TWI519612B - Pigment composition and color filter - Google Patents
Pigment composition and color filter Download PDFInfo
- Publication number
- TWI519612B TWI519612B TW102144768A TW102144768A TWI519612B TW I519612 B TWI519612 B TW I519612B TW 102144768 A TW102144768 A TW 102144768A TW 102144768 A TW102144768 A TW 102144768A TW I519612 B TWI519612 B TW I519612B
- Authority
- TW
- Taiwan
- Prior art keywords
- pigment
- group
- resin
- meth
- ether
- Prior art date
Links
Classifications
-
- 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
- C09B67/0085—Non common dispersing agents
- C09B67/009—Non common dispersing agents polymeric dispersing agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
本發明係關於一種分散性、流動性、保存安定性及亮度優異的顏料組成物。 The present invention relates to a pigment composition excellent in dispersibility, fluidity, storage stability, and brightness.
一般,製造顏料組成物時,已知很難使顏料安定地以高濃度分散,對於製造步驟、製品本身會引起各種之問題。 In general, when a pigment composition is produced, it is known that it is difficult to stably disperse the pigment at a high concentration, which causes various problems in the production steps and the product itself.
例如,含有含細微粒子所構成的顏料之顏料組成物,往往顯示高黏度,不僅從製品的分散機之取出或傳送變困難,於惡劣時,保存中引起凝膠化,甚至變得使用困難。再者,關於顏料組成物的顯色物的表面,會產生光澤降低、流平不良等的不良狀態。又,混合各種的顏料而使用時,有時因凝集造成的色分離、或因沈澱等的現象,於顯色物出現色不均勻、或顯著的著色力之降低。 For example, a pigment composition containing a pigment composed of fine particles tends to exhibit high viscosity, which is difficult to remove or transport from a disperser of a product, and causes gelation during storage and even difficulty in use. Further, regarding the surface of the coloring matter of the pigment composition, a poor state such as a decrease in gloss and a poor leveling property may occur. Further, when various pigments are used in combination, color separation due to aggregation or precipitation or the like may cause color unevenness in the color former or a significant decrease in coloring power.
因此,一般為了保持良好的分散狀態,利用分散劑。分散劑一併具有吸附於顏料的部位、以及對作為分散介質的溶劑之親和性高的部位之構造,以該2種功能部位的均衡,決定分散劑的性能。分散劑係配合被分散物的顏料之表面狀態,可使用各種分散劑,但於具有偏鹼 性的表面之顏料,一般係使用具有進行靜電吸附的酸性官能基之分散劑。此時,酸性官能基成為顏料的吸附部位。具有羧酸作為酸性官能基之分散劑,例如記載於專利文獻1、專利文獻2、專利文獻3、專利文獻4等。 Therefore, in general, a dispersant is used in order to maintain a good dispersion state. The dispersant has a structure in which a portion adsorbed to the pigment and a portion having a high affinity for a solvent as a dispersion medium, and the performance of the dispersant is determined by the balance of the two functional sites. The dispersant is used in combination with the surface state of the pigment of the dispersion, and various dispersants can be used, but with a partial alkali The pigment of the surface is generally a dispersing agent having an acidic functional group for electrostatic adsorption. At this time, the acidic functional group becomes an adsorption site of the pigment. A dispersing agent having a carboxylic acid as an acidic functional group is described in, for example, Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4.
但是,另一方面具有酸性官能基之分散劑,對於具有酸性表面的顏料,大多無效。因此,對於具有酸性表面的顏料,係使用鹼性之分散劑,該鹼性分散劑的構造係被控制為如具有嵌段型構造或梳型構造的構造。但是,於嵌段型之時,於其製造必須使用例如活性自由基聚合等的複雜聚合法(參考專利文獻5)。又,於梳型之時,係有:使具有羧基、或丙烯醯基等的官能基之成為梳子齒部分,朝具有1級及/或2級胺的聚胺化合物接枝化,並形成殘留的1級及/或2級胺吸附於顏料表面的官能基之方法(參考專利文獻6、7),使1級及/或2級胺具有反應性高的活性氫,而會有隨顏料的種類而改變化學構造而使色相變化的情形,故不佳。而且,鹼性分散劑係因包含鹼性度高的胺部位,故樹脂會受熱而黃變。因而降低彩色濾光片的亮度。 However, on the other hand, a dispersing agent having an acidic functional group is mostly ineffective for a pigment having an acidic surface. Therefore, for a pigment having an acidic surface, a basic dispersant is used, and the structure of the alkaline dispersant is controlled to have a configuration such as a block type configuration or a comb type configuration. However, in the case of a block type, a complicated polymerization method such as living radical polymerization or the like must be used for its production (refer to Patent Document 5). Further, in the case of a comb type, a functional group having a carboxyl group or an acryloyl group is used as a comb tooth portion, and a polyamine compound having a primary and/or secondary amine is grafted to form a residue. The method of adsorbing a functional group on the surface of the pigment by the amine of the first and/or second order (refer to Patent Documents 6 and 7), so that the amine of the first-order and/or the second-order amine has a highly reactive active hydrogen, and there is a pigment-containing It is not preferable because the chemical structure is changed in kind and the hue is changed. Further, since the alkaline dispersant contains an amine moiety having a high basicity, the resin is heated and yellowed. Thus, the brightness of the color filter is lowered.
又,亦已提出不使用構造被控制的分散劑而併用具有酸性官能基的分散劑以及構造不被控制的鹼性樹脂,可良好地保持顏料的分散狀態之方法(參考專利文獻8、9)。但是,此處記載的鹼性樹脂,係於一般塗料的用途、平版印墨的用途、凹版印墨的用途等顏料粒徑較大時,雖可充分發揮效果,但對於噴墨印墨的用途、彩色濾光片印 墨的用途等更細微的顏料,係流動性、保存安定性不足。 In addition, it has been proposed to use a dispersant having a structurally controlled dispersant and a basic resin having an uncontrolled structure to maintain the dispersed state of the pigment well (refer to Patent Documents 8 and 9). . However, the basic resin described herein is sufficient for the effect of inkjet inks when the pigment particle size is large when the pigment particle size is large, such as the use of a general coating material, the use of a lithographic ink, or the use of a gravure ink. Color filter Finer pigments such as the use of ink are insufficient in fluidity and storage stability.
就彩色濾光片的用途而言,已提出使用如上述的專利文獻8、9記載的分離型分散劑,且分散性、流動性、保存安定性優異的顏料組成物(參考專利文獻10)。但是,此處記載的含有3級胺基的鹼性樹脂,與1級或2級胺比較,鹼性度低者之胺價高,有亮度降低的問題,無法達成近年要求昇提的高亮度彩色濾光片。 In the use of the color filter, a pigment composition having excellent dispersibility, fluidity, and storage stability is disclosed in the above-described Patent Document Nos. 8 and 9 (refer to Patent Document 10). However, the basic resin containing a tertiary amine group described herein has a higher amine value than a primary or secondary amine, and has a problem of lowering the brightness, and cannot achieve a high brightness which has been demanded in recent years. Color filter.
又,已提出使用來自具有脂環式3級胺基之受阻胺骨架之乙烯性不飽和單體的聚合物之彩色濾光片用著色組成物(參考專利文獻11)。但是,因單獨使用來自受阻胺骨架的樹脂,故結果分散性低,經時安定性低。而且,沒有記載關於併用具有芳香族羧基的分散劑。 Further, a coloring composition for a color filter using a polymer derived from an ethylenically unsaturated monomer having a hindered amine skeleton of an alicyclic tertiary amine group has been proposed (refer to Patent Document 11). However, since the resin derived from the hindered amine skeleton is used alone, the dispersibility is low and the stability with time is low. Further, there is no description about the use of a dispersing agent having an aromatic carboxyl group in combination.
專利文獻1:特開昭61-61623號公報 Patent Document 1: JP-A-61-61623
專利文獻2:特開平1-141968號公報 Patent Document 2: Japanese Patent Publication No. 1-141968
專利文獻3:特開平2-219866號公報 Patent Document 3: JP-A-2-219866
專利文獻4:特開平11-439842號公報 Patent Document 4: Japanese Laid-Open Patent Publication No. Hei 11-439842
專利文獻5:特表2002-534542號公報 Patent Document 5: Japanese Patent Publication No. 2002-534542
專利文獻6:特開平08-038875號公報 Patent Document 6: Japanese Patent Publication No. 08-038875
專利文獻7:特開平08-143813號公報 Patent Document 7: Japanese Patent Publication No. 08-143813
專利文獻8:特開平5-9405號公報 Patent Document 8: Japanese Patent Publication No. 5-9405
專利文獻9:特開平10-338835號公報 Patent Document 9: Japanese Laid-Open Patent Publication No. Hei 10-338835
專利文獻10:特開2009-185277號公報 Patent Document 10: JP-A-2009-185277
專利文獻11:特開2010-54808號公報 Patent Document 11: JP-A-2010-54808
本發明之目的在於提供一種顏料組成物,對於塗料、平版印墨及凹版印墨等的顏料粒徑較大的用途當然不用說,即使對於噴墨印墨、彩色濾光片印墨等更細微的顏料粒徑的用途,亦可發揮分散性、流動性、保存安定性、密著性及亮度優異的性能。 It is an object of the present invention to provide a pigment composition which is of course used for coatings, lithographic inks and gravure inks, and the like, even if it is finer for inkjet inks, color filter inks, and the like. The use of the pigment particle size also exhibits excellent dispersibility, fluidity, storage stability, adhesion, and brightness.
本發明係關於一種顏料組成物,其特徵為包含顏料、具有芳香族羧基之樹脂型分散劑(A)以及具有哌啶基(piperidyl)骨架之乙烯基系樹脂型分散劑(B)而成。 The present invention relates to a pigment composition comprising a pigment, a resin type dispersant (A) having an aromatic carboxyl group, and a vinyl resin type dispersant (B) having a piperidyl skeleton.
而且,本發明係關於前述顏料組成物,其中具有芳香族羧基之樹脂型分散劑(A)為使具有羥基的聚合物(C)與芳香族三羧酸酐(D1)及/或芳香族四羧酸二酐(D2)反應而成的樹脂型分散劑。 Furthermore, the present invention relates to the above pigment composition, wherein the resin type dispersant (A) having an aromatic carboxyl group is a polymer (C) having a hydroxyl group and an aromatic tricarboxylic anhydride (D1) and/or an aromatic tetracarboxylic acid. A resin type dispersant obtained by reacting acid dianhydride (D2).
而且,本發明係關於前述顏料組成物,其中顏料的胺吸附能為50~700微莫耳/克(μmol/g)。 Further, the present invention relates to a pigment composition, wherein the pigment is capable of adsorbing the amine of 50 to 700 micromolar / g (μ mol / g).
而且,本發明係關於前述顏料組成物,其中具有羥基的聚合物(C)為於單末端具有羥基之聚合物(C1)。 Moreover, the present invention relates to the aforementioned pigment composition, wherein the polymer (C) having a hydroxyl group is a polymer (C1) having a hydroxyl group at a single terminal.
而且,本發明係關於前述顏料組成物,其中具有羥基的聚合物(C)為於側鏈具有羥基之聚合物(C2)。 Moreover, the present invention relates to the aforementioned pigment composition, wherein the polymer (C) having a hydroxyl group is a polymer (C2) having a hydroxyl group in a side chain.
而且,本發明係關於前述顏料組成物,其中於單末端具有羥基的聚合物(C1)為於單末端具有2個羥基之聚合物(C3)。 Moreover, the present invention relates to the aforementioned pigment composition, wherein the polymer (C1) having a hydroxyl group at a single terminal is a polymer (C3) having two hydroxyl groups at a single terminal.
而且,本發明係關於前述顏料組成物,其中具有哌啶基骨架之乙烯基系樹脂型分散劑(B)的胺價為50~350mgKOH/g。 Furthermore, the present invention relates to the above pigment composition, wherein the vinyl resin type dispersant (B) having a piperidinyl skeleton has an amine value of 50 to 350 mgKOH/g.
而且,本發明係關於前述顏料組成物,其中顏料為鹵化鋅酞菁(phthalocyanine)顏料。 Moreover, the present invention relates to the aforementioned pigment composition, wherein the pigment is a zinc phthalocyanine pigment.
而且,本發明係關於前述顏料組成物,其中更含有光聚合性單體及/或光聚合起始劑。 Moreover, the present invention relates to the aforementioned pigment composition, which further contains a photopolymerizable monomer and/or a photopolymerization initiator.
再者,本發明係關於彩色濾光片,其特徵為於基板上,具備由前述顏料組成物所形成之濾光片段。 Furthermore, the present invention relates to a color filter characterized in that a filter segment formed of the pigment composition is provided on a substrate.
若依本發明,藉由於分散之顏料使用具有芳香族羧基之樹脂型分散劑(A)以及具有哌啶基骨架之乙烯基系樹脂型分散劑(B),可提供一種分散性、流動性與保存安定性、以及密著性與亮度兼備的顏料組成物,以及使用其之亮度優異的彩色濾光片。 According to the present invention, by using a resin-type dispersant (A) having an aromatic carboxyl group and a vinyl-based resin type dispersant (B) having a piperidinyl skeleton, a dispersibility, fluidity, and A pigment composition having both stability and adhesion and brightness, and a color filter excellent in brightness using the same are stored.
首先,說明有關本發明的顏料組成物的各構成成分。 First, each constituent component of the pigment composition of the present invention will be described.
再者,於本案中,係表記為「(甲基)丙烯醯 基」、「(甲基)丙烯酸基」、「(甲基)丙烯酸」、「(甲基)丙烯酸酯」及「(甲基)丙烯醯氧基」之時,只要無特別說明,分別表示為「丙烯醯基及/或甲基丙烯醯基」、「丙烯酸基及/或甲基丙烯酸基」、「丙烯酸及/或甲基丙烯酸」、「丙烯酸酯及/或甲基丙烯酸酯」及「丙烯醯氧基及/或甲基丙烯醯氧基」。 Furthermore, in this case, the note is "(meth) acrylonitrile. When "(meth)acrylic acid group", "(meth)acrylic acid", "(meth)acrylic acid ester", and "(meth)acryloxyloxy group", unless otherwise specified, "Acrylhydrazine and/or methacrylic acid", "acrylic and/or methacrylic", "acrylic and/or methacrylic", "acrylate and/or methacrylate" and "propylene" Alkoxy and/or methacryloxycarbonyl.
〈顏料〉 <pigment>
本發明的顏料組成物,係包含顏料、具有芳香族羧基之樹脂型分散劑(A)以及具有哌啶基骨架之乙烯基系樹脂型分散劑(B),該具有哌啶基骨架之乙烯基系樹脂型分散劑(B)係吸附於顏料的表面,即使具有中性~酸性的表面之顏料,亦可使其表面鹼性化。另一方面,具有芳香族羧基之樹脂型分散劑(A),係藉由吸附於表面的具有哌啶基骨架之乙烯基系樹脂型分散劑(B)之剩餘的胺基、與芳香族羧基進行靜電相互作用,又同時藉由存在於具有芳香族羧基之樹脂型分散劑(A)的聚合物部與分散介質之溶劑親和,可使顏料安定地存在於分散介質中。 The pigment composition of the present invention comprises a pigment, a resin type dispersant (A) having an aromatic carboxyl group, and a vinyl resin type dispersant (B) having a piperidinyl skeleton, the vinyl group having a piperidinyl skeleton The resin-type dispersant (B) is adsorbed on the surface of the pigment, and the surface of the resin can be made alkaline even if it has a neutral-acidic surface. On the other hand, the resin-type dispersant (A) having an aromatic carboxyl group is the remaining amine group and aromatic carboxyl group of the vinyl-based resin type dispersant (B) having a piperidinyl skeleton adsorbed on the surface. The electrostatic interaction is carried out, and at the same time, by the affinity of the polymer portion present in the resin-type dispersant (A) having an aromatic carboxyl group and the solvent of the dispersion medium, the pigment can be stably present in the dispersion medium.
本發明可使用的紅色顏料,可舉例如C.I.(色指數)顏料紅1、2、3、4、5、6、7、8、9、10、14、17、22、23、31、38、41、48、48:1、48:2、48:3、48:4、49、49:1、49:2、52、53、57、57:1、81、81:1、81:2、81:3、81:4、83、88、90、97、105、112、119、122、123、144、146、149、150、155、166、168、169、170、171、172、175、176、177、178、179、184、185、187、188、 190、200、202、206、207、208、209、210、216、220、221、224、226、238、242、246、254、255、264、270、272、273、274、276、277、278、279、280、281、282、283、284、285、286、287、或日本專利特表2011-523433號公報記載之二酮吡咯並吡咯(Diketopyrrolopyrrole)顏料等,但未特別限制於該等。而且,亦可使用氧雜蒽(xanthene)系、偶氮系、雙偶氮系、蒽醌系等的紅色染料。具體地,可舉例如C.I.酸性紅52、87、92、289、338等的氧雜蒽系酸性染料的造鹽化合物等。 The red pigment which can be used in the present invention may, for example, be CI (color index) pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52, 53, 57, 57:1, 81, 81:1, 81:2 81:3, 81:4, 83, 88, 90, 97, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 221, 224, 226, 238, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, or the diketopyrrolopyrrole pigment described in Japanese Patent Laid-Open Publication No. 2011-523433, but is not particularly limited to these. . Further, a red dye such as xanthene, azo, disazo or fluorene may also be used. Specific examples thereof include a salt-forming compound of a xanthene-based acid dye such as C.I. Acid Red 52, 87, 92, 289, and 338.
本發明可使用的橘色顏料,可舉例如C.I.顏料橘13、36、37、38、43、51、55、59、61、64、71、73或74等,但未特別限制於該等。 The orange pigment which can be used in the present invention may, for example, be C.I. Pigment Orange 13, 13, 37, 38, 43, 51, 55, 59, 61, 64, 71, 73 or 74, but is not particularly limited thereto.
本發明可使用的黃色顏料,可舉例如C.I.顏料黃1、2、3、4、5、6、10、11、12、13、14、15、16、17、18、20、24、31、32、34、35、35:1、36、36:1、37、37:1、40、42、43、53、55、60、61、62、63、65、73、74、77、81、83、86、93、94、95、97、98、100、101、104、106、108、109、110、113、114、115、116、117、118、119、120、123、125、126、127、128、129、137、138、139、147、150、151、152、153、154、155、156、161、162、164、166、167、168、169、170、171、172、173、174、175、176、177、179、180、181、182、185、187、188、193、194、198、199、213、214、218、219、220或221等,但未特別限制於該等。而且,亦可使用喹啉系、偶氮系、雙偶氮系、次甲基系等 的黃色染料。 The yellow pigment which can be used in the present invention may, for example, be CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127,128,129,137,138,139,147,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221, etc., but is not particularly limited to such . Further, a quinoline system, an azo system, a disazo system, a methine group or the like can also be used. Yellow dye.
本發明可使用的綠色顏料,可舉例如C.I.顏料綠7、10、36、37、58、日本公開專利特開2008-19383號公報、特開2007-320986號公報、特開2004-70342號公報記載的鋅酞菁顏料等,但未特別限制於該等。 The green pigment which can be used in the present invention, for example, CI Pigment Green 7, 10, 36, 37, and 58, Japanese Laid-Open Patent Publication No. 2008-19383, JP-A-2007-320986, and JP-A-2004-70342 The zinc phthalocyanine pigment or the like described is not particularly limited to these.
本發明可使用的藍色顏料,可舉例如C.I.顏料藍1、1:2、9、14、15、15:1、15:2、15:3、15:4、15:6、16、22、60、64、日本公開專利特開2004-333817號公報、日本專利第4893859號公報記載的鋁酞菁顏料等,但未特別限制於該等。 The blue pigment which can be used in the present invention may, for example, be CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22 The aluminum phthalocyanine pigments described in Japanese Patent Publication No. 2004-333817 and Japanese Patent No. 4893859 are not particularly limited.
本發明可使用的紫色顏料,可舉例如C.I.顏料紫1、1:1、2、2:2、3、3:1、3:3、5、5:1、14、15、16、19、23、27、29、30、31、32、37、39、40、42、44、47、49、50等,但未特別限制於該等。 The purple pigment which can be used in the present invention may, for example, be CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 27, 29, 30, 31, 32, 37, 39, 40, 42, 44, 47, 49, 50, etc., but are not particularly limited to these.
本發明可使用的較佳的顏料,可舉例如二酮吡咯並吡咯系有機顏料、萘酚系有機顏料、蒽醌系有機顏料、酞菁系有機顏料、喹酞酮(quinophthalone)系有機顏料。 Preferred pigments which can be used in the present invention include, for example, a diketopyrrolopyrrole-based organic pigment, a naphthol-based organic pigment, an anthraquinone-based organic pigment, a phthalocyanine-based organic pigment, and a quinophthalone-based organic pigment.
二酮吡咯並吡咯系有機顏料係紅~橘色的顏料,具有優異的耐光性、耐熱性。二酮吡咯並吡咯系有機顏料的具體例,以色指數號碼表示時,可舉例如C.I.顏料紅254、255、264或272、或者C.I.顏料橘71、73或81等。而且,較宜使用日本專利特表2011-523433號公報記載之溴化二酮吡咯並吡咯顏料。 The diketopyrrolopyrrole type organic pigment is a red-orange pigment having excellent light resistance and heat resistance. Specific examples of the diketopyrrolopyrrole-based organic pigment, when represented by a color index number, may, for example, be C.I. Pigment Red 254, 255, 264 or 272, or C.I. Pigment Orange 71, 73 or 81, or the like. Further, the brominated diketopyrrolopyrrole pigment described in JP-A-2011-523433 is preferably used.
萘酚偶氮系有機顏料係紅色的有機顏料,具有優異的耐光性、耐熱性。萘酚偶氮系有機顏料的具體例,以色指數號碼表示時,可舉例如C.I.顏料紅30、112、114、119、150、163、170、176、183、187、188、208、253、268、269等。 The naphthol azo organic pigment is a red organic pigment having excellent light resistance and heat resistance. Specific examples of the naphthol azo organic pigments, which are represented by color index numbers, may be, for example, CI Pigment Red 30, 112, 114, 119, 150, 163, 170, 176, 183, 187, 188, 208, 253, 268, 269, etc.
蒽醌系有機顏料係紅色的有機顏料,具有優異的耐光性、耐熱性。蒽醌系有機顏料的具體例,以色指數號碼表示時,可舉例如C.I.顏料紅177等。 The lanthanide organic pigment is a red organic pigment having excellent light resistance and heat resistance. Specific examples of the lanthanoid organic pigments, which are represented by color index numbers, may be, for example, C.I. Pigment Red 177 or the like.
酞菁系有機顏料係藍色或綠色的有機顏料,具有優異的耐光性、耐熱性。藍色用酞菁系有機顏料的具體例,以色指數號碼表示時,可舉例如C.I.顏料藍15:1、15:2、15:3、15:4、15:5、15:6、16或17等,綠色用酞菁系有機顏料的具體例,以色指數號碼表示時,可舉例如C.I.顏料綠7、36或58等。而且,亦可較宜使用日本專利第4893859號公報等記載的鋁酞菁顏料。 The phthalocyanine-based organic pigment is a blue or green organic pigment having excellent light resistance and heat resistance. Specific examples of the blue phthalocyanine-based organic pigment, when represented by a color index number, may be, for example, CI Pigment Blue 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16 Or a specific example of the green phthalocyanine-based organic pigment, such as 17 or the like, may be, for example, CI Pigment Green 7, 36 or 58. Further, an aluminum phthalocyanine pigment described in Japanese Patent No. 4893859 or the like can be preferably used.
〈染料〉 <dye>
本發明的顏料組成物係可併用染料,使用來作為著色組成物。染料可舉例如偶氮系染料、偶氮金屬錯合物系染料、蒽醌系染料、靛藍(indigo)系染料、硫靛藍系染料、酞菁系染料、次甲基系染料、二芳基甲烷系染料、三芳基甲烷系染料、氧雜蒽系染料、噻嗪(thiazine)系染料、陽離子系染料、花青系染料、硝基系染料、喹啉系染料、萘醌系染料、噁嗪(oxazine)系染料、苝(perylene)系染料、二酮吡咯並吡咯系染料、喹吖啶酮系染料、苯並芘二酮 (anthanthrone)系染料、異吲哚啉酮系染料、異吲哚啉系染料、陰丹酮(indanthrone)系染料、香豆素系染料、喹吖啶酮系染料、皮蒽酮(pyanthrone)系染料、黃士酮(flavanthrone)系染料、紫環酮(perinone)系染料等,但不限於該等。 The pigment composition of the present invention can be used in combination as a coloring composition. Examples of the dye include an azo dye, an azo metal complex dye, an anthraquinone dye, an indigo dye, a thioblue dye, a phthalocyanine dye, a methine dye, and a diarylmethane. Dyes, triarylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes, oxazines Oxazine) dye, perylene dye, diketopyrrolopyrrole dye, quinacridone dye, benzoindoledione (anthanthrone) dye, isoindolinone dye, isoporphyrin dye, indanthrone dye, coumarin dye, quinacridone dye, pyanthrone Dyes, flavanthrone-based dyes, perinone-based dyes, and the like, but are not limited thereto.
可使用於本發明的顏料組成物之顏料係可舉例如使用於印墨等的各種顏料。有機顏料係可舉例如可溶性偶氮顏料、不溶性偶氮顏料、酞菁顏料、鹵化酞菁顏料、偶氮次甲基顏料、喹吖啶酮顏料、異吲哚啉酮顏料、異吲哚啉顏料、苝顏料、紫環酮顏料、二噁嗪顏料、蒽醌顏料、二蒽醌基顏料、蒽嘧啶顏料、苯並芘二酮顏料、陰丹士林顏料、黃士酮顏料、皮蒽酮顏料、二酮吡咯並吡咯顏料等。 The pigment which can be used in the pigment composition of the present invention is, for example, various pigments used in inks and the like. The organic pigment may, for example, be a soluble azo pigment, an insoluble azo pigment, a phthalocyanine pigment, a halogenated phthalocyanine pigment, an azomethine pigment, a quinacridone pigment, an isoindolinone pigment, an isoindoline pigment. , anthraquinone pigment, benzalkonium pigment, dioxazine pigment, anthraquinone pigment, diterpene based pigment, pyrimidine pigment, benzoindoledione pigment, indanthrene pigment, yellow ketone pigment, dermatone pigment , diketopyrrolopyrrole pigments, and the like.
又,於本發明的顏料組成物,亦可使用二氧化鈦、氧化鐵、五氧化二銻、氧化鋅、二氧化矽等的金屬氧化物、硫化鎘、碳酸鈣、碳酸鋇、硫酸鋇、黏土、滑石、鉻黃、碳黑等的無機顏料。 Further, in the pigment composition of the present invention, a metal oxide such as titanium oxide, iron oxide, antimony pentoxide, zinc oxide or cerium oxide, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, or talc may be used. Inorganic pigments such as chrome yellow and carbon black.
本發明的顏料組成物,不限於前述例示的顏料,只要為細微粉狀者,皆可使用,特別是使本發明的顏料組成物在彩色濾光片的用途展開時,使用進行鹽磨(salt milling)處理,進行細微化者較佳。 The pigment composition of the present invention is not limited to the above-exemplified pigments, and may be used as long as it is a fine powder. In particular, when the pigment composition of the present invention is used in the development of a color filter, salt milling is used (salt It is better to process and fine-tune.
所謂鹽磨處理係指使顏料、水溶性無機鹽及水溶性有機溶劑的混合物,利用揉合機、2根輥磨機、3根輥磨機、球磨機、磨碎機、砂磨機等混練機,一邊加熱一邊機械混練後,藉由水洗,除去水溶性無機鹽及水溶性 有機溶劑之處理。認為水溶性無機鹽係作為粉碎助劑的作用者,於鹽磨時,利用無機鹽的硬度高而粉碎顏料,藉此產生活性面,引起結晶成長。因此,混練時,係同時產生顏料的粉碎以及結晶成長,藉混練條件所得之顏料的一次粒徑相異。 The salt milling treatment refers to a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent, using a kneading machine, two roll mills, three roll mills, a ball mill, an attritor, a sand mill, and the like. After mechanical mixing by heating, water-soluble inorganic salts and water-soluble are removed by washing with water. Treatment of organic solvents. It is considered that the water-soluble inorganic salt acts as a pulverization aid, and when the salt is ground, the inorganic salt has a high hardness and the pigment is pulverized, whereby an active surface is generated to cause crystal growth. Therefore, at the time of kneading, the pulverization of the pigment and the growth of the crystal are simultaneously caused, and the primary particle diameters of the pigments obtained by the kneading conditions are different.
為藉加熱促進結晶成長,以加熱溫度為40~150℃較佳。於加熱溫度未達40℃時,無法充分產生結晶成長,顏料粒子的形狀接近無固定形態,故不佳。另一方面,加熱溫度超過150℃時,結晶成長太過度,顏料的一次粒徑變大,故不適宜作為彩色濾光片用著色組成物的著色材料。又,鹽磨處理的混練時間,從鹽磨處理顏料的一次粒徑的粒度分佈與鹽磨處理所需的費用之平衡的點,以2~24小時較佳。 In order to promote crystal growth by heating, it is preferred to have a heating temperature of 40 to 150 °C. When the heating temperature is less than 40 ° C, crystal growth cannot be sufficiently caused, and the shape of the pigment particles is close to a non-fixed form, which is not preferable. On the other hand, when the heating temperature exceeds 150 ° C, the crystal growth is too excessive, and the primary particle diameter of the pigment becomes large, so that it is not suitable as a coloring material for a coloring composition for a color filter. Further, the kneading time of the salt milling treatment is preferably from 2 to 24 hours from the point of balance between the particle size distribution of the primary particle diameter of the salt-treated pigment and the cost required for the salt milling treatment.
藉由鹽磨處理顏料時的條件最佳化,一次粒徑非常細微,又分佈的寬度窄,可得到具有陡峭的粒度分佈之顏料。 The conditions for the treatment of the pigment by salt milling are optimized, the primary particle diameter is very fine, and the width of the distribution is narrow, and a pigment having a steep particle size distribution can be obtained.
使用於本發明的顏料組成物之顏料藉由TEM(穿透式電子顯微鏡)所求得之一次平均粒徑係以2~100nm的範圍較佳。若比2nm小,有時分散變困難,又若比100nm大,有時對比降低。特別佳的範圍為5~20nm的範圍。 The primary average particle diameter of the pigment used in the pigment composition of the present invention by TEM (transmission electron microscope) is preferably in the range of 2 to 100 nm. If it is smaller than 2 nm, the dispersion may become difficult, and if it is larger than 100 nm, the contrast may be lowered. A particularly preferred range is from 5 to 20 nm.
又,鹽磨處理所使用的水溶性無機鹽,係可使用氯化鈉、氯化鋇、氯化鉀及硫酸鈉等,但從價格的觀點,以使用氯化鈉(食鹽)較佳。水溶性無機鹽,從處理 效率及生產效率之兩方面,以顏料的全部量作為基準,以使用50~2000質量%較佳,以使用300~1000質量%最佳。 Further, sodium chloride, barium chloride, potassium chloride, sodium sulfate or the like can be used as the water-soluble inorganic salt used in the salt milling treatment, but sodium chloride (salt) is preferably used from the viewpoint of price. Water soluble inorganic salt, from treatment In terms of efficiency and production efficiency, it is preferable to use 50 to 2000% by mass, and 300 to 1000% by mass, based on the total amount of the pigment.
又,水溶性有機溶劑係潤濕顏料及水溶性無機鹽之作用者,只要溶解(混合)於水且實質上不溶解所使用的無機鹽者即可,無特別限制。但是,鹽磨處理時,溫度上升,因溶劑變成容易蒸發的狀態,從安全性的點,沸點120℃以上的高沸點溶劑較佳。可舉例如,使用2-甲氧基乙醇、2-丁氧基乙醇、2-(異戊氧基)乙醇、2-(己氧基)乙醇、二乙二醇、二乙二醇單乙醚、二乙二醇單丁醚、三乙二醇、三乙二醇單甲醚、液狀聚乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、二丙二醇、二丙二醇單甲醚、二丙二醇單乙醚及液狀聚丙二醇等。水溶性有機溶劑相對於顏料100質量份,使用5~1000質量份較佳,使用50~500質量份最佳。 Further, the water-soluble organic solvent-based wetting pigment and the water-soluble inorganic salt are not particularly limited as long as they are dissolved (mixed) in water and do not substantially dissolve the inorganic salt used. However, in the salt milling treatment, the temperature rises and the solvent becomes easily evaporated, and from the viewpoint of safety, a high boiling point solvent having a boiling point of 120 ° C or higher is preferred. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, Dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and liquid polypropylene glycol. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.
進行鹽磨處理時,依需要,可添加樹脂。所使用的樹脂之種類,無特別限制,可使用天然樹脂、改性天然樹脂、合成樹脂、以天然樹脂改性之合成樹脂。所使用的樹脂,在室溫下為固體,於上述有機溶劑一部分可溶為更佳。樹脂的使用量,相對於顏料100質量份,使用5~200質量份的範圍較佳。 When salt grinding is performed, a resin may be added as needed. The kind of the resin to be used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, or a synthetic resin modified with a natural resin can be used. The resin to be used is a solid at room temperature, and is preferably soluble in a part of the above organic solvent. The amount of the resin to be used is preferably in the range of 5 to 200 parts by mass based on 100 parts by mass of the pigment.
本發明使用的顏料係具有酸性表面者較佳。於酸性表面吸附具有哌啶基骨架之乙烯基系樹脂型分散劑(B)及具有芳香族羧基之樹脂型分散劑(A),可為使該顏料粒子在分散液中之分散性優異者。 The pigment used in the present invention is preferably an acidic surface. The vinyl-based resin-based dispersant (B) having a piperidinyl skeleton and the resin-based dispersant (A) having an aromatic carboxyl group are adsorbed on the acidic surface, and the pigment particles are excellent in dispersibility in the dispersion.
酸性表面之指標係可使用顏料的胺吸附能。於本發明中,以胺之吸附量換算,可使用具有25~700微莫耳/克(μmol/g)的胺吸附能之顏料,較佳為50~700微莫耳/克,更佳為100~600微莫耳/克,特別佳為200~600微莫耳/克。於本發明中,胺吸附能係根據色材、67[9]、547-554(1994)記載的方法,使用正己基胺作為被吸附胺物質而進行測定時定義。 The indicator of the acidic surface is the use of the amine adsorption energy of the pigment. In the present invention, a pigment having an amine adsorption energy of 25 to 700 μm /g (μmol/g) may be used in terms of the amount of adsorption of the amine, preferably 50 to 700 μm/g, more preferably. It is 100~600 micromoles/gram, especially preferably 200~600 micromoles/gram. In the present invention, the amine adsorption energy is defined in accordance with the method described in the color material, 67 [9], and 547-554 (1994), using n-hexylamine as the adsorbed amine substance.
表面偏酸性的有機顏料,係可舉例如顏料綠58(鹵化鋅酞菁顏料、胺吸附量200~700微莫耳/克)以及顏料黃150(偶氮次甲基黃顏料、胺吸附量100~250微莫耳/克)等。特別是顏料綠58(鹵化鋅酞菁顏料)係藉由併用具有芳香族羧基之樹脂型分散劑(A)與具有哌啶基骨架之乙烯基系樹脂型分散劑(B)而分散,可使顏料的分散性、分散安定性及亮度形成特別優異者。 The organic pigment having a slightly acidic surface may, for example, be Pigment Green 58 (a zinc halide phthalocyanine pigment, an amine adsorption amount of 200 to 700 μmol/g), and Pigment Yellow 150 (azomethine yellow pigment, an amine adsorption amount of 100). ~250 micromoles / gram) and so on. In particular, Pigment Green 58 (a zinc halide phthalocyanine pigment) can be dispersed by using a resin-based dispersant (A) having an aromatic carboxyl group and a vinyl-based resin-based dispersant (B) having a piperidinyl skeleton. The dispersibility, dispersion stability, and brightness of the pigment are particularly excellent.
(具有酸性取代基的衍生物) (derivatives with acidic substituents)
於本發明的顏料組成物,進一步,係可使用選自由具有酸性官能基的色素衍生物、具有酸性官能基的蒽醌衍生物、具有酸性官能基的吖啶酮(acridone)衍生物及具有酸性官能基的三嗪衍生物所成之群的1種以上的具有酸性官能基的衍生物(以下有時簡略記為具有酸性官能基的衍生物)。 Further, in the pigment composition of the present invention, a pigment derivative selected from an acidic functional group, an anthracene derivative having an acidic functional group, an acridon derivative having an acidic functional group, and an acidic group can be used. One or more kinds of derivatives having an acidic functional group (hereinafter sometimes referred to simply as a derivative having an acidic functional group) in which the triazine derivative of the functional group is formed.
說明有關本發明所使用的具有酸性官能基的衍生物。本發明所使用的具有酸性官能基之衍生物,係可使用選自由下述通式(1)、下述通式(2)及下述通式(3)所 示的衍生物所成之群的至少1種以上的衍生物。具有酸性官能基的衍生物,係可分類為下述通式(1)所示的不具有相對離子之衍生物,以及下述通式(2)及(3)所示的具有相對離子之衍生物。 Derivatives relating to the acidic functional groups used in the present invention are described. The derivative having an acidic functional group used in the present invention may be selected from the group consisting of the following general formula (1), the following general formula (2), and the following general formula (3). At least one or more derivatives of the group represented by the derivative. The derivative having an acidic functional group can be classified into a derivative having no opposite ion represented by the following formula (1), and a derivative having relative ions represented by the following formulas (2) and (3) Things.
通式(1):P-Z1 General formula (1): P-Z1
(通式(1)中,P為有機色素殘基、可具有取代基的雜環殘基或可具有取代基的芳香族殘基,Z1為磺酸基或羧基。) (In the formula (1), P is an organic dye residue, a heterocyclic residue which may have a substituent or an aromatic residue which may have a substituent, and Z1 is a sulfonic acid group or a carboxyl group.)
通式(2):(P-Z2)[N+(R5,R6,R7,R8)] General formula (2): (P-Z2) [N+(R5, R6, R7, R8)]
(通式(2)中,P為有機色素殘基、可具有取代基的雜環殘基或可具有取代基的芳香族殘基,R5為碳數5~20的烷基,R6、R7及R8分別獨立為氫原子或碳數1~20的烷基,Z2為SO3 -或COO-。) (In the formula (2), P is an organic dye residue, a heterocyclic residue which may have a substituent or an aromatic residue which may have a substituent, and R5 is an alkyl group having 5 to 20 carbon atoms, R6 and R7 and R8 is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Z2 is SO 3 - or COO - .)
通式(3):(P-Z2)xMy+ General formula (3): (P-Z2) x My+
(通式(3)中,P為有機色素殘基、可具有取代基的雜環殘基或可具有取代基的芳香族殘基,My+為金屬離子,可舉例如鋰、鈉、鉀、鎂、鈣、鋇、鐵、鈷、鎳、銅、鋅或鋁的離子,y為離子的價數,x為以x=y÷(Z2的個數)的式所求得之值,Z2為SO3 -或COO-。) (In the formula (3), P is an organic dye residue, a heterocyclic residue which may have a substituent or an aromatic residue which may have a substituent, and My+ is a metal ion, and examples thereof include lithium, sodium, potassium, and magnesium. An ion of calcium, barium, iron, cobalt, nickel, copper, zinc or aluminum, y is the valence of the ion, x is the value obtained by the formula x=y÷(the number of Z2), and Z2 is the SO 3 - or COO - .)
通式(1)~(3)中之P為有機色素殘基時,該有機色素係可舉例如二酮吡咯並吡咯系色素、偶氮、雙偶氮、聚偶氮等偶氮系色素、酞菁系色素、二胺基二蒽醌、蒽嘧啶、黃 士酮、苯並芘二酮、陰丹酮、皮蒽酮、蒽酮紫(violanthrone)等蒽醌系色素、喹吖啶酮系色素、二噁嗪系色素、紫環酮系色素、苝系色素、硫靛藍系色素、異吲哚啉系色素、異吲哚啉酮系色素、喹酞酮系色素、陰丹士林(indanthrene)系色素及金屬錯合物系色素。 When P in the general formulae (1) to (3) is an organic dye residue, the organic dye may, for example, be a diketopyrrolopyrrole dye, an azo dye such as azo, disazo or polyazo, or Phthalocyanine pigment, diaminodiguanide, pyrimidine, yellow Anthraquinone dyes such as ketone, benzoindoledione, indanthrone, dermatanone, violanthrone, quinacridone dyes, dioxazine dyes, purple ketone dyes, lanthanides A pigment, a sulphur blue pigment, an isoporphyrin dye, an isoindolinone dye, a quinophthalone dye, an indanthrene dye, and a metal complex dye.
又,通式(1)~(3)之P為雜環殘基及芳香族環殘基時,該雜環及芳香族環係 可舉例如噻吩、呋喃、吡啶、吡唑(pyrazole)、吡咯、咪唑、異吲哚啉、異吲哚啉酮、苯並咪唑酮(benzimidazolone)、苯並噻唑、苯並三唑、吲哚(indole)、喹啉(quinoline)、咔唑、吖啶(acridine)、苯、萘、蒽、茀(fluorene)、菲(phenanthrene)、蒽醌及吖啶酮等。該等之雜環殘基及芳香族環殘基係可具有烷基(甲基、乙基及丙基等)、胺基、烷基胺基(二甲基胺基、二乙基胺基及二丁基胺基等)、硝基、羥基、烷氧基(甲氧基、乙氧基及丁氧基等)、鹵素(氯、溴及氟等)、苯基(可被烷基、胺基、烷基胺基、硝基、羥基、烷氧基及鹵素等取代)以及苯基胺基(可被烷基、胺基、烷基胺基、硝基、羥基、烷氧基及鹵素等取代)等之取代基。 Further, when P of the general formulae (1) to (3) is a heterocyclic residue and an aromatic ring residue, the heterocyclic ring and the aromatic ring system are For example, thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoporphyrin, isoindolinone, benzimidazolone, benzothiazole, benzotriazole, anthracene ( Indole), quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone and acridone. The heterocyclic residue and the aromatic ring residue may have an alkyl group (methyl group, ethyl group, propyl group, etc.), an amine group, an alkylamino group (dimethylamino group, diethylamino group, and Dibutylamine, etc.), nitro, hydroxy, alkoxy (methoxy, ethoxy, butoxy, etc.), halogen (chlorine, bromine and fluorine, etc.), phenyl (can be alkyl, amine) a base, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, a halogen, etc.) and a phenylamine group (which may be an alkyl group, an amine group, an alkylamine group, a nitro group, a hydroxyl group, an alkoxy group, a halogen group, etc.) Substituting a substituent such as).
以通式(1)~(3)所示的具有酸性官能基的衍生物中的P,未必一定要與顏料組成物所使用的顏料之化學構造相同。但是,若考慮最後所製造的印墨等的色相,使用於綠色系的顏料時如藍色系、綠色系或黃色系的有機色素殘基,使用於黃色系顏料時如黃色系的有機色素殘 基,使用於紅色系顏料時如紅色系、橘色系或黃色系的有機色素殘基,與使用於藍色系顏料時如藍色或紫色之有機色素殘基般使用的顏料之色相接近者、或無色者較佳。 P in the derivative having an acidic functional group represented by the general formulae (1) to (3) is not necessarily required to be the same as the chemical structure of the pigment used in the pigment composition. However, when considering the hue of the ink or the like which is finally produced, when it is used for a green-based pigment, such as a blue-based, green-based or yellow-based organic dye residue, when used as a yellow-based pigment, such as a yellow-based organic pigment residue The base is used in red pigments such as red, orange or yellow organic pigment residues, and is similar to the color of pigments used in blue pigments such as blue or purple organic pigment residues. Or colorless is preferred.
通式(1)的Z1,相對於通式(1)的P,可存在0.5~8.0個的範圍,較佳為0.7~3.0個。 Z1 of the formula (1) may be in the range of 0.5 to 8.0, preferably 0.7 to 3.0, relative to the P of the formula (1).
通式(2)的Z2,相對於通式(2)的P,可存在0.5~8.0個的範圍,較佳為0.7~3.0個。同時對應於Z2的個數,[N+(R5,R6,R7,R8)]亦可存在相同的數目。 Z2 of the formula (2) may be in the range of 0.5 to 8.0, preferably 0.7 to 3.0, relative to the P of the formula (2). At the same time, corresponding to the number of Z2, [N+(R5, R6, R7, R8)] may also have the same number.
通式(3)的Z2,相對於通式(3)的P,可存在0.5~8.0個的範圍,較佳為0.7~3.0個。同時符合Z2的個數與M的離子價數y而x的數目亦可適當改變。 Z2 of the formula (3) may be in the range of 0.5 to 8.0, preferably 0.7 to 3.0, relative to the P of the formula (3). At the same time, the number of Z2 and the ion number y of M and the number of x can be appropriately changed.
上述具有酸性官能基的衍生物的使用量,相對於顏料100質量份,較佳為0.1質量份以上50質量份以下。再者,以1質量份以上30質量份以下較佳。未達0.1質量份時,沒有效果,超過50質量份時,色相的偏移變得顯著,顏料組成物的黏度變高,有時經時增黏,故不佳。 The amount of the derivative having an acidic functional group to be used is preferably 0.1 part by mass or more and 50 parts by mass or less based on 100 parts by mass of the pigment. Further, it is preferably 1 part by mass or more and 30 parts by mass or less. When it is less than 0.1 part by mass, there is no effect. When the amount is more than 50 parts by mass, the shift of the hue becomes remarkable, and the viscosity of the pigment composition becomes high, which may increase the viscosity over time, which is not preferable.
於本發明中,以通式(1)~(3)所示的具有酸性官能基的衍生物中,特別是使用以通式(2)所示的具有酸性官能基的衍生物較佳。 In the present invention, among the derivatives having an acidic functional group represented by the general formulae (1) to (3), it is preferred to use a derivative having an acidic functional group represented by the general formula (2).
〈具有芳香族羧基之樹脂型分散劑(A)〉 <Resin type dispersant (A) having an aromatic carboxyl group>
本發明的具有芳香族羧基之樹脂型分散劑(A),係藉由與後述的具有哌啶基骨架之乙烯基系樹脂型分散劑(B)併用,相較於顏料分散單獨使用乙烯基系樹脂型分散劑(B) 分散顏料時,可使顏料藉分散介質安定地存在,因此可得到顏料組成物顯示分散安定性及高亮度之顏料組成物。 The resin-type dispersing agent (A) having an aromatic carboxyl group of the present invention is used in combination with a vinyl-based resin-based dispersing agent (B) having a piperidinyl skeleton to be described later, and a vinyl-based one is used separately from the pigment dispersion. Resin type dispersant (B) When the pigment is dispersed, the pigment can be stably present by the dispersion medium, so that a pigment composition exhibiting dispersion stability and high brightness can be obtained.
本發明的具有芳香族羧基之樹脂型分散劑(A),係以數目平均分子量為800~30,000較佳。即使未達800,或超過30,000,有時顏料分散體的黏度及黏度安定性變差,故不佳。 The resin type dispersant (A) having an aromatic carboxyl group of the present invention preferably has a number average molecular weight of 800 to 30,000. Even if it is less than 800 or more than 30,000, the viscosity and viscosity stability of the pigment dispersion may be deteriorated, which is not preferable.
又,本發明的具有芳香族羧基之樹脂型分散劑(A),係以酸價為10~200mgKOH/g較佳。 Further, the resin-type dispersant (A) having an aromatic carboxyl group of the present invention preferably has an acid value of 10 to 200 mgKOH/g.
本發明的具有芳香族羧基之樹脂型分散劑(A),係於其分子內具有芳香族羧基者。於其製造方法中,可舉例如於具有羥基的聚合物(C)使芳香族三羧酸酐(D1)及/或芳香族四羧酸二酐(D2)反應之製造方法1;使用具有芳香族羧基的單體而製作聚合物的製造方法2;一邊聚合具有羥基的單體一邊使芳香族三羧酸酐(D1)及/或芳香族四羧酸二酐(D2)反應之製造方法3;中任一種。其中,從顏料分散性的觀點,藉由樹脂型分散劑(A)中芳香族羧基的個數更容易控制的製造方法1來製作較佳。 The resin-type dispersant (A) having an aromatic carboxyl group of the present invention is one which has an aromatic carboxyl group in its molecule. In the production method, for example, the production method 1 of reacting an aromatic tricarboxylic anhydride (D1) and/or an aromatic tetracarboxylic dianhydride (D2) with a polymer (C) having a hydroxyl group; Method 2 for producing a polymer of a monomer of a carboxyl group; and a method 3 for producing an aromatic tricarboxylic anhydride (D1) and/or an aromatic tetracarboxylic dianhydride (D2) while polymerizing a monomer having a hydroxyl group; Any one. Among them, from the viewpoint of the pigment dispersibility, the production method 1 in which the number of aromatic carboxyl groups in the resin-type dispersant (A) is more easily controlled is preferably produced.
(具有羥基的聚合物(C)) (polymer with hydroxyl group (C))
使用來作為本發明的具有芳香族羧基之樹脂型分散劑(A)的前驅物之具有羥基的聚合物(C),係可分為於單末端具有羥基的聚合物(C1)及於側鏈具有羥基的聚合物(C2)。再者,於單末端具有羥基的聚合物(C1)中,於單末端具有2個羥基者為於單末端具有2個羥基的聚合物(C3)。 The polymer (C) having a hydroxyl group as a precursor of the aromatic carboxyl group-containing resin type dispersant (A) of the present invention can be classified into a polymer (C1) having a hydroxyl group at a single terminal and a side chain. A polymer having a hydroxyl group (C2). Further, in the polymer (C1) having a hydroxyl group at one terminal, a polymer (C3) having two hydroxyl groups at a single terminal in a single terminal having two hydroxyl groups.
〔於單末端具有羥基的聚合物(C1)、於單末 端具有2個羥基的聚合物(C3)〕 [Polymer (C1) having a hydroxyl group at one end, in the end Polymer (C3) having 2 hydroxyl groups at the end]
首先,說明有關於單末端具有羥基的聚合物(C1)。本發明所使用的於單末端具有羥基的聚合物(C1),係可舉例如於單末端具有羥基的聚酯及/或聚醚系聚合物(C1-1)、及於單末端具有羥基的乙烯基系聚合物(C1-2)。於單末端具有2個羥基的聚合物(C3)為乙烯基系聚合物較佳。 First, a description will be given of a polymer (C1) having a hydroxyl group at a single terminal. The polymer (C1) having a hydroxyl group at a single terminal used in the present invention may, for example, be a polyester having a hydroxyl group at one terminal and/or a polyether polymer (C1-1), and having a hydroxyl group at a single terminal. Vinyl polymer (C1-2). The polymer (C3) having two hydroxyl groups at one terminal is preferably a vinyl polymer.
〔於單末端具有羥基的聚酯及/或聚醚系聚合物(C1-1)〕 [Polyester and/or polyether polymer (C1-1) having a hydroxyl group at a single terminal]
於單末端具有羥基的聚酯及/或聚醚系聚合物(C1-1),較佳為以下述通式(4)所示者。 The polyester and/or polyether polymer (C1-1) having a hydroxyl group at a single terminal is preferably represented by the following formula (4).
[通式(4)中,Y1為碳原子數1~20、氧原子數0~12及氮原子數0~3的1價末端基,X2為-O-、-S-或-N(Rb)-(但Rb為氫原子或碳原子數1~18的直鏈狀或分支狀的烷基),Z1為-OH,G1為以-R11O-所示的重複單元,G2為以-C(=O)R12O-所示的重複單元,G3為以-C(=O)R13C(=O)-OR14O-所示的重複單元,R11為碳原子數2~8的直鏈狀或分支狀的伸烷基或碳 原子數3~8的環伸烷基,R12為碳原子數1~8的直鏈狀或分支狀的伸烷基或碳原子數4~8的環伸烷基,R13為碳原子數2~6的直鏈狀或分支狀的伸烷基、碳原子數2~6的直鏈狀或分支狀的伸烯基、碳原子數3~20的環伸烷基或碳原子數6~20的伸芳香基,R14為-CH(R15)-CH(R16)-,R15及R16係任一者均為氫原子,另一者為碳原子數1~20的烷基、碳原子數2~20的烯基、碳原子數6~20的芳香基、烷基部分的碳原子數1~20之烷氧基亞甲基、烯基部分的碳原子數2~20之烯氧基亞甲基、芳香基部分的碳原子數6~20之芳香基部分視情況有時被鹵原子取代之芳香氧基亞甲基、N-亞甲基-鄰苯二甲醯亞胺(phthalimide)基,R17為前述R11、-C(=O)R12-或-C(=O)R13C(=O)-OR14-,m1為0~100的整數,m2為0~60的整數,m3為0~30的整數,但是m1+m2+m3為1以上100以下,通式(4)之前述重複單元G1~G3的配置,係不限定其順序,表示於以通式(4)所示的聚合物,於基X2與基R17之間以任意順序包含重複單元G1~G3,再者,該等重複單元G1~G3分別可為無規則型或嵌段型的任一種。] [In the formula (4), Y 1 is a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms, and X 2 is -O-, -S- or -N. (Rb)- (but Rb is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms), Z 1 is -OH, and G 1 is a repeating unit represented by -R11O-, G 2 as in -C (= O) R12O- repeating unit represented, G 3 is to -C (= O) R13C (= O) -OR14O- repeating unit represented by, R11 is a linear carbon atoms 2 to 8 a chain or branched alkyl group or a cycloalkyl group having 3 to 8 carbon atoms, and R12 is a linear or branched alkyl group having 1 to 8 carbon atoms or a ring having 4 to 8 carbon atoms. An alkyl group, R13 is a linear or branched alkyl group having 2 to 6 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms, and a ring having 3 to 20 carbon atoms. An alkyl group or an extended aromatic group having 6 to 20 carbon atoms, R14 is -CH(R15)-CH(R16)-, and any of R15 and R16 is a hydrogen atom, and the other is a carbon number of 1~ An alkyl group of 20, an alkenyl group having 2 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an alkoxymethylene group having 1 to 20 carbon atoms in the alkyl moiety, and a carbon number of the alkenyl moiety 2~20 oxymethylene, aromatic moiety Carbon atoms, an aromatic moiety of 6 to 20 optionally may be substituted with a halogen atom of an aromatic-oxy-methylene, N- methylene - phthalimide (PEI) (phthalimide) group, R 17 is the R11, -C(=O)R12- or -C(=O)R13C(=O)-OR14-, m1 is an integer from 0 to 100, m2 is an integer from 0 to 60, and m3 is an integer from 0 to 30, but m1 + m2 + m3 is 1 or more and 100 or less, the configuration of the general formula (4) of the repeating unit. 1 ~ G. 3 is G, based not limited to the order, the polymer was expressed in a general formula (4), and in group X The repeating unit G 1 to G 3 are contained between the base 2 and the base R 17 in an arbitrary order. Further, the repeating units G 1 to G 3 may be either of a random type or a block type. ]
前述通式(4)係Y1為碳原子數1~18的直鏈狀或分支狀烷基,從顏料分散體的低黏度化及保存安定性的觀點較佳。 In the above formula (4), Y 1 is a linear or branched alkyl group having 1 to 18 carbon atoms, and is preferred from the viewpoints of low viscosity of the pigment dispersion and storage stability.
又,就其他形態而言,前述通式(4)中,Y1具有乙烯性不飽和雙鍵較佳。此時,可對具有芳香族羧基之樹脂型分散劑賦予活性能量線硬化性。 Further, in another embodiment, in the above formula (4), Y 1 preferably has an ethylenically unsaturated double bond. In this case, active energy ray curability can be imparted to the resin type dispersant having an aromatic carboxyl group.
又,於前述通式(4)中,m2為3~15的整數,從顏料分散體的低黏度化及保存安定性的觀點較佳。 Further, in the above formula (4), m2 is an integer of from 3 to 15, and is preferable from the viewpoint of low viscosity of the pigment dispersion and storage stability.
又,於前述通式(4)中,m2=0、m3=0之時Y1為碳原子數1~7的直鏈狀或分支狀烷基、或具有乙烯性不飽和雙鍵較佳。 Further, in the above formula (4), when m2=0 and m3=0, Y 1 is a linear or branched alkyl group having 1 to 7 carbon atoms, or preferably has an ethylenically unsaturated double bond.
以前述通式(4)所示的於單末端具有羥基的聚酯及/或聚醚系聚合物(C1-1),係可以習知的方法製造,以選自單醇、1級單胺、2級單胺及單硫醇之群的化合物作為起始劑,可使選自環氧烷(alkylene oxide)、內酯、交酯(lactide)、二羧酸酐及環氧化物所成之群的環狀化合物開環聚合而容易地得到。 The polyester and/or polyether polymer (C1-1) having a hydroxyl group at a single terminal represented by the above formula (4) can be produced by a conventional method selected from monoalcohol and monoamine monoamine. a compound of a group of a monoamine and a monothiol as a starting agent, which can be selected from the group consisting of an alkylene oxide, a lactone, a lactide, a dicarboxylic anhydride, and an epoxide. The cyclic compound is easily obtained by ring-opening polymerization.
單醇係只要為具有1個羥基的化合物即可,可為任一之化合物。可舉例如甲醇、乙醇、1-丙醇、異丙醇、1-丁醇、異丁醇、第3丁醇、1-戊醇、異戊醇、1-己醇、環己醇、4-甲基-2-戊醇、1-庚醇、1-辛醇、異辛醇、2-乙基己醇、1-壬醇、異壬醇、1-癸醇、十二烷基醇、1-十四烷基醇、十六烷基醇、1-硬脂醇、異硬脂醇、2-辛基癸醇、2-辛基十二烷基醇、2-己基癸醇、二十二烷基醇或油醇等的脂肪族單醇類;苯甲醇、苯氧基乙基醇、對異丙苯基苯氧基乙基醇等具有芳香環的單醇類;或 乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、乙二醇單己醚、乙二醇單-2-乙基己基醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚、丙二醇單己醚、丙二醇單-2-乙基己基醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丙醚、二乙二醇單丁醚、二乙二醇單己醚、二乙二醇單-2-乙基己基醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單丙醚、二丙二醇單丁醚、二丙二醇單己醚、二丙二醇單-2-乙基己基醚、三乙二醇單甲醚、三乙二醇單乙醚、三乙二醇單丙醚、三乙二醇單丁醚、三乙二醇單己醚、三乙二醇單-2-乙基己基醚、三丙二醇單甲醚、三丙二醇單乙醚、三丙二醇單丙醚、三丙二醇單丁醚、三丙二醇單己醚、三丙二醇單-2-乙基己基醚、四乙二醇單甲醚、四乙二醇單乙醚、四乙二醇單丙醚、四乙二醇單丁醚、四乙二醇單己醚、四乙二醇單-2-乙基己基醚、四丙二醇單甲醚、四丙二醇單乙醚、四丙二醇單丙醚、四丙二醇單丁醚、四丙二醇單己醚、四丙二醇單-2-乙基己基醚或四二乙二醇單甲醚等烷二醇單烷醚類等。 The monool type may be any compound as long as it is a compound having one hydroxyl group. For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, third butanol, 1-pentanol, isoamyl alcohol, 1-hexanol, cyclohexanol, 4- Methyl-2-pentanol, 1-heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isodecyl alcohol, 1-nonanol, dodecyl alcohol, 1 - myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octyl decyl alcohol, 2-octyldodecanol, 2-hexyl decyl alcohol, twenty-two An aliphatic monool such as an alkyl alcohol or an oleyl alcohol; a monoalcohol having an aromatic ring such as benzyl alcohol, phenoxyethyl alcohol or p-cumylphenoxyethyl alcohol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether , propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol single Propyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, two Propylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol single Butyl ether, triethylene glycol monohexyl ether, triethylene glycol mono-2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol single Hexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, four Glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol An alkanediol monoalkyl ether such as mono-2-ethylhexyl ether or tetraethylene glycol monomethyl ether.
單醇係可使用具有乙烯性不飽和雙鍵的單醇。此時,可對所生成的具有芳香族羧基的分散劑賦予活性能量線硬化功能。 As the monool, a monool having an ethylenically unsaturated double bond can be used. At this time, an active energy ray hardening function can be imparted to the produced dispersant having an aromatic carboxyl group.
前述具有乙烯性不飽和雙鍵的例,係可舉例如乙烯基或(甲基)丙烯醯基(再者此處,此後表記為「(甲基)丙烯醯基」或「(甲基)丙烯酸酯」時,分別表示為「丙烯醯基及/或甲基丙烯醯基」或「甲基丙烯酸酯及/或丙烯 酸酯」),較佳為(甲基)丙烯醯基。該等具有雙鍵的基之種類係可為一種類,亦可為複數種類。 Examples of the ethylenically unsaturated double bond include a vinyl group or a (meth) acrylonitrile group (hereinafter, hereafter referred to as "(meth)acryl fluorenyl group" or "(meth)acrylic acid. "ester", respectively, is expressed as "acryloyl fluorenyl and / or methacryl fluorenyl" or "methacrylate and / or propylene The acid ester") is preferably a (meth) acrylonitrile group. The types of the groups having the double bond may be one type or plural types.
具有乙烯性不飽和雙鍵的單醇,係可使用包含1個、2個及3個以上的乙烯性不飽和雙鍵之化合物。乙烯性不飽和雙鍵的數目為1個單醇,係可舉例如(甲基)丙烯酸2-羥基乙酯(再者,表記為「(甲基)丙烯酸酯」之時係表示丙烯酸酯及/或甲基丙烯酸酯。以下相同)、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸2-羥基丁酯、丙烯酸乙基2-(羥基甲基)酯、丙烯酸2-羥基-3-苯氧基丙酯、1,4-環己烷二甲醇單(甲基)丙烯酸酯、2-羥基乙基乙烯基醚、二乙二醇單乙烯基醚或4-羥基丁基乙烯基醚等。乙烯性不飽和雙鍵的數目為2個單醇,可舉例如2-羥基-3-丙烯醯氧基丙基甲基丙烯酸酯或甘油二(甲基)丙烯酸酯等。乙烯性不飽和雙鍵的數目為3個單醇,可舉例如新戊四醇三丙烯酸酯,乙烯性不飽和雙鍵的數目為5個單醇,可舉例如二新戊四醇五丙烯酸酯。 As the monool having an ethylenically unsaturated double bond, a compound containing one, two or three or more ethylenically unsaturated double bonds can be used. The number of the ethylenically unsaturated double bonds is one monohydric alcohol, and, for example, 2-hydroxyethyl (meth)acrylate (hereinafter, the expression "(meth)acrylate" means acrylate and / Or methacrylate. The same as the following), 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-(meth)acrylate Hydroxybutyl ester, 2-hydroxybutyl (meth)acrylate, ethyl 2-(hydroxymethyl) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexane dimethanol (meth) acrylate, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether or 4-hydroxybutyl vinyl ether. The number of ethylenically unsaturated double bonds is two monols, and examples thereof include 2-hydroxy-3-acryloxypropyl methacrylate or glycerol di(meth)acrylate. The number of ethylenically unsaturated double bonds is 3 monohydric alcohols, for example, neopentyl alcohol triacrylate, and the number of ethylenically unsaturated double bonds is 5 monools, and for example, dipentaerythritol pentaacrylate .
其中,新戊四醇三丙烯酸酯及二新戊四醇五丙烯酸酯,係分別以新戊四醇四丙烯酸酯及二新戊四醇六丙烯酸酯的混合物得到,故為了控制所生成的分散劑之分子量,必須藉由HPLC(高速液相層析)法或羥基價的測定決定單醇體的比率。依單醇體的數目與形成G1~G3的原料之比率,決定分散劑之分子量之故。 Among them, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are obtained by a mixture of pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate, respectively, so that the generated dispersant is controlled. The molecular weight must be determined by HPLC (high-speed liquid chromatography) or the measurement of the hydroxyl value to determine the ratio of the monool. The molecular weight of the dispersant is determined by the ratio of the number of monohydric alcohols to the raw material forming G 1 to G 3 .
前述單醇之中,乙烯性不飽和雙鍵的數目 為2個以上者,就硬化性之點,使用於活性能量線硬化型顏料組成物時較佳。 The number of ethylenically unsaturated double bonds among the aforementioned monools In the case of two or more, it is preferable to use it for the active energy ray-curable pigment composition in terms of hardenability.
1級單胺係可舉例如甲基胺、乙基胺、1-丙基胺、異丙基胺、1-丁基胺、異丁基胺、第3丁基胺、1-戊基胺、異戊基胺、3-戊基胺、1-己基胺、環己基胺、4-甲基-2-戊基胺、1-庚基胺、1-辛基胺、異辛基胺、2-乙基己基胺、1-壬基胺、異壬基胺、1-癸基胺、1-十二烷基胺、1-十四烷基胺、十六烷基胺、1-十八烷基胺、異十八烷基胺、2-辛基癸基胺、2-辛基十二烷基胺、2-己基癸基胺、二十二烷基胺或油基胺等脂肪族1級單胺類;3-甲氧基丙基胺、3-乙氧基丙基胺、3-丙氧基丙基胺、3-丁氧基丙基胺、2-乙基己氧基丙基胺、3-異丁氧基丙基胺、3-癸氧基丙基胺或3-十四烷氧基丙基胺等烷氧基烷基1級胺類;或苯甲基胺等芳香族1級單胺類。 The monoamine monoamine may, for example, be methylamine, ethylamine, 1-propylamine, isopropylamine, 1-butylamine, isobutylamine, butylamine, 1-pentylamine, Isoamylamine, 3-pentylamine, 1-hexylamine, cyclohexylamine, 4-methyl-2-pentylamine, 1-heptylamine, 1-octylamine, isooctylamine, 2- Ethylhexylamine, 1-decylamine, isodecylamine, 1-decylamine, 1-dodecylamine, 1-tetradecylamine, hexadecylamine, 1-octadecyl Aliphatic grade 1 single such as amine, isostearylamine, 2-octyldecylamine, 2-octyldodecylamine, 2-hexyldecylamine, behenylamine or oleylamine Amines; 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 2-ethylhexyloxypropylamine, An alkoxyalkyl 1- to amine such as 3-isobutoxypropylamine, 3-methoxypropylamine or 3-tetradecyloxypropylamine; or aromatic grade 1 such as benzylamine Monoamines.
2級單胺係可舉例如二甲基胺、二乙基胺、二-1-丙基胺、二異丙基胺、二-1-丁基胺、二異丁基胺、二-1-戊基胺、二異戊基胺、二-1-己基胺、二環己基胺、二-(4-甲基-2-戊基)胺、二-1-庚基胺、二-1-辛基胺、異辛基胺、二-(2-乙基己基)胺、二-1-壬基胺、二異壬基胺、二-1-癸基胺、二-1-十二烷基胺、二-1-十四烷基胺、二-十六烷基胺、二-1-十八烷基胺、二異十八烷基胺、二-(2-辛基癸基)胺、二-(2-辛基十二烷基)胺、二-(2- 己基癸基)胺、N-甲基乙基胺、N-甲基丁基胺、N-甲基異丁基胺、N-甲基丙基胺、N-甲基己基胺、哌嗪(piperazine)或烷基取代哌嗪等的脂肪族2級單胺類。 The second-stage monoamine may, for example, be dimethylamine, diethylamine, di-1-propylamine, diisopropylamine, di-1-butylamine, diisobutylamine, di-1- Amylamine, diisoamylamine, di-1-hexylamine, dicyclohexylamine, bis-(4-methyl-2-pentyl)amine, di-1-heptylamine, di-1-octyl Amine, isooctylamine, bis-(2-ethylhexyl)amine, di-1-indenylamine, diisodecylamine, di-1-indenylamine, di-1-dodecylamine , di-1-tetradecylamine, di-hexadecylamine, di-1-octadecylamine, diisooctadecylamine, di-(2-octyldecyl)amine, two -(2-octyldodecyl)amine, di-(2- Hexyl decyl)amine, N-methylethylamine, N-methylbutylamine, N-methylisobutylamine, N-methylpropylamine, N-methylhexylamine, piperazine Or an alkyl group-substituted aliphatic class 2 monoamine such as piperazine.
單硫醇係可舉例如甲基硫醇、乙基硫醇、1-丙基硫醇、異丙基硫醇、1-丁基硫醇、異丁基硫醇、第3丁基硫醇、1-戊基硫醇、異戊基硫醇、3-戊基硫醇、1-己基硫醇、環己基硫醇、4-甲基-2-戊基硫醇、1-庚基硫醇、1-辛基硫醇、異辛基硫醇、2-乙基己基硫醇、1-壬基硫醇、異壬基硫醇、1-癸基硫醇、1-十二烷基硫醇、1-十四烷基硫醇、十六烷基硫醇、1-十八烷基硫醇、異十八烷基硫醇、2-辛基癸基硫醇、2-辛基十二烷基硫醇、2-己基癸基硫醇、二十二烷基硫醇或油基硫醇等脂肪族單硫醇類;或硫二醇酸甲酯、硫二醇酸辛酯、硫二醇酸甲氧基丁酯等硫二醇酸烷酯、巰基丙酸甲酯、巰基丙酸辛酯、巰基丙酸甲氧基丁酯或巰基丙酸十二烷基酯等巰基丙酸烷酯類。 Examples of the monothiol include methyl mercaptan, ethyl mercaptan, 1-propyl mercaptan, isopropyl mercaptan, 1-butyl mercaptan, isobutyl mercaptan, and third butyl mercaptan. 1-pentyl mercaptan, isoamyl mercaptan, 3-pentyl mercaptan, 1-hexyl mercaptan, cyclohexyl mercaptan, 4-methyl-2-pentyl mercaptan, 1-heptyl mercaptan, 1-octyl mercaptan, isooctyl mercaptan, 2-ethylhexyl mercaptan, 1-mercapto mercaptan, isodecyl mercaptan, 1-mercapto mercaptan, 1-dodecyl mercaptan, 1-tetradecyl mercaptan, hexadecyl mercaptan, 1-octadecyl mercaptan, isostearyl mercaptan, 2-octyl mercapto mercaptan, 2-octyl dodecyl An aliphatic monothiol such as a mercaptan, a 2-hexyl mercapto mercaptan, a behenyl mercaptan or an oil-based mercaptan; or a methyl thioglycolate, an octyl thioglycolate or a thioglycolate An alkyl thioglycolate such as an alkyl thioglycolate such as oxybutyl ester, methyl cyanopropionate, octyl decyl propyl acrylate, methoxybutyl decyl propionate or lauryl decyl propionate.
於本發明中,選自由單醇、1級單胺、2級單胺及單硫醇所成之群的化合物,係不限於前述例示,只要具有1個羥基、1級胺基、2級胺基或硫醇基之化合物即可,亦可使用任意的化合物,又可單獨使用,亦可併用2種以上而使用。 In the present invention, the compound selected from the group consisting of monoalcohol, monoamine monoamine, quaternary monoamine and monothiol is not limited to the above exemplified, as long as it has one hydroxyl group, one amine group, and two amine group. The compound of the thiol group or the thiol group may be used alone or in combination of two or more kinds.
此處,單醇、1級單胺、2級單胺或單硫醇分別除去1個羥基、1級胺基、2級胺基或硫醇基的部分,為構成前述通式(4)之Y1。 Here, the monool, the mono-monoamine, the 2-stage monoamine or the monothiol are respectively removed by a hydroxyl group, a first-group amine group, a 2-stage amine group or a thiol group, and constitute the above formula (4). Y 1 .
以前述例示的選自由單醇、1級單胺、2級單胺及單硫醇所成之群的化合物作為起始劑,而使選自由環氧烷、內酯、交酯及二羧酸酐與環氧化物的組合所成之群的環狀化合物進行開環聚合,可製造以前述通式(4)所示的聚合物中Z1為-OH者。但是,二羧酸酐與環氧化物的組合,必須同時使用,交替聚合。 The above-exemplified compound selected from the group consisting of a monoalcohol, a mono-monoamine, a 2-stage monoamine, and a monothiol is used as a starter, and is selected from the group consisting of alkylene oxides, lactones, lactides, and dicarboxylic anhydrides. When the cyclic compound of the group formed by the combination with the epoxide is subjected to ring-opening polymerization, Z 1 in the polymer represented by the above formula (4) can be produced as -OH. However, the combination of the dicarboxylic anhydride and the epoxide must be used simultaneously and alternately polymerized.
此處,選自由環氧烷、內酯、交酯及二羧酸酐與環氧化物的組合所成之群的環狀化合物的反應順序,係可為任意順序,例如就第一階段而言,於前述起始劑聚合環氧烷後,於第二階段聚合內酯,再於第三階段可交替聚合二羧酸酐與環氧化物。於該例中,於第二階段聚合內酯時的起始劑,係成為第一階段被聚合的於單末端具有羥基的環氧烷聚合物。又於第三階段交替聚合二羧酸酐與環氧化物時的起始劑,成為至第二階段為止被聚合的於單末端具有羥基的環氧烷聚合物及內酯聚合物的嵌段共聚物。於本發明的製造方法中,製造此後說明的前述以通式(4)所示的聚合物時之起始劑,如前述以通式(4)所示的聚合物中Z1為-OH者、或後述以通式(6)所示的聚合物亦可成為起始劑。 Here, the reaction sequence of the cyclic compound selected from the group consisting of alkylene oxide, lactone, lactide, and a combination of a dicarboxylic acid anhydride and an epoxide may be in any order, for example, in the first stage, After the starting agent polymerizes the alkylene oxide, the lactone is polymerized in the second stage, and the dicarboxylic acid anhydride and the epoxide are alternately polymerized in the third stage. In this example, the initiator in the polymerization of the lactone in the second stage is an alkylene oxide polymer having a hydroxyl group at a single terminal which is polymerized in the first stage. Further, in the third stage, the initiator of the alternating polymerization of the dicarboxylic anhydride and the epoxide is a block copolymer of an alkylene oxide polymer having a hydroxyl group at one end and a lactone polymer polymerized until the second stage. . In the production method of the present invention, the initiator of the above-described polymer represented by the formula (4) is produced, and as described above, in the polymer represented by the formula (4), Z 1 is -OH. The polymer represented by the formula (6), which will be described later, may also be a starter.
前述環狀化合物的反應順序,係不限於第一階段的環氧烷、第二階段的內酯、第三階段的二羧酸酐與環氧化物的組合,使環氧烷、內酯(及/或交酯)及二羧酸酐與環氧化物之組合以任意順序分別實施1至複數次。或者,對於環氧烷、內酯(及/或交酯)及二羧酸酐與環氧化物 的組合,不實施全部的開環聚合而可從其等之中,選擇任意環狀化合物,亦可實施開環聚合。 The reaction sequence of the above cyclic compound is not limited to the first stage alkylene oxide, the second stage lactone, the third stage combination of the dicarboxylic anhydride and the epoxide, and the alkylene oxide, lactone (and / The combination of the lactide and the dicarboxylic anhydride and the epoxide is carried out 1 to several times in any order. Alternatively, for alkylene oxides, lactones (and/or lactides) and dicarboxylic anhydrides and epoxides In the combination, any ring-opening polymerization can be carried out without selecting any ring-opening polymerization, and ring-opening polymerization can also be carried out.
環氧烷係可舉例如環氧乙烷、環氧丙烷、1,2-環氧丁烷、1,4-環氧丁烷、2,3-環氧丁烷或1,3-環氧丁烷等,該等可單獨或併用2種以上而使用。併用2種以上的環氧烷時的鍵結形式,可為無規則及/或嵌段的任一種。相對於1莫耳起始劑,環氧烷的聚合莫耳數為0~100較佳。 The alkylene oxide may, for example, be ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide or 1,3-epoxybutylene. An alkane or the like may be used alone or in combination of two or more. Further, in the case of using two or more kinds of alkylene oxides, the bonding form may be any of random and/or block. The number of polymerized moles of the alkylene oxide is preferably from 0 to 100 with respect to 1 mole of the initiator.
環氧烷的聚合,係可以習知方法,例如鹼觸媒的存在下,100~200℃的溫度,加壓狀態下進行。於單醇的羥基聚合環氧烷所得之單末端具有羥基的環氧烷聚合物,係有市售品,可舉例如日本油脂公司製UNIOX系列、日本油脂公司製BLEMMER系列等,前述以通式(4)所示的聚合物中Z1為-OH之G1~G3的重複單元中只有G1者,亦可直接使用於本發明之具有芳香族羧基的分散劑的原料。若例示市售品的具體例,有UNIOX M-400、M-550、M-2000、BLEMMER PE-90、PE-200、PE-350、AE-90、AE-200、AE-400、PP-1000、PP-500、PP-800、AP-150、AP-400、AP-550、AP-800、50PEP-300、70PEP-350B、AEP系列、55PET-400、30PET-800、55PET-800、AET系列、30PPT-800、50PPT-800、70PPT-800、APT系列、10PPB-500B、10APB-500B等。 The polymerization of the alkylene oxide can be carried out by a known method, for example, in the presence of a base catalyst at a temperature of 100 to 200 ° C under a pressurized state. An alkylene oxide polymer having a hydroxyl group at a single terminal of a hydroxyl group-polymerized alkylene oxide of a monool is commercially available, and examples thereof include a UNIOX series manufactured by Nippon Oil & Fats Co., Ltd., and a BLEMMER series manufactured by Nippon Oil & Fats Co., Ltd. In the polymer shown in (4), in the repeating unit of G 1 to G 3 wherein Z 1 is -OH, only G 1 may be used, and it may be used as it is as a raw material of the dispersing agent having an aromatic carboxyl group of the present invention. Specific examples of commercial products include UNIOX M-400, M-550, M-2000, BLEMMER PE-90, PE-200, PE-350, AE-90, AE-200, AE-400, PP- 1000, PP-500, PP-800, AP-150, AP-400, AP-550, AP-800, 50PEP-300, 70PEP-350B, AEP series, 55PET-400, 30PET-800, 55PET-800, AET Series, 30PPT-800, 50PPT-800, 70PPT-800, APT series, 10PPB-500B, 10APB-500B, etc.
此處,環氧烷的伸烷基為構成前述通式(4)之重複單元G1中的R11。 Here, the alkylene group of the alkylene oxide is R11 in the repeating unit G1 constituting the above formula (4).
內酯具體地係可舉例如β-丁內酯、γ-丁內酯、γ-戊內酯、δ-戊內酯、δ-己內酯、ε-己內酯或被烷 基取代的ε-己內酯,其中使用δ-戊內酯、ε-己內酯或被烷基取代的ε-己內酯,就開環聚合性之點,為較佳。 The lactone may specifically be, for example, β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone or an alkane. The radically substituted ε-caprolactone in which δ-valerolactone, ε-caprolactone or alkyl-substituted ε-caprolactone is used is preferable in terms of ring-opening polymerizability.
於本發明所使用的製造方法,內酯係不限於使用前述例示,又可單獨使用,亦可併用2種以上而使用。以併用2種以上而使用,有時結晶性降低,室溫下變成液狀,從操作性的點及與其他樹脂的相溶性的點,為較佳。 In the production method used in the present invention, the lactone is not limited to the above-described examples, and may be used singly or in combination of two or more. When it is used in combination of two or more kinds, the crystallinity may be lowered, and it may become liquid at room temperature, and it is preferable from the point of handling property and the compatibility with other resin.
交酯較佳為以下述通式(5)所示者(包含乙交酯)。 The lactide is preferably one represented by the following formula (5) (including glycolide).
[通式(5)中,R31及R32分別獨立為氫原子、飽和或不飽和的直鏈或分支的碳原子數1~20的烷基;R33及R34分別獨立為氫原子、鹵原子以及飽和或不飽和的直鏈或分支的碳原子數1~9的低級烷基。] [In the formula (5), R 31 and R 32 each independently represent a hydrogen atom, a saturated or unsaturated linear or branched alkyl group having 1 to 20 carbon atoms; and R 33 and R 34 each independently represent a hydrogen atom; A halogen atom and a saturated or unsaturated linear or branched lower alkyl group having 1 to 9 carbon atoms. ]
本發明之具有芳香族羧基的分散劑的原料,特別適合的交酯為交酯(3,6-二甲基-1,4-二噁烷-2,5-二酮)及乙交酯(1,4-二噁烷-2,5-二酮)。又,就本發明之具有芳香族羧基的分散劑的原料而言,前述內酯或交酯中,以使用內酯較佳。 Particularly suitable lactides for the raw materials of the aromatic carboxyl group-containing dispersing agent of the present invention are lactide (3,6-dimethyl-1,4-dioxane-2,5-dione) and glycolide ( 1,4-Dioxane-2,5-dione). Further, in the raw material of the dispersant having an aromatic carboxyl group of the present invention, it is preferred to use a lactone in the lactone or lactide.
內酯及/或交酯的開環聚合,係可以習知方法,例如於連接有脫水管、冷凝管的反應器中,放入起始劑、內酯及/或交酯及聚合觸媒,在氮氣氣流下進行。於使用低沸點的單醇時,使用高壓釜,在加壓下進行反應。又,於單醇使用具有乙烯性不飽和雙鍵者之時,添加聚合抑制劑,在乾燥空氣氣流下進行反應較佳。 The ring-opening polymerization of a lactone and/or a lactide may be carried out by a conventional method, for example, in a reactor to which a dehydration tube or a condenser is connected, and an initiator, a lactone, and/or a lactide and a polymerization catalyst are placed. It was carried out under a nitrogen stream. When a low boiling point monool is used, the reaction is carried out under pressure using an autoclave. Further, when a monomer having an ethylenically unsaturated double bond is used as the monool, a polymerization inhibitor is added, and the reaction is preferably carried out under a dry air stream.
相對於1莫耳起始劑之內酯及/或交酯的聚合莫耳數,較佳為1~60莫耳的範圍,更佳為2~20莫耳,最佳為3~15莫耳。 The number of polymerized moles of lactone and/or lactide relative to 1 mole of initiator is preferably in the range of 1 to 60 moles, more preferably 2 to 20 moles, and most preferably 3 to 15 moles. .
內酯及/或交酯的聚合觸媒,係無限制而可使用習知者,可舉例如氯化四甲基銨、氯化四丁基銨、溴化四甲基銨、溴化四丁基銨、碘化四甲基銨、碘化四丁基銨、氯化苯甲基三甲基銨、溴化苯甲基三甲基銨或碘化苯甲基三甲基銨等四級銨鹽;氯化四甲基鏻、氯化四丁基鏻、溴化四甲基鏻、溴化四丁基鏻、碘化四甲基鏻、碘化四丁基鏻、氯化苯甲基三甲基鏻、溴化苯甲基三甲基鏻、碘化苯甲基三甲基鏻、氯化四苯基鏻、溴化四苯基鏻或碘化四苯基鏻等四級鏻鹽;三苯基膦等磷化合物;乙酸鉀、乙酸鈉、安息香酸鉀或安息香酸鈉等有機羧酸鹽;鈉醇化物或鉀醇化物等鹼金屬醇化物;3級胺類;有機錫化合物、有機鋁化合物或有機鈦酸鹽化合物等 有機金屬化合物;或氯化鋅等鋅化合物等。 The polymerization catalyst of the lactone and/or lactide may be used without any limitation, and examples thereof include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, and tetrabutyl bromide. Tetrabasic ammonium such as tetraammonium iodide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide or benzyltrimethylammonium iodide Salt; tetramethylguanidine chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyl chloride a quaternary phosphonium salt such as methyl hydrazine, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide or tetraphenylphosphonium iodide; a phosphorus compound such as triphenylphosphine; an organic carboxylate such as potassium acetate, sodium acetate, potassium benzoate or sodium benzoate; an alkali metal alkoxide such as a sodium alkoxide or a potassium alkoxide; a tertiary amine; an organotin compound, organic Aluminum compound or organic titanate compound An organometallic compound; or a zinc compound such as zinc chloride.
觸媒的使用量為0.1ppm~3000ppm,較佳為1ppm~1000ppm。觸媒量超過3000ppm時,樹脂的著色有時變激烈。相反地,觸媒的使用量未達0.1ppm時,內酯及/或交酯的開環聚合的速度有時變慢。 The amount of the catalyst used is from 0.1 ppm to 3,000 ppm, preferably from 1 ppm to 1000 ppm. When the amount of the catalyst exceeds 3,000 ppm, the color of the resin sometimes becomes intense. Conversely, when the amount of the catalyst used is less than 0.1 ppm, the rate of ring-opening polymerization of the lactone and/or lactide may be slow.
內酯及/或交酯的聚合溫度為100℃~220℃,較佳為110℃~210℃的範圍下進行。若反應溫度未達100℃,反應速度有時變慢,若超過220℃,內酯及/或交酯的加成反應以外的副反應,例如內酯的加成物的朝內酯單體之去聚合,容易引起環狀的內酯二聚物、三聚物的生成等。 The polymerization temperature of the lactone and/or lactide is from 100 ° C to 220 ° C, preferably from 110 ° C to 210 ° C. If the reaction temperature is less than 100 ° C, the reaction rate may be slow. If it exceeds 220 ° C, side reactions other than the addition reaction of lactone and/or lactide, such as the lactone monomer of the lactone adduct. The polymerization is carried out, and it is easy to cause formation of a cyclic lactone dimer or a trimer.
此處,內酯及/或交酯的酯基以外的部分,為構成前述通式(4)之重複單元G2中的R12。 Here, the portion other than the ester group of the lactone and/or the lactide is R12 in the repeating unit G 2 constituting the above formula (4).
二羧酸酐係可舉例如琥珀酸酐、順丁烯二酸酐、酞酸酐、亞甲基丁二酸酐、戊二酸酐、十二烯基琥珀酸酐或氯橋酸酐(chlorendic anhydride)等。 Examples of the dicarboxylic anhydride include succinic anhydride, maleic anhydride, decanoic anhydride, methylene succinic anhydride, glutaric anhydride, dodecenyl succinic anhydride, or chlorendic anhydride.
環氧化物係可舉例如甲基環氧丙基醚、乙基環氧丙基醚、丁基環氧丙基醚、2-乙基己基環氧丙基醚、十二烷基環氧丙基醚、苯基環氧丙基醚、對-第3丁基苯基環氧丙基醚、2,4-二溴苯基環氧丙基醚、3-甲基-二溴苯基環氧丙基醚(但溴的取代位置為任意)、烯丙基環氧丙基醚、乙氧基苯基環氧丙基醚、環氧丙基(甲基)丙烯酸酯、環氧丙基鄰苯二甲醯亞胺或氧化苯乙烯等。 Examples of the epoxide include methyl epoxypropyl ether, ethyl epoxypropyl ether, butyl epoxypropyl ether, 2-ethylhexyl epoxypropyl ether, and dodecyl epoxypropyl group. Ether, phenylepoxypropyl ether, p-butyl butyl epoxide, 2,4-dibromophenyl epoxypropyl ether, 3-methyl-dibromophenyl epoxide Ether (but the substitution position of bromine is arbitrary), allylepoxypropyl ether, ethoxyphenylepoxypropyl ether, epoxypropyl (meth) acrylate, epoxy propyl phthalate Formamidine or styrene oxide.
二羧酸酐與環氧化物係對於起始劑而同時使用,交替反應。此時,對於起始劑的羥基、1級胺基、2級胺基或硫醇基,首先二羧酸酐的酸酐基反應,產生羧基,然後於該羧基,環氧化物的環氧基反應而產生羥基。再者,如同該羥基與二羧酸酐的酸酐基反應般,以下依照順序可進行與前述相同的反應。相對於1莫耳起始劑之二羧酸酐與環氧化物的聚合莫耳數,分別為0~30莫耳較佳。又,二羧酸酐與環氧化物的反應比例([D]/[E])為以0.8≦[D]/[E]≦1.0 The dicarboxylic anhydride and the epoxide are used simultaneously for the initiator, and are alternately reacted. At this time, for the hydroxyl group of the initiator, the amine group of the first stage, the amine group of the second stage or the thiol group, first, the acid anhydride group of the dicarboxylic acid anhydride reacts to generate a carboxyl group, and then the epoxy group of the epoxide reacts with the carboxyl group. Hydroxyl groups are produced. Further, as the hydroxyl group reacts with the acid anhydride group of the dicarboxylic anhydride, the same reaction as described above can be carried out in the following order. The number of polymerized moles of the dicarboxylic anhydride and the epoxide relative to the 1 molar initiator is preferably from 0 to 30 moles. Further, the reaction ratio ([D]/[E]) of the dicarboxylic anhydride to the epoxide is 0.8 ≦ [D] / [E] ≦ 1.0
([D]為二羧酸酐的莫耳數,[E]為環氧化物的莫耳數)較佳。若未達0.8,容易殘留環氧化物,若超過1.0,無法得到於單末端具有羥基的聚合物,有時可得到於單末端具有羧基的聚合物,故不佳。 ([D] is the molar number of the dicarboxylic anhydride, and [E] is the molar number of the epoxide). If it is less than 0.8, the epoxide is likely to remain. When it exceeds 1.0, a polymer having a hydroxyl group at a single terminal cannot be obtained, and a polymer having a carboxyl group at a single terminal may be obtained, which is not preferable.
二羧酸酐與環氧化物的交替聚合,較佳為50℃~180℃,更佳為60℃~150℃的範圍下進行。反應溫度為未達50℃時,或超過180℃時,有時反應速度變慢。 The alternating polymerization of the dicarboxylic anhydride and the epoxide is preferably carried out at a temperature of from 50 ° C to 180 ° C, more preferably from 60 ° C to 150 ° C. When the reaction temperature is less than 50 ° C or exceeds 180 ° C, the reaction rate may be slow.
此處,二羧酸酐的二羧酸酐基以外的部分構成前述通式(4)之重複單元G3中的R13,環氧化物的形成環狀醚的氧原子以外的部分構成前述通式(4)之重複單元G3中的R14。 Here, the moiety other than the dicarboxylic anhydride group of the dicarboxylic anhydride forms R13 in the repeating unit G 3 of the above formula (4), and the moiety other than the oxygen atom forming the cyclic ether of the epoxide constitutes the above formula (4). ) of the repeating units G in 3 R14.
於製造前述以通式(4)所示的聚合物時,使用具有乙烯性不飽和雙鍵的單醇、二羧酸酐或環氧化物時,以使用聚合抑制劑較佳。就聚合抑制劑而言,可舉例如氫醌、甲基氫醌、氫醌單甲醚、對-苯醌、2,4-二甲基-6- 第3丁基酚、吩噻嗪(phenothiazine)等較佳,該等以單獨或併用在0.01%~6%,較佳為0.05%~1.0%的範圍使用。 In the case of producing the above-mentioned polymer represented by the formula (4), when a monool, a dicarboxylic anhydride or an epoxide having an ethylenically unsaturated double bond is used, it is preferred to use a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6- may be mentioned. The third butyl phenol, phenothiazine or the like is preferably used alone or in combination in the range of 0.01% to 6%, preferably 0.05% to 1.0%.
〔於單末端具有羥基的乙烯基系聚合物(C1-2)〕 [Vinyl polymer (C1-2) having a hydroxyl group at a single terminal]
於單末端具有羥基的乙烯基系聚合物(C1-2),較佳為以下述通式(6)所示的聚合物。 The vinyl polymer (C1-2) having a hydroxyl group at a single terminal is preferably a polymer represented by the following formula (6).
[通式(6)中,Y2為乙烯基聚合物的聚合停止基,X4為-O-或-S-,Z2為-R27-OH或-R28(OH)2,R27為碳數1~18的直鏈狀、分支狀或環狀的伸烷基,R28為碳原子數1~18的脂肪族、脂環式或芳香族的3價烴基,R21及R22分別獨立為氫原子或甲基,R23及R24係任一者均為氫原子,另一者為芳香族基或-C(=O)-X6-R25(其中,X6為-O-或-N(R26)-),R25、R26為氫原子、碳原子數1~18的直鏈狀、分支狀或環狀的烷基、具有芳香族基作為取代基之碳原子數1~18的直鏈狀或分支狀的烷基或具有醚基的碳原子數 1~18的直鏈狀、分支狀或包含環狀構造的烷基,n為2~50。] [In the formula (6), Y 2 is a polymerization stop group of a vinyl polymer, X 4 is -O- or -S-, Z 2 is -R27-OH or -R28(OH) 2 , and R27 is a carbon number. a linear, branched or cyclic alkyl group of 1 to 18, R28 is an aliphatic, alicyclic or aromatic trivalent hydrocarbon group having 1 to 18 carbon atoms, and R21 and R22 are each independently a hydrogen atom or A methyl group, any of R23 and R24 is a hydrogen atom, and the other is an aromatic group or -C(=O)-X6-R25 (wherein X6 is -O- or -N(R26)-), R25 and R26 are a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a linear or branched alkane having 1 to 18 carbon atoms having an aromatic group as a substituent. The base or the alkyl group having an ether group having 1 to 18 carbon atoms, a branched chain or an alkyl group having a cyclic structure, and n is 2 to 50. ]
前述以通式(6)所示的聚合物,係使乙烯性不飽和單體聚合之乙烯基系聚合物。 The polymer represented by the above formula (6) is a vinyl polymer obtained by polymerizing an ethylenically unsaturated monomer.
前述以通式(6)所示的聚合物的重複單元的部分,亦即{-[C(R21)(R23)-C(R22)(R24)]n-},可為互相相同者所構成(同元聚合物),亦可為相異者所構成(共聚物)。前述以通式(6)所示的聚合物的較佳態樣,係R21及R22中任一者為氫原子,另一者為氫原子或甲基,R23及R24中任一者為氫原子,另一者為-C(=O)-O-R29(R29為碳原子數1~18的直鏈狀、分支狀或環狀的烷基,可具有芳香族基作為取代基者或具有醚基的碳原子數1~18的直鏈狀、分支狀或包含環狀構造的烷基),-X4-Z2為-S-CH2CH2-OH或S-CH2CH(OH)CH2-OH之時。 The portion of the repeating unit of the polymer represented by the formula (6), that is, {-[C(R 21 )(R 23 )-C(R 22 )(R 24 )]n-}, may be mutually The same structure (homopolymer) can also be composed of different (copolymer). In a preferred embodiment of the polymer represented by the formula (6), any one of R 21 and R 22 is a hydrogen atom, and the other is a hydrogen atom or a methyl group, and any of R 23 and R 24 The one is a hydrogen atom, and the other is -C(=O)-O-R29 (R29 is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and may have an aromatic group as a substituent. Or a linear, branched or cyclic alkyl group having an ether group having 1 to 18 carbon atoms, and -X 4 -Z 2 is -S-CH 2 CH 2 -OH or S-CH 2 When CH(OH)CH 2 -OH.
前述通式(6)的Y2,亦即乙烯基聚合物的聚合停止基,可以一般的方法實施一般的乙烯性不飽和單體的聚合之時所導入的任意習知的聚合停止基,係熟悉此技藝者所熟知。具體地,可舉例如來自聚合起始劑的基、來自鏈轉移劑的基、來自溶劑的基或來自乙烯性不飽和單體的基。Y2即使具有該等任一種化學構造,本發明的分散劑亦不受聚合停止基Y2的影響,而可發揮其效果。 Y 2 of the above formula (6), that is, a polymerization stop group of a vinyl polymer, can be any conventional polymerization stop group introduced when a general ethylenically unsaturated monomer is polymerized by a general method. It is well known to those skilled in the art. Specifically, for example, a group derived from a polymerization initiator, a group derived from a chain transfer agent, a group derived from a solvent, or a group derived from an ethylenically unsaturated monomer may be mentioned. Even if Y 2 has any of these chemical structures, the dispersant of the present invention is not affected by the polymerization stopper Y 2 and exerts its effects.
前述以通式(6)所示的聚合物中Z2為-R27-OH者,可以習知的方法製造,例如可使具有羥基與硫醇基之化合物與乙烯性不飽和單體混合而加熱來得到。 In the polymer represented by the formula (6), Z 2 is -R27-OH, which can be produced by a known method. For example, a compound having a hydroxyl group and a thiol group can be mixed with an ethylenically unsaturated monomer to be heated. Come and get.
於分子內具有羥基與硫醇基之化合物,可舉例如巰基甲醇、2-巰基乙醇、3-巰基-1-丙醇、1-巰基-2-丁醇或2-巰基-3-丁醇等。 The compound having a hydroxyl group and a thiol group in the molecule may, for example, be mercapto methanol, 2-mercaptoethanol, 3-mercapto-1-propanol, 1-mercapto-2-butanol or 2-mercapto-3-butanol. .
前述以通式(6)所示的聚合物中Z2為-R28(OH)2者,,可以習知的方法製造,可舉例如使具有2個羥基及1個硫醇基的化合物與乙烯性不飽和單體混合而加熱來得到。此時,於單末端具有羥基的聚合物(C)中,成為最佳的態樣之於單末端具有2個羥基的聚合物(C3)。 In the polymer represented by the formula (6), Z 2 is -R28(OH) 2 , and it can be produced by a known method, and for example, a compound having two hydroxyl groups and one thiol group and ethylene can be produced. The unsaturated monomers are mixed and heated to obtain. In this case, in the polymer (C) having a hydroxyl group at one terminal, the polymer (C3) having two hydroxyl groups at the single terminal is the most preferable.
於分子內具有2個羥基及1個硫醇基的化合物,係可舉例如1-巰基-1,1-甲二醇、1-巰基-1,1-乙二醇、3-巰基-1,2-丙二醇(硫甘油)、2-巰基-1,2-丙二醇、2-巰基-2-甲基-1,3-丙二醇、2-巰基-2-乙基-1,3-丙二醇、1-巰基-2,2-丙二醇、2-巰基乙基-2-甲基-1,3-丙二醇或2-巰基乙基-2-乙基-1,3-丙二醇等。 The compound having two hydroxyl groups and one thiol group in the molecule may, for example, be 1-decyl-1,1-methylglycol, 1-mercapto-1,1-ethanediol or 3-mercapto-1. 2-propanediol (thioglycerol), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1- Mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol or 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.
較佳為相對於乙烯性不飽和單體100質量份,使用1~30質量份的具有羥基及硫醇基的化合物,進行塊狀聚合或溶液聚合。反應溫度較佳為40~150℃,更佳為50~110℃,反應時間較佳為3~30小時,更佳為5~20小時。具有羥基及硫醇基的化合物未達1質量份時,分子量會變大,分散體的黏度變高,有時不佳。若超過30質量份,分子量變小,因溶劑親和性的乙烯基聚合物部分所造成之立體回彈效果變差,故有時不佳。 It is preferred to carry out bulk polymerization or solution polymerization using 1 to 30 parts by mass of a compound having a hydroxyl group and a thiol group with respect to 100 parts by mass of the ethylenically unsaturated monomer. The reaction temperature is preferably from 40 to 150 ° C, more preferably from 50 to 110 ° C, and the reaction time is preferably from 3 to 30 hours, more preferably from 5 to 20 hours. When the compound having a hydroxyl group or a thiol group is less than 1 part by mass, the molecular weight is increased, and the viscosity of the dispersion is increased, which may be poor. When the amount is more than 30 parts by mass, the molecular weight becomes small, and the stereoscopic rebound effect due to the solvent-affinity vinyl polymer portion is deteriorated, which may be poor.
硫醇基係成為用以聚合乙烯性不飽和單體的自由基產生基,該聚合係未必需要其他的聚合起始劑, 但亦可使用。於使用該聚合起始劑之時,相對於乙烯性不飽和單體100質量份,以0.001~5質量份較佳。 The thiol group is a radical generating group for polymerizing an ethylenically unsaturated monomer, and the polymerization system does not necessarily require another polymerization initiator. But it can also be used. When the polymerization initiator is used, it is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the ethylenically unsaturated monomer.
聚合起始劑係可使用例如偶氮系化合物及有機過氧化物。偶氮系化合物之例係可舉例如2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烷1-甲腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基-4-甲氧基戊腈)、二甲基2,2’-偶氮雙(2-甲基丙酸酯)、4,4’-偶氮雙(2-氰基戊酸)、2,2’-偶氮雙(2-羥基甲基丙腈)或2,2’-偶氮雙[2-(2-咪唑啉-2-基)丙烷]等。有機過氧化物之例係可舉例如過氧化苯甲醯、過氧化苯甲酸第3丁酯、過氧化氫異丙苯、過氧化二碳酸二異丙酯、過氧化二碳酸二正丙酯、過氧化二碳酸二(2-乙氧基乙基)酯、過氧化新癸酸第3丁酯、過氧化新戊酸第3丁酯、過氧化(3,5,5-三甲基己醯基)、過氧化二丙醯基或過氧化二乙醯基等。該等聚合起始劑係可單獨或組合2種以上而使用。 As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compound include, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 1,1'-azobis (cyclohexane). Alkane 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxypenta Nitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(2-cyanovaleric acid), 2,2'-azobis ( 2-hydroxymethylpropionitrile or 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of the organic peroxides include, for example, benzamidine peroxide, butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, Di(2-ethoxyethyl) peroxydicarbonate, 3 butyl peroxy neodecanoate, 3 butyl peroxypivalate, peroxidation (3,5,5-trimethylhexanide) Base), dipropenyl peroxide or diethylperoxy peroxide. These polymerization initiators can be used singly or in combination of two or more.
乙烯性不飽和單體係只要為可共聚合的單體即可,並無特別限制,可依據用途而適當地選擇。 The ethylenically unsaturated single system is not particularly limited as long as it is a copolymerizable monomer, and may be appropriately selected depending on the use.
可舉例如:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第3丁酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-甲基己酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基) 丙烯酸十三烷基酯、(甲基)丙烯酸異十四烷基酯、(甲基)丙烯酸硬脂酯及(甲基)丙烯酸異硬脂酯等直鏈或分支的(甲基)丙烯酸烷酯類;(甲基)丙烯酸環己酯、(甲基)丙烯酸第3丁基環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯及(甲基)丙烯酸異莰酯等環狀(甲基)丙烯酸烷酯類;四氫呋喃甲基(甲基)丙烯酸酯及3-甲基-3-氧雜環丁烷基(oxetanyl)(甲基)丙烯酸酯等具有雜環的(甲基)丙烯酸酯類;(甲基)丙烯酸苯甲酯、(甲基)丙烯酸苯氧基乙酯的具有芳香環的(甲基)丙烯酸酯類;(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-甲氧基丙酯、二乙二醇單甲醚(甲基)丙烯酸酯、二乙二醇單乙醚(甲基)丙烯酸酯、二乙二醇單-2-甲基己醚(甲基)丙烯酸酯、二丙二醇單甲醚(甲基)丙烯酸酯、三乙二醇單甲醚(甲基)丙烯酸酯、三乙二醇單乙醚(甲基)丙烯酸酯、三丙二醇單甲醚(甲基)丙烯酸酯、四乙二醇單乙醚(甲基)丙烯酸酯、聚乙二醇單乙醚(甲基)丙烯酸酯、聚丙二醇單乙醚(甲基)丙烯酸酯、聚乙二醇單月桂醚(甲基)丙烯酸酯、聚乙二醇單硬脂醚(甲基)丙烯酸酯及辛氧基聚乙二醇-聚丙二醇(甲基)丙烯酸酯等(聚)烷二醇單烷醚(甲基)丙烯酸酯類;(甲基)丙烯酸苯氧基乙酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基四乙二醇(甲基)丙烯酸酯、苯氧基六乙二醇 (甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸對異丙苯基苯氧基乙酯、對異丙苯基苯氧基乙二醇(甲基)丙烯酸酯、對異丙苯基苯氧基聚乙二醇(甲基)丙烯酸酯、壬基苯氧基聚乙二醇(甲基)丙烯酸酯、壬基苯氧基聚丙二醇(甲基)丙烯酸酯及壬基苯氧基聚(乙二醇-丙二醇)(甲基)丙烯酸酯等具有芳香族環的(聚)烷二醇單烷醚(甲基)丙烯酸酯類;3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷及3-丙烯醯氧基丙基三甲氧基矽烷等具有烷氧基矽烷基之(甲基)丙烯酸酯類;(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸八氟戊酯、(甲基)丙烯酸全氟辛基乙酯及(甲基)丙烯酸四氟丙酯等(甲基)丙烯酸氟烷酯類;(甲基)丙烯醯氧基改性的聚二甲基矽氧烷(矽氧樹脂大分子)類;(甲基)丙烯醯胺、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)丙烯醯胺及丙烯醯基嗎啉(morpholine)等N取代型(甲基)丙烯醯胺類;以及(甲基)丙烯腈等腈類等。 For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid Isobutyl ester, 3 butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-methyl methacrylate Ester, hexadecyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, (methyl) Linear or branched alkyl (meth)acrylates such as tridecyl acrylate, isotetradecyl (meth) acrylate, stearyl (meth) acrylate and isostearyl (meth) acrylate Cyclohexyl (meth)acrylate, 3 butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and (meth)acrylic acid Cyclic (meth)acrylic acid alkyl esters such as isodecyl ester; tetrahydrofuran methyl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate, etc. Ring (meth) acrylates; benzyl (meth) acrylate, (meth) acrylates having an aromatic ring of phenoxyethyl (meth) acrylate; 2-methyl (meth) acrylate Oxyethyl ester, 2-ethoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol single Ethyl (meth) acrylate, diethylene glycol mono-2-methylhexyl (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (methyl) Acrylate, triethylene glycol monoethyl ether (methyl) propylene Ester, tripropylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, polypropylene glycol monoethyl ether (meth) acrylate , polyethylene glycol monolaurate (meth) acrylate, polyethylene glycol monostearyl ether (meth) acrylate and octyloxy polyethylene glycol - polypropylene glycol (meth) acrylate, etc. (poly) Alkylene glycol monoalkyl ether (meth) acrylates; phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxytetraethylene glycol (methyl) Acrylate, phenoxy hexaethylene glycol (Meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, p-cumyl phenoxyethyl (meth) acrylate, p- cumyl phenoxy glycol (A) Acrylate, p-cumylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polypropylene glycol (methyl (poly)alkylene glycol monoalkyl ether (meth) acrylates having an aromatic ring such as acrylate and nonylphenoxy poly(ethylene glycol-propylene glycol) (meth) acrylate; 3-methyl Propylene methoxypropyl methyl dimethoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3-methyl propylene methoxy propyl methyl diethoxy decane, 3-methyl (meth) acrylates having alkoxyalkylene groups such as acryloxypropyltriethoxydecane and 3-propenyloxypropyltrimethoxydecane; and trifluoroethyl (meth)acrylate , fluoroalkyl (meth) acrylate such as octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate and tetrafluoropropyl (meth) acrylate; (meth) propylene oxime Modified polydimethyl oxirane Lipid macromolecules; (meth) acrylamide, dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) propylene N-substituted (meth) acrylamides such as decylamine, diacetone (meth) acrylamide, and morpholine; and nitriles such as (meth)acrylonitrile.
而且,可使用苯乙烯及α-甲基苯乙烯等苯乙烯類; 乙基乙烯基醚、正丙基乙烯基醚、異丙基乙烯基醚、正丁基乙烯基醚及異丁基乙烯基醚等乙烯基醚類;以及乙酸乙烯酯及丙酸乙烯酯等的脂肪酸乙烯酯類等。 Further, styrene such as styrene or α-methylstyrene may be used; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; and vinyl acetate and vinyl propionate Fatty acid vinyl esters, etc.
再者,亦可併用含有羧基的乙烯性不飽和單體。含有羧基的乙烯性不飽和單體係可舉例如(甲基)丙烯酸、(甲基)丙烯酸二聚物、亞甲基丁二酸、順丁烯二酸、反丁烯二酸、2-丁烯酸、鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基丙酯、六氫鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、六氫鄰苯二甲酸2-(甲基)丙烯醯氧基丙酯、(甲基)丙烯酸β-羧基乙酯及ω-羧基聚己內酯(甲基)丙烯酸酯等。 Further, an ethylenically unsaturated monomer having a carboxyl group may also be used in combination. The ethylenically unsaturated single system containing a carboxyl group may, for example, be (meth)acrylic acid, (meth)acrylic acid dimer, methylene succinic acid, maleic acid, fumaric acid, 2-butyl Acrylic acid, 2-(methyl) propylene methoxyethyl phthalate, 2-(methyl) propylene methoxy propyl phthalate, 2-(methyl) propylene hexahydrophthalate醯 methoxyethyl ester, 2-(meth) propylene methoxy propyl hexaphthalate, β-carboxyethyl (meth) acrylate and ω-carboxy polycaprolactone (meth) acrylate, etc. .
以上所舉出的乙烯性不飽和單體之中,可選擇1種或2種以上,使用至少選自(甲基)丙烯酸苯甲酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯及(甲基)丙烯酸甲氧基乙酯所成群的乙烯性不飽和單體為較佳。 One or two or more kinds of the above-mentioned ethylenically unsaturated monomers may be used, and at least one selected from the group consisting of benzyl (meth)acrylate, methyl (meth)acrylate, and (meth)acrylic acid B may be used. Ethylene-unsaturated monomers in which the ester and methoxyethyl (meth)acrylate are grouped are preferred.
於製造前述以通式(6)所示的聚合物的步驟中,可使用無溶劑或視情況而使用溶劑。溶劑係可使用例如乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲苯、二甲苯、丙酮、己烷、甲基乙基酮、環己酮、丙二醇單甲醚乙酸酯、二丙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、乙二醇單丁醚乙酸酯、二乙二醇單乙醚乙酸酯或二乙二醇單丁醚乙酸酯等,但不限於該等。該等的聚合溶劑係可混合2種以上而使用。 In the step of producing the polymer represented by the above formula (6), a solvent may be used or a solvent may be used as the case may be. As the solvent, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol single can be used. Methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate or diethylene glycol monobutyl ether acetate, but not limited to These are the same. These polymerization solvents can be used by mixing two or more types.
使用的溶劑量係相對於乙烯性不飽和單體100質量份,較佳為0~300質量份,0~100質量份更佳。使用的溶劑係在反應結束後,藉由蒸餾等的操作除去,或亦可直接使用來作為分散劑的製品之一部分。 The amount of the solvent to be used is preferably from 0 to 300 parts by mass, more preferably from 0 to 100 parts by mass, per 100 parts by mass of the ethylenically unsaturated monomer. The solvent to be used is removed by an operation such as distillation after completion of the reaction, or may be used as a part of a dispersant.
〔於側鏈具有羥基的聚合物(C2)〕 [Polymer (C2) having a hydroxyl group in a side chain]
本發明的於側鏈具有羥基的聚合物(C2),係可使具有羥基的乙烯性不飽和單體與依據需要的其他乙烯性不飽和單體聚合而得。具有羥基的乙烯性不飽和單體係可舉例如:具有羥基的(甲基)丙烯酸酯系單體例如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2(或3)-羥基丙酯、(甲基)丙烯酸2(或3或4)-羥基丁酯或環己烷二甲醇單(甲基)丙烯酸酯等(甲基)丙烯酸羥基烷酯或α-羥基甲基丙烯酸乙酯等α-羥基烷基丙烯酸烷酯;或具有羥基的(甲基)丙烯醯胺系單體例如N-(2-羥基乙基)(甲基)丙烯醯胺、N-(2-羥基丙基)(甲基)丙烯醯胺或N-(2-羥基丁基)(甲基)丙烯醯胺等N-(2-羥基烷基)(甲基)丙烯醯胺;或具有羥基的乙烯基醚系單體例如2-羥基乙基乙烯基醚、2-(或3-)羥基丙基乙烯基醚或2-(或3-或4-)羥基丁基乙烯基醚等羥基烷基乙烯基醚;或具有羥基的烯丙基醚系單體例如2-羥基乙基烯丙基醚、2-(或3-)羥基丙基烯丙基醚或2-(或3-或4-)羥基丁基烯丙基醚等羥基烷基烯丙基醚等。 The polymer (C2) having a hydroxyl group in a side chain of the present invention can be obtained by polymerizing an ethylenically unsaturated monomer having a hydroxyl group with other ethylenically unsaturated monomers as needed. The ethylenically unsaturated single system having a hydroxyl group may, for example, be a (meth)acrylate monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or 2 (or 3)-hydroxyl (meth)acrylate. Propyl ester, 2 (or 3 or 4)-hydroxybutyl (meth)acrylate or hydroxyalkyl (meth)acrylate or ethyl α-hydroxyethyl methacrylate such as cyclohexanedimethanol mono(meth)acrylate Or an α-hydroxyalkyl acrylate alkyl ester; or a (meth) acrylamide amine monomer having a hydroxyl group such as N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl) N-(2-hydroxyalkyl)(meth)acrylamide such as (meth)acrylamide or N-(2-hydroxybutyl)(meth)acrylamide; or vinyl ether having a hydroxyl group a monomer such as 2-hydroxyethyl vinyl ether, 2-(or 3-)hydroxypropyl vinyl ether or a hydroxyalkyl vinyl ether such as 2-(or 3- or 4-)hydroxybutyl vinyl ether Or an allyl ether-based monomer having a hydroxyl group such as 2-hydroxyethylallyl ether, 2-(or 3-)hydroxypropylallyl ether or 2-(or 3- or 4-)hydroxybutyl A hydroxyalkyl allyl ether such as allyl ether or the like.
又,亦可舉例如甘油單(甲基)丙烯酸酯等具 有2個羥基的單體。再者,於具有環氧基等的環狀醚基之乙烯性不飽和單體,使(甲基)丙烯酸等含有羧基的乙烯性不飽和單體反應者,或於(甲基)丙烯酸等含有羧基的乙烯性不飽和單體,使單官能基環氧化合物等單官能基環狀醚化合物反應者等。 Further, for example, a glycerin mono(meth)acrylate or the like may be mentioned. A monomer having 2 hydroxyl groups. In addition, the ethylenically unsaturated monomer having a cyclic ether group such as an epoxy group is reacted with a carboxyl group-containing ethylenically unsaturated monomer such as (meth)acrylic acid or (meth)acrylic acid or the like. The ethylenically unsaturated monomer of a carboxyl group is a reaction of a monofunctional cyclic ether compound such as a monofunctional epoxy compound.
又,於上述(甲基)丙烯酸羥基烷酯、α-羥基烷基丙烯酸烷酯、N-(羥基烷基)(甲基)丙烯醯胺、羥基烷基乙烯基醚、羥基烷基烯丙基醚或甘油單(甲基)丙烯酸酯,使環氧烷及/或內酯加成所得之乙烯性不飽和單體,於本發明的方法中,可使用來作為具有羥基的乙烯性不飽和單體。所加成的環氧烷係可舉例如環氧乙烷、環氧丙烷或1,2-、1,4-、2,3-或1,3-環氧丁烷,亦可使用該等2種以上的組合。併用2種以上的環氧烷時的鍵結形式,可為無規則及/或嵌段的任一種。所加成的內酯係可舉例如δ-戊內酯、ε-己內酯或碳原子數1~6的烷基取代之ε-己內酯,亦可使用該等2種以上的組合。亦可為環氧烷及內酯兩者皆加成者。 Further, the above-mentioned (meth)acrylic acid hydroxyalkyl ester, α-hydroxyalkylalkyl acrylate, N-(hydroxyalkyl)(meth)acrylamide, hydroxyalkyl vinyl ether, hydroxyalkyl allyl Ether or glycerol mono(meth) acrylate, an ethylenically unsaturated monomer obtained by adding an alkylene oxide and/or a lactone, can be used as an ethylenically unsaturated monomer having a hydroxyl group in the process of the present invention. body. The alkylene oxide to be added may, for example, be ethylene oxide, propylene oxide or 1,2-, 1,4-, 2,3- or 1,3-epoxybutane, or may be used. More than one combination. Further, in the case of using two or more kinds of alkylene oxides, the bonding form may be any of random and/or block. The lactone to be added may, for example, be δ-valerolactone, ε-caprolactone or an alkyl-substituted ε-caprolactone having 1 to 6 carbon atoms, or a combination of two or more kinds thereof. It can also be added to both alkylene oxide and lactone.
具有羥基的乙烯性不飽和單體與其他乙烯性不飽和單體的共聚合比例,以使於聚合後的一分子平均至少置入0.3~177個羥基之方式來決定為較佳。 The copolymerization ratio of the ethylenically unsaturated monomer having a hydroxyl group to the other ethylenically unsaturated monomer is preferably determined so that at least one molecule after polymerization is placed at least 0.3 to 177 hydroxyl groups.
其他乙烯性不飽和單體係可舉例如製造前述以通式(6)所示的聚合物的步驟說明的乙烯性不飽和單體,可任意使用。 The other ethylenically unsaturated single system may, for example, be an ethylenically unsaturated monomer described in the step of producing the polymer represented by the above formula (6), and may be used arbitrarily.
聚合起始劑係可使用例如製造以前述通式 (6)所示的聚合物的步驟說明的偶氮系化合物或有機過氧化物。於使用該聚合起始劑時,相對於乙烯性不飽和單體100質量份,較佳為0.01~20質量份。 The polymerization initiator can be used, for example, in the production of the above formula (6) An azo compound or an organic peroxide described in the step of the polymer shown. When the polymerization initiator is used, it is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the ethylenically unsaturated monomer.
聚合溶劑係例如可使用與製造前述以通式(6)所示的聚合物的步驟說明的溶劑相同者。 The polymerization solvent can be, for example, the same solvent as that described in the step of producing the polymer represented by the above formula (6).
〈具有羥基的聚合物(C)與芳香族三羧酸酐(D1)以及/或芳香族四羧酸二酐(D2)的反應〉 Reaction of a polymer having a hydroxyl group (C) with an aromatic tricarboxylic anhydride (D1) and/or an aromatic tetracarboxylic dianhydride (D2)
接著,說明有關使具有羥基的聚合物(C)與芳香族三羧酸酐(D1)以及/或芳香族四羧酸二酐(D2)反應之步驟。 Next, a step of reacting a polymer (C) having a hydroxyl group with an aromatic tricarboxylic anhydride (D1) and/or an aromatic tetracarboxylic dianhydride (D2) will be described.
關於上述反應,係於單末端具有羥基的聚合物(C1)或於側鏈具有羥基的聚合物(C2)與芳香族三羧酸酐(D1)以及/或芳香族四羧酸二酐(D2)反應為較佳。 The above reaction is a polymer (C1) having a hydroxyl group at one terminal or a polymer (C2) having a hydroxyl group in a side chain, and an aromatic tricarboxylic anhydride (D1) and/or an aromatic tetracarboxylic dianhydride (D2). The reaction is preferred.
藉由前述於單末端具有羥基的聚合物(C1)或於側鏈具有羥基的聚合物(C2)的羥基、與芳香族三羧酸酐(D1)以及/或芳香族四羧酸二酐(D2)的酸酐基反應,可得到本發明的具有芳香族羧基之樹脂型分散劑(A)。 By the above-mentioned polymer (C1) having a hydroxyl group at a single terminal or a hydroxyl group of a polymer (C2) having a hydroxyl group in a side chain, and an aromatic tricarboxylic anhydride (D1) and/or an aromatic tetracarboxylic dianhydride (D2) The acid anhydride group reaction of the present invention can obtain the resin type dispersant (A) having an aromatic carboxyl group of the present invention.
芳香族三羧酸酐(D1)係可舉例如苯三羧酸酐(1,2,3-苯三羧酸酐、偏苯三羧酸酐(1,2,4-苯三羧酸酐)等)、萘三羧酸酐(1,2,4-萘三羧酸酐、1,4,5-萘三羧酸酐、2,3,6-萘三羧酸酐、1,2,8-萘三羧酸酐等)、3,4,4’-二苯基酮三羧酸酐、3,4,4’-聯苯醚三羧酸酐、3,4,4’-聯苯三羧酸酐、2,3,2’-聯苯三羧酸酐、3,4,4’-聯苯甲烷三羧酸酐或3,4,4’-聯苯碸三羧酸酐等。 Examples of the aromatic tricarboxylic anhydride (D1) include benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride (1,2,4-benzenetricarboxylic anhydride), etc.), and naphthalene Carboxylic anhydride (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, etc.), 3 , 4,4'-diphenyl ketone tricarboxylic anhydride, 3,4,4'-diphenyl ether tricarboxylic anhydride, 3,4,4'-biphenyl tricarboxylic anhydride, 2,3,2'-biphenyl Tricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride or 3,4,4'-biphenylfluorene tricarboxylic anhydride.
芳香族四羧酸二酐(D2)係可舉例如均苯四 甲酸二酐(pyromellitic anhydride)、乙二醇二偏苯三羧酸酐酯、丙二醇二偏苯三羧酸酐酯、丁二醇二偏苯三羧酸酐酯、3,3’,4,4’-二苯基酮四羧酸二酐、2,2’,3,3’-二苯基酮四羧酸二酐、3,3’,4,4’-聯苯碸四羧酸二酐、2,2’,3,3’-聯苯碸四羧酸二酐、1,4,5,8-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、3,3’,4,4’-聯苯醚四羧酸二酐、3,3’,4,4’-二甲基二苯基矽烷四羧酸二酐、3,3’,4,4’-四苯基矽烷四羧酸二酐、1,2,3,4-呋喃四羧酸二酐、4,4’-雙(3,4-二羧基苯氧基)二苯硫醚二酐、4,4’-雙(3,4-二羧基苯氧基)二苯基碸二酐、4,4’-雙(3,4-二羧基苯氧基)二苯基丙烷二酐、3,3’,4,4’-全氟次異丙基鄰苯二甲酸二酐、3,3’,4,4’-聯苯四羧酸二酐、雙(鄰苯二甲酸)苯基氧化膦二酐、對-伸苯基-雙(三苯基鄰苯二甲酸)二酐、間-伸苯基-雙(三苯基鄰苯二甲酸)二酐、雙(三苯基鄰苯二甲酸)-4,4’-二苯基醚二酐、雙(三苯基鄰苯二甲酸)-4,4’-二苯基甲烷二酐、9,9-雙(3,4-二羧基苯基)茀二酐或9,9-雙[4-(3,4-二羧基苯氧基)苯基]茀二酐等。 The aromatic tetracarboxylic dianhydride (D2) is, for example, a pyromelli-4 Pyromellitic anhydride, ethylene glycol di trimellitic anhydride, propylene glycol di trimellitic anhydride, butanediol di trimellitic anhydride, 3,3', 4,4'- Phenyl ketone tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl fluorene tetracarboxylic dianhydride, 2, 2',3,3'-biphenylfluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3',4,4'-four Phenylnonane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3' , 4,4'-perfluoroisopropylidene phthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride , p-phenyl-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)- 4,4'- Phenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)ruthenium anhydride or 9, 9-bis[4-(3,4-dicarboxyphenoxy)phenyl]ruthenium hydride.
本發明所使用的芳香族三羧酸酐(D1)及芳香族四羧酸二酐(D2),係不限於前述例示的化合物,可為任意構造者。該等可單獨使用,亦可併用。本發明所使用者,較佳為偏苯三羧酸酐、均苯四甲酸二酐。 The aromatic tricarboxylic anhydride (D1) and the aromatic tetracarboxylic dianhydride (D2) used in the present invention are not limited to the above-exemplified compounds, and may be any structure. These may be used alone or in combination. The user of the present invention is preferably trimellitic anhydride or pyromellitic dianhydride.
聚合物(C)的羥基之莫耳數為〈H〉,芳香族三羧酸酐(D1)或芳香族四羧酸二酐(D2)的羧酸酐基之莫耳數為〈N〉時,反應比例為0.3≦〈H〉/〈N〉≦3較佳,更佳為0.5≦〈H〉/〈N〉≦2時。特別是使用聚合物(C3)作 為聚合物(C)時,較佳為1<〈H〉/〈N〉≦2。若以〈H〉/〈N〉<1反應時,殘存的酸酐,可以需要量的水進行水解,亦可以單官能基醇進行醇解。 When the number of moles of the hydroxyl group of the polymer (C) is <H>, and the number of moles of the carboxylic anhydride group of the aromatic tricarboxylic anhydride (D1) or the aromatic tetracarboxylic dianhydride (D2) is <N>, the reaction The ratio is preferably 0.3 ≦ < H > / < N > ≦ 3, more preferably 0.5 ≦ < H > / < N > ≦ 2 . Especially using polymer (C3) When it is a polymer (C), it is preferable that it is 1 < < H> / <N> ≦2. When the reaction is carried out by <H>/<N><1, the remaining acid anhydride may be hydrolyzed by a required amount of water, or may be subjected to alcoholysis with a monofunctional alcohol.
於使用聚合物(C2)時,於一分子內導入0.3個至3個芳香族三羧酸酐及或芳香族四羧酸二酐為較佳。具體地,測定聚合物(C2)的數目平均分子量,該測定值為〔X〕之時,於使用芳香族三羧酸酐(D1)時,可對樹脂〔X〕g使0.3莫耳以上3莫耳以下的芳香族三羧酸酐反應。另一方面,於使用芳香族四羧酸二酐(D2)時,可對樹脂〔X〕g使0.15莫耳以上1.5莫耳以下的芳香族四羧酸二酐反應。此係芳香族四羧酸二酐具有2個酸酐基,故為了橋接聚合物(C2)分子,於使用芳香族四羧酸二酐(D2)時,只要一半量即可。 When the polymer (C2) is used, it is preferred to introduce 0.3 to 3 aromatic tricarboxylic anhydrides or aromatic tetracarboxylic dianhydrides in one molecule. Specifically, the number average molecular weight of the polymer (C2) is measured. When the measured value is [X], when the aromatic tricarboxylic anhydride (D1) is used, the resin [X]g can be made 0.3 mol or more. The aromatic tricarboxylic anhydride below the ear is reacted. On the other hand, when the aromatic tetracarboxylic dianhydride (D2) is used, the aromatic tetracarboxylic dianhydride of 0.15 mol or more and 1.5 mol or less can be reacted with respect to the resin [X]g. Since the aromatic tetracarboxylic dianhydride has two acid anhydride groups, in order to bridge the polymer (C2) molecule, when the aromatic tetracarboxylic dianhydride (D2) is used, it may be used in half.
於具有羥基的聚合物(C)、與芳香族三羧酸酐(D1)以及/或芳香族四羧酸二酐(D2)的反應,亦可使用觸媒。觸媒係可使用3級胺系化合物,可舉例如三乙基胺、三伸乙基二胺、N,N-二甲基苯甲基胺、N-甲基嗎啉、1,8-二氮雜雙環-[5.4.0]-7-十一烯或1,5-二氮雜雙環-[4.3.0]-5-壬烯等。 A catalyst may also be used for the reaction of the polymer (C) having a hydroxyl group with the aromatic tricarboxylic anhydride (D1) and/or the aromatic tetracarboxylic dianhydride (D2). As the catalyst system, a tertiary amine compound can be used, and examples thereof include triethylamine, triethylamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-di. Azabicyclo-[5.4.0]-7-undecene or 1,5-diazabicyclo-[4.3.0]-5-decene.
於具有羥基的聚合物(C)、與芳香族三羧酸酐(D1)以及/或芳香族四羧酸二酐(D2)的反應,係可在無溶劑下進行,亦可使用適當的脫水有機溶劑。反應所使用的溶劑,係在反應結束後,藉由蒸餾等的操作除去,或亦可直接使用來作為分散劑的製品之一部分。使用的溶劑,無 特別限制,可使用與製造前述以通式(6)所示的聚合物的步驟說明的溶劑相同者。 The reaction of the polymer (C) having a hydroxyl group with the aromatic tricarboxylic anhydride (D1) and/or the aromatic tetracarboxylic dianhydride (D2) can be carried out without a solvent, or an appropriate dehydrated organic can be used. Solvent. The solvent used in the reaction is removed by an operation such as distillation after the completion of the reaction, or may be used as a part of the dispersant. Solvent used, none It is particularly limited to use the same solvent as that described in the step of producing the polymer represented by the above formula (6).
具有羥基的聚合物(C)、與芳香族三羧酸酐(D1)或芳香族四羧酸二酐(D2)的反應溫度,較佳為50℃~180℃,更佳為60℃~160℃的範圍下進行。反應溫度未達50℃時,反應速度變慢,若超過180℃,進行反應而開環的酸酐再次生成環狀酐,有時反應很難結束。 The reaction temperature of the polymer (C) having a hydroxyl group, the aromatic tricarboxylic anhydride (D1) or the aromatic tetracarboxylic dianhydride (D2) is preferably from 50 ° C to 180 ° C, more preferably from 60 ° C to 160 ° C. Under the scope of the. When the reaction temperature is less than 50 ° C, the reaction rate becomes slow. When the reaction temperature exceeds 180 ° C, the reaction-opened acid anhydride forms a cyclic anhydride again, and the reaction may be difficult to complete.
〈具有哌啶基骨架之乙烯基系樹脂型分散劑(B)〉 <Vinyl Resin Type Dispersant (B) having a piperidinyl skeleton>
本發明的具有哌啶基骨架之乙烯基系樹脂型分散劑(B),可使以通式(7)所示的具有哌啶基骨架之單體與依據需要的其他乙烯性不飽和單體聚合而得。 The vinyl-based resin type dispersing agent (B) having a piperidinyl skeleton of the present invention can have a monomer having a piperidinyl skeleton represented by the formula (7) and other ethylenically unsaturated monomers as required. Aggregated.
(式(7)中,R1表示氫原子、碳數1~18的烷基、碳數6~20的芳香基、碳數7~12的芳烷基、醯基、氧自由基或OR4,R4表示氫原子、碳數1~18的烷基、碳數6~20的芳香基、碳數7~12的芳烷基、醯基,R2及R3分別獨立表示甲基、乙基或苯基。「*」表示鍵結手。) (In the formula (7), R 1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an anthracenyl group, an oxygen radical or OR 4 , R 4 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and an aromatic group having a carbon number 6 to 20 carbon atoms, an aralkyl group having 7 to 12 acyl, R 2 and R 3 independently represent methyl, ethyl, Base or phenyl. "*" means bonding.)
上述於通式(7)中,R1及R4之碳數1~18的烷基,係可舉例如直鏈狀、分支狀、環狀之烷基,具體上可舉例如甲 基、乙基、正丙基、異丙基、正丁基、第3丁基、正己基、環己基、正辛基、十六烷基等。 In the above formula (7), the alkyl group having 1 to 18 carbon atoms of R 1 and R 4 may, for example, be a linear, branched or cyclic alkyl group, and specific examples thereof include methyl group and ethyl group. Base, n-propyl, isopropyl, n-butyl, butyl, n-hexyl, cyclohexyl, n-octyl, hexadecyl and the like.
而且,於上述通式(7)中R1及R4之碳數6~20的芳香基,可舉例如苯基、1-萘基、2-萘基等。 Further, in the above formula (7), the aromatic group having 6 to 20 carbon atoms of R 1 and R 4 may, for example, be a phenyl group, a 1-naphthyl group or a 2-naphthyl group.
而且,於上述通式(7)中R1及R4之碳數7~12的芳烷基,可舉例如於碳數6~20的芳香基鍵結碳數1~8的烷基之基,具體地可舉例如苯甲基、苯乙基、α-甲基苯甲基、2-苯基丙-2-基等。 Further, in the above formula (7), the aralkyl group having 7 to 12 carbon atoms of R 1 and R 4 may, for example, be an alkyl group having a carbon number of 6 to 20 bonded to an alkyl group having 1 to 8 carbon atoms. Specific examples thereof include a benzyl group, a phenethyl group, an α-methylbenzyl group, and a 2-phenylpropan-2-yl group.
而且,於上述通式(7)中R1及R4之醯基,可舉例如碳數2~8的烷醯基及芳醯基,具體上可舉例如乙醯基、苯甲醯基等。 Further, examples of the fluorenyl group of R 1 and R 4 in the above formula (7) include an alkanoyl group and an aryl group having 2 to 8 carbon atoms, and specific examples thereof include an ethyl fluorenyl group and a benzamidine group. .
於本發明中,R1較佳為氫原子、碳數1~5的烷基、氧自由基,更佳為氫原子、甲基,特別佳為甲基。 In the present invention, R 1 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an oxygen radical, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.
只要具有以通式(7)所示的哌啶基骨架即可,並無特別限制,較佳為來自乙烯性不飽和單體的部分構造。 The piperidinyl skeleton represented by the formula (7) is not particularly limited, and is preferably a partial structure derived from an ethylenically unsaturated monomer.
具有哌啶基骨架之乙烯性不飽和單體,從顏料分散體的黏度及黏度安定性的觀點,相對於乙烯性不飽和單體固體成分,含有1質量%~100質量%為較佳,含有25質量%~100質量%為更佳,含有40質量%~100質量%為特別佳。 The ethylenically unsaturated monomer having a piperidinyl group is preferably contained in an amount of from 1% by mass to 100% by mass based on the solid content of the ethylenically unsaturated monomer, from the viewpoint of the viscosity and the viscosity stability of the pigment dispersion. 25% by mass to 100% by mass is more preferable, and 40% by mass to 100% by mass is particularly preferable.
哌啶基骨架因具有抗氧化功能,即使少量含有,亦可防止彩色濾光片材料的氧化,結果可防止亮度的降低。 Since the piperidinyl skeleton has an antioxidant function, even if it is contained in a small amount, the oxidation of the color filter material can be prevented, and as a result, the decrease in brightness can be prevented.
再者,本發明的具有哌啶基骨架之乙烯基系樹脂型分散劑(B),其胺價為50~350mgKOH/g較佳。胺價未達50mgKOH/g時,顏料分散體的黏度及黏度安定性有時變差。超過350mgKOH/g時,亮度有時降低。 Further, the vinyl-based resin type dispersant (B) having a piperidinyl skeleton of the present invention preferably has an amine value of 50 to 350 mgKOH/g. When the amine price is less than 50 mgKOH/g, the viscosity and viscosity stability of the pigment dispersion sometimes deteriorate. When it exceeds 350 mgKOH/g, the brightness sometimes decreases.
再者,本發明的具有哌啶基骨架之乙烯基系樹脂型分散劑(B)的數目平均分子量,較佳為500~30,000,更佳為2000~30,000。未達500,或超過30,000時,顏料分散體的黏度及黏度安定性有時變差。 Further, the number average molecular weight of the vinyl-based resin type dispersant (B) having a piperidinyl skeleton of the present invention is preferably from 500 to 30,000, more preferably from 2,000 to 30,000. When it is less than 500 or exceeds 30,000, the viscosity and viscosity stability of the pigment dispersion sometimes deteriorate.
上述具有哌啶基骨架之乙烯性不飽和單體的具體例,可舉例如下述以通式(8-1)所示的化合物、下述通式(8-2)所示的化合物等。 Specific examples of the ethylenically unsaturated monomer having a piperidinyl group are, for example, a compound represented by the formula (8-1), a compound represented by the following formula (8-2), and the like.
(於通式(8-1)及通式(8-2)中,R5及R7互相表示氫原子或甲基,R6表示亞甲基或碳數2~5的伸烷基,X表示上述以通式(7)所示的基,Y表示-CONH-*、-SO2-*、-SO2NH-*(其中,附有「*」之鍵結手係與X鍵結),n表示0~9的整數。)R6較佳為伸乙基、伸丙基,特別佳為伸乙基。n為0~8的整數,特別佳為0~6的整數。 (In the formula (8-1) and the formula (8-2), R 5 and R 7 each represent a hydrogen atom or a methyl group, and R 6 represents a methylene group or a C 2 to 5 alkyl group, X The above is represented by the formula (7), and Y represents -CONH-*, -SO 2 -*, -SO 2 NH-* (wherein the "*" bond hand and X bond are attached) , n represents an integer of 0 to 9.) R 6 is preferably an ethyl group, a propyl group, and particularly preferably an ethyl group. n is an integer of 0 to 8, and particularly preferably an integer of 0 to 6.
上述以通式(8-1)所示的單體之具體例,可 舉例如下述以通式(9-1)~(9-7)所示的化合物等。 Specific examples of the monomer represented by the formula (8-1) above may be used. Examples thereof include compounds represented by the general formulae (9-1) to (9-7) and the like.
(於通式(9-1)~通式(9-7)中,R5係與通式(8-1)之R5意義相同。) (In the formulae (9-1) to (9-7), the R 5 group has the same meaning as the R 5 of the formula (8-1).)
而且,通式(8-2)所示的單體之具體例,可舉例如下述以通式(10-1)~(10-4)所示的化合物等。 Further, specific examples of the monomer represented by the formula (8-2) include, for example, the compounds represented by the following formulas (10-1) to (10-4).
(於通式(10-1)~通式(10-4)中,R7係與通式(8-2)之R7意義相同。) (In the formulae (10-1) to (10-4), the R 7 group has the same meaning as R 7 of the formula (8-2).)
該等之中,較佳為2,2,6,6-四甲基哌啶基甲基丙烯酸酯(上述通式9-1)中,R5為甲基的化合物)、1,2,2,6,6-五甲基哌啶基甲基丙烯酸酯(上述通式9-2)中,R5為甲基的化合物),特別佳為1,2,2,6,6-五甲基哌啶基甲基丙烯酸酯(上述通式9-2)。 Among these, a compound of 2,2,6,6-tetramethylpiperidyl methacrylate (in the above formula 9-1, wherein R 5 is a methyl group), 1, 2, 2 is preferable. 6,6-pentamethylpiperidinyl methacrylate (in the above formula 9-2, a compound wherein R 5 is a methyl group), particularly preferably 1,2,2,6,6-pentamethyl Piperidinyl methacrylate (formula 9-2 above).
其他乙烯性不飽和單體係只要是可與具有哌啶基骨架之乙烯性不飽和單體共聚合的單體即可,無特別限制,可依據用途適當選擇。 The other ethylenically unsaturated monomer system is not particularly limited as long as it is a monomer copolymerizable with the ethylenically unsaturated monomer having a piperidinyl skeleton, and may be appropriately selected depending on the use.
可舉例如於製造前述以通式(6)所示的聚合物以及前述於側鏈具有羥基的聚合物(C2)的步驟說明的乙烯性不飽和單體,可任意使用。而且,亦可併用含有胺基的乙烯性不飽和單體,可舉例如,(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸N,N-二乙基胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基丙酯及(甲基)丙烯酸N,N-二乙基胺基丙酯等具有3級胺基的(甲基)丙烯酸酯類;N,N-二甲基胺基乙基(甲基)丙烯醯胺、N,N-二乙基胺基乙基(甲基)丙烯醯胺、N,N-二甲基胺基丙基(甲基)丙烯醯胺及N,N-二乙基胺基丙基(甲基)丙烯醯胺等具有3級胺基的(甲基)丙烯醯胺類;以及二甲基胺基苯乙烯、二乙基胺基苯乙烯等。 For example, the ethylenically unsaturated monomer described in the step of producing the polymer represented by the formula (6) and the polymer (C2) having a hydroxyl group in the side chain can be used arbitrarily. Further, an ethylenically unsaturated monomer having an amine group may also be used in combination, and examples thereof include N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylamine (meth)acrylate. (meth) acrylate having a 3-stage amine group, such as ethyl ethyl ester, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate N,N-dimethylaminoethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl a (meth) acrylamide having a tertiary amino group such as a (meth) acrylamide and an N,N-diethylaminopropyl (meth) acrylamide; and a dimethylamino benzene Ethylene, diethylaminostyrene, and the like.
而且,亦可併用製造前述以通式(6)所示的聚合物以及前述於側鏈具有羥基的聚合物的步驟說明的具有烷氧基矽烷基的(甲基)丙烯酸酯。而且,具有烷氧基矽烷基的(甲基)丙烯酸酯,從對基材的密著性、顏料分散體的黏度及黏度安定性的觀點,相對於乙烯性不飽和單體固體成分,含有0.01質量%~10質量%為較佳,含有0.05質量%~5質量%為特別佳。 Further, a (meth) acrylate having an alkoxyalkylene group described above in the step of producing the polymer represented by the formula (6) and the polymer having a hydroxyl group in the side chain may be used in combination. Further, the (meth) acrylate having an alkoxyalkyl group has 0.01 with respect to the ethylenically unsaturated monomer solid component from the viewpoint of adhesion to the substrate, viscosity of the pigment dispersion, and viscosity stability. The mass % to 10% by mass is preferable, and the content of 0.05% by mass to 5% by mass is particularly preferable.
聚合起始劑係可使用例如製造前述以通式 (6)所示的聚合物的步驟說明的偶氮系化合物或有機過氧化物。於使用該聚合起始劑時,相對於乙烯性不飽和單體100質量份,以0.01~20質量份較佳。 As the polymerization initiator, for example, the above-mentioned general formula can be used. (6) An azo compound or an organic peroxide described in the step of the polymer shown. When the polymerization initiator is used, it is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the ethylenically unsaturated monomer.
於上述製造具有哌啶基骨架之乙烯基系樹脂型分散劑(B)的步驟,係與製造前述以通式(6)所示的聚合物的步驟同樣地,可使用無溶劑或視情況而使用溶劑。溶劑係可使用例如乙酸乙酯、乙酸正丁酯、乙酸異丁酯、己烷、甲苯、二甲苯、丙酮、甲基乙基酮、乙酸甲氧基丙酯、環己酮、丙二醇單甲醚乙酸酯、二丙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、乙二醇單丁醚乙酸酯、二乙二醇單乙醚乙酸酯或二乙二醇單丁醚乙酸酯等,但不特別限於該等,可依據用途、成本等任意選擇。聚合溶劑係可混合2種以上而使用。 The step of producing the vinyl-based resin-type dispersant (B) having a piperidinyl skeleton as described above can be carried out in the same manner as in the step of producing the polymer represented by the above formula (6), or as the case may be. Use a solvent. As the solvent, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexane, toluene, xylene, acetone, methyl ethyl ketone, methoxypropyl acetate, cyclohexanone, propylene glycol monomethyl ether can be used. Acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate or diethylene glycol monobutyl ether The acid ester or the like is not particularly limited to these, and may be arbitrarily selected depending on the use, cost, and the like. The polymerization solvent can be used by mixing two or more types.
使用的溶劑量係相對於乙烯性不飽和單體100質量份,較佳為0~300質量份,0~100質量份更佳。使用的溶劑係在反應結束後,藉由蒸餾等的操作除去,或亦可直接使用來作為分散劑的製品之一部分。 The amount of the solvent to be used is preferably from 0 to 300 parts by mass, more preferably from 0 to 100 parts by mass, per 100 parts by mass of the ethylenically unsaturated monomer. The solvent to be used is removed by an operation such as distillation after completion of the reaction, or may be used as a part of a dispersant.
而且,具有芳香族羧基之樹脂型分散劑(A)以及具有哌啶基骨架之乙烯基系樹脂型分散劑(B),宜使用於顏料分散。 Further, a resin type dispersant (A) having an aromatic carboxyl group and a vinyl resin type dispersant (B) having a piperidinyl skeleton are preferably used for pigment dispersion.
使用在顏料分散,具有哌啶基骨架之乙烯基系樹脂型分散劑(B)變得更容易吸附於顏料表面,與顏料的相互作用變強,而提高分散性。 When the pigment dispersion is carried out, the vinyl-based resin type dispersant (B) having a piperidinyl skeleton becomes more easily adsorbed on the surface of the pigment, and the interaction with the pigment becomes stronger, thereby improving the dispersibility.
〈顏料組成物〉 <Pigment Composition>
(調配比例) (mixing ratio)
於本發明的顏料組成物中,顏料、具有芳香族羧基之樹脂型分散劑(A)以及具有哌啶基骨架之乙烯基系樹脂型分散劑(B)的調配比例,相對於顏料100質量份,具有芳香族羧基之樹脂型分散劑(A)為5~100質量份,具有哌啶基骨架之乙烯基系樹脂型分散劑(B)為1~20質量份較佳,再者相對於顏料100質量份,具有芳香族羧基之樹脂型分散劑(A)為10~50質量份,具有哌啶基骨架之乙烯基系樹脂型分散劑(B)為2~10質量份更佳。 In the pigment composition of the present invention, the blending ratio of the pigment, the resin-type dispersing agent (A) having an aromatic carboxyl group, and the vinyl-based resin-based dispersing agent (B) having a piperidinyl skeleton is 100 parts by mass based on the pigment. The resin type dispersant (A) having an aromatic carboxyl group is 5 to 100 parts by mass, and the vinyl resin type dispersant (B) having a piperidinyl skeleton is preferably 1 to 20 parts by mass, more preferably relative to the pigment. The resin-type dispersant (A) having an aromatic carboxyl group is 10 to 50 parts by mass, and the vinyl-based resin type dispersant (B) having a piperidinyl skeleton is preferably 2 to 10 parts by mass, more preferably 100 parts by mass.
(顏料分散) (pigment dispersion)
本發明的顏料組成物係混合顏料、具有芳香族羧基之樹脂型分散劑(A)、具有哌啶基骨架之乙烯基系樹脂型分散劑(B)、依需要之具有酸性取代基的色素衍生物、除此之外視情況之各種溶劑、黏結劑樹脂、添加劑等,藉由橫型砂磨機、縱型混砂機、環形珠磨機、磨碎機(attritor)等分散,可調製顏料組成物分散成清漆之顏料分散體。 The pigment composition of the present invention is a mixed pigment, a resin type dispersant (A) having an aromatic carboxyl group, a vinyl resin type dispersant (B) having a piperidinyl skeleton, and a dye derivative having an acidic substituent as needed. In addition to the various solvents, binder resins, additives, etc., depending on the situation, the pigment can be prepared by dispersion such as a horizontal sand mill, a vertical sand mixer, a ring bead mill, an attritor or the like. The composition is dispersed into a pigment dispersion of varnish.
又,在藉由橫型砂磨機、縱型砂磨機、環形珠磨機、磨碎機等進行分散前,可進行使用揉合機(kneader)、3根滾輪等的揉肉攪拌機之前分散、藉由2根輥磨機等之固體分散。又,高速混合器、均質混合器、球磨機、輥磨機、石臼式碾磨機、超音波分散機等的所謂分散機、或混合機,可利用於本發明的分散體之製造。 Further, before being dispersed by a horizontal sand mill, a vertical sand mill, a ring bead mill, an attritor or the like, it can be dispersed before using a kneader or a three-roller meat mixer. It is dispersed by solids such as two roll mills. Further, a so-called disperser or a mixer such as a high-speed mixer, a homomixer, a ball mill, a roll mill, a ballast mill, or an ultrasonic disperser can be used for the production of the dispersion of the present invention.
(分散溶劑) (dispersion solvent)
可使用於本發明的顏料組成物之各種溶劑,係可舉例 如有機溶劑、水等。有機溶劑係亦可直接使用在具有芳香族羧基之樹脂型分散劑(A)及具有哌啶基骨架之乙烯基系樹脂型分散劑(B)的合成過程所使用的溶劑。又,在合成過程所使用的有機溶劑,反應結束後,藉由蒸餾等操作除去後,亦可使用相同的有機溶劑或不同的溶劑。又,依據目的,亦可併用2種以上的有機溶劑。 The various solvents which can be used in the pigment composition of the present invention can be exemplified. Such as organic solvents, water, and the like. The solvent used in the synthesis of the resin-type dispersant (A) having an aromatic carboxyl group and the vinyl-based resin dispersant (B) having a piperidinyl skeleton can be used as it is. Further, after the completion of the reaction in the organic solvent used in the synthesis, the same organic solvent or a different solvent may be used after the removal by distillation or the like. Further, depending on the purpose, two or more organic solvents may be used in combination.
有機溶劑係可舉例如己烷、異佛酮、甲苯、鄰-二甲苯、間-二甲苯、間-二乙基苯、正丁基苯、鄰-二乙基苯、對-二乙基苯、第2丁基苯、第3丁基苯、乙酸乙酯、乙酸正戊酯、乙酸正丁酯、乙酸異戊酯、乙酸正丁酯、乙酸異丁酯、乙酸丙酯、二元酸酯、乙酸正丙酯、環己醇乙酸酯、3-乙氧基丙酸乙酯、乙酸3-甲氧基-3-甲基丁酯、乙酸3-甲氧基丁酯、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、γ-丁內酯、乙腈、1,2,3-三氯丙烷、鄰-氯甲苯、對-氯甲苯、鄰-二氯苯、間-二氯苯、丙酮、甲基乙基酮、甲基異丁基酮、2-庚酮、4-庚酮、二異丁基酮、環己酮、3,5,5-三甲基-2-環己烯-1-酮、3,3,5-三甲基環己酮、正丁醇、異丁醇、苯甲醇、環己醇、3-甲氧基丁醇、甲基環己醇、3-甲氧基-3-甲基-1-丁醇、二丙酮醇、1,3-丁二醇、2-甲基-1,3-丙二醇、3-甲基-1,3-丁二醇、乙二醇二乙醚、乙二醇二丁醚、1,4-二噁烷、二乙二醇二甲醚、乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單異丙醚、乙二醇單丁醚、乙二醇單第3丁醚、乙二醇單己醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丙醚、二 乙二醇單異丙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚、丙二醇苯基醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單丙醚、二丙二醇單丁醚、三丙二醇單甲醚、三丙二醇單乙醚、三丙二醇單丙醚、三丙二醇單丁醚、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、乙二醇單丁醚乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、丙二醇單丁醚乙酸酯、丙二醇單甲醚丙酸酯、二丙二醇單甲醚乙酸酯、二丙二醇單乙醚乙酸酯、二丙二醇單丙醚乙酸酯、二丙二醇單丁醚乙酸酯、1,3-丁二醇二乙酸酯、丙二醇二乙酸酯、乙二醇二乙酸酯、二乙二醇二乙酸酯、三乙二醇二乙酸酯、丙二醇二乙酸酯、二丙二醇二乙酸酯、丁二醇二乙酸酯、戊二醇二乙酸酯、於丁二醇二乙酸酯,1,4-丁二醇二乙酸酯、戊二醇二乙酸酯、1,5-戊二醇二乙酸酯或三乙酸甘油酯等,但不必然限定於該等。 The organic solvent may, for example, be hexane, isophorone, toluene, o-xylene, m-xylene, m-diethylbenzene, n-butylbenzene, o-diethylbenzene or p-diethylbenzene. , 2 butyl benzene, 3 butyl benzene, ethyl acetate, n-amyl acetate, n-butyl acetate, isoamyl acetate, n-butyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester , n-propyl acetate, cyclohexanol acetate, ethyl 3-ethoxypropionate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, N, N- Dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, γ-butyrolactone, acetonitrile, 1,2,3-trichloropropane, o-chlorotoluene, p-chloro Toluene, o-dichlorobenzene, m-dichlorobenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, cyclohexanone, 3 ,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, n-butanol, isobutanol, benzyl alcohol, cyclohexanol, 3-methyl Oxybutanol, methylcyclohexanol, 3-methoxy-3-methyl-1-butanol, diacetone alcohol, 1,3-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,3-butanediol, Glycol diethyl ether, ethylene glycol dibutyl ether, 1,4-dioxane, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene Alcohol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl Ether, two Ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol phenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol single Ethyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether Acid ester, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, 1,3-butylene glycol diacetate, propylene glycol diacetate, ethylene glycol diacetate, diethylene glycol Alcohol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, butyl Diol diacetate, pentanediol diacetate, butanediol diacetate, 1,4-butanediol diacetate, pentanediol diacetate, 1,5-pentane Alcohol diacetate or triacetin, etc., but is not necessarily limited to these.
(用途) (use)
本發明的顏料組成物係可利用於非水系、水系或無溶劑系的塗料、凹版印墨、平版印墨、噴墨印墨、彩色濾光片印墨、數位紙用印墨、塑膠著色劑等,特別適合轉用於噴墨印墨、彩色濾光片印墨。 The pigment composition of the present invention can be used for non-aqueous, water-based or solvent-free coatings, gravure inks, lithographic inks, inkjet inks, color filter inks, digital paper inks, plastic colorants, etc. It is especially suitable for transfer to inkjet inks and color filter inks.
使用本發明的顏料組成物作為彩色濾光片印墨時,使顏料組成物分散於清漆的顏料分散體,添加彩 色濾光片用著色組成物(顏料分散體),進一步添加光聚合性單體以及/或光聚合起始劑,可使用來作為彩色濾光片用感光性著色組成物(光阻材料)。 When the pigment composition of the present invention is used as a color filter ink, the pigment composition is dispersed in the pigment dispersion of the varnish, and color is added. The coloring composition (pigment dispersion) of the color filter is further added with a photopolymerizable monomer and/or a photopolymerization initiator, and can be used as a photosensitive coloring composition (photoresist material) for a color filter.
〈光聚合性單體〉 <Photopolymerizable monomer>
使用於本發明的光聚合性單體,係包含藉由紫外線或熱等硬化而生成樹脂之單體或寡聚物,該等係可單獨或混合2種以上而使用。 The photopolymerizable monomer to be used in the present invention contains a monomer or an oligomer which is formed by curing by ultraviolet rays or heat, and these may be used singly or in combination of two or more.
光聚合性單體係可舉例如甲基丙烯酸甲酯、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、新戊四醇三甲基丙烯酸酯、新戊四醇四甲基丙烯酸酯、1,6-己二醇二環氧丙基醚二甲基丙烯酸酯、雙酚A二環氧丙基醚二甲基丙烯酸酯、新戊二醇二環氧丙基醚二甲基丙烯酸酯、二新戊四醇六甲基丙烯酸酯、二新戊四醇五甲基丙烯酸酯、甲基丙烯酸三環癸酯、丙烯酸酯、羥甲基化三聚氰胺的甲基丙烯酸酯、環氧基甲基丙烯酸酯、胺基甲酸乙酯丙烯酸酯等各種丙烯酸酯及甲基丙烯酸酯、丙烯酸、甲基丙烯酸、苯乙烯、乙酸乙烯酯、羥基乙基乙烯基醚、乙二醇二乙烯基醚、新戊四醇三乙烯基醚、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,但不必然限定於該等。 The photopolymerizable single system may, for example, be methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate or methacrylic acid β. -carboxyethyl ester, polyethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylol Propane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, 1,6-hexanediol diepoxypropyl ether dimethacrylate, bisphenol A Epoxypropyl ether dimethacrylate, neopentyl glycol diepoxypropyl ether dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethyl acrylate, A Various acrylates and methacrylates, acryls, methyl groups, such as tricyclononyl acrylate, acrylate, methyl methacrylate methacrylate, epoxy methacrylate, and urethane acrylate. Acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol diethyl Alkenyl ether, pentaerythritol trivinyl ether, methacrylamide, N-hydroxymethylmethacrylamide, N-vinylformamide, acrylonitrile, etc., but are not necessarily limited thereto.
光聚合性單體的含量係相對於顏料100質 量份,較佳為5~400質量份,從光硬化性及顯像性的觀點,更佳為10~300質量份。 The content of the photopolymerizable monomer is relative to the pigment 100 The amount of the component is preferably from 5 to 400 parts by mass, more preferably from 10 to 300 parts by mass from the viewpoint of photocurability and development.
〈光聚合起始劑〉 <Photopolymerization initiator>
光聚合起始劑係可使用4-苯氧基二氯苯乙酮、4-第3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-1-酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲基硫基)苯基]-2-嗎啉基丙-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-苯甲基-2-甲基胺基-1-(4-嗎啉基苯基)-丁-1-酮等的苯乙酮系化合物;安息香、安息香甲醚、安息香乙醚、安息香異丙醚或苯甲基二甲基縮酮等安息香系化合物;二苯基酮、苯甲醯基安息香酸、苯甲醯基安息香酸甲酯、4-苯基二苯基酮、羥基二苯基酮、丙烯酸基化二苯基酮、4-苯甲醯基-4’-甲基二苯硫醚或3,3’,4,4’-四(第3丁基過氧化羰基)二苯基酮等二苯基酮系化合物;噻吨酮(thioxanthone)、2-氯噻吨酮、2-甲基噻吨酮、異丙基噻吨酮、2,4-二異丙基噻吨酮或2,4-二乙基噻吨酮等噻吨酮系化合物;2,4,6-三氯-s-三嗪(triazine)、2-苯基-4,6-雙(三氯甲基)-s-三嗪、2-(對-甲氧基苯基)-4,6-雙(三氯甲基)-s-三嗪、2-(對-甲苯基)-4,6-雙(三氯甲基)-s-三嗪、2-胡椒基(piperonyl)-4,6-雙(三氯甲基)-s-三嗪、2,4-雙(三氯甲基)-6-苯乙烯基-s-三嗪、2-(萘-1-醯基)-4,6-雙(三氯甲基)-s-三嗪、2-(4-甲氧基-萘-1-醯基)-4,6-雙(三氯甲基)-s-三嗪、2,4-三氯甲基-(胡椒基)-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-(苯基硫基)-,2-(O-苯甲醯肟)]或O-(乙醯基)-N-(1-苯基-2-氧基(oxo)-2-(4-甲氧基-萘基)次乙基)羥基胺等肟酯系化合物;雙(2,4,6-三甲基苯甲醯基)苯基氧化膦或2,4,6-三甲基苯甲醯基二苯基氧化膦等膦系化合物;9,10-菲醌(phenanthrenequinone)、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(titanocene)系化合物等。 As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl) can be used. )-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl Propan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butene Acetophenone-based compound such as ketone or 2-benzyl-2-methylamino-1-(4-morpholinylphenyl)-butan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin compounds such as isopropyl ether or benzyl dimethyl ketal; diphenyl ketone, benzamidine benzoic acid, methyl benzyl benzoyl benzoate, 4-phenyl diphenyl ketone, hydroxy diphenyl Ketone, acrylated diphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide or 3,3',4,4'-tetra(t-butylperoxycarbonyl)diphenyl Diphenyl ketone compound such as ketone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Or a thioxanthone compound such as 2,4-diethylthioxanthone; 2,4,6-trichloro-s-three Triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl) -s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl) )-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthalen-1-yl)-4,6-bis(trichloromethane) -s-triazine, 2-(4-methoxy-naphthalen-1-indolyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl a triazine-based compound such as (sodium)-6-triazine or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzhydryl)] or O-(ethenyl)-N-(1-phenyl-2-oxy(oxo)-2 An oxime ester compound such as -(4-methoxy-naphthyl)ethenyl)hydroxylamine; bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide or 2,4,6- a phosphine compound such as trimethylbenzhydryldiphenylphosphine oxide; an anthraquinone compound such as phenanthrenequinone, camphorquinone or ethylhydrazine; a borate ester compound; an oxazole compound; An imidazole compound; or a titanocene compound or the like.
該等聚合起始劑係可單獨1種或依據需要而以任意比例混合2種以上使用。 These polymerization initiators may be used alone or in combination of two or more kinds in any ratio as needed.
聚合起始劑的含量係相對於顏料100質量份,較佳為5~200質量份,從光硬化性及顯像性的觀點,更佳為10~150質量份。 The content of the polymerization initiator is preferably 5 to 200 parts by mass based on 100 parts by mass of the pigment, and more preferably 10 to 150 parts by mass from the viewpoint of photocurability and development.
(增感劑) (sensitizer)
再者,於本發明的顏料組成物中係可含有增感劑。 Further, a sensitizer may be contained in the pigment composition of the present invention.
增感劑係可舉例如查耳酮(chalcone)衍生物、二亞苄基丙酮(dibenzalacetone)等為代表之不飽和酮類、苯甲基或樟腦醌等為代表之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(xanthene)衍生物、噻吨(thioxanthene)衍生物、氧雜蒽酮(xanthone)衍生物、噻吨酮(thioxanthone)衍生物、香豆素衍生物、香豆素酮(ketocoumarin)衍生物、花青(cyanine)衍生物、部花青(merocyanine)衍生物、氧醇(oxonol)衍生物等聚次甲基色素、吖啶(acridine)衍生物、吖嗪(azine)衍生物、噻嗪(thiazine)衍生物、噁嗪(oxazine)衍生物、吲哚啉 (indoline)衍生物、薁(azulene)衍生物、薁鎓(azulenium)衍生物、方酸(squarylium)衍生物、卟啉(porphyrin)衍生物、四苯基卟啉衍生物、三芳香基甲烷衍生物、四苯並卟啉衍生物、四吡嗪並卟啉(tetropyrazinoporphyrin)衍生物、酞菁(phthalocyanine)衍生物、四氮雜卟啉(porphyrazine)衍生物、四喹噁啉並卟啉(tetraquinoxalinoporphyrazine)衍生物、萘酞菁(naphthalocyanine)衍生物、亞酞菁(subphthalocyanine)衍生物、吡喃鎓(pyrylium)衍生物、噻喃鎓(thiopyrylium)衍生物、四葉蘿芙靈(tetraphylline)衍生物、輪烯(annulene)衍生物、螺吡喃(spiropyran)衍生物、螺噁嗪(spirooxazine)衍生物、硫螺吡喃衍生物、金屬芳香烴錯合物、有機釕錯合物或米氏酮(Michler’s ketone)衍生物、α-醯氧基酯、醯基氧化膦、甲基苯基乙醛酸酯、苯甲基、9,10-菲醌、樟腦醌、乙基蒽醌、4,4’-二乙基間苯二甲酸基二苯基酮、3,3’-或4,4’-二乙基胺基二苯基酮等。 The sensitizer may, for example, be a 1,2-diketone derivative represented by an unsaturated ketone represented by chalcone derivatives, dibenzalacetone or the like, benzyl or camphorquinone. , benzoin derivatives, anthraquinone derivatives, naphthoquinone derivatives, anthracene derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone (thioxanthone) derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, etc. Base pigment, acridine derivative, azine derivative, thiazine derivative, oxazine derivative, porphyrin (indoline) derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives , tetrabenzoporphyrin derivative, tetrapyrazine porphyrin derivative, phthalocyanine derivative, porphyrazine derivative, tetraquinoxalinoporphyrazine a derivative, a naphthalocyanine derivative, a subphthalocyanine derivative, a pyrylium derivative, a thiopyrylium derivative, a tetraphylline derivative, An annulen derivative, a spiropyran derivative, a spirooxazine derivative, a thiopyran derivative, a metal aromatic hydrocarbon complex, an organic ruthenium complex or a methyl ketone ( Michler's ketone) derivative, α-methoxyl ester, decylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylhydrazine, 4,4' -diethylisophthalic acid diphenyl ketone, 3,3'- or 4,4'-diethylamine Diphenyl ketone and the like.
該等增感劑係可單獨1種或依據需要而以任意比例混合2種以上使用。 These sensitizers may be used alone or in combination of two or more kinds in any ratio as needed.
更具體地,可舉例如大河原信等編著「色素手冊」(1986年、講談社)、大河原信等編著「功能性色素化學」(1981年、CMC)、持森忠三朗等編著及「特殊功能材料」(1986年、CMC)記載的增感劑,但不限於該等。而且,亦可含有其他對從紫外線至近紅外線的光顯示吸收的增感劑。 More specifically, for example, the "Pigment Handbook" (1986, Kodansha), Okawa Shinko, etc., "Compact Pigment Chemistry" (1981, CMC), and the writing of "Mr. The sensitizer described in (1986, CMC) is not limited to these. Further, it may contain other sensitizers which exhibit absorption of light from ultraviolet rays to near-infrared rays.
增感劑的含量係相對於包含於顏料組成物 的光聚合起始劑100質量份,較佳為3~60質量份,從光硬化性、顯像性的觀點,更佳為5~50質量份。 The content of the sensitizer is relative to the pigment composition The amount of the photopolymerization initiator is preferably from 3 to 60 parts by mass, more preferably from 5 to 50 parts by mass, from the viewpoint of photocurability and development.
(胺系化合物) (amine compound)
而且,於本發明的顏料組成物中,可含有具有還原溶存的氧功能之胺系化合物。如此的胺系化合物係可舉例如三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基安息香酸甲酯、4-二甲基胺基安息香酸乙酯、4-二甲基胺基安息香酸異戊酯、安息香酸2-二甲基胺基乙酯、4-二甲基胺基安息香酸2-乙基己酯及N,N-二甲基對甲苯胺等。 Further, the pigment composition of the present invention may contain an amine compound having a function of reducing and storing oxygen. Such an amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-di Isoamyl methylamino benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.
(流平劑) (leveling agent)
再者,於本發明的顏料組成物中,為了透明基板上的組成物的流平性變家,以添加流平劑為較佳。流平劑較佳為於主鏈具有聚醚構造或聚酯構造的二甲基矽氧烷。於主鏈具有聚醚構造的二甲基矽氧烷之具體例,可舉例如東麗道康寧(Toray Dow Corning)公司製FZ-2122、BYK公司製BYK-333等。於主鏈具有聚酯構造的二甲基矽氧烷之具體例,可舉例如BYK公司製BYK-310、BYK-370等。於主鏈具有聚醚構造的二甲基矽氧烷與主鏈具有聚酯構造的二甲基矽氧烷亦可併用。流平劑的含量,一般於著色組成物的全部質量100質量%中,以使用0.003~0.5質量%較佳。 Further, in the pigment composition of the present invention, it is preferred to add a leveling agent in order to improve the leveling property of the composition on the transparent substrate. The leveling 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, for example, FZ-2122 manufactured by Toray Dow Corning Co., Ltd., BYK-333 manufactured by BYK Corporation, and the like. Specific examples of the dimethyloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Corporation. Dimethyl decane having a polyether structure in the main chain and dimethyl methoxy alkane having a polyester structure in the main chain may be used in combination. The content of the leveling agent is generally from 100% by mass to the total mass of the coloring composition, and is preferably from 0.003 to 0.5% by mass.
作為流平劑特別佳者,係可使用於分子內具有疏水基及親水基之所謂界面活性劑的一種,即使具有親水基,對水的溶解性小,添加於著色組成物之時,具有所謂表面張力降低能力低的特徵,又儘管表面張力降低能 力低,亦可用於對玻璃板的潤濕性良好者,在未顯現起泡造成的塗膜缺陷之添加量中可充分抑制帶電性者較佳。作為具有如此佳的特性之流平劑,可使用具有聚環氧烷單元的二甲基聚矽氧烷為較佳。聚環氧烷單元係有環氧乙烷單元、環氧丙烷單元,二甲基聚矽氧烷亦可同時具有聚環氧乙烷單元及具環氧丙烷單元。 A particularly preferred leveling agent is one which is a so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule. Even if it has a hydrophilic group, it has little solubility in water, and when added to a coloring composition, it has a so-called surfactant. Low surface tension reducing ability, although surface tension can be reduced If the force is low, the wettability to the glass sheet can be improved, and the chargeability can be sufficiently suppressed in the amount of the coating film defect which is not caused by foaming. As the leveling agent having such excellent characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit is an ethylene oxide unit or a propylene oxide unit, and the dimethyl polyoxyalkylene may have both a polyethylene oxide unit and a propylene oxide unit.
而且,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之垂飾型、鍵結於二甲基聚矽氧烷的末端的末端改性型、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,係東麗道康寧公司有販賣,可舉例如FZ-2110、FZ-2122、FZ-2130、FZ-2166、FZ-2191、FZ-2203、FZ-2207,但不限於該等。 Moreover, 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, and bonded to the second Any of the terminal block-modified type of the terminal of the methyl polyoxyalkylene and the linear block copolymer type which is alternately and repeatedly bonded to the dimethyl polyoxyalkylene. Dimethyl polyoxyalkylene having a polyalkylene oxide unit, which is sold by Toray Dow Corning, for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2207, but not limited to these.
於流平劑係亦可輔助地添加陰離子性、陽離子性、非離子性或兩性的界面活性劑。界面活性劑係可混合2種以上而使用。 An anionic, cationic, nonionic or amphoteric surfactant may also be added to the leveling agent. The surfactant can be used by mixing two or more types.
輔助地添加於流平劑之陰離子性界面活性劑,係可舉例如聚氧乙烯烷基醚硫酸鹽、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、聚氧乙烯烷基醚磷酸鹽等。 The anionic surfactant which is additionally added to the leveling agent may, for example, be a polyoxyethylene alkyl ether sulfate, a sodium dodecylbenzenesulfonate, an alkali salt of a styrene-acrylic acid copolymer, or an 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, polyoxyethylene alkyl ether phosphate, etc. of an acrylic copolymer.
輔助地添加於流平劑之陽離子性界面活性劑,係可舉例如烷基4級銨鹽、或該等的環氧乙烷加成物。輔助地添加於流平劑之非離子性界面活性劑,係可舉例如聚氧乙烯油基醚、聚氧乙烯月桂基醚、聚氧乙烯壬基苯基醚、聚氧乙烯烷基醚磷酸酯、聚氧乙烯山梨糖醇單硬脂酸酯、聚乙二醇單月桂酸酯等;烷基二甲基胺基乙酸甜菜鹼等的烷基甜菜鹼、烷基咪唑啉等的兩性界面活性劑、亦或氟系或聚矽氧樹脂系界面活性劑。 The cationic surfactant to be added to the leveling agent in an auxiliary manner may, for example, be an alkyl 4-based ammonium salt or an ethylene oxide adduct. The nonionic surfactant to be added to the leveling agent in an auxiliary manner is, for example, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate. , polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc.; alkyl betaine such as alkyl dimethylamino acetic acid betaine, alkyl imidazoline and the like amphoteric surfactant Or a fluorine-based or polyoxyxene-based surfactant.
(硬化劑、硬化促進劑) (hardener, hardening accelerator)
又,於本發明的顏料組成物中,為了輔助熱硬化性樹脂的硬化,依據需要,亦可包含硬化劑、硬化促進劑等。硬化劑係可舉例如酚系樹脂、胺系化合物、酸酐、活性酯、羧酸系化合物、磺酸系化合物等為有效,但不限於該等,只要是可與熱硬化性樹脂反應者即可,可使用任意之硬化劑。而且,該等之中,亦可舉例如1分子內具有2個以上酚性羥基的化合物、胺系硬化劑為較佳。前述硬化促進劑係可使用例如胺化合物(例如雙氰二醯胺、苯甲基二甲基胺、4-(二甲基胺基)-N,N-二甲基苯甲基胺、4-甲氧基-N,N-二甲基苯甲基胺、4-甲基-N,N-二甲基苯甲基胺等)、4級銨鹽化合物(例如氯化三乙基苯甲基銨等)、嵌段異氰酸酯化合物(例如二甲基胺等)、咪唑衍生物二環式脒(amidine)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、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(guanamine) 化合物(例如三聚氰胺、胍胺、乙醯基胍胺、苯並胍胺等)、S-三嗪衍生物(例如2,4-二胺基-6-甲基丙烯醯氧基乙基-S-三嗪、2-乙烯基-2,4-二胺基-S-三嗪、2-乙烯基-4,6-二胺基-S-三嗪、異氰脲酸加成物、2,4-二胺基-6-甲基丙烯醯氧基乙基-S-三嗪.異氰脲酸加成物等)等。該等係可單獨1種使用,亦可併用2種以上。前述硬化促進劑的含量係以熱硬化性樹脂的全部質量為基準(100質量份),較佳為0.01~15質量份。 Further, in the pigment composition of the present invention, in order to assist the curing of the thermosetting resin, a curing agent, a curing accelerator, or the like may be contained as needed. The curing agent may be, for example, a phenol resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, or a sulfonic acid compound, but is not limited thereto, and may be any one that can react with a thermosetting resin. Any hardener can be used. Further, among these, for example, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferable. As the hardening accelerator, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4- Methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), a 4-grade ammonium compound (for example, triethylbenzyl chloride) Ammonium, etc.), blocked isocyanate compounds (eg dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and salts thereof (eg imidazole, 2-methylimidazole, 2-ethylimidazole, 2-B) a group of 4-methylimidazole, 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., a phosphorus compound (for example, triphenylphosphine, etc.), hydrazine Guanamine Compounds (eg, melamine, guanamine, acetammine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methylpropenyloxyethyl-S-) Triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine, isocyanuric acid adduct, 2,4 -diamino-6-methacryloxyethyl-S-triazine, isocyanuric acid adduct, etc.). These systems may be used alone or in combination of two or more. The content of the curing accelerator is based on the total mass of the thermosetting resin (100 parts by mass), preferably 0.01 to 15 parts by mass.
(其他添加劑成分) (Other additive ingredients)
於本發明的顏料組成物中,為了使組成物的經時黏度安定化,可含有貯存安定劑。而且,為了提高與透明基板的密著性,亦可含有矽烷偶合劑等的密著提高劑。 In the pigment composition of the present invention, a storage stabilizer may be contained in order to stabilize the viscosity of the composition over time. Further, in order to improve the adhesion to the transparent substrate, a adhesion improving agent such as a decane coupling agent may be contained.
貯存安定劑係可舉例如苯甲基三甲基氯化物、二乙基羥基胺等的4級銨氯化物、乳酸、草酸等的有機酸及其甲基醚、第3丁基鄰苯二酚、四乙基膦、四苯基膦等的有機膦、亞磷酸鹽等。貯存安定劑係相對於著色劑(a)的全部質量100質量份,可使用0.1~10質量份的量。 Examples of the storage stabilizer include a 4-stage ammonium chloride such as benzyltrimethyl chloride or diethylhydroxylamine, an organic acid such as lactic acid or oxalic acid, a methyl ether thereof, and a third butyl catechol. An organic phosphine such as tetraethylphosphine or tetraphenylphosphine, or a phosphite. The storage stabilizer is used in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the total mass of the colorant (a).
密著提高劑係可舉例如乙烯基參(β-甲氧基乙氧基)矽烷、乙烯基乙氧基矽烷、乙烯基三甲氧基矽烷等乙烯基矽烷類、γ-甲基丙烯醯氧基丙基三甲氧基矽烷等(甲基)丙烯酸基矽烷類、β-(3,4-環氧基環己基)乙基三甲氧基矽烷、β-(3,4-環氧基環己基)甲基三甲氧基矽烷、γ-環氧丙基丙基三甲氧基矽烷、γ-環氧丙基丙基三乙氧基矽烷等環氧基矽烷類、N-β(胺基乙基)γ-胺基丙基三甲氧基矽 烷、N-β(胺基乙基)γ-胺基丙基三乙氧基矽烷、N-β(胺基乙基)γ-胺基丙基甲基二乙氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、N-苯基-γ-胺基丙基三乙氧基矽烷等胺基矽烷類、γ-巰基丙基三甲氧基矽烷、γ-巰基丙基三乙氧基矽烷等硫基矽烷類等矽烷偶合劑。密著提高劑,相對於顏料的全部質量100質量份,可使用0.01~10質量份的量,較佳為0.05~5質量份的量。 Examples of the adhesion enhancer include vinyl decane such as vinyl ginate (β-methoxyethoxy) decane, vinyl ethoxy decane, and vinyl trimethoxy decane, and γ-methyl propylene oxy group. (meth)acrylic decane such as propyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, β-(3,4-epoxycyclohexyl)methyl Epoxy decane, γ-glycidylpropyltrimethoxydecane, γ-glycidylpropyltriethoxydecane, etc., N-β(aminoethyl)γ- Aminopropyltrimethoxyfluorene Alkane, N-β(aminoethyl)γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropylmethyldiethoxydecane, γ-amino group Propyltriethoxydecane, γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltriethoxy A decane coupling agent such as an alkyl decane such as decane, a thiodecane such as γ-mercaptopropyltrimethoxydecane or γ-mercaptopropyltriethoxydecane. The adhesion enhancer may be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the total mass of the pigment.
(黏結劑樹脂) (adhesive resin)
於顏料分散時,亦可使用本發明的具有芳香族羧基之樹脂型分散劑(A)以及/或具有哌啶基骨架之乙烯基系樹脂(B)作為黏結劑樹脂。 When the pigment is dispersed, the resin-type dispersant (A) having an aromatic carboxyl group and/or the vinyl-based resin (B) having a piperidinyl skeleton of the present invention can also be used as the binder resin.
又,與前述具有芳香族羧基之樹脂型分散劑(A)及前述具有哌啶基骨架之乙烯基系樹脂型(B)不同,可使用於本發明的顏料組成物之黏結劑樹脂的例,係可舉例如熱塑性樹脂、熱硬化性樹脂及活性能量線硬化性樹脂。 Further, unlike the resin-based dispersant (A) having an aromatic carboxyl group and the vinyl-based resin (B) having a piperidinyl skeleton, an example of a binder resin to be used in the pigment composition of the present invention can be obtained. For example, a thermoplastic resin, a thermosetting resin, and an active energy ray-curable resin can be mentioned.
於使用本發明的顏料組成物作為彩色濾光片用等的光阻印墨時,前述黏結劑樹脂之中,可使用鹼可溶性或溶劑可溶性樹脂。 When the pigment composition of the present invention is used as a resist ink for a color filter or the like, an alkali-soluble or solvent-soluble resin can be used among the binder resins.
熱塑性樹脂係可舉例如丙烯酸樹脂、縮丁醛樹脂、苯乙烯-順丁烯二酸共聚物、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、聚胺酯系樹脂、聚酯樹脂、乙烯基系樹脂、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(HDPE、LDPE)、聚丁二烯及聚醯亞胺樹脂等。 The thermoplastic resin may, for example, be an acrylic resin, a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, or a polyacetic acid. Vinyl ester, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber tree Fat, cellulose, polyethylene (HDPE, LDPE), polybutadiene and polyimine resin.
熱硬化性樹脂係可舉例如環氧樹脂、苯並胍胺樹脂、松香改性順丁烯二酸樹脂、松香改性反丁烯二酸樹脂、三聚氰胺樹脂、尿素樹脂以及酚樹脂等。 Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.
與含有酸性取代基的乙烯性不飽和單體共聚合之乙烯基系鹼可溶性樹脂,係可舉例如具有羧基、碸基等的酸性取代基之樹脂。鹼可溶性樹脂具體地係可舉例如具有酸性取代基之丙烯酸樹脂、α-烯烴/順丁烯二酸酐共聚物、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/順丁烯二酸酐共聚物等。其中,選自具有酸性取代基之丙烯酸樹脂及苯乙烯/苯乙烯磺酸共聚物中至少1種樹脂,特別是具有酸性取代基之丙烯酸樹脂,因為耐熱性、透明性高而適合使用。 The vinyl-based alkali-soluble resin copolymerized with the ethylenically unsaturated monomer having an acidic substituent may, for example, be a resin having an acidic substituent such as a carboxyl group or a fluorenyl group. The alkali-soluble resin may specifically be, for example, an acrylic resin having an acidic substituent, an α-olefin/maleic anhydride copolymer, a styrene/styrenesulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer or an isobutylene. / maleic anhydride copolymer and the like. Among them, at least one resin selected from the group consisting of an acrylic resin having an acidic substituent and a styrene/styrenesulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, is suitably used because of its high heat resistance and transparency.
具有乙烯性不飽和雙鍵的活性能量線硬化性樹脂,可舉例如藉由以下表示的(i)或(ii)之方法而導入乙烯性不飽和雙鍵之樹脂。 The active energy ray-curable resin having an ethylenically unsaturated double bond may, for example, be a resin obtained by introducing an ethylenically unsaturated double bond by the method (i) or (ii) shown below.
〔方法(i)〕 [method (i)]
方法(i)係可舉例如藉由具有環氧基的乙烯性不飽和單體與其他1種以上的單體共聚合所得之共聚物的側鏈環氧基,使具有乙烯性不飽和雙鍵的不飽和一元酸的羧基進行加成反應,再於所生成的羥基,使多元酸酐反應,導入乙烯性不飽和雙鍵及羧基的方法。 The method (i) is, for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers, and having an ethylenically unsaturated double bond. The carboxyl group of the unsaturated monobasic acid is subjected to an addition reaction, and then the polyhydroxy acid anhydride is reacted with the generated hydroxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.
具有環氧基的乙烯性不飽和單體係可舉例 如(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸甲基環氧丙酯、(甲基)丙烯酸2-環氧丙氧基乙酯、(甲基)丙烯酸3,4-環氧基丁酯及(甲基)丙烯酸3,4-環氧基環己酯,該等係可單獨使用,亦可併用2種以上。從下一步驟的與不飽和一元酸的反應性之觀點,較佳為(甲基)丙烯酸環氧丙酯。 An ethylenically unsaturated single system having an epoxy group can be exemplified For example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxy (meth)acrylate Butyl ester and 3,4-epoxycyclohexyl (meth)acrylate may be used alone or in combination of two or more. From the viewpoint of the reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)acrylate is preferred.
不飽和一元酸係可舉例如(甲基)丙烯酸、2-丁烯酸、o-,m-,p-乙烯基安息香酸、(甲基)丙烯酸的α位鹵素烷基、烷氧基、鹵素、硝基、氰基取代物等的單羧酸等,該等係可單獨使用,亦可併用2種以上。 Examples of the unsaturated monobasic acid include (meth)acrylic acid, 2-butenoic acid, o-, m-, p-vinylbenzoic acid, α-halogenalkyl group of (meth)acrylic acid, alkoxy group, and halogen. A monocarboxylic acid such as a nitro group or a cyano substituent may be used alone or in combination of two or more.
多元酸酐係可舉例如四氫鄰苯二甲酸酐、鄰苯二甲酸酐、六氫鄰苯二甲酸酐、琥珀酸酐、順丁烯二酸酐等,該等係可單獨使用,亦可併用2種以上。亦可增加羧基的數目等,依據需要,使用偏苯三羧酸酐等三羧酸酐,或使用均苯四甲酸二酐等的四羧酸二酐,水解所殘留的酸酐基等。而且,多元酸酐係若使用具有乙烯性不飽和雙鍵之四氫鄰苯二甲酸酐或順丁烯二酸酐,可更增加乙烯性不飽和雙鍵。 Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used singly or in combination of two. the above. The number of the carboxyl groups may be increased, and if necessary, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride may be used to hydrolyze the remaining acid anhydride group or the like. Further, in the case of a polybasic acid anhydride, if tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used, an ethylenically unsaturated double bond can be further increased.
方法(i)的類似方法係可舉例如藉由具有羧基的乙烯性不飽和單體、與其他1種以上的單體共聚合所得之共聚物的側鏈羧基的一部分,使具有環氧基的乙烯性不飽和單體進行加成反應,導入乙烯性不飽和雙鍵及羧基的方法。 A similar method of the method (i) is, for example, a part of a side chain carboxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another one or more monomers, and having an epoxy group. A method in which an ethylenically unsaturated monomer is subjected to an addition reaction to introduce an ethylenically unsaturated double bond and a carboxyl group.
〔方法(ii)〕 [method (ii)]
方法(ii)係可舉例如使用具有羥基的乙烯性不飽和單 體,與其他具有羧基的不飽和一元酸的單體、或其他單體共聚合所得之共聚物的側鏈羥基,使具有異氰酸酯基的乙烯性不飽和單體的異氰酸酯基反應之方法。 The method (ii) is exemplified by using an ethylenically unsaturated monomer having a hydroxyl group. A method in which an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group is reacted with a side chain hydroxyl group of a copolymer obtained by copolymerizing a monomer having another carboxyl group-containing unsaturated monobasic acid or another monomer.
具有羥基的乙烯性不飽和單體係可舉例如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-或3-羥基丙酯、(甲基)丙烯酸2-或3-或4-羥基丁酯、甘油(甲基)丙烯酸酯或環己烷二甲醇單(甲基)丙烯酸酯等的(甲基)丙烯酸羥基烷酯,該等係可單獨使用,亦可併用2種以上。而且,於上述(甲基)丙烯酸羥基烷酯,使環氧乙烷、環氧丙烷及/或環氧丁烷等加成聚合之聚醚單(甲基)丙烯酸酯、或使聚γ-戊內酯、聚ε-己內酯、及/或聚12-羥基硬脂酸等加成的聚酯單(甲基)丙烯酸酯。從抑制塗膜異物的觀點,較佳為(甲基)丙烯酸2-羥基乙酯、甘油(甲基)丙烯酸酯。 The ethylenically unsaturated single system having a hydroxyl group may, for example, be 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-(meth)acrylate. a hydroxyalkyl (meth)acrylate such as hydroxybutyl ester, glycerin (meth) acrylate or cyclohexane dimethanol mono(meth) acrylate, and these may be used singly or in combination of two or more. Further, in the above (meth)acrylic acid hydroxyalkyl ester, a polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide, or a poly-γ-pentane An addition of a polyester mono(meth)acrylate such as lactone, poly-ε-caprolactone, and/or poly 12-hydroxystearic acid. From the viewpoint of suppressing the foreign matter of the coating film, 2-hydroxyethyl (meth)acrylate or glycerin (meth) acrylate is preferable.
具有異氰酸酯基的乙烯性不飽和單體係可舉例如2-(甲基)丙烯醯氧基乙基異氰酸酯或1,1-雙[甲基丙烯醯氧基]乙基異氰酸酯等,不限於該等,亦可併用2種以上。 The ethylenically unsaturated single system having an isocyanate group may, for example, be 2-(meth)acryloxyethyl isocyanate or 1,1-bis[methylpropenyloxy]ethyl isocyanate, and is not limited thereto. Two or more types may be used in combination.
為了使顏料良好地分散,樹脂的重量平均分子量(Mw)為10,000~100,000的範圍較佳,更佳為10,000~80,000的範圍。而且,數目平均分子量(Mn)為5,000~50,000的範圍較佳,Mw/Mn的值為10以下較佳。 In order to disperse the pigment well, the weight average molecular weight (Mw) of the resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. Further, the number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably 10 or less.
而且,從顏料的分散性、安定性、顯像性及耐熱性的觀點,作用為著色劑吸附基及顯像時的鹼可溶性基之羧基、作用為對著色劑支持體及溶劑之親和性基之 脂肪族基及芳香族基的平衡,對顏料的分散性、塗膜的顯像液滲透性、未硬化部分的顯像液溶解性,又對耐久性而言很重要,使用酸價20~300mgKOH/g的樹脂較佳。酸價未達20mgKOH/g時,對顯像液的溶解性差,形成細微圖形有困難。而且,若超過300mgKOH/g,有時細微圖形有無法殘留。 Further, from the viewpoints of dispersibility, stability, development, and heat resistance of the pigment, it acts as a carboxyl group of the alkali-soluble group at the time of adsorption of the colorant and the development, and acts as an affinity group for the colorant support and the solvent. It The balance between the aliphatic group and the aromatic group, the dispersibility of the pigment, the permeability of the developing solution of the coating film, the solubility of the developing solution in the uncured portion, and the durability are important, and the acid value is 20 to 300 mgKOH. The resin of /g is preferred. When the acid value is less than 20 mgKOH/g, the solubility in the developing solution is poor, and it is difficult to form a fine pattern. Further, when it exceeds 300 mgKOH/g, the fine pattern may not remain.
樹脂係由於成膜性及各種耐性良好,相對於顏料的全部質量100質量份,使用30質量份以上的量較佳,由於著色劑濃度高,可顯現良好的顏色特性,使用500質量份以下的量較佳。更佳為100~400質量份,再更佳為160~320質量份。如此的顏料之構成比例,可更擴展色度區域。 The resin is excellent in film formability and various kinds of resistance, and is preferably used in an amount of 30 parts by mass or more based on 100 parts by mass of the total mass of the pigment, and a high colorant concentration can exhibit good color characteristics, and 500 parts by mass or less is used. The amount is better. More preferably, it is 100 to 400 parts by mass, and more preferably 160 to 320 parts by mass. Such a composition ratio of the pigment can further expand the chromaticity region.
〈顏料組成物的製造方法〉 <Method for Producing Pigment Composition>
本發明的顏料組成物係將顏料、具有芳香族羧基之樹脂型分散劑(A)、具有哌啶基骨架之乙烯基系樹脂(B)及溶劑等,一起使用3根輥磨機、2根輥磨機、砂磨機、揉合機、三混機(trimix)、磨碎機等各種分散手段,進行細微分散而可製造(顏料分散體)。而且,本發明的顏料組成物係可與綠色顏料或黃色顏料等其他著色劑一起分散,亦可混合各別分散者而製造。 In the pigment composition of the present invention, a pigment, a resin-based dispersant (A) having an aromatic carboxyl group, a vinyl-based resin (B) having a piperidinyl skeleton, a solvent, and the like are used, and three roll mills and two are used together. Various dispersing means such as a roll mill, a sand mill, a kneader, a trimix, and an attritor can be produced by finely dispersing (pigment dispersion). Further, the pigment composition of the present invention may be dispersed together with other coloring agents such as a green pigment or a yellow pigment, or may be produced by mixing the respective dispersers.
而且,於使用來作為彩色濾光片用感光性顏料組成物(光阻材料)時,可調製來作為溶劑顯像型或鹼顯像型著色組成物。溶劑顯像型或鹼顯像型著色組成物係可將前述顏料分散體、光聚合性單體及/或光聚合起始劑、依需要之溶 劑、其他分散劑及添加劑等混合而調整。光聚合起始劑係可在調製著色組成物的階段添加,亦可在調製著色組成物後添加。 Further, when used as a photosensitive pigment composition (photoresist material) for a color filter, it can be prepared as a solvent development type or an alkali development type coloring composition. The solvent-developing type or the alkali-developing type coloring composition may dissolve the pigment dispersion, the photopolymerizable monomer, and/or the photopolymerization initiator, as needed The agent, other dispersing agents and additives are mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added after the coloring composition is prepared.
(粗大粒子的除去) (removal of coarse particles)
本發明的顏料組成物係可以離心分離、燒結過濾、薄膜過濾等手段,除去5μm以上的粗大粒子,較佳為除去1μm以上的粗大粒子,更佳為除去0.5μm以上的粗大粒子以及混入的灰塵。如此的顏料組成物,實質上不含0.5μm以上的粒子較佳。更佳為0.3μm以下。 The pigment composition of the present invention can remove coarse particles of 5 μm or more by means of centrifugation, sintering filtration, membrane filtration, etc., preferably removes coarse particles of 1 μm or more, and more preferably removes coarse particles of 0.5 μm or more. Particles and dust that is mixed in. Such a pigment composition is preferably substantially free of particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.
〈彩色濾光片〉 <Color Filter>
然後,說明有關本發明的彩色濾光片。本發明的彩色濾光片係具備使用本發明的彩色濾光片用著色組成物所形成之濾光片段(filter segment)者。彩色濾光片係可舉例如具備紅色濾光片段、綠色濾光片段及藍色濾光片段者,前述濾光片段係藉由旋轉塗佈方式或狹縫塗佈方式,塗佈彩色濾光片用著色組成物後,照射紫外線等活性能量線而成為濾光片段的部分硬化,然後藉由顯像,形成於基板上。 Next, a color filter relating to the present invention will be described. The color filter of the present invention includes a filter segment formed by using the colored composition for a color filter of the present invention. The color filter may be, for example, a red filter segment, a green filter segment, and a blue filter segment, and the filter segment may be coated by a spin coating method or a slit coating method. After the colored filter is colored with a composition, it is irradiated with an active energy ray such as an ultraviolet ray to partially cure the filter segment, and then formed on the substrate by development.
本發明的彩色濾光片用著色組成物,係使用於至少一個濾光片段之形成,其以外的各色濾光片段,係可使用習知所使用的紅色著色組成物、藍色著色組成物、綠色著色組成物而形成。本發明的彩色濾光片用著色組成物以外的各色著色組成物,係可使用含有著色劑(顏料、染料的任一種)、前述黏結劑樹脂、前述光聚合性組成物等之各著色組成物而形成。 The coloring composition for a color filter of the present invention is used for formation of at least one filter segment, and other color filter segments other than the color filter composition can be used by using a conventionally used red coloring composition and blue coloring composition. The object is formed by a green coloring composition. In the coloring composition of each color other than the coloring composition of the color filter of the present invention, each coloring composition containing a coloring agent (any one of a pigment and a dye), the above-mentioned binder resin, and the photopolymerizable composition can be used. And formed.
本發明的彩色濾光片係具備紅色濾光片段、綠色濾光片段及藍色濾光片段。而且,彩色過濾片進一步亦可為具備紫紅色濾光片段、青藍色濾光片段及黃色濾光片段者。本發明的彩色濾光片係紅色濾光片段、綠色濾光片段及黃色濾光片段中至少一個為從本發明的顏料組成物中形成。特別是綠色濾光片段由本發明的顏料組成物中形成者較佳。 The color filter of the present invention is provided with a red filter segment, a green filter segment, and a blue filter segment. Further, the color filter may further be a member having a magenta filter segment, a cyan filter segment, and a yellow filter segment. At least one of the color filter of the present invention, which is a red filter segment, a green filter segment, and a yellow filter segment, is formed from the pigment composition of the present invention. In particular, green filter segments are preferably formed from the pigment composition of the present invention.
藍色濾光片段係可使用包含藍色顏料及著色劑支持體的一般藍色著色組成物而形成。藍色顏料係可舉例如使用C.I.顏料藍1、1:2、9、14、15、15:1、15:2、15:3、15:4、15:6、16、22、60、64等。而且,於藍色著色組成物係可併用紫色顏料。可併用的紫色顏料係可舉例如C.I.顏料紫1、1:1、2、2:2、3、3:1、3:3、5、5:1、14、15、16、19、23、27、29、30、31、32、37、39、40、42、44、47、49、50等紫色顏料。而且,亦可使用呈現藍色或紫色的鹼性染料、酸性染料的成鹽化合物。於使用染料時,三芳香基甲烷系染料或氧雜蒽系染料,從亮度的點較佳。 The blue filter segment can be formed using a general blue coloring composition comprising a blue pigment and a colorant support. The blue pigment may be, for example, CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64. Wait. Further, a violet pigment can be used in combination with the blue coloring composition. The purple pigments which can be used in combination are, for example, CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, Purple pigments such as 27, 29, 30, 31, 32, 37, 39, 40, 42, 44, 47, 49, 50. Further, a salt-forming compound which exhibits a blue or violet basic dye or an acid dye can also be used. When a dye is used, a triarylmethane dye or an oxonium dye is preferred from the viewpoint of brightness.
(彩色濾光片的製造方法) (Manufacturing method of color filter)
本發明的彩色濾光片係可藉由印刷法、光微影蝕刻法製造。 The color filter of the present invention can be produced by a printing method or a photolithography method.
以印刷法所形成之彩色濾光片的形成,係只要重複進行調製作為印刷印墨的顏料組成物的印刷以及乾燥,均可圖型化,彩色濾光片的製造方法係低成本且量 產性優。再者,由於印刷技術的發展,可進行具有更高尺寸精度及平滑度之細微圖型的印刷。為了進行印刷,於印刷的版上,或敷層(blanket)上,以印墨為不乾燥、固化的組成較佳。而且,在印刷機上控制印墨的流動性也重要,亦可進行以分散劑或體質顏料調整印墨黏度。 The formation of the color filter formed by the printing method can be repeated as long as the printing and drying of the pigment composition as the printing ink are repeated, and the method of manufacturing the color filter is low-cost and Excellent productivity. Furthermore, due to the development of printing technology, it is possible to perform printing with a fine pattern of higher dimensional accuracy and smoothness. For printing, on a printed plate, or on a blanket, it is preferred that the ink is not dried and cured. Moreover, it is also important to control the fluidity of the ink on the printing press, and it is also possible to adjust the ink viscosity with a dispersing agent or an extender pigment.
於藉由光微影蝕刻法形成彩色濾光片時,藉由噴塗、旋轉塗佈、狹縫塗佈、滾輪塗佈等塗佈方法,於透明基板上,塗佈調製作為上述溶劑顯像型或鹼顯像型的著色光阻材料之顏料組成物,使乾燥膜厚成為0.2至5μm。依據需要被乾燥的膜,通過與該膜在接觸或非接觸狀態設置的具有既定圖型的光罩,進行紫外線曝光。然後,浸漬於溶劑或鹼顯像液,或藉由噴霧,噴霧顯像液,除去未硬化部,而形成所期望的圖型後,對其他顏色,重複同樣的操作,可製造彩色濾光片。再者,為了促進著色光阻材料的聚合,依據需要,亦可實施加熱。根據光微影蝕刻法,可製造比上述印刷法更高精度的彩色濾光片。 When a color filter is formed by photolithography, a coating method such as spray coating, spin coating, slit coating, or roll coating is applied to a transparent substrate to prepare a solvent for the above-described solvent development type. Or the pigment composition of the alkali-developing colored resist material, so that the dry film thickness is 0.2 to 5 μm . According to the film to be dried, ultraviolet exposure is performed by a mask having a predetermined pattern which is provided in contact or non-contact with the film. Then, it is immersed in a solvent or an alkali developing solution, or sprayed, and the developing solution is sprayed to remove the uncured portion to form a desired pattern, and then the same operation is repeated for other colors to manufacture a color filter. . Further, in order to promote polymerization of the colored photoresist material, heating may be performed as needed. According to the photolithography method, a color filter having higher precision than the above printing method can be manufactured.
顯像時,可使用碳酸鈉、氫氧化鈉等水溶液作為鹼顯像液,亦可使用二甲基苯甲基胺、三乙醇胺等有機鹼。而且,於顯像液,亦可添加消泡劑、界面活性劑。 In the case of development, an aqueous solution such as sodium carbonate or sodium hydroxide can be used as the alkali developing solution, and an organic base such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant may be added to the developing solution.
再者,為了提高紫外線曝光感度,塗佈乾燥上述著色光阻後,塗佈乾燥水溶性或鹼水溶性樹脂,例如塗佈乾燥聚乙烯醇或水溶性丙烯酸樹脂等,形成防止因氧氣所造成之聚合阻礙的膜後,亦可進行紫外線曝光。 Further, in order to increase the ultraviolet exposure sensitivity, after drying and drying the colored photoresist, a dry water-soluble or alkali-soluble resin is applied, for example, coated with a dry polyvinyl alcohol or a water-soluble acrylic resin to prevent the formation of oxygen. After the film which is hindered by polymerization, ultraviolet exposure can also be performed.
本發明的彩色濾光片,係上述方法之外, 可藉由電沈積法、轉印法、噴墨法等製造,但本發明的顏料組成物中,可使用任意之方法。再者,電沈積法係利用形成於基板上的透明導電膜,藉由膠體粒子的電泳,於透明導電膜上電沈積形成各色濾光片段,可製造彩色濾光片。而且,轉印法係於剝離性的轉印基材片的表面上,預先形成濾光片段,使該濾光片段轉印至所期望的基板上之方法。 The color filter of the present invention is in addition to the above method, It can be produced by an electrodeposition method, a transfer method, an inkjet method, or the like, but any method can be used for the pigment composition of the present invention. Further, the electrodeposition method utilizes a transparent conductive film formed on a substrate, and electrophoretically deposits the filter segments of the respective colors on the transparent conductive film by electrophoresis of the colloidal particles, thereby producing a color filter. Further, the transfer method is a method in which a filter segment is formed in advance on the surface of the peelable transfer substrate sheet, and the filter segment is transferred onto a desired substrate.
於透明基板或反射基板上形成各色濾光片段之前,可預先形成黑色矩陣。黑色矩陣係使用鉻或鉻/氧化鉻的多層膜、氮化鈦等的無機膜、分散有遮光劑之樹脂膜,但不限於該等。而且,於上述透明基板或反射基板上,可預先形成薄膜電晶體(TFT),然後亦可形成各色濾光片段。而且,於本發明的彩色濾光片上,依據需要,可形成保護(overcoat)膜或透明導電膜等。 A black matrix may be formed in advance before each color filter segment is formed on the transparent substrate or the reflective substrate. The black matrix is a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed, but is not limited thereto. Further, on the transparent substrate or the reflective substrate, a thin film transistor (TFT) may be formed in advance, and then each color filter segment may be formed. Further, on the color filter of the present invention, an overcoat film, a transparent conductive film, or the like can be formed as needed.
彩色濾光片係使用密封劑而與對向基板貼合,從設置於密封部之注入口,注入液晶後,密封注入口,依據需要,藉由使偏光膜或相位差膜貼合於基板的外側,製造液晶顯示面板。 The color filter is bonded to the counter substrate by using a sealant, and the liquid crystal is injected from the injection port provided in the sealing portion, and then the injection port is sealed, and if necessary, the polarizing film or the retardation film is bonded to the substrate. On the outside, a liquid crystal display panel is manufactured.
如此的液晶顯示面板係可使用於一種使用扭曲向列型(TN)、超扭曲向列型(STN)、橫向電場效應型(IPS)、垂直排列型(VA)、光學補償彎曲型(OCB)等的彩色濾光片而進行彩色化之液晶顯示模式。 Such a liquid crystal display panel can be used for a twisted nematic (TN), super twisted nematic (STN), lateral electric field effect (IPS), vertical alignment (VA), optically compensated bend (OCB). A liquid crystal display mode in which color filters are colored.
以下,列舉實施例,具體地說明本發明, 但本發明並非特別限定於此等實施例者。再者,實施例中,「份」表示「質量份」。又,Mn及Mw分別指數目平均分子量及重量平均分子量。 Hereinafter, the present invention will be specifically described by way of examples. However, the invention is not particularly limited to the embodiments. Further, in the examples, "parts" means "parts by mass". Further, Mn and Mw refer to a number average molecular weight and a weight average molecular weight, respectively.
(具有芳香族羧基之樹脂型分散劑(A)的平均分子量) (Average molecular weight of resin type dispersant (A) having an aromatic carboxyl group)
使用作為顏料支持體的樹脂之丙烯酸樹脂的數目平均分子量(Mn)及重量平均分子量(Mw),係使用TSKgel管柱(東曹(Tosoh)公司製),配備RI檢測器之GPC(東曹公司製、HLC-8120GPC),使用THF作為展開溶劑,所測定的換算聚苯乙烯之數目平均分子量(Mn)及重量平均分子量(Mw)。 The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the acrylic resin using the resin as the pigment support were TSKgel column (manufactured by Tosoh Co., Ltd.) and GPC equipped with an RI detector (Tosoh Corporation) , HLC-8120GPC), using THF as a developing solvent, the number average molecular weight (Mn) and weight average molecular weight (Mw) of the converted polystyrene.
(具有芳香族羧基之樹脂型分散劑(A)的酸價) (acid value of resin type dispersant (A) having an aromatic carboxyl group)
使用來作為顏料支持體的樹脂之丙烯酸樹脂的酸價,係根據JIS K0070的電位差滴定法,使所測定的酸價(mgKOH/g)經換算固體成分之值。 The acid value of the acrylic resin used as the resin of the pigment support is a value obtained by converting the measured acid value (mgKOH/g) to the solid content according to the potential difference titration method of JIS K0070.
(具有哌啶基骨架之乙烯基系樹脂型分散劑(B)的平均分子量) (Average molecular weight of the vinyl-based resin type dispersant (B) having a piperidinyl skeleton)
乙烯基系樹脂型分散劑(B)的數目平均分子量(Mn)及重量平均分子量(Mw),係使用HLC-8320GPC(東曹公司製)作為裝置,使用SUPER-AW3000作為管柱,使用30mM三乙基胺及10mM LiBr的N,N-二甲基甲醯胺溶液作為溶析液,所測定的換算聚苯乙烯之數目平均分子量(Mn)及重量平均分子量(Mw)。 The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the vinyl resin type dispersant (B) are HLC-8320GPC (manufactured by Tosoh Corporation), and SUPER-AW3000 is used as a column, and 30 mM is used. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the converted polystyrene as a solution of ethylamine and 10 mM LiBr in N,N-dimethylformamide solution.
(具有哌啶基骨架之乙烯基系樹脂型分散劑 (B)的胺價) (Vinyl resin type dispersant having a piperidinyl skeleton) (B) amine price)
乙烯基系樹脂型分散劑的胺價,係根據ASTM D2074的方法,使所測定的全部胺價(mgKOH/g)經換算固體成分之值。 The amine value of the vinyl resin type dispersant is such that the total amine value (mgKOH/g) measured is converted to the value of the solid content according to the method of ASTM D2074.
〈製造例〉 <Manufacturing example>
(具有芳香族羧基之樹脂型分散劑(A)的製造例1(A-1)) (Production Example 1 (A-1) of the resin type dispersant (A) having an aromatic carboxyl group)
於具備氣體導入管、冷凝管、攪拌翼及溫度計之反應槽中,放入1-十二烷基醇62.6份、ε-己內酯287.4份、作為觸媒之氧化單丁基錫(IV)0.1份,以氮氣取代後,於120℃加熱、攪拌4小時。藉由測定固體成分,確認98%反應後,於其中,添加均苯四甲酸二酐36.6份,於120℃反應2小時。以酸價的測定,確認98%以上的酸酐半酯化,反應結束,得到分散劑。藉此,得到每固體成分的酸價49mgKOH/g、數目平均分子量(Mn)2,500的具有芳香族羧基之樹脂型分散劑(A-1)。然後,於合成的樹脂溶液中,添加丙二醇單甲醚乙酸酯,以使不揮發成分成為40重量%,調製樹脂型分散劑(A-1)的溶液。 In a reaction tank equipped with a gas introduction tube, a condenser tube, a stirring blade and a thermometer, 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin oxide (IV) as a catalyst were placed. After replacing with nitrogen, it was heated and stirred at 120 ° C for 4 hours. After confirming the solid content, it was confirmed that 98% of the reaction was carried out, and then 36.6 parts of pyromellitic dianhydride was added thereto, and the mixture was reacted at 120 ° C for 2 hours. From the measurement of the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was completed to obtain a dispersing agent. Thus, a resin-type dispersant (A-1) having an aromatic carboxyl group having an acid value of 49 mgKOH/g and a number average molecular weight (Mn) of 2,500 per solid component was obtained. Then, propylene glycol monomethyl ether acetate was added to the synthesized resin solution so that the nonvolatile content was 40% by weight to prepare a solution of the resin type dispersant (A-1).
(具有芳香族羧基之樹脂型分散劑(A)的製造例2(A-2)) (Production Example 2 (A-2) of the resin type dispersant (A) having an aromatic carboxyl group)
於具備氣體導入管、冷凝管、攪拌翼及溫度計之反應槽,放入甲氧基丙基乙酸酯60份,升溫至110℃,反應容器內以氮氣取代後,從滴入槽,花費2小時滴入預先均勻混合有甲基丙烯酸甲酯40份、甲基丙烯酸苯甲酯28份、丙烯酸正丁酯20份、甲基丙烯酸2-羥基乙酯12份、甲氧 基丙基乙酸酯40份及二甲基-2,2’-偶氮雙二異丁酸酯6份之混合液,然後3小時,在相同溫度下持續攪拌,反應結束。藉此,得到數目平均分子量(Mn)3,800、1分子中羥基的平均個數為3.5個的中間物。該中間物在固體成分100份下添加偏苯三羧酸酐5.1份及二甲基苯甲基胺0.1份,於100℃反應6小時。藉此,得到每1分子的偏苯三羧酸酐的平均個數為1個、每固體成分的酸價30mgKOH/g、數目平均分子量(Mn)4,000的具有芳香族羧基之樹脂型分散劑(A-2)。然後,於合成的樹脂溶液中,添加丙二醇單甲醚乙酸酯,以使不揮發成分成為40重量%,調製樹脂型分散劑(A-2)的溶液。 In a reaction tank equipped with a gas introduction tube, a condenser tube, a stirring blade, and a thermometer, 60 parts of methoxypropyl acetate was placed, and the temperature was raised to 110 ° C. After the reaction vessel was replaced with nitrogen, it was dropped into the tank, and it took 2 40 parts of methyl methacrylate, 28 parts of benzyl methacrylate, 20 parts of n-butyl acrylate, 12 parts of 2-hydroxyethyl methacrylate, and methoxy are uniformly mixed in advance. A mixture of 40 parts of propyl acetate and 6 parts of dimethyl-2,2'-azobisisobutyrate was then stirred for 3 hours at the same temperature, and the reaction was completed. Thereby, an intermediate having a number average molecular weight (Mn) of 3,800 and an average number of hydroxyl groups in one molecule of 3.5 was obtained. In the intermediate, 5.1 parts of trimellitic anhydride and 0.1 part of dimethylbenzylamine were added to 100 parts of the solid component, and the mixture was reacted at 100 ° C for 6 hours. Thus, the resin-type dispersant having an aromatic carboxyl group per one molecule of trimellitic anhydride was one, the acid value per solid component was 30 mgKOH/g, and the number average molecular weight (Mn) was 4,000. -2). Then, propylene glycol monomethyl ether acetate was added to the synthesized resin solution so that the nonvolatile content was 40% by weight to prepare a solution of the resin type dispersant (A-2).
(具有芳香族羧基之樹脂型分散劑(A)的製造例3(A-3)) (Production Example 3 (A-3) of the resin type dispersant (A) having an aromatic carboxyl group)
於具備氣體導入管、冷凝管、攪拌翼及溫度計之反應槽,放入甲基丙烯酸甲酯15份、甲基丙烯酸5份、甲基丙烯酸第3丁酯20份、丙烯酸2-甲氧基乙酯60份、甲氧基丙基乙酸酯45份,以氮氣取代。反應容器內加熱至80℃,添加3-巰基-1,2-丙二醇6份後,分20次每30分鐘添加2,2’-偶氮雙異丁腈0.3份溶解於甲氧基丙基乙酸酯60份者,直接在80℃反應12小時,藉由測定固體成分,確認95%反應後,然後,追加均苯四甲酸二酐9.7份、作為觸媒之1,8-二氮雜雙環-[5.4.0]-7-十一烯0.2份,於120℃反應7小時。以滴定確認98%以上的酸酐半酯化,反應結束,得到每固體成分的酸價71mgKOH/g、數目平均分子量(Mn) 5000的具有芳香族羧基之樹脂型分散劑(A-3)。然後,於合成的樹脂溶液中,添加丙二醇單甲醚乙酸酯,以使不揮發成分成為40重量%,調製樹脂型分散劑(A-3)的溶液。 In a reaction tank equipped with a gas introduction tube, a condenser tube, a stirring blade and a thermometer, 15 parts of methyl methacrylate, 5 parts of methacrylic acid, 20 parts of butyl methacrylate, and 2-methoxy acrylate were placed. 60 parts of ester and 45 parts of methoxypropyl acetate were substituted with nitrogen. The reaction vessel was heated to 80 ° C, 6 parts of 3-mercapto-1,2-propanediol was added, and then 2 parts of 2,2'-azobisisobutyronitrile was added in 20 portions every 30 minutes to dissolve in methoxypropyl B. 60 parts of the acid ester was directly reacted at 80 ° C for 12 hours, and after measuring the solid content, it was confirmed that 95% of the reaction was carried out, and then 9.7 parts of pyromellitic dianhydride was added, and 1,8-diazabicyclo ring as a catalyst was added. -[5.4.0]0.2-undecene 0.2 parts, and reacted at 120 ° C for 7 hours. It was confirmed by titration that 98% or more of the acid anhydride was half-esterified, and the reaction was completed, and the acid value per solid component was 71 mgKOH/g, and the number average molecular weight (Mn) was obtained. A resin-type dispersant (A-3) having an aromatic carboxyl group of 5,000. Then, propylene glycol monomethyl ether acetate was added to the synthesized resin solution so that the nonvolatile content was 40% by weight to prepare a solution of the resin type dispersant (A-3).
(具有芳香族羧基之樹脂型分散劑(A)的製造例4(A-4)) (Production Example 4 (A-4) of the resin type dispersant (A) having an aromatic carboxyl group)
於具備氣體導入管、冷凝管、攪拌翼及溫度計之反應槽,放入甲基丙烯酸甲酯80份、甲基丙烯酸正丁酯20份、甲氧基丙基乙酸酯44份,以氮氣取代。於反應容器內加熱至80℃,添加3-巰基-1,2-丙二醇2.2份後,分20次每30分鐘添加2,2’-偶氮雙異丁腈0.3份溶解於甲氧基丙基乙酸酯24份者,直接在80℃反應12小時,藉由測定固體成分,確認95%反應。然後,追加偏苯三羧酸酐7.4份、作為觸媒之1,8-二氮雜雙環-[5.4.0]-7-十一烯0.2份,於120℃反應2小時,於80℃反應5小時。以滴定確認90%以上的酸酐半酯化,得到每固體成分的酸價40mgKOH/g、數目平均分子量(Mn)5200的具有芳香族羧基之樹脂型分散劑(A-4)。然後,於合成的樹脂溶液中,添加丙二醇單甲醚乙酸酯,以使不揮發成分成為40重量%,調製樹脂型分散劑(A-4)的溶液。 In a reaction tank equipped with a gas introduction tube, a condenser tube, a stirring blade and a thermometer, 80 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 44 parts of methoxypropyl acetate were placed, and replaced with nitrogen. . After heating to 80 ° C in a reaction vessel and adding 2.2 parts of 3-mercapto-1,2-propanediol, 0.3 parts of 2,2'-azobisisobutyronitrile was added in 20 portions every 30 minutes to dissolve in methoxypropyl group. 24 parts of the acetate was directly reacted at 80 ° C for 12 hours, and 95% of the reaction was confirmed by measuring the solid content. Then, 7.4 parts of trimellitic anhydride and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120 ° C for 2 hours, and reacted at 80 ° C. hour. It was confirmed by titration that 90% or more of the acid anhydride was half-esterified, and a resin type dispersant (A-4) having an aromatic carboxyl group having an acid value of 40 mgKOH/g and a number average molecular weight (Mn) of 5,200 per solid component was obtained. Then, propylene glycol monomethyl ether acetate was added to the synthesized resin solution so that the nonvolatile content was 40% by weight to prepare a solution of the resin type dispersant (A-4).
(具有芳香族羧基之樹脂型分散劑(A)的製造例5(A-5)) (Production Example 5 (A-5) of the resin type dispersant (A) having an aromatic carboxyl group)
於具備氣體導入管、冷凝管、攪拌翼及溫度計之反應槽中,放入甲基丙烯酸甲酯15份、甲基丙烯酸5份、甲基丙烯酸第3丁酯20份、丙烯酸2-甲氧基乙酯60份、甲氧 基丙基乙酸酯44份,以氮氣取代。反應容器內加熱至80℃,添加3-巰基-1,2-丙二醇2.0份後,分20次每30分鐘添加2,2’-偶氮雙異丁腈0.3份溶解於甲氧基丙基乙酸酯58份者,直接在80℃反應12小時,藉由測定固體成分,確認95%反應。然後,追加均苯四甲酸二酐3.4份、作為觸媒之1,8-二氮雜雙環-[5.4.0]-7-十一烯0.2份,於120℃反應2小時,於80℃反應5小時。以滴定確認90%以上的酸酐半酯化,得到每固體成分的酸價46mgKOH/g、數目平均分子量(Mn)143000的具有芳香族羧基之樹脂型分散劑(A-5)。然後,於合成的樹脂溶液中,添加丙二醇單甲醚乙酸酯,以使不揮發成分成為40重量%,調製樹脂型分散劑(A-5)的溶液。 15 parts of methyl methacrylate, 5 parts of methacrylic acid, 20 parts of butyl methacrylate, and 2-methoxy acrylate were placed in a reaction vessel equipped with a gas introduction tube, a condenser tube, a stirring blade and a thermometer. Ethyl acetate 60 parts, methoxy 44 parts of propyl acetate, substituted with nitrogen. The reaction vessel was heated to 80 ° C, and after adding 2.0 parts of 3-mercapto-1,2-propanediol, 20 parts of 2,2'-azobisisobutyronitrile was added in 20 portions every 30 minutes to dissolve in methoxypropyl B. The acid ester of 58 parts was directly reacted at 80 ° C for 12 hours, and by measuring the solid content, 95% of the reaction was confirmed. Then, 3.4 parts of pyromellitic dianhydride and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120 ° C for 2 hours, and reacted at 80 ° C. 5 hours. It was confirmed by titration that 90% or more of the acid anhydride was half-esterified, and a resin type dispersant (A-5) having an aromatic carboxyl group having an acid value of 46 mgKOH/g and a number average molecular weight (Mn) of 143,000 per solid component was obtained. Then, propylene glycol monomethyl ether acetate was added to the synthesized resin solution so that the nonvolatile content was 40% by weight to prepare a solution of the resin type dispersant (A-5).
(具有哌啶基骨架之乙烯基系樹脂型分散劑(B)的製造例6(B-1)) (Production Example 6 (B-1) of the vinyl-based resin type dispersant (B) having a piperidinyl skeleton)
於具備氣體導入管、冷凝管、攪拌翼及溫度計之反應槽中,放入甲氧基丙基乙酸酯133份,一邊進行氮氣取代,一邊升溫至110℃。於滴入槽,放入四甲基哌啶基甲基丙烯酸酯120份(日立化成工業(股)製、FANCRYL FA-712HM)、丙烯酸甲酯70份、甲基丙烯酸2-羥基乙酯10份、甲氧基丙基乙酸酯61份及2,2’-偶氮雙(2,4-二甲基戊腈)6份,攪拌至均勻後,朝反應槽花費2小時滴入,然後在相同溫度繼續反應3小時。藉此,得到每固體成分的胺價145mgKOH/g、數目平均分子量(Mn)3500的具有哌啶基骨架之乙烯基系樹脂型分散劑(B-1)。 In a reaction vessel equipped with a gas introduction tube, a condenser tube, a stirring blade, and a thermometer, 133 parts of methoxypropyl acetate was placed, and the temperature was raised to 110 ° C while nitrogen substitution was performed. Into the tank, 120 parts of tetramethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FANCRYL FA-712HM), 70 parts of methyl acrylate, and 10 parts of 2-hydroxyethyl methacrylate were placed. 6 parts of methoxypropyl acetate and 6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), after stirring until uniform, it took 2 hours to the reaction tank, and then The reaction was continued at the same temperature for 3 hours. Thus, a vinyl-based resin type dispersant (B-1) having a piperidinyl skeleton having an amine value of 145 mgKOH/g and a number average molecular weight (Mn) of 3,500 per solid component was obtained.
(具有哌啶基骨架之乙烯基系樹脂型分散劑(B)的製造例7~14(B-2~B-9)) (Production Examples 7 to 14 (B-2 to B-9) of the vinyl-based resin type dispersant (B) having a piperidinyl skeleton)
除使用記載於表1的原料及放入量以外,其餘係與製造例6同樣地進行合成,得到具有哌啶基骨架之乙烯基系樹脂型分散劑(B-2)~(B-9)的溶液。各別的胺價、數目平均分子量如表1的記載。 The synthesis was carried out in the same manner as in Production Example 6 except that the materials and the amounts shown in Table 1 were used, and a vinyl resin-based dispersant (B-2) to (B-9) having a piperidinyl skeleton was obtained. The solution. The respective amine valence and number average molecular weight are as described in Table 1.
表中,2,2,6,6-四甲基哌啶基甲基丙烯酸酯,係使用日立化成工業(股)製的FANCRYL FA-712HM,1,2,2,6,6,6-五甲基哌啶基甲基丙烯酸酯係使用日立化成工業(股)製的FANCRYL FA-711MM。 In the table, 2,2,6,6-tetramethylpiperidinyl methacrylate is a FANCRYL FA-712HM manufactured by Hitachi Chemical Co., Ltd., 1, 2, 2, 6, 6, 6-five. As the methylpiperidinyl methacrylate, FANCRYL FA-711MM manufactured by Hitachi Chemical Co., Ltd. was used.
(不具有哌啶基骨架之乙烯基系樹脂型分散劑的比較製造例1(C-1)) (Comparative Production Example 1 (C-1) of a vinyl-based resin type dispersant having no piperidinyl skeleton)
於具備氣體導入管、冷凝管、攪拌翼及溫度計之反應槽中,放入甲氧基丙基乙酸酯133份,一邊進行氮氣取代,一邊升溫至110℃。於滴入槽,放入甲基丙烯酸N,N-二甲基胺基乙酯200份、甲氧基丙基乙酸酯61份及2,2’-偶氮雙(2,4-二甲基戊腈)6份,攪拌至均勻後,朝反應槽花費2小時滴入,然後在相同溫度繼續反應3小時。藉此,得到每固體成分的胺價345mgKOH/g、數目平均分子量(Mn)3000的不具有哌啶基骨架之乙烯基系樹脂型分散劑(C-1)。 In a reaction vessel equipped with a gas introduction tube, a condenser tube, a stirring blade, and a thermometer, 133 parts of methoxypropyl acetate was placed, and the temperature was raised to 110 ° C while nitrogen substitution was performed. Into the tank, 200 parts of N,N-dimethylaminoethyl methacrylate, 61 parts of methoxypropyl acetate and 2,2'-azobis (2,4-dimethyl) 6 parts of valeronitrile, and after stirring until uniform, it took 2 hours to the reaction tank, and then the reaction was continued at the same temperature for 3 hours. Thus, a vinyl resin-type dispersant (C-1) having no amine group 345 mg KOH/g and a number average molecular weight (Mn) of 3000 and having no piperidinyl skeleton was obtained.
(不具有哌啶基骨架之乙烯基系樹脂型分散劑的比較製造例2(C-2)) (Comparative Production Example 2 (C-2) of a vinyl-based resin type dispersant having no piperidinyl skeleton)
除使用記載於表2的原料及放入量以外,其餘係與比較製造例1同樣地進行合成,得到不具有哌啶基骨架之乙烯基系樹脂型分散劑(C-2)的溶液。胺價、數目平均分子量如表2的記載。 The mixture was synthesized in the same manner as in Comparative Production Example 1 except that the materials and the amounts of the materials described in Table 2 were used, and a solution of a vinyl resin-based dispersant (C-2) having no piperidinyl skeleton was obtained. The amine value and the number average molecular weight are as described in Table 2.
(丙烯酸樹脂溶液1的調整) (Adjustment of Acrylic Resin Solution 1)
於反應容器,放入丙二醇單甲醚乙酸酯370份,一邊於容器注入氮氣,一邊加熱至80℃,在相同溫度,花費1小時滴入甲基丙烯酸12.3份、甲基丙烯酸苯甲酯49.2份、 對異丙苯基酚環氧乙烷改性丙烯酸酯(東亞合成公司製「ARONIX M-110」)24.2份、甲基丙烯酸2-羥基乙酯14.3份的混合物,進行聚合反應。滴入結束後,再於80℃反應3小時後,添加偶氮雙異丁腈1.0份溶解於丙二醇單甲醚乙酸酯50份者,再持續於80℃反應1小時,得到丙烯酸樹脂的溶液。丙烯酸樹脂的重量平均分子量約為30000。冷卻至室溫後,取樣樹脂溶液約2g,在180℃、20分鐘加熱乾燥,測定不揮發成分,於先前所合成的樹脂溶液中,添加丙二醇單甲醚乙酸酯,以使不揮發成分成為40質量%,調製丙烯酸樹脂1溶液。 370 parts of propylene glycol monomethyl ether acetate was placed in the reaction vessel, and while heating to 80 ° C while injecting nitrogen gas into the container, 12.3 parts of methacrylic acid and benzyl methacrylate 49.2 were added dropwise at the same temperature for 1 hour. Share, A mixture of 24.2 parts of cumene phenol ethylene oxide-modified acrylate ("ARONIX M-110" manufactured by Toagosei Co., Ltd.) and 14.3 parts of 2-hydroxyethyl methacrylate was subjected to a polymerization reaction. After the completion of the dropwise addition, the reaction was further carried out at 80 ° C for 3 hours, and then 1.0 part of azobisisobutyronitrile was added and dissolved in 50 parts of propylene glycol monomethyl ether acetate, and the reaction was continued at 80 ° C for 1 hour to obtain a solution of an acrylic resin. . The acrylic resin has a weight average molecular weight of about 30,000. After cooling to room temperature, about 2 g of the resin solution was sampled, and dried by heating at 180 ° C for 20 minutes to measure a nonvolatile matter, and propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution to make the nonvolatile matter 40% by mass, a solution of the acrylic resin 1 was prepared.
〈顏料的胺吸附能的確認〉 <Confirmation of amine adsorption energy of pigment>
於可密閉的玻璃容器中,拾取實施例使用之C.I.顏料綠58(以下記為PG58)1g,添加0.02莫耳/升的正己基胺(吸附物質)的甲氧基丙基乙酸酯溶液30毫升。於容器塞入栓塞,在超音波洗淨機花費1小時,使其吸附於顏料表面。施用於離心分離機,使顏料沈澱,得到上層澄清液。採取15毫升的上層澄清液,以0.02莫耳/升的過氯酸二噁烷溶液,藉由電位差滴定裝置,反滴定殘存的正己基胺。測定定量空白組時,確認為具有550微莫耳/克的胺吸附能之顏料。 In a glass container which can be sealed, 1 g of CI Pigment Green 58 (hereinafter referred to as PG58) used in the examples was picked up, and a methoxypropyl acetate solution of 0.02 mol/liter of n-hexylamine (adsorbed material) was added. ML. The plug was inserted into the container and it took 1 hour in the ultrasonic cleaner to adsorb it on the surface of the pigment. It is applied to a centrifugal separator to precipitate a pigment to obtain an upper clear liquid. 15 ml of the upper clear liquid was used, and the residual n-hexylamine was back-titrated by a potentiometric titration apparatus using a solution of 0.02 mol/liter of dichloroperchloric acid. When the quantitative blank group was measured, it was confirmed to be a pigment having an amine adsorption energy of 550 μmol/g.
同樣地對於本發明的實施例使用的C.I.顏料黃150顏料(以下記為PY150)以及C.I.顏料黃138(以下記為PY138)以及C.I.顏料藍15:6(以下記為PB15:6),也與PY150同樣地確認。結果表示於表3。 Similarly, CI Pigment Yellow 150 pigment (hereinafter referred to as PY150) and CI Pigment Yellow 138 (hereinafter referred to as PY138) and CI Pigment Blue 15:6 (hereinafter referred to as PB15:6) used in the examples of the present invention are also PY150 is confirmed in the same way. The results are shown in Table 3.
〈彩色濾光片用顏料組成物的製作〉 <Production of Pigment Composition for Color Filters>
〔實施例1〕 [Example 1]
(顏料分散體(顏料組成物)D-1的調整) (Adjustment of pigment dispersion (pigment composition) D-1)
將顏料(PG58)12.0份、有機溶劑(丙二醇單甲醚乙酸酯;略記為PGMAc)56.0份、製造例1合成的分散劑(A-1)溶液7.68份、製造例9合成的乙烯基系樹脂(B-4)溶液1.92份的混合物均勻攪拌混合後,使用直徑0.5mm的氧化鋯顆粒,以艾格研磨機(Eiger mill)(日本艾格公司製「Minimodel M-250 MKII」),分散5小時後,以5.0μm過濾器過濾,製作顏料分散體D-1。 12.0 parts of a pigment (PG58), 56.0 parts of an organic solvent (propylene glycol monomethyl ether acetate; abbreviated as PGMAc), 7.68 parts of a dispersant (A-1) solution synthesized in Production Example 1, and a vinyl system synthesized in Production Example 9. After the mixture of 1.92 parts of the resin (B-4) solution was uniformly stirred and mixed, zirconia particles having a diameter of 0.5 mm were used, and dispersed by an Eiger mill ("Minimodel M-250 MKII" manufactured by Aegis, Japan) for 5 hours. Thereafter, the mixture was filtered through a 5.0 μm filter to prepare a pigment dispersion D-1.
〔實施例2~52〕及〔比較例1~16〕 [Examples 2 to 52] and [Comparative Examples 1 to 16]
(顏料分散體D-2~D-68的調整) (Adjustment of pigment dispersion D-2~D-68)
除使用表4~7所示的材料、調配比以外,其餘係與實施例1同樣地進行,得到顏料分散體D-2~D-53。 The pigment dispersions D-2 to D-53 were obtained in the same manner as in Example 1 except that the materials and the mixing ratios shown in Tables 4 to 7 were used.
表4~7中的簡稱係如下述。 The abbreviations in Tables 4 to 7 are as follows.
‧PG58:顏料綠58、鹵化鋅酞菁顏料、胺吸附能550μmol/g(微莫耳/克) ‧PG58: Pigment Green 58, zinc halide phthalocyanine pigment, amine adsorption energy 550 μ mol / g (micromol / g)
‧PY150:顏料黃150:偶氮次甲基黃顏料、胺吸附能215μmol/g ‧PY150: Pigment Yellow 150: Azomethine yellow pigment, amine adsorption energy 215 μ mol/g
‧PY138:顏料黃138:喹酞酮黃顏料、胺吸附能34μmol/g ‧PY138: Pigment Yellow 138: Quinone yellow pigment, amine adsorption energy 34 μ mol/g
‧PB15:6:顏料藍:15:6:酞菁藍顏料、胺吸附能26μmol/g ‧PB15: 6: Pigment Blue: 15: 6: phthalocyanine blue pigment, amine adsorption energy 26 μ mol / g
‧分散劑A-1~A-5:製造例1~5所製造的具有芳香族羧基之樹脂型分散劑(A)溶液 ‧Dispersant A-1~A-5: Resin-type dispersant (A) solution having aromatic carboxyl groups produced in Production Examples 1 to 5
‧乙烯基系樹脂B-1~B-9:製造例6~14所製造的具有哌啶基骨架之乙烯基系樹脂型分散劑(B)溶液 Vinyl resin B-1 to B-9: a vinyl resin type dispersant (B) solution having a piperidinyl skeleton produced in Production Examples 6 to 14
‧乙烯基系樹脂C-1~C-2:比較製造例1~2所製造的不具有哌啶基骨架之乙烯基系樹脂溶液 ‧ Vinyl resin C-1 to C-2: a vinyl resin solution having no piperidinyl skeleton produced in Comparative Production Examples 1 and 2
‧溶劑PGMAC:丙二醇單甲醚乙酸酯 ‧ solvent PGMAC: propylene glycol monomethyl ether acetate
‧衍生物A:色素骨架為喹酞酮系,色素衍生物的金屬鹽的金屬離子為具有鋁離子的衍生物
〈彩色濾光片用顏料組成物(顏料分散體D-1~D-68)的評估〉 <Evaluation of Pigment Composition for Color Filters (Pigment Dispersions D-1 to D-68)>
實施例及比較例所得之顏料分散體(D-1~D-68)的亮度、對比、黏度、保存安定性的評估,以下述的方法進行。結果表示於表8~11。 The evaluation of the brightness, contrast, viscosity, and storage stability of the pigment dispersions (D-1 to D-68) obtained in the examples and the comparative examples was carried out by the following method. The results are shown in Tables 8-11.
關於評估結果,B~AA為實用程度。 Regarding the evaluation results, B~AA is practical.
(亮度) (brightness)
於100mm×100mm、1.1mm厚的玻璃基板上,塗佈所得之顏料分散體,於70℃乾燥20分鐘後,再於230℃加熱40分鐘,得到所得之基板的色度成為〔PG58時〕於C光源,x=0.224、y=0.600 The obtained pigment dispersion was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thick, dried at 70 ° C for 20 minutes, and then heated at 230 ° C for 40 minutes to obtain a chromaticity of the obtained substrate of [PG58]. C light source, x=0.224, y=0.600
〔PY150時〕於C光源,x=0.440、y=0.510 [PY150] at C light source, x=0.440, y=0.510
〔PG58/PY138時〕於C光源,x=0.268、y=0.600 [PG58/PY138] at C source, x=0.268, y=0.600
〔PB15:6時〕於C光源,x=0.140、y=0.150 [PB15: 6 o'clock] at C light source, x=0.140, y=0.150
之塗佈基板。所得之基板的亮度(Y),以顯微分光光度計(奧林巴斯(Olympus)光學公司製「OSP-SP200」)測定。 Coating the substrate. The brightness (Y) of the obtained substrate was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).
判定結果,於表8~11中,以AA:表示特別亮,最適合實用的情況;A:表示明亮,適合實用的情況;C:表示暗,不適合實用的情況。 The judgment results are shown in Tables 8 to 11 as AA: particularly bright, and most suitable for practical use; A: Bright, suitable for practical use; C: Dark, not suitable for practical use.
(對比(CR)) (comparative (CR))
將所得之顏料分散體使用旋轉塗佈機塗佈於100mm×100mm、1.1mm厚的玻璃基板上,改變旋轉數,使乾燥膜厚成為約2μm左右,製作3點的塗佈基板。塗佈後,於80℃以熱風烤箱乾燥30分鐘後,測定各別的膜厚及對比,從3點的數據,膜厚2μm之對比(CR)以一次關連法求得。 The obtained pigment dispersion was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thick using a spin coater, and the number of rotations was changed to have a dry film thickness of about 2 μm to prepare a coated substrate of three points. After coating, the film was dried in a hot air oven at 80 ° C for 30 minutes, and the respective film thicknesses and contrasts were measured. From the data of 3 points, the contrast (CR) of the film thickness of 2 μm was determined by a single correlation method.
判定結果,於表8~11中,以A:表示對比良好,最適合實用的情況;B:表示對比在一般的程度,適合實用的情況;C:表示對比差,不適合實用的情況。 The judgment results are shown in Tables 8 to 11, with A: indicating good contrast and being most suitable for practical use; B: indicating that the comparison is suitable for general use, and C: indicating poor contrast and not suitable for practical use.
(黏度) (viscosity)
顏料分散體的黏度係使用E型黏度計(東機產業公司製「ELD型黏度計」),測定25℃之初期黏度。 The viscosity of the pigment dispersion was measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.), and the initial viscosity at 25 ° C was measured.
(保存安定性) (save stability)
對於所得之顏料分散體,在40℃的恆溫機保存1週,使其經時促進後,經時後的顏料分散體的黏度以與前述黏度測定相同的方法測定,計算40℃下保存1週前後的黏度變化率,根據以下的基準,以3階段評估。 The obtained pigment dispersion was stored in a thermostat at 40 ° C for 1 week, and the viscosity of the pigment dispersion after the passage was measured by the same method as the viscosity measurement described above, and the temperature was kept at 40 ° C for 1 week. The rate of change in viscosity before and after is evaluated in three stages according to the following criteria.
A:黏度變化率(增黏率)為±10%以內,不產生沈澱物的情況。 A: The viscosity change rate (viscosity increase rate) is within ±10%, and no precipitate is generated.
B:黏度變化率(增黏率)為±10~15%以內,不產生沈澱物的情況。 B: The viscosity change rate (viscosity increase rate) is within ±10 to 15%, and no precipitate is generated.
C:黏度變化率(增黏率)超過±15%的情況,或即使黏度變化率為±15%以內,亦產生沈澱物的情況。 C: A case where the viscosity change rate (viscosity increase rate) exceeds ±15%, or even if the viscosity change rate is within ±15%, a precipitate is generated.
如此,具有550μmol/g的胺吸附能之PG58,使用具有芳香族羧基之樹脂型分散劑(A)以及具有哌啶基骨架之乙烯基系樹脂型分散劑(B)而分散的實施例1~13,係可得到低黏度的顏料組成物,但是只具有芳香族接基之樹脂型分散劑(A)、以及只有具有哌啶基骨架之乙烯基系樹脂型分散劑(B)係經時黏度惡化。而且,與具有芳香族羧基之樹脂型分散劑(A)併用的乙烯基樹脂,係以具有哌 啶基骨架之乙烯基系樹脂(B)分散的顏料分散體的亮度,係比不具有哌啶基骨架之乙烯基系樹脂(C-1、2)分散的顏料分散體的亮度更高的值。 Thus, with an amine PG58 adsorption energy of 550 μ mol / g, the resin having an aromatic carboxyl dispersant (A) and a vinyl-piperidyl skeleton of the resin dispersant (B) dispersed in the embodiment 1 to 13, a low viscosity pigment composition is obtained, but a resin type dispersant (A) having only an aromatic substituent, and a vinyl resin type dispersant (B) having only a piperidinyl skeleton are The viscosity deteriorates. Further, the vinyl resin used in combination with the resin-type dispersant (A) having an aromatic carboxyl group is a pigment dispersion dispersed with a vinyl-based resin (B) having a piperidinyl skeleton, and has no ratio of piperidine. The pigment dispersion in which the vinyl-based resin (C-1, 2) of the base skeleton is dispersed has a higher brightness.
由表8~11得知,使用具有芳香族羧基之樹脂型分散劑(A)以及具有哌啶基骨架之乙烯基系樹脂(B)而分散的實施例1~52,係任一者均對比(相當於分散性)、初期黏度(相當於流動性)、增黏率(相當於保存安定性)以及亮度Y佳。另一方面,使用具有芳香族羧基之樹脂型分散劑(A)以及不具有哌啶基骨架之乙烯基系樹脂(C-1或C-2)而分散者係任一者均亮度低的結果。而且,只以具有芳香族羧基之樹脂型分散劑(A)或具有哌啶基骨架之乙烯基系樹脂(B)分散者,係全部的物性不佳。 From Tables 8 to 11, it is known that Examples 1 to 52 in which a resin type dispersant (A) having an aromatic carboxyl group and a vinyl resin (B) having a piperidinyl group are dispersed are used. (equivalent to dispersibility), initial viscosity (corresponding to fluidity), viscosity increase rate (corresponding to preservation stability), and brightness Y. On the other hand, the resin-type dispersant (A) having an aromatic carboxyl group and the vinyl-based resin (C-1 or C-2) having no piperidinyl skeleton are used, and the dispersion is low. . Further, all of the physical properties of the resin-based dispersant (A) having an aromatic carboxyl group or the vinyl-based resin (B) having a piperidinyl skeleton are not preferable.
〈彩色濾光片用感光性著色組成物的調整〉 <Adjustment of photosensitive coloring composition for color filter>
〔實施例53〕 [Example 53]
(彩色濾光片用感光性著色組成物R-1的調整) (Adjustment of photosensitive coloring composition R-1 for color filter)
將下述的混合物攪拌混合成均一後,以1.0μm過濾器過濾,得到鹼顯像型彩色濾光片用感光性著色組成物R-1。 The mixture was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to obtain a photosensitive coloring composition R-1 for an alkali development type color filter.
〔實施例54~104〕及〔比較例17~32〕 [Examples 54 to 104] and [Comparative Examples 17 to 32]
(彩色濾光片用感光性著色組成物R-2~R-68的調整) (Adjustment of photosensitive coloring composition R-2 to R-68 for color filters)
除使用表4~7所示的顏料分散體外,其餘係與實施例53同樣地進行,得到彩色濾光片用著色組成物R-2~R-68。 The coloring compositions R-2 to R-68 for color filters were obtained in the same manner as in Example 53 except that the pigments shown in Tables 4 to 7 were used.
〈彩色濾光片用感光性著色組成物(R-1~R-68)的評估〉 <Evaluation of photosensitive coloring composition (R-1 to R-68) for color filters>
實施例及比較例所得之感光性著色組成物(R-1~R-68)的亮度、對比、黏度、保存安定性的評估,以下述的方法進行。結果表示於表12~15。關於評估結果,B~AA為實用程度。 The evaluation of the brightness, contrast, viscosity, and storage stability of the photosensitive coloring compositions (R-1 to R-68) obtained in the examples and the comparative examples was carried out by the following method. The results are shown in Tables 12-15. Regarding the evaluation results, B~AA is practical.
(亮度) (brightness)
於100mm×100mm、1.1mm厚的玻璃基板上,塗佈所得之感光性著色組成物,於70℃、20分鐘乾燥後,使用超高壓水銀燈,以累積光量150mJ進行紫外線曝光,再於230℃加熱40分鐘,得到使所得之基板的色度成為〔PG58之時〕於C光源,x=0.224、y=0.600 The obtained photosensitive colored composition was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thick, dried at 70 ° C for 20 minutes, and then exposed to ultraviolet light at a cumulative light amount of 150 mJ using an ultrahigh pressure mercury lamp, and then heated at 230 ° C. After 40 minutes, the chromaticity of the obtained substrate was changed to [C58] at the C light source, x=0.224, y=0.600.
〔PY150之時〕於C光源,x=0.440、y=0.510 [At the time of PY150] at C light source, x=0.440, y=0.510
〔PG58/PY138之時〕於C光源,x=0.268、y=0.600 [At the time of PG58/PY138] at C light source, x=0.268, y=0.600
〔PB15:6之時〕於C光源,x=0.140、y=0.150 [PB15: 6 o'clock] at C light source, x=0.140, y=0.150
之塗佈基板。所得之基板的亮度(Y),以顯微分光光度計(奧林巴斯(Olympus)光學公司製「OSP-SP200」)測定。 Coating the substrate. The brightness (Y) of the obtained substrate was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).
(對比(CR)) (comparative (CR))
將所得之感光性著色組成物,使用旋轉塗佈機,塗佈 於100mm×100mm、1.1mm厚的玻璃基板上使 〔PG58之時〕C光源下的色度y為0.595、0.600、0.605 The obtained photosensitive coloring composition was coated using a spin coater. Made on a glass substrate of 100 mm × 100 mm and 1.1 mm thick [At the time of PG58] The chromaticity y under the C light source is 0.595, 0.600, 0.605
〔PY150之時〕C光源下的色度x為0.395、0.440、0.445 [PY150] The chromaticity x under the C light source is 0.395, 0.440, 0.445
〔PG58/PY138之時〕C光源下的色度y為0.595、0.600、0.605 [At the time of PG58/PY138] The chromaticity y under the C light source is 0.595, 0.600, 0.605
〔PB15:6之時〕C光源下的色度y為0.145、0.150、0.155 [PB15: 6] The chromaticity y under C light source is 0.145, 0.150, 0.155
改變旋轉數,塗佈3片,得到塗佈基板。使該彩色濾光片用感光性著色組成物塗佈基板,於70℃乾燥20分鐘後,使用超高壓水銀燈,以累積光量150mJ進行紫外線曝光,再於230℃加熱40分鐘,放置冷卻後,測定對比。 The number of rotations was changed, and three sheets were applied to obtain a coated substrate. The color filter was coated with a photosensitive coloring composition, and dried at 70 ° C for 20 minutes, and then exposed to ultraviolet light at a cumulative light amount of 150 mJ using an ultrahigh pressure mercury lamp, and then heated at 230 ° C for 40 minutes, left to stand for cooling, and then measured. Compared.
(黏度)及(保存安定性) (viscosity) and (preservation stability)
將前述彩色濾光片用著色組成物(顏料分散體D-1~D-68)以相同的方法進行評估。 The color filters described above were evaluated in the same manner as the coloring compositions (pigment dispersions D-1 to D-68).
(密著性測試) (adhesion test)
1.著色塗膜的形成 1. Formation of colored coating film
將所得之感光性著色組成物藉由旋轉塗佈法塗佈於10cm×10cm的玻璃基板上後,在潔淨烤箱中於70℃加溫15分鐘,除去溶劑,得到約2μm的著色塗膜。然後,使該基板冷卻至室溫後,以超高壓水銀燈,照射紫外線,以使累積曝光量成為50mJ/cm2。又,曝光量係使用OPHIR公司製「PE10 B-V2」測定。 The obtained photosensitive colored composition was applied onto a 10 cm × 10 cm glass substrate by a spin coating method, and then heated at 70 ° C for 15 minutes in a clean oven to remove the solvent to obtain a colored coating film of about 2 μm . . Then, after the substrate was cooled to room temperature, ultraviolet rays were irradiated with an ultrahigh pressure mercury lamp so that the cumulative exposure amount became 50 mJ/cm 2 . Further, the exposure amount was measured using "PE10 B-V2" manufactured by OPHIR.
再者,藉由0.2質量%的碳酸鈉水溶液所構成的顯像液,進行噴塗顯像,鹼顯像後,以離子交換水洗 淨,該基板於230℃加熱20分鐘,得到著色塗膜基板。 Further, the developing solution composed of a 0.2% by mass aqueous sodium carbonate solution was subjected to spray development, and after alkali development, it was washed with ion exchanged water. The substrate was heated at 230 ° C for 20 minutes to obtain a colored coating film substrate.
2.保護膜製作方法 2. Protective film manufacturing method
使上述圖型製作方法所得之各色彩色濾光片於基板上,使用UV/臭氧裝置(岩崎電氣(股)製、OC-4010-S),以既定的曝光量,進行洗淨處理後,藉由旋轉塗佈法塗佈保護膜材(JSR製「NN901」)後,使其乾燥,形成2μm厚的透明保護層。然後,於90℃加熱乾燥10分鐘(預烤),以紫外線、既定的曝光量進行曝光。然後,藉由0.2質量%的碳酸鈉水溶液所構成的顯像液,進行噴塗顯像,進行水洗,完成圖型化。顯像時間係分別為洗去未曝光的塗佈膜之合理時間。然後,於230℃加熱處理30分鐘,形成保護膜。 The color filters of the respective colors obtained by the above-described pattern forming method are subjected to a cleaning treatment with a predetermined exposure amount using a UV/ozone apparatus (made by Iwasaki Electric Co., Ltd., OC-4010-S), and then borrowed. The protective film ("NN901" manufactured by JSR) was applied by a spin coating method, and then dried to form a transparent protective layer having a thickness of 2 μm . Then, it was dried by heating at 90 ° C for 10 minutes (pre-baked), and exposed to ultraviolet light at a predetermined exposure amount. Then, the developing solution composed of a 0.2% by mass aqueous sodium carbonate solution was subjected to spray development, and washed with water to complete patterning. The development time is a reasonable time to wash away the unexposed coating film, respectively. Then, it was heat-treated at 230 ° C for 30 minutes to form a protective film.
3.評估方法 3. Evaluation method
於上述製作方法所得之各著色塗膜,貼黏根據JIS-Z-1522之玻璃紙膠帶,以根據JISS-6050之橡皮擦,塗擦貼黏的部分。保護膜密著性評估係根據JIS-K-5400之棋盤格測試方法之十字剝離測試進行。 Each of the colored coating films obtained by the above production method was adhered to a cellophane tape according to JIS-Z-1522, and the adhered portion was rubbed according to the eraser of JISS-6050. The protective film adhesion evaluation was carried out in accordance with the cross peel test of the checkerboard test method of JIS-K-5400.
評估的等級係如下述。B~AA為實用程度。 The rating of the assessment is as follows. B~AA is practical.
AA:缺陷面積未達全部面積的5% AA: The defect area is less than 5% of the total area
A:缺陷面積為全部面積的5%以上、未達10% A: The defect area is 5% or more of the total area, and less than 10%.
B:缺陷面積為全部面積的10%以上、未達20% B: The defect area is more than 10% of the total area, less than 20%
C:缺陷面積為全部面積的20%以上 C: The defect area is more than 20% of the total area
如此,使用具有芳香族羧基之樹脂型分散劑(A)、以及具有哌啶基骨架之乙烯基系樹脂(B)而分散的實施例,係任一者對比(相當於分散性)、初期黏度(相當於流動性)、增黏率(相當於保存安定性)以及亮度Y皆優。另一方面,使用具有芳香族羧基之樹脂型分散劑(A)、以及不具有哌啶基骨架之乙烯基系樹脂(C-1或C-2)而分散者係任一者亮度均為低的結果。而且,只以具有芳香族羧基之樹 脂型分散劑(A)或具有哌啶基骨架之乙烯基系樹脂型分散劑(B)分散者,係全部的物性不佳。 As described above, the examples in which the resin-type dispersing agent (A) having an aromatic carboxyl group and the vinyl-based resin (B) having a piperidinyl skeleton are dispersed are used for comparison (corresponding to dispersibility) and initial viscosity. (equivalent to fluidity), viscosity increase rate (corresponding to preservation stability) and brightness Y are excellent. On the other hand, the resin type dispersant (A) having an aromatic carboxyl group and the vinyl resin (C-1 or C-2) having no piperidinyl skeleton are used, and the dispersion is low in either of them. the result of. Moreover, only trees with aromatic carboxyl groups When the lipid dispersing agent (A) or the vinyl resin type dispersing agent (B) having a piperidinyl skeleton is dispersed, all of the physical properties are not good.
而且,關於密著性係於使用使烷氧基矽烷基共聚合之具有哌啶基骨架之乙烯基系樹脂(B-8)之系中,顯示良好的結果。 Further, the adhesion is in the system using a vinyl-based resin (B-8) having a piperidinyl skeleton copolymerized with an alkoxyfluorenyl group, and shows good results.
〈彩色濾光片的製作〉 <Production of Color Filters>
首先,製作使用於彩色濾光片的製作之紅色感光性顏料組成物及藍色感光性顏料組成物。 First, a red photosensitive pigment composition and a blue photosensitive pigment composition for use in the production of a color filter are produced.
(紅色感光性顏料組成物(RR-1)的製作) (Production of Red Photosensitive Pigment Composition (RR-1))
將下述組成的混合物攪拌混合成均勻後,使用直徑0.5mm的氧化鋯顆粒,以艾格研磨機(Eiger mill)(日本艾格公司製「Minimodel M-250 MKII」)分散5小時後,以5.0μm過濾器過濾,製作紅色著色組成物(DR-1)。 After the mixture of the following composition was stirred and homogenized, zirconia particles having a diameter of 0.5 mm were used, and dispersed by an Eiger mill ("Minimodel M-250 MKII" manufactured by Aegis, Japan) for 5 hours, and then 5.0 μm. The m filter was filtered to prepare a red colored composition (DR-1).
然後,將下述組成的混合物均勻攪拌混合成均勻後,以1.0μm過濾器過濾,製作紅色感光性著色組成物(RR-1)。 Then, the mixture of the following composition was uniformly stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a red photosensitive coloring composition (RR-1).
(藍色感光性著色組成物(RB-1)的製作) (Production of blue photosensitive coloring composition (RB-1))
將下述組成的混合物攪拌混合成均勻後,使用直徑0.5mm的氧化鋯顆粒,以艾格研磨機(Eiger mill)(日本艾格公司製「Minimodel M-250 MKII」)分散5小時後,以5.0μm過濾器過濾,製作藍色著色組成物(DB-1)。 After the mixture of the following composition was stirred and homogenized, zirconia particles having a diameter of 0.5 mm were used, and dispersed by an Eiger mill ("Minimodel M-250 MKII" manufactured by Aegis, Japan) for 5 hours, and then 5.0 μm. The m filter was filtered to prepare a blue colored composition (DB-1).
然後,將下述組成的混合物攪拌混合成均勻後,以1.0μm過濾器過濾,製作藍色感光性著色組成物(RB-1)。 Then, the mixture of the following composition was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-1).
(彩色濾光片的製作) (production of color filter)
於玻璃基板上,圖型加工黑色矩陣,於該基板上以旋轉塗佈機塗佈紅色感光性著色組成物(RR-1),形成著色覆膜。於該覆膜,隔著光罩,使用超高壓水銀燈,照射150mJ/cm2的紫外線。然後,藉由0.2質量%的碳酸鈉水溶液所構成的顯像液,進行噴塗顯像,除去未曝光部分後,以離子交換水洗淨,該基板於220℃進行加熱20分鐘,形成紅色濾光片段。此處,紅色濾光片段係在200℃的加熱處理後,於C光源中(以下綠色、藍色也使用)符合x=0.640、y=0.330的色度。而且,藉由相同的方法,綠色濾光片段係使用本發明的綠色感光性著色組成物(R-1),符合x=0.290、y=0.600的色度,藍色濾光片段係使用藍色感光性著色組成物(RB-1),符合x=0.150、y=0.060的色度,形成各濾光片段,得到彩色濾光片。 A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (RR-1) was applied onto the substrate by a spin coater to form a colored film. In the film, an ultrahigh pressure mercury lamp was used to irradiate ultraviolet rays of 150 mJ/cm 2 through a photomask. Then, the developing solution composed of a 0.2% by mass aqueous sodium carbonate solution was subjected to spray development to remove the unexposed portion, and then washed with ion-exchanged water. The substrate was heated at 220 ° C for 20 minutes to form a red filter. Fragment. Here, the red filter segment was subjected to heat treatment at 200 ° C, and the chromaticity of x = 0.640 and y = 0.330 was satisfied in the C light source (the following green and blue are also used). Further, by the same method, the green filter segment uses the green photosensitive coloring composition (R-1) of the present invention, conforming to the chromaticity of x=0.290 and y=0.600, and the blue filter segment is used. The blue photosensitive coloring composition (RB-1) conformed to the chromaticities of x=0.150 and y=0.060, and each of the filter segments was formed to obtain a color filter.
藉由使用本發明的綠色感光性著色組成物(R-1),可使彩色濾光片高亮度化,其他物性也無問題地適合使用。 By using the green photosensitive coloring composition (R-1) of the present invention, the color filter can be made brighter, and other physical properties can be suitably used without any problem.
Claims (9)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013074299A JP6111801B2 (en) | 2012-06-08 | 2013-03-29 | Pigment composition and color filter |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201439233A TW201439233A (en) | 2014-10-16 |
TWI519612B true TWI519612B (en) | 2016-02-01 |
Family
ID=51625713
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW102144768A TWI519612B (en) | 2013-03-29 | 2013-12-06 | Pigment composition and color filter |
Country Status (4)
Country | Link |
---|---|
KR (1) | KR102168385B1 (en) |
CN (1) | CN105121568B (en) |
TW (1) | TWI519612B (en) |
WO (1) | WO2014155842A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI721087B (en) * | 2016-01-27 | 2021-03-11 | 日商住友化學股份有限公司 | Colored curable resin composition, color filter and display device including same |
CN110997828B (en) * | 2017-07-28 | 2021-07-20 | 住友化学株式会社 | Ink composition, film and display |
JP7081775B2 (en) | 2017-10-16 | 2022-06-07 | 花王株式会社 | Inkjet recording ink set |
JP6981624B2 (en) * | 2017-10-16 | 2021-12-15 | 花王株式会社 | Water-based ink |
JP7315330B2 (en) | 2018-02-06 | 2023-07-26 | 住友化学株式会社 | Colored photosensitive resin composition |
JP7263759B2 (en) * | 2018-08-29 | 2023-04-25 | 東洋インキScホールディングス株式会社 | Coloring composition, photosensitive coloring composition, color filter, color liquid crystal display device |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6161623A (en) | 1984-08-31 | 1986-03-29 | Dainippon Ink & Chem Inc | Pigment dispersant |
JPH0819365B2 (en) | 1987-11-30 | 1996-02-28 | 日本油脂株式会社 | Pigment dispersant |
JPH02219866A (en) | 1989-02-22 | 1990-09-03 | Nippon Oil & Fats Co Ltd | Pigment dispersing agent |
JP3313897B2 (en) | 1994-08-01 | 2002-08-12 | ダイセル化学工業株式会社 | Pigment dispersant |
JP3534859B2 (en) | 1994-11-22 | 2004-06-07 | ダイセル化学工業株式会社 | Pigment dispersant, coating composition and printing ink composition |
JP3895004B2 (en) | 1997-06-10 | 2007-03-22 | サカタインクス株式会社 | Pigment dispersion and ink composition for offset printing using the same |
CN1333790A (en) | 1998-12-31 | 2002-01-30 | 西巴特殊化学品控股有限公司 | pigment composition containing ATRP polymers |
JP4235476B2 (en) * | 2002-03-29 | 2009-03-11 | 関西ペイント株式会社 | Pigment dispersion resin and aqueous pigment dispersion containing the same |
JP4930494B2 (en) * | 2008-01-11 | 2012-05-16 | 東洋インキScホールディングス株式会社 | Pigment composition |
JP5141448B2 (en) | 2008-08-28 | 2013-02-13 | Jsr株式会社 | Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element |
JP5741049B2 (en) | 2011-02-23 | 2015-07-01 | 東洋インキScホールディングス株式会社 | Pigment dispersion and ink |
-
2013
- 2013-12-05 WO PCT/JP2013/082729 patent/WO2014155842A1/en active Application Filing
- 2013-12-05 KR KR1020157027808A patent/KR102168385B1/en active IP Right Grant
- 2013-12-05 CN CN201380075155.5A patent/CN105121568B/en active Active
- 2013-12-06 TW TW102144768A patent/TWI519612B/en active
Also Published As
Publication number | Publication date |
---|---|
KR102168385B1 (en) | 2020-10-21 |
KR20150135340A (en) | 2015-12-02 |
CN105121568A (en) | 2015-12-02 |
CN105121568B (en) | 2017-02-15 |
WO2014155842A1 (en) | 2014-10-02 |
TW201439233A (en) | 2014-10-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6150154B2 (en) | Pigment composition for color filter and color filter | |
TWI519612B (en) | Pigment composition and color filter | |
JP6340868B2 (en) | Pigment composition and color filter | |
JP6589305B2 (en) | Coloring composition for color filter, and color filter | |
TWI500711B (en) | Coloring composition for use in color filter and color filter | |
JP6705212B2 (en) | Coloring composition for color filter and color filter | |
KR102004436B1 (en) | Colored composition for color filter, and color filter | |
JP2016191909A (en) | Colored composition for color filter, and color filter | |
JP6167882B2 (en) | Pigment composition, method for producing the same, coloring composition using the same, and color filter | |
CN109696803A (en) | Colored filter photosensitive coloring composition and colored filter | |
JP2013254127A (en) | Colored composition for color filter, and color filter | |
JP2016218433A (en) | Colored composition for color filter, and color filter | |
JP2017138417A (en) | Colored composition for color filter and color filter | |
JP2016170370A (en) | Coloring composition for color filter, and color filter | |
JP2016191866A (en) | Manufacturing method for pigment composition, pigment composition, coloring composition, color filter, and dispersion resin for kneading pigment | |
JP2015138133A (en) | photosensitive coloring composition and color filter | |
JP2015110711A (en) | Pigment composition and color filter | |
JP6136723B2 (en) | Pigment composition and color filter | |
JP2017062334A (en) | Colored composition for color filter and color filter | |
JP5564823B2 (en) | Printing ink and color filter substrate | |
JP7484204B2 (en) | Coloring composition for color filters and color filters | |
JP2014189614A (en) | Pigment composition and color filter | |
JP2018066778A (en) | Coloring composition for color filter and color filter | |
JP2018101039A (en) | Coloring composition for color filter and color filter | |
JP2021067817A (en) | Coloring composition for color filter and color filter |