WO2023132012A1 - Composition contenant de fines fibres de cellulose, matière de revêtement et épaississant - Google Patents

Composition contenant de fines fibres de cellulose, matière de revêtement et épaississant Download PDF

Info

Publication number
WO2023132012A1
WO2023132012A1 PCT/JP2022/000113 JP2022000113W WO2023132012A1 WO 2023132012 A1 WO2023132012 A1 WO 2023132012A1 JP 2022000113 W JP2022000113 W JP 2022000113W WO 2023132012 A1 WO2023132012 A1 WO 2023132012A1
Authority
WO
WIPO (PCT)
Prior art keywords
fine cellulose
cellulose fibers
mass
sulfonated
water
Prior art date
Application number
PCT/JP2022/000113
Other languages
English (en)
Japanese (ja)
Inventor
祥 日浅
朱十 西村
通誉 杉野
聖示 西山
Original Assignee
丸住製紙株式会社
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 丸住製紙株式会社 filed Critical 丸住製紙株式会社
Priority to PCT/JP2022/000113 priority Critical patent/WO2023132012A1/fr
Publication of WO2023132012A1 publication Critical patent/WO2023132012A1/fr

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • A61K47/38—Cellulose; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
    • C08B5/14—Cellulose sulfate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/16—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
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols

Definitions

  • the present invention relates to fine cellulose fiber-containing compositions, paints and thickeners. More particularly, it relates to compositions containing fine cellulose fibers for use in target liquids, and paints and thickeners containing the compositions containing fine cellulose fibers.
  • CNF Cellulose nanofibers
  • TEMPO nano-processing plant-derived cellulose
  • the use of CNF-containing composite materials is expected in various fields. In particular, it is expected to exert excellent thickening action (high viscosity and thixotropic properties), so development as a novel thickener with less environmental load is underway. For example, in the field of paints, the inclusion of CNF as a thickener is expected to improve coatability and strength of the coating film after drying.
  • Patent Document 1 discloses a composition comprising a fibrous cellulose-containing composition, a resin, and an isocyanate curing agent, wherein the fibrous cellulose-containing composition contains fine particles having a phosphite group or a substituent derived from a phosphite group.
  • a paint containing fibers, a water-soluble low-molecular-weight compound such as urea, and a predetermined saccharide is disclosed.
  • Patent Document 2 discloses a water-based paint containing CNF in a predetermined metal salt, silicate, resin, and water-based solvent.
  • Patent Document 3 discloses a thickener composition for paints or pharmaceuticals containing a predetermined polymer compound, water and CNF having a substituent derived from a carboxyl group.
  • Patent Documents 1 to 3 Although CNF can be dispersed in paints, pharmaceuticals, etc. to some extent, the dispersibility of CNF is insufficient and some CNF precipitates as aggregates. There are problems such as In addition, the techniques of these documents contain predetermined polymers, sugars, metal salts, etc. in order to disperse CNF in paints, pharmaceuticals, etc., so there are problems such as limited target paints and pharmaceuticals. There is room for improvement from the viewpoint of handleability.
  • an object of the present invention is to provide a fine cellulose fiber-containing composition capable of improving the dispersibility and handleability of CNF, and a paint and a thickener containing such a fine cellulose fiber-containing composition. do.
  • the present inventors have made intensive studies to solve the above problems, and found that the above problems can be solved by using fine cellulose fibers obtained by introducing sulfo groups in a water-soluble solvent. Completed.
  • the fine cellulose fiber-containing composition of the present invention has a sulfo group introduction amount of 0.4 mmol/g to 3.0 mmol/g, and a sulfone having a haze value of 30% or less at a solid content concentration of 0.5% by mass. It is a mixture of denatured fine cellulose fibers, water, and a water-soluble solvent.
  • the paint of the present invention is a paint containing the fine cellulose fiber-containing composition of the present invention, and the content of sulfonated fine cellulose fibers in the fine cellulose fiber-containing composition is 0.05% by mass to 10% by mass. is.
  • the thickener of the present invention is a thickener containing the fine cellulose fiber-containing composition of the present invention, and the content of the sulfonated fine cellulose fibers is 0.1 mass based on the total amount of the thickener. % to 95% by mass.
  • the fine cellulose fiber-containing composition of the present invention by containing fine cellulose fibers exhibiting predetermined physical property values and having an amount of sulfo groups adjusted within a predetermined range, in a solution containing a water-soluble solvent can maintain the fine cellulose fibers in a dispersed state. Then, if the fine cellulose fiber-containing composition of the present invention is used for a target liquid having affinity for a water-soluble solvent, the fine cellulose fibers can be appropriately dispersed in the target liquid. Excellent properties can be imparted. According to the paint of the present invention, since the fine cellulose fibers are appropriately dispersed in the paint, the coatability and the stability of the coating film can be improved.
  • the thickener of the present invention since fine cellulose fibers are appropriately dispersed in the thickener, it is possible to improve thickening properties and thixotropic properties. Therefore, if a thickening agent is used for the target liquid, appropriate thickening properties and thixotropic properties can be imparted.
  • FIG. 4 is a diagram showing experimental results, and a table showing characteristics (physical properties) of a slurry containing sulfonated cellulose fine fibers (corresponding to the composition containing fine cellulose fibers of the present embodiment).
  • FIG. 4 is a diagram showing experimental results, and a table showing properties (physical properties) of slurry containing sulfonated fine cellulose fibers.
  • FIG. 3 is a diagram showing experimental results, and a table showing properties (physical properties) of a paint containing a slurry containing sulfonated fine cellulose fibers (corresponding to the paint of the present embodiment).
  • FIG. 4 is a diagram showing experimental results, and a table showing characteristics (physical properties) of a slurry containing sulfonated cellulose fine fibers (corresponding to the composition containing fine cellulose fibers of the present embodiment).
  • FIG. 4 is a diagram showing experimental results, and a table showing properties (physical properties) of slurry containing sulfonated fine cellulose fibers
  • FIG. 3 is a diagram showing experimental results, and a table showing properties (physical properties) of a paint containing a slurry containing sulfonated fine cellulose fibers (corresponding to the paint of the present embodiment).
  • FIG. 3 is a diagram showing experimental results, and a table showing properties (physical properties) of a paint containing a slurry containing sulfonated fine cellulose fibers (corresponding to the paint of the present embodiment).
  • FIG. 3 is a diagram showing experimental results, and a table showing characteristics (physical properties) of cosmetics containing a slurry containing sulfonated fine cellulose fibers (corresponding to the cosmetics of the present embodiment).
  • the fine cellulose fiber-containing composition of the present embodiment is characterized by being able to impart excellent properties to the target liquid by containing the sulfonated fine cellulose fibers having affinity with the water-soluble solvent. are doing.
  • the fine cellulose fiber-containing composition of the present embodiment is a composition containing water, a water-soluble solvent, and sulfonated fine cellulose fibers.
  • the water-soluble solvent of the fine cellulose fiber-containing composition of the present embodiment is not particularly limited as long as it is a solvent that is miscible with water.
  • water-soluble solvents that are industrially used can be used. For example, those having a solubility in water (g/100 mL water) of 10 g or more are suitable as water-soluble solvents.
  • water-soluble solvents examples include lower alcohols such as methanol, ethanol, propanol, isopropyl alcohol, and butanol, ethylene glycol, acetic acid, tetrahydrofuran, dioxane, acetone, ethyl methyl ketone, acetonitrile, pyridine, dimethyl sulfoxide, and derivatives thereof. etc., and these substances can be used alone or in combination of two or more.
  • the water-soluble solvent is not limited to these substances as long as it has the functions described above.
  • the target liquid is cosmetics that are used on humans, ethanol, isopropyl alcohol, etc., which have little effect on humans, can be used as water-soluble solvents.
  • a highly volatile solvent such as methanol or propylene glycol monomethyl ether 1-methoxy-2-propanol (PM) can be used as the water-soluble solvent.
  • the target liquid in which the composition containing fine cellulose fibers of the present embodiment can be used (liquid to which the composition containing fine cellulose fibers of the present embodiment is added or mixed) has affinity with a water-soluble solvent.
  • a water-soluble solvent There is no particular limitation as long as it is a liquid.
  • a liquid for example, not only complete liquids such as water, but also water-based or oil-based paints containing insoluble substances such as pigments, liquid cosmetics such as lotions and liquid medicines, as well as gels such as cleansing agents and moisturizing creams.
  • Various liquids such as external skin preparations of various properties such as cosmetics in the form of liquids and slurries can be mentioned as target liquids, but it is needless to say that the liquids are not limited to these.
  • Water of the fine cellulose fiber-containing composition of the present embodiment Water contained in the fine cellulose fiber-containing composition of the present embodiment is not particularly limited.
  • Water contained in the fine cellulose fiber-containing composition of the present embodiment is not particularly limited.
  • pure water, distilled water, ion-exchanged water, RO water, Milli-Q water, ultrapure water, and the like can be used.
  • the sulfonated fine cellulose fibers contained in the fine cellulose fiber-containing composition of the present embodiment are fine cellulose fibers obtained by refining cellulose fibers.
  • the sulfonated fine cellulose fibers contain a plurality of finer cellulose fibers (hereinafter referred to as unit fibers).
  • sulfonated fine cellulose fibers are fibers formed by connecting multiple unit fibers.
  • this unit fiber at least part of the hydroxyl group (--OH group) of cellulose (chain polymer in which D-glucose is ⁇ (1 ⁇ 4) glycoside-bonded, general formula (1)) constituting such fiber is It is sulfated with a sulfo group represented by the general formula (2).
  • the sulfonated fine cellulose fibers are obtained by substituting some of the hydroxyl groups of the fine cellulose fibers with sulfo groups.
  • substitution refers to the replacement of hydroxyl groups of cellulose with sulfo groups, and means that at least some of the hydroxyl groups constituting the cellulose after the reaction are bonded with sulfo groups through a substitution reaction or the like.
  • the hydroxyl groups of cellulose are substituted with sulfo groups, meaning that at least part of the hydroxyl groups (--OH groups) of cellulose are substituted with sulfo groups.
  • a part of the hydroxyl group means to include not only the "H” (hydrogen atom) of the "--OH group” but also the "OH".
  • the sulfo group is bonded to the oxygen atom of the hydroxyl group instead of the hydrogen atom (H), and the carbon of the cellulose and the oxygen atom of the hydroxyl group (O ) and a sulfo group (so-called ester bond, for example, general formula (3)).
  • the structure in which a portion of the hydroxyl groups of cellulose is substituted with a sulfo group includes a structure in which a sulfo group is directly bonded to the carbon to which the hydroxyl group of cellulose is bonded (e.g., general formula (4)).
  • R represents a structure obtained by removing some hydroxyl groups from cellulose (general formula (1)).Z represents a hydrogen ion, a metal ion, an onium ion, or a cationic organic compound.
  • the sulfo group in general formula (3) can be represented by (--SO 3 ⁇ ) r ⁇ Z r+ .
  • Z is at least selected from the group consisting of hydrogen ions, alkali metal cations, monovalent transition metal ions, onium ions (ammonium ions, aliphatic ammonium ions, aromatic ammonium ions, etc.), and cationic polymers. It is one type. In some cases, Z is at least one selected from the group consisting of compounds containing two or more cationic functional groups in the molecule, such as alkaline earth metal cations, polyvalent metal cations, and diamines. .
  • R represents a structure obtained by removing some hydroxyl groups from cellulose (general formula (1)).Z represents a hydrogen ion, a metal ion, an onium ion, or a cationic organic compound.
  • the sulfo group in general formula (4) can also be represented in the same manner as in general formula (3), and Z can also include similar compounds.
  • sulfonated fine cellulose fibers functional groups other than sulfo groups may be bonded to some of the hydroxyl groups of the fine cellulose fibers. may contain.
  • sulfo groups may be introduced into the hydroxyl groups of the cellulose fibers constituting the sulfonated fine cellulose fibers.
  • the amount of sulfo groups introduced into the sulfonated fine cellulose fibers can be represented by the amount of sulfur derived from the sulfo groups, and the amount of sulfo groups introduced is not particularly limited.
  • the amount of sulfo groups introduced per 1 g (mass) of sulfonated fine cellulose fibers is preferably adjusted to be higher than 0.4 mmol/g, more preferably 0.4 mmol/g to 9.9 mmol. /g, more preferably 0.5 mmol/g to 9.9 mmol/g, even more preferably 0.6 mmol/g to 9.9 mmol/g.
  • the amount of sulfo groups introduced is preferably higher than 0.4 mmol/g, more preferably 0. .5 mmol/g or more is preferable.
  • the amount of sulfur introduced approaches 9.9 mmol/g, there is concern that the crystallinity will decrease, and the cost of introducing sulfur tends to increase.
  • the amount of sulfo groups introduced into the sulfonated fine cellulose fibers is preferably adjusted to be higher than 0.4 mmol/g and 3.0 mmol/g or less, more preferably 0.5 mmol/g to 3.0 mmol/g. .0 mmol/g, more preferably 0.5 mmol/g to 2.0 mmol/g, even more preferably 0.5 mmol/g to 1.7 mmol/g, more preferably 0.5 mmol/g ⁇ 1.5 mmol/g. Also from the viewpoint of the transparency of the sulfonated fine cellulose fibers, it is preferable to adjust the amount of the sulfo group to be introduced so as to fall within the same range as the above range.
  • the sulfonated fine cellulose fibers preferably have the transparent structure described above. Specifically, it is a sulfonated fine cellulose fiber having a structure prepared so that the haze value of a dispersion liquid in which the sulfonated fine cellulose fiber has a solid content concentration of 0.5% by mass is 30% or less.
  • the structure of the sulfonated fine cellulose fibers preferably has a haze value of 20% or less, more preferably has a haze value of 15% or less, and still more preferably has a haze value of 10% or less. Those having a structure are preferred.
  • the composition containing fine cellulose fibers of the present embodiment contains sulfonated fine cellulose fibers having a predetermined structure, the fine cellulose fibers can be maintained in a dispersed state in the presence of a water-soluble solvent. can.
  • the composition containing fine cellulose fibers of the present embodiment is a composition having a predetermined transparency, and such transparency is due to the sulfonated fine cellulose fibers having the structure described above.
  • the coexistence of the sulfonated fine cellulose fibers having such a structure with the water-soluble solvent suppresses the formation of aggregates (lumps).
  • the composition containing fine cellulose fibers of the present embodiment is added to a target liquid (liquid having affinity for a water-soluble solvent), the target liquid can The sulfonated fine cellulose fibers can be easily dispersed therein. As a result, the effects of the sulfonated fine cellulose fibers on the target liquid, such as improved viscosity and desired thixotropy, can be exhibited. In other words, if the composition containing fine cellulose fibers of the present embodiment is used in a target liquid, it is possible to impart excellent properties resulting from the sulfonated fine cellulose fibers to the target liquid.
  • the sulfo groups possessed by the sulfonated fine cellulose fibers and the hydrophilic groups of the water-soluble solvent interact with each other through, for example, hydrogen bonding, whereby the sulfonated fine cellulose fibers are separated from each other. It is estimated that the aggregation of is suppressed.
  • the fine cellulose fiber-containing composition of the present embodiment is added to or mixed with a target liquid and used, the water-soluble solvent is mixed with the component in the target liquid with affinity in the target liquid.
  • the aggregation of the sulfonated fine cellulose fibers is suppressed by the combination, and the sulfonated fine cellulose fibers are easily dispersed in the target liquid.
  • the water-soluble solvent of the fine cellulose fiber-containing composition of the present embodiment has the property of being easily mixed with the components in the target liquid, or has affinity, the sulfonated fine It is thought that the cellulose fibers can be dispersed more appropriately.
  • the amount of sulfo groups introduced into the sulfonated fine cellulose fibers may be evaluated by directly measuring the sulfo groups, or may be evaluated by the amount of sulfur introduced due to the sulfo groups.
  • the conductivity can be calculated based on the value obtained by measuring the electrical conductivity while dropping an aqueous sodium hydroxide solution.
  • a predetermined amount of sulfonated fine cellulose fibers is combusted, and the sulfur content in the combusted material is measured using a combustion ion chromatograph in accordance with IEC 62321. It can be calculated based on the value.
  • the amount of sulfur introduced is 1:1.
  • the amount of sulfur introduced per 1 g (mass) of sulfonated fine cellulose fibers is 0.4 mmol/g
  • the amount of sulfo groups introduced is naturally 0.4 mmol/g.
  • the former measuring method (method using electrical conductivity) will be described more specifically.
  • 1/10 by volume of a slurry containing 0.2% by mass of nanocellulose fibers is added with a strongly acidic ion exchange resin (Amberjet 1024; conditioned by Organo Co., Ltd.) and shaken for 1 hour or more. (Treatment with ion exchange resin). Then, it is poured onto a mesh with an opening of about 90 ⁇ m to 200 ⁇ m to separate the resin from the slurry.
  • the change in electrical conductivity value is measured while adding 0.5N aqueous sodium hydroxide solution to the slurry containing sulfonated fine cellulose fibers after treatment with the ion exchange resin.
  • the titration amount of sodium hydroxide at this point of inflection corresponds to the amount of sulfo groups, and the amount of sodium hydroxide at this point of inflection is divided by the solid content of the sulfonated fine cellulose fibers used for measurement, thereby introducing sulfo groups. You can ask for the quantity.
  • the amount of sulfur introduced into the sulfonated pulp before refining may be used.
  • the structure of the sulfonated fine cellulose fibers is described in detail below.
  • the sulfonated fine cellulose fibers are fine cellulose fibers obtained by making cellulose fibers fine as described above, and the fibers are prepared to have a very fine structure.
  • Such a structure improves dispersibility in a water-soluble solvent and enables proper dispersion in a solution.
  • by evaluating the transparency it is possible to identify the sulfonated fine cellulose fibers contained in the fine cellulose fiber-containing composition of the present embodiment.
  • the sulfonated fine cellulose fibers having such a structure are maintained in a dispersed state in the presence of a water-soluble solvent in the fine cellulose fiber-containing composition of the present embodiment.
  • the sulfonated fine cellulose fibers of the fine cellulose fiber-containing composition of the present embodiment are preferably prepared so that the average fiber width is 1 nm to 30 nm when observed with an electron microscope, and more preferably. is prepared to be 2 nm to 30 nm.
  • the average fiber width of the sulfonated fine cellulose fibers exceeds 30 nm, the aspect ratio tends to decrease. There is a possibility that it may become difficult to exert an appropriate effect (for example, viscosity, etc.) when it is added.
  • the average fiber width of the sulfonated fine cellulose fibers is preferably 2 nm to 30 nm, more preferably 2 nm to 20 nm, still more preferably 2 nm to 10 nm, in terms of improving viscosity.
  • the aspect ratio (average fiber length/average fiber width) of the sulfonated fine cellulose fibers is preferably 20 or more, more preferably 50 or more, and still more preferably 100 or more, depending on the average fiber length described later. be.
  • the average fiber width when the average fiber width is larger than 30 nm, it approaches 1/10 of the wavelength of visible light, and when it is combined with a matrix material, refraction and scattering of visible light easily occur at the interface, and scattering of visible light occurs. As a result, transparency, which will be described later, tends to decrease.
  • the fiber width is 30 nm or less, the fiber width is 1/10 or less of the wavelength of visible light, and when combined with the paint composition, the light is not scattered and the fiber is transparent. The advantage is that a paint with high toughness can be obtained.
  • the sulfonated fine cellulose fibers are preferably prepared so that the average fiber width is 20 nm or less, more preferably 10 nm or less. .
  • the average fiber width is adjusted to 10 nm or less, scattering of visible light can be further reduced, so sulfonated fine cellulose fibers having high transparency can be obtained.
  • the average fiber width of sulfonated microcellulose fibers can be measured using known techniques. For example, sulfonated fine cellulose fibers are dispersed in a solvent such as pure water to prepare a mixed solution having a predetermined mass %. Then, this mixed solution is spin-coated on a silica substrate coated with PEI (polyethyleneimine), and sulfonated fine cellulose fibers on this silica substrate are observed. As an observation method, for example, a scanning probe microscope (eg, SPM-9700 manufactured by Shimadzu Corporation) can be used. By randomly selecting 20 sulfonated fine cellulose fibers in the observed image and measuring and averaging the width of each fiber, the average fiber width of the sulfonated fine cellulose fibers can be obtained.
  • a scanning probe microscope eg, SPM-9700 manufactured by Shimadzu Corporation
  • the sulfonated fine cellulose fibers have a structure having the average fiber width described above, they exhibit a certain level of transparency in a slurry state.
  • sulfonated fine cellulose fibers exhibit a total light transmittance of 90% or more when prepared to have a solid content concentration of 0.5% by mass. This total light transmittance is more preferably 95% or more.
  • the sulfonated fine cellulose fibers exhibit a haze value of 30% or less when prepared to have a solid content concentration of 0.5% by mass. This haze value is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. Details of the measurement method will be described later.
  • the sulfonated fine cellulose fibers have the above-described average fiber width and have an elongated fibrous structure (for example, the aspect ratio is 20 or more), so that they exhibit predetermined viscosity characteristics in a slurry state.
  • the sulfonated fine cellulose fiber has a viscosity of 3000 mPa ⁇ when measured using a Brookfield viscometer at a solid content concentration of 0.5% by mass at 20 ° C. and a rotation speed of 6 rpm for 3 minutes. s (3 Pa ⁇ s) or more.
  • the sulfonated fine cellulose fibers were measured using a Brookfield viscometer at a solid content concentration of 0.5% by mass at 20 ° C. and a rotation speed of 6 rpm and a rotation speed of 60 rpm. is calculated, and the thixotropic index calculated from each viscosity ratio (viscosity at 6 rpm/viscosity at 60 rpm) exhibits 5.0 or more. Details of the measurement method will be described later.
  • the content ratio (mixture ratio) of water, water-soluble solvent and sulfonated fine cellulose fibers contained in the composition containing fine cellulose fibers of the present embodiment is not particularly limited, but is prepared so as to have the following ratios. can do.
  • the content of water can be blended to 20 to 300 parts by mass with respect to 1 part by mass of sulfonated fine cellulose fibers. It is preferably 40 parts by mass or more, more preferably 100 parts by mass or more based on 1 part by mass of the sulfonated fine cellulose fibers.
  • the content of the water-soluble solvent can be blended so as to be 10 to 300 parts by mass with respect to 100 parts by mass of water. That is, the content of the water-soluble solvent can be blended so as to be 2 to 900 parts by mass with respect to 1 part by mass of the sulfonated fine cellulose fibers.
  • the content of the water-soluble solvent may be within the above range, preferably 300% by mass or less, more preferably 200% by mass or less, and still more preferably 150% or less with respect to 100 parts by mass of water, Even more preferably, it is 100% by mass.
  • the lower limit is 10% by mass or more, more preferably 20% by mass or more, relative to 100 parts by mass of water.
  • the mixing ratio of water and water-soluble solvent can be adjusted so that the mass ratio (g of water/g of solvent) is 0.25 to 100.
  • the mixing ratio (mixing ratio) of the two is 0.25 in mass ratio.
  • the fine cellulose fiber-containing composition of the present embodiment may contain components other than those mentioned above.
  • Optional components include, for example, antifoaming agents, lubricants, ultraviolet absorbers, dyes, pigments, stabilizers, surfactants, coupling agents, inorganic layered compounds, inorganic compounds, leveling agents, organic particles, antistatic agents. , magnetic powders, orientation promoters, plasticizers, preservatives, cross-linking agents, and the like.
  • the cellulose microfiber-containing composition of this embodiment may combine sulfonated cellulose microfibers with certain ingredients. For example, both can be provided separately, optionally in combination with other ingredients. In this case, the combined amounts and ratios of the sulfone fine cellulose fibers and specific components may be adjusted so as to be the same as the compounding amounts of the fine cellulose fiber-containing composition.
  • the form of the fine cellulose fiber-containing composition of the present embodiment is not particularly limited.
  • they can exist in various forms such as slurries and dispersions.
  • transparency is a concept that includes both or either of the properties of liquid transparency and turbidity. That is, in the evaluation of transparency in this specification, the haze value can be used to more appropriately evaluate the turbidity of the liquid, and the total light transmittance can be used to more appropriately evaluate the transparency.
  • the fine cellulose fiber-containing composition of the present embodiment has a total light transmittance of 90% or more when the sulfonated fine cellulose fibers are prepared to have a solid content concentration of 0.5% by mass. This total light transmittance is more preferably 95% or more.
  • the haze value can evaluate the turbidity of the liquid, and therefore, like the total light transmittance, the dispersibility of the sulfonated fine cellulose fibers in the fine cellulose fiber-containing composition of the present embodiment can be evaluated. can do.
  • the fine cellulose fiber-containing composition of the present embodiment has a haze value of 30% or less when the sulfonated fine cellulose fibers are prepared to have a solid content concentration of 0.5% by mass.
  • the haze value is preferably 20% or less, more preferably 15% or less, even more preferably 10% or less.
  • the composition containing fine cellulose fibers of the present embodiment has a haze value of 30% or less
  • the sulfonated fine cellulose fibers are maintained in an appropriately dispersed state in the presence of a water-soluble solvent.
  • handleability is improved.
  • the fine cellulose fiber-containing composition has transparency, the color of the paint can be exhibited appropriately.
  • the film after coating can exhibit good transparency.
  • the total light transmittance is also the advantage that the effect of a transparent paint when formed into a coating film can be easily exhibited.
  • the fact that the fine cellulose fiber-containing composition of the present embodiment has the transparency as described above means that the contained sulfonated fine cellulose fibers have excellent dispersibility. be.
  • the sulfonated fine cellulose fibers having such excellent dispersibility have a structure suitable for dispersibility. That is, the fact that the fine cellulose fiber-containing composition of the present embodiment has the transparency as described above means that the contained sulfonated fine cellulose fibers have the above-described predetermined structure. If the composition containing fine cellulose fibers of the present embodiment has transparency as described above, the sulfonated fine cellulose fibers have a structure capable of maintaining a dispersed state in the presence of a water-soluble solvent. It's becoming
  • the total light transmittance and haze value can be measured by a method using a spectroscopic haze meter described in Examples below.
  • a spectroscopic haze meter described in Examples below.
  • the composition containing fine cellulose fibers of the present embodiment in which sulfonated fine cellulose fibers are dispersed at a predetermined concentration is measured using a spectrophotometer in accordance with JIS K 7105 to determine the haze value and total light transmittance. can be asked for.
  • the fine cellulose fiber-containing composition of the present embodiment preferably has predetermined viscosity characteristics. Specifically, the fine cellulose fiber-containing composition of the present embodiment is prepared to have a predetermined viscosity and thixotropic index.
  • the viscosity for example, the viscosity measured at 20° C., 6 rpm, and 3 minutes using a Brookfield viscometer in a state where the solid content concentration of the sulfonated fine cellulose fibers is 0.5% by mass. , 3000 mPa ⁇ s (3 Pa ⁇ s) or more and 40,000 mPa ⁇ s (40 Pa ⁇ s) or less (see Examples 1 to 5).
  • the upper limit of the viscosity is preferably 35,000 mPa ⁇ s (35 Pa ⁇ s) or less, more preferably 10,000 mPa ⁇ s (10 Pa ⁇ s) or less.
  • the lower limit of the viscosity is preferably higher than 3,000, more preferably 4,000 mPa ⁇ s (4 Pa ⁇ s) or more, and still more preferably 5,000 mPa ⁇ s (5 Pa ⁇ s). or more, and more preferably 6,000 mPa ⁇ s (6 Pa ⁇ s) or more.
  • the thixotropic index is measured, for example, using a Brookfield viscometer at a solid content concentration of 0.5% by mass of the sulfonated fine cellulose fibers at 20° C. at 6 rpm and 60 rpm. , Each viscosity is calculated, and the thixotropic index calculated from each viscosity ratio (viscosity at a rotation speed of 6 rpm/viscosity at a rotation speed of 60 rpm) is 5.0 or more, preferably 7.0 or more ( See Examples 1-5).
  • Such viscosity characteristics of the composition containing fine cellulose fibers of the present embodiment are presumed to be due to the fiber structure of the sulfonated fine cellulose fibers contained therein. In other words, it is speculated that the sulfonated fine cellulose fibers having the above-described predetermined structure can exhibit such characteristics in the fine cellulose fiber-containing composition. Since the fine cellulose fiber-containing composition of the present embodiment exhibits excellent viscosity characteristics as described above, it is possible to impart effects based on such viscosity characteristics to the target liquid.
  • the paint of this embodiment is a paint containing the composition containing fine cellulose fibers of this embodiment described above. Since the coating material of the present embodiment contains the composition containing fine cellulose fibers of the present embodiment, the viscosity characteristic of the composition containing fine cellulose fibers of the present embodiment is set to the lower limit value or higher, so that when a coating film is formed, It is possible to optimize the dispersibility of the fibers, Young's modulus and strength. Therefore, coatability and coating performance can be improved. A specific description will be given below.
  • the content ratio (content rate) of the fine cellulose fiber-containing composition of the present embodiment in the paint of the present embodiment is as long as the content of the sulfonated fine cellulose fibers in the paint of the present embodiment is within the range shown below. , is not particularly limited.
  • the content of the sulfonated fine cellulose fibers in the paint of this embodiment is adjusted to 0.05% by mass to 10% by mass.
  • the content of the sulfonated fine cellulose fibers is adjusted to 0.05% by mass to 10% by mass in the total amount of the paint of this embodiment.
  • the lower limit of the content of the sulfonated fine cellulose fibers is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.3% by mass or more. is.
  • the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less.
  • the paint of the present embodiment can be prepared by mixing the fine cellulose fiber-containing composition of the present embodiment in which the solid content concentration of sulfonated fine cellulose fibers is 1%, and a mixing paint.
  • the mass ratio g of fine cellulose fiber-containing composition/g of paint for mixing
  • the paint of the present embodiment may contain a resin such as a thermoplastic resin, a thermosetting resin, or a photocurable resin.
  • resins include styrene resins, acrylic resins, aromatic polycarbonate resins, aliphatic polycarbonate resins, aromatic polyester resins, aliphatic polyester resins, aliphatic polyolefin resins, cyclic olefin resins, and polyamides.
  • thermoplastic polyimide resin polyacetal resin
  • polysulfone resin amorphous fluorine resin
  • rosin resin nitrocellulose
  • vinyl chloride resin chlorinated rubber resin
  • vinyl acetate resin examples include, but are not limited to, phenolic resins, epoxy resins, and the like.
  • the resin content is preferably 30 parts by mass or more, more preferably 70 parts by mass or more, and still more preferably 100 parts by mass or more, relative to 1 part by mass of the sulfonated fine cellulose fibers.
  • the upper limit of the resin content is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and still more preferably 200 parts by mass or less per 1 part by mass of the sulfonated fine cellulose fibers.
  • the paint of this embodiment may contain a curing agent.
  • a curing agent a known one can be appropriately used, and examples thereof include isocyanate curing agents (polyisocyanate, etc.), epoxy (oxirane) curing agents, oxetane curing agents, and the like. In the present invention, isocyanate-based curing agents are particularly preferred.
  • the content of the curing agent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more with respect to 1 part by mass of the sulfonated fine cellulose fibers.
  • the upper limit of the content of the curing agent is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and still more preferably 60 parts by mass or less with respect to 1 part by mass of the sulfonated fine cellulose fibers. .
  • the paint of this embodiment may contain components other than the components described above.
  • Other components include, for example, antifoaming agents, lubricants, ultraviolet absorbers, dyes, pigments, stabilizers, surfactants, coupling agents, inorganic layered compounds, inorganic compounds, leveling agents, organic particles, antistatic agents. , magnetic powders, orientation promoters, plasticizers, preservatives, cross-linking agents, and the like.
  • the paint of the present embodiment preferably has predetermined viscosity characteristics (viscosity, thixotropy). By exhibiting such viscosity characteristics, handleability can be improved.
  • Viscosity measured under conditions can be adjusted to 10 mPa ⁇ s (0.01 Pa ⁇ s) or more (see Examples 8 to 10).
  • the upper limit of the viscosity is not particularly limited, it is preferable to prepare the viscosity so as not to affect the coatability.
  • the upper limit of the viscosity of the paint of the present embodiment is preferably 4,000 mPa s (4 Pa s) or less, more preferably 3,000 mPa s (3 Pa s) or less. , more preferably 2,000 mPa ⁇ s (2 Pa ⁇ s) or less, and still more preferably 1,000 mPa ⁇ s (1 Pa ⁇ s) or less.
  • the lower limit of the viscosity is preferably 10 mPa s (0.01 Pa s) or more, more preferably 100 mPa s (0.1 Pa s) or more, and still more preferably It is 300 mPa ⁇ s (0.3 Pa ⁇ s) or more, and more preferably 500 mPa ⁇ s (0.5 Pa ⁇ s) or more.
  • thixotropic index for example, using a Brookfield viscometer in a state where the solid content concentration of the sulfonated fine cellulose fiber is 0.1% by mass to 1.0% by mass, 20 ° C., 6 rpm and rotation
  • a thixotropic index calculated from each viscosity ratio is preferably 1.5 or more, preferably 2.0 or more (see Examples 8-10).
  • the paint of the present embodiment can form a coating film when applied.
  • a coating film can be formed by a step of applying the coating material of the present embodiment onto a substrate and a step of drying it.
  • the formed coating film may be peeled off from the base material and used in the form of a sheet.
  • the thickness of the coating film thus formed is not particularly limited, but when considering the form of use as a paint, it is preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less, and 300 ⁇ m or less. is more preferable, 100 ⁇ m or less is more preferable, and 80 ⁇ m or less is particularly preferable.
  • the lower limit is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, and particularly preferably 10 ⁇ m or more.
  • the transparency of the coating film is not particularly limited. For example, it preferably has a high total light transmittance or a low haze value.
  • the total light transmittance is preferably 80% or more.
  • the total light transmittance (%) of a methacrylic film having high transparency is about 90%, it is more preferably 90% or more, and 95% or more when exhibiting the same transparency. It is even more preferable to have The haze value is preferably 30% or less, for example.
  • the haze value (%) of a film made of polyethylene, which is a general-purpose resin is about 20%, it is more preferably 20% or less, more preferably 10% or less, when exhibiting the same transparency. % or less is particularly preferred.
  • the transparency of the film after drying is such that the total light transmittance of the coated film after coating is 90% or more, and the haze value is 30% or less is sufficient.
  • the Young's modulus of the coating film is not particularly limited, but when considering a higher Young's modulus, for example, it is preferably 0.3 GPa or more, more preferably 0.5 GPa or more, and 0.7 GPa or more. is more preferable, and 0.8 GPa or more is particularly preferable. It is practical that the upper limit is 8 GPa or less. Since the present invention can achieve such a high Young's modulus, it can be suitably applied to applications requiring a high elastic modulus.
  • the Young's modulus of the coating film was measured using a tensile tester Tensilon (manufactured by A&D Co., Ltd.) according to JIS P 8113:2006 except that the test piece length between the grips was 50 mm and the tensile speed was 5 mm / min. Measure in compliance.
  • a test piece conditioned at 23° C. and a relative humidity of 50% for 24 hours is used. The measurement is performed 5 times per level, and the average value is adopted.
  • the quick-drying property of the coating film is not particularly limited.
  • the quick-drying property is high.
  • the mass due to volatilization of the solvent after 10 minutes is preferably 70% or less of the mass before drying, more preferably 60% or less, 50 % or less is more preferable.
  • the thickener of the present embodiment is a thickener containing the fine cellulose fiber-containing composition of the present embodiment described above.
  • the thickener of this embodiment can be used for various purposes. For example, it can be used by mixing with skin medicinal agents such as cosmetic agents and moisturizing cream agents. Since the thickener of the present embodiment contains the fine cellulose fiber-containing composition of the present embodiment, by setting the viscosity characteristics of the fine cellulose fiber-containing composition of the present embodiment to the lower limit or more, the applicability is improved. can be improved. A specific description will be given below.
  • the content ratio of the fine cellulose fiber-containing composition of the present embodiment is not particularly limited.
  • the content of the sulfonated fine cellulose fibers is adjusted to 0.1% by mass or more based on the total amount (the total amount of the thickener). More specifically, it is 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more with respect to the total amount (total amount of the thickener). is.
  • This content may be 30% by mass or more, 40% by mass or more, 50% by mass or more, 55% by mass or more, or 90% by mass or 95% by mass. From the viewpoint of handleability, the content of the fine cellulose fiber-containing composition of the present embodiment is preferably 90% by mass or less.
  • the thickener of the present embodiment is preferably prepared so that the amount of the fine cellulose fiber-containing composition of the present embodiment contained is 80% by mass or more with respect to the total amount of the thickener. It is more preferably 90% by mass or more, and still more preferably 95% by mass or more.
  • the thickener of the present embodiment preferably exhibits the thixotropic index described above as the viscosity characteristic of the composition containing fine cellulose fibers of the present embodiment.
  • a skin medicinal agent such as a cosmetic agent or a moisturizing cream agent
  • the viscosity is reduced due to shear stress caused by stirring during use, and the viscosity is reduced. It is advantageous in that the viscosity can be recovered after application and the fixability can be improved.
  • application properties are collectively referred to as application properties.
  • sunscreen cosmetics generally contain metals such as titanium oxide and zinc oxide, and derivatives thereof, as UV scattering agents.
  • a substance such as titanium oxide settles and separates when left standing. For this reason, it is necessary to shake firmly before use to disperse the anti-ultraviolet material such as titanium oxide. In addition, when the action of shaking is insufficient, the sunscreen function may not be exhibited appropriately.
  • other cosmetics that require sebum adsorption such as mica, zinc oxide, talc, hydroxyapatite, aluminum silicate, etc., described in the examples described later, are sebum-adsorbing materials that settle and need to be shaken firmly when used. Examples include lotions and milky lotions containing ingredients.
  • the thickener of the present embodiment is used by adding it to the cosmetics as described above, it is possible to suppress the sedimentation of the useful ingredients as described above in a still state.
  • the uniformly dispersed state of the UV inhibitor can be maintained without performing an action such as shaking to uniformly disperse the UV inhibitor during use. For this reason, even if it is used as it is in a stationary state, it is possible to obtain the advantage that the skin protection performance from ultraviolet rays and the like can be appropriately exhibited.
  • the thickener of the present embodiment is mixed or added and used, it can function as a dispersion stabilizer for other useful ingredients.
  • the method for producing the sulfonated fine cellulose fibers contained in the fine cellulose fiber-containing composition of the present embodiment involves finely treating sulfonated pulp produced by the following production method (sulfonated pulp production method). However, it is not limited to such a manufacturing method.
  • the outline of this sulfonated pulp manufacturing method is that the sulfonated pulp contained in the redispersible pulp of the present embodiment (hereinafter simply referred to as sulfonated pulp) is obtained by subjecting a fibrous raw material containing cellulose (for example, wood pulp) to a chemical treatment process. ) is a method of manufacturing.
  • This chemical treatment step is a method of bringing the supplied fiber raw material into contact with a reaction solution (contact step) and then subjecting it to a heating reaction (reaction step) to sulfonate the hydroxyl groups of cellulose.
  • the fiber raw material refers to a fibrous pulp or the like containing cellulose molecules.
  • Pulp is a fibrous member in which a plurality of cellulose fibers are aggregated.
  • the cellulose fibers are aggregates of a plurality of fine fibers (for example, microfibrils).
  • the fine fibers are aggregates of a plurality of cellulose molecules (hereinafter sometimes simply referred to as cellulose), which are chain polymers in which D-glucose is ⁇ (1 ⁇ 4) glycoside-bonded.
  • pulp is an aggregate of cellulose fibers having a size of 200 mesh or 235 mesh that can be a residue. Details of the fiber raw material will be described later.
  • the chemical treatment step includes a contact step of contacting cellulose fibers of a fiber raw material containing cellulose such as pulp with sulfamic acid, which is a sulfonating agent having a sulfo group, and urea, and the pulp after this contact step. and a reaction step of substituting and introducing a sulfo group into at least part of the hydroxyl groups of the cellulose fibers contained.
  • the contacting step is a step of bringing sulfamic acid and urea into contact with a fibrous raw material containing cellulose.
  • This contacting step is not particularly limited as long as it is a method capable of causing the above contact.
  • the fibrous raw material for example, wood pulp
  • the fibrous raw material may be immersed in a reaction liquid obtained by dissolving sulfamic acid and urea in a solvent to impregnate the fibrous raw material with the reaction liquid.
  • sulfamic acid and urea may be separately applied, impregnated, or sprayed onto the fiber raw material.
  • the solvent for dissolving sulfamic acid and urea is not particularly limited.
  • water alone including pure water such as ion-exchanged water and distilled water, as well as tap water, etc.
  • ammonia water polar solvents acetone, ethyl acetate, tetrahydrofuran (THF), dimethylformamide (DMF), acetonitrile, dimethylsulfoxide (DMSO), dimethylsulfide (DMS), aprotic polar solvents such as dimethylacetamide (DMA),
  • Non-polar solvents such as diethyl ether, benzene, toluene, hexane, chloroform, and 1,4-dioxane can be mentioned, and these may be used alone or in combination of two or more. may In particular, water is preferable from the viewpoint of easily
  • the mixing ratio of sulfamic acid and urea contained in the reaction liquid is not particularly limited.
  • the mixing ratio described in Examples described later can be used.
  • the concentration ratio (g/L) of the sulfonating agent and urea or/and its derivative is 4:1 (1:0.25), 2:1 (1:0.5), 1:1, 2 :3 (1:1.5) and 1:2.5.
  • the amount of the reaction liquid to be brought into contact with the fiber raw material is such that the sulfamic acid and urea in the reaction liquid are brought into contact with the fiber raw material at a predetermined ratio.
  • the sulfonating agent contained in the reaction liquid is 1 part by mass to 20,000 parts by mass with respect to 100 parts by mass of the dry mass of the fiber raw material.
  • Urea and/or a derivative thereof contained in can be prepared so as to be 1 to 100,000 parts by mass with respect to 100 parts by mass of the dry mass of the fiber raw material.
  • the fiber material impregnated with the reaction liquid when subjected to the reaction process of the next step is in the state of being impregnated with the reaction liquid, that is, the state of contact between the fiber material and the reaction liquid.
  • Examples include a state in which no reaction is performed, and a state in which water is actively removed from a state in which the fiber raw material and the reaction liquid are brought into contact with each other.
  • the fiber raw material is taken out from the state in which the reaction liquid and the fiber raw material are brought into contact with each other, and the fiber raw material is dried naturally by air drying or the like, or the reaction liquid and the fiber raw material are dehydrated after being brought into contact with each other.
  • reaction step The fiber raw material impregnated with the reaction solution prepared in the contacting step as described above is supplied to the reaction step in the next step.
  • this reaction step the cellulose fibers contained in the fiber raw material supplied from the contacting step, sulfamic acid, and urea are reacted to substitute the sulfo groups of sulfamic acid for the cellulose hydroxyl groups in the cellulose fibers.
  • This is a step of introducing a sulfo group into the cellulose fibers contained in the fiber raw material. That is, this reaction step is a step of carrying out a sulfonation reaction in which sulfo groups are substituted for the cellulose hydroxyl groups in the cellulose fibers contained in the fiber raw material impregnated with the reaction solution.
  • This reaction step is not particularly limited as long as it is a method capable of a sulfonation reaction in which the hydroxyl groups of the cellulose fibers in the fiber raw material are substituted with sulfo groups.
  • a method of accelerating the sulfonation reaction by heating the fiber raw material can be employed.
  • the case where the sulfonation reaction is performed by this heating method will be described as a representative.
  • the reaction temperature in the reaction step is not particularly limited as long as it is a temperature at which sulfo groups can be introduced into the cellulose fibers forming the fiber raw material while suppressing the thermal decomposition and hydrolysis reaction of the fibers.
  • the ambient temperature of the fiber raw material supplied to the reaction step is adjusted to 100° C. or higher and 200° C. or lower.
  • the ambient temperature is preferably 120° C. or higher and 200° C. or lower. If the ambient temperature during heating is higher than 200° C., thermal decomposition of the fibers may occur, or discoloration of the fibers may accelerate.
  • the reaction temperature is lower than 100° C., the resulting sulfonated pulp tends to be less transparent.
  • the reaction temperature (specifically, the ambient temperature) in the reaction step is 100° C. or higher and 200° C. or lower, preferably 120° C. or higher and 180° C. or lower.
  • the temperature is preferably 120°C or higher and 160°C or lower.
  • the heater or the like used in the reaction step is not particularly limited as long as it can directly or indirectly heat the fiber raw material after the contact step while satisfying the above requirements.
  • a hot press method using a known dryer, vacuum dryer, microwave heating device, autoclave, infrared heating device, or heat press for example, AH-2003C manufactured by AS ONE Co., Ltd.
  • the heating time (that is, the reaction time) when the above heating method is employed as the reaction step is not particularly limited as long as the sulfo groups can be appropriately introduced into the cellulose fibers as described above.
  • the reaction time in the reaction step is adjusted to 1 minute or more when the reaction temperature is adjusted to fall within the above range.
  • the time is preferably 5 minutes or longer, more preferably 10 minutes or longer, and still more preferably 15 minutes or longer. If the reaction time is shorter than 1 minute, it is presumed that the substitution reaction of the sulfo groups with respect to the hydroxyl groups of the cellulose fibers has hardly progressed.
  • the reaction time when the above heating method is employed as the reaction step is not particularly limited, but from the viewpoint of reaction time and operability, it is preferably 5 minutes or more and 300 minutes or less, more preferably 5 minutes or more and 120 minutes or less.
  • the fiber raw material used in the sulfonated pulp manufacturing method is not particularly limited as long as it contains cellulose as described above.
  • pulp what is generally called pulp may be used, and what contains cellulose isolated from sea squirts, seaweed, etc. can be used as the fiber raw material, but as long as it is composed of cellulose molecules, , can be anything.
  • the pulp include wood pulp (hereinafter simply referred to as wood pulp), dissolving pulp, cotton pulp such as cotton linter, straw, bagasse, kozo, mitsumata, hemp, kenaf, fruits, and the like.
  • wood pulp wood pulp
  • this wood pulp there are various types of this wood pulp, but there are no particular restrictions on their use. Examples thereof include softwood kraft pulp (NBKP), hardwood kraft pulp (LBKP), thermomechanical pulp (TMP), and other papermaking pulps. When the above pulp is used as the fiber raw material, one type of the pulp described above may be used alone, or two or more types may be mixed and used.
  • a washing step of washing the sulfonated pulp after introduction of the sulfo group may be included.
  • the surface of the sulfonated pulp after introduction of the sulfo group is acidified due to the influence of the sulfonating agent.
  • unreacted reaction liquid also exists. For this reason, if a washing step is provided to ensure that the reaction is completed and to neutralize the excess reaction solution by removing the excess reaction solution, the handleability can be improved.
  • This washing step is not particularly limited as long as the sulfonated pulp after introduction of the sulfo group can be made substantially neutral.
  • a method of washing with pure water or the like until the sulfonated pulp after introduction of the sulfo group becomes neutral can be adopted.
  • neutralization cleaning using an alkali or the like may be performed.
  • alkaline compounds contained in the alkaline solution include inorganic alkaline compounds and organic alkaline compounds.
  • examples of inorganic alkali compounds include hydroxides, carbonates, and phosphates of alkali metals.
  • examples of organic alkali compounds include ammonia, aliphatic amines, aromatic amines, aliphatic ammoniums, aromatic ammoniums, heterocyclic compounds, and hydroxides of heterocyclic compounds.
  • the sulfonated pulp prepared using the sulfonated pulp manufacturing method as described above is fed to the micronization step and micronized to obtain sulfonated fine cellulose fibers.
  • the sulfonated pulp is dried until its moisture content (%) reaches an equilibrium state before being supplied to the pulverization treatment step.
  • the refining step is a step of refining the sulfonated pulp into fine fibers of a predetermined size (for example, nano-level).
  • a processing apparatus used in this miniaturization process is not particularly limited as long as it has the above functions.
  • a low-pressure homogenizer, a high-pressure homogenizer, a grinder (stone mill type grinder), a ball mill, a cutter mill, a jet mill, a short-screw extruder, a twin-screw extruder, an ultrasonic agitator, a domestic mixer, etc. can be used.
  • the processing device is not limited to these devices.
  • a high-pressure homogenizer is preferable because it can uniformly apply a force to the material and is excellent in homogenization, but it is not limited to such a device.
  • the sulfonated pulp obtained by the above-described manufacturing method is supplied in a state of being dispersed in a mixed solution of water and a water-soluble solvent.
  • a state in which the sulfonated pulp is dispersed in this mixed solution is called a slurry.
  • the solid content concentration of the sulfonated pulp in this slurry is not particularly limited.
  • a solution adjusted so that the solid content concentration of the sulfonated pulp in the slurry is 0.1% by mass to 20% by mass may be supplied to a processing apparatus such as a high-pressure homogenizer.
  • a processing apparatus such as a high-pressure homogenizer
  • sulfonated fine cellulose fibers having the same solid content concentration are dispersed in the mixed solution.
  • a dispersion of states can be obtained. That is, in this case, it is possible to obtain the fine cellulose fiber-containing composition of the present embodiment in which the solid content concentration of the sulfonated fine cellulose fibers is adjusted to 0.5% by mass.
  • the pulp was added to the reaction solution prepared as follows and stirred to form a slurry.
  • the step of adding the pulp to the reaction liquid to form a slurry corresponds to the contacting step of the chemical treatment step of the present embodiment.
  • Step of preparing reaction solution A sulfonating agent and urea and/or a derivative thereof were prepared so as to have the following solid content concentrations.
  • sulfamic acid purity 98.5%, manufactured by Fuso Chemical Industries
  • urea solution purity 99%, manufactured by Wako Pure Chemical Industries, model number; special grade reagent
  • reaction solution An example of preparation of the reaction solution is shown below. 85 mL of water was added to the container. Then, 15 g of sulfamic acid and 15 g of urea were added to this container to prepare a reaction solution. That is, urea was added so as to be 100 parts by mass with respect to 100 parts by mass of sulfamic acid. In the experiment, 20 g of absolute dry pulp was added to the prepared reaction solution. That is, in the case of a reaction solution having a sulfamic acid/urea ratio ((g/L)/(g/L)) of 200/200 (1:1), sulfamic acid is 75 parts by mass per 100 parts by mass of pulp. , Urea was prepared to be 75 parts by mass.
  • a slurry prepared by adding pulp to the reaction solution is placed in a dryer (manufactured by Isuzu Manufacturing Co., Ltd., model number: VTR-115) in which the temperature of the constant temperature bath is set to 50 ° C.
  • Moisture content (%) obtained from the following formula dried to equilibrium.
  • drying until the moisture content (%) reaches an equilibrium state was defined as the end point when the moisture in the atmosphere in the treatment facility and the moisture in the sample apparently stopped coming in and out.
  • the weighing bottle is capped in the drying apparatus, the sample is removed from the dryer while still in the weighing bottle, and the desiccant is added.
  • the mass of the sample was measured.
  • the end point of drying was a state in which the amount of change in the mass measured twice was within 1% of the mass at the start of drying (however, the second mass measurement was taken after the drying time required for the first time). more than half).
  • a heating reaction was carried out.
  • a dryer manufactured by Isuzu Manufacturing Co., Ltd., model number: VTR-115
  • the reaction conditions are as follows. Constant temperature bath temperature: 120°C, heating time: 25 minutes
  • the reacted pulp is diluted with pure water so that the solid content is 1% by mass or less, and an excess amount of sodium bicarbonate is added. After neutralization, it was thoroughly washed with pure water. The washed sulfonated pulp was dried until the moisture content reached equilibrium.
  • Preliminary fibrillation treatment This dried sulfonated pulp was then subjected to a micronization process.
  • the main defibration treatment was performed after performing the preliminary defibration treatment.
  • the preliminary defibration treatment was carried out for 1 minute with a mixer (fiber mixer MX-X701 manufactured by Panasonic, high speed setting). The conditions at this time were adjusted so that the solid content concentration (% by mass) of the sulfonated pulp in water was 1% by mass. If this pre-fibrillation treatment is carried out as it is, the solid content concentration after main fibrillation will also be 1% by mass.
  • the dispersion obtained by the preliminary fibrillation treatment is fractionated, water and ethanol (corresponding to the water-soluble solvent in the present embodiment) are added to the dispersion, and the main fibrillation treatment is performed to obtain a predetermined mixing ratio (water /ethanol ratio (g/g)) (see figure).
  • preliminarily defibrated pulp was dispersed in a prepared mixed solution of water and ethanol, and the dispersion was subjected to the main fibrillation treatment step.
  • fibrillation treatment (10 times (10 passes) at a fibrillation pressure of 100 MPa) is performed using a high-pressure homogenizer (Yoshida Kikai N2000-2C-045 model), and the sulfonated fine cellulose fibers are mixed with the above mixed solution.
  • a slurry containing sulfonated fine cellulose fibers dispersed in was prepared (Examples 1, 2, 4). This sulfonated fine cellulose fiber-containing slurry corresponds to the fine cellulose fiber-containing composition of the present embodiment.
  • the solid content concentration (% by mass) of the sulfonated fine cellulose fibers in the slurry containing the sulfonated fine cellulose fibers of Example 1 is 0.5 mass %.
  • Example 3 The preparation of the sulfonated fine cellulose fiber slurry of Example 3 was carried out in the same manner as in Example 1 above, except for the method described below.
  • Example 3 Using the obtained sulfonated pulp, a slurry containing sulfonated fine cellulose fibers of Example 3 as shown in FIG. 2 was prepared.
  • Example 5 The preparation of the sulfonated fine cellulose fiber slurry of Example 5 was carried out in the same manner as in Example 1 above, except for the method described below.
  • sulfamic acid is 1000 parts per 100 parts by mass of pulp. Parts by mass, urea was prepared so as to be 2500 parts by mass.
  • the slurry was suction filtered using filter paper (No. 2). Suction filtration was performed until the solution stopped dripping. After suction filtration, the pulp was peeled off from the filter paper, and the filtered pulp was placed in a drier whose constant temperature bath temperature was set to 50° C. and dried until the moisture content reached an equilibrium state.
  • This sulfonated pulp having a degree of reactivity of 2 times was reacted again in the same manner as described above using a reaction solution having a mass ratio of sulfamic acid and urea of 200 (g/L):200 (g/L). A sulfonated pulp after the reaction was obtained.
  • Example 5 having a solid content concentration (mass%) of the sulfonated fine cellulose fibers of 0.5 mass% is obtained.
  • a fiber-containing slurry (see Figure 2) was prepared.
  • the haze value and the total light transmittance were measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model number: SH- 7000).
  • the measurement method was performed according to the method of JIS K 7105.
  • An optional glass cell (part number: 2277, square cell, optical path length 10 mm ⁇ width 40 ⁇ height 55) of the haze meter filled with pure water was used as a blank measurement value, and the light transmittance of the slurry for measurement was measured.
  • the light source was D65, the field of view was 10°, and the measurement wavelength range was 380 to 780 nm.
  • the total light transmittance (%) and the haze value (%) were calculated using values obtained from a control unit of a haze meter (model number CUII, Ver2.00.02).
  • B type viscosity measurement The viscosity of the prepared slurry containing 0.5% by mass of sulfonated fine cellulose fibers was measured using a Brookfield viscometer. Measurement conditions, etc. for viscosity measurement are shown below.
  • B-type viscometer manufactured by BLOOKFIELD, DV2T (RV type)
  • Measurement conditions rotation speed 6 rpm, measurement temperature 20 ° C., measurement time 3 minutes, suitable spindle selected from RV-02 to 07
  • data recording method is single point Single point is B used in this experiment This is a setting item for the recording method for acquiring only the value at the end of measurement in the viscometer. In other words, the instantaneous value after 3 minutes from the start of measurement is recorded.
  • the thixotropic index (TI value) was determined. The TI value was calculated by using the Brookfield viscometer described above and measuring at 6 rpm and 60 rpm, and dividing the viscosity value obtained at 6 rpm by the viscosity value obtained at 60 rpm.
  • a sulfonated fine cellulose fiber-containing slurry for inclusion in a sulfonated fine cellulose fiber slurry-containing paint was prepared as follows.
  • the slurry containing sulfonated fine cellulose fibers was prepared in the same manner as in Example 1 above for Example 6 and in Example 2 above, except for the method described below.
  • the refining treatment step after the preliminary defibration treatment is performed at a solid content concentration of 2% by mass, water and ethanol are added so that the solid content concentration of the sulfonated fine cellulose fibers is 1% by mass, and the main defibration treatment is performed. was adjusted to a predetermined mixing ratio (water/ethanol ratio (g/g)) to prepare sulfonated fine cellulose fiber-containing slurries for Examples 6 and 7.
  • the prepared slurries containing sulfonated fine cellulose fibers were mixed with predetermined coating ingredients to prepare sulfonated fine cellulose fiber slurry-containing coatings (Examples 6 and 7).
  • the paint containing the sulfonated fine cellulose fiber slurry corresponds to the paint containing the composition containing fine cellulose fibers of the present embodiment.
  • Example 6 the sulfonated fine cellulose fiber-containing slurry prepared in Example 1 and the acrylic paint were prepared at a mass ratio (g/g) of 20 g (sulfonated fine cellulose fiber-containing slurry) and 80 g (acrylic paint), respectively. It was prepared by mixing to be 0.25.
  • the content of the sulfonated fine cellulose fibers in Example 6 was adjusted to 0.2% by mass (the solid content concentration of the sulfonated fine cellulose fibers was 0.2% by mass).
  • the content of sulfonated fine cellulose fibers was calculated using the following formula.
  • Content of sulfonated fine cellulose fibers in paint (%) ((sulfonated fine cellulose fibers in slurry containing sulfonated fine cellulose fibers (g))/total amount of paint (g)) x 100 (%)
  • Example 7 was prepared by mixing 20 g and 80 g of the sulfonated fine cellulose fiber-containing slurry prepared in Example 2 and the acrylic paint, respectively, at a mass ratio (g/g) of 0.25. That is, the content of the sulfonated fine cellulose fibers in Example 7 was adjusted to 0.2% by mass.
  • Viscosity measurement Viscosity was measured using the above-mentioned B-type viscometer after putting the prepared paint in a beaker, tightly covering it with aluminum foil, and allowing it to stand overnight in an environment at 20°C. The measurement conditions were the same as above.
  • the strength of the coating film formed using the prepared sulfonated fine cellulose fiber slurry-containing coating was evaluated.
  • 5.0 g of a paint containing a slurry of sulfonated fine cellulose fibers was cast on a Teflon sheet (registered trademark), formed into a circle with a diameter of 8 cm, and dried with a blower dryer whose constant temperature bath was set at 50°C. It was dried until it became a coating film.
  • the coating film was pulled by hand to determine the strength of the coating film. The sample was rated as ⁇ if it was not broken, ⁇ if it was broken when it was pulled strongly, and x if it was broken when it was pulled with a light force.
  • Examples 8, 9, 10 In Examples 8, 9, and 10, as shown in FIG. 5, a 1% CNF slurry prepared so that the solid content concentration of the sulfonated fine cellulose fibers was 1% by mass, water, and an acrylic paint were prepared. The procedure was carried out in the same manner as in Example 6 above, except that the mixture was prepared so as to have a mixing ratio of .
  • dispersion characteristics were evaluated by the following method.
  • this dispersion characteristic is shown as dispersion maintenance property.
  • a predetermined amount of the paint containing the prepared sulfonated fine cellulose fiber slurry was dispensed into a transparent test tube (Laboran screw tube bottle manufactured by AS ONE), and after closing the cap, it was shaken well and allowed to stand.
  • the height of the fractionated liquid from the inner bottom surface of the test tube was 9 cm, which corresponds to the distance of the fractionated liquid fractionated into the test tube in the following formula.
  • the acrylic paint was evenly dispersed to form an emulsion in all cases including the comparative examples.
  • the water and the acrylic paint were homogeneously mixed and no interface was formed between them.
  • the dispersion characteristics are excellent.
  • the dispersion characteristics (%) were evaluated according to the following formula.
  • the distance in the following formula means the distance between the bottom surface and the top surface of the liquid.
  • Dispersion characteristics (%) (distance cm of emulsion-formed part)/(distance cm of sampled liquid collected in test tube) x 100.
  • Comparative Examples 14 to 17 used phosphate groups, and Comparative Examples 17 to 20 were blanks to which fine cellulose fibers were not added.
  • Examples 11, 12, 13 In Examples 11, 12, and 13, as shown in FIG. 6, a 0.5% CNF slurry prepared so that the solid content concentration of the sulfonated fine cellulose fibers was 0.5% by mass was used instead of the acrylic paint.
  • a lotion a commercially available lotion containing sebum-adsorbing ingredients (the sebum-adsorbing ingredients form precipitates when left standing)
  • a cosmetic containing a sulfonated fine cellulose fiber slurry at a predetermined mixing ratio Then, the viscosity characteristics and dispersion characteristics were evaluated. Viscosity properties were evaluated in the same manner as in Example 8 above. In addition, in FIG. 6, this dispersion characteristic is shown as dispersion maintenance property.
  • Dispersion characteristic (%) (Distance cm of fractionated liquid fractionated in test tube - Distance cm of transparent part) / (Distance cm of fractionated liquid fractionated into test tube) x 100
  • the test tube has a transparent part in the upper part and an emulsion (emulsion-forming part) in the lower part, there is a gap between the bottom surface of the transparent part (interface between the emulsion-forming part and the transparent part) and the upper surface of the transparent part (equivalent to the upper surface inside the test tube). The distance was measured and taken as the transparent part distance (cm).
  • the distance of the transparent portion is 0 cm and the dispersion characteristic is 100%.
  • Comparative Example 1 was prepared in the same manner as Examples 1, 2 and 4, except that the water/ethanol ratio (g/g) was adjusted to 100/0.
  • Comparative Example 5 was the same as the sulfonated fine cellulose fibers used in Examples 1, 2 and 4, except that the amount of sulfo groups introduced into the sulfonated fine cellulose fibers was adjusted to 0.3 mmol/g. gone. Also, the water/ethanol ratio (g/g) was adjusted to 60/40.
  • Comparative Example 6 was the same as the sulfonated fine cellulose fibers used in Examples 1, 2 and 4, except that the sulfonated fine cellulose fibers were prepared so that the amount of sulfo groups introduced was 0.6 mmol/g. gone. Also, the water/ethanol ratio (g/g) was adjusted to 40/60. Comparative Example 7 was prepared in the same manner as Examples 1, 2 and 4, except that the water/ethanol ratio (g/g) was adjusted to 40/60.
  • Comparative Examples 2-4 slurries containing phosphate-esterified fine cellulose fibers were prepared in which phosphoric acid groups were introduced instead of sulfo groups.
  • ammonium dihydrogen phosphate (purity 99.0%, manufactured by Fujifilm Wako Pure Chemical Industries, model number; special grade reagent), urea (purity 99.0%, manufactured by Fujifilm Wako Pure Chemical Industries, model number; Special grade reagent) was weighed out, 80 mL of pure water was added, and the mixture was stirred to prepare a phosphoric acid esterification solution.
  • the raw material, dry pulp was prepared as follows.
  • a softwood kraft pulp sheet (NBKP sheet manufactured by Marusumi Paper Co., Ltd.) was used. Below, the NBKP used in the experiment will be simply described as pulp.
  • the pulp sheet used was dried to a moisture content of 7% and had a basis weight of 3000 g/m2.
  • Phosphate esterified pulp was produced as follows. 5 g (solid mass) of the prepared pulp was placed in a beaker, and 100 g of the phosphating solution was added. After allowing the pulp to absorb the solution well, it was spread on an aluminum vat and placed in a dryer at 80° C. to dry water until the moisture content reached 5% or less. After that, it was placed in a dryer under an atmosphere of 160° C. to 180° C. and reacted for 25 minutes.
  • the resulting phosphate ester pulp was micronized under the same conditions as in the method for preparing the sulfonated fine cellulose fibers to prepare slurries containing phosphate ester fine cellulose fibers (Comparative Examples 2 to 4).
  • Comparative Examples 8-13 Comparative Examples 8 to 13 were prepared as comparative examples of paints.
  • Comparative Example 8 was prepared by mixing 20 g and 80 g, respectively, of the slurry containing sulfonated fine cellulose fibers prepared in Comparative Example 1 and the acrylic paint at a mass ratio (g/g) of 0.25. That is, the content of the sulfonated fine cellulose fibers in Comparative Example 8 was adjusted to 0.2% by mass.
  • Comparative Example 9 was prepared by mixing 20 g and 80 g, respectively, of the phosphoric esterified fine cellulose fiber-containing slurry prepared in Comparative Example 2 and the acrylic paint at a mass ratio (20 g/80 g) of 0.25.
  • Comparative Example 10 was prepared by mixing 20 g and 80 g, respectively, of the phosphoric esterified fine cellulose fiber-containing slurry prepared in Comparative Example 3 and the acrylic paint at a mass ratio (20 g/80 g) of 0.25.
  • Comparative Example 11 was prepared by mixing 20 g and 80 g of the slurry containing phosphoric esterified fine cellulose fibers prepared in Comparative Example 2 and the acrylic paint in a mass ratio (20 g/80 g) of 0.25.
  • Comparative Example 12 was prepared by mixing 20 g and 80 g of the slurry containing phosphoric esterified fine cellulose fibers prepared in Comparative Example 3 and the acrylic paint at a mass ratio (20 g/80 g) of 0.25.
  • Comparative Example 13 was prepared by mixing 20 g and 80 g of water (pure water) and acrylic paint, respectively, at a mass ratio (20 g/80 g) of 0.25.
  • Comparative Examples 14, 15, and 16 the same measurements and measurements as in Example 8 were performed, except that the slurry containing phosphorylated esterified fine cellulose fibers prepared in Comparative Example 3 was used as 1% CNF, and the blending ratio in FIG. made an evaluation.
  • Comparative Examples 17 to 20 were measured and evaluated in the same manner as in Example 8, except that they were adjusted to the blend ratio shown in FIG. 5 without containing fine cellulose fibers.
  • Comparative Examples 21, 22, and 23 were the same as Example 11, except that the phosphorylated esterified fine cellulose fiber-containing slurry prepared in Comparative Example 3 was used as 0.5% CNF, and the blending ratio in FIG. 6 was prepared. Measurements and evaluations were made.
  • Comparative Example 24 was measured and evaluated in the same manner as in Example 11, except that it was adjusted to the blend ratio shown in FIG. 6 without containing fine cellulose fibers.
  • FIGS. 1-4 are tables showing properties (physical properties) of slurries containing sulfonated fine cellulose fibers.
  • 3 and 4 are tables showing the properties (physical properties) of paints containing sulfonated fine cellulose fiber-containing slurries.
  • the sulfonated fine cellulose fiber-containing slurry had high transparency and predetermined viscosity characteristics. From the results of Comparative Example 1, it can be seen that the sulfonated fine cellulose fibers contained in the slurry containing sulfonated fine cellulose fibers are fibers having a structure exhibiting transparency. In addition, it had excellent transparency and viscosity as compared with the slurry containing phosphate-esterified fine cellulose fibers of the comparative example.
  • Example 3 and Comparative Example 6 the amount of sulfo groups introduced was the same, but the former (water/ethanol is 60/40) was able to be defibrated. In contrast, the latter (40/60 water/ethanol) could not be defibrated.
  • Example 4 and Comparative Example 7 the amount of sulfo groups introduced is the same, but in the former (water/ethanol is 60/40) and the latter (water/ethanol is 40/60), the former is It shows high transparency (that is, it shows that a sulfonated fine cellulose fiber with a structure having dispersibility is obtained) and shows appropriate viscosity characteristics, whereas the latter shows a defibration treatment.
  • the transparency was poor (ie no suitable sulfonated microcellulose fibers could be prepared) and the viscosity properties could not be properly measured.
  • the amount of sulfo groups introduced is 1.3 mmol/g or less, the defibration treatment tends to be difficult to perform in a slurry state in which the ratio of ethanol is higher than that of water. It has also been found to be difficult to prepare the desired sulfonated fine cellulose fibers.
  • the paint containing the slurry containing sulfonated fine cellulose fibers had superior properties compared to the comparative example.
  • the fine cellulose fibers when only water was mixed with the acrylic paint, there was a tendency for the fine cellulose fibers to aggregate and form lumps in the paint.
  • almost no lumps were observed by mixing a slurry containing sulfonated fine cellulose fibers dispersed in a mixed solution of water and ethanol with the acrylic paint.
  • the mixed solution mixed with ethanol has a high affinity with the paint component, if the sulfonated fine cellulose fibers are uniformly dispersed in the ethanol mixed solution (slurry containing sulfonated fine cellulose fibers is transparent If it is in a good state, that is, if the haze value is low), even if it is mixed with a paint component such as an acrylic paint, it is considered that both can be mixed appropriately.
  • a paint component such as an acrylic paint
  • Example 8-10 The experimental results of Examples 8-10 are shown in FIG. In the coating liquids containing no fine cellulose fibers (Comparative Examples 18 to 20), water and coating components are separated, whereas in the coating containing the sulfonated fine cellulose fiber slurry of the present invention, the coating component (acrylic coating) is separated. It was confirmed that there was no separation, that is, the dispersion characteristics were 100%. Moreover, the sulfonated fine cellulose fiber slurry-containing paints of Examples 8 to 10 have excellent dispersion characteristics compared to the fine cellulose fiber-containing paints (Comparative Examples 14 to 16) in which phosphoric acid groups are introduced instead of sulfo groups. It was confirmed that it works.
  • the paints containing the sulfonated fine cellulose fiber slurry of Examples 8-10 have similar viscosities to the paints of Comparative Examples 14-16, and while exhibiting a predetermined TI value, they have an appropriate dispersion. It was confirmed that the properties (a state in which the sulfonated fine cellulose fibers are appropriately dispersed) are exhibited.
  • the coating composition containing the sulfonated fine cellulose fiber slurry of the present invention has excellent dispersion characteristics (coating components are uniformly It was confirmed that the state of being dispersed in) was exhibited. Therefore, it was confirmed that the use of the coating composition containing the sulfonated fine cellulose fiber slurry of the present invention enables the formation of a coating film in which the components of the coating composition are homogeneously contained. In addition, it was confirmed that the low viscosity and the predetermined TI value can be exhibited, so that the handleability as a paint can be improved.
  • the dispersion characteristics are lower than the paint containing the sulfonated fine cellulose fiber slurry of the present invention, so the paint component in the paint film contains the sulfonated fine cellulose fiber slurry of the present invention. It was found that the homogeneity was reduced compared to the coating film of the paint.
  • Example 11-13 The experimental results of Examples 11-13 are shown in FIG. In the cosmetic liquid containing no fine cellulose fibers (Comparative Example 24), the cosmetic components separated to form precipitates, whereas in the cosmetic liquid containing the sulfonated fine cellulose fiber slurry of Examples 11 and 12, the cosmetic No sedimentation of the components occurred, and it was confirmed that even the cosmetic containing the sulfonated fine cellulose fiber slurry of Example 13 exhibited a dispersibility of 70% or more. Moreover, the cosmetic compositions containing sulfonated fine cellulose fiber slurries of Examples 11 to 13 had excellent dispersion compared to cosmetic liquids containing fine cellulose fibers (Comparative Examples 21 to 23) in which phosphoric acid groups were introduced instead of sulfo groups.
  • the sulfonated fine cellulose fiber slurry-containing paint of this experiment contains sulfonated fine cellulose fibers having a predetermined structure (a structure that exhibits a predetermined transparency), so that it has excellent dispersion characteristics (cosmetic ingredients are dispersed homogeneously). It was confirmed that the state of being dispersed in) was exhibited. Therefore, by including the fine cellulose fiber-containing composition of the present invention in a cosmetic, a cosmetic composition that tends to precipitate can be maintained in a homogeneous state at all times. Since even a cosmetic composition that is easy to apply can be appropriately applied, the effect of the cosmetic can be appropriately exhibited.
  • composition containing fine cellulose fibers and the thickening agent of the present invention are used for dispersing fine cellulose fibers in various fields such as the medical field, food field, environmental field, industrial field, and papermaking field. Suitable as a sticky agent.
  • the paint of the present invention can be widely used in environmental fields, industrial fields, etc., as it exhibits the properties of fine cellulose fibers.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Public Health (AREA)
  • Polymers & Plastics (AREA)
  • Animal Behavior & Ethology (AREA)
  • Inorganic Chemistry (AREA)
  • Biochemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Dispersion Chemistry (AREA)
  • Birds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention a pour but de proposer une composition contenant de fines fibres de cellulose dans laquelle les nanofibres de carbone (CNF) peuvent avoir une dispersibilité et une maniabilité améliorées ainsi qu'une matière de revêtement et un épaississant qui comprennent chacun la composition contenant de fines fibres de cellulose. À cet effet, l'invention porte sur une composition qui comprend de l'eau, un solvant soluble dans l'eau et de fines fibres de cellulose sulfonée qui sont dispersées dans une solution mélangée composée du solvant soluble dans l'eau et de l'eau et dans lesquelles une partie des groupes hydroxyle a été remplacée par des groupes sulfo de façon à conduire à une quantité de groupes sulfo introduits de 0,4 à 3,0 mmol/g. Cette composition a un trouble inférieur ou égal à 30 % lorsqu'elle contient les fines fibres de cellulose sulfonée en une concentration de matières solides de 0,5 % en masse. À l'aide de la composition contenant de fines fibres de cellulose pour un liquide d'intérêt qui a une affinité pour le solvant soluble dans l'eau, les fines fibres de cellulose peuvent être dispersées de manière suffisante dans le liquide et d'excellentes propriétés peuvent ainsi être conférées au liquide.
PCT/JP2022/000113 2022-01-05 2022-01-05 Composition contenant de fines fibres de cellulose, matière de revêtement et épaississant WO2023132012A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2022/000113 WO2023132012A1 (fr) 2022-01-05 2022-01-05 Composition contenant de fines fibres de cellulose, matière de revêtement et épaississant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2022/000113 WO2023132012A1 (fr) 2022-01-05 2022-01-05 Composition contenant de fines fibres de cellulose, matière de revêtement et épaississant

Publications (1)

Publication Number Publication Date
WO2023132012A1 true WO2023132012A1 (fr) 2023-07-13

Family

ID=87073460

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/000113 WO2023132012A1 (fr) 2022-01-05 2022-01-05 Composition contenant de fines fibres de cellulose, matière de revêtement et épaississant

Country Status (1)

Country Link
WO (1) WO2023132012A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019194389A (ja) * 2018-04-25 2019-11-07 丸住製紙株式会社 スルホン化微細セルロース繊維、スルホン化パルプ繊維および誘導体パルプ
JP2019194300A (ja) * 2018-04-25 2019-11-07 丸住製紙株式会社 スルホン化微細セルロース繊維の製造方法およびスルホン化パルプ繊維の製造方法
JP2022014915A (ja) * 2020-07-07 2022-01-20 丸住製紙株式会社 微細セルロース繊維含有組成物、塗料および増粘剤

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019194389A (ja) * 2018-04-25 2019-11-07 丸住製紙株式会社 スルホン化微細セルロース繊維、スルホン化パルプ繊維および誘導体パルプ
JP2019194299A (ja) * 2018-04-25 2019-11-07 丸住製紙株式会社 スルホン化微細セルロース繊維、スルホン化パルプ繊維および誘導体パルプ
JP2019194300A (ja) * 2018-04-25 2019-11-07 丸住製紙株式会社 スルホン化微細セルロース繊維の製造方法およびスルホン化パルプ繊維の製造方法
JP2022014915A (ja) * 2020-07-07 2022-01-20 丸住製紙株式会社 微細セルロース繊維含有組成物、塗料および増粘剤

Similar Documents

Publication Publication Date Title
US20230054106A1 (en) Sulfate ester modified cellulose nanofibers and method for producing cellulose nanofibers
JP7006375B2 (ja) 増粘剤、組成物及びシート
JP6754885B2 (ja) 微細セルロース繊維含有乾燥固形物、微細セルロース繊維再分散液
US20150361616A1 (en) Process for isolating cellulose from cellulosic biomass, isolated cellulose of type i and composite materials comprising same
JP6751811B2 (ja) 微細セルロース繊維含有乾燥固形物、微細セルロース繊維再分散液
WO2017022830A1 (fr) Produit cosmétique
JP2022014915A (ja) 微細セルロース繊維含有組成物、塗料および増粘剤
WO2023132012A1 (fr) Composition contenant de fines fibres de cellulose, matière de revêtement et épaississant
JP2022075638A (ja) 防虫組成物、防虫剤および害虫忌避方法
JPWO2018198399A1 (ja) 増粘剤、組成物及びシート
WO2020129855A1 (fr) Procédé de production d'un solide sec contenant de fines fibres de cellulose, solide sec contenant de fines fibres de cellulose, redispersion de fines fibres de cellulose
JP7191616B2 (ja) ゲル状組成物
JP2023028832A (ja) Ｃｎｆ含有組成物
JP7427889B2 (ja) 硫酸エステル化繊維状セルロース、組成物、シート及び硫酸エステル化繊維状セルロースの製造方法
KR20210040430A (ko) 섬유상 셀룰로오스 함유 조성물, 액상 조성물 및 성형체
JP2020172461A (ja) 粉末状液体
JP6835270B1 (ja) 硫酸エステル化繊維状セルロース、組成物、シート及び硫酸エステル化繊維状セルロースの製造方法
JP7215554B1 (ja) 微細セルロース繊維粉末、及び微細セルロース繊維粉末の製造方法
JP7127005B2 (ja) 微細繊維状セルロース含有物
JP7215553B1 (ja) 微細セルロース繊維固形物、及び微細セルロース繊維固形物の製造方法
EP4029983A1 (fr) Microfibres de cellulose sulfonée et procédé de production desdites microfibres
Rissanen Process optimization of cellulose fibril production-the effect of process medium composition on energy efficiency and product quality
JP2022133063A (ja) 消毒組成物
CN112930364A (zh) 含有微细纤维素纤维的干燥固体物质的制造方法、含有微细纤维素纤维的干燥固体物质、微细纤维素纤维再分散液
EP3986963A1 (fr) Particules de cellulose microfibrillée séchée et leur utilisation

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: 22918603

Country of ref document: EP

Kind code of ref document: A1