JP6351509B2 - Carboxymethylated cellulose fiber - Google Patents

Description

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

  Compounds derived from natural polymer compounds such as cellulose or cellulose derivatives are used as additives 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 has a cellulose I-type crystal structure, and C6 of a glucose unit in a cellulose molecule. In which the hydroxyl group at the position is selectively oxidized and modified to an aldehyde group and a carboxyl group, and the aldehyde group is 0.08 to 0.3 mmol / g and the carboxyl group is 0.6 to 2.0 mmol / g A gel-like composition containing fibers in the range of 0.3 to 5.0% by weight in water is disclosed. This gel-like composition retains high viscosity even in the presence of salts and ionic surfactants and can maintain a gel state, so it can be used as a base material for toiletries such as cosmetics and fragrances. It is stated that you can.

JP 2010-37348 A

  However, the present inventors have found that the cellulose-derived gel-like composition described in Patent Document 1 tends to decrease in viscosity when exposed to high temperatures.

  Accordingly, an object of the present invention is to provide a cellulose-derived material that is not easily reduced in viscosity even when exposed to high temperatures.

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 having a carboxymethyl substitution degree per glucose unit of 0.01 to 0.30 is a high temperature. It has been found that even if it is exposed to water, it is difficult to reduce viscosity, and it is difficult to color, that is, it has high heat resistance. Further, the present inventors have found that this specific carboxymethylated cellulose fiber hardly drips when applied to a vertical surface or an inclined surface and has high fixability (adhesion) to an adherend. Furthermore, it has been found that this specific carboxymethylated cellulose fiber has excellent redispersibility after drying, can be stably mixed with various compounds, and 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], having an average fiber diameter of 3 to 20 nm.
[3] In the carboxymethylated cellulose fiber, the crystal type I of cellulose is 60% or more, and the crystal type II of cellulose is 10 to 50% with respect to the crystal type I of cellulose. [1] or [2 ] The carboxymethylated cellulose fiber as described in any one of.
[4] Additives for foods, beverages, cosmetics, medicine, papermaking, civil engineering, paints, inks, agricultural chemicals, architecture, epidemics, electronic materials, flame retardants, household goods, or cleaning agents, from [1] to [1] [3] The 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 coefficient of friction of a substrate, comprising applying the carboxymethylated cellulose fiber according to any one of [1] to [3] to the substrate.
[7] An agent containing the carboxymethylated cellulose fiber according to any one of [1] to [3], which improves iron slipping during ironing.
[8] Applying the carboxymethylated cellulose fiber according to any one of [1] to [3] to the cloth, and ironing the applied cloth when ironing the cloth. To improve slipperiness.
[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 for reducing the occurrence of wrinkles in a garment after washing, comprising washing the applied cloth and drying the washed cloth.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the material derived from the cellulose which has the outstanding fixability, it is hard to spill, it is hard to reduce viscosity even if it exposes to high temperature, and is hard to color (namely, it has high heat resistance). . Further, the carboxymethylated cellulose fiber of the present invention has advantages such that it can be redispersed well after drying and can be stably mixed with various compounds.

  The additive comprising the carboxymethylated cellulose fiber of the present invention is generally used in various fields in which the additive is used, such as food, beverages, cosmetics, pharmaceuticals, various chemicals, papermaking, civil engineering, paints, inks, agricultural chemicals, It can be used in construction, epidemic medicines, electronic materials, flame retardants, household goods, cleaning agents, etc. Specifically, thickeners, gelling agents, glues, 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, mud adjuster, filter aid and anti-sludge agent, etc., and rubber / plastic materials, paints, adhesives, coated paper coatings and coats containing them as constituents It can be applied to paper, binders, cosmetics, lubricating compositions, polishing compositions, wrinkle reducing agents for clothing, ironing slip agents, and the like.

  The present invention relates to a fibrous carboxymethylated cellulose having a specific average fiber diameter and an aspect ratio and having a degree of carboxymethyl substitution per glucose unit of 0.01 to 0.30. Carboxymethylcellulose cellulose (CMC) used for normal 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 the fiber shape by having a specific degree of carboxymethyl substitution. Such fibrous carboxymethylated cellulose (that is, carboxymethylated cellulose fiber) can be obtained by fibrillating the cellulose raw material to a specific degree of carboxymethyl substitution and then defibrating.

(Cellulose raw material)
The cellulose raw material for producing the carboxymethylated cellulose fiber of the present invention includes natural cellulose such as cellulose produced by microorganisms such as bleached or unbleached wood pulp, refined linter, acetic acid bacteria, etc .; cellulose in copper ammonia solution, morpholine Regenerated cellulose produced by spinning in a solvent such as a derivative and the like; fine cellulose obtained by depolymerizing these by hydrolysis, alkaline hydrolysis, enzymatic degradation, explosion treatment, vibration ball mill treatment, and the like; and these Fine cellulose obtained by mechanically treating is used.

(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 aqueous medium method is a method in which an etherifying agent such as monochloroacetic acid and a catalyst alkali metal hydroxide (sodium hydroxide, potassium hydroxide, etc.) are added to a cellulose raw material, and the reaction is carried out in a medium containing water as a main component. In the solvent method, an etherifying agent such as monochloroacetic acid and a catalyst alkali metal hydroxide (sodium hydroxide, potassium hydroxide, etc.) are added to the cellulose raw material, and methanol, ethanol, N-propyl alcohol, isopropyl alcohol, N-butanol are added. , Isobutanol, tertiary butanol, and other lower alcohols are reacted in a medium containing a main component. The aqueous medium method is preferable because a drying step is not required 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 easily proceed uniformly. When larger than this, uniform mixing of the chemical and the cellulose raw material tends to be difficult. Moreover, when smaller than this, there exists a tendency for the viscosity of the carboxymethylated cellulose fiber obtained to become low, or for washing | cleaning to become difficult.

  In the reaction, it is preferable to use a stirrer capable of uniformly mixing the chemical solution and the cellulose raw material. For example, a batch type stirring apparatus in which two shafts are stirred to mix a raw material and a chemical solution is preferable in terms of both uniform mixing and productivity. Moreover, it is preferable to add the chemical solution to the cellulose raw material using an apparatus such as a spray because it is easily mixed uniformly.

  In the present invention, it is important that the degree of carboxymethyl substitution per glucose unit of cellulose is 0.01 to 0.30. By introducing a carboxymethyl substituent into cellulose, the celluloses are electrically repelled. For this reason, the cellulose which introduce | transduced the carboxymethyl substituent can be fibrillated easily to a nano-order fiber diameter. When the carboxymethyl substituent per glucose unit is smaller than 0.01, the fiber cannot be sufficiently defibrated. On the other hand, when the carboxymethyl substituent per glucose unit is larger than 0.30, the fiber form cannot be maintained because it swells or dissolves and may not be obtained as a nanofiber. In both the aqueous medium method and the solvent method, the degree of carboxymethyl substitution can be adjusted by controlling the addition amount of the etherifying agent to be reacted, the alkali amount as a catalyst, and the composition ratio of a solvent such as water or lower alcohol.

  The crystallinity of cellulose can be controlled by the concentration of alkali metal and the temperature during processing, as well as the degree of carboxymethyl modification. Since a high concentration of alkali is used in carboxymethyl modification, cellulose type I crystals are easily converted to type II, but it is desirable to adjust the degree of modification by adjusting the amount of alkali used. The crystallinity of can be maintained. The present inventors have found that when the aqueous medium method is used, it 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 above carboxymethylated cellulose raw material is then fibrillated so that the average fiber diameter is 3 to 500 nm and the aspect ratio is 100 or more to obtain the carboxymethylated cellulose fiber of the present invention. The average fiber diameter is preferably 3 to 150 nm, more preferably 3 to 20 nm, further preferably 5 to 19 nm, and further preferably 5 to 15 nm. By setting the average fiber diameter and aspect ratio within the above ranges, various physical properties such as difficulty of dripping, fixability, suspension stability, emulsion stability, and thickening effect are dramatically improved. Further, carboxymethylated cellulose fibers having an average fiber diameter and an aspect ratio in the above range 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 for 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. In view of ease of handling, it is preferable to defibrate using a carboxymethylated cellulose raw material dispersed in water.

  An apparatus for defibrating is not particularly limited. For example, an apparatus 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 ultrahigh-pressure homogenizer that can apply a pressure of 50 MPa or more to the aqueous dispersion and can apply a strong shearing force. The pressure is more preferably 100 MPa or more, and further preferably 140 MPa or more. Prior to defibration with a high-pressure homogenizer, a cellulose raw material that has been carboxymethylated by a known mixing, stirring, emulsifying, and dispersing device such as a high-speed shear mixer may be pretreated as 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 and redispersed in water as necessary. The drying method is not limited in any way, for example, freeze drying method, spray drying method, shelf drying method, drum drying method, belt drying method, method of thinly extending and drying on a glass plate, fluidized bed drying method, microwave drying And known methods such as a heating fan type vacuum drying method can be used. You may grind | pulverize with a cutter mill, a hammer mill, a pin mill, a jet mill etc. as needed after drying. Further, the method for redispersion in water is not particularly limited, and a known dispersion apparatus 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 the fibers. As a result, it exhibits high viscosity under static conditions with a low shear rate, and exhibits excellent fixability and resistance to dripping.

  On the other hand, ordinary water-soluble carboxymethylcellulose and its salts that do not have crystallinity cannot form a network structure between the additives, so that the fixability and dripping of the liquid can be prevented. It seems to be inferior to bitterness.

  As for the crystal form of cellulose in the carboxymethylated cellulose fiber of the present invention, crystal I type is preferably 60% or more, and crystal II type is preferably 10 to 50% with respect to crystal I type. 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 to the above range, various physical properties such as difficulty of 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 stability effect in hydrophilic media such as water. Further, for example, by dispersing in water or a hydrophilic organic solvent, high thixotropy is exhibited, and depending on conditions, the gel is formed. Therefore, it is also effective as a gelling agent. Further, by forming a film by a papermaking method or a casting method, a material having high strength, excellent heat resistance, and low thermal expansion is obtained. The film thus obtained is also useful as a coating layer for the purpose of imparting hydrophilicity. Furthermore, when the carboxymethylated cellulose fiber is compounded with other materials such as a resin material, it is excellent in dispersibility in other materials, and therefore, a composite having excellent transparency is provided in a suitable case. Can do. Also, it functions as a reinforcing filler, and when the fibers form a high network in the composite, it shows higher strength than the resin itself used, and it can reduce the coefficient of thermal expansion. it can. In addition, since the carboxymethylated cellulose fiber of the present invention has the amphipathic properties of cellulose, it functions as, for example, an emulsifier or a dispersion stabilizer. Furthermore, since the carboxylmethyl group forms a counter ion with the metal ion, it is also effective as a metal ion scavenger or the like.

  Hereinafter, the embodiments of the present invention will be described by way of examples, but the present invention is not limited thereto.

(Measurement method of carboxymethyl substitution degree per glucose unit)
About 2.0 g of carboxymethylated cellulose fiber (absolutely dry) was precisely weighed and placed in a 300 mL Erlenmeyer flask with a stopper. A solution obtained by adding 100 mL of special concentrated nitric acid to 1000 mL of nitric acid methanol was added and shaken for 3 hours to convert the carboxymethyl cellulose salt (CM cellulose) into hydrogenated CM cellulose. 1.5-2.0 g of hydrogenated CM-modified cellulose (absolutely dry) 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 of hydrogenated CM-modified cellulose (g))
DS = 0.162 × A / (1−0.058 × A)
A: 1N NaOH amount (mL) required for neutralizing 1 g of hydrogenated CM-modified cellulose
F ′: Factor of 0.1N H ₂ SO ₄ F: Factor of 0.1N NaOH

(Measuring method of average fiber diameter and aspect ratio)
The average fiber diameter and average fiber length of the carboxymethylated cellulose fiber are determined using an atomic force microscope (AFM) when the diameter is 20 nm or less, and a field emission scanning electron microscope (FE-SEM) when the diameter is 20 nm or more. 200 randomly selected fibers were analyzed. 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 using liquid nitrogen and compressed to create tablet shaped pellets. Then, this sample was measured with the X-ray-diffraction measuring apparatus (LabX XRD-6000, Shimadzu Corporation make). The obtained graph was peak-separated by graph analysis software PeakFit (manufactured by Hulinks), and crystal I type, II type, and non-crystal were discriminated based on the following diffraction angles. The ratio of crystal type I and type 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 °
The crystallinity of cellulose type I was calculated from the value of the diffraction intensity (Ia) of 18 ° and the diffraction intensity (Ic) of 22.5 ° by the following formula called the Segal method:
Crystallinity of type I = (Ic−Ia) / Ic × 100

(Method for measuring B-type viscosity)
An aqueous dispersion of carboxymethylated cellulose fibers (solid content 1% (w / v)) was allowed to stand at 25 ° C. for 24 hours, and then rotated at 30 rpm (3 minutes) using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.). ) To measure the viscosity.

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

<Production Example 1>
To a stirrer capable of mixing pulp, 200 g of pulp (NBKP (conifer bleached kraft pulp), manufactured by Nippon Paper Industries Co., Ltd.) in dry mass and 50 g of sodium hydroxide in dry mass are added, and the pulp solid content is 20% (w / v Water was added so that Then, after stirring for 30 minutes at 30 ° C., 50 g (in terms of active ingredient) of sodium monochloroacetate was added. After stirring for 30 minutes, the temperature was raised to 70 ° C. and stirred for 1 hour. Thereafter, 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. Thereafter, the carboxymethylated pulp was made 1% solids with water, and fibrillated 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, a crystallinity of type I of 75%, a ratio of type II to type I of 25%, a type B viscosity of 10,000 mPa · s, and a transparency of 90%. Met.

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

<Production Example 3>
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 II-type I-type ratio 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 obtained, and a carboxymethylated pulp having a degree of carboxymethyl substitution of 0.3 was obtained. The obtained fiber has an average fiber diameter of 5 nm, an aspect ratio of 500, a crystallinity of type I of 65%, a ratio of type II to type I of 40%, a type B 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 obtained and a carboxymethylated pulp having a degree of carboxymethyl substitution of 0.3 was obtained. The obtained fiber has an average fiber diameter of 5 nm, an aspect ratio of 400, a crystallinity of type I of 58%, a ratio of type II to type I of 50%, a type B viscosity of 7000 mPa · s, and a transparency of 95%. Met.

<Production Example 6>
The same procedure as in Example 1 was conducted except that LBKP (hardwood bleached kraft pulp) (manufactured by Nippon Paper Industries Co., Ltd.) was used. The obtained fiber has an average fiber diameter of 10 nm, an aspect ratio of 500, a crystallinity of type I of 75%, a ratio of type II to type I of 25%, a type B viscosity of 10,000 mPa · s, and a transparency of 90%. Met.

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

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

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

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

<Comparative Example A>
Pulp (NBKP, manufactured by Nippon Paper Industries Co., Ltd.) was suspended in water to obtain a slurry having a solid content of 1% (w / v). The pulp slurry was treated three times with an ultrahigh pressure homogenizer at 20 ° C. and a pressure of 150 MPa. The resulting liquid was a cloudy slurry that did not exhibit 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 obtained and a carboxymethylated cellulose having a degree of carboxymethyl substitution of 0.4 was obtained. The obtained carboxymethylated cellulose had an average fiber diameter 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, Nippon Paper Industries Co., Ltd.) 5 g (absolutely dried) was added to 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 the dissolved aqueous solution and stirred until the pulp was uniformly dispersed. After adding 16 ml of a 2M aqueous sodium hypochlorite solution to the reaction system, the pH was adjusted to 10.3 with a 0.5N aqueous hydrochloric acid solution to initiate an oxidation reaction (oxidation treatment). During the reaction, the pH in the system was lowered, but a 0.5N aqueous sodium hydroxide solution was successively added to adjust the pH to 10. After making it react for 2 hours, it filtered with the glass filter and obtained the oxidized pulp by fully washing with water. It was 1.60 mmol / g when the carboxyl group amount of the obtained oxidized pulp was measured as follows.

(Measurement of carboxyl group content)
Prepare 60 ml of 0.5% by weight slurry of oxidized pulp, add 0.1 M hydrochloric acid aqueous solution to pH 2.5, then add 0.05 N aqueous sodium hydroxide solution dropwise until the pH is 11 Was calculated from the amount (a) of sodium hydroxide consumed in the neutralization step of the weak acid where the change in electrical conductivity was gradual, using the following equation.
Amount of carboxyl group [mmol / g pulp] = a [ml] × 0.05 / oxidized pulp mass [g].

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

<Example 1>
About the said manufacture examples 1-10 and comparative examples AC, the fluctuation | variation of the viscosity after heat processing, the rheometer viscosity, the film property, the difficulty of dripping, dispersibility, water retention, and coloring after heat processing were evaluated. . The results are shown in Table 1.

(Evaluation of viscosity change after heat treatment)
The obtained aqueous dispersion of fiber (solid content 1% (w / v)) was held at 80 ° C. for 5 hours. Then, it stood to cool to 25 degreeC and measured the B-type viscosity by the said method.

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

(Evaluation of film properties)
The obtained aqueous dispersion of fiber (solid content 1% (w / v)) was applied onto a glass plate using a # 16 coating rod, and baked in a blast dryer at 100 ° C. for 30 minutes to form a membrane. The thickness was adjusted to 20 to 25 μm. The glass test plate was immersed in warm water at 40 ° C., and the degree of whitening, peeling, and blistering of the coating was visually determined.
3: Stable even when immersed for 5 days or more 2: Abnormality occurs within 5 days of immersion 1: Abnormality occurs within 1 day of immersion

(Evaluation of difficulty in dripping)
The obtained aqueous fiber dispersion was made to have a solid content of 0.1% (w / v), placed in a spray container, and sprayed onto a vertical surface. The degree of dripping of the liquid adhering to the vertical surface was visually judged.
3: Almost no dripping.
2: Some dripping is observed 1: There is clearly dripping.

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

(Evaluation of water retention)
Three drops of the obtained aqueous dispersion of fiber (1% (w / v)) on fine paper (made by Nippon Paper Industries, trade name: NPi Fine (registered trademark), basis weight 64.0 g / m ² ). The degree of penetration into the paper was determined visually.
3: Good Does not soak into fine paper 2: Slightly soaks into fine paper 1: Poor soaks into fine paper

(Evaluation of coloring after heat treatment)
The resulting fiber dispersion in water (1% (w / v)) was dried at 105 ° C. overnight. The state of coloring of the fiber after drying was visually determined.
2: Almost no color 1: Coloration is observed

<Example 2> Properties 1 of a 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 types of additives (inorganic salts, surfactants, oils, moisturizers, preservatives, inorganic fine particles, organic fine particles, organic solvents, fragrances / deodorants) in each container. In addition to preparing (w / v), 21 types 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 liquid dripping attached to the vertical surface for each sample 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] dimethylpolysiloxane, glyceryl triisooctanoate, squalane [humectant] glycerin [preservative] methyl paraben [inorganic fine particles] Titanium oxide, Bengala (organic fine particle) urethane emulsion (Daiichi Kogyo Seiyaku Co., Ltd., Superflex (registered trademark) 150)
[Organic solvents] Ethanol, isopropanol [Flavorants and deodorants] D limonene, orange oil

  As a result, when the fibers of Production Examples 1 to 10 and Comparative Example C were used, no dripping was observed even when mixed with any additive. On the other hand, in the fibers of Comparative Example A, dripping was observed in all samples (21 types). Moreover, in the water-soluble carboxymethylcellulose of Comparative Example B, it can be said that dripping does not easily occur as compared with Comparative Example A, but slightly dripped compared with those of Production Examples 1 to 10.

<Example 3> Properties 2 of a 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 types of additives (inorganic salts, surfactants, oils, moisturizers, preservatives, inorganic fine particles, organic fine particles, organic solvents, fragrances / deodorants) in each container. (W / v) was added, and carbon black was further added to 2% (w / v) to prepare 21 samples 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] dimethylpolysiloxane, glyceryl triisooctanoate, squalane [humectant] glycerin [preservative] methyl paraben [inorganic fine particles] Titanium oxide, Bengala (organic fine particle) urethane emulsion (Daiichi Kogyo Seiyaku Co., Ltd., Superflex (registered trademark) 150)
[Organic solvents] Ethanol, isopropanol [Flavorants and deodorants] D limonene, orange oil

  As a result, when the fibers of Production Examples 1 to 9 and Comparative Example C were used, carbon black was well dispersed even when mixed with any additive. On the other hand, in the fiber of Comparative Example A, the dispersibility of the carbon black was poor, and precipitation of the carbon black occurred in all the samples. Moreover, although the water-soluble carboxymethylcellulose of Comparative Example B can be said to have better dispersibility than Comparative Example A, it was inferior to those of Production Examples 1-10.

  As described above, the carboxymethylated cellulose fiber of the present invention is excellent in heat resistance, coating properties, difficulty of dripping, dispersibility, and water retention, and even when mixed with various additives, Does not decrease, keeps liquid from dripping and maintains dispersion stability. Therefore, it is useful as an additive in various fields such as foods, beverages, cosmetics, medicines, various chemicals, civil engineering, paints, inks, agricultural chemicals, architecture, epidemics, electronic materials, flame retardants, household goods, and cleaning agents. . Specifically, thickeners, gelling agents, glues, food additives, excipients, compounding materials for rubber and plastics, additives for adhesives, water retention agents, shape retention agents, mud adjusters, filter aids Can be used as agents and anti-sludge agents, rubber and plastic materials containing them as constituents, paints, adhesives, cosmetics, lubricating compositions, polishing compositions, wrinkle reducing agents for clothing, ironing It can be applied to slip agents. In addition, since it has high coating properties, high stability of the film to be formed in water, and high water retention, it can be suitably used as a material for papermaking and printing, for example, a coated paper coating material and a binder.

  Specific usage methods are exemplified below.

<Example 4>
(Lubricating composition)
An aqueous lubricating composition was prepared using the fiber obtained above (hereinafter also referred to as a cellulose-based additive). Cellulose-based additive (absolutely dry) 20% by mass, hydrogenated beef tallow oil 10% by mass, paraffin 15% by mass, boric acid 2% by mass, polyethylene fatty acid ether 3% by mass, sorbic acid 1% by mass, water content 49% by mass were mixed. . First, the oil and the cellulose additive were heated above the freezing point of the oil, and the cellulose additive was impregnated into the cellulose additive by spraying and cooling the oil to the stirring cellulose additive. The resulting cellulose-based additive impregnated with oil and various additives were dissolved or dispersed in water to obtain a lubricating composition. The lubrication performance was evaluated by measuring the coefficient of friction by the known ring compression test method shown below:
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 with smooth and parallel surfaces coated with a composition for aquatic lubrication (10 g / m ² ), pressed, and known from the change rate of the height and inner diameter of the ring. The coefficient of friction was calculated by

  The results are shown in Table 2. When the carboxymethylated cellulose fiber of the present invention is used as a composition for aqueous lubrication, the effect of lowering the friction coefficient is obtained. Therefore, the carboxymethylated cellulose fiber of the present invention is free from cutting fluid, lubricating fluid, and hydrostatic pressure. It is suitable for hydraulic fluid such as a step transmission and other uses.

(Coated paper)
Using the fiber obtained above (hereinafter also referred to as a cellulose-based additive), a coating liquid mainly composed of a pigment (Kaolin clay 70 parts by mass, heavy calcium carbonate 30 parts by mass, cellulose-based additive 5 parts by mass , 0.3 parts by weight of dispersant, 0.1 parts by weight of NaOH, 3 parts by weight of starch, 13 parts by weight of SB latex, 62% by weight of total solids), and a bench coater is used on the base paper made from chemical pulp After coating on one side at a speed of 10 m / min, it was dried at 150 ° C. The coating amount was 12 g / m ² . The resulting coated paper was conditioned overnight at 20 ° C and 65% relative humidity, then supercalendered (roll temperature 60 ° C, linear pressure 150 kg / cm, two passes), again at 20 ° C relative to The test piece was conditioned at a humidity of 65% for a whole day and night. The obtained test piece was solid-printed with printing ink (Toyo Ink TV-24 ink, ink tack = 24, 0.5 cc) using an RI-II type print aptitude tester (Made Seisakusho), and the printing surface The degree of picking was visually judged with 5 being the best level in a five-step evaluation. In addition, using a RI-II type printing aptitude tester, a test piece was printed with offset rotary printing ink (Toyo Ink TK Mark V New 617 Black M, 0.5 cc) and immersed in heated silicone oil. The temperature at which blisters occurred was read. Further, the gloss of the test piece was measured using a Murakami gloss meter with a reflectance of 75 ° to 75 °.

  The results are shown in Table 2. When the coating liquid containing the carboxymethylated cellulose fiber of the present invention is used, a coated paper having a strong dry pick, hardly causing blistering, and having a high white glossiness is obtained. Therefore, the carboxymethylated cellulose fiber of the present invention is obtained. Is suitable as a material for papermaking and printing.

(Cosmetics: Liquid foundation)
(8) was added to purified water (9) and heated to 70 ° C., and then (6) and (7) were added and sufficiently stirred. To this, the mixture of (1) to (5) sufficiently mixed and ground was added with stirring, and homomixed at 70 ° C. Next, (10) to (14) dissolved by heating at 70 to 80 ° C. was gradually added, and then (15) was added and homogenized at 70 ° C. This was cooled to room temperature with stirring, and finally degassed and filled into a container to obtain a cosmetic (liquid foundation). According to the following criteria, the stability and uniformity of the cosmetic product after one week were visually determined. The results are shown in Table 2.
3: A uniform state is maintained.
2: Almost uniform state is maintained, but a part of the precipitate is formed.
1: Precipitate is present.
(1) Talc: 3.0wt%
(2) Titanium dioxide: 5.0 wt%
(3) Bengala: 0.5wt%
(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) Glycerol monostearate: 2.0 wt%
(13) Liquid lanolin: 2.0 wt%
(14) Liquid paraffin: 2.0 wt%
(15) Fiber obtained above: 1 wt% as pure cellulose
(16) Add preservatives, fragrances, etc. as necessary.

(Cosmetics: Eyeliner)
(3) and (4) were added to purified water (7), dissolved by heating at 70 ° C., and then (1) was added and treated with a colloid mill. After adding (2), (5) and (6), homogenizer treatment was performed at 70 ° C. This was cooled to room temperature while stirring to obtain a cosmetic (eyeliner). The stability and uniformity of the cosmetic after one week were visually determined. The results are shown in Table 2.
3: A uniform state is maintained.
2: Almost uniform state is maintained, but a part of the precipitate is formed.
1: Precipitate is present.
(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 pure cellulose
(7) Purified water: Residue (8) If necessary, add preservatives, fragrances and the like.

(Cosmetics: Eye shadow)
(1) to (3) were mixed with a blender and then processed with a pulverizer. (8) and (9) were added to purified water (7) and heated to 70 to 75 ° C. To this, the mixture of (4) to (6) dissolved by heating 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 and homogenized. The mixture was cooled to room temperature with stirring to obtain a cosmetic (eye shadow). The stability and uniformity of the cosmetic product after 1 week were visually determined. The results are shown in Table 2.
2: A uniform state is maintained.
1: Precipitate is present.
(1) Talc: 10.0wt%
(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: Residue (8) Butylene glycol: 5.0 wt%
(9) Glycerin: 1.0 wt%
(10) Fiber obtained above: 1.2 wt% as pure cellulose
(11) Add antioxidants, fragrances, preservatives, sequestering agents, etc. as necessary.

(Cosmetics: milk cream)
Emulsion cosmetic composition (stearic acid 4% by mass, squalane 5% by mass, glycerin 5% by mass, propylene glycol 5% by mass, sucrose fatty acid ester 2% by mass, fiber obtained above: 3% as pure cellulose %, 70% by mass of water). The obtained emulsion cream was used by 15 female panelists for one month, and evaluated for dispersibility, no roughness, no stickiness, elongation, moisture retention, and adhesion. The results are shown in Table 2.
3: 11-15 people judged good 2: 6-10 people judged good 1: 0-5 people judged good.

(Daily Goods: Abrasive Composition (Dental Dentifrice))
(3), (4), (5) was added to purified water (7) with a vacuum mixer. Next, (6) was added, and (1) and (2) were further added and mixed until uniform, and then degassed under reduced pressure to obtain a toothpaste. The stability and uniformity of the toothpaste after one week was visually determined. The results are shown in Table 2.
3: A uniform state is maintained.
2: Almost uniform state is maintained, but a part of the precipitate is formed.
1: Water has been removed.
(1) Dicalcium phosphate dihydrate: 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 pure cellulose
(7) Purified water: Residue (8) Add an appropriate amount of perfume, preservative, etc. as necessary.

(Daily necessities: Wrinkle reducing agent for clothing)
The clothing for evaluation was pretreated for the purpose of uniformizing the oil agent and the fiber surface state adhering to the new clothing. In other words, a two-bath washing machine (Toshiba, Galaxy (registered trademark)) using a commercially available weak alkaline detergent (Kao, Attack (registered trademark)) for women's blouse (100% cotton) and cut-and-sew (cotton knit 100%) (Trademark) VH-360S1) Repeated washing three times (detergent concentration: 0.0667%, using 36 L of tap water (20 ° C.), washing for 10 minutes-dehydration for 3 minutes-rinsing until no bubbles are present (flowing water rinsing water amount: 15 L / min)) And air-dried to obtain evaluation clothes.

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

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

Five panelists evaluated the degree of wrinkle generation on the dried clothes treated by the above method. It was evaluated from the viewpoint of whether wrinkles were less than clothes that were similarly washed and dehydrated without applying a cellulose-based additive. The results are shown in Table 2.
2: Less wrinkles than comparison.
1: There are many wrinkles equal to or higher than the comparison.

(Daily necessities: ironing slip agent)
A cotton broad cloth (manufactured by Color Dyeing Co., Ltd., cotton broad not sill, finishing width 90 cm) was repeatedly washed three times (detergent concentration 0.0667%, with a 2-tank washing machine (manufactured by Toshiba, Galaxy (registered trademark) VH-360S1)). Using 36 L of tap water (20 ° C.), washing for 10 minutes—dehydration for 3 minutes—rinsing until no bubbles were found (flowing water rinsing water amount: 15 L / min)), followed by natural drying to obtain a cloth for evaluation.

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

The test cloth was ironed (iron temperature: cotton setting). The following criteria were used to evaluate the smoothness of the iron movement and the absence of catching when ironing. In addition, the evaluation result of the comparative clothing obtained by not drying a cellulose additive and spraying water instead and drying naturally was "2".
3: The iron moves smoothly and there is no catching feeling.
2: The iron is difficult to move smoothly and feels a little stuck.
1: The iron is difficult to move smoothly and has a strong feeling of being caught.

Claims (4)

  Contains 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. Agent to improve. Applying 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 to the cloth, and ironing the applied cloth A method of improving iron slipping when ironing cloth, including scoring.   A wrinkle reducing agent for clothing containing 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. Applying a carboxymethylated cellulose fiber 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 to a cloth;
A method for reducing the occurrence of wrinkles in a garment after washing, comprising washing the applied cloth and drying the washed cloth.