Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/02—Cellulose; Modified cellulose
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/08—Cellulose derivatives

Definitions

• 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.
• viscous compositions are sometimes mixed with UV absorbers (especially water-soluble UV absorbers) and used as sunscreens.
• UV absorbers especially water-soluble UV absorbers
• 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.
• 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).
• 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.
• 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.
• 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).
• 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.
• 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.
• 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”.
• water-soluble means exhibiting a solubility of 0.1% by mass or more in water at 25°C.
• 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.
• 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.
• Non-cross-linked HEC hydroxyethyl cellulose not cross-linked with a cross-linking agent
• cross-linked HEC hydroxyethyl cellulose cross-linked with a cross-linking agent
• Cross-linked 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.
• polyvalent aziridine compounds such as diethylene urea
• polyvalent isocyanate compounds such as tolylene diisocyanate and hexamethylene diisocyanate.
• 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.
• 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.
• 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 ⁇ 12
• HEC (including non-crosslinked HEC and crosslinked HEC) preferably has a molecular weight of about 1,800,000 to 4,300,000. ⁇ 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.
• the said molecular weight is a weight average molecular weight calculated
• GPC gel permeation chromatography
• 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.
• GPC gel permeation chromatography
• 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.
• water-insoluble means something that is not “water-soluble”.
• cellulose crystalline cellulose and nanocellulose are preferable, and nanocellulose is more preferable.
• nanocelluloses cellulose nanocrystals (CNC) are preferred.
• cellulose nanocrystals are a type of nanocellulose.
• cellulose nanofibers (CNF) and cellulose nanocrystals (CNC) are examples of nanocellulose made from wood or the like.
• CNF cellulose nanofibers
• CNC cellulose nanocrystals
• nanocellulose with a length of approximately 5-10 ⁇ m or more is often referred to as cellulose nanofibers (CNF)
• CNC cellulose nanocrystals
• 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 ⁇ -1,4-glycosidic bonds. Cellulose is formed into linear chains by ⁇ -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.
• 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.
• nanocellulose is rod-shaped fibrils with a length/diameter ratio of approximately 20-200.
• 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 ( ⁇ m) 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.
• the cellulose nanocrystals 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).
• 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.
• cellulose nanocrystal indicates nano-sized cellulose crystals
• the cellulose may be unmodified or modified.
• modified cellulose include cellulose sulfate (especially sodium cellulose sulfate), as described above.
• 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,
• 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.
• 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,
• UV-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.
• 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.
• 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.
• 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.
• 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.
• the compositions of the present invention preferably have a loss tangent (tan ⁇ ) of less than 1 (ie, tan ⁇ 1).
• the loss tangent (tan ⁇ ) 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.
• the loss tangent is used as an index of sol and gel, and usually tan ⁇ >1 is sol and tan ⁇ 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''.
• 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.
• 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.
• 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, 11
• 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.
• 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.
• 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.
• 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.
• 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.
• 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%.
• 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.
• 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.
• polyhydric alcohols examples include dihydric or trihydric alcohols and sugar alcohols.
• Alditols thritol, tetritol, pentitol, hexitol
• 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.
• 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.
• 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%.
• 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.
• 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.
• 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.
• 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.
• Cellulose Nanocrystals manufactured by Alberta-Pacific Forest Industries Inc. was used as crystal nanocellulose.
• a part of Cellulose Nanocrystals is sodium cellulose sulfate.
• 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.
• xanthan gum echo gum/Keltrol
• DSP Gokyo Food & Chemical Co., Ltd. DSP Gokyo Food & Chemical Co., Ltd.
• 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.
• 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%.
• 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.
• n-heptane 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.
• 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.
• Example 1 (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.
• HEC water-soluble polymer
• 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.
• 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.
• 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.

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• 2022
  • 2022-07-29 JP JP2023540310A patent/JPWO2023013535A1/ja active Pending
  • 2022-07-29 WO PCT/JP2022/029242 patent/WO2023013535A1/ja not_active Ceased

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