阅读说明：本技术 一种高成膜性的化妆品定妆组合物 (Cosmetic makeup fixing composition with high film forming property ) 是由 喻竟 于 2021-07-02 设计创作，主要内容包括：本发明公开了一种高成膜性的化妆品定妆组合物,包含：a)至少一种聚氨酯A),该聚氨酯A)可通过一种或多种水不溶性、非水分散性的异氰酸酯官能化聚氨酯预聚物A1)与一种或多种氨基官能化合物A2)反应来获得；和b)至少一种聚甲基硅树脂B)。本发明通过聚氨酯搭配聚甲基硅树脂的技术,提升了硅树脂和皮肤的兼容性、以及粉底的持久性,特别是在四个小时到八个小时以后的持久性,达到持久定妆的效果；本发明具有高成膜性以及在正常环境下的持妆保持性的同时,还具有好的洗去性、优良的膜硬度和弹性以及舒适的皮肤感觉。(The invention discloses a cosmetic makeup-fixing composition with high film-forming property, which comprises the following components in part by weight: a) at least one polyurethane a) obtainable by reacting one or more water-insoluble, non-water-dispersible isocyanate-functional polyurethane prepolymers a1) with one or more amino-functional compounds a 2); and B) at least one polymethylsilicone B). According to the invention, by adopting the technology of matching polyurethane with polymethyl silicone resin, the compatibility of silicone resin and skin and the durability of foundation make-up are improved, especially the durability after four hours to eight hours, so that the effect of lasting make-up fixation is achieved; the invention has high film-forming property and long-lasting makeup retention property in normal environment, and also has good washing-off property, excellent film hardness and elasticity and comfortable skin feeling.)

1. A cosmetic makeup-fixing composition with high film-forming property is characterized in that: comprises the following steps:

a) at least one polyurethane a) obtainable by reacting one or more water-insoluble, non-water-dispersible isocyanate-functional polyurethane prepolymers a1) with one or more amino-functional compounds a 2); and

b) at least one polymethylsilicone resin B).

2. The high film-forming cosmetic makeup-fixing composition according to claim 1, characterized in that: wherein the amino-functional compound a2) is optionally a primary and/or secondary amine and/or a diamine; wherein the amino-functional compound A2) comprises at least one diamine.

3. The high film-forming cosmetic makeup-fixing composition according to claim 2, characterized in that: wherein amino-functional compound a2) comprises an amino-functional compound a2-I having no ionic or ionogenic groups and an amino-functional compound a2-II having ionic and/or ionogenic groups, wherein a2-I is a diamine having no ionic or ionogenic groups.

4. A high film-forming cosmetic makeup-fixing composition according to claim 3, characterized in that: wherein the isocyanate-functional polyurethane prepolymer a1) is obtainable by reacting one or more polyols selected from polyether polyols, polycarbonate polyols, polyether polycarbonate polyols and/or polyester polyols with one or more polyisocyanates; wherein the polyisocyanate comprises hexamethylene diisocyanate and/or isophorone diisocyanate.

5. The high film-forming cosmetic makeup-fixing composition according to claim 1, characterized in that: the polymethyl silicone resin B) is methyl MQ type silicone resin, wherein the methyl MQ type silicone resin is a novel organosilicon material with a three-dimensional (nonlinear) structure formed by taking Si-O bonds as a framework in molecules.

6. The high film-forming cosmetic makeup-fixing composition according to claim 5, characterized in that: the structural formula of the methyl MQ type silicon resin is [ (CH)₃)₃Si0_1/2]a[Si0_4/2]b, wherein [ (CH)₃)₃SiO_1/2]Is M, [ SiO ]_4/2]Q, and the molar ratio of M to Q mer is 0.6-0.9.

7. The high film-forming cosmetic makeup composition according to any one of claims 1 to 6, characterized in that: the solid component in the polyurethane A) accounts for 0.1 to 20 percent of the weight of the cosmetic composition; the solid component in the polymethyl silicone resin B) accounts for 0.1 to 20 percent of the weight of the cosmetic composition; the sum of the weights of polyurethane A) and polymethylsilicone B) is 0.1% to 30% of the total weight of the cosmetic composition.

8. The high film-forming cosmetic makeup-fixing composition according to claim 7, characterized in that: the weight ratio of the polyurethane A) to the polymethyl silicone resin B) is 1-5: 1-10.

9. The cosmetic fixing composition with high film forming property according to any one of claims 1 to 6, further comprising at least one of polyol, surfactant, preservative, essence, humectant and active.

10. The use of a high film-forming cosmetic makeup composition according to claim 1 in skin makeup.

Technical Field

The invention relates to the technical field of cosmetics, in particular to a cosmetic makeup fixing composition with high film-forming property.

Background

The epidermis of both humans and animals belongs to the stratum corneum protein. The composition for fixing the skin is one of cosmetic compositions, and can be used for fixing the skin and stabilizing different makeup. The skin make-up composition is primarily in the form of a make-up spray or a make-up lotion. The makeup mist and the makeup water have little difference in their compositions, but are different in their applications. A makeup spray is applied to the moist skin as an aid to model the makeup. In contrast, a make-up spray is sprayed onto dry, already patterned skin to secure the makeup. In addition to the make-up spray or make-up lotion, there are also forms of skin make-up gels.

The development of the prior art is still limited in the stage of water-in-silicone oil, and the durability of foundation is mainly brought by a polymer with better compatibility with silicone oil, such as silicone, but the compatibility of silicone and skin is not good enough, and the makeup-keeping effect is also not good. Therefore, the cosmetic makeup fixing composition with high film forming property provided by the invention has the characteristics of good makeup holding property, high film forming property, good washing property and the like.

Disclosure of Invention

In view of the above-mentioned deficiencies of the prior art, it is an object of the present invention to provide a cosmetic composition comprising a polyurethane, in particular a cosmetic make-up composition with high film-forming properties. The composition has good wash-off, excellent film hardness and elasticity, and a pleasant skin feel while having high film-forming properties and long-lasting makeup retention under normal conditions.

A high film forming cosmetic make-up fixative composition comprising:

a) at least one polyurethane a) obtainable by reacting one or more water-insoluble, non-water-dispersible isocyanate-functional polyurethane prepolymers a1) with one or more amino-functional compounds a 2); and

b) at least one polymethylsilicone resin B).

Preferably, the amino-functional compound a2) is optionally a primary and/or secondary amine and/or diamine; wherein the amino-functional compound A2) comprises at least one diamine.

Preferably, the amino-functional compound A2) comprises an amino-functional compound A2-I having no ionic groups or ionogenic groups and an amino-functional compound A2-II having ionic groups and/or ionogenic groups.

Preferably, the amino-functional compound A2) comprises an amino-functional compound A2-I having no ionic or ionogenic groups and an amino-functional compound A2-II having ionic and/or ionogenic groups, wherein A2-I is a diamine having no ionic or ionogenic groups.

Preferably, the isocyanate-functional polyurethane prepolymer a1) is obtainable by reacting one or more polyols selected from polyether polyols, polycarbonate polyols, polyether polycarbonate polyols and/or polyester polyols with one or more polyisocyanates; wherein the polyisocyanate comprises hexamethylene diisocyanate and/or isophorone diisocyanate.

Preferably, the polymethyl silicone resin B) is a methyl MQ type silicone resin, wherein the methyl MQ type silicone resin is a novel silicone material having a three-dimensional (nonlinear) structure in which the molecule thereof has a Si — O bond as a skeleton.

Preferably, the methyl MQ type silicone resin has the structural formula of [ (CH)₃)₃Si0_1/2]a[Si0_4/2]b, wherein [ (CH)₃)₃SiO_1/2]Is M, [ SiO ]_4/2]Q, and the molar ratio of M to Q mer is 0.6-0.9.

Preferably, the solid component of polyurethane a) represents from 0.1% to 20% by weight of the cosmetic composition; the solid component in the polymethyl silicone resin B) accounts for 0.1 to 20 percent of the weight of the cosmetic composition; the sum of the weights of polyurethane A) and polymethylsilicone B) is 0.1% to 30% of the total weight of the cosmetic composition.

Preferably, the weight ratio of the polyurethane A) to the polymethyl silicone resin B) is 1-5: 1-10.

Preferably, the cosmetic also comprises at least one of polyalcohol, surfactant, preservative, essence, humectant and active substance.

Preferably, the cosmetic makeup composition with high film-forming property is applied to skin makeup

The invention has the beneficial effects that:

according to the invention, by adopting the technology of matching polyurethane with polymethyl silicone resin, the compatibility of silicone resin and skin and the durability of foundation make-up are improved, particularly the durability after four hours to eight hours, and the effect of lasting make-up fixation is achieved.

The invention has high film-forming property and long-lasting makeup retention property in normal environment, and also has good washing-off property, excellent film hardness and elasticity and comfortable skin feeling.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention easier to clearly understand, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated herein may be arranged and designed in a wide variety of different configurations.

A high film forming cosmetic make-up fixative composition comprising:

a) at least one polyurethane a) obtainable by reacting one or more water-insoluble, non-water-dispersible isocyanate-functional polyurethane prepolymers a1) with one or more amino-functional compounds a 2); and

b) at least one polymethylsilicone resin B).

Wherein the amino-functional compound a2) is optionally a primary and/or secondary amine and/or a diamine; wherein the amino-functional compound A2) comprises at least one diamine.

Wherein amino-functional compound a2) comprises an amino-functional compound a2-I having no ionic or ionogenic groups and an amino-functional compound a2-II having ionic and/or ionogenic groups, wherein a2-I is a diamine having no ionic or ionogenic groups.

Wherein the isocyanate-functional polyurethane prepolymer a1) is obtainable by reacting one or more polyols selected from polyether polyols, polycarbonate polyols, polyether polycarbonate polyols and/or polyester polyols with one or more polyisocyanates; wherein the polyisocyanate comprises hexamethylene diisocyanate and/or isophorone diisocyanate.

The polymethyl silicone resin B) is methyl MQ type silicone resin, wherein the methyl MQ type silicone resin is a novel organosilicon material with a three-dimensional (nonlinear) structure formed by taking Si-O bonds as a framework in molecules.

The structural formula of the methyl MQ type silicon resin is [ (CH)₃)₃Si0_1/2]a[Si0_4/2]b, wherein [ (CH)₃)₃SiO_1/2]Is M, [ SiO ]_4/2]Is Q, andthe molar ratio of M to Q mer is 0.6-0.9.

The silicone resin types mainly comprise methyl phenyl silicone resin, methyl silicone resin, low phenyl methyl silicone resin, silicone resin emulsion, self-drying silicone resin, high-temperature silicone resin, epoxy modified silicone resin, silicone polyester modified resin, self-drying environment-friendly silicone resin, non-stick coating silicone resin, highlight silicone resin, benzyl transparent silicone resin, methyl transparent silicone resin, mica bonded silicone resin, polymethyl silicone resin, amino silicone resin, fluorosilicone resin, silicone resin solution, silicone-epoxy resin, silicone polyester resin, solvent-resistant silicone resin, silicone resin adhesive, fluorosilicone sealant, high-temperature-resistant methyl silicone resin, self-drying silicone insulating paint, methyl MQ silicone resin, vinyl silicone resin and silicone acrylic resin coating.

The properties of the silicone resin are also closely related to the type of the organic group R, and when the organic group is-CH 3, the silicone resin is rendered thermally stable and hydrophobic, and is within the scope of the present invention, so that the use of methyl MQ silicone resin is preferred.

The methyl MQ silicon resin is generally hydrolyzed by methyl trichlorosilane, dimethyl dichlorosilane and various mixtures in the presence of organic solvents such as toluene at a lower temperature to obtain an acidic hydrolysate. The initial product of hydrolysis is a mixture of cyclic, linear and crosslinked polymers, which usually also contain a considerable number of hydroxyl groups. Washing the hydrolysate with water to remove acid, thermally oxidizing the neutral initial polymer in air or further polycondensing in the presence of catalyst to form a highly crosslinked stereo network structure.

The number of organic groups contained in the MQ silicone resin, i.e., the M/Q value, is one of the main indicators for controlling the quality of the silicone resin, and it is preferable that the molar ratio of the M to Q mer is 0.6 to 0.9 within the scope of the present invention. The MQ silicon resin within the range has good film forming property, flexibility, durability, heat resistance, thermal cracking resistance and the like.

The solid component in the polyurethane A) accounts for 0.1 to 20 percent of the weight of the cosmetic composition; the solid component in the polymethyl silicone resin B) accounts for 0.1 to 20 percent of the weight of the cosmetic composition; the sum of the weight of polyurethane A) and polymethylsilicone B) is 0.1% to 30% of the total weight of the cosmetic composition.

The weight ratio of the polyurethane A) to the polymethyl silicone resin B) is preferably 1-5: 1-10.

In the context of the present invention, the term "water-insoluble, water-non-dispersible polyurethane prepolymer" means that the solubility of the prepolymer in water at 23 ℃ is less than 10 g/l, preferably less than 5 g/l, and that the prepolymer does not give rise to sedimentation-stable dispersions in water (in particular deionized water) at 23 ℃. In other words, in any experiment in which it was dispersed in water, the prepolymer precipitated out. Water here refers to deionized water without added surfactant.

In some embodiments, it is preferred that the polyurethane prepolymers used in the present invention have terminal isocyanate groups, i.e., the isocyanate groups are at the chain ends of the prepolymer. Further preferably, all chain ends of the prepolymer have an isocyanate group.

Further, the polyurethane prepolymer used in the present invention preferably has substantially neither an ionic group nor an ionogenic group, that is, the content of the ionic group and the ionogenic group is suitably less than 15 milliequivalents (Mil1iequivalent)/100g of the polyurethane prepolymer, preferably less than 5 milliequivalents, further preferably less than 1 milliequivalents, particularly preferably less than 0.1 milliequivalents/l 00g of the polyurethane prepolymer.

In some embodiments, preferably, the amino-functional compound is selected from at least one of primary amines, secondary amines, and diamines; further preferably, the amino-functional compound is selected from at least one of diamines. Still further preferably, the amino-functional compound is an amino-functional compound having an ionic group or a ionogenic group.

In some embodiments, it is preferable that the alkyl tin compound has a primary structure having a mono-substituent, a di-substituent, a tri-substituent and a tetra-substituent (referring to the number of R). The structural general formula of the compound is RnSnX4-n, and R is alkyl. The total is methyl, ethyl, propyl, butyl and octyl. When n is 1-4, there are one, two, three and four alkyl tin compounds. X can be oxygen, sulfur, chlorine, bromine, iodine and organic acids.

The present invention provides cosmetic compositions, especially aqueous (i.e. water-based) compositions, wherein the polyurethane is present in dispersed form, i.e. substantially in non-dissolved form. Water generally constitutes the major constituent of the dispersion medium, in addition to other liquid media such as solvents that may be present, and is greater than 50% by weight based on the total amount of liquid dispersion medium in the cosmetic composition.

In some embodiments, preferably, the cosmetic composition of the present invention preferably has a Volatile Organic Compound (VOC) content of less than 80 wt%, more preferably less than 55 wt%, even more preferably less than 40 wt%, based on the cosmetic composition.

In some embodiments, it is further preferred that the aqueous polyurethane dispersion used to prepare the cosmetic composition has a Volatile Organic Compound (VOC) content of less than 10 wt%, preferably less than 3 wt%, more preferably less than 1 wt%, based on the aqueous polyurethane dispersion.

The acid number of the prepolymer is suitably below 30mg KOH/g, preferably below 10mg KOH/g, in respect of the acidic ionic groups and/or ionogenic groups. The acid number represents the mass (mg) of potassium hydroxide required to neutralize 1g of the investigated sample (measured according to DIN EN ISO 211). The neutralized acid (i.e., the corresponding salt) naturally has no acid value or has a reduced acid value. Lower acid numbers ensure film hardness within the appropriate range.

In some embodiments, preferably, the prepolymer used in the preparation of the polyurethane is obtained by reacting at least one of a polyether polyol, a polycarbonate polyol, a polyether polycarbonate polyol, and a polyester polyol with at least one polyisocyanate.

In some embodiments, more preferably, each of the above-described polymer polyols has a number average molecular weight of preferably about 400-6000g/mol (as determined by gel permeation chromatography in tetrahydrofuran at 23 ℃ C. relative to polystyrene standards here and for the molecular weight data below). Their use in the preparation of polyurethanes or polyurethane prepolymers will, as a result of reaction with polyisocyanates, lead to the formation of corresponding polyether and/or polycarbonate and/or polyether-polycarbonate segments or polyester segments in the polyurethanes having the corresponding molecular weights of these segments. Further preferably, the various polymer polyols described above are polymer polyols having a linear structure.

In some embodiments, it is still further preferred that the polyurethane is preferably a substantially linear molecule. Of course, in other embodiments, it may be branched.

In some embodiments, the number average molecular weight of the polyurethane used is about 1000-.

In some preferred embodiments herein, the polyurethane is added to the cosmetic composition, especially in the form of an aqueous dispersion.

The polyurethanes or polyurethane dispersions used in the examples of the present application can be obtained by methods known in the art using known components, for example, U.S. patent publication No. US 2011/002721[ nintendril 1]1, which is hereby incorporated by reference in its entirety.

The corresponding steps are briefly described as follows:

a) preparation of an isocyanate-functional polyurethane prepolymer formed from

An organic polyisocyanate, wherein the polyisocyanate is selected from the group consisting of,

the polymer polyols preferably have a number average molecular weight of 400-8000g/mol (determined here and for the following molecular weight data by gel permeation chromatography in tetrahydrofuran at 23 ℃ relative to polystyrene standards), more preferably 400-6000g/mol and particularly preferably 600-3000g/mol, and an OH functionality of preferably 1.5 to 6, more preferably 1.8 to 3, particularly preferably 1.9 to 2.1, optionally hydroxy-functional compounds having a molecular weight of preferably 62 to 399g/mol, and optionally nonionic hydrophilicizing agents.

b) Some or all of their free NCO groups are then reacted with one or more amino-functional compounds A2), such as primary and/or secondary amines and/or diamines. The polyurethane used according to the invention is preferably dispersed in water before, during or after step b).

The reaction with the diamine or two or more diamines in step b) is particularly preferably carried out with chain extension. In this regard, monofunctional amines can additionally be added as chain terminators to control molecular weight.

As component A2), it is possible in particular to use compounds which have no ionic groups or ions

The invention is illustrated by the following examples, which should not be construed as limiting. Unless otherwise indicated, all quantitative data, fractions and percentages are by weight or based on the total weight of the composition.

Raw materials and reagents:

table 1:

the examples and comparative examples of the present invention can be prepared as follows: at a stirring speed of 500-600rpm, the polyurethane A according to the inventionP500-1 Water-in-oil emulsifier is added with stirring, followed by the addition of the oil phase to participate in the emulsification, silicone Polymer B: (P620) adding cyclomethicone (1:4), and continuously stirring to uniformly disperse the cyclomethicone; the formulation was added after emulsification was complete.

Table 2: comparative examples 1 to 8

Table 3: examples 1 to 4

Wherein wt% refers to the weight percent of the solid component of the composition based on the total weight of the formulation sample. And the sum of the percentages by weight of the solid components in polyurethane A) and polymethyl silicone B) is kept at 2% by weight.

Evaluation experiment:

the skin used in the following experiments was asian skin. All skin was healthy and undamaged.

The prepared products are respectively smeared on the skin, after the skin is completely dried, the evaluation group consisting of five trained people scores each item, wherein 1 score is the lowest and the worst, and 10 scores are the best and the strongest. Since the scores are relative, there is no comparability between the scores of the respective groups.

For the "leave-on" experiment, the skin was subjected to a standardized washing procedure. The skin softened in water for 15 minutes was rinsed for 2 minutes by washing the skin with a 12 wt% sodium lauryl sulfate solution, rinsed thoroughly with warm water, and blown dry on a cold air screen.

Foundation samples were applied in 2 x 2cm areas and the "leave-on" experiments were performed in a special climate laboratory with a relative humidity > 60%. The temperature of the chamber was 25 ℃.

Test conditions, water resistance, scratch resistance, and durability of 1h, 2h, 4h and 8 h.

Table 4: evaluation results

	Water-proof property	Scratch resistance	1h	2h	4h
						Comparative example 1	7	7	8	6.5	5
Comparative example 2	7.5	6.5	8.5	7	5.5
						Comparative example 3	6.5	5.5	8	6.5	5
Comparative example 4	7	6	8.5	7	5.5
						Comparative example 5	7	7	8	7	6
Comparative example 6	7.5	7.5	8.5	7.5	6.5
						Comparative example 7	7.5	7.5	8	7	6
Comparative example 8	8	8	8.5	7.5	6.5
						Example 1	8	8.5	9.5	9	8
Example 2	8.5	9	9.5	9.5	9
						Example 3	7.5	8	9.5	9	8
Example 4	8	8.5	9.5	9.5	8.5

The above experiments again demonstrate that the formulations using both polyurethane a) and polymethylsilicone B) have a significantly improved make-up-holding effect relative to the formulations using polyurethane a) alone.

According to the invention, by adopting the technology of matching polyurethane with polymethyl silicone resin, the compatibility of silicone resin and skin and the durability of foundation make-up are improved, particularly the durability after four hours to eight hours, and the effect of lasting make-up fixation is achieved.

The invention has high film-forming property and long-lasting makeup retention property in normal environment, and also has good washing-off property, excellent film hardness and elasticity and comfortable skin feeling.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.