、N,N-二甲基十二烷基胺0.142份及對苯二酚0.1份，於150℃下攪拌3小時。冷卻後，利用己烷3,000份使該反應溶液再沈澱，獲得白色粉末87.5份。進而，一面攪拌所得的白色粉末80份、琥珀酸酐17.8份及1-甲氧基-2-丙基乙酸酯160份的混合溶液，一面使之於90℃下反應6小時。利用乙酸乙酯200份將反應溶液稀釋，利用己烷3000份進行再沈澱，獲得73.6份作為白色粉末的具有含羧基的重複單元的巨單體(MM-2)。 (Synthesis Example 17: Resin Q) Addition of methacrylic acid to the reaction vessel A 32.5 parts of acid-2-hydroxyethyl ester, 75.1 parts of methyl methacrylate, and 2.65 parts of thioglycolic acid were stirred while stirring under a nitrogen stream to a temperature of 80 °C. 0.082 parts of 2,2'-azobisisobutyronitrile was added and reacted for 2 hours, and further 30 parts of tetrahydrofuran was added and reacted for 3 hours. After cooling, the reaction solution was diluted with 200 parts of ethyl acetate, using hexane 3,000 The fraction was reprecipitated to obtain 99.2 parts of a white powder. Then, 200 parts of xylene, 13.5 parts of glycidyl methacrylate, 0.142 parts of N,N-dimethyldodecylamine, and 0.1 part of hydroquinone were added to 90 parts of the white powder at 150 ° C. Stir for 3 hours. After cooling, the reaction solution was reprecipitated with 3,000 parts of hexane to obtain 87.5 parts of a white powder. Further, while stirring a mixed solution of 80 parts of the obtained white powder, 17.8 parts of succinic anhydride, and 160 parts of 1-methoxy-2-propyl acetate, the mixture was reacted at 90 ° C for 6 hours. The reaction solution was diluted with 200 parts of ethyl acetate, and reprecipitated with 3000 parts of hexane to obtain 73.6 parts of a macromonomer (MM-2) having a carboxyl group-containing repeating unit as a white powder.
關於以後的步驟，除了對合成例15的調配組成將甲基丙烯酸的添加量變更為0份、將單末端經甲基丙烯醯化的聚甲基丙烯酸甲酯的添加量變更為14.0份、進而添加24.0份的所述MM-2以外，與合成例15同樣地進行操作，獲得樹脂Q。 In the subsequent steps, the addition amount of methacrylic acid was changed to 0 part, and the amount of polymethyl methacrylate which was mono-terminally methacrylate-diminated was changed to 14.0 parts, and further, The resin Q was obtained in the same manner as in Synthesis Example 15 except that 24.0 parts of the MM-2 was added.
(合成例18：樹脂AF)於反應容器中添加丙二醇單甲醚乙酸酯800份，一面於容器中注入氮氣一面加熱至100℃，於該溫度下用1小時滴加下述單體及熱聚合起始劑的混合物，進行反應。 (Synthesis Example 18: Resin AF) 800 parts of propylene glycol monomethyl ether acetate was added to a reaction container, and the mixture was heated to 100 ° C while injecting nitrogen gas into the container, and the following monomers and heat were added dropwise at this temperature for 1 hour. A mixture of polymerization initiators is used to carry out the reaction.
．苯乙烯：60.0份 . Styrene: 60.0 parts
．甲基丙烯酸：60.0份 . Methacrylic acid: 60.0 parts
．甲基丙烯酸甲酯：65.0份 . Methyl methacrylate: 65.0 parts
．甲基丙烯酸丁酯：65.0份 . Butyl methacrylate: 65.0 parts
．偶氮雙異丁腈：10.0份 . Azobisisobutyronitrile: 10.0 parts
滴加後，進而於100℃下反應3小時後，添加使偶氮雙異丁腈2.0份溶解於丙二醇單甲醚乙酸酯50份中所得的溶液，進而於100℃下繼續反應1小時。冷卻至室溫為止後，將樹脂溶液取樣約2g並於180℃下進行20分鐘加熱乾燥，測定不揮發成分，於先合成的樹脂溶液中以不揮發成分成為20質量%的方式添加丙二醇單甲醚乙酸酯，獲得樹脂AF。 After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, and then a solution obtained by dissolving 2.0 parts of azobisisobutyronitrile in 50 parts of propylene glycol monomethyl ether acetate was added, and the reaction was further continued at 100 ° C for 1 hour. After cooling to room temperature, the resin solution was sampled at about 2 g, and dried at 180 ° C for 20 minutes, and the non-volatile component was measured. The propylene glycol monomethyl group was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Ether acetate to obtain resin AF.
(合成例19：樹脂AG)於具備攪拌機、回流冷凝管、乾燥空氣導入管及溫度計的四口燒瓶(以下將具備該些構件的四口燒瓶簡稱為「四口燒瓶A」)中，添加聯苯四羧酸二酐80.0份、季戊四醇三丙烯酸酯250.0份、對苯二酚0.16份及環己酮141.2份，升溫至85℃為止。繼而添加作為觸媒的1,8-二氮雜雙環[5.4.0]-7-十一烯1.65份，於85℃下攪拌8小時。其後，添加甲基丙烯酸縮水甘油酯77.3份及環己酮33.9份，繼而添加作為觸媒的二甲基苄基胺2.65份，於85℃下攪拌6小時，冷卻至室溫為止而結束反應，獲得淡黃色透明的樹脂AG。 (Synthesis Example 19: Resin AG) was added to a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introduction tube, and a thermometer (hereinafter, a four-necked flask having these members is simply referred to as "four-necked flask A"). 80.0 parts of benzenetetracarboxylic dianhydride, 250.0 parts of pentaerythritol triacrylate, 0.16 parts of hydroquinone, and 141.2 parts of cyclohexanone were heated to 85 °C. Then, 1.65 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 85 ° C for 8 hours. Thereafter, 77.3 parts of glycidyl methacrylate and 33.9 parts of cyclohexanone were added, followed by addition of 2.65 parts of dimethylbenzylamine as a catalyst, and the mixture was stirred at 85 ° C for 6 hours, and cooled to room temperature to terminate the reaction. A yellowish transparent resin AG was obtained.
(合成例20：樹脂AH)於四口燒瓶A中添加丁烷四羧酸二酐50.0份、二季戊四醇五丙烯酸酯413.4份、對苯二酚0.23份及環己酮463.4份，升溫至85℃為止。繼而添加作為觸媒的1,8-二氮雜雙環[5.4.0]-7-十一烯2.32份，於85℃下攪拌8小時。其後，添加甲基丙烯酸縮水甘油酯71.7份及環己酮74.3份，繼而添加作為觸媒的二甲基苄基胺3.73份，於85℃下攪拌6小時，冷卻至室溫為止而結束反應，獲得淡黃色透明的樹脂AH。 (Synthesis Example 20: Resin AH) 50.0 parts of butane tetracarboxylic dianhydride, 413.4 parts of dipentaerythritol pentaacrylate, 0.23 parts of hydroquinone, and 463.4 parts of cyclohexanone were added to a four-necked flask A, and the temperature was raised to 85 ° C. until. Then, 2.32 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 85 ° C for 8 hours. Thereafter, 71.7 parts of glycidyl methacrylate and 74.3 parts of cyclohexanone were added, followed by 3.73 parts of dimethylbenzylamine as a catalyst, and the mixture was stirred at 85 ° C for 6 hours, and cooled to room temperature to terminate the reaction. A yellowish transparent resin AH was obtained.
(合成例21：樹脂AI)於四口燒瓶A中添加分子量為 2,000的聚四亞甲基二醇218.9份及異佛爾酮二異氰酸酯57.4份，一面導入氮氣一面緩緩升溫至90℃，進行反應直至異氰酸酯基成為4.5%為止。繼而添加二乙基胺基乙醇12.2份，進而於90℃下進行3小時反應。使用乙酸乙酯115份，移至滴加槽中獲得預聚物。繼而，於反應槽中添加異佛爾酮二胺11.5份、二丁基胺0.003份、異丙醇350.0份及乙酸乙酯235.0份，自滴加槽中用30分鐘將預聚物滴加至反應槽中。其後，於40℃下反應1小時，獲得固體成分為30%的樹脂AI。 (Synthesis Example 21: Resin AI) The molecular weight was added to the four-necked flask A. 218.9 parts of 2,000 polytetramethylene glycol and 57.4 parts of isophorone diisocyanate were gradually heated to 90 ° C while introducing nitrogen gas, and the reaction was carried out until the isocyanate group became 4.5%. Then, 12.2 parts of diethylaminoethanol was added, and the reaction was further carried out at 90 ° C for 3 hours. Using 115 parts of ethyl acetate, it was transferred to a dropping tank to obtain a prepolymer. Then, 11.5 parts of isophoronediamine, 0.003 parts of dibutylamine, 350.0 parts of isopropyl alcohol and 235.0 parts of ethyl acetate were added to the reaction tank, and the prepolymer was added dropwise from the dropping tank for 30 minutes. In the reaction tank. Thereafter, the reaction was carried out at 40 ° C for 1 hour to obtain a resin AI having a solid content of 30%.
(合成例22：樹脂AJ)於四口燒瓶A中添加包含己二 酸與3-甲基-1,5-戊二醇的分子量為5000的聚酯二醇263.6份、分子量為1,000的聚四亞甲基二醇13.3份及異佛爾酮二異氰酸酯19.3份，一面導入氮氣一面緩緩升溫至90℃，進行反應直至NCO%成為0.6%為止。繼而添加二乙基胺基乙醇0.25份，進而於90℃下進行3小時反應。使用乙酸乙酯115.0份，移至滴加槽中獲得預聚物。繼而，於反應槽中添加異佛爾酮二胺3.38份、二丁胺0.176份、異丙醇350.0份及乙酸乙酯235.0份，自滴加槽中用30分鐘將預聚物滴加至反應槽中。其後，於40℃下反應1小時，獲得固體成分為30%的樹脂AJ。 (Synthesis Example 22: Resin AJ) was added to a four-necked flask A containing 263.6 parts of a polyester diol having a molecular weight of 5000 with an acid and 3-methyl-1,5-pentanediol, 13.3 parts of a polytetramethylene glycol having a molecular weight of 1,000, and 19.3 parts of isophorone diisocyanate. The temperature was gradually raised to 90 ° C while introducing nitrogen gas, and the reaction was carried out until the NCO% became 0.6%. Then, 0.25 parts of diethylaminoethanol was added, and the reaction was further carried out at 90 ° C for 3 hours. Using 115.0 parts of ethyl acetate, it was transferred to a dropping tank to obtain a prepolymer. Then, 3.38 parts of isophorone diamine, 0.176 parts of dibutylamine, 350.0 parts of isopropyl alcohol and 235.0 parts of ethyl acetate were added to the reaction tank, and the prepolymer was added dropwise to the reaction from the dropping tank for 30 minutes. In the slot. Thereafter, the reaction was carried out at 40 ° C for 1 hour to obtain a resin AJ having a solid content of 30%.
樹脂R~樹脂Z、樹脂AA~樹脂AE是使用以下產品。 The following products were used for Resin R~Resin Z and Resin AA~Resin AE.
樹脂R：日本畢克化學(BYK Chemie Japan)公司製造的「迪斯帕畢克(DISPERBYK)-110」 Resin R: "DISPERBYK-110" manufactured by BYK Chemie Japan
樹脂S：日本畢克化學(BYK Chemie Japan)公司製造的「迪斯帕畢克(DISPERBYK)-111」 Resin S: "DISPERBYK-111" manufactured by BYK Chemie Japan
樹脂T：味之素精密技術(Ajinomoto Fine-techno)公司製造的「阿吉斯帕(Ajisper)PA111」 Resin T: "Ajisper PA111" manufactured by Ajinomoto Fine-techno
樹脂U：巴斯夫(BASF)公司製造的「莊克麗(Joncryl)678」 Resin U: "Joncryl 678" manufactured by BASF
樹脂V：日本畢克化學(BYK Chemie Japan)公司製造的「迪斯帕畢克(DISPERBYK)-161」 Resin V: "DISPERBYK-161" manufactured by BYK Chemie Japan
樹脂W：日本畢克化學(BYK Chemie Japan)公司製造的「迪斯帕畢克(DISPERBYK)-21116」 Resin W: "DISPERBYK-21116" manufactured by BYK Chemie Japan
樹脂X：日本畢克化學(BYK Chemie Japan)公司製造的「迪斯帕畢克(DISPERBYK)-21715」 Resin X: "DISPERBYK-21715" manufactured by BYK Chemie Japan
樹脂Y：味之素精密技術(Ajinomoto Fine-techno)公司製造的「阿吉斯帕(Ajisper)PB821」 Resin Y: "Ajisper PB821" manufactured by Ajinomoto Fine-techno
樹脂Z：巴斯夫(BASF)公司製造的「埃夫卡(Efka)PX4300」 Resin Z: "Efka PX4300" manufactured by BASF
樹脂AA：日本路博潤(Lubrizol Japan)公司製造的「索努帕斯(SOLSPERSE)24000」 Resin AA: "SOLSPERSE 24000" manufactured by Lubrizol Japan
樹脂AB：日本路博潤(Lubrizol Japan)公司製造的「索努帕斯(SOLSPERSE)17000」 Resin AB: "SOLSPERSE 17000" manufactured by Lubrizol Japan
樹脂AC：日本路博潤(Lubrizol Japan)公司製造的「索努帕斯(SOLSPERSE)32000」 Resin AC: "SOLSPERSE 32000" manufactured by Lubrizol Japan
樹脂AD：川研精化公司製造的「海諾特(Hinoact)T-8000」 Resin AD: "Hinoact T-8000" manufactured by Kawasaki Seiki Co., Ltd.
樹脂AE：共榮社化學公司製造的「弗洛蘭(Flowlen) KDG-2400」 Resin AE: "Flowlen" manufactured by Kyoeisha Chemical Co., Ltd. KDG-2400"
(合成例23：二溴二酮基吡咯并吡咯(dibromoDPP，dibromo diketopyrrolopyrrole))於帶有回流管的不鏽鋼製反應容器中，於氮氣環境下添加經分子篩(molecular sieve)脫水的第三戊醇200份、及第三戊基烷氧化鈉140份，一面攪拌一面加熱至100℃，製備醇化物(alcoholate)溶液。另一方面，於玻璃製燒瓶中添加琥珀酸二異丙酯88份及4-溴苯甲腈153.6份，一面攪拌一面加熱至90℃而使之溶解，製備該等的混合物的溶液。於經加熱至100℃的所述醇化物溶液中，一面劇烈攪拌，一面用2小時以一定速度緩慢地滴加所述混合物的加熱溶液。滴加結束後，於90℃下繼續進行2小時加熱攪拌，獲得二酮基吡咯并吡咯系化合物的鹼金屬鹽。進而，於帶有玻璃製套管的反應容器中添加甲醇600份、水600份及乙酸304份，冷卻至-10℃。對該經冷卻的混合物使用高速攪拌分散機，一面使直徑為8cm的分配圓盤(share disk)以4,000rpm旋轉，一面於其中逐次少量地添加經冷卻至75℃為止的之前所得的二酮基吡咯并吡咯系化合物的鹼金屬鹽溶液。此時，以包含甲醇、乙酸及水的混合物的溫度一直保持-5℃以下的溫度的方式冷卻，且同時一面調整75℃的二酮基吡咯并吡咯系化合物的鹼金屬鹽的添加速度，一面用大約120分鐘逐次少量地添加。添加鹼金屬鹽後，析出紅色結晶，生成紅色懸浮液。繼而，利用超濾裝置於5℃下將所得的紅色懸浮液清洗後，過濾分離而獲得紅色膏。將 該膏於經冷卻至0℃的甲醇3,500份中再分散，製成甲醇濃度約90%的懸浮液，於5℃下攪拌3小時，進行伴隨著結晶轉變(crystal transition)的粒子整粒及清洗。繼而，利用超濾機進行過濾分離，將所得的二酮基吡咯并吡咯系化合物的含水膏於80℃下乾燥24小時，加以粉碎，藉此獲得溴化二酮基吡咯并吡咯顏料150.8份。 (Synthesis Example 23: dibromo DPP, dibromo diketopy rrolopyrrole) was added to a third pentanol 200 dehydrated by a molecular sieve in a stainless steel reaction vessel equipped with a reflux tube under a nitrogen atmosphere. A portion and 140 parts of sodium tripentyl alkoxide were heated to 100 ° C while stirring to prepare an alcoholate solution. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask, and the mixture was heated to 90 ° C while stirring to dissolve the solution, and a solution of the mixture was prepared. The heated solution of the mixture was slowly added dropwise at a constant rate over 2 hours in the alcoholate solution heated to 100 ° C while vigorously stirring. After completion of the dropwise addition, the mixture was heated and stirred at 90 ° C for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were placed in a reaction vessel equipped with a glass sleeve, and the mixture was cooled to -10 °C. The cooled mixture was subjected to a high-speed stirring disperser, and a share disk having a diameter of 8 cm was rotated at 4,000 rpm while a previously obtained diketone group cooled to 75 ° C was added thereto in small portions. A solution of an alkali metal salt of a pyrrolopyrrole compound. In this case, the temperature of the mixture containing methanol, acetic acid, and water is kept at a temperature of -5 ° C or lower, and the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C is adjusted. It was added in small portions one by one for about 120 minutes. After the addition of the alkali metal salt, red crystals were precipitated to form a red suspension. Then, the obtained red suspension was washed with an ultrafiltration apparatus at 5 ° C, and then separated by filtration to obtain a red paste. will The paste was redispersed in 3,500 parts of methanol cooled to 0 ° C to prepare a suspension having a methanol concentration of about 90%, and stirred at 5 ° C for 3 hours to carry out particle granulation and cleaning accompanied by crystal transition. . Then, the mixture was separated by filtration using an ultrafiltration machine, and the obtained aqueous solution of the diketopyrrolopyrrole compound was dried at 80 ° C for 24 hours, and pulverized to obtain 150.8 parts of a brominated diketopyrrolopyrrole pigment.
以下列舉實施例或比較例中所用的顏料。 The pigments used in the examples or comparative examples are listed below.
．PR242：科萊恩(Clariant)公司製造的「諾瓦帕猩紅(Novoperm Scarlet)4RF」 . PR242: "Novoperm Scarlet 4RF" manufactured by Clariant
．PR177-1：先尼科(CINIC)公司製造的「先尼萊克斯紅(Cinilex Red)SR4C」 . PR177-1: "Cinilex Red SR4C" manufactured by CINIC
．PR177-2：先尼科(CINIC)公司製造的「先尼萊克斯紅(Cinilex Red)SR4C」 . PR177-2: "Cinilex Red SR4C" manufactured by CINIC
．PR254-1：巴斯夫(BASF)公司製造的「豔佳鮮紅(Irgazin Red)L 3660 HD」 . PR254-1: "Irgazin Red L 3660 HD" by BASF
．PR254-2：巴斯夫(BASF)公司製造的「豔佳芳紅(Irgaphor Red)S 3610 CF」 . PR254-2: "Irgaphor Red S 3610 CF" manufactured by BASF
．PR269：山陽色素公司製造的「永久胭脂紅(Permanent Carmine)3810」 . PR269: "Permanent Carmine 3810" manufactured by Shanyang Pigment Co., Ltd.
．PG36：東洋色彩(Toyo Color)公司製造的「利諾爾綠(LIONOL GREEN)6YK」 . PG36: "LIONOL GREEN 6YK" by Toyo Color
．PG58：迪愛生(DIC)公司製造的「法斯特根綠(FASTOGEN Green)A110」 . PG58: "FASTOGEN Green A110" by DiCai (DIC)
．PY138：巴斯夫(BASF)公司製造的「葩麗特黃(Paliotol Yellow)K 0961 HD」 . PY138: "Paliotol Yellow K 0961 HD" manufactured by BASF
．PY150：朗盛(LANXESS)公司製造的「黃色顏料(Yellow Pigment)E4GN」 . PY150: "Yellow Pigment E4GN" manufactured by LANXESS
．PY139：巴斯夫(BASF)製造的「葩麗特黃(Paliotol Yellow)D 1819」 . PY139: "Paliotol Yellow D 1819" by BASF
．PB15：6：東洋色彩(Toyo Color)公司製造的「利諾爾藍(LIONOL BLUE)ES」 . PB15:6: "LIONOL BLUE ES" manufactured by Toyo Color
．PV23：東洋色彩(Toyo Color)公司製造的「利諾吉紫(LIONOGEN VIOLET)FG-6240」 . PV23: "LIONOGEN VIOLET FG-6240" manufactured by Toyo Color
．PB15：3：東洋色彩(Toyo Color)公司製造的「利諾爾藍(LIONOL BLUE)FG-7351」 . PB15:3: "LIONOL BLUE FG-7351" manufactured by Toyo Color
．PR122：迪愛生(DIC)公司製造的「法斯特根超級洋紅(FASTOGEN Super Magenta)RGT」 . PR122: "FASTOGEN Super Magenta RGT" manufactured by Di Love (DIC)
．PV19：科萊恩(Clariant)公司製造的「噴墨洋紅(Ink Jet Magenta)E5B02 VP2984」 . PV19: "Ink Jet Magenta E5B02 VP2984" manufactured by Clariant
．PY74：巴斯夫(BASF)公司製造的「豔佳麗黃(Irgalite Yellow)D 1245」 . PY74: "Irgalite Yellow D 1245" by BASF
．PB7：卡博特(Cabot)公司製造的「艾爾芙泰克斯(ELFTEX)415瑞佳爾(REGAL)400R」 . PB7: "Elftex 415 Regal 400R" manufactured by Cabot
以下，於表1A、表1B中列舉實施例或比較例中所用的色素 衍生物。 Hereinafter, the pigments used in the examples or comparative examples are listed in Table 1A and Table 1B. derivative.
列舉實施例及比較例中所用的溶劑及其記號。 The solvents and symbols used in the examples and comparative examples are listed.
．PGMAc：丙二醇單甲醚乙酸酯 . PGMAc: propylene glycol monomethyl ether acetate
．DEDG：二乙二醇二*** . DEDG: diethylene glycol diethyl ether
．CBAc：二乙二醇單***乙酸酯 . CBAc: diethylene glycol monoethyl ether acetate
(顏料組成物1的製作)將偶氮系紅色顏料PR242(科萊恩(Clariant)公司製造的「諾瓦帕猩紅(Novoperm Scarlet)4RF」)120份、10份的色素衍生物a、氯化鈉1,500份及單乙酸甘油酯250份添加至不鏽鋼製1加侖捏合機(井上製作所公司製造)中，於70℃下混練6小時。將該混合物投入至水10,000份中，一面加熱至40℃±5℃一面利用高速攪拌機(high speed mixer)攪拌1小時而製成漿料狀，過濾後，利用40℃±5℃的水10,000份進行清洗，去除氯化鈉及單乙酸甘油酯，於90℃下乾燥而獲得顏料組成物1。 (Production of Pigment Composition 1) An azo red pigment PR242 ("Novoperm Scarlet 4RF" manufactured by Clariant Co., Ltd.) 120 parts, 10 parts of a pigment derivative a, sodium chloride 1,500 parts and 250 parts of monoacetin were added to a stainless steel one-gallon kneader (manufactured by Inoue Co., Ltd.), and kneaded at 70 ° C for 6 hours. The mixture was poured into 10,000 parts of water, and heated to 40 ° C ± 5 ° C while stirring in a high speed mixer for 1 hour to prepare a slurry. After filtration, 10,000 parts of water at 40 ° C ± 5 ° C was used. The cleaning was carried out, sodium chloride and monoacetin were removed, and dried at 90 ° C to obtain Pigment Composition 1.
(顏料組成物2~顏料組成物132的製作)除了變更為表2A~表5B所示的混練組成、混練條件及乾燥條件以外，與實施例1-1同樣地進行操作，獲得顏料組成物2~顏料組成物132。其中，關於含有溶劑的樹脂溶液，適當地更換為混練溶劑而使用，或使用在減壓下於80℃下經乾燥的固體樹脂，以成為表2A~表5B的 組成的方式實施。 (Production of Pigment Composition 2 to Pigment Composition 132) The same procedure as in Example 1-1 was carried out except that the kneading composition, the kneading conditions, and the drying conditions shown in Tables 2A to 5B were changed, and the pigment composition 2 was obtained. ~ Pigment composition 132. In addition, the resin solution containing a solvent is used suitably, it is used as a kneading solvent, or the solid resin dried at 80 degreeC under pressure reduction is used, and it is set as Table 2A - Table 5B. The way the composition is implemented.
(平均一次粒徑的測定)關於所得的顏料組成物的平均 一次粒徑，使用穿透式電子顯微鏡(日本電子公司製造的「JEM-1200EX」)，對10萬倍時的觀察試樣中的所有顏料粒子的一次粒徑進行測量，使用其平均值。再者，於粒子形狀並非球狀的情形時，測量長徑及短徑，將藉由(長徑+短徑)/2所求出的值作為粒徑。再者，以下的實施例及比較例的平均一次粒徑亦是藉由所述方法測定。 (Measurement of average primary particle size) Regarding the average of the obtained pigment composition The primary particle diameter was measured using a transmission electron microscope ("JEM-1200EX" manufactured by JEOL Ltd.), and the primary particle diameter of all the pigment particles in the observation sample at 100,000 times was measured, and the average value was used. In the case where the particle shape is not spherical, the long diameter and the short diameter are measured, and the value obtained by (long diameter + short diameter)/2 is used as the particle diameter. Further, the average primary particle diameters of the following examples and comparative examples were also measured by the above method.
殘留溶劑是藉由以下方式算出：藉由氣相層析法對相對於顏料組成物的固體成分之本發明的水溶性有機溶劑的殘留溶劑量進行定量，根據固體成分中的顏料的比例，算出相對於顏料100質量份的水溶性有機溶劑的殘留溶劑量。 The residual solvent is calculated by gas chromatography using a residual solvent amount of the water-soluble organic solvent of the present invention with respect to the solid content of the pigment composition, and calculating the ratio of the pigment in the solid component. The amount of residual solvent of the water-soluble organic solvent with respect to 100 parts by mass of the pigment.
以下示出氣相層析法的條件。 The conditions of the gas chromatography are shown below.
分離設備：島津製作所公司製造的GC2010 Separation equipment: GC2010 manufactured by Shimadzu Corporation
管柱：DM-5MS(30m×0.25mm×0.25μm膜(Film)，安捷倫科技(Agilent Technologies)) Column: DM-5MS (30m × 0.25mm × 0.25μm film (Film), Agilent Technologies)
載氣：氦氣(He) Carrier gas: helium (He)
壓力：120.0kPa Pressure: 120.0kPa
總流量：50.0ml/min Total flow: 50.0ml/min
管柱流量：1.77ml/min Column flow: 1.77ml/min
線速度：49.0cm/sec Line speed: 49.0cm/sec
沖洗(purge)流量：3.0ml/min Purge flow rate: 3.0ml/min
管柱溫度：於80℃下保持4分鐘後，以16分鐘升溫，於320℃下保持5分鐘 Column temperature: After holding at 80 ° C for 4 minutes, the temperature is raised in 16 minutes and kept at 320 ° C for 5 minutes.
注入模式：不分流模式(Split-less Mode) Injection mode: Split-less Mode
注入量：1μl Injection volume: 1μl
以下示出質量分析計的條件。 The conditions of the mass spectrometer are shown below.
測定設備：島津製作所公司製造的GCMS-GP2010 Measuring equipment: GCMS-GP2010 manufactured by Shimadzu Corporation
介面溫度：250℃ Interface temperature: 250 ° C
離子源溫度：200℃ Ion source temperature: 200 ° C
測定模式：掃描模式(Scan Mode) Measurement mode: Scan Mode
測定範圍：m/z=30~500 Measuring range: m/z=30~500
測定時間：5min~20min Measurement time: 5min~20min
事件時間(event time)：0.5sec Event time: 0.5sec
(試樣的製備方法)於50ml的量測瓶中準確秤量樣品0.1g，添加四氫呋喃而調整為50ml。其後，進行15分鐘超音波處理，利用0.20μm的膜濾器進行過濾，將濾液作為測定用試樣。再者，以下的實施例及比較例的殘留溶劑的測定亦是藉由所述方法來測定。 (Preparation method of sample) 0.1 g of the sample was accurately weighed in a 50 ml measuring bottle, and tetrahydrofuran was added thereto to adjust to 50 ml. Thereafter, ultrasonic treatment was performed for 15 minutes, and filtration was carried out using a 0.20 μm membrane filter, and the filtrate was used as a sample for measurement. Further, the measurement of the residual solvent in the following examples and comparative examples was also measured by the above method.
將實施例1-1~實施例1-66及比較例1-1~比較例1-66中所得的顏料組成物1~顏料組成物132的平均一次粒徑及殘留溶劑的結果示於表2A~表5B中。 The results of the average primary particle diameter and residual solvent of the pigment composition 1 to the pigment composition 132 obtained in Examples 1-1 to 1-66 and Comparative Examples 1-1 to 1-66 are shown in Table 2A. ~ Table 5B.
(顏料組成物133的製作)調配下述所示的化合物，添加直徑為1.2mm的氧化鋯珠100份，利用塗料調節器(paint conditioner)進行3小時分散，製作顏料組成物133。顏料組成物133中的相對於顏料100質量份的單乙酸甘油酯濃度為0.05%。 (Production of Pigment Composition 133) A compound shown below was prepared, and 100 parts of zirconia beads having a diameter of 1.2 mm were added, and dispersed by a paint conditioner for 3 hours to prepare a pigment composition 133. The concentration of monoacetin in 100 parts by mass of the pigment composition 133 was 0.05%.
．顏料組成物1：6.5份 . Pigment composition 1: 6.5 parts
．色素衍生物a：0.5份 . Pigment derivative a: 0.5 parts
．樹脂C：3.0份 . Resin C: 3.0 parts
．丙二醇單甲醚乙酸酯：40.0份 . Propylene glycol monomethyl ether acetate: 40.0 parts
(顏料組成物134~顏料組成物166的製作)除了變更為表6所示的調配組成以外，與實施例2-1同樣地進行操作，製作顏料組成物134~顏料組成物166。 (Production of Pigment Composition 134 to Pigment Composition 166) A pigment composition 134 to a pigment composition 166 were produced in the same manner as in Example 2-1 except that the composition shown in Table 6 was changed.
(顏料組成物167的製作)調配下述所示的化合物，於具備4cm的帶齒圓盤(toothed disc)的溶解器中，於80℃下以7,000rpm攪拌60分鐘，製作顏料組成物167。顏料組成物167中的相對於顏料100質量份的單乙酸甘油酯濃度為0.06%。 (Production of Pigment Composition 167) A compound shown below was prepared, and the mixture was stirred at 7,000 rpm at 80 ° C for 60 minutes in a dissolver equipped with a 4 cm toothed disc to prepare a pigment composition 167. The monoacetin concentration in the pigment composition 167 with respect to 100 parts by mass of the pigment was 0.06%.
．顏料組成物35：10.0份 . Pigment composition 35: 10.0 parts
．丙二醇單甲醚乙酸酯：40.0份 . Propylene glycol monomethyl ether acetate: 40.0 parts
(顏料組成物168~顏料組成物264的製作)除了變更為表7~表9所示的調配組成以外，與實施例2-18同樣地進行操作，製作顏料組成物168~顏料組成物264。如表所示，實施例2-18~實施例2-49及比較例2-18~比較例2-49為不添加色素衍生物及樹脂型分散劑的顏料組成物。另外，如表所示，實施例2-50~實施例2-66及比較例2-50~比較例2-66為不添加色素衍生物的顏料組成物。 (Pigment Composition 168 - Preparation of Pigment Composition 264) A pigment composition 168 to a pigment composition 264 were produced in the same manner as in Example 2-18 except that the composition shown in Tables 7 to 9 was changed. As shown in the table, Example 2-18 to Example 2-49 and Comparative Example 2-18 to Comparative Example 2-49 are pigment compositions in which no dye derivative or resin-type dispersant was added. Further, as shown in the table, Example 2-50 to Example 2-66 and Comparative Example 2-50 to Comparative Example 2-66 are pigment compositions in which no dye derivative was added.
為了評價本發明的顏料組成物的性能，使用B型黏度計(25℃)來測定所得的組成物的黏度，使用霧度計(光透射率為20%)來測定霧值，評價顏料組成物的性能。初始黏度及霧值是於分散後於室溫下放置1天後測定，經時黏度是於40℃下放置一週後進行測定。關於黏度穩定性，將初始黏度與經時黏度之差為±10%以內評價為○，超過±10%評價為×。將結果示於表6~表9中。 In order to evaluate the performance of the pigment composition of the present invention, the viscosity of the obtained composition was measured using a B-type viscometer (25 ° C), and the haze value was measured using a haze meter (light transmittance: 20%) to evaluate the pigment composition. Performance. The initial viscosity and the haze value were measured after being allowed to stand at room temperature for one day after dispersion, and the time-dependent viscosity was measured after leaving it at 40 ° C for one week. Regarding the viscosity stability, the difference between the initial viscosity and the time-dependent viscosity was evaluated as ○ within ±10%, and × was exceeded as ±10%. The results are shown in Tables 6 to 9.
由表6~表9的結果得知，本發明的實施例與比較例相比，均顯示出優異的黏度穩定性。另外得知，關於霧值，本發明的實施例的值亦較比較例更小而透明性優異。由該些結果表明：顏料組成物中的固體成分並未凝聚，具有良好的分散性。 From the results of Tables 6 to 9, the examples of the present invention showed excellent viscosity stability as compared with the comparative examples. Further, it was found that the values of the examples of the present invention were smaller than those of the comparative examples and excellent in transparency. From these results, it was revealed that the solid component in the pigment composition was not aggregated and had good dispersibility.
以下對各具體用途的實施例加以說明，但本發明的顏料組成物的用途不限定於以下用途。 Hereinafter, examples of each specific use will be described, but the use of the pigment composition of the present invention is not limited to the following uses.
繼而，對適於彩色濾光片用油墨的顏料組成物的製造例加以說明。再者，亦可較佳地用於彩色濾光片用油墨以外的用途。 Next, a production example of a pigment composition suitable for an ink for a color filter will be described. Further, it can also be preferably used for applications other than inks for color filters.
(顏料組成物265的製作)將偶氮系紅色顏料PR242(科萊恩(Clariant)公司製造的「諾瓦帕猩紅(Novoperm Scarlet)4RF」)90份、10份的色素衍生物a、氯化鈉1,000份及三乙酸甘油酯170份添加至不鏽鋼製1加侖捏合機(井上製作所公司製造)中，於70℃下混練10小時。將該混合物投入至水10,000份中，一面加熱至約40℃一面利用高速攪拌機攪拌約1小時而製成漿料狀，反覆進行過濾、水洗而去除氯化鈉及水溶性有機溶劑，於減壓下於40℃下乾燥而獲得顏料組成物265。 (Production of Pigment Composition 265) Azo-based red pigment PR242 ("Novoperm Scarlet 4RF" manufactured by Clariant Co., Ltd.) 90 parts, 10 parts of pigment derivative a, sodium chloride 1,000 parts and 170 parts of triacetin were added to a stainless steel 1 gallon kneader (manufactured by Inoue Co., Ltd.), and kneaded at 70 ° C for 10 hours. The mixture was poured into 10,000 parts of water, and heated to about 40° C., and stirred in a high-speed stirrer for about 1 hour to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and a water-soluble organic solvent. The pigment composition 265 was obtained by drying at 40 ° C.
(顏料組成物266~顏料組成物384的製作)除了變更為表10A~表12B所示的混練組成以外，與實施例3-1同樣地進行操 作，獲得顏料組成物266~顏料組成物384。其中，關於含有溶劑的樹脂溶液，適當地替換為作為混練溶劑的水溶性有機溶劑而使用，或使用在減壓下於80℃下經乾燥的固體樹脂，設定為表10A~表12B的組成。 (Production of Pigment Composition 266 to Pigment Composition 384) Operations were carried out in the same manner as in Example 3-1 except that the kneading composition shown in Tables 10A to 12B was changed. The pigment composition 266 to the pigment composition 384 were obtained. In addition, the resin solution containing a solvent is suitably used instead of the water-soluble organic solvent as a kneading solvent, or the solid resin dried at 80 degreeC under reduced pressure is set as the composition of Table 10A - Table 12B.
將實施例3-1~實施例3-66及比較例3-1~比較例3-60 中所得的顏料組成物265~顏料組成物384的平均一次粒徑及殘留溶劑的結果示於表10A~表12B中。 Example 3-1 to Example 3-66 and Comparative Example 3-1 to Comparative Example 3-60 The results of the average primary particle diameter and residual solvent of the pigment composition 265 to the pigment composition 384 obtained in the above are shown in Tables 10A to 12B.
(顏料組成物385的製作)調配下述所示的化合物，添加直徑為1.2mm的氧化鋯珠100份，利用塗料調節器進行3小時分散，製作顏料組成物385。顏料組成物385中的相對於顏料100質量份的三乙酸甘油酯濃度為0.25%。 (Production of Pigment Composition 385) A compound shown below was prepared, and 100 parts of zirconia beads having a diameter of 1.2 mm were added, and dispersed by a paint adjuster for 3 hours to prepare a pigment composition 385. The concentration of triacetin in the pigment composition 385 with respect to 100 parts by mass of the pigment was 0.25%.
．顏料組成物265：11.0份 . Pigment composition 265: 11.0 parts
．樹脂C：3.85份 . Resin C: 3.85 parts
．樹脂AF：7.15份 . Resin AF: 7.15 parts
．丙二醇單甲醚乙酸酯：78.0份 . Propylene glycol monomethyl ether acetate: 78.0 parts
[實施例4-2~實施例4-20、比較例4-1~比較例4-20](顏料組成物386~顏料組成物424的製作)除了變更為表13A、表13B所示的調配組成以外，與實施例4-1同樣地進行操作，製作顏料組成物386~顏料組成物424。 [Examples 4-2 to 4-20, Comparative Example 4-1 to Comparative Example 4-20] (Production of Pigment Composition 386 to Pigment Composition 424) were changed to those shown in Tables 13A and 13B. A pigment composition 386 to a pigment composition 424 were produced in the same manner as in Example 4-1 except for the composition.
(顏料組成物425的製作)調配下述所示的化合物，於具備4cm的帶齒圓盤的溶解器中，於70℃下以5000rpm進行60分鐘攪拌，製作顏料組成物425。顏料組成物425中的相對於顏料100質量份的三乙酸甘油酯濃度為0.28%。 (Production of Pigment Composition 425) A compound shown below was prepared, and the mixture was stirred at 5,000 rpm for 60 minutes at 70 ° C in a dissolver equipped with a 4 cm toothed disk to prepare a pigment composition 425. The concentration of triacetin in 100 parts by mass of the pigment composition 425 was 0.28%.
．顏料組成物305：22.0份 . Pigment composition 305: 22.0 parts
．丙二醇單甲醚乙酸酯：78.0份 . Propylene glycol monomethyl ether acetate: 78.0 parts
(顏料組成物426~顏料組成物504的製作)除了變更為表14~表15所示的調配組成以外，與實施例4-21同樣地進行操作，製作顏料組成物426~顏料組成物504。 (Pigment Composition 426 - Preparation of Pigment Composition 504) A pigment composition 426 to a pigment composition 504 were produced in the same manner as in Example 4-21 except that the composition shown in Tables 14 to 15 was changed.
(顏料組成物的評價)為了評價本發明的顏料組成物的性能，利用B型黏度計(25℃)來測定所得的組成物的黏度，利用霧度計(光透射率為20%)來測定霧度，藉由初始黏度及霧度來評價顏料組成物的性能。初始黏度及霧度是於分散後於室溫下放置1天後進行測定，經時黏度是於40℃下放置一週後進行測定。關於黏度穩定性，將初始黏度與經時黏度之差為±10%以內評價為○，超過±10%評價為×。將結果示於表13A~表15中。 (Evaluation of Pigment Composition) In order to evaluate the performance of the pigment composition of the present invention, the viscosity of the obtained composition was measured by a B-type viscometer (25 ° C), and it was measured by a haze meter (light transmittance: 20%). Haze, the properties of the pigment composition were evaluated by initial viscosity and haze. The initial viscosity and haze were measured after being allowed to stand at room temperature for one day after dispersion, and the viscosity was measured after standing at 40 ° C for one week. Regarding the viscosity stability, the difference between the initial viscosity and the time-dependent viscosity was evaluated as ○ within ±10%, and × was exceeded as ±10%. The results are shown in Tables 13A to 15.
由表13A~表15的結果得知，本發明的實施例與比較例相比，均顯示出優異的黏度穩定性。另外得知，關於霧值，本發明的實施例的值亦較比較例更小而透明性優異。這一情況表明：顏料組成物中的固體成分並未凝聚，具有良好的分散性。 From the results of Tables 13A to 15, the examples of the present invention showed excellent viscosity stability as compared with the comparative examples. Further, it was found that the values of the examples of the present invention were smaller than those of the comparative examples and excellent in transparency. This indicates that the solid component in the pigment composition is not agglomerated and has good dispersibility.
(顏料組成物505的製作)將下述組成的混合物攪拌混合以使之變均勻後，利用1μm的過濾器進行過濾，製作紅色的顏料組成物505。 (Preparation of Pigment Composition 505) A mixture of the following composition was stirred and mixed to make it uniform, and then filtered using a 1 μm filter to prepare a red pigment composition 505.
．顏料組成物385、顏料組成物387：51.0份 . Pigment composition 385, pigment composition 387: 51.0 parts
．樹脂AF溶液：1.0份 . Resin AF solution: 1.0 part
．活性能量線硬化性單體：4.0份 . Active energy ray hardening monomer: 4.0 parts
．活性能量線聚合性起始劑：3.4份 . Active energy ray polymerizable initiator: 3.4 parts
．增感劑：0.4份 . Sensitizer: 0.4 parts
．丙二醇單甲醚乙酸酯：40.2份 . Propylene glycol monomethyl ether acetate: 40.2 parts
(顏料組成物506~顏料組成物511、顏料組成物529~顏料組成物535、顏料組成物553~顏料組成物559、顏料組成物517~顏料組成物523、顏料組成物541~顏料組成物547、顏料組成物565~顏料組成物571的製作)除了變更為表16~表18所示的調配組成以外，與實施例5-1同樣地進行操作，製作紅色的組成顏料組成物506~顏料組成物511、顏料組成物529~顏料組成物535、顏料組成物553~顏料組成物559、顏料組成物517~顏料組成物523、顏料組成物541~顏料組成物547、顏料組成物565~顏料組成物571。 (Pigment Composition 506 to Pigment Composition 511, Pigment Composition 529 to Pigment Composition 535, Pigment Composition 553 to Pigment Composition 559, Pigment Composition 517 to Pigment Composition 523, Pigment Composition 541 to Pigment Composition 547 In the same manner as in Example 5-1 except that the composition of the pigment composition 565 to the pigment composition 571 was changed to the composition shown in Tables 16 to 18, a red component pigment composition 506 to a pigment composition was produced. 511, pigment composition 529 to pigment composition 535, pigment composition 553 to pigment composition 559, pigment composition 517 to pigment composition 523, pigment composition 541 to pigment composition 547, pigment composition 565 to pigment composition Matter 571.
(顏料組成物512的製作)將下述組成的混合物攪拌混合以使之變均勻後，利用1μm的過濾器進行過濾，製作綠色的顏料組成物512。 (Preparation of Pigment Composition 512) A mixture of the following composition was stirred and mixed to make it uniform, and then filtered using a 1 μm filter to prepare a green pigment composition 512.
．顏料組成物394、顏料組成物399：52.0份 . Pigment composition 394, pigment composition 399: 52.0 parts
．活性能量線硬化性單體：4.8份 . Active energy ray hardening monomer: 4.8 parts
(新中村化學公司製造的「NK酯(NK Ester)ATMPT」，三 羥甲基丙烷三丙烯酸酯) ("NK Ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd., III Hydroxymethylpropane triacrylate)
．活性能量線聚合性起始劑：2.8份 . Active energy ray polymerizable initiator: 2.8 parts
(巴斯夫(BASF)公司製造的「豔佳固(Irgacure)907」，2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮) (Irgacure 907, manufactured by BASF), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one)
．增感劑：0.2份 . Sensitizer: 0.2 parts
．丙二醇單甲醚乙酸酯：40.2份 . Propylene glycol monomethyl ether acetate: 40.2 parts
(顏料組成物513、顏料組成物514、顏料組成物536~顏料組成物538、顏料組成物560~顏料組成物562、顏料組成物524~顏料組成物526、顏料組成物548~顏料組成物550、顏料組成物572~顏料組成物574的製作)除了變更為表16~表18所示的調配組成以外，與實施例5-8同樣地進行操作，製作綠色的顏料組成物513、顏料組成物514、顏料組成物536~顏料組成物538、顏料組成物560~顏料組成物562、顏料組成物524~顏料組成物526、顏料組成物548~顏料組成物550、顏料組成物572~顏料組成物574。 (pigment composition 513, pigment composition 514, pigment composition 536 to pigment composition 538, pigment composition 560 to pigment composition 562, pigment composition 524 to pigment composition 526, pigment composition 548 to pigment composition 550 In the same manner as in Example 5-8, the green pigment composition 513 and the pigment composition were produced except that the composition of the pigment composition 572 to the pigment composition 574 was changed to the composition shown in Tables 16 to 18. 514, pigment composition 536 to pigment composition 538, pigment composition 560 to pigment composition 562, pigment composition 524 to pigment composition 526, pigment composition 548 to pigment composition 550, pigment composition 572 to pigment composition 574.
(顏料組成物515的製作)將下述組成的混合物攪拌混合以 使之變均勻後，利用1μm的過濾器進行過濾，製作藍色的顏料組成物515。 (Production of Pigment Composition 515) A mixture of the following composition was stirred and mixed to After making it uniform, it filtered by the 1 micrometer filter, and the blue pigment composition 515 was produced.
．顏料組成物401、顏料組成物404：42.0份 . Pigment composition 401, pigment composition 404: 42.0 parts
．樹脂AF溶液：10.0份 . Resin AF solution: 10.0 parts
．活性能量線硬化性單體：5.6份 . Active energy ray hardening monomer: 5.6 parts
．活性能量線聚合性起始劑：2.0份 . Active energy ray polymerizable initiator: 2.0 parts
(巴斯夫(BASF)公司製造的「豔佳固(Irgacure)907」」，2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮) (Irgacure 907" manufactured by BASF, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one)
．增感劑：0.2份 . Sensitizer: 0.2 parts
(保土谷化學工業公司製造的「EAB-F」，4,4'-雙(二乙基胺基)二苯甲酮) (EAB-F, manufactured by Hodogaya Chemical Industry Co., Ltd., 4,4'-bis(diethylamino)benzophenone)
．丙二醇單甲醚乙酸酯：40.2份 . Propylene glycol monomethyl ether acetate: 40.2 parts
(顏料組成物516、顏料組成物539、顏料組成物540、顏料組成物563、顏料組成物564、顏料組成物527、顏料組成物528、顏料組成物551、顏料組成物552、顏料組成物575、顏料組成物576的製作)除了變更為表16~表18所示的調配組成以外，與實施例5-11同樣地進行操作，製作藍色的顏料組成物516、顏料組 成物539、顏料組成物540、顏料組成物563、顏料組成物564、顏料組成物527、顏料組成物528、顏料組成物551、顏料組成物552、顏料組成物575、顏料組成物576。 (pigment composition 516, pigment composition 539, pigment composition 540, pigment composition 563, pigment composition 564, pigment composition 527, pigment composition 528, pigment composition 551, pigment composition 552, pigment composition 575 In the same manner as in Example 5-11 except that the composition of the pigment composition 576 was changed to the composition shown in Tables 16 to 18, a blue pigment composition 516 and a pigment group were produced. The product 539, the pigment composition 540, the pigment composition 563, the pigment composition 564, the pigment composition 527, the pigment composition 528, the pigment composition 551, the pigment composition 552, the pigment composition 575, and the pigment composition 576.
繼而，對塗佈有彩色濾光片用顏料組成物的基板的對比度的測定法進行說明。 Next, a method of measuring the contrast of a substrate on which a pigment composition for a color filter is applied will be described.
將塗佈有彩色濾光片用的顏料組成物的基板夾持於2片偏光板之間，自一個偏光板側使用液晶顯示器用背光單元照射光。自背光單元出射的光透過第1片偏光板而經偏光，繼而透過塗佈有彩色濾光片用顏料組成物的基板而到達第2片偏光板。若一對偏光板的透過軸彼此平行，則光透過第2片偏光板，於一對偏光板的透過軸彼此正交的情形時，光經第2片偏光板遮蔽。然而，經第1片偏光板偏光的光於透過塗佈有彩色濾光片用顏料組成物的基板時，若發生由顏料粒子所致的散射等而於偏光面的一部分上發生偏移，則於將一對偏光板的透過軸平行配置時透過第2片偏光板的光量減少，於將一對偏光板的透過軸正交配置時光的一部分透過第2片偏光板。以偏光板上的亮度的形式來測定該透過光，將偏光板的透過軸為平行配置的亮度、與偏光板的透過軸為正交配置的亮度之比作為對比度。 The substrate on which the pigment composition for a color filter is applied is sandwiched between two polarizing plates, and light is irradiated from a polarizing plate side using a backlight unit for a liquid crystal display. The light emitted from the backlight unit is polarized by the first polarizing plate, and then passes through the substrate on which the pigment composition for a color filter is applied, and reaches the second polarizing plate. When the transmission axes of the pair of polarizing plates are parallel to each other, light is transmitted through the second polarizing plates, and when the transmission axes of the pair of polarizing plates are orthogonal to each other, the light is shielded by the second polarizing plates. However, when the light which is polarized by the first polarizing plate is transmitted through the substrate on which the pigment composition for a color filter is applied, if a scattering due to the pigment particles occurs, and a part of the polarizing surface is shifted, When the transmission axes of the pair of polarizing plates are arranged in parallel, the amount of light transmitted through the second polarizing plates is reduced, and a part of the light is transmitted through the second polarizing plates when the transmission axes of the pair of polarizing plates are arranged orthogonally. The transmitted light was measured in the form of luminance on the polarizing plate, and the ratio of the luminance in which the transmission axes of the polarizing plates were arranged in parallel and the luminances arranged orthogonally to the transmission axis of the polarizing plate was used as the contrast.
對比度=(一對偏光板的透過軸平行時的出射光的亮度)/(一對偏光板的透過軸正交時的出射光的亮度) Contrast = (luminance of the emitted light when the transmission axes of the pair of polarizers are parallel) / (the brightness of the emitted light when the transmission axes of the pair of polarizers are orthogonal)
若因塗佈有彩色濾光片用顏料組成物的膜中的顏料引起散射，則平行時的亮度降低，且正交時的亮度增加，故對比度變低。 When the scattering is caused by the pigment in the film coated with the pigment composition for a color filter, the luminance in parallel is lowered, and the luminance in the orthogonal direction is increased, so that the contrast is lowered.
再者，亮度測定時使用色彩亮度計(拓普康(Topcon)公司製造的「BM-5A」)及偏光板(日東電工公司製造的「NPF-G1220DUN」)。測定時設定為2°視場的條件，為了遮蔽不需要的光，放置在測定部分上開有1cm見方的孔的黑色遮罩來進行測定。塗佈有彩色濾光片用顏料組成物的基板的厚度於實施例及比較例中均設定為一定。 Further, in the measurement of the brightness, a color luminance meter ("BM-5A" manufactured by Topcon Corporation) and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) were used. In the measurement, the condition of 2° field of view was set, and in order to shield unnecessary light, a black mask having a hole of 1 cm square on the measurement portion was placed and measured. The thickness of the substrate on which the pigment composition for a color filter was applied was set to be constant in both the examples and the comparative examples.
(對比度的測定樣品)使用旋轉塗佈機以500rpm、1000rpm、1500rpm的轉速將實施例及比較例中所得的彩色濾光片用顏料組成物塗佈於100mm×100mm、0.7mm厚的玻璃基板上，藉此獲得膜厚不同的3種塗佈基板。將塗佈有彩色濾光片用顏料組成物的基板於70℃下乾燥20分鐘後，使用超高壓水銀燈以累計光量150mJ進行紫外線曝光，於230℃下加熱1小時後，進行放置冷卻，測定對比度。繼而，使用顯微分光光度計(奧林巴斯(Olympus)光學公司製造的「OSP-SP100」)來測定塗膜於C光源下的色度(Y，x，y)。根據3組的對比度及色度測定結果，對塗佈有彩色濾光片用顏料組成物的基板分別使用近似法對藍色塗膜求出y=0.14時的對比度，對綠色塗膜求出y=0.60時的對比度，對紅色塗膜求出x=0.64時的對比度。 (Measurement sample of contrast) The color filter pigment composition obtained in the examples and the comparative examples was applied onto a glass substrate of 100 mm × 100 mm and 0.7 mm thickness by using a spin coater at 500 rpm, 1000 rpm, and 1500 rpm. Thereby, three kinds of coated substrates having different film thicknesses were obtained. The substrate coated with the pigment composition for a color filter was dried at 70 ° C for 20 minutes, and then exposed to ultraviolet light at an integrated light amount of 150 mJ using an ultrahigh pressure mercury lamp, and heated at 230 ° C for 1 hour, and then left to stand for cooling to measure contrast. . Then, the chromaticity (Y, x, y) of the coating film under a C light source was measured using a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.). According to the results of the contrast and chromaticity measurement of the three groups, the contrast of the y = 0.14 was obtained for the blue coating film on the substrate on which the pigment composition for a color filter was applied, and the green coating film was determined by y. Contrast at =0.60, and the contrast at x=0.64 was obtained for the red coating film.
確認到實施例5-1~實施例5-36中所得的彩色濾光片用顏料組成物與比較例5-1~比較例5-36中所得的彩色濾光片用顏料組成物相比較，分別具有更優異的對比度特性。 It was confirmed that the pigment compositions for color filters obtained in Examples 5-1 to 5-36 were compared with the pigment compositions for color filters obtained in Comparative Examples 5-1 to 5-36. Each has better contrast characteristics.
(彩色濾光片的製造例)使用本發明的紅色的顏料組成物530、綠色的顏料組成物537及藍色的顏料組成物540，藉由旋 轉塗佈以乾燥膜厚成為1.7μm的方式塗佈於基板上，加以乾燥。然後，經由以與塗膜非接觸的狀態設置的具有既定圖案的遮罩進行紫外線曝光，其後藉由噴霧來噴霧鹼顯影液，將未硬化部去除而形成所需的圖案後，於230℃下進行1小時加熱。對綠色、藍色亦重複進行同樣的操作，製造彩色濾光片，從而製作紅色-綠色-藍色(Red Green Blue，RGB)三色彩色濾光片。確認到所得的彩色濾光片的明度高，另外耐熱性優異。 (Production Example of Color Filter) The red pigment composition 530, the green pigment composition 537, and the blue pigment composition 540 of the present invention are used by spinning The transfer coating was applied to the substrate so that the dry film thickness was 1.7 μm, and dried. Then, ultraviolet exposure is performed through a mask having a predetermined pattern provided in a state of being non-contact with the coating film, and then the alkali developing solution is sprayed by spraying, and the uncured portion is removed to form a desired pattern, and then at 230 ° C. Heat for 1 hour. The same operation was repeated for green and blue, and a color filter was produced to produce a red-green-blue (Red Green Blue, RGB) three-color filter. It was confirmed that the obtained color filter has high brightness and is excellent in heat resistance.
(顏料組成物713的製作)將偶氮系紅色顏料PR242(科萊恩(Clariant)公司製造的「諾瓦帕猩紅(Novoperm Scarlet)4RF」)95份、5份的色素衍生物a、35份的樹脂B、65份的樹脂AF、氯化鈉1,000份及三乙酸甘油酯70份添加至不鏽鋼製1加侖捏合機(井上製作所公司製造)中，於70℃下混練10小時。將該混合物投入至水10,000份中，一面加熱至40℃±5℃一面利用高速攪拌機攪拌1小時而製成漿料狀，過濾後，利用40℃±5℃的水10,000份進行清洗。將濕濾餅(wet cake)投入至丙二醇單甲醚乙酸酯709份中，於25℃下混合攪拌1小時。將溶液中的水於40℃下減壓蒸餾去除，獲得固體成分濃度為22%的顏料組成物713。 (Production of Pigment Composition 713) 95 parts of azo-based red pigment PR242 (Novoperm Scarlet 4RF) manufactured by Clariant Co., Ltd., 5 parts of pigment derivative a, 35 parts Resin B, 65 parts of resin AF, 1,000 parts of sodium chloride, and 70 parts of triacetin were added to a stainless steel 1 gallon kneader (manufactured by Inoue Co., Ltd.), and kneaded at 70 ° C for 10 hours. The mixture was poured into 10,000 parts of water, and heated to 40 ° C ± 5 ° C while stirring in a high-speed mixer for 1 hour to prepare a slurry. After filtration, the mixture was washed with 10,000 parts of water at 40 ° C ± 5 ° C. A wet cake was placed in 709 parts of propylene glycol monomethyl ether acetate, and the mixture was stirred and mixed at 25 ° C for 1 hour. The water in the solution was distilled off under reduced pressure at 40 ° C to obtain a pigment composition 713 having a solid concentration of 22%.
(顏料組成物714~顏料組成物752的製作)除了變更為表 19A、表19B所示的混練組成以外，與實施例17-1同樣地進行操作，獲得顏料組成物714~顏料組成物752。其中，關於含有溶劑的樹脂溶液，適當地替換為作為混練溶劑的水溶性有機溶劑而使用，或使用在減壓下於80℃下經乾燥的固體樹脂，設定為表19A、表19B的組成。 (Production of Pigment Composition 714 to Pigment Composition 752) The pigment composition 714 to the pigment composition 752 were obtained in the same manner as in Example 17-1 except for the kneading composition shown in 19A and 19B. In addition, the resin solution containing a solvent is suitably used instead of the water-soluble organic solvent as a kneading solvent, or the solid resin dried at 80 degreeC under reduced pressure is set to the composition of Table 19A and Table 19B.
由表19A、表19B的結果得知，本發明的實施例與比較例相比，均顯示出優異的黏度穩定性。另外得知，關於霧值，本發明的實施例的值亦較比較例更小而透明性優異。這一情況表明：顏料組成物中的固體成分並未凝聚，具有良好的分散性。 From the results of Tables 19A and 19B, the examples of the present invention showed excellent viscosity stability as compared with the comparative examples. Further, it was found that the values of the examples of the present invention were smaller than those of the comparative examples and excellent in transparency. This indicates that the solid component in the pigment composition is not agglomerated and has good dispersibility.
本發明的顏料組成物可用於以如下用途為代表的各種用途中：塗料，以噴墨油墨、凹版/柔版油墨等為代表的各種油墨，塑膠用著色劑，電子方式顯影劑，印染，彩色碳粉(color toner)，彩色濾光片用顏料組成物，感光性顏料組成物，磁記錄媒體，積層體的硬塗用途。 The pigment composition of the present invention can be used in various applications typified by the following applications: paints, various inks represented by inkjet inks, gravure/flexographic inks, colorants for plastics, electronic developers, printing and dyeing, color A color toner, a pigment composition for a color filter, a photosensitive pigment composition, a magnetic recording medium, and a hard coat for a laminate.
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| TWI765572B (en) * | 2020-03-16 | 2022-05-21 | 財團法人工業技術研究院 | Pigment composite particle |
| TWI767076B (en) * | 2017-10-31 | 2022-06-11 | 日商山陽色素股份有限公司 | Blue pigment composition containing C.I. Pigment Blue 16, method for producing the same, and green coloring composition |
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| JP6631656B2 (en) * | 2018-05-28 | 2020-01-15 | 東洋インキＳｃホールディングス株式会社 | Inorganic oxide dispersion with high transparency |
| WO2021065643A1 (en) * | 2019-10-01 | 2021-04-08 | Dic株式会社 | Aqueous pigment dispersion, pigment kneaded product, and production method for aqueous pigment dispersion |
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| US11767431B2 (en) | 2016-01-08 | 2023-09-26 | Fujifilm Corporation | Coloring composition, method for producing coloring composition, color filter, pattern forming method, solid-state imaging device, and image display device |
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