WO2021187551A1 - 水性塗料組成物 - Google Patents

水性塗料組成物 Download PDF

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WO2021187551A1
WO2021187551A1 PCT/JP2021/011013 JP2021011013W WO2021187551A1 WO 2021187551 A1 WO2021187551 A1 WO 2021187551A1 JP 2021011013 W JP2021011013 W JP 2021011013W WO 2021187551 A1 WO2021187551 A1 WO 2021187551A1
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water
coating composition
cellulose
cellulose nanofibers
based coating
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PCT/JP2021/011013
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English (en)
French (fr)
Japanese (ja)
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中村　健治
俊博 岩井
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愛媛県
大王製紙株式会社
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Priority to JP2022508427A priority Critical patent/JPWO2021187551A1/ja
Publication of WO2021187551A1 publication Critical patent/WO2021187551A1/ja

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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
    • C09D11/00—Inks

Definitions

  • the present invention relates to a water-based coating composition.
  • This water-based paint composition contains a colored base material such as a pigment, and if the water-based paint composition poured into a dairy pot is left unattended, the colored base material precipitates in the water-based paint composition due to gravity. However, it separates into the phase of the colored base material and the aqueous phase. Color unevenness and coating unevenness may occur when drawing with the separated water-based coating composition. In order to prevent these, for example, an operation of sufficiently stirring the aqueous coating composition with a pestle to make it uniform is added at an appropriate frequency.
  • Patent Document 1 is a technique for adding a thickener.
  • a thickener rheology control agent
  • a thickener that exerts an effect in a small amount is included in the aqueous coating composition to ensure a desired viscosity.
  • the water-based paint composition does not spread well and is difficult to draw.
  • One method is to dilute the aqueous coating composition with water or an organic solvent in order to improve the elongation, but since the concentration of the thickener decreases and the viscosity decreases, the diluted aqueous coating composition is used.
  • the paint composition will separate over time.
  • an object to be solved by the present invention is to provide a water-based coating composition in which the colored base material does not easily settle even after a long period of time.
  • the inventor has conducted extensive research and focused on the fact that cellulose nanofibers esterified with phosphorus oxo acid have extremely high dispersibility and the property that the dispersed state lasts for a long time. It was found that by containing this cellulose nanofiber in the water-based coating composition, the state in which the colored base material was dispersed for a long time was maintained. The following shows how the problem was solved based on this finding.
  • (First aspect) Contains a colored substrate and cellulose nanofibers modified with an ester group of phosphoric acid, When the solid content concentration of the liquid level portion immediately after adjusting to the polybin is 100, the solid content concentration of the liquid level portion after preparing the polybin and allowing it to stand for 24 hours is 90 or more.
  • a water-based coating composition characterized by this.
  • Cellulose nanofibers modified with an ester group of phosphorus oxo acid have an excellent viscosity, and therefore do not settle and maintain a dispersed state.
  • the colored base material adheres to the cellulose nanofibers or stays in the gaps formed between the cellulose nanofibers to maintain a dispersed state. Therefore, in the water-based coating composition of this embodiment, the state in which the colored base material does not settle for a long time is maintained.
  • the cellulose nanofibers are contained in an amount of 2 to 4% by mass.
  • the cellulose nanofibers have cellulose nanofibers obtained by defibrating chemical pulp.
  • the cellulose nanofiber obtained by defibrating the chemical pulp is a cellulose nanofiber in which a part of the hydroxy group of the cellulose fiber is replaced with a functional group represented by the following structural formula (1) and an ester of phosphoroxo acid is introduced.
  • Has (A) The water-based coating composition of the first aspect.
  • a, b, m, and n are natural numbers. At least one of A1, A2, ..., An and A'is O, and the rest is one of R, OR, NHR, and none.
  • R is a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched chain hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched chain hydrocarbon group. , Aromatic groups, and any of these inducing groups.
  • ⁇ is a cation composed of an organic substance or an inorganic substance.
  • Cellulose nanofibers can be obtained, for example, by defibrating mechanical pulp or chemical pulp. Among them, the inventor has found that chemical pulp has a low lignin content and a relatively high purity, so that it is easy to defibrate. When the purity is high, the dispersion of the fiber diameter and the fiber length is small when the fiber is defibrated, that is, the cellulose nanofiber has a small variation in the fiber diameter and the fiber length. Cellulose nanofibers having a small variation in fiber diameter and fiber length are excellent in dispersibility in the water-based coating composition, so that the water-based coating composition has good fixability, is hard to drip, and has good elongation. Further, since the cellulose nanofiber (A) has a relatively high viscosity, the dispersed state is maintained and it is difficult to settle. Therefore, the colored base material is also maintained in a stably dispersed state without settling for a long time.
  • the cellulose nanofibers of this embodiment include those introduced with an ester of phosphoroxo acid and those introduced with carbamate.
  • the interaction between the phosphoxoic acid ester and the carbamate increases the shear force of the aqueous coating composition and improves the viscosity.
  • the high viscosity makes it difficult for the cellulose nanofibers dispersed in the aqueous coating composition to settle, and excellent dispersibility is maintained for a long time.
  • the cellulose nanofiber (A) is obtained by substituting two or more of the hydroxy groups of the cellulose fiber with the functional group represented by the structural formula (1) and introducing an ester of phosphorus oxo acid.
  • the water-based coating composition of the second aspect is obtained by substituting two or more of the hydroxy groups of the cellulose fiber with the functional group represented by the structural formula (1) and introducing an ester of phosphorus oxo acid.
  • the ester group of phosphorus oxo acid has polarity, it is presumed that hydrogen bonds easily occur. In the hydrogen-bonded state, the cellulose nanofibers are suppressed from free movement and difficult to settle. In this embodiment, since the ester of phosphoroxo acid is introduced at two or more places, there are relatively many sites where hydrogen bonds occur, and the free movement of the cellulose nanofibers is further suppressed.
  • the ratio (D50 / D90) of the cumulative 50% diameter (D50) to the cumulative 90% diameter (D90) on a volume basis is 0.50 to 1.
  • the water-based coating composition of the first aspect is 0.50 to 1.
  • the present invention is a water-based coating composition in which the colored base material does not easily settle even after a long time.
  • the embodiment of the present invention is an example of the present invention.
  • the scope of the present invention is not limited to the scope of the present embodiment.
  • the aqueous coating composition of the present embodiment has a colored base material and cellulose nanofibers, and the cellulose nanofibers have cellulose nanofibers (A) into which an ester of phosphoroxo acid is introduced, and is measured by a laser diffraction method. It has a single peak in the pseudo-cellulose distribution curve.
  • the colored base material is a substance that colors a pottery base, and exhibits various colors depending on the type of the base material.
  • overpainting and underpainting as a method of painting the pottery base with the water-based paint composition.
  • the underpainting is performed before glazing, and can be performed by the following method as an example.
  • a pattern is drawn on the unglazed pottery base with a water-based paint composition containing a colored base material, and then glaze is applied and fired.
  • the sketching may be performed a plurality of times, but if the secondary firing is not performed, the manufacturing cost is low and the labor is not required.
  • Colored substrates such as some pigments react with the glaze, such as by dissolving in the glaze. This reaction can cause the drawing to blur or blur.
  • the above reaction can be suppressed and bleeding and blurring can be avoided.
  • the drawing may be intentionally blurred or blurred.
  • Overpainting can be done by the following method as an example.
  • a glaze is applied to the unglazed pottery base and fired at a high temperature to form a glaze layer.
  • the pottery base on which this glaze layer is formed is called a glaze layer molded body.
  • a pattern is drawn on the surface of this glaze molded product using a water-based paint composition with a brush or the like.
  • the drawn pottery base is fired at a low temperature.
  • a coloring pigment As the color of this pigment, various colors such as red, blue, yellow, other colors, and gold can be used.
  • the coloring substrate includes silica, alumina, a silica-alumina composite in which a metal oxide is dissolved in a solid solution, or a composite compound of these in a solid solution.
  • the metal oxide is not particularly limited, and examples thereof include cobalt oxide, iron oxide, copper oxide, manganese oxide, chromium oxide, nickel oxide, and tin oxide.
  • the colored substrate includes zirconium, silicon, praseodymium, vanadium, titanium, antimony, zinc, manganese, cobalt, nickel, aluminum, copper, lead, cadmium or a compound thereof, chromium or a compound thereof (for example, oxide of. Chromium, viridian, cobalt turquoise) can be exemplified.
  • the colored base material can include a ceramic pigment.
  • Ceramic pigments have excellent heat resistance, weather resistance, and chemical resistance, and some are mainly composed of oxides, composite oxides, silicates, and the like. However, it is not limited to these. Ceramic pigments include spinel-based solid solutions, antimonth tin gray, zircon gray, placeozim yellow, vanadium tin yellow (Sn-V series and Sn-Ti-V series, etc.), vanadium zirconium yellow, peacock, Victoria green, and chromium.
  • Green (Al-Cr series), navy blue, azure, Co-Zn-Si series, Co-Si series, vanadium zircon blue, chrome tin lilac, lilac, chrome tin pink, pottery red, salmon pink, chrome alumina pink, fire Red can be exemplified.
  • the average particle size of the colored substrate according to this embodiment is, for example, 1 ⁇ m to 20 ⁇ m, preferably 5 ⁇ m to 10 ⁇ m. If it exceeds 20 ⁇ m, unevenness due to the colored base material may occur in the drawing portion when the water-based coating composition is thinly applied, and the apparent color tone may not be uniform. Further, if it is less than 1 ⁇ m, the dispersibility of the colored base material in the water-based coating composition may be insufficient, which causes uneven coating. Further, in order for the colored base material to be appropriately dispersed in the aqueous coating composition via the cellulose nanofibers, the particle size distribution of the colored base material and the pseudo particle size distribution of the cellulose nanofibers are close to each other. Better. If it exceeds or falls below the range of 1 ⁇ m to 20 ⁇ m, the deviation from the diameter of the cellulose nanofibers becomes large, the dispersibility becomes poor, and the water-based coating composition easily separates into two phases.
  • the main component of the surface of the pottery base is silicic acid or a silicic acid compound (for example, glass or other solid solution)
  • the above-mentioned production of the glaze layer molded body is omitted, and a brush or the like is applied to the pottery base.
  • the pattern may be drawn using the water-based paint composition in. In this case, the pottery base after being drawn is fired at a low temperature.
  • Cellulose nanofibers have a role of increasing the hydrogen bond points of the cellulose fibers and thereby improving the strength of the molded product.
  • Cellulose nanofibers can be obtained by defibrating (miniaturizing) the raw material pulp, and can be produced by a known treatment method such as chemical treatment or mechanical treatment.
  • raw material pulp for cellulose nanofibers examples include wood pulp made from broadleaf trees, coniferous trees, etc., non-wood pulp made from straw, bagasse, cotton, hemp, carrot fiber, etc., recovered waste paper, waste paper, etc.
  • DIP waste paper pulp
  • the above-mentioned various raw materials may be in the state of a pulverized product called, for example, a cellulosic powder.
  • wood pulp in order to avoid contamination with impurities as much as possible.
  • wood pulp for example, one kind from chemical pulp such as broadleaf kraft pulp (LKP), coniferous kraft pulp (NKP), sulfite pulp (SP), dissolving pulp and the like (DP), and mechanical pulp (TMP) or Two or more types can be selected and used.
  • thermomechanical pulp examples include stone ground pulp (SGP), pressurized stone ground pulp (PGW), refiner ground pulp (RGP), chemi-grand pulp (CGP), thermo-grand pulp (TGP), ground pulp (GP), and the like.
  • SGP stone ground pulp
  • PGW pressurized stone ground pulp
  • RGP refiner ground pulp
  • CGP chemi-grand pulp
  • TGP thermo-grand pulp
  • GP ground pulp
  • thermomechanical pulp TMP
  • CMP chemithermomechanical pulp
  • RMP refiner mechanical pulp
  • BTMP bleached thermomechanical pulp
  • Pretreatments by chemical methods include, for example, hydrolysis of polysaccharides with acid (acid treatment), hydrolysis of polysaccharides with enzymes (enzyme treatment), swelling of polysaccharides with alkali (alkali treatment), and oxidation of polysaccharides with oxidizing agents (alkaline treatment).
  • acid treatment hydrolysis of polysaccharides with acid
  • enzyme treatment hydrolysis of polysaccharides with enzymes
  • swelling of polysaccharides with alkali alkali treatment
  • oxidation of polysaccharides with oxidizing agents alkaline treatment.
  • Oxidization treatment reduction of polysaccharides with a reducing agent
  • oxidation with a TEMPO catalyst oxidation treatment
  • phosphoric acid esterification chemical treatment
  • Enzyme treatment, acid treatment, and oxidation treatment prior to defibration can reduce the water retention rate and increase the homogeneity.
  • the degree of water retention of the cellulose nanofibers is too high, the water-based coating composition will not spread well. It is presumed that this is probably because the water-based paint composition contains a large amount of water, so that the water molecules are easily aggregated and formed into droplets due to hydrogen bonds between the water molecules.
  • the raw material pulp is subjected to enzyme treatment, acid treatment, or oxidation treatment, the hemicellulose and cellulose amorphous regions of the pulp are decomposed, and as a result, the energy of the micronization treatment can be reduced, and the uniformity and dispersibility of the cellulose fibers can be improved. Can be improved.
  • the dispersibility of the cellulose fibers contributes to, for example, improving the homogeneity of the molded product.
  • the pretreatment reduces the aspect ratio of the cellulose nanofibers, it is preferable to avoid excessive pretreatment.
  • an aqueous coating composition having cellulose nanofibers obtained by defibrating mechanical pulp when drawing on an object to be drawn (for example, a glaze layer molding base in which the pottery base is covered with a glaze layer or a pottery base) with an aqueous coating composition having cellulose nanofibers obtained by defibrating mechanical pulp, this
  • the water-based coating composition has good spreadability, good adhesion to the object to be drawn, and is less likely to cause uneven coating.
  • Some conventional water-based coating compositions have a thickener such as carboxymethyl cellulose added to the composition in order to increase the viscosity and improve the adhesion.
  • Carboxymethyl cellulose increases the viscosity of the aqueous coating composition, but when the glaze is applied, it elutes because it is water-soluble, causing cracks after firing.
  • Cellulose nanofibers can be mixed with a liquid such as water or an organic solvent and dispersed to form a dispersion liquid.
  • the water-based coating composition at the time of drawing it is preferable to use mechanical pulp, and it is more preferable to use bleached mechanical pulp in order to bring out the original color of the colored base material, and BTMP. Is particularly preferred. Good adhesion of the water-based paint composition when drawing. If the adhesiveness of the water-based coating composition at the time of drawing is good, the water-based coating composition is less likely to be peeled off from the object to be coated after drying, and the drawing work can be performed efficiently.
  • cellulose nanofibers contained in the water-based coating composition those obtained by defibrating mechanical pulp or those obtained by defibrating chemical pulp can be preferably used.
  • a chemical pulp an additive containing at least one of a phosphorus oxo acid and a phosphorus oxo acid metal salt is added to the cellulose fiber to defibrate the pulp in which a part of the hydroxy group of the cellulose fiber is esterified with the phosphorus oxo acid.
  • These cellulose nanofibers are preferably contained in the aqueous coating composition in an amount of 2 to 4% by mass, preferably 3 to 4% by mass based on the solid content. If it exceeds 4% by mass, the concentration of the cellulose nanofibers is high, the interaction between the cellulose nanofibers works strongly, the viscosity becomes high, and the elongation of the water-based coating composition becomes insufficient. If it is less than 2% by mass, it is difficult to settle for a long time, but there is a concern that the water-based coating composition may drip outward from the drawn portion when drawing.
  • the water-based coating composition contains cellulose nanofibers obtained by defibrating mechanical pulp and cellulose nanofibers obtained by defibrating chemical pulp
  • cellulose nanofibers obtained by defibrating mechanical pulp and chemical pulp are used.
  • the aqueous coating composition is less likely to drip outward from the drawing portion, but since the concentration of the cellulose nanofibers obtained by defibrating the mechanical pulp is low, the dispersion provided by the cellulose nanofibers is provided. The sexual effect is weakened.
  • Esterification (chemical treatment) with phosphoroxo acid is performed prior to defibration to make the fiber raw material finer, and the cellulose nanofibers produced have a large aspect ratio, excellent strength, and high light transmittance and viscosity. It becomes.
  • Esterification with a phosphorus oxo acid can be carried out by the method described in Patent Document 3 (Japanese Unexamined Patent Publication No. 2019-199671).
  • Patent Document 3 Japanese Unexamined Patent Publication No. 2019-199671
  • An example of the cellulose nanofiber (A) esterified with phosphoric acid is shown below.
  • a part of the hydroxy group of the cellulose fiber is substituted with the functional group represented by the following structural formula (1) and esterified with phosphoroxoic acid, and the amount of the functional group introduced in the structural formula (1) is 1 g of the cellulose fiber.
  • the cellulose nanofibers exceeding 2 mm Wennl per unit can be exemplified.
  • the upper limit of the amount of the functional group introduced is 3.4 mm réellel per 1 g of cellulose fiber. If this upper limit is exceeded, the cellulose nanofibers may become more soluble in water.
  • At least one of A1, A2, ..., An and A' is O, and the rest is one of R, OR, NHR, and none.
  • R is a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched chain hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched chain hydrocarbon group.
  • ⁇ is a cation composed of an organic substance or an inorganic substance.
  • the cellulose nanofiber (A) may be one in which an ester of a phosphorus oxo acid is introduced by substituting two or more of the hydroxy groups of the cellulose fiber with the functional group represented by the structural formula (1). .. Viscosity is improved by the interaction of cellulose nanofibers due to hydrogen bonds and the like.
  • Cellulose fiber forms a structure in which a plurality of ⁇ -glucose are polymerized with ⁇ -glucose as one constituent unit.
  • the ester group of the phosphorus oxo acid is substituted with one particular ⁇ -glucose and may not be substituted with another ⁇ -glucose. Further, the ester group of the phosphorus oxo acid may be substituted and introduced at a plurality of places in a specific ⁇ -glucose.
  • Cellulose nanofibers esterified with this phosphorus oxo acid have extremely high light transmittance and viscosity.
  • a solution having a pH of less than 3.0 consisting of an additive (A) containing at least one of phosphorus oxo acids and phosphorus oxo acid metal salts is added to the cellulose fibers, and the fibers are heated and defibrated. Proceed with that.
  • Examples of the additive (A) include phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, ammonium polyphosphate, lithium dihydrogen phosphate, trilithium phosphate, and phosphorus.
  • Each of these additives can be used alone or in combination of two or more.
  • Cellulose nanofibers into which an ester of phosphoroxo acid has been introduced may be contained in the aqueous coating composition in an amount of 2 to 4% by mass, preferably 3 to 4% by mass based on the solid content. If it exceeds 4% by mass, the concentration of the cellulose nanofibers is high, the interaction between the cellulose nanofibers works strongly, the viscosity becomes high, the elongation of the water-based coating composition becomes insufficient, and it is difficult to draw with a uniform color. It will be something like that. If it is less than 2% by mass, it is difficult to settle for a long time, but there is a concern that the water-based coating composition may drip outward from the drawn portion when drawing.
  • Cellulose fibers esterified with phosphoric acid can also include those in which some of the hydroxy groups of the cellulose fibers are replaced with carbamate groups and carbamate is introduced.
  • the additive (B) used for substitution with a carbamate group contains at least one of urea and a urea derivative.
  • this additive for example, urea, thiourea, biuret, phenylurea, benzylurea, dimethylurea, diethylurea, tetramethylurea and the like can be used.
  • ureas or urea derivatives can be used alone or in combination of two or more. However, it is preferable to use urea.
  • the amount of the additive (B) added is preferably 0.01 to 100 mol, more preferably 0.2 to 20 mol, based on 1 mol of the additive (A). If the amount added is less than 0.01 mol, the introduction of carbamate may not proceed. On the other hand, even if the amount added exceeds 100 mol, the effect of adding urea may reach a plateau.
  • Known pulp can be appropriately used for the introduction of the ester by phosphoroxoic acid and the introduction of carbamate, but it is preferable to use softwood bleached kraft pulp or broadleaf bleached kraft pulp, and softwood bleached kraft pulp is preferable. .. Softwood bleached kraft pulp and hardwood bleached kraft pulp are easily decomposed by hemicellulase-based enzymes, and subsequent defibration treatment is also easy.
  • hemicellulase-based enzyme for example, xylanase, which is an enzyme that decomposes xylan, mannase, which is an enzyme that decomposes mannan, and arabanase, which is an enzyme that decomposes alabang, can be used.
  • xylanase which is an enzyme that decomposes xylan
  • mannase which is an enzyme that decomposes mannan
  • arabanase which is an enzyme that decomposes alabang
  • pectinase which is an enzyme that decomposes pectin
  • Cellulose fiber defibration is performed by one or two of, for example, a high-pressure homogenizer, a homogenizer such as a high-pressure homogenizer, a millstone friction machine such as a grinder and a grinder, a refiner such as a conical refiner and a disc refiner, and various bacteria. It can be done by selectively using more than a kind of means. However, it is preferable to defibrate the cellulose fibers by using a device / method for refining the cellulose fibers with a water stream, particularly a high-pressure water stream. According to this device / method, the dimensional uniformity and dispersion uniformity of the obtained cellulose fine fibers are very high. On the other hand, for example, when a grinder that grinds between rotating grindstones is used, it is difficult to uniformly refine the cellulose fibers, and in some cases, there is a possibility that undissolved fiber lumps may remain.
  • a high-pressure homogenizer such as a high-pressure homogen
  • a grinder used for defibrating cellulose fibers for example, there is a mass colloider of Masuko Sangyo Co., Ltd.
  • a device for miniaturizing with a high-pressure water flow for example, Starburst (registered trademark) of Sugino Machine Limited, Nanovater (registered trademark) of Yoshida Kikai Kogyo Co., Ltd., and the like exist.
  • a high-speed rotary homogenizer used for defibrating cellulose fibers there is Clairemix-11S manufactured by M-Technique Co., Ltd. and the like.
  • the present inventors have defibrated cellulose fibers by a method of grinding between rotating grindstones and a method of miniaturizing with a high-pressure water stream, and when each of the obtained fibers is observed under a microscope, the high-pressure water stream is used. It has been found that the fibers obtained by the miniaturization method have a more uniform fiber width.
  • the dispersion liquid of cellulose fibers is pressurized to, for example, 30 MPa or more, preferably 100 MPa or more, more preferably 150 MPa or more, particularly preferably 220 MPa or more (high pressure conditions), and the pore diameter is 50 ⁇ m or more. It is preferable to use a method of ejecting the fiber from the nozzle of No. 1 and reducing the pressure so that the pressure difference is, for example, 30 MPa or more, preferably 80 MPa or more, more preferably 90 MPa or more (decompression condition). Pulp fibers are defibrated by the cleavage phenomenon caused by this pressure difference.
  • the high-pressure homogenizer refers to a homogenizer having an ability to eject a slurry of cellulose fibers at a pressure of, for example, 10 MPa or more, preferably 100 MPa or more.
  • a high-pressure homogenizer When the cellulose fibers are treated with a high-pressure homogenizer, collisions between the cellulose fibers, pressure difference, microcavitation, etc. act to effectively defibrate the cellulose fibers. Therefore, the number of defibration treatments can be reduced, and the production efficiency of cellulose fine fibers can be increased.
  • the high-pressure homogenizer it is preferable to use one in which a slurry of cellulose fibers collides with each other in a straight line.
  • a counter-collision type high-pressure homogenizer microwavefluidizer / MICROFLUIDIZER®, wet jet mill.
  • microfluidizer / MICROFLUIDIZER® wet jet mill.
  • two upstream flow paths are formed so that the pressurized cellulose fiber slurries collide with each other at the confluence. Further, the cellulose fiber slurries collide at the confluence, and the collided cellulose fiber slurries flow out from the downstream flow path.
  • the downstream flow path is provided perpendicular to the upstream side flow path, and a T-shaped flow path is formed by the upstream side flow path and the downstream side flow path.
  • a counter-collision type high-pressure homogenizer When such a counter-collision type high-pressure homogenizer is used, the energy given by the high-pressure homogenizer is converted to the collision energy to the maximum, so that the cellulose fibers can be defibrated more efficiently.
  • the average fiber diameter, average fiber length, water retention, peak value of pseudo particle size distribution, and B-type viscosity of the water-based coating composition of the obtained cellulose nanofibers are desired values as shown below. It is preferable to carry out the evaluation.
  • the ratio (D50 / D90) of the cumulative 50% diameter (D50) to the cumulative 90% diameter (D90) on a volume basis is 0.5 to 1. It is preferable because it is difficult to settle and the state in which the colored base material is dispersed is maintained.
  • the average fiber diameter (average fiber width; average diameter of single fibers) of cellulose nanofibers is 1 to 200 nm, preferably 2 to 100 nm, more preferably 3 to 80 nm, and particularly preferably 3 to 60 nm.
  • Cellulose nanofibers having an average fiber diameter of less than 1 nm require high cost to manufacture.
  • the average fiber diameter of the cellulose nanofibers exceeds 200 nm, the effect of increasing the hydrogen bond points may not be obtained.
  • the cellulose nanofibers in the dispersion liquid gel and have a viscosity. In particular, when the average fiber diameter is 100 nm or less, the gelled cellulose nanofibers have a relatively high static viscosity, so that sedimentation is suppressed. Sedimentation of the colored substrate is also suppressed.
  • the average fiber diameter of cellulose nanofibers can be adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
  • the method for measuring the average fiber diameter of cellulose nanofibers is as follows. First, 100 ml of an aqueous dispersion of cellulose nanofibers having a solid content concentration of 0.01 to 0.1% by mass is filtered through a membrane filter made of Teflon (registered trademark), and the solvent is once with 100 ml of ethanol and three times with 20 ml of t-butanol. Replace. Next, it is freeze-dried and coated with osmium to prepare a sample. This sample is observed by an electron microscope SEM image at a magnification of 3,000 to 30,000 times depending on the width of the constituent fibers.
  • the average fiber length (length of a single fiber) of the cellulose nanofibers is preferably 200 to 1300 ⁇ m, more preferably 200 to 1000 ⁇ m, and particularly preferably 200 to 800 ⁇ m. If the average fiber length of the cellulose nanofibers is less than 200 ⁇ m, it may be difficult for the cellulose nanofibers to be uniformly dispersed in the aqueous coating composition. Poor dispersibility causes problems in terms of resistance to sagging and good elongation.
  • the average fiber length of cellulose nanofibers can be adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
  • the average fiber length of cellulose nanofibers is measured by visually measuring the length of each fiber in the same manner as in the case of the average fiber diameter.
  • the average fiber length is the medium length of the measured value.
  • the cellulose nanofibers have an aspect ratio of 100 to 300, preferably 100 to 250, and more preferably 100 to 200. It is presumed that cellulose nanofibers having an aspect ratio in this range are elongated and are maintained in a dispersed state (that is, a three-dimensional network) by being three-dimensionally entangled with each other or hydrogen-bonded. When the aspect ratio exceeds 300, the cellulose nanofibers are often entangled with each other, resulting in a water-based coating composition having poor elongation. If the aspect ratio is less than 100, the so-called three-dimensional network structure is difficult to maintain for a long period of time, and the colored substrate may settle in a short time.
  • the water retention level of the cellulose nanofibers is, for example, preferably 150% or more, preferably 200%, more preferably 220%, and even more preferably 250%. If the water retention level of the cellulose nanofibers is less than 150%, the dispersibility of the cellulose nanofibers may be deteriorated, and eventually the dispersibility of the colored base material adhering to the cellulose nanofibers may be deteriorated.
  • the water retention level of the cellulose nanofibers should be, for example, 500% or less. If it exceeds 500%, since the water retention capacity of the cellulose nanofibers themselves is high, droplet formation occurs due to mutual water molecules, and it becomes difficult to form a thin film with the water-based coating composition in the substrate or the glaze layer.
  • the water retention of cellulose nanofibers can be adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
  • the degree of water retention of cellulose nanofibers is JAPAN TAPPI No. It is a value measured according to 26 (2000).
  • the cumulative 50% diameter (hereinafter, also referred to as D50, medium diameter) on a volume basis in the pseudo particle size distribution of cellulose nanofibers is preferably 1 to 20 ⁇ m, more preferably 5 to 15 ⁇ m.
  • D50 medium diameter
  • the cellulose nanofibers are appropriately dispersed in the water-based coating composition, and uniform drawing can be performed by the water-based coating composition. If the median diameter exceeds 20 ⁇ m, it becomes difficult for the cellulose nanofibers to be uniformly dispersed in the aqueous coating composition. The production of cellulose nanofibers having a median diameter of less than 1 ⁇ m is technically difficult.
  • the median diameter of the pseudo-particle size distribution of cellulose nanofibers obtained by defibrating mechanical pulp and the median diameter of the pseudo-particle size distribution of cellulose nanofibers esterified with phosphoroxoic acid are both 5 to 20 ⁇ m. Since the pseudo-particle size of the cellulose nanofibers as a whole is almost uniform and the entire cellulose nanofibers are dispersed with little bias, drawing can be performed without color unevenness, which is preferable.
  • the peak value in the pseudo particle size distribution curve of the water-based coating composition of the present embodiment is preferably one peak.
  • the cellulose nanofibers defibrated from one or more kinds of pulp have high uniformity of fiber length and fiber diameter, and the dispersibility of the cellulose nanofibers in the water-based coating composition is excellent. It becomes a thing.
  • the peak value is a value measured according to ISO-13320 (2009).
  • Cellulose nanofibers preferably have a single peak in the pseudo-particle size distribution curve measured by laser diffraction in an aqueous dispersion. As described above, the cellulose nanofiber having one peak has been sufficiently miniaturized, can exhibit good physical properties as the cellulose nanofiber, and the drawing by the obtained water-based coating composition is uniform.
  • the "pseudo particle size distribution curve” means a curve showing a volume-based particle size distribution measured using a particle size distribution measuring device (for example, a particle size distribution measuring device "LA-960S” manufactured by HORIBA, Ltd.).
  • a water-based coating composition having a structure having a single peak in the pseudo particle size distribution curve is preferable.
  • the particle size of the entire solid content specifically, the colored base material, the cellulose nanofiber
  • the cellulose nanofibers are less likely to be unevenly distributed in the water-based coating composition and easily dispersed throughout the water-based coating composition.
  • the water-based coating composition having cellulose nanofibers and carboxylated cellulose fine fibers obtained by defibrating mechanical pulp, there are a plurality of peak values in the pseudo particle size distribution curve.
  • the phase of the colored substrate and the liquid phase are separated.
  • the mechanism of action of this aqueous coating composition separating into two phases is not clear, but it is presumed as follows.
  • the hydroxyl group at the C6 position of glucose, which is a constituent unit of the carboxylated cellulose fine fiber and the cellulose fiber is selectively modified into an aldehyde group and a carboxy group, and the charge of glucose is biased. Therefore, the interaction between the cellulose fibers is also biased, and it is difficult to maintain uniform dispersion.
  • cellulose nanofibers esterified with phosphoric acid are those in which any one or more of the six C atoms of glucose, which is a constituent unit of cellulose fibers, are randomly esterified with phosphoric acid. Is. Therefore, the charge bias is alleviated in the entire esterified glucose group. Therefore, uniform dispersion is maintained for a long time.
  • the mode of the particle size of the cellulose nanofibers and the medium diameter of the pseudo-particle size distribution can be adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
  • the cellulose nanofibers obtained by defibration can be dispersed in an aqueous medium to prepare a dispersion liquid prior to mixing with the colored base material.
  • the total amount of the aqueous medium is water (aqueous solution).
  • the aqueous medium may be another liquid that is partially compatible with water.
  • the other liquid for example, lower alcohols having 3 or less carbon atoms can be used.
  • the dispersion liquid of cellulose nanofibers has the property of dispersing in the entire liquid. However, when the dispersion liquid of cellulose nanofibers is left for a while, it separates into a phase of cellulose nanofibers and an aqueous phase, and an interface between the two phases appears, and this interface may be lowered. It is presumed that the phenomenon of this phase separation is related to the viscosity.
  • the dispersion of cellulose nanofibers has a viscosity. Viscosity varies depending on the raw material, processing means, physical characteristics, etc. of cellulose nanofibers.
  • cellulose nanofibers obtained by defibrating mechanical pulp have a relatively low viscosity
  • cellulose nanofibers obtained by defibrating chemical pulp have a relatively high viscosity
  • cellulose nanofibers into which a phosphorus oxo acid ester or carbamate has been introduced have a local charge bias and easily form hydrogen bonds with water or an organic solvent in the dispersion liquid, so that the viscosity becomes high. Conceivable.
  • the viscosity differs depending on the concentration of the cellulose nanofibers, and the higher the concentration, the higher the viscosity.
  • the viscosity can be evaluated by the B-type viscosity.
  • the colored base material is attached to the cellulose nanofibers. Therefore, since the cellulose nanofibers are appropriately dispersed in the water-based coating composition, the colored base material also has excellent dispersibility. Then, in order to maintain the dispersion of the colored base material for a long time, it is effective to impart high viscosity by the cellulose nanofibers into which the ester of phosphoroxo acid is introduced.
  • a form in which the mixing ratio of the colored base material and the cellulose nanofiber into which the ester of phosphoroxo acid is introduced is 1: 0.005 to 0.045, preferably 1: 0.010 to 0.045 can be exemplified.
  • the amount of cellulose nanofibers in which the ester of phosphoroxo acid is introduced exceeds this mixing ratio, the amount of cellulose nanofibers is too large with respect to the colored base material, and the dispersibility of the colored base material in the entire paint is biased. Occurs. Further, when the cellulose nanofibers in which the ester of phosphoroxo acid is introduced is contained below this mixing ratio, the amount of cellulose nanofibers is small and the dispersibility of the colored base material in the entire water-based coating composition is not good, and drawing is performed. It may cause color unevenness.
  • the B-type viscosity of the cellulose nanofibers constituting the water-based coating composition is, for example, 600 cP or more, more preferably 700 cP or more, and particularly preferably 800 cP or more in the dispersion liquid having a solid content concentration of 2.0% by mass. If the B-type viscosity is less than 600 cP, the aqueous coating composition may unexpectedly flow out from the drawn portion to a portion other than the portion.
  • the B-type viscosity of the aqueous coating composition is preferably 2000 cP or less. If the B-type viscosity exceeds 2000 cP, the paint does not spread well when the paint is drawn, which causes uneven coating and blurring. Water was used as the solvent for the dispersion liquid.
  • the cellulose nanofibers constituting the water-based coating composition of the present embodiment are a dispersion liquid having a solid content concentration of 2.0% by mass, and have a minimum value of high shear viscosity of 3.5 cP or less, preferably a shear rate of 1 ⁇ 10 5 to 2 ⁇ .
  • the minimum value of high-share viscosity is 3.3 cP or less up to 10 5 (1 / sec), more preferably the minimum value of high-share viscosity between 1 ⁇ 10 5 and 2 ⁇ 10 5 (1 / sec). Is 3.0 cP or less, more preferably the minimum value of high shear viscosity is 3.5 cP or less between the shear rates of 1 ⁇ 10 5 and 2 ⁇ 10 5 (1 / sec).
  • silica stone powder SiO 2 powder
  • a thickener can be added to the coating composition.
  • the thickener should not be added excessively because it increases the B-type viscosity and the high shear viscosity, but it is possible to increase the viscosity auxiliaryly by adding an appropriate amount.
  • Known thickeners can be appropriately used, and for example, carboxymethyl cellulose (CMC), xanthan gum, guar gum, pectin, and carrageenan can be used.
  • the thickener is contained in the aqueous coating composition in an amount of 20 to 30% by mass.
  • the thickener does not necessarily have to be included in the aqueous coating composition.
  • the pottery base is not particularly limited as long as it is a known base, and examples thereof include pottery, porcelain, glassware, enamel, earthenware, and unglazed material.
  • clay, silica stone, feldspar, and a mixture thereof can be used as a raw material for the pottery base.
  • the pottery base is a glassware, for example, silicic acid, silicic acid compound, boric acid, boric acid compound, phosphoric acid, phosphoric acid compound, titanic acid, titanic acid compound, tellurium, tellurium compound, alumina, alumina compound,
  • these compounds and mixtures can be used to make glassware.
  • the glaze is glassy and contains a known composition.
  • ash medium-melting raw material
  • clay asdhesive material
  • feldspar asdhesive material / medium-melting raw material / glass raw material
  • talc glass raw material
  • Ash is mainly composed of limestone such as calcium oxide, and has a function of melting at a high temperature to vitrify it or making it easier to dissolve other components as a raw material for medium melting to enhance the fluidity of the glaze.
  • a coloring component copper, iron, etc.
  • the chemical components of the glaze are silicic acid and silicic acid compounds, alumina and alumina compounds, potassium oxide and potassium oxide compounds, potassium oxide and potassium oxide compounds, sodium oxide and sodium oxide compounds, iron oxide and iron oxide compounds, etc. Cadmium and cadmium compounds, lead and lead compounds and the like may be contained.
  • silicic acid and silicic acid compounds are the main components of the calcined glaze and occupy about 45 to 80% of the glaze, depending on the type of glaze.
  • the glaze can have, for example, the following composition, but is not limited to this.
  • the same amount of water was added to 35.4 wt% of Fukushima feldspar, 18.6 wt% of limestone, 17 wt% of Korean kaolin, and 29 wt% of silica stone, stirred with a ball mill, deironed through a sieve, and water was added to adjust the specific gravity. Let the thing be glaze A. Further, 297 g of this glaze A is dissolved by adding 3 g of CMC to obtain glaze B.
  • the solid content concentration of the liquid level portion immediately after adjusting the water-based coating composition to polybin is 100, the solid content concentration of the liquid level portion after preparing the polybin and allowing it to stand for 24 hours (concentration of the liquid level portion).
  • a form in which the index) is 90 or more, preferably 95 or more is preferable. If the concentration index of the liquid surface portion is less than 90, the dispersion stability is lacking, and it is necessary to appropriately stir the composition so that the composition does not separate in the adjusted aqueous coating composition.
  • the liquid level portion is in a depth range of up to 5 mm in the depth direction from the liquid surface when the aqueous coating composition is prepared in the polybin used in the example and made up to 30 mL, particularly in the depth direction from the liquid surface. Refers to a water-based paint composition at 3 mm.
  • the water-based paint composition can be drawn on the base material 11 which is the base of finished products such as Japanese and Western tableware, ornaments, and interior accessories.
  • the base material 11 is glazed (that is, glazed), dried at room temperature to 105 ° C. (manufacturing step S11), and fired at 1200 to 1300 ° C. to cover the surface of the base material with a glaze layer (glaze layer).
  • a molding base is obtained (manufacturing step 12).
  • the firing conditions include, for example, raising the temperature to 950 ° C. over 9 hours and 30 minutes, and then raising the temperature to 1250 ° C. over 5 hours. Maintain 1250 ° C. for 30 minutes, then allow to cool naturally.
  • the finished product can be used as an example of a ceramic product or an enamel product.
  • Glazing may be applied to the entire surface of the substrate or a part of the surface of the substrate. Penetration may occur, but a form that covers the entire surface of the substrate is preferable. Moisture does not easily penetrate into the glaze layer.
  • the case where the glaze is dispersed in water or the like is applied to the substrate is also included in the glaze.
  • a base material for glassware it can be manufactured from the drawing process by omitting the above-mentioned glazed layer forming process.
  • a pattern 30a is drawn on the obtained glaze layer molding base with the water-based coating composition, and dried at 60 to 105 ° C. for 1 hour to obtain a drawn molded product (manufacturing step S13).
  • the firing conditions include, for example, raising the temperature to 950 ° C. over 9 hours and 30 minutes, and then raising the temperature to 1220 ° C. over 5 hours. Maintain 1220 ° C. for 30 minutes, then allow for natural cooling.
  • this glaze layer molded product can be used as a finished product, it is possible to manufacture a finished product composed of a plurality of layers in which one or more glaze layers are further overlapped on the glaze layer molded product.
  • a pattern 30a is drawn on the base material with a water-based paint composition, and dried at 60 to 105 ° C. for 1 hour to obtain a drawn molded product (manufacturing step S33).
  • the drawing molded product is glazed (immersed), the pattern is glazed, and for example, it is dried again at 60 to 105 ° C. for 1 hour (manufacturing step S41) and fired at 580 to 780 ° C. to obtain a fired water-based paint.
  • the composition is coated with a glaze to form a glaze layer 20a. That is, the glaze layer 20a is formed by coating the fired water-based paint composition with a glaze, and the drawing molded body is coated with the glaze layer 20a to form the glaze layer molded body (manufacturing step S42).
  • the firing conditions are, for example, raising the temperature to 550 ° C. over 5 hours and 30 minutes, and then raising the temperature to 780 ° C. over 5 hours. Maintain 780 ° C. for 30 minutes, then allow to cool naturally.
  • this glaze layer molded product can be used as a finished product, it is possible to manufacture a finished product composed of a plurality of layers in which one or more glaze layers are further overlapped on the glaze layer molded
  • Cellulose nanofibers are mainly composed of organic substances, and also contain a small amount of inorganic substances. The organic content of the cellulose nanofibers disappears in the firing process.
  • the surface of the glaze layer molded body that is, the surface of the glaze layer is very smooth, and even if the surface is drawn with the water-based coating composition, the surface repels the water-based coating composition and the water-based coating composition is the same surface. It was difficult to settle in.
  • the coating material containing the cellulose nanofibers is easily fixed on the same surface, it is difficult to be repelled from the same surface and becomes hydrophilic after drying, so that the glaze can be easily applied. Therefore, it is possible to draw the water-based coating composition and subsequently coat it with a glaze layer.
  • Overpainting is known as a method of drawing on the surface of the glaze layer, but it is inferior in durability because the glaze layer cannot be formed on the surface of the pattern. It is known that the color easily fades due to repeated washing.
  • aqueous coating composition 1.0 g of pigment (Nitto Ganryo Co., Ltd. Green M-142), cellulose nanofiber dispersion, and water are mixed to form an aqueous coating composition, Comparative Examples 1 to 5 and Examples 1 to 3.
  • the cellulose nanofiber dispersions are BTMP cellulose nanofiber aqueous dispersion (mechanical pulp bleached product), LBKP cellulose nanofiber aqueous dispersion (chemical pulp bleached product derived from broadleaf tree pulp), phosphite esterified cellulose nanofiber, and carboxylation.
  • One or more of the cellulose fine fibers were selected and the mixing amount was changed, and the mixture was used.
  • the mixing amount of each composition is as shown in Table 1.
  • BTMP cellulose nanofibers are beaten to a fine fiber ratio of 80% or more with a Niyagara beater or a single disc refiner to obtain a processed product, and the processed product is circulated 10 to 20 times with a high-pressure homogenizer to be refined. Then, it was prepared by measuring up with water so that the obtained product became 3 to 4% by mass.
  • a processed product is obtained by beating to a fine fiber ratio of 80% or more with a Niagara beater or a single disc refiner, and the processed product is circulated 3 to 4 times with a high-pressure homogenizer to be refined. Adjusted.
  • phosphite esterified cellulose nanofibers water containing phosphorous acid and urea was impregnated with chemical pulp and reacted at 170 ° C. for 2 hours to obtain a product. The product was washed with water and circulated 2-3 times with a high-pressure homogenizer to be finely divided for preparation.
  • the phosphite esterified cellulose nanofiber is a cellulose nanofiber dispersion liquid produced by the phosphite esterification method.
  • Comparative Example 1 is a1
  • Comparative Example 2 is a2
  • Comparative Example 3 is a3
  • Comparative Example 4 is a4
  • Comparative Example 5 is a5
  • Comparative Example 6 is a6
  • Example 1 is b1
  • Example 2 is b2
  • Example. 3 was labeled b3.
  • the degree of sedimentation of the interface of the colored substrate was evaluated after 10 minutes, 60 hours, and 130 hours after allowing these Test Examples and Examples to stand at room temperature.
  • the condition of sedimentation after 10 minutes is shown in FIG. 5
  • the condition of sedimentation after 60 hours is shown in FIG. 6
  • the condition of sedimentation after 130 hours is shown in FIGS. 7 and 2.
  • the evaluation criteria are as follows.
  • the aqueous coating composition was only the phase 50 of the colored base material, and the foam phase 51 and the liquid phase 52 were not confirmed.
  • ⁇ The water coating composition is separated into the phase 50 of the colored base material and the phase 51 and / or the liquid phase 52 of the foam, and the colored base material is formed within 5 mm below the liquid surface of the water-based coating composition. The interface of phase 50 was created.
  • X The water coating composition is separated into a phase 50 of the colored substrate and a phase 51 and / or a liquid phase 52 of the foam, and the phase 50 of the colored substrate is 5 mm or more below the liquid surface of the aqueous coating composition. An interface has arisen.
  • the aqueous coating composition has a colored base material phase 50, a foam phase 51, and a liquid phase 52.
  • ⁇ Consideration condition 2> Comparative Example 5 and Example 2 were each prepared in the above polybin. The degree of sedimentation of the interface of the colored substrate was evaluated after 16 hours after allowing these Test Examples and Examples to stand at room temperature. The results are shown in FIG. 8 and Table 5. The evaluation criteria are the same as ⁇ Consideration condition 1>.
  • Example 5 16 hours after allowing to stand, in Example 5, an interface was formed between the phase 50 of the colored substrate and the phase 51 of the foam.
  • Example 2 and water diluted 1: 1 Test Example c1, Example 2 and water diluted 1: 2 Test Example c2, Example 2 and water diluted 1: 3 Test Example c3 was allowed to stand at room temperature for 24 hours, and the degree of sedimentation of the interface of the colored substrate was evaluated. The results are shown in FIG. 9 and Table 6. The evaluation criteria are the same as ⁇ Consideration condition 1>.
  • the concentration index of the liquid level portion is determined by preparing the water-based coating composition in polybin and allowing it to stand for 24 hours when the solid content concentration of the liquid level portion immediately after adjusting the water-based coating composition to polybin is 100. It refers to the solid content concentration of the liquid surface portion after placement, and is a value obtained by the following formula (1).
  • Concentration index of the liquid surface portion after standing for 24 hours (solid content concentration (mass%) of the surface portion after standing for 24 hours in the aqueous coating composition / solid content concentration immediately after the surface immediately after preparation in the aqueous coating composition (Mass%)) x 100
  • a1 shows Comparative Example 1
  • a3 shows Comparative Example 3
  • a5 shows Comparative Example 5
  • a6 shows Comparative Example 6
  • b2 shows Example 2.
  • the frequency (%) on the vertical axis of FIG. 4 represents, for example, the number (%) of particles in a specific particle size ( ⁇ m) of Comparative Example 1 when the total number of particles of Comparative Example 1 is 100%. ..
  • the frequency (%) is the same for Comparative Example 3, Comparative Example 5, Comparative Example 6, and Example 2.
  • the cumulative 10% diameter is represented by D10
  • the cumulative 50% diameter is represented by D50
  • the cumulative 90% diameter is represented by D90.
  • the form of the cellulose nanofibers can be applied to any form such as powder, paste, slurry, etc., and the medium for dispersing the cellulose nanofibers is not limited to water, but an organic solvent or other fluid can be appropriately applied. ..
  • the viscosity corresponding to the shear rate in the non-Newtonian fluid can be obtained.
  • the centrifuge used was the HITAHI cooling centrifuge CR22N.
  • the average particle size of pigments and others is a value measured in accordance with JIS Z 8825: 2013.
  • -Room temperature refers to a general temperature inside a house, for example, 1 to 30 ° C, more preferably 15 to 25 ° C.
  • the B-type viscosity (the solid content concentration is appropriately adjusted) is a value measured in accordance with the "method for measuring the viscosity of a liquid" of JIS-Z8803 (2011).
  • the B-type viscosity is the resistance torque when the dispersion liquid (or water dispersion liquid) is stirred, and the higher the viscosity, the more energy required for stirring.
  • the B-type viscosity was measured at 25 ° C.
  • the present invention can be used as a water-based paint composition for drawing on traditional crafts, Japanese and Western tableware, ornaments, interior accessories, and the like.

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017066272A (ja) * 2015-09-30 2017-04-06 王子ホールディングス株式会社 微細繊維状セルロース含有物
JP2017106012A (ja) * 2015-12-08 2017-06-15 王子ホールディングス株式会社 塗料用組成物および筆記具
WO2018212012A1 (ja) * 2017-05-15 2018-11-22 大王製紙株式会社 セルロース微細繊維及びその製造方法
JP2019172482A (ja) * 2018-03-27 2019-10-10 愛媛県 多層絵付け方法
JP2021054917A (ja) * 2019-09-27 2021-04-08 愛媛県 水性塗料と陶磁器類と絵付け方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017066272A (ja) * 2015-09-30 2017-04-06 王子ホールディングス株式会社 微細繊維状セルロース含有物
JP2017106012A (ja) * 2015-12-08 2017-06-15 王子ホールディングス株式会社 塗料用組成物および筆記具
WO2018212012A1 (ja) * 2017-05-15 2018-11-22 大王製紙株式会社 セルロース微細繊維及びその製造方法
JP2019172482A (ja) * 2018-03-27 2019-10-10 愛媛県 多層絵付け方法
JP2021054917A (ja) * 2019-09-27 2021-04-08 愛媛県 水性塗料と陶磁器類と絵付け方法

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