WO2023013535A1 - Viscous composition - Google Patents

Abstract

Provided is a stable composition which has a suitable viscosity and contains a water-soluble polymer thickener and a water-soluble ultraviolet absorber. Specifically provided is a viscous composition which contains a water-soluble cellulose derivative, a water-insoluble cellulose, a water-soluble ultraviolet absorber and water.

Description

Viscous composition

The present invention relates to a viscous composition and the like, and more particularly to a viscous composition containing a water-soluble cellulose derivative.

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

Especially in the field of cosmetics, viscous compositions are sometimes mixed with UV absorbers (especially water-soluble UV absorbers) and used as sunscreens.

Japanese Patent Publication No. 2012-531478 Japanese Patent Publication No. 2014-510846

Langmuir 2012, 28, 6114-6123

According to the studies of the present inventors, when an ultraviolet absorber (especially a water-soluble ultraviolet absorber) is applied to a composition containing a polymer thickener, the viscosity often fluctuates greatly, making it very difficult to handle and stable. Concerns about lack of sexuality were found. Therefore, it was not easy to prepare a stable composition containing a water-soluble polymeric thickener and a water-soluble UV absorber and having an appropriate viscosity.

Therefore, the present inventors conducted further studies to find a method for easily preparing a stable composition having an appropriate viscosity containing a water-soluble polymer thickener and a water-soluble ultraviolet absorber. gone.

The present inventors have found that a viscous composition containing a water-soluble cellulose derivative as a water-soluble polymer thickener, and further containing cellulose and water has a large viscosity variation even when a water-soluble ultraviolet absorber is added. In addition, we found the possibility of being excellent in stability, and conducted further investigations.

The invention includes, for example, the subject matter described in the following sections.
Section 1.
A viscous composition containing a water-soluble cellulose derivative, a water-insoluble cellulose, a water-soluble ultraviolet absorber, and water.
Section 2.
Item 2. The viscous composition according to Item 1, wherein the water-soluble cellulose derivative is hydroxyalkylcellulose (preferably HEC).
Item 3.
Item 3. The viscous composition according to Item 1 or 2, wherein the water-insoluble cellulose is nanocellulose (preferably cellulose nanocrystals).
Section 4.
Water-soluble UV absorbers include terephthalylidene dicamphorsulfonic acid, bisbenzoxazolyl derivatives, p-aminobenzoic acid and its derivatives, phenylbenzimidazolesulfonic acid, ferulic acid, salicylic acid, diethanolamine methoxycinnamate (DEA). , benzylidene camphorsulfonic acid, camphor benzalkonium methosulfate, benzophenone-4, benzophenone-5, benzophenone-9, 2,4-dihydroxybenzophenone, and at least one selected from the group consisting of trisbiphenyltriazine, Item 4. The viscous composition according to any one of Items 1 to 3.
Item 5.
Item 5. The viscous composition according to any one of Items 1 to 4, which has a viscosity of 4000 to 15000 mPa·s at 25°C.
Item 6.
The magnitude relationship between the storage elastic modulus G′ and the loss elastic modulus G″ obtained by frequency dispersion measurement is that the storage elastic modulus G′>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 5, which is
Item 7.
the water-soluble cellulose derivative is hydroxyethyl cellulose,
the water-insoluble cellulose is a cellulose nanocrystal,
Water-soluble UV absorbers include terephthalylidene dicamphorsulfonic acid, bisbenzoxazolyl derivatives, p-aminobenzoic acid and its derivatives, phenylbenzimidazolesulfonic acid, ferulic acid, salicylic acid, diethanolamine methoxycinnamate (DEA). , benzylidene camphorsulfonic acid, camphor benzalkonium methosulfate, benzophenone-4, benzophenone-5, benzophenone-9, 2,4-dihydroxybenzophenone, and at least one selected from the group consisting of trisbiphenyltriazine,
Viscosity at 25 ° C. is 4000 to 15000 mPa s,
The magnitude relationship between the storage elastic modulus G′ and the loss elastic modulus G″ obtained by frequency dispersion measurement is that the storage elastic modulus G′>loss elastic modulus G″ in the entire frequency range of 0.1 rad/s to 100 rad/s. is
Item 1. The viscous composition according to item 1.

A stable composition containing a water-soluble polymer thickener and a water-soluble ultraviolet absorber and having an appropriate viscosity and a method for easily preparing the composition are provided.

Each embodiment included in the present invention will be described in further detail below. The present invention preferably includes, but is not limited to, a viscous composition, a method for producing the same, and the like, and the present invention includes everything disclosed herein and recognized by a person skilled in the art.

The viscous composition included in the present invention contains a water-soluble cellulose derivative, a water-insoluble cellulose, a water-soluble ultraviolet absorber, and water. The viscous composition included in the present invention is sometimes referred to as "the composition of the present invention".

In this specification, "water-soluble" means exhibiting a solubility of 0.1% by mass or more in water at 25°C. The term "exhibiting solubility" refers to, for example, a state in which a transparent solution can be visually confirmed after a water-soluble cellulose derivative is added to water and sufficiently stirred, or a state in which precipitation does not occur.

As the water-soluble cellulose derivative, a cellulose derivative having a hydroxy group is preferable, and a hydroxyalkyl cellulose is more preferable. The alkyl group of hydroxyalkylcellulose is preferably an alkyl group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), more preferably a methyl group, an ethyl group, or a propyl group. Hydroxyalkyl cellulose may have different alkyl groups. More specifically, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and the like are preferred. Among them, hydroxyethyl cellulose (HEC) is particularly preferred.

Both 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 invention. Crosslinked HEC is more preferred. Crosslinking agents include polyaldehyde compounds (preferably dialdehyde compounds) such as glutaraldehyde and glyoxal, 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate], 1,8-hexamethylene. Preferred are polyvalent aziridine compounds such as diethylene urea, and polyvalent isocyanate compounds such as tolylene diisocyanate and hexamethylene diisocyanate. Among them, dialdehyde compounds are preferred, and glyoxal is particularly preferred. A crosslinking agent can be used individually by 1 type or in combination of 2 or more types.

The crosslinked HEC preferably has a crosslinker content of 0.05% by mass or more, more preferably about 0.05 to 2% by mass. The upper limit or lower limit of the content ratio range of the cross-linking agent is 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, 0.88 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, 1.89, 1.9, 1.91, 1.92, 1.93, 1.94, 1.95, 1.96, 1.97, 1.98, or 1.99 wt%. More preferably, the cross-linking agent content ratio range is 0.1 to 1% by mass, particularly preferably 0.35% by mass or more, and most preferably 0.35 to 1% by mass.

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 known methods. For example, the method described in JP-B-58-43402 can be used.

HEC (including non-crosslinked HEC and crosslinked HEC) preferably has a viscosity of 4000 mPa s or more at 25°C in a 1.33% by mass (w/w%) aqueous solution, more preferably 4000 to 18000 mPa s. preferable. The upper or lower limit of the viscosity range is 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, 110000, 110000 、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 . More preferably, the viscosity range is from 4100 to 17900 mPa·s, particularly preferably from 5000 to 16000 mPa·s.

In addition, HEC (including non-crosslinked HEC and crosslinked HEC) preferably has a molecular weight of about 1,800,000 to 4,300,000.当該分子量範囲の上限または下限は、１９０００００、２００００００、２１０００００、２２０００００、２３０００００、２４０００００、２５０００００、２６０００００、２７０００００、２８０００００、２９０００００、３００００００、３１０００００、３２０００００、３３０００００、３４０００００、３５０００００、３６０００００、３７０００００、３８０００００、３９０００００ , 4000000, 4100000, or 4200000. More preferably, the molecular weight range is from 1,900,000 to 4,200,000.

In addition, the said molecular weight is a weight average molecular weight calculated|required by measuring by a gel permeation chromatography (GPC) and polyethylene oxide conversion. As a column for measuring the weight average molecular weight by polyethylene glycol conversion by GPC, Shodex OHpak SB-807HQ, Shodex OHpak SB-806HQ, Shodex OHpak SB-804HQ and the like are preferable. Detailed GPC measurement conditions are shown below.
Apparatus: TOSOH HLC-8220 GPC
Column: Shodex OHpak SB-807HQ, OHpak SB-806 HQ, OHpak SB-804 HQ
Mobile phase: 0.2M- _NaNO3
Flow rate: 0.6ml/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
HEC is a compound in which the OH group of cellulose is OR (R represents H or CH ₂ CH ₂ OH). include), a group other than H or CH ₂ CH ₂ OH may be present as R of the OR, but it is preferable that R be not a hydrophobic group. The R is an alkyl group, especially a linear or branched chain having 6 to 20 carbon atoms (6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) Those having an alkyl group (more specifically, for example, a cetyl group) may be used, but are preferably not used.

Cellulose is a water-insoluble substance, and the cellulose used in the composition of the present invention is also water-insoluble cellulose.

As used herein, "water-insoluble" means something that is not "water-soluble".

As cellulose, crystalline cellulose and nanocellulose are preferable, and nanocellulose is more preferable. Among nanocelluloses, cellulose nanocrystals (CNC) are preferred.

It should be noted that, as described above, cellulose nanocrystals are a type of nanocellulose. In particular, cellulose nanofibers (CNF) and cellulose nanocrystals (CNC) are examples of nanocellulose made from wood or the like. Among nanocelluloses, those with a relatively long length are called cellulose nanofibers (CNF), and those with a relatively short length are called cellulose nanocrystals (CNC). Although not limited, nanocellulose with a length of approximately 5-10 μm or more is often referred to as cellulose nanofibers (CNF), and those with a length shorter than CNF are often referred to as cellulose nanocrystals (CNC). It seems

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

Cellulose is a natural polymeric material that together with hemicellulose and lignin constitute woody and agricultural biomass. It is a homopolymer of repeating units of glucose linked by β-1,4-glycosidic bonds. Cellulose is formed into linear chains by β-1,4-glycosidic bonds, which interact strongly with each other through hydrogen bonds. Due to their regular structure and strong hydrogen bonding, cellulose polymers are highly crystalline and aggregate to form substructures and microfibrils. The microfibrils then aggregate to form cellulosic fibers.

Purified cellulose from woody or agricultural biomass can be degraded or produced on a large scale by bacterial processes. When cellulosic materials are composed of nano-sized fibers and the properties of the material are determined by the structure of the nanofibers, these polymers are said to be nanocellulose. Generally, nanocellulose is rod-shaped fibrils with a length/diameter ratio of approximately 20-200.

In general, the preparation of nanocellulose can be described by two methods. In the first method, nanocellulose can be prepared from chemical pulps, for example wood fibers or agricultural fibers, by removing the amorphous regions, mainly by acid hydrolysis, to produce nano-sized fibrils. Cellulose nanocrystals can be generated and stabilized in aqueous suspension by, for example, sonicating the fibrils or passing them through a high shear microfluidizer.

The second method is mainly physical processing. Microfibril bundles, usually called cellulose microfibrils or microfibrillated cellulose, with a diameter of several tens of nanometers (nm) to several micrometers (μm) are produced by using high-pressure homogenization and pulverization processes. . A process using high intensity sonication has also been used to isolate fibrils from native cellulose fibers. High-intensity ultrasound can produce very strong mechanical vibratory forces, thus enabling the separation of cellulose fibrils from biomass. This method produces microfibrillated cellulose having a diameter of less than about 60 nm, more preferably from about 4 nm to about 15 nm, and a length of less than 1000 nm. The microfibrillated cellulose can, for example, also be subjected to further chemical, enzymatic and/or mechanical treatments. The microfibrillated cellulose can also be used as cellulose nanocrystals.

In other words, in general, when cellulose nanocrystals are used as cellulose in the composition of the present invention, the cellulose nanocrystals can be obtained, for example, from pulp by removing non-crystalline regions by acid hydrolysis, or by high pressure treatment, pulverization treatment. , by physical treatment such as ultrasonic treatment (or by using them in combination).

In addition, the cellulose portion of the cellulose nanocrystals used in the composition of the present invention is preferably cellulose sulfate (cellulose sulfate). A sodium salt is preferred as the salt. That is, the cellulose portion of the cellulose nanocrystals used in the composition of the present invention is preferably sodium cellulose sulfate.

Therefore, in the present invention, the term "cellulose nanocrystal" or "CNC" indicates nano-sized cellulose crystals, and the cellulose may be unmodified or modified. Preferred examples of modified cellulose include cellulose sulfate (especially sodium cellulose sulfate), as described above.

For CNC, nanocellulose with a thickness of about 1 to 100 nm and a length of about 50 to 500 nm is preferable. The upper or lower limit of the thickness range (1 to 100 nm) is 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, It can be 94, 95, 96, 97, 98, or 99 nm, and more preferably the thickness range is from 2 to 99 nm. In addition, the upper or lower limit of the length range (50 to 500 nm) is 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, It can be 470, 480, or 490 nm. More preferably, the length range is 60-490 nm.

Also, the CNC preferably has a ratio of length (nm) to thickness (nm) (length/thickness) of about 1 to 200. The upper or lower limits of the range of said ratios are 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 can be 197, 198, or 199. More preferably, the ratio ranges from 2 to 190.

As the water-soluble UV absorber, for example, a water-soluble UV absorber known in the field of cosmetics (particularly in the field of sunscreen compositions) can be used. UV-A absorbers and UV-B absorbers are preferred. It should be noted that UV-A absorbers can absorb UV rays of about 320-400 nm, and UV-B absorbers can absorb UV rays of about 280-320 nm.

More specifically, terephthalylidene dicamphorsulfonic acid, bisbenzoxazolyl derivatives (more specifically, disodium phenyldibenzimidazole tetrasulfonate, etc.), p-aminobenzoic acid (PABA) and derivatives thereof (eg glyceryl PABA, PEG-25 PABA, etc.), phenylbenzimidazole sulfonic acid, ferulic acid, salicylic acid, diethanolamine methoxycinnamate (DEA), benzylidene camphorsulfonic acid, camphor benzalkonium methosulfate, benzophenone-4, benzophenone -5, and benzophenone-9, 2,4-dihydroxybenzophenone, trisbiphenyltriazine and the like are particularly preferred. Among them, phenylbenzimidazole sulfonic acid is preferred.

The water-soluble ultraviolet absorbers can be used singly or in combination of two or more.

In addition, many of the water-soluble ultraviolet absorbers are acidic substances, but when the composition of the present invention is used as, for example, an external preparation, the pH may become too low due to the water-soluble ultraviolet absorbers, which is not preferable. could be. In such cases, the pH of the compositions of the present invention may be adjusted by pH adjusting agents.

The pH of the composition of the present invention is preferably about 5-8, more preferably about 5.5-7.5.

The pH value in the present invention is a value obtained by measuring with a pH meter at 25°C.

The composition of the present invention contains water as a solvent. Further, as long as the effect of the composition of the present invention is not impaired, a solvent other than water may be further included. Examples of the solvent other than water include water-soluble solvents, such as water-soluble organic solvents. preferable. Specific examples of water-soluble organic solvents include monohydric alkyl alcohols having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), and more specific examples include ethanol. be done.

Further, in the composition of the present invention, the value of the storage modulus (G') is larger than the value of the loss modulus (G'') (that is, the storage modulus G'>loss modulus G''). things are preferred. In other words, the compositions of the present invention preferably have a loss tangent (tan δ) of less than 1 (ie, tan δ<1). The loss tangent (tan δ) is the ratio (G″/G′) of the storage elastic modulus (G′) to the loss elastic modulus (G″), and is used as one index of viscoelastic properties. The larger the value of the loss tangent, the smaller the rebound resilience. 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 storage elastic modulus G' and loss elastic modulus G'' can be measured at 25°C using a viscoelasticity measuring device (rheometer). More specifically, by strain dispersion measurement at 1 Hz, after confirming the linear region, select an appropriate strain within the range of the linear region, frequency dispersion at 25 ° C. (frequency: 0.1 rad / s to 100 rad / s) is measured to observe the magnitude relationship between G' and G''.

In the composition of the present invention, the magnitude relationship between the storage elastic modulus G′ and the loss elastic modulus G″ obtained by frequency dispersion measurement is in the entire frequency range of 0.1 rad/s to 100 rad/s. '> Loss modulus G'' is preferred.

When the composition has such properties, it can be said that the composition is a preferable gel composition. preferable. In addition, an improvement in stability can also be expected.

In addition, the composition of the present invention preferably has a viscosity of 4000 to 15000 mPa·s at 25°C. The upper or lower limit of the viscosity range is 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, 110000, 110000 、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, or 14900 mPa·s. More preferably, the viscosity range is from 5000 to 10000 mPa·s, more preferably from 6000 to 10000 mPa·s.

In the present invention, the viscosity is a value measured at 25°C using a rotational viscometer manufactured by BrookField (model number: DV1MRVTJ0) with a rotational speed of 20 revolutions per minute. As a guideline, the spindle used for measurement should be rotor No. when the pressure is less than 2,000 mPa·s. 3. Rotor No. in the case of 2,000 mPa·s or more and less than 5,000 mPa·s. 4, 5,000 mPa·s or more and less than 15,000 mPa·s, rotor No. 5, 15,000 mPa·s or more and less than 40,000 mPa·s, rotor No. Rotor No. 6, 40,000 mPa·s or more. 7.

The content ratio of the water-soluble cellulose derivative and the water-insoluble cellulose in the composition of the present invention is preferably about 0.05 to 1 part by mass of the water-insoluble cellulose per 1 part by mass of the water-soluble cellulose derivative. The upper or lower limit of the range is 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.55, 0.25, 0.35, 0.4, 0.45, 0.5, 0.55. It can be 6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, or 0.95. More preferably, the range is 0.1 to 0.8.

In addition, the water-insoluble cellulose content in the composition of the present invention is preferably 0.05 to 5% by mass. The upper or lower limit of the range is 0.1, 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, or 4.9% by mass be able to. More preferably, the range is 0.1-2% by weight.

In addition, the content of the water-soluble cellulose derivative in the composition of the present invention is preferably 0.1 to 5% by mass. The upper or lower limit of the range is 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, or 4.9 wt%. More preferably, the range is 0.2-2% by weight.

In addition, the content of the water-soluble ultraviolet absorber in the composition of the present invention is preferably about 0.5 to 10% by mass. The upper or lower limit of the range can be 1, 2, 3, 4, 5, 6, 7, 8, or 9 wt%. More preferably, the range is 1-5% by weight.

In addition, the composition of the present invention preferably suppresses a decrease in viscosity. More specifically, for example, even if the composition of the present invention is stored at 50 ° C. for 30 days immediately after production, the ratio of the viscosity after storage compared to the viscosity before storage (viscosity retention rate) is preferably 65% to 100%, more preferably 70% to 95%.

The composition of the present invention may contain ingredients other than those mentioned above as long as the effects are not impaired. Examples of such components include carriers and components known in the fields of pharmaceuticals, cosmetics, and foods. Examples include pH adjusters and polyhydric alcohols.

As the pH adjuster, a known pH adjuster that can be used in the field of pharmaceuticals, cosmetics, or foods can be used, and sodium hydroxide, potassium hydroxide, citric acid, ascorbic acid or salts thereof (sodium salt, potassium salt, etc.) can be used.

Examples of polyhydric alcohols include dihydric or trihydric alcohols and sugar alcohols. Alkyl glycols having 2 to 6 carbon atoms (2, 3, 4, 5, or 6), more specifically ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, dipropylene glycol, hexylene glycol and the like. be done. Alditols (thritol, tetritol, pentitol, hexitol) are also included, more specifically glycerin, sorbitol, and the like. A polyhydric alcohol can be used individually by 1 type or in combination of 2 or more types.

The composition of the present invention can be prepared, for example, by mixing a water-soluble cellulose derivative, a water-insoluble cellulose, a water-soluble ultraviolet absorber, and water. First, it is desirable to mix the water-soluble cellulose derivative and the water-insoluble cellulose, and then mix this with water. Both the water-soluble cellulose derivative and the water-insoluble cellulose used for mixing before adding to water are preferably powder. Moreover, when preparing a mixture of a water-soluble cellulose derivative and a water-insoluble cellulose to be added to water, the mixture is preferably powder.

In particular, when a water-soluble cellulose derivative, water-insoluble cellulose, and water mixed composition is further added and mixed with a water-soluble ultraviolet absorber (and other components as necessary), the water-soluble ultraviolet absorber Even if the agent is added, the viscosity of the composition is suppressed from fluctuating, and the viscosity does not fluctuate greatly, so the viscosity of the final composition can be easily adjusted, which is preferable. It is considered that this is achieved by using a water-soluble cellulose derivative as a water-soluble polymer thickener and using a water-insoluble cellulose in combination.

Accordingly, the present invention encompasses a method for producing the composition of the present invention, which method preferably comprises (1) mixing a water-soluble cellulose derivative, a water-insoluble cellulose, and water, and (2) further admixing a water-soluble UV absorber.

The viscosity of the mixture of the water-soluble cellulose derivative, the water-insoluble cellulose, and water, and the viscosity of the composition obtained by further adding the water-soluble ultraviolet absorber to this, is 100% of the viscosity (mPa s) of the former mixture. , the viscosity of the latter composition is preferably about 70 to 130%, more preferably 75 to 125%.

In addition, the composition of the present invention can preferably be placed in a spray container and sprayed smoothly. Since the composition of the present invention contains a water-soluble cellulose derivative and inorganic oxide compound particles and is a viscous composition that can be sprayed, it can be preferably used as a composition for spraying. When the composition of the present invention is used by spraying, it is preferably used by filling a manual sprayer.

Since the composition of the present invention has excellent viscosity and viscoelasticity, it is useful in technical fields where there are products that require such properties, such as pharmaceutical fields, cosmetics fields, and food fields. That is, the composition of the present invention can be preferably used as, for example, pharmaceutical compositions, cosmetic compositions, food compositions and the like. Since the composition of the present invention contains a water-soluble ultraviolet absorber, it is particularly suitable for application to the skin as a sunscreen or the like.

In this specification, the term "comprising" includes "consisting essentially of" and "consisting of." In addition, the present invention encompasses all arbitrary combinations of the constituent elements described herein.

In addition, the various characteristics (property, structure, function, etc.) described for each of the embodiments of the present invention described above may be combined in any way to specify the subject matter included in the present invention. That is, the invention encompasses all subject matter consisting of any and all possible combinations of the features described herein.

Hereinafter, the embodiments of the present invention will be described more specifically with examples, but the embodiments of the present invention are not limited to the following examples.

[Viscoelasticity measurement]
For each viscous composition, G′ (storage modulus) and G″ (loss modulus) were determined by frequency dispersion using a commercially available viscoelasticity measuring device (rheometer).
Measurement conditions Rheometer: TA Instruments AR-2000ex
Plate: 60 mm, 1° cone plate Measurement temperature: 25°C
Strain: 0.1 to 10% (selected within the range of linear region obtained in strain dispersion measurement at 1 Hz)
Frequency: 0.1rad/s to 100rad/s

[pH measurement]
The pH of the composition was measured using a pH meter at 25°C.

[Viscosity measurement]
The viscosity of each composition was measured at 25° C. using a rotational viscometer manufactured by BrookField (model number: DV1MRVTJ0) at a rotational speed of 20 revolutions per minute. As a guideline, the spindle used for measurement should be rotor No. when the pressure is less than 2,000 mPa·s. 3. Rotor No. in the case of 2,000 mPa·s or more and less than 5,000 mPa·s. 4, 5,000 mPa·s or more and less than 15,000 mPa·s, rotor No. 5, 15,000 mPa·s or more and less than 40,000 mPa·s, rotor No. Rotor No. 6, 40,000 mPa·s or more. 7.

[Preparation and Evaluation of Viscous Composition]
Cellulose Nanocrystals (manufactured by Alberta-Pacific Forest Industries Inc.) was used as crystal nanocellulose. A part of Cellulose Nanocrystals is sodium cellulose sulfate.

As HEC, HEC (CF-Y) (manufactured by Sumitomo Seika Co., Ltd.) was used. This is a crosslinked HEC crosslinked with a crosslinking agent (glyoxal), and the content of the crosslinking agent in HEC (CF-Y) is 0.55% by weight.

In addition, commercially available xanthan gum (echo gum/Keltrol) (manufactured by DSP Gokyo Food & Chemical Co., Ltd.) was purchased and used.
A water-soluble polymer prepared as follows was also used for the study.

<Production Example 1: Preparation of alkyl-modified carboxyl group-containing water-soluble copolymer>
A 500 mL four-necked flask equipped with a stirrer, a thermometer, a nitrogen blowing tube and a condenser was charged with 45 g (0.625 mol) of acrylic acid, Blenmer VMA70 (manufactured by NOF Co., Ltd.: 10 to 20 stearyl methacrylate). 10 to 20 parts by mass of eicosanyl methacrylate, 59 to 80 parts by mass of behenyl methacrylate and 1 part by mass or less of tetracosanyl methacrylate) 1.35 g, pentaerythritol tetraallyl ether 0.02 g, 150 g of normal hexane and 0.081 g (0.00035 mol) of 2,2'-azobismethyl isobutyrate were charged. After the solution was stirred and uniformly mixed, nitrogen gas was blown into the solution in order to remove oxygen present in the upper space of the reaction vessel (four-necked flask), raw materials and solvent. Then, the mixture was kept at 60 to 65° C. under a nitrogen atmosphere and reacted for 4 hours. After completion of the reaction, the resulting slurry was heated to 90° C. to distill off normal hexane, and dried under reduced pressure at 110° C. and 10 mmHg for 8 hours to obtain a water-soluble alkyl-modified carboxyl group-containing white fine powder. 43 g of copolymer were obtained. Hereinafter, this copolymer may be referred to as Production Example 1 polymer.

<Production Example 2: Preparation of carboxyvinyl polymer Na>
A 1000 mL separable flask was equipped with a stirrer, a reflux condenser and a dropping funnel. In this, 48 g of sodium hydroxide was dissolved in 144 g of water. Then, 136.8 g of sucrose was added and stirred at 70 to 85° C. for 120 minutes to obtain an alkaline sucrose aqueous solution. To the resulting alkaline sucrose aqueous solution, 145.2 g of allyl bromide was added dropwise at 70 to 85° C. over 1.5 hours, followed by reaction at 80° C. for 3 hours to allyl etherify the sucrose. After cooling, 440 g of water was added, excess oil was separated with a separating funnel, and a crude sucrose allyl ether aqueous solution was obtained. Hydrochloric acid was added to the resulting crude sucrose allyl ether to adjust the pH to 6 to 8, and water was removed using a rotary evaporator until the mass of the aqueous solution reached 480 g. Next, 200 g of ethanol was added to precipitate salts such as sodium bromide as a by-product, and the precipitate was removed from the aqueous solution by filtration. Further, excess water was removed from the aqueous solution using an evaporator to obtain 166 g of sucrose allyl ether having a degree of etherification of 2.4.

A stirrer, a reflux condenser and a dropping funnel were attached to a 500 mL separable flask. 72 g of acrylic acid and water were put thereinto to prepare 90 g of an 80 mass % acrylic acid aqueous solution. While cooling the acrylic acid aqueous solution, 54 g of a 30% by mass sodium hydroxide aqueous solution was added dropwise to prepare an acrylic acid neutralized aqueous solution having a degree of neutralization of 40%. Then, 0.32 g of sucrose allyl ether obtained above and 0.04 g of 2,2'-azobis(2-methylpropionamidine) dihydrochloride ("V-50" manufactured by Wako Pure Chemical Industries, Ltd.) were added. to prepare an ethylenically unsaturated carboxylic acid monomer aqueous solution.

Separately, put 330 g of n-heptane into a 2000 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, and further sorbitan monostearate ("Nonion SP" manufactured by NOF Corporation). -60R”) was added, which was dispersed and dissolved in n-heptane. Then, the previously prepared ethylenically unsaturated carboxylic acid monomer aqueous solution was added. In order to remove oxygen present in the atmosphere, raw materials and solvent in the reaction vessel, nitrogen gas is blown into the solution to replace the inside of the system with nitrogen, while the bath temperature is maintained at 60 ° C. and the stirring speed is was stirred at 1000 rpm, and the reaction was carried out for 1 hour. After completion of the reaction, water and n-heptane were distilled off to obtain a polymer of acrylic acid and its sodium salt (carboxyvinyl polymer Na). Hereinafter, this polymer may be referred to as Production Example 2 polymer.

Water-insoluble cellulose (crystal nanocellulose: CNC) powder and water-soluble polymer powder are mixed according to the composition shown in Table 1 or Table 2, and the mixed powder is stirred and mixed with ion-exchanged water to form a mixture. A viscous composition was prepared by mixing a water-soluble ultraviolet absorber (phenylbenzimidazole sulfonic acid) with a disper. More specifically, it was prepared as follows.

(1) Method for preparing a 2% by mass aqueous solution of a water-soluble thickener [Examples 1 and 2]
0.5 g of crystal nanocellulose powder and 1.5 g of water-soluble polymer (HEC) powder were mixed, and the mixed powder was dissolved in 98 g of ion-exchanged water with stirring to obtain a 2% by mass viscous composition. prepared. More specifically, the mixture was stirred for 4 hours with a 4-paddle stirring blade at 550 rpm.

[Comparative Examples 1 to 4]
2 g of each water-soluble polymer powder was dissolved in deionized water by stirring and mixing to prepare a 2% by mass aqueous solution. More specifically, Comparative Examples 1 and 4 are 4 hours at 550 rpm with 4-paddle stirring blades, Comparative Example 2 is 1 hour at 550 rpm with 4-paddle stirring blades, and Comparative Example 3 is 1 hour with Disper. Stirred.

However, for Comparative Examples 2 and 3, a 2% aqueous solution was prepared by adding an 18% NaOH aqueous solution after stirring for 1 hour and further stirring to neutralize.

(2) Preparation method of viscous composition Using the obtained 2% by mass aqueous solution, according to the composition in Table 1, the viscous composition of each example and comparative example was prepared. Specifically, 10.5 g of phenylbenzimidazole sulfonic acid was added to deionized water and neutralized with a 30% NaOH aqueous solution to prepare an aqueous phenylbenzimidazole sulfonic acid solution. In another container, 50 g of a 2% aqueous solution of a water-soluble polymer was added to 21.43 g of ion-exchanged water and mixed with stirring. More specifically, the mixture was stirred with a 4-paddle stirring blade at 550 rpm. Next, 28.57 g of a 10.5% phenylbenzimidazole sulfonic acid aqueous solution was added, and the mixture was stirred and mixed again. More specifically, the composition was prepared by stirring with a disper or homomixer at 3000 rpm. In Example 2, the amount of ion-exchanged water and the amount of 10.5% phenylbenzimidazole sulfonic acid aqueous solution used were adjusted so that the phenylbenzimidazole sulfonic acid content in the resulting viscous composition conformed to Table 1.

In Table 1, the unit (%) of the added amount of each component indicates mass%.

A 1% aqueous solution was prepared by diluting the 2% by mass aqueous solution of the water-soluble thickener, and the viscosity of this and the resulting viscous composition was measured. The results are also shown in Table 1. The viscosity of the "single gel physical properties" is the viscosity of a 1% by mass aqueous solution of the water-soluble thickener.

In addition, the viscosity was measured again after the viscous composition was stored at 50°C for one month. The results are also shown in Table 1. The ratio of the viscosity after storage compared to the viscosity before storage is indicated as viscosity retention (%). Also, the absolute value of "100 (%) - viscosity retention rate (%)" is shown as the viscosity change rate (%).

Furthermore, in Table 1, in the entire range of frequencies: 0.1 rad/s to 100 rad/s, when G' is greater than G'', G'>G'', in the entire range of 0.1 rad/s to 100 rad/s When G' is smaller than G'' in the range, it is described as G'<G''. Also, a case where the magnitude relationship of G' and G'' is reversed in the range of 0.1 rad/s to 100 rad/s is described as "having an intersection". In addition, since the viscous composition of Comparative Example 3 caused phase separation, the measurement could not be performed.

Claims (7)

A viscous composition containing a water-soluble cellulose derivative, a water-insoluble cellulose, a water-soluble ultraviolet absorber, and water. The viscous composition according to claim 1, wherein the water-soluble cellulose derivative is hydroxyalkylcellulose. 3. The viscous composition according to claim 1 or 2, wherein the water-insoluble cellulose is nanocellulose. Water-soluble UV absorbers include terephthalylidene dicamphorsulfonic acid, bisbenzoxazolyl derivatives, p-aminobenzoic acid and its derivatives, phenylbenzimidazolesulfonic acid, ferulic acid, salicylic acid, diethanolamine methoxycinnamate (DEA). , benzylidene camphorsulfonic acid, camphor benzalkonium methosulfate, benzophenone-4, benzophenone-5, benzophenone-9, 2,4-dihydroxybenzophenone, and at least one selected from the group consisting of trisbiphenyltriazine, The viscous composition according to claim 1 or 2. 3. The viscous composition according to claim 1, which has a viscosity at 25° C. of 4000 to 15000 mPa·s. The magnitude relationship between the storage elastic modulus G′ and the loss elastic modulus G″ obtained by frequency dispersion measurement is that the storage elastic modulus G′>loss elastic modulus G″ in the entire frequency range of 0.1 rad/s to 100 rad/s. The viscous composition according to claim 1 or 2, which is the water-soluble cellulose derivative is hydroxyethyl cellulose,
the water-insoluble cellulose is a cellulose nanocrystal,
Water-soluble UV absorbers include terephthalylidene dicamphorsulfonic acid, bisbenzoxazolyl derivatives, p-aminobenzoic acid and its derivatives, phenylbenzimidazolesulfonic acid, ferulic acid, salicylic acid, diethanolamine methoxycinnamate (DEA). , benzylidene camphorsulfonic acid, camphor benzalkonium methosulfate, benzophenone-4, benzophenone-5, benzophenone-9, 2,4-dihydroxybenzophenone, and at least one selected from the group consisting of trisbiphenyltriazine,
Viscosity at 25 ° C. is 4000 to 15000 mPa s,
The magnitude relationship between the storage elastic modulus G′ and the loss elastic modulus G″ obtained by frequency dispersion measurement is that the storage elastic modulus G′>loss elastic modulus G″ in the entire frequency range of 0.1 rad/s to 100 rad/s. is
A viscous composition according to claim 1 .