1308583 .九、發明說明： 【發明所屬之技術領域】 本發明關於一種顏料組成物及一種其製造方法、其用 途、一種用於塗覆紙或紙板的方法、以及由該方法所可獲 得的紙或紙板。 噴墨印表機的開發已經造成一種對於適合此目的之紙 的需求。特別地，對於能簡單製造但是仍然能高品質噴墨 印刷之紙係有需求。 【先前技術】 已經有揭示使用各種塗料於製造適合於噴墨印刷的 紙。 美國專利申請案公開2002/0039639揭示在一含有顏料 ^知黏結劑的印墨接受層中併入水溶性金屬鹽。 美國專利45541 8 1揭示一種記錄表面，其包含水溶性 多價金屬與陽離子聚合物的組合。 血赢 美國專利申請案公開2004/0255820揭示一種表面經水 ··'合性多價金屬鹽所處理的顏料。 美國專利申請案公開2005/0106317揭示一種製備噴墨 ^己錄材料的方法，其包括以下步驟：形成含有平均二次粒 子大丨、為5OOnm或更小的矽石粒子之至少一多孔層，及塗 .—牙香田 於製備含無機粒子的層之塗料溶液，以使在多孔 ^覆的無機粒子之固體含量變成0.33 g/m2或更少。 杲國專利6797347揭示一種喷墨紙，其包括基紙及在 其上的务腐 jj.. _ '"層’其中该塗層含有經帶正電錯合物所改質的無 6 1308583 孔聚集體對於增量粒子的重量比係約〇.㈤至 • ' 0·01:1至約2:卜最佳約〇.05:1至約i 5卜 膠體-次粒子的平均粒子直徑 ’. 乃，最佳約3_至約50nm。一： 2_至約 約一至約_/2，最佳約二佳係 士-具體態樣中，表面積係最高達約_ g 4之乾含讀佳係約〇.5重量％ ••1重量％至約50重量％。 重里/。’最佳約 本文中所用的術語直徑係指等效球體直徑。 矽石或鋁矽酸鹽的膠體一次粒 :石夕酸鹽的水溶液所形成，”…係已經由鹼金屬 . 狀㈣成其中鹼金屬離子係經離子交換方 .法而去除，或其中驗金層石夕酸鹽溶液的pH已經藉由酸的 二加而減低。-種基_子交換的方法係遵循rk』 「石夕石的化學」㈣年，第机334頁中所敛述的基本原 理而產生一種水溶踢’纟包括膠態帶負電或正電的石夕石或 鋁石夕酉夂鹽之粒子。一種基於驗金屬石夕酸鹽的減低之方 法係遵循例如美國專利號數5176891 '5剛55、5853616、 5482693、6_523及62741 12中所敘述的基本原理。 特仏的冷膠包括可經或可不經表面改質之矽石的膠體 -次粒子’該改質例如係用金屬氧化物如鋁、鈦、鉻、鍅、 石朋或任何其它適合的金屬之氧化物。 適合的矽石或鋁矽酸鹽的膠體一次粒子之水溶膠係可 .由商業上取得的，例如在商標名稱LudoxTM、Sn〇WtexTM、 8 13085831308583. EMBODIMENT OF THE INVENTION: TECHNICAL FIELD The present invention relates to a pigment composition, a method for producing the same, a use thereof, a method for coating paper or paperboard, and paper obtainable by the method Or cardboard. The development of ink jet printers has created a need for paper suitable for this purpose. In particular, there is a need for a paper system that can be easily manufactured but still capable of high quality inkjet printing. [Prior Art] It has been disclosed to use various coatings for producing paper suitable for inkjet printing. U.S. Patent Application Publication No. 2002/0039639 discloses the incorporation of a water-soluble metal salt in an ink receiving layer containing a pigment binder. U.S. Patent No. 4,541,1,1, discloses a recording surface comprising a combination of a water-soluble polyvalent metal and a cationic polymer. Blood Winning US Patent Application Publication No. 2004/0255820 discloses a pigment treated on the surface of a water-soluble polyvalent metal salt. US Patent Application Publication No. 2005/0106317 discloses a method of preparing an ink jet recording material comprising the steps of: forming at least one porous layer comprising vermiculite particles having an average secondary particle size greater than 5 nm or less, And coating the tooth-like field to prepare a coating solution of the inorganic particle-containing layer so that the solid content of the porous inorganic particles becomes 0.33 g/m 2 or less. Japanese Patent No. 6,797,347 discloses an ink jet paper comprising a base paper and a sap on it, wherein the coating contains a 6 1308583 hole modified by a positively charged complex. The weight ratio of the aggregate to the incremental particles is about 〇. (5) to • '0·01:1 to about 2: Bu is about 〇.05:1 to about i 5 pu colloid-average particle diameter of the secondary particles'. Preferably, it is about 3 to about 50 nm. One: 2_ to about 1 to about _/2, the best about two good stewards - in the specific aspect, the surface area is up to about _ g 4 of the dry reading system is about 5. 5 wt% ••1 weight % to about 50% by weight. Heavy /. The term "best diameter" as used herein refers to the equivalent sphere diameter. A colloidal primary particle of vermiculite or aluminosilicate: formed by an aqueous solution of a sulphuric acid salt, "... has been removed from an alkali metal. (4) into which the alkali metal ion is removed by an ion exchange method, or a gold test thereof The pH of the layer solution has been reduced by the addition of acid. The method of seed exchange is follows the principle of rk "Chemistry of Shi Xishi" (four), the basics condensed on page 334 of the machine. The principle produces a water-soluble kicking '纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 。 。 A method based on the reduction of metal oxides follows the basic principles as described, for example, in U.S. Patent Nos. 5,176,891, 5, 5, 5, er, 5, 536, 316, 5, 482, 693, 6, 523, and 62, 741. Special cold glues include colloidal-sub-particles of vermiculite that may or may not be surface modified. The modification is, for example, a metal oxide such as aluminum, titanium, chromium, ruthenium, sapphire or any other suitable metal. Oxide. A suitable colloidal or aluminosilicate colloidal primary particle hydrosol system is commercially available, for example under the trade name LudoxTM, Sn〇WtexTM, 8 1308583
BindzilTM、NyacolTM、VinnsilT1^^ FennosirM 之下。 已發現若讓矽石或鋁矽酸鹽乾燥成粉末，則一種藉由 分散該粉末而形成的溶膠係具有不同於膠體粒子從未被乾 燥成粉末的溶膠者，如在當溶膠已經藉由離子交換或 減低而從鹼金屬矽酸鹽所製備的情況。 可用任何適合的方法，如R.K. Uer的「矽石的化學」 1979年，第364_4〇7頁中所敘述者，來使溶膠中的一次粒 子進仃聚集以形成多孔聚集體的分散液。聚 and Moone^；： 式（見例如R_K. 〗】er的「矽石的化學」1979年，第36〇_364 頁）來追蹤。聚集可當作一分開的步驟來進行或在一亦含其 它顏料粒子的混合物中進行。 在—具體態樣中，陰離子溶膠（包含帶負電的膠體一次 粒子）與陽離子溶膠（包含帶正電的膠體一次粒子）混合，而 導致來自兩種溶膠H粒子之多孔聚集體的形成。 在另一具體態樣中，將鹽，較佳為選自於二價、多價 或錯1加到陰離子或陽離子溶膠中亦導致多孔聚集體的 形成。鹽的例子係氯化紹、聚氯化紹、聚石夕酸硫酸銘、疏 酉义#炭|σ、醋醆錯' 驗金屬删酸鹽及其混合物。 在尚一具體態樣中，使用橋連物質來從一次粒子形成 聚集體。適合的橋連物質之例子係合成及天然高分子電解 質，如CMC(羧甲基纖維素）、ΡΑΜ(聚丙烯醯胺）、聚 DADMAC(聚二稀丙基二甲基氣化錢）、聚稀丙基胺、多胺、 殿粉、瓜耳樹膠及其混合物。 9 1308583 ' 佳约1重量〇/〇至約60重景〇/牡v+ 〇/ π 直里/〇,特佳約5重量％至約5〇重量 -./〇，隶佳約10重量％至約50舌旦。/ 、 重里八。組成物可更含有盆 添加劑，如溶解化劑亦 八 中I自原料的其餘 作用的物質如鹽及橋連劑。 又疋木自聚集 趟方法’組成物可更包含至少一種水溶性銘 ;算\二集體和增量粒子上的Al2〇3之重量%來 存在讀佳係約U重量％至約％重量％，最佳 約0 _ 2重量％至約1 5重景 赢赢v 重里/〇。鹽的例子包括氯化鋁、聚氯 _籲化銘、聚⑦酸硫gH硫 、 物。紹可部分或完全存^ 醋酸錯及其混合 / 存在矽石或鋁矽酸鹽的粒子之表面上 在水相中。水溶性紹鹽的總含量可起源於用於製備声貝料 .: 且成物的陽離子紹改質石夕石溶膠中所存在者。然而 組成物亦可包含另外的鋁鹽。 〆 •不：於聚集方法，組成物可更包含至少一種陽離子聚 °物’較佳為具㈣2_至約1__的分子量，更佳 的至約5。。_的分子量，最佳約5_至約_ ，刀子！。聚合物的電荷密度較佳係約〇 Μ响至約 1⑻q/g’更佳約G_3meq/g至約1Gmeq/g，最㈣G 5叫/g 至、J 8meq/g。以乾多孔聚集體和增量粒子的量為基準，陽 離子聚合物在組成物中的存在量係約Q1重量％至約3〇重 量％，更佳約0.5重量％至約2〇重量％，最佳約】重量％至 :15重量％。適合的陽離子聚合物之例子包括合成及天然 南分子電解質，如PAM(聚丙烯酿胺）、聚Μ贿AC(聚二 稀丙基二甲基氣化銨）、聚稀丙基胺、多胺、多醣及其混合 11 1308583 ' 2式為水性分散液或任何其它適合的形式1 .體：形成’就添加任何視需要選用的添加劑及其：： 體恐'樣而言，請參照顏料組成物的上述說明。、匕八 她尚-觀點係關於一種適合 料組成物，其包括黏結劑及如上述的顏料組成 j子係♦乙料、視需要經改質的搬粉、樹膠、 蛋白貝黏結劑(例如赂蛋白及大豆蛋白質黏結劑)、 :混合物。乳膠例如可為基於苯乙稀丁二婦、丙稀酸醋、 ··=乙^、乙埽與醋酸乙稀醋的共聚物、笨乙稀丙烯酸 酉曰專。聚乙烯醇係特佳的。(塗料組成物亦可包括常用料 它添加劑，流變改質劑、光學增白劑、潤滑劑、不溶黏劑二 -染料、加膠劑等。/塗料組成物的乾含量較佳係約2重量％ .，約乃重量％’最佳約10重量％至約7〇重量％。以乾含。 量為基準，顏料組成物的多孔聚集體和增量粒子較佳係約 30至約99重量％，最佳約5〇至約9〇重量％。以乾含量為 基準，黏結劑的量較佳係約！至約7〇重量％，最佳約⑺ ••至約5。重量％。以乾含量為基準，其它添加劑和可能的雜 質之總量較佳係〇至約50重量％，最佳〇至約3〇重量％。 不拘於適合且較佳的具體態樣，請參照顏料組成物的上述 說明。 本發明又一觀點係關於一種製造塗料組成物的方法， 其包括使黏結劑與如上述的顏料組成物混合之步驟。黏結 劑及視需要選用的添加劑可以任何適當形式如固體材料、 液體材料或當作水溶液、分散液或漿體加到顏料組成物 13 1308583 - 含其它方法如著色。 -. 所要塗覆的紙和紙板可由任何種類的紙漿所製成，例 如由化學紙漿如硫酸鹽、亞硫酸鹽及有機溶膠紙漿、機器 紙漿如熱機器紙漿（TMP)、化學-熱-機器紙漿（CTMp)、精 煉紙漿或碎木紙漿，來自硬木和軟木的經漂白或未經漂白 之紙漿，其係基於新鮮或回收纖維，或其之任何組合。依 照本發明，亦可塗覆來自任何其它種類的紙漿之紙和紙 板。 籲籲 Μ於塗料组成物的進—步細節和具體態樣，請參照相 同的上述說明。 / ·· 本發明最後關⑥一種ϋ由上述方法所可獲#的適合於 喷墨印刷之紙或紙板。該紙或紙板包含一較佳實質上不透 明的層，此層包含來自塗料組成物的多孔聚集體和增量粒 子，較佳係形成奈米結構。塗料的乾量較佳係至少約 〇.6g/m2,更佳約〇.7g/m2至約5〇g/m2，最佳約1^化2至 約25g/m、在紙或紙板的每一經塗覆側，纟自顏料組成物 的多孔聚集體和增量粒子之量較佳係至少約〇 4咖2，更佳 約0.5g/m2至約4〇g/m2,最佳約lg/m2至約2〇^也2。較佳 為尚沒有其它種類的塗料已塗佈在此層的頂上。 已發現’本發明的紙或紙板對於噴墨印刷係具有反好 的特J·生即给予低的線模糊和斑紋以及高的印刷顏色密 度，但是亦可有利地用於其它印刷m色粉、膠版、 :版、凹版、平版石印術及網版印刷。特別有利的是可以 藉由僅塗佈少量的塗料而不需要塗佈許多不同的塗層在紙 15 13〇8583 或紙板上，以簡單的方式獲得該良好沾姑 用加膠祐懕*蒱姐、 的特性。此亦使得能 俜有利°…施壓來塗佈塗料，其就實用的理由而言 係有利的。再者，顏料 的原料來製造。 。主成刀可容易地由可取得 否則戶trr施例將進一步說明本發明。除非另有指明， 、有的伤和百分率係指以重量計的份和百分率。 ^^Ll：製備四種顏料組成物： ♦♦ CAT A):陽離子水㈣石溶膠，咖化學公司AB的㈣… AT22G’含有3G重量咖2,具有約15_的平均一次 徑’其被稀釋至1G重量％。_釋㈣石溶膠在玻 燒杯中被擾掉，及逐滴添加〇屬莫耳/升硫酸銘溶液直 ^膠變成白色且黏度增加為止，此係發生在 酸=的濃度達到0.0125莫耳/升時。聚集體的平均直徑被 ，疋為〇加（在Malvern儀器公司的zetamaster上測量， 單模式分析）。 B ··從塗覆用黏土（SPS， 增量粒子的水性分散液。 Mastersizer Micro Plus(方法 大小，結果為1.64μιη。BindzilTM, NyacolTM, VinnsilT1^^ FennosirM. It has been found that if the vermiculite or aluminosilicate is dried to a powder, a sol formed by dispersing the powder has a different sol that the colloidal particles have never been dried into a powder, such as when the sol has been ionized. The case of being prepared from an alkali metal ruthenate by exchange or reduction. The primary particles in the sol can be aggregated to form a dispersion of porous aggregates by any suitable method, such as those described in R. K. Uer, "Chemistry of Vermiculite", 1979, pp. 364_4, page 7. Poly and Moone^;: (see, for example, R_K. 〗 er "The Chemistry of Meteorite", 1979, pp. 36〇_364). Aggregation can be carried out as a separate step or in a mixture also containing other pigment particles. In a specific aspect, the anionic sol (comprising a negatively charged colloidal primary particle) is mixed with a cationic sol (containing positively charged colloidal primary particles) resulting in the formation of porous aggregates from the two sol H particles. In another embodiment, the addition of a salt, preferably selected from divalent, polyvalent or erroneous 1, to an anionic or cationic sol also results in the formation of a porous aggregate. Examples of the salt are chlorinated sulphate, polychlorinated sulphate, polysulphate sulphate, sulphide sulphide, sigma, vinegar, sulphuric acid, and the like. In yet another embodiment, a bridging material is used to form aggregates from primary particles. Examples of suitable bridging materials are synthetic and natural polymeric electrolytes such as CMC (carboxymethyl cellulose), hydrazine (polyacrylamide), polyDADMAC (polydipropyl dimethyl vaporized money), poly Dilylamine, polyamine, temple powder, guar gum and mixtures thereof. 9 1308583 'Good about 1 weight 〇 / 〇 to about 60 weights 牡 / v v + 〇 / π straight / 〇, particularly good about 5 wt% to about 5 〇 weight -. / 〇, Li Jia about 10% by weight to About 50 tongues. /, heavy eight. The composition may further contain a potting additive such as a dissolving agent and a substance such as a salt and a bridging agent from the rest of the raw material. The composition of the eucalyptus self-aggregating enthalpy method may further comprise at least one water-soluble imprint; the weight % of Al 2 〇 3 on the two collective and incremental particles is present in a reading system of about U% by weight to about % by weight, The best is about 0 _ 2% by weight to about 1 5. Examples of the salt include aluminum chloride, polychlorine _ yuhuaming, poly 7 acid sulfur gH sulfur, and substances. Partial or complete storage of acetic acid error and its mixing / presence of vermiculite or aluminosilicate on the surface of the particles in the aqueous phase. The total content of the water-soluble salt can be derived from the preparation of the acoustic scallops: and the cations of the product are present in the smectite sol. However, the composition may also contain additional aluminum salts. 〆 • No: In the aggregation method, the composition may further comprise at least one cationic polymer' preferably having a molecular weight of (4) 2 to about 1 _, more preferably up to about 5. . _ molecular weight, best about 5_ to about _, knife! . The charge density of the polymer is preferably from about 1 (8) q/g' to about G_3 meq/g to about 1 Gmeq/g, and most (iv) G 5 is /g to J 8meq/g. The cationic polymer is present in the composition in an amount of from about Q1% by weight to about 3% by weight, more preferably from about 0.5% by weight to about 3% by weight, based on the amount of dry porous aggregates and extender particles, most Good about 】% by weight to: 15% by weight. Examples of suitable cationic polymers include synthetic and natural south molecular electrolytes such as PAM (polypropylene amine), poly brix AC (polydimethylidene dimethyl vaporized ammonium), polyallylamine, polyamines , polysaccharides and their blends 11 1308583 'Formula 2 is an aqueous dispersion or any other suitable form 1. Body: Form 'add any optional additives and their:: Body fear', please refer to the pigment composition The above description.匕 她 她 尚 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点 观点Protein and soy protein binder), : Mixture. The latex may be, for example, a copolymer based on styrene, acrylonitrile, acetonitrile, ethyl acetate and ethyl acetate, and styrene. Polyvinyl alcohol is particularly preferred. (The coating composition may also include commonly used additives, rheology modifiers, optical brighteners, lubricants, insoluble binders, dyes, sizing agents, etc. / The dry content of the coating composition is preferably about 2 % by weight, preferably from about 10% by weight to about 7% by weight. The porous aggregate and the extender particles of the pigment composition are preferably from about 30 to about 99% by weight on a dry basis. %, preferably from about 5 Torr to about 9% by weight. The amount of the binder is preferably from about 7% by weight to about 7% by weight, preferably from about (7) • to about 5% by weight. Based on the dry content, the total amount of other additives and possible impurities is preferably from about 50% by weight, most preferably from about 3% by weight. Regardless of the suitable and preferred embodiment, please refer to the pigment composition. The above description is directed to a method of making a coating composition comprising the steps of mixing a binder with a pigment composition as described above. The binder and optionally additives may be in any suitable form such as a solid material. , liquid material or as an aqueous solution, dispersed Or the slurry is added to the pigment composition 13 1308583 - including other methods such as coloring. - The paper and paperboard to be coated can be made of any kind of pulp, such as chemical pulp such as sulfate, sulfite and organosol pulp. Machine pulp such as hot machine pulp (TMP), chemical-thermal-machine pulp (CTMp), refined pulp or wood pulp, bleached or unbleached pulp from hardwood and softwood, based on fresh or recycled fibre, Or any combination thereof. In accordance with the present invention, paper and paperboard from any other type of pulp may also be applied. For the details and specific aspects of the coating composition, please refer to the same description above. The present invention is directed to a paper or paperboard suitable for ink jet printing obtainable by the above method. The paper or paperboard comprises a layer which is preferably substantially opaque, the layer comprising a porous material from the coating composition. The aggregates and the incremental particles are preferably formed into a nanostructure. The dry amount of the coating is preferably at least about 〇6 g/m2, more preferably from about 77 g/m2 to about 5 〇g/m2, most preferably about 1. ^ 2 to about 25g / m, in Or on each coated side of the paperboard, the amount of porous aggregates and incremental particles derived from the pigment composition is preferably at least about 4 Å 2, more preferably from about 0.5 g/m 2 to about 4 〇 g/m 2 , most Preferably, lg/m2 to about 2 〇^ is also 2. It is preferred that no other type of coating has been applied on top of the layer. It has been found that the paper or paperboard of the present invention has an inverse effect on the ink jet printing system. J·sheng gives low line blur and marking and high printing color density, but can also be advantageously used for other printing m toner, offset, plate, gravure, lithographic and screen printing. Particularly advantageous is The characteristics of the good-adhesive gelatin can be obtained in a simple manner by applying only a small amount of coating without coating a plurality of different coatings on the paper 15 138583 or paperboard. This also makes it possible to apply pressure by applying pressure, which is advantageous for practical reasons. Furthermore, the raw materials of the pigment are manufactured. . The main knives can be easily obtained by the invention, otherwise the invention will be further illustrated. Unless otherwise indicated, the injuries and percentages refer to parts and percentages by weight. ^^Ll: Preparation of four pigment compositions: ♦♦ CAT A): cationic water (four) stone sol, coffee chemical company AB (four)... AT22G' contains 3G weight coffee 2, with an average primary diameter of about 15 _ which is diluted Up to 1G wt%. _ release (four) stone sol was disturbed in the glass beaker, and the addition of sputum Moer / liter of sulfuric acid solution directly into the white gel and increased viscosity, this occurs in the acid = concentration of 0.0125 m / liter Time. The average diameter of the aggregates was measured by 疋 (measured on the Zetamaster of Malvern Instruments, single mode analysis). B · · From coating clay (SPS, an aqueous dispersion of incremental particles. Mastersizer Micro Plus (method size, the result is 1.64 μιη.
Imerys ’ UK)來製作20重量％ 使用Malvern儀器公司的 50HD)來測定黏土的平均粒子 C:使30毫升B中所製備的黏土分散液混合15毫升 相同於A中的經稀釋石夕石’但是沒有先前的聚集。 D:使！5毫升A中所製備的經聚集矽石混合3〇毫升 B中所製備的黏土分散液，而得到一種含有石夕石聚集體和 增量粒子的顏料組成物。 16 1308583 使用上述各顏料組成物，藉由混合一溶解在水中的實 驗室級聚乙烯醇（MW 15〇〇〇〇)，以成為10重量％溶液，以 製備塗料調配物。所有的調配物具有約15重量％的固體含 量而且聚乙烯醇對於固體顏料的重量比係0.5:1。 藉由刮漆法，用線桿將塗料調配物塗佈在未經塗覆的 影印紙（A4尺寸，M_real公司的Data Copy)之表面上，然後 在乾燥筒上使紙乾燥。用惠普公司的噴墨印表機（HpImerys 'UK) to make 20% by weight using Malvern Instruments' 50HD) to determine the average particle C of the clay: Mix 15 ml of the clay dispersion prepared in B with the same dilution of A Shishi in A' but There is no previous aggregation. D: Make! The clay dispersion prepared in 5 ml of B was mixed with the aggregated vermiculite prepared in 5 ml of A to obtain a pigment composition containing the aggregate and the incremental particles. 16 1308583 Using each of the above pigment compositions, a paint formulation was prepared by mixing a laboratory grade polyvinyl alcohol (MW 15 Torr) dissolved in water to obtain a 10% by weight solution. All formulations had a solids content of about 15% by weight and the weight ratio of polyvinyl alcohol to solid pigment was 0.5:1. The coating formulation was applied to the surface of uncoated photocopying paper (A4 size, Data Copy of M_real Co., Ltd.) by a squeegee method, and then the paper was dried on a drying cylinder. Using HP's inkjet printer (Hp
DeskJet 970Cxi)將一含有藍綠、洋紅、黃色及黑色之區域 "的試驗圖晝印刷在每—乾紙上。用色密度計（⑺咖邮咖化 D19C’ Gretag AG)來測定各顏色和色密度，且數字係顯示 於以下表中： ’ 顏料組成物 塗層重量 藍綠 洋紅 黃色 里芦 /”、 广 A ---- 空白 0 1.08 1.18 1.01 Ί 40 A 3.0 1.23 1.38 1 〇4 9 QQ B 2.8 1.31 1.56 1 12 9 1Π C 3.5 0.95 1.10 0 80 ώ . I U 0 7 Λ 2.5 ------------ 1.41 1.66 1.16 -ώ . / u 2.80 ·· 曰由此貝驗可知，含顏料組成物D的塗料調配物係給予 最佳的總體印刷摩声。介 又亦〉主思到經顏料組成物A所塗覆的 、，氏上之印刷顏色係有強烈色斑。 實施例2 : A :使用兩 製備四種顏料組成物： 夂丨生矽石溶朦，即一種陰離子矽石溶膠 17 1308583 • . (Blndzi1® 15/500)和一種陽離子矽石溶膠（Bindzil® cAT)， --兩者白來自Eka化學公司且含有15重量0/〇Si〇2並具有約 6nm的平均一次粒子直徑。於劇烈攪拌下，使37 $克3〇 重置0/〇水性黏土分散液（相同於實施例1中的黏土，平均粒 子大小1，64μηι)、90克陽離子溶膠、135克陰離子溶膠及375 克水混合’以得到一種高黏性顏料組成物，此顏料組成物 包含來自溶膠的一次石夕石粒子之聚集體及來自黏土的增量 粒子。在增量劑添加之前，測定經聚集的矽石溶膠之平均 ••直控’結果為0.57μιη(在⑽刪如上的單模式分析）。 B 1 〇2克沈贏石夕石，其為來自Rh〇dia公司的 365 SP，具有22重量％的固體含量及3.4_(Masterslzer) .的平均粒子大小，係與6G克陽離切石溶膠、9G克陰離 子:石轉及48克以相同於A中的方式進行混合，:得 :卜種高黏性顏料組成物，此顏料組成物包含來自溶膠的 =次石夕石粒子之聚集體及來自沈;殿石夕石的增量粒子。在增 加之前，測定經聚集的妙石轉之平均直徑，結果 為〇.69_(在Zetamaster上的單模式分析）。 C:相同於A中所用的黏土分散液。 D ·相同於B中所用的沈;殿石夕石。 使用上述各顏料組成物，藉 ΓΑΓΡΤΡν X 曰w此σ ♦乙烯醇黏結劑 (ACETEX 公司的 erk〇ltm 26 ，邴铷，曲班牙），以製備塗料 凋配物。所有的調配物具有約15重 r ，说两台m 士人 夏/◦的固體含量而且聚 乙席知對於固體顏料的重量比係0.25:1。 ❹料塗佈於如糊1中的影印紙上。用愛普生 18 1308583 - Stylus C84噴墨印表機，使用全彩的著色墨水，將一含有 • 藍綠、洋紅、黃色、綠色、藍色、紅色及黑色之區域的試 驗圖畫印刷在每一經塗覆的紙上。用分光光度計 (Technidyne公司的Color Touch 2)來測量已印刷的區域和 未印刷的紙’及計算色域體積。用CEI L*a*b*色空間中的 十二面體來趨近色域體積，而且顏色的測量係給予十二面 體中的角洛（見 Rydefalk Staffan，Wedin Michael;對於印 刷方法-基礎的色域之文獻評論，PTF-report no 32，1997年 •鲁5月，，）。 結果示於以下表中： 顏料組成物 塗層重量 (g/m2) 色域體積 空白 ------ 0 148600 A ----— 3.7 214000 B — 3.6 221900 C *—-- 3.3 187300 D L---- 3.3 188900DeskJet 970Cxi) Prints a test chart containing areas of blue-green, magenta, yellow, and black on each dry paper. Colors and color densities were measured using a densitometer ((7) café, D19C' Gretag AG), and the numbers are shown in the following table: 'Pigment composition coating weight blue green magenta yellow reed /", wide A ---- Blank 0 1.08 1.18 1.01 Ί 40 A 3.0 1.23 1.38 1 〇 4 9 QQ B 2.8 1.31 1.56 1 12 9 1Π C 3.5 0.95 1.10 0 80 ώ . IU 0 7 Λ 2.5 --------- --- 1.41 1.66 1.16 -ώ . / u 2.80 ·· 曰 According to this test, the paint formulation containing the pigment composition D gives the best overall printing sound. The printed color on the coating of the substance A was strongly stained. Example 2: A: Two pigment compositions were prepared using two: axillary vermiculite, ie an anionic vermiculite sol 17 1308583 • (Blndzi1® 15/500) and a cationic vermiculite sol (Bindzil® cAT), both from Eka Chemical Company and containing 15 wt% 〇Si〇2 and having an average primary particle diameter of about 6 nm. 37 gram 3 〇 reset 0 / hydrophobic clay dispersion (with the same clay as in Example 1) with vigorous stirring An average particle size of 1,64 μηι), 90 g of cationic sol, 135 g of anionic sol, and 375 g of water are mixed to obtain a highly viscous pigment composition comprising aggregates of primary stone particles from the sol and Incremental particles from clay. Before the addition of the extender, the average of the aggregated vermiculite sol was measured and the result was 0.57 μιη (in the single mode analysis as above (10). B 1 〇 2 g Shen Win Shi Xishi, which is 365 SP from Rh〇dia Company, has a solid content of 22% by weight and an average particle size of 3.4_(Masterslzer). It is combined with 6G ke cation stone, 9G gram anion: stone turn 48 g is mixed in the same manner as in A: to obtain: a high-viscosity pigment composition comprising aggregates of granules from the sol and from the sink; Incremental particles. Before the increase, the average diameter of the aggregated fine stones was measured and the result was 〇.69_ (single mode analysis on Zetamaster) C: the same as the clay dispersion used in A. D · identical to Shen used in B; Stone. Using the above pigment compositions, σν X 曰w σ ♦ vinyl alcohol binder (ACETEX erk〇ltm 26 , 邴铷, 曲班牙) to prepare coatings. All formulations have a solids content of about 15 weights, which is said to be 0.25:1 by weight of the solids of the two m. The dip is applied to a photocopying paper such as paste 1. Using Epson 18 1308583 - Stylus C84 inkjet printer, use a full-color tinted ink to print a test picture containing areas of blue, magenta, yellow, green, blue, red and black on each coated On the paper. A spectrophotometer (Color Touch 2 from Technidyne) was used to measure the printed area and unprinted paper' and calculate the color gamut volume. The dodecahedron in the CEI L*a*b* color space is used to approximate the gamut volume, and the measurement of color is given to the horn in the dodecahedron (see Rydefalk Staffan, Wedin Michael; for printing methods - basics) A review of the gamut literature, PTF-report no 32, 1997 • Lu May, ,). The results are shown in the following table: Pigment composition Coating weight (g/m2) Gamut volume blank ------ 0 148600 A ----- 3.7 214000 B — 3.6 221900 C *—-- 3.3 187300 D L---- 3.3 188900
〇由這些結果可知，顏料組成物A及B給予較高的印刷 品質’如由色域體積所測量者： .製備兩種顏料組成物： 5 t.使16.7克30重量％塗覆用黏土的水性分散液（相 同=貝知例1中，粒子大小i 64_)、1〇克Bindzil 5〇/8〇(5〇 ，量％發石溶膠，平均粒子大小為40麵，來自聊化學公 5 克Eka ATC 8210(25重量％聚氣化鋁，來自£ka化 19 !3〇8583 ' 學八 rrj :=二二）及70克水在劇烈搜拌下於mtraTurrax(i〇〇00rpm) 仃此合。此產生一種10重量％顏料分散液，具有石夕石對 於'觀 4- 6½ X 〇 1比係1:1。在增量劑添加之前，測定經聚集 、石夕石溶勝之平均直徑，砝 且1 、巾果為 〇.45μηι(在 Zetamaster 上 的單模式分析）。 5 B .使16.7克30重量％塗覆用黏土的水性分散液（相 同於實施例1中）、5切凝膠型產物（乾粉）及78克水混合 U A中的ultraTurrax)，以獲得重量％顏料分散液（石夕 石/黏土比：1:1)。此矽凝膠型產物（Grace Davis〇n)具有i 的二次粒子大小及400g/m2的表面積，其對應於7至8nm 的一次粒子大小。 如於實施例2中，製備一種具有丨〇重量％固體含量及 ♦乙烯醇對於固體顏料的重量比為〇乃：丨的塗料調配物。 將塗料塗佈於紙及在紅外線乾燥器（瑞典的Heds〇n Technologies AB)上乾燥。用如於實施例2中所述的愛普 赢▲生StyIus C84及惠普HP5652的噴墨印表機來進行印刷試 ^^驗。結果示於以下表中： 顏料 組成物 塗層重量 (g/m2) 色域體積 賫普生 色域體積 惠普 空白 0 185700 空白 0 —-- - 162100 A 2.5 220500 - A 2.7 - 232900 B 2.3 200000 - B 2.3 - 193700 20 1308583 . 含矽石溶膠聚集體（A)的顏料組成物之色域體積係高於 對應之含有凝膠型矽石的顏料組成物。小心的目視檢查顯 示良好的線銳度以及印出物沒有色滲。 ^ΜΛ'製備兩種顏料組成物： A :將由離子交換法所製備且含有重量％si〇2和具 有約865m2/g表面積的陰離子矽石溶膠聚集，其為藉由在 鲁鲁連續攪拌下將14_2克2.5重量％經改質羧甲基纖維素（CMC) 的水溶液徐徐加到1〇〇克矽石溶膠中以產生一種高黏性澄 清溶液。該經改質CMC就羧基而言具有〇 65的DS且係 藉由併入四級氮基（DS 0.43)以賦予產物陽離子特性而被進 步改負。使用Zetamaster來測量分散液中的聚集體之平 均粒子直徑，結果為〇·7μιη。然後使分散液與45克沈殿石夕 石（Tlx〇sii 365 SP，平均粒子大小3 4μιη，見實施例”及“ 克水進行劇烈攪拌。 ·· Β:製備1。重量％沈殿妙石（Tix〇sil 365 sp)的水性分 散液。 如於實施例2中製備具有固體含量乡勺1〇重量％且聚乙 稀醇對於固體顏料的重量比為Q.25:1的塗料調配物。如於 實施例3中將塗料塗佈於紙及使乾燥。如於實施例2中用 兩種噴墨印表機愛普生C84及惠普觀來進行印刷試驗。 測量色域體積而獲得以下結果。 21 1308583 顏料 組成物 塗層重量 (g/m2) 色域體積 愛普生 色域體積 惠普 A 2.7 225000 - A 2.7 - 230700 B 2.5 209700 - B 2.4 - 222400 其顯不顏料組成物A所得到的印刷品質係優於組成物 B。 【圖式簡單說明】 無 【主要元件符號說明】 無 ·· 22From these results, it is known that pigment compositions A and B give higher print quality 'as measured by gamut volume: . Prepare two pigment compositions: 5 t. Make 16.7 g of 30 wt% coated clay Aqueous dispersion (same = Baye example 1, particle size i 64_), 1 gram Bindzil 5 〇 / 8 〇 (5 〇, amount % stone sol, average particle size of 40 faces, from Liao Chemical Gong 5 grams Eka ATC 8210 (25% by weight of polyaluminized aluminum from £ka=19!3〇8583 'Study eight rrj:=22) and 70g of water in a vigorous search at mtraTurrax (i〇〇00rpm) This produces a 10% by weight pigment dispersion with ishixi stone 1:1 for the '4- 4⁄2 X 〇 1 ratio. Before the addition of the extender, the average diameter of the aggregated, Shi Xi stone is determined. And 1, the towel is 〇.45μηι (single mode analysis on Zetamaster). 5 B. Making an aqueous dispersion of 16.7 g of 30% by weight of coating clay (same as in Example 1), 5 cut gel type The product (dry powder) and 78 g of water were mixed with ultraTurrax in UA to obtain a weight percent pigment dispersion (Shi Xishi/clay ratio: 1:1)This gel-type product (Grace Davis〇n) has a secondary particle size of i and a surface area of 400 g/m 2 , which corresponds to a primary particle size of 7 to 8 nm. As in Example 2, a coating formulation having a solids content by weight of 丨〇 and a weight ratio of vinyl alcohol to solid pigment of ruthenium: iridium was prepared. The coating was applied to paper and dried on an infrared dryer (Hedsn Technologies AB, Sweden). The printing test was carried out using an inkjet printer such as the Ayurveda StyIus C84 and the HP HP5652 as described in Example 2. The results are shown in the following table: Pigment composition Coating weight (g/m2) Color gamut volume 賫 色 gamut volume HP blank 0 185700 Blank 0 —-- - 162100 A 2.5 220500 - A 2.7 - 232900 B 2.3 200000 - B 2.3 - 193700 20 1308583. The colorant volume of the pigment composition containing the vermiculite sol aggregate (A) is higher than the corresponding pigment composition containing the gel-type vermiculite. Careful visual inspection revealed good line sharpness and no color bleeding of the printed matter. ^ΜΛ'Preparation of two pigment compositions: A: an anionic vermiculite sol prepared by an ion exchange process and containing % by weight of si〇2 and having a surface area of about 865 m 2 /g, which is obtained by continuous stirring in Lulu 14 to 2 grams of a 2.5% by weight aqueous solution of modified carboxymethylcellulose (CMC) was slowly added to the 1 gram vermiculite sol to produce a highly viscous clear solution. The modified CMC has a DS of 〇 65 in terms of carboxyl groups and is further modified by incorporating a quaternary nitrogen group (DS 0.43) to impart cation characteristics to the product. Zetamaster was used to measure the average particle diameter of the aggregates in the dispersion, and the result was 〇·7 μιη. Then, the dispersion was mixed with 45 g of pedestal stone (Tlx〇sii 365 SP, average particle size 3 4 μιη, see Example) and “g water was vigorously stirred. ··Β: Preparation 1. Weight% Shen Dian Miao Shi (Tix An aqueous dispersion of 〇sil 365 sp). A coating formulation having a solids content of 1% by weight and a polyethylene glycol to solid pigment weight ratio of Q.25:1 was prepared as in Example 2. The coating was applied to paper and allowed to dry in Example 3. The printing test was carried out using Epson C84 and Hewlett Packard, two ink jet printers as in Example 2. The color gamut volume was measured to obtain the following results: 21 1308583 Pigment Composition coating weight (g/m2) Color gamut volume Epson color gamut volume HP A 2.7 225000 - A 2.7 - 230700 B 2.5 209700 - B 2.4 - 222400 The printing quality obtained by the non-pigment composition A is better than the composition Object B. [Simple description of the diagram] No [Main component symbol description] None·· 22