TWI308583B - Pigment composition - Google Patents

Description

1308583. 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. 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) 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) 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

From 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

Claims (1)

1308583 V X. Scope of application: You are a pigment composition in the form of an aqueous dispersion comprising: a) a colloid of agglomerated vermiculite, aluminosilicate or a mixture thereof in an aqueous sol a porous aggregate formed of secondary particles having an average diameter of from about 3 to about 25 μm, and b) an additional particle having an average size at least larger than that of the porous aggregate Wherein the weight ratio of the porous aggregate to the incremental particles is from about 0.01 :1 to about 3:1. 2. The composition of claim 1, wherein the colloidal primary particles of the vermiculite or aluminosilicate have been formed from an aqueous solution of an alkali metal silicate, wherein the alkali metal ion is via an ion exchange method. Removal or in which the alkali metal citrate has been neutralized due to the addition of acid. The composition of any one of claims 1-2, wherein at least some of the porous agglomerates adhere to the incremental particles. The composition of any one of claims 1-2, wherein the W porous aggregate has an opposite net charge to the incremental particles. 5. The composition of any one of claims 2-1, wherein the incremental particle belongs to a type selected from the group consisting of kaolin, smectite, talc, calcium carbonate mineral, sedite, gel-type vermiculite, A material composed of igneous vermiculite, precipitated calcium carbonate, and mixtures thereof. 6. The composition of any one of claims 1 to 2 wherein the total content of the porous aggregates and the incremental particles in the composition is from about 1 to about 6 weight percent. The composition of any one of the inventions, wherein the colloidal primary particles of the vermiculite, the aluminosilicate or a mixture thereof have an average diameter of from about 2 nm to about 75 nm. 8. A method of producing a pigment composition according to any one of the preceding claims, comprising the step of mixing: a) colloid by agglomerating vermiculite, aluminosilicate or a mixture thereof in an aqueous sol An aqueous dispersion of porous aggregates formed by primary particles having an average diameter of from about 0.03 to about 25 μm, and b) an average size of at least the dimension of the enhancer is greater than the average diameter of the porous aggregate The weight ratio of the medium porous t collective to the incremental particles is from about 0.0 U to about 3:1. 9. A method of producing a pigment composition according to any one of claims 7-1, which comprises the steps of: a) mixing σ a colloidal primary particle containing a stone or an aluminite Water·/Glue and Incremental Particles' The weight ratio of the primary particles of the vermiculite or aluminosilicate to the incremental particles is from about 0.01:1 to about 3:1; and b) the aggregated vermiculite or aluminosilicate The colloidal primary particles of the salt form a porous aggregate having an average diameter of from about 0.03 μηη to about 2祚〇1 but not exceeding an average size of the largest dimension of the incremental particles. 〇 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 11. A coating composition suitable for coating paper or paperboard, comprising a binder and a pigment composition 24' as set forth in claim 7 or 10, which comprises a bonding agent and Mixed pigment composition Ϊ 308583 object. i: A coating composition yarn according to the scope of claim U, wherein the binder is selected from the group consisting of polyvinyl alcohol, starch modified as needed, gum, protein binder, latex and mixtures thereof. 13. A method of manufacturing a coating composition Patenting any of the steps 1-7 or 1 . 14. A method of making coated paper or paperboard comprising the step of applying a coating composition of any of the items of the U.S. Patent Application Serial No. U. 2 to at least one side of a paper or paperboard roll. [15] The method of claim 14, wherein the coating amount of the coating is sufficient to produce a pigment composition of from about 4 g/m2 to about 4 g/m2 on each coated side of the paper or paperboard roll. Porous aggregates and incremental particles of matter. 16. A paper or paperboard obtainable by the method of claim 14 or 15 of the patent application. XI. Ming style: (none) 25