JP2008519177A - Pigment composition in the form of an aqueous dispersion - Google Patents
Pigment composition in the form of an aqueous dispersion Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
Abstract
本発明は、（ａ）水性ゾル中でのシリカ、アルミノケイ酸塩又はこれらの混合物のコロイド一次粒子の凝集により形成され、約０．０３〜約２５μmの平均直径を有する、多孔質凝集体と、（ｂ）少なくとも１つの直径の平均サイズが、前記多孔質凝集体の平均直径よりも大きい増量剤粒子とを含み、該多孔質凝集体と増量剤粒子の重量比が、約０．０１：１〜約３：１である、水性分散液又はスラリーの形態の顔料組成物に関する。本発明は、更に、その製造方法、紙又は板紙を被覆する組成物、その製造方法、紙又は板紙を被覆する方法、およびその方法により得られる紙又は板紙に関する。 The present invention comprises (a) a porous aggregate formed by agglomeration of colloidal primary particles of silica, aluminosilicate or a mixture thereof in an aqueous sol and having an average diameter of about 0.03 to about 25 μm; (B) extender particles having an average size of at least one diameter larger than the average diameter of the porous aggregate, wherein the weight ratio of the porous aggregate to the extender particles is about 0.01: 1. Relates to a pigment composition in the form of an aqueous dispersion or slurry, which is about 3: 1. The present invention further relates to a method for producing the same, a composition for coating paper or paperboard, a method for producing the same, a method for coating paper or paperboard, and a paper or paperboard obtained by the method.
Description
本発明は、顔料組成物、その製造方法、紙又は板紙を被覆する組成物、その製造方法、紙又は板紙を被覆する方法、およびその方法により得られる紙又は板紙に関する。 The present invention relates to a pigment composition, a method for producing the same, a composition for coating paper or paperboard, a method for producing the same, a method for coating paper or paperboard, and a paper or paperboard obtained by the method.
インクジェットプリンタの開発は、その目的に適切な紙の需要をもたらした。特に、製造するのが容易であるが、依然として高品質のインクジェット印刷を可能にする紙への需要が存在する。 The development of inkjet printers has resulted in demand for paper that is appropriate for that purpose. In particular, there is a need for paper that is easy to manufacture but still allows high quality ink jet printing.
インクジェット印刷に適切な紙を製造するために、多様な種類の被覆を使用することが開示されてきた。 It has been disclosed to use various types of coatings to produce paper suitable for ink jet printing.
特許文献１は、水溶性金属塩を、顔料及び従来の結合剤を含むインク受容層に組み込むことを開示する。 U.S. Patent No. 6,057,031 discloses incorporating a water soluble metal salt into an ink receiving layer comprising a pigment and a conventional binder.
特許文献２は、水溶性多価金属とカチオン性ポリマーとの組み合わせを含む記録表面を開示する。 Patent Document 2 discloses a recording surface containing a combination of a water-soluble polyvalent metal and a cationic polymer.
特許文献３は、水溶性多価金属塩で表面処理されている顔料を開示する。 Patent Document 3 discloses a pigment that has been surface-treated with a water-soluble polyvalent metal salt.
特許文献４は、インクジェット記録材料の調製方法であって、５００nm以下の平均二次粒径を有するシリカ粒子を含有する少なくとも１つの多孔質層を形成する工程、及び被覆無機粒子の固形分が多孔質層上で０．３３g/m2以下になるように無機粒子含有層を調製するために、被覆溶液を被覆する工程、を含む方法を開示する。 Patent Document 4 is a method for preparing an inkjet recording material, in which a step of forming at least one porous layer containing silica particles having an average secondary particle size of 500 nm or less and a solid content of the coated inorganic particles are porous. Disclosed is a method including the step of coating a coating solution to prepare an inorganic particle-containing layer so as to be 0.33 g / m 2 or less on the porous layer.
特許文献５は、原紙及びその上の被覆を含むインクジェット紙を開示し、ここで前記被覆は、正電荷を帯びた錯体及び結合剤により変性されている無機顔料を含有する。この正電荷を帯びた錯体は、多価金属イオン及び無機リガンドを含有する。 U.S. Patent No. 6,057,031 discloses an inkjet paper comprising a base paper and a coating thereon, wherein the coating contains an inorganic pigment that is modified with a positively charged complex and a binder. This positively charged complex contains a polyvalent metal ion and an inorganic ligand.
特許文献６は、基材を含み、結合剤と、非晶質シリカ粒子を分散し、強い機械的応力を適用してこれらの粒子を分裂することにより形成された複数の粒子とを含む透明インク受容層を含む、インクジェット記録材料を開示する。 Patent Document 6 includes a base material, a transparent ink including a binder, and a plurality of particles formed by dispersing amorphous silica particles and applying strong mechanical stress to divide these particles. An ink jet recording material comprising a receiving layer is disclosed.
被覆紙に関する開示の他の例は、特許文献７、特許文献８、特許文献９、特許文献１０、特許文献１１及び特許文献１２である。
本発明の目的は、インクジェット印刷用に紙又は板紙を被覆するのために適切であり、製造することが簡単である顔料組成物を提供することである。 The object of the present invention is to provide a pigment composition which is suitable for coating paper or paperboard for ink jet printing and which is simple to manufacture.
本発明の別の目的は、インクジェット印刷に適するように、紙又は板紙の表面に塗布することが簡単である被覆配合物を提供することである。 Another object of the present invention is to provide a coating formulation that is simple to apply to the surface of paper or paperboard to be suitable for ink jet printing.
本発明のさらに別の目的は、インクジェット印刷に適切であり、製造することが簡単である紙又は板紙を提供することである。 Yet another object of the present invention is to provide a paper or paperboard that is suitable for inkjet printing and is simple to manufacture.
したがって、本発明の一つの態様は、
ａ）水性ゾル中でのシリカ、アルミノケイ酸塩又はこれらの混合物のコロイド一次粒子の凝集により形成され、約０．０３μm〜約２５μmの平均直径を有する、多孔質凝集体と、
ｂ）少なくとも１つの直径の平均サイズが、多孔質凝集体の平均直径よりも大きい増量剤粒子とを含み、
前記多孔質凝集体と増量剤粒子の重量比が、約０．０１：１〜約３：１、好ましくは約０．０１：１〜約２：１、最も好ましくは約０．０５：１〜約１．５：１である
水性分散液の形態の顔料組成物に関する。
Accordingly, one aspect of the present invention is
a) a porous agglomerate formed by agglomeration of colloidal primary particles of silica, aluminosilicate or a mixture thereof in an aqueous sol and having an average diameter of about 0.03 μm to about 25 μm;
b) extender particles having an average size of at least one diameter greater than the average diameter of the porous aggregates;
The weight ratio of the porous aggregate to extender particles is about 0.01: 1 to about 3: 1, preferably about 0.01: 1 to about 2: 1, most preferably about 0.05: 1. It relates to a pigment composition in the form of an aqueous dispersion which is about 1.5: 1.
前記コロイド一次粒子シリカの平均粒子直径は、好ましくは約２nm〜約７５nm、最も好ましくは約３nm〜約５０nmである。この一次粒子の表面積は、好ましくは３５m2/g〜約１４００m2/g、最も好ましくは約５０m2/g〜約１０００m2/gである。一つの実施態様において、表面積は、約６００m2/gまで、好ましくは約４５０m2/gまで、最も好ましくは約３００m2/gまでである。一次粒子の水性ゾルの乾燥含有量は、好ましくは約０．５重量％〜約６０重量％、最も好ましくは約１重量％〜約５０重量％である。 The colloidal primary particle silica preferably has an average particle diameter of about 2 nm to about 75 nm, most preferably about 3 nm to about 50 nm. The surface area of the primary particles is preferably 35m 2 / g to about 1400 m 2 / g, most preferably from about 50 m 2 / g to about 1000 m 2 / g. In one embodiment, the surface area is up to about 600 m 2 / g, preferably up to about 450 m 2 / g, and most preferably up to about 300 m 2 / g. The dry content of the aqueous sol of primary particles is preferably from about 0.5% to about 60%, most preferably from about 1% to about 50%.
本明細書で使用されるとき、直径という用語は球形の直径と同等であることを意味する。 As used herein, the term diameter means equivalent to a spherical diameter.
シリカ又はアルミノケイ酸塩の前記コロイド一次粒子は、好ましくはアルカリ金属ケイ酸塩の水溶液から形成され、ここで、アルカリ金属イオンはイオン交換法を通して除去されるか、又はアルカリ金属ケイ酸塩溶液のｐＨは酸の添加により低減される。イオン交換に基づく方法は、R.K. IIer, "The Chemistry of Silica" 1979, pages 333-334に記載された基本原理、及びシリカ又はアルミノケイ酸塩の負若しくは正電荷を帯びたコロイド粒子を含む水性ゾル中での結果に従う。アルカリ金属ケイ酸塩のｐＨ低減に基づく方法は、例えば、米国特許第５，１７６，８９１号、同第５，６４８，０５５号、同第５，８５３，６１６号、同第５，４８２，６９３号、同第６，０６０，５２３号及び同第６，２７４，１１２号に記載された基本原理に従う。 Said colloidal primary particles of silica or aluminosilicate are preferably formed from an aqueous solution of an alkali metal silicate, wherein alkali metal ions are removed through an ion exchange process or the pH of the alkali metal silicate solution. Is reduced by the addition of acid. The method based on ion exchange is based on the basic principle described in RK IIer, “The Chemistry of Silica” 1979, pages 333-334, and in aqueous sols containing negative or positively charged colloidal particles of silica or aluminosilicate. Follow the results in Methods based on alkali metal silicate pH reduction include, for example, US Pat. Nos. 5,176,891, 5,648,055, 5,853,616, and 5,482,693. No. 6,060,523 and 6,274,112.
特に好ましいゾルは、例えばアルミニウム、チタン、クロム、ジルコニウム、ホウ素又は他の任意の適切な金属の酸化物のような金属酸化物により、表面が変性されていても、いなくてもよい、シリカのコロイド一次粒子を含む。 Particularly preferred sols are silica, which may or may not be surface modified with a metal oxide such as, for example, aluminum, titanium, chromium, zirconium, boron or any other suitable metal oxide. Contains colloidal primary particles.
シリカ又はアルミノケイ酸塩のコロイド一次粒子の適切な水性ゾルは、例えば、商標名Ludox（商標）、Snowtex（商標）、Bindzil（商標）、Nyacol（商標）、Vinnsil（商標）又はFennosil（商標）で市販されている。 Suitable aqueous sols of colloidal primary particles of silica or aluminosilicate are, for example, trade names Ludox ™, Snowtex ™, Bindzil ™, Nyacol ™, Vinnsil ™ or Fennosil ™ It is commercially available.
シリカ又はアルミノケイ酸塩を乾燥させて粉末を形成する場合、そのような粉末を分散して形成されるゾルは、そのゾルがアルカリ金属ケイ酸塩からイオン交換又はｐＨ低減により調製される場合のように、コロイド粒子を粉末にするために乾燥していないゾルと異なる特性を有することが、見出されている。 When silica or aluminosilicate is dried to form a powder, the sol formed by dispersing such powder is as if the sol was prepared from alkali metal silicate by ion exchange or pH reduction. In particular, it has been found that the colloidal particles have different properties from sols that have not been dried to make a powder.
多孔質凝集体の分散液を形成するゾル中の一次粒子の凝集は、R. K. IIer, "The Chemistry of Silica" 1979, pages 364-407で記載されているような、任意の適切な方法により実施してもよい。この凝集度は、粘度を測定し、アインシュタインとムーニーの方程式を適用すること（例えば、R.K. IIer, "The Chemistry of Silica" 1979, pages 360-364を参照すること）によって、追うことができる。この凝集は、別個の工程として、又は増量剤粒子も含む混合物中で実施してもよい。 Aggregation of the primary particles in the sol to form a dispersion of porous aggregates is performed by any suitable method as described in RK IIer, “The Chemistry of Silica” 1979, pages 364-407. May be. This degree of aggregation can be followed by measuring the viscosity and applying the Einstein and Mooney equations (see, for example, R.K. IIer, “The Chemistry of Silica” 1979, pages 360-364). This agglomeration may be carried out as a separate step or in a mixture that also contains extender particles.
一つの実施態様において、アニオン性ゾル（負電荷を帯びたコロイド一次粒子を含む）及びカチオン性ゾル（正電荷を帯びたコロイド一次粒子を含む）が混合され、両方のゾルからの一次粒子の多孔質凝集体の形成をもたらす。 In one embodiment, an anionic sol (including negatively charged colloidal primary particles) and a cationic sol (including positively charged colloidal primary particles) are mixed and the porosity of the primary particles from both sols is mixed. Resulting in the formation of mass aggregates.
別の実施態様において、好ましくは二価、多価又は錯体塩から選択される塩が、アニオン性又はカチオン性ゾルに添加され、これも、多孔質凝集体の形成をもたらす。これらの塩の例は、塩化アルミニウム、ポリ塩化アルミニウム、ポリ硫酸ケイ酸アルミニウム、硫酸アルミニウム、炭酸ジルコニウム、酢酸ジルコニウム、アルカリ金属ホウ酸塩、及びこれらの混合物である。 In another embodiment, a salt, preferably selected from divalent, multivalent or complex salts, is added to the anionic or cationic sol, which also results in the formation of porous aggregates. Examples of these salts are aluminum chloride, polyaluminum chloride, polyaluminum sulfate silicate, aluminum sulfate, zirconium carbonate, zirconium acetate, alkali metal borates, and mixtures thereof.
なお別の実施態様において、架橋物質が、一次粒子から凝集体を形成するために使用される。適切な架橋物質の例は、ＣＭＣ（カルボキシメチルセルロース）、ＰＡＭ（ポリアクリルアミド）、ポリＤＡＤＭＡＣ（ポリジアリルジメチルアンモニウムクロリド）、ポリアリルアミン、ポリアミン、デンプン、グアーゴム、及びこれらの混合物のような、合成及び天然の高分子電解質である。 In yet another embodiment, a cross-linking material is used to form aggregates from the primary particles. Examples of suitable cross-linking materials are synthetic and natural, such as CMC (carboxymethylcellulose), PAM (polyacrylamide), polyDADMAC (polydiallyldimethylammonium chloride), polyallylamine, polyamine, starch, guar gum, and mixtures thereof. The polymer electrolyte.
上記の凝集方法の１、２又は３つ全てを含むあらゆる組み合わせを利用することもできる。 Any combination including one, two or all three of the above aggregation methods can also be utilized.
それぞれの多孔質凝集体は、本質的に少なくともいくつかの孔を与える少なくとも３つの一次粒子から形成される。これらの凝集体の平均粒子直径は、好ましくは約０．０５〜約１０μm、最も好ましくは約０．１μm〜約１．５μmである。前記多孔質凝集体の平均直径は、それらを形成する一次粒子の平均直径よりも常に大きいことが理解されるべきである。 Each porous aggregate is formed from at least three primary particles that essentially provide at least some pores. The average particle diameter of these aggregates is preferably from about 0.05 to about 10 μm, and most preferably from about 0.1 μm to about 1.5 μm. It should be understood that the average diameter of the porous aggregates is always larger than the average diameter of the primary particles that form them.
前記増量剤粒子は、多様な幾何学的形状、例えば、実質的にフレーク形状、ロッド様又は球状であることができ、少なくとも１つの寸法の平均サイズは、前記多孔質凝集体の平均直径よりも、大きい、好ましくは約１．３〜約５００倍大きい、最も好ましくは約１．３〜約２００倍大きい。これらの増量剤粒子は、好ましくは、天然又は合成の鉱物のような無機物質である。有用な物質の例は、カオリナイト、スメクタイト、タルサイト、炭酸カルシウム鉱物、沈降シリカ、ゲル型シリカ、ヒュームドシリカ、沈降炭酸カルシウム、及びこれらの混合物である。 The extender particles can be of various geometric shapes, for example, substantially flake-shaped, rod-like or spherical, with an average size of at least one dimension being greater than the average diameter of the porous aggregate. Larger, preferably about 1.3 to about 500 times larger, most preferably about 1.3 to about 200 times larger. These extender particles are preferably inorganic materials such as natural or synthetic minerals. Examples of useful materials are kaolinite, smectite, talcite, calcium carbonate mineral, precipitated silica, gel silica, fumed silica, precipitated calcium carbonate, and mixtures thereof.
前記多孔質凝集体及び増量剤粒子は、反対の実効電荷を有することが好ましい。したがって、該多孔質凝集体が正の実効電荷を有する場合、負の実効電荷を持つ増量剤粒子を使用することが好ましく、逆の場合も同じである。 The porous aggregate and extender particles preferably have opposite net charges. Therefore, when the porous aggregate has a positive net charge, it is preferable to use extender particles having a negative net charge, and vice versa.
前記多孔質凝集体の少なくとも一部、例えば約１〜約１００重量％、好ましくは約５〜約１００重量％、最も好ましくは約３０〜約１００重量％が、増量剤粒子に付着していることが好ましい。前記顔料組成物全体の平均粒径は、好ましくは約０．５μm〜約５０μm、最も好ましくは約１μm〜約２５μmである。該組成物全体の比表面積は、好ましくは３５m2/g〜約１０００m2/g、最も好ましくは約５０m2/g〜約７００m2/gである。一つ実施態様において、この比表面積は、約６００m2/gまで、好ましくは約４５０m2/gまで、最も好ましくは約４００m2/gまでである。該組成物中の多孔質凝集体と増量剤粒子の全含有量は、好ましくは約１重量％〜約６０重量％、最も好ましくは約５重量％〜約５０重量％、特に最も好ましくは約１０重量％〜約５０重量％である。該組成物は、更に、安定剤のような、又は塩や架橋剤などの凝集の原材料若しくは物質からの残留不純物のような他の添加剤を含んでもよい。 At least a portion of the porous aggregate, for example about 1 to about 100% by weight, preferably about 5 to about 100% by weight, most preferably about 30 to about 100% by weight, is attached to the extender particles. Is preferred. The average particle size of the entire pigment composition is preferably from about 0.5 μm to about 50 μm, most preferably from about 1 μm to about 25 μm. The specific surface area of the entire composition is preferably 35m 2 / g to about 1000 m 2 / g, most preferably from about 50 m 2 / g to about 700m 2 / g. In one embodiment, the specific surface area is up to about 600 m 2 / g, preferably up to about 450 m 2 / g, and most preferably up to about 400 m 2 / g. The total content of porous aggregates and extender particles in the composition is preferably from about 1% to about 60%, most preferably from about 5% to about 50%, particularly most preferably about 10%. % By weight to about 50% by weight. The composition may further comprise other additives such as stabilizers or residual impurities from aggregate raw materials or substances such as salts and crosslinkers.
前記凝集の方法にかかわらず、本組成物は、少なくとも１つの水溶性アルミニウム塩を、乾燥多孔性凝集体及び増量剤粒子に対するＡl2Ｏ3の重量％として計算して、好ましくは約０．１重量％〜約３０重量％、最も好ましくは約０．２重量％〜約１５重量％の量で含んでもよい。これらの塩の例には、塩化アルミニウム、ポリ塩化アルミニウム、ポリ硫酸ケイ酸アルミニウム、硫酸アルミニウム、炭酸ジルコニウム、酢酸ジルコニウム、及びこれらの混合物が挙げられる。このアルミニウムは、シリカ若しくはアミノケイ酸塩の粒子の表面上に、又は水相中に、部分的に又は完全に存在してもよい。水溶性アルミニウム塩の総含有量は、前記顔料組成物を調製するのに使用される、カチオン性アルミニウム変性シリカゾルに存在するものから由来してもよい。しかしこの顔料組成物は、また、追加的なアルミニウム塩を含んでもよい。 Regardless of the method of agglomeration, the composition preferably comprises at least one water-soluble aluminum salt, calculated as a weight percent of Al 2 O 3 based on dry porous agglomerates and extender particles, of about 0.1. It may be included in an amount of from wt% to about 30 wt%, most preferably from about 0.2 wt% to about 15 wt%. Examples of these salts include aluminum chloride, polyaluminum chloride, polyaluminum sulfate silicate, aluminum sulfate, zirconium carbonate, zirconium acetate, and mixtures thereof. The aluminum may be present partially or completely on the surface of the silica or aminosilicate particles or in the aqueous phase. The total content of the water-soluble aluminum salt may be derived from that present in the cationic aluminum-modified silica sol used to prepare the pigment composition. However, the pigment composition may also contain additional aluminum salts.
前記凝集の方法にかかわらず、本組成物は、好ましくは約２０００〜約１００００００、より好ましくは約２０００〜約５０００００、最も好ましくは約５０００〜約２０００００の分子量を有する、少なくとも１つのカチオン性ポリマーを含んでもよい。このポリマーの電荷密度は、好ましくは約０．２meq/g〜約１２meq/g、より好ましくは約０．３meq/g〜約１０meq/g、最も好ましくは約０．５meq/g〜約８meq/gである。前記カチオン性ポリマーは、乾燥多孔質凝集体及び増量剤粒子の量に基づき、好ましくは約０．１重量％〜約３０重量％、より好ましくは約０．５重量％〜約２０重量％、最も好ましくは約１重量％〜約１５重量％の量で組成物に存在する。適切なカチオン性ポリマーの例には、カチオン性であり、かつ好ましくは分子量及び電荷密度が上記の要件を満たすのであれば、ＰＡＭ（ポリアクリルアミド）、ポリＤＡＤＭＡＣ（ポリジアリルジメチルアンモニウムクロリド）、ポリアリルアミン、ポリアミン、多糖類、及びこれらの混合物のような合成及び天然の高分子電解質が挙げられる。前記カチオン性ポリマーは、シリカ若しくはアミノケイ酸塩の粒子の表面上に、又は水相中に、部分的に又は完全に存在してもよい。 Regardless of the method of aggregation, the composition preferably comprises at least one cationic polymer having a molecular weight of about 2000 to about 1000000, more preferably about 2000 to about 500000, and most preferably about 5000 to about 200000. May be included. The charge density of the polymer is preferably from about 0.2 meq / g to about 12 meq / g, more preferably from about 0.3 meq / g to about 10 meq / g, most preferably from about 0.5 meq / g to about 8 meq / g. It is. The cationic polymer is preferably about 0.1 wt% to about 30 wt%, more preferably about 0.5 wt% to about 20 wt%, most preferably based on the amount of dry porous agglomerates and extender particles. Preferably present in the composition in an amount of from about 1% to about 15% by weight. Examples of suitable cationic polymers are PAM (polyacrylamide), polyDADMAC (polydiallyldimethylammonium chloride), polyallylamine, if they are cationic and preferably the molecular weight and charge density meet the above requirements And synthetic and natural polyelectrolytes such as polyamines, polysaccharides, and mixtures thereof. The cationic polymer may be present partially or completely on the surface of the silica or aminosilicate particles or in the aqueous phase.
上記で記載された顔料組成物は、好ましくは少なくとも１週間、最も好ましくは少なくとも１か月間は貯蔵安定している。本組成物は、紙又は板紙を被覆するために直接使用してもよいか、又は被覆組成物を調製するための中間生成物を形成してもよい。 The pigment compositions described above are preferably shelf stable for at least 1 week, most preferably for at least 1 month. The composition may be used directly to coat paper or paperboard or may form an intermediate product for preparing a coating composition.
本発明の更なる態様は、上記で記載された顔料組成物の製造方法に関する。一つの代替的方法は、
（ａ）水性ゾル中でのシリカ、アルミノケイ酸塩又はこれらの混合物のコロイド一次粒子の凝集により形成され、約０．０３μm〜約２５μmの平均直径を有する、多孔質凝集体の水性分散液と、
（ｂ）少なくとも一つの直径の平均サイズが、前記多孔質凝集体の平均直径よりも大きい増量剤粒子とを混合する工程を含み、
ここで、前記多孔質凝集体と増量剤粒子の重量比は、約０．０１：１〜約３：１、好ましくは約０．０３：１〜約２：１、最も好ましくは約０．０５：１〜約１．５：１である。
A further aspect of the present invention relates to a method for producing the pigment composition described above. One alternative method is
(A) an aqueous dispersion of porous aggregates formed by agglomeration of colloidal primary particles of silica, aluminosilicate or a mixture thereof in an aqueous sol and having an average diameter of about 0.03 μm to about 25 μm;
(B) mixing with extender particles having an average size of at least one diameter larger than the average diameter of the porous aggregate;
Here, the weight ratio of the porous aggregate to the extender particles is about 0.01: 1 to about 3: 1, preferably about 0.03: 1 to about 2: 1, most preferably about 0.05. : 1 to about 1.5: 1.
別の代替的方法は、
ａ）シリカ又はアルミノケイ酸塩の一次粒子と増量剤粒子との重量比が約０．０１：１〜約３：１、好ましくは約０．０３：１〜約２：１、最も好ましくは約０．０５：１〜約１．５：１である、シリカ又はアルミノケイ酸塩のコロイド一次粒子と増量剤粒子を含む水性ゾルを混合する工程、及び
ｂ）シリカ又はアルミノケイ酸塩のコロイド一次粒子を凝集して、約０．０３μm〜約２５μmの平均直径を有するが、前記増量剤粒子の最大寸法の平均サイズを超えない多孔質凝集体を形成する工程
を含む。
Another alternative method is
a) The weight ratio of silica or aluminosilicate primary particles to extender particles is about 0.01: 1 to about 3: 1, preferably about 0.03: 1 to about 2: 1, most preferably about 0. Mixing an aqueous sol comprising silica or aluminosilicate colloidal primary particles and extender particles, wherein: b) agglomerating the silica or aluminosilicate colloidal primary particles being from 0.05: 1 to about 1.5: 1; Forming a porous aggregate having an average diameter of about 0.03 μm to about 25 μm, but not exceeding the average size of the largest dimension of the extender particles.
いずれかの代替的方法において、前記増量剤粒子は、固体粉末として、水性分散液の形態で、又は他のあらゆる適切な形態で添加されてもよい。前記多孔質凝集体の形成、あらゆる任意の添加剤の添加及び他の多様な実施態様に関しては、上記記載の顔料組成物が参照される。 In any alternative method, the extender particles may be added as a solid powder, in the form of an aqueous dispersion, or in any other suitable form. With respect to the formation of the porous aggregates, the addition of any optional additives and other various embodiments, reference is made to the pigment compositions described above.
本発明のなお更なる態様は、結合剤及び上記で記載された顔料組成物を含む、紙又は板紙を被覆するのに適切な被覆組成物に関する。可能な結合剤の例は、ポリビニルアルコール、場合により変性されているデンプン、ゴム、タンパク質結合剤（例えば、カゼイン及び大豆タンパク質結合剤）、ラテックス、並びにこれらの混合物である。ラテックスは、スチレンブタジエン、アクリレート、酢酸ビニル、エチレンと酢酸ビニルのコポリマー、スチレンアクリルエステルなどに基づくことができる。ポリビニルアルコールが特に好ましい。前記被覆組成物は、また、レオロジー変性剤、蛍光増白剤、潤滑剤、不溶化剤、染料、サイズ剤などのような慣用的に使用される他の添加剤を含んでもよい。前記被覆組成物の乾燥含有量は、好ましくは約２重量％〜約７５重量％、最も好ましくは約１０重量％〜約７０重量％である。前記顔料組成物の多孔質凝集体及び増量剤粒子の量は、乾燥含有量に基づき、好ましくは３０〜約９９重量％、最も好ましくは約５０〜約９０重量％である。前記結合剤の量は、乾燥含有量に基づき、好ましくは約１〜約７０重量％、最も好ましくは約１０〜約５０重量％である。他の添加剤及び可能な不純物の総量は、乾燥含有量に基づき、０〜約５０重量％、最も好ましくは０〜約３０重量％である。適切であり、かつ好ましい実施態様に関しては、上記記載の顔料組成物が参照される。 A still further aspect of the invention relates to a coating composition suitable for coating paper or paperboard comprising a binder and a pigment composition as described above. Examples of possible binders are polyvinyl alcohol, optionally modified starches, gums, protein binders (eg casein and soy protein binders), latex, and mixtures thereof. The latex can be based on styrene butadiene, acrylate, vinyl acetate, copolymers of ethylene and vinyl acetate, styrene acrylic esters, and the like. Polyvinyl alcohol is particularly preferred. The coating composition may also contain other commonly used additives such as rheology modifiers, optical brighteners, lubricants, insolubilizers, dyes, sizing agents and the like. The dry content of the coating composition is preferably about 2% to about 75% by weight, and most preferably about 10% to about 70% by weight. The amount of porous aggregates and extender particles in the pigment composition is preferably from 30 to about 99% by weight, and most preferably from about 50 to about 90% by weight, based on the dry content. The amount of binder is preferably about 1 to about 70% by weight, most preferably about 10 to about 50% by weight, based on dry content. The total amount of other additives and possible impurities is 0 to about 50% by weight, most preferably 0 to about 30% by weight, based on the dry content. With regard to suitable and preferred embodiments, reference is made to the pigment compositions described above.
本発明のなお更なる態様は、結合剤と上記で記載された顔料組成物とを混合する工程を含む、被覆組成物の製造方法に関する。該結合剤及びあらゆる任意の添加剤を、あらゆる適切な形態で、例えば固体物質として、液体物質として、又は水溶液、水性分散液、若しくは水性スラリーとして、前記顔料組成物に添加してもよい。適切であり、かつ好ましい実施態様に関しては、上記記載の被覆組成物及び顔料組成物が参照される。 A still further aspect of the present invention relates to a method for producing a coating composition comprising the step of mixing a binder and a pigment composition as described above. The binder and any optional additives may be added to the pigment composition in any suitable form, for example, as a solid material, as a liquid material, or as an aqueous solution, aqueous dispersion, or aqueous slurry. With regard to suitable and preferred embodiments, reference is made to the coating compositions and pigment compositions described above.
本発明の別の態様は、上記で記載された被覆組成物を、紙又は板紙ウエブの少なくとも１つの面に塗布する工程を含む、被覆紙又は板紙の製造方法に関する。 Another aspect of the invention relates to a method for producing a coated paper or paperboard comprising the step of applying the coating composition described above to at least one surface of a paper or paperboard web.
前記被覆は、好ましくは、紙又は板紙の被覆面１つあたり、前記顔料組成物から、少なくとも約０．４g/m2から、好ましくは約０．５g/m2から約４０g/m2、最も好ましくは約１g/m2から約２０g/m2の多孔質凝集体及び増量剤粒子を生じるのに十分な量で塗布される。大部分の場合において、紙又は板紙の被覆面１つあたりに塗布される被覆の乾燥量は、好ましくは少なくとも約０．６g/m2から、好ましくは約０．７g/m2から約５０g/m2、最も好ましくは約１．５g/m2から約２５g/m2である。 The coating is preferably from at least about 0.4 g / m 2 , preferably from about 0.5 g / m 2 to about 40 g / m 2 , most preferably from the pigment composition per coated surface of paper or paperboard. Preferably, it is applied in an amount sufficient to produce about 1 g / m 2 to about 20 g / m 2 of porous agglomerates and extender particles. In most cases, the dry amount of coating applied per coated surface of paper or paperboard is preferably at least about 0.6 g / m 2 , preferably from about 0.7 g / m 2 to about 50 g / m 2. m 2 , most preferably from about 1.5 g / m 2 to about 25 g / m 2 .
前記被覆は、紙又は板紙の非被覆面に塗布されるが、また、既に塗布されている被覆層の上に、同じ又は別の被覆組成物により塗布されてもよい。本明細書で記載された前記被覆から形成される層の上に、他の種類のあらゆる更なる被覆を塗布しないことが好ましい。 The coating is applied to the uncoated surface of paper or paperboard, but may also be applied over the already applied coating layer with the same or another coating composition. It is preferred not to apply any other types of further coatings on the layers formed from the coatings described herein.
前記被覆を塗布することは、紙若しくは板紙抄紙機の上、又は紙若しくは板紙抄紙機の外のいずれかで、実施することができる。いずれの場合でも、あらゆる種類の被覆方法が使用できる。これらの被覆方法の例は、ブレードコーティング、エアナイフコーティング、ロールコーティング、カーテンコーティング、スプレーコーティング、サイズプレスコーティング（例えば、フィルムプレスコーティング）、及びキャストコーティングである。 Applying the coating can be carried out either on a paper or paperboard machine or outside the paper or paperboard machine. In any case, any kind of coating method can be used. Examples of these coating methods are blade coating, air knife coating, roll coating, curtain coating, spray coating, size press coating (eg film press coating), and cast coating.
前記被覆を塗布した後、この紙は乾燥され、機械上の場合は、被覆は好ましくは機械の乾燥セクションで達成される。赤外線放射、熱風、加熱シリンダー、又はこれらの任意の組み合わせのような、あらゆる乾燥方法を使用してもよい。 After applying the coating, the paper is dried and, if on the machine, the coating is preferably accomplished in the drying section of the machine. Any drying method may be used, such as infrared radiation, hot air, a heated cylinder, or any combination thereof.
本明細書で使用されるとき、被覆という用語は、顔料が紙又は板紙の表面に塗布されるあらゆる方法を意味し、したがって、従来の被覆のみならず、例えば顔料着色のような他の方法も含む。 As used herein, the term coating means any method by which a pigment is applied to the surface of a paper or paperboard, and thus not only conventional coatings, but also other methods such as pigmenting. Including.
前記被覆される紙及び板紙は、硫酸塩、亜硫酸及びオルガノソルブパルプのような化学パルプ、サーモメカニカルパルプ（ＴＭＰ）、ケムサーモメカニカルパルプ（ＣＴＭＰ）のような機械パルプ、未使用若しくは回収繊維又はこれらの任意の組み合わせに基づく硬材及び軟材のさらし又は未さらしパルプの両方からの精砕パルプ又は砕木パルプのような、あらゆる種類のパルプから作製できる。他のあらゆる種類のパルプからの紙及び板紙もまた、本発明により被覆されてもよい。 The paper and paperboard to be coated are chemical pulp such as sulfate, sulfite and organosolv pulp, mechanical pulp such as thermomechanical pulp (TMP), chemthermomechanical pulp (CTMP), unused or recovered fiber, or these Can be made from any type of pulp, such as refined pulp or groundwood pulp from both hardwood and softwood bleached or unbleached pulp based on any combination of Paper and paperboard from any other type of pulp may also be coated according to the present invention.
前記被覆組成物の更なる詳細及び実施態様に関しては、上記記載のものが参照される。 For further details and embodiments of the coating composition, reference is made to what has been described above.
本発明は、最後に、上記で記載された方法により得られる、インクジェット印刷に適切な紙又は板紙に関する。そのような紙又は板紙は、好ましくはナノ構造を形成する被覆組成物からの多孔質凝集体及び増量剤粒子を含む、好ましくは実質的に非透明な層を含む。この被覆の乾燥量は、好ましくは少なくとも約０．６g/m2から、好ましくは約０．７g/m2から約５０g/m2、最も好ましくは約１．５g/m2から約２５g/m2である。紙又は板紙の被覆面１つあたりの、前記顔料組成物からの多孔質凝集体及び増量剤粒子の量は、好ましくは少なくとも約０．４g/m2から、好ましくは約０．５g/m2から約４０g/m2、最も好ましくは約１g/m2から約２０g/m2である。好ましくは、この層の上に他の種類の被覆が適用されない。 The present invention finally relates to paper or paperboard suitable for ink jet printing, obtained by the method described above. Such paper or paperboard preferably comprises a substantially non-transparent layer comprising porous aggregates and extender particles from the coating composition forming the nanostructures. The dry weight of the coating is preferably at least about 0.6 g / m 2 , preferably about 0.7 g / m 2 to about 50 g / m 2 , most preferably about 1.5 g / m 2 to about 25 g / m 2. 2 . The amount of porous agglomerates and extender particles from the pigment composition per coated surface of paper or paper board is preferably at least about 0.4 g / m 2 and preferably about 0.5 g / m 2. To about 40 g / m 2 , most preferably about 1 g / m 2 to about 20 g / m 2 . Preferably, no other type of coating is applied over this layer.
本発明の紙又は板紙は、線の低いぼやけ及び色むら、並びに色の高い印刷濃度を与えるインクジェット印刷に良好な特性を有するが、有利には、トナー、フレキソ印刷、凸版印刷、グラビア印刷、オフセット印刷及びスクリーン印刷のような他の種類の印刷法にも使用できることが、見出されている。少量の被覆を適用するだけの、多数の異なる被覆層を紙又は板紙に適用する必要のない簡単な方法によって、そのような良好な特性を得ることができることが特に有利である。これは、そのような被覆を、フィルムプレスのようなサイズプレスにより適用することを可能にし、このことは、実用的な理由から有利である。更に、前記顔料組成物の主要成分は、容易に入手可能な原材料から作製できる。 The paper or paperboard of the present invention has good properties for ink jet printing which gives low line blur and color unevenness and high color print density, but advantageously toner, flexographic printing, letterpress printing, gravure printing, offset It has been found that it can also be used for other types of printing methods such as printing and screen printing. It is particularly advantageous to be able to obtain such good properties by a simple method in which only a small amount of coating is applied and a large number of different coating layers need not be applied to the paper or paperboard. This allows such a coating to be applied by a size press such as a film press, which is advantageous for practical reasons. Furthermore, the main components of the pigment composition can be made from readily available raw materials.
ここで本発明を以下の実施例で更に説明する。特に記述のない限り、全ての部及び百分率は、重量部及び重量％を意味する。 The invention will now be further described in the following examples. Unless otherwise stated, all parts and percentages refer to parts by weight and percentages by weight.
実施例１：４つの顔料組成物を調製した：
Ａ：平均粒子直径約１５nmのＳｉＯ2を３０重量％含有する、Eka Chemicals ABからのカチオン性水性シリカゾルBindzil（登録商標）CAT 220を希釈して１０重量％とした。この希釈シリカゾルをガラスビーカー中で撹拌し、０．０６mol/lの硫酸アルミニウム溶液を、ゾルが白色になり、粘度が増加するまで滴加し、これは、硫酸アルミニウムの濃度が溶液中で０．０１２５mol/lに達したときに起こった。凝集体の平均直径は０．３μmであると決定した（Malvern instrumentからのZetamasterで測定、単峰性分析）。
Ｂ：増量剤粒子の２０重量％水性分散液を被覆粘土（SPS, Imerys, UK）から調製した。この粘土の平均粒径は、Malvern InstrumentからのMastersizer Micro Plusを使用して（方法５０ＨＤ）、１．６４μmであると決定した。
Ｃ：Ｂで調製された粘土分散液３０mlを、事前に凝集しないで、Ａと同じ希釈シリカゾル１５mlと混合した。
Ｄ：Ａで調製された凝集シリカゾル１５mlを、Ｂで調製された粘土分散液３０mlと混合して、シリカの凝集体と増量剤粒子を含む顔料組成物を得た。
Example 1: Four pigment compositions were prepared:
A: Cationic aqueous silica sol Bindzil® CAT 220 from Eka Chemicals AB containing 30% by weight of SiO 2 with an average particle diameter of about 15 nm was diluted to 10% by weight. The diluted silica sol is stirred in a glass beaker and 0.06 mol / l aluminum sulfate solution is added dropwise until the sol turns white and the viscosity increases, so that the concentration of aluminum sulfate is 0. Occurs when reaching 0125 mol / l. The average diameter of the aggregates was determined to be 0.3 μm (measured with Zetamaster from Malvern instrument, unimodal analysis).
B: A 20 wt% aqueous dispersion of extender particles was prepared from coated clay (SPS, Imerys, UK). The average particle size of the clay was determined to be 1.64 μm using a Mastersizer Micro Plus from Malvern Instrument (Method 50HD).
C: 30 ml of the clay dispersion prepared in B was mixed with 15 ml of the same diluted silica sol as A without agglomeration in advance.
D: 15 ml of the agglomerated silica sol prepared in A was mixed with 30 ml of the clay dispersion prepared in B to obtain a pigment composition containing silica agglomerates and extender particles.
上記の顔料組成物を、それぞれ、水に１０重量％溶液として溶解した実験室等級ポリビニルアルコール（ＭＷ１５００００）と混合して、被覆配合物の調製に使用した。全ての配合物は、約１５重量％の固形分、及びポリビニルアルコールと固体顔料の重量比の０．５：１を有した。 Each of the above pigment compositions was mixed with laboratory grade polyvinyl alcohol (MW 150,000) dissolved as a 10 wt% solution in water and used to prepare coating formulations. All formulations had a solids content of about 15% by weight and a weight ratio of polyvinyl alcohol to solid pigment of 0.5: 1.
被覆配合物を、未被覆コピー用紙（M-realからのＡ４サイズData Copy）の表面に、ワイヤ付ロッドを用いたドローダウン法により適用し、それから、紙を乾燥ドラムで乾燥した。シアン、マゼンタ、イエロー及びブラックのブロックを含んだ試験画像を、Hewlett-Packard（HP Deskjet 970Cxi）からのインクジェットプリンタによりそれぞれの乾燥紙に印刷した。それぞれの色について、色密度を色濃度計（GretagMacbeth D19C, Gretag AG）で決定し、数字を下記の表で示す。 The coating formulation was applied to the surface of uncoated copy paper (A4 size Data Copy from M-real) by a drawdown method using a wire rod, and then the paper was dried in a drying drum. Test images containing cyan, magenta, yellow and black blocks were printed on each dry paper by an inkjet printer from Hewlett-Packard (HP Deskjet 970Cxi). For each color, the color density is determined with a color densitometer (GretagMacbeth D19C, Gretag AG), and the numbers are shown in the table below.
この実験から、前記顔料組成物Ｄを含む被覆配合物が、最良の総合的な印刷密度を与えたことを見ることができる。組成物Ａで被覆された紙に印刷された色には強い色むらがあることも、注目された。 From this experiment it can be seen that the coating formulation containing the pigment composition D gave the best overall print density. It was also noted that the color printed on the paper coated with Composition A had strong color irregularities.
実施例２：４つの顔料組成物を調製した：
Ａ：２つの水性シリカゾルを使用し、アニオン性シリカゾルBindzil（登録商標）15/500と、カチオン性シリカゾルBindzil（登録商標）CATであり、両方ともEka Chemicalsからのものであり、１５重量％のＳｉＯ2を含有し、約６nmの平均一次粒子直径を有した。３０重量％の水性粘土分散液（実施例１と同じ粘土、平均粒径１．６４μm）３７．５ｇ、カチオン性ゾル９０ｇ、アニオン性ゾル１３５ｇ及び水３７．５ｇを、激しい撹拌下で混合し、ゾルからの一次シリカ粒子の凝集体と粘土からの増量剤粒子とを含む高粘度の顔料組成物を得た。増量剤の添加前の凝集シリカゾルの平均直径は、０．５７μmであると決定した（Zetamasterによるmonomodal分析）。
Ｂ：沈降シリカ、２２重量％の固形分及び３．４μmの平均粒径（Mastersizer）を有するRhodiaからのTixosil（商標）365 SP、１０２ｇを、カチオン性シリカゾル６０ｇ、アニオン性シリカゾル９０ｇ及び水４８ｇと、Ａと同様に混合して、ゾルからの一次シリカ粒子の凝集体と沈降シリカからの増量剤粒子とを含む高粘度の顔料組成物を得た。増量剤の添加前の凝集シリカゾルの平均直径は、０．６９μmであると決定した（Zetamasterによる測定）。
Ｃ：Ａで使用したのと同じ粘度分散液。
Ｄ：Ｂで使用したのと同じ沈降シリカ。
Example 2: Four pigment compositions were prepared:
A: Two aqueous silica sols, anionic silica sol Bindzil® 15/500 and cationic silica sol Bindzil® CAT, both from Eka Chemicals, 15 wt% SiO 2 and had an average primary particle diameter of about 6 nm. 37.5 g of 30% by weight aqueous clay dispersion (same clay as in Example 1, average particle size 1.64 μm), 90 g of cationic sol, 135 g of anionic sol and 37.5 g of water are mixed under vigorous stirring. A highly viscous pigment composition comprising an aggregate of primary silica particles from the sol and extender particles from clay was obtained. The average diameter of the agglomerated silica sol before addition of the bulking agent was determined to be 0.57 μm (monomodal analysis by Zetamaster).
B: 102 g of Tixosil ™ 365 SP from Rhodia with precipitated silica, 22 wt% solids and 3.4 μm mean particle size (Mastersizer), 60 g of cationic silica sol, 90 g of anionic silica sol and 48 g of water A high-viscosity pigment composition containing agglomerates of primary silica particles from the sol and extender particles from precipitated silica was mixed in the same manner as in A. The average diameter of the agglomerated silica sol before addition of the bulking agent was determined to be 0.69 μm (measured by Zetamaster).
C: Same viscosity dispersion as used in A.
D: The same precipitated silica used in B.
上記の顔料組成物を、それぞれ、ポリビニルアルコール結合剤（ACETEX Co., SpainからのERKOL（商標）26/88）と混合して、被覆配合物の調製に使用した。全ての配合物は、約１５重量％の固形分、及びポリビニルアルコールと固体顔料の重量比の０．２５：１を有した。 Each of the above pigment compositions was mixed with a polyvinyl alcohol binder (ERKOL ™ 26/88 from ACETEX Co., Spain) and used to prepare coating formulations. All formulations had a solids content of about 15% by weight and a polyvinyl alcohol to solid pigment weight ratio of 0.25: 1.
前記被覆を実施例１のようにコピー用紙に塗布した。シアン、マゼンタ、イエロー、グリーン、ブルー、レッド及びブラックのブロックを含む試験画像を、全ての色に顔料着色インクを使用して、Epson Stylus C84インクジェットプリンタによりそれぞれの被覆紙に印刷した。これらの印刷されたブロック及び印刷されていない紙を、分光光度計（TechnidyneからのColor Touch 2）で測定し、色域量を計算した。この域量を、CEI L*a*b*色空間の十二面体で概算し、これらの色の測定値は、十二面体の角を与える（"Rydefalk Staffan, Wedin Michael; Litterature review on the colour Gamut in the Printing Process-Fundamentals, PTF-report no 32, May 1997"を参照すること）。 The coating was applied to copy paper as in Example 1. Test images containing cyan, magenta, yellow, green, blue, red and black blocks were printed on each coated paper with an Epson Stylus C84 inkjet printer using pigmented inks for all colors. These printed blocks and unprinted paper were measured with a spectrophotometer (Color Touch 2 from Technidyne) and the color gamut was calculated. This range is approximated by dodecahedrons in the CEI L * a * b * color space, and these color measurements give dodecahedron angles ("Rydefalk Staffan, Wedin Michael; Litterature review on the color Gamut in the Printing Process-Fundamentals, PTF-report no 32, May 1997 ").
結果を以下の表に示す。 The results are shown in the table below.
この結果から、顔料組成物Ａ及びＢが、域量で測定すると、より高い印刷品質を与えたことを見ることができる。 From this result, it can be seen that pigment compositions A and B gave higher print quality when measured by area weight.
実施例３：２つの顔料組成物を調製した：
Ａ：被覆粘度（実施例１と同じ、粒径１．６４μm）の３０重量％水性分散液１６．７ｇ、Bindzil 50/80（平均粒径４０nmのシリカゾル５０重量％、Eka Chemicalsから）１０ｇ、Eka ATC 8210（Eka Chemicalsからのポリ塩化アルミニウム２５重量％）３ｇ及び水７０ｇを、UltraTurrax中、激しい撹拌下（１００００rpm）で混合した。これにより、シリカと粘度の重量比が１：１の顔料分散液１０重量％を得た。増量剤の添加前の凝集シリカゾルの平均直径は、０．４５μmであると決定した（Zetamasterによるmonomodal分析）。
Ｂ：被覆粘度（実施例１と同じ）の３０重量％水性分散液１６．７ｇ、シリカゲル型の生成物（乾燥粉末）５ｇ、及び水７８ｇを混合（Ａと同じUltraTurrax）して、１０重量％の顔料分散液（シリカ／粘土の比１：１）を得た。このシリカゲル型生成物（Grace Davison）は、１２μmの二次粒径及び４００m2/gの表面積を有し、７〜８nmの一次粒径に相当した。
Example 3: Two pigment compositions were prepared:
A: 16.7 g of a 30 wt% aqueous dispersion with a coating viscosity (same as in Example 1, particle size 1.64 μm), 10 g of Bindzil 50/80 (50 wt% silica sol with an average particle size of 40 nm, from Eka Chemicals), Eka 3 g ATC 8210 (25% by weight polyaluminum chloride from Eka Chemicals) and 70 g water were mixed in an UltraTurrax under vigorous stirring (10000 rpm). As a result, 10% by weight of a pigment dispersion having a silica to viscosity weight ratio of 1: 1 was obtained. The average diameter of the agglomerated silica sol before addition of the bulking agent was determined to be 0.45 μm (monomodal analysis by Zetamaster).
B: 16.7 g of a 30 wt% aqueous dispersion of the coating viscosity (same as in Example 1), 5 g of a silica gel type product (dry powder), and 78 g of water (UltraTurrax same as A) were mixed to give 10 wt% A pigment dispersion (silica / clay ratio 1: 1) was obtained. This silica gel type product (Grace Davison) had a secondary particle size of 12 μm and a surface area of 400 m 2 / g, corresponding to a primary particle size of 7-8 nm.
１０重量％の固形分及びポリビニルアルコールと固体顔料の重量比の０．２５：１を有する被覆配合物を、実施例２と同様に調製した。これらの被覆物を紙に塗布し、ＩＲ乾燥機（Hedson Technologies AB Sweden）で乾燥した。印刷試験を、Epson Stylus C84及びHP5652（Hewlett Packard）インクジェットプリンタにより、実施例２で記載されたように実施した。結果を下記の表に表わす。 A coating formulation having a solids content of 10% by weight and a weight ratio of polyvinyl alcohol to solid pigment of 0.25: 1 was prepared as in Example 2. These coatings were applied to paper and dried with an IR dryer (Hedson Technologies AB Sweden). The print test was performed as described in Example 2 with an Epson Stylus C84 and HP5652 (Hewlett Packard) inkjet printer. The results are shown in the table below.
シリカゾル凝集体（Ａ）を含有する顔料組成物は、ゲル型のシリカを含有する対応する顔料組成物よりも、高い域量を与えた。注意深い可視検査は、プリントアウトにおいて良好な線の鮮鋭度、及び色のブリーディングがないことを明らかにした。 The pigment composition containing the silica sol aggregate (A) gave a higher amount than the corresponding pigment composition containing the gel type silica. Careful visual inspection revealed good line sharpness and no color bleeding in the printout.
実施例４：２つの顔料組成物を調製した：
Ａ：１０重量％のＳｉＯ2を含有し、約８６５m2/ｇの表面積を有する、イオン交換法により調製されたアニオン性シリカゾルを、変性カルボキシメチルセルロース（ＣＭＣ）の２．５重量％水溶液１４．２ｇをシリカゾル１００ｇに連続撹拌下でゆっくりと加えて高粘度の透明溶液を得ることによって、凝集した。変性ＣＭＣは、カルボキシル基に関して０．６５のＤＳを有し、第四級窒素基（ＤＳ０．４３）を組み込むことによって更に変性して、生成物のカチオン特性を得た。この分散液中の凝集物の平粒子均直径は、Zetamasterを使用して、０．７μmであると決定した。次にこの分散液を、沈降シリカ（Tixosil 365 SP、平均粒径３．４μm、実施例２を参照すること）４５ｇ及び水４５ｇと激しく混合した。
Ｂ：沈降シリカ（Tixosil 365 SP）の１０重量％水性分散液を調製した。
Example 4: Two pigment compositions were prepared:
A: Anionic silica sol prepared by ion exchange method containing 10% by weight of SiO 2 and having a surface area of about 865 m 2 / g was converted into 14.2 g of a 2.5% by weight aqueous solution of modified carboxymethylcellulose (CMC). Was slowly aggregated into 100 g of silica sol under continuous stirring to obtain a highly viscous transparent solution. The modified CMC had a DS of 0.65 with respect to the carboxyl group and was further modified by incorporating a quaternary nitrogen group (DS 0.43) to obtain the cationic properties of the product. The average particle diameter of the aggregates in this dispersion was determined to be 0.7 μm using a Zetamaster. This dispersion was then vigorously mixed with 45 g of precipitated silica (Tixosil 365 SP, average particle size 3.4 μm, see Example 2) and 45 g of water.
B: A 10% by weight aqueous dispersion of precipitated silica (Tixosil 365 SP) was prepared.
約１０重量％の固形分及びポリビニルアルコールと固体顔料の重量比の０．２５：１を有する被覆配合物を、実施例２と同様に調製した。これらの被覆を、実施例３と同様に、紙に塗布し、乾燥した。印刷試験を、実施例２と同様に、２台のインクジェットプリンタ、Epson C84及びHP 5652で実施した。この域量を測定し、以下の結果を得た。 A coating formulation having a solids content of about 10% by weight and a weight ratio of polyvinyl alcohol to solid pigment of 0.25: 1 was prepared as in Example 2. These coatings were applied to paper and dried as in Example 3. The printing test was conducted with two inkjet printers, Epson C84 and HP 5652, as in Example 2. This area was measured and the following results were obtained.
顔料組成物Ａが組成物Ｂよりも良好な印刷品質を与えると思われる。 It appears that Pigment Composition A gives better print quality than Composition B.
Claims (14)
（ｂ）少なくとも１つの直径の平均サイズが、前記多孔質凝集体の平均直径よりも大きい増量剤粒子とを含み、
多孔質凝集体と増量剤粒子の重量比が、約０．０１：１〜約３：１である
水性分散液の形態の顔料組成物。 (A) a porous agglomerate formed by agglomeration of colloidal primary particles of silica, aluminosilicate or a mixture thereof in an aqueous sol and having an average diameter of about 0.03 to about 25 μm;
(B) extender particles having an average size of at least one diameter larger than the average diameter of the porous aggregate;
A pigment composition in the form of an aqueous dispersion wherein the weight ratio of porous aggregates to extender particles is from about 0.01: 1 to about 3: 1.
（ａ）シリカ、アルミノケイ酸塩又はこれらの混合物のコロイド一次粒子の水性ゾル中での凝集により形成され、かつ約０．０３〜約２５μmの平均直径を有する、多孔質凝集体の水性分散液と、
（ｂ）少なくとも一つの直径の平均サイズが、多孔質凝集体の平均直径よりも大きい増量剤粒子とを混合する工程を含み、
多孔質凝集体と増量剤粒子の重量比が、約０．０１：１〜約３：１である
方法。 It is a manufacturing method of the pigment composition as described in any one of Claims 1-6,
(A) an aqueous dispersion of porous aggregates formed by agglomeration of colloidal primary particles of silica, aluminosilicate or mixtures thereof in an aqueous sol and having an average diameter of about 0.03 to about 25 μm; ,
(B) mixing the extender particles with an average size of at least one diameter larger than the average diameter of the porous aggregate,
The method wherein the weight ratio of the porous aggregate to the extender particles is from about 0.01: 1 to about 3: 1.
（ａ）シリカ又はアルミノケイ酸塩の一次粒子と増量剤粒子との重量比が約０．０１：１〜約３：１である、シリカ又はアルミノケイ酸塩のコロイド一次粒子と増量剤粒子を含む水性ゾルを混合する工程、及び
（ｂ）シリカ又はアルミノケイ酸塩のコロイド一次粒子を凝集して、約０．０３μm〜約２５μmの平均直径を有するが、増量剤粒子の最大寸法の平均サイズを超えない多孔質凝集体を形成する工程
を含む方法。 It is a manufacturing method of the pigment composition as described in any one of Claims 1-6,
(A) an aqueous solution comprising silica or aluminosilicate colloidal primary particles and extender particles, wherein the weight ratio of silica or aluminosilicate primary particles to extender particles is from about 0.01: 1 to about 3: 1. Mixing the sol; and (b) aggregating the colloidal primary particles of silica or aluminosilicate to have an average diameter of about 0.03 μm to about 25 μm, but not exceeding the average size of the largest dimension of the extender particles. Forming a porous aggregate.
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| EP04105595 | 2004-11-08 | ||
| EP04105595.5 | 2004-11-08 | ||
| PCT/SE2005/001522 WO2006049545A1 (en) | 2004-11-08 | 2005-10-13 | Pigment composition in the form of aqueous dispersion |
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| Publication Number | Publication Date |
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| JP2008519177A true JP2008519177A (en) | 2008-06-05 |
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| JP2007540279A Expired - Fee Related JP4897694B2 (en) | 2004-11-08 | 2005-10-13 | Pigment composition in the form of an aqueous dispersion |
| JP2007540281A Pending JP2008519178A (en) | 2004-11-08 | 2005-10-13 | Method for producing coated paper |
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| JP2007540280A Expired - Fee Related JP5159312B2 (en) | 2004-11-08 | 2005-10-13 | Pigment composition in the form of an aqueous dispersion |
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| JP (3) | JP4897694B2 (en) |
| KR (3) | KR100855144B1 (en) |
| CN (3) | CN101056955B (en) |
| AR (3) | AR055816A1 (en) |
| AU (3) | AU2005301351B2 (en) |
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