JP5702590B2 - Composite particles, composite particle internal paper and coated paper - Google Patents

Description

  The present invention relates to composite particles containing calcium carbonate particles and titanium dioxide particles, composite particle-containing paper, and coated paper.

  In order to improve opacity, whiteness, printability, and the like, various fillers suitable for improving these functions are internally added to the paper. As the filler, titanium dioxide, calcium carbonate, kaolin, talc, hydrated silicic acid (white carbon), urea-formalin polymer fine particles and the like are used. Among these, titanium dioxide is effective in improving opacity because it has a high refractive index and excellent light scattering ability. However, the titanium dioxide particles are expensive, have a low oil absorption capacity, and have a disadvantage that the yield during papermaking is low due to the small particle diameter.

  Under such circumstances, various methods have been proposed to improve the yield of titanium dioxide particles as a filler. As this method, (1) a method of aggregating calcium carbonate particles and titanium oxide particles using a specific aggregating agent (cationic polymer, amphoteric polymer, acrylic acid monomer, etc.) to obtain agglomerated particles (Japanese Patent Application Laid-Open No. 2004-2005). 18336 and JP-A-6-93204) and (2) a carbonation reaction in which a carbon dioxide-containing gas is blown into an aqueous suspension of calcium hydroxide to generate calcium carbonate. A method of incorporating titanium dioxide particles into the surface layer of calcium carbonate particles in the process (see JP-A-2002-201592) can be mentioned.

  However, (1) According to the method using a specific flocculant, since the binding between the calcium carbonate particles and the titanium oxide particles by the flocculant is not strong, this aggregation state is not maintained during papermaking, etc. A sufficient yield improvement effect cannot be obtained, and as a result, the opacity of the resulting paper cannot be improved effectively. In addition, according to the method (2) using the carbonation reaction, although the two types of particles are combined with a certain degree of strength, the oil absorption of the obtained particles is not sufficient.

JP 2004-18336 A JP-A-6-93204 JP 2002-201592 A

  The present invention has been made based on the above-mentioned circumstances, and uses titanium dioxide particles, and composite particles having excellent yield, opacity improving ability and oil absorption, and using these composite particles and excellent An object of the present invention is to provide composite particle-added paper and coated paper having opacity and the like.

The invention made to solve the above problems is
It is a composite particle having an aggregate obtained by aggregating calcium carbonate particles and titanium dioxide particles with an aggregating agent, and silica covering at least a part of the surface of the aggregate.

  Since the composite particles have aggregates of calcium carbonate particles and titanium dioxide particles as nuclei, the composite particles have a relatively large particle size and can exhibit excellent yield and opacity improving ability. Furthermore, since the composite particles are at least partly coated with silica, the two types of particles are firmly fixed, and this agglomerated state can be maintained even in a process such as papermaking. Excellent yield. In addition, the composite particles can exhibit a high oil absorption due to the excellent oil absorption ability of the porous silica covering at least a part of the surface.

  The silica coverage is preferably 5% by mass or more and 30% by mass or less. According to the composite particles, by setting the silica coverage within the above range, the aggregation state of the two types of particles can be sufficiently maintained even during papermaking, and as a result, the yield can be further improved. In addition to being able to achieve this, it is possible to achieve both excellent white paper opacity and printing opacity due to the balance between silica and other particles.

  The calcium carbonate particles may be heavy calcium carbonate particles. Heavy calcium carbonate has a wide particle size distribution, is irregular, and has a number of knife edges on its surface. By using such heavy calcium carbonate particles, the composite particles, in the case of calcium carbonate particles having a small particle size, are in an aggregated state of a plurality of calcium carbonate particles and titanium dioxide particles. In the case of calcium particles, since titanium dioxide particles having a small particle diameter are aggregated on the surface, the particle size distribution is narrowed as a result, and the yield can be further improved. Furthermore, the composite particles have a porous shape due to precipitation on the surface of silica, and the oil absorption is high while using heavy calcium carbonate having a high particle density, and the opacity after printing can be increased.

  The average particle size is preferably 2 μm or more and 15 μm or less. When the composite particles have an average particle diameter in the above range, when used as a filler, the composite particles can exhibit better yield while suppressing a decrease in paper strength.

  The average particle diameter (primary particle diameter) of the calcium carbonate particles is preferably 0.5 μm or more and 3 μm or less, and the average particle diameter (primary particle diameter) of the titanium dioxide particles is preferably 0.2 μm or more and 1 μm or less. According to the composite particle, by using two types of particles having a particle size in the above range, a plurality of titanium dioxides having a small particle size so as to cover the surface with calcium carbonate particles having a relatively large particle size as a core. Since it is easy to form a state in which the particles are aggregated and the excellent light scattering ability of the titanium dioxide particles can be sufficiently exhibited, the opacity can be further increased.

  The composite particle internal paper of the present invention contains the above composite particles. According to the composite particle-added paper, since composite particles having the above performance are internally added, the yield of the composite particles as the filler is high, and the white paper opacity and the printing opacity can be increased.

  The coated paper of the present invention is a coated paper having a base paper and one or more coating layers formed on at least one surface of the base paper, wherein the coating layer is the composite particle. It is characterized by containing. Since the coated paper contains the composite particles as a pigment in the coating layer, the coated paper is excellent in blank paper opacity and the like.

Here, the average particle diameter refers to a volume average particle diameter in the measured particle size distribution by laser diffraction scattering method (D _50).

  As described above, according to the composite particles of the present invention, despite the use of titanium dioxide particles having a small particle diameter, the yield is improved during papermaking, and the ability to improve opacity and oil absorption are high. Can be demonstrated. Therefore, composite particle-added paper and coated paper using this composite particle can exhibit excellent opacity and the like.

  Hereinafter, embodiments of the composite particles, composite particle-added paper, and coated paper of the present invention will be described in detail.

<Composite particle>
The composite particle of the present invention is a composite particle having an aggregate obtained by aggregating calcium carbonate particles and titanium dioxide particles with an aggregating agent, and silica covering at least a part of the surface of the aggregate.

  Since the composite particles have aggregates of calcium carbonate particles and titanium dioxide particles as nuclei, the composite particles have a relatively large particle size and can exhibit excellent yield and opacity improving ability. Furthermore, since the composite particles are at least partly coated with silica, the two types of particles are firmly fixed, and this agglomerated state can be maintained even in a process such as papermaking. Excellent yield. In addition, the composite particles can exhibit a high oil absorption due to the excellent oil absorption ability of the porous silica covering at least a part of the surface.

  The average particle size of the composite particles is preferably 2 μm or more and 15 μm or less, and more preferably 4 μm or more and 10 μm or less. Since the composite particles have an average particle diameter in the above range, when used as a filler, the composite particles can exhibit better yield performance while suppressing a decrease in paper strength. Moreover, the uniform dispersibility, such as when contained in a coating liquid and used as a pigment, can be improved. Therefore, the opacity when used as a filler or pigment can be efficiently increased.

  When the average particle size of the composite particles is less than the above lower limit, the yield may not be sufficiently improved when used as a filler, and the opacity improving ability is not sufficient. On the other hand, when this average particle diameter exceeds the upper limit, when used as a filler, as a result of reducing the strength between the pulp fibers, the paper strength may be reduced, and because the particle size is large, slurry or coating Uniform dispersibility in the liquid may be reduced, and opacity and opacity after printing may be reduced.

  The content ratio (mass ratio) of the calcium carbonate particles and titanium dioxide particles is preferably 30:70 to 90:10, and more preferably 50:50 to 90:10. By setting the content ratio of both particles in such a range, the aggregate can be made into a state where titanium carbonate particles having a small particle diameter are efficiently aggregated on the surface with calcium carbonate particles as nuclei. Therefore, according to the composite particle, it is possible to exhibit a better yield by increasing the particle size as an aggregate while utilizing the excellent light scattering ability of the titanium dioxide particles.

<Calcium carbonate particles>
The calcium carbonate particles used for the composite particles preferably have an average particle size (primary particle size) of 0.5 μm to 3 μm, and more preferably 0.8 μm to 2.5 μm. By making the average particle diameter of the calcium carbonate particles in such a range, combined with the titanium dioxide particles and the coating with silica, the yield and opacity when the composite particles are used as a filler or pigment in papermaking, etc. The wire wear resistance can be improved.

  When the average particle size of the calcium carbonate particles is less than the above lower limit, the light scattering ability of the individual calcium carbonate particles is small and the opacity is difficult to improve. In addition, the particle size is small so that the flocculant can sufficiently agglomerate. Does not progress, and the yield during papermaking is difficult to improve. On the contrary, when the average particle diameter exceeds the above upper limit, it may be difficult to obtain an aggregate having a desired size at the time of agglomeration, and the wear property may be increased and the papermaking tool may be damaged. .

  The calcium carbonate particles may be either light calcium carbonate or heavy calcium carbonate, but it is preferable to use heavy calcium carbonate. Heavy calcium carbonate has a wide particle size distribution, is irregular, and has a number of knife edges on its surface. By using such heavy calcium carbonate particles, the composite particle agglomerates are in the aggregated state of a plurality of calcium carbonate particles and titanium dioxide particles in the case of calcium carbonate particles having a small particle size. In the case of calcium carbonate particles having a large particle size, titanium dioxide particles having a small particle size are aggregated on the surface, so that the particle size distribution is narrowed and the yield can be further improved. Further, the composite particles have a porous shape due to precipitation on the surface of silica, and have high oil absorption while using heavy calcium carbonate having a high particle density, and can increase opacity after printing.

  This heavy calcium carbonate can be prepared by a method of pulverizing and classifying natural limestone, and commercially available heavy calcium carbonate available as a powder can be pulverized and classified as necessary. . Examples of the pulverization here include pulverization using a dry pulverizer such as a roll mill, jet mill, dry ball mill, and impact pulverizer, wet pulverization such as a wet ball mill, a vibration mill, a stirring tank mill, a flow tube mill, and a coball mill. The pulverization by a mill can be mentioned, and these pulverizers can be used in appropriate combination.

  The classification method includes, for example, sieving such as resonant vibration sieve, low head screen, electromagnetic screen, etc., dry classification such as micron separator, cyclone, etc., wet classification such as decanter type centrifuge, liquid cyclone, drug classifier, etc. These classifiers can be used in appropriate combination.

<Titanium dioxide particles>
The titanium dioxide particles used for the composite particles preferably have an average particle size (primary particle size) of 0.2 μm or more and 1 μm or less, and more preferably 0.3 μm or more and 0.8 μm or less. The average particle diameter of the titanium dioxide particles relative to the average particle diameter of the calcium carbonate is preferably 0.1 to 0.5 times.

  By making the average particle diameter of the titanium dioxide particles in such a range, the composite particles have an appropriate size due to aggregation with the calcium carbonate particles described above, and the composite particles having excellent yield and opacity are efficiently obtained. Can be obtained. That is, according to the composite particles, preferably, by using two types of particles having a particle size in the above range, the calcium carbonate particles having a relatively large particle size are used as nuclei and the particle size is small so as to cover the surface. Since it is easy to form a state in which a plurality of titanium dioxide particles are aggregated, and the excellent light scattering ability of the titanium dioxide particles can be sufficiently exhibited, opacity can be further increased.

  The titanium dioxide particles are not particularly limited, and those known for papermaking can be used. As the crystal form of the titanium dioxide particles, any of anatase type, rutile type, brookite type and the like can be used, but it is preferable to use rutile type or anatase type.

<Flocculant>
The flocculant is not particularly limited as long as it can entangle and aggregate a plurality of particles with the polymer chain, and a polymer such as a cationic polymer, an anionic polymer, or a nonionic polymer. Although a compound can be used, according to the knowledge of the present inventors, a cationic polymer is used in order to cause aggregation using calcium carbonate particles as a core using a slurry containing calcium carbonate particles and titanium dioxide particles. It is preferable to use, and it is more preferable to use a cationic synthetic polymer. It is preferable to use a cationic polymer as the aggregating agent because not only the action of entanglement of the particles by the polymer chain but also each negatively charged particle can be electrically aggregated. Moreover, the cationic charge density and suitable molecular weight of this flocculant can be easily adjusted by using a cationic synthetic polymer.

  The lower limit of the mass average molecular weight of the flocculant is preferably 4 million, more preferably 6 million, and particularly preferably 7 million. On the other hand, the upper limit of the mass average molecular weight is preferably 20 million, more preferably 12 million, and particularly preferably 10 million. By setting the molecular weight of the flocculant within the above range, aggregation with calcium carbonate particles as nuclei can be effectively generated. In particular, for each particle having the average particle diameter as described above, an agglomerate having a desired particle diameter can be efficiently obtained by using an aggregating agent having a molecular weight in such a range. The mass average molecular weight is a numerical value measured using a gel permeation chromatography method (GPC method).

  When the mass average molecular weight of the flocculant is less than the above lower limit, sufficient aggregating ability cannot be exhibited, and the particles are not agglomerated, so that the yield may not be improved. Conversely, if this average molecular weight exceeds the above upper limit, the agglomeration ability is too strong, the occurrence of partial agglomeration, the viscosity of the slurry is increased, the paper workability is reduced, the paper strength of the resulting paper is It may decrease.

  Further, the upper limit of the cationic charge density of the flocculant is preferably 10 meq / g, more preferably 5 meq / g, and particularly preferably 3 meq / g. On the other hand, the lower limit of the cationic charge density is preferably 0.1 meq / g, more preferably 0.5 meq / g, and particularly preferably 1 meq / g. By setting the cation charge density of the flocculant within the above range, the above-described preferable aggregation property can be exhibited. In addition, when using a some component as an aggregating agent, the cation charge density as the whole aggregating agent is said.

The cationic charge density is a value measured by the following method. After adjusting the sample to an aqueous solution of pH 4.0, the anion demand was measured by titration using a 1/1000 normal aqueous potassium potassium sulfate solution with a particle charge measuring device (Muteck PCD-03) based on the streaming potential method. To do. The cationic charge density per 1 g of sample is calculated by the following formula (1).
Cationic charge density = A / B (1)
A: Anion requirement (μeq / L) of the flocculant aqueous solution adjusted to pH 4.0
B: Solid content concentration (g / L) of flocculant aqueous solution

  When the cationic charge density of the flocculant exceeds the above upper limit, the entire surface of each particle has a cationic charge, and aggregation may not easily occur due to repulsion due to the charge. Conversely, when the cation charge density of the flocculant is less than the above lower limit, the effect of being able to electrically agglomerate negatively charged particles cannot be sufficiently exhibited, resulting in a broad particle size distribution. There is a case.

  Cationic synthetic polymers that can be suitably used as flocculants include homopolymers of (meth) acrylate-based cationic monomers or copolymers with nonionic monomers, and Mannich modification of polyacrylamide. Products, poly (dimethyldiallylammonium chloride), dialkylamine-epichlorohydrin condensate, alkylene dichloride-polyalkylene polyamine condensate, polyethyleneimine, dicyandiamide-formalin condensate, polyvinylamidine, chitosan, polyalkylene polyamine, etc. These can be used alone or in combination of two or more.

<Silica>
The silica for covering the aggregate of the calcium carbonate particles and the titanium dioxide particles is not particularly limited, and known ones can be used. As will be described later, by depositing and coating silica in an aqueous solution, it is possible to efficiently coat the aggregate and to exhibit a superior oil absorption ability because it can be coated in a porous state. Can do.

  The silica coverage is preferably 5% by mass or more and 30% by mass or less, and more preferably 10% by mass or more and 25% by mass or less. By making the silica coverage in such a range, it is possible to sufficiently maintain the aggregation state of the two types of particles even during papermaking, and as a result, in addition to being able to further increase the yield, silica and It is possible to achieve both excellent white paper opacity and printing opacity due to the balance with other particles. This silica coverage can be calculated from the content of the silica component after silica coating by conducting elemental analysis of the particles, estimating the content ratio of clay, calcium carbonate, talc and the like from the constituent components contained. The silica coverage refers to the ratio of the mass of silica to the total mass of the composite particles.

  If the silica coverage is less than the above lower limit, this silica may not function sufficiently as a binder for the two types of particles, and aggregates may break during papermaking, and yield and blank paper opacity may not be sufficiently improved. . Moreover, the sufficient oil absorption improvement effect by silica is not exhibited, and the printing opacity may not be improved. On the other hand, when the silica coverage exceeds the above upper limit, the silica coating amount becomes too large, so that the light scattering function of the titanium dioxide particles is not sufficiently exhibited, and the blank paper opacity may be lowered.

<Application, quality, etc.>
The composite particles are suitably used alone or mixed with ordinary pigments such as calcium carbonate, kaolin clay, talc, titanium dioxide, satin white, and plastic pigment as an internal filler or coating pigment in papermaking. be able to.

  When the composite particles are used as an internal additive or a coating pigment, for example, the composite particles are preferably contained in an amount of 5 to 100% by mass with respect to the total amount of the normal internal additive or coating pigment. Can be used by adding 10 to 100% by mass.

  In the case of using heavy calcium carbonate particles that have been subjected to mineral-derived wet pulverization, the composite particles have a wide particle size distribution, but the agglomeration of fine particles and the silica sol to heavy calcium carbonate having a relatively large particle size. Due to the coating, the hardness of the particles is relatively low and the particle size distribution width is narrow. Therefore, when the composite particles are used as a filler or pigment for papermaking, it is possible to avoid wear troubles such as a paper machine or a coating machine. In addition, the composite particles preferably have a high specific surface area because the surface of the aggregate of heavy calcium carbonate particles and titanium dioxide particles with high density is originally coated with silica, and this is used as a filler for internal addition. When used as a coating pigment, paper with high whiteness and opacity and high filler yield can also be obtained.

  The oil absorption of the composite particles is preferably 30 mL / 100 g or more and 100 mL / 100 g or less, more preferably 40 mL / 100 g or more and 80 mL / 100 g or less. When composite particles having such an oil absorption are used as an internal filler, the composite particles absorb ink vehicle or organic solvent impregnated in the paper layer in the paper layer, and the printing opacity of the paper is reduced. By suppressing the reduction and absorbing the ink vehicle, the organic solvent, and the like, the ink drying property and the effect of preventing blurring can be remarkably exhibited. When the oil absorption is less than 30 mL / 100 g, the above effect is not sufficient, and the composite particles may tend to inhibit the ink absorption and drying properties. On the other hand, if the oil absorption exceeds 100 mL / 100 g, there is a case where the ink sinks and the so-called color developability is inferior due to high ink absorbability.

  The composite particles can be used as fillers for rubber, plastics, paints, inks, etc. in addition to papermaking. By using the composite particle as a filler, high whiteness and concealment can be imparted.

<Method for producing composite particles>
Although it does not specifically limit as the manufacturing method of the said composite particle, For example,
(1) A method comprising an aggregation step of aggregating calcium carbonate particles and titanium dioxide particles with an aggregating agent to obtain an aggregate, and (2) a silica coating step of covering at least a part of the aggregate surface with silica. be able to. Hereinafter, each step will be described in detail.

<(1) Aggregation step>
This aggregating step can be performed, for example, by adding an aggregating agent to a particle slurry in which calcium carbonate particles and titanium dioxide particles are dispersed in water. The two particles may be dispersed in water by dispersing the two kinds of particles in water at the same time, or by dispersing titanium dioxide particles in a calcium carbonate particle slurry in which calcium carbonate particles are dispersed in water. The reverse may be possible.

  The solid content concentration of both particles (total of calcium carbonate particles and titanium dioxide particles) in the particle slurry is preferably 5% by mass to 40% by mass, more preferably 10% by mass to 35% by mass, and further preferably 15% by mass. The content is particularly preferably 25% by mass or less. By making the concentration of the particle slurry in the above range, the efficiency of particle aggregation can be improved.

  When the concentration of the particle slurry is less than the lower limit, the particles may not aggregate to a suitable particle size even by the addition of a flocculant. On the other hand, when the concentration of the particle slurry exceeds the above upper limit, the viscosity is too high and workability may be deteriorated, or the particle size distribution of the composite particles may be widened to reduce the yield.

  Moreover, as the addition amount of the flocculant, the total solid content of the calcium carbonate particles and the titanium dioxide particles is preferably 200 ppm or more and 3000 ppm or less, more preferably 1,000 ppm or more and 2500 ppm or less in terms of solid content, In the broad particle size distribution of heavy calcium carbonate particles, for example, in the range of 1,500 ppm to 2,000 ppm, the aggregation of particles having a small particle size proceeds, while the particle having an originally large particle size is less likely to proceed with aggregation. This is particularly preferable because it is effective.

  When the addition amount of the flocculant is less than the above lower limit, sufficient aggregation cannot be exhibited, and the yield improvement effect may not be exhibited. On the contrary, if the addition amount of the flocculant exceeds the above upper limit, the viscosity of the slurry may be significantly increased, or tertiary and quaternary aggregation may occur, and the paper strength of the obtained paper may be reduced.

  According to the knowledge of the inventors, the viscosity of the preferred aggregate slurry largely changes at the boundary of 500 cps. When the viscosity exceeds 500 cps, the workability is deteriorated and the inconvenience that the stain in the papermaking system becomes obvious arises. . Particularly preferably, by adjusting to 450 cps or less, and further to 350 cps or less, the workability can be improved and the particle size distribution of the resulting composite particles can be made sharper.

<(2) Silica coating step>
In this silica coating step, silica is coated on the surface of the aggregate obtained in the above step. As a method for coating this silica, an alkali silicate aqueous solution and a mineral acid are added to the aggregate slurry in this order, and the surface of the aggregate is coated with silica, or the aggregate slurry is added to the alkali silicate aqueous solution and mixed. Then, a method of adding a mineral acid to coat silica can be exemplified.

  Although the said alkali silicate aqueous solution is not specifically limited, A sodium silicate solution (No. 3 water glass) is desirable at the point which is easy to acquire. The concentration of the alkali silicate solution is preferably 3 to 10% by mass in terms of the silicic acid content in the aqueous solution (in terms of SiO2). The composite particles in which the aggregate formed when silica exceeds 10% by mass is coated with white carbon, not silica-coated composite particles, and is formed of calcium carbonate and titanium dioxide forming a core (aggregate). There is a risk that the optical characteristics may not be exhibited at all. On the other hand, if it is less than 3% by mass, the silica component in the resulting composite particles may be lowered.

  Examples of the mineral acid include diluted solutions of mineral acids such as dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid, etc., but it is price, handling, calcium elution in calcium carbonate, and measures against corrosion of equipment and equipment. For this reason, dilute sulfuric acid is most preferable. Further, the concentration when adding dilute sulfuric acid is preferably 0.2 to 4.0 molar. Moreover, since silica precipitates in a short time, so that there is much mineral acid addition amount, it is preferable to adjust an addition rate according to those conditions. In addition, there is a possibility that the addition within 5 minutes may result in an insufficient uniform reaction system configuration.

  The reaction temperature in this step is preferably in the range of 60 to 100 ° C. As a result of the diligent investigations by the present inventors, the reaction temperature between the aggregate of calcium carbonate particles and titanium dioxide particles used in the present invention and silica depends on the formation of silica, the crystal growth rate, and the dynamics of the formed silica-coated composite particles. Affects the strength of the machine. If the reaction temperature is less than 60 ° C, the silica formation / growth rate is slow, the coverage of the formed silica-coated composite particles is inferior, the coating is easily peeled off, and the coating breaks due to the shearing force applied when making the filler-added paper. Cheap. Moreover, when it exceeds 100 degreeC, since it is a water-system reaction, since an autoclave must be used, a reaction process will become complicated.

  In addition, the reaction holding time (mineral acid addition time) in this step is preferably 20 minutes or longer and 3 hours or shorter, and more preferably 30 minutes or longer and 2 hours or shorter. When the reaction holding time is less than the above lower limit, sufficient silica coating may not be performed. On the other hand, when the reaction holding time exceeds the above upper limit, the silica coating amount is too large, and the particle size of the composite particles becomes too large. As a result, the paper strength and opacity may be lowered.

  In addition, when silica coating of aggregates of calcium carbonate particles and titanium dioxide particles is performed, for example, the aggregates are added to and dispersed in an alkali silicate aqueous solution to prepare a slurry. The slurry concentration is preferably 3 to 35% by mass. . By adjusting the slurry concentration, the particle size of the silica-coated composite particles to be formed can be controlled, and at the same time, the composition ratio of the aggregate and silica can be determined.

  As a preferable silica coating step, an aggregate of both particles is added and dispersed in an aqueous alkali silicate solution to prepare an aggregate slurry. Thereafter, while stirring the slurry, the liquid temperature is maintained in the range of 60 to 100 ° C., and a mineral acid is added to form a silica sol. Silica-coated composite particles can be obtained by adjusting the pH of the mixed solution (mixed solution of agglomerates, alkali silicate and mineral acid) to neutral to weakly alkaline, and preferably the mixed solution to a pH of 8 to 11. .

<Composite particle paper>
The composite particle internal paper of the present invention is one in which the composite particles are internally added. According to the composite particle internal paper, since the composite particles are internally added, the yield of the composite particles as the filler is high, and the white paper opacity and the printing opacity can be increased.

  The method for producing a composite particle-added paper using the composite particles of the present invention as an internal filler is the same as the method for producing an ordinary filler-added paper. For example, the composite particles and, if necessary, other fillers and It is obtained by adding a slurry mixed with a pulp raw material slurry and making a paper slurry containing additives such as a paper strength enhancer, a sizing agent, and a yield improver, if necessary, and papermaking. The filler addition rate with respect to the pulp raw material (solid content) is 1 to 50% by mass, preferably 3 to 30% by mass.

  As additives to be added to the pulp raw material slurry, known ones can be used. For example, starch, vegetable gum, aqueous cellulose derivative, polyacrylamide and the like are used as a paper strength enhancer, and rosin, starch, CMC (carboxyl methyl cellulose), polyvinyl alcohol, alkyl ketene dimer, ASA (alkenyl succinic anhydride), neutral rosin, etc., and yield improvers include polyacrylamide and copolymers thereof, quaternary ammonium salts, etc. be able to. You may add coloring materials, such as dye and a pigment, to a data slurry further as needed.

By making the paper stock slurry with a known paper machine, composite particle-containing paper can be produced. The basis weight of the composite paper-added paper is not particularly limited, but is usually about 10 to 300 g / m ² .

<Coated paper>
The coated paper of the present invention is a coated paper having a base paper and one or more coating layers formed on at least one surface of the base paper, wherein the coating layer is the composite It is characterized by containing particles. According to the coated paper, since the composite particles are used as a pigment in the coating layer, the white paper opacity is excellent.

  The method for producing coated paper using the composite particles of the present invention is the same as the method for producing ordinary coated paper. For example, the composite particles of the present invention are mixed with other pigments as necessary, and a dispersing agent is used. It is obtained by mixing the slurry obtained by adding an adhesive and other additives to prepare a coating material, and coating the slurry on a paper material such as medium-quality paper or high-quality paper.

  Also when manufacturing coated paper using the said composite particle, the range of 30-100 mL / 100g of the oil absorption degree of the said composite particle is preferable. This is because when mixed with an adhesive, the composite particles absorb the adhesive in the coating solution, and the true density is reduced, so that sedimentation is suppressed, and the composite particles are biased in the coating layer. This is because the effect of being uniformly dispersed in the coating layer appears remarkably. When the oil absorption is 30 mL / 100 g or less, the above effect is insufficient, and the composite particles settle out due to the difference between the true specific gravity of the composite particles and the specific gravity of the coating liquid, and are not uniform in the coating layer. Since it will be in a dispersed state, it is not preferable. Conversely, when the oil absorption exceeds 100 mL / 100 g, when blended as a coating pigment in the coating layer, binders such as latex and starch are absorbed, resulting in a disadvantage that the coating layer strength decreases.

  In addition, when heavy calcium carbonate is used as calcium carbonate, the surface of heavy calcium carbonate is coated with titanium dioxide particles and silica, so the shape of heavy calcium carbonate having an angular shape is rounded, Wear of blades, coating rolls, equipment for discharging coating liquid, and the like due to heavy calcium carbonate can be reduced. Furthermore, even when recycled as waste paper or waste paper, it is possible to reduce wear of wires and equipment due to inorganic particles remaining in the obtained recycled pulp.

  As the adhesive contained in the coating liquid, known ones can be used, for example, conjugated diene copolymer latex such as styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, acrylic acid ester, and the like. // Acrylic polymer latex such as a polymer or copolymer of methacrylic acid ester, vinyl polymer latex such as ethylene-vinyl acetate copolymer, or a functional group such as a carboxyl group containing these various polymer latexes An alkali partially soluble or alkali insoluble polymer latex modified with a monomer is used.

  In addition to the above synthetic adhesives, for example, cationized starch, oxidized starch, oxygen-modified starch, thermochemically modified starch, etherified starch, esterified starch, starch such as cold water soluble starch, carboxymethylcellulose, hydroxy Celluloses such as methylcellulose, water-soluble synthetic adhesives such as polyvinyl alcohol and olefin-maleic anhydride resin can be appropriately selected and used in combination. Moreover, various additives, such as an antifoamer, a water resistance agent, a fluidity modifier, a coloring agent, and a fluorescent brightening agent, are added to the pigment slurry and paint as necessary. Examples of the dispersant include sodium hexametaphosphate and sodium polyacrylate.

As a coating method of the coating liquid, it can be performed by a known coating machine (coater) such as an air knife, a blade, a gate roll, a rod, a bar, a cast, a gravure, or a curtain depending on the coating amount. The coating amount is usually about several to several tens g / m ^{2 in} terms of dry mass per side.

  The coated paper obtained after drying is generally subjected to pressure finishing by passing it through a calendar for the purpose of imparting printability (for example, high smoothness and high gloss). As the calendar device in this case, for example, various calenders such as a super calender, a gloss calender, a soft compact calender, or a combination of a drum and an elastic roll can be used as appropriate in an on-machine or off-machine specification.

  EXAMPLES Hereinafter, although a synthesis example and an Example demonstrate this invention further in detail, this invention is not limited to these Examples.

  In addition, each measured value in a present Example is a value measured with the following method.

[Average particle size (μm)]
A volume average particle diameter (μm) was measured using a laser diffraction particle size distribution measuring device [Microtrack / Nikkiso Co., Ltd.] (model number: MT-3300). In the preparation of the measurement sample, particles were added to a 0.1% sodium hexametaphosphate aqueous solution and dispersed with an ultrasonic wave for 1 minute.

[Silica coverage (mass%)]
Using an X-ray microanalyzer manufactured by HORIBA, the elemental analysis is performed at an acceleration voltage (15 KV), the content ratio of clay, calcium carbonate, talc, etc. is estimated from the contained components, and the silica component after silica coating is contained From the rate, the silica coverage (mass%) was calculated.

[Oil absorption (mL / 100g)]
It measured according to the kneading method described in JIS-K5101. That is, 2 g to 5 g of a sample dried at 105 ° C. to 110 ° C. for 2 hours is taken on a glass plate, and refined linseed oil (having an acid value of 4 or less) is dropped from the burette to the center of the sample little by little and kneaded with a spatula each time. The kneading operation was repeated, and the dripping amount of refined linseed oil was determined with the end point when the whole was first assembled into one rod shape, and the oil absorption was calculated by the following formula (2).
Oil absorption (mL / 100g)
= [Look of Linseed Oil (mL) x 100] / Paper (g) (2)

[Basis weight (g / m ² )]
It measured based on "Paper and board-Basis weight measuring method" described in JIS-P8142.

[Ash yield (%)]
The calculation was performed by dividing the ash content (measured in accordance with JIS-P8251) of the composite particle-added paper obtained by hand-drawing with the ash content in the paper material used for hand-drawing.

[Blank Opacity (%)]
It measured based on the method of JIS-P8149.

[Opacity after printing (%)]
J. et al. In accordance with TAPPI 45, newspaper offset printing ink (black) was used, and solid printing was performed by changing the amount of ink with an RI printing tester (manufactured by Meisei Seisakusho). From the ratio of the back surface reflectance after printing to the back surface reflectance before printing (opposite side of the printing surface) when the printing surface reflectance is 9%, the printing opacity (Y) is calculated using the following formula (3). did. In addition, the spectral whiteness meter (made by Suga Test Instruments) was used for the reflectance measurement.
Y = {(back surface reflectance after printing) / (unprinted back surface reflectance)} × 100 (3)

<Example 1>
50 parts by mass of calcium carbonate particles (heavy calcium carbonate) having an average particle size of 2.2 μm and 50 parts by mass of titanium dioxide particles having an average particle size of 0.5 μm are dispersed in water, and 17.4% by mass (solid content concentration) ) Particle slurry was obtained. To this particle slurry, 1,750 ppm of a flocculant (“Himoloc FR-740” manufactured by Hymo Co., Ltd.) was added to obtain an aggregate slurry.

  The aggregate slurry is adjusted to a solid content concentration of 10%, 60 g of sodium silicate aqueous solution (5% by mass) is added to 200 g of the slurry, and dispersion treatment is performed for 20 minutes at 3,000 rpm using a homomixer. A slurry containing sodium silicate was prepared. Next, this slurry was put into a 1 L four-necked flask equipped with a stirrer, a temperature sensor, and a reflux condenser, and heated to 85 ° C. in an oil bath while stirring. Next, while maintaining the slurry in the container at 85 ° C., 150 mL of 1N sulfuric acid was dropped over 100 minutes at a dropping rate of 2.5 mL / min using a metering pump, and the composite particles 1 coated with silica were separated. A composite particle slurry containing was obtained.

  The obtained composite particles 1 had a silica coverage of 20% by mass, an average particle size of 5.2 μm, and an oil absorption of 83 mL / 100 g.

<Examples 2-16 and Comparative Examples 1-3>
Examples 2 to 16 and Comparative Examples 1 to 1 were the same as Example 1 except that the calcium carbonate particles, titanium dioxide particles, the compounding ratio (mass ratio) thereof, and the reaction conditions in silica coating described in Table 1 were used. 3, composite particles 1 to 16 and i to iii were obtained. In Comparative Example 1, only calcium carbonate particles were aggregated and then coated with silica. In Comparative Example 2, only titanium dioxide particles were aggregated and then coated with silica. In Comparative Example 3, calcium carbonate particles and carbon dioxide were aggregated. The titanium particles were agglomerated and silica coating was not performed.

  Table 1 shows the silica coverage, average particle diameter, and oil absorption of each composite particle obtained.

<Example 17>
Using the obtained composite particles 1, a slurry having a solid content concentration of 10% was prepared. A pulp slurry containing 10 parts by mass of NBKP (freeness = CSF 520 mL) and 90 parts by mass of LBKP (freeness = CSF 480 mL) was mixed with 15 parts by mass of the slurry, 0.5 parts by mass of sulfuric acid band, 0. 7 parts by mass, 1.0 part by mass of a neutral rosin sizing agent, and 0.1 part by mass of a yield improver were added to prepare a paper material having a solid content concentration of 0.9% by mass. The paper stock was hand-made, and a pulp sheet was prepared with a paper machine. After drying, the pulp sheet was passed through a lab super calender to obtain a composite particle-containing paper of Example 17 having a rice basis weight of 64.9 g / m ² .

<Examples 18 to 32 and Comparative Examples 4 to 6>
Except that the composite particles used were those shown in Table 2, the same operation as in Example 17 was performed to obtain each composite particle-added paper of Examples 18 to 32 and Comparative Examples 4 to 6.

  Table 2 shows the basis weight, ash yield, opacity, and post-print opacity of the resulting composite particle-containing paper.

<Example 33>
As pigments, 20 parts by mass of composite particles 1, 40 parts by mass of calcium carbonate particles (Hydrocurve # 90: Omiya) and 20 parts by mass of kaolin (HF-90: Huber), SBR latex (PA4098: Japan A & L) 11 Part by weight, 2 parts by weight of starch (star coat: Nippon Food Processing Co., Ltd.) and 0.3 parts by weight of a dispersant (Aron A-6028: Toa Gosei Chemical Industry) are mixed in water, slurried with a Coreless mixer, and a solid content of 50 A mass% coating solution was prepared.

The coating liquid was coated by a roll test coater each side as one side of fine base paper having a basis weight of 41.5 g / m ² a dry weight 6.8 g / m ^2, then dried and further testing supercalendered ( A linear pressure of 160 kg / cm × 2 passes through) to obtain a coated paper.

<Examples 34 to 48 and Comparative Examples 7 to 9>
Each composite particle shown in Table 3 was used in place of the composite particle 1, and the same operation as in Example 33 was performed except that the coating amount in Table 3 was used, and Examples 34 to 48 and Comparative Examples 7 to 9 Each coated paper was obtained.

  Table 3 shows the blank opacity of each coated paper obtained.

  From the results shown in Tables 2 and 3, the composite particle internal paper to which the composite particles of the present invention are internally added and the coated paper coated with the composite particles of the present invention have excellent blank paper opacity and post-print opacity. You can see that

  The composite particles of the present invention can be suitably used as an internal filler in papermaking or a pigment in a coating solution.

Claims (7)

A composite particle comprising calcium carbonate particles as a core, and aggregates formed by aggregating titanium dioxide particles with a flocculant on the surface of the calcium carbonate particles , and silica covering at least a part of the surface of the aggregates. The composite particle according to claim 1, wherein the flocculant is a polymer compound having a mass average molecular weight of 4 million to 20 million. A composite particle-added paper in which the composite particle according to claim 1 or 2 is internally added. A coated paper having a base paper and one or more coating layers formed on at least one surface of the base paper,
A coated paper, wherein the coated layer contains the composite particles according to claim 1 or 2 . A step of obtaining an agglomerate in which titanium carbonate particles are agglomerated with a flocculant on the surface of the calcium carbonate particles with the calcium carbonate particles as a core; and
The step of coating silica on at least a part of the surface of the aggregate
A method for producing composite particles having the above in this order. The average particle diameter of the calcium carbonate particles is 0.8 μm or more and 3 μm or less,
  The method for producing composite particles according to claim 5, wherein the titanium dioxide particles have an average particle size of 0.2 μm or more and 0.8 μm or less. The method for producing composite particles according to claim 5 or 6, wherein the flocculant is a polymer compound having a mass average molecular weight of 4 million to 20 million.