JPH0147513B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a continuation-in-part of US Patent Application No. 101615, filed on December 10, 1979, and the original application was abandoned after this filing. The present invention relates to compositions for increasing the viscosity of aqueous systems. More particularly, it relates to mixtures of clay minerals and acrylic acid or methacrylic acid emulsion copolymers that exhibit synergistic thickening activity and form self-retaining, hard, and very strong gels. This application is filed by CJChang and
Relates to what is recognized as a jointly assigned pending application of TEStevens. Application No. 974466 (filed December 29, 1978); Continuation of this application in part, Application No. 075862 (filed September 1979);
17th); and this continuation in part, application no.
No. 101615 (filed December 10, 1979). Thickeners are used in aqueous systems for a variety of reasons.
Increasing viscosity with thickeners is often required to reduce flowability and retain the active agent on the substrate. Typical compositions that utilize thickeners include hand lotions, pharmaceuticals, manual and industrial cleansers, and fluid agricultural pesticide formulations. The range of viscosity that can be increased with thickeners is from slightly increasing the viscosity of moderately fluid systems to generally fixed systems such as gels. In addition to improving viscosity, many thickeners are pseudoplastic, so aqueous compositions containing the thickener can be mixed with other ingredients by stirring. However, many thickeners, whether synthetic or derived from natural sources, are expensive, are incompatible with other components of the aqueous system, or require high concentrations, making them unreasonably expensive. For these reasons, research continued in search of new thickeners. There continues to be a need for improvements in thickeners, particularly in the area of aqueous gels. For example, natural rubbers such as carrageenan gum require high concentrations to create very strong gels. Since natural rubber is initially expensive, if it is used in high concentrations, the price of water-based systems using it will become even more expensive. Natural rubber also exhibits varying performance from lot to lot and has a tendency to exude water (syneresis) during freeze-thaw cycles. Currently available synthetic water-soluble polymers and inorganic thickeners (e.g. clay minerals)
Even this cannot provide very strong self-retaining gels. Furthermore, inorganic thickeners do not have sufficient elasticity and plasticity to withstand the weight of handling and loading. In the latter case, the aqueous gel based on the inorganic thickener will crumble or turn into powder as it begins to lose water. In one aspect, the present invention is a thickener composition that can be used to increase the viscosity of a wide range of aqueous systems, from loosely flowing liquids to stiff gels.
Viewed from another perspective, the thickener composition is pseudoplastic, but does not exhibit maximum viscosity, and the viscosity decreases as the amount in the aqueous system increases. This is in contrast to many known thickeners based on synthetic ingredients and clay minerals, such as discussed in US Pat. No. 4,087,365 and other technical literature. In yet another aspect, the thickeners of the present invention, especially when used to form gels, are capable of retaining and immobilizing large amounts of water and active ingredients dispersed therein at low concentrations. Thus, the present thickener composition can be used as a highly efficient and economical absorbent when compared to currently known absorbents based on high concentrations of synthetic polymers. Briefly, the thickener composition of the present invention comprises a mixture of (A) a water-swellable clay mineral and (B) an acrylic or methacrylic acid emulsion copolymer characterized in that it includes a monomer with hydrophobic groups. It is. The proportions of clay mineral and acrylic acid or methacrylic acid copolymer and the total amount of the mixture in the aqueous system can vary within a wide range, depending on the degree of thickening required and the strength of the gelatinous state created by the thickener composition; Depends on other properties such as elasticity and plasticity. Unless otherwise noted in the text, the term "acrylic" used in the following discussion refers to acrylic acids,
Contains methacrylic acids, esters, and polymers. and the term "(meth)acrylic" shall mean optionally one acrylic acid, methacrylic acid, monomer, or polymer. Mixtures of acrylic polymers and clay minerals as thickeners or viscosity agents for aqueous systems are known, and the subject of the above-mentioned co-pending application describes the use of the (meth)acrylic acid copolymer component of the present invention. However, while the compositions of the present invention exhibit an unexpectedly high degree of thickening, even synergistic thickening, they do not exhibit many of the deficiencies of known thickeners mentioned above. Representative of the prior art disclosing thickeners based on mixtures of clay minerals and synthetic polymers is U.S. Pat. No. 3,976,580, which discloses the combination of polyacrylamide and bentonite in water to form a fire extinguishing gel. U.S. Pat. No. 4,060,678 which discloses cationic hydrosols useful for reaction or conjugation with oppositely charged substances such as pesticides, cosmetics, pharmaceuticals and various industrial chemicals; U.S. Pat.
Circulating mud compositions such as 3323603, 3472325 and US Pat.
Numerous patents relate to improving the properties of clays used in circulating muds, such as Nos. 3838047 and 4087365. In summary, the thickener compositions of the present invention exhibit high thickening efficiency (low concentration Effective for thickening a wide range of aqueous systems (with good viscosity increase), it enables economical thickening and product quality control for each sample. Additionally, the present thickener compositions are readily solubilized (by neutralization of the emulsifying copolymer component) and readily shear thinned to thicken aqueous systems containing alkalis and electrolytes. Therefore,
This thickener composition has virtually no restrictions on the range of use;
gel air freshener
household uses such as lotions, creams and other cosmetics, liquid cleansers, napkins, tampons and other personal uses, and oil well circulation muds, fluid agrochemicals, seed coatings, potting soil and industrial effluents. It has numerous industrial and agricultural uses such as absorption. The clay mineral component of the present thickener composition is a well-known material and may be any clay mineral that swells with water. Clay minerals are mineral aggregates of earth or stone;
It consists mainly of hydrated silicates of aluminum, iron and/or magnesium. Clay minerals are amorphous and/or
Or it may be crystalline and may contain various other (non-clay) minerals such as quartz, calcite, feldspar and pyrite. The clay minerals useful in this invention hydrate and swell to form a colloidal dispersion, which is reversible and becomes free when the material loses water. Preferred clay minerals are minerals of the montmorillonite genus, such as beidellite, bentonite, hectorite, montmorillonite itself, nontronite, and saponite. The best known members of the bentonite genus are sodium bentonite and calcium bentonite, also known as Wyoming bentonite. The latter has almost no swelling property, but can be converted into a swelling type by adding sodium alkali such as sodium carbonate to replace calcium ions with sodium ions by known methods. If the thickener composition is to be flowable, the particle size of the clay mineral component should be on the order of about 50 microns or less, preferably with an average particle size of about 20 microns or less. However, particle size is not critical and can be varied as desired to obtain the required flowability. Many other clay minerals can also be used in combination with these montmorillonites. For example, metabentonite is believed to be a mixture of one or more clay minerals of the illite family and montmorillonite. The properties and uses of these and other clay minerals are summarized in the following references for reference: Kirk-Othmer, Encyclopedia of Chemical
Technology, 2nd edition, Interscience
Publishers (1964) Volume 5, Pages 541-586.
and Lange's Handbook of Chemistry, 10th edition,
McGraw Hill Book Company (1967) pages 220-223. The (meth)acrylic acid copolymers of the present thickener compositions are described in the aforementioned patent application Ser. No. 974,466 and its continuation-in-part, both of which are cited as references. However, for convenience, the characteristics of this copolymer are summarized below. This copolymer component consists of (1) acrylic acid or methacrylic acid (hereinafter referred to as “AA”);
(abbreviated as “MAA”) (2) General formula (): H ₂ C=C(R)-C(O)-O-
(CH ₂ CH ₂ O) _o −R ⁰ (wherein: R is H or CH ₃
CH ₃ is preferred; n is at least 2, preferably the average value is at least 10, preferably up to 60;
R ⁰ has at least 8 carbon atoms, such as about 8 to 24 carbon atoms, preferably 12 to 18 carbon atoms, or an average of about 12 to 24 carbon atoms.
at least 2 of the 18 or more hydrophobic groups)
(meth)acrylic acid esters of ( _C8 - _C24 ) alkyl monoethers of polyethylene glycol having oxyethylene units, (3) ( _C1 - _C4 ) alkyl (meth)acrylates,
Preferably, it is a water-insoluble emulsion copolymer consisting of ethyl acrylate (hereinafter abbreviated as "EA") and (4) any small amount of a polyethylenically unsaturated monomer effective for cross-linking. This copolymer component is further characterized as an alkali-soluble and alkali-thickening material;
Although this is the purpose of this specification, British Patent No.
Addition of an alkali to an aqueous dispersion containing a water-insoluble emulsifying copolymer (in an amount that at least partially neutralizes the copolymer) as described in No. 870994;
It means to simultaneously dissolve and swell the copolymer to increase the viscosity of the dispersion. The weight average molecular weight of the copolymer should be from about 100,000 to several million, so it is prepared by emulsion polymerization to have a solids content of about 25-50% by weight. Reduce the molecular weight to the lower range of the above range, or reduce the weight average molecular weight to approx.
If a reduction to 80,000 is desired, a chain transfer agent may be used. Monomer component (4)
helps provide molecular weights in the high range of the above range and provides mild cross-linking. The above monomer components (1) to (4) are respectively (1) 20 to 50% by weight, (2) 0.5 to 25% by weight, and (3) at least 30% by weight;
(4), if present, can be used in a range of about 0.05% to about 1.0%, making the percentage of all monomers add up to 100%. The above range of each component is the ratio of combination for most accurately obtaining the effects of the present invention, and outside this range, the effects of the present invention are diminished. The preferred ranges are (1) 35 to 45% by weight, respectively;
(2) 1 to 15% by weight, and (3) 40 to 60% by weight. Typically ^R0 is an alkyl ( _C8 - _C24 ) group, an aralkyl group, or the residue of a polycyclic hydrocarbon compound such as lanolin or cholesterol. Examples of the alkyl group include lauryl group, tridecyl group, myristyl group, pentadecyl group, cetyl group, palmityl group, stearyl group, and eicosyl group. Mixtures can also be used, such as alkyl groups resulting from the ethoxylation of mixtures of lauryl alcohol, stearyl alcohol, cetyl alcohol and palmityl alcohol. Aralkyl groups include alkylphenyl groups such as octylphenyl and nonylphenyl groups. Tables A and B list various monomers of general formula (2) useful in making the emulsion copolymer component of the clay mineral/emulsion copolymer mixtures of this invention. Table A lists methacrylate monomers made from methacrylic acid and the indicated alkyl monoethers of polyethylene glycols (19
No.) is listed. Also listed in Table A are 19 examples (numbers 21-39) of acrylate monomers made from alkyl, aralkyl or polycyclic hydrocarbon monoethers of acrylic acid and polyethylene glycol. Table B
includes various methacrylate monomers (numbers 41-52) made from methacrylic acid and the indicated alkylpoly(ethyleneoxy)ethanol or alkylphenoxypoly(ethyleneoxy)ethanol.
is listed. In both tables, n is the number of ethyleneoxy (EO) units in the ester group. Table A
Suitable methods for making the monomers B and B are described in the aforementioned Application No. 101615 (filed December 10, 1979) and its parent applications. For example, Example A below is a suitable procedure for producing the ester of acrylic acid and methacrylic acid forming component (2). Alternatively, as shown in Example B,
There is a transesterification reaction of monomeric alkyl acrylates or methacrylates, and it is also possible to use ethyl acrylate or methyl methacrylate and ( _C8 - _C24 ) alkyloxypolyethoxyethanol. Example A: In a reactor fitted with a condenser and Dean-Stark trap, 2140 g of octadecyloxy(ethyleneoxy)ethanol containing an average of 20 oxyethylene units, 207 g of methacrylic acid, and 1000 g.
of toluene, 17.4 g of concentrated sulfuric acid and 4.6 g of hydroquinone monomethyl ether. The mixture is stirred and heated to reflux. The water produced during esterification is removed as a water-toluene azeotrope,
Toluene is returned to the reactor. This reaction is carried out in contact with air to avoid polymerization. When no more water distills out, the mixture is cooled, neutralized with sodium carbonate, filtered, and the solvent is distilled off to give octadecyloxypoly(ethyleneoxy) ₂₀ ethyl methacrylate as a yellow waxy solid. obtain.
This product is monomer number 8 in Table A. Example B: 786 g (0.5 mol) of n-dodecyloxy containing an average of 30 oxyethylene units was placed in a 2 liter, 4-necked flask equipped with a stirrer, thermometer, dry air blowing tube, and an older distillation column. Poly(ethyleneoxy)ethanol, 400g (4.0
mol) of methyl methacrylate, 1.7 g of hydroquinone monomethyl ether. The mixture is stirred and heated to reflux and the water is distilled off as an azeotrope. The mixture is then cooled to 60° C. and charged with 6.21 g of dibutyltin oxide (catalyst). The mixture is again heated to reflux. As the transesterification reaction progresses and methanol is produced, the temperature at the top of the head increases to 100
°C to 64 °C (MMA/methanol azeotrope). The distillate is collected over a period of 4 hours until the crown temperature rises to 100°C. The mixture was then evaporated in vacuo to remove excess methyl methacrylate.
A wax-like solid n-dodecyloxypoly(ethyleneoxy) ₃₀ methacrylate is obtained. This product is monomer number 46 in Table B.

【table】

【table】

[Table] The emulsion polymerization method for making the polymers of the present invention is well known. For example, the monomers are polymerized in an aqueous dispersion containing an anionic surfactant such as sodium lauryl sulfate and a water-soluble free radical initiator such as an alkali metal persulfate or ammonium persulfate. When molecular weights at the lower end of the range are desired, small amounts of chain transfer agents, such as alkyl mercaptans of about 4 to 22 carbon atoms, can be added to the polymerization system. Since low molecular weight substances reduce the thickening efficiency of the copolymer, it is preferable to exclude them in many applications of the present invention. Monomer component (4) is monomer component (1), (2) and (3)
Any polyethylenically unsaturated monomer that copolymerizes with the monomer may be used. Typical monomers include diallyl phthalate, divinylbenzene, allyl methacrylate and ethylene glycol dimethacrylate. The resulting polymers are highly branched or have a three-dimensional network structure. After at least partial neutralization, the copolymer substantially swells and forms a "micro-gel".
Due to its structure, it has thickening properties. The clay mineral and copolymer can be mixed in a variety of ways to provide the thickening agent or thickening composition of the present invention. For example, mixing the components while one or both are aqueous dispersions or dry matter;
Next, add the neutralizer. Alternatively, the copolymer composition may be first neutralized in the form of an aqueous dispersion and then mixed with the clay mineral. In either case, the mixture is then added to the aqueous system for thickening, or additives are added to the copolymer/clay mixture (before or after neutralization) to form the final product. Preferably,
The ingredients are mixed separately (either as dry ingredients or as a dispersion or slurry) into an aqueous dispersion to thicken and then neutralize. An aqueous concentrate of clay minerals and copolymers in acid form may be prepared and added to the aqueous dispersion to thicken as required and then neutralized,
Such concentrates tend to be too viscous;
Not easy to handle. Nevertheless,
It is also possible to prepare a dry mixture or an aqueous high solids composition that is so low in viscosity that it can be pumped or flowed, and then add an alkaline material to the mixture to further increase the viscosity. The thickener composition can also be provided in dry form in a number of ways. For example, unneutralized copolymers can be spray dried and mixed with dried clay minerals. However, it is possible to spray dry or otherwise dehydrate the neutralized thickener composition, alone or in a mixture with clay minerals, and later reconstitute the aqueous thickener dispersion, if the dispersion may be added to the aqueous medium with stirring if the pH of the mixture is maintained at 7 or above. PH of the aqueous dispersion of components A and B of the thickener composition
Any alkali metal suitable for raising the value of 7 or more may be used. Suitable neutralizing agents include alkalis such as sodium hydroxide, potassium hydroxide, or lithium hydroxide, volatile amines such as triethylamine, triethanolamine, or aqueous ammonia, used alone or in mixtures. If necessary, you can neutralize to a higher pH, such as 13, but there is no particular benefit to raising the pH above about 7. At least about 0.5 equivalents of alkali are effective in neutralizing the copolymer, but since there is generally a linear relationship between the degree of neutralization and the increase in viscosity, depending on the thickening effect desired. More or less neutralizing agents can be used. The proportions of clay mineral component A and copolymer component B are not critical and can be varied depending on the viscosity increase and solubilization desired for the intended end use. In general, thickening occurs due to an increase in the amount of copolymer rather than an increase in the amount of clay mineral, resulting in a viscosity of approximately
100000cps or more (Brookfield Viscometer, 75〓,
0.5 rpm), the mixture becomes gelatinous.
From an economic point of view, a lower concentration of thickener in the final aqueous dispersion is desirable. For this reason, the aqueous system desirably contains about 0.1 to 5% by weight of the copolymer component (per solid polymer) and about 0.1 to 10% by weight of clay mineral; and more preferably about 1-5% by weight of clay minerals. The thickened or gelled aqueous dispersion according to the invention can contain various active or inactive ingredients, depending on its end use. For example, one or more of the following can be added to the aqueous dispersion: Fragrance oils, dyes, evaporation inhibitors such as cetyl alcohol, abrasives such as silica and calcium carbonate, fillers such as barite, oils, emollients and preservatives. Small amounts of surfactants can also be added. In some cases, surfactants may further enhance thickening, plasticity, and other properties, while also reducing certain desirable properties, such as resistance to powdering, of the gelling composition. Surfactants that can be used are
Nonionic and anionic species may be used alone or in combination, the selection of which should depend on their compatibility with the other components of the thickened or thickenable dispersions of the present invention. Cationic and amphoteric surfactants may also be used if the copolymer and other components of the aqueous system are compatible, or they may be used in small amounts without incompatibility. The appropriate amount of surfactant is about 0.01 to 1 part by weight of the copolymer.
5 parts by weight, or about 0.1 to 1% by weight surfactant per aqueous system containing 0.1 to 5% by weight solid polymer. The amount of surfactant can also vary outside these ranges depending on the type of copolymer and surfactant and the end use of the aqueous system in which they are included. Anionic surfactants suitable for use are 8
Higher fatty alcohol sulfates such as sodium or potassium sulfates of alcohols with ~18 carbon atoms, alkali metal or amine salts of higher fatty acids with 8 to 18 carbon atoms and dodecylbenzenesulfonic acid sodium salts and sulfonated alkylaryl compounds such as. Examples of nonionic surfactants include alkyl groups of about 7 to 18 carbon atoms and oxy groups of about 9 to 40 or more, such as octylphenoxypolyethoxyethanols and dodecylphenoxypolyethoxyethanols. Alkylphenoxypolyethoxyethanol with ethylene units, lauric acid, myristic acid,
These include ethylene oxide derivatives of long-chain carboxylic acids such as palmitic acid and oleic acid, and ethylene oxide condensates of long-chain alcohols such as lauryl alcohol or cetyl alcohol. Examples of cationic surfactants are laurylpyridinium chloride, octylbenzyltrimethylammonium chloride, dodecyltrimethylammonium chloride, condensates of primary fatty amines and ethylene oxide, and the like. As an amphoteric surfactant, "Miranol" (trademark)
It is a quaternary amine derivative of a fatty acid, such as a surfactant. These and other useful ionic, nonionic and amphoteric surfactants are described in the following literature. McCutcheon's Detergents &
Emulsifiers1978, North American Edition, MC
Publishing CO., Glen Rock, NJ07452 U.
SA The invention is further illustrated in the following examples, in which all parts and percentages are by weight and temperatures are expressed in units unless otherwise indicated. Example 1 (A) Preparation of Methacrylic Acid Copolymer An emulsion of monomers in water was prepared with 118 g of ethyl acrylate, 23.6 g of stearyloxypoly(ethyleneoxy)20 ethyl methacrylate (monomer no. 8 in Table A above), It was prepared by mixing 94.5 g of methacrylic acid, 6.3 g of 28% sodium lauryl sulfate solution, and 271 g of water. 206
g of water and 6.3 g of sodium lauryl sulfate.
At 85°C, add 5% to a reaction vessel containing a 28% solution.
of monomer emulsion and 20.3 g of 1.25% ammonium persulfate aqueous solution were added. After 10 minutes, the remaining monomer emulsion and 817 grams of 1.25% ammonium persulfate were slowly added over 1 hour. The temperature of the mixture was kept at 84-86°C. After the monomer and initiator additions were completed, the mixture was kept at 85 °C for 15 minutes;
Then 30g of 0.3% ammonium persulfate solution was added. After holding at 85°C for an additional 15 minutes, the mixture was cooled and filtered. The liquid is an approximately 30% solid emulsion copolymer dispersion (virtually 100% yield) whose copolymer composition consists of 10% stearyloxypoly(ethyleneoxy)20 ethyl methacrylate,
50% ethyl acrylate and 40% methacrylic acid
It is. (B) Preparation of aqueous gel The following components were prepared separately. (1) 4.2 parts of a 30% polymer emulsion of A in 31.7 parts of deionized (DI) water. (2) Bentonite clay 2.5 parts added to 60 parts DI water and stirred for 2 hours to disperse and hydrate the clay.
Department. Mix components (1) and (2) and add 1.6 parts of 10% sodium hydroxide (per carboxylic acid content of the emulsion copolymer).
0.7 equivalent) to neutralize and solubilize the copolymer,
The dispersion was then stirred. The obtained gel weighs 62g.
gel strength (see footnote (1) to table for test method)
), was self-supporting in the temperature range of 0 to 50°C, and showed no syneresis even after repeated freezing and thawing three times. Appropriate amount of pigments and fragrances are added to the ingredients before neutralization.
When added to an aqueous mixture of (1) and (2), the resulting gel is useful as an air freshener. Example 2 A series of aqueous dispersions were prepared from components (1) and (2) of Example 1B with different total solids contents of methacrylic acid copolymer and bentonite clay, and the dispersions were prepared as described in Example 1B. and neutralized with sodium hydroxide. The viscosity of the dispersion was compared at various solid concentrations and the results are shown in the table. This table shows the ethyl acrylate-methacrylic acid copolymer (EA/MAA) prepared by the same procedure as Example 1A, including sodium hydroxide neutralization as in Example 1B, with a monomer composition of 60/40. Also includes a comparison. This type of polymer is described in British Patent No. 870994;
In particular, it is stated in the table on page 8, line 11. The data in the following table shows that thickening is achieved synergistically by mixing and neutralizing the methacrylic acid copolymer of the present invention with bentonite. Additionally, this data shows that even at low component concentrations (e.g., 0.14% polymer and 0.1%
% of clay) thickening activity, indicating that when the EA/MAA copolymer is used in place of the copolymer of the present invention, the thickening activity is significantly reduced.

[Table] Example 3 Mg instead of bentonite
Examples except using Veagum clay, a Mg-Al silicate with a high content and believed to be a saponite species of the montmorillonite genus of clay minerals.
Aqueous dispersions were prepared as described in 1B and 2. As shown in the table, this mixture also exhibits synergistic thickening.

[Table] 〓
(2) Trademark, RTVanderbilt Co.
Example 4 Aqueous gels of the methacrylic acid copolymer and inorganic powder of Example 1A were prepared, neutralized in the same manner as in Example 1B, and gel strengths were compared. The results are shown in the table. Compared to the greater strength of gels produced from mixtures of copolymers with bentonite and Mg-Al clay, the gel strength of clay-free copolymers is weak;
Non-swelling clays such as talc, silica and alumina have been shown to provide little or no improvement in gel strength. Less than 2% (and even up to about 8%)
Solid clay alone (without copolymers) does not gel an aqueous system.

[Table] Example 5 Copolymer of Example 1A, bentonite clay and
A 0.5/1/0.1 part ratio of NaOH is slurried with 98.4 parts of water and unbound water is forced out under pressure. The resulting percake retains 41 parts of water per part of solids. Bentonite clay alone retains only 3 parts of water after similar operations. A neutralized copolymer solution alone (without clay) will pass through a filter (or other porous medium). These results indicate a binding capacity to adsorb and fix significant amounts of water, making it useful as an adsorbent for aqueous fluids, such as dry impregnation agents for napkins, tampons, etc. Example 6 Exactly the same as Example 1A, except that the monomer composition was alkoxy (mixture of _C22 to _C26 ) poly(ethyleneoxy)33, and the polymerization ratio of ethyl methacrylate, ethyl acrylate, and methacrylic acid was 5/55/40. An emulsion copolymer was prepared. The copolymer was neutralized by blending it with bentonite clay and cetyl alcohol in water. The proportions were as follows. Copolymer 1.5% polymer solids Clay 2.5% NaOH 0.7% Cetyl alcohol 1.0% Water Amount to make 100% Example instead of copolymer in this example
The gel produced in this example has a gel strength of 78, compared to a gel strength of 78 for a gel prepared from the same mixture, but with a copolymer of (same as ) 130 strong gel. Example 7 A liquid abrasive cleaner was prepared by mixing the ingredients listed below. 36.18 parts water 50 parts calcium carbonate 1.67 parts 30% polymer emulsion of Example 1A 6.25 parts 8% bentonite clay aqueous dispersion 2.5 parts sodium tripolyphosphate 2.5 parts "Triton"(TM) Ionic surfactant 0.9 parts of 10% sodium hydroxide The abrasive cleaner does not separate when left standing and the viscosity is
It is 5500cps at 0.5rpm. Example 8 A smooth hand cream that blends into the skin without leaving any oily residue and has a viscosity of 1200000 cps (at 0.5 rpm) is prepared with the following formulation. Part A 67.75 parts water 12 parts glycerin 1 part 30% polymer emulsion of Example 1A 6.25 parts 8% aqueous dispersion of bentonite clay 0.5 parts triethanolamine Part B 2 parts mineral oil 10 parts cetyl alcohol 0.5 part "Ethomeen"("TradeMark") C-25 ⁽¹⁾ Heat Parts A and B to 75°C. The composition of Part B is then added to Part A with vigorous stirring and the mixture is rapidly cooled to 30°C. (1) Armark Chemicals

Claims (1)

[Scope of Claims] 1 (A) a water-swellable clay mineral and (B) a water-insoluble emulsion polymer, comprising (1) 20 to 50% by weight of (meth)acrylic acid, (2) the general formula ( ): _H2C =C ₍ R)-C(O)-O-( _CH2CH2O ) _o - ^R0 (wherein R is H or _CH3 , n is at least 2
The average value is 60 or less, R ⁰ is an alkyl group,
0.5 to 25% by weight of at least one of the monomers (functional groups having at least 8 carbon atoms selected from aralkyl groups and polycyclic hydrocarbon groups); (3) alkyl groups having 1 to 4 carbon atoms; At least 30% of (meth)acrylate
% by weight, and (4) consisting of a mixture of up to 1.0% by weight of a polyethylenically unsaturated monomer, the aqueous dispersion of which emulsion polymer thickens with the addition of a neutralizing agent, and (A) and (B) A thickener composition for an aqueous composition, characterized in that the ratio of (B) to (B) is effective for thickening an aqueous dispersion formed from the mixture when the neutralizing agent is added. 2. The composition of claim 1, wherein the proportions of (A) and (B) are effective to at least partially neutralize and form a strong gel when mixed with water. 3. The composition according to claim 1, wherein (A) is a montmorillonite clay mineral. 4 (B) is (1) 30 to 45% by weight of (meth)acrylic acid, (2) 1 to 15% by weight of the general formula () (wherein R ⁰ is approximately 8
3. The composition of claim 1, wherein the composition is a copolymer of about 40-60% by weight of the alkyl (meth)acrylate. 5 Monomer (2) is 5. The composition of claim 1 or claim 4, wherein R ⁰ is an alkyl group having 12 to 18 carbon atoms, and the average value of n is at least about 10. 6 (B) is (1) 30-45% by weight of methacrylic acid, (2) 1-15% by weight of the monomer of the general formula () (wherein the average value of n is about 10-60, R ⁰ is 12 (3) 40 to 60% by weight of ethyl acrylate. 7 The amount of (A) is approximately 0.1 to 10 parts by weight, and the amount of (B) is approximately 0.1 to 10 parts by weight.
5 parts by weight, and (A) is a montmorillonite clay mineral. 8 (A) a water-swellable clay mineral and (B) a water-insoluble emulsion polymer, comprising (1) 20-50% by weight of (meth)acrylic acid, (2) general formula (): H ₂ C= C(R)-C( _O )-O-( _CH2CH2O ) _o - ^R0 (wherein R is H or _CH3 , n is at least 2
The average value is 60 or less, R ⁰ is an alkyl group,
0.5 to 25% by weight of at least one of the monomers (functional groups having at least 8 carbon atoms selected from aralkyl groups and polycyclic hydrocarbon groups); (3) alkyl groups having 1 to 4 carbon atoms; At least 30% of (meth)acrylate
% by weight, and (4) consisting of a mixture of up to 1.0% by weight of a polyethylenically unsaturated monomer, the aqueous dispersion of which emulsion polymer thickens with the addition of a neutralizing agent, and (A) and (B) The ratio of (B) to (B) is such that, upon addition of the neutralizing agent, the thickener composition for an aqueous composition is at least partially effective to thicken the aqueous dispersion formed from the mixture. A composition comprising a neutralized and thickened aqueous dispersion using an effective amount thereof. 9 (B) is (1) 30-45% by weight of (meth)acrylic acid, (2) 1-15% by weight of the general formula () (wherein R ⁰ is about 8
9. The composition of claim 8, wherein the composition is a copolymer of about 40-60% by weight of the alkyl (meth)acrylate. 10 (B) is (1) 30-45% by weight of methacrylic acid, (2) 1-15% by weight of a monomer of the general formula () (wherein the average value of n is about 10-60, R ⁰ is 12 9. The composition of claim 8, wherein the composition is a copolymer of 40 to 60% by weight of ethyl acrylate. 11 The amount of (A) is about 0.1 to 10 parts by weight, and the amount of (B) is about 0.1
9. The composition of claim 8, wherein (A) is a montmorillonite clay mineral in an amount of ~5 parts by weight. 12 (A) a water-swellable clay mineral and (B) a water-insoluble emulsion polymer, containing (1) 20 to 50% by weight of (meth)acrylic acid, (2) general formula (): H ₂ C= C(R)-C( _O )-O-( _CH2CH2O ) _o - ^R0 (wherein R is H or _CH3 , n is at least 2
The average value is 60 or less, R ⁰ is an alkyl group,
0.5 to 25% by weight of at least one of the monomers (functional groups having at least 8 carbon atoms selected from aralkyl groups and polycyclic hydrocarbon groups); (3) alkyl groups having 1 to 4 carbon atoms; At least 30% of (meth)acrylate
% by weight, and (4) consisting of a mixture of up to 1.0% by weight of a polyethylenically unsaturated monomer, the aqueous dispersion of which emulsion polymer thickens with the addition of a neutralizing agent, and (A) and (B) prepared by dispersing in water and at least partially neutralizing a thickening agent composition, the proportion of which is at least partially neutralized and effective to form a strong gel when mixed with water; A composition consisting of an aqueous gel. 13 (A) a clay mineral that swells in water and (B) an emulsion polymer that is insoluble in water, (1) 20 to 50% by weight of (meth)acrylic acid, (2) General formula (): H ₂ C= C(R)-C( _O )-O-( _CH2CH2O ) _o - ^R0 (wherein R is H or _CH3 , n is at least 2
The average value is 60 or less, R ⁰ is an alkyl group,
(3) 0.5 to 25% by weight of at least one monomer of a functional group having at least 8 carbon atoms selected from aralkyl groups and polycyclic hydrocarbon groups; (3) alkyl groups having 1 to 4 carbon atoms; At least 30% of (meth)acrylate
% by weight, and (4) consisting of a mixture of up to 1.0% by weight of a polyethylenically unsaturated monomer, the aqueous dispersion of which emulsion polymer thickens with the addition of a neutralizing agent, and (A) and (B) The ratio of (B) to (B) is one that is effective to thicken the aqueous dispersion formed from the mixture when the neutralizing agent is added to the thickener composition for an aqueous composition; A process for thickening an aqueous dispersion, characterized in that it is at least partially neutralized before, after or during mixing. 14 (B) is (1) 30 to 45% by weight of (meth)acrylic acid, (2) 1 to 15% by weight of the general formula () (wherein the average value of n is about 10 to 60, and R ⁰ (3) a copolymer of about 40 to 60% by weight of said alkyl (meth)acrylate. Method of thickening dispersion. 15 (B) is (1) 30 to 45% by weight of methacrylic acid, (2) 1 to 15% by weight of a monomer of the general formula () (wherein the average value of n is about 10 to 60, R ⁰ is 12 (3) A method for thickening an aqueous dispersion according to claim 13, wherein the copolymer is a copolymer comprising 40 to 60% by weight of ethyl acrylate. 16 The amount of (A) is about 0.1 to 10 parts by weight, and the amount of (B) is about 0.1
14. The method of thickening an aqueous dispersion according to claim 13, wherein (A) is a montmorillonite clay mineral in an amount of 5 parts by weight. 17 (A) a water-swellable clay mineral and (B) a water-insoluble emulsion polymer, containing (1) 20-50% by weight of (meth)acrylic acid, (2) general formula (): H ₂ C= C(R)-C( _O )-O-( _CH2CH2O ) _o - ^R0 (wherein R is H or _CH3 , n is at least 2
The average value is 60 or less, R ⁰ is an alkyl group,
(3) 0.5 to 25% by weight of at least one monomer of a functional group having at least 8 carbon atoms selected from aralkyl groups and polycyclic hydrocarbon groups; (3) alkyl groups having 1 to 4 carbon atoms; At least 30% of meth)acrylate
% by weight, and (4) up to 1.0% by weight of a polyethylenically unsaturated monomer, the aqueous dispersion of which emulsion polymer is thickened by the addition of a neutralizing agent, and the amount of (A) is approximately 0.1 to 10 parts by weight,
dispersing in water a thickener composition in which the amount of (B) is about 0.1 to 5 parts by weight and where (A) is a montmorillonite clay mineral, and at least partially neutralized before, after, or during said dispersion; A method for forming an aqueous gel, characterized by: