MXPA98003989A

MXPA98003989A - Polim compositions

Info

Publication number: MXPA98003989A
Application number: MXPA/A/1998/003989A
Authority: MX
Inventors: Lau Willie; Dewayne Kelly Michael; Paul Lorah Dennis; Ralph Heinley David
Original assignee: Rohm And Haas Company
Priority date: 1997-05-21
Filing date: 1998-05-20
Publication date: 1999-06-01

Abstract

Polymer compositions which are useful in the polishing compositions are disclosed as wax substitutes. The compositions provide improved repair properties in floor waxes, and provide a floor polish does not slip

Description

Polymer Compositions This invention relates to polymer compositions, more specifically, this invention relates to polymer compositions that are useful in compositions for polishing floors. Floor polishing compositions typically contain wax to increase strength and ease of maintenance. A waxed floor is exposed to multiple footsteps, so the waxing wears and black heel marks appear. Repair of damaged waxing is typically done using a polishing machine. It is expected that with the repair the wear and black markings will disappear, increase the brilliance of the waxing and the waxing will not be marked. Although floor waxes containing wax can be repaired through polishing processes, there is a continuing need for floor polish compositions that provide improved repair properties. The compositions for polishing floors containing wax can be slippery. The slippery surface can cause damage due to slips and falls. There is a continuing need for polishing compositions for non-slip floors. It is believed that the addition of a mild hydrophobic emulsion polymer composition with putative crystallinity for a floor polishing composition will improve the repair properties of the floor polish, and make it less slippery. The mild compositions of hydrophobic emulsion polymer with alleged crystallinity are difficult to prepare due to the hydrophobicity of the monomers needed to prepare the polymers. U.S. Patent No. 5,521,266 shows a method for forming polymers from hydrophobic monomers. The disclosed method uses macromolecular organic compounds having a hydrophobic cavity for complex monomers having a water solubility. This allows the formation of polymers from monomers of low water solubility by means of emulsion polymerization. Suitable monomers for use in the polymer forming method include lauryl methacrylate. Despite the disclosure of the prior art, there is a continuing need for a mild hydrophobic emulsion polymer composition with putative crystallinity, for use in floor polishing compositions. Surprisingly, we have found that the use of the polymer compositions of this invention allows a reduction in the amount of wax in the polishing compositions of floors, while improving the repair properties for the waxing of floors, and making the waxing for floors less slippery. The present invention provides a polymer composition comprising as polymerized units: a) from 9.5 to 100 parts by weight of at least one C ?S to C alquilo alkyl ester of (meth) acrylic acid; b) from 0 to 90 parts by weight of at least one ethylenically unsaturated monomer; c) from 0 to 90 parts by weight of at least one monomer containing ethylenically unsaturated acid or salts thereof, and d) from 0 to 60 parts by weight of at least one alkali-soluble resin. In another embodiment, the present invention provides a method for making a floor polishing composition comprising: Mixing: a) from 10 to 90 parts by weight of a polymer composition containing polymerized units; from 9.5 to 100 parts by weight of at least one C16 to C40 alkyl ester of (meth) acrylic acid; from 0 to 90 parts by weight of at least one ethylenically unsaturated monomer; from O to 90 parts by weight of at least one monomer containing ethylenically unsaturated acid or salts thereof; and from 0 to 60 parts by weight of at least one alkali-soluble resin; with c) from 0 to 90 parts by weight of alkali-soluble resin; d) from 10 to 90 parts by weight of a floor finish carrier with emulsion polymer; and e) from 10 to 80 parts by weight of water. The present invention also provides a floor polishing composition comprising: e '10 to 90 parts by weight of a floor finish carrier with emulsion polymer, from 0 to 90 parts by weight of alkali soluble resin, from 10 to 90 parts by weight of a polymer composition comprising as polymerized units: from 9.5 to 100 parts by weight of at least one C.sub.1 to C.sub.4 alkyl ester of (meth) acrylic acid; from 0 to 90 parts by weight of at least one ethylenically unsaturated monomer; from 0 to 90 parts by weight of at least one monomer containing ethylenically unsaturated acid or salts thereof; from 0 to 60 parts by weight of at least one alkali-soluble resin; and from 10 to 80 parts by weight of water.

The compositions of this invention can be prepared by means of a single-step or multi-step process. The process may be an emulsion polymerization such as the process described in U.S. Pat. 5,521,266. The process can also be solution polymerization followed by emulsification as described in U.S. Pat. 5,539,021, mini-emulsion polymerization or micro-emulsion polymerization. Emulsion polymerization is preferred. In the process used to prepare the samples of this application, a first step was prepared by adding an emulsion of monomer and sodium persulfate for a solution containing methyl-β-cyclodextrin ("CD"), deionized water and surfactant. The first stage was reacted at 85 ° C. A second stage was prepared by making a second monomer emulsion and feeding the second monomer emulsion and a sodium persulfate solution to the first reacted stage. The second stage was reacted at 85 ° C ..

The polymer compositions of this invention are compositions containing as polymerized units from 0 to 100 parts by weight, preferably from 40 to 99 parts by weight, more preferably from 90 to 98 parts by weight of at least one C 16 alkyl ester to C40 of (meth) acrylic acid. It is preferred that the alkyl ester of (meth) acrylic acid is a Cie a alkyl ester. C30 of (meth) acrylic acid. It is preferred even more than the acid alkyl ester (meth) acrylic is a C 16 to C 8 alkyl ester of (meth) acrylic acid. Alkyl esters of (meth) acrylic acid include cetyl (meth) acrylate, stearyl (meth) acrylate, (meth) behenyl acrylate and eicosyl (meth) acrylate. The beneficial properties in floor waxes can be obtained by using more than one C 16 to C 40 alkyl ester of (meth) acrylic acid. The polymer composition of this invention also contains as polymerized units from 0 to 90 parts by weight, preferably from 0 to 50 parts by weight, more preferably from 1 to 20 parts by weight of at least one ethylenically unsaturated monomer. Ethylenically unsaturated monomers suitable for use in the preparation of the polymer compositions of this invention include, but are not limited to, (meth) acrylic ester monomers which include methyl acrylate, ethyl acrylate, butyl acrylate, acrylate 2-ethylhexyl, decyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate; Acrylamide or substituted acrylamides; styrene or substituted styrene, vinyl acetate or other vinyl esters; vinyl monomers such as vinyl chloride, vinylidene chloride.

N-vinyl pyrolidone; and acrylonitrile or methacrylonitrile. Preferred are butyl acrylate, methyl methacrylate and styrene. More preferred are butyl acrylate and methyl methacrylate. The polymer composition of this invention also contains as polymerized units from 0 to 90 parts by weight, preferably from 0 to 50 parts by weight, more preferably from 1 to 15 parts by weight of monomer containing ethylenically unsaturated acid or salts thereof. East. Suitable ethylenically unsaturated acid containing monomers include, but are not limited to, acrylic acid, methacrylic acid, crotonic acid, phosphoethyl methacrylate, 2-arylamido-2-methyl-1-propanesulfonic acid, sodium vinyl sulfonate, itaconic acid , fumaric acid, maleic acid, monomethyl itaconate, monomethyl fumarate, monobutyl fumarate and maleic anhydride. Acrylic acid and methacrylic acid are preferred. Methacrylic acid is more preferred. The polymer composition of this invention also contains as polymerized units from 0 to 60 parts by weight, preferably from 0 to 40 parts by weight, more preferably from 0 to 20 parts by weight of alkali soluble resin. The alkali soluble resins useful in this invention are those that typically have a weight average molecular weight below 500, 000, preferably below 100,000, more preferably below 50,000. The polymer compositions of this invention are useful in floor polishing compositions. The floor polishing compositions are typically emulsions containing a floor finish carrier with emulsion polymer, water, alkali soluble resin, biocide, polyethylene wax, polypropylene wax and coalescing solvents. The compositions of this invention are also useful in applications such as industrial and architectural coatings including paints, wood coatings, inks; adhesives; putties; plastics; plastic additives; oil additives and the like. The polymer compositions of this invention are typically used in floor polishing compositions by mixing 10 to 90 parts by weight of the polymer composition of this invention by weight with a floor polishing composition. It is preferred that from 10 to 50 parts by weight of the polymer composition of this invention by weight be mixed with the floor polish composition. It is further preferred that from 15 to 25 parts by weight of the polymer composition of this invention by weight be mixed with the floor polish composition. The emulsion polymer floor finishing carrier can be prepared by means of single-stage or multi-stage emulsion polymerization. Emulsion polymerization processes are known in the art and are disclosed, for example, in U.S. Pat. 5,346,954. Multi-stage polymer processes are also known in the art and are disclosed, for example, in U.S. Pat. 4,325,856, 4,654,397 and 4,814,373. Monomers suitable for use in the preparation of the finished emulsion polymer flooring carrier include, but are not limited to, acrylic ester monomers including methyl (meth) acrylate, ethyl (meth) acrylate, (met, ) butyl acrylate; Acrylamide or substituted acrylamides; styrene or substituted styrene; vinyl acetate or other vinyl esters; vinyl monomers such as vinyl chloride, vinylidene chloride, N-vinyl pyrolidone; and acrylonitrile or methacrylonitrile. Low levels of copolymerized ethylenically unsaturated acid monomers, such as, 0.1% to 10% by weight, based on the weight of the emulsion polymerized polymer, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid and maleic anhydride, They can also be used in the finishing carrier for floors with emulsion polymer. The chain transfer agents can be used to control the molecular weight of the floor finish carrier with emulsion polymer. Suitable chain transfer agents are mercaptans, such as dodecyl mercaptan. The chain transfer agent can be used from 0.1% to 10%, based on the total weight of the polymer composition. Conventional crosslinking agents, such as a polyaziridine, polyisocyanate, polycarbodiimide, polyamine and a polyvalent metal compound, can be used in the finishing carrier of floors with emulsion polymer, as long as the crosslinking agent does not inhibit film formation. . Typically, 0.05% to 25% of the crosslinking agent is used, based on the weight of the polymer solids. Emulsion polymer floor finish carriers such as Rhoplex®1421, Acrysol®644 and Acrysol®Plus are typically used in floor polish compositions to provide strong films with impact resistance. The emulsion polymer floor finish carrier index typically used in floor waxes is 10 to 90 parts by weight. It is preferred to use from 50 to 90 parts by weight of the floor finish carrier with emulsion polymer in the floor polish. It is even more preferred to use from 70 to 90 parts by weight of the finished floor carrier with emulsion polymer in the floor polish. Alkali-soluble resins are disclosed in U.S. Pat. 3,037,952. With alkali-soluble resin we refer to a resin typically with a weight average molecular weight below 500,000, preferably below 100,000, and more preferably below 50,000. The alkali-soluble resin contains a functional acid group that is typically present in more than 10% of the resin on a weight basis. The alkali-soluble resin forms a clear to translucent solution typically in an index of pH 6 to pH 10. The alkali-soluble resin can be prepared by the same process and with the same materials as the above-described emulsion polymer floor finish carrier. The alkali-soluble resin index typically used in floor waxes is from 0 to 90 parts by weight. It is preferred to use in floor polish 5 to 50 parts by weight of alkali-soluble resin. It is even more preferred to use in floor polish 10 to 30 parts by weight of alkali-soluble resin. Coalescents are typically used to aid film formation in floor waxes. Suitable coalescents include diethylene glycol ethyl ether and tripropylene glycol methyl ether. Coalescents are typically used in floor polishing compositions of 0.1 to 10 parts by weight. A biocide such as Kathon®CG / ICP can be added to the composition to polish floors to preserve the composition while it is in the bottle. Biocides are typically used in floor polishing compositions from 0.01% to 0.2% by weight. Wax emulsions such as Epolene® E-43N and A-C 325N are typically used in floor polish compositions, to provide resistance to black marks and wear. Wax emulsions are typically used in the compositions for polishing floors of 10 to 90 parts by weight on a solid basis. It is preferred to use in the waxing for floors of 10 to 50 parts by weight, on a solid basis, of the wax emulsion. It is even more preferred to use wax emulsion in the floor polish of 10 to 20 parts by weight, on a solids basis.

When the polymer compositions of this invention are incorporated into the floor polishing compositions, the resulting floor wax improves its repair properties and slip resistance. The following abbreviations are used through this patent application: MAL = lauryl methacrylate MAE = stearyl methacrylate Est = styrene MAM = methyl methacrylate AB = butyl acrylate AMA = methacrylic acid MAIBO = isobornyl methacrylate MnDD = mercaptan n- dodecyl ID = sample identification number CD = methyl-β-cyclodextrin gr. = grams ° C = degrees centigrade NH4OH = aqueous ammonia J-678 = Joncryl®-678 Comp. = comparative NMR = resistance to black marks RD = wear resistance CL = long chain (met) acrylate = methacrylate and acrylate The following table lists some of the materials used in this patent application, and their sources: Material Function Source Triton®XN-45S anionic Union Carbide surfactant Pluronic®L31 surfactant agent BASF Joncryl®-678 alkali soluble SC Johnson resin Siponate®DS-4 Rhone-Poulenc surfactant Rhoplex®1421 polymer Rohm and Haas Acrysol®644 polymer Rohm and Haas Acrysol®Plus polymer Rohm and Haas Kathon®CG / lCP biocide Rohm and Haas Poly Emulsion®325N35 ChemCor wax Epolene®E-43N ChemCor wax Fluorad® FC-129 Surfactant Agent 3M Company SE-21 Silicone Wacker Silicones Corporation Example 1 For stage 1, 400 gr. of water deionized, anionic surface active agent Triton® XN-45S (T # l) and 28.6 gr. of CD in a four liter round bottom flask, with four necks and equipped with a mechanical stirrer, temperature control device, condenser, initiator and monomer feed lines, and an inlet for nitrogen at room temperature. The content was heated to 85 ° C. while stirring under a nitrogen purge. A monomer emulsion of 31.3 gr. deionized water, 0.4 gr. of tesactive agent Triton® XN-45S, 33.8 gr. of MAL, 7.5 gr. of AB, 33 gr. of MAM and 0.75 gr. of AMA was prepared separately. The solutions of 0.35% by weight of sodium carbonate (based on the weight of total monomer in stage 1 and stage 2) in 25 gr. of deionized water, and 0.35% by weight of sodium persulfate (based on the weight of total monomer in stage 1 and stage 2) in 30 g. of deionized water were introduced into a reaction vessel. The monomer emulsion was fed for a period of 20 minutes together with a starter solution of 0.05% sodium persulfate (based on the weight of total monomer in stage 1 and stage 2) in 210 g. of deionized water. For step 2, a monomer emulsion was prepared using 625 gr. deionized water, 7.8 gr. of anionic surface active agent Triton® XN-45S and the monomers according to table 1. Immediately after finishing the emulsion feed of the monomer from stage 1, the monomer emulsion from stage 2 was fed over a period of 3 hours together with the sodium persulphate initiator solution.

Table 1 Id. MAL MAE AB MAM Est MAIBO MnDD AMA t #? 1 0 1395 0 75 0 0 0 30 11.9 2 0 1395 0 75 0 0 7.5 30 11.9 3 0 975 0 510 0 0 0 15 11.9 4 705 690 0 75 0 0 0 30 11.9 1020 375 0 75 0 0 0 30 11.9 6 0 780 0 705 0 0 0 15 11.9 7 0 675 150 660 0 0 0 15 24.5 8 0 525 150 150 660 0 0 15 24.5 9 0 600 150 150 585 0 0 15 24.5 0 675 150 150 510 0 0 15 24.5 11 0 750 150 150 435 0 0 15 24.5 12 0 675 0 150 0 650 0 15 24.5 13 * 1395 0 0 75 0 0 0 30 11.9 = comparative 3 for testing purposes (MAL) Example 2 A second group of samples to be tested in floor waxes was prepared by combining water, surfactant, J-678, CD and NH4OH in a container. A solution of sodium persulfate in water was then added to the vessel. Finally, a monomer emulsion containing water, surfactant and MAE, and a solution of persulfate in water were added to the container. The monomers were reacted at 85 ° C. Using the same equipment as described in example 1, 543 gr. of deionized water in the reaction flask at room temperature. The content was heated to 55 ° C. while stirring under a nitrogen purge. The NH4OH that is established in table 2, the CD that is established in table 2, the J-678 that is established in table 2 and 16 gr. of Pluronic® L31 were introduced into the reaction flask at 55 ° C. The contents were stirred for two hours at 55 ° C. and heated to 85 ° C. A monomer emulsion containing 104 g. deionized water, 2.8 gr. of a 23% solution of Siponate® DS-4, MAE as set out in table 2 and 16 gr. of Pluronic L31. It was prepared separately. A solution of 7 gr. of ammonium persulfate in 25 gr. of deionized water was added to the container. The monomer emulsion was then added to the vessel at an index of 5.5 g. per minute. A starter solution of 7 gr. of ammonium persulfate in 165 gr. of deionized water was co-fed at a rate of 1 gr. per minute.

Table 2 H4OH CD Id. (28%) (50%) J-678 MAE 14 37.1 0 160 640 15 92.8 14.9 400 400 16 37.1 14.9 160 640 Example 3 - Application of floor waxing, and test. The waxes for floors were prepared according to the following formulation: Material in order of addition Percentage by weight Water 30.73 Kathon®CG / lCP 0. 03 Acrysol®644 (42%) 5. 52 Fluorad® FC-129 (50%) 0. 02 Diethylene glycol ethyl ether 5. 78 Tripropilene-glycol-methyl-ether 1. 02 Rhoplex®1421 (38%) 4? 5.76 Epolene®E-43N (40%) 4. 35 Poly Emulsion® 325N35 (35%) 4. 97 SE-21 0. 02 The above sample is Comparative 2, for test purposes. For the samples of the invention, an equal weight of the polymer composition of the invention was replaced by Epolene® E-43N and Poly Emulsion® 325N35. For the samples of the invention with alkali-soluble resin, an equal weight of Acrysol® Plus was replaced by Acrysol®644. For the control sample without wax (comparative 1 for testing purposes), the level of Rhoplex®1421 was increased on an equal weight basis to consider the removal of Epolene® E-43N and Poly Emulsion® 325N35. The floor waxes were tested for use in a corridor that had a porcelain tile floor with vinyl asbestos. First, the residual wax was applied to the corridor in the manner of stripes. Then the floor was polished again as follows: The intact floor was divided into equal sections perpendicular to the normal flow direction of the corridor. Each section was covered with a waxed cover that was to be tested. The waxing was applied with a mohair applicator at an index of approximately 186 square meters / 3.8 liters. Three additional covers were applied after allowing the previous cover to dry for one hour. The polished earthenware floor was subjected to a daily traffic load of 800 to 1,200 steps. All waxed durability in terms of wear resistance and black heel marks, after being subjected to traffic, was estimated at weekly intervals on a scale of 1 to 10 in ascending order of improved development. Wear was estimated based on the number, size and depth of wear marks. The index of black marks was based on the number, size and blackness of the black marks. The waxes were then polished at high speed with a propane-powered polishing machine that operated at approximately 2,100 rotations per minute to repair the damage caused by traffic. The repair was subjectively estimated in terms of all the increase in brightness, elimination of wear and black marks and scratching due to the high speed of polishing. The results of the floor polish tests that did not contain alkali-soluble resin are listed in Table 3. The results of the floor polish tests containing alkali-soluble resin are listed in list 4.

Table 3 Sample RD RMN Repair Metacri Comp. 1 4 6 regular none Comp. 2 7 9 good none Comp. 3 6 7 regular MAL 1 7 9 very good MAE 3 6 8 very good MAE 4 8 9 excellent MAE / MAL The above data demonstrate that the compositions of this invention can be replaced by wax in floor waxes without alkali-soluble resin without losing development in terms of wear resistance and black marks. Floor waxes prepared with the compositions of this invention have better repair properties than conventional floor waxes containing wax.

Table 4 Sample RD RMN Repair Methacrylate CL Comp. 1 5 5 poor none Comp. 2 7 8 regular none 16 8 8 regular MAE 15 9 8 good MAE The above data demonstrate that the compositions of this invention can be replaced by wax in floor polishes containing alkali-soluble resin without losing development in terms of wear resistance and black marks. The waxes for floors prepared with the compositions of this invention have better repair properties than conventional floor waxes containing wax. The samples were also tested for slip resistance. Three slabs with vinyl composition were covered with floor waxing, applying a quantity of 4ml. of the waxing in a mortar in the center of the area that was going to be covered. With a gauze of twelve two by two inches of Johnson &; Johnson absorbed as much as possible of the waxing. The waxing was uniformly dispersed over the surface of the earthenware with the saturated gauze pad, first with strokes from top to bottom and then transverse. No pressure was used when applying the test wax to the earthenware. After the waxing had dried at 70 degrees Fahrenheit / 55% constant relative humidity conditions, a second coating was applied in the same manner as the first.

After the tiles were dried overnight, the test was developed. The test was developed on the James friction test machine. Slip resistance was reported as the static coefficient of friction, which is a number between 0.00 and 1.00. The number is the average of four determinations carried out in the waxing, the crockery having been rotated 90 ° between each determination. The closer the number is to 1.00, the less slippery is the waxing. The results of the tests are shown in table 5.

Table 5 Id. Slip resistance Comp. 2 0.63 Comp. 1 > 0.9 3 0.85 1 0.81 The above results demonstrate that the compositions of this invention provide floor waxes with better slip resistance than waxes for floors containing wax.

Claims

Claims 1. A polymer composition comprising as polymerized units: a) from 9.5 to 100 parts by weight of at least one C 16 alkyl ester a. C0 of methacrylic acid; b) from 0 to 90 parts by weight of at least one ethylenically unsated monomer; c) from 0 to 90 parts by weight of at least one monomer containing ethylenically unsated acid or salts thereof, and d) from 0 to 60 parts by weight of at least one alkali-soluble resin.
2. A composition according to claim 1, wherein the composition comprises: a) from 40 to 99 parts by weight of at least one C6 to C0 alkyl ester of (meth) acrylic acid, b) from 0 to 50 parts by weight of at least one monomer selected from the group consisting of methyl methacrylate and butyl acrylate; and c) from 0 to 50 parts by weight of methacrylic acid.
3. A composition according to claim 1, wherein the composition comprises: a) from 90 to 98 parts by weight of stearyl (meth) acrylate, b) from 1 to 20 parts by weight of methyl methacrylate; and c) from 1 to 15 parts by weight of methacrylic acid.
4. A method for making a floor polishing composition, comprising: mixing a) from 10 to 90 parts by weight of a polymer composition comprising as polymerized units: from 9.5 to 100 parts by weight of at least one alkyl ester C16 to C40 of methacrylic acid; from 0 to 90 parts by weight of at least one ethylenically unsated monomer; from 0 to 90 parts by weight of at least one monomer containing ethylenically unsated acid or salts thereof; and from 0 to 60 parts by weight of at least one alkali-soluble resin; with b) from 0 to 90 parts by weight of alkali soluble resin; c) from 10 to 90 parts by weight of a floor finish carrier with emulsion polymer; and d) from 10 to 80 parts by weight of water.
5. A floor polishing composition, comprising: from 10 to 90 parts by weight of a floor finish carrier with emulsion polymer, from 0 to 90 parts by weight of an alkali-soluble resin, from 10 to 90 parts by weight weight of a polymer composition comprising as polymerized units: from 9.5 to 99 parts by weight of at least one C to C40 alkyl ester of (meth) acrylic acid; from 0 to 90 parts by weight of at least one ethylenically unsated monomer; from 0 to 90 parts by weight of at least one monomer containing ethylenically unsated acid or salts thereof; from 0% to 60% by weight of at least one alkali-soluble resin; and from 10 to 80 parts by weight of water.