TW581791B

TW581791B - High gloss calcium carbonate coating compositions and coated paper and paper board manufactured from same

Info

Publication number: TW581791B
Application number: TW091105469A
Authority: TW
Inventors: Amy Christine Dimmick; Kenneth Mueller
Original assignee: Specialty Minerals Michigan
Priority date: 2001-12-20
Filing date: 2002-03-21
Publication date: 2004-04-01
Also published as: WO2003054300A1; CA2470848A1; BR0117205A; JP2005513296A; NZ534043A; EP1456470B1; CN1582357A; NO20043070L; IL162520A0; AU2002234075A1; DE60141228D1; AU2002234075B2; EP1456470A1; CN100350098C; AR037949A1; ATE456702T1

Abstract

A paper coating pigment is provided which includes a blend of a first and a second discrete aragonitic precipitated calcium carbonate (PCC) particles. The first particles of the blended pigment have an average particle size (APS) of about 0.4 microns and the second particles of the blended pigment have an average particle size (APS) of about 0.5 microns. The blended pigment preferably includes a weight ratio of about 50:50 to about 80:20 with a 60:40 weight ratio being most preferred, respectively, of the first 0.4 micron particles to the second 0.5 micron particles. Also provided are a method for preparing coated paper, which includes preparing the blended aragonitic PCC pigment, adding a binder, and applying the pigment to the paper basestock in a slurry containing a binder and or additives. Preferably, blended aragonitic precipitated calcium carbonate pigment is present in an amount of from about 30 weight percent to about 85 weight percent of the mixture with about 70 weight percent to about 15 weight percent balance being clay prior to preparing the slurry.

Description

581791581791

本發明係關於一種用酸鈣粒子混合物。曼J3範圍於製作具高紙張光澤塗覆紙張之碳The present invention relates to a mixture of calcium acid particles. MAN J3 range for producing carbon with high paper gloss coated paper

I明背景在製作紙張過程中，碟酸㈣有極佳白度性質，故用於塗佈施加以改良各種性質’域張亮度。天然與合成竣酸每兩者均可用在造紙工業。天然碳_，或稱石灰石者，在用於紙張前先經研磨，而合成碳_由沉摄反應製造，稱為沉殿硬酸舞（p C C)。沉殿碳酸舞在造紙時較研磨碳酸約為佳’因其形體結構’粒徑，粒子粒徑分佈，以及純度各方面在製造時均可控制。裝Bright background In the process of making paper, dish acid has excellent whiteness properties, so it is used for coating and application to improve the brightness of various properties. Both natural and synthetic acids are used in the paper industry. Natural carbon, or limestone, is ground before being used in paper, while synthetic carbon is produced by the Shen-Sheng reaction, called Shen Dian Suan Wu Wu (p C C). Shen Dian carbonated carbon dioxide is better than ground carbonic acid in papermaking because of its size, particle size distribution, particle size distribution, and purity can be controlled during manufacturing. Hold

當使用於造紙業時，沉澱碳酸鈣一般是以二氧化碳氣體與氯氧化舞水性漿液（”石灰乳”）行碳酸化反應製備。沉澱出之碳酸鈣色料再以含該沉澱碳酸鈣及—黏著劑水性漿液塗佈紙張而施加於紙張之上。When used in the paper industry, precipitated calcium carbonate is generally prepared by carbonation of carbon dioxide gas and chlorine-oxidized water-soluble slurry ("lime milk"). The precipitated calcium carbonate colorant is then coated on the paper with an aqueous slurry containing the precipitated calcium carbonate and an adhesive.

線碳酸鈣可以三種不同晶型自水性溶液沉澱：熱力性不安定之vatente型式，最安定及自然界最普遍之方解石剂式，以及在正常環境溫度及壓力下半安定，但在高^轉為 vatente型式之文石型式。該文石型式具有鄰斜方型，結晶成為可集結或不集結之長薄針狀。該方解石型式以數種不同形狀存在’其中最常見為斜方系形狀，其結晶體可為集結或不集結，而其scalenohedral形狀結晶體—般為不隹妙。所有這些碳酸鈣形式均可藉由該藝所知加工條件之·適合變化，由石灰乳碳酸化製備。 @ -4- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 581791Linear calcium carbonate can be precipitated from three different crystalline forms from aqueous solutions: the vatice type of thermal instability, the most stable and most common calcite agent in nature, and the semi-stable at normal ambient temperature and pressure, but at high temperatures, it changes to vantete. Type of aragonite type. This type of aragonite has an orthorhombic shape and crystallizes into long thin needles that can be aggregated or not. This calcite pattern exists in several different shapes, the most common of which is the orthorhombic shape. Its crystals can be aggregated or unaggregated, and its scalenohedral shape crystals are generally not wonderful. All of these calcium carbonate forms can be prepared from lime milk by carbonation of the processing conditions known in the art. @ -4- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 581791

雖然比較含片狀粒子高嶺土之下，作為紙張塗覆色料具有極佳白度及對印墨之吸收性，然而傳統碳酸m料在塗覆、”氏張時之紙張光澤度會不足。今日使用大量沉澱碳酸鈣於塗覆配方，尤其單塗覆施加作業下.，係因較高嶺土基配方的光澤不足之故。因此，沉澱碳酸鈣粒子在高嶺土基組成内為色料時’其量不高，如在約2 5重量％或更少的量。相關技藝 X國專利丰號第5,861，209號揭示用於塗佈凹版印刷紙之文石沉澱碳酸鈣色料，製造該色料之方法，以該塗佈色料塗覆之紙張，以及製備該紙張方法。該沉澱碳酸鈣粒子之相比例由約3 : 1到約丨5 : i，較佳為由約4 : i到約7 : i ’以及多樣的粒徑分佈，其較佳為二樣或三樣式。較佳情況下’該文石沉澱碳酸鈣佔該塗佈色料量由約2 〇到約1 〇〇重量％。該色料可併用於二氧化鈦，滑石粉，燒結黏土，鍛白’塑膠色料，三元鋁酸，雲母，或其混合物。在 J. Drechsel (1999 Coating Conference，ρρ· 413-432)於文獻 nIn Search of Synergy: Engineering Coatings for MaximumAlthough compared with kaolin clay containing flake particles, it has excellent whiteness and absorption of printing ink as a paper coating color, but the traditional carbonic acid m material will lack the gloss of the paper when it is coated. The use of a large amount of precipitated calcium carbonate in coating formulations, especially for single coating application operations, is due to insufficient gloss of higher kaolin-based formulations. Therefore, when the precipitated calcium carbonate particles are colored in the kaolin-based composition, the amount is not High, such as in an amount of about 25% by weight or less. Related Techniques Country X Patent No. 5,861,209 discloses aragonite precipitated calcium carbonate colorants for coating gravure printing paper, and a method for manufacturing the colorants. , Paper coated with the coating colorant, and method for preparing the paper. The comparative example of the precipitated calcium carbonate particles is from about 3: 1 to about 5: i, preferably from about 4: i to about 7: i 'and a variety of particle size distributions, which are preferably two or three styles. Preferably, the aragonite precipitated calcium carbonate accounts for about 20% to about 100% by weight of the coating pigment. The Colorants can be used in combination with titanium dioxide, talc, sintered clay, wrought white Plastic pigment, ternary aluminate, mica, or mixtures thereof J. Drechsel (1999 Coating Conference, ρρ · 413-432) in the literature nIn Search of Synergy:. Engineering Coatings for Maximum

Performance: Optimizing Pigment Blends for Maximum Performance，”揭示使用微細粒徑高嶺土及微細研磨碳酸鈣於塗料，以增加塗覆紙之印刷光澤。 L. Jarnstrom 等人於 Wochenblatt f. Papierfabrikation 17, 736-741，（1996)，文獻 Structure of the Coating Layer andPerformance: Optimizing Pigment Blends for Maximum Performance, "Reveals the use of fine particle size kaolin and finely ground calcium carbonate in coatings to increase the print gloss of coated paper. L. Jarnstrom et al. Wochenblatt f. Papierfabrikation 17, 736-741, ( 1996), Structure of the Coating Layer and

Optical Properties of Coated Paper，，，揭示以沉殿碳酸 I弓色料混合片狀高嶺土供塗佈組合物時，可得到較高之不透明低 -5- 本紙蒗尺度逋用中國國家標準(CNS) A4規格(210X 297公釐) 581791 A7 B7___ 五、發明説明（3 ) 及正面之協調效果。 R. Knappich 等人於 PTS Coating Symposium (1999), pp. 13E 到 13E-16 之文獻 ’’Optimized Binder Systems for Natural Calcium Carbonate Pigments with Narrow Particle Size Distribution，"揭示以具有粒徑較小分佈天然研磨沉殿碳酸鈣色料，可達成高亮度，高不透明度，以及極佳覆蓋於塗覆紙張與紙板。 P. G. Drage 等人於 1998 TAPPI Coating/Papermakers Conference，pp. 413-433 文獻 ’’Factors Governing Print Performance in Offset Printing of Matt Papers，’’ 中揭示使用二型式摻配粗與超細成分及G C C於霧面及低光澤紙張之霧面色料製造時，重點在於粗質部份。日本專利字號第10232253號揭示一種供網版旋轉印刷之多層塗覆紙，具有乾強度，白紙光澤，多色彩印刷光澤，及抗氣泡產生。該多層紙張包含具中空或半球面聚合物粒子之塗覆層。曰本專利字號第10-340790號揭示一種平版印刷塗覆紙張 ’具有白紙張光澤，其係使用一種色料成份之塗料底層液體’由佔色料成份4 0重量％到1 0 0重量％量之溼粉末針狀或柱形沉澱碳酸鈣組成。曰本專利字號第1 1 - 0 6 5 7 0 3號揭示一種平版印刷塗覆紙張 ’具有印刷光澤，含主要具有6 0重量％到9 0重量％量紡錘型渔鹼性沉澱碳酸鈣及具平均粒徑50 nm-80 nm共聚物乳膠 ’及3 0重量％到5 0重量％作為黏劑之膠的色料之塗覆層。 -6 - 本紙張尺度適用中國國家標準((：;^3) A4規格(210 X 297公釐） 581791 A7 B7 五、發明説明（4 ) 曰本專利字號第1 1-008 162號揭示一種供網版刷霧面塗覆紙張，具極低白色紙張光澤度。至少基層紙一側是以具7 5 重量％到85重量％集結餘錘狀’平均粒徑3〇卜1〇1到5.〇 μπι 第二級粒型沉澱碳酸鈣及1 5重量％到2 5重量。/q平均粒徑 1.0 μηι到2·0 μιη高嶺土之組合物塗佈。曰本專利字5虎弟1 1 - 0 6 9 4 2 6號揭示一種供平版印刷輕質塗覆紙張，具有空白紙光澤及印刷光澤。該紙張具有兩塗覆層，均含色料與黏劑，上塗覆層含5 0重量比到8 5重量比，平均粒徑不小於0.2 μπι之碳酸鈣，且作為色料時不小於 0·5 μιτι ’及8重f比到1 5重量比具50 nm到70 nm平均粒徑共聚物乳膠，以及5 0 %到7 0 %相對於1〇〇%色料重量之黏著用膠。因此，仍需要一種可產生高紙張片光澤紙張之改良塗覆及碳酸鈣色料。發明摘要本發明係關於一種紙張塗覆色料，其包含第一及第二型文石沉澱碳酸鈣（PCC)粒子之摻配物。該摻配色料第一種粒子平均粒徑（APS)約〇·4微米，而第二種掺配色料粒子平均粒位（APS)為約0.5微米。該色料較佳含約5〇 : 5〇到約8〇 : 20重量比之第一種〇·4微米粒子對第二種〇 5微米粒子，又以約6 0 : 4 0重量比為最佳。本發明亦關於一種製造該塗覆紙張之方法，其包含製備違摻配文石沉殿碳酸辦色料，加入黏土，並令色料加入含結合劑與其它添加劑漿料之紙張基料中。較佳情況下，該本紙張尺度適财S g家標準(CNS) A4規格(210X297公爱)Optical Properties of Coated Paper, reveals that when flaky kaolin is mixed with Shendian Carbonate I bow colorant for coating composition, higher opacity can be obtained. -5- This paper (standard) uses China National Standard (CNS) A4. Specifications (210X 297 mm) 581791 A7 B7___ 5. Description of the invention (3) and positive coordination effect. R. Knappich et al., PTS Coating Symposium (1999), pp. 13E to 13E-16, `` Optimized Binder Systems for Natural Calcium Carbonate Pigments with Narrow Particle Size Distribution, '' revealing natural milling with a smaller particle size distribution Shendian calcium carbonate pigment can achieve high brightness, high opacity, and excellent coverage on coated paper and cardboard. PG Drage et al. In the 1998 TAPPI Coating / Papermakers Conference, pp. 413-433 document `` Factors Governing Print Performance in Offset Printing of Matt Papers, '' discloses the use of two types of blending coarse and ultrafine components and GCC on the matte surface. When manufacturing matte pigments for low-gloss papers, the emphasis is on the coarse parts. Japanese Patent No. 10232253 discloses a multi-layer coated paper for screen printing, which has dry strength, white paper gloss, multi-color printing gloss, and resistance to bubble generation. The multilayer paper includes a coating layer with hollow or hemispherical polymer particles. Japanese Patent No. 10-340790 discloses a lithographic coated paper having a white paper gloss, which is a coating base liquid using a colorant component, which accounts for 40% to 100% by weight of the colorant component. Needle powder or columnar precipitated calcium carbonate. The Japanese Patent No. 1 1-0 6 5 7 0 3 discloses a lithographic coated paper having a printing gloss, containing mainly 60% by weight to 90% by weight of a spindle-type fishery alkali-precipitated calcium carbonate, and a Copolymer latex 'with an average particle diameter of 50 nm-80 nm and a coating layer of 30% to 50% by weight as a colorant for a glue. -6-This paper size applies Chinese national standards ((:; ^ 3) A4 size (210 X 297 mm) 581791 A7 B7 V. Description of the invention (4) Japanese Patent No. 1 1-008 162 discloses a supply Screen-printed matte coated paper, with extremely low white paper gloss. At least one side of the base paper is hammer-shaped with an aggregate weight of 75 to 85% by weight, with an average particle size of 30 to 101. 〇μπι The second-stage granular precipitated calcium carbonate and 15% by weight to 25% by weight / q average particle size of 1.0 μm to 2.0 μm kaolin composition coating. Japanese patent word 5 虎弟 1 1-0 No. 6 9 4 2 6 discloses a light-coated paper for lithographic printing, which has blank paper gloss and printing gloss. The paper has two coating layers, each containing a colorant and an adhesive, and the upper coating layer contains 50 weight ratio to 8 5 weight ratio, calcium carbonate with an average particle size of not less than 0.2 μπι, and no less than 0,5 μιτι 'when used as a colorant, and 8 weight ratio to 15 weight ratio, 50 nm to 70 nm average particle size copolymer latex , And 50% to 70% adhesive for 100% pigment weight adhesive. Therefore, there is still a need for a paper that can produce high paper sheet gloss Improved coating and calcium carbonate pigment. Summary of the Invention The present invention relates to a paper coating pigment, which comprises a blend of first and second aragonite precipitated calcium carbonate (PCC) particles. The blended pigment is the first The average particle size (APS) of this kind of particles is about 0.4 micrometers, and the average particle size (APS) of the second blended colorant particles is about 0.5 micrometers. The colorant preferably contains about 50: 50 to about 80: The 20 weight ratio of the first 0.4 micron particles to the second 05 micron particles is preferably about 60:40 weight ratio. The present invention also relates to a method for manufacturing the coated paper, which comprises Preparation of miscellaneous blended aragonite Shendian carbonic acid coloring material, adding clay, and adding the coloring material to a paper base material containing a binder and other additive pastes. In the best case, the paper size is suitable for financial standards. (CNS) A4 specifications (210X297 public love)

裝Hold

^«1791^ «1791

摻配文石沉澱碳酸鈣在製、，认Q ^曰 I備水硬又珂，為佔約3 0重量％到約8 5重！％，而其餘記、、曰人^ <、，々7 0里I %到約1 5重量。/。為黏土 (混合物狀態存在。查~~塑之詳細敍诚― 除非另作說明’以下之比例或百分比約為以重量計。本發明係關於一種含有碳酸鈣粒子摻配物之紙張塗覆組合物種使用該組合物以增加紙光澤方法，以及一種產生具有㊅紙張片光澤紙張方法，以及以該法製造之紙張。該碳酸飼較佳為沉殿文石（亦即鄰斜方晶型式）。當作於色料配万内’本發明之碳酸鈣色料摻配物提供紙張光澤改良 :尤其是與傳統技藝塗覆級硬酸鹽比較下，特別利於製造高光澤紙張及紙板。使用本摻配色料產生塗覆紙張片光澤改良係意料之外，其原因來自使用粒子具有粒徑分佈平均f由約Gi微米到約 0.2微米之不同摻配色料間之協調性。此外，本發明碳酸鈣色料較它種碳酸鈣色料尚具有優點包括易於對紙張壓光’ 以及使用該色料摻配物塗覆紙張所得之紙張光澤與紙張印刷光澤。本發明摻配之碳酸鈣色料摻配物可用之碳酸鈣成份粒子，較佳係由水性氫氧化鈣漿液（”石灰乳”）之二氧化碳氣體石反Sk化反應產生I各別合成（亦即沉殿）之文石粒子為佳。較佳一具體實例中，本發明摻配碳酸鈣製備方式，係混合平均粒徑在0.40微米及0·50微米粒子而成，其係Minerals Technologies Inc·’ New York, New York提供，各別編號為 -8- 本纸張尺度適用中國國家標準(CNS) A4規格(210X297公釐)Blended with aragonite to precipitate calcium carbonate, it is recognized that I prepare hydraulic and keel, which accounts for about 30% by weight to about 85% weight! %, And the rest of the note, 曰, ^^, 、, 70%, 1% to about 15 weight. /. Clay (mixture state exists. Check ~ ~ plastic details of the sincerity-unless otherwise stated 'The following ratios or percentages are about by weight. This invention relates to a paper coating composition containing calcium carbonate particle admixtures. A method for using the composition to increase paper gloss, and a method for producing glossy paper with a paper sheet, and a paper manufactured by the method. The carbonic acid feed is preferably Shen Dian Wenshi (ie, an orthorhombic type). When Used as a coloring agent, the calcium carbonate coloring agent of the present invention provides paper gloss improvement: especially compared with the traditional technology coating grade hard acid salt, it is particularly beneficial to the manufacture of high-gloss paper and paperboard. It is unexpected that the gloss improvement of the coated paper sheet is caused by the use of particles that have different particle size distributions with an average f from about Gi micrometers to about 0.2 micrometers. In addition, the calcium carbonate pigments of the present invention Compared with other calcium carbonate pigments, it also has advantages including easy calendering of the paper and the gloss of the paper and the printing gloss of the paper obtained by coating the paper with the colorant blend. The calcium carbonate component particles that can be mixed with the calcium carbonate coloring compound are preferably synthesized by the anti-Sk reaction of the carbon dioxide gas stone of the aqueous calcium hydroxide slurry ("lime milk") (i.e. Hall) of aragonite particles is preferred. In a preferred embodiment, the present invention is prepared by blending calcium carbonate with a mixture of particles having an average particle size of 0.40 microns and 0.50 microns, which is Minerals Technologies Inc. 'New Provided by York, New York, each number is -8- This paper size applies to China National Standard (CNS) A4 (210X297 mm)

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線 581791 A7 _ B7__ 五、發明説明（6 ) OPACARB® A40 PCC及OPACARB® A50 PCC。具體言之，OPACARB® A40 PCC 及OPACARB® A50 PCC 為文石沉澱碳酸鈣粒子平均粒徑約0.4微米及0.5微米，偏差值在平均質之± 0.02微米内分佈。根據本發明粒子平均粒係由Micromeritics Sedigraph 5 1 〇〇分佈儀定出，其係為一種應用Stokes定律測量粒徑分佈儀為（參考 CRC Handbook of Chemistry and Physics, 69th Edition 1988-1989, page F-1 05)，其提供在黏性流體中小球體之墜落速率。經由此點，判斷得到以質量（重量）為基礎的粒徑分佈及平均粒徑。本發明文石P C C色料可得到改良之塗覆結果，無論是單一或摻配任何傳統塗覆色料狀況。與黏土混合時，色料中 p c C成份可佔總塗料配方的約3 〇重量％到約8 5重量％範圍，而以6 0重量％較佳。本發明色料混合物特別適用於高光澤印刷紙張，且可混合一或多種傳統結合劑，增濃劑及/或潤滑劑’如該技藝原所熟知者。該塗料亦可含稀釋水，其量足可使塗料最終固成份到約5 〇重量％到約7 〇重量％範圍。本發明具體實例特於參考以下範例方式，舉例說明。以下非限制範例僅用以敘述說明本發明，並不為限制本發明 ’發明範疇係由所附申請專利範圍項界定之。以下各實驗配方中。取4 〇份沉澱碳酸鈣色料於一傳統平板Cowles式混合機中，與具72%固成份塗料及黏土混合。以下所有範例所用黏土為ALPHAGLOSS®黏土，由HuberLine 581791 A7 _ B7__ V. Description of the invention (6) OPACARB® A40 PCC and OPACARB® A50 PCC. Specifically, OPACARB® A40 PCC and OPACARB® A50 PCC are aragonite precipitated calcium carbonate particles with an average particle diameter of about 0.4 microns and 0.5 microns, and the deviation is distributed within ± 0.02 microns of the average quality. The average particle size of the particles according to the present invention is determined by a Micromeritics Sedigraph 5 1 00 distribution meter, which is a particle size distribution meter that uses Stokes' law to measure (refer to CRC Handbook of Chemistry and Physics, 69th Edition 1988-1989, page F- 1 05), which provides the rate of fall of small spheres in a viscous fluid. From this point, it is judged that the particle size distribution and average particle size based on mass (weight) are obtained. The aragonite P C C colorant of the present invention can obtain improved coating results, either alone or in combination with any conventional coating colorant condition. When mixed with clay, the p c C component in the colorant may range from about 30% to about 85% by weight of the total coating formulation, and more preferably 60% by weight. The colorant mixture of the present invention is particularly suitable for high-gloss printing papers, and may be mixed with one or more conventional binders, thickeners and / or lubricants' as is well known in the art. The coating may also contain dilution water in an amount sufficient to achieve a final solids content of the coating of from about 50% to about 70% by weight. The specific examples of the present invention are specifically illustrated with reference to the following exemplary modes. The following non-limiting examples are only used to describe the present invention and are not intended to limit the present invention. The scope of the invention is defined by the scope of the attached patent application. The following experimental formulations. Take 40 parts of precipitated calcium carbonate color in a traditional flat-plate Cowles type mixer, and mix with 72% solids coating and clay. The clay used in all the examples below is ALPHAGLOSS® clay, Huber

Corporation 提供。各別及結合〇pACARB@ A4〇 · -9- 581791 A7 B7___ 五、發明説明（7 ) OPACARB® A50 PCC，及ALBAGLOS® S PCC粒子使用’以評估各種碳酸鈣粒子效果。具體而言，塗料混合物第1及第7號係單獨配合 ALPHAGLOSS®黏土，以各另評估OPACARB ⑧ A40PCC 文石粒子與OPACARB® A50 PCC文石粒子效果。塗料混合物第2 ，3，及4號係評估OPACARB® A40 PCC文石粒子在與傳統用作黏土基紙塗料組合物之ALBAGLOS® S PCC方解石粒子在約4 0 : 6 0到約6 0 : 4 0不同重量比值範圍下之效果。塗料混合物第6及第5號係用來評估具有根據本發明重量比例之 OPACARB® A40 PCC 文石粒子對 OPACARB® A50 PCC 文石粒子的摻配文石P C C色料。下表1為所製塗料混合物組成，碳酸鈣粒子與黏土以重量％表示：表1 色料混合物編號 1 2 3 4 5 * 6 * 7 ALBAGLOS ® S PCC (重量％) 2 5 20 15 OPACARB ® A40 PCC (重量％) 40 15 20 2 5 2 5 20 OPACARB ® A50 PCC (重量％) 15 2 0 40 ALPHAGLOSS® CLAY (重量％) 60 60 60 60 60 60 60 *根據本發明碳酸鈣色料上列塗料配方經混合後，各加入結合劑，同樣以傳統平板Cowles式混合機混合。各項碳酸鈣色料配方含相同結合 -10- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 581791 A7 B7_ 五、發明説明（8 ) 劑，含 1 1 份 Gencorp Corporation (如今為Omnova Corporation)之 GENFLO® 5905 苯乙婦 / 丁二晞乳膠，3 份 Penford Starch Corporation之PENFORD® 280 Gum烴基乙烯基澱粉，及1份硬月旨酸 #5 潤滑劑。取 Hercules Corporation 之 ADMIRAL® 3089標準紙增濃劑加入各塗料樣本，以達到目標之 Brookfield 1 00 rpm時之1200 cps黏度。一般而言，達到目標黏度之增濃劑用量隨碳酸化程度增加而增加。色料塗料經配方成約6 0 %固成份，以AA-GWR方法 (Kaltec ScientiHc，USA)測定固成份％及殘水特性。低剪力 cp s黏度以Brookfield之RVT型式黏度對於10 rpm，20 rpm， 50 rpm，及10 rpm下測定。高剪力黏度以Kaltec ScientiHp， USA之Hercules高剪力黏度計測量。該Hercules黏度以下列條件操作：E bob，400,000 dyne-cm/cm 彈簧常數，0巧111-4400 rpm，室溫下。塗料測試後之配方數據如下表2。表2 塗料編號___ 1 2 3 4 5* 6 * 7 固成份，％ β 60.4 60.2 60.5 60.3 60.2 60.1 60.2 AA-GWR，每平方公尺公克(gsm) 89 90 84 91 94 88 97 HERCULES黏度，cps於 4400 rpm 50.0 47.9 46.5 42.5 45.1 41.0 38.9 BROOKFIELD 黏度 cps於 100 rpm 1420 1100 1200 1060 1310 1310 1120 cps於50 rpm 2560 1800 1940 1720 2090 2240 1840 cps於20 rpm 5250 3650 3900 3500 4275 4700 3800 cps於 10 rpm 9600 6600 7000 6400 76001 8600 7000 pH值(以 NaOH調到 8.5-8.9) 8.5 8.5 8.5 8.5 8.5 8.5 8.5 外加增濃劑 27 30 30 30 25 30 25 *根據本發明之文石沉澱碳酸鈣色料。 -11 - 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐）Corporation. Separate and combine 〇pACARB @ A4〇 · -9- 581791 A7 B7___ V. Description of the invention (7) OPACARB® A50 PCC and ALBAGLOS® S PCC particles are used to evaluate the effect of various calcium carbonate particles. Specifically, Coating Mixtures Nos. 1 and 7 were separately formulated with ALPHAGLOSS® clay to evaluate the effect of OPACARB ⑧ A40PCC aragonite particles and OPACARB® A50 PCC aragonite particles separately. Coating Mixtures Nos. 2, 3, and 4 evaluated OPACARB® A40 PCC aragonite particles in comparison with ALBAGLOS® S PCC calcite particles traditionally used as clay-based paper coating compositions at about 40:60 to about 60: 4. 0 Effect under different weight ratio range. Coating Mixtures No. 6 and No. 5 were used to evaluate the blending of aragonite P C C colorants with OPACARB® A40 PCC aragonite particles to OPACARB® A50 PCC aragonite particles in weight proportions according to the present invention. The following table 1 shows the composition of the prepared coating mixture. The calcium carbonate particles and clay are expressed in weight%. Table 1 Colorant mixture number 1 2 3 4 5 * 6 * 7 ALBAGLOS ® S PCC (wt%) 2 5 20 15 OPACARB ® A40 PCC (% by weight) 40 15 20 2 5 2 5 20 OPACARB ® A50 PCC (% by weight) 15 2 0 40 ALPHAGLOSS® CLAY (% by weight) 60 60 60 60 60 60 60 * Calcium carbonate pigments according to the invention After the formula is mixed, each binder is added, and the mixture is also mixed by a traditional flat Cowles type mixer. Each calcium carbonate colorant formula contains the same combination-10- This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 581791 A7 B7_ V. Description of the invention (8) Agent, containing 11 parts of Gencorp Corporation ( GENFLO® 5905 Acetophenone / Butadiene Latex (now Omnova Corporation), 3 parts of Penford Starch Corporation's PENFORD® 280 Gum Hydrocarbyl Vinyl Starch, and 1 part of Hard Moon Purpose Acid # 5 Lubricant. Add ADMIRAL® 3089 standard paper thickener from Hercules Corporation to each coating sample to achieve the target Brookfield viscosity of 1200 cps at 100 rpm. Generally speaking, the amount of thickener that reaches the target viscosity increases with the degree of carbonation. The colorant coating was formulated into about 60% solid content, and the solid content% and residual water characteristics were measured by the AA-GWR method (Kaltec ScientiHc, USA). Low-shear cp s viscosity was measured using Brookfield's RVT type viscosity at 10 rpm, 20 rpm, 50 rpm, and 10 rpm. High shear viscosity was measured with a Hercules High Shear Viscometer from Kaltec ScientiHp, USA. The Hercules viscosity was operated under the following conditions: E bob, 400,000 dyne-cm / cm spring constant, 0-111-4400 rpm, at room temperature. The formula data after coating test are shown in Table 2 below. Table 2 Coating No. ___ 1 2 3 4 5 * 6 * 7 Solid content,% β 60.4 60.2 60.5 60.3 60.2 60.1 60.2 AA-GWR, grams per square meter (gsm) 89 90 84 91 94 88 97 HERCULES viscosity, cps At 4400 rpm 50.0 47.9 46.5 42.5 45.1 41.0 38.9 BROOKFIELD viscosity cps at 100 rpm 1420 1100 1200 1060 1310 1310 1120 cps at 50 rpm 2560 1800 1940 1720 2090 2240 1840 cps at 20 rpm 5250 3650 3900 3500 4275 4700 3800 cps at 10 rpm 9 6600 7000 6400 76001 8600 7000 pH value (adjusted to 8.5-8.9 with NaOH) 8.5 8.5 8.5 8.5 8.5 8.5 8.5 Adding thickener 27 30 30 30 25 30 25 * The aragonite precipitated calcium carbonate pigment according to the present invention. -11-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

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線 581791 A7 B7 五、發明説明（9 ) 塗料製備後，以 Cylindrical Laboratory Coater (CLC-6000) 施加於每令5 1.1磅（每平方公尺7 〇公克）紙張基材。塗料目標量為3300平方英呎佈有9磅。塗覆紙於華氏1 5 0度下，以具兩滾輪’輪間壓力為每平方英吋8 〇〇磅（psi)實驗室級超壓光機進行壓光。塗覆紙張進行標準測試，.包含紙張光澤，印刷光澤，亮度，及透光性。塗覆紙張試驗數據如表3，印刷光澤值是由 Nancy Plowman Test Method (NPA)測定，而其餘數值依據T A P PI測試方法，如熟諳此藝者所熟知者。Line 581791 A7 B7 V. Description of the invention (9) After the coating is prepared, apply Cylindrical Laboratory Coater (CLC-6000) to 51.1 pounds per ream (70 grams per square meter) of paper substrate. The coating target is 3,300 square feet of cloth with 9 pounds. The coated paper was calendered at 150 degrees Fahrenheit with a roller-to-wheel pressure of 800 pounds per square inch (psi) in a laboratory grade calender. Coated paper is subjected to standard tests including paper gloss, printing gloss, brightness, and light transmission. The coated paper test data is shown in Table 3. The printing gloss value is determined by the Nancy Plowman Test Method (NPA), and the rest of the values are based on the T A PI PI test method, as known to those skilled in the art.

表3 塗料編號 1 1 2 3 4 5* 6* 7 紙張光澤，％ 73.6 72.6 72.1 72.7 75.7 74.6 73.3 NPA印刷光澤，％Rapida SFO Black 90.6 ! 92.8 92.1 91.2 91.8 91.6 92.4 亮度TAPPI，％ 86.0 85.7 86.0 85.8 86.0 85.9 85.9 透光度TAPPI，％ 89.6 90.2 89.7 89.9 90.1 90.0 90.0 色彩 HUNTER L HUNTER A HUNTER B 92.4 92.4 92.4 92.4 92.5 92.4 92.4 0.0 0.0 0.0 0.0 -0.1 -0.1 -0.1 2.3 2.3 2.3 2.3 2.4 2,4 2.4 Gurley透孔性(秒於10 cc) 83 93 86 91 94 91 95 PPS-10粗糙度 1.32 1.41 1.45 1.36 1.34 1.37 1.42 IGT Pick (公分於3.0 m/s) 91 91 91 76 82 82 76 固成份，％ 60.4 60.2 60.5 60,3 60.2 60.1 60.2 *根據本發明之文石沉澱碳酸鈣色料。裝Table 3 Coating No. 1 1 2 3 4 5 * 6 * 7 Paper gloss,% 73.6 72.6 72.1 72.7 75.7 74.6 73.3 NPA printing gloss,% Rapida SFO Black 90.6! 92.8 92.1 91.2 91.8 91.6 92.4 Brightness TAPPI,% 86.0 85.7 86.0 85.8 86.0 85.9 85.9 Light transmittance TAPPI,% 89.6 90.2 89.7 89.9 90.1 90.0 90.0 Color HUNTER L HUNTER A HUNTER B 92.4 92.4 92.4 92.4 92.5 92.4 92.4 0.0 0.0 0.0 0.0 -0.1 -0.1 -0.1 2.3 2.3 2.3 2.3 2.4 2,4 2.4 Gurley transparent Porosity (seconds at 10 cc) 83 93 86 91 94 91 95 PPS-10 roughness 1.32 1.41 1.45 1.36 1.34 1.37 1.42 IGT Pick (cm 3.0 cm / s) 91 91 91 76 82 82 76 Solid content,% 60.4 60.2 60.5 60,3 60.2 60.1 60.2 * The aragonite precipitated calcium carbonate pigment according to the present invention. Hold

線 -12- ______ 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐） 581791 A7 B7 __ 五、發明説明（1〇 ) 以上數據顯示本發明塗料色料提供之更佳紙張光澤，且同時顯示本碳酸鈣塗料色料可與大量黏土併用，不致降低印刷光澤性質。比較塗料第6與第5號紙張光澤時，可看出採用含OPACARB⑧A40 PCC文石粒子與OPACARB® A50 PCC文石粒子重量比例由約5 0 : 5 0到約8 0 : 2 0，較佳為約6 0 : 4 0情況下，有極大的改良。此外，這些粒子混合物提供改良紙張光澤時，不會發生一般使用高含量碳酸鈣時產生之印刷光澤降氐。特定言之，在使用根據本發明之OPACARB® A40 PCC粒子與OPACARB® A50 PCC粒子重量比例時所達到之74.6%-75,7%紙張及印刷光澤範圍及91.6% Rapida SF〇Black-91.8% Rapida SF〇 Black，高於單獨使用 OPACARB® A40 PCC於塗料編號 1 (73.6%，90.6% Rapida SFO Black)所得之紙張及印刷光澤，且高於單獨使用OPACARB® A50 PCC於塗料編號 7 (73.3%，92.4% Rapida SFO Black)紙張光澤，而印刷光澤相同。此外，使用較高OPACARB® A40 PCC對 OPACARB® A50 PCC比例時之協調效果可出現，相反於單獨使用OPACARB® A40 PCC與黏土（塗料編號1號）所得之甚低印刷光澤（90.6% Rapida SFO Black)，以及單獨使用 OPACARB® A50 PCC與黏土（塗料編號第7號）之低印刷光澤 (92.4% Rapida SF〇 Black)。對照使用本發明文石摻配色料與含方解石粒子之文石混合物時，亦可見到紙張光澤之改良。特定言之，在使用本發明 OPACARB® A40 PCC 對OPACARB® A50 PCC 粒子重量 -13- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐） 581791 A7 B7 五、發明説明（11 ) 比例時（塗料編號第6與第5號），其紙張光澤值範園在 74.6%到75.7% ’明顯優於使用〇p acARB® A40 PCC文石粒子對ALBAGLOS® S PCC方解石粒子（塗料編號第2到第4號）重量比例4 0 : 6 0到6 0 : 4 0之72,1%-72.7%紙張光澤。除此之外’在比較同級含該文石/方解石色料混合物者印刷光澤性質時’該摻配文石色料之改良紙張光澤性更加明確。根據本發明掺配物所用粒子之粒徑分佈中，其平均值差異在由約0·1微米到約0.2微米。其它具有類似粒徑分佈差異之摻配物，在塗覆紙張性質上會呈現類似協調效果。另外’咸k在文石/文石掺配物之外，其它能符合上述粒徑分佈條件之類似故紅|弓結晶混合物（例如方解石/方解石）者 ’亦能於塗覆紙張性質方面呈現相似協調效果。以上雖已以本發明具體實例及應用闡述說明，然熟諳此蟄者當可知曉多種不脫離上述本發明概念之調整及具體實例。因此，所附申請專利範圍所涵蓋全體調整及具體實例均屬於本發明之真實精神及範疇。 -14- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)Line -12- ______ This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 581791 A7 B7 __ V. Description of the invention (10) The above data shows that the paper colorant provided by the present invention provides better paper gloss, and At the same time, it shows that the calcium carbonate paint colorant can be used in combination with a large amount of clay, without reducing the printing gloss properties. When comparing the gloss of papers No. 6 and No. 5, it can be seen that the weight ratio of particles containing OPACARB⑧A40 PCC aragonite and OPACARB® A50 PCC aragonite is from about 50:50 to about 80:20, preferably In the case of about 60:40, there is a great improvement. In addition, when these particle mixtures provide improved paper gloss, there is no reduction in printing gloss that would normally occur with high levels of calcium carbonate. In particular, when using the weight ratio of OPACARB® A40 PCC particles to OPACARB® A50 PCC particles according to the present invention, 74.6% -75,7% of paper and printing gloss range and 91.6% Rapida SF Black-91.8% Rapida SF〇Black, higher than the paper and printing gloss obtained by using OPACARB® A40 PCC alone in coating number 1 (73.6%, 90.6% Rapida SFO Black), and higher than using OPACARB® A50 PCC alone in coating number 7 (73.3%, 92.4% Rapida SFO Black) paper gloss, while printing gloss is the same. In addition, the coordination effect can be seen when using a higher OPACARB® A40 PCC to OPACARB® A50 PCC ratio, as opposed to the very low printing gloss (90.6% Rapida SFO Black) obtained using OPACARB® A40 PCC and clay (Paint No. 1) alone. ), And low print gloss (92.4% Rapida SF〇Black) of OPACARB® A50 PCC and clay (Paint No. 7) alone. In contrast, when the aragonite blended coloring material of the present invention is used in combination with the aragonite mixture containing calcite particles, an improvement in paper gloss can also be seen. In particular, when using the present invention OPACARB® A40 PCC vs. OPACARB® A50 PCC particle weight -13- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 581791 A7 B7 V. Description of the invention (11 ) Ratio (Paint No. 6 and No. 5), the paper gloss value range of the paper garden is from 74.6% to 75.7% 'significantly better than using acARB® A40 PCC aragonite particles versus ALBAGLOS® S PCC calcite particles (Paint No. Nos. 2 to 4) Weight ratio 4 0: 60 to 6 0: 4 of 72,1% -72.7% paper gloss. In addition, 'when comparing the printing gloss properties of the same grade containing the aragonite / calcite colorant mixture', the improved paper glossiness of the blended aragonite colorant is clearer. In the particle size distribution of the particles used in the compound according to the present invention, the average value varies from about 0.1 micrometers to about 0.2 micrometers. Other blends with similar differences in particle size distribution exhibit similar coordination effects on the properties of coated paper. In addition, 'salt k is outside of the aragonite / aragonite blend, and other similar red-red | bow crystal mixtures (such as calcite / calcite) that can meet the above particle size distribution conditions can also show similar properties in coated paper Coordinate effect. Although the above has been explained with specific examples and applications of the present invention, those skilled in the art will know a variety of adjustments and specific examples without departing from the concept of the present invention described above. Therefore, all adjustments and specific examples covered by the scope of the attached patent application belong to the true spirit and scope of the present invention. -14- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims

581791 ABCD 第 0911054pEW?ir^~ 中文申請圍#本_-4月) 六、申請專利範圍一 ’ 1· 一種用於塗料組合物以產生高紙張光澤表面處理之碳酸鈣產物，該產物包括：具有第一平均值第一粒徑分佈之第一種碳酸鈣粒子，及具有第二平均值第二粒徑分佈之第二種碳酸鈣粒子，該第一及第二平均值差值在O.i微米到0.2微米，該第一種碳酸鈣粒子及第二種碳酸鈣粒子，係以由5〇 :5 0到8 0 : 2 0重量比例提供。 2·如申請專利範圍第1項之碳酸鈣產物，其中該第一種碳酸鈣粒子對第二種碳酸鈣粒子重量比例為6〇 : 40。 3 ·如申请專利範圍第1項之碳酸躬產物，其中該第一種碳酸鈣粒子及第二種碳酸鈣粒子為文石沉澱碳酸鈣（PCC) 粒子。 4 ·如申請專利範圍第1項之碳酸躬產物，其中該第一種碳酸鈣粒子平均粒徑（APS)為〇·4微米，而第二種碳酸鈣粒子平均粒徑（APS)為0.5微米。 5 .如申请專利範圍第2項之碳酸躬產物，其中該第一種碳酸鈣粒子平均粒徑（APS)為〇.4微米，而第二種碳酸鈣粒子平均粒徑（APS)為0.5微米。 6 ·如申請專利範圍第4項之碳酸舞產物，其中該第一種碳酸鈣粒子平均粒徑（APS)為〇.4微米，而第二種碳酸鈣粒子平均粒徑（APS)為0.5微米。 7. —種紙張塗料色料，其包含：具有第一平均值第一粒徑分佈之第一種碳酸鈣粒子本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐)581791 ABCD No. 0911054 pEW? Ir ^ ~ Chinese application encirclement # 本 _- 4 月) Six, the scope of patent application a '1. A calcium carbonate product for coating composition to produce a high paper gloss surface treatment, the product includes: The first type of calcium carbonate particles having a first average first particle size distribution and the second type of calcium carbonate particles having a second average second particle size distribution, and the difference between the first and second average values is between 0 μm to 0.2 micron, the first calcium carbonate particles and the second calcium carbonate particles are provided in a weight ratio of 50:50 to 80:20. 2. The calcium carbonate product according to item 1 of the application, wherein the weight ratio of the first calcium carbonate particles to the second calcium carbonate particles is 60:40. 3. The carbonate product according to item 1 of the scope of the patent application, wherein the first calcium carbonate particles and the second calcium carbonate particles are aragonite precipitated calcium carbonate (PCC) particles. 4. The carbonic acid product according to item 1 of the patent application scope, wherein the average particle size (APS) of the first calcium carbonate particles is 0.4 micrometers, and the average particle size (APS) of the second calcium carbonate particles is 0.5 micrometers. . 5. The carbonic acid product according to item 2 of the patent application, wherein the average particle size (APS) of the first calcium carbonate particles is 0.4 micrometers, and the average particle size (APS) of the second calcium carbonate particles is 0.5 micrometers. . 6. The carbonic acid dance product according to item 4 of the application, wherein the average particle size (APS) of the first calcium carbonate particles is 0.4 micrometers, and the average particle size (APS) of the second calcium carbonate particles is 0.5 micrometers. . 7. A paper coating pigment, comprising: the first calcium carbonate particles having a first average and a first particle size distribution. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm).

79 ，及具有第二平均值第二粒徑分佈之第二種碳酸鈣粒子 ’其中該第一與第二平均值差值在O.i微米到0.2微米遠第一種碳酸鈣粒子及第二種碳酸鈣粒子，係以由5 〇 :5 0到8 0 : 2 0重量比例提供。 8 ·如申請專利範圍第7項之紙張塗料色料，其中該第一種碳酸鈣色料對第二種碳酸鈣色料重量比例為6〇 : 40。 9 .如申請專利範圍第7項之紙張塗料色料，其中該第一種碳酸躬色料及該第二種碳酸鈣色料為文石沉澱碳酸鈣 (PCC)色料。 10·如申請專利範圍第7項之紙張塗料色料，其中該第一種碳酸鈣粒子平均粒徑（APS)為0.4微米，而第二種碳酸鈣粒子平均粒徑（APS)為0.5微米。 11·如申請專利範圍第8項之紙張塗料色料，其中該第一種碳酸鈣粒子平均粒徑（APS)為0.4微米，而第二種碳酸鈣粒子平均粒徑（APS)為0.5微米。 12. 如申請專利範圍第9項之紙張塗料色料，其中該第一種碳酸鈣粒子平均粒徑（APS)為〇·4微米，而第二種碳酸鈣粒子平均粒徑（APS)為0.5微米。 13. —種製造具高紙張光澤紙張之方法，其包含步驟為·· a) 提供具第一平均值第一粒徑分佈之第一種碳酸鈣粒子，及 b) &供具第一平均值第二粒徑分佈之第二種碳酸舞粒 -2 -本紙張尺度適用中國國家標準(CNS) A4規格(210 X297公釐）79, and a second calcium carbonate particle having a second average and a second particle size distribution, wherein the difference between the first and second average values is between 0.1 micron and 0.2 micron away from the first calcium carbonate particle and the second carbonic acid The calcium particles are provided in a weight ratio of 50:50 to 80:20. 8. The paper coating colorant according to item 7 of the patent application scope, wherein the weight ratio of the first calcium carbonate colorant to the second calcium carbonate colorant is 60:40. 9. The paper coating colorant according to item 7 of the application, wherein the first carbonic acid colorant and the second calcium carbonate colorant are aragonite precipitated calcium carbonate (PCC) colorant. 10. The paper coating colorant according to item 7 of the application, wherein the first calcium carbonate particles have an average particle size (APS) of 0.4 micrometers and the second calcium carbonate particles have an average particle diameter (APS) of 0.5 micrometers. 11. The paper coating colorant according to item 8 of the application, wherein the first calcium carbonate particles have an average particle size (APS) of 0.4 micrometers and the second calcium carbonate particles have an average particle diameter (APS) of 0.5 micrometers. 12. The paper coating colorant according to item 9 of the patent application, wherein the average particle size (APS) of the first calcium carbonate particles is 0.4 micrometers, and the average particle size (APS) of the second calcium carbonate particles is 0.5. Microns. 13. —A method for manufacturing a paper with high paper gloss, comprising the steps of: a) providing first calcium carbonate particles having a first average first particle size distribution, and b) & supplying a first average The second carbonic acid dance particle with the second particle size distribution -2-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X297 mm)

子，该第一及第二平均值差值為〇1微米到〇.2微米， c) 以由5 0 · 5 0到8 0 : 2 0重量比例，混合第一種碳酸鈣粒子與第二種碳酸鈣粒子，以形成色料摻配物， d) 令该色料摻配混合物與至少一結合劑混合，形成一塗料漿液， e) 以該塗料漿液塗覆紙張形成塗覆，及 f) 乾燥並壓光該紙張、以形成具高紙張光澤之塗覆紙張。 14·如申請專利範圍第1 3項之方法，其中該第一種碳酸鈣粒子對該第二種碳酸鈣粒子之重量比例為6 〇 ·· 4 〇。 15·如申請專利範圍第1 3項之方法，其中該第一種碳酸鈣粒子及該第二種碳酸鈣粒子為文石沉澱碳酸鈣（pcc)粒子。 16·如申請專利範圍第1 3項之方法，其中尚包含在步驟c ) 中提供黏土，並混合黏土與該塗料混合物，含量範圍由1 5重量％到7 0重量％。 17·如申請專利範圍第1 3項之方法，其中該第一種碳酸鈣粒子平均粒徑（APS)為〇 4微米，而第二種碳酸鈣粒子平均粒徑（APS)為0.5微米。 18·如申請專利範圍第} 4項之方法，其中該第一種碳酸鈣粒子平均粒徑（八!>8)為0.4微米，而第二種碳酸鈣粒子平均粒徑（APS)為0.5微米。 19.如申請專利範圍第1 5項之方法，其中該第一種碳酸鈣粒子平均粒徑（八1^)為〇4微米，而第二種碳酸鈣粒子平 3- 581791 A8 B8 C8 D8 、申請專利範圍均粒徑（APS)為0.5微米。 20. 如申請專利範圍第1 6項之方法，其中該第一種碳酸鈣粒子平均粒徑（APS)為0.4微米，而第二種碳酸鈣粒子平均粒徑（APS)為0.5微米。 21. —種如申請專利範圍第1 3項方法製造之紙張產物。 -4 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐)The difference between the first and second average values is 0.001 μm to 0.2 μm, and c) mixing the first type of calcium carbonate particles with the second type at a weight ratio of 50.50 to 80:20. Seed calcium carbonate particles to form a colorant blend, d) mixing the colorant blend with at least one binder to form a coating slurry, e) coating the paper with the coating slurry to form a coating, and f) The paper is dried and calendered to form a coated paper with high paper gloss. 14. The method according to item 13 of the scope of patent application, wherein the weight ratio of the first type of calcium carbonate particles to the second type of calcium carbonate particles is 60.0.40. 15. The method of claim 13 in the scope of patent application, wherein the first calcium carbonate particles and the second calcium carbonate particles are aragonite precipitated calcium carbonate (pcc) particles. 16. The method according to item 13 of the patent application scope, further comprising providing clay in step c), and mixing the clay and the coating mixture in an amount ranging from 15% to 70% by weight. 17. The method according to item 13 of the scope of patent application, wherein the average particle size (APS) of the first calcium carbonate particles is 0.4 m, and the average particle size (APS) of the second calcium carbonate particles is 0.5 m. 18. The method according to item 4 of the scope of patent application, wherein the average particle size (eight!) Of the first calcium carbonate particles is 0.4 micrometers, and the average particle size (APS) of the second calcium carbonate particles is 0.5 Microns. 19. The method according to item 15 of the scope of patent application, wherein the average particle size (eight 1 ^) of the first type of calcium carbonate particles is 0.4 micron, and the second type of calcium carbonate particles are 3-581791 A8 B8 C8 D8, The patent application range has an average particle size (APS) of 0.5 microns. 20. The method according to item 16 of the patent application, wherein the first calcium carbonate particles have an average particle size (APS) of 0.4 micrometers and the second calcium carbonate particles have an average particle diameter (APS) of 0.5 micrometers. 21. —A paper product manufactured by the method described in item 13 of the scope of patent application. -4-This paper size applies to China National Standard (CNS) A4 (210X297 mm)