CN115322844A - Biological enzyme capsule and preparation method thereof - Google Patents

Biological enzyme capsule and preparation method thereof Download PDF

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Publication number
CN115322844A
CN115322844A CN202211024705.8A CN202211024705A CN115322844A CN 115322844 A CN115322844 A CN 115322844A CN 202211024705 A CN202211024705 A CN 202211024705A CN 115322844 A CN115322844 A CN 115322844A
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capsule
hydrogel
enzyme
biological enzyme
biological
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Inventor
赵顺祥
陈文福
宗蔚
丁泳锋
李林
沈兵兵
张利萍
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Guangzhou Liby Enterprise Group Co Ltd
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Guangzhou Liby Enterprise Group Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672Granulated or coated enzymes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • B01J13/04Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B01J13/046Making microcapsules or microballoons by physical processes, e.g. drying, spraying combined with gelification or coagulation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)

Abstract

The invention belongs to the technical field of daily chemical products, and discloses a biological enzyme capsule and a preparation method thereof. The biological enzyme capsule is a core-shell structure hydrogel capsule, the wall material of the hydrogel capsule comprises gel materials and water-soluble film-forming materials, and the capsule core material comprises a biological enzyme preparation and polyhydric alcohol. The preparation method comprises the following steps: fully dissolving the capsule wall material in water at 70-80 ℃, and uniformly mixing the biological enzyme of the capsule core material and the polyalcohol; preparing hydrogel capsules by using a dripping method, wherein a uniformly stirred capsule wall material solution flows out of a dripper, a capsule core material flows out of the dripper to form a sandwiched liquid column, then the liquid column is cut off by a cutter to form a series of liquid drops with a certain diameter, a calcium chloride aqueous solution is dripped into the liquid drops to be solidified into hydrogel, and the hydrogel capsules wrapping biological enzymes are obtained after filtration and dehydration. According to the invention, biological enzyme is embedded in the capsule core, so that good enzyme activity stability can be maintained.

Description

Biological enzyme capsule and preparation method thereof
Technical Field
The invention belongs to the technical field of daily chemical products, and particularly relates to a biological enzyme capsule and a preparation method thereof.
Background
The biological enzyme is a high-activity biological catalyst, has high catalytic efficiency and strong specificity. Such as protease, which can rapidly decompose protein dirt; lipase, which can rapidly remove greasy dirt; amylase, which can remove starch dirt; the cellulase can remove the small hair bulbs of the fabric and smoothen clothes. Due to its highly effective decontamination, many enzyme preparations are widely used in washing products such as washing powders, laundry soaps, and laundry detergents.
In recent years, with the increasing sales of laundry detergents, the problem of enzyme activity stability in the laundry detergents is a difficult problem for engineers to research and improve. Because the laundry detergent is a water phase system, the biological enzyme is protein, except part of the biological enzyme can be subjected to self digestion in the water phase, and the stability of the biological enzyme is also influenced by factors such as a surfactant, a pH value and the like in the laundry detergent.
At present, the enzyme activity stability of biological enzymes in laundry detergents is mainly protected by four ways, one way is to modify the biological enzymes, for example, the CN201810286656.2 patent discloses a starch-based dextrin modified casein polypeptide conjugate, a preparation method and an application thereof, wherein the preparation method is to perform covalent grafting reaction on casein polypeptide and starch-based dextrin, and an oil-in-water type starch-based dextrin modified protein polypeptide nano emulsion is obtained by adopting a high-pressure homogenization technology. The nano emulsion has better antioxidant activity, antibacterial property and the like. The second method is to wrap the silk nano-beads with enzyme, for example, the patent CN201710046253.6 discloses a method for preparing enzyme-wrapped silk nano-beads, which first prepares a silk solution, and then wraps the enzyme into the silk to form the enzyme-wrapped silk nano-beads. The silk nano-spheres prepared by the method can effectively protect the activity of the encapsulated enzyme, realize the series reaction of multiple enzymes and have good biocompatibility. The two ways of protecting the biological enzyme have complex preparation methods and higher cost. The third mode is to achieve the effect of stabilizing the enzyme by adding an enzyme stabilizer, for example, CN201110005054.3 discloses a laundry detergent and a preparation method thereof, the stability of the enzyme activity of a laundry detergent system is improved by adding propylene glycol, sodium borate, calcium chloride and the like, and the stability of the enzyme can be improved to a certain extent by the mode, but because the type of a surfactant has a large influence on the stability of the enzyme, when the contents of sulfonic acid and fatty acid in the laundry detergent system are high, the enzyme activity cannot be stabilized by adding a stabilizer, so that the mode of adding the enzyme stabilizer has no universality. The fourth way is by polymer encapsulation, for example, CN 108949372A discloses a way of encapsulating biological enzyme with pH sensitive polymer, where the polymer expands in the range of pH 7-7.5 to release the encapsulated enzyme, and the polymer contracts in the range of pH 8-10 to immobilize the enzyme in the polymer segment, but many of the currently claimed mild laundry detergents have pH around 7, and this encapsulation is not suitable.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a biological enzyme capsule. The biological enzyme capsule can solve the problem that the enzyme activity of the existing laundry detergent enzyme preparation is reduced due to the influence of factors such as moisture, pH value, surfactant and the like in the laundry detergent.
Another object of the present invention is to provide a method for preparing the above-mentioned bio-enzyme capsule.
The purpose of the invention is realized by the following technical scheme:
a biological enzyme capsule is a core-shell structure hydrogel capsule, wherein the capsule wall material of the hydrogel capsule comprises a gel material and a water-soluble film-forming material, and the capsule core material is a biological enzyme preparation and polyhydric alcohol.
Further, the gel material is at least one of acacia, aloe gel, hyaluronic acid, sodium alginate, agar, dextran and cyclodextrin.
Further, the water-soluble film forming material is at least one of carboxymethyl cellulose, methyl cellulose, chitosan, hydroxypropyl methyl cellulose, ethyl cellulose, carboxypropyl cellulose, polyvinyl alcohol and polyvinylpyrrolidone.
Further preferably, the gel material is agar and sodium alginate, and the water-soluble film-forming material is polyvinyl alcohol, wherein the weight ratio of the agar, the sodium alginate and the polyvinyl alcohol in the capsule wall is (10-20): (45-60): (15-25). The hydrogel with a triple interpenetrating network structure is constructed by agar, sodium alginate and polyvinyl alcohol in a proper proportion, has proper mechanical strength, and has small volume change under the physical and chemical stimulation conditions of different temperatures, pH values, ionic strengths, solvent components and the like, thereby effectively protecting the stability of the capsule core material.
Further, the biological enzyme preparation is any one of protease, amylase, lipase, cellulase, lysozyme, pectinase and mannanase; the polyalcohol is at least one of glycerol, propylene glycol, sorbitol, maltitol and mannitol, and is preferably propylene glycol.
Further preferably, the mass ratio of the biological enzyme preparation to the polyhydric alcohol is 3 to 1, the biological enzyme preparation can be more stable in the presence of the polyhydric alcohol, and the hydrogel capsule can be fuller and is not easy to shrink.
Further preferably, the mass fraction of the biological enzyme preparation in the biological enzyme hydrogel capsule is 15-25%, and the crushing pressure of the hydrogel capsule is 0.5-1.0N.
Furthermore, the hydrogel capsule is in a shape of a bead, and the diameter of the hydrogel capsule is 1-10 mm.
The preparation method of the biological enzyme capsule comprises the following steps:
fully dissolving the capsule wall material in water at 70-80 ℃ to ensure that the concentration of the capsule wall material is 15-20 wt%, then cooling to 30-40 ℃, and uniformly mixing the core material biological enzyme and the polyhydric alcohol; preparing hydrogel capsules by a dripping method, wherein uniformly stirred capsule wall material solution flows out of a dripper, capsule core material flows out of the dripper to form a sandwiched liquid column, then the liquid column is cut off by a cutter to form a series of liquid drops with certain diameters, calcium chloride aqueous solution is dripped into the liquid drops to be solidified into hydrogel, and the hydrogel capsules wrapping biological enzymes are obtained after filtration and dehydration. If a plurality of biological enzyme capsules need to be prepared, the various biological enzymes are wrapped one by one according to the steps.
Further, the concentration of the calcium chloride aqueous solution is 1-2 wt%.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the biological enzyme is embedded in the capsule core, so that the biological enzyme is prevented from being interfered by factors such as moisture, pH value, surfactant and the like in the laundry detergent, and even if various types of biological enzyme capsules are added into the laundry detergent, various types of biological enzyme can still keep good enzyme activity stability; when the laundry detergent is used, the bio-enzyme capsule is easily broken under the action of the suction force of the pump head, and the bio-enzyme in the capsule core can be effectively released, so that the fabric washing effect is enhanced.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
In the following examples, the following abbreviations will be used and have the indicated functions.
And (3) LAS: C10-C13 linear alkyl benzene sulfonic acid and anionic surfactant.
AES: ethoxylated fatty alcohol sulfate, fatty alcohol with C12-C14 carbon number and average ethoxylation degree of 2, and anionic surfactant.
AEO9: ethoxylated fatty alcohol, average degree of ethoxylation 9, nonionic surfactant.
TO 5: ethoxylated isomeric tridecanol, average degree of ethoxylation 5, nonionic surfactant.
Acrylic copolymer: the monomer composition comprises: (a) acrylic acid; (b) An aminoalkyl methacrylate selected from the following structures:
Figure BDA0003815114580000041
wherein R1 is a C3-C5 linear alkylene group, and R2 and R3 are C1-C2 alkyl groups.
The BIT:1, 2-benzisothiazolin-3-one and preservative.
MIT: 2-methylisothiazoline-3-one and a preservative.
CMIT: 5-chloro-2-methylisothiazoline-3-one and a preservative.
Example 1
(1) Dissolving 10g of agar, 45g of sodium alginate and 15g of polyvinyl alcohol in 400g of water at 70 ℃ to form a capsule wall solution, and cooling to 40 ℃ for later use.
(2) Uniformly mixing 100g of protease solution and 34g of propylene glycol for later use;
(3) Preparing a hydrogel capsule by using a dripping method, enabling a capsule wall material solution to flow out of a dripping head, enabling a capsule core material to flow out of the dripping head to form a sandwiched liquid column, cutting off the liquid column by using a cutter to form a series of liquid drops with the diameter of 5-6mm, dripping the liquid drops into a calcium chloride aqueous solution (with the concentration of 1.0 wt%) to be solidified into hydrogel, and filtering to remove water to obtain the protease capsule 1.
The amylase capsule 1, the fatty acid capsule 1 and the cellulase capsule 1 are respectively prepared under the conditions.
Example 2
(1) Dissolving 20g of agar, 60g of sodium alginate and 15g of polyvinyl alcohol in 400g of water at 70 ℃ to form a capsule wall solution, and cooling to 40 ℃ for later use.
(2) Uniformly mixing 150g of amylase solution and 38g of propylene glycol for later use;
(3) Preparing a hydrogel capsule by using a dripping method, wherein a capsule wall material solution flows out of a dripping head, a capsule core material flows out of the dripping head to form a sandwiched liquid column, then the liquid column is cut off by a cutter to form a series of liquid drops with the diameter of 5-6mm, the liquid drops are dripped into a calcium chloride aqueous solution (with the concentration of 1.0 wt%) to be solidified into hydrogel, and the amylase capsule 2 is obtained after filtering and dewatering.
The protease capsule 2, the lipase capsule 2 and the cellulase capsule 2 were prepared under the above conditions, respectively.
Example 3
(1) Dissolving 20g of agar, 45g of sodium alginate and 25g of polyvinyl alcohol in 400g of water at 80 ℃ to form a capsule wall solution, and cooling to 35 ℃ for later use.
(2) 160g of lipase solution and 32g of propylene glycol are uniformly mixed for later use;
(3) Preparing a hydrogel capsule by using a dripping method, wherein a capsule wall material solution flows out of a dripping head, a capsule core material flows out of the dripping head to form a sandwiched liquid column, then the liquid column is cut off by a cutter to form a series of liquid drops with the diameter of 8-9mm, the liquid drops are dripped into a calcium chloride aqueous solution (with the concentration of 1.0 wt%) to be solidified into hydrogel, and the lipase capsule 3 is obtained after filtering and dewatering.
The protease capsule 3, the amylase capsule 3 and the cellulase capsule 3 are respectively prepared under the conditions.
Example 4
(1) Dissolving 15g of agar, 50g of sodium alginate and 20g of polyvinyl alcohol in 400g of water at 80 ℃ to form a capsule wall solution, and cooling to 35 ℃ for later use.
(2) Uniformly mixing 150g of cellulase solution and 30g of propylene glycol for later use;
(3) Preparing a hydrogel capsule by using a dripping method, enabling a capsule wall material solution to flow out of a dripping head, enabling a capsule core material to flow out of the dripping head to form a sandwiched liquid column, cutting off the liquid column by using a cutter to form a series of liquid drops with the diameter of 5-6mm, dripping the liquid drops into a calcium chloride aqueous solution (with the concentration of 1.0 wt%) to be solidified into hydrogel, and filtering to remove water to obtain the cellulase capsule 4.
The protease capsule 4, the amylase capsule 4 and the lipase capsule 4 are respectively prepared under the conditions.
Example 5
(1) Dissolving 15g of agar, 60g of sodium alginate and 20g of polyvinyl alcohol in 500g of water at 75 ℃ to form a capsule wall solution, and cooling to 30 ℃ for later use.
(2) Uniformly mixing 120g of pectinase solution and 30g of propylene glycol for later use;
(3) Preparing a hydrogel capsule by using a dripping method, wherein a capsule wall material solution flows out of a dripper, a capsule core material flows out of the dripper to form a sandwiched liquid column, the liquid column is cut off by a cutter to form a series of liquid drops with the diameter of 3-4mm, the liquid drops are dripped into a calcium chloride aqueous solution (the concentration is 1.0 wt%) to be solidified into hydrogel, and the pectinase capsule 1 is obtained after filtration and dehydration.
The protease capsule 5 and the cellulase capsule 5 were prepared under the above conditions, respectively.
Example 6
(1) Dissolving 10g of agar, 50g of sodium alginate and 25g of carboxymethyl cellulose in 400g of water at 75 ℃ to form a capsule wall solution, and cooling to 30 ℃ for later use.
(2) Uniformly mixing 100g of mannase solution and 34g of propylene glycol for later use;
(3) Preparing a hydrogel capsule by using a dropping method, wherein a capsule wall material solution flows out of a dropping head, a capsule core material flows out of the interior of the dropping head to form a sandwiched liquid column, then a cutter is used for cutting off the liquid column to form a series of liquid drops with the diameter of 3-4mm, the liquid drops are dropped into a calcium chloride aqueous solution (with the concentration of 1.0 wt%) to be solidified into hydrogel, and the mannase capsule 1 is obtained after filtration and dehydration.
Comparative example 1
This comparative example is a method of making a biocellulose-coated enzyme granulate, comprising the steps of:
mechanically compressing and dehydrating the biological cellulose gel film obtained by fermentation to about 25% of water content, preparing protease into 4wt% of enzyme solution, soaking the dehydrated biological cellulose gel film in the enzyme solution for 48 hours, taking out the biological cellulose gel film, and dehydrating to about 70% of water content. Cutting the biological cellulose gel film into 1mm 3 The biological cellulose coated protease particle 1 is obtained.
Preparing lipase granule 1, cellulase granule 1, amylase granule 1, pectinase granule 1 and mannanase granule 1 under the above conditions.
The enzyme capsules and enzyme granules obtained in the above examples and comparative examples are applied in laundry detergent:
adding protease capsules 1-5, amylase capsules 1-4, lipase capsules 1-4, cellulase capsules 1-5, pectinase capsules 1, mannanase capsules 1 corresponding to examples 1-6 and various enzyme granules and liquid enzyme preparations added with enzyme activity stabilizers in comparative example 1 into different laundry detergent systems to prepare enzyme-added laundry detergents for performance investigation and test, wherein the compositions of the enzyme-added laundry detergents are shown in table 1.
TABLE 1 compositions of ingredients of examples 7-14, comparative examples 2-5 enzyme-added laundry detergents
Figure BDA0003815114580000071
Figure BDA0003815114580000081
And (3) testing the enzyme activity stability of the laundry detergent, wherein the test method comprises the following steps: samples of examples 7-14 and comparative examples 2-5 were added with the enzyme laundry detergent and placed at (37 + -1) deg.C for 4 weeks and 8 weeks; returning to room temperature (25 +/-5) deg.C, and detecting enzyme activity retention rate according to the method specified in determination method of biological enzyme activity in detergent (detection standard of Chaibao). The results are shown in tables 2 and 3 below.
TABLE 2 enzyme activity retention rates of 4 weeks for examples 7-14 and comparative examples 2-5 enzyme-added laundry detergent samples
Figure BDA0003815114580000082
Figure BDA0003815114580000091
TABLE 3 enzyme activity retentions at 8 weeks for examples 7-14 and comparative examples 2-5 of enzyme-added laundry detergent samples
Figure BDA0003815114580000092
As can be seen from tables 2 and 3, in comparative examples 2 to 5, when the liquid enzyme preparation is added with the enzyme particles coated with the biological cellulose or the enzyme activity stabilizer, the activity of each enzyme is reduced rapidly after the laundry detergent sample is placed at 37 ℃ for 4 weeks and 8 weeks, while the coated type biological enzyme capsules of examples 7 to 14 have relatively stable and slow activity of the enzyme under the same test conditions, and the activity of each enzyme in the test time of 4 weeks and 8 weeks is obviously better than that of the comparative examples in the same period.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (9)

1. The biological enzyme capsule is characterized in that the biological enzyme capsule is a core-shell structure hydrogel capsule, the wall material of the hydrogel capsule comprises a gel material and a water-soluble film-forming material, and the core material is a biological enzyme preparation and polyhydric alcohol.
2. The bio-enzyme capsule according to claim 1, wherein the gel material is at least one of acacia, aloe gel, hyaluronic acid, sodium alginate, agar, dextran, and cyclodextrin.
3. The bioenzyme capsule according to claim 1, wherein the water-soluble film-forming material is at least one of carboxymethyl cellulose, methyl cellulose, chitosan, hydroxypropyl methyl cellulose, ethyl cellulose, carboxypropyl cellulose, polyvinyl alcohol and polyvinylpyrrolidone.
4. The biological enzyme capsule according to claim 2 or 3, wherein the gel material is agar and sodium alginate, and the water-soluble film-forming material is polyvinyl alcohol, wherein the weight ratio of the agar, the sodium alginate and the polyvinyl alcohol in the capsule wall is (10-20) to (45-60) to (15-25).
5. The bioenzyme capsule according to claim 1, wherein the bioenzyme preparation is any one of protease, amylase, lipase, cellulase, lysozyme, pectinase and mannanase; the polyalcohol is at least one of glycerol, propylene glycol, sorbitol, maltitol and mannitol, and is preferably propylene glycol.
6. The bioenzyme capsule according to claim 5, wherein the mass ratio of the bioenzyme preparation to the polyol is 3; the mass fraction of the biological enzyme preparation in the biological enzyme hydrogel capsule is 15-25%, and the crushing pressure of the hydrogel capsule is 0.5-1.0N.
7. The bioenzyme capsule according to claim 1, wherein the hydrogel capsule is in the shape of a bead with a diameter of 1 to 10mm.
8. The method for preparing a bio-enzyme capsule according to any one of claims 1 to 7, comprising the steps of:
fully dissolving the capsule wall material in water at 70-80 ℃ to ensure that the concentration of the capsule wall material is 15-20 wt%, then cooling to 30-40 ℃, and uniformly mixing the core material biological enzyme and the polyhydric alcohol; preparing hydrogel capsules by a dripping method, wherein uniformly stirred capsule wall material solution flows out of a dripper, capsule core material flows out of the dripper to form a sandwiched liquid column, then the liquid column is cut off by a cutter to form a series of liquid drops with certain diameters, calcium chloride aqueous solution is dripped into the liquid drops to be solidified into hydrogel, and the hydrogel capsules wrapping biological enzymes are obtained after filtration and dehydration.
9. The method for preparing a bio-enzyme capsule according to claim 8, wherein the concentration of the calcium chloride aqueous solution is 1 to 2wt%.
CN202211024705.8A 2022-08-25 2022-08-25 Biological enzyme capsule and preparation method thereof Pending CN115322844A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115992120A (en) * 2023-02-13 2023-04-21 中山市南方新元食品生物工程有限公司 Enzyme preparation special for caramel treats and preparation method thereof

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CN104434548A (en) * 2014-12-16 2015-03-25 重庆小丸科贸有限公司 Hydrogel microcapsule with sunscreen effect
CN104434549A (en) * 2014-12-16 2015-03-25 重庆小丸科贸有限公司 Hydrogel microcapsule with anti-wrinkle effect
CN104434547A (en) * 2014-12-16 2015-03-25 重庆小丸科贸有限公司 Hydrogel microcapsule with skin-whitening effect
CN104523446A (en) * 2014-12-16 2015-04-22 重庆小丸科贸有限公司 Hydrogel microcapsule with moisturizing effect
CN114317140A (en) * 2022-01-24 2022-04-12 广州立白企业集团有限公司 Fragrance-enhancing softening detergent composition

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
CN104434548A (en) * 2014-12-16 2015-03-25 重庆小丸科贸有限公司 Hydrogel microcapsule with sunscreen effect
CN104434549A (en) * 2014-12-16 2015-03-25 重庆小丸科贸有限公司 Hydrogel microcapsule with anti-wrinkle effect
CN104434547A (en) * 2014-12-16 2015-03-25 重庆小丸科贸有限公司 Hydrogel microcapsule with skin-whitening effect
CN104523446A (en) * 2014-12-16 2015-04-22 重庆小丸科贸有限公司 Hydrogel microcapsule with moisturizing effect
CN114317140A (en) * 2022-01-24 2022-04-12 广州立白企业集团有限公司 Fragrance-enhancing softening detergent composition

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