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CN-121972101-A - Collagen-containing pH responsive microcapsule emulsion and preparation method thereof

CN121972101ACN 121972101 ACN121972101 ACN 121972101ACN-121972101-A

Abstract

The invention relates to the technical field of microcapsule emulsion, and discloses a pH response type microcapsule emulsion containing collagen and a preparation method thereof. The microcapsule emulsion comprises a capsule core component, a capsule wall component, a continuous phase component and an oil phase component, wherein the capsule core component contains collagen, the capsule wall component comprises an inner layer composite wall component, a locking component and an outer layer pH response wall component, and the microcapsule emulsion is formed by firstly forming capsule core liquid drops, then sequentially constructing the inner layer composite wall, the locking structure and the outer layer pH response wall to obtain pH response microcapsules, and dispersing the pH response microcapsules and the oil phase liquid drops in the continuous phase. The technical scheme can improve the dispersion and the holding state of the collagen in an emulsion system, and enables the collagen to show differential release characteristics under different pH conditions, and is suitable for preparing functional emulsion products.

Inventors

  • HUANG LILI
  • SHI BEIBEI
  • WEN DAN
  • HU DELONG
  • CHEN BINGGUO

Assignees

  • 杭州达维先医药科技有限公司
  • 江西续创医学科技有限公司

Dates

Publication Date
20260505
Application Date
20260407

Claims (10)

  1. 1. The pH response type microcapsule emulsion containing collagen is characterized by comprising a capsule core group, a capsule wall group, a continuous phase group and an oil phase group in parts by weight; Wherein the capsule core group comprises 1-8 parts of collagen, 2-12 parts of a polyol humectant, 0.1-2 parts of a hydrophilic protective polymer, 0.2-5 parts of cyclodextrin inclusion auxiliary materials and 0.05-2 parts of amino acid salt regulating auxiliary materials; The capsule wall group comprises an inner layer composite wall group, a locking group and an outer layer pH response wall group, wherein the inner layer composite wall group comprises 0.2-6 parts of a polyphenol film forming substance, 0.1-4 parts of cationic polysaccharide and 0.1-4 parts of anionic polysaccharide, the locking group comprises 0.05-2 parts of phytic acid, 0.02-1.5 parts of polyvalent metal salt and 0-0.5 part of genipin, and the outer layer pH response wall group comprises 0.5-8 parts of a component containing a carboxyl structural unit, 0.3-6 parts of a component containing a tertiary amine structural unit, 0.2-5 parts of a component containing a nonionic hydrophilic structural unit and 0.05-3 parts of a component containing a phenylboronic acid structural unit; the continuous phase group comprises 0.2-6 parts of emulsifying agent, 0.05-2.5 parts of rheology modifier, 0.1-5 parts of surface modified inorganic particles, 0.05-2 parts of buffer salt and 50-150 parts of water; the oil phase group comprises 5-40 parts of oil phase medium and 0.1-8 parts of oil phase structural auxiliary materials; the capsule core groups form capsule core liquid drops, and the inner layer composite wall sub-groups are coated on the outer sides of the capsule core liquid drops to form inner layer composite walls; The locking sub-groups are distributed between the inner layer composite wall and the outer layer pH response wall, or are distributed in the inner layer composite wall, or are distributed between the inner layer composite wall and the outer layer pH response wall and in the inner layer composite wall at the same time; The outer layer pH response wall sub-group is coated on the outer side of the inner layer composite wall to form an outer layer pH response wall, so that a pH response microcapsule is obtained, the pH response microcapsule is dispersed in the continuous phase group, and the oil phase group is dispersed in the continuous phase group in the form of oil phase liquid drops; The volume median particle diameter of the pH response microcapsule is 0.5-12 mu m, the volume median particle diameter of the oil phase liquid drop is 1-25 mu m, and the pH value of the microcapsule emulsion is 4.2-7.2.
  2. 2. The collagen-containing pH responsive microcapsule emulsion according to claim 1, wherein in the core group, collagen is fish collagen or hydrolyzed collagen, the polyhydric alcohol humectant is glycerin and butanediol, the hydrophilic protective polymer is sodium hyaluronate, the cyclodextrin inclusion auxiliary material is hydroxypropyl-beta-cyclodextrin, the amino acid salt regulating auxiliary material is arginine, and the weight ratio of the collagen, the polyhydric alcohol humectant, the hydrophilic protective polymer, the cyclodextrin inclusion auxiliary material and the amino acid salt regulating auxiliary material is 1-8:2-12:0.1-1.5:0.2-3:0.05-1.
  3. 3. The collagen-containing pH responsive microcapsule emulsion according to claim 1, wherein the inner layer composite wall group consists of tannic acid, chitosan and sodium alginate, the weight ratio of tannic acid to chitosan to sodium alginate is 0.2-4:0.1-2.5:0.1-2.5, and the thickness of the inner layer composite wall is 50-300 nm.
  4. 4. The collagen-containing pH-responsive microcapsule emulsion according to claim 1, wherein the outer layer pH-responsive wall sub-group comprises a methacrylic acid segment-containing component, a dimethylaminoethyl methacrylate segment-containing component, an N-vinylpyrrolidone segment-containing component and a 3-acrylamidophenylboronic acid segment-containing component, and the weight ratio of the methacrylic acid segment-containing component, the dimethylaminoethyl methacrylate segment-containing component, the N-vinylpyrrolidone segment-containing component and the 3-acrylamidophenylboronic acid segment-containing component is 1-6:0.5-4:0.3-3:0.05-1.5.
  5. 5. The collagen-containing pH responsive microcapsule emulsion according to claim 1, wherein the locking group consists of phytic acid, zinc lactate and genipin, wherein the weight ratio of the phytic acid to the zinc lactate to the genipin is 0.1-1.5:0.05-1:0.02-0.5, and the locking group is distributed between an inner layer composite wall and an outer layer pH responsive wall and is partially embedded in the inner layer composite wall.
  6. 6. The collagen-containing pH-responsive microcapsule emulsion according to claim 1, wherein the continuous phase group comprises lecithin as an emulsifier, xanthan gum as a rheology modifier, aminated silica as a surface-modified inorganic particle, and citrate as a buffer salt, wherein the average particle size of the aminated silica is 30-150 nm.
  7. 7. The collagen-containing pH-responsive microcapsule emulsion according to claim 1, wherein the oil phase group consists of caprylic/capric triglyceride, squalane and glycerol stearate, the weight ratio of the caprylic/capric triglyceride, the squalane and the glycerol stearate is 5-30:1-10:0.1-5, and the ratio of the volume median particle diameter of the pH-responsive microcapsule to the volume median particle diameter of the oil phase liquid drops is 1:1.5-1:4.
  8. 8. A method for preparing a collagen-containing pH-responsive microcapsule emulsion according to any one of claims 1 to 7, comprising the steps of: S1, weighing collagen, a polyalcohol humectant, a hydrophilic protective polymer, cyclodextrin inclusion auxiliary materials, amino acid salt regulation auxiliary materials and part of water according to parts by weight, and mixing to obtain a capsule core liquid; s2, dispersing the capsule core liquid to form capsule core liquid drops, and sequentially adding a polyphenol film forming substance, cationic polysaccharide and anionic polysaccharide to form an inner layer composite wall coated on the outer sides of the capsule core liquid drops; s3, adding phytic acid and polyvalent metal salt into the system obtained in the step S2, and adding genipin to form a locking sub-group; S4, adding a component containing a carboxyl structural unit, a component containing a tertiary amine structural unit, a component containing a nonionic hydrophilic structural unit and a component containing a phenylboronic acid structural unit into the system obtained in the step S3, and coating the outer side of the inner layer composite wall to form an outer layer pH response wall, so as to obtain a pH response microcapsule dispersion liquid; s5, weighing an emulsifier, a rheology modifier, surface modified inorganic particles, buffer salt, the rest of water, an oil phase medium and an oil phase structure auxiliary material according to parts by weight, and respectively preparing a continuous phase group and an oil phase group; S6, adding the pH response type microcapsule dispersion liquid into the continuous phase group, adding the oil phase group, and regulating the pH of the system to 4.2-7.2 after emulsification treatment to obtain the pH response type microcapsule emulsion containing collagen.
  9. 9. The preparation method of the chitosan/chitosan composite material, according to claim 8, wherein the forming mode of the capsule core liquid drops in the step S2 is one of membrane emulsification, micro-jet dispersion or high-speed shearing dispersion, the polyphenol film forming substance, the cationic polysaccharide and the anionic polysaccharide are added step by step, the time interval between two adjacent adding steps is 2-30 min, the pH of the system in the step S2 is 3.8-6.2, the treatment temperature is 10-35 ℃, and the treatment time is 20-150 min.
  10. 10. The preparation method of the high-pressure ceramic material according to claim 8, wherein the forming mode of the outer pH response wall in the step S4 is prepolymer deposition coating or in-situ polymerization coating, when in-situ polymerization coating is adopted, the treatment temperature is 15-45 ℃, the treatment time is 0.5-6 h, the emulsification treatment in the step S6 comprises at least one of shearing emulsification and high-pressure homogenization, the shearing emulsification rotating speed is 1500-10000 rpm, the high-pressure homogenization pressure is 10-50 MPa, and the curing step is further included after the step S6, the curing temperature is 15-30 ℃, and the curing time is 4-48 h.

Description

Collagen-containing pH responsive microcapsule emulsion and preparation method thereof Technical Field The invention relates to the technical field of microcapsule emulsion, and discloses a pH response type microcapsule emulsion containing collagen and a preparation method thereof. Background Collagen is used as a natural polymer substance with wide sources and good biocompatibility, and in an emulsion system, the collagen can be used as an active ingredient to participate in formula construction, and can also endow the system with certain moisture retention, film forming and interface regulating capability. Along with the development of functional emulsion products in the direction of refinement and intellectualization, the combination of collagen, microcapsule technology and stimulus response materials to construct an emulsion system with environmental adaptability has become an important research direction in the related material design and preparation fields. The pH response type microcapsule emulsion has good application prospect in the aspects of active ingredient protection and directional release because the pH response type microcapsule emulsion can have a structural or release behavior regulating effect on the change of the external acid-base environment. In the prior art, an emulsion system containing functional active substances is generally prepared by adopting technical routes such as direct emulsification, wall material coating, complex coacervation embedding or polymer network limiting. One of the schemes is to directly add collagen into water-in-oil or oil-in-water emulsion, maintain a dispersion state through an emulsifier and a stabilizer, the other scheme is to construct a microcapsule wall layer by using materials such as gelatin, acacia, chitosan, alginate or synthetic polymer, encapsulate active components and then re-disperse the active components in a continuous phase, and the other scheme is to introduce an acid-base sensitive polymer to expand, shrink, swell or dissociate a coating structure under a specific pH condition, so that the responsive release is realized. Although the above technical route improves the functionality and application range of the system to a certain extent, some disadvantages still exist. For example, when collagen is directly dispersed in emulsion, the collagen is easily influenced by external environment to generate structural change, thus leading to insufficient activity retention and system stability, the conventional microcapsule system has limited embedding protection effect on the collagen, and has unsatisfactory dispersion uniformity and long-term storage stability in the emulsion, and partial pH response system has certain sensitivity to environmental change, but has difficult compromise between response behavior and emulsion stability, and is easy to generate the conditions of inaccurate release regulation, interface damage, particle aggregation or layering and the like. Therefore, how to consider the stable loading of collagen, the structural integrity of microcapsules and the adaptability to pH change in an emulsion system is still an important direction for continuous optimization of the technology. Based on the above, it is necessary to provide a pH-responsive microcapsule emulsion containing collagen, which can satisfy the requirements of the related products for functionalization and fine preparation, and has the advantages of satisfying the collagen loading requirement, emulsion dispersion stability and environmental response characteristics Disclosure of Invention In order to solve the problems, the invention aims to provide a pH response microcapsule emulsion containing collagen, which comprises a capsule core group, a capsule wall group, a continuous phase group and an oil phase group in parts by weight; Wherein the capsule core group comprises 1-8 parts of collagen, 2-12 parts of a polyol humectant, 0.1-2 parts of a hydrophilic protective polymer, 0.2-5 parts of cyclodextrin inclusion auxiliary materials and 0.05-2 parts of amino acid salt regulating auxiliary materials; The capsule wall group comprises an inner layer composite wall group, a locking group and an outer layer pH response wall group, wherein the inner layer composite wall group comprises 0.2-6 parts of a polyphenol film forming substance, 0.1-4 parts of cationic polysaccharide and 0.1-4 parts of anionic polysaccharide, the locking group comprises 0.05-2 parts of phytic acid, 0.02-1.5 parts of polyvalent metal salt and 0-0.5 part of genipin, and the outer layer pH response wall group comprises 0.5-8 parts of a component containing a carboxyl structural unit, 0.3-6 parts of a component containing a tertiary amine structural unit, 0.2-5 parts of a component containing a nonionic hydrophilic structural unit and 0.05-3 parts of a component containing a phenylboronic acid structural unit; the continuous phase group comprises 0.2-6 parts of emulsifying agent, 0.05-2.5 parts of r