JPS623870B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to aqueous dye compositions. More specifically, the present invention relates to a novel aqueous floor polishing composition prepared from a low molecular weight resin soluble in aqueous base, a resin cut resin composition. It is known to produce resins that are soluble in aqueous bases. Among these resins are polymers with relatively low molecular weights, for example less than about 5000. The polymer contains at least one polymerizable ethylenically unsaturated monomer that does not contain carboxyl groups and at least one polymerizable ethylenically unsaturated monomer that contains carboxyl groups, and has a relative reactivity ratio of less than about 1 at 80°C. Contains at least two types of monomer units. The resulting polymer, when mixed with an aqueous base such as aqueous ammonia, has a pH of 7.
This results in a substantially clear solution of, for example, 7 to 12.
This polymer is particularly useful as a component of water-based, or water-based, floor polishing compositions to help form a homogeneous and continuous adherent film on the surface to which it is applied, as well as the resulting film or finish after drying. It becomes an important part of the surface. Traditionally used resins include styrene/maleic anhydride resins and rosin maleic resins; high solubility)
It is produced by base radical initiated solution polymerization method or emulsion polymerization method using high boiling point alcohols such as. According to the known technology, the solvent has to be recovered from the polymerization product. I mean,
Attempting to dissolve the alcohol-containing product in an aqueous base to form a resin solution results in a milky, heterogeneous product rather than the desired clear one. (U.S. patent application cited in UK Patent No. 1107249 and US Patent No. 3308078)
See specification SN 467121 - Applicant LAkaminski, title of invention "Resin"). Removal of high boiling reactants is costly and sometimes requires tedious concentration or azeotropic distillation operations and may require vacuum stripping of the solvent. This stripping process is time consuming and is exposed to high temperatures for a long period of time, which accelerates the deterioration of the resin. The drawbacks of the prior art described above are overcome by the present invention which provides an aqueous base-soluble solid resin having an acid number of about 60-250, preferably 120-185, and an average molecular weight of about 600-4000, preferably 900-2500. Can be removed. The above molecular weights are number average molecular weights and are for resins containing about 10% alcohol mixture, as described in (C) below. The resin of the present invention is a polymerization product of a mixture consisting of the following components. (A) Approximately 20 to 70 mol% of at least one polymerizable ethylenically unsaturated monomer that does not contain carboxyl; (B) Approximately 15 to 60 mol% of at least one polymerizable ethylenically unsaturated monomer that is substituted with carboxyl. , (C) Organic free radical generating polymerization initiator from about 0.3 to
(D) about 3 to 20 moles of a solvent alcohol mixture containing about 10 to 90% by weight of a water-insoluble liquid alcohol and about 10 to 90% by weight of a water-soluble alcohol having a normal boiling point of about 175°C or higher; The present invention also relates to an aqueous floor polishing composition containing a resin solution or resin composition obtained from the above-mentioned resin, or a resin solution or resin composition obtained during the production of the resin. The carboxyl groups are in the range of 1.2 to 4, preferably 2.1 to 3.3 mequiv/g of resin. Surprisingly, despite containing an alcoholic polymerization solvent containing a significant proportion of water-insoluble alcohols, the novel resins of the present invention exhibit a non-yellowing transparent effect when ground and solubilized with an aqueous base. It has been found that the present invention provides a homogeneous, clear, substantially colorless resin solution that is excellent as a floor polishing composition. The resins of the invention are prepared by first mixing the alcohol, advantageously at ambient temperature, using a conventional resin can, preferably with stirring means, and then heating the resulting mixture to about 150-200°C. is suitable. The monomers mixed with the initiator are gradually added to the hot stirred mixture, usually over a period of about 0.5 to 1.5 hours. After the addition is complete, the reactants are heated to a temperature of up to 250°C, preferably about 177-220°C, more advantageously about 205°C, and heated to a temperature of about 10-30°C.
Maintain for minutes. The reactants are then removed from the resin can and allowed to cool to room temperature, yielding a solid resin product. Alternatively, a continuous method, ie, the solvent, monomer, and catalyst may be continuously premixed and reacted through a heated tube to form a resin solution, followed by solidification of the resin by cooling. The alcohol-containing resin products of the present invention are prepared by grinding or pulverizing the resin according to conventional methods and preparing the pulverized resin in water with an aqueous base, conveniently at a moderately elevated temperature, e.g. about 60-70°C. About 5~
It can be converted into a clear, homogeneous aqueous resin solution by stirring for 10 minutes. The resulting resin preparation is then allowed to cool to room temperature. The amount of aqueous base required to neutralize the carboxyl groups of the resin and thereby solubilize it is easily calculated from the acid number of the resin, which can be easily calculated from the acid number of the resin by neutralization with potassium hydroxide in acetone. It is determined. The pH of the resin solution of the present invention is greater than about 7, usually about 8 to 12, most often about 9.
and 10, the concentration of the resin solution (or emulsion) is in the range of about 1% or less to 25% or more, with a preferred concentration of about 10-20%;
More preferred is about 15-18%. If desired, deionized water can be used in preparing the solution, and is often preferred. The carboxyl-free monomer or monomers used to prepare the resins of the present invention are not new per se and are described in the prior art and need not be described in detail here. These include styrene, acrylate, methacrylate, N-vinylpyrrolidone, acrylonitrile,
ethylenically unsaturated monomers including fumarate esters such as diethyl fumarate and dimethyl fumarate and itaconate esters such as dimethyl itaconate and mixtures thereof. The carboxyl-free monomer or monomers used preferably correspond to the following structural formula. () CH ₂ = CR-Z In the formula, R represents hydrogen or a methyl group, and Z is a carbalkoxy group (here, the alkoxy group includes a straight chain or branched alkyl group having 1 to 12 carbon atoms)
or when Z is allyl, phenyl and lower alkyl-substituted phenyl, with the proviso that R is always hydrogen (wherein the term lower alkyl refers to a straight or branched alkyl of 1 to 4 carbon atoms). represents an allyl group selected from the group consisting of Representative preferred carboxyl-free monomers include the aforementioned styrene and methyl methacrylate, as well as n-butyl acrylate, ethyl acrylate, methyl acrylate, n-propyl acrylate, isobutyl acrylate, p-ethylstyrene, o-vinyltoluene, m- - Vinyltoluene, lauryl acrylate, ethyl methacrylate, n-propyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate. According to a particularly preferred embodiment of the invention, as carboxyl-free monomer, Z is allyl in one of the compounds;
In the remaining compounds there are mixtures of compounds corresponding to the above formula in which alkoxy is carbo-lower alkoxy having 1 to 4 carbon atoms. Still more preferred is a mixture of styrene and lower alkyl acrylate or methacrylate in a molar ratio of about 1.6:1 to 3:1 as the carboxyl-free monomer. The carboxyl-substituted styrenic unsaturated monomer used in producing the aqueous base-soluble resin according to the present invention preferably has the following structural formula. () CH ₂ = CR ² COOH where R ² represents hydrogen or a methyl group,
Thus, the best carboxy-substituted monomers are selected from the group consisting of acrylic acid and mecacrylic acid. Preferably, the molar ratio of carboxyl-free monomer to carboxy-substituted monomer is within the range of about 1.2:1 to 2.7:1. Typically up to four different ethylenically unsaturated monomers, both carboxyl-free and carboxyl-substituted types, are used in the preparation of the resins of this invention. Initiators for polymerization reactions are organic compounds that generate free radicals when heated. Examples of initiators commonly used in the art of ethylenically unsaturated compound polymerization are benzoyl peroxide, p
- lower alkyl esters of aliphatic or aromatic carboxyl peracids such as trioloyl, p-methoxybenzoyl peroxide, aroyl peroxides, t-butyl peroctoate or t-butyl perbenzoate, and azo-bis - Contains isobutyronitrile. Preferred initiators of the present invention are aroyl peroxides and lower alkyl esters of aromatic or aliphatic carboxyl peracids. Particularly good results are generally obtained using benzoyl peroxide as the initiator. It is desirable to provide about 0.3 to 0.9 mole percent initiator to the polymerization vessel or reaction mixture components. The alcohol used in the present invention should have a normal boiling point, that is, a boiling point at atmospheric pressure, above the highest temperature stage of polymerization, that is, at least about 175°C or above, such as 177°C or above, in order to avoid solvent boiling during the polymerization reaction. be. Optionally, alcohols boiling below 175° C. can also be used; however, such reactions are preferably carried out under pressure to keep the alcohol in a liquid state, but pressure reactions are not desirable. Preferably, the alcohol used has a boiling point of about 205°C or higher. Usually the alcohol used in the present invention has a normal boiling point of 300°C or less.
The alcohols contemplated by the present invention are ethers in which the aliphatic chain is one or more, i.e. -o
- aliphatic monohydric or polyhydric straight-chain and branched alcohols which may be interrupted by chains. Preferably the alcohol is a monohydric alcohol, diol or triol. The water-soluble and water-insoluble alcohols contemplated by this invention are preferably saturated. ambient temperature, i.e. 25
℃, the water-insoluble alcohol used as a solvent should be liquid with no appreciable water solubility. Representative examples of suitable water-insoluble alcohols include: 2-Ethylhexanol, boiling point 183.5℃; n-nonyl alcohol, boiling point
215℃; n-decyl alcohol, boiling point 239.9℃; n
-Dodecyl alcohol, boiling point 259℃; 2.6.8
-trimethyl-nonyl-4 alcohol, boiling point
225.2° C. and isodecanol (mixed isomers corresponding to the formula C ₁₀ H ₂₁ OH); and equivalent alcohols of 8 to 12 carbon atoms. The water-insoluble alcohol charged according to the invention is a primary aliphatic alcohol having 9 to 12 carbon atoms. Most preferred is n-decyl alcohol, as are mixtures with other such higher alcohols. A typical example of a suitable water-soluble alcohol is diethylene glycol monobutyl ether, boiling point 230.6.
°C; Glycerol, boiling point 290 °C; Diethylene glycol monoethyl ether, boiling point 195-202 °C; Ethylene glycol, boiling point 197.2 °C; Ethylene glycol monohexyl ether, boiling point 208.1 °C; Diethylene glycol monomethyl ether, boiling point
194℃; 1,3-propanediol, boiling point 210~
211℃; 1,4-butylene glycol, boiling point 230
°C; 2,3-butylene glycol, boiling point 179-182
°C; 1,3-butylene glycol, boiling point 207.5
°C; diethylene glycol, boiling point 245 °C; 2.
2,4-trimethyl-1,3-pentanediol, boiling point 215-235°C; and triethylene glycol, boiling point 287.4°C; and mixtures of equivalent alcohols. Preferably, the diol is used as a water-soluble alcohol, 2.2.
4-Trimethyl 1,3-pentanediol is particularly preferred, but others having 4 to 8 carbon atoms are also useful. Generally, the alcohol mixture comprises 10-90% by weight of one or more water-insoluble alcohols and 10-90% by weight of one or more water-insoluble alcohols.
% by weight of one or more water-soluble alcohols. In a preferred embodiment of the invention the alcohol mixture is
30-60% by weight of one or more water-insoluble alcohols and 40-70% by weight of one or more water-soluble alcohols. The most preferred mixture is 40-55% by weight water-insoluble alcohol and 45-60%
% by weight of one or more water-soluble alcohols. Particularly good results are obtained using mixtures containing about 50% by weight of water-insoluble alcohol and about 50% by weight of water-soluble alcohol. The mole percent of the alcoholic mixture is for all components A to D.
Calculated based on 3 to 20%, preferably about 10
The content ranges from 20 mol%. The aqueous bases used to prepare the aqueous resin cuts or solutions of this invention are those conventionally used in the art. Most commercially available aqueous bases can be used. Thus, water-soluble organic amines such as ammonium hydroxide, aqueous ammonia, sodium hydroxide, potassium hydroxide, borax, and lower alkyl amines can be used. Representative suitable amines are methylamine, ethylamine, dimethylamine, diethylamine, isobutylamine, n-
Those containing alkyl of 1 to 4 carbon atoms such as propylamine, isopropylamine, trimethylamine, triisopropylamine and mixtures thereof. Preferably, aqueous ammonia dissolved in water at a concentration of 5 to 28% is utilized as the aqueous base during resin solution preparation. The alcohol-containing resins and resin solutions or cuts of the present invention are substantially colorless, with only a slight, sometimes slight yellow tinge. The resin solution is kept at ambient temperature, e.g.
It is a relatively viscous liquid with a viscosity in the range of about 15 to 200 centipoise measured at 25°C. When the resin solution of the present invention is blended into a floor polishing composition, it provides extremely excellent smoothness. The floor polishing composition of the present invention is a water-based type, and about 1
~3% by weight of the resin solution, preferably in an amount sufficient to provide 1.4-2.9% by weight of dissolved resin;
about 7 to 12% by weight, preferably an emulsion or solution of a metallized acrylic and/or methacrylic polymer or copolymer in an amount sufficient to provide a concentration of 10 to 11.5% by weight of the polymer; about 0% by weight of auxiliary agents from the group consisting of antifoaming agents, antifoaming agents, organic solvents and/or organic bases.
It can be described as an aqueous medium containing about 1 to 5% by weight. As shown in Examples 14, 15, 16, 19 and 20, the floor polishing compositions of the present invention also preferably incorporate emulsions of natural waxes such as carnauba wax and/or various known polyethylene wax compositions. include. The wax emulsion is incorporated in an amount sufficient to provide 1 to 7% by weight of the floor polishing composition. The metallized acrylic polymers incorporated into the floor polishing composition are known organic film-forming agents containing heavy metals such as zinc, zirconium, cadmium, copper or nickel crosslinked and/or complexed to the acrylic polymer. Metallized polymers are available in the form of aqueous emulsions or solutions. In order to prepare the floor polishing composition of the present invention in the form of a transparent liquid, a suitable metallized acrylic and/or methacrylic polymer or coat, without the addition of a wax emulsion, as shown in Example 13, is used. Polymers can be used. Other useful metallized acrylic copolymers include Rholex B832; Utabol DW−3036 and DW
−855 (Staley Chemical Division of AE
Staley Mfg.Co.); NH-425 Letex (Morton
Chemical Company, a division of Morton
Norwich Products, Inc.); and Richamer R
−747 (Organic Chemicals Division of the
Richardson Company). There is. Auxiliary agents include, for example, trialkyl phosphate plasticizers such as tributoxyethyl phosphate, surfactants such as octylphenyl polyethoxyethanol, organic bases such as morpholine, alcohols (other than the alcohol added to the resin solution) such as diethylene glycol. These include organic solvents such as monoethyl ether, and antifoaming agents such as known silicone compositions (one of which was used in Example 20). The components of the floor polishing composition are mixed according to mixing methods known for floor polishing agents. Example 13
16 and 18-20, particularly desirable properties of the floor polishing composition can be improved by varying the known waxes and metallized acrylic polymers. For example, resistance to water droplet spreading can be improved, and buffing after polishing can be simplified to eliminate the effects of heavy foot traffic. The novel resin cuts of the present invention, when incorporated into the floor polishing composition according to the present invention, provide very good gloss. The floor polishing composition obtained from substantially colorless resin cuts according to the invention provides a finish that exhibits excellent resistance to yellowing, even after prolonged exposure to air and when applied in multiple layers. . In the examples below, parts and percentages are by weight and temperatures are by °C unless otherwise noted. Note that this example is for explaining the present invention and is not intended to limit it. Example 1

[Table] The decyl alcohol and diol described above are mixed in a resin can and the resulting liquid solvent mixture is heated to about 149°C. Over a period of about 90 minutes, a mixture of methacrylic acid, methyl methacrylate, styrene and benzoyl peroxide is added to a stirred solvent maintained at about 149°C. After the addition is complete, the polymerization mixture is heated to approximately 205°C and held at this temperature for 15 minutes. The reactants are removed from the resin can and allowed to cool to ambient temperature. The product is
It is a hard, transparent, glassy solid with a ring and ball melting point of 138.5°C and an acid number of 162.3, determined by potassium hydroxide titration in acetone. The milliequivalent number of carboxyl groups per gram of resin is 2.893. Part B The alcohol-containing product was ground to a particle size fine enough to pass through a 10 mesh sieve (US sieve series). The resulting powder product is stirred at ambient temperature in 81 parts of water and 4 parts of 28% aqueous ammonia are added. Heat the mixture to 66° C. with stirring and hold at that mixing temperature for 10 minutes. The resulting aqueous product, in which about 15% of Product A is dissolved, is a clear, colorless, viscous liquid with a pH of about 9.2. In Examples 2-12, a hard glassy resin similar to the product of Example 1A was made using a method substantially identical to that of Example 1A. By a method similar to that of Example 1B, the product resin was ground and dissolved in aqueous ammonia to form a clear, virtually colorless solution with a viscosity ranging from 15 to 200 centipoise at 25°C. Example 2

[Table] The ring and ball melting point of the polymerization product is approximately 116°C. The acid value and milliequivalent number of carboxyl groups per gram of resin are 160.7 and 2.864, respectively. Example 3

【table】 Example 4

【table】

【table】 Example 5

[Table] The ring and ball melting points of transparent hard glassy polymerization products are
The temperature is 125℃. Example 6

【table】 Example 7

【table】 Example 8

【table】 Example 9

【table】 Example 10

【table】 Example 11

【table】 Example 12

[Table] Examples 13-16 are resin cuts of Example 1B.
The preparation of a floor polishing composition using a 15% resin aqueous solution will be described. Example 13 parts Resin cut of Example 1B 20.0 Rohm and diluted to 15% concentration by addition of water
(Rhoplex B-505) from Haas, a base-soluble zinc-crosslinked acrylic copolymer.
% aqueous solution 80.0 (Ucar 2LM from Union Carbide) dipropylene glycol monomethyl ether 2.0 deethylene glycol monomethyl ether 1.0 tributoxyethyl phosphate 1.0 (FC-128 from 3M) 1% aqueous fluorocarbon surfactant 0.5 at ambient temperature Add the ingredients in the above order to the stirred resin cut. The PH of the product mixture is adjusted to 9.1 by addition of ammonia and the product is stirred for 30 minutes. Further ammonia is added to readjust the PH of the product to 9.1 to obtain a clear, substantially colorless floor polishing composition. If you apply this to the floor, you will get a durable, glossy film. The applied brighteners are also characterized by excellent resistance to yellowing, even after multiple coatings and after prolonged exposure to air. Example 14 parts Resin cut of Example 1B 10.0 38% aqueous alkali soluble acrylate polymer crosslinked with metal (Richamer R-747 from Richardson) diluted to 15% concentration by addition of water Emulsion 80.0 15% aqueous anionic synthetic organic wax emulsion 10.0 Tributoxyethyl phosphate 1.0 1% aqueous fluorocarbon surfactant (FC-128 manufactured by 3M) 0.5 37% aqueous formaldehyde (formalin) 0.15 Tux emulsion is a styrene-organic copolymer wax (A-C) containing 84.0 parts.
Copolymer.Allied Chemical) and 14.0 parts of refined tall oil aliphatic (Acintol FA-3, Arizona
Chemical) and heated to 127°C.
A solution of 1.7 parts of flaked potassium hydroxide gently warmed in 3.4 parts of ethylene glycol was added to the resulting wax melt. Generated wax
After stirring the hydroxide mixture at 125°C for 5 minutes,
14.0 parts of morpholine are added and the product is stirred for an additional 5 minutes at 125°C. The heated wax melt is then gradually charged into the stirred water at about 95-99°C. Once the addition is complete, the mixture is rapidly cooled to ambient temperature. The resin cut is added to the metal crosslinked aqueous polymer with thorough stirring. After the addition is complete, the aqueous wax emulsion is added to the product mixture with stirring. Stirring and mixing the above ether, phosphate, surfactant and formaldehyde,
Add to the mixture of resin cut, metal crosslinked polymer and wax emulsion. The product is stirred for 30 minutes to produce floor polishing material. When applied to floors, this product yields a tough, bright, glossy film that is very pale (virtually colorless) and has excellent resistance to water droplets, yet is easily removed with ammonia. can. Example 15 parts Resin cut of Example 1B 10.0 Diluted to 15% by addition of water (Polyvinyl
Neocryl SR−270 manufactured by Chemical Industries)
40% aqueous acrylic polymer emulsion cross-linked with a metal of 70.0 diluted to 15% by addition of water (Cosden Oil
40% is Poly-Em 40) manufactured by
Aqueous nonionic polyethylene wax emulsion 20.0 Diethylene glycol monoethyl ether 2.5 Tributoxyethyl phosphate 1.0 1% aqueous fluorocarbon surfactant (FC-170 manufactured by 3M) 0.5 Add the resin cut to the above polymer emulsion while stirring. Added. The above wax emulsion,
The glycol ether, phosphate, and surfactant are mixed and incorporated into the resulting mixture of resin cut and polymer emulsion by stirring. This is then stirred for a further 30 minutes at ambient temperature. The floor polish produces a brilliant gloss finish that is particularly resistant to heavy traffic, does not yellow and is easily removed when necessary. Example 16 parts Resin cut of Example 1B 10.0 Diluted to 15% by addition of water (Morton
A 40% aqueous acrylic polymer emulsion cross-linked with a metal (NH-425 Latex) manufactured by Chemical.
80.0 15% aqueous anionic synthetic organic wax emulsion of Example 14 10.0 Diethylene glycol monoethyl ether 2.5 Tributoxyethyl phosphate 1.0 Octylphenyl polyethoxyethanol nonionic emulsifier with 40 ethylene oxide residues for the octylphenyl moiety (Rohm and Haas
1% aqueous fluorocarbon surfactant (Triton
The remaining ingredients are mixed and incorporated into the resin cut and polymer emulsion mixture with stirring. After stirring the product for 30 minutes, the PH of the mixture was brought to PH8.0-8.3 by addition of aqueous ammonia. A floor polishing composition is obtained which provides a high gloss floor finish characterized by excellent resistance to traffic, resistance to water droplet spreading and recoatability. Examples 17-18 now illustrate the preparation of aqueous resin cuts containing polymerized products at a greater concentration than the product of Example 1B. Example 17 The procedure of Example 1B was repeated substantially as described except that the amount of water added to the ground alcoholic solvent-containing resin was 71.5 parts. A clear, virtually colorless 17% aqueous solution of the resin is obtained. Example 18 The procedure of Example 1B was repeated substantially as described except that the amount of water added to the resin containing the ground alcoholic solvent was 67.5 parts. A clear and virtually colorless 18% resin aqueous solution is obtained. Examples 19-20 are Example 17 as water-based resin cuts
and 18 products, respectively. Example 19 parts 38% aqueous metal-complexed acrylic copolymer emulsion (DW-855, manufactured by Staley Chemical) Diluted to 17% by adding water 25.0 38% aqueous metal-complexed all-acrylic copolymer emulsion (Ubatol- 3036, manufactured by Staley Chemical Co.) Diluted to 17% by adding water 40.0 Resin cut of Example 17 12.5 17% aqueous anionic synthetic organic wax emulsion 22.5 Diethylene glycol monoethyl ether 2.0 Tributoxyethyl phosphate 1.0 N- Methyl-2-pyrrolidone 0.5 1% aqueous fluorocarbon surfactant (FC-
123, manufactured by 3M) 0.5 The above wax emulsion is a highly viscous emulsifying polyethylene wax (Epolene F-10,
Eastman Chemical Product) 30.0 parts, low melt viscosity low molecular weight emulsifying polyethylene wax (Epolen E-14, Eastman Chemical Product) 10.0 parts, refined tall oil fatty acid (Acentol)
It is obtained by heating a mixture with 7.0 parts of FA-3 (manufactured by Arizona Chemical) to 125°C, stirring the mixture, and adding 7.0 parts of morpholine thereto. The product is stirred at 125°C for 5 minutes and slowly added to stirred water at 95-99°C. The resulting mixture is then rapidly cooled to room temperature. Combine the ingredients in the order listed in the table above with thorough stirring. Stirring the resulting mixture for 30 minutes yields a floor polishing composition that, upon application, dries to a clear, shiny, durable finish, exhibits excellent resistance to water droplet spreading, and eliminates the effects of heavy traffic. It can be polished to a shine. Example 20 parts Resin cut of Example 18 15.0 40% aqueous modified acrylic metal crosslinked polymer emulsion (Rhoplex B-832, manufactured by Rohm and Hass) Diluted to 18% with water 45.0 40% aqueous anionic polyethylene wax Emulsion (Poly-Em20, Cosden Oil and
Chemical) diluted to 18% with water 40.0 Diethylene glycol monoethyl ether 3.0 Tributoxyethyl phosphate 1.0 1% aqueous fluorocarbon surfactant (FC-
128, manufactured by 3M) 0.5 1% aqueous silicone antifoam emulsion (SWS-
1211, Stauffer−Wacker Silicon Corporation
0.2 37% aqueous formaldehyde (formalin) 0.15 The above aqueous resin cut and polymer emulsion were mixed, and the resulting mixture was added to the wax emulsion. The remaining ingredients were mixed and added to the wax-resin cut-polymer mixture with stirring.
After stirring the resulting mixture for 30 minutes, a floor polishing composition was obtained. This forms a clear finish on the floor, which is polished to a very deep, high gloss and has a strong resistance to the spread of water droplets. Although the superior transparent resin of the present invention contains at least one water-insoluble alcohol and at least one water-soluble alcohol, a transparent gloss is nevertheless obtained, which also applies to the modified method of the working example above. It can be made even if it is twisted. Regarding Examples 11-12, in each example the diol or ether was 1.3
- Substitution with propanediol, 1,4-butylene glycol, diethylene glycol, 2,2,4-trimethyl-1,3-pentanediol, and triethylene glycol is possible and does not adversely affect resin properties. Similarly, n-decyl alcohol is the preferred intermediate or higher primary monohydric aliphatic alcohol, but other insoluble alcohols may also be used.
-ethylhexanol, n-nonyl alcohol,
It includes n-dodecyl alcohol, isodecanol, and 2,6,8-trimethyl-nonyl-4-alcohol and can be used alone or in combination without any adverse effects. Similarly, useful products result when the proportions of water-soluble alcohols, water-insoluble alcohols, and other types of water-soluble alcohols are varied within the ranges indicated herein. Although it is highly desirable to utilize water-soluble alcohols in practice, in some cases the compositions of the examples may be made solely from water-insoluble alcohols. Similarly, although preferred monomers have been mentioned, carboxyl-free monomers of the invention are substituted by fumarate and itaconate esters such as diethyl fumarate and dimethyl itaconate, acrylonitrile and n-vinylpyrrolidone in the examples. The carboxyl-containing or carboxyl-substituted monomer can be acrylic acid, methacrylic acid or other corresponding ethylenically unsaturated acid and the resulting resin is satisfactory. The initiators of the examples shown herein may be substituted with other organic peroxides without deleterious effects on satisfactory resin production. Such free radical generators include p-triloyl peroxide, t-butyl peroctate, t-butyl perbenzoate, and azo-
Bis-isobutyronitrile can also be used. The base used to solubilize the resin as part B of the examples can be converted to sodium hydroxide solution, potassium hydroxide solution or amine-containing compounds as described in the specification to yield good water-soluble products.
Useful resins are produced when the proportions of the various components are varied within the ranges indicated in the specification. Similarly, different resins and different auxiliary agents than those mentioned in the formulation of the polishing agents of the working examples may be utilized, or various components of the working examples may be replaced and the formulations shown in the specification It can be varied by using a percentage range. The resulting product forms a good coating composition, especially a light-colored floor polish that is resistant to water droplet spreading and can be easily removed with ammonia. Instead of being used in floor polishes, the above-mentioned resins can be used in place of conventional resins in printing inks, adhesives, paints, varnishes, and a variety of other coating compositions, and in such applications, the surfaces to be applied. It has been found to be particularly good at promoting the binding of other composition ingredients to. Although the invention has been described with respect to specific examples and illustrations thereof, it is not limited thereto. Those skilled in the art may utilize equivalents and substitutions herein while still remaining within the concept and scope of the invention.

Claims (1)

[Scope of Claims] 1. An aqueous coating composition comprising an acidic resin dissolved in an aqueous base, a metallized acrylic polymer or copolymer, and optionally other known components, wherein the acidic resin contains (A) carboxyl. (B) About 15-60 mol% of at least one polymerizable ethylenically unsaturated monomer substituted with carboxyl; (C) Organic Free radical generating polymerization initiator approx. 0.3~
1.0 mol% (D) An alcohol mixture 3 to 3 containing approximately 10 to 90% by weight of one or more water-insoluble liquid alcohols and approximately 10 to 90% by weight of one or more water-soluble alcohols with a standard boiling point higher than approximately 175°C. It is obtained by polymerization in the presence of 20 mol%, has an average molecular weight of 600 to 4000, and an acid value of 60 to 4000.
250, and the amount thereof is 1 to 3% by weight based on the weight of the composition. 2. Claim 1, wherein the component (D) is an alcohol mixture containing 30 to 60% by weight of one or more water-insoluble alcohols and 40 to 70% by weight of one or more water-soluble alcohols. The water-based paint composition described in Section. 3. Claim 1, wherein the component (D) is an alcohol mixture containing 40 to 55% by weight of one or more water-insoluble alcohols and 45 to 60% by weight of one or more water-soluble alcohols. The water-based coating composition according to item 1 or 2. 4. An alcohol mixture with a normal boiling point of 205°C or higher, in which the component (D) is present in an amount of 10 to 20%,
The aqueous coating composition according to any one of claims 1 to 3, which is selected from the group consisting of monohydric alcohols, diols, and triols. 5 A saturated aliphatic primary monohydric alcohol having 8 to 12 carbon atoms, in which one or more aliphatic diols having 4 to 8 carbon atoms, optionally containing ether-oxygen, are present as water-soluble alcohols. The aqueous coating composition according to any one of claims 1 to 4, wherein the water-insoluble alcohol is present as a water-insoluble alcohol. 6 Any one of claims 1 to 5, wherein 2,2,4-trimethyl-1,3-pentanediol is a water-soluble alcohol and n-decyl alcohol is a water-insoluble alcohol. The water-based paint composition described in . 7 The component (A) is a mixture obtained by mixing styrene and one or more lower alkyl esters of acrylic acid or methacrylic acid at a molar ratio of 1.6:1 to 3:1, and the component (B) is acrylic acid or methacrylic acid, and the ratio of carboxyl-free monomer to carboxyl-substituted monomer is 1.2:
1 to 2.7:1, the aqueous coating composition according to any one of claims 1 to 6. 8 The acid value is between 120 and 185, and the average molecular weight is between 120 and 185.
900 to 2500, the aqueous coating composition according to any one of claims 1 to 7.