WO2021187552A1 - Composition aqueuse de matériau de revêtement - Google Patents

Composition aqueuse de matériau de revêtement Download PDF

Info

Publication number
WO2021187552A1
WO2021187552A1 PCT/JP2021/011014 JP2021011014W WO2021187552A1 WO 2021187552 A1 WO2021187552 A1 WO 2021187552A1 JP 2021011014 W JP2021011014 W JP 2021011014W WO 2021187552 A1 WO2021187552 A1 WO 2021187552A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
cellulose fine
fine fibers
coating composition
cellulose
Prior art date
Application number
PCT/JP2021/011014
Other languages
English (en)
Japanese (ja)
Inventor
中村　健治
俊博 岩井
Original Assignee
愛媛県
大王製紙株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 愛媛県, 大王製紙株式会社 filed Critical 愛媛県
Publication of WO2021187552A1 publication Critical patent/WO2021187552A1/fr

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G19/00—Table service
    • 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
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/16—Esters of inorganic acids
    • 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.
  • the conventional water-based paint used for drawing on a pottery substrate has a composition of a pigment used for coloring, a fixing agent such as gelatin powder for improving fixation on an object to be coated, and a dispersibility of pigment such as Arabic glue. It contains a dispersant for enhancing and a solvent (Patent Document 1).
  • the painter draws with a water-based paint composition of various colors in order to produce an aesthetically pleasing work.
  • the dried water-based paint composition may exhibit a color immediately after drawing on the pottery substrate, in other words, a color different from the original color.
  • the dispersant One of the factors that causes this is the dispersant.
  • the Arabic glue used as a dispersant has a transparent color or a white color depending on the water content. Therefore, in order to reduce the influence of the color change due to the dispersant, it seems that the dispersant should be blended at a concentration that does not affect the color tone of the aqueous coating composition.
  • other defects for example, the dispersibility may be lowered, and color unevenness or coating unevenness may occur.
  • an object to be solved by the present invention is to provide a water-based coating composition in which the color after drying is close to the original color of the water-based coating composition.
  • the original color of the water-based paint composition means the color of the water-based paint composition immediately after drawing on the pottery substrate.
  • Colored base material and It has cellulose fine fibers modified with an ester group of phosphoxoic acid, and has.
  • the fluctuation range of the L * value between application to the object to be coated and drying is within 25%.
  • a water-based coating composition characterized by this.
  • the cellulose fine fibers have a whitish color, but the cellulose fine fibers modified with the ester group of phosphoroxo acid have a color closer to the transparent color.
  • the aqueous coating composition becomes whitish after drying.
  • the fluctuation range of the L * value is within the above range, the change in color tone is small even when dried, and the color tone is close to the original color tone of the water-based coating composition.
  • the surface roughness of the coating film surface formed on the object to be coated is 20% or less.
  • the water-based coating composition of the first aspect is 20% or less.
  • the color that a person perceives is the color of light that is reflected by a certain object. If the surface of the object is uneven, that is, the surface roughness is large, light is reflected randomly. When this phenomenon is considered for the object to be coated, if the surface roughness of the coating film surface of the object to be coated is large, a person perceives a color different from the original color of the pigment.
  • the surface roughness is 20% or less, the unevenness of the coating film surface is not large, and the coating film surface is relatively smooth. Since light is less likely to be reflected randomly on a smooth coating film surface, it is presumed that the color tone is close to the original color tone of the colored base material.
  • the cellulose fine fibers are Of the 1st to 6th carbon sites of glucose that make up cellulose fine fibers First cellulose fine fibers in which at least one carbon moiety is modified with an ester group of phosphoric acid, It has a second cellulose fine fiber in which a carbon moiety other than the carbon moiety is modified with an ester group of a phosphoric acid.
  • the water-based coating composition of the first aspect is of the 1st to 6th carbon sites of glucose that make up cellulose fine fibers.
  • the cellulose fine fibers are likely to be unevenly distributed due to the uneven charge, and the dispersibility is not relatively large. ..
  • the cellulose fine fibers of the above-described embodiment are present in the aqueous coating composition, it is presumed that the cellulose fine fibers disperse while canceling each other's charge bias. Since the colored base material is dispersed together with the cellulose fine fibers, the shade of the water-based coating composition is alleviated.
  • B-type viscosity is 600 cp or more and 1500 cp or less.
  • the maximum value of high shear viscosity is 3.5 cp or less in the range of shear rate 1 ⁇ 10 5 (1 / sec) or more.
  • a water-based coating composition according to any one of the first to third aspects.
  • the water-based coating composition is highly fluid and easily smoothes the coating film surface under the influence of external force such as gravity.
  • the water-based paint composition has a color after drying that is close to the original color of the water-based paint composition.
  • 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.
  • aqueous coating composition of the present embodiment has a colored base material and cellulose fine fibers, and the cellulose fine fibers have cellulose fine fibers into which an ester of a phosphoric acid is introduced.
  • Each composition will be described in detail below.
  • the colored base material is a substance that colors an object to be coated (for example, a pottery base), and exhibits various colors depending on the type of the base material.
  • As a method of painting the object to be coated with the water-based coating composition having this colored base material there are overpainting and underpainting.
  • the underpainting is performed before glazing, and can be performed by the following method as an example.
  • a pattern is drawn on the unglazed object to be coated 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.
  • a colored base material of a metal chloride or nitric acid compound which is a pigment that is refractory to the glaze, 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, 5 ⁇ m to 60 ⁇ m, preferably 5 ⁇ m to 40 ⁇ m. If it exceeds 60 ⁇ 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. If it is less than 5 ⁇ 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 fine fibers, the particle size distribution of the colored base material and the pseudo particle size distribution of the cellulose fine fibers are close to each other. Better.
  • the difference between the peak value in the particle size distribution of the colored substrate and the peak value in the pseudo particle size distribution of the cellulose fine fibers is preferably less than 20 ⁇ m, preferably less than 10. m.
  • the difference is in such a range, the colored base material can be more effectively dispersed in the aqueous coating composition.
  • 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 fine fibers have a role of increasing the hydrogen bond points of the cellulose fibers and thereby improving the strength of the molded product.
  • Cellulose fine fibers 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 fine fibers for example, wood pulp made from broadleaf tree, coniferous tree, etc., non-wood pulp made from straw, bagasse, cotton, hemp, carrot fiber, etc., recovered waste paper, waste paper, etc. are used as raw materials.
  • One type or two or more types can be selected and used from the waste paper pulp (DIP) and the like.
  • 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 or two of chemical pulp such as broadleaf kraft pulp (LKP), coniferous kraft pulp (NKP), sulfite pulp (SP), and dissolving pulp (DP), and mechanical pulp (TMP). More than a species 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 water retention level of the cellulose fine fibers is too high, the water-based coating composition does not stretch 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 fine fibers, it is preferable to avoid excessive pretreatment.
  • an aqueous coating composition having cellulose fine fibers obtained by defibrating mechanical pulp when drawing on an object to be coated (for example, a glaze layer molding base in which a pottery base is covered with a glaze layer or a pottery base) with an aqueous coating composition having cellulose fine fibers obtained by defibrating mechanical pulp, this is obtained.
  • the water-based coating composition has good spreadability, good adhesion to the object to be coated, 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. While carboxymethyl cellulose increases the viscosity of the water-based paint composition, it is a water-soluble thickener, so it dissolves in water when a glaze is applied, causing cracks after firing.
  • Cellulose fine fibers 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. If the adhesiveness of the water-based coating composition at the time of drawing is good, the water-based coating composition will not be peeled off from the object to be coated after drying, and the drawing work will be facilitated efficiently.
  • cellulose fine fibers 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.
  • All of these cellulose fine fibers are preferably contained in the aqueous coating composition in an amount of 2% by mass or more and 4% by mass or less, preferably 3% by mass or more and 4% by mass or less on a solid content basis.
  • concentration of the cellulose fine fibers is high, the interaction between the cellulose fine fibers works strongly, and the high share viscosity is less likely to be relatively low, so that the elongation of the water-based coating composition becomes insufficient and uniform. It becomes difficult to draw with various colors.
  • it is less than 2% by mass the cellulose fine fibers are difficult to disperse over the entire water-based coating composition, and the concentration of the cellulose fine fibers tends to be non-uniform in the water-based coating composition.
  • the water-based coating composition contains cellulose fine fibers obtained by defibrating mechanical pulp and cellulose fine fibers obtained by defibrating chemical pulp
  • cellulose fine fibers obtained by defibrating mechanical pulp and chemical pulp are used.
  • the water-based coating composition is less likely to drip outward from the drawing portion, but the concentration of the cellulose fine fibers obtained by defibrating the mechanical pulp is low, so that the flow of the cellulose fine fibers is provided. The effect of improving the property and adhesion is weakened.
  • esterification (chemical treatment) with phosphoroxo acid is performed prior to defibration, the fiber raw material can be made finer, and the produced cellulose fine fibers 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 fine fiber (A) esterified with phosphoric acid is shown below.
  • a part of the hydroxy groups of the cellulose fiber is substituted with the functional group shown in 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.
  • Examples of cellulose fine fibers 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 fine fibers 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.
  • a part of the hydroxy group (-OH group) of the cellulose fiber was replaced with the functional group represented by the following structural formula (2), and the ester of phosphite was introduced (modified, modified) (esterified).
  • It may be a cellulose fine fiber.
  • it may be a cellulose fine fiber in which a part of the hydroxy group of the cellulose fiber is replaced with a carbamate group and a carbamate (ester of carbamic acid) is also introduced.
  • ⁇ is one of none, R, and NHR.
  • 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 fine fiber (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). .. Dispersibility is improved by the interaction of cellulose fine fibers due to hydrogen bonds and the like.
  • Cellulose fiber has a structure in which a plurality of glucoses 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 fine fibers 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 fine fibers into which an ester of phosphoroxo acid has been introduced 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 fine fibers is high, the interaction between the cellulose fine fibers 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, the concentration of the cellulose fine fibers modified with the ester group of phosphorus oxo acid is small, and a sufficient dispersion effect cannot be obtained.
  • 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 defibration of the raw material pulp has the average fiber diameter, average fiber length, water retention, peak value of pseudo particle size distribution, light transmittance of dispersion, B-type viscosity of water-based coating composition, and high shear viscosity of the obtained cellulose fine fibers. , It is preferable to obtain a desired value or evaluation as shown below.
  • the average fiber diameter (average fiber width; average diameter of single fibers) of the cellulose fine fibers is preferably 1 to 200 nm, more preferably 2 to 100 nm, and particularly preferably 3 to 60 nm.
  • Cellulose fine fibers having an average fiber diameter of less than 1 nm require high cost for production.
  • the average fiber diameter of the cellulose fine fibers exceeds 200 nm, the effect of increasing the hydrogen bond points may not be obtained.
  • Cellulose fine fibers in the dispersion liquid gel and have viscosity.
  • the average fiber diameter is 100 nm or less, the dispersibility of the cellulose fine fibers is high and the three-dimensional network is easily maintained, so that the colored base material is sufficient. The difference in shade of the water-based coating composition due to the precipitation of the colored base material is unlikely to appear.
  • the average fiber diameter of the cellulose fine fibers 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 the cellulose fine fibers is as follows. First, 100 ml of an aqueous dispersion of cellulose fine fibers 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 single fiber) of the cellulose fine fibers 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 fine fibers is less than 200 ⁇ m, it may be difficult for the cellulose fine fibers to be uniformly dispersed in the aqueous coating composition. The decrease in dispersibility causes agglomeration of the colored base material, and causes problems in terms of resistance to dripping and good elongation of the water-based coating composition.
  • the average fiber length of the cellulose fine fibers exceeds 1300 ⁇ m, the fibers are easily entangled with each other, the area of contact between the fibers and the colored base material becomes small, the degree of adhesion becomes relatively small, and the colored base material becomes good. It will be difficult to disperse.
  • the average fiber length of cellulose fine fibers can be adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
  • the average fiber length of cellulose fine fibers is measured visually 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 fine fibers have an aspect ratio of 100 to 300, preferably 100 to 250, and more preferably 100 to 200. When the aspect ratio exceeds 300, the cellulose fine fibers 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.
  • the water retention of the cellulose fine fibers is, for example, preferably 150% or more, preferably 200%, more preferably 220%, and further preferably 250%. If the water retention level of the cellulose fine fibers is less than 150%, the dispersibility of the cellulose fine fibers may be deteriorated, and eventually the dispersibility of the colored base material adhering to the cellulose fine fibers may be deteriorated.
  • the water retention level of the cellulose fine fibers should be, for example, 500% or less. If it exceeds 500%, since the water retention capacity of the cellulose fine fibers 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 fine fibers can be adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
  • the water retention of cellulose fine fibers is determined by JAPAN TAPPI No. It is a value measured according to 26 (2000).
  • the light transmittance is 87% (mass / volume) or more, preferably 90%. It is preferably (mass / volume) or more, more preferably 92% (mass / volume) or more. If it is less than 87% (mass / volume), the color tone of the coating film surface of the water-based coating composition may give an impression different from the color tone of the colored base material.
  • the light transmittance of the cellulose fine fibers can be adjusted by, for example, selection of pulp fibers, pretreatment, defibration and the like.
  • the colored base material is also dispersed.
  • the cellulose fine fibers those modified with an ester group of phosphoric acid Cellulose fine fibers have many hydrogen bond sites, easily construct a three-dimensional network structure, and are appropriately dispersed in the water-based coating composition. Guessed.
  • the cellulose fine fibers have excellent light transmittance (see Patent Document 2), the color of the colored base material is not easily blocked by the cellulose fine fibers, and the colored base material exhibits a color close to the original color.
  • the crystallinity of the cellulose fine fibers is preferably 80% or less, preferably 80 to 50%, and more preferably 80 to 60%. If the crystallinity exceeds 60%, the B-type viscosity of the water-based coating composition becomes too high, and the smoothness is impaired.
  • the crystallinity can be adjusted by, for example, selection of pulp fibers, pretreatment, defibration and the like.
  • the cellulose fine fibers having a relatively low crystallinity do not have a relatively high viscosity.
  • the aqueous coating composition containing the cellulose fine fibers having the above-mentioned crystallinity has a viscosity approaching that of the cellulose fine fibers. Since the viscosity is not relatively high, the coating film surface becomes smooth.
  • the crystallinity is a value measured by the X-ray diffraction method in accordance with the "general rule of X-ray diffraction analysis" of JIS-K0131 (1996).
  • the cellulose fine fiber has an amorphous portion and a crystalline portion, and the crystallinity means the ratio of the crystalline portion in the entire cellulose fine fiber.
  • the cumulative 50% diameter (hereinafter, also referred to as D50, medium diameter) on a volume basis in the pseudo particle size distribution of cellulose fine fibers is preferably 5 to 60 ⁇ m, more preferably 5 to 40 ⁇ m.
  • D50 medium diameter
  • the cellulose fine fibers 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 60 ⁇ m, it becomes difficult for the cellulose fine fibers to be uniformly dispersed in the aqueous coating composition. The production of cellulose fine fibers having a median diameter of less than 5 ⁇ m is technically difficult.
  • 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 fine fibers defibrated from one or more kinds of pulp have high uniformity of fiber length and fiber diameter, and the dispersibility of the cellulose fine fibers 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 fine fibers 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 fine fibers having one peak have been sufficiently refined, can exhibit good physical properties as the cellulose fine fibers, 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.).
  • the carbon moiety modified by the ester group of the phosphorus oxo acid may be any carbon moiety from the 1st to 6th carbon moieties of glucose constituting the cellulose fine fibers.
  • An aqueous coating composition containing cellulose fine fibers having second cellulose fine fibers modified with an ester group is preferable because the cellulose fine fibers as a whole have little bias in polarity and have high dispersibility.
  • an aqueous coating composition containing cellulose fine fibers in which at least one of the carbon moieties 1 to 6 of glucose and a carbon moiety other than this carbon moiety are modified with an ester group of phosphoric acid, respectively. is also preferable.
  • the carboxylated cellulose fine fiber is one in which the hydroxyl group at the C6 position of glucose, which is one constituent unit of 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 fine fibers is also biased, and it is difficult to maintain uniform dispersion.
  • the mode of the particle size of the cellulose fine fibers and the median 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 fine fibers obtained by defibration can be dispersed in an aqueous medium and stored as a dispersion liquid prior to being mixed with the colored base material. It is particularly preferable that the total amount of the aqueous medium is water (aqueous solution). However, the aqueous medium may be another liquid that is partially compatible with water. As the other liquid, for example, lower alcohols having 3 or less carbon atoms can be used.
  • the dispersion liquid of cellulose fine fibers has a property of dispersing in the entire liquid. However, when the dispersion liquid of cellulose fine fibers is left for a while, it separates into a phase of cellulose fine fibers 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 dispersibility, which is a characteristic of cellulose fine fibers. The degree of dispersion varies depending on the raw material, processing means, physical characteristics, etc. of the cellulose fine fibers.
  • cellulose fine fibers obtained by defibrating mechanical pulp and cellulose fine fibers obtained by defibrating chemical pulp have predetermined dispersibility, but are modified with an ester group of phosphoroxoic acid. Not as dispersive as it is.
  • Cellulose fine fibers into which a phosphoric 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 they have excellent dispersibility. The inventor knows. It is thought that it will be high.
  • the viscosity differs depending on the concentration of the cellulose fine fibers, and the higher the concentration, the higher the viscosity.
  • the viscosity can be evaluated by the B-type viscosity.
  • the amount of cellulose fine fibers in which the ester of phosphoroxo acid is introduced exceeds this mixing ratio, the amount of cellulose fine fibers 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 fine fibers into which the ester of phosphoroxo acid is introduced are contained below this mixing ratio, the amount of the cellulose fine fibers 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 coating film surface formed by applying the water-based coating composition tends to maintain the morphology of the coating film surface immediately after application. If the morphology of the coating film surface immediately after coating is uneven, the morphology of the coating film surface is maintained, and the coating film surface is dried in that form. If the viscosity is not relatively high, it is presumed that the morphology of the coating film surface is smoothed by the action of an external force such as gravity and dried in the smoothed form to determine the morphology of the coating film surface.
  • the B-type viscosity of the water-based coating composition is, for example, 2000 cP or less, more preferably 800 cP or less. If the B-type viscosity of the water-based coating composition exceeds 2000 cP, smoothing of the coating film surface due to gravity is unlikely to occur immediately after the water-based coating composition is applied until it is dried, which is not preferable. In addition, the interaction such as hydrogen bonds between the cellulose fine fibers becomes large, and a large amount of energy is used to disperse the cellulose fine fibers in the aqueous coating composition, which increases the cost of producing the aqueous coating composition. It may lead to an increase.
  • the aqueous coating composition of the present embodiment the following minimum value of the high shear viscosity of 3.5 cps, preferably in the range of more than a shear rate 1 ⁇ 10 5, in the maximum value of the high shear viscosity of 3.3cP less, more preferably shear speed 1 ⁇ maximum value of high shear viscosity at 10 5 or more ranges may or less 3.2CP.
  • the maximum value of the high shear viscosity exceeds 3.5 cP, the smoothing of the coating film surface due to the action of gravity is suppressed immediately after drawing. Further, when the water-based coating composition is included in the brush and drawn, the water-based coating composition does not spread well and is difficult to draw.
  • the water-based coating composition exhibits a color close to the original color.
  • the lower limit of the B-type viscosity is preferably 600 cp or more so that the water-based coating composition drawn on the pottery substrate does not drip on a portion other than the drawing portion.
  • the aqueous coating composition In the production of a baked product, there is a step of allowing the object to be coated on which the aqueous coating composition is drawn to be left at 105 ° C. for 1 hour to dry.
  • One of the factors that causes the color tone of the water-based paint composition immediately after drawing to differ from the color tone after drying is the water content of the material constituting the water-based paint composition.
  • the water content of each of the colored base material, cellulose fine fibers, resin, etc. may affect the color tone.
  • the hue can be evaluated using the L * value, the a * value, and the b * value.
  • the L * value which is an index of lightness, affects the vividness of the water-based coating composition.
  • the constituent material refers to a substance constituting the aqueous coating composition, for example, a colored base material, cellulose fine fibers, a resin, or the like.
  • the fluctuation range of the L * value between application to the object to be coated and drying is within 25%, preferably within 15%, and more preferably within 10%. It is good. If the fluctuation range of the L * value exceeds 25%, the change in color tone before and after drying is too large, and the color tone after drying may be far from the color tone expected by the painter.
  • the fluctuation range of the a * value from application to the baking material to drying is preferably within 20%, preferably within 15%, and the b * value.
  • the fluctuation range is preferably 20% or less, preferably 10% or less. If the fluctuation range of the a * value exceeds 20% and / or the fluctuation range of the b * value exceeds 10%, the change in color tone is too large before and after drying, and the color tone after drying is far from the color tone expected by the painter. There is a risk of
  • the surface of the coating film has irregularities. This unevenness is considered to be due to the viscosity of the water-based coating composition and the bias of the constituent materials of the water-based coating composition.
  • the viscosity for example, the coating film surface formed by coating with a high-viscosity aqueous coating composition is not easily deformed, and is dried and solidified in the form immediately after coating.
  • the coating film surface made of the low-viscosity water-based coating composition is smoothed by the action of gravity due to the weight of the water-based coating composition, and dried and solidified.
  • the coating film surface becomes smooth.
  • the coating film surface portion where the constituent materials are dense becomes convex relative to the base ground in the normal direction, and the constituent materials are sparse.
  • the degree of the coating film surface portion being relatively convex in the normal direction with respect to the base surface of the pottery is small. Therefore, the bias of the constituent materials can be a factor of forming unevenness on the coating film surface.
  • the degree of unevenness on the coating film surface can be evaluated by the index of surface roughness.
  • the surface roughness of the coating film surface formed by applying the water-based coating composition to the pottery base is preferably 20% or less, preferably 18% or less, and more preferably 15%. If the surface roughness exceeds 20%, the coating film surface of the water-based coating composition may exhibit a color tone far from the original color tone.
  • a colored base material, cellulose fine fibers, silica stone powder (SiO 2 powder), and 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.
  • CMC carboxymethyl cellulose
  • xanthan gum xanthan gum
  • guar gum guar gum
  • pectin pectin
  • carrageenan carrageenan
  • the object to be coated is not particularly limited as long as it is a known substrate, 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 object to be coated, particularly the base material for pottery.
  • 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 water-based paint composition can be drawn on the base material 11 which is the basis of works 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).
  • Also referred to as 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 products can be used as ceramic products and enamel products as an example.
  • 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 product, it is possible to produce a 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 product, it is possible to produce a product composed of a plurality of layers in which one or more glaze layers are further overlapped on the glaze layer molded product.
  • Cellulose fine fibers are mainly composed of organic substances, and also contain a small amount of inorganic substances. The organic content of the cellulose fine fibers 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 paint containing the cellulose fine fibers 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.
  • the BTMP cellulose fine fibers are beaten to a ratio of fine fibers 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 finely divided. Then, it was prepared by measuring up with water so that the obtained product would be 3 to 4% by mass.
  • a processed product is obtained by beating to a ratio of fine fibers 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.
  • the phosphite esterified cellulose fine fibers 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 fine fiber is a cellulose fine fiber dispersion produced by the phosphite esterification method.
  • the high-share viscosity was measured with a high-share viscometer in each test example.
  • the shear rate was gradually increased from 0 (1 / sec) to 183580 (1 / sec). Then, the shear rate was gradually reduced to 0 (1 / sec).
  • the painter brings the brush into contact with the object to be coated, moves the brush at a high speed while following the object to be coated until a predetermined speed is reached, and then slows down the brush. It imitates the process of separating from the object to be coated.
  • the speed at which the painter moves the brush corresponds to a range of about 183580 (1 / sec) or less in terms of shear speed.
  • the measurement results of high shear viscosity are shown in Table 1.
  • Table 1 the shear rate and the rotation speed are correlated.
  • the maximum and minimum values in Table 1 indicate the maximum and minimum values of the high shear viscosities measured at different shear rates.
  • the final values in Table 1 show the high shear viscosities at 11470 (1 / sec) when the shear rate is gradually reduced.
  • the restoration rate in Table 1 shows the value obtained by dividing the final value by the high shear viscosity at 11470 (1 / sec) when the shear rate is gradually increased and multiplying by 100.
  • ⁇ Stretching condition> The elongation of the water-based coating composition was evaluated by drawing with a brush impregnating the water-based coating composition on the surface of a ceramic base material entirely covered with a glaze.
  • the evaluation criteria are as follows. ⁇ : The pattern drawn on the ceramic was not blurred and could be applied evenly. X: The pattern drawn on the pottery was blurred and uneven coating occurred.
  • ⁇ Dripping condition> The degree of sagging of the water-based paint composition was evaluated by drawing with a brush soaked in the water-based paint composition on the surface of a ceramic base material entirely covered with a glaze.
  • the evaluation criteria are as follows. ⁇ : When the ceramic base was turned upside down so that the drawn portion of the drawn ceramic base was on the bottom, the water-based paint composition did not drip on the outside of the drawn portion. X: When the ceramic base was turned upside down so that the drawn portion of the drawn ceramic base was on the bottom, the water-based paint composition hung down on the outside of the drawn portion.
  • the water-based coating composition was drawn on the base material for ceramics, dried at 105 ° C., and then the roughness of the coating film surface of the drawn water-based coating composition was evaluated.
  • the evaluation method is as follows.
  • the paint was applied to the ceramics, and after drying, the coated surface was photographed with a microscope (Keyence, product "VHX-6000") at a magnification of 500 times.
  • the coated surface was analyzed with 3D software, and the height difference (degree of unevenness) of the coated surface was calculated. This calculated numerical value is expressed as a percentage and can be used as an index of surface roughness.
  • the lower the height difference the smaller the surface roughness (%), the better the smoothness, the better the color development property, and the water-based coating composition exhibits a color tone close to the original color tone.
  • Table 2 shows the evaluation results of the B-type viscosity, the degree of elongation, the degree of sagging, and the surface roughness of the coating film.
  • BTMP cellulose fine fibers Those with a relatively high concentration of BTMP cellulose fine fibers did not stretch well.
  • the addition of LBKP cellulose fine fibers, phosphite esterified cellulose fine fibers, or carboxylated cellulose fine fibers had a good dripping condition and made it difficult for the liquid to drip.
  • the form of the cellulose fine fibers can be applied to any form such as powder, paste, slurry, etc., and the medium for dispersing the cellulose fine fibers 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 of the dispersion liquid (or water dispersion liquid) of cellulose fine fibers is a value measured at a temperature of 25 ° C. in accordance with JIS-Z8803 (2011 "Method for measuring liquid viscosity".
  • the B-type viscosity is a value. It is the resistance torque when the dispersion liquid is stirred, and the higher it is, the more energy is required for stirring.
  • -Drying means that the object to be dried is left at 105 ° C. for 1 hour, unless otherwise specified in the present specification.
  • the concept of glucose includes ⁇ -glucose, ⁇ -glucose, and other glucoses.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Table Devices Or Equipment (AREA)

Abstract

Le but de la présente invention concerne une composition aqueuse de matériau de revêtement dans laquelle la teinte après séchage est similaire à la teinte inhérente de la composition aqueuse de matériau de revêtement. La solution selon l'invention porte sur une composition aqueuse de matériau de revêtement qui est appliquée à un matériau de base de poterie et qui est caractérisée en ce qu'elle comprend : un substrat coloré ; et de fines fibres de cellulose qui sont modifiées par un groupe ester dans un oxoacide de phosphore et qui dispersent le substrat coloré et caractérisée en ce que la plage de variation de la valeur L* est située dans les 25 % dans une période entre l'application de la composition sur le matériau de base de poterie et le séchage de la composition.
PCT/JP2021/011014 2020-03-19 2021-03-18 Composition aqueuse de matériau de revêtement WO2021187552A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020049773A JP2021147533A (ja) 2020-03-19 2020-03-19 水性塗料組成物
JP2020-049773 2020-03-19

Publications (1)

Publication Number Publication Date
WO2021187552A1 true WO2021187552A1 (fr) 2021-09-23

Family

ID=77770997

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/011014 WO2021187552A1 (fr) 2020-03-19 2021-03-18 Composition aqueuse de matériau de revêtement

Country Status (2)

Country Link
JP (1) JP2021147533A (fr)
WO (1) WO2021187552A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023234129A1 (fr) * 2022-05-31 2023-12-07 日本製紙株式会社 Procédé de production de cellulose fibreuse fine et procédé de fibrillation de cellulose
JP7377397B1 (ja) 2022-05-31 2023-11-09 日本製紙株式会社 微細繊維状セルロースの製造方法およびセルロースの解繊方法

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
JP2019172482A (ja) * 2018-03-27 2019-10-10 愛媛県 多層絵付け方法
JP2019199671A (ja) * 2018-05-18 2019-11-21 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
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
JP2019172482A (ja) * 2018-03-27 2019-10-10 愛媛県 多層絵付け方法
JP2019199671A (ja) * 2018-05-18 2019-11-21 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
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

Also Published As

Publication number Publication date
JP2021147533A (ja) 2021-09-27

Similar Documents

Publication Publication Date Title
WO2021187552A1 (fr) Composition aqueuse de matériau de revêtement
CN104245858B (zh) 涂料用组合物
CN102753752B (zh) 造纸填料组合物
WO2021060480A1 (fr) Peinture à base aqueuse, céramique et procédé de peinture
JP6139404B2 (ja) フィブリル化セルロースを含む組成物の製造方法及び組成物
US2949397A (en) Mineral filled paper
TW201540753A (zh) 用於製造奈米纖維狀纖維素凝膠之方法
JP7481341B2 (ja) 自動車用光輝性塗料
JP2016069618A (ja) 水系塗料組成物
CA2387681A1 (fr) Liant alcool polyvinylique pour pigment de carbonate de calcium
JP7334773B2 (ja) 繊維状セルロース含有組成物及び塗料
WO2021187551A1 (fr) Composition aqueuse de revêtement
WO2021187550A1 (fr) Composition de revêtement aqueuse
JP7344496B2 (ja) 水性塗料と陶磁器類と絵付け方法
US3239475A (en) Coatings for fibrous boards
CN102666985A (zh) 用于纸张涂料中的包含细碳酸钙颗粒的水性浆料
US9951196B2 (en) Cationic polyoxometalate-coated alumina trihydrate dispersants
DE60001554T2 (de) Wässrige lackzusammensetzung
JP2020063351A (ja) 繊維状セルロース、繊維状セルロース分散液及び繊維状セルロースの製造方法
WO1994025672A1 (fr) Compositions liquides destinees a ameliorer la resistance et l'hydrophobicite de produits a base de filtres cellulosiques moulees
JP2015193832A (ja) 光触媒コーティング組成物
JP7040576B2 (ja) 繊維状セルロース、繊維状セルロース分散液及び繊維状セルロースの製造方法
JPH05163445A (ja) 水性樹脂塗料組成物
CA1075726A (fr) Methode de raffinage et de reduction de la viscosite des argiles de kaolin
SU1261995A1 (ru) Способ получени бумажного декоративно-облицовочного материала

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21771643

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21771643

Country of ref document: EP

Kind code of ref document: A1