CN114405423A

CN114405423A - Porous chitosan microcapsule fragrance retaining bead and high-stability laundry gel bead

Info

Publication number: CN114405423A
Application number: CN202210025234.6A
Authority: CN
Inventors: 苏广胜
Original assignee: Guangzhou Leju Daily Chemical Products Co ltd
Current assignee: Guangdong Leju Daily Necessities Co.,Ltd.
Priority date: 2022-01-11
Filing date: 2022-01-11
Publication date: 2022-04-29
Anticipated expiration: 2042-01-11
Also published as: CN114405423B

Abstract

The invention belongs to the technical field of functional composite materials and daily chemicals, and discloses a porous chitosan microcapsule fragrance retaining bead and a high-stability laundry gel bead. Adding chitosan and PVA into an acetic acid aqueous solution, dissolving uniformly, and then carrying out spray drying to obtain mixed powder, washing the mixed powder by adopting an alkaline aqueous solution to remove PVA, and washing the mixed powder by pure water to be neutral to obtain porous chitosan microspheres; dispersing the microcapsule essence into an ethanol water solution, adding essence, stirring and adsorbing to obtain a microcapsule essence solution; and finally, mixing the mixture with PEG 8000-10000 aqueous solution, drying and granulating to obtain the porous chitosan microcapsule fragrance-retaining bead. The invention adopts the special porous chitosan microspheres to adsorb and fix the essence, and can obviously improve the embedding rate of the microcapsule essence. Meanwhile, the microcapsule essence is coated and fixed by PEG 8000-10000 with high molecular weight, so that the storage stability of the washing gel bead can be obviously improved.

Description

Porous chitosan microcapsule fragrance retaining bead and high-stability laundry gel bead

Technical Field

The invention belongs to the technical field of functional composite materials and daily chemicals, and particularly relates to a porous chitosan microcapsule fragrance retaining bead and a high-stability laundry gel bead.

Background

The microcapsule technology is a microcapsule technology which utilizes a high polymer material to embed active substances to form a microcapsule with semi-permeability or a sealed capsule membrane. It can improve the physical property of the coated substance, isolate the active ingredient from the external environment, enhance stability, reduce volatility, prolong shelf life, and control release.

The washing gel bead is specially designed for machine washing, is simple to operate, is convenient and does not dirty hands, and can wash a cylinder of clothes by one small washing gel bead. The washing liquid has the advantages of fragrant smell, soft, smooth and thick texture, mild property, no damage to clothes, unique low-foam concentrated color-locking formula, easy rinsing, no residue after the condensed beads are dissolved in water, and capability of effectively and quickly removing stubborn stains to clean the clothes as new. In addition, the clothes have the functional characteristics of protecting clothes, being soft and smooth, keeping fragrance and the like in the market. Wherein the fragrance-retaining laundry condensation bead is deeply loved by consumers due to the lasting fragrance.

Two methods are generally adopted for increasing the fragrance durability of the fragrance-retaining laundry gel bead, one method is to increase the consumption of the essence, and the other method is to add microcapsule essence adopting a wrapping technology. The pure increase of the essence dosage can cause the initial fragrance to be too strong, and the adverse effect is caused to the formula stability of the washing gel bead, and the essence components are generally required to be separately wrapped by a film, so that the preparation process difficulty is increased. Therefore, the microcapsule technology is a more promising method.

Patent CN 103233368A discloses a preparation and application of a modified melamine resin essence microcapsule finishing agent, firstly, a styrene-maleic anhydride copolymer is used as an emulsifier, essence is used as a capsule core, and low methyl ether melamine resin is used as a wall material to prepare modified melamine resin essence microcapsules, and then the modified melamine resin essence microcapsule finishing agent is prepared by using the modified melamine resin essence microcapsule finishing agent as a raw material. The modified melamine resin essence microcapsule obtained by the method has the solid content of 30-35 percent and the essence wrapping rate of 90-95 percent, and has good stability. Meanwhile, the modified melamine resin essence microcapsule finishing agent prepared by taking the essence microcapsule as a raw material has good bonding effect with fabric fibers, the fabric fragrance-retaining time is long, the fragrance-retaining period after standing can reach 6 months, and the fragrance has no obvious change after washing for 3 times. However, the preparation method of the essence microcapsule is complex, is mainly suitable for carrying out dipping finishing and baking treatment on fabrics, and cannot be suitable for a washing condensation bead formula under the condition of simple machine washing.

Patent CN 110026139 a discloses a preparation method of a long-acting antibacterial chitosan essence microcapsule, which comprises the following specific operation methods: weighing chitosan quaternary ammonium salt, adding water to dissolve the chitosan quaternary ammonium salt, adding polyethylene glycol 400 and essence, heating, stirring and emulsifying, and then dropwise adding glutaraldehyde aqueous solution to perform crosslinking reaction to obtain the chitosan essence microcapsule. The microcapsule produced by the method has good fragrance-adding effect on fabrics, the fabric fragrance-retaining time is long, the fabric fragrance has fragrance burst property after being kneaded, and the fabric fragrance still has aftertaste after being washed for 5 times. However, the embedding rate of pure chitosan to the essence is low, high-content essence needs to be added in the preparation process, the adding amount of the essence reaches 3 times of the mass of the chitosan, the utilization rate of the essence is low, and the preparation cost is high.

Sunweilan et al disclose a method for preparing chitosan essence microcapsules (Sunweilan, Tanshan Tianwei, Zhouyangqi et al. preparation of chitosan essence microcapsules. food and fermentation industry, 2005 Vol.31 No. 3). Preparing a chitosan acetic acid solution with a certain mass fraction, and adding an emulsifier compound solution; dissolving essence in anhydrous ethanol, and dripping essence solution into acetic acid solution of chitosan under stirring to form O/W emulsion. Spray drying to obtain microcapsule product. The method also has the problem of low embedding rate of the essence, and the embedding rate can only reach about 60 percent.

In addition, in order to enhance the system stability, the existing fragrance-retaining laundry gel beads usually wrap the essence component and the cleaning component separately, on one hand, the manufacturing process and the cost can be increased to a certain extent, on the other hand, the essence component and the cleaning component are wrapped by the same water-soluble film and released simultaneously in the laundry process, and the cleaning component can wash off part of the essence in the laundry process, so that the loss of the fragrance-retaining effect is caused. Therefore, a new generation of the shaking aroma-retaining washing gel bead begins to appear, the shaking aroma-retaining washing gel bead directly wraps the aroma-retaining bead capsules and the cleaning components in the same water-soluble film, on one hand, the difficulty of a manufacturing process can be reduced, on the other hand, in the process that the cleaning components are released to start cleaning after the water-soluble film is dissolved, the aroma-retaining bead capsules cannot be immediately dissolved to release essence, the loss of the essence in the clothes cleaning process can be reduced to a certain extent, the essence utilization rate is higher, and the aroma-retaining effect is better. However, as the fragrance-retaining bead capsules and the cleaning component are directly wrapped in the same water-soluble film, the surface of the fragrance-retaining bead capsules is easily dissolved by the cleaning component in the storage process, so that the condensed bead laundry detergent is turbid, the appearance is not attractive enough, and the slow-release effect of the fragrance-retaining bead capsules is reduced. Therefore, the formula research on how to manufacture the high-stability shake fragrance-retaining laundry gel bead has wide market prospect.

Disclosure of Invention

Aiming at the defects and shortcomings of the prior art, the invention aims to provide a preparation method of porous chitosan microcapsule fragrance-retaining beads.

The invention also aims to provide the porous chitosan microcapsule fragrance-retaining bead prepared by the method.

It is a further object of the present invention to provide a high stability laundry bead.

The purpose of the invention is realized by the following technical scheme:

a preparation method of porous chitosan microcapsule fragrance-retaining beads comprises the following preparation steps:

(1) adding chitosan and polyvinyl alcohol (PVA) into an acetic acid aqueous solution, heating, stirring and dissolving uniformly to obtain a mixed solution, and performing spray drying to obtain mixed powder;

(2) adding the mixed powder obtained in the step (1) into an alkaline aqueous solution, stirring and washing, dissolving to remove PVA (polyvinyl alcohol) components, separating solid phase substances, and washing with pure water to be neutral to obtain porous chitosan microspheres;

(3) dispersing the porous chitosan microspheres obtained in the step (2) into an ethanol water solution, adding essence, stirring and adsorbing to obtain a microcapsule essence solution;

(4) and (3) dissolving polyethylene glycol (PEG) 8000-10000 in hot water, then uniformly mixing with the microcapsule essence solution obtained in the step (3), drying and granulating to obtain the porous chitosan microcapsule fragrance-retaining bead.

Further, the mass ratio of the chitosan to the PVA in the step (1) is 1: 0.4-0.8. The addition amount of PVA has a great influence on the porosity of the porous chitosan microspheres, and finally influences the adsorption effect of the porous chitosan microspheres on essence.

Further, the acetic acid aqueous solution in the step (1) refers to an acetic acid aqueous solution with a mass concentration of 0.5% to 1.5%.

Further, the mass concentration of the chitosan added into the acetic acid water solution in the step (1) is 1.5-2.5%.

Further, the alkaline aqueous solution in the step (2) is an aqueous solution of NaOH with a mass concentration of 0.5% to 1%.

Further, the dissolving and PVA component removing in the step (2) is carried out at a temperature of 60-85 ℃.

Further, the alcohol-water ratio (v/v) of the ethanol aqueous solution in the step (3) is 1: 0.6-0.8. Experiments show that under the condition of the alcohol-water ratio, the adsorption rate of the porous chitosan microspheres to the essence is remarkably improved, and the further remarkable improvement of the embedding rate of the essence is finally reflected.

Further, the adding amount of the essence in the step (3) is 0.5-5% of the mass of the porous chitosan microspheres.

Further, the mass percentage of the PEG 8000-10000 in the step (4) mixed with the solid content in the microcapsule essence solution is 80-90: 10-20.

A porous chitosan microcapsule fragrant bead is prepared by the method.

The high-stability laundry gel bead comprises a water-soluble film and a content wrapped by the water-soluble film, wherein the content comprises the following components in percentage by mass:

compared with the prior art, the invention has the beneficial effects that:

(1) the invention adopts the porous chitosan microspheres prepared by a specific method to adsorb and fix the essence, and can obviously improve the embedding rate of the microcapsule essence.

(2) According to the invention, the microcapsule essence is coated and fixed by using PEG 8000-10000 with high molecular weight, and simultaneously, the use amount of small molecular solvents such as water and propylene glycol is replaced or reduced by using PEG 200-400, so that the anti-dissolving performance of the fragrance-retaining beads can be obviously improved, and the storage stability of the laundry gel beads can be obviously improved.

Drawings

FIGS. 1 to 4 are graphs showing the stability test results of the laundry gel beads obtained by coating the fragrance retaining beads with PEG 4000, PEG 6000, PEG8000 and PEG 10000 respectively in example 4 of the present invention.

Detailed Description

The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.

Example 1

The preparation method of the porous chitosan microcapsule fragrance-retaining bead comprises the following preparation steps:

(1) adding Chitosan (CS) and PVA into a 1 wt.% acetic acid aqueous solution according to the mass ratio of 1:0.2, 1:0.4, 1:0.5, 1:0.6, 1:0.8 and 1:1 respectively, wherein the mass concentration of the CS is 2%. Heating to 75-80 ℃, stirring and dissolving uniformly to obtain a mixed solution, and spray-drying the mixed solution at 105-115 ℃ to obtain mixed powder.

(2) And (2) adding the mixed powder obtained in the step (1) into a NaOH aqueous solution with the mass concentration of 0.5%, heating to 75-80 ℃, stirring and washing, dissolving to remove PVA (polyvinyl alcohol) components, and centrifugally separating solid phase substances, and washing with pure water to be neutral to obtain the porous chitosan microspheres.

(3) And (3) dispersing the porous chitosan microspheres obtained in the step (2) into an ethanol water solution with the alcohol-water ratio of 1:0.7, adding essence with the mass of 3% of that of the porous chitosan microspheres, stirring, and adsorbing to obtain a microcapsule essence solution.

(4) And (3) dissolving PEG8000 in hot water, then uniformly mixing with the microcapsule essence solution obtained in the step (3), wherein the mass ratio of the PEG8000 to the microcapsule essence is 85:15, drying and granulating to obtain the porous chitosan microcapsule fragrance-retaining bead.

The embedding rate of the microcapsule essence obtained in this example under different proportions of chitosan and PVA was determined. The determination method comprises the steps of taking the microcapsule essence solution obtained in the step (3) for centrifugation, taking the solid phase substance, determining the surface essential oil content by adopting a rapid extraction method, and determining the total essential oil content by adopting a Soxhlet extraction method. The embedding rate is (total essential oil content-surface essential oil content)/original essential oil addition amount x 100%. The test results are shown in table 1 below.

TABLE 1

As can be seen from the results in Table 1, the ratio of CS to PVA has a great influence on the embedding rate of the microcapsule essence. When the mass ratio of CS/PVA is within the range of 1: 0.4-0.8, the embedding rate of the essence can reach more than 80%. The reason is that the addition amount of PVA has great influence on the porosity of the porous chitosan microspheres, and when the mass ratio of CS to PVA is within the range of 1: 0.4-0.8, the formed porous chitosan microspheres can better adsorb and fix essence inside the porous chitosan microspheres.

Example 2

(1) chitosan (CS) and PVA were added to a 1 wt.% aqueous acetic acid solution at a mass ratio of 1:0.5, with the mass concentration of CS added being 2%. Heating to 75-80 ℃, stirring and dissolving uniformly to obtain a mixed solution, and spray-drying the mixed solution at 105-115 ℃ to obtain mixed powder.

(3) And (3) respectively dispersing the porous chitosan microspheres obtained in the step (2) into ethanol water solutions with alcohol-water ratios (v/v) of 1:0.5, 1:0.6, 1:0.7, 1:0.8 and 1:0.9, adding essence with the mass of 3% of that of the porous chitosan microspheres, stirring and adsorbing to obtain a microcapsule essence solution.

The embedding rate of the microcapsule essence obtained in this example under different alcohol-water ratio conditions was measured. The measurement method was the same as in example 1. The test results are shown in table 2 below.

TABLE 2

Alcohol to water ratio	1:0.5	1:0.6	1:0.7	1:0.8	1:0.9
						Embedding rate	77％	85％	93％	88％	79％

As can be seen from the results in Table 2, the alcohol-water ratio of the adsorption process system has a great influence on the embedding rate of the microcapsule essence. When the alcohol-water ratio is within the range of 1: 0.6-0.8, the embedding rate of the essence can reach more than 85%. The water with a proper proportion is beneficial to promoting the adsorption and fixation of the essential oil by the porous chitosan microspheres.

Example 3

(3) And (3) dispersing the porous chitosan microspheres obtained in the step (2) into an ethanol water solution with the alcohol-water ratio (v/v) of 1:0.7, and then respectively adding essence with the mass of 0.5%, 1%, 2%, 3% and 5% of that of the porous chitosan microspheres, stirring and adsorbing to obtain a microcapsule essence solution.

The embedding rate of the microcapsule essence obtained in this example under the condition of different essence adding amounts was measured. The measurement method was the same as in example 1. The test results are shown in table 3 below.

TABLE 3

Perfume quantity	0.5％	1％	2％	3％	5％
						Embedding rate	94％	92％	92％	93％	91％

As can be seen from the results in Table 3, the embedding rate of the microcapsule essence can reach more than 90% within the range of 0.5-5% of the added amount of the essence.

Example 4

The high-stability laundry gel bead comprises a PVA water-soluble film and a content wrapped by the water-soluble film, wherein the content comprises the following components in percentage by mass:

the porous chitosan microcapsule fragrance-retaining bead of the present example was prepared by the following method:

(3) And (3) dispersing the porous chitosan microspheres obtained in the step (2) into an ethanol water solution with the alcohol-water ratio (v/v) of 1:0.7, adding essence accounting for 3% of the mass of the porous chitosan microspheres, stirring, and adsorbing to obtain a microcapsule essence solution.

(4) And (3) respectively dissolving PEG 4000, PEG 6000, PEG8000 and PEG 10000 in hot water, then uniformly mixing with the microcapsule essence solution obtained in the step (3), wherein the mass ratio of the PEG to the microcapsule essence is 85:15, and drying and granulating to obtain the porous chitosan microcapsule fragrance-retaining bead.

The stability of the laundry beads obtained by coating fragrance-retaining beads with PEG of different molecular weights according to this example was tested. The test method is an accelerated test in a thermostat at 48 ℃, and the clothes are stood and stored for 3 months to observe whether the content of the clothes washing condensation beads is turbid or not. The test results are shown in table 4 below. The corresponding test result graphs are respectively shown in FIGS. 1-4.

TABLE 4

PEG 4000	PEG 6000	PEG 8000	PEG 10000
				Turbidity	Turbidity	No turbidity	No turbidity

As can be seen from the results of Table 4 and figures 1-4, the microcapsule essence is coated and fixed by using PEG 8000-10000 with high molecular weight, so that the anti-dissolution performance of the fragrance retaining beads can be remarkably improved, and the storage stability of the laundry gel beads is finally improved.

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

1. A preparation method of porous chitosan microcapsule fragrance-retaining beads is characterized by comprising the following preparation steps:

(1) adding chitosan and PVA into an acetic acid aqueous solution, heating, stirring and dissolving uniformly to obtain a mixed solution, and performing spray drying to obtain mixed powder;

(4) and (3) dissolving PEG 8000-10000 in hot water, then uniformly mixing with the microcapsule essence solution obtained in the step (3), drying and granulating to obtain the porous chitosan microcapsule fragrance-retaining bead.

2. The preparation method of the porous chitosan microcapsule fragrance-retaining bead as claimed in claim 1, wherein the mass ratio of the chitosan to the PVA added in the step (1) is 1: 0.4-0.8.

3. The method for preparing porous chitosan microcapsule perfume-retaining beads according to claim 1, wherein the acetic acid aqueous solution in step (1) is 0.5-1.5% by mass concentration.

4. The method for preparing porous chitosan microcapsule perfume-retaining beads according to claim 1, wherein the mass concentration of the chitosan added into the acetic acid aqueous solution in the step (1) is 1.5-2.5%.

5. The preparation method of the porous chitosan microcapsule flavor-retaining bead as claimed in claim 1, wherein the alkaline aqueous solution in the step (2) is an aqueous solution of NaOH with a mass concentration of 0.5-1%; the PVA component is dissolved and removed at the temperature of 60-85 ℃.

6. The preparation method of the porous chitosan microcapsule perfume-retaining bead as claimed in claim 1, wherein the alcohol-water ratio of the ethanol aqueous solution in the step (3) is 1: 0.6-0.8.

7. The preparation method of the porous chitosan microcapsule flavor-retaining bead as claimed in claim 1, wherein the adding amount of the essence in the step (3) is 0.5-5% of the mass of the porous chitosan microsphere.

8. The preparation method of the porous chitosan microcapsule flavor-retaining bead as claimed in claim 1, wherein the mass percentage of the PEG 8000-10000 mixed with the solid content in the microcapsule flavor solution in the step (4) is 80-90: 10-20.

9. A porous chitosan microcapsule fragrance-retaining bead, characterized by being prepared by the method of any one of claims 1 to 8.

10. The high-stability laundry gel bead is characterized by comprising a water-soluble film and a content wrapped by the water-soluble film, wherein the content comprises the following components in percentage by mass:

the sum of all components is 100%.