A polyurethane-cationic polymer emulsion with an interpenetrating network structure and a preparation method thereof and its application in the field of personal care

Abstract

The present invention relates to a polyurethane-cationic polymer emulsion with an interpenetrating network structure, a preparation method and an application thereof in the field of personal care. The present invention adds a polyol containing vinyl in the preparation process of aqueous polyurethane, and can obtain a polyurethane-cationic polymer emulsion with an interpenetrating network structure through free radical polymerization with cationic and non-ionic vinyl monomers. The polymer prepared by the present invention can improve the fullness and combing properties of hair, has the effects of toughening, fullness and smoothness, and has a good thickening effect in shampoo.

Description

Technical Field

[0001] The invention relates to the field of cleaning and washing, and in particular to a method for preparing a polyurethane-cationic polymer emulsion with an interpenetrating network structure and application thereof in the field of personal care. Background Art

[0002] There are two main reasons why hair becomes dirty. On the one hand, hair is negatively charged and easily absorbs suspended particles in the air. More importantly, a large amount of sebum accumulates. Therefore, shampoo compositions contain a large amount of surfactants, usually anionic, which clean the hair and remove secretions and dirt accumulated on the human body by metabolism. However, excessive and frequent use will also remove the natural oils and other ingredients that are beneficial to the hair, leading to frizzy hair, tangles, loss of flexibility, poor hair quality, and easy generation of static electricity. At present, shampoos on the market not only have the function of washing hair, but also add some functional substances to play the role of removing dandruff, plumping and smoothing, so as to achieve two-in-one washing and care.

[0003] In recent years, amino acid surfactants have replaced sulfate anionic surfactants and begun to be used in some formulations due to their excellent properties such as low irritation, low toxicity, antibacterial properties and biodegradability. In addition to the cleaning function, surfactants have a thickening effect under the action of inorganic salts such as sodium chloride. However, the synergistic thickening effect of amino acid surfactants and inorganic salts such as sodium chloride is poor, which has become a pain point in its development.

[0004] From the perspective of hair structure, hair is composed of the epidermis, cortex, and medulla from the outside to the inside. The epidermis is composed of many hair scales. The deep-seated reason for frizzy and tangled hair is that the hair scales are damaged, and damaged hair scales are prone to negative charges. Based on this principle, in the past, in order to make hair smoother, some positively charged cationic conditioning agents were usually added, such as polyquaternium-10, cationic guar gum, polyquaternium-7, polyquaternium-44, etc. These positively charged conditioning agents combine with the hair scales through the charge effect, making the hair smoother, more shiny, and stronger. However, this charge attraction is weak, and the combing properties will be significantly reduced after multiple rinses, and the smoothness will decrease.

[0005] In addition to adding cationic polyquaternium salts, silicone oil is usually also added. Silicone oil easily precipitates on the hair to make it brighter, smoother and fuller. However, silicone oil also has many side effects, such as being difficult to biodegrade and unable to prepare transparent shampoo. More importantly, in recent years many manufacturers have advertised that silicone oil may cause hair loss. Although there is no clear evidence that silicone oil can cause hair loss, this statement has been deeply rooted in people's minds. Therefore, silicone-free shampoo has become the mainstream of the market.

[0006] Patents CN201811491204.4 and CN201811155999.1 disclose an aqueous polyurethane dispersion, which can make hair naturally strong and prolong the duration of hair fullness when added to shampoo. At the same time, it is more compatible with shampoo and avoids the introduction of silicone oil. However, its smoothing effect on hair is poor, and some conditioners still need to be added to enhance the smoothing effect on hair. Summary of the invention

[0007] In view of the above problems existing in the prior art, the present invention provides a polyurethane-cationic polymer emulsion with an interpenetrating network structure, which has the effects of toughening, plumping and smoothing hair; at the same time, it has a good thickening effect in a shampoo and hair care system.

[0008] The polyurethane-cationic polymer emulsion with an interpenetrating network structure of the present invention connects the polymer with cationic groups and the aqueous polyurethane through the interpenetrating network structure. The polymer emulsion prepared by this method is added to shampoo, which not only has the fullness and toughening effect of the polyurethane structure on the hair, but also can play the effect of the cationic group making the hair smoother; at the same time, the polyurethane is combined with the hair through hydrogen bonds, and this action force is relatively strong, and good combing properties can be maintained after multiple flushings. In addition, the polyurethane-cationic polymer with the structure of the present invention has a certain thickening effect in addition to conditioning, and the thickening mechanism is mainly based on alkali swelling and entanglement. However, shampoo products usually contain a large amount of ionic surfactants, which will limit its thickening effect. Since the polyurethane in the polymer of the present invention belongs to a non-ionic structure and has a certain charge shielding effect, it can enhance the alkali swelling thickening effect of the cationic group, and also make the molecular weight larger and the entanglement thickening effect stronger.

[0009] In order to achieve the above-mentioned invention object, the present invention adopts the following technical scheme:

[0010] The present invention provides a polyurethane-cationic polymer emulsion with an interpenetrating network structure, which is prepared from the following components in parts by weight:

[0011] A) 47.5-142.5 parts of diisocyanate, preferably 104.5-142.5 parts;

[0012] B) 19-190 parts of macromolecular polyol, preferably 114-190 parts;

[0013] C) 4.75-19 parts, preferably 9.5-19 parts, of a vinyl-containing polyol;

[0014] D) 0.95-47.5 parts, preferably 28.5-47.5 parts, of monohydric alcohol and / or dihydric alcohol containing polyethylene oxide segments in the main chain and / or side chain;

[0015] E) 9.5-38 parts, preferably 9.5-28.5 parts, of a diol small molecule chain extender containing active hydrogen;

[0016] F) 0.95-19 parts, preferably 0.95-6.65 parts, of a diamine small molecule chain extender containing active hydrogen;

[0017] G) a catalyst in an amount of 100-500 ppm, preferably 200-300 ppm, based on the total mass of components A)-F);

[0018] H) a low boiling point organic solvent, the amount of which is 1-3 times, preferably 1-2 times, the total mass of components A)-F);

[0019] 1) 538-660 parts of water;

[0020] J) 9.5-47.5 parts of nonionic monomer containing unsaturated double bonds, preferably 9.5-19 parts;

[0021] K) 47.5-95 parts, preferably 47.4-57 parts, of a cationic monomer containing an unsaturated double bond;

[0022] L) 0.19-0.95 parts of chelating agent, preferably 0.475-0.95 parts;

[0023] M) initiator 0.076-0.247 parts, preferably 0.076-0.114 parts;

[0024] N) reducing agent 0.112-0.996 parts, preferably 0.112-0.996 parts.

[0025] In the present invention, the diisocyanate in component A) is selected from one or more of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) and dicyclohexylmethane diisocyanate (HMDI), preferably hexamethylene diisocyanate.

[0026] In the present invention, the macromolecular polyol of component B) has a number average molecular weight of 500-3000 g / mol, preferably 1000-2000 g / mol, and is preferably selected from one or more of polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetramethylene glycol, polycaprolactone diol, polycarbonate diol, polyethylene adipate diol, polybutylene adipate diol, polyneopentyl adipate diol, polyhexanediol adipate 1,6-hexanediol and polyneopentyl adipate 1,6-hexanediol, more preferably one or more of polypropylene glycol.

[0027] In the present invention, the vinyl group-containing polyol described in component C) is selected from one or more of vinyl polyoxypropylene polyol or vinyl polyethylene oxide polyol, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate, preferably one or more of diethylene glycol dimethacrylate and polyethylene glycol diacrylate; the vinyl group-containing polyol can not only react with diisocyanate to form polyurethane structural units, but also provide double bonds to react with other vinyl monomers to form an interpenetrating network structure.

[0028] In the present invention, the monohydric alcohol and / or dihydric alcohol containing polyethylene oxide segments in the main chain and / or side chain of component D) is selected from one or more of polyethylene oxide ether glycol and polyethylene glycol methyl ether, preferably polyethylene oxide ether glycol.

[0029] In the present invention, the diol small molecule chain extender containing active hydrogen as component E) is selected from one or more of 1,3-propylene glycol, 1,4-butanediol, diethylene glycol, neopentyl glycol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol, preferably neopentyl glycol.

[0030] In the present invention, the diamine small molecule chain extender containing active hydrogen in component F) is selected from one or more of ethylenediamine, 1,6-hexanediamine, hexamethylenediamine, pentamethylenediamine, diethylenetriamine, isophoronediamine, 4,4-diphenylmethanediamine, and diethanolamine, preferably one or more of ethylenediamine and 1,6-hexanediamine.

[0031] In the present invention, the catalyst of component G) is selected from dibutyltin dilaurate and / or organic bismuth 8108 of a leading American company.

[0032] In the present invention, the low boiling point organic solvent of component H) is selected from acetone and / or butanone.

[0033] In the present invention, the nonionic monomer containing an unsaturated double bond in component J) is selected from one or more of hydroxyethyl acrylate, acrylamide, N,N-dimethylacrylamide, methacrylamide, polyethylene glycol monomethyl ether methacrylate, methacrylic acid, N,N-dimethylaminoethyl ester, N-isopropylacrylamide, and hydroxyethyl methacrylate, preferably one or more of acrylamide and hydroxyethyl acrylate.

[0034] In the present invention, the cationic monomer containing an unsaturated double bond in component K) is selected from one or more combinations of acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride, methacrylamidopropyl trimethyl ammonium chloride, and diallyl dimethyl ammonium chloride, preferably one or more combinations of acryloyloxyethyl trimethyl ammonium chloride and diallyl dimethyl ammonium chloride.

[0035] In the present invention, the chelating agent in component L) is selected from one or more of ethylenediaminetetraacetic acid sodium salt, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminetetrapropionic acid sodium salt, sodium citrate, and sodium gluconate, preferably one or more of ethylenediaminetetraacetic acid sodium salt, sodium citrate, and sodium gluconate, more preferably ethylenediaminetetraacetic acid sodium salt.

[0036] In the present invention, the initiator of component M) is a free radical initiator, preferably one or more of hydrogen peroxide, tert-butyl hydroperoxide, potassium persulfate, sodium persulfate, and ammonium persulfate.

[0037] In the present invention, the reducing agent in component N) is selected from one or more of sodium sulfite, sodium pyrosulfite and sodium metabisulfite.

[0038] The present invention also provides a method for preparing the polyurethane-cationic polymer emulsion having the above interpenetrating network structure, the steps comprising:

[0039] 1) Mix diisocyanate, macromolecular polyol, vinyl-containing polyol, monool and / or diol containing polyethylene oxide segments in the main chain and / or side chain, and catalyst uniformly, raise the temperature to 60-80° C., preferably 70-80° C., and carry out polymerization reaction for 1-2 hours, preferably 1-1.5 hours;

[0040] 2) cooling the reaction system of step 1) to 50-60° C., preferably 55-60° C., adding a diol small molecule chain extender containing active hydrogen and a portion of a low boiling point organic solvent, heating to 70-80° C., preferably 75-80° C., to carry out a chain extension reaction, reacting until NCO reaches a theoretical value and stopping the reaction, then cooling to 40-50° C., preferably 45-50° C., adding the remaining low boiling point organic solvent, and continuing to cool to 20° C.-40° C., preferably 25-35° C., to obtain a prepolymer;

[0041] 3) adding water to the prepolymer of step 2) under shear dispersion conditions to obtain an aqueous polyurethane emulsion, then adding a diamine small molecule chain extender containing active hydrogen, performing end-capping and chain extension reactions at 30-50° C., preferably 30-40° C. for 10-30 min, preferably 10-20 min, and then removing the low-boiling point organic solvent by reduced pressure distillation to obtain a polyurethane prepolymer;

[0042] 4) The temperature of the polyurethane prepolymer in step 3) is adjusted to 20-25° C., and a nonionic monomer containing an unsaturated double bond, a cationic monomer containing an unsaturated double bond, a chelating agent, and an initiator are added thereto. Then, under stirring, a reducing agent is added over 15-30 minutes, and the temperature is raised to 65-80° C., preferably 65-75° C., and the reaction is carried out for 2-4 hours, preferably 3-4 hours, to obtain a polyurethane-cationic polymer emulsion with an interpenetrating network structure.

[0043] In the present invention, the low boiling point organic solvent in step 2) is added twice during the reaction, and the ratio of the two additions is 1:10-1:5, preferably 1:5-1:3.

[0044] The polyurethane-cationic polymer emulsion with an interpenetrating network structure prepared by the above method of the present invention comprises a polyurethane structural unit and a cationic structural unit;

[0045] The polyurethane structural unit is generated by polymerization reaction of diisocyanate, macromolecular polyol, vinyl-containing polyol, monohydric alcohol and / or dihydric alcohol containing polyethylene oxide segments in the main chain and / or side chain, dihydric alcohol small molecule chain extender containing active hydrogen, and diamine small molecule chain extender containing active hydrogen under the action of a catalyst;

[0046] The cationic structural unit is generated by free radical polymerization of a nonionic monomer containing an unsaturated double bond and a cationic monomer containing an unsaturated double bond.

[0047] The polyurethane-cationic polymer emulsion with an interpenetrating network structure of the present invention has a solid content of 30-50wt%, preferably 30-40wt%.

[0048] The polyurethane-cationic polymer emulsion with an interpenetrating network structure of the present invention is suitable for the fields of personal care, fabric care, etc., and is particularly suitable for the field of personal care as a hair conditioner.

[0049] Preferably, the present invention provides a shampoo prepared therefrom, wherein the addition amount of the polyurethane-cationic polymer emulsion with an interpenetrating network structure is 0.2-2wt%, preferably 0.5-1wt%;

[0050] Specifically, the shampoo formula comprises, in parts by weight:

[0051] 10-16 parts of sodium cocoyl sarcosinate, preferably 12-14 parts;

[0052] 1-4 parts of cocamide betaine, preferably 2-3 parts;

[0053] Sodium benzoate 0.1-0.7 parts, preferably 0.2-0.5 parts;

[0054] Salicylic acid 0.1-0.3 parts, preferably 0.15-0.2 parts;

[0055] 1-4 parts, preferably 2-3 parts, of a polyurethane-cationic polymer emulsion with an interpenetrating network structure;

[0056] Sodium chloride 0.5-2 parts, preferably 0.7-1.5 parts;

[0057] Add water to make up to 100 parts.

[0058] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0059] (1) In the polyurethane-cationic monomer interpenetrating network structure composite emulsion of the present invention, by combining the polyurethane structural unit and the vinyl unit and limiting the mass ratio within a specific range, the hair can be made more full. It not only has the advantages of polyurethane and cationic polymer, but also has a stronger conditioning effect on the hair. At the same time, the polyurethane structure is combined with the hair through hydrogen bonds, which solves the problem of being easily washed away by water during shampooing and having poor durability.

[0060] (2) The polyurethane-cationic monomer interpenetrating network structure composite emulsion of the present invention has a good thickening effect on amino acid shampoo due to its special structure. The polyurethane structure is easy to thicken by associating with the surfactant, but this thickening effect is weak; the thickening effect of the cationic vinyl polymer is achieved by alkali swelling and entanglement. The presence of ions has an inhibitory effect on alkali swelling. Shampoo formulas usually contain a large amount of inorganic salts, which will limit the thickening effect of the vinyl polymer; the polyurethane structural unit has a certain shielding effect on the charge, which can enhance the alkali swelling effect of the vinyl unit. At the same time, the introduction of the polyurethane structural unit can increase the molecular weight of the vinyl polymer, which is conducive to the entanglement thickening effect. DETAILED DESCRIPTION

[0061] The present invention is further described below by means of specific examples. The examples described in the present invention are only used to illustrate the present invention and do not limit the scope of the present invention.

[0062] The main sources of raw materials used in the examples of the present invention are as follows. Other raw materials are common commercially available unless otherwise specified:

[0063] Isophorone diisocyanate: Wanhua Chemical Group Co., Ltd.

[0064] Dicyclohexylmethane diisocyanate: Wanhua Chemical Group Co., Ltd.;

[0065] Polyethylene oxide ether glycol: Perstorp, Sweden;

[0066] Poly(neopentyl glycol hexanediol adipate) diol: Yantai Huada Chemical;

[0067] Hexamethylene diisocyanate: Wanhua Chemical Group Co., Ltd.

[0068] (Sodium 2-(2-aminoethyl)aminoethanesulfonate: Wacker Chemicals, Germany;

[0069] 1,4-Cyclohexanedimethanol: Kailing Chemical Co., Ltd.;

[0070] Neopentyl glycol: Wanhua Chemical Group Co., Ltd.;

[0071] Ethylenediamine: BASF, Germany;

[0072] 8108 organic bismuth catalyst: leading in the United States;

[0073] Polypropylene glycol PPG-1000: Shandong Bluestar Co., Ltd.;

[0074] IPDA (isophorone diamine): Wanhua Chemical Group Co., Ltd.;

[0075] Acryloyloxyethyl trimethyl ammonium chloride: Jiangsu Fumiao Technology Co., Ltd.;

[0076] Methacryloyloxyethyl trimethylammonium chloride: Jiangsu Fumiao Technology Co., Ltd.;

[0077] Diallyldimethylammonium chloride: Jiangsu Fumiao Technology Co., Ltd.;

[0078] Acrylamide: Jiangsu Changjiu Agricultural Science and Chemical Industry;

[0079] Hydroxyethyl acrylate: Hubei Jusheng;

[0080] Potassium persulfate: Chinese medicine;

[0081] Tert-butyl hydroperoxide: Sinopharm;

[0082] Sodium bisulfite: Chinese medicine;

[0083] Sodium Cocoyl Sarcosinate: Clariant;

[0084] Cocopropyl Betaine: Shanghai Yuyu.

[0085] Example 1

[0086] The polyurethane-cationic polymer emulsion A with an interpenetrating network structure is prepared by the following steps:

[0087] 1) 85.5 g TDI, 38 g PPG1000, 4.75 g ethylene glycol dimethyl methacrylate, 0.95 g polyethylene oxide ether glycol, and 0.0456 g 8108 organic bismuth catalyst were mixed evenly, and the temperature was raised to 60° C. for polymerization reaction for 2 h;

[0088] 2) Cooling the reaction system of step 1) to 50° C., adding 38 g of diethylene glycol and 46.9 g of low-boiling-point organic solvent acetone, heating to 70° C. to carry out chain extension reaction, reacting until NCO reaches the theoretical value to stop the reaction, then cooling to 40° C., adding 469 g of low-boiling-point organic solvent acetone, and continuing to cool to 20° C. to obtain a prepolymer;

[0089] 3) adding 580 g of water to the prepolymer of step 2) under shear dispersion conditions to obtain an aqueous polyurethane emulsion, then adding 4.75 g of ethylenediamine, performing end-capping and chain extension reactions at 30° C. for 10 min, and removing the low-boiling organic solvent by reduced pressure distillation to obtain a polyurethane prepolymer;

[0090] 4) The temperature of the polyurethane prepolymer in step 3) was adjusted to 20° C. 47.5 g of N-isopropylacrylamide, 95 g of methacryloyloxyethyltrimethylammonium chloride, 0.19 g of disodium ethylenediaminetetraacetate, and 0.1425 g of hydrogen peroxide were added thereto. Then, 30 g of an aqueous solution containing 0.125 g of sodium bisulfite was slowly added dropwise under stirring for 15 min. The temperature was raised to 65° C. and the reaction was carried out for 2 h to obtain a polyurethane-cationic polymer emulsion A with an interpenetrating network structure.

[0091] Example 2

[0092] The polyurethane-cationic polymer emulsion B with an interpenetrating network structure is prepared by the following steps:

[0093] 1) 104.5g HMDI, 190g PPG2000, 19g polyethylene glycol diacrylate, 4.75g polyethylene oxide ether glycol, and 0.0973g 8108 organic bismuth catalyst were mixed evenly, and the temperature was raised to 70°C for polymerization reaction for 1.5h;

[0094] 2) Cooling the reaction system of step 1) to 55° C., adding 9.5 g of 1,6-hexanediol and 109.9 g of low-boiling-point organic solvent acetone, heating to 75° C. to carry out chain extension reaction, reacting until NCO reaches the theoretical value and stopping the reaction, then cooling to 45° C., adding 549.5 g of low-boiling-point organic solvent acetone, and continuing to cool to 25° C. to obtain a prepolymer;

[0095] 3) adding 538 g of water to the prepolymer of step 2) under shear dispersion conditions to obtain an aqueous polyurethane emulsion, then adding 9.5 g of hexamethylenediamine, performing end-capping and chain extension reactions at 40° C. for 15 min, and removing the low-boiling organic solvent by reduced pressure distillation to obtain a polyurethane prepolymer;

[0096] 4) The temperature of the polyurethane prepolymer in step 3) was adjusted to 25°C, and 9.5g of hydroxyethyl acrylate, 47.5g of acryloyloxyethyl trimethylammonium chloride, 0.475g of disodium ethylenediaminetetraacetate, and 0.114g of sodium persulfate were added thereto. Then, 25g of an aqueous solution containing 0.996g of sodium bisulfite was slowly added dropwise under stirring for 20 minutes. The temperature was raised to 70°C and the reaction was carried out for 3 hours to obtain a polyurethane-cationic polymer emulsion B with an interpenetrating network structure.

[0097] Example 3

[0098] The polyurethane-cationic polymer emulsion C with an interpenetrating network structure is prepared by the following steps:

[0099] 1) 142.5 g IPDI, 114 g PPG1000, 9.5 g diethylene glycol dimethacrylate, 28.5 g polyethylene oxide ether glycol, and 0.0607 g 8108 organic bismuth catalyst were mixed evenly, and the mixture was heated to 75° C. for polymerization reaction for 2 h;

[0100] 2) Cooling the reaction system of step 1) to 60° C., adding 28.5 g of 1,4-butanediol and 82.4 g of low-boiling-point organic solvent acetone, heating to 75° C. to carry out chain extension reaction, reacting until NCO reaches the theoretical value and stopping the reaction, then cooling to 50° C., adding 246.8 g of low-boiling-point organic solvent acetone, and continuing to cool to 30° C. to obtain a prepolymer;

[0101] 3) adding 569 g of water to the prepolymer of step 2) under shear dispersion conditions to obtain an aqueous polyurethane emulsion, then adding 6.65 g of 1,6-hexanediamine, performing end-capping and chain extension reactions at 35° C. for 20 min, and removing the low-boiling organic solvent by reduced pressure distillation to obtain a polyurethane prepolymer;

[0102] 4) The temperature of the polyurethane prepolymer in step 3) was adjusted to 23° C. 19 g acrylamide, 57 g diallyldimethylammonium chloride, 0.95 g disodium ethylenediaminetetraacetate, and 0.076 g tert-butyl hydroperoxide were added thereto. Then, 25 g of an aqueous solution containing 0.112 g of sodium pyrosulfite solution was slowly added dropwise under stirring. The addition was completed within 25 min. The reaction was continued for 4 h to obtain a polyurethane-cationic polymer emulsion C with an interpenetrating network structure.

[0103] Example 4

[0104] The polyurethane-cationic polymer emulsion D with an interpenetrating network structure is prepared by the following steps:

[0105] 1) 47.5 g HDI, 19 g PEG1000, 9.5 g triethylene glycol diacrylate, 47.5 g polyethylene oxide ether glycol, and 0.0266 g 8108 organic bismuth catalyst were mixed evenly, and the mixture was heated to 80° C. for polymerization reaction for 1 h;

[0106] 2) cooling the reaction system of step 1) to 52° C., adding 9.5 g of 1,4-cyclohexanedimethanol and 50.7 g of low-boiling-point organic solvent acetone, heating to 72° C. to carry out chain extension reaction, reacting until NCO reaches the theoretical value to stop the reaction, then cooling to 40° C., adding 253.3 g of low-boiling-point organic solvent acetone, to obtain a prepolymer;

[0107] 3) adding 660 g of water to the prepolymer of step 2) under shear dispersion conditions to obtain an aqueous polyurethane emulsion, then adding 19 g of isophorone diamine, performing end-capping and chain extension reactions at 50° C. for 10 min, and removing the low-boiling organic solvent by reduced pressure distillation to obtain a polyurethane prepolymer;

[0108] 4) The temperature of the polyurethane prepolymer in step 3) was adjusted to 25° C. 38 g of vinyl pyrrolidone, 85.5 g of acrylamidopropyltrimethylammonium chloride, 0.475 g of disodium ethylenediaminetetraacetate, and 0.247 g of ammonium persulfate were added thereto. 25 g of an aqueous solution of 0.163 g of sodium bisulfite was added dropwise over 30 min. The mixture was reacted for 4 h to obtain a polyurethane-cationic polymer emulsion D with an interpenetrating network structure.

[0109] Comparative Example 1

[0110] The method in Example 3 is referred to, except that component K) diallyldimethylammonium chloride, a cationic monomer containing an unsaturated double bond, is not added in step 4), and other parameters and operations remain unchanged to obtain a polymer solution.

[0111] Comparative Example 2

[0112] The method in Example 3 is referred to, except that in step 4), the component K) containing an unsaturated double bond cationic monomer diallyldimethylammonium chloride is replaced by sodium acryloyldimethyltaurate, and other parameters and operations remain unchanged to obtain a polymer solution.

[0113] Comparative Example 3

[0114] The method in Example 3 is referred to, except that component J) acrylamide, a nonionic monomer containing an unsaturated double bond, is not added in step 4), and other parameters and operations remain unchanged to obtain a polymer solution.

[0115] Comparative Example 4

[0116] The method in Example 3 was referred to, except that the component diethylene glycol dimethacrylate was not added in step 4), and other parameters and operations remained unchanged to obtain a polymer solution.

[0117] Performance evaluation of the polyurethane-cationic polymer emulsion with interpenetrating network structure prepared in the embodiment of the present invention:

[0118] The polymer emulsions prepared in the above embodiments and comparative examples of the present invention were used to prepare hair care products, and their properties were tested. The results are shown in Table 1.

[0119] The shampoo formula is as follows:

[0120]

[0121] The shampoo performance test method is as follows:

[0122] Shampoo viscosity test: Use Brookfield DV2T viscometer, 4# at 20 rpm to test the shampoo viscosity.

[0123] Combability test: Prepare slightly damaged Asian hair, first wet it with 40℃ tap water, weigh the sample according to the amount of shampoo used per gram of hair, scrub for 30 seconds, let it stand for 1 minute, rinse with tap water for 30 seconds, and perform a combability test. Each hair bundle is tested five times; take three hair bundles for testing, scrub with blank samples and samples containing polymers, calculate the percentage of combability reduction, and calculate the average value. Then scrub the hair bundles with tap water for 5 times, perform a combability test, and calculate the percentage of combability reduction.

[0124] Fullness test: Wash unused hair with blank shampoo without adding the embodiment and comparative example, weigh a sample according to the amount of 0.2g shampoo per gram of hair, scrub for 30s, let stand for 1min, rinse with tap water for 30s, and after drying, use DIASTRON MTT175 hair tester to test the compression work of the test hair bundle when it is pulled 15cm in a 1cm hole as the initial pulling work and record it as Winitial; wash the above hair bundle with the composition of the above embodiment and comparative example, and repeat the above test steps using MTT175 hair tester to obtain the pulling work and record it as Wtest;

[0125] The difference between the test tensile work and the initial tensile work is recorded as Wtreatment = Wtest – Winitial; the difference between the test tensile work and the initial tensile work of a certain brand of transparent volumizing shampoo on the market is used as the top control (Wtopcontrol), and the difference between the test tensile work and the initial tensile work of blank shampoo (without polymer) is used as the bottom control (Wbottomcontrol);

[0126] The composition fullness index is calculated by the following formula:

[0127]

[0128] Table 1

[0129]

[0130] It can be clearly seen from the test results in Table 1 that the polyurethane-cationic polymer can significantly increase the viscosity of the amino acid shampoo, reduce the wet combing performance, and maintain good wet hair combing performance after multiple rinses, and has a good improvement effect on the volume effect of the hair; compared with the addition of aqueous polyurethane emulsion and cationic polyacrylamide emulsion at the same time, the shampoo containing polyurethane-cationic interpenetrating network polymer has a higher viscosity, good thickening performance, volume effect, combing properties and combing properties after multiple rinses are also better, indicating that there is an interaction between the polyurethane structural unit and the vinyl structural unit, and the interpenetrating network structure polymer formed by the two has better application performance in shampoo.

Claims

1. A polyurethane-cationic polymer emulsion with an interpenetrating network structure, characterized in that: The composition is prepared by including the following components in parts by weight: A) 47.5-142.5 parts of diisocyanate; B) 19-190 parts of macromolecular polyol; C) 4.75-19 parts of vinyl-containing polyols; D) 0.5-47.5 parts of monohydric alcohol and / or dihydric alcohol containing polyethylene oxide segments in the main chain and / or side chain; E) 9.5-38 parts of a diol small molecule chain extender containing active hydrogen; F) 0.95-19 parts of a diamine small molecule chain extender containing active hydrogen; G) a catalyst in an amount of 100-500 ppm based on the total mass of components A)-F); H) a low boiling point organic solvent, the amount of which is 1-3 times the total mass of components A)-F); 1) 538-660 parts of water; J) 9.5-47.5 parts of a nonionic monomer containing an unsaturated double bond; K) 47.5-95 parts of a cationic monomer containing an unsaturated double bond; L) 0.19-0.95 part of chelating agent; M) 0.076-0.247 part of initiator; N) 0.112-0.996 part of reducing agent; The vinyl-containing polyol is selected from one or more of ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; The nonionic monomer containing unsaturated double bonds is selected from one or more of hydroxyethyl acrylate, acrylamide, N,N-dimethylacrylamide, methacrylamide, polyethylene glycol monomethyl ether methacrylate, methacrylic acid, N,N-dimethylaminoethyl ester, N-isopropylacrylamide, and hydroxyethyl methacrylate; The cationic monomer containing an unsaturated double bond is selected from one or more combinations of acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride, methacryamidopropyl trimethyl ammonium chloride, and diallyl dimethyl ammonium chloride.

2. The polyurethane-cationic polymer emulsion according to claim 1, characterized in that The composition is prepared by including the following components in parts by weight: A) 104.5-142.5 parts of diisocyanate; B) 114-190 parts of macromolecular polyol; C) 9.5-19 parts of vinyl-containing polyols; D) 28.5-47.5 parts of monohydric alcohol and / or dihydric alcohol containing polyethylene oxide segments in the main chain and / or side chain; E) 9.5-28.5 parts of a diol small molecule chain extender containing active hydrogen; F) 0.95-6.65 parts of a diamine small molecule chain extender containing active hydrogen; G) catalyst, used in an amount of 200-300 ppm based on the total mass of components A)-F); H) a low boiling point organic solvent, the amount of which is 1-2 times the total mass of components A)-F); 1) 538-660 parts of water; J) 9.5-19 parts of a nonionic monomer containing an unsaturated double bond; K) 47.4-57 parts of a cationic monomer containing an unsaturated double bond; L) 0.475-0.95 part of chelating agent; M) 0.076-0.114 parts of initiator; N) 0.112-0.996 parts of reducing agent.

3. The polyurethane-cationic polymer emulsion according to claim 1, characterized in that Component A) The diisocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.

4. The polyurethane-cationic polymer emulsion according to claim 1, characterized in that Component B) the macromolecular polyol has a number average molecular weight of 500-3000 g / mol; and / or Component C) the vinyl-containing polyol is selected from one or more of diethylene glycol dimethacrylate and polyethylene glycol diacrylate; and / or Component D) The monohydric alcohol and / or dihydric alcohol containing polyethylene oxide segments in the main chain and / or side chain is selected from one or more of polyethylene oxide ether glycol and polyethylene glycol methyl ether.

5. The polyurethane-cationic polymer emulsion according to claim 4, characterized in that Component B) the macromolecular polyol has a number average molecular weight of 1000-2000 g / mol.

6. The polyurethane-cationic polymer emulsion according to claim 1, characterized in that Component B) The macromolecular polyol is selected from one or more of polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetramethylene glycol, polycaprolactone diol, polycarbonate diol, polyethylene adipate diol, polybutylene adipate diol, polyneopentyl adipate diol, polyhexanediol adipate diol and polyneopentyl adipate 1,6-hexanediol diol.

7. The polyurethane-cationic polymer emulsion according to claim 1, characterized in that Component E) the diol small molecule chain extender containing active hydrogen is selected from one or more of 1,3-propylene glycol, 1,4-butanediol, diethylene glycol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol; and / or Component F) the diamine small molecule chain extender containing active hydrogen is selected from one or more of ethylenediamine, 1,6-hexamethylenediamine, hexamethylenediamine, pentamethylenediamine, diethylenetriamine, isophoronediamine, 4,4-diphenylmethanediamine, and diethanolamine; and / or Component G) The catalyst is selected from dibutyltin dilaurate and / or organic bismuth 8108 of a leading American company; and / or Component H) The low boiling point organic solvent is selected from acetone and / or butanone.

8. The polyurethane-cationic polymer emulsion according to claim 1, characterized in that Component J) the nonionic monomer containing unsaturated double bonds is selected from one or more of acrylamide and hydroxyethyl acrylate; and / or Component K) The cationic monomer containing an unsaturated double bond is selected from one or more of acryloyloxyethyltrimethylammonium chloride and diallyldimethylammonium chloride.

9. The polyurethane-cationic polymer emulsion according to claim 1, characterized in that: Component L) the chelating agent is selected from one or more of ethylenediaminetetraacetic acid sodium salt, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminetetrapropionic acid sodium salt, sodium citrate, sodium gluconate; and / or Component M) The initiator is a free radical initiator; and / or Component N) The reducing agent is selected from one or more of sodium sulfite, sodium pyrosulfite and sodium metabisulfite.

10. The polyurethane-cationic polymer emulsion according to claim 9, characterized in that: The free radical initiator is selected from one or more of hydrogen peroxide, tert-butyl hydroperoxide, potassium persulfate, sodium persulfate, and ammonium persulfate.

11. A method for preparing the interpenetrating network structure polyurethane-cationic polymer emulsion according to any one of claims 1 to 10, characterized in that the steps include: 1) Mix diisocyanate, macromolecular polyol, vinyl-containing polyol, monool and / or diol containing polyethylene oxide segments in the main chain and / or side chain, and catalyst uniformly, and heat to 60-80° C. for polymerization reaction for 1-2 hours; 2) cooling the reaction system of step 1) to 50-60° C., adding a diol small molecule chain extender containing active hydrogen and a portion of a low-boiling point organic solvent, heating to 70-80° C. to carry out a chain extension reaction, reacting until NCO reaches a theoretical value and stopping the reaction, then cooling to 40-50° C., adding the remaining low-boiling point organic solvent, and continuing to cool to 20° C.-40° C. to obtain a prepolymer; 3) adding water to the prepolymer of step 2) under shear dispersion conditions to obtain an aqueous polyurethane emulsion, then adding a diamine small molecule chain extender containing active hydrogen, performing end-capping and chain extension reactions at 30-50° C. for 10-30 minutes, and then removing the low-boiling point organic solvent by reduced pressure distillation to obtain a polyurethane prepolymer; 4) The temperature of the polyurethane prepolymer in step 3) is adjusted to 20-25° C., and a nonionic monomer containing an unsaturated double bond, a cationic monomer containing an unsaturated double bond, a chelating agent, and an initiator are added thereto. Then, under stirring, a reducing agent is added over 15-30 minutes, the temperature is raised to 65-80° C., and the reaction is performed for 2-4 hours to obtain a polyurethane-cationic polymer emulsion with an interpenetrating network structure.

12. The preparation method according to claim 11, characterized in that the steps include: 1) Mix diisocyanate, macromolecular polyol, vinyl-containing polyol, monool and / or diol containing polyethylene oxide segments in the main chain and / or side chain, and catalyst uniformly, and heat to 70-80° C. for polymerization reaction for 1-1.5 hours; 2) cooling the reaction system of step 1) to 55-60° C., adding a diol small molecule chain extender containing active hydrogen and a portion of a low boiling point organic solvent, heating to 75-80° C. to carry out a chain extension reaction, reacting until NCO reaches a theoretical value and stopping the reaction, then cooling to 45-50° C., adding the remaining low boiling point organic solvent, and continuing to cool to 25-35° C. to obtain a prepolymer; 3) adding water to the prepolymer of step 2) under shear dispersion conditions to obtain an aqueous polyurethane emulsion, then adding a diamine small molecule chain extender containing active hydrogen, performing end-capping and chain extension reactions at 30-40° C. for 10-20 minutes, and then removing the low-boiling point organic solvent by reduced pressure distillation to obtain a polyurethane prepolymer; 4) The temperature of the polyurethane prepolymer in step 3) is adjusted to 20-25° C., and a nonionic monomer containing an unsaturated double bond, a cationic monomer containing an unsaturated double bond, a chelating agent, and an initiator are added thereto. Then, under stirring, a reducing agent is added over 15-30 minutes, the temperature is raised to 65-75° C., and the reaction is carried out for 3-4 hours to obtain a polyurethane-cationic polymer emulsion with an interpenetrating network structure.

13. The preparation method according to claim 11, characterized in that: Step 2) The low boiling point organic solvent is added twice during the reaction, and the ratio of the two additions is 1:10-1:

5.

14. The preparation method according to claim 12, characterized in that: Step 2) The low boiling point organic solvent is added twice during the reaction, and the ratio of the two additions is 1:5-1:

3.

15. The preparation method according to claim 11, characterized in that: A polyurethane-cationic polymer emulsion with an interpenetrating network structure is prepared, wherein the polymer comprises a polyurethane structural unit and a cationic structural unit; The polyurethane structural unit is generated by polymerization reaction of diisocyanate, macromolecular polyol, vinyl-containing polyol, monohydric alcohol and / or dihydric alcohol containing polyethylene oxide segments in the main chain and / or side chain, dihydric alcohol small molecule chain extender containing active hydrogen, and diamine small molecule chain extender containing active hydrogen under the action of a catalyst; The cationic structural unit is generated by free radical polymerization of a nonionic monomer containing an unsaturated double bond and a cationic monomer containing an unsaturated double bond; The polyurethane-cationic polymer emulsion with an interpenetrating network structure has a solid content of 30-50 wt %.

16. The preparation method according to claim 15, characterized in that: The polyurethane-cationic polymer emulsion with an interpenetrating network structure has a solid content of 30-40 wt%.

17. The polyurethane-cationic polymer emulsion with an interpenetrating network structure according to any one of claims 1 to 10 or the polyurethane-cationic polymer emulsion with an interpenetrating network structure prepared by the preparation method according to any one of claims 11 to 16 is suitable for the fields of personal care and fabric care.

18. The interpenetrating network structure polyurethane-cationic polymer emulsion according to any one of claims 1 to 10 or the interpenetrating network structure polyurethane-cationic polymer emulsion prepared by the preparation method according to any one of claims 11 to 16 is suitable for use as a hair conditioner.

19. A shampoo, characterized in that: The addition amount of the interpenetrating network structure polyurethane-cationic polymer emulsion according to any one of claims 1 to 10 or the interpenetrating network structure polyurethane-cationic polymer emulsion prepared by the preparation method according to any one of claims 11 to 16 is 0.2-2wt%.

20. The shampoo according to claim 19, characterized in that The addition amount of the interpenetrating network structure polyurethane-cationic polymer emulsion is 0.5-1 wt %.

21. The shampoo according to claim 19, characterized in that The shampoo formula comprises, in parts by weight: 10-16 parts of sodium cocoyl sarcosinate; 1-4 parts of cocamide betaine; Sodium benzoate 0.1-0.7 parts; Salicylic acid 0.1-0.3 parts; 1-4 parts of polyurethane-cationic polymer emulsion with interpenetrating network structure; Sodium chloride 0.5-2 parts; Add water to make up to 100 parts.

22. The shampoo according to claim 21, characterized in that The shampoo formula comprises, in parts by weight: Sodium cocoyl sarcosinate 12-14 parts; 2-3 parts of cocamide betaine; Sodium benzoate 0.2-0.5 part; Salicylic acid 0.15-0.2 parts; 2-3 parts of polyurethane-cationic polymer emulsion with interpenetrating network structure; Sodium chloride 0.7-1.5 parts; Add water to make up to 100 parts.

Images