WO2022071463A1

WO2022071463A1 - Viscous composition

Info

Publication number: WO2022071463A1
Application number: PCT/JP2021/036041
Authority: WO
Inventors: 香澄茂川; 博史山口
Original assignee: 住友精化株式会社
Priority date: 2020-10-02
Filing date: 2021-09-30
Publication date: 2022-04-07
Also published as: JPWO2022071463A1

Abstract

Provided is a viscous composition that, while containing hydroxyethyl cellulose and a salt, has excellent viscosity and stability. More specifically, provided is a viscous composition that contains cellulose nanocrystals, hydroxyethyl cellulose, a water-soluble salt, and water, and has a viscosity of at least 10,000 mPa∙s at 25°C.

Description

Viscous composition

The present disclosure relates to a viscous composition and the like, and more particularly to a viscous composition containing cellulose nanocrystals. The contents of all documents described in this specification are incorporated herein by reference.

Polymer thickeners are widely used for preparing viscous compositions in various fields, such as cosmetics and food fields.

However, the thickening effect of the polymer thickener generally tends to be reduced by the salt. In addition, a composition containing a polymer thickener and a salt generally tends to have poor stability. For example, hydroxyethyl cellulose (HEC) is also a component widely used as a polymer thickener, but since the thickening effect may be reduced by a salt, it contains hydroxyethyl cellulose and a salt and has excellent viscosity. And it was not easy to prepare a viscous composition with stability.

Special Table 2012-531478 Gazette Japanese Patent Publication No. 2014-510846

Therefore, the present inventors have studied to find a novel means for providing a viscous composition containing hydroxyethyl cellulose and a salt but having excellent viscosity and stability.

The present inventors have prepared a viscous composition obtained by mixing nanocellulose, particularly cellulose nanocrystal, with hydroxyethyl cellulose and dissolving it in water, which is a stable composition in which the viscosity does not easily decrease even when a salt is added. I found something and repeated further studies.

The present disclosure includes, for example, the subjects described in the following sections.
Item 1.
Contains cellulose nanocrystals, hydroxyethyl cellulose, water-soluble salts, as well as water,
The viscosity at 25 ° C. is 10,000 mPa · s or more (preferably 10,000 to 20,000 mPa · s).
Viscous composition.
Item 2.
Item 2. The viscous composition according to Item 1, wherein the hydroxyethyl cellulose is hydroxyethyl cellulose crosslinked with a cross-linking agent.
Item 3.
Hydroxyethyl cellulose crosslinked with the crosslinking agent
A crosslinked hydroxyethyl cellulose containing 0.35% by mass or more (preferably 0.35 to 2% by mass) of a crosslinking agent.
Item 2. The viscous composition according to Item 2.
Item 4.
Item 2. The viscous composition according to Item 2 or 3, wherein the cross-linking agent is a dialdehyde compound.
Item 5.
Item 2. The viscous composition according to any one of Items 1 to 4, wherein the content of the water-soluble salt is 0.1% by mass or more (preferably 1 to 10% by mass).
Item 6.
Item 2. The viscous composition according to any one of Items 1 to 5, which has a transmittance of 10% or more.
Item 7.
The magnitude relationship between the storage elastic modulus G'and the loss elastic modulus G'' obtained by the frequency dispersion measurement is the storage elastic modulus G'> the loss elastic modulus G'> in the entire frequency range of 0.1 rad / s to 100 rad / s. Item 3. The viscous composition according to any one of Items 1 to 6.
Item 8.
A method for producing a viscous composition, which comprises mixing (1) a mixture of cellulose nanocrystals and hydroxyethyl cellulose with water, and (2) adding a water-soluble salt to the mixture.
Item 9.
(1) A method for producing a viscous composition for adding a water-soluble salt, which comprises mixing a mixture of cellulose nanocrystals and hydroxyethyl cellulose with water.
Item 10.
Item 8. The method according to Item 8 or 9, further comprising mixing (0) cellulose nanocrystals and hydroxyethyl cellulose before (1).

A viscous composition containing hydroxyethyl cellulose and a salt but having excellent viscosity and stability is provided.

Hereinafter, each embodiment included in the present disclosure will be described in more detail. The present disclosure preferably includes, but is not limited to, a viscous composition, a method for producing the same, and the like, and the present disclosure includes all disclosed in the present specification and recognized by those skilled in the art.

The viscous composition included in the present disclosure contains cellulose nanocrystals, hydroxyethyl cellulose, and water. The viscous composition included in the present disclosure may be referred to as "the composition of the present disclosure". The compositions of the present disclosure also include viscous compositions containing salts in addition to cellulose nanocrystals, hydroxyethyl cellulose, and water. Among the compositions of the present disclosure, those containing salt may be referred to as "salt-containing compositions of the present disclosure", and those containing no salt may be referred to as "salt-free compositions of the present disclosure".

Cellulose nanocrystal is a kind of nanocellulose. In particular, examples of nanocellulose made from wood or the like include cellulose nanofibers (CNF) and cellulose nanocrystals (CNC). Among nanocellulose, those having a relatively long length are called cellulose nanofibers (CNF), and those having a relatively short length are called cellulose nanocrystals (CNC). Although not limited, nanocellulose having a length of about 5 to 10 μm or more is often referred to as cellulose nanofiber (CNF), and those having a length shorter than CNF are often referred to as cellulose nanocrystal (CNC). It seems.

As the CNC used in the composition of the present disclosure, for example, the nanocrystalline cellulose described in Patent Document 1 (Japanese Patent Laid-Open No. 2012-531478) can be preferably used.

Cellulose is a natural polymer material that constitutes woody biomass and agricultural biomass together with hemicellulose and lignin. It is a homopolymer of repeating units of glucose linked by β-1,4-glycosidic bonds. Cellulose is formed linearly by β-1,4-glycosidic bonds, and they interact strongly with each other through hydrogen bonds. Due to its regular structure and strong hydrogen bonds, the cellulose polymer is highly crystalline and aggregates to form partial structures and microfibrils. Then, the microfibrils aggregate to form cellulosic fibers.

Cellulose purified from woody biomass or agricultural biomass can be disrupted or produced on a large scale by bacterial processes. When a cellulosic material is composed of nano-sized fibers and the properties of the material are determined by the structure of the nanofibers, these polymers are referred to as nanocellulose. In general, nanocellulose is a rod-shaped fibril with a length / diameter ratio of approximately 20-200.

Generally, the preparation of nanocellulose can be explained by two methods. In the first method, nanocellulose can be prepared, for example, from chemical pulp of wood fiber or agricultural fiber by removing the amorphous region mainly by acid hydrolysis to produce nano-sized fibril. Cellulose nanocrystals can be formed and stabilized in an aqueous suspension by, for example, sonicating the fibrils or passing them through a high shear microfluidizer.

The second method is mainly physical processing. Bundles of microfibrils, usually tens of nanometers (nm) to several micrometer (μm) in diameter, called cellulose microfibrils or microfibrillated cellulose, are produced by using high pressure homogenization and grinding. .. Steps with high intensity sonication have also been used to isolate fibril from natural cellulose fibers. High-intensity ultrasound can generate very strong mechanical vibration forces, which allows the separation of cellulose fibrils from biomass. This method produces microfibrillated cellulose having a diameter of less than about 60 nm, more preferably about 4 nm to about 15 nm, and a length of less than 1000 nm. Microfibrillated cellulose can also be subjected to, for example, further chemical, enzymatic and / or mechanical treatments. The microfibrillated cellulose can also be used as a cellulose nanocrystal.

In other words, the cellulose nanocrystals used in the compositions of the present disclosure are, for example, by removing amorphous regions from pulp by acid hydrolysis, or by physical treatment such as high pressure treatment, pulverization treatment, and ultrasonic treatment. It can be appropriately prepared by treatment (and even by using these in combination).

Further, the cellulose portion of the cellulose nanocrystal used in the composition of the present disclosure may be a cellulose sulfate (cellulose sulfate). As the salt, a sodium salt is preferable. That is, the cellulose portion of the cellulose nanocrystal used in the composition of the present disclosure may be cellulose sulfate sodium sulfate. As described above, the composition of the present disclosure can have excellent viscosity and stability even if a salt is contained.

Therefore, in the present disclosure, the wording "cellulose nanocrystal" or "CNC" indicates a crystal of nano-sized cellulose, and the cellulose may be an unmodified form or a modified form. As described above, as the cellulose modified product, for example, cellulose sulfate (particularly sodium cellulose sulfate) is preferably mentioned.

Although not particularly limited, examples of the CNC include nanocellulose having a thickness of about 1 to 100 nm and a length of about 50 to 500 nm. The upper or lower limit of the thickness range (1 to 100 nm) is, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, and so on. 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, It may be 93, 94, 95, 96, 97, 98, or 99 nm. For example, the thickness range may be 2 to 99 nm. Further, the upper limit or the lower limit of the length range (50 to 500 nm) is, for example, 60, 70, 80, 90, 100,
110, 120, 130, 140, 150, 160, 170, 180, 190, 200,
210, 220, 230, 240, 250, 260, 270, 280, 290, 300,
310, 320, 330, 340, 350, 360, 370, 380, 390, 400,
410, 420, 430, 440, 450, 460, 470, 480, or 490 nm
May be. For example, the length range may be 60 to 490 nm.

Further, as the CNC, the ratio (length / thickness) of the length (nm) to the thickness (nm) can be, for example, about 1 to 200. The upper or lower limit of the range of the ratio is, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21. , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46. , 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71. , 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 , 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121. , 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146. 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171 , 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 193, 194, 195, 196. It may be 197, 198, or 199. For example, the range of the ratio may be 2 to 190.

The hydroxyethyl cellulose (HEC) used in the composition of the present disclosure is not particularly limited as long as the effect is not impaired.

For example, hydroxyethyl cellulose not cross-linked with a cross-linking agent (non-cross-linked HEC) and hydroxyethyl cellulose cross-linked with a cross-linking agent (cross-linked HEC) can be preferably used as the HEC of the composition of the present disclosure. Cross-linked HEC is more preferred.

Examples of the cross-linking agent include polyvalent aldehyde compounds (preferably dialdehyde compounds) such as glutaraldehyde and glioxal, 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 1,8-. Examples thereof include polyvalent aziridin compounds such as hexamethylene diethylene urea and polyvalent isocyanate compounds such as tolylene diisocyanate and hexamethylene diisocyanate. Of these, dialdehyde compounds are preferred, and glyoxal is particularly preferred. The cross-linking agent may be used alone or in combination of two or more.

Cross-linking of hydroxyethyl cellulose with a cross-linking agent can be carried out by a known method or a method that can be easily conceived from a known method. For example, it can be carried out by the method described in Japanese Patent Publication No. 58-43402.

The cross-linked HEC preferably has a cross-linking agent content of, for example, 0.05% by mass or more, and more preferably about 0.05 to 2% by mass. The upper or lower limit of the cross-linking agent content ratio range is, for example, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0. 26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.5, 0. 51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.6, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.7, 0.71, 0.72, 0.73, 0.74, 0.75, 0. 76, 0.77, 0.78, 0.79, 0.8, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.9, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, 1, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.1, 1.11, 1.12, 1.13, 1. 14, 1.15, 1.16, 1.17, 1.18, 1.19, 1.2, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.3, 1.31, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38 1. 39, 1.4, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, 1.5, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, 1.6, 1.61, 1.62, 1.63, 1. 64, 1.65, 1.66, 1.67, 1.68, 1.69, 1.7, 1.71, 1.72, 1.73, 1.74, 1.75, 1.76, 1.77, 1.78, 1.79, 1.8, 1.81, 1.82, 1.83, 1.84, 1.85, 1.86, 1.87, 1.88, 1. It may be 89, 1.9, 1.91, 1.92, 1.93, 1.94, 1.95, 1.96, 1.97, 1.98, or 1.99% by mass. For example, the cross-linking agent content ratio range may be 0.1 to 1% by mass. In particular, 0.35% by mass or more is preferable.

The HEC (including non-crosslinked HEC and crosslinked HEC) preferably has a viscosity of a 1.33% by mass (w / w%) aqueous solution at 25 ° C. of 4000 mPa · s or more, and more preferably 4000 to 18000 mPa · s. preferable. The upper or lower limit of the viscosity range is, for example, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400, 5500, 5600, 5700, 5800, 5900, 6000. , 6100, 6200, 6300, 6400, 6500, 6600, 6700, 6800, 6900, 7000, 7100, 7200, 7300, 7400, 7500, 7600, 7700, 7800, 7900, 8000, 8100, 8200, 8300, 8400, 8500. , 8600, 8700, 8800, 8900, 9000, 9100, 9200, 9300, 9400, 9500, 9600, 9700, 9800, 9900, 10000, 10100, 10200, 10300, 10400, 10500, 10600, 10700, 10800, 10900, 11000 , 11100, 11200, 11300, 11400, 11500, 11600, 11700, 11800, 11900, 12000, 12100, 12200, 12300, 12400, 12500, 12600, 12700, 12800, 12900, 13000, 13100, 13200, 13300, 13400, 13500. , 13600, 13700, 13800, 13900, 14000, 14100, 14200, 14300, 14400, 14500, 14600, 14700, 14800, 14900, 15000, 15100, 15200, 15300, 15400, 15500, 15600, 15700, 15800, 15900, 16000. , 16100, 16200, 16300, 16400, 16500, 16600, 16700, 16800, 16900, 17000, 17100, 17200, 17300, 17400, 17500, 17600, 17700, 17800, or 17900 mPa · s. For example, the viscosity range may be 4100 to 17900 mPa · s.

Further, the HEC (including the non-crosslinked HEC and the crosslinked HEC) is not particularly limited, but the molecular weight is preferably, for example, about 1800000 to 430000. The upper or lower limit of the molecular weight range is, for example, 19000000, 2000000, 210000, 2200, 230000, 2400000, 25, 260000, 2700, 280000, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 380000, It may be 3900000, 4000, 410000, or 4200000. For example, the molecular weight range may be 1900000 to 4200000.

The molecular weight is a mass average molecular weight obtained by gel permeation chromatography (GPC) and converted into polyethylene oxide. Examples of the column for measuring the mass average molecular weight in terms of polyethylene glycol by GPC include Shodex OHpak SB-807HQ, Shodex OHpak SB-806HQ, Shodex OHpak SB-804HQ and the like. Detailed GPC measurement conditions are shown below.
Equipment: TOSOH HLC-8220 GPC
Columns: Shodex OHpak SB-807HQ, OHpak SB-806 HQ, OHpak SB-804 HQ
Mobile phase: 0.2M-NaNO ₃
Flow velocity: 0.6 ml / min
Column temperature: 40 ° C
Standard sample: PEO Mw: 3.76 × 10 ⁴ , 1.07 × 10 ⁵ , 1.43 × 10 ⁵ , 2.77 × 10 ⁵ , 5.8 × 10 ⁵ , 7.86 × 10 ⁵
Sample concentration: 0.06% by mass
Further, although not particularly limited, HEC is a compound in which the OH group of cellulose is OR (R indicates H or CH ₂ CH ₂ OH), and is contained in the composition of the present disclosure. In HEC (including non-crosslinked HEC and crosslinked HEC), a group other than H or CH ₂ CH ₂ OH may be present as R of the OR, but it is preferable that no hydrophobic group is present as R. For example, as the R, an alkyl group, particularly a linear chain having 6 to 20 carbon atoms (6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) or Those having a branched chain alkyl group (more specifically, for example, a cetyl group) may be used, but it is preferable not to use them.

The composition of the present disclosure contains water as a solvent. Further, a solvent other than water may be further contained as long as the effect of the composition of the present disclosure is not impaired. Examples of the solvent other than water include water-soluble solvents, and for example, water-soluble organic solvents are preferable. Examples of the water-soluble organic solvent include monohydric or divalent alkyl alcohols having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), and more specifically, for example. Examples thereof include ethanol and butylene glycol.

Further, in the composition of the present disclosure, the value of the storage elastic modulus (G') is larger than the value of the loss elastic modulus (G'') (that is, the storage elastic modulus G'> the loss elastic modulus G''). The one is preferable. In other words, the composition of the present disclosure preferably has a loss tangent (tan δ) of less than 1 (that is, tan δ <1). The loss tangent (tan δ) is the ratio (G ″ / G ′) of the storage elastic modulus (G ′) and the loss elastic modulus (G ″), and is used as one of the indexes of the viscoelastic property. The larger the value of the loss tangent, the smaller the elastic modulus. For example, the loss tangent is used as an index of sol and gel, and usually tan δ> 1 is sol and tan δ <1 is gel.

The values of the storage elastic modulus G ′ and the loss elastic modulus G ″ can be measured at 25 ° C. using a viscoelasticity measuring device (leometer). More specifically, after confirming the linear region by measuring the strain dispersion at 1 Hz, an appropriate distortion is selected within the range of the linear region, and the frequency dispersion at 25 ° C. (frequency: 0.1 rad / s to 100 rad / s). And observe the magnitude relationship between G'and G''.

In the composition of the present disclosure, the storage elastic modulus G'and the loss elastic modulus G'' obtained by frequency dispersion measurement have a magnitude relationship of the storage elastic modulus G in the entire range of frequency: 0.1 rad / s to 100 rad / s. '> Loss elastic modulus G'' is preferable.

Further, the composition of the present disclosure has a viscosity at 25 ° C. of 10,000 mPa · s or more, preferably 10,000 to 20,000 mPa · s. The upper or lower limit of the viscosity range is, for example, 10100, 10200, 10300, 10400, 10500, 10600, 10700, 10800, 10900, 11000, 11100, 11200, 11300, 11400, 11500, 11600, 11700, 11800, 11900, 12000. , 12100, 12200, 12300, 12400, 12500, 12600, 12700, 12800, 12900, 13000, 13100, 13200, 13300, 13400, 13500, 13600, 13700, 13800, 13900, 14000, 14100, 14200, 14300, 14400, 14500. , 14600, 14700, 14800, 14900, 15000, 15100, 15200, 15300, 15400, 15500, 15600, 15700, 15800, 15900, 16000, 16100, 16200, 16300, 16400, 16500, 16600, 16700, 16800, 16900, 17000. , 17100, 17200, 17300, 17400, 17500, 17600, 17700, 17800, 17900, 18000, 18100, 18200, 18300, 18400, 18500, 18600, 18700, 18800, 18900, 19000, 19100, 19200, 19300, 19400, 19500. , 19600, 19700, 19800, or 19900 mPa · s. For example, the viscosity range may be 8100 to 19,900 mPa · s.

In the present disclosure, the viscosity is a value measured at 25 ° C. using a rotary viscometer manufactured by BrookField (model number: DVE, spindle: LV) at a rotation speed of 20 rpm. As a guide, the spindle used for measurement is spindle LV-1 when it is less than 200 mPa · s, spindle LV-2 when it is 200 mPa · s or more and less than 1000 mPa · s, and 1000 mPa · s or more and less than 4000 mPa · s. Is Spindle LV-3, and Spindle LV-4 in the case of 4000 mPa · s or more.

Further, when the composition of the present disclosure contains a salt (that is, the salt-containing composition of the present disclosure), a water-soluble salt is preferable as the salt. Examples of the water-soluble salt include water-soluble inorganic salts and organic salts. Examples of the inorganic salt include hydrochloride, hydrobromide, sulfate, nitrate, phosphate, phosphate ester salt and the like, and examples of the organic salt include acetate, 2,2-dichloroacetate and the like. Adipate, alginate, ascorbate, ascorbic acid phosphate, asparagate, benzenesulfonate, benzoate, 4-acetamide benzoate, camphorate, camphor-10-sulfonate, caprin Acids, capronates, caprilates, carbonates, cinnamic acid salts, citrates, cyclamates, dodecylsulfonates, ethane-1,2-disulfonates, ethanesulfonates, 2-hydroxyethane Sulfonate, grate, fumarate, galactalate, gentisate, glucoheptone, gluconate, glucronate, glutamate, glutarate, 2-oxo-glutarate, glycerophosphate, Glycolate, horse urate, isobutyrate, lactate, lactobionate, laurate, maleate, malate, malonate, mandelate, methanesulfonate, mucilage, naphthalene- 1,5-Disulfonate, Naphthalene-2-sulfonate, 1-hydroxy-2-naphthoate, nicotinate, oleate, olotinate, oxalate, palmitate, pamoate, Propionate, pyroglutamate, pyruvate, salicylate, 4-aminosalicylate, cevacinate, stearate, succinate, tartrate, thiocyanate, p-toluenesulfonate, trifluoroacetic acid Examples thereof include salt and undecylene salt. More specifically, examples of these salts include sodium salt, potassium salt, lithium salt, ammonium salt, calcium salt, magnesium salt, iron salt, zinc salt, copper salt, manganese salt, aluminum salt and the like. .. Among them, hydrochloride, phosphate, phosphate ester salt, acetate, ascorbate, ascorbic acid phosphate, asparagate, carbonate, citrate, fumarate, lactate, maleate, apple Acid salts, malonates, oxalates and the like are preferable, and these sodium salts, potassium salts, ammonium salts, calcium salts, magnesium salts and the like are more preferable.

More specifically, examples of the salt include sodium chloride, sodium ascorbate, magnesium ascorbate, sodium ascorbate, and the like. Of these, sodium chloride, ascorbic acid salt, ascorbic acid derivative salt (for example, ascorbic acid phosphate) and the like are preferable.

The salt can be used alone or in combination of two or more.

The content ratio of CNC and HEC (including non-crosslinked HEC and crosslinked HEC) in the composition of the present disclosure is not particularly limited as long as the effect is not impaired, but is not particularly limited, for example, with respect to 1 part by mass of HEC. , CNC is preferably about 0.05 to 1 part by mass. The upper or lower limit of the range is, for example, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, It may be 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, or 0.95. For example, the range may be 0.1 to 0.8.

Further, the CNC content in the composition of the present disclosure is not particularly limited as long as the effect is not impaired, and examples thereof include about 0.1 to 5% by mass. The upper or lower limit of the range is, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2. , 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5 , 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8 It may be 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, or 4.9% by mass. .. For example, the range may be 0.2 to 2% by mass.

The HEC (including non-crosslinked HEC and crosslinked HEC) content in the composition of the present disclosure is not particularly limited as long as the effect is not impaired, but is, for example, about 0.1 to 5% by mass. Can be mentioned. The upper or lower limit of the range is, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2. , 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5 , 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8 It may be 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, or 4.9% by mass. .. For example, the range may be 0.2 to 2% by mass.

Further, the salt content in the salt-containing composition of the present disclosure is preferably 0.1% by mass or more, more preferably about 0.1 to 10% by mass. The upper or lower limit of the range (0.1 to 10% by mass) is, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2. 3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3. 6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4. 9, 55.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6. 3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7. 6, 7.7, 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.8. It may be 9, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, or 9.9 mass%. For example, the range may be 1 to 10% by mass or 1.5 to 8% by mass.

Further, the composition of the present disclosure preferably has a transmittance of 10% or more. The transmittance is, for example, 11% or more, 12% or more, 13% or more, 14% or more, 15% or more, 16% or more, 17% or more, 18% or more, 19% or more, 20% or more, 21% or more. , 22% or more, 23% or more, 24% or more, 25% or more, 26% or more, 27% or more, 28% or more, 29% or more, 30% or more, 31% or more, 32% or more, 33% or more, 34 % Or more, 35% or more, 36% or more, 37% or more, 38% or more, 39% or more, 40% or more, 41% or more, 42% or more, 43% or more, 44% or more, 45% or more, 46% or more , 47% or more, 48% or more, 49% or more, or 50% or more. The upper limit of the transmittance is not particularly limited, but for example, 95% or less can be exemplified. 94% or less, 93% or less, 92% or less, 91% or less, 90% or less, 89% or less, 88% or less, 87% or less, 86% or less, 85% or less, 84% or less, 83% or less, 82% 81% or less, 80% or less, 79% or less, 78% or less, 77% or less, 76% or less, 75% or less, 74% or less, 73% or less, 72% or less, 71% or less, 70% or less, It may be 69% or less, 68% or less, 67% or less, 66% or less, or 65% or less. More preferably, the transmittance is about 15 to 95%.

The transmittance is specifically a value obtained by measuring the transmittance (% T) of UV (425 nm) (calibrated so that the distilled water has a transmittance of 100%).

The high transmittance of the composition means that the transparency of the composition is high. It is not always required that the composition be transparent, but it is preferable because it is in high demand especially in the cosmetics field.

Such excellent transmittance can be achieved when the HEC used is a crosslinked HEC and the crosslinker content ratio of the crosslinked HEC is relatively high. As described above, the ratio is preferably 0.35% by mass or more, more preferably about 0.35 to 2% by mass.

The composition of the present disclosure may contain components other than CNC, HEC (including non-crosslinked HEC and crosslinked HEC), salt, and water as long as the effect is not impaired. Examples of such an ingredient include simple substances and ingredients known in the fields of pharmaceuticals, cosmetics, and foods.

The composition of the present disclosure can be prepared, for example, by mixing CNC and HEC (including non-crosslinked HEC and crosslinked HEC) and then mixing the mixture with water. Thus, it is desirable to mix CNC and HEC before adding to water. By adjusting by the method, the composition of the present disclosure can have the above-mentioned excellent viscosity not only when it does not contain a salt but also when it contains a salt.

It is preferable that both CNC and HEC used for mixing before being added to water are powders. Further, the mixture of CNC and HEC to be added to water is preferably a powder.

The salt-containing composition of the present disclosure can be prepared, for example, by adding a salt to a viscous composition prepared by adding a mixture of CNC and HEC to water and mixing them as necessary. A viscous composition prepared by adding a mixture of CNC and HEC to water and mixing them as necessary is useful as a viscous composition for salt addition.

Since the composition of the present disclosure has excellent viscosity and viscoelasticity, it is useful in technical fields in which products required to have such properties exist, for example, in the fields of pharmaceuticals, cosmetics, and foods. That is, the composition of the present disclosure can be preferably used, for example, as a pharmaceutical composition, a cosmetic composition, a food composition, or the like.

In addition, in this specification, "includes" also includes "consisting of" and "consisting of" (The term "comprising" includes "consisting essentially of" and "consisting of."). In addition, the present disclosure includes all combinations of the constituent elements described herein.

Further, the various characteristics (property, structure, function, etc.) described for each embodiment of the present disclosure described above may be combined in any way in specifying the subject matter included in the present disclosure. That is, the present disclosure includes all subjects consisting of any combination of each of the combinable properties described herein.

Hereinafter, embodiments of the present disclosure will be described in more detail with reference to examples, but the embodiments of the present disclosure are not limited to the following examples.
[Viscoelasticity measurement]
For each viscous composition, G'(storage elastic modulus) and G "(loss elastic modulus) were determined by frequency dispersion using a commercially available viscoelasticity measuring device (leometer).

Measurement conditions Leometer: TA Instrument AR-2000ex
Plate: 60 mm, 1 ° cone plate Measurement temperature: 25 ° C
Distortion: 0.1 to 10% (selected within the range of the linear region obtained in the distortion dispersion measurement at 1 Hz)
Frequency: 0.1 rad / s to 100 rad / s
[Viscosity measurement]
The viscosity of each viscous composition was measured at 25 ° C. using a rotary viscometer (model number: DVE, spindle: LV) manufactured by BrookField at a rotation speed of 20 rpm. As a guide, the spindle used for measurement is spindle LV-1 when it is less than 200 mPa · s, spindle LV-2 when it is 200 mPa · s or more and less than 1000 mPa · s, and 1000 mPa · s or more and less than 4000 mPa · s. Is Spindle LV-3, and Spindle LV-4 in the case of 4000 mPa · s or more.
[Transmittance]
The transmittance of each viscous composition was measured as follows.

A spectrophotometer (model number: UV-1850) manufactured by Shimadzu Corporation was used for the measurement. First, the sample was placed in a cell for UV measurement (optical path length 1 cm), and defoamed by a centrifuge at 2,000 rpm for 5 minutes. If the defoaming was not completed, the same operation was performed with a centrifuge, and it was confirmed that the bubbles were completely removed from the upper part of the sample. Then, the sample was set in a spectrophotometer, and the transmittance was measured with the measurement wavelength set to 425 nm. The distilled water was calibrated so as to have a transmittance of 100%.
[Stability]
It was visually confirmed whether the components contained in each viscous composition did not separate.
[Preparation and evaluation of viscous composition]
Cellulose Nanocrystals (manufactured by Alberta-Pacific Forest Industries Inc.) was used as the crystal nanocellulose. A part of Cellulose Nanocrystals is sodium cellulose sulfate.

In addition, various commercially available water-soluble polymers (all powders) were purchased and used. HEC (CF-Y), HEC (SZ-25F), AQUAPEC HV-505E, and AQUAPEC HV-501ER are manufactured by Sumitomo Seika Chemical Co., Ltd. AQUAPEC HV-505E is a carbomer (carboxyvinyl polymer), and AQUAPEC HV-501ER is a (Acrylate / alkyl acrylate (C10-30)) cross polymer. The HECs used were all cross-linked HECs cross-linked with a cross-linking agent (glyoxal), and the content of the cross-linking agent in each cross-linked HEC was 0.55% by mass for HEC (CF-Y) and HEC (SZ-25F). Is 0.29% by mass.

According to the composition shown in Table 1, a powder of crystal nanocellulose and a powder of a water-soluble polymer (HEC) are mixed, and the mixed powder is stirred and mixed with ion-exchanged water to dissolve it, and a water-soluble salt (specifically, a water-soluble salt (specifically)) is added thereto. Specifically, sodium chloride or L-ascorbic acid phosphate magnesium) was mixed to prepare a viscous composition. More specifically, 0.33 g of cellulose nanocrystals and 1 g of hydroxyethyl cellulose are mixed in a powder state, the mixed powder is put into 93.67 g of water, and the mixture is stirred with a 4-paddle stirring blade at 500 rpm for 4 hours to gel. I made it. 5 g of a water-soluble salt was added to the obtained 95 g of gel, and the mixture was further stirred with a paddle for about 10 minutes to prepare a viscous composition. Then, after defoaming with a centrifuge, viscoelasticity, viscosity, and transmittance were measured.

However, the viscous compositions of Comparative Examples 3 to 4 were prepared by dispersing crystal nanocellulose in ion-exchanged water, dissolving a water-soluble salt in the viscous composition, and finally dissolving a water-soluble polymer. For Examples 1 to 4, the viscoelasticity, viscosity, and transmittance of the composition before mixing the water-soluble salt were also measured. The viscous compositions of Comparative Examples 1 and 2 were prepared by stirring and mixing a water-soluble polymer (AQUAPEC) in ion-exchanged water, dispersing the mixture, neutralizing the pH to 7 with NaOH, and further mixing and mixing a water-soluble salt. For Comparative Examples 1 and 2, the viscoelasticity and viscosity of the composition before mixing the water-soluble salt were also measured. The results are also shown in Table 1.

In Table 1, when G'is larger than G'' in the whole range of frequency: 0.1 rad / s to 100 rad / s, G'> G'' and all of 0.1 rad / s to 100 rad / s. When G'is smaller than G'in the range, it is described as G'<G'. In addition, there are cases where the magnitude relationship between G'and G'is reversed in the range of 0.1 rad / s to 100 rad / s, and G'and G'match in the entire range of 0.1 rad / s to 100 rad / s. There was no case.

Claims

Contains cellulose nanocrystals, hydroxyethyl cellulose, water-soluble salts, as well as water,
The viscosity at 25 ° C. is 10,000 mPa · s or more.
Viscous composition.
The viscous composition according to claim 1, wherein the hydroxyethyl cellulose is hydroxyethyl cellulose crosslinked with a cross-linking agent.
Hydroxyethyl cellulose crosslinked with the crosslinking agent
A crosslinked hydroxyethyl cellulose containing 0.35% by mass or more of a crosslinking agent.
The viscous composition according to claim 2.
The viscous composition according to claim 2 or 3, wherein the cross-linking agent is a dialdehyde compound.
The viscous composition according to any one of claims 1 to 4, wherein the content of the water-soluble salt is 0.1% by mass or more.
The viscous composition according to any one of claims 1 to 5, which has a transmittance of 10% or more.
The magnitude relationship between the storage elastic modulus G'and the loss elastic modulus G'' obtained by the frequency dispersion measurement is the storage elastic modulus G'> the loss elastic modulus G'> in the entire frequency range of 0.1 rad / s to 100 rad / s. The viscous composition according to any one of claims 1 to 6.
A method for producing a viscous composition, which comprises mixing (1) a mixture of cellulose nanocrystals and hydroxyethyl cellulose with water, and (2) adding a water-soluble salt to the mixture.
(1) A method for producing a viscous composition for adding a water-soluble salt, which comprises mixing a mixture of cellulose nanocrystals and hydroxyethyl cellulose with water.
The method according to claim 8 or 9, further comprising mixing (0) cellulose nanocrystals and hydroxyethyl cellulose before (1).