A method for continuously spraying a liquid composition containing fine cellulose fibers.

Abstract

The present invention aims to provide a method for continuously spraying a liquid composition containing fine cellulose fibers in a simple manner at various locations. [Solution] A liquid composition containing fine cellulose fibers, From a sprayer having a spray nozzle, a liquid tank, and piping connecting the spray nozzle and the liquid tank, a spray is applied to a target surface at a distance of 10 cm or more from the tip of the spray nozzle. A method of continuously spraying while maintaining a spray volume of 100 ml / min or more. The spraying method is further characterized in that the fine cellulose fibers are chemically modified.

Description

Technical Field

[0001] The present invention relates to a method for continuously spraying a liquid composition containing microcrystalline cellulose fibers.

Background Art

[0002] It is expected that various convenient new materials and devices will be produced from nanotechnology, which is a technology for freely controlling substances in the nanometer region, that is, at the atomic and molecular scale. Microcrystalline cellulose fibers, including cellulose nanofibers obtained by finely decomposing plant fibers, are one of them. Microcrystalline cellulose fibers are highly crystalline, characterized by a low coefficient of thermal expansion and a high elastic modulus. In addition, due to their high aspect ratio, effects such as strength improvement and shape stabilization are expected by compounding them with rubber and resin. Further, microcrystalline cellulose fibers have viscosity characteristics such as pseudoplasticity and thixotropy in the state of a dispersion liquid, and effects are also expected as additives such as thickeners.

[0003] The development of microcrystalline cellulose fibers having such excellent characteristics for various industrial uses has been studied. For example, in Patent Document 1, a dispersion liquid for improving the livestock housing environment containing microcrystalline cellulose fibers and a method for improving the livestock housing environment by spraying the dispersion liquid have been proposed. However, the dispersion liquid for improving the livestock housing environment disclosed in Patent Document 1 has a problem that fine fibers clog the spraying nozzle or the like as the spraying time elapses, and continuous spraying cannot be performed. Therefore, in Patent Document 2, a spraying method using a spraying device having a special nozzle or the like has been proposed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] While it has been proposed that the apparatus disclosed in Patent Document 2 can be used to continuously disperse fine cellulose fibers, in many cases, such specialized apparatus cannot be used at various locations where the dispersal of such a dispersion is required, and there is a need for a simpler method to enable continuous dispersal.

[0006] Therefore, the object of the present invention is to provide a method for continuously spraying a liquid composition containing fine cellulose fibers in a simple manner at various locations. [Means for solving the problem]

[0007] As a result of diligent study, the inventors of this application have found that the problem can be solved by the following configurations (1) to (6). (1) A liquid composition containing fine cellulose fibers, From a sprayer having a spray nozzle, a liquid tank, and piping connecting the spray nozzle and the liquid tank, For a target surface that is more than 10 cm away from the tip of the spray nozzle, A method of continuously spraying while maintaining a spray volume of 100 ml / min or more. (2) The spraying method according to (1), characterized in that the fine cellulose fibers are chemically modified. (3) A spraying method according to any one of (1) to (2), characterized in that the fine cellulose fibers are anionically modified. (4) The spraying method according to either (1) or (2), characterized in that the spray nozzle has a nozzle installed such that the spray angle is 20° or more. (5) The spraying method according to any one of (1) to (2), characterized in that the spray nozzle is a two-fluid nozzle. (6) The spraying method according to any one of (1) to (2), characterized in that the liquid composition further comprises a water-soluble polymer. [Effects of the Invention]

[0008] According to the present invention, a method for continuously spraying a liquid composition containing fine cellulose fibers in a simple manner at various locations can be provided. [Modes for carrying out the invention]

[0009] The details of the present invention will be described below, but unless otherwise specified, any notation such as "AA~BB%" shall mean "AA% or more and BB% or less".

[0010] In other words, the present invention is a method for continuously spraying a liquid composition containing fine cellulose fibers onto a target surface at a distance of 10 cm or more from the tip of the spray nozzle, using a sprayer having a spray nozzle, a liquid tank, and piping connecting the spray nozzle and the liquid tank, while maintaining a spray volume of 100 ml / min or more.

[0011] <Fine Cellulose Fibers> Fine cellulose fibers are cellulose in the form of fine fibers derived from cellulose raw materials. Fine fibrous cellulose is defined as a dispersion of fine cellulose fibers (1 wt%) that exhibits a light transmittance in the range of 1 to 99% when analyzed using a visible light spectrometer (UV-1800, Shimadzu Corporation) with a path length of 1 cm / 660 nm. Methods for manufacturing fine cellulose fibers include defibration treatment of pulp, and, if necessary, chemical modification treatment before or after defibration (usually before defibration). Fine cellulose fibers with a fiber diameter on the nano-order are called cellulose nanofibers, and fine cellulose fibers with a fiber diameter on the micron-order are called cellulose microfibrils. The size of fine cellulose fibers can be adjusted by conditions such as micronization treatment and chemical modification treatment.

[0012] (Cellulose nanofiber) In this specification, cellulose nanofiber (CNF) means cellulose fibers having a fiber diameter on the nanoscale, which are prepared through a micronization process.

[0013] The average fiber diameter (length-weighted average fiber diameter) of CNF is 500 nm or less, preferably 300 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. The lower limit is not particularly limited, but is usually 1 nm or more, preferably 2 nm or more. Therefore, the average fiber diameter (length-weighted average fiber diameter) of CNF is usually 1 to 500 nm or 2 to 500 nm, preferably 2 to 300 nm or 2 to 100 nm, more preferably 2 to 50 nm or 3 to 30 nm. The average fiber length (length-weighted average fiber length) is usually 50 to 2000 nm, preferably 100 to 1000 nm. The aspect ratio of CNF is usually 10 or more, preferably 50 or more. The upper limit is not particularly limited, but is usually 1000 or less.

[0014] The average fiber diameter and average fiber length of fine cellulose fibers can be determined using a fractionator manufactured by Valmet Co., Ltd. When using the fractionator, these can be determined as length-weighted fiber width and length-weighted average fiber length, respectively. The average aspect ratio of fine cellulose fibers can be calculated using the formula: Average aspect ratio = Average fiber length / Average fiber diameter.

[0015] (Cellulose microfibrils) In this specification, cellulose microfibrils (microfibrillated cellulose, MFCs) refer to cellulose fibers having a micro-order fiber diameter, which are prepared by micronization treatment.

[0016] The average fiber diameter (average fiber width) of MFC is usually 500 nm or more, preferably 1 μm or more, and more preferably 3 μm or more. Thereby, it is possible to exhibit higher water retention than undefibrated cellulose fibers, and a high strength imparting effect and a yield improvement effect can be obtained even with a small amount compared to finely defibrated CNF. The upper limit of the average fiber diameter is preferably 60 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and even more preferably 20 μm or less, but there is no particular limitation. The average fiber length is usually 10 μm or more, 20 μm or more, or 40 μm or more, preferably 200 μm or more, 300 μm or more, or 400 μm or more. More preferably, it is 500 μm or more or 550 μm or more, still more preferably 600 μm or more, 700 μm or more, 800 μm or more. The upper limit is not particularly limited, but is usually 3,000 μm or less, preferably 2,500 μm or less, more preferably 2,000 μm or less, still more preferably 1,500 μm or less, 1,400 μm or less, or 1,300 μm or less. The aspect ratio of MFC is preferably 3 or more, more preferably 5 or more, still more preferably 7 or more, and may be 10 or more, 20 or more, or 30 or more. The upper limit of the aspect ratio is not particularly limited, but is preferably 1000 or less, more preferably 100 or less, and still more preferably 80 or less.

[0017] [Modified] The fine cellulose fiber may be a modified fine cellulose fiber or an unmodified fine cellulose fiber. The modified fine cellulose fiber means a fine cellulose fiber (for example, cellulose nanofiber, cellulose microfibril) in which at least any one of the three hydroxyl groups contained in the glucose unit is chemically modified (hereinafter simply referred to as "modified"). By the chemical modification treatment, the fibrillation of the cellulose fiber proceeds sufficiently, and cellulose nanofibers having a uniform average fiber length and average fiber diameter can be obtained by defibrillation. Therefore, when added to a dispersion medium such as water to form a dispersion, it is easy to exhibit stable viscosity, and the distribution of fiber length is also suppressed, so that entanglement between fibers is reduced and clogging during spraying can be suppressed. Modified cellulose fibers are preferred.

[0018] Examples of the modification include esterification such as oxidation, etherification, and phosphoric acid esterification, silane coupling, fluorination, cationization, etc. Among them, oxidation (carboxylation), etherification, cationization, and esterification are preferable, and oxidation (carboxylation) is more preferable.

[0019] - Oxidation (carboxylation) - The oxidized microcrystalline cellulose fibers usually have a structure in which at least one carbon atom having a primary hydroxyl group contained in the glucopyranose unit constituting the cellulose molecular chain (for example, the carbon atom having a primary hydroxyl group at the C6 position) is oxidized. The amount of carboxyl groups in the oxidized cellulose fibers or oxidized cellulose nanofibers is preferably 0.5 mmol / g or more, more preferably 0.8 mmol / g or more, and still more preferably 1.0 mmol / g or more based on the absolute dry mass. The upper limit of the amount is preferably 3.0 mmol / g or less, more preferably 2.5 mmol / g or less, and still more preferably 2.0 mmol / g or less. The amount of carboxyl groups is preferably 0.5 to 3.0 mmol / g, more preferably 0.8 to 2.5 mmol / g, and still more preferably 1.0 to 2.0 mmol / g. The amount of carboxyl groups can be adjusted by controlling the conditions (for example, the addition amount of the oxidizing agent, the reaction time) when oxidizing the cellulose fibers. Also, by controlling these conditions, the amounts of carboxyl groups and aldehyde groups can be adjusted.

[0020] The amount of carboxyl groups can be calculated by the following procedure. Prepare 60 ml of a 0.5 mass% slurry (aqueous dispersion) of oxidized cellulose. Add 0.1 M hydrochloric acid aqueous solution to the prepared slurry to adjust the pH to 2.5. Then, dropwise add 0.05 N sodium hydroxide aqueous solution and measure the electrical conductivity until the pH reaches 11. From the amount of sodium hydroxide (a) consumed in the neutralization stage of the weak acid where the change in electrical conductivity is gentle, the amount of carboxyl groups is calculated using the following formula: Amount of carboxyl groups [mmol / g oxidized cellulose] = a [ml] × 0.05 / mass of oxidized cellulose [g] <The oxidation method is not particularly limited, but one example is to oxidize the cellulose raw material in water using an oxidizing agent in the presence of an N-oxyl compound and a bromide, iodide, or a mixture thereof. In this method, the primary hydroxyl group at the C6 position of the glucopyranose ring on the surface of the cellulose is selectively oxidized, producing at least one group selected from the group consisting of an aldehyde group, a carboxyl group (-COOH), and a carboxylate group (-COO-). The concentration of the cellulose raw material during the reaction is not particularly limited, but 5% by mass or less is preferred.

[0021] An N-oxyl compound is a compound capable of generating a nitroxyl radical. Examples of nitroxyl radicals include 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) and its derivatives (e.g., 4-hydroxyTEMPO). Any compound that promotes the desired oxidation reaction can be used as the N-oxyl compound. The amount of N-oxyl compound used is not particularly limited as long as it is a catalytic amount that can oxidize the cellulose raw material. For example, 0.01 mmol or more is preferred, and 0.02 mmol or more is more preferred, per 1 g of oven-dried cellulose raw material. The upper limit is preferably 10 mmol or less, more preferably 1 mmol or less, and even more preferably 0.5 mmol or less. The amount of N-oxyl compound used is preferably 0.01 to 10 mmol, more preferably 0.01 to 1 mmol, and even more preferably 0.02 to 0.5 mmol, per 1 g of oven-dried cellulose raw material. The amount of N-oxyl compound used in the reaction system is usually 0.1 to 4 mmol / L.

[0022] Bromides are compounds containing bromine, such as alkali metal bromides that can dissociate and ionize in water. Iodides are compounds containing iodine, such as alkali metal iodides. The amount of bromide or iodide used can be selected within a range that promotes the oxidation reaction. The total amount of bromide and iodide is preferably 0.1 to 100 mmol, more preferably 0.1 to 10 mmol, and even more preferably 0.5 to 5 mmol per 1 g of oven-dried cellulose raw material.

[0023] As an oxidizing agent, known substances can be used, such as halogens, hypohalous acids, halogenous acids, perhalous acids or their salts, halogen oxides, and peroxides. Among these, hypohalous acids or their salts are preferred because they are inexpensive and have a low environmental impact, hypochlorous acid or its salts are more preferred, and sodium hypochlorite is preferred. The appropriate amount of oxidizing agent to use is, for example, 0.5 to 500 mmol, more preferably 0.5 to 50 mmol, even more preferably 1 to 25 mmol, and even more preferably 3 to 10 mmol per 1 g of oven-dried cellulose raw material. Also, for example, 1 to 40 mol per 1 mol of N-oxyl compound is preferred.

[0024] The oxidation process of cellulose raw materials proceeds efficiently even under relatively mild conditions. Therefore, the reaction temperature is preferably 4 to 40°C, and can also be around 15 to 30°C, i.e., room temperature. As the reaction progresses, carboxyl groups are formed in the cellulose, causing a decrease in the pH of the reaction solution. To ensure the oxidation reaction proceeds efficiently, it is preferable to add an alkaline solution such as an aqueous sodium hydroxide solution to maintain the pH of the reaction solution at around 8 to 12, or 10 to 11. Water is preferred as the reaction medium due to its ease of handling and the low likelihood of side reactions.

[0025] The reaction time in an oxidation reaction can be set appropriately according to the degree of oxidation, and is usually 0.5 to 6 hours, for example, 0.5 to 4 hours.

[0026] The oxidation reaction may be carried out in two stages. For example, by filtering the oxidized cellulose obtained after the first stage of the reaction and then oxidizing it again under the same or different reaction conditions, the oxidation can be carried out efficiently without being inhibited by the salt produced as a by-product in the first stage of the reaction.

[0027] Another example of a carboxylation (oxidation) method is oxidation by contacting a cellulose raw material with an ozone-containing gas (ozone oxidation). This oxidation reaction oxidizes at least the hydroxyl groups at positions 2, 3, and 6 of the glucopyranose ring, and also causes decomposition of the cellulose chain. The ozone concentration in the ozone-containing gas is preferably 50 to 250 g / m³, and more preferably 50 to 220 g / m³. The amount of ozone added is preferably 0.1 to 30 parts by mass, and more preferably 5 to 30 parts by mass, based on 100 parts by mass of the solid content of the cellulose raw material. The ozone treatment temperature is preferably 0 to 50°C, and more preferably 20 to 50°C. The ozone treatment time is not particularly limited, but is preferably 1 to 360 minutes, and more preferably 30 to 360 minutes. When the ozone treatment conditions are within these ranges, it is possible to prevent excessive oxidation and decomposition of the cellulose raw material, and a good yield of oxidized cellulose can be obtained.

[0028] After ozone treatment, a follow-up oxidation treatment may be performed using an oxidizing agent. The oxidizing agent used in the follow-up oxidation treatment is not particularly limited, but examples include chlorine compounds such as chlorine dioxide and sodium chlorite, as well as oxygen, hydrogen peroxide, persulfuric acid, and peracetic acid. The procedure for the follow-up oxidation treatment may involve, for example, dissolving these oxidizing agents in water or a polar organic solvent such as alcohol to prepare an oxidizing agent solution, and then immersing the oxidized cellulose in the solution.

[0029] The method for measuring the amount of carboxyl groups can be the same as described above.

[0030] - Acid-type oxidized cellulose and desalting - Oxidized cellulose contains carboxyl groups as a result of oxidation, but it may contain more acidic carboxyl groups (-COOH) than salty carboxyl groups (e.g., -COO-, -COONa), or more salty carboxyl groups than acidic carboxyl groups. The amounts of salty carboxyl groups and acidic carboxyl groups can be adjusted by desalting. Desalting can convert salty carboxyl groups to acidic carboxyl groups. In this specification, oxidized cellulose (after desalting) is called acidic oxidized cellulose, and oxidized cellulose (without undergoing the desalting treatment described later) is called salty oxidized cellulose. Salty oxidized cellulose usually mainly contains salty carboxyl groups. On the other hand, acidy oxidized cellulose has many acidic carboxyl groups, and the proportion of acidic carboxyl groups to carboxyl groups is preferably 40% or more, more preferably 60% or more, and even more preferably 85% or more. Acidy oxidized cellulose can exhibit a better reinforcing effect together with component C. The proportion of acidic carboxyl groups can be calculated by the following procedure.

[0031] 1) First, prepare 250 mL of an aqueous dispersion of acid-type oxidized cellulose with a solid content of 0.1% by mass before desalting. Add 0.1 M hydrochloric acid aqueous solution to the prepared aqueous dispersion to adjust the pH to 2.5, then add 0.1 N sodium hydroxide aqueous solution and measure the electrical conductivity until the pH becomes 11. From the amount of sodium hydroxide consumed during the neutralization stage of the weak acid, where the change in electrical conductivity is gradual (a), calculate the amount of acid-type carboxyl groups and salt-type carboxyl groups, i.e., the total amount of carboxyl groups, using the following formula: Total amount of carboxyl groups (mmol / g cellulose oxide (salt type)) = a (ml) × 0.1 / mass of cellulose oxide (salt type) (g) 2) Prepare 250 mL of a 0.1% by mass aqueous dispersion of desalted acid-type oxidized cellulose. Add a 0.1 N sodium hydroxide aqueous solution to the prepared aqueous dispersion and measure the electrical conductivity until the pH reaches 11. From the amount of sodium hydroxide consumed during the neutralization stage of the weak acid, where the change in electrical conductivity is gradual (b), calculate the amount of acid-type carboxyl groups using the following formula: Amount of acid-type carboxyl groups (mmol / g acid-type oxidized cellulose) = b (ml) × 0.1 / Mass of acid-type oxidized cellulose (g) 3) From the calculated total amount of carboxyl groups and the amount of acidic carboxyl groups, calculate the proportion of acidic carboxyl groups using the following formula.

[0032] Percentage of acidic carboxyl groups (%) = (Amount of acidic carboxyl groups / Total amount of carboxyl groups) × 100

[0033] Desalting can be performed after oxidation, either before or after defibration (before or after step (2)), but is usually done after oxidation, preferably before step (2). Desalting is usually carried out by replacing the salt (e.g., sodium salt) contained in the salt-type oxidized cellulose with a proton. Methods of desalting include adjusting the system to be acidic and contacting the oxidized cellulose with a cation exchange resin. In the case of adjusting the system to be acidic, the pH of the system is preferably adjusted to 2-6, more preferably 2-5, and even more preferably 2.3-5. Acids (e.g., inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, sulfurous acid, nitrite, and phosphoric acid; organic acids such as acetic acid, lactic acid, oxalic acid, citric acid, and formic acid) are usually used to adjust the pH. After adding the acid, washing treatment may be performed as appropriate. The cation exchange resin can be either a strongly acidic ion exchange resin or a weakly acidic ion exchange resin, as long as the counterion is H+. The ratio of oxidized cellulose to the cation exchange resin when contacting them is not particularly limited and can be appropriately set by those skilled in the art from the viewpoint of efficiently performing proton substitution. The cation exchange resin after contact can be recovered by conventional methods such as suction filtration.

[0034] -Etherification- Examples of etherification include carboxyalkylation, methylation, ethylation, cyanoethylation, hydroxyethylation, hydroxypropylation, ethylhydroxyethylation, and hydroxypropylmethylation, with carboxyalkylation being preferred and carboxymethylation being more preferred.

[0035] Carboxyalkylated cellulose fibers typically have a structure in which at least one carbon atom constituting the cellulose molecular chain (for example, a carbon atom with a primary hydroxyl group at the C6 position that constitutes a glucopyranose unit) is carboxymethylated.

[0036] The degree of carboxyalkyl substitution (DS, preferably carboxymethyl substitution) per anhydrous glucose unit of carboxyalkylated cellulose is preferably 0.01 or higher, 0.02 or higher, or 0.05 or higher, more preferably 0.10 or higher, even more preferably 0.15 or higher, even more preferably 0.20 or higher, and particularly preferably 0.25 or higher. This ensures a degree of substitution necessary to obtain the effects of chemical modification. The upper limit of this degree of substitution is preferably 0.50 or lower, more preferably 0.45 or lower, 0.40 or lower, or 0.35 or lower. This makes it difficult for cellulose fibers to dissolve in water, and allows the fiber form to be maintained in water. Therefore, the degree of carboxyalkyl substitution is preferably 0.01 to 0.50, more preferably 0.01 to 0.45, and even more preferably 0.02 to 0.40, 0.10 to 0.35, or 0.20 to 0.30.

[0037] The degree of substitution, for example, the degree of carboxymethyl substitution, can be measured by the following method. Approximately 2.0 g of carboxymethylated cellulose (dry) is accurately weighed and placed in a 300 mL stoppered Erlenmeyer flask. 100 mL of a solution of 1,000 mL of methanol and 100 mL of special grade concentrated nitric acid is added, and the mixture is shaken for 3 hours to convert the salt-type carboxymethylated cellulose (hereinafter also called "salt-type CM-cellulose") to the acid-type carboxymethylated cellulose (hereinafter also called "acid-type CM-cellulose"). 1.5 to 2.0 g of the acid-type CM-cellulose (dry) is accurately weighed and placed in a 300 mL stoppered Erlenmeyer flask. The acid-type CM-cellulose is moistened with 15 mL of 80% methanol, 100 mL of 0.1 N NaOH is added, and the mixture is shaken at room temperature for 3 hours. Using phenolphthalein as an indicator, the excess NaOH is back-titrated with 0.1 N H2SO4, and the degree of carboxymethyl substitution (DS) can be calculated by the following formula: A = [(100 × F - (0.1N H₂SO₄ (mL)) × F') × 0.1] / (Oven-dry mass of acid-type CM-modified cellulose (g)) DS = 0.162 × A / (1 - 0.058 × A) A: Amount of 1N NaOH required to neutralize 1g of acid-type C-mercured cellulose (mL) F': Factor of 0.1N H2SO4 F: Factor of 0.1N NaOH

[0038] The degree of carboxyalkyl substitution can be adjusted by controlling reaction conditions such as the amount of carboxyalkylating agent added, the amount of mercerizing agent, and the composition ratio of water to organic solvent.

[0039] One method of carboxyalkylation is to merce a cellulosic raw material (starting material) and then etherify it. The following explanation will use carboxymethylation as an example.

[0040] Carboxymethylated cellulose can be produced by using unmodified cellulose fibers (cellulose raw material: e.g., pulp) as a starting material, performing a mercerization treatment, and then carrying out an etherification reaction. This reaction is usually carried out in the presence of a solvent. As the solvent, for example, water, lower alcohols (e.g., methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tertiary butanol) can be used individually or as a mixture of two or more solvents. When lower alcohols are mixed, the mixing ratio of the lower alcohols is preferably 60 to 95% by mass. The amount of solvent is approximately 3 times the mass of the cellulose raw material. There is no particular upper limit to this amount, but it is 20 times or less. Preferably, the amount of solvent is 3 to 20 times the mass of the cellulose raw material.

[0041] Examples of mercerizing agents include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The amount of mercerizing agent used is preferably 0.5 times or more per anhydrous glucose residue of the starting material, more preferably 1.0 times or more, and even more preferably 1.5 times or more, on a molar basis. The upper limit of this amount is usually 20 times or less, preferably 10 times or less, and more preferably 5 times or less. The amount of mercerizing agent used is preferably 0.5 to 20 times, more preferably 1.0 to 10 times, and even more preferably 1.5 to 5 times, on a molar basis.

[0042] The reaction temperature for mercellation is usually 0°C or higher, preferably 10°C or higher. The upper limit is usually 70°C or lower, preferably 60°C or lower. The reaction temperature is usually 0 to 70°C, preferably 10 to 60°C. The reaction time for mercellation is usually 15 minutes or more, preferably 30 minutes or more. The upper limit is usually 8 hours or less, preferably 7 hours or less. The reaction time is usually 15 minutes to 8 hours, preferably 30 minutes to 7 hours.

[0043] The etherification reaction is usually carried out by adding a carboxymethylating agent to the reaction system after mercerization. Examples of carboxymethylating agents include sodium monochloroacetate. The amount of carboxymethylating agent added is preferably 0.05 times or more per glucose residue of the cellulose raw material, more preferably 0.5 times or more, and even more preferably 0.8 times or more, on a molar basis. The upper limit of this amount is usually 10.0 times or less, preferably 5 times or less, and more preferably 3 times or less. The amount of carboxymethylating agent added is preferably 0.05 to 10.0 times, more preferably 0.5 to 5 times, and even more preferably 0.8 to 3 times, on a molar basis.

[0044] The reaction temperature is usually 30°C or higher, preferably 40°C or higher. The upper limit is usually 90°C or lower, preferably 80°C or lower. The reaction temperature is usually 30 to 90°C, preferably 40 to 80°C. The reaction time is usually 30 minutes or more, preferably 1 hour or more. The upper limit is usually 10 hours or less, preferably 4 hours or less. The reaction time is usually 30 minutes to 10 hours, preferably 1 hour to 4 hours. During the carboxymethylation reaction, the reaction solution may be stirred as needed.

[0045] -Differences from carboxymethylcellulose- It is preferable that carboxyalkylated cellulose fibers maintain at least a portion of their fibrous shape even when dispersed in water. Carboxyalkylated cellulose fibers are distinct from cellulose powders such as carboxymethylcellulose, which are a type of water-soluble polymer that dissolves in water and imparts viscosity. When an aqueous dispersion of carboxyalkylated cellulose fibers is observed with an electron microscope, fibrous material can be observed. On the other hand, when an aqueous dispersion of carboxymethylcellulose, a type of water-soluble polymer, is observed, no fibrous material is observed. Furthermore, when anionically modified cellulose fibers are measured by X-ray diffraction, peaks of at least one of cellulose type I and type II crystals can be observed, but when carboxymethylcellulose powder, a water-soluble polymer, is measured in the same way, such cellulose type I and type II crystals are usually not observed.

[0046] - Acid-type carboxyalkylated cellulose and desalting - Carboxylated cellulose may contain more acidic carboxyl groups than saltic carboxyl groups, or vice versa. The amounts of saltic carboxyl groups and acidic carboxyl groups can be adjusted by desalting. Desalting can convert saltic carboxyl groups to acidic carboxyl groups. In this specification, carboxylated cellulose (after desalting) is referred to as acidic carboxylated cellulose, and carboxylated cellulose (without undergoing the desalting treatment described later) is referred to as saltic carboxylated cellulose. Saltic carboxylated cellulose usually mainly contains saltic carboxyl groups (-COO-). On the other hand, acidic carboxylated cellulose has many acidic carboxyl groups, and the ratio of acidic carboxyl groups to the amount of carboxyl groups in acidic carboxylated cellulose is preferably 40% or more, more preferably 60% or more, and even more preferably 85% or more. Acidic carboxylated cellulose is presumed to have superior reinforcing effects with component C. The method for calculating the proportion of acidic carboxyl groups is as described above.

[0047] Desalting is usually performed after carboxyalkylation, preferably after etherification and before fibrillation. One method of desalting is to contact the carboxyalkylated cellulose with a cation exchange resin. Both strongly acidic and weakly acidic cation exchange resins can be used, as long as their counterions are H+. The ratio of carboxyalkylated cellulose to the cation exchange resin when contacting them is not particularly limited and can be appropriately set by those skilled in the art from the viewpoint of efficient proton substitution. For example, the ratio can be adjusted so that the pH of the aqueous dispersion after adding the cation exchange resin to the carboxyalkylated cellulose aqueous dispersion is preferably 2-6, more preferably 2-5. The cation exchange resin after contact can be recovered by conventional methods such as suction filtration.

[0048] - Esterification (Phosphate esterification) - One example of esterified cellulose fibers is phosphorylated cellulose. Phosphorylated cellulose typically has a structure in which at least one carbon atom constituting the cellulose molecular chain (for example, the carbon atom with a primary hydroxyl group at position C6 that constitutes the glucopyranose unit) is phosphorylated.

[0049] The degree of substitution of phosphate groups per glucose unit in phosphate-esterified CNF (hereinafter simply referred to as "degree of phosphate group substitution") is preferably 0.001 or more and less than 0.40. The degree of phosphate group substitution can be measured by the following method. A slurry of phosphate-esterified CNF with a solid content of 0.2% by mass is prepared. A strongly acidic ion exchange resin is added to the slurry by volume at 1 / 10, and after shaking for 1 hour, the slurry is poured onto a mesh with a mesh opening of 90 μm to separate the resin from the slurry and obtain hydrogen-type phosphate-esterified CNF. Next, 0.1 N sodium hydroxide aqueous solution is added to the slurry after treatment with the ion exchange resin in 50 μL increments once every 30 seconds, and the change in the electrical conductivity value of the slurry is measured. The amount of alkali (mmol) required in the region where the electrical conductivity rapidly decreases is divided by the solid content (g) in the slurry to be titrated to calculate the amount of phosphate groups (mmol / g) per 1 g of hydrogen-type phosphate-esterified CNF. Furthermore, the degree of phosphate substitution (DS) per glucose unit of phosphate-esterified CNF is calculated using the following formula: DS = 0.162 × A / (1 - 0.079 × A) where A is the amount of phosphate groups per gram of hydrogen-type phosphate-esterified CNF (mmol / g).

[0050] The degree of phosphate group substitution can be adjusted by controlling reaction conditions such as the amount of phosphate-containing compound added and, if necessary, the amount of basic compound added.

[0051] One method of phosphorylation is to react a compound having a phosphate group with unmodified cellulose fibers (phosphate esterification). Examples of phosphate esterification methods include mixing a powder or aqueous solution of a compound having a phosphate group with a cellulosic raw material (e.g., a suspension (solid content concentration of about 0.1 to 10% by mass)) or adding an aqueous solution of a compound having a phosphate group to an aqueous dispersion of a cellulosic raw material, with the latter being preferred. This improves the uniformity of the reaction and increases the esterification efficiency. The pH of the aqueous solution of the compound having a phosphate group is preferably 7 or less from the viewpoint of improving the efficiency of phosphate group introduction, and more preferably 3 to 7 from the viewpoint of suppressing hydrolysis.

[0052] Examples of compounds containing a phosphate group include phosphoric acid, polyphosphate, phosphorous acid, phosphonic acid, polyphosphonic acid, esters and salts thereof. These compounds are low-cost, easy to handle, and allow for the introduction of phosphate groups into cellulose, thereby improving the defibrillation efficiency. Specific examples of compounds containing a phosphate group include phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, sodium metaphosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, potassium metaphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, and ammonium metaphosphate. One or more compounds containing a phosphate group can be used in combination. The amount of compound containing a phosphate group added to the cellulose raw material is preferably 0.1 to 500 parts by mass, more preferably 1 to 400 parts by mass, and even more preferably 2 to 200 parts by mass, in terms of phosphorus element, per 100 parts by mass of solid content of the cellulose raw material. This allows for the efficient acquisition of a yield commensurate with the amount of compound containing a phosphate group used. The reaction temperature is preferably 0 to 95°C, and more preferably 30 to 90°C. The reaction time is not particularly limited, but is usually about 1 to 600 minutes, and preferably 30 to 480 minutes. If the esterification reaction conditions are within any of these ranges, it is possible to suppress excessive esterification of cellulose and its increased solubility, thereby improving the yield of phosphate-esterified cellulose. When reacting compounds having a phosphate group, basic compounds (for example, compounds having basic amino groups such as urea, methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, hexamethylenediamine, etc.) may also be added to the reaction system. The suspension obtained after esterification is preferably dehydrated as needed, and then heat-treated. This suppresses the hydrolysis of the cellulose raw material. The heating temperature is preferably 100 to 170°C. During the heat treatment, it is preferable to heat at 130°C or lower (preferably 110°C or lower) while water is present, and then, after removing the water, to heat-treat at 100 to 170°C.It is preferable to perform a washing treatment, such as boiling followed by washing with cold water. This allows for efficient defibration. Washing can be performed by adding water and then dehydrating (e.g., by filtration), and may be repeated two or more times. It is preferable to continue washing until the electrical conductivity of the filtrate decreases. For example, it can be continued until the electrical conductivity is preferably 200 or less, more preferably 150 or less, and even more preferably 120 or less. After washing, neutralization treatment may be performed as needed. Neutralization treatment can be performed, for example, by adding alkali (e.g., sodium hydroxide). Washing may be performed again after neutralization.

[0053] - Esterification (phosphorite esterification) - A second example of a method for producing esterified cellulose fibers is phosphite-esterified cellulose fibers. Phosphite-esterified cellulose fibers typically have a structure in which at least one carbon atom constituting the cellulose molecular chain (for example, the carbon atom at position C6 that has a primary hydroxyl group constituting the glucopyranose unit) is phosphite-oxidized. The degree of substitution of phosphite groups per glucose unit in phosphite-esterified cellulose fibers (hereinafter simply referred to as "degree of phosphite group substitution") is preferably 0.001 to 0.60. This makes electrical repulsion between cellulose cells easier, facilitating nanofibrillation. The degree of substitution of phosphite groups can be measured using the same method as for measuring the degree of phosphate group substitution. The degree of phosphite group substitution can be adjusted by controlling reaction conditions such as the amount of phosphite or its salt added, and, if necessary, the amount of alkali metal ion-containing substances, urea or its derivatives added.

[0054] One method for esterifying phosphorous acid is to react unmodified cellulose fibers with phosphorous acid or its metal salt (preferably sodium hydrogen phosphite) to introduce an ester group of phosphorous acid.

[0055] Examples of phosphorous acid and its metal salts include phosphorous acid compounds such as phosphorous acid, sodium hydrogen phosphite, ammonium hydrogen phosphite, potassium hydrogen phosphite, sodium dihydrogen phosphite, sodium phosphite, lithium phosphite, potassium phosphite, magnesium phosphite, calcium phosphite, triethyl phosphite, triphenyl phosphite, and pyrophosphorous acid, and combinations of two or more selected from these, with sodium hydrogen phosphite being preferred. This also allows alkali metal ions to be introduced into the cellulose fibers. The amount of phosphorous acid or its metal salt added is preferably 1 to 10,000 g, more preferably 100 to 5,000 g, and even more preferably 300 to 1,500 g per 1 kg of unmodified cellulose fiber. In addition to phosphorous acid and its metal salt, alkali metal ion-containing substances (e.g., hydroxides, metal sulfates, metal nitrates, metal chlorides, metal phosphates, metal carbonates) may be further added to the reaction system.

[0056] Furthermore, urea or its derivatives may be added to the reaction system. This allows carbamate groups to be introduced into the cellulose fibers. Examples of urea and urea derivatives include urea, thiourea, biuret, phenylurea, benzylurea, dimethylurea, diethylurea, tetramethylurea, and two or more combinations selected from these, with urea being preferred. The amount of urea and urea derivatives added is preferably 0.01 to 100 mol, more preferably 0.2 to 20 mol, and even more preferably 0.5 to 10 mol per 1 mol of phosphorous acid or its metal salt.

[0057] The reaction temperature is preferably 100-200°C, more preferably 100-180°C, and even more preferably 100-170°C. During the heat treatment, it is preferable to heat at 130°C or below (preferably 110°C or below) while water is present, and then, after removing the water, to heat-treat at 100-170°C. The reaction time is usually about 10-180 minutes, more preferably 30-120 minutes. It is preferable to wash the phosphite-esterified cellulose fibers before defibration. The degree of substitution of phosphite groups per glucose unit is preferably 0.01 or more and less than 0.23.

[0058] - Esterification (Sulfuric acid esterification) - A third example of a method for producing esterified cellulose fibers is sulfated esterified cellulose fibers. Sulfated esterified cellulose typically has a structure in which at least one of the carbon atoms constituting the cellulose molecular chain (for example, a carbon atom with a primary hydroxyl group at the C6 position that constitutes a glucopyranose unit) is phosphorylated.

[0059] The amount of sulfate groups per glucose unit in sulfated esterified cellulose fibers (hereinafter simply referred to as "amount of sulfate groups") is preferably 0.1 to 3.0 mmol / g. By introducing cationic substituents into the cellulose raw material, the cellulose molecules repel each other electrically. For this reason, cationized cellulose with introduced cationic substituents can be easily nanofibrillated. If the degree of cationic substitution per glucose unit is 0.02 or higher, sufficient nanofibrillation can be achieved due to the electrical repulsion between the cellulose molecules. On the other hand, if the degree of cationic substitution per glucose unit is 0.50 or lower, swelling or dissolution can be suppressed, preventing situations where nanofibers cannot be obtained. To efficiently perform fibrillation, it is preferable to wash the cationized cellulose obtained above.

[0060] The amount of sulfate groups per glucose unit can be measured by the following method: A aqueous dispersion of sulfated CNF is solvent-substituted with ethanol and then t-butanol, and then freeze-dried. 200 mg of the resulting sample is mixed with 15 ml of ethanol and 5 ml of water, and stirred for 30 minutes. Then, 10 ml of 0.5 N sodium hydroxide aqueous solution is added, and the mixture is stirred at 70°C for 30 minutes, followed by stirring at 30°C for 24 hours. Next, phenolphthalein is added as an indicator, and the mixture is titrated with hydrochloric acid. The amount of sulfate groups is then calculated using the following formula: Sulfate group amount [mmol / g sample] = (5 - (0.1 × hydrochloric acid titration volume [ml] × 2)) / 0.2. The amount of sulfate groups can be adjusted by controlling reaction conditions such as the amount of sulfate-based compound added to the reaction.

[0061] One method of sulfuric acid esterification is to react unmodified cellulose fibers with a sulfuric acid compound, thereby introducing sulfuric acid groups derived from the sulfuric acid compound into the cellulose to produce sulfuric acid-esterified cellulose. Examples of sulfuric acid compounds include sulfuric acid, sulfamic acid, chlorosulfonic acid, sulfur trioxide, or esters or salts thereof. Among these, sulfamic acid is preferred because it has low cellulose solubility and low acidity.

[0062] For example, when sulfamic acid is used as the sulfate compound, the amount of sulfamic acid used can be appropriately adjusted considering the amount of anionic group introduced into the cellulose chain. For example, the amount is preferably 0.01 to 50 mol, more preferably 0.1 to 3.0 mol, per mol of glucose units in the cellulose molecule.

[0063] - Salt type / Acid type - Esterified cellulose may contain more acidic carboxyl groups than salt-type carboxyl groups, or vice versa. Esterified cellulose that has not undergone desalting treatment and that has undergone desalting treatment are called salt-type esterified cellulose and acid-type esterified cellulose, respectively. Salt-type esterified cellulose mainly contains salt-type carboxyl groups. Acid-type esterified cellulose is presumed to be superior due to its reinforcing effect with component C. The countercation of the salt-type carboxyl group and its preparation method are as described in the description of oxidized cellulose.

[0064] -Cationization- Cationized cellulose typically has a structure in which at least one carbon atom constituting the cellulose molecular chain (for example, the carbon atom with a primary hydroxyl group at the C6 position constituting the glucopyranose unit) is cationized, and usually contains cations such as ammonium, phosphonium, sulfonium, or groups having such cations in the molecule. The degree of cation substitution per glucose unit in cationized cellulose is preferably 0.02 to 0.50. The degree of cation substitution per glucose unit can be measured by the following method: After drying the cationized cellulose fibers, the nitrogen content is measured using a total nitrogen analyzer (TN-10, manufactured by Mitsubishi Chemical Corporation), and the degree of cation substitution (average number of moles of substituents per mole of anhydrous glucose unit) is calculated using the following formula: Degree of cation substitution = (162 × N) / (1 - 151.6 × N), where N is the nitrogen content.

[0065] The degree of cation substitution can be adjusted by reaction conditions such as the amount of cationizing agent added and the composition ratio of water or C1-C4 alcohols.

[0066] One method of cationization involves reacting unmodified cellulose fibers with a cationizing agent (e.g., glycidyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrialkylammonium hydrate, or its halohydrin form) and an alkali metal hydroxide catalyst (e.g., sodium hydroxide, potassium hydroxide) in the presence of water and / or an alcohol having 1 to 4 carbon atoms. By using any of the cationizing agents exemplified above, cationized cellulose having a quaternary ammonium group can be obtained. The cationization reaction is usually carried out in the presence of water or alcohol.

[0067] The amount of cationizing agent is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, per 100 parts by mass of cellulose raw material. The upper limit of this amount is usually 800 parts by mass or less, preferably 500 parts by mass or less. Examples of catalysts used as needed during cationization include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The amount of catalyst is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, per 100 parts by mass of cellulose raw material. The upper limit of this amount is usually 7 parts by mass or less, preferably 3 parts by mass or less.

[0068] -Basic-type cationized cellulose fiber- It is preferable to convert the cationized cellulose fibers, after cationization, into basic-type cationized cellulose or basic-type cationized cellulose nanofibers by desalting. Desalting allows the salts in the cationized cellulose to be converted into bases. In this specification, cationized cellulose (nanofibers) that have undergone desalting are referred to as basic-type cationized cellulose (nanofibers) or cationized cellulose (nanofibers) (basic type). Furthermore, cationized cellulose and cationized cellulose nanofibers that have not undergone desalting are referred to as salt-type cationized cellulose (nanofibers) or cationized cellulose (nanofibers) (salt type). Desalting may be performed at either the pre-fibrillation (cationized cellulose) or post-fibrillation (cationized cellulose nanofibers) stage described later. Desalting means replacing the salts (e.g., Cl-) contained in cationized cellulose (salt type) and cationized cellulose nanofibers (salt type) with bases to make them basic type. An example of a desalting method after cationization is to contact cationized cellulose or cationized cellulose nanofibers with an anion exchange resin. As long as the counterion is OH-, either a strongly basic ion exchange resin or a weakly basic ion exchange resin can be used. The ratio of modified cellulose to the anion exchange resin when contacting them is not particularly limited and can be appropriately set by those skilled in the art from the viewpoint of efficiently performing cation substitution. For example, the ratio can be adjusted so that the pH of the aqueous dispersion after adding the anion exchange resin to the cationized cellulose nanofiber aqueous dispersion is preferably 8 to 13, more preferably 9 to 13. The anion exchange resin after contact can be recovered by conventional methods such as suction filtration.

[0069] [Miniaturization (fibrillation, fibrillation)] Micronization is usually carried out by mechanical processes. These mechanical processes (preferably beating or disintegration) are usually carried out in a wet manner (i.e., in the form of an aqueous dispersion of cellulose fibers). Examples of equipment used for mechanical processing include refiners (e.g., disc type, conical type, cylinder type), high-speed defibrators, shear-type agitators, colloid mills, high-pressure jet dispersers, beaters, PFI mills, kneaders, dispersers, high-speed dissociators (top finers), high-pressure or ultra-high-pressure homogenizers, grinders (stone mill type grinders), ball mills, vibratory mills, bead mills, single-screw, twin-screw or multi-screw kneaders / extruders, homomixers under high-speed rotation, refiners, defibrators, friction grinders, high-shear defibrators, dispersers, homogenizers (e.g., microfluidizers), and other equipment capable of providing mechanical defibration. Equipment capable of providing defibration in a wet manner is preferred, and high-speed dissociators and refiners are more preferred, but are not particularly limited.

[0070] When defibration is performed by a wet process, an aqueous dispersion of cellulose fibers is usually prepared. The solid content concentration of modified cellulose in the aqueous dispersion is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, and even more preferably 1.5% by mass or more. The upper limit of the concentration is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less. During mechanical processing, pH adjustment (e.g., 7 or less, 6 or less, 5 or less) may be performed as needed.

[0071] Prior to preparing the aqueous dispersion, pretreatment such as dry grinding (e.g., grinding after drying) may be performed. Examples of equipment used for dry grinding include, but are not limited to, hammer mills, pin mills and other impact mills, ball mills, tower mills and other media mills, and jet mills. Posttreatment may also be performed after defibration. Examples of posttreatment include drying (e.g., freeze-drying, spray drying, shelf drying, drum drying, belt drying, drying by spreading thinly on a glass plate, etc., fluidized bed drying, microwave drying, heated fan-type vacuum drying, vacuum (deaeration) drying), redispersion in water (dispersion equipment is not limited), and grinding (e.g., grinding using equipment such as cutter mills, hammer mills, pin mills, and jet mills), but are not particularly limited.

[0072] [Optional post-processing] The fine cellulose fibers may be in the form of an aqueous dispersion obtained after manufacturing, and may undergo post-treatment as necessary. Post-treatments include, but are not limited to, drying (e.g., freeze-drying, spray drying, shelf drying, drum drying, belt drying, drying by spreading thinly on a glass plate, etc., fluidized bed drying, microwave drying, and vacuum drying with a heated fan), redispersion in water (dispersion equipment is not limited), and grinding (e.g., grinding using equipment such as a cutter mill, hammer mill, pin mill, or jet mill).

[0073] [Physical properties of fine cellulose fibers] Fine cellulose fibers preferably have the following physical properties.

[0074] -Specific surface area- The BET specific surface area of ​​the fine cellulose fibers is preferably 25 m². 2 / g or more, comfortably 50m 2 / g or more, more preferably 100m 2 The value is 1 / g or greater. The BET specific surface area can be measured using a BET specific surface area meter after replacing the aqueous dispersion with t-BuOH and then freeze-drying the sample, according to the nitrogen gas adsorption method (JIS Z 8830).

[0075] -Crystallization of Cellulose Type I- The crystallinity of type I cellulose in fine cellulose fibers is usually 10% or more, preferably 30% or more, and 50% or more. There is no particular upper limit, but in reality, it is considered to be around 90%. The crystallinity of cellulose can be controlled by the degree of chemical modification. The crystallinity of type I cellulose can be calculated by measuring and comparing the intensities of the (200) peak around 22.6° and the valley between (200) and (110) (around 18.5°) using X-ray diffraction. If the fine cellulose fibers contain type II crystals, it is preferable to separate the peaks based on type II crystals (around 12.3°, 20.2°, and 21.9°) before calculating the intensity of the type I crystals.

[0076] Because the fine cellulose fibers have the aforementioned degree of crystallinity, they are more likely to exert their abrasive effect when sprayed under high pressure, thereby improving the polishing, crushing, and cutting performance of the object being sprayed.

[0077] -viscosity- When fine cellulose fibers are used as an aqueous dispersion, a low viscosity of the aqueous dispersion is preferable. This allows for a material with good handling properties despite being fibrillated. For example, the B-type viscosity (25°C, 60 rpm) of an aqueous dispersion with 1% solids by mass is usually 5,000 mPa·s or less, preferably 4,500 mPa·s or less, and more preferably 4,000 mPa·s or less. The lower limit is preferably 10 mPa·s or more, more preferably 20 mPa·s or more, even more preferably 50 mPa·s or more, 100 mPa or more, 500 mPa or more, and 1,000 mPa or more. The B-type viscosity can be measured, for example, by the following method: After fibrillation (e.g., defibrillation), let it stand for at least one day, dilute as necessary, stir with a homodisperser (e.g., 3000 rpm, 5 min), and then measure the viscosity (measure the viscosity after 60 rpm, 3 minutes of rotation).

[0078] The fine cellulose fibers exhibit the viscosity described above, making it possible to obtain a dispersion that is less likely to clog nozzles, especially when spraying chemically modified fine cellulose fibers.

[0079] <Liquid composition> The liquid composition used in the present invention preferably further contains a water-soluble polymer in addition to fine cellulose fibers. The coexistence of fine cellulose fibers and the water-soluble polymer makes it easier for the water-soluble polymer to inhibit the aggregation of the fine cellulose fibers, and also improves the redispersibility when the fine cellulose fibers are dried into a solid, making it suitable for use in the purpose of the present invention. Examples of such water-soluble polymers include cellulose derivatives (carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, ethylcellulose), xanthan gum, xyloglucan, dextrin, dextran, carrageenan, locust bean gum, alginic acid, alginate, pullulan, starch, potato starch, kudzu starch, positive starch, phosphorylated starch, corn starch, gum arabic, locust bean gum, gellan gum, polydextrose, pectin, chitin, water-soluble chitin, chitosan, casein, albumin, soy protein lysate, peptone, and poly This refers to vinyl alcohol, polyacrylamide, sodium polyacrylate, polyvinylpyrrolidone, polyvinyl acetate, polyamino acids, polylactic acid, polymalic acid, polyglycerin, latex, rosin-based sizing agents, petroleum resin-based sizing agents, urea resin, melamine resin, epoxy resin, polyamide resin, polyamide / polyamine resin, polyethyleneimine, polyamine, plant gum, polyethylene oxide, hydrophilic crosslinked polymer, polyacrylate salt, starch-polyacrylic acid copolymer, tamarind gum, gellan gum, pectin, guar gum, and colloidal silica, as well as mixtures of one or more of these. Among these, carboxymethylcellulose and its salts are preferred from the viewpoint of compatibility.

[0080] The amount of water-soluble polymer is preferably in the range of 1 to 50% by weight relative to the oven-dry weight of the fine cellulose fibers, more preferably 5 to 50% by weight, and even more preferably 10 to 50% by weight. By having the water-soluble polymer within the above range, it is possible to effectively inhibit aggregation while preventing the sedimentation of the fine cellulose fibers.

[0081] In addition, any other additives can be used as long as they do not hinder the effects of the present invention. Examples of such additives include auxiliary agents such as surfactants, binders, tackifiers, thickeners other than the water-soluble polymers mentioned above, colorants, antifreezes, desiccants, antioxidants, ultraviolet absorbers, deodorizers, pH adjusters, preservatives, attractants, emulsifiers, emulsions, film-forming agents, and gelling agents, as well as known functional agents such as pesticides, insecticides / insect repellents, fungicides, antibacterial agents, disinfectants, synergists, repellents, fungicides, antioxidants, fragrances, and herbicides.

[0082] <Sprayer> The sprayer used in the present invention may be any device having a spray nozzle, a liquid tank, and piping connecting the spray nozzle and the liquid tank.

[0083] [Spray nozzle] As for the spray nozzle, any commonly used type can be used without particular restrictions, but it is preferable that the nozzle is set up so that the spray angle is 20° or more, more preferably 25° or more, 30° or more, and even more preferably 35° or more, 40° or more. As an upper limit, it is preferable that the spray angle is 120° or less, and more preferably 110° or less. When using the two-fluid nozzle described later, the mixed fluid of liquid and gas is sprayed at high pressure, so the spray angle is usually acute, but if a swirling mechanism is provided in the gas flow path, for example, a swirling force can be applied to the gas, which can increase the mixing efficiency of the liquid and gas, making it possible to spray the mixed fluid at a wide angle.

[0084] The spray nozzle of the present invention may be a one-fluid nozzle that sprays only liquid as the fluid, or a two-fluid nozzle equipped with a nozzle that sprays both liquid and gas as the fluid. However, to spray at higher pressure and extend the spray distance, it is preferable to use a two-fluid nozzle. Normally, such a high-pressure spray structure would raise concerns that fine cellulose fibers would cause clogging, but the spraying method of the present invention can suppress clogging in the nozzle, making it highly suitable for two-fluid nozzles.

[0085] The nozzle opening for discharging the liquid fluid of such a spray nozzle preferably has a width of 0.05 to 0.3 mm, and in the case of a two-fluid nozzle, the relationship between the widths of the gaseous fluid nozzle and the liquid fluid nozzle is preferably such that the ratio of the width of the gaseous fluid nozzle to the width of the liquid fluid nozzle is 1:1 to 5:1.

[0086] [Liquid Tank] As a liquid tank, any commonly used tank capable of storing the liquid composition of the present invention can be used without particular limitations. In particular, by using a chemically modified product of the present invention, the fine cellulose fibers can maintain stable dispersibility in the liquid composition without settling, and therefore, settling of the fine cellulose fibers can be sufficiently suppressed by the operation of a pump or other power source for spraying that operates on gasoline or electricity. However, a circulator or the like may be installed as needed to further improve the flow of liquid in the liquid tank.

[0087] [Piping] As for the piping, there are no particular restrictions as long as it is a commonly used pipe, and metal or rubber materials can be used. However, if the piping has connections where multiple pipes are joined together, there is a concern that fine cellulose fibers may accumulate at the joints, causing blockages. Therefore, it is preferable to use sanitary piping. Accordingly, it is preferable to use piping with an inner wall surface that is smooth and free of irregularities.

[0088] [Sprayer] The sprayer used in this invention has the spray nozzle, liquid tank, and piping described above, but it may also be equipped with a pump or the like, which serves as a power source for supplying and spraying the liquid composition. When using a two-fluid nozzle as the spray nozzle, the liquid fluid can be supplied by the negative pressure of the gaseous fluid, so it is not essential, but it is preferable to have a power source so that the amount of liquid supplied can be finely adjusted. Such a power source can be gasoline, electricity, or any other commonly used power source and is not particularly limited.

[0089] Furthermore, when a two-fluid nozzle is used as the spray nozzle, a gas supply source such as a compressor may also be provided. In such cases, it is preferable to provide a regulator so that the gas flow rate can be adjusted in relation to the liquid flow rate. In addition, as mentioned above, a swirling mechanism may be provided in the gas flow path, and such a swirling mechanism may be formed by creating swirling grooves or swirling walls (helical or wall-shaped) on the inner and outer surfaces of the pipe or the inner wall of the nozzle body.

[0090] <Spraying method> In the spraying method of the present invention, it is important to spray the aforementioned liquid composition onto a target surface at a distance of 10 cm or more from the tip of the spray nozzle. The spraying method of the present invention allows for continuous application to the target surface without clogging, making it suitable for application to a target surface together with, for example, additives. In order to apply the composition evenly to the target surface in this manner, if the spraying distance is not maintained above a certain level, even if the spraying angle is set to a wide angle, uniform application over a wide area will not be achieved, and the expected spraying effect will be difficult to realize. For this reason, the spraying distance is preferably 15 cm or more, more preferably 20 cm or more, and even more preferably 30 cm or more.

[0091] Furthermore, when spraying the liquid composition of the present invention, it is important to spray continuously while maintaining a spray volume of 100 ml / min or more. Continuous spraying in the present invention means that even when operated continuously for at least 5 minutes, the spray volume is maintained at 100 ml / min or more, and conditions (hereinafter also referred to as holding conditions) do not cause nozzle clogging or the like due to fine cellulose fibers. Preferably, the holding conditions are 10 minutes or more, more preferably 20 minutes or more, and even more preferably 30 minutes or more. If the fine cellulose fibers are not chemically modified but mechanically defibrated, a large number of long cellulose fibers remain in the fiber distribution. Therefore, if spraying continuously, there is a concern that clogging of the nozzle or the like due to fiber entanglement may occur at some point, making continuous spraying impossible. In such cases, it becomes an obstacle to uniformly spraying the liquid composition onto the target surface and is unsuitable. When using a two-fluid nozzle, it is preferable to spray at a gaseous fluid flow rate of 10 to 500 NL / min. [Examples]

[0092] The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to these. Unless otherwise specified, parts and % refer to parts by mass and mass%.

[0093] (Manufacturing example 1: Carboxymethylated cellulose nanofibers) In a stirrer capable of mixing pulp, 200g of pulp (NBKP (coniferous bleached kraft pulp), manufactured by Nippon Paper Industries Co., Ltd.) by dry weight and 111g of sodium hydroxide by dry weight were added, and water was added to achieve a pulp solid content of 20% (w / v). After stirring at 30°C for 30 minutes, 216g of sodium monochloroacetate (calculated as active ingredient) was added. After stirring for 30 minutes, the temperature was raised to 70°C and stirred for 1 hour. The reaction product was then removed, neutralized, and washed to obtain carboxymethylated pulp with a carboxymethyl substitution degree of 0.25 per glucose unit. The carboxymethylated pulp was then diluted with water to a solid content of 1%, and defibrated by processing it five times in a high-pressure homogenizer at 20°C and a pressure of 150MPa to obtain carboxymethylated cellulose fibers. The obtained fibers had an average fiber diameter of 15 nm and an aspect ratio of 50.

[0094] To a 0.7 wt% aqueous suspension of the above-mentioned carboxymethylated cellulose fibers (cellulose nanofibers), carboxymethylcellulose (product name: F350HC-4, manufactured by Nippon Paper Industries Co., Ltd.) was added at a concentration of 10 wt% relative to the cellulose nanofibers, and the mixture was stirred for 60 minutes using a TK homomixer (12,000 rpm). A 0.5% aqueous sodium hydroxide solution was added to this aqueous suspension to adjust the pH to 9. The mixture was then dried in a drum dryer D0405 (manufactured by Katsuragi Industries Co., Ltd.) at a vapor pressure of 0.5 MPa.G and a drum rotation speed of 2 rpm to obtain a mixed dried solid of cellulose nanofibers and carboxymethylcellulose with a moisture content of 5 wt%. The dried solid was pulverized in a dry mill to obtain cellulose nanofiber powder.

[0095] (Manufacturing example 2: Oxidized cellulose microfibrils) 100.0 g (oven-dry) of bleached, unbeaten kraft pulp derived from coniferous trees (NBKP, manufactured by Nippon Paper Industries Co., Ltd., whiteness 85%) was added to 10,000 ml of an aqueous solution containing 780 mg of TEMPO (Sigma Aldrich) (0.05 mmol per 1 g of oven-dry cellulose) and 1280 mg of sodium bromide (1.0 mmol per 1 g of oven-dry cellulose), and the mixture was stirred until the pulp was uniformly dispersed. Sodium hypochlorite aqueous solution was added to the reaction system until the sodium hypochlorite concentration reached 5.5 mmol / g, and the oxidation reaction was started at room temperature. During the reaction, the pH of the system decreased, but 3M sodium hydroxide aqueous solution was added sequentially to adjust the pH to 10. The reaction was terminated when the sodium hypochlorite was consumed and the pH of the system no longer changed. Hydrochloric acid was added to the reaction mixture to adjust the pH to 2, and the mixture was filtered through a glass filter to separate the pulp. The separated pulp was thoroughly washed with water to obtain TEMPO oxidized pulp (oxidized pulp / TOP). The pulp yield at this time was 90%, the oxidation reaction took 90 minutes, the carboxyl group content was 1.37 mmol / g, and the pH was 4.5.

[0096] An aqueous dispersion of the obtained oxidized pulp with a solid content of 2.0% by mass was prepared, and after adding a 5% NaOH aqueous solution and sodium bicarbonate to adjust the pH to 8.0, it was treated with a Top Finer (manufactured by Aikawa Iron Works Co., Ltd.) for 10 minutes to prepare an oxidized cellulose microfibril (oxidized microfibril / T-MFC) dispersion. The obtained oxidized cellulose microfibril had a carboxyl group content of 1.37 mmol / g, cellulose type I crystallinity of 80.4%, average fiber width of 17.8 μm, average fiber length of 0.37 mm, aspect ratio of 21, specific surface area of ​​182 m2 / g, and type B viscosity (25℃ / 60 rpm / 1 wt%) of 1710 mPa·s.

[0097] (Manufacturing example 3: Unmodified cellulose fiber) A pulp sheet (whiteness 47.2%, solids content 53% by mass / moisture content 47% by mass) obtained by oxygen delignin treatment of unbleached pulp derived from hardwoods was dispersed in water to obtain a 4% by mass aqueous dispersion. Next, the obtained aqueous dispersion was processed in a single-disc refiner (product name: 14-inch Lab Refiner (manufactured by Aikawa Iron Works Co., Ltd.), clearance 0.15 mm) and beaten until a Canadian standard filtration efficiency (CSF) of 400 ml was achieved. Subsequently, the beaten aqueous dispersion was adjusted in a centrifugal dehydrator to a solids content of 30% by mass to obtain a wet sheet-like material. The obtained wet sheet-like material was crushed by processing it in a single-disc refiner (product name: BR-300CB Lab Refiner (manufactured by Kumagai Riki Kogyo Co., Ltd.), clearance 3.95 mm) to obtain unmodified cellulose fibers with an average fiber length of 0.92 mm.

[0098] (Example 1) The cellulose nanofiber powder obtained in Production Example 1 was dissolved in water to prepare a 10 L liquid composition with a cellulose nanofiber solid content of 0.5% by weight. The obtained liquid composition was sprayed using a backpack-type power sprayer (Maruyama Manufacturing Co., Ltd., MSB100Li (Kirihime), spray angle of 20° or more) under the conditions of a pressure of 0.3 MPa and a spray volume of 800 ml / min. The nozzle tip was used to spray a target surface (a smooth wall) at a distance of 45 cm, and the spray was continuously applied for 10 minutes while maintaining a horizontal position.

[0099] The continuity of spray shape and volume during spraying, as well as the distribution on a symmetrical surface after spraying, were visually evaluated according to the following criteria. The results are shown in Table 1.

[0100] [Continuity during spraying] ○: The spray shape and volume did not change significantly from the beginning of spraying, and spraying was stable without nozzle clogging or other issues. △: Although some changes were observed in the spray shape and volume, continuous spraying was possible for 10 minutes. ×: During spraying, changes in spray shape and volume occurred, likely due to nozzle clogging or other issues, resulting in unstable spraying.

[0101] [Condition of the symmetry plane after spraying] ○: The sprayed areas on the target surface were evenly wet, and no unevenness in the spray was observed. ×: Uneven spraying was observed on the target surface.

[0102] (Example 2) The spray evaluation was performed in the same manner as in Example 1, except that the oxidized cellulose microfibril dispersion obtained in Production Example 2 was used, adjusted to have a solid content of 0.5% by weight, instead of an aqueous solution of cellulose nanofiber powder.

[0103] (Comparative Example 1) The spray evaluation was performed in the same manner as in Example 1, except that instead of an aqueous solution of cellulose nanofiber powder, an aqueous dispersion of unmodified cellulose fibers obtained in Production Example 3, adjusted to a solid content of 0.5% by weight, was used.

[0104] [Table 1]

[0105] As shown in the examples, the spraying method of the present invention allows for uniform spraying of the symmetrical surface after spraying. Furthermore, when modification treatments such as carboxymethylation and water-soluble polymers are used in combination, the spray shape and spray volume become more stable, enabling continuous spraying. Therefore, it is suitable for continuous and uniform application to a target surface, for example, when used in combination with pesticides or insecticides.

Claims

1. A liquid composition containing fine cellulose fibers, From a sprayer having a spray nozzle, a liquid tank, and piping connecting the spray nozzle and the liquid tank, For a target surface that is more than 10 cm away from the tip of the spray nozzle, A method of continuously spraying while maintaining a spray volume of 100 ml / min or more.

2. The spraying method according to claim 1, characterized in that the fine cellulose fibers are chemically modified.

3. A spraying method according to any one of claims 1 to 2, characterized in that the fine cellulose fibers are anionically modified.

4. The spraying method according to any one of claims 1 to 2, characterized in that the spray nozzle has a nozzle installed such that the spray angle is 20° or more.

5. The spraying method according to any one of claims 1 to 2, characterized in that the spray nozzle is a two-fluid nozzle.

6. The spraying method according to any one of claims 1 to 2, characterized in that the liquid composition further comprises a water-soluble polymer.

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