阅读说明：本技术 一种聚氨酯弹性体的合成工艺及微孔发泡材料的制备工艺 (Synthesis process of polyurethane elastomer and preparation process of microporous foam material ) 是由 张宝玲 于 2021-06-17 设计创作，主要内容包括：本发明适用化妆品技术领域,提供一种聚氨酯弹性体的合成工艺及微孔发泡材料的制备工艺,所述聚氨酯弹性体包括以下原料：聚合物二元醇、二异氰酸化合物、扩链剂、抗氧化剂、催化剂、反应介质和终止剂；本发明实施例将聚氨酯合成混合浆料,通过物理方法起泡,形成微孔结构,孔与孔互相重叠、连通；表面细腻光滑,弹性好不容易变形,不容易吸粉残留化妆品,本发明实施例所制备的产品的吸水性较小；解决了现有粉扑、美妆蛋等美妆产品,材料表面粗糙,湿水后体积增大,流动性强、容易吸粉的问题。(The invention is suitable for the technical field of cosmetics, and provides a synthesis process of a polyurethane elastomer and a preparation process of a microcellular foam material, wherein the polyurethane elastomer comprises the following raw materials: polymer dihydric alcohol, diisocyanate compound, chain extender, antioxidant, catalyst, reaction medium and terminator; in the embodiment of the invention, polyurethane is synthesized into mixed slurry, and the slurry is foamed by a physical method to form a microporous structure, wherein holes are mutually overlapped and communicated; the surface is fine and smooth, the elasticity is good, the deformation is not easy, the powder absorption residual cosmetics are not easy, and the water absorption of the product prepared by the embodiment of the invention is small; solves the problems of rough material surface, increased volume after wetting, strong fluidity and easy powder absorption of the existing makeup products such as powder puff, makeup eggs and the like.)

1. The polyurethane elastomer is characterized by comprising the following raw materials in parts by mass:

12.38-33.42% of polymer diol, 3.73-10.06% of diisocyanate compound, 0.55-1.48% of chain extender, 0.1-0.2% of antioxidant, 0.01-0.03% of catalyst, 54.87-83.29% of reaction medium and 0.05-0.13% of terminator.

2. The polyurethane elastomer according to claim 1, wherein the polymer diol comprises polyester diol and polyether diol, and the molar ratio of the polyester diol to the polyether diol in the polymer diol is 1: 5 to 5: 1.

3. a process for the synthesis of a polyurethane elastomer according to any one of claims 1-2, comprising the steps of;

adding polymer dihydric alcohol, a diisocyanate compound, a chain extender, an antioxidant, a catalyst and a reaction medium into a reaction tank according to a ratio, uniformly stirring for more than 30 minutes, heating the materials to 75-85 ℃, reacting for 2-6 hours, supplementing the reaction medium according to viscosity change during the reaction, stopping heating reaction when the viscosity reaches more than 180 million CPS, adding a terminator, cooling, and hermetically storing the polyurethane elastomer slurry.

4. A microcellular foam material comprising polyurethane elastomer slurry prepared by the polyurethane elastomer synthesis process according to claim 3, wherein the microcellular foam material comprises the following raw materials in parts by mass:

10.02-16.98% of polyurethane elastomer slurry, 66.65-83.03% of filler, 0.73-1.19% of surfactant, 0.002-0.3% of pigment, 0.04-0.3% of slip agent and 0.05-0.25% of flame retardant.

5. The microcellular foamed material according to claim 4, wherein the surfactant is one or more than one of nonionic surfactants, or a mixture between an anionic surfactant and a nonionic surfactant.

6. The microcellular foam material according to claim 4, wherein the anionic surfactant is one selected from the group consisting of sodium lauryl sulfate, sodium alkylbenzenesulfonate, disodium lauryl sulfosuccinate, lauramide group, disodium MEA-sulfosuccinate, sodium isoethersulfate, sodium fatty alcohol ether sulfate, sodium octylphenol polyoxyethylene ether sulfate, ammonium allyloxy fatty alcohol polyoxyethylene ether sulfate; the non-ionic surfactant is one or two of Tween 20(TWEEN-20), Tween 21(TWEEN-21), Tween 40(TWEEN-40), Tween 60(TWEEN-60), Tween 61(TWEEN-61), Tween 80(TWEEN-80), Tween 81(TWEEN-81), Tween 85(TWEEN-85), span SP-20, SP-40, SP-60, SP-80, SP-85, octylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether and isomeric alcohol polyoxyethylene ether.

7. A process for the preparation of a microcellular foamed material according to any one of claims 4 to 6, comprising the steps of;

(1) adding a filler: sequentially adding pigment, surfactant, flame retardant, slip agent and polyurethane elastomer slurry into a dispersion machine, uniformly mixing, finally adding corresponding filler, and continuously stirring for 2 hours to obtain a pasty slurry mixture A;

(2) extruding: extruding the slurry mixture A into a die through an extruder, keeping the temperature of each section of the extruder at 30-45 ℃, and avoiding bubbles through vacuumizing equipment in the extruding process;

(3) soaking in water: soaking the pulp filled in the mold in water for 3-20 days to form microporous foam;

(4) and taking the foam out of the water, drying the water, processing the foam into various shapes required by the product by adopting a grinding machine according to the requirement of the product, and then warehousing the foam after the foam is qualified by detection.

Technical Field

The invention belongs to the technical field of cosmetics, and particularly relates to a synthesis process of a polyurethane elastomer and a preparation process of a microcellular foam material.

Background

Along with the improvement of living standard of people, people pay more and more attention to external beauty, people who make up the makeup also get more and more, and the market of cosmetic cotton shows a growing trend. The cosmetic cotton products on the market at present comprise powder puff, makeup eggs and the like. The materials used by the latex are natural latex and non-natural latex, wherein the non-natural latex has high popularity due to the advantages of long service life, low use allergy rate and the like; among the non-natural latex materials, polyurethane is used mostly, the polyurethane has good rebound resilience, low temperature resistance and good wear resistance, is not sensitive to skin contact, and is very suitable for powder puff and makeup egg products; in the preparation process, most of the base makeup products are chemical foaming processes, due to material reasons, the surface of the base makeup products is rough, the volume is increased by 15% after the base makeup products are wetted, and the base makeup products with strong fluidity and high water content are easy to absorb powder.

Disclosure of Invention

The embodiment of the invention aims to provide a synthesis process of a polyurethane elastomer and a preparation process of a microcellular foam material, so as to solve the problems in the background technology.

In order to achieve the above object, an embodiment of the present invention provides a polyurethane elastomer, which includes the following raw materials by mass:

12.38-33.42% of polymer diol, 3.73-10.06% of diisocyanate compound, 0.55-1.48% of chain extender and antioxidant: 0.1-0.2 percent of catalyst, 0.01-0.03 percent of reaction medium, 54.87-83.29 percent of reaction medium and 0.05-0.13 percent of terminator.

Preferably, the polymer diol comprises polyester diol and polyether diol, and the molar ratio of the polyester diol to the polyether diol in the polymer diol is 1: 5 to 5: 1.

preferably, the polyester diol comprises one or two of polyester diol with the molecular weight of 1000-4000, polycaprolactone diol with the molecular weight of 1000-3000 and polycarbonate diol with the molecular weight of 500-3000; the polyether diol is one or two of PPG type with molecular weight of 500-5000, polyoxyethylene glycol with molecular weight of 400-2000 and polytetrahydrofuran glycol with molecular weight of 1000-3000. The hydroxyl group of the above-mentioned polymer diol is generally selected from the range of 30 to 200 mgKOH/g.

Preferably, the diisocyanate compound includes diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI).

Preferably, the chain extender comprises one of an amine chain extender and an alcohol chain extender; the amine chain extender is one or two of ethylenediamine, N-dihydroxy (diisopropyl) aniline, Moca (MOCA), 3, 5-diethyltoluenediamine, 3, 5-dimethylthiotoluenediamine, N-di-sec-butyl-p-phenylenediamine and N, N-bisaminopropyl methylamine; the alcohol chain extender is one or two of ethylene glycol, 1, 4-butanediol, ethylene glycol, 1, 6-hexanediol, neopentyl glycol, 2-methylpropanediol, 1, 2-propanediol, diethylene glycol, dipropylene glycol, 1, 4-cyclohexanediol and 2-butyl-2-ethyl-1, 3-propanediol.

Preferably, the catalyst is one of triethylene diamine, dimethylethanolamine, dibutyltin dilaurate, organic bismuth, triethylamine, stannous octoate, dibutyltin diacetate, bismuth isooctanoate and zinc isooctanoate.

Preferably, the reaction medium is one or two of dimethylformamide and dimethylacetamide.

Preferably, the antioxidant is one of triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, 4' -butylidenebis- (3-methyl-6-tert-butylphenyl) -tetrakis (tridecyl) diphosphite, diisoproylether diphosphite, distearyl pentaerythritol diphosphite, hydrogenated bisphenol a pentaerythritol phosphite.

The synthesis process of the polyurethane elastomer comprises the following steps;

adding polymer dihydric alcohol, a diisocyanate compound, a chain extender, an antioxidant, a catalyst and part of reaction medium into a reaction tank according to the proportion, uniformly stirring for more than 30 minutes, heating the materials to 75-85 ℃, reacting for 2-6 hours, supplementing the reaction medium according to viscosity change during the reaction, stopping heating reaction when the viscosity reaches more than 180 million CPS, adding a terminator, cooling, and hermetically storing the polyurethane elastomer slurry.

A microcellular foam material of polyurethane elastomer slurry prepared by the polyurethane elastomer synthesis process comprises the following raw materials in parts by mass:

10.02-16.98% of polyurethane elastomer slurry, 66.65-83.03% of filler, 0.73-1.19% of surfactant, 0.002-0.3% of pigment, 0.04-0.3% of slip agent and 0.05-0.25% of flame retardant.

Preferably, the filler is one or a mixture of more than one of sodium chloride, anhydrous calcium carbonate, sodium bicarbonate, anhydrous sodium sulfate and polyvinyl alcohol powder.

Preferably, the surfactant is one or more than one mixture of nonionic surfactants, or the surfactant is a mixture between an anionic surfactant and a nonionic surfactant.

Preferably, the anionic surfactant is one of sodium dodecyl sulfate, sodium alkyl benzene sulfonate, disodium lauryl sulfosuccinate, lauramide group, disodium MEA-sulfosuccinate, sodium isomeric alcohol ether sulfate, sodium fatty alcohol ether sulfate, sodium octylphenol polyoxyethylene ether sulfate and ammonium allyloxy fatty alcohol polyoxyethylene ether sulfate; the non-ionic surfactant is one or two of Tween 20(TWEEN-20), Tween 21(TWEEN-21), Tween 40(TWEEN-40), Tween 60(TWEEN-60), Tween 61(TWEEN-61), Tween 80(TWEEN-80), Tween 81(TWEEN-81), Tween 85(TWEEN-85), span SP-20, SP-40, SP-60, SP-80, SP-85, octylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether and isomeric alcohol polyoxyethylene ether.

Preferably, the pigment is one of a basf Heliogen pigment, a Cinquasia series pigment, a Cromophtal series pigment, a Heliogen pigment, a Paliogen series pigment, a Microlith series pigment.

Preferably, the slip agent is an organosilicon slip agent, and the organosilicon slip agent is one or a mixture of more than one of dimethyl silicone oil, diethyl silicone oil, benzyl silicone oil, polyether modified silicone oil containing hydroxyl, amino silicone oil, block silicone oil and vinyl silicone oil.

Preferably, the flame retardant is one of tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (dichloropropyl) phosphate, dimethyl methylphosphonate, diethyl ethylphosphonate, dimethyl propylphosphonate, triethyl phosphate, tris (butoxyethyl) phosphate, isopropylated triphenyl phosphate, melamine cyanurate, melamine (poly) phosphate, tris (dipropylene glycol) phosphite, tetraphenyldipropylene glycol diphosphite, diethyl N, N-bis (2-hydroxyethyl) aminomethylene phosphonate, dimethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate and mixtures of one or more thereof.

The preparation process of the microcellular foam material comprises the following steps;

(1) adding a filler: sequentially adding pigment, surfactant, flame retardant, slip agent and polyurethane elastomer slurry into a dispersion machine, uniformly mixing, finally adding corresponding filler, and continuously stirring for 2 hours to obtain a pasty slurry mixture A;

(2) extruding: extruding the slurry mixture A into a die through an extruder, keeping the temperature of each section of the extruder at 30-45 ℃, and avoiding bubbles through vacuumizing equipment in the extruding process;

(3) soaking in water: soaking the pulp filled in the mold in water for 3-20 days to form microporous foam;

(4) and taking the foam out of the water, drying the moisture by using an oven, processing the foam into various shapes required by the product by using a grinding machine according to the requirement of the product, and then warehousing the foam after the foam is qualified by detection.

In summary, due to the adoption of the technical scheme, the method has the following beneficial effects:

the embodiment of the invention provides a synthesis process of a polyurethane elastomer and a preparation process of a microcellular foam material, the production process of the embodiment of the invention is different from the traditional two-component form chemical foaming polyurethane, the polyurethane is synthesized into mixed slurry and is foamed by a physical method to form a microcellular structure, the particle size of the microcells is smaller, and the cells are overlapped and communicated with each other; the surface is fine and smooth, the elasticity is good, the deformation is not easy, the powder residual cosmetics are not easy to absorb, and the water absorption of the product prepared by the embodiment of the invention is small.

Drawings

FIG. 1 is a diagram of a microcellular foam material prepared according to an embodiment of the present invention under high power microscope detection.

FIG. 2 is a photograph of a comparative sample product in the market under high power microscope detection.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the embodiments of the present invention are described in further detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the embodiments of the invention and are not limiting of the embodiments of the invention.

Most of the existing powder puff and makeup egg products are chemical foaming processes in the preparation process, and due to the material, the surface of the material is rough, the volume is increased by 15% after wet water, and the makeup base products with strong fluidity and high water content are easy to absorb powder; the polyurethane synthesis mixed slurry provided by the embodiment of the invention is foamed by a physical method to form a microporous structure, and the pores are mutually overlapped and communicated; the surface is fine and smooth, the elasticity is good, the deformation is not easy, and the powder absorption residual cosmetics are not easy.

Example 1

Preparation of polyurethane elastomer slurry: adding 15.09% of polymer diol, 9.33% of diisocyanate compound, 74.87% of reaction medium, 0.55% of chain extender, 0.1% of antioxidant and 0.01% of catalyst into a reaction tank according to the corresponding proportion, uniformly stirring for more than 30 minutes at the stirring speed of 50 revolutions per minute, heating the materials to 75 ℃, reacting for 2 hours, stopping heating reaction when the viscosity reaches more than 180 million CPS, adding 0.05% of terminator, cooling, and hermetically storing polyurethane elastomer slurry;

sequentially adding 0.002% of pigment, 0.73% of surfactant, 0.05% of flame retardant, 0.04% of slip agent and 10.02% of polyurethane elastomer slurry into a dispersion machine according to corresponding proportions, uniformly mixing, finally adding 66.65% of corresponding filler, and continuously stirring for 2 hours to obtain a pasty slurry mixture A;

extruding the slurry mixture A into a die through an extruder, keeping the temperature of each section of the extruder at 30 ℃, and avoiding bubbles through vacuumizing equipment in the extruding process;

soaking the pulp filled in the mold in water for 3 days to form microporous foam;

and taking the foam out of the water, drying the moisture by using an oven, processing the foam into various shapes required by the product by using a grinding machine according to the requirement of the product, and then warehousing the foam after the foam is qualified by detection.

The polymer diol comprises polyester diol and polyether diol, and the molar ratio of the polyester diol to the polyether diol in the polymer diol is 1: 5.

the polyester diol is polycaprolactone diol with molecular weight of 1000.

The diisocyanate compound is MDI.

The chain extender is an amine chain extender.

The catalyst is triethylenediamine.

The reaction medium is dimethylformamide.

The antioxidant is triphenyl phosphite.

The terminator is methanol.

The surfactant is a mixture of an anionic surfactant and a nonionic surfactant, and the molar ratio of the anionic surfactant to the nonionic surfactant is 1: 1 to 1: 10, the surfactant has a function of regulating micropores.

The anionic surfactant is sodium dodecyl sulfate; the non-ionic surfactant is Tween 20 (TWEEN-20).

The filler is sodium chloride.

The slip agent is dimethyl silicone oil, and the slip agent can improve the silky smoothness.

The flame retardant is tris (2-chloroethyl) phosphate.

Example 2

Preparation of polyurethane elastomer slurry: adding 16.59% of polymer diol, 10.06% of diisocyanate compound, 71.59% of reaction medium, 1.48% of chain extender, 0.12% of antioxidant and 0.03% of catalyst into a reaction tank according to a corresponding proportion, uniformly stirring for more than 30 minutes at a stirring speed of 50 rpm, heating the materials to 85 ℃, reacting for 6 hours, stopping heating reaction when the viscosity reaches more than 180 ten thousand CPS, adding 0.13% of terminator, cooling, and hermetically storing polyurethane elastomer slurry;

sequentially adding 0.3% of pigment, 1.19% of surfactant, 0.25% of flame retardant, 0.3% of slip agent and 16.98% of polyurethane elastomer slurry into a dispersion machine according to corresponding proportion, uniformly mixing, finally adding corresponding 80.98% of filler, and continuously stirring for 2h to obtain pasty slurry mixture A;

extruding the slurry mixture A into a die through an extruder, keeping the temperature of each section of the extruder at 45 ℃, and avoiding bubbles through vacuumizing equipment in the extruding process;

soaking the pulp filled in the mold in water for 20 days to finally form microporous foam;

and taking the foam out of the water, drying the moisture by using an oven, processing the foam into various shapes required by the product by using a grinding machine according to the requirement of the product, and then warehousing the foam after the foam is qualified by detection.

The polymer diol comprises polyester diol and polyether diol, and the molar ratio of the polyester diol to the polyether diol in the polymer diol is 5: 1.

the polyester diol is polycaprolactone diol with molecular weight of 1000 and polycarbonate diol with molecular weight of 500; the polyether glycol is polyoxyethylene glycol with molecular weight of 400 and polytetrahydrofuran glycol with molecular weight of 1000.

The diisocyanate compound is TDI.

The chain extender is an alcohol chain extender.

The catalyst is dibutyltin dilaurate.

The reaction medium is a mixture between dimethylformamide and dimethylacetamide.

The antioxidant is tridecyl phosphite.

The terminating agent is a mixture of ethanol and isopropanol.

The surfactant is a mixture of an anionic surfactant and a nonionic surfactant, and the molar ratio of the anionic surfactant to the nonionic surfactant is 1: 1 to 1: 10, the surfactant has a function of regulating micropores.

The anionic surfactant is disodium lauryl sulfosuccinate; the non-ionic surfactant is a mixture of Tween 20(TWEEN-20) and Tween 21 (TWEEN-21).

The filler is a mixture of sodium chloride and anhydrous calcium carbonate.

The slip agent is a mixture of dimethyl silicone oil and diethyl silicone oil, and the slip agent can improve the silk smoothness.

The flame retardant is a mixture of tris (2-chloroethyl) phosphate and tris (2-chloropropyl) phosphate.

Example 3

Preparation of polyurethane elastomer slurry: adding 13.85% of polymer diol, 6.9% of diisocyanate compound, 78% of reaction medium, 1.0% of chain extender, 0.15% of antioxidant and 0.02% of catalyst into a reaction tank according to a corresponding proportion, uniformly stirring for more than 30 minutes at a stirring speed of 50 rpm, heating the materials to 80 ℃, reacting for 4 hours, stopping heating reaction when the viscosity reaches more than 180 million CPS, adding 0.08% of terminator, cooling, and hermetically storing polyurethane elastomer slurry;

sequentially adding 0.2% of pigment, 1.1% of surfactant, 0.2% of flame retardant, 0.2% of slip agent and 16.3% of polyurethane elastomer slurry into a dispersion machine according to corresponding proportions, uniformly mixing, finally adding 82% of corresponding filler, and continuously stirring for 2h to obtain a pasty slurry mixture A;

extruding the slurry mixture A into a die through an extruder, keeping the temperature of each section of the extruder at 40 ℃, and avoiding bubbles through vacuumizing equipment in the extruding process;

soaking the pulp filled in the mold in water for 15 days to finally form microporous foam;

and taking the foam out of the water, drying the moisture by using an oven, processing the foam into various shapes required by the product by using a grinding machine according to the requirement of the product, and then warehousing the foam after the foam is qualified by detection.

The polymer diol comprises polyester diol and polyether diol, and the molar ratio of the polyester diol to the polyether diol in the polymer diol is 1: 5; the polyester diol is polycaprolactone diol with the molecular weight of 1000-3000, and the polyether diol is polyoxyethylene diol with the molecular weight of 400-2000; the diisocyanate compound is MDI; the chain extender is an amine chain extender, and the amine chain extender is N, N-dihydroxy (diisopropyl) aniline; the catalyst is triethylenediamine; the reaction medium is dimethylformamide; the antioxidant is tridecyl phosphite; the terminator is methanol; the surfactant is a mixture of an anionic surfactant and a nonionic surfactant, and the molar ratio of the anionic surfactant to the nonionic surfactant is 1: 1; the anionic surfactant is sodium dodecyl sulfate; the nonionic surfactant is isomeric alcohol polyoxyethylene ether; the filler is sodium chloride. The slip agent is diethyl silicone oil; the flame retardant is tris (2-chloroethyl) phosphate.

The product prepared in example 3 and the same kind of sample in the market were examined by a high power microscope, and the product prepared in example 3 and the same kind of sample in the market were examined by a high power microscope with a view enlarged by 50 times. The results are shown in FIGS. 1 and 2.

As can be seen from FIG. 1, the product prepared in example 3 of the present invention has relatively small and dense holes, and the holes are overlapped and communicated with each other, so that it is not easy to suck residual cosmetics.

As can be seen from FIG. 2, the samples on the market are not durable because the cells are large and sparse and there is no connection between the cells, and thus a large amount of cosmetics is easily absorbed.

In summary, the embodiment of the present invention provides a synthesis process of a polyurethane elastomer and a preparation process of a microcellular foam material, the production process of the embodiment of the present invention is different from the traditional two-component form chemical foaming polyurethane, the polyurethane is synthesized into a mixed slurry, the slurry is foamed by a physical method to form a microcellular structure, and the holes are overlapped and communicated with each other; the surface is fine and smooth, the elasticity is good, the deformation is not easy, the powder residual cosmetics are not easy to absorb, the water absorption of the product prepared by the embodiment of the invention is smaller, and the particle size of the micropores is smaller.

It will be evident to those skilled in the art that the embodiments of the present invention are not limited to the details of the foregoing illustrative embodiments, and that the embodiments of the present invention are capable of being embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the embodiments being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.