KR101901386B1 - Method of manufacturing Hydrogel - Google Patents

Abstract

The present invention relates to a method for manufacturing a hydrogel, which comprises the following steps: preparing a first mixed solution by mixing water with an additive comprising at least one of a gelling rate modifier, a metal ion cross-linking agent, and an adsorption aid; mixing the first mixed solution and polyacrylate salt to prepare a second mixed solution; mixing a mixture of glycerin and polyacrylate with the second mixed solution to prepare a third mixed solution; reacting the third mixed solution to prepare a hydrogel solution; and drying the hydrogel solution to obtain a hydrogel. An object of the present invention is to provide the method for manufacturing the hydrogel which is easy to control physical properties.

Description

TECHNICAL FIELD The present invention relates to a method of manufacturing a hydrogel,

The present invention relates to a method for producing a hydrogel.

Polymer hydrogels are commonly used in diapers, contact lenses, medical electrodes, cell cultures, and are used extensively in special applications such as molding materials, soil moisture storage, and burn wound dressings.

This is a hydrophilic polymer crosslinked by a cohesive force such as covalent bond, hydrogen bond, van der waals bond or physical bond, and has a three-dimensional polymer network structure capable of swelling a large amount of water in an aqueous solution Lt; / RTI > Such water absorption shows similar behavior to the tissue of the living body.

A hydrophilic group containing a polymeric hydrogel added to a hydrophilic group is referred to as a bi-hydrophilic polymer hydrogel or a bi-hydrophilic polymer chain (APN), which is swollen to a smaller extent corresponding to the hydrophilic chain, The absorption of the hydrophobic substance increases.

The hydrogels formed are not only quite robust up to 90 ° C, but also re-arrange quickly when stress is applied to restore the original structure. Both of these hydrophilic polymers can be applied to drug delivery systems (DDS) such as drugs. The advantage of such a polymer hydrogel is that the high fluidity of the polymer chain on the surface exhibits low surface tension which can facilitate mass transfer from within and outside the hydrogel. A hydrophilic, diffusive surface and a soft and spongy nature can contain a large amount of water and exhibit high biocompatibility.

In addition, hydrogels can be added with functions such as controlled release to control the delivery of the contained material, and sensitivity to swelling, swelling and tingling to pH, temperature, electric field and light. Hydrogels with these properties are widely used in the pharmaceutical industry as well as in beauty and biomedical applications because of their structure similar to human cell matrix, inert biocompatibility, elasticity such as rubber, permeability of oxygen and nutrients.

In the prior art, a hydrogel was prepared using a natural polymer, or acrylic acid was dissolved in water and then lyophilized to prepare a hydrogel. However, in such conventional techniques, it is difficult to control the viscosity, the adhesive force, and the tensile force, and there is a limit to the introduction of the active ingredient, thereby making it difficult to obtain a hydrogel of desired physical properties.

Patent Publication No. 2018-0018737 (Feb. 21, 2018)

An object of the present invention is to provide a method for producing a hydrogel which is easy to control physical properties.

It is an object of the present invention to provide a method for preparing a hydrogel, comprising: preparing a first mixed solution by mixing water with an additive including at least one of a gelling rate modifier, a metal ion crosslinking agent, and an adsorption aid; Preparing a second mixed solution by mixing the first mixed solution and the polyacrylate salt; Mixing a mixture of glycerin and polyacrylate with the second mixed solution to prepare a third mixed solution; Reacting the third mixed solution to prepare a hydrogel solution; And drying the hydrogel solution to obtain a hydrogel.

The drying may be carried out in a warmed state.

The hydrogel solution is formed with ionic crosslinking, and the ionic crosslinking can be activated by the drying.

The drying may be carried out at 40 to 140 DEG C for 10 minutes to 20 hours.

The drying may be performed at 100 to 140 ° C for 10 minutes to 60 minutes.

The drying may be carried out at 40 to 70 DEG C for 1 to 20 hours.

The drying may be performed using microwave.

0.01 to 4 parts by weight of the gelling rate regulator, 0.01 to 4 parts by weight of the metal ion crosslinking agent, 0.005 to 1 part by weight of the adsorption auxiliary agent, and 1 to 15 parts by weight of the polyacrylate salt, based on 100 parts by weight of water, , The glycerin may be used in an amount of 3 to 30 parts by weight, and the polyacrylate may be used in an amount of 0.5 to 10 parts by weight.

The weight ratio of the polyacrylate to the polyacrylate salt may be from 1: 1 to 1: 6.

The molecular weight of the polyacrylate is 100,000 to 1,000,000, and the polyacrylate salt may have a molecular weight of 1,000,000 to 7,000,000.

The polyacrylate salt may include at least one of sodium acrylate and potassium acrylate.

The metal ion cross-linking agent may include at least one selected from aluminum chloride, aluminum hydroxide, magnesium chloride, aluminum acetate, aluminum lactate, and calcium chloride.

The gelling rate controlling agent may include at least one selected from EDTA, acetic acid, lactic acid, oxalic acid, citric acid, tartaric acid, EDTA-2 sodium, calcium citrate and sodium citrate.

The adsorption aid may comprise kaolin.

According to the present invention, there is provided a process for producing a hydrogel which is easy to control physical properties.

1 is a flowchart of a method for producing a hydrogel according to the present invention,
2 is a photograph of the manufacturing process in the embodiment,
3 to 7 are photographs of the manufacturing processes in Comparative Examples 1 to 5, respectively,
Fig. 8 is a comparative photograph according to whether or not thermosetting is performed.

The present invention relates to a method for producing a hydrogel.

Water, an additive, a polyacrylate salt, glycerin and polyacrylate may be used as the method for producing the hydrogel of the present invention. The additive may be, but not limited to, a gelling rate modifier, a metal ion cross-linker, and / or an adsorption aid.

Water may be purified water, and 75% to 95% by weight of the total formulation may be used. When the amount of water used is 75 wt% or less, there is a problem that the amount of the crosslinked polymer is relatively increased and the hydrogel has a viscosity of 100,000 cps or more at 30 캜. When the amount of water used is higher than 95% by weight, the amount of crosslinked polymer is relatively decreased, and the viscosity is lowered and the osmotic pressure and the absorption power are lowered.

0.01 to 4 parts by weight of a gelling rate regulator, 0.01 to 4 parts by weight of a metal ion crosslinking agent, 0.005 to 1 part by weight of an adsorption aid, 1 to 15 parts by weight of a polyacrylate salt, 3 to 15 parts by weight of a glycerin, To 30 parts by weight, and the polyacrylate may be used in an amount of 0.5 to 10 parts by weight.

The gelling rate regulator may be selected from one or more of EDTA, acetic acid, lactic acid, oxalic acid, citric acid, tartaric acid, EDTA-2 sodium, calcium citrate and sodium citrate. When the content of the gelling rate modifier is less than 0.01 part by weight, the gelation does not proceed sufficiently and the strength of the hydrogel tends to become insufficient. When the content of the gelling rate controlling agent is more than 4 parts by weight, the gelation reaction rate becomes too fast, the gelation becomes nonuniform, and the strength of the hydrogel becomes strong, so that the workability tends to become insufficient.

The metal ion cross-linking agent may be at least one selected from the group consisting of aluminum chloride, aluminum hydroxide, magnesium chloride, aluminum acetate, aluminum lactate and calcium chloride. When the metal ion cross-linking agent is used in an amount exceeding 4 parts by weight, the crosslinking degree is high and the adhesive strength is low. When the amount is less than 0.01 part by weight, the gel strength is low and the gel component appears on the skin.

The hydrogel to be produced can be used as a hydrogel sheet composition for cosmetic use or wound healing, so that when used for wound healing, an adsorption aid capable of acting as an auxiliary for the absorption of wound exudates can be used.

 Kaolin can be used as an adsorption aid. Kaolin is a naturally occurring hydrated aluminum silicate, white or milky powder with a slight clay-like odor. It is a powder that does not dissolve in water and tissue fluid. It spreads in skin diseases such as epithelial deprivation, ulcer, sputum, or eczema, protects skin from external stimuli and absorbs the leach solution to promote drying and eschar .

In the present invention, an acrylic crosslinked polymer is used as the hydrophilic polymer, and polyacrylate and polyacrylate salts are used. The weight ratio of polyacrylate to polyacrylate salt may be from 1: 1 to 1: 6.

Acrylic crosslinked polymer acts as a crosslinking agent and forms a thin film, which provides excellent adhesion to skin, maintains moisture, and provides a soft touch to the hydrogel.

The molecular weight of the polyacrylate is 100,000 to 1,000,000, and the polyacrylate salt may have a molecular weight of 1,000,000 to 7,000,000. The polyacrylate salt may be any one of sodium acrylate and potassium acrylate, but is not limited thereto.

If the weight ratio of the polyacrylate and the polyacrylate salt is out of the range of 1: 1 to 1: 6, the viscosity of the hydrogel may change when the hydrogel is used on the skin, causing the hydrogel to flow down from the skin, It is difficult for the cosmetic agent or the medicament to be filled in the hydrogel.

When the polyacrylate salt is used in an amount of 1 part by weight or less, the strength and elasticity of the gel are lowered. When the polyacrylate salt is used in an amount of 15 parts by weight or more, the hydrogel breaks off and the viscosity thereof increases sharply.

When the polyacrylate is used in an amount of 0.5 parts by weight or less, the viscosity of the gel is lowered and the stickiness of the gel is lowered. When the polyacrylate is used in an amount of 10 parts by weight or more, the hydrogel does not uniformly cross-link and the hydrogel breaks off.

Glycerin serves not only to moisturize but also to disperse the gelling polymer.

When glycerin is less than 3 parts by weight, water is liable to be volatilized and it is difficult to disperse the gelled polymer. When the amount is more than 30 parts by weight, the composition tends to become too sticky, resulting in poor feeling of use and cost of raw materials.

Further, other additives such as a preservative, a perfume, a surfactant, a thickening agent and the like may be further added to the adhesive hydrogel composition of the present invention as needed, and the other additives are not particularly limited.

The hydrogel can be made into a film form according to the manufacturing method, so that it is easy to adhere to the skin itself and has excellent peeling property after use, so that no foreign matter remains on the skin.

Depending on the use, the hydrogel may be coated on a support to form a hydrogel sheet. In this case, the shape and the stability can be improved by the support.

The support may be selected from among paper, nonwoven fabric, polyethylene terephthalate or polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polybutadiene, ethylene-vinyl acetate copolymer and polyvinyl chloride film.

1 is a flowchart of a method for producing a hydrogel according to the present invention.

First, a first mixed solution is prepared by mixing water with an additive including at least one of a gelling rate modifier, a metal ion cross-linking agent, and an adsorption aid (S100).

Next, the first mixed solution and the polyacrylate salt are mixed to prepare a second mixed solution (S200)

It is not possible to perform a proper role when a gelling rate modifier is added after polyacrylate salt introduction.

When the polyacrylate salt is added prior to the additive, the solid additive is not clumped and dissolved, and the liquid additive is converted into a white lump and is not dissolved in the gel. In addition, when the polyacrylate salt is added before the addition, crosslinking of the gel can not be carried out, so that the solidified gel may dissolve in water.

Thereafter, the third mixture solution is prepared by mixing the mixture of glycerin and polyacrylate and the second mixture solution (S300). When glycerin and polyacrylate are not mixed first, each polyacrylate is not dissolved in the gel but remains in a solid mass form.

When the polyacrylate is added before the polyacrylate salt, the acrylic salt does not dissolve in the liquid gel having a high viscosity, and it is agglomerated.

Further, when the polyacrylate and the polyacrylate salt are simultaneously added, white and transparent color gels are generated.

On the other hand, if polyacrylate is not used, the gel is not crosslinked and the solidified gel dissociates into water.

Thereafter, the third mixed solution is reacted to prepare a hydrogel solution (S400)

In the above process, the mixing is carried out at 50 rpm to 1300 rpm, and the temperature may be 55 ° C to 80 ° C.

Thereafter, the hydrogel solution is dried to obtain a hydrogel (S500).

Drying can be done at elevated temperature. In the hydrogel solution, the ionic crosslinking is formed in the hydrogel. Upon drying at the elevated temperature, the ionic crosslinking is activated. When it is put into water by activation of ionic crosslinking, a hydrogel which does not melt and absorbs water and expands can be obtained.

The hydrogel is thermally cured (thermally dried) upon activation of ionic crosslinking.

The range of temperature rise can vary. The thermal drying at a raised temperature can be carried out at 40 to 140 ° C for 10 minutes to 20 hours. Concretely, it may include a step at 100 to 140 ° C for 10 minutes to 60 minutes, in which case it may be further carried out at 25 to 35 ° C for 10 minutes to 30 minutes. Or thermal drying can be carried out at 40 to 70 DEG C for 1 to 20 hours.

Such thermal curing at elevated temperatures may be performed in a variety of ways, for example, using microwaves.

The resulting hydrogel may have a viscosity of 90,000 to 100,000 cps at 30 ° C.

INDUSTRIAL APPLICABILITY According to the present invention described above, hydrogels can be stably prepared using polyacrylates and polyacrylates having a high molecular weight. In addition, according to the present invention, hydrogels having desired physical properties can be prepared by controlling kinds and / or amounts of polyacrylate and polyacrylate salts.

The hydrogel prepared can be used for cosmetics or medical use.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples.

Example

To 500 g of purified water, 0.7 g of EDTA, 0.6 g of AlCl 3 and 0.1 g of kaolin were added to a paper filter and mixed at 60 rpm for 20 minutes at 200 rpm to obtain a first mixed solution.

Then, 12 g of the polyacrylate salt was added and the temperature was raised to 70 ° C and the mixture was stirred at 300 rpm for 30 minutes to obtain a second mixed solution. As the polyacrylate salt, sodium acrylate was used.

Next, 20 g of glycerin and 2 g of polyacrylate were mixed and sufficiently dissolved, and then added to the second mixed solution to obtain a third mixed solution.

The third mixed solution was reacted at 300 rpm for 20 minutes at 70 캜 and then at 300 rpm for 20 minutes at 60 캜 to prepare a hydrogel.

And then thermally cured at 120 캜 for 20 minutes and at 30 캜 for 10 minutes.

Comparative Example 1

In the method of the Example, the polyacrylate salt was added first before adding the additive.

Comparative Example 2

In the method of the examples, glycerin and polyacrylate were each added without first mixing.

Comparative Example 3

In the method of the examples, the polyacrylate was added before the polyacrylate salt.

Comparative Example 4

In the method of the example, the polyacrylate was added simultaneously with the polyacrylate salt.

Comparative Example 5

No polyacrylate was used in the method of the examples.

Comparative Example 6

The heat curing was not carried out in the method of the example.

FIG. 2 shows the manufacturing process of the embodiment, and FIGS. 3 to 7 show the manufacturing processes of the comparative example 1 to the comparative example 5, respectively.

When the polyacrylate salt was added before the addition of the additive as in Comparative Example 1, the powdery additive did not melt into the gelled polyacrylate salt, and thus the desired hydrogel could not be obtained.

When the glycerin and the polyacrylate were each charged without first mixing them as in Comparative Example 2, the glycerin was mixed with the gelled polyacrylate salt, but the polyacrylate was not gelled and a hydrogel with desired physical properties could not be obtained.

When a polyacrylate having a relatively small molecular weight is introduced before a polyacrylate salt having a relatively large molecular weight as in Comparative Example 3, the polyacrylate salt is added in a state in which the polyacrylate is gelled to form a polyacrylate salt as a lump It is not aggregated and gelated.

When the polyacrylate is added simultaneously with the polyacrylate salt as in Comparative Example 4, the polyacrylate salt having a high molecular weight can not sufficiently gel and aggregate into a mass.

When polyacrylate was not used as in Comparative Example 5, crosslinking by polyacrylate did not proceed, and desired physical properties could not be obtained in a gelatinous sheet after the planarization process.

8 is a comparative photograph of the hydrogel of Comparative Example 6 according to whether the hydrogel is thermally cured.

As shown in the photograph on the left side of FIG. 8, when thermosetting is not carried out, water is dispersed in water while being dispersed. On the other hand, when thermosetting is performed as shown in the right side of FIG. 8, ion crosslinking is strengthened, It becomes an expanded form.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventions. It will be clear to those who have knowledge of.

Claims (14)

In the method for producing a hydrogel,
Preparing a first mixed solution by mixing water with an additive comprising at least one of a gelling rate modifier, a metal ion crosslinking agent, and an adsorption aid;
Preparing a second mixed solution by mixing the first mixed solution and the polyacrylate salt;
Mixing a mixture of glycerin and polyacrylate with the second mixed solution to prepare a third mixed solution;
Reacting the third mixed solution to prepare a hydrogel solution;
And drying the hydrogel solution to obtain a hydrogel. The method according to claim 1,
Wherein the drying is performed in a warmed state. 3. The method of claim 2,
The hydrogel solution is formed with ion bridging,
And the ion bridging is activated by the drying. 3. The method of claim 2,
Wherein the drying is carried out at 40 to 140 DEG C for 10 minutes to 20 hours. 5. The method of claim 4,
Wherein the drying is performed at 100 to 140 ° C for 10 minutes to 60 minutes. 5. The method of claim 4,
Wherein the drying is carried out at 40 to 70 DEG C for 1 to 20 hours. 3. The method of claim 2,
Wherein the drying is performed using a microwave. 8. The method according to any one of claims 1 to 7,
With respect to 100 parts by weight of water,
0.01 to 4 parts by weight of the gelling rate regulator, 0.01 to 4 parts by weight of the metal ion crosslinking agent, 0.005 to 1 part by weight of the adsorption aid, 1 to 15 parts by weight of the polyacrylate salt, 3 to 30 parts by weight of the glycerin, And 0.5 to 10 parts by weight of the polyacrylate is used. 9. The method of claim 8,
Wherein the weight ratio of the polyacrylate to the polyacrylate salt is from 1: 1 to 1: 6. delete 10. The method of claim 9,
Wherein the polyacrylate salt comprises at least one of sodium acrylate and potassium acrylate. 10. The method of claim 9,
Wherein the metal ion cross-linking agent comprises at least one selected from aluminum chloride, aluminum hydroxide, magnesium chloride, aluminum acetate, aluminum lactate, and calcium chloride. 10. The method of claim 9,
Wherein the gelling rate modifier comprises at least one selected from the group consisting of EDTA, acetic acid, lactic acid, oxalic acid, citric acid, tartaric acid, EDTA-2 sodium, calcium citrate and sodium citrate. 10. The method of claim 9,
Wherein the adsorption aid comprises kaolin. ≪ RTI ID = 0.0 > 21. < / RTI >

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