JP6727243B2 - Carboxymethyl cellulose fiber - Google Patents

Description

The present invention relates to fibrous carboxymethylated cellulose having a specific average fiber diameter, aspect ratio, and degree of carboxymethyl substitution.

A compound derived from a natural polymer compound such as cellulose or a cellulose derivative is used as an additive in various fields such as foods, cosmetics, water-based paints, sprays, agricultural chemicals and fragrances.

Patent Document 1 discloses a cellulose fiber having a maximum fiber diameter of 1000 nm or less and a number average fiber diameter of 2 to 150 nm, the cellulose having a cellulose type I crystal structure, and C6 of glucose unit in a cellulose molecule. A cellulose having a hydroxyl group at a position selectively oxidized to be modified into an aldehyde group and a carboxyl group, and having 0.08 to 0.3 mmol/g of the aldehyde group and 0.6 to 2.0 mmol/g of the carboxyl group. A gel composition containing fibers in water in the range of 0.3 to 5.0% by weight is disclosed. This gel composition retains a high viscosity even in the presence of a salt or an ionic surfactant and can maintain a gel state. Therefore, it can be used as a gel base material for toiletries such as cosmetic base materials and fragrances. It is described that it is possible.

JP, 2010-37348, A

However, the present inventors have found that the gel-like composition derived from cellulose described in Patent Document 1 easily loses its viscosity when exposed to high temperatures.
Then, this invention aims at providing the material derived from cellulose which is hard to lose viscosity even if it exposes to high temperature.

As a result of intensive studies, the present inventors have found that a carboxymethylated cellulose fiber having a specific average fiber diameter and an aspect ratio and a carboxymethyl substitution degree per glucose unit of 0.01 to 0.30 has a high temperature. It was found that even when exposed to water, it is difficult to reduce the viscosity and to be colored, that is, it has high heat resistance. It has also been found that this specific carboxymethyl cellulose fiber does not drip when applied to a vertical surface or an inclined surface, and has high fixability (adhesion) to an adherend. Furthermore, it was found that this specific carboxymethylated cellulose fiber has excellent redispersibility after drying, and that it can be stably mixed with various compounds, and that it can be used as an additive in various fields. .. That is, the present invention includes, but is not limited to, the following [1] to [10].
[1] Carboxymethylated cellulose fibers having an average fiber diameter of 3 to 500 nm, an aspect ratio of 100 or more, and a degree of carboxymethyl substitution per glucose unit of 0.01 to 0.30.
[2] The carboxymethylated cellulose fiber according to [1], which has an average fiber diameter of 3 to 20 nm.
[3] In the carboxymethylated cellulose fiber, the crystalline type I of cellulose is 60% or more, and the crystalline type II of cellulose is 10 to 50% of the crystalline type I of cellulose, [1] or [2]. ] The carboxymethylated cellulose fiber of statement.
[4] Additives for foods, beverages, cosmetics, pharmaceuticals, papermaking, civil engineering, paints, inks, agricultural chemicals, construction, epidemics, electronic materials, flame retardants, household sundries, or cleaning agents, from [1] 3] A carboxymethylated cellulose fiber according to any one of 3).
[5] A lubricating composition containing the carboxymethylated cellulose fiber according to any one of [1] to [3].
[6] A method for reducing the friction coefficient of a base material, which comprises applying the carboxymethylated cellulose fiber according to any one of [1] to [3] to the base material.
[7] An agent which improves the slipping of the iron during ironing, containing the carboxymethylated cellulose fiber according to any one of [1] to [3].
[8] An iron for ironing a cloth, which comprises applying the carboxymethylated cellulose fiber according to any one of [1] to [3] to a cloth, and ironing the applied cloth. How to improve your slippage.
[9] A wrinkle reducing agent for clothing, containing the carboxymethylated cellulose fiber according to any one of [1] to [3].
[10] Applying the carboxymethylated cellulose fiber according to any one of [1] to [3] to a cloth,
A method of reducing the occurrence of wrinkles in clothing after washing, comprising washing the applied cloth and drying the washed cloth.

According to the present invention, it is possible to provide a material derived from cellulose, which has excellent fixability, is resistant to dripping, is resistant to viscosity reduction even when exposed to high temperatures, and is resistant to coloration (that is, has high heat resistance). .. Further, the carboxymethylated cellulose fiber of the present invention has advantages that it can be favorably redispersed after being dried, and that it can be stably mixed with various compounds.

Additives comprising carboxymethyl cellulose fibers of the present invention, various fields in which additives are generally used, for example, food, beverages, cosmetics, pharmaceuticals, various chemical supplies, papermaking, civil engineering, paints, inks, pesticides, It can be used in construction, epidemics, electronic materials, flame retardants, household sundries, cleaning agents, etc. Specifically, thickeners, gelling agents, sizing agents, food additives, excipients, rubber/plastic compounding materials, paint additives, adhesive additives, papermaking additives, abrasives, It can be used as a water retention agent, shape retention agent, muddy water conditioner, filter aid, overflow preventive agent, etc., and rubber/plastic materials, paints, adhesives, coated paper coatings, coats containing them as constituents. It can be applied to papers, binders, cosmetics, lubricating compositions, polishing compositions, wrinkle reducing agents for clothing, sliding agents for ironing, etc.

The present invention relates to fibrous carboxymethylated cellulose having a specific average fiber diameter and aspect ratio, and having a degree of carboxymethyl substitution per glucose unit of 0.01 to 0.30. Carboxymethyl-cellulosic cellulose (CMC) used for ordinary food thickeners and the like is a water-soluble polymer and does not have a fibrous form. The carboxymethylated cellulose of the present invention is characterized by maintaining a fiber shape by having a specific degree of carboxymethyl substitution. Such fibrous carboxymethyl cellulose (that is, carboxymethyl cellulose fibers) can be obtained by carboxymethylating a cellulose raw material so as to have a specific degree of carboxymethyl substitution, and then defibrating it.

(Cellulose raw material)
Examples of the cellulose raw material for producing the carboxymethylated cellulose fiber of the present invention include bleached or unbleached wood pulp, purified linter, natural cellulose such as cellulose produced by microorganisms such as acetic acid bacteria; cellulose in copper ammonia solution, morpholine. Regenerated cellulose produced by dissolving in a solvent such as a derivative and then spinning; fine cellulose obtained by depolymerization of these by hydrolysis, alkali hydrolysis, enzymatic decomposition, explosion treatment, vibration ball mill treatment, and the like; and An example is fine cellulose obtained by mechanically treating.

(Carboxymethylation)
Carboxymethylation of a cellulose raw material can be performed using a known method (for example, a water medium method or a solvent method). The water medium method is a method in which an etherifying agent such as monochloroacetic acid and an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, etc.) serving as a catalyst are added to a cellulose raw material and reacted in a medium containing water as a main component. In the solvent method, an etherifying agent such as monochloroacetic acid and an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, etc.) as a catalyst are added to a cellulose raw material, and methanol, ethanol, N-propyl alcohol, isopropyl alcohol, N-butanol is added. , A lower alcohol such as isobutanol or tertiary butanol is used as a main component in the reaction. The water medium method is preferable because it does not require a drying step before defibration.

The concentration of the cellulose raw material in the carboxymethylation reaction is not particularly limited, but is preferably 10% (w/v) or more, more preferably 20% (w/v) or more, from the viewpoint of increasing the effective utilization rate of monochloroacetic acid. More preferably, it is 30% (w/v) or more.

It is preferable that the cellulose raw material has a size of 0.5 to 3 cm square because carboxymethylation can be easily progressed uniformly. If it is larger than this, uniform mixing of the drug solution and the cellulose raw material tends to be difficult. On the other hand, if it is smaller than this, the viscosity of the obtained carboxymethyl cellulose fibers tends to be low, and washing tends to be difficult.

During the reaction, it is preferable to use a stirring device capable of uniformly mixing the chemical liquid and the cellulose raw material. For example, a batch type stirrer in which two shafts stir to mix a raw material and a chemical solution is preferable from the viewpoint of both uniform mixing and productivity. In addition, it is preferable that the chemical solution is added to the cellulose raw material by using a device such as a sprayer because it is easily mixed uniformly.

In the present invention, it is important that the carboxymethyl substitution degree of glucose per glucose unit is 0.01 to 0.30. By introducing a carboxymethyl substituent into cellulose, the cellulose electrically repels each other. Therefore, the cellulose having the carboxymethyl substituent introduced therein can be easily defibrated to a nano-order fiber diameter. If the carboxymethyl substituent group per glucose unit is less than 0.01, the defibration cannot be sufficiently performed. On the other hand, if the carboxymethyl substituent is more than 0.30 per glucose unit, the fiber morphology cannot be maintained because it swells or dissolves, and it may not be possible to obtain nanofibers. The degree of carboxymethyl substitution can be adjusted by controlling the addition amount of an etherifying agent to be reacted, the amount of alkali as a catalyst, and the composition ratio of a solvent such as water or a lower alcohol in both the water medium method and the solvent method.

The crystallinity of cellulose can be controlled by the concentration of alkali metal, the temperature at the time of treatment, and the degree of carboxymethyl modification. Since a high concentration of alkali is used in carboxymethyl modification, type I crystals of cellulose are easily converted to type II, but by adjusting the amount of alkali to be used, the degree of modification can be adjusted to the desired value. The crystallinity of can be maintained. The present inventors have found that the aqueous medium method is easier to produce a carboxymethylated cellulose raw material in a state where type I and type II coexist, as compared with the solvent method.

(Defibration)
The carboxymethylated cellulose raw material is then defibrated to have an average fiber diameter of 3 to 100 nm and an aspect ratio of 100 or more to obtain the carboxymethylated cellulose fiber of the present invention. The average fiber diameter is preferably 3 to 20 nm, more preferably 5 to 19 nm, further preferably 5 to 15 nm. By setting the average fiber diameter and the aspect ratio within the above ranges, various physical properties such as difficulty in dripping, fixability, suspension stability, emulsion stability, and thickening effect are dramatically improved. In addition, carboxymethylated cellulose fibers having an average fiber diameter and an aspect ratio within the above ranges have high transparency (for example, the transparency of an aqueous dispersion having a solid content of 0.1% (w/v) is 70% or more), It can also be used in applications where transparency is required.

The maximum fiber diameter is not particularly limited, but is preferably 1000 nm or less.
The method for defibrating is not particularly limited. From the viewpoint of easy handling, it is preferable to disintegrate using a carboxymethylated cellulose raw material dispersed in water.

The device for defibrating is not particularly limited. For example, a device capable of applying a strong shearing force such as a high-speed rotation type, a colloid mill type, a high pressure type, a roll mill type, and an ultrasonic type is preferable. In particular, for efficient defibration, it is preferable to use a wet high-pressure or ultra-high-pressure homogenizer that can apply a pressure of 100 MPa or more and a strong shearing force to the water dispersion. The pressure is more preferably not less than 140 MPa. Prior to defibration with a high-pressure homogenizer, the carboxymethylated cellulose raw material may be pretreated with a known mixing, stirring, emulsifying, or dispersing device such as a high-speed shear mixer, if necessary.

(Dry)
The carboxymethylated cellulose fiber of the present invention can be used in the state of a dispersion obtained after defibration, but can also be dried if necessary and redispersed in water before use. Although the drying method is not limited at all, for example, a freeze drying method, a spray drying method, a tray drying method, a drum drying method, a belt drying method, a method of thinly spreading and drying on a glass plate, a fluidized bed drying method, a microwave drying method. Known methods such as a vacuum drying method and a heating fan type vacuum drying method can be used. After drying, it may be ground with a cutter mill, a hammer mill, a pin mill, a jet mill or the like, if necessary. Further, the method of redispersion in water is not particularly limited, and a known dispersing device can be used.

(Carboxymethylated cellulose fiber)
The carboxymethylated cellulose fiber of the present invention preferably has crystallinity. By having crystallinity, a three-dimensional network structure is formed between fibers. As a result, it exhibits high viscosity under static conditions where the shear rate is low, and exhibits excellent fixability and resistance to dripping.

On the other hand, the usual water-soluble carboxymethyl cellulose having no crystallinity and its cellulosic additives such as salts thereof cannot form a network structure between the additives, so that the fixability and the dripping It is considered to be inferior in difficulty.

Regarding the crystal type of cellulose in the carboxymethylated cellulose fiber of the present invention, the crystal type I is preferably 60% or more, and the crystal type II is preferably 10 to 50% with respect to the crystal type I. More preferably, the crystal type I is 70% or more, and the crystal type II is 20 to 50% with respect to the cellulose type I. When the crystallinity is adjusted within the above range, various physical properties such as difficulty in dripping, fixability, suspension stability, emulsion stability, and thickening effect are improved.

Carboxymethylated cellulose fibers having such characteristics are excellent in miscibility with other materials and exhibit a high dispersion stabilizing effect in a hydrophilic medium such as water. Further, for example, when it is dispersed in water or a hydrophilic organic solvent, high thixotropy is exhibited, and it becomes a gel depending on the conditions, so that it is also effective as a gelling agent. In addition, by forming a film by a papermaking method or a casting method, a material having high strength, excellent heat resistance, and low thermal expansion can be obtained. The film thus obtained is also useful as a coating layer for the purpose of imparting hydrophilicity. Further, when the carboxymethylated cellulose fiber is compounded with another material such as a resin material, since it has excellent dispersibility in the other material, it is preferable to provide a composite having excellent transparency. You can Further, it also functions as a reinforcing filler, and when the fibers form a network in the composite to a high degree, it becomes higher in strength than the resin used alone, and the coefficient of thermal expansion can be lowered. it can. In addition to the above, the carboxymethylated cellulose fiber of the present invention has the amphipathic property of cellulose, and therefore functions as, for example, an emulsifier or a dispersion stabilizer. Further, the carboxylmethyl group forms a counter ion with a metal ion, and is therefore effective as a metal ion collector and the like.

Hereinafter, embodiments of the present invention will be described with reference to examples, but the present invention is not limited thereto.
(Method of measuring the degree of carboxymethyl substitution per glucose unit)
About 2.0 g of carboxymethyl cellulose fibers (extra-dried) was precisely weighed and placed in a 300 mL Erlenmeyer flask with a stopper. 100 mL of a liquid containing 100 mL of special grade concentrated nitric acid added to 1000 mL of nitric acid methanol was added and shaken for 3 hours to convert the carboxymethyl cellulose salt (CMized cellulose) into hydrogenated CM-modified cellulose. 1.5 to 2.0 g of hydrogenated CM-modified cellulose (absolutely dried) was precisely weighed and placed in a 300 mL Erlenmeyer flask with a stopper. The hydrogenated CM cellulose was wetted with 15 mL of 80% methanol, 100 mL of 0.1 N NaOH was added, and the mixture was shaken at room temperature for 3 hours. Excess NaOH was back titrated with 0.1 N H ₂ SO ₄ using phenolphthalein as an indicator. The degree of carboxymethyl substitution (DS) was calculated by the following formula:
A=[(100×F′−(0.1N H ₂ SO ₄ )(mL)×F)×0.1]/(absolute dry mass (g) of hydrogenated CM cellulose)
DS=0.162×A/(1-0.058×A)
A: 1N NaOH amount (mL) required to neutralize 1 g of hydrogenated CM cellulose
F′: Factor of 0.1 N H ₂ SO ₄ F: Factor of 0.1 N NaOH (Measurement method of average fiber diameter and aspect ratio)
The average fiber diameter and the average fiber length of the carboxymethyl cellulose fiber are 20 nm or less, an atomic force microscope (AFM), and 20 nm or more using a field emission scanning electron microscope (FE-SEM). Analysis was performed on 200 randomly selected fibers. The aspect ratio was calculated by the following formula:
Aspect ratio = average fiber length / average fiber diameter (measurement method of crystallinity)
Carboxymethylated cellulose fibers were lyophilized with liquid nitrogen and compressed to form tablet-shaped pellets. After that, this sample was measured by an X-ray diffraction measurement device (LabX XRD-6000, manufactured by Shimadzu Corporation). The obtained graph was subjected to peak separation using the graph analysis software PeakFit (manufactured by Hulinks), and crystalline I type and II type as well as non-crystalline were distinguished based on the following diffraction angles. The ratio of crystalline Form I to Form II was calculated from the area ratio of the following peaks:
Crystal type I: 2θ=14.7°, 16.5°, 22.5° Crystal type II: 2θ=12.3°, 20.2°, 21.9° Amorphous component: 2θ=18° Cellulose I The crystallinity of the mold was calculated from the values of the diffraction intensity (Ia) of 18° and the diffraction intensity (Ic) of 22.5° by the following formula called the Segal method:
Type I crystallinity=(Ic-Ia)/Ic×100
(Method of measuring B type viscosity)
After leaving an aqueous dispersion of carboxymethyl cellulose fibers (solid content 1% (w/v)) at 25° C. for 24 hours, a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.) was used to rotate at 30 rpm (3 minutes). ) Was used to measure the viscosity.

(Measurement method of transparency)
The transmittance of 660 nm light of an aqueous dispersion of carboxymethyl cellulose fibers (solid content 0.1% (w/v)) was measured using a UV-VIS spectrophotometer UV-265FS (manufactured by Shimadzu Corporation). , With transparency.

<Production Example 1>
To a stirrer with which pulp can be mixed, pulp (NBKP (softwood bleached kraft pulp), made by Nippon Paper Industries) is added in a dry mass of 200 g, and sodium hydroxide is added in a dry mass of 50 g to give a pulp solid content of 20% (w/v). ) Was added. Then, after stirring at 30° C. for 30 minutes, 50 g of sodium monochloroacetate (active ingredient conversion) was added. After stirring for 30 minutes, the temperature was raised to 70° C. and the mixture was stirred for 1 hour. Then, the reaction product was taken out, neutralized and washed to obtain a carboxymethylated pulp having a carboxymethyl substitution degree of 0.05 per glucose unit. Then, the carboxymethylated pulp was made to have a solid content of 1% with water, and was defibrated by treating with a high-pressure homogenizer three times at 20° C. and a pressure of 150 MPa to obtain carboxymethylated cellulose fibers. The obtained fiber has an average fiber diameter of 10 nm, an aspect ratio of 500, an I-type crystallinity of 75%, a ratio of the II-type to the I-type of 25%, a B-type viscosity of 10000 mPa·s, and a transparency of 90%. Met.

<Production Example 2>
The procedure of Example 1 was repeated, except that the pressure during defibration was 100 MPa. The obtained fiber has an average fiber diameter of 19 nm, an aspect ratio of 200, an I-type crystallinity of 75%, a ratio of II-type to I-type of 25%, a B-type viscosity of 5000 mPa·s, and a transparency of 88%. Met.

<Production Example 3>
The procedure of Example 1 was repeated, except that the pressure during defibration was 80 MPa. The obtained fiber has an average fiber diameter of 100 nm, an aspect ratio of 500, an I-type crystallinity of 75%, a ratio of II-type to I-type of 25%, a B-type viscosity of 3000 mPa·s, and a transparency of 85%. Met.

<Production Example 4>
Example 1 was repeated except that 110 g of sodium hydroxide and 210 g of sodium monochloroacetate were used to obtain a carboxymethylated pulp having a carboxymethyl substitution degree of 0.3. The obtained fiber has an average fiber diameter of 5 nm, an aspect ratio of 500, an I-type crystallinity of 65%, a ratio of II-type to I-type of 40%, a B-type viscosity of 9000 mPa·s, and a transparency of 95%. Met.

<Production Example 5>
Example 1 was repeated except that 170 g of sodium hydroxide and 250 g of sodium monochloroacetate were used to obtain a carboxymethylated pulp having a carboxymethyl substitution degree of 0.3. The obtained fiber has an average fiber diameter of 5 nm, an aspect ratio of 400, an I-type crystallinity of 58%, a II-type I-type ratio of 50%, a B-type viscosity of 7,000 mPa·s, and a transparency of 95%. Met.

<Production Example 6>
Example 1 was repeated except that the pulp used was LBKP (hardwood bleached kraft pulp) (manufactured by Nippon Paper Industries). The obtained fiber has an average fiber diameter of 10 nm, an aspect ratio of 500, an I-type crystallinity of 75%, a ratio of the II-type to the I-type of 25%, a B-type viscosity of 10000 mPa·s, and a transparency of 90%. Met.

<Production Example 7>
Example 1 was the same as Example 1 except that the pulp used was NDSP (softwood dissolved sulfite pulp) (manufactured by Nippon Paper Industries). The obtained fiber has an average fiber diameter of 10 nm, an aspect ratio of 300, an I-type crystallinity of 75%, a ratio of II-type to I-type of 25%, a B-type viscosity of 8000 mPa·s, and a transparency of 95%. Met.

<Production Example 8>
The procedure of Example 1 was repeated except that the pulp used was NDKP (softwood dissolving kraft pulp) (manufactured by Nippon Paper Industries). The obtained fiber has an average fiber diameter of 10 nm, an aspect ratio of 300, an I-type crystallinity of 75%, a ratio of II-type to I-type of 25%, a B-type viscosity of 8000 mPa·s, and a transparency of 95%. Met.

<Production Example 9>
Example 1 was repeated except that the pulp used was LDSP (hardwood-dissolved sulfite pulp) (manufactured by Nippon Paper Industries). The obtained fiber has an average fiber diameter of 10 nm, an aspect ratio of 300, an I-type crystallinity of 75%, a ratio of II-type to I-type of 25%, a B-type viscosity of 8000 mPa·s, and a transparency of 95%. Met.

<Production Example 10>
Example 1 was repeated except that the pulp used was LDKP (hardwood dissolving kraft pulp) (manufactured by Nippon Paper Industries). The obtained fiber has an average fiber diameter of 10 nm, an aspect ratio of 300, an I-type crystallinity of 75%, a ratio of II-type to I-type of 25%, a B-type viscosity of 8000 mPa·s, and a transparency of 95%. Met.

<Comparative Example A>
Pulp (NBKP, manufactured by Nippon Paper Industries) was suspended in water to obtain a slurry having a solid content of 1% (w/v). The pulp slurry was treated with an ultrahigh pressure homogenizer at 20° C. and a pressure of 150 MPa three times. The obtained liquid was a cloudy slurry showing no viscosity.

<Comparative Example B> The procedure of Example 1 was repeated, except that 150 g of sodium hydroxide and 290 g of sodium monochloroacetate were used to obtain carboxymethylated cellulose having a carboxymemethyl substitution degree of 0.4. The average fiber diameter of the obtained carboxymethyl cellulose was so small that it could not be measured by either AFM or FE-SEM. The transparency was 99% and the viscosity was 5000 mPa·s.

<Comparative Example C>
Pulp (NBKP, made by Nippon Paper Industries) 5 g (absolutely dried), TEMPO (2,2,6,6-tetramethylpiperidine-1-oxy radical, Sigma Aldrich) 78 mg (0.5 mmol) and sodium bromide 755 mg ( (7.4 mmol) was added to 500 ml of a dissolved aqueous solution, and the mixture was stirred until the pulp was uniformly dispersed. After adding 16 ml of a 2M sodium hypochlorite aqueous solution to the reaction system, the pH was adjusted to 10.3 with a 0.5N hydrochloric acid aqueous solution to start the oxidation reaction (oxidation treatment). Although the pH in the system was lowered during the reaction, 0.5N sodium hydroxide aqueous solution was sequentially added to adjust the pH to 10. After reacting for 2 hours, it was filtered with a glass filter and washed sufficiently with water to obtain oxidized pulp. When the amount of carboxyl groups in the obtained oxidized pulp was measured as described below, it was 1.60 mmol/g.

(Measurement of the amount of carboxyl group)
After preparing 60 ml of 0.5 mass% slurry of oxidized pulp and adding 0.1M hydrochloric acid aqueous solution to pH 2.5, 0.05N sodium hydroxide aqueous solution was added dropwise until the pH reached 11 Was calculated and calculated from the amount (a) of sodium hydroxide consumed in the neutralization stage of the weak acid, whose electrical conductivity changes slowly, using the following formula.
Amount of carboxyl group [mmol/g pulp]=a [ml]×0.05/mass of oxidized pulp [g].

500 mL of a 1% (w/v) oxidized cellulose slurry was defibrated by treatment with an ultrahigh pressure homogenizer at 20° C. and a pressure of 150 MPa three times. The obtained nanofibers had an average fiber diameter of 5 nm, transparency of 99%, and viscosity of 10,000 mPa·s.

<Example 1>
With respect to the above Production Examples 1 to 10 and Comparative Examples A to C, changes in viscosity after heat treatment, rheometer viscosity, film-forming property, difficulty in dripping, dispersibility, water retention, and coloring after heat treatment were evaluated. .. The results are shown in Table 1.

(Evaluation of fluctuation of viscosity after heat treatment)
The resulting aqueous dispersion of fibers (solid content 1% (w/v)) was kept at 80° C. for 5 hours. Then, it was left to cool to 25° C., and the B-type viscosity was measured by the above method.

(Rheometer measurement)
When the aqueous dispersion of the obtained fiber (solid content 1% (w/v)) is set to 30° C. and the shear rate is 0.01 (1/s) by viscoelastic rheometer MCR301 (manufactured by Anton Paar) Was measured. A parallel type plate (PP25) was used for the measurement, and the gap of the measurement part was set to 1 mm.

(Evaluation of coating property)
The obtained aqueous dispersion of fibers (solid content 1% (w/v)) was applied onto a glass plate using a #16 coating rod, and baked at 100° C. for 30 minutes in a blow dryer to form a film. The thickness was adjusted to 20 to 25 μm. The glass test plate was immersed in warm water of 40° C., and the degree of blistering, peeling and blistering of the coating was visually determined.
3: Stable even after immersion for 5 days or more 2: Abnormality occurred within 5 days of immersion 1: Abnormality occurred within 1 day of immersion (Evaluation of dripping resistance)
The obtained aqueous dispersion of fibers was adjusted to a solid content of 0.1% (w/v), put in a spray container and sprayed on a vertical surface. The degree of sagging of the liquid adhering to the vertical surface was visually determined.
3: Almost no liquid dripping.
2: Slight dripping is observed 1: Clear dripping occurs.

(Evaluation of dispersibility)
The aqueous dispersion of the obtained fiber was adjusted to a solid content of 0.2% (w/v), and carbon black was added to have a concentration of 2% (w/v). Then, the mixture was stirred at 1000 rpm for 10 minutes, placed in a colorimetric tube and allowed to stand. The degree of dispersibility of the carbon black after one week was visually evaluated.
3: Carbon black is well dispersed.
2: Carbon black is slightly settled 1: Dispersibility of carbon black is poor and settling occurs.

(Evaluation of water retention)
3 drops of the obtained aqueous dispersion of fibers (1% (w/v)) was placed on high-quality paper (manufactured by Nippon Paper Industries, trade name: NPi high-quality (registered trademark), basis weight 64.0 g/m ² ). The degree of penetration into the paper was visually evaluated.
3: Good, not soaked in high-quality paper 2: Slightly soaked in high-quality paper 1: Poor, soaked in high-quality paper (Evaluation of coloring after heat treatment)
The resulting aqueous dispersion of fibers (1% (w/v)) was dried overnight at 105°C. The state of coloring of the fibers after drying was visually judged.
2: Almost no coloring 1: Coloring is recognized

<Example 2> Properties 1 of mixture with various additives
The aqueous dispersion of each fiber obtained above was adjusted to a solid content of 0.1% (w/v), and each fiber was divided into 21 containers. 1% of each of the following 21 kinds of additives (inorganic salts, surfactants, oils, humectants, preservatives, inorganic fine particles, organic fine particles, organic solvents, fragrances and deodorants) are added to each of these containers. In addition to (w/v), 21 kinds of samples were prepared for each fiber. Each of the obtained samples was put in a spray container and sprayed on a vertical surface, and the degree of dripping of the liquid adhering to the vertical surface was visually determined for each sample.
[Inorganic salts] NaCl, KCl, CaCl ₂ , MgCl ₂ , (NH ₄ ) ₂ SO ₄ , Na ₂ CO ₃
[Surfactant] Polyoxyethylene lauryl ether, alkyl polyglucoside, polyoxyethylene lauryl ether sodium sulfate [oils] dimethyl polysiloxane, glyceryl triisooctanoate, squalane [moisturizer] glycerin [preservative] methylparaben [inorganic particles] Titanium oxide, red iron oxide [organic fine particles] urethane emulsion (Daiichi Kogyo Seiyaku Co., Ltd., Superflex (registered trademark) 150)
[Organic solvent] Ethanol, isopropanol [Flavor/deodorant] D limonene, orange oil As a result, when the fibers of Production Examples 1 to 10 and Comparative Example C were used, it was found that they were mixed with any additive. But no dripping was seen. On the other hand, in the fiber of Comparative Example A, dripping was observed in all the samples (21 kinds). Further, with the water-soluble carboxymethyl cellulose of Comparative Example B, it can be said that liquid sagging is less likely to occur as compared with Comparative Example A, but it was slightly dripping compared with those of Production Examples 1-10.

<Example 3> Property 2 of mixture with various additives
The obtained aqueous dispersion of each fiber was adjusted to a solid content of 0.2% (w/v), and each fiber was divided into 21 containers. 1% of each of the following 21 kinds of additives (inorganic salts, surfactants, oils, humectants, preservatives, inorganic fine particles, organic fine particles, organic solvents, fragrances and deodorants) are added to each of these containers. In addition to (w/v), carbon black was further added to 2% (w/v), and 21 kinds of samples were prepared for each fiber. The obtained sample was stirred at 1000 rpm for 10 minutes, placed in a colorimetric tube and allowed to stand. For each sample, the degree of carbon black dispersibility after one week was visually determined.
[Inorganic salts] NaCl, KCl, CaCl ₂ , MgCl ₂ , (NH ₄ ) ₂ SO ₄ , Na ₂ CO ₃
[Surfactant] Polyoxyethylene lauryl ether, alkyl polyglucoside, polyoxyethylene lauryl ether sodium sulfate [oils] dimethyl polysiloxane, glyceryl triisooctanoate, squalane [moisturizer] glycerin [preservative] methylparaben [inorganic particles] Titanium oxide, red iron oxide [organic fine particles] urethane emulsion (Daiichi Kogyo Seiyaku Co., Ltd., Superflex (registered trademark) 150)
[Organic solvent] Ethanol, isopropanol [Flavor/deodorant] D limonene, orange oil As a result, when the fibers of Production Examples 1 to 9 and Comparative Example C were used, it was found that they were mixed with any additive. However, the carbon black was well dispersed. On the other hand, in the fiber of Comparative Example A, the dispersibility of carbon black was poor, and the sedimentation of carbon black occurred in all the samples. Further, the water-soluble carboxymethyl cellulose of Comparative Example B had better dispersibility than Comparative Example A, but was inferior to those of Production Examples 1-10.

As described above, the carboxymethylated cellulose fiber of the present invention has excellent heat resistance, film-forming property, difficulty in dripping, dispersibility, and water retention, and also has viscosity even when mixed with various additives. Does not decrease, and it is difficult to drip and maintains dispersion stability. Therefore, it is useful as an additive in various fields such as foods, beverages, cosmetics, pharmaceuticals, various chemical products, civil engineering, paints, inks, agricultural chemicals, construction, epidemic prevention chemicals, electronic materials, flame retardants, household miscellaneous goods, and cleaning agents. .. Specifically, thickeners, gelling agents, sizing agents, food additives, excipients, rubber/plastic compounding materials, adhesive additives, water retention agents, shape retention agents, mud conditioners, filter aids. It can be used as an agent and an anti-sludging agent, and contains them as constituents, rubber/plastic materials, paints, adhesives, cosmetics, lubricating compositions, polishing compositions, clothing wrinkle reducing agents, ironing It can be applied to slip agents. Further, since it has high film-forming properties, high stability of the formed film in water, and high water retention, it can be suitably used as a material for papermaking and printing, for example, as a coating agent or binder for coated paper.

The specific usage is illustrated below.
<Example 4>
(Lubricating composition)
An aqueous lubricating composition was prepared using the fiber obtained above (hereinafter, also referred to as a cellulosic additive). 20% by mass of cellulosic additives (absolutely dry), 10% by mass of hardened tallow oil, 15% by mass of paraffin, 2% by mass of boric acid, 3% by mass of polyethylene fatty acid ether, 1% by mass of sorbic acid, and 49% by mass of water were mixed. .. First, the oil content and the cellulosic additive were heated above the freezing point of the oil content, and the oil content was impregnated into the cellulosic additive by spraying and cooling the cellulosic additive under stirring. The obtained oil-impregnated cellulosic additive and various additives were dissolved or dispersed in water to obtain a lubricating composition. For lubrication performance, the coefficient of friction was measured and evaluated by the following known ring compression test methods:
A ring test piece made of SUS304 having an outer diameter of 3 mmφ, an inner diameter of 15 mmφ and a thickness of 7.5 mm was prepared. A ring test piece is set between a pair of flat plates having a smooth and parallel surface coated with a composition for aquatic lubrication (10 g/m ² ), and the ring test piece is pressed to obtain a known method from the rate of change in ring height and inner diameter. The friction coefficient was calculated by

The results are shown in Table 2. When the carboxymethyl cellulose fiber of the present invention is used as a composition for water-based lubrication, the effect of lowering the friction coefficient is obtained, and therefore the carboxymethyl cellulose fiber of the present invention is a cutting fluid, a lubricating fluid, and a hydrostatic fluid. It is suitable for hydraulic fluids such as gear transmissions and other applications.

(Coated paper)
A coating liquid containing a pigment as a main component using the fiber obtained above (hereinafter, also referred to as a cellulosic additive) (kaolin clay 70 parts by mass, ground calcium carbonate 30 parts by mass, cellulosic additive 5 parts by mass) , 0.3 parts by mass of dispersant, 0.1 part by mass of NaOH, 3 parts by mass of starch, 13 parts by mass of SB latex, and 62% by mass of total solid content) were produced, and a bench coater was used for the base paper made from the chemical pulp. After coating on one surface at a speed of 10 m/min, it was dried at 150°C. The coating amount was 12 g/m ² . The coated paper obtained was conditioned at 20° C. and 65% relative humidity for one day and then subjected to super calendering (roll temperature 60° C., linear pressure 150 kg/cm, two passes) and again 20° C. relative. A test piece was prepared by controlling the humidity all day under the condition of a humidity of 65%. The obtained test piece was solid-printed with a printing ink (Toyo Ink TV-24 ink, ink tack=24, 0.5 cc) using a RI-II type printability tester (manufactured by Meisei Seisakusho), and the printed surface The degree of picking was evaluated by visual inspection, with 5 being the best level in a 5-level evaluation. Further, an offset rotary printing ink (Toyo Ink TK Mark V New 617 Black M, 0.5 cc) was solidly printed on the test piece using a RI-II type printability tester, and immersed in heated silicon oil. , The temperature at which the blister is generated was read. Further, the gloss of the test piece was measured at a reflectance of 75°-75° using a Murakami type gloss meter.

The results are shown in Table 2. When the coating liquid containing the carboxymethyl cellulose fiber of the present invention is used, the dry pick is strong, the blister is less likely to occur, and the white glossy coated paper is high, so that the carboxymethyl cellulose fiber of the present invention is obtained. Is suitable as a material for papermaking and printing.

(Cosmetics: Liquid foundation)
After adding (8) to purified water (9) and heating to 70° C., (6) and (7) were added and sufficiently stirred. The mixture of (1) to (5), which had been thoroughly mixed and pulverized, was added thereto with stirring, and a homomixer treatment was carried out at 70°C. Next, after gradually adding (10) to (14) heated and dissolved at 70 to 80°C, (15) was added and a homogenizer treatment was performed at 70°C. This was cooled to room temperature with stirring, and finally deaerated and filled in a container to obtain a cosmetic (liquid foundation). According to the following criteria, the stability and uniformity of the cosmetics after 1 week were visually judged. The results are shown in Table 2.
3: A uniform state is maintained.
2: Almost uniform state is maintained, but precipitation is generated in a small part.
1: There is a precipitate.
(1) Talc: 3.0 wt%
(2) Titanium dioxide: 5.0 wt%
(3) Red iron oxide: 0.5 wt%
(4) Yellow iron oxide: 1.4 wt%
(5) Black iron oxide: 0.1 wt%
(6) Polyoxyethylene sorbitan monostearate: 0.9 wt%
(7) Triethanolamine: 1.0 wt%
(8) Propylene glycol: 10.0 wt%
(9) Purified water: Residual (10) Stearic acid: 2.2 wt%
(11) Isohexadecyl alcohol: 7.0 wt%
(12) Glycerin monostearate: 2.0 wt%
(13) Liquid lanolin: 2.0 wt%
(14) Liquid paraffin: 2.0 wt%
(15) Fiber obtained above: 1 wt% as cellulose pure content
(16) Preservatives, fragrances, etc. are added if necessary.

(Cosmetics: Eyeliner)
(3) and (4) were added to purified water (7), and the mixture was heated and dissolved at 70°C, then (1) was added and treated with a colloid mill. After adding (2), (5) and (6), the mixture was homogenized at 70°C. This was cooled to room temperature with stirring to obtain a cosmetic (eyeliner). The stability and uniformity of the cosmetics after 1 week were visually evaluated. The results are shown in Table 2.
3: A uniform state is maintained.
2: Almost uniform state is maintained, but precipitation is generated in a small part.
1: There is a precipitate.
(1) Black iron oxide: 14.0 wt%
(2) Vinyl acetate resin emulsion: 45.0 wt%
(3) Glycerin: 5.0 wt%
(4) Polyoxyethylene sorbitan monooleate: 1.0 wt%
(5) Acetyltributyl citrate: 1.0 wt%
(6) Fiber obtained above: 1 wt% as cellulose pure content
(7) Purified water: Residual (8) Add preservatives, fragrances, etc. as needed.

(Cosmetics: Eye shadow)
After mixing (1) to (3) with a blender, they were treated with a crusher. (8) and (9) were added to purified water (7), and the mixture was heated to 70 to 75°C. To this, the mixture of (4) to (6) heated and dissolved at 70 to 80° C. was added with stirring. The mixture of (1) to (3) was added to the mixture of (4) to (9) thus obtained at 70 to 75° C. with stirring, and then (10) was added to perform a homogenizer treatment. The mixture was cooled to room temperature with stirring to obtain a cosmetic (eye shadow). The stability and uniformity of the cosmetics after 1 week were visually evaluated. The results are shown in Table 2.
2: A uniform state is maintained.
1: There is a precipitate.
(1) Talc: 10.0 wt%
(2) Kaolin: 2.0 wt%
(3) Pigment: 5.0 wt%
(4) Isopropyl myristate: 8.0 wt% 20
(5) Liquid paraffin: 5.0 wt%
(6) Propylene glycol monolaurate: 3.0 wt%
(7) Purified water: Residual (8) Butylene glycol: 5.0 wt%
(9) Glycerin: 1.0 wt%
(10) Fiber obtained above: 1.2 wt% as cellulose pure content
(11) Add antioxidants, fragrances, preservatives, sequestering agents, etc., if necessary.

(Cosmetics: Milky cream)
Emulsion cosmetic composition (4% by mass of stearic acid, 5% by mass of squalane, 5% by mass of glycerin, 5% by mass of propylene glycol, 2% by mass of sucrose fatty acid ester, fiber obtained above: 3% as cellulose pure content %, 70% by mass of water). The obtained milky liquid cream was used by 15 female panelists for 1 month, and the dispersibility, lack of rough feeling, lack of stickiness, elongation, moisturizing property, and adhesive property were evaluated. The results are shown in Table 2.
3: 11 to 15 were judged to be good 2:6 to 10 were judged to be good 1:0 to 5 were judged to be good.

(Daily necessities: Abrasive composition (toothpaste))
(3), (4) and (5) were added to purified water (7) with a vacuum mixer. Next, (6) was added, and (1) and (2) were further added and mixed until uniform, followed by degassing under reduced pressure to obtain a toothpaste. The stability and uniformity of the toothpaste after 1 week were visually evaluated. The results are shown in Table 2.
3: A uniform state is maintained.
2: Almost uniform state is maintained, but precipitation is generated in a small part.
1: Water is taking off.
(1) Dicalcium phosphate dihydrate salt: 45.0 wt%
(2) Silicic anhydride: 2.0 wt%
(3) Glycerin: 15.0 wt% 50
(4) Sodium lauryl sulfate: 1.0 wt%
(5) Saccharin sodium: 0.1 wt%
(6) Fiber obtained above: 1 wt% as cellulose pure content
(7) Purified water: Residual (8) Add an appropriate amount of perfume, preservative, etc., if necessary.

(Daily goods: Wrinkle reducing agent for clothing)
Pretreatment of the apparel for evaluation was carried out for the purpose of homogenizing the oil agent adhering to the new apparel and the surface condition of the fiber. That is, using a commercially available weak alkaline detergent (Kao, Attack (registered trademark)) for a female blouse (100% cotton) and a cut sew (100% cotton knit), a two-tub washing machine (Toshiba, Galaxy (registered) Repeatedly washed 3 times with (trademark) VH-360S1) (detergent concentration 0.0667%, using 36 L of tap water (20° C.), washing 10 minutes-dehydration 3 minutes-rinsing until bubbles disappear (running water rinsing water amount 15 L/min)) After that, it was naturally dried to give a garment for evaluation.

A commercially available manual spray container is filled with 0.25% (w/v) of an aqueous dispersion of the fibers (hereinafter, also referred to as a cellulosic additive) obtained in Production Examples 1 to 10 and Comparative Examples A to C. Then, the evaluation garment prepared above was uniformly spray-coated. The treated clothing was hung on a hanger, hung in a constant temperature room (20° C., 40% RH) for 12 hours, and naturally dried. The dried clothes were washed with water using a washing machine (Matsushita Electric Industrial Co., Ltd., MiNiMini Washer National NA-35, operating time 5 minutes). At this time, one piece of clothing was put into the tank, and 4 L of tap water (20° C.) was used.

Then, it dehydrated for 5 minutes using the dehydration tank of a two-tub type washing machine (Hitachi, PS-H35L). The treated clothing was hung on a hanger, hung in a constant temperature room (20° C., 40% RH) for 12 hours, and naturally dried.

The dry clothes treated by the above method were evaluated by five panelists for the degree of wrinkling. It was evaluated from the viewpoint of whether or not wrinkles were less than those of clothes that were washed and dehydrated in the same manner without applying the cellulosic additive. The results are shown in Table 2.
2: Less wrinkles than the comparison.
1: There are many wrinkles equal to or more than the comparison.

(Daily goods: slipper for ironing)
A cotton broad cloth (manufactured by Shikiso Co., Ltd., cotton broad unsill, finishing width 90 cm) is repeatedly washed three times with a two-tub type washing machine (Toshiba, Galactic (registered trademark) VH-360S1) (detergent concentration 0.0667%, Using 36 L of tap water (20° C.), washing for 10 minutes-dehydration for 3 minutes-rinsing until the bubbles disappeared (running water rinsing water amount 15 L/min), and naturally dried to obtain an evaluation cloth.

A commercially available manual spray container is filled with 0.25% (w/v) of an aqueous dispersion of the fibers (hereinafter, also referred to as a cellulosic additive) obtained in Production Examples 1 to 10 and Comparative Examples A to C. Then, the evaluation cloth (25 cm×15 cm) prepared above was uniformly spray-coated. The treated cloth was hung in a thermostatic chamber (20° C., 40% RH) for 12 hours and dried naturally to give a test cloth.

The test cloth was ironed (iron temperature: cotton setting). The following criteria were used to evaluate the smoothness of iron movement and the absence of a feeling of being caught during ironing. The evaluation result of the comparative garment obtained by spraying water instead of applying the cellulosic additive and naturally drying was “2”.
3: The iron moves smoothly and there is no feeling of being caught.
2: The iron is difficult to move smoothly and there is a slight feeling of being caught.
1: The iron is difficult to move smoothly and has a strong feeling of being caught.

Claims (5)

660 nm light in an aqueous dispersion having an average fiber diameter of 3 to 19 nm, an aspect ratio of 100 or more, a carboxymethyl substitution degree per glucose unit of 0.01 to 0.30, and a solid content of 0.1% (w/v). A carboxymethylated cellulose fiber having a transmittance of 70% or more. In the carboxymethyl cellulose fibers, the crystalline type I of cellulose is 60% or more, and the crystalline type II of cellulose is 10 to 50% with respect to the crystalline type I of cellulose (provided that crystalline type I of cellulose is The carboxymethylated cellulose fiber according to claim 1, wherein the total crystal type II of cellulose exceeds 100%). The additive for foods, beverages, cosmetics, pharmaceuticals, paper manufacturing, civil engineering, paints, inks, agricultural chemicals, construction, epidemics, electronic materials, flame retardants, household sundries, or detergents, according to claim 1 or 2 . Carboxymethylated cellulose fiber. A lubricating composition containing the carboxymethylated cellulose fiber according to claim 1 or 2 . A method for reducing the coefficient of friction of a substrate, which comprises applying the carboxymethylated cellulose fiber according to claim 1 or 2 to the substrate.