JP2015521168A - Polymers of trialkyl quaternary ammonium ethyl methacrylate salts as squeak enhancing agents in cleaning compositions - Google Patents

Abstract

A detergent composition comprising a homopolymer incorporating a monomer that is a trialkyl quaternary ammonium ethyl methacrylate salt and a non-soap synthetic detergent is provided. The composition exhibits a squeaky SQ1 value in the range of 5 to 100 g when measured with an acoustic friction meter tester.

Description

  The present invention relates to skin and hair cleansing compositions in toilet bars, body wash, liquid hand detergents, shampoos and related products.

  So far soap has been the main active substance for detergents. Soap is cheap and efficient. But soaps can be harsh on the skin. Therefore, synthetic surfactants have been introduced as a substitute for soap. Some of the surfactants produce another foam equivalent to soap foam, with the additional advantage of being milder.

  The skin feel characteristics of synthetic surfactants are often very different from the skin feel characteristics of soaps. Indeed, as mildness increases, the deposition of synthetic surfactants and other humectants generally increases. This forms a protective barrier against peeling of natural oils and fats from the epidermis.

  However, most Japanese consumers and many consumers in other countries do not like the oily feel of synthetic detergents. They see humectant deposits as a sign that cleaning is not effective. Consumers need to feel reassured about cleanliness by the traditional squeaky, non-moist feel of soap.

  GB 2104091 (Kao) discloses an amphoteric copolymer obtained by copolymerizing an anionic vinyl monomer having a polymerizable unsaturated group and a cationic vinyl monomer having a polymerizable unsaturated group as well. A detergent composition comprising One of the latter has been identified as dimethylaminoethyl methacrylate (DMAEMA) quaternized with methyl chloride.

  U.S. Pat. No. 3,547,950 (Johnson & Johnson) discloses a water-soluble acrylate polymer having skin adhesive properties. These polymers are prepared through copolymerization of dimethylaminoethyl methacrylate with esters of acrylic acid and / or esters of methacrylic acid, and the amine groups are quaternized.

British Patent No. 2104091 US Pat. No. 3,547,950

(I) a homopolymer comprising monomer units formed from a trialkyl quaternary ammonium ethyl methacrylate salt;
(Ii) a detergent composition comprising a non-soap synthetic surfactant,
A detergent composition is provided that exhibits a squeaky SQ1 value in the range of 5 to 100 g as measured with an acoustic friction meter tester.

This figure is an enlarged view of an important aspect of the instrument of the acoustic friction meter testing machine.

  Currently, it has been found that homopolymers containing monomer units of trimethylammonium ethyl methacrylate salt can add a squeaky feel to the feel of a non-soap surfactant containing a cleaning system without compromising mildness.

  The inventors have associated squeakiness with the output from the acoustic tribometer tester. This instrument measures the coefficient of friction of the liquid system during the detergent wash with a finger vibration device. After first applying and rinsing the sample to the skin area, this application is 5-100, usually 10-90, especially 23-80, and more specifically when measured at 34 ° C. and an instrument speed of 17 mm / sec. It should show a squeaky SQ1 value of 30-80 g.

The squeak-sensitizing homopolymer of the present invention has the structure (I)

(Wherein, X ^- is chloride, bromide, hydroxyl, sulfate, phosphate, methosulfate, carboxyl, is an anion chosen from the group consisting of citrate and tartrate .X ^- Most preferred Is formed from monomer units having a chloride).

  The amount of homopolymer is 0.01 to about 2%, preferably 0.1 to about 1%, more preferably about 0.3 to about 1% and optimally about 0.3% by weight of the composition. Up to about 0.8% by weight.

  The polymer of the present invention is a homopolymer. In certain embodiments, the homopolymer may be crosslinked with a polyvinyl crosslinking monomer. The homopolymer is in the range of 10,000 to 1,000,000, preferably 10,000 to 800,000, more preferably 15,000 to 500,000, and optimally 20,000 to 300,000 daltons. It may have a number average molecular weight. Most preferred is a homopolymer of structure (I) with a number average molecular weight in the range of 30,000 to about 100,000 daltons.

  There is no limitation on the cross-linking agent when the homopolymer is cross-linked, and the cross-linking agent may be selected from, for example, polyolefinic unsaturated compounds commonly used for cross-linked polymers obtained by free radical polymerization.

  Examples of crosslinking agents that may be mentioned include divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol or tetraethylene glycol di (meth) acrylate, trimethylol. Propane triacrylate, methylenebisacrylamide, methylenebismethacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth) acrylate Allyl ethers of sugar-based alcohols, or other allyls of polyfunctional alcohols The mixtures of vinyl ethers and further allyl ether of phosphoric acid and / or vinylphosphonic acid derivatives or their compounds.

  According to one embodiment of the invention, the cross-linking agent is selected from methylene bisacrylamide, allyl methacrylate and trimethylol propane triacrylate (TMPTA). The degree of crosslinking is not limited, but generally may range from 0.01 mol% to 10 mol% and more specifically from 0.2 mol% to 2 mol% compared to the polymer.

  Another component of the compositions disclosed herein is a non-soap synthetic foaming surfactant. These can be selected from anionic, cationic, amphoteric and combinations thereof. The amount may range from 0.1 to about 30%, preferably from about 1 to about 20%, and optimally from about 3 to about 15% by weight of the composition.

  Suitable amphoteric surfactants for use herein include aliphatic radicals that may be linear or branched, one of the aliphatic substituents containing from about 8 to about 18 carbon atoms. And one substituent includes derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds containing anionic groups such as carboxy, sulfonate, sulfate, phosphate, or phosphonate. It is not limited to them. Exemplary amphoteric compounds are cocodimethylcarboxymethylbetaine, cocoamidopropylbetaine, cocobetaine, oleylbetaine, cetyldimethylcarboxymethylbetaine, laurylbis- (2-hydroxyethyl) carboxymethylbetaine, stearylbis- (2-hydroxypropyl) ) Carboxymethyl betaine, oleyldimethyl γ-carboxypropyl betaine, lauryl bis- (2-hydroxypropyl) α-carboxyethyl betaine, cocoamphoacetate and mixtures thereof. The sulfobetaines can include stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis- (2-hydroxyethyl) sulfopropyl betaine, and mixtures thereof. Most preferred is cocoamidopropyl betaine.

Anionic surfactants, C ₈ -C ₂₂ alkane sulphates, may be ether sulfates and sulfonates, but not limited to. Particularly suitable sulfonates, primary _C 8 _{-C 22} alkanesulfonates, primary _C 8 _{-C 22} alkane _sulfonate, C 8 _{-C 22} alkene _sulfonate, C 8 _{-C 22} hydroxyalkane sulfonate or alkyl glyceryl ether sulfonate It is.

  Specific examples of suitable anionic surfactants for use herein include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, lauryl sulfate Monoethanolamine, laureth sulfate monoethanolamine, lauryl sulfate diethanolamine, laureth sulfate diethanolamine, sodium laurate monoglyceride sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, potassium lauryl sulfate, Sodium tridecesulphate, sodium methyl lauroyl taurate, sodium laureuylisethionate Um, sodium laureth sulfosuccinate, sodium lauroyl sulfosuccinate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, and mixtures thereof.

  Particularly useful anionic surfactants are 0.5 to 1.5 moles, preferably 0.8 to 1.2 moles per unit of hydrophobic material (ie, lauryl sulfate), and optimally about 1 on average. An ammonium or alkali metal salt of laureth sulfate having a degree of ethoxylation within the molar ethoxylation range.

Particularly useful as a synthetic anionic surfactant is a C ₈ -C ₂₂ acyl glycinate salts. Suitable glycinate salts include sodium cocoyl glycinate, potassium cocoyl glycinate, sodium lauroyl glycinate, potassium lauroyl glycinate, sodium myristoyl glycinate, potassium myristoyl glycinate, sodium palmitoyl glycinate, potassium palmitoyl glycinate, sodium stearoyl glycinate. Nates, potassium stearoyl glycinate, ammonium cocoyl glycinate and mixtures thereof.

  The cationic counterion for forming the salt of the anionic surfactant can be selected from sodium, potassium, ammonium, alkanolammonium and mixtures of these cations, for illustration only.

Nonionic surfactants that can be used include the reaction product of a compound having a hydrophobic group and a reactive hydrogen atom. Typical are alcohols, acids, amides or alkylphenols reacted with alkylene oxides, in particular either ethylene oxide alone or with propylene oxide. Certain nonionics, C ₆ -C ₂₂ alkyl phenol - condensation products of ethylene oxide condensates, C ₈ -C ₁₈ aliphatic primary or secondary linear or branched alcohols with ethylene oxide, and A product made by condensation of ethylene oxide with the reaction product of propylene oxide and ethylenediamine. Other nonionic materials include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides. Also useful are alkyl polysaccharides.

  A surfactant should be selected that allows the composition to have a SITA Foam test value in the range of 200-800 mL, preferably 300-700 mL and optimally 400-600 mL. For this evaluation, a SITA foam tester R-2000 model manufactured by Future Digital Scientific is usually used. The experimental protocol involves loading (without predilution) 10 g of product into a graduated cylinder. Into it is added 250 mL of water at 40-45 ° C. The foam volume is the volume recorded after stirring the sample for 30 seconds at 1,000 rpm using a rotor. The final foam volume is obtained as an average value obtained by repeatedly measuring the foam volume 10 times by stirring the sample at 1,000 rpm for 30 seconds.

C ₈ -C ₂₂ fatty acids may also be included in the compositions of the present invention. Suitable fatty acids are lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, behenic acid and combinations of these acids. Particularly useful _are C 12 _{-C 14} fatty acids, such as lauric acid and myristic acid. The amount of fatty acid, if present, may range from 0.1 to 15%, preferably from 0.5 to 10% and optimally from 1 to 5% by weight of the composition.

Components useful in the same manner of the present composition may be a C ₈ -C ₂₂ fatty alcohols. Suitable fatty alcohols are lauryl alcohol, myristyl alcohol, cetearyl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol, behenyl alcohol and mixtures thereof. The amount of fatty alcohol, if present, may range from 0.1 to 15%, preferably from 0.5 to 10% and optimally from 1 to 5% by weight of the composition.

  Water may be present in the composition in an amount of 5-95% by weight, preferably 50-90% by weight and optimally 65-85% by weight.

  A water soluble / water dispersible polymer is an optional ingredient that may be included in the composition. These polymers may be cationic, anionic, amphoteric or nonionic. These polymers are known to increase the viscosity and stability of liquid detergent compositions, enhance skin feel during and after use, and enhance foam creaminess and foam stability. The amount of polymer, if present, can range from 0.1 to 10% by weight of the composition.

  Examples of water soluble / dispersible polymers include carbohydrate gums such as cellulose gum, microcrystalline cellulose, cellulose gel, hydroxyethylcellulose, hydroxypropylcellulose, sodium carboxymethylcellulose, methylcellulose, ethylcellulose, guar gum, karaya gum, tragacanth gum, gum arabic , Acacia gum, agar gum, xanthan gum and combinations thereof; processed and unprocessed starch granules and pregelatinized cold water-soluble starch; emulsion polymers such as Acculyn® 28, Acculyn® 22 or Carbopol® Aqua SF1; a cationic polymer, such as the brand names Jaguar C13S, Jaguar C14S, Jaguar C17 or Jag modified polysaccharides containing cationic guars available from Rhodia under ar C16; cationic modified cellulose, such as UCARE polymer JR30 or JR40 from Amerchol; N-Hance® 3000 from Hercules, N-Hance (R) 3196, N-Hance (R) GPX215 or N-Hance (R) GPX196; synthetic cationic polymers such as Merquat (R) 100, Merquat (R) sold by Nalco 280, Merquat 281 and Merquat 550; cationic starches such as StaLok® 100, 200, 300 and 400 sold by Staley. Cationic galactomannan, such as Henkel Corporation by Galactasol (TM) 800 Series; Quadrosoft (R) LM-200; a and Polyquaternium -24. Also suitable are high molecular weight polyethylene glycols such as Polyox® WSR-205 (PEG14M), Polyox® WSR-N-60K (PEG45) and Polyox® WSR-301 (PEG90M).

  In the present composition, a water-soluble skin benefit agent may be blended. A variety of water soluble skin benefit agents can be used, the concentration of which can be 0.1-50% by weight of the composition, but preferably 1-30% by weight. These materials include, but are not limited to, polyhydroxy alcohols. Preferred water soluble skin benefit agents are glycerin, sorbitol and polyethylene glycol.

  In the present compositions, water-insoluble skin benefit agents may also be formulated as conditioners and humectants. Examples include silicone oils; carbohydrates such as liquid paraffin, petroleum, microcrystalline waxes and mineral oils; and vegetable triglycerides such as sunflower seed oil and cottonseed oil.

  Desirably, a preservative can be incorporated into the composition to protect against the growth of potentially harmful microorganisms. Suitable conventional preservatives for the composition are alkyl esters of parahydroxybenzoic acid. Other preservatives that have been used more recently include hydantoin derivatives, propionate salts and a wide variety of quaternary ammonium compounds. Particularly preferred preservatives are phenoxyethanol, methyl paraben, propyl paraben, imidazolidinyl urea, sodium dehydroacetate and benzyl alcohol. Preservatives must be selected that take into account the use of the composition and possible incompatibilities between the preservative and other ingredients. Preservatives are preferably used in amounts ranging from 0.01% to 2% by weight of the composition.

  Various other optional materials can be incorporated into the composition. These include antibacterial agents such as 2-hydroxy-4,2 ′, 4′-trichlorodiphenyl ether (triclosan), 2,6-dimethyl-4-hydroxychlorobenzene and 3,4,4′-trichlorocarbanilide; And exfoliating particles such as polyethylene and silica or alumina; coolants such as menthol; skin soothing agents such as aloe vera; and coolants.

  In addition, the composition of the present invention comprises 0.5 to 10% by weight of a sequestering agent such as ethylenediaminetetraacetic acid tetrasodium (EDTA), EHDP or mixtures; opacifiers and pearling agents such as ethylene glycol distearate, Titanium dioxide or Lytron 621 (styrene / acrylate copolymer) can further be included. These are all useful for enhancing the appearance or properties of the product.

  The term “comprising” is not intended to be limiting to the elements described thereafter, but rather is intended to include non-specific elements that are of greater or lesser functional importance. That is, the listed steps, elements, or options need not be exhaustive. Whenever the terms “include” or “have” are used, these terms are intended to be equivalent to the above “include”.

  Unless otherwise indicated in the examples and comparative examples, or unless explicitly indicated, all numbers indicating the amount of material herein should be understood to be rhetorical by the term “about”.

  In defining any range of concentrations or amounts, it should be noted that any particular upper concentration can be associated with any particular lower concentration or amount.

  The following examples illustrate embodiments of the invention in more detail. All parts, percentages and ratios referred to herein and in the appended claims are by weight unless otherwise indicated.

  Evaluation of squeaky feeling was carried out using an acoustic friction meter tester illustrated in the figure.

Instruments of the acoustic friction meter tester This figure is an enlarged view of an important aspect of the instrument of the acoustic friction meter tester. These aspects include sample stage (2), load cell (4, 6), finger vibration device (8), accelerometer (10), support base (12), position guider (14), optical sensor (16), A motor and boundary plate at the end of the hydrophone (18) and position guide (not shown) are included. The motor drives the rotary stage through a time belt (not shown) that can attenuate vibration noise generated by the rotation of the motor. The sample stage immersed in water is connected to the support base by two load cells (Honeywell AL311AR, 1,000 g range) capable of sensing a vertical load from DC to a frequency of 300 Hz. Near the sample stage, hydrophone (B & K 1803 hydrophone) is used to detect underwater sound generated from a stationary sample substrate and a movable artificial finger. An accelerometer (PCB 352A24) is attached to the artificial finger directly above water in order to detect the vibration of the artificial finger. The electromagnetic coil attached to the artificial finger allows application of finger load while rubbing the substrate and lifting of the artificial finger during reverse movement by reversing the voltage applied to the coil. The pivot in the artificial finger provides a free response to stick-slip generated during sliding through the test surface. Limiting the lift limits the length of the artificial finger, and therefore suppresses the depth of the sample stage in the water. A large water tank (50-53L) is used to avoid the detrimental effects that occur as the surfactant is washed from the substrate in water. To make data processing easier, an optical sensor with a position guider is used to generate a “gate” signal, where the “low to high” movement is the contact position at the right post on the sample stage. Related, “high to low” movement is related to the contact position at the left post. The electromagnetic relay system (USB-ERB24, Measurement Computing, Inc.) is controlled by a computer to switch between finger load application (sliding) or finger lifting (backward movement). Further details regarding a number of aspects of the instrumentation can be found in EP 1684631 (B1), which is incorporated herein by reference.

Experimental Protocol After mounting a set of substrates, the substrate and sample stage are submerged in water for immersion. Prior to applying the sample test composition on the substrate, 10 rubbing motions are performed to establish a baseline for the blank substrate. The sample stage is then removed from the water by lowering the water bath and 0.25 g of the test composition is applied to a substrate (eg, synthetic skin). The sample stage is then placed back into the water by raising the water tank. The sample test composition is then rubbed against the surface 40 times using an artificial finger. The latter has the same substrate surface as on the sample stage.

Water Hardness and Temperature The rinsability of the test composition sample can depend on the water hardness. Test water is prepared using calcium chloride and magnesium chloride to mimic various water conditions. The ratio of calcium to magnesium is set within the range of 3: 1 to 4: 1. The water temperature is adjusted by mixing hot water and cold water. The total amount of water in the test tank is approximately 14 gallons (about 53 L).

Rotation speed The rotation speed of the artificial finger can be fixed at 10 to 100 mm / second, but is maintained at 17 mm / second for the present invention.

Coefficient of friction The configuration with two vertical load cells creates a system that can measure normal force and coefficient of friction. As the system goes to the squeeze region (stick slip), the load cell (4) and load (6) signals oscillate as the stick slip generates normal force. The two load cells have the same phase in excitation and the sum of the two signals provides the amplitude of the stick-slip event.

  The squeaking sensation parameter SQ1 is based on the average deviation of normal force with respect to 40 rubbing of the first application. Normal force is the force applied through an artificial finger minus the dissipation due to friction. SQ1 is the average value of all 40 rubbing of the rinse while the rotational speed is 17 mm / sec. This is an excellent indicator of squeaky feeling.

The polymer evaluated in the sample detergent composition was prepared in the following manner, but the reactant / catalyst / polymer structure is described below.

  Statistical free radical polymerization was performed using the Chemspeed Swing robot platform using the following general method.

-About 20-50K for low molecular weight polymers
Dimethylaminoethyl methacrylate (DMAEMA) quat (40 mL of 25% aqueous solution) in 4,4′-azobis (4-cyanovaleric acid) (ACVA) (200 mg) water (5 mL) to maintain polymerization at 20% solids And isopropyl alcohol (IPA) (5 mL). The reaction mixture was heated and stirred at 75 ° C. for 4 hours. The IPA was evaporated and residual monomer was removed by ultrafiltration. Poly (DMAEMA quat) was isolated as a white solid (9.0 g) by lyophilization.

-About 100-200K for high molecular weight polymers
DMAEMA quat (40 mL of 25% aqueous solution) was added to 4,4′-azobis (4-cyanovaleric acid) (ACVA) (100 mg) with water (10 mL) to maintain polymerization at 20% solids. The reaction mixture was heated and stirred at 75 ° C. for 4 hours. The polymer was purified by ultrafiltration. Poly (DMAEMA quat) was isolated as a white solid (9.0 g) by lyophilization.

Molecular weight was measured using Viscotek GPCmax 2001 triple detection GPC. Chemical characterization was performed using a Bruker Avance 400 MHz NMR equipped with a Samplejet autosampling robot. The purified proton NMR spectrum (D ₂ O) shows no residual olefinic monomer peak and the signal for the polymer is 4.5 ppm for C (O) OCH 2 CH 2; 3.82 ppm for C (O) OCH 2 CH 2; N + ( Me) 3 was 3.25; the polymer main chain was 0.9 to 2.2 ppm.

A series of test compositions was prepared. These test compositions and their squeaky SQ1 values are listed in Tables I-II.

  The poly (trimethylammonium ethyl methacrylate chloride) homopolymer improved the squeaky sensation reaction for compositions containing either cocoamidopropyl betaine, sodium laureth sulfate or sodium cocoyl glycinate as a surfactant. The best performance was seen when sodium laureth sulfate was used as the surfactant. For the latter, the improvement in squeakiness ranged from about 54 to 68 g when associated with a control containing no homopolymer. For example, compare control sample A with samples B, C, J and K. Homopolymers associated with either cocoamidopropyl betaine or sodium cocoyl glycinate were less effective but useful.

  The above description is presented to enable one of ordinary skill in the art to make and use the invention and is provided in the context of a particular application and its requirements. Various modifications to the preferred embodiment will be readily apparent to those skilled in the art, and the generic principles defined herein may be used in other embodiments and applications without departing from the spirit and scope of the invention. Applicable. Thus, the present invention is not intended to be limited to the embodiments shown herein, but is intended to harmonize with a very wide range consistent with the principles and features disclosed herein.

Claims (10)

(I) a homopolymer comprising monomer units formed from a trialkyl quaternary ammonium ethyl methacrylate salt;
(Ii) a detergent composition comprising a non-soap synthetic surfactant,
A detergent composition showing a squeaky SQ1 value in the range of 5 to 100 g when measured with an acoustic friction meter tester.   The composition of claim 1, wherein the homopolymer has a number average molecular weight in the range of 10,000 to 800,000 daltons.   The composition of claim 1, wherein the homopolymer has a number average molecular weight in the range of 20,000 to 300,000 daltons.   The composition of claim 1, wherein the homopolymer has a number average molecular weight in the range of 30,000 to 100,000 daltons. The monomer unit has the structure (I):

(Wherein, X ^- is chloride, bromide, hydroxyl, sulfate, phosphate, methosulfate, carboxyl, anionic and is selected from the group consisting of citrate and tartrate) has the claim 2. The composition according to 1.   The composition of claim 1, wherein the homopolymer is crosslinked with a polyolefinic unsaturated compound.   The composition of claim 1, wherein the non-soap surfactant is sodium laureth sulfate.   8. The composition of claim 7, wherein the sodium laureth sulfate has an average of 1 mole of ethoxylation.   The composition of claim 1, wherein the homopolymer is present in an amount of 0.01 to about 2 wt%.   The composition of claim 1, wherein the homopolymer is present in an amount of 0.3 to about 1 wt%.

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