Gradient polymer
A gradient polymer with specific monomer ratios addresses the thickenability and temperature sensitivity of amino acid-based surfactant formulations by enhancing viscosity at low shear rates and maintaining flow at higher rates.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- DOW GLOBAL TECHNOLOGIES LLC
- Filing Date
- 2023-07-06
- Publication Date
- 2026-07-02
AI Technical Summary
Formulations containing amino acid-based surfactants are difficult to thicken efficiently, leading to issues such as inadequate viscosity at high shear rates, sensitivity to temperature changes, and potential phase separation.
A gradient polymer comprising specific ratios of (meth)acrylic acid, alkyl (meth)acrylate, and special associative monomer units, which maintains viscosity at low shear rates while ensuring flow properties at higher shear rates.
The gradient polymer effectively increases viscosity at low shear rates while maintaining product flow at higher shear rates, addressing the thickenability and temperature sensitivity issues of amino acid-based surfactant formulations.
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Abstract
Description
Technical Field
[0001] The present invention relates to gradient polymers. In particular, the present invention relates to (a) 5 to 35% by weight, based on the dry weight of the gradient polymer, of a structural monomer unit of a (meth)acrylic acid monomer, and (b) 35 to 65% by weight, based on the dry weight of the gradient polymer, of C 5 , 4 , , , 1-4 , 1-4 , 3 , , a structural monomer unit of an alkyl (meth)acrylate monomer, and (c) more than 10 to 30% by weight, based on the dry weight of the gradient polymer, of Structure I:
[0002]
Chemical Formula
[0004] Amino acid-based surfactants possess a range of desirable properties for use in personal care products (e.g., shampoos). Such surfactants are often naturally derived and readily biodegradable. Amino acid-based surfactants are significantly milder than more traditional sulfate and sulfonate surfactants such as sodium lauryl sulfate and sodium lauryl ether sulfate, resulting in less irritation to the skin and hair. Amino acid-based surfactants tend to be less toxic and have less adverse environmental impact than more traditional sulfate and sulfonate surfactants. Amino acid-based surfactants also possess good cleansing and foaming properties.
[0005] Nevertheless, formulations containing amino acid-based surfactants are difficult to thicken efficiently. Some conventional thickeners achieve the target viscosity at high usage levels, which may adversely affect foaming performance. In other cases, conventional thickeners can provide adequate thickness, but the viscosity of the formulation is sensitive to temperature changes, becoming watery at high temperatures and gel-like at low temperatures. Some conventional thickeners, such as xanthan gum or cellulose esters, exhibit potential mismatch issues that can lead to phase separation.
[0006] Therefore, there is a continuing need for viscosity modifiers that facilitate the formulation of aqueous cleaning products, particularly aqueous cleaning products containing amino acid surfactants (e.g., shampoos), which maintain desired flow properties at higher shear rates while exhibiting increased viscosity at lower shear rates. [Overview of the Initiative]
[0007] The present invention comprises (a) 5 to 35% by weight of structural monomer units of (meth)acrylic acid monomer based on the dry weight of the gradient polymer, and (b) 35 to 65% by weight of C based on the dry weight of the gradient polymer. 1-8 Structure monomer units of alkyl (meth)acrylate monomers, and (c) Structure I, based on the dry weight of the gradient polymer, in amounts of 10 to 30% by weight:
[0008] [ka] (In the formula, each R 1 Independently, linear saturated C 12-26 Selected from alkyl groups, each R 2 (These are independently selected from hydrogen and methyl groups, and n is between 10 and 30.) (d) structural monomer units of a special associative monomer having, and 0.01 to 2% by weight of a polyvalent ethylenically unsaturated monomer based on the weight of the gradient polymer, A gradient polymer comprising, based on the dry weight of the gradient polymer, less than 0.05% by weight of structural monomer units of the sulfonated monomer, and less than 0.02% by weight of structure II:
[0009] [ka] (In the formula, each R 3 These are independently selected from -H and -CH3, and each R 4 These are independently -H and -C 1-4 Selected from alkyl groups, each R 5 -C 1-4 The present invention provides a gradient polymer having a gradient polymer form, comprising monomer structural monomer units (selected from alkyl groups, where a is 0-50, b is 0-20, c is 0-50, a+c is 1-100, and d is 1-4).
[0010] The present invention comprises (a) 5 to 35% by weight of structural monomer units of (meth)acrylic acid monomer based on the dry weight of the gradient polymer, and (b) 35 to 65% by weight of C based on the dry weight of the gradient polymer. 1-8 (c) Structural monomer units of alkyl (meth)acrylate monomers, and structural monomer units of special associable monomers having structure I, in an amount of more than 10 to 30% by weight based on the dry weight of the gradient polymer, wherein structure Ia:
[0011] [ka] (In the formula, each R 1a Independently, linear saturated C 12-19 Selected from alkyl groups, each R 2a A first special associative monomer having a hydrogen and a methyl group (where Na is 10-30), and structure Ib:
[0012] [ka] (In the formula, each R 1b Independently, linear saturated C 20-26 Selected from alkyl groups, each R 2b A second special associative monomer having (independently selected from linear saturated hydrogen and methyl groups, with nb being 10-30), A blend of structural monomer units of special associative monomers having structure I, A gradient polymer comprising, based on the dry weight of the gradient polymer, less than 0.05% by weight of structural monomer units of the sulfonated monomer, and based on the dry weight of the gradient polymer, less than 0.02% by weight of structure II: (wherein each R 3 These are independently selected from -H and -CH3, and each R 4 These are independently -H and -C 1-4 Selected from alkyl groups, each R 5 -C 1-4The present invention provides a gradient polymer having a gradient polymer form, comprising monomer structural monomer units (selected from alkyl groups, where a is 0-50, b is 0-20, c is 0-50, a+c is 1-100, and d is 1-4). [Modes for carrying out the invention]
[0013] The inventors have surprisingly found that gradient polymers as described herein facilitate the formulation of aqueous cleaning products, particularly aqueous cleaning products containing amino acid surfactants (e.g., shampoos), by increasing viscosity at low shear rates while maintaining the flow properties of the product at higher shear rates.
[0014] Unless otherwise specified, ratios, percentages, and parts are expressed by weight.
[0015] The percentage of monomer units in a polymer is the percentage of solids or undiluted monomer weight. In other words, any water present in the polymer emulsion is excluded.
[0016] As used herein and in the appended claims, the term “structural monomer unit” refers to the remnant of a specified monomer, and therefore the structural monomer unit of ethyl acrylate is:
[0017] [ka] (In the formula, the dotted lines represent the bonding points to the polymer backbone.)
[0018] As used herein and in the appended claims, the term "(meth)acrylic acid" is intended to function as a general expression encompassing both acrylic acid and methacrylic acid.
[0019] As used herein and in the appended claims, the term "(meth)acrylate" is intended to function as a general expression encompassing both acrylate and methacrylate.
[0020] As used herein and in the appended claims, the term “gradient polymer form” refers to a polymer having a continuously changing monomer composition content. The preparation of gradient polymers having a gradient polymer form is well known in the art. U.S. Patent No. 3,804,881, which is incorporated herein by reference in its entirety, discloses a process for preparing a gradient polymer having a gradient polymer form, comprising polymerizing at least one primary polymerizable monomer feedstock while changing its composition content by continuously adding at least one different secondary polymerizable monomer feedstock to at least one primary polymerizable monomer feedstock.
[0021] Preferably, the gradient polymer of the present invention comprises (a) 5 to 35% by weight (preferably 10 to 35% by weight, more preferably 20 to 34% by weight, most preferably 26 to 32% by weight) of structural monomer units of (meth)acrylic acid monomer, based on the dry weight of the gradient polymer, and (b) 35 to 65% by weight (preferably 40 to 60% by weight, more preferably 45 to 55% by weight, most preferably 48 to 54% by weight) of C 1-8 Structure monomer units of alkyl (meth)acrylate monomers and (c) 10 to 30% by weight (preferably 12 to 30% by weight, more preferably 15 to 25% by weight, most preferably 16 to 20% by weight) of the gradient polymer based on the dry weight, Structure I:
[0022] [ka] (In the formula, each R 1 Independently, linear saturated C 12-26 Alkyl alkyl group (preferably C 12-24alkyl group, more preferably C 14-24 Alkyl alkyl group, most preferably C 16-22 Selected from alkyl groups, each R 2 These are independently selected from hydrogen and methyl groups (preferably R 2 (d) a structural monomer unit of a special associative monomer having n = 10-30 (preferably 12-30, more preferably 15-28, most preferably 18-26), and (d) 0.01-2% by weight (preferably 0.05-1% by weight, more preferably 0.08-0.5% by weight, most preferably 0.1-0.2% by weight) of a polyvalent ethylenically unsaturated monomer based on the dry weight of the gradient polymer, wherein the gradient polymer comprises (d) a structural monomer unit of a special associative monomer having n = 10-30 (preferably 12-30, more preferably 15-28, most preferably 18-26), and (d) 0.01-2% by weight (preferably 0.05-1% by weight, more preferably 0.08-0.5% by weight, most preferably 0.1-0.2% by weight) of a polyvalent ethylenically unsaturated monomer based on the dry weight of the gradient polymer. The gradient polymer contains, based on the amount, <0.05% by weight (preferably <0.01% by weight, more preferably <0.001% by weight, even more preferably <0.0001% by weight, most preferably below the detection limit) of structural monomer units (e.g., AMPS) of the sulfonated monomer, and the gradient polymer contains, based on the dry weight of the gradient polymer, <0.02% by weight (preferably <0.01% by weight, more preferably <0.001% by weight, even more preferably <0.0001% by weight, most preferably below the detection limit) of structure II:
[0023] [ka] (In the formula, each R 3 These are independently selected from -H and -CH3, and each R 4 These are independently -H and -C 1-4 Selected from alkyl groups, each R 5 -C 1-4The gradient polymer comprises a monomer structure monomer unit having selected alkyl groups, where a is 0-50, b is 0-20, c is 0-50, a+c is 1-100, and d is 1-4, and the gradient polymer has a gradient polymer form. More preferably, the gradient polymer of the present invention comprises (a) 5-35% by weight (preferably 10-35% by weight, more preferably 20-34% by weight, most preferably 26-32% by weight) of (meth)acrylic acid monomer structure monomer units based on the dry weight of the gradient polymer, and (b) 35-65% by weight (preferably 40-60% by weight, more preferably 45-55% by weight, most preferably 48-54% by weight) of C based on the dry weight of the gradient polymer. 1-8 (c) Structural monomer units of alkyl (meth)acrylate monomers, and structural monomer units of special associable monomers having structure I, in an amount of more than 10 to 30% by weight (preferably 12 to 30% by weight, more preferably 15 to 25% by weight, most preferably 16 to 20% by weight) based on the dry weight of the gradient polymer, wherein structure Ia:
[0024] [ka] (In the formula, each R 1 Independently, linear saturated C 12-19 Alkyl alkyl groups (preferably linear saturated C) 12-18 Alkyl alkyl groups, more preferably linear saturated C chains. 14-18 Alkyl alkyl groups, most preferably linear saturated C 16-18 Selected from alkyl groups, each R 2a These are independently selected from hydrogen and methyl groups (preferably R 2 A first special associated monomer having structure Ia) and structure Ib: (where is a methyl group), na is 10-30 (preferably 12-30, more preferably 15-28, most preferably 18-26) (preferably 51-99% by weight, more preferably 75-97% by weight, most preferably 85-95% by weight, based on the weight of the special associated monomer having structure Ia), and structure Ib:
[0025] [ka] (In the formula, each R 1b Independently, linear saturated C 20-26 Alkyl alkyl groups (preferably linear saturated C) 20-24 Alkyl alkyl groups, more preferably linear saturated C chains. 21-23 Alkyl alkyl groups, most preferably linear saturated C 22 Selected from alkyl groups, each R 2b (d) Based on the dry weight of the gradient polymer, 0.01 to 2% by weight (preferably 0.05 to 1% by weight, more preferably 0.08 to 0.5% by weight, most preferably 20 to 28%) of a first special associated monomer having structure Ib, and a blend of (d) a structural monomer unit of the special associated monomer having structure I, which is independently selected from linear saturated hydrogen and methyl groups (preferably methyl groups), and nb is 10 to 30 (preferably 15 to 30, more preferably 18 to 28, most preferably 20 to 28) (preferably 1 to 49% by weight, more preferably 3 to 25% by weight, most preferably 6 to 15%) of a first special associated monomer having structure Ib. Preferably comprising 0.1 to 0.2% by weight of polyvalent ethylenically unsaturated monomer structural monomer units, the gradient polymer comprises <0.05% by weight (preferably <0.01% by weight, more preferably <0.001% by weight, even more preferably <0.0001% by weight, most preferably below the detection limit) of sulfonated monomer structural monomer units (e.g., AMPS) based on the dry weight of the gradient polymer, and the gradient polymer comprises <0.02% by weight (preferably <0.01% by weight, more preferably <0.001% by weight, even more preferably <0.0001% by weight, most preferably below the detection limit) of structure II (wherein each R 3 These are independently selected from -H and -CH3, and each R 4 These are independently -H and -C 1-4 Selected from alkyl groups, each R 5-C 1-4 The gradient polymer comprises monomer structural monomer units having alkyl groups selected from alkyl groups, where a is 0-50, b is 0-20, c is 0-50, a+c is 1-100, and d is 1-4, and the gradient polymer has a gradient polymer form.
[0026] Preferably, the gradient polymer of the present invention contains 90 to 100% by weight (preferably 95 to 100% by weight, more preferably 98 to 100% by weight, even more preferably 99 to 100% by weight, even more preferably 99.9 to 100% by weight, most preferably 100% by weight) of structural monomer units present in the gradient polymer, which are structural monomer units of (a) to (d). The structural monomer units of the gradient polymer do not contain terminal groups on the gradient polymer derived from a chain transfer agent or initiator (e.g., residues of a chain transfer agent).
[0027] Preferably, the gradient polymer of the present invention contains 5 to 35% by weight (preferably 10 to 35% by weight, more preferably 20 to 34% by weight, most preferably 26 to 32% by weight) of structural monomer units of (meth)acrylic acid monomer based on the dry weight of the gradient polymer, wherein the (meth)acrylic acid monomer is selected from the group consisting of methacrylic acid, acrylic acid, and mixtures thereof. More preferably, the gradient polymer of the present invention contains 5 to 35% by weight (preferably 10 to 35% by weight, more preferably 20 to 34% by weight, most preferably 26 to 32% by weight) of structural monomer units of (meth)acrylic acid monomer based on the dry weight of the gradient polymer, wherein the (meth)acrylic acid monomer is a mixture of methacrylic acid and acrylic acid. Most preferably, the gradient polymer of the present invention comprises 5 to 35% by weight (preferably 10 to 35% by weight, more preferably 20 to 34% by weight, most preferably 26 to 32% by weight) of structural monomer units of (meth)acrylic acid monomer based on the dry weight of the gradient polymer, wherein the (meth)acrylic acid monomer is a mixture of 30 to 60% by weight (preferably 32 to 58% by weight, most preferably 33 to 55% by weight) of methacrylic acid and 40 to 70% by weight (preferably 32 to 58% by weight, more preferably 33 to 55% by weight) of acrylic acid based on the weight of the mixture.
[0028] Preferably, the gradient polymer of the present invention contains 35-65% by weight (preferably 40-60% by weight, more preferably 45-55% by weight, most preferably 48-54% by weight) of C based on the dry weight of the gradient polymer. 1-8 Alkyl (meth)acrylate monomer (preferably C 1-6 Alkyl (meth)acrylate monomer, more preferably C 2-3The gradient polymer of the present invention contains structural units of alkyl (meth)acrylate monomers, most preferably C2 alkyl acrylate monomers. More preferably, the gradient polymer of the present invention contains 35 to 65% by weight (preferably 40 to 60% by weight, more preferably 45 to 55% by weight, most preferably 48 to 54% by weight) of C based on the dry weight of the gradient polymer. 1-8 It contains the structural unit of alkyl (meth)acrylate monomer, C 1-8 The alkyl (meth)acrylate monomer is selected from the group consisting of ethyl (meth)acrylate, propyl (meth)acrylate, and mixtures thereof (preferably ethyl acrylate, propyl acrylate, and mixtures thereof). Most preferably, the gradient polymer of the present invention contains 35 to 65% by weight (preferably 40 to 60% by weight, more preferably 45 to 55% by weight, most preferably 48 to 54% by weight) of C based on the dry weight of the gradient polymer. 1-8 It contains the structural unit of alkyl (meth)acrylate monomer, C 1~8 Alkyl (meth)acrylate monomers are ethyl acrylates.
[0029] Preferably, the gradient polymer of the present invention has a structure I of 10 to 30% by weight (preferably 12 to 30% by weight, more preferably 15 to 25% by weight, most preferably 16 to 20% by weight) based on the dry weight of the gradient polymer.
[0030] [ka] (In the formula, each R 1 Independently, linear saturated C 12-26 Alkyl alkyl group (preferably C 12-24 alkyl group, more preferably C 14-24 Alkyl alkyl group, most preferably C 16-22 Selected from alkyl groups, each R 2 These are independently selected from hydrogen and methyl groups (preferably R 2The present invention comprises structural monomer units of a special associative monomer having a methyl group, n being 10 to 30 (preferably 12 to 30, more preferably 15 to 28, most preferably 18 to 26). More preferably, the gradient polymer of the present invention comprises more than 10 to 30% by weight (preferably 12 to 30% by weight, more preferably 15 to 25% by weight, most preferably 16 to 20% by weight) of structural monomer units of a special associative monomer having structure I, based on the dry weight of the gradient polymer, wherein the structural monomer units of the special associative monomer having structure Ia:
[0031] [ka] (In the formula, each R 1 Independently, linear saturated C 12-19 Alkyl alkyl groups (preferably linear saturated C) 12-18 Alkyl alkyl groups, more preferably linear saturated C chains. 14-18 Alkyl alkyl groups, most preferably linear saturated C 16-18 Selected from alkyl groups, each R 2a These are independently selected from hydrogen and methyl groups (preferably R 2 A first special associative monomer having structure Ia (based on the weight of the special associative monomer having structure I, preferably 51-99% by weight, more preferably 75-97% by weight, most preferably 85-95% by weight), and structure Ib:
[0032] [ka] (In the formula, each R 1b Independently, linear saturated C 20-26 Alkyl alkyl groups (preferably linear saturated C) 20-24 Alkyl alkyl groups, more preferably linear saturated C chains. 21-23 Alkyl alkyl groups, most preferably linear saturated C22 is selected from (alkyl group), and each R 2b is independently selected from linear saturated hydrogen and methyl group (preferably, methyl group), nb is 10 to 30 (preferably, 15 to 30, more preferably 18 to 28, most preferably 20 to 28) (preferably, the difference between R 1a and R 1b is less than 8 carbon atoms (more preferably, less than 7 carbon atoms)), and a second special associative monomer (preferably, 1 to 49% by weight, more preferably 3 to 25% by weight, most preferably 6 to 15% by weight based on the weight of the special associative monomer having Structure I) of the first special associative monomer having Structure Ib).
[0033] Preferably, the gradient polymer of the present invention contains 0.01 to 2% by weight (preferably 0.05 to 1% by weight, more preferably 0.08 to 0.5% by weight, most preferably 0.1 to 0.2% by weight) of polyvalent ethylenically unsaturated monomer structural monomer units based on the dry weight of the gradient polymer.More preferably, the gradient polymer of the present invention comprises 0.01 to 2% by weight (preferably 0.05 to 1% by weight, more preferably 0.08 to 0.5% by weight, most preferably 0.1 to 0.2% by weight) of polyvalent ethylenically unsaturated monomer structural monomer units based on the dry weight of the gradient polymer, wherein the polyvalent ethylenically unsaturated monomer is a polyunsaturated aromatic monomer (e.g., divinylbenzene, divinylnaphthalene, trivinylbenzene); or a polyunsaturated alicyclic monomer (e.g., 1,2,4-trivinylcyclohexane). ; Difunctional esters of phthalates (e.g., diallyl phthalate); Polyunsaturated aliphatic monomers (e.g., isoprene, butadiene, 1,5-hexadiene, 1,5,9-decatriene, 1,9-decadiene, 1,5-heptadiene); Polyalkenyl ethers (e.g., triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, octaaryl sucrose, trimethylolpropanediallyl ether); Polyunsaturated esters of polyhydric alcohols or polyacids (e.g., 1,6-hexanediol di(meth) Selected from the group consisting of acrylates, tetramethylene tri(meth)acrylate, allyl acrylate, diarylluitaconate, diallyl fumarate, diallyl maleate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, polyethylene glycol di(meth)acrylate); alkylene bisacrylamide (e.g., methylenebisacrylamide, propylenebisacrylamide); hydroxy and carboxy derivatives of methylenebisacrylamide (e.g., N,N'-bismethylolmethylenebisacrylamide); polyethylene glycol di(meth)acrylate (e.g., ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate); polyunsaturated silanes (e.g., dimethyldivinylsilane, methyltrivinylsilane, allyldimethylvinylsilane, diallyldimethylsilane, tetravinylsilane); polyunsaturated stannanes (e.g., tetraallylutin, diallyldimethyltin), and mixtures thereof.More preferably, the gradient polymer of the present invention contains 0.01 to 2% by weight (preferably 0.05 to 1% by weight, more preferably 0.08 to 0.5% by weight, most preferably 0.1 to 0.2% by weight) of polyvalent ethylenically unsaturated monomer structural monomer units based on the dry weight of the gradient polymer, wherein the polyvalent ethylenically unsaturated monomer is a polyalkenyl ether. Most preferably, the gradient polymer of the present invention contains 0.01 to 2% by weight (preferably 0.05 to 1% by weight, more preferably 0.08 to 0.5% by weight, most preferably 0.1 to 0.2% by weight) of polyvalent ethylenically unsaturated monomer structural monomer units based on the dry weight of the gradient polymer, wherein the polyvalent ethylenically unsaturated monomer is trimethylolpropanediallyl ether.
[0034] Preferably, the gradient polymer of the present invention further comprises 0.01 to 2% by weight (preferably 0.02 to 1% by weight, more preferably 0.04 to 0.5% by weight, most preferably 0.06 to 0.1% by weight) of chain transfer agent residues based on the dry weight of the gradient polymer. More preferably, the gradient polymer of the present invention further comprises 0.01 to 2% by weight (preferably 0.02 to 1% by weight, more preferably 0.04 to 0.5% by weight, most preferably 0.06 to 0.1% by weight) of chain transfer agent residues based on the dry weight of the gradient polymer, wherein the chain transfer agent is a thio and disulfide-containing compound (e.g., C 1-18 Alkyl mercaptans, mercaptocarboxylic acids, mercaptocarboxylic acid esters, thioesters, C 1-18 The group consists of alkyl disulfides, aryl disulfides, polyfunctional thiols; phosphates and hypophosphates; haloalkyl compounds (e.g., carbon tetrachloride, bromotrichloromethane); unsaturated chain transfer agents (e.g., alpha-methylstyrene); and mixtures thereof. More preferably, the gradient polymer of the present invention further comprises 0.01 to 2% by weight (preferably 0.02 to 1% by weight, more preferably 0.04 to 0.5% by weight, most preferably 0.06 to 0.1% by weight) of chain transfer agent residues based on the dry weight of the gradient polymer, wherein the chain transfer agent is C1-18 It is an alkyl mercaptan. Most preferably, the gradient polymer of the present invention further contains residues of a chain transfer agent in an amount of 0.01 to 2% by weight (preferably 0.02 to 1% by weight, more preferably 0.04 to 0.5% by weight, most preferably 0.06 to 0.1% by weight) based on the dry weight of the gradient polymer, and the chain transfer agent is n-dodecyl mercaptan.
[0035] Preferably, the gradient polymer of the present invention contains structural monomer units of a sulfonated monomer in an amount of <0.05% by weight (preferably <0.01% by weight, more preferably <0.001% by weight, still more preferably <0.0001% by weight, most preferably less than the detection limit) based on the dry weight of the gradient polymer, and the sulfonated monomer is selected from the group consisting of 2-acrylamido-2-methylpropane sulfonic acid (AMPS), 2-methacrylamido-2-methylpropane sulfonic acid, 4-styrene sulfonic acid, vinyl sulfonic acid, 3-allyloxy sulfonic acid, 2-hydroxy-1-propane sulfonic acid (HAPS), 2-sulfoethyl (meth)acrylate, 2-sulfopropyl (meth)acrylate, 3-sulfopropyl (meth)acrylate, 4-sulfobutyl (meth)acrylate, salts thereof, and mixtures thereof.
[0036] Preferably, the gradient polymer of the present invention contains <0.02% by weight (preferably <0.01% by weight, more preferably <0.001% by weight, still more preferably <0.0001% by weight, most preferably less than the detection limit) of Structure II based on the dry weight of the gradient polymer:
[0037] [Chemical formula] (In the formula, each R 3 is independently selected from -H and -CH3, and each R 4 is independently selected from -H and -C 1-4 alkyl group, and each R 5 [[ID=2The monomer structure comprises monomer units having selected alkyl groups, where a is 0-50, b is 0-20, c is 0-50, a+c is 1-100, and d is 1-4.
[0038] Preferably, the gradient polymer of the present invention contains, based on the dry weight of the gradient polymer, <0.01% by weight (preferably <0.005% by weight, more preferably <0.001% by weight, even more preferably <0.0001% by weight, most preferably below the detection limit) of structural monomer units of monomers selected from the group consisting of styrene, butyl acrylate, ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, and mixtures thereof.
[0039] Preferably, the gradient polymer of the present invention contains <2% by weight (preferably <1% by weight, more preferably <0.5% by weight, even more preferably <0.1% by weight, still more preferably <0.01% by weight, even more preferably <0.001% by weight, most preferably less than the detection limit) of C based on the dry weight of the gradient polymer. 6-18 The material comprises a monomer structure monomer unit selected from the group consisting of alkyl (meth)acrylates, vinyl alkanoates having 6 to 18 carbon atoms, N-vinylalkylamides having 6 to 18 carbon atoms, N-alkyl(meth)acrylamides having 6 to 18 carbon atoms, and mixtures thereof.
[0040] Preferably, the gradient polymer of the present invention comprises (a) 5 to 35% by weight (preferably 10 to 35% by weight, more preferably 20 to 34% by weight, most preferably 26 to 32% by weight), based on the dry weight of the gradient polymer, structural monomer units of (meth)acrylic acid monomer, and (b) 35 to 65% by weight (preferably 40 to 60% by weight, more preferably 45 to 55% by weight, most preferably 48 to 54% by weight), based on the dry weight of the gradient polymer, C 1-8(c) Structural monomer units of alkyl (meth)acrylate monomers and (c) structural monomer units of special associative monomers having structure I, in amounts of 10 to 30% by weight (preferably 12 to 30% by weight, more preferably 15 to 25% by weight, most preferably 16 to 20% by weight) based on the dry weight of the gradient polymer, wherein a first special associative monomer having structure Ia (preferably 51 to 99% by weight, more preferably 75 to 97% by weight, most preferably 85 to 95% by weight) based on the weight of the special associative monomer having structure I) (wherein each R 1 Independently, linear saturated C 12-19 Alkyl alkyl groups (preferably linear saturated C) 12-18 Alkyl alkyl groups, more preferably linear saturated C chains. 14-18 Alkyl alkyl groups, most preferably linear saturated C 16-18 Selected from alkyl groups, each R 2a These are independently selected from hydrogen and methyl groups (preferably R 2 (wherein R is a methyl group), na is 10 to 30 (preferably 12 to 30, more preferably 15 to 28, most preferably 18 to 26) and a second special associative monomer having structure Ib (preferably 1 to 49% by weight, more preferably 3 to 25% by weight, most preferably 6 to 15% by weight, based on the weight of the special associative monomer having structure I), the first special associative monomer having structure Ib) (wherein each R 1b Independently, linear saturated C 20-26 Alkyl alkyl groups (preferably linear saturated C) 20-24 Alkyl alkyl groups, more preferably linear saturated C chains. 21-23 Alkyl alkyl groups, most preferably linear saturated C 22 Selected from alkyl groups, each R 2b(d) a blend of structural monomer units of a special associative monomer having structure I (independently selected from linear saturated hydrogen and methyl groups (preferably methyl groups), nb being 10-30 (preferably 15-30, more preferably 18-28, most preferably 20-28), and (d) 0.01-2% by weight (preferably 0.05-1% by weight, more preferably 0.08-0.5% by weight, most preferably 0.1-0.2% by weight) of polyvalent ethylenically unsaturated monomer structural monomer units based on the dry weight of the gradient polymer, and the gradient polymer - comprises <0.05% by weight (preferably <0.01% by weight, more preferably <0.001% by weight, even more preferably <0.0001% by weight, most preferably below the detection limit) of sulfonated monomer structural monomer units (e.g., AMPS) based on the dry weight of the gradient polymer, and the gradient polymer comprises <0.02% by weight (preferably <0.01% by weight, more preferably <0.001% by weight, even more preferably <0.0001% by weight, most preferably below the detection limit) of structure II (wherein each R 3 These are independently selected from -H and -CH3, and each R 4 These are independently -H and C 1-4 Selected from alkyl groups, each R 5 -C 1-4 The structure of the monomer comprises monomer units selected from alkyl groups, where a is 0-50, b is 0-20, c is 0-50, a+c is 1-100, and d is 1-4, and the gradient polymer has a gradient polymer form, provided that it has one or more of the following conditions (i) to (v): (i)R 1a and R 1b(ii) The difference is less than 8 carbon atoms (preferably less than 7 carbon atoms); (ii) The structural monomer units of the (meth)acrylic acid monomer include structural monomer units of both methacrylic acid and acrylic acid; (iii) The gradient polymer contains <0.01% by weight (preferably <0.005% by weight, more preferably <0.001% by weight, even more preferably <0.0001% by weight, most preferably less than the detection limit) of structural monomer units of monomers selected from the group consisting of styrene, butyl acrylate, ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, butyl acrylate, and mixtures thereof, based on the dry weight of the gradient polymer; (iv) The gradient polymer contains <2% by weight (preferably <1% by weight, more preferably <0.5% by weight, even more preferably less than the detection limit) based on the dry weight of the gradient polymer. (v) The gradient polymer comprises structural monomer units of monomers selected from the group consisting of alkyl (meth)acrylates having 6 to 18 carbon atoms, vinyl alkanoates having 6 to 18 carbon atoms, N-vinylalkylamides having 6 to 18 carbon atoms, N-alkyl (meth)acrylamides having 6 to 18 carbon atoms, and mixtures thereof, in amounts of <0.1% by weight, more preferably <0.01% by weight, even more preferably <0.001% by weight, most preferably less than the detection limit; and / or (v) the gradient polymer comprises structural monomer units of (a) to (d) present in the gradient polymer in amounts of 90 to 100% by weight (preferably 95 to 100% by weight, more preferably 98 to 100% by weight, even more preferably 99 to 100% by weight, even more preferably 99.9 to 100% by weight, most preferably 100% by weight).
[0041] Herein, several embodiments of the present invention will be described in detail in the following examples. [Examples]
[0042] Synthetic S1: Gradient polymer Deionized water (350 g) and sodium lauryl sulfate (9.1 g) were added to a 3 L four-necked round-bottom reactor equipped with a mechanical stirrer, thermocouple, condenser, and nitrogen sparge. The reactor was purged with nitrogen and heated to 85°C. Separately, the following was prepared: (1) Deionized water (450 g), sodium lauryl sulfate (16.4 g), ethyl acrylate (EA) (262 g), with the following structure:
[0043] [ka] (In the formula, R 1 is a straight-chain saturated C 16-18 A lipophilic modified monomer (Lipo1) (82.1g) having an alkyl group where n is on average 18-26, with the following structure:
[0044] [ka] (In the formula, R 1 is a straight-chain saturated C 22 Lipophilic modified monomer (Lipo2) (9.6g) having an alkyl group, where n is on average 20-28, methacrylic acid (MAA A (1) Prepare monomer emulsion A from (45.68g), acrylic acid (AA) (101.1g), and n-dodecyl mercaptan (n-DDM) (0.4g); (2) Prepare monomer emulsion A from deionized water (70g), sodium lauryl sulfate (9.1g), trimethylolpropanediallyl ether (x-link) (0.81g), and methacrylic acid (MAA BMonomer emulsion additive B was prepared by mixing (4.82g) (3) ammonium persulfate (0.35g) with deionized water (15g) to prepare initiator solution (C1), and (4) ammonium persulfate (0.55g) with deionized water (84g) to prepare initiator solution (C2). Initiator solution (C1) was added to the reactor at a reactor temperature of approximately 85°C. Next, monomer emulsion (A) was added to the reactor, and at the same time, monomer emulsion additive (B) was added to monomer emulsion (A). The rate of supply of monomer emulsion (A) was controlled so that it started at half speed for the first 10 minutes and continued at full speed until it ended at 120 minutes, and the rate of supply of monomer emulsion additive (B) was controlled so that it ended at 100 minutes. At the same time, initiator solution (C2) was supplied to the reactor over 125 minutes. After these additions were completed, the monomer emulsion and initiator supply lines were rinsed with deionized water, and then the monomers were removed with a free radical catalyst and activator.
[0045] Synthetic S2-S4: Gradient polymer Except for the changes in composition as shown in Table 1, the gradient polymers in synthesis S2-S4 were prepared according to the procedure described in synthesis S1.
[0046] [Table 1]
[0047] Synthetic S5: Non-gradient polymer Deionized water (275 g) and sodium lauryl sulfate (9.1 g) were added to a 3 L four-neck round-bottom reactor equipped with a mechanical stirrer, thermocouple, condenser, and nitrogen sparge. The reactor was purged with nitrogen and heated to 85°C. Separately, the following was prepared: (1) Monomer emulsion A was prepared by adding deionized water (570 g), sodium lauryl sulfate (25.5 g), ethyl acrylate (EA) (262 g), and the following structure:
[0048] [ka] (In the formula, R 1 is a straight-chain saturated C 16-18 A lipophilic modified monomer (Lipo1) (82.1g) having an alkyl group where n is on average 18-26, with the following structure:
[0049] [ka] (In the formula, R 1 is a straight-chain saturated C 22 (1) A lipophilic modified monomer (Lipo2) (9.6 g) having an alkyl group (where n is on average 20-28), methacrylic acid (MAA) (50.5 g), acrylic acid (AA) (101.1 g), n-dodecyl mercaptan (n-DDM) (0.4 g), and trimethylolpropanediallyl ether (x-link) (0.81 g) was prepared; (2) Initiator solution (C1) was prepared by dissolving ammonium persulfate (0.35 g) in deionized water (15 g), and (3) Initiator solution (C2) was prepared by dissolving ammonium persulfate (0.55 g) in deionized water (84 g). Initiator solution (C1) was added to the reactor at a reactor temperature of approximately 85°C. Then, monomer emulsion (A) was added to the reactor. The supply of monomer emulsion (A) was controlled to start at half speed for the first 10 minutes and then at full speed until it was finished at 120 minutes. Separately, the initiator solution (C1) was started simultaneously with the supply of monomer emulsion (A) and supplied to the reactor over 125 minutes. After these additions were complete, the monomer and initiator supply lines were rinsed with deionized water, and then the monomers were removed with a free radical catalyst and activator.
[0050] Synthetic S6-S8: Non-gradient polymers Except for the changes in composition as shown in Table 2, the non-gradient polymers in synthesis S6-S8 were prepared according to the procedure described in synthesis S5.
[0051] [Table 2]
[0052] Viscosity and turbidity measurement Using the following procedure, the solubilization viscosity and turbidity of solutions containing 0.75% polymer active material were determined for each polymer prepared according to synthesis S1-S8, as reported in Table 3. 1. Sufficient polymer was weighed to provide 0.75% polymer in the final formulation. 2. A 169g solution was prepared by pre-diluting with deionized water. 3. Add 11.0 g of 20% w / w sodium hydroxide aqueous solution and stir efficiently with an overhead stirrer until homogeneous. 4. The solution was equilibrated in a war water bath for 10-15 minutes until its internal temperature reached 20°C. 5. The pH was measured to be between 7.8 and 10. It was adjusted with 20% sodium hydroxide as needed. 6. Viscosity was measured at 20°C and at 0.3, 3, 6, 12, 20, 30, and 60 rpm using a Brookfield viscometer with a corresponding spindle, and measurements were obtained to a scale of at least 10%. 7. The sample was transferred to a 1 oz vial for turbidity measurement. 8. The 1 oz vial was centrifuged at 3,500 rpm for 20 minutes. 9. Turbidity was measured at 20°C using a turbidimeter in nephelometric turbidity units (NTU).
[0053] The measurement results for viscosity and turbidity are reported in Table 3.
[0054] [Table 3]
[0055] Comparative Examples CF1-CF6 and Examples F1-F6: Washing Compounds Aqueous personal care cleansing formulations were prepared for each of the comparative examples CF1 to CF6 and examples F1 to F6, which have the formulations listed in Table 4.
[0056] For each of Comparative Examples CF1-CF6 and Examples F1-F6, the components of Phase A, if present, were mixed with gentle stirring until dissolved. The components of Phase B were mixed together in a separate container. The mixed components of Phase B were then slowly added to the mixed components of Phase A, if present. The components of Phase C were then added to the mixed components of Phase A and Phase B, if present. The appropriate components of Phase D were then mixed in as needed to adjust the pH to the level listed in Table 4. The viscosity of the resulting aqueous personal care cleaning formulations was then measured at 20°C using a Brookfield viscometer equipped with the corresponding spindles as listed in Table 5.
[0057] [Table 4]
[0058] [Table 5]
[0059] Comparative Examples CF7-CF10 and Examples F7-F10: Washing Formulations Aqueous personal care cleansing formulations were prepared for each of the comparative examples CF7 to CF10 and examples F7 to F10, each having the formulation described in Table 6.
[0060] The components of Phase A were mixed together. Then, the components of mixed Phase B were slowly added to the components of mixed Phase A. To adjust the pH, appropriate components of Phase C were mixed into the mixed components of Phase A and Phase B as needed. The viscosity of the resulting aqueous personal care cleaning formulations was then measured at 20°C using a Brookfield viscometer with a corresponding 20 rpm spindle, as listed in Table 7. The turbidity of each formulation was measured using a Micro 100 turbidimeter (HF Scientific, Inc.), as listed in Table 7.
[0061] [Table 6]
[0062] [Table 7]
[0063] Rheology data The rheology of aqueous personal care cleansing formulations prepared according to Comparative Examples CF7-CF10 and Examples F7-F10 was characterized using a Discovery HR-3 Hybrid Rheometer (TA Instruments) with a 40 mm parallel plate configuration. All tests were performed at 25°C. The tests involved amplitude sweeps with vibration displacements of 0.0002-0.15 rad at 1 rad / s, and 0.01-500 s. -1 The study included flow sweeps at shear rates. As listed in Table 8, the G', G'', and tanδ values were obtained from the amplitude in the linear viscoelastic region, and the viscosity values were obtained from the shear rate sweeps.
[0064] [Table 8]
Claims
1. (a) 5 to 35% by weight of structural monomer units of (meth)acrylic acid monomer, based on the dry weight of the gradient polymer, (b) 35 to 65% by weight of C based on the dry weight of the gradient polymer １－８ The structural monomer units of alkyl (meth)acrylate monomers, (c) More than 10 to 30% by weight of the gradient polymer, structure I: 【Chemistry 1】 (In the formula, each R １ Independently, linear saturated C １２－２６ Selected from alkyl groups, each R ２ (These are independently selected from hydrogen and methyl groups, and n is 10 to 30.) A structural monomer unit of a special associative monomer having, (d) 0.01 to 2% by weight of the gradient polymer, comprising structural monomer units of a polyvalent ethylenically unsaturated monomer, A gradient polymer comprising, The gradient polymer contains less than 0.05% by weight of structural monomer units of the sulfonated monomer, based on the dry weight of the gradient polymer. Structure II of less than 0.02% by weight based on the dry weight of the gradient polymer: 【Chemistry 2】 (where each R ３ is independently selected from -H and -CH ３ , each R ４ is independently selected from -H and -C １－４ alkyl group, each R ５ is independently selected from -C １－４ alkyl group, a is 0 to 50, b is 0 to 20, c is 0 to 50, a + c is 1 to 100, and d is 1 to 4), and contains a structural monomer unit of a monomer having A gradient polymer having a gradient polymer form.
2. The structural monomer units of the special associate monomer having the structure I are Structure Ia: 【Transformation 3】 (In the formula, each R １ａ Independently, linear saturated C １２－１９ Selected from alkyl groups, each R ２ａ (The group is independently selected from hydrogen and methyl groups, and Na is 10 to 30.) A first special associable monomer having, Structure Ib: 【Chemistry 4】 (In the formula, each R １ｂ Independently, linear saturated C ２０－２６ Selected from alkyl groups, each R ２ｂ The gradient polymer according to claim 1, which is a blend of a second special associative monomer having (independently selected from linear saturated hydrogen and methyl groups, and NB being 10 to 30).
3. The gradient polymer according to claim 1, wherein the structural monomer units of the (meth)acrylic acid monomer include structural monomer units of both methacrylic acid and acrylic acid.
4. The gradient polymer according to claim 1, wherein the gradient polymer contains structural monomer units of monomers selected from the group consisting of styrene, butyl acrylate, ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, butyl acrylate, and mixtures thereof, in an amount of less than 0.01% by weight based on the dry weight of the gradient polymer.
5. The gradient polymer according to claim 1, wherein the gradient polymer comprises less than 2% by weight of alkyl (meth)acrylates having 6 to 18 carbon atoms, vinyl alkanoates having 6 to 18 carbon atoms, N-vinylalkylamides having 6 to 18 carbon atoms, N-alkyl (meth)acrylamides having 6 to 18 carbon atoms, and mixtures thereof, based on the dry weight of the gradient polymer.
6. The gradient polymer according to claim 1, wherein the gradient polymer contains 90 to 100% by weight of structural monomer units present in the gradient polymer, and the structural monomer units are (a) to (d).
7. The gradient polymer according to claim 2, wherein the gradient polymer comprises structural monomer units of monomers selected from the group consisting of styrene, butyl acrylate, ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, butyl acrylate, and mixtures thereof, in less than 0.01% by weight based on the dry weight of the gradient polymer.
8. R １ａ and R １ｂ The gradient polymer according to claim 2, wherein the difference from is less than 8 carbon atoms.
9. The gradient polymer according to claim 2, wherein the gradient polymer comprises structural monomer units of monomers selected from the group consisting of alkyl (meth)acrylates having 6 to 18 carbon atoms, vinyl alkanoates having 6 to 18 carbon atoms, N-vinylalkylamides having 6 to 18 carbon atoms, N-alkyl (meth)acrylamides having 6 to 18 carbon atoms, and mixtures thereof, in less than 2% by weight based on the dry weight of the gradient polymer.
10. The following conditions (i) to (v), that is, (i) R １ａ and R １ｂ The difference is less than 8 carbon atoms. (ii) The structural monomer units of the (meth)acrylic acid monomer include structural monomer units of both methacrylic acid and acrylic acid, (iii) The gradient polymer contains structural monomer units of monomers selected from the group consisting of styrene, butyl acrylate, ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, butyl acrylate, and mixtures thereof, in an amount of less than 0.01% by weight based on the dry weight of the gradient polymer. (iv) The gradient polymer contains, based on the dry weight of the gradient polymer, less than 2% by weight of a monomer selected from the group consisting of alkyl (meth)acrylates having 6 to 18 carbon atoms, vinyl alkanoates having 6 to 18 carbon atoms, N-vinylalkylamides having 6 to 18 carbon atoms, N-alkyl (meth)acrylamides having 6 to 18 carbon atoms, and mixtures thereof, and / or (V) The gradient polymer according to claim 2, wherein the gradient polymer contains 90 to 100% by weight of structural monomer units present in the gradient polymer, and has one or more of the structural monomer units (a) to (d).