JPH05439B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to cleaning compositions containing specific amphoteric polymers. More specifically, a cleaning composition that has significantly improved cleaning performance by containing a specific amphoteric polymer obtained by copolymerizing a cationic vinyl monomer, an anionic vinyl monomer, and a nonionic vinyl monomer. Regarding. Traditionally, polymers have been used as additives in detergent systems for a variety of purposes. For example, systems added to detergents as thickeners, stabilizers, protective colloids, builders, softeners, encapsulating agents, clouding agents, pearling agents, skin and hair protectants, etc. are known. However, these methods have merely utilized properties that have been generally recognized as properties of polymers. However, as the present inventors investigated new applications of polymers in detergent systems, they surprisingly found that certain polymers, especially in coexistence with surfactants, can improve the cleaning performance of detergent compositions. The present invention was completed based on the discovery of a fact that can significantly improve the above. That is, the present invention is a detergent composition in which a specific amphoteric polymer obtained by copolymerization of a cationic vinyl monomer, an anionic vinyl monomer, and a nonionic vinyl monomer is contained in a cleaning composition. In view of this, the effects of the amphoteric polymer in the present invention are completely different from the effects of conventionally known polymeric surfactants that are not directly related to cleaning, such as dispersion effects. That is, the amphoteric copolymer used in the present invention consists of cationic vinyl monomer units, anionic vinyl monomer units, and nonionic vinyl monomer units, and contains at least 10 mol% of cationic vinyl monomer units and at least 10 mol% of anionic vinyl monomer units. It is an amphoteric copolymer containing at least 10 mol% or more and at least 10 mol% or more of nonionic vinyl monomer units. The amphoteric polymer according to the present invention can be obtained by copolymerizing a cationic vinyl monomer, an anionic vinyl monomer, and a nonionic vinyl monomer. These amphoteric polymers can be produced by known methods. That is, water or a lower alcohol is generally used as a solvent, and as an initiator, potassium peroxodisulfate, potassium peroxodisulfate-sodium bisulfite, hydrogen peroxide-
Fe ²⁺ series, adobis isobutyronitrile, etc. can be used. The obtained copolymer is used as it is or after being purified. Purification methods include dialysis and reprecipitation. The copolymerizable amphoteric polymer of the present invention consists of a cationic vinyl monomer structural unit, an anionic vinyl monomer structural unit, and a nonionic vinyl monomer structural unit, and each structural unit contains at least 10 mol% of each structural unit.
An amphoteric polymer having a molecular weight of 1,000 to 3,000,000, which contains anionic vinyl monomer units and cationic vinyl monomer units in a molar ratio of 1/2 to 2/1, wherein the cationic vinyl monomer and the anionic vinyl monomer unit are The ratio of total to nonionic vinyl monomer is 90/10 to 20/80 (mole ratio)
It is preferable that The above-mentioned polymer used in the present invention can be prepared, for example, by preparing a mixture of the above-mentioned anionic vinyl monomer, cationic vinyl monomer, and nonionic vinyl monomer at a predetermined ratio in a solvent such as water or a lower alcohol using a polymerization initiator, usually under a nitrogen stream. Obtained by polymerization. The polymerization temperature is generally room temperature to 90°C, and the reaction is carried out for 2 to 24 hours, preferably to obtain a copolymer having a molecular weight of 3,000 to 1,000,000. The obtained polymer can also be made into a salt by reacting with an alkali metal hydroxide, ammonia, or an alkanolamine. As the anionic monomer to be used, all anionic monomers having a polymerizable unsaturated group can be used. For example, acrylic acid, methacrylic acid, itaconic acid, aconitic acid, hydroxyacrylic acid, maleic anhydride, fumaric acid, vinylsulfonic acid, allylsulfonic acid, methalylsulfonic acid, styrenesulfonic acid, 2-acrylamide-2methylpropanesulfone Examples include acids. The cationic monomer to be used may also be one having a polymerizable unsaturated group, such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dipropylaminoethyl methacrylate, dimethylamino Examples thereof include propylmethacrylamide, allyldimethylamine, allyldiethylamine, allyldipropylamine, methalyldimethylamine, methalyldiethylamine, methalyldipropylamine, and quaternized products thereof such as methyl, ethyl, or propylated products. As the nonionic monomer to be used, all nonionic monomers having a polymerizable unsaturated group can be used. For example, acrylic acid alkyl esters such as methyl, ethyl and butyl acrylate, methacrylic acid alkyl esters such as methyl methacrylate, ethyl and lauryl, acrylic acid and methacrylic acid such as hydroxyethyl esters of acrylic acid and methacrylic acid. Examples include hydroxyalkyl esters, vinyl alcohol fatty acid esters such as vinyl acetate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, vinylpyrrolidone, itaconic acid esters, aconitic acid esters, maleic anhydride esters, fumaric acid esters, and the like. Two or more types of each of the above cationic monomers, anionic monomers, and nonionic monomers can be selected. The cleaning composition of the present invention generally contains 0.01 to 10% by weight, preferably 0.05 to 5% by weight of the amphoteric polymer. In addition, the cleaning composition contains a surfactant as a cleaning component, and the surfactants that can be used in the present invention include ordinary anionic, nonionic, cationic, and amphoteric surfactants. Used according to purpose. Such surfactants include alkyl sulfates, alkylbenzene sulfonates, alkyl polyoxyethylene sulfates, alphaolefin sulfonates, alkanesulfonates, alkyl glyceryl ether sulfonates, alkyl or alkenyl carboxylates, and alkenyl succinic acids. Anionic surfactants such as salts, N-acyl sarcosinates, salts of alkyl polyoxyethylene carboxymethylates, alkyl phosphate ester salts, fatty acid diethanolamides, dimethylalkylamine oxides, alkyl polyoxyethylenes, alkylaryl polys Nonionic surfactants such as oxyethylene, alkyltrimethylammonium salts, dialkyldimethylammonium salts,
Examples include cationic surfactants such as alkyl-(N-hydroxyethyl)dimethylammonium salts, amphoteric surfactants such as alkylimidazole derivatives, dimethylalkylbetaine, and dimethylalkylsulfobetaine, but the amphoteric polymer according to the present invention These surfactants are used in an amount of 0.02 to 50% by weight, preferably 0.25 to 25% by weight. An appropriate amount of surfactant can be used depending on the intended use of the cleaning agent, and surfactant may not be used in carrying out the present invention. Other components of the cleaning composition of the present invention include monoalcohols, dialcohols, glycerin,
Solvents such as ethylene glycol monobutyl ether and diethylene glycol monomethyl ether, hydrotropes such as benzene sulfonate, para-toluene sulfonate, metaxylene sulfonate, urea, chelating agents, preservatives, pigments, fragrances,
Ultraviolet absorbers, oxidation stabilizers, clouding agents, thickeners, etc. are used. The detergent composition of the present invention is generally in the form of a liquid detergent by adding water, but it can also be made into a solid detergent. The cleaning composition of the present invention can be applied to metals, machines, ships,
It can be used as a cleaning agent and shampoo base material for textiles, glassware, food, tableware, textiles, household goods, etc. The performance required of such cleaning agents is cleaning power, foam increasing ability, rinsing ability (foaming ability, hand feel, etc.)
However, in the present invention, as the amount of amphoteric polymer added increases, performance such as detergency improves significantly. However, if it is added in too large a quantity, it may have a negative effect on the physical properties of the product such as stability and viscosity. The present invention will be described below with reference to synthesis examples and examples of amphoteric polymers, but the present invention is not limited thereto. Synthesis Examples 1 to 5 300 g of ethanol was placed in a flask equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube, and a thermometer.
156 g of dimethylaminoethyl methacrylate, 72 g of acrylic acid, and 100 g of methyl methacrylate were charged, and after purging the system with nitrogen for 30 minutes at room temperature while stirring, 2.5 g of azobisisobutyronitrile dissolved in 20 g of ethanol was added. The system was heated to 78°C and reacted for an additional 10 hours. The reaction mixture is then cooled to room temperature, poured into about 3 ml of acetone, and the precipitated polymer is filtered off. Weight after vacuum drying is 321
g, and the polymerization yield was 98%. In exactly the same manner as in Synthesis Example 1 above, cationic monomers, anionic monomers, and nonionic monomers shown in Table 1 below were copolymerized in the charged mole numbers shown in the table.

【table】

[Table] Examples in which the polymers of Synthesis Examples 1 to 5 shown in Table 1 were used in detergent compositions are shown below.The test methods for various performances of the detergents in the experimental compositions are as follows. be. <Test method> (a) Cleaning power Sudan (red pigment) is added to beef tallow as an indicator.
Add 0.1% and place 5g of this in a magnetic dish (25cm diameter).
The number of dishes that have been cleaned is shown as the number of dishes that have been cleaned until the beef tallow can no longer be removed by scrubbing with a sponge soaked with 10g of detergent and 20g of water. (b) Foaming power Commercially available butter is used as a stain ingredient at a detergent concentration of 0.5.
Measure the foaming power when 0.1% is added to a % detergent solution. The measurement method is to place 40 cc of the above detergent solution to which butter has been added into a glass cylinder with a diameter of 5 cm, rotate and stir for 10 minutes, and measure the foam height immediately after stopping. (c) Water repellency After thoroughly washing a commercially available 200ml glass bottle with a cleanser, etc., and making sure that it does not repel water,
Rinse with deionized water and dry. Pour 150 ml of a 1% aqueous solution into this pot, rotate and stir for 30 minutes, and then drain the aqueous solution. Next, pour 200ml of tap water into the pot, let it stand for 30 seconds, then drain the water. This is 3
Repeat several times. Observe the water repellency when water is poured for the fourth time and the finished state of the pot after leaving it for one day. (d) Rinse 100c.c. of detergent concentration 0.25% (temperature 20℃) aqueous solution.
Pour into a 500c.c. separating funnel and shake a certain number of times. Pour out the liquid and measure the amount of foam. Next, pour in 50 c.c. of rinsing water (temperature 20°C) and slowly rotate the separating funnel 10 times. Repeat this and find the number of times until the bubbles disappear and use it as the number of rinses. Example 1 A liquid detergent was prepared with a balanced composition of linear alkylbenzene sulfonate 20wt% coconut fatty acid diethanolamide 5 polymer 1 water and its detergency, foaming power, and rinsability were measured. The results are shown in Table 2.

【table】 Example 2

[Formula] 5wt% Polymer 0.5 Ethanol 2 Water A liquid detergent was made with a balanced composition and a water repellency test was conducted. The results are shown in Table 3.

[Table] Example 3 <Test method for foam palatability> Comparison of foam palatability of two types of detergent compositions A and B when washed by 30 women using a method similar to the detergency test method. investigated by law. Evaluation method +2 I like A +1 I like A very much 0 I can't say either -1 I like B The composition of the cleaning composition of the present invention (A) is as follows, and the comparison cleaning composition (B) This formulation contained no polymer. Alkyl ether sulfate 20wt% Coconut fatty acid diethanolamide 5 Ethanol 5 Polymer 0.3 Water Balance The test results are shown in Table 4.

【table】

Claims (1)

[Scope of Claims] 1 Consisting of cationic vinyl monomer units, anionic vinyl monomer units, and nonionic vinyl monomer units, with at least 10 mol% or more of cationic vinyl monomer units and at least 10 mol% or more of anionic vinyl monomer units. , and at least 10 mol% nonionic vinyl monomer units
A cleaning composition characterized by containing an amphoteric copolymer containing the above. 2 The molar ratio of cationic vinyl monomer units and anionic vinyl monomer units is 1:2 to 2:1.
The cleaning composition according to claim 1, wherein the molar ratio of the total of cationic vinyl monomer units and anionic monomer units to nonionic vinyl monomer units is from 90:10 to 20:80. 3. The cleaning composition according to claim 1, which contains one or more surfactants as a cleaning component.