Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described herein. For the purposes of the present invention, the following terms are defined below.
The term "about" as used herein refers to an amount, level, value, dimension, size, or amount that differs by up to 30%, 20%, or 10% as compared to the amount, level, value, dimension, size, or amount of a reference. The percentages used herein are by weight unless otherwise indicated.
Throughout the specification and claims, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
Acrylic acid ester polymer
The gel composition of the present invention comprises an acrylate-based polymer. The acrylate polymers used in the gel composition of the present invention include, but are not limited to: carbomer, acrylic ester/C10-30 alkanol acrylic ester cross-linked copolymer, acrylic acid (ester)/acrylamide copolymer, acrylic acid (ester)/ammonium methacrylate copolymer, acrylic acid (ester)/C12-22 alkanol methacrylate copolymer, acrylic acid (ester) cross-linked polymer, acrylic acid (ester)/ethylhexyl acrylate/styrene copolymer, acrylic acid (ester)/hydroxy ester acrylic acid (ester) copolymer, acrylic acid (ester)/octyl acrylamide copolymer, acrylic acid (ester)/tert-butyl acrylamide copolymer, acrylic acid (ester)/urethane copolymer, acrylic acid (ester)/octyl acrylamide copolymer, acrylic acid (ester)/TDI/trimethylolpropane copolymer, Acrylic acid (ester)/VA copolymer, acrylic acid (ester)/VA crosslinked polymer, acrylic acid (ester)/vinyl isodecanoate crosslinked polymer, acrylic acid (ester)/vinyl neodecanoate crosslinked polymer, acrylic acid (ester)/VP copolymer, acrylic acid (ester) copolymer ammonium, acrylic acid (ester)/acrylamide copolymer potassium salt, acrylic acid (ester)/C10-30 alcohol acrylate crosslinked polymer potassium salt.
The acrylate polymer is widely applied in the fields of personal care products, medicines and the like, can become transparent or semitransparent gel after being thickened, can help a preparation to realize the function of suspension stability, and is an important rheology regulator.
In some embodiments, the gel composition of the present invention comprises an acrylate polymer supplied by Lubrizol corporation under the trade name Carbopol Ultrez 10 (abbreviated as U10). In some embodiments, the gel compositions of the present invention comprise an acrylate/C10-30 alkanol acrylate cross-linked copolymer available from Lubrizol corporation under the trade name Carbopol Ultrez 20 (abbreviated U20). In some embodiments, the gel compositions of the present invention comprise an acrylate/C10-30 alkanol acrylate cross-linked copolymer available from Lubrizol under the trade name Carbopol Ultrez 21 (abbreviated U21). In some embodiments, the gel composition of the present invention comprises an acrylate polymer supplied by Lubrizol corporation under the trade name Carbopol Ultrez 30 (abbreviated as U30). In some embodiments, the gel composition of the present invention comprises an acrylate polymer available under the trade name Carbopol 980 (980 for short) from Lubrizol. In some embodiments, the gel compositions of the present invention comprise an acrylate polymer available from Lubrizol corporation under the trade name Carbopol 981 (abbreviation 981). In some embodiments, the gel compositions of the present invention comprise an acrylate/C10-30 alkanol acrylate cross-linked copolymer available from Lubrizol corporation under the trade name Pemulen TR-1 (abbreviated TR-1). In some embodiments, the gel compositions of the present invention comprise an acrylate/C10-30 alkanol acrylate cross-linked copolymer available from Lubrizol corporation under the trade name Pemulen TR-2 (abbreviated TR-2).
In some embodiments, the gel composition of the present invention comprisesAcrylic acid ester polymerSelected from: u10, U20, U21, U30, 980, 981, TR-1, TR-2 or combinations thereof.
In some embodiments, the gel composition may comprise about 0.1 to 10 weight percent of the acrylate-based polymer, based on the total weight of the composition. In a preferred embodiment, the gel composition may comprise about 0.1 to 5 wt% of the acrylate-based polymer, based on the total weight of the composition. In a preferred embodiment, the gel composition may comprise at least 0.2 wt% of an acrylate-based polymer, based on the total weight of the composition. In a preferred embodiment, the gel composition may comprise about 0.2 to 1 wt% of the acrylate-based polymer, based on the total weight of the composition. In a preferred embodiment, the gel composition may comprise about 0.2 to 0.3 weight percent of the acrylate-based polymer, based on the total weight of the composition.
Amino acids
The amino acid acts on the skin of a human body to provide multiple skin care effects, is a natural moisturizing factor of the human body, and can help to absorb water and lock water, so that the skin is full, fine and glossy; helps to promote skin metabolism and accelerate protein synthesis, and is often used as an effective raw material in skin care products.
In some embodiments, the gel composition comprises an amino acid. In some embodiments, the gel composition comprises an alpha-amino acid. In some embodiments, the gel composition comprises alpha amino acids from C3-C6.
The alpha-amino acids included in the gel composition of the present invention include, but are not limited to: alanine, asparagine, aspartic acid, methionine, glutamine, glutamic acid, glycine, isoleucine, leucine, cysteine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine.
In some embodiments, the gel composition may comprise 0.5 to 20 weight percent of the amino acid based on the total weight of the composition. In some embodiments, the gel composition may comprise 1-10 wt% amino acids based on the total weight of the composition. In some embodiments, the gel composition may comprise 1-5 wt% amino acids based on the total weight of the composition.
Gel composition
The invention mixes the acrylic ester polymer water gel dispersion system and amino acid according to different proportions, and can realize that the viscosity of the gel composition is different from hundreds to thousands or even thousands (unit mPa & s or cp). The gel composition with higher viscosity prepared by the invention also has better suspension capacity and can stably suspend the essence particles.
In some embodiments, the weight ratio of the acrylate polymer to the amino acid in the gel composition is about 1:50 to 1: 2. In a preferred embodiment, the weight ratio of acrylate polymer to amino acid in the gel composition is about 1:30 to 1: 5. In a more preferred embodiment, the weight ratio of acrylate polymer to amino acid in the gel composition is 1: 10.
In some embodiments, the method of preparing the gel composition comprises the steps of:
(a) dispersing an acrylate polymer into a personal care art-acceptable carrier;
(b) dispersing the alpha amino acid into the mixture under stirring to obtain the required gel composition;
or
(a) Dispersing an alpha amino acid in a personal care art-acceptable carrier;
(b) the acrylic polymer is dispersed in the above mixture under stirring to obtain the desired gel composition.
In some embodiments, the personal care art-acceptable carrier is an aqueous carrier. In some embodiments, the personal care art-acceptable carrier is a water-alcohol system. In some embodiments, the personal care art-acceptable carrier is a glycerin-water, butylene glycol-water, propylene glycol-water system.
In some embodiments, the agitation conditions comprise stirring at 500-. In some embodiments, the agitation state comprises stirring at 500 rpm. In some embodiments, the stirring regime comprises stirring for 5 minutes to 1 hour. In some embodiments, the stirring regime comprises stirring for 5-10 minutes.
The pH value of the prepared gel composition is between 4.0 and 5.0, and the gel composition meets the control requirement of the cosmetic industry on the pH value. In some embodiments, the gel composition of the present invention has a pH of 4.5.
The present invention also enables the use of the gel composition to prepare personal care products in different dosage forms. These personal care products include, for example, lotions, essences, gels, lotions, creams, and the like.
Examples
The invention will be further illustrated by the following specific examples. It should be noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the above teachings. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the manufacturer. All percentages and parts are by weight unless otherwise indicated.
The experimental reagents used in the following examples include:
the laboratory instruments used in the following examples include:
example 1: preparation of gel compositions
0.1 part by mass of U20 was scattered on the surface of 97.9 parts by mass of deionized water at room temperature, after sufficiently wetting, 2.0 parts by mass of glycine was scattered while rapidly stirring at 500rpm, and stirred for 5 minutes to dissolve uniformly, to finally obtain a U20 hydrogel composition which was colorless and transparent in appearance as a mobile gel, and the pH was measured to be 4.861, and the viscosity was measured to be 2242 mPas.
Example 2: preparation of gel compositions
0.2 part by mass of U20 was scattered on the surface of 97.8 parts by mass of deionized water at room temperature, after sufficiently wetting, 2.0 parts by mass of glycine was scattered while rapidly stirring at 500rpm, and stirred for 5 minutes to dissolve uniformly, to finally obtain a U20 hydrogel composition which was a colorless transparent semi-fluid gel in appearance, measured to have a pH of 4.568, and measured to have a viscosity of 12220 mPas.
Example 3: preparation of gel compositions
0.3 part by mass of U20 was scattered on the surface of 97.7 parts by mass of deionized water at room temperature, after sufficiently wetting, 2.0 parts by mass of glycine was scattered while rapidly stirring at 500rpm, and stirred for 5 minutes to dissolve uniformly, to finally obtain a U20 hydrogel composition which was colorless and transparent thick gel in appearance, measured at pH4.347, and measured as viscosity 19770 mPas.
Example 4: preparation of gel compositions
0.2 part by mass of U20 is sprinkled on the surface of 98.8 parts by mass of deionized water at room temperature, after fully wetting, 1.0 part by mass of glycine is sprinkled in the state of starting 500rpm rapid stirring, and stirred for 5 minutes until uniformly dissolved, finally obtaining the hydrogel composition of U20, the appearance is colorless transparent gel, the pH is measured to be 4.169, and the viscosity is measured to be 14780 mPas.
Example 5: preparation of gel compositions
0.2 part by mass of U20 is sprinkled on the surface of 99.3 parts by mass of deionized water at room temperature, after the deionized water is fully wetted, 0.5 part by mass of glycine is sprinkled in the state of starting to rapidly stir at 500rpm, and the mixture is stirred for 5 minutes until the glycine is uniformly dissolved, so that a U20 hydrogel composition is finally obtained, the appearance is colorless and transparent flowing gel, the pH value is measured to be 4.213, and the viscosity is measured to be 3000 mPas.
Example 6: preparation of gel compositions
0.3 part by mass of U20 was scattered on the surface of 99.2 parts by mass of deionized water at room temperature, after sufficiently wetting, 0.5 part by mass of glycine was scattered while rapidly stirring at 500rpm, and stirred for 5 minutes to dissolve uniformly, to finally obtain a U20 hydrogel composition which was colorless and transparent in appearance, measured as a mobile gel, pH4.086, and measured as viscosity 8330 mPas.
Example 7: preparation of gel compositions
0.3 part by mass of U20 was scattered on the surface of 98.7 parts by mass of deionized water at room temperature, after sufficiently wetting, 1 part by mass of glycine was scattered while rapidly stirring at 500rpm, and stirred for 5 minutes until uniformly dissolved, to finally obtain a U20 hydrogel composition which was colorless and transparent gel in appearance, measured pH4.189, and measured viscosity 14900 mPas.
Example 8: preparation of gel compositions
0.1 part by mass of U20 is scattered on the surface of 98.9 parts by mass of deionized water at room temperature, after the deionized water is fully wetted, 1 part by mass of glycine is scattered in the state of starting 500rpm and rapidly stirring for 5 minutes until the glycine is uniformly dissolved, and finally the hydrogel composition of U20 is obtained, the appearance is colorless and transparent flowing gel, the pH value is measured to be 4.673, and the viscosity is measured to be 1683mPa & s.
Example 9: preparation of gel compositions
0.1 part by mass of U20 is scattered on the surface of 96.9 parts by mass of deionized water at room temperature, after the deionized water is fully wetted, 3 parts by mass of glycine is scattered in the quick stirring state at 500rpm, the mixture is stirred for 5 minutes until the glycine is uniformly dissolved, finally, the hydrogel composition of U20 is obtained, the appearance is colorless and transparent flowing gel, the pH value is measured to be 4.774, and the viscosity is measured to be 4542mPa & s.
Example 10: preparation of gel compositions
0.2 part by mass of U20 is scattered on the surface of 96.8 parts by mass of deionized water at room temperature, after the deionized water is fully wetted, 3 parts by mass of glycine is scattered in the state of starting 500rpm and rapidly stirring for 5 minutes until the glycine is uniformly dissolved, and finally the hydrogel composition of U20 is obtained, the appearance of the gel is colorless and transparent, the pH value is measured to be 4.404, and the viscosity is measured to be 15570 mPas.
Example 11: preparation of gel compositions
Accurately weighing 2 parts by mass of glycerol at room temperature, adding 95.8 parts by mass of deionized water, and uniformly stirring and dispersing to obtain a glycerol-water mixed solution for later use.
0.2 part by mass of U20 was sprinkled on the surface of the glycerin-water mixed solution at room temperature, after sufficiently wetting, 2 parts by mass of glycine was sprinkled in the state of rapidly stirring at 500rpm, and stirred for 5 minutes to be dissolved uniformly, to finally obtain a U20 hydrogel composition which was a colorless transparent semi-fluid gel in appearance, measured pH4.578, and measured viscosity 13130 mPas.
Example 12: preparation of gel compositions
Accurately weighing 2 parts by mass of 1, 3-butanediol at room temperature, adding 95.8 parts by mass of deionized water, and uniformly stirring and dispersing to obtain a butanediol-water mixed solution for later use.
After 0.2 part by mass of U20 was sprinkled onto the surface of the butanediol-water mixed solution at room temperature and sufficiently wetted, 2 parts by mass of glycine was sprinkled while rapidly stirring at 500rpm and stirred for 5 minutes until uniformly dissolved, to finally obtain a U20 hydrogel composition which was a colorless and transparent semi-fluid gel in appearance, measured at pH4.526, and measured to have a viscosity of 12730 mPas.
Example 13: preparation of gel compositions
Accurately weighing 2 parts by mass of 1, 3-propanediol at room temperature, adding 95.8 parts by mass of deionized water, and uniformly stirring and dispersing to obtain a propanediol-water mixed solution for later use.
0.2 part by mass of U20 was sprinkled on the surface of the propylene glycol-water mixed solution at room temperature, after sufficiently wetting, 2 parts by mass of glycine was sprinkled in the rapidly stirred state at 500rpm, and stirred for 5 minutes to dissolve uniformly, to finally obtain a U20 hydrogel composition which was a colorless transparent semi-fluid gel in appearance, measured pH4.510, and measured viscosity 12420 mPas.
Example 14: preparation of gel compositions
0.2 part by mass of U10 was scattered on the surface of 97.8 parts by mass of deionized water at room temperature, after sufficiently wetting, 2.0 parts by mass of glycine was scattered while rapidly stirring at 500rpm, and stirred for 5 minutes to dissolve uniformly, to finally obtain a U10 hydrogel composition which was a colorless transparent semi-fluid gel in appearance, measured to have a pH of 4.564, and measured to have a viscosity of 13780 mPas.
Example 15: preparation of gel compositions
0.2 part by mass of U21 is scattered on the surface of 97.8 parts by mass of deionized water at room temperature, after the deionized water is fully wetted, 2.0 parts by mass of glycine is scattered in the state of starting 500rpm and rapidly stirring for 5 minutes until the glycine is uniformly dissolved, and finally, a U21 hydrogel composition which is colorless and transparent semi-flow gel is obtained, the pH value is measured to be 4.517, and the viscosity is measured to be 12560 mPas.
Example 16: preparation of gel compositions
0.2 part by mass of U30 is scattered on the surface of 97.8 parts by mass of deionized water at room temperature, after the deionized water is fully wetted, 2.0 parts by mass of glycine is scattered in the state of starting 500rpm and rapidly stirring for 5 minutes until the glycine is uniformly dissolved, and finally, a U30 hydrogel composition is obtained, the appearance of the gel is colorless and transparent, the pH value is measured to be 4.463, and the viscosity is measured to be 14360 mPas.
Example 17: preparation of gel compositions
At room temperature, 0.2 part by mass of TR-1 is scattered on the surface of 97.8 parts by mass of deionized water, after the deionized water is fully wetted, 2.0 parts by mass of glycine is scattered in the state of starting 500rpm and rapidly stirring for 5 minutes until the glycine is uniformly dissolved, and finally, the hydrogel composition of TR-1 is obtained, the appearance is colorless and transparent flowing gel, the pH value is measured to be 4.432, and the viscosity is measured to be 6560 mPas.
Example 18: preparation of gel compositions
And (2) scattering 0.2 part by mass of carbomer 980 onto the surface of 97.8 parts by mass of deionized water at room temperature, after fully wetting, scattering 2.0 parts by mass of glycine under the state of starting 500rpm and rapidly stirring, stirring for 5 minutes until the glycine is uniformly dissolved, finally obtaining the carbomer 980-based hydrogel composition, wherein the appearance of the carbomer 980-based hydrogel is colorless and transparent gel, and the viscosity is 15240mPa & s when the pH is measured to be 4.578.
Comparative example 1:
0.2 part by mass of U20 was sprinkled onto the surface of 99.8 parts by mass of deionized water at room temperature, and after sufficient wetting, 500rpm was turned on and stirring was rapidly carried out for 5 minutes, to finally obtain an aqueous gel dispersion composition containing a more U20-clumpy appearance.
Comparative example 2:
0.2 part by mass of U20 was sprinkled onto the surface of 99.8 parts by mass of deionized water at room temperature, and after sufficient wetting, 500rpm was turned on and stirring was rapidly carried out for 15 minutes, to finally obtain an aqueous gel dispersion composition containing a more U20-like floc appearance.
Comparative example 3:
0.2 part by mass of U20 was sprinkled onto the surface of 99.8 parts by mass of deionized water at room temperature, and after sufficient wetting, 500rpm was turned on and stirring was rapidly carried out for 30 minutes, to finally obtain an aqueous gel dispersion composition containing a more U20-clumpy appearance.
Comparative example 4:
0.2 part by mass of U20 is scattered on the surface of 99.8 parts by mass of deionized water at room temperature, after the deionized water is fully wetted, 5000rpm is started for homogenization for 3 minutes, and finally the aqueous gel dispersion system composition of U20 is obtained, the appearance of the aqueous gel dispersion system composition is fine, uniform and semi-transparent flowing liquid, and the upper surface layer of the aqueous gel dispersion system composition is provided with a plurality of bubbles.
From these experimental results the following conclusions can be drawn:
(1) it is demonstrated by examples 1 to 3 that amino acids (glycine as presented in the examples of the present invention) can help carbomer to disperse uniformly and thicken rapidly, glycine has obvious thickening effect on carbomer gel dispersions with different concentrations under the condition that the proportion of glycine is not changed, and the thickening effect depends on the actual concentration of carbomer.
(2) The group of references of example 2, example 4, example 5 and example 10, the group of references of example 1, example 8 and example 9, and the group of references of example 3, example 6 and example 7 respectively show that the viscosity of the gel is also influenced by the different addition ratios of glycine under the condition of constant carbomer concentration, namely, the higher the glycine ratio is, the higher the viscosity of the gel is when the carbomer concentration is the same; and the same concentration of glycine, the concentration of carbomer is a critical factor in affecting the final viscosity of the gel composition.
(4) Examples 11 to 13 show that amino acid thickening carbomers are also suitable for use in the alcohol-hydrogel system of carbomers, and that when carbomers are dispersed in a mixed solution of glycerin-water, butylene glycol-water and propylene glycol-water, a gel composition of the present invention can be obtained by adding glycine.
(5) Examples 14-18 illustrate that the amino acids described in the present patent (glycine as described in the examples) can help the carbomer to rapidly swell, disperse and thicken, and have thickening effects and universality for different types of carbomers.
(6) Comparative examples 1 to 3 show that the carbomer dispersion alone does not achieve rapid and uniform dispersion of the carbomer without the addition of glycine, and that even if the stirring dispersion time is increased, the desired effect is not achieved at all, and certainly there is no appearance that the carbomer dispersion can be swelled into a gel having a certain viscosity.
(7) The comparison example 4 shows that, although the high-energy mechanical external force action such as homogeneous shearing can help carbomer to realize the uniform dispersion process in water, the high energy consumption is required, and the homogeneous shearing causes more bubbles to be generated in the hydrogel dispersion system, so that the defoaming process is required to be additionally carried out, and the production steps are complicated. In addition, the homogenization process merely forms the carbomer aqueous dispersion into a uniform, translucent, fluid liquid and does not help to form a viscous gel, so the rapid thickening and swelling process described in the present invention is not realized.
It can be seen from the above experiments that the process of thickening acrylate polymers with amino acids is different from the prior art of alkali neutralization. During the neutralization thickening process, the pH will go from acidic to neutral or alkaline while forming a gel. In contrast, the process pH for amino acid thickening of acrylic polymers of the present application is still in the acidic range.
The composition containing the acrylate polymer and the amino acid can form a uniform and transparent gel composition, while the acrylate polymer in the prior art needs to be homogenized into a uniform and transparent dispersion system, and then added with alkali to neutralize and viscosity to form gel.
The invention has the advantages of reducing homogenization steps and alkali neutralization, reducing energy consumption and reducing cost.
Application example
The compositions of the present invention may be used as an intermediate material in the preparation of personal care products, preferably cosmetic compositions, including but not limited to the preparation of products in the form of creams, lotions, gels, lotions, serums, masks, eye creams, aerosols (cleansing foams), sprays, body washes, massage oils, facial cleansers, and the like.
The weight percentage of the composition of the present invention in the personal care product is 0.0001% to 20% (w/w); preferably 0.001-10% (w/w); more preferably 0.001-5% (w/w); most preferably 0.01% to 5% (w/w).
The following are specific examples of the use of the gel compositions obtained in examples 2-8 in personal care products, as well as the formulations and methods of preparation of these dosage forms. The specific application examples are as follows:
application example 1: preparation of astringent
Application example 2: preparation of essence
Application example 3: preparation of the emulsion
Application example 4: preparation of gel mask
Application example 5: preparation of face cream