WO2021187550A1 - Composition de revêtement aqueuse - Google Patents

Composition de revêtement aqueuse Download PDF

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Publication number
WO2021187550A1
WO2021187550A1 PCT/JP2021/011012 JP2021011012W WO2021187550A1 WO 2021187550 A1 WO2021187550 A1 WO 2021187550A1 JP 2021011012 W JP2021011012 W JP 2021011012W WO 2021187550 A1 WO2021187550 A1 WO 2021187550A1
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WIPO (PCT)
Prior art keywords
water
cellulose nanofibers
coating composition
based coating
viscosity
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PCT/JP2021/011012
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English (en)
Japanese (ja)
Inventor
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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Publication of WO2021187550A1 publication Critical patent/WO2021187550A1/fr

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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
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/02—Cellulose; Modified cellulose
    • 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.
  • Patent Document 1 discloses a technique relating to a water-based paint to which a predetermined viscosity is imparted as a technique relating to the water-based paint used for this drawing.
  • Patent Document 1 states that the aqueous coating composition can be used in the form of a viscous emulsion.
  • One of the purposes of imparting viscosity to the water-based coating composition is to draw and fix the water-based coating material on the substrate and prevent the water-based coating material from dripping from the drawn portion to the outside.
  • an object to be solved by the present invention is to provide a water-based coating composition which is hard to drip and has good spreadability.
  • the water-based paint When drawing on a substrate with a low-viscosity water-based paint, the water-based paint is repelled by the substrate at the interface between the substrate and the water-based paint due to the action of surface tension, and attempts to reduce the surface area.
  • the water-based paint which has a small surface area, hangs down on the outside of the drawing part along the surface of the substrate.
  • the water-based paint In order to draw a desired drawing on the substrate with the water-based paint, it is preferable that the water-based paint has a viscosity such that it is not easily repelled by the substrate.
  • the water-based coating composition of this embodiment contains cellulose nanofibers, it is viscous.
  • the viscosity can be evaluated, for example, by the B-type viscosity. When the B-type viscosity is within the above range, the water-based coating composition is less likely to be repelled by the substrate, fixed, and less likely to drip.
  • the water-based coating composition has good elongation. That is, it is preferable that the viscosity of the water-based coating composition is low while drawing along the surface of the substrate with a brush or the like containing the water-based coating composition.
  • the inventor found that the viscosity during drawing was related to the high shear viscosity.
  • the viscosity of the cellulose nanofibers was measured in the range of rotation speed 550 to 8800 rpm and shear rate 1 ⁇ 10 4 to 2 ⁇ 10 5 (1 / sec).
  • the aqueous coating composition is less likely to be smeared and stretches satisfactorily.
  • the cellulose nanofibers are appropriately dispersed in the water-based coating composition and the colored base material is attached to the cellulose nanofibers. Since the colored base material is appropriately dispersed in the aqueous coating composition via the cellulose nanofibers, color unevenness is less likely to occur when drawing.
  • the minimum value of the high shear viscosity of cellulose nanofibers is 3.5 cP or less at a shear rate of 1 ⁇ 10 5 to 2 ⁇ 10 5 (1 / sec).
  • the water-based coating composition of the first aspect is 3.5 cP or less at a shear rate of 1 ⁇ 10 5 to 2 ⁇ 10 5 (1 / sec).
  • a painter draws with different speeds of the brush. Among them, most of the brush speed is about 1 ⁇ 10 5 to 2 ⁇ 10 5 (1 / sec) in terms of shear velocity. If the minimum value of the high shear viscosity in this shear rate range is in the above range, the water-based coating composition has better elongation, and the painter can work without worrying about blurring.
  • the cellulose nanofibers have a median diameter of 5 to 60 ⁇ m in the pseudo particle size distribution, one peak value in the pseudo particle size distribution curve, and the peak value is in the range of 5 to 60 ⁇ m.
  • the water-based coating composition according to the first aspect according to the first aspect.
  • the cellulose nanofibers fall within the above-mentioned range, so that the size variation is small. Since the size variation is small, there is little bias in the water-based coating composition and the dispersibility is good. Since the cellulose nanofibers can be hydrogen-bonded to each other by the hydroxyl group of cellulose, the aqueous coating composition has a high viscosity as a whole. Then, when a shearing force is applied, the hydrogen bond is broken, so that the high shear viscosity of the aqueous coating composition is lowered. Therefore, the water-based coating composition has good fixability, is hard to drip, and has good spreadability.
  • the cellulose nanofibers are contained in an amount of 4% by mass or less, Cellulose nanofibers obtained by defibrating chemical pulp among the cellulose nanofibers contain 1 to 49% by mass.
  • the water-based coating composition according to the first aspect is not limited to the first aspect.
  • 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.
  • 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 having one esterified with phosphorus oxo acid have high viscosity (see Patent Document 2). Therefore, the water-based coating composition containing the cellulose nanofibers is less likely to drip.
  • it is a water-based coating composition that does not easily drip and has good spreadability.
  • 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 water-based coating composition in this embodiment contains a colored base material and cellulose nanofibers, and has a predetermined B-type viscosity and a predetermined high share viscosity.
  • the water-based paint composition used for drawing a pottery base (including a pottery base covered with a glaze layer) has a predetermined range of B-type viscosity, which improves the adhesion to the pottery base and causes dripping. Is suppressed, which is preferable.
  • B-type viscosity improves the adhesion to the pottery base and causes dripping. Is suppressed, which is preferable.
  • cracks may occur in the drawn portion. The cause of this crack is not clear, but it is presumed that it is due to uneven coating.
  • the coating unevenness refers to the thickness unevenness of the coating film formed by drawing the water-based coating composition on the base material of the pottery. If there is this coating unevenness, there will be some parts of the paint film where a large amount of water evaporates during firing, and some parts where it will not.
  • an aqueous coating composition having a predetermined range of B-type viscosity and a predetermined range of high shear viscosity could be produced from the following materials.
  • the water-based coating composition is shown below.
  • the colored base material is a substance that colors a pottery base, and exhibits various colors depending on the type of the base material.
  • As a method of painting the pottery base with the water-based paint 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 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.
  • 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 after firing at a high temperature, a glaze layer is formed by firing.
  • 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.
  • 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
  • water-based paint composition composed of cellulose nanofibers made from mechanical pulp
  • an object to be drawn for example, a pottery base or a glaze layer
  • the water-based paint composition spreads well and adheres to the object to be drawn. It has good properties 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 improve 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.
  • the dispersion liquid in which the cellulose nanofibers are dispersed has a relationship that the B-type viscosity increases when the concentration of the cellulose nanofibers is increased.
  • 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 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 made from mechanical pulp have a relatively large average fiber diameter, and have a relatively low degree of water retention and B-type viscosity, compared to cellulose nanofibers made from other pulps.
  • these physical characteristics improve the elongation of the water-based coating composition and make it difficult for uneven coating to occur. Therefore, it is presumed that small swellings that are likely to occur on the drawing surface after firing when drawn with a conventional paint are difficult to form when drawn with the water-based paint composition of the present embodiment.
  • cellulose nanofibers contained in the water-based coating composition those obtained by defibrating mechanical pulp and those obtained by defibrating chemical pulp can be preferably used. Further, among the chemical pulps, those obtained by adding an additive containing at least one of a phosphorus oxo acid and a phosphorus oxo acid metal salt to the cellulose fiber and defibrating the cellulose fiber esterified with the phosphorus oxo acid. You may use it.
  • These cellulose nanofibers 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 based on the solid content.
  • the concentration of the cellulose nanofibers is high, the interaction between the cellulose nanofibers 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 a different color. If it is less than 2% by mass, the cellulose nanofibers are difficult to disperse over the entire water-based coating composition, and the concentration of the cellulose nanofibers tends to be non-uniform in the water-based coating composition.
  • the aqueous coating composition has a relative B-type viscosity. It can be made as high as possible, or the high share viscosity can be set to a predetermined value or less.
  • 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 mass ratio exceeds 9: 1 cellulose nanofibers obtained by defibrating mechanical pulp are used in a relatively large amount, so that liquid dripping is likely to occur from the drawing portion and uneven coating is likely to occur. Become.
  • the aqueous coating composition is less likely to drip outward from the drawing portion, but the concentration of the cellulose nanofibers obtained by defibrating the mechanical pulp is low, so that the flow of the cellulose nanofibers is provided. The effect of improving the property and adhesion is weakened.
  • a form containing 1 to 49% by mass, more preferably 10 to 30% by mass, of cellulose nanofibers obtained by defibrating chemical pulp among the cellulose nanofibers in the water-based coating composition is preferable. Since the chemical pulp has an excellent viscosity, a water-based coating composition having a desired B-type viscosity can be obtained by including cellulose nanofibers obtained by defibrating the chemical pulp in the above range. When the cellulose nanofibers obtained by defibrating the chemical pulp exceed 49% by mass, the aqueous coating composition becomes highly viscous and does not have the desired high shear viscosity, resulting in poor elongation. If it is less than 1% by mass, the water-based coating composition may easily drip.
  • Pretreatment by chemical method includes, for example, hydrolysis of polysaccharide with acid (acid treatment), hydrolysis of polysaccharide with enzyme (enzyme treatment), swelling of polysaccharide with alkali (alkali treatment), oxidation of polysaccharide with oxidizing agent (alkaline treatment).
  • acid treatment hydrolysis of polysaccharide with acid
  • alkali treatment hydrolysis of polysaccharide with enzyme
  • alkali treatment oxidation of polysaccharide with oxidizing agent
  • Oxidization treatment reduction of polysaccharides with a reducing agent
  • oxidation with a TEMPO catalyst oxidation treatment
  • phosphoric acid esterification including phosphite esterification
  • 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.
  • esterification chemical treatment
  • phosphoric acid or phosphoric acid typified by phosphoric acid is performed prior to defibration
  • the fiber raw material can be made finer, and the produced cellulose nanofibers have a large aspect ratio and become strong. It is excellent and has high light transmittance and viscosity.
  • Esterification with a phosphorus oxo acid can be carried out by the method described in Patent Document 2 (Japanese Unexamined Patent Publication No. 2019-199671).
  • Patent Document 2 Japanese Unexamined Patent Publication No. 2019-199671
  • An example of cellulose nanofibers esterified with phosphoric acid is shown below.
  • a part of the hydroxy group of the cellulose fiber is replaced with the functional group represented by the following structural formula (1) to introduce an ester of phosphoroxo acid, and the amount of the functional group introduced in the structural formula (1) is the amount of the cellulose fiber introduced.
  • Examples thereof include cellulose nanofibers exceeding 2 mm Albanyl per gram.
  • Structural formula (1) In the structural formula (1), 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. This cellulose nanofiber has extremely high light transmittance and viscosity.
  • the esterification reaction with phosphorus oxo acid proceeds by adding a solution having an pH of less than 3.0 consisting of an additive containing at least one of phosphorus oxo acids and phosphorus oxo acid metal salts to cellulose fibers, heating and defibrating. do.
  • additives include phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, ammonium polyphosphate, lithium dihydrogen phosphate, trilithium dihydrogen phosphate, and dihydrogen phosphate.
  • the amount of the phosphorus oxo acid ester or phosphonic acid ester introduced is more than 2.0 mmol, preferably 2.1 mmol or more, and more preferably 2.2 mmol or more per 1 g of cellulose fine fibers. Further, it is 3.4 mmol or less, preferably 3.2 mmol or less, and more preferably 3.0 mmol or less. If the amount introduced is 2.0 mmol or less, the viscosity of the aqueous coating composition may not be extremely increased. On the other hand, if the amount introduced exceeds 3.4 mmol, the cellulose fibers may dissolve in water.
  • the cellulose fiber esterified with phosphoric acid may include one in which a part of the hydroxy group of the cellulose fiber is replaced with a carbamate group and carbamate is introduced.
  • urea additive used for substitution with carbamate groups include at least one of urea and urea derivatives.
  • 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.
  • beaters high-pressure homogenizers, homogenizers such as high-pressure homogenizers, stone mill type friction machines such as grinders and grinders, single-screw kneaders, multi-screw kneaders, kneader refiners, jet mills, etc. It can be done by beating the raw material pulp in use. However, it is preferable to use a refiner or a jet mill.
  • 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 average fiber diameter (average fiber width; average diameter of single fibers) of the cellulose nanofibers is preferably 1 to 200 nm, more preferably 1 to 100 nm, and particularly preferably 3 to 60 nm. If the average fiber diameter of the cellulose nanofibers is less than 1 nm, the degree of water retention of the cellulose nanofibers becomes too large, and the elongation of the water-based coating composition may deteriorate.
  • the average fiber diameter of the cellulose nanofibers exceeds 200 nm, the effect of increasing the hydrogen bond points may not be obtained.
  • 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 single fiber) of cellulose nanofibers obtained from mechanical pulp 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 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 median diameter of the cellulose nanofibers in the pseudo particle size distribution is preferably 5 to 60 ⁇ m, more preferably 5 to 40 ⁇ m.
  • the medium diameter is the above size, 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 5 ⁇ 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 5 ⁇ m is technically difficult.
  • the peak value in the pseudo particle size distribution curve of cellulose nanofibers 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. Is preferable.
  • 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 cellulose nanofibers When the peak value in the pseudo particle size distribution curve is in the range of 5 to 60 ⁇ m, the cellulose nanofibers have almost the same pseudo particle size as a whole and are dispersed with little bias, so that it is preferable that the cellulose nanofibers can be drawn without color unevenness.
  • 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 colored base material In the paint containing the cellulose nanofibers and the colored base material, it is presumed that 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. For example, a form in which 0.02 to 0.04 parts by mass, more preferably 0.03 to 0.04 parts by mass of cellulose nanofibers are contained with respect to 1 part by mass of the colored base material can be exemplified. If it exceeds this range, 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. Further, if it is less than this range, the amount of cellulose nanofibers is small, the dispersibility of the colored base material is not good in the entire paint, and it causes color unevenness when drawing.
  • the B-type viscosity of 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. 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 cellulose nanofibers is preferably 2000 cP or less. If the B-type viscosity exceeds 2000 cP, the paint will not spread well when the paint is drawn. In addition, the interaction such as hydrogen bonds between the cellulose nanofibers becomes large, and a large amount of energy is used to disperse the cellulose nanofibers in the aqueous coating composition, which may lead to an increase in manufacturing cost.
  • the water-based coating composition of the present embodiment has a shear rate of 0.8 ⁇ 10 5 (1 / sec) or more and a minimum value of high shear viscosity of 3.5 cP or less, preferably a shear rate of 1 ⁇ 10 5 to 2 ⁇ 10 5.
  • the minimum value of high-share viscosity is 3.5 cP or less up to (1 / sec), and more preferably the minimum value of high-share viscosity is 3 up to shear rate 1 ⁇ 10 5 to 2 ⁇ 10 5 (1 / sec).
  • cP or less more preferably shear velocity between 1 ⁇ 10 5 and 2 ⁇ 10 5 (1 / sec), with a minimum value of high shear viscosity of 3.0 cP or less, preferably shear rate 1 ⁇ 10 5 to 2 ⁇
  • the maximum value of high shear viscosity up to 10 5 (1 / sec) is preferably 3.0 cP or less.
  • 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 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.
  • Pigment Green M-142 from Nikko Pigment Industry Co., Ltd.
  • BTMP cellulose nanofiber aqueous dispersion mechanical pulp bleached product
  • LBKP cellulose nanofiber aqueous dispersion chemical pulp bleached product derived from broadleaf tree pulp
  • a paint was produced by mixing subphosphorylated cellulose nanofibers and water.
  • 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.
  • the obtained product was concentrated and prepared so as to have a concentration of 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.
  • 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.
  • ⁇ Test Example 5> The composition of each substance in the water-based coating composition of Test Example 5 is as follows. ⁇ Pigment 1.0g -2.0% BTMP cellulose nanofiber 0.05g -1.0% phosphite esterified cellulose nanofiber 0.01 g ⁇ Water 3.45g Each of these substances was blended to obtain a water-based coating composition (Test Example 5). ⁇ Test Example 6> The composition of each substance in the water-based coating composition of Test Example 6 is as follows. ⁇ Pigment 1.0g -2.2% BTMP cellulose nanofiber 0.06 g -2.0% LBKP cellulose nanofiber 0.02g ⁇ Water 3.56 Each of these substances was blended to obtain a water-based coating composition (Test Example 6).
  • 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 touches the brush to the object to be drawn, moves the brush at a high speed while following the object to be drawn up to a predetermined speed, and then slows down the brush. It imitates the process of moving the image away from the object to be drawn.
  • 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 surface roughness was evaluated by photographing with an optical microscope (Keyence, Inc., product "VHX-6000") at a magnification of 500 times in a 3D photographing mode, and evaluating by the height difference of the unevenness of the surface. An image with few protrusions of the paint on the surface was judged to have good surface roughness.
  • Table 2 shows the evaluation results of the B-type viscosity, the degree of elongation, the degree of sagging, and the smoothness of the coating film surface.
  • Test Example 1 the concentration of cellulose nanofibers was relatively low, and the result was that the B-type viscosity was low, making it easy to drip.
  • Test Example 2 and Test Example 3 had a relatively high high-share viscosity and did not have good elongation.
  • Test Examples 4 to 6 had good elongation and did not easily drip.
  • Test Example 5 having subphosphoesterified cellulose nanofibers had a relatively high B-type viscosity and a low high-share viscosity, that is, it had excellent thixotropic properties. This is presumed to be due to the following reasons. Since the subphosphorus esterified cellulose nanofibers have excellent viscosities as described in Patent Document 2, Test Example 5 has a predetermined B-type viscosity even if the blending amount is relatively small.
  • the average fiber diameter of the subphosphorylated cellulose nanofibers is about 3 nm, and the average fiber length is about 100 to 300 nm, which are relatively smaller than those of BTMP cellulose nanofibers and LBKP cellulose nanofibers.
  • 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 of the dispersion liquid of cellulose nanofibers is a value measured in accordance with "Method for measuring liquid viscosity" of JIS-Z8803 (2011).
  • the B-type viscosity is the resistance torque when the dispersion liquid is stirred, and the higher it is, the more energy is 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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  • 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)

Abstract

La présente invention concerne une composition de revêtement aqueuse qui ne goutte presque pas et qui s'étale bien. L'invention propose une composition de revêtement aqueuse caractérisée en ce qu'elle comprend un matériau de base coloré et des nanofibres de cellulose, et caractérisée en ce que la viscosité de type B est de 600 cP ou plus, la vitesse de cisaillement est de 0,8×105(1/sec) ou plus, et la valeur minimale de la viscosité de cisaillement élevée est de 3,5 cP ou moins.
PCT/JP2021/011012 2020-03-19 2021-03-18 Composition de revêtement aqueuse WO2021187550A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013181167A (ja) * 2012-03-05 2013-09-12 Dai Ichi Kogyo Seiyaku Co Ltd 水性インク組成物およびそれを用いた筆記具
JP2016065173A (ja) * 2014-09-25 2016-04-28 三菱鉛筆株式会社 筆記具用水性インク組成物
JP2016069617A (ja) * 2014-09-28 2016-05-09 第一工業製薬株式会社 水性インク組成物およびそれを用いた筆記具
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 (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013181167A (ja) * 2012-03-05 2013-09-12 Dai Ichi Kogyo Seiyaku Co Ltd 水性インク組成物およびそれを用いた筆記具
JP2016065173A (ja) * 2014-09-25 2016-04-28 三菱鉛筆株式会社 筆記具用水性インク組成物
JP2016069617A (ja) * 2014-09-28 2016-05-09 第一工業製薬株式会社 水性インク組成物およびそれを用いた筆記具
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

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