CN101489526B - Hydrogel particle - Google Patents
Hydrogel particle Download PDFInfo
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- CN101489526B CN101489526B CN2007800275799A CN200780027579A CN101489526B CN 101489526 B CN101489526 B CN 101489526B CN 2007800275799 A CN2007800275799 A CN 2007800275799A CN 200780027579 A CN200780027579 A CN 200780027579A CN 101489526 B CN101489526 B CN 101489526B
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- hydrogel particle
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- 239000002245 particle Substances 0.000 title claims abstract description 130
- 239000000017 hydrogel Substances 0.000 title claims abstract description 120
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 239000010954 inorganic particle Substances 0.000 claims abstract description 18
- 239000000499 gel Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000013459 approach Methods 0.000 claims description 16
- 229920001817 Agar Polymers 0.000 claims description 8
- 239000008272 agar Substances 0.000 claims description 8
- 238000002663 nebulization Methods 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 230000005484 gravity Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000003599 detergent Substances 0.000 description 13
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- 239000000203 mixture Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007863 gel particle Substances 0.000 description 6
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- 238000001816 cooling Methods 0.000 description 5
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- 238000007599 discharging Methods 0.000 description 5
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 4
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- 230000000694 effects Effects 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
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- 235000013305 food Nutrition 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
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- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000832 Cutin Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002581 Glucomannan Polymers 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 235000015125 Sterculia urens Nutrition 0.000 description 1
- 240000001058 Sterculia urens Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229940125717 barbiturate Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- KXKPYJOVDUMHGS-OSRGNVMNSA-N chondroitin sulfate Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](OS(O)(=O)=O)[C@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](C(O)=O)O1 KXKPYJOVDUMHGS-OSRGNVMNSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004438 eyesight Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229940046240 glucomannan Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 230000003779 hair growth Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001341 hydroxy propyl starch Substances 0.000 description 1
- 235000013828 hydroxypropyl starch Nutrition 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940078812 myristyl myristate Drugs 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- 239000005017 polysaccharide Substances 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102220114731 rs748073251 Human genes 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- DZKXJUASMGQEMA-UHFFFAOYSA-N tetradecyl tetradecanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCC DZKXJUASMGQEMA-UHFFFAOYSA-N 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 235000010487 tragacanth Nutrition 0.000 description 1
- 239000000196 tragacanth Substances 0.000 description 1
- 229940116362 tragacanth Drugs 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
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- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Landscapes
- Cosmetics (AREA)
- Colloid Chemistry (AREA)
Abstract
Disclosed is a hydrogel particle containing an air bubble, which has a specific gravity of 0.7-1.00 and an average particle diameter of 50-500 mum. Also disclosed is a method for producing such a hydrogel particle. The hydrogel particle may contain a hollow inorganic particle.
Description
Technical field
The present invention relates to be suitable for washing the hydrogel particle of object.
Background technology
In recent years, the various wash type skin detergents (whole body detergent, cleansing milk, massage cream etc.) that are combined with particle (abrasive cleaner (scrub agent)) are sold and are used.Its reason is, except its fresh usability, can also enumerate out following advantage, promptly can and enter into the foul that the common skin detergent of usefulness such as dirt of pore is difficult to remove with unnecessary cutin (dirt) and utilize the physical effect of particle to remove.
Known in addition, consider problems such as the stimulation of skin and pachylosiies, through the size and the hardness of control particle diameter, can obtain the abrasive cleaner (JP-A 2-151693, JP-A9-31492) of high washing performance and low irritant.
But; The detergent that is combined with the abrasive cleaner of having controlled size and hardness exists when massage, to have and the problem of using such as is difficult to take out when being difficult to wash out, enter in the eyes after foreign body sensation, the washing, so the demand of the particle after these problems are able to improve increases.In JP-A 6-57293, disclose a kind of good composition of detergent of washability that washs the back particle, it is the monomeric cross-linking type polymer particles of (methyl) acrylic ester below 1 that this composition of detergent contains proportion.
On the other hand, in JP-A 62-81432, disclose and a kind ofly contained bubble and proportion is lower than 1 water soluble polymer article shaped, wherein put down in writing, when particularly using, can not sink in the water, had special nature as bath foam as bath foam.This molded polymer is through water-soluble high-molecular compound and the aqueous solution that contains bladder regulator are contained bubble, is configured as lamellar etc. then and makes its dry obtaining, and during use, itself can be dissolved in the water (about 40 ℃ hot water).
Summary of the invention
The present invention provides a kind of hydrogel particle, and it contains bubble, and proportion is 0.7～1.00, and mean diameter is 50～500 μ m.
The present invention also provides a kind of manufacturing approach of above-mentioned hydrogel particle, and it comprises: the aqueous solution that will contain gel former and bladder regulator mixes the hydrogel that contains bubble with modulation, carries out particlized then.
The purposes that the present invention also provides a kind of hydrogel particle to process abrasive cleaner, said hydrogel particle are above-mentioned hydrogel particle or the hydrogel particle that is obtained by above-mentioned manufacturing approach.
The specific embodiment
Disclosed particle is hydrophobic cross-linking type polymer particles among the JP-A 6-57293, in water, takes place easily interparticlely to adhere to and condense, so that apparent particle diameter can become is big.
The hydrogel particle that the present invention provides a kind of and has that high washing force and usability are good, can be easily after the washing remove from eyes or skin.
The inventor finds; Contain bubble in the hydrogel through making; Proportion is set for below the proportion of water or tear; And then set the particle that mean diameter is 50～500 μ m for, can obtain having high washing force, usability is good, interparticle in water system adheres to and condense less, wash after the hydrogel particle can be easily removed from eyes or skin.
The inventor finds; Contain the hollow inorganic particle in the hydrogel through making; Proportion is set for below the proportion of water or tear, can obtain having high washing force, usability is good, interparticle in water system adheres to and condense less, wash after the hydrogel particle can be easily removed from eyes or skin.
Hydrogel particle of the present invention is to have excellent physics clean result; And to the washing object the surface for example skin, scalp etc. stimulation and the damage extremely low; Sense of touch during washing is also good, and then the safer hydrogel particle that can easily remove from eyes and skin etc. after the washing.
The present invention relates to a kind of washing force and massage effect that the washing object is had excellence, have the hydrogel particle of extremely good washability with washings or tear.
Hydrogel particle of the present invention has excellent physics washing force, through the proportion of hydrogel particle being set for below the proportion of water or tear, makes extremely well with the washability of washings or tear, can be used in the composition of detergent etc.
Hydrogel particle of the present invention is to contain that bubble and hydrogel, proportion are 0.7～1.00, mean diameter is the hydrogel particle of 50～500 μ m.
" hydrogel " among the present invention is meant; With water is solvent; Utilize cohesion to form the gel that agent is formed by gelation; Gelation be not meant through with ion for example the reaction of potassium ion or calcium ion etc. generate gel, and be meant the situation when being agar as gel former, the thermal reversibility through sol-gel generates gel.
The shape of hydrogel particle of the present invention is not special to be limited, and as preferred shape of particle, can enumerate out spherical or ellipticity.In addition, from giving the viewpoint of cleaning sense, the mean diameter of hydrogel particle of the present invention is more than the 50 μ m, is preferably more than the 60 μ m.In addition, from reducing being blended into the worry the eyes and being difficult for showing sense of discomfort and skin irritant viewpoint, above-mentioned mean diameter is below the 500 μ m, is preferably below the 400 μ m.
In addition; In the present invention; The mean diameter that water-setting gathers particle is to observe particle with low range zoom lens (Keyence manufactured VH-6300 (main body), Keyence manufactured VH-Z05 (CCD camera lens)), and the particle diameter through 10 particles will selecting at random and division ratio are and carry out the proportional meter calculation and obtain.
In addition, remove and be difficult for producing the viewpoint of foreign body sensation during from flushing easily from skin or eyes etc., the proportion of hydrogel particle of the present invention is below 1.00, preferably is lower than 1.00, more preferably below 0.99, is preferably below 0.98 especially.In addition, have the viewpoint of the intensity of appropriate hydrogel particle from making it, above-mentioned proportion is more than 0.7, is preferably more than 0.8, more preferably more than 0.85.
In addition; In the present invention; The proportion of hydrogel particle is to measure in the various ethanol water through at random modulating 25 ℃ ethanol water of chemical brief guide (Japanization association adapts and orders the kind Co., Ltd. of 4 editions II-12 page or leaf balls) record, hydrogel particle being floated over.
Hydrogel particle of the present invention preferably contains the hydrophilic hydrogel particle that the cohesion that is obtained by the natural series macromolecular compound forms agent.Cohesion as being obtained by the natural series macromolecular compound forms agent; For example can enumerate out that agar, gelatin, Radix Acaciae senegalis, Fructus cydoniae oblongae seed phlegmatic temperament, tragacanth, guar gum, karaya, locust bean gum, glucomannan, pectin, galactan, pulullan polysaccharide, xanthan gum, casein, casein potassium salt, casein sodium salt, sodium chondroitin sulfate, starch are semi-synthetic macromolecular compound (for example carboxymethyl starch, methyl hydroxypropyl starch, methyl hydroxymethyl starch etc.), dextrin etc., be preferably agar.Cohesion forms agent and can use a kind of in above-mentioned separately or mix more than two kinds and use, but from obtaining the viewpoint of effect of the present invention, is preferably agar especially, more preferably it is constituted hydrogel particle as main constituent.
In addition, the viewpoint of the sense of touch when using from being applicable to that cosmetics are isochronous, the gel strength of agar is preferably 147kPa (1500g/cm
2) below, 19.6kPa (200g/cm more preferably
2)～127kPa (1300g/cm
2).Gel strength can be tried to achieve with the chilled water system method.Particularly; Make the aqueous solution of 1.5 quality % of gel former; The gel that this aqueous solution was solidified with formation 20 ℃ of held in 15 hours; With chilled water system gel strength determinator (Co., Ltd. log cabin make manufacturing) gel that solidifies is applied load, the every 1cm in the time of can bearing this and loaded for 20 seconds with 20 ℃ of following gels
2The form of the biggest quality of surface area (g) is tried to achieve gel strength.
Consider that from the viewpoint of shape of particle the gelling temperature of hydrogel is preferably more than 30 ℃, more preferably more than 35 ℃.The viewpoint consideration of the dissolved shape of particle when preventing to wash when being coupled to the cosmetics etc., the fusing point of hydrogel is preferably more than 50 ℃, more preferably more than 60 ℃.
The viewpoint consideration of feeling good, prevent the disintegrate of hydrogel particle when washing and when being coupled to the cosmetics etc. when using from being applicable to that cosmetics are isochronous; The content of gel former is preferably 0.1～8.0 quality % in the hydrogel particle of the present invention; 0.3～7.0 quality % more preferably; Further be preferably 0.4～6.0 quality %, be preferably 0.5～5.0 quality % especially.
Hydrogel particle of the present invention contains bubble, contains bubble in order to make hydrogel particle, preferably when making hydrogel particle, uses bladder regulator.As bladder regulator, can use various surfactants, be preferably and be selected from least a in anionic surfactant and the nonionic surfactant.As the anionic surfactant, can enumerate out fatty acid salt, phosphoric acid ester, acylated amino class, sulfosuccinic acids etc.As nonionic surfactant, can enumerate out alkyl saccharide, oxirane add-on type surfactant etc.Above-mentioned surfactant can use a kind of or more than two kinds; But particularly aspect the fineness of the stability of bubble and safety or bubble; Preferred anionic surfacant, more preferably fatty acid salt, phosphoric acid ester, further preferred fat Barbiturates.As fatty acid salt, preferred carbon number is the alkali metal salt of 8～24 fatty acid.
From obtaining the viewpoint that proportion is 0.7～1.00 hydrogel particle, the content of the bladder regulator in the hydrogel particle of the present invention is preferably 0.5～5.0 quality %, more preferably 1.0～5.0 quality %.
Hydrogel particle of the present invention can also contain the spy and open water-soluble organic compounds such as the saccharide put down in writing in the 2000-126586 communique, polyhydric alcohol, water-soluble high-molecular compound, water soluble flavours etc. except that mentioned component.
Hydrogel particle of the present invention can mix the hydrogel that contains bubble with modulation through the aqueous solution that will contain gel former and bladder regulator, carries out particlized then and makes.
Not special qualification of stirring means of containing the aqueous solution of gel former and bladder regulator through known stirring means in the past, can easily make and contain bubble in the hydrogel.For example, with common blender or dispersion machine etc. the aqueous solution that contains gel former and bladder regulator is handled.Through the amount of suitable selection bladder regulator and the treatment conditions of blender or dispersion machine, bubble can be contained so that the proportion of hydrogel reaches below 1.The proportion here is meant the ratio with the density of 4 ℃ distilled water.In addition, about making the temperature when containing bubble in the hydrogel, be can not carry out under the solidified temperature at hydrogel, for example between 60 ℃～100 ℃, carry out, be preferably 70 ℃～90 ℃ especially.
The hydrogel that will contain bubble through known method in the past as described above carries out particlized, can obtain hydrogel particle of the present invention.As the method for particlized, can enumerate out for example common drop method, nebulization etc.
Drop method is following method: the hydrogel that will contain bubble is discharged from the hole; Utilize the hydrogel of discharging to become the character of drop because of its surface tension or interfacial tension; Make this drop cooling curing in gas phases such as air or in the cooling wet goods liquid phase, thereby make hydrogel particle.In addition, from making the viewpoint of the uniform hydrogel particle of particle diameter, preferably the hydrogel of from the hole, discharging is applied vibration.
Nebulization is following method: use spray nozzle, the hydrogel that will contain bubble is ejected into from spray nozzle in the gas phase, utilizes its surface tension to make it form drop simultaneously, and makes this drop cooling curing in gas phase, thereby make hydrogel particle.
In the time of all preferably will discharging under any situation of drop method and nebulization or the temperature of the hydrogel that contains bubble in when spraying be set at more than or equal to gelling temperature but smaller or equal to 100 ℃.In addition, from can easily making the viewpoint of the excellent spherical particle of aesthetic property, the temperature that preferably will contain the hydrogel of bubble is set at more than or equal to (gelling temperature+10 ℃), more preferably is set at more than or equal to (gelling temperature+20 ℃).In addition, the upper limit of this temperature is promptly 100 ℃ of the boiling points of water.On the other hand, the temperature of cooling water gel when carrying out particlized is preferably between 0～30 ℃, to carry out, and more preferably between 0～20 ℃, carries out.
In addition, the distance that falls of the hydrogel particle during cooling is preferably carried out in 1～10m, more preferably in 1～5m, carries out.
Can contain various other compositions according to its purposes in the hydrogel particle of the present invention.Can cooperate for example wetting agent, detergent, spice, pigment, antioxidant, antiseptic etc.In addition, can also cooperate UV absorbent, antibacterial etc.
Hydrogel particle of the present invention can also be widely used for skin detergent, shampoo, scalp detergent, dish washing detergent, contact lenss such as cleansing milk, whole body detergent, solid soap with in detergent, toothpaste, hair growth promoter etc. and the massage agent etc.
Hydrogel particle of the present invention preferably contains the hollow inorganic particle as bubble.Also can be that proportion is the hydrogel particle below 1.00.Describe in the face of this form down.
The hollow inorganic particle that uses among the present invention is the particle that is had the cavity by the center that inorganic substances form.Also can enclose inactive gas etc. in this cavity.
As the hollow inorganic particle that uses among the present invention, be preferably the hydrophilic hollow inorganic particle that the surface has hydrophilic groups such as hydroxyl, silicic acid base, sulfate, ammonium, more preferably the double glazing particle.As the double glazing particle, can enumerate out hollow silicate glasses, hollow pyrex etc.From the viewpoint of safety, the volume average particle size of hollow inorganic particle is preferably below the 50 μ m, more preferably 3～40 μ m.In addition, the volume average particle size of hollow inorganic particle can be tried to achieve with laser diffraction formula particles distribution instrument.
In addition, the proportion of hollow inorganic particle is preferably below 0.95, and more preferably 0.1～0.8.
Among the present invention; The hollow inorganic particle can use commercially available article; As commercially available article, can enumerate out the double glazing particle (trade name: Fuji BalloonH30, H35, H40, S-35, S-40, S-45) of for example Fuji Silysia Chemical Co., Ltd. manufacturing, the Hollow Glass Sphere that Suzuki oils and fats Co., Ltd. makes etc.
The viewpoint of the sensation during from washing, the content of the hollow inorganic particle in the hydrogel particle of the present invention is preferably 0.1～35 quality %, more preferably 0.5～25 quality %.
The shape of hydrogel particle of the present invention is not special to be limited, and can be spherical, ellipticity, amorphous etc. any, but as preferred shape of particle, can enumerate out spherical or ellipticity.In addition, from giving the viewpoint of cleaning sense, the mean diameter of hydrogel particle of the present invention is preferably more than the 50 μ m, more preferably more than the 60 μ m.In addition, from reducing being blended into the worry the eyes and being difficult for showing sense of discomfort and skin irritant viewpoint, above-mentioned mean diameter is preferably below the 500 μ m, more preferably below the 450 μ m, further is preferably below the 400 μ m
From the viewpoint of shape of particle, the gelling temperature of hydrogel is preferably more than 30 ℃, more preferably more than 35 ℃.The viewpoint of the dissolved shape of particle when preventing to wash when being coupled to the cosmetics etc., the fusing point of hydrogel is preferably more than 50 ℃, more preferably more than 60 ℃.
The manufacturing approach of hydrogel particle of the present invention is not special to be limited, and after for example can mixing through the aqueous solution that will contain gel former, adds the hollow inorganic particle and contains the hydrogel of hollow inorganic particle with modulation, and then carry out particlized and make.
Contain not special qualification of stirring means of the aqueous solution of gel former, can be with known blender or dispersion machine etc. mixed in the past.Temperature during relevant mixing is can not carry out under the solidified temperature at hydrogel, for example between 60 ℃～100 ℃, carries out, and is preferably 70 ℃～90 ℃ especially.
The hydrogel that will contain the hollow inorganic particle through known method in the past carries out particlized, can obtain hydrogel particle of the present invention.The method of particlized is not special to be limited, and can enumerate out for example common drop method, nebulization etc.
The hydrogel that contains the hollow inorganic particle can likewise be made through drop method, nebulization with above-mentioned.
In the time of all preferably will discharging under any situation of drop method and nebulization or the temperature of the hydrogel in when spraying be set at more than or equal to gelling temperature but smaller or equal to 100 ℃.In addition, from can easily making the viewpoint of the excellent spherical particle of aesthetic property, in the time of preferably will discharging or the temperature of the hydrogel when spraying be set at more than or equal to (gelling temperature+10 ℃), more preferably be set at more than or equal to (gelling temperature+20 ℃).In addition, the upper limit of this temperature is promptly 100 ℃ of the boiling points of water.On the other hand, the temperature of cooling water gel when carrying out particlized is preferably between 0～30 ℃, to carry out, and more preferably between 0～25 ℃, carries out.In addition, the hydrogel particle during cooling to fall distance same as described above.
Embodiment
Following embodiment describes with regard to enforcement of the present invention.Embodiment is used for illustration the present invention, rather than is used to limit the present invention.
In the following example,, then be meant quality % and mass parts if % does not specialize with part.
Embodiment 1
(she makes the gel former agar powder that weighing 30.0g is processed by the natural series macromolecular compound in 1000mL detachable flask in that food industry; AX-200); Add the 870.0g ion exchange water; Stir on one side at 80～90 ℃ of following heating for dissolving gel formers with anchor agitator on one side; In this solution, add 10% aqueous solution 96.6g of bladder regulator potassium laurate, 10% aqueous solution 3.4g of potassium stearate then, making gross mass is 1000g.
Then, (special machine Co., Ltd. makes trade name: T.K.HomomixerMARK II2.5 type), with 10000r/ minute rotating speed this mixed liquor was stirred 2 minutes, modulation obtains having the hydrogel of bubble to use mulser.
With this hydrogel that has a bubble with 12kg/ hour flow from spray nozzle (Ikeuchi Co., Ltd. system hollow cone nozzle; K-008) in; Height at 3.4m is sprayed in 25 ℃ gas phase, will in gas phase, reclaim by settled particle, obtains hydrogel particle thus.The mean diameter of the hydrogel particle that obtains is 234 μ m, and proportion is 0.96.
Embodiment 2～4
Except the kind of such change bladder regulator as shown in table 1, obtain hydrogel particle with the modulator approach shown in the embodiment 1.
Comparative example 1
Except the kind of change bladder regulator with the amount, obtain hydrogel particle with the modulator approach shown in the embodiment 1.
Comparative example 2
Except not adding the bladder regulator, obtain hydrogel particle with the modulator approach shown in the embodiment 1.
Measure the mean diameter and the particle proportion of the hydrogel particle that obtains in embodiment 1～4 and the comparative example 1～2 with above-mentioned method.In addition, washing performance and washability are estimated with following method.Their result is shown in table 1.
< assessment method of washing performance >
(1) modulation of cleaning mixture
Make the hydrogel particle that obtains in potassium laurate (with the pure pharmaceutical worker of light industry) 10%, embodiment 1～4 or the comparative example 1～2 each 20%, ion exchange water 70% at room temperature dissolves equably and disperse.
(2) washing performance evaluation
Modulation is dispersed with the sooty model sebum of forming shown in following, its 20mg is coated in the circle of the Φ 25mm on the artificial leather, on this coated portion, drips the above-mentioned cleaning mixture of 200mg, carries out 20 massage washings, with tap water flushing and air-dry.
The model sebum is formed
(model sebum)
9.0 parts of squalanes (Wako Pure Chemical Industries, Ltd.'s manufacturing)
Myristyl myristate
(trade name: Exepearl MY-M, Kao Corp's manufacturing) 24.0 parts
47.0 parts of Oleum Gossypii semens (Kanto Kagaku K. K.'s manufacturing)
2.0 parts in cholesterol (Wako Pure Chemical Industries, Ltd.'s manufacturing)
2.0 parts of cholesterol cetylates (Tokyo HuaCheng Industry Co., Ltd's manufacturing)
0.2 part of lauric acid (trade name: LUNAC L-98, Kao Corp's manufacturing)
2.5 parts of myristic acids (trade name: LUNAC MY-98, Kao Corp's manufacturing)
6.0 parts of Palmic acids (trade name: LUNAC P-95, Kao Corp's manufacturing)
0.9 part of stearic acid (trade name: LUNAC S-98, Kao Corp's manufacturing)
6.4 parts of oleic acid (Wako Pure Chemical Industries, Ltd.'s manufacturing)
Add up to 100 parts
(label)
5 parts of white carbon blacks (Mitsubishi chemical Co., Ltd's manufacturing)
Use color colour difference meter CR-200 (Minolta manufacturings) to measure the colourity (Lab) of arm in each moment of (model sebum coating back) and washing back before (before the coating of model sebum) before the processing in the above-mentioned washing process, the washing (flushing with air-dry after); With the colourity before handling as reference value, through colour difference meter measure and show before the washing with washing after each aberration.
Then by before handling with washing before aberration and handle before with washing after aberration; Calculate the washing rate of model sebum according to following formula; Use washing rate to be set at 1 o'clock relative value, estimate according to following benchmark with 10% aqueous solution (anhydrous gel particle) of potassium laurate.
Washing rate (%)=(1-(aberration before the aberration/washing after the washing)) * 100
The metewand of washing performance
*: the washing rate during washing rate＜anhydrous gel particle
△: the washing rate≤washing rate during the anhydrous gel particle＜[washing rate * 1.1 during the anhydrous gel particle]
Zero: [washing rate * 1.1 during the anhydrous gel particle]≤washing rate
< assessment method of washability >
On the black artificial leather, leave standstill 0.1g and be adjusted to the hydrogel particle aqueous solution of 20% aqueous solution.After above-mentioned black artificial leather tilted to 10 °, with the ion exchange water of suction pipe drippage 2g.Observe the state of drippage with the stero microscope (SM2-2T) of Nikon manufactured, the quantity of dripping the hydrogel particle that (about 1cm) is remaining in 10 seconds rearward visions is counted, according to following benchmark judgement washability.
*: the hydrogel particle in the visual field more than visible 10
△: visible 1～9 hydrogel particle in the visual field
Zero: water breakthrough gel particles not in the visual field
Table 1
* 1MAP-115K: have 30% aqueous solution of single alkyl phosphonic acid potassium salt that alkyl consists of the alkyl chain length of C11/C13/C15=48/31/21 (mass ratio)
* 2 quality % with respect to the hydrogel particle total amount
Embodiment 5
(she makes the gel former agar powder that weighing 30.0g is processed by the natural series macromolecular compound in 1000mL detachable flask in that food industry; UM-11KS); Add the 940.0g ion exchange water, with anchor agitator stir on one side at 80～90 ℃ following heating for dissolving gel formers on one side.In this solution, add 30.0g double glazing particle (the FujiBalloon H30 that Fuji Silysia Chemical Co., Ltd. makes then; Volume average particle size is that 40 μ m, true specific gravity are 0.30 spherical hollow pyrex particle), making gross mass is 1000g.
With this hydrogel that contains the double glazing particle with 12kg/ hour flow from spray nozzle (the empty circular cone nozzle of Ikeuchi Co., Ltd. system, K-008); Height at 3.4m is sprayed in 25 ℃ gas phase; To in gas phase, reclaim by settled particle, obtain hydrogel particle thus.The mean diameter of the hydrogel particle that obtains is 320 μ m, and proportion is 0.94.
Embodiment 6
Except using Hollow Glass Sphere (volume average particle size is that 10 μ m, proportion are 0.2) that 30.0g Suzuki oils and fats Co., Ltd. makes as the double glazing particle, with and embodiment 5 same modulator approaches obtain hydrogel particle.
Comparative example 3
Except the bead (volume average particle size is that 8.5 μ m, proportion are 1.1) that uses 30.0g Fuji Silysia Chemical Co., Ltd. to make replaces the double glazing particle, usefulness and embodiment 5 same modulator approaches obtain hydrogel particle.
Comparative example 4
Except using 30.0g crosslinked polypropylene acid metal salt particle (Kao Corp makes, trade name: Polymer SK, volume average particle size is 100 μ m) to replace beyond the double glazing particle, with and embodiment 5 same modulator approaches obtain hydrogel particle.
Measure the mean diameter and the proportion of the hydrogel particle that obtains in embodiment 5～6 and the comparative example 3～4 with above-mentioned method.In addition, estimate washing performance and washability with following method.Their result is shown in Table 2.
Table 2
* 1 quality % with respect to the hydrogel particle total amount
Claims (6)
1. the manufacturing approach of a hydrogel particle; Said hydrogel particle contains bubble; Proportion is 0.7～1.00; Mean diameter is 50～500 μ m, and said manufacturing approach comprises following operation: the aqueous solution that will contain gel former and bladder regulator mixes the hydrogel that contains bubble with modulation, after the aqueous solution that perhaps will contain gel former mixes; Add the hollow inorganic particle and contain the hydrogel of hollow inorganic particle as bubble with modulation; Then said hydrogel is carried out particlized through drop method or nebulization, wherein said gel former is an agar, and said bladder regulator is to be selected from least a in anionic surfactant and the nonionic surfactant; The content of gel former described in the said hydrogel particle is 0.1～8.0 quality %, and the content of bladder regulator described in the said hydrogel particle is 0.5～5.0 quality %.
2. the manufacturing approach of hydrogel particle according to claim 1, wherein, the hollow inorganic particle is the double glazing particle.
3. the manufacturing approach of hydrogel particle according to claim 1 and 2, wherein, the gelling temperature of hydrogel is more than 30 ℃.
4. the manufacturing approach of hydrogel particle according to claim 1 and 2, wherein, said hydrogel particle is spherical or ellipticity.
5. abrasive cleaner, it comprises the hydrogel particle that obtains through each described manufacturing approach in the claim 1～4.
6. a hydrogel particle is as the purposes of abrasive cleaner, wherein, and the hydrogel particle of said hydrogel particle for obtaining through each described manufacturing approach in the claim 1～4.
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| Application Number | Priority Date | Filing Date | Title |
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| JP198288/2006 | 2006-07-20 | ||
| JP2006198288A JP5154037B2 (en) | 2006-07-20 | 2006-07-20 | Hydrogel particles |
| JP2006270855A JP5154049B2 (en) | 2006-10-02 | 2006-10-02 | Hydrogel particles |
| JP270855/2006 | 2006-10-02 | ||
| PCT/JP2007/063194 WO2008010402A1 (en) | 2006-07-20 | 2007-06-26 | Hydrogel particle |
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| GB2492138B (en) | 2011-06-23 | 2016-07-06 | Cosmetic Warriors Ltd | Solid cosmetic composition with dispersed gas bubbles |
| JP2013079300A (en) * | 2011-10-03 | 2013-05-02 | User Kk | Aqueous gel composition containing bubbles |
| GB2508825B (en) | 2012-12-11 | 2018-04-04 | Cosmetic Warriors Ltd | Composition |
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| JP2000226322A (en) * | 1999-02-03 | 2000-08-15 | Ichimaru Pharcos Co Ltd | Agar or sodium alginate granule-containing cosmetic composition |
| JP2004075762A (en) * | 2002-08-13 | 2004-03-11 | Kuraray Co Ltd | Method for producing polyvinyl alcohol-based hydrogel |
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| JPS6281432A (en) * | 1985-10-04 | 1987-04-14 | Shiseido Co Ltd | Water-soluble high-molecular molding |
| JPH0633415B2 (en) * | 1988-12-02 | 1994-05-02 | 花王株式会社 | Skin cleanser composition |
| JPH0657293A (en) * | 1992-08-07 | 1994-03-01 | Kao Corp | Detergent composition |
| JPH06239733A (en) * | 1993-02-16 | 1994-08-30 | Kanebo Ltd | Facial cleansing agent |
| JPH06321728A (en) * | 1993-05-07 | 1994-11-22 | Noevir Co Ltd | Scrubbing cosmetic |
| JP2000159628A (en) * | 1998-11-27 | 2000-06-13 | Ichimaru Pharcos Co Ltd | Granule-formulated cosmetic composition |
| JP3932473B2 (en) * | 1999-06-02 | 2007-06-20 | 清水化学株式会社 | Production method and use of water-insoluble glucomannan gel particles |
| JP2001131054A (en) * | 1999-10-29 | 2001-05-15 | Nishikawa Rubber Co Ltd | Scrubbing agent and its production |
| JP3775784B2 (en) * | 2002-03-14 | 2006-05-17 | 花王株式会社 | Liquid cosmetics |
| JP3857182B2 (en) * | 2002-05-24 | 2006-12-13 | 株式会社ファンケル | Skin cleansing composition |
| JP4457303B2 (en) * | 2004-12-14 | 2010-04-28 | 清水化学株式会社 | Method for producing glucomannan gel particles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000226322A (en) * | 1999-02-03 | 2000-08-15 | Ichimaru Pharcos Co Ltd | Agar or sodium alginate granule-containing cosmetic composition |
| JP2004075762A (en) * | 2002-08-13 | 2004-03-11 | Kuraray Co Ltd | Method for producing polyvinyl alcohol-based hydrogel |
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