JPH0321698A - Polyelectrolyte builder and detergent composition - Google Patents

Abstract

PURPOSE:To obtain the subject builder, composed of a sulfonated aromatic vinyl polymer (salt), excellent in ability to prevent redeposition on cloth fouled with oil, having high detergent ratio, safe even in water quality conservation and substitutive for phosphates. CONSTITUTION:The objective builder composed of a sulfonated aromatic vinyl polymer and/or salt thereof composed of a copolymer consisting essentially of preferably an aromatic vinyl monomer and an ethylenically unsaturated monomer having carboxylic acid (anhydride) group and/or hydroxyl group. Furthermore, sulfuric anhydride is preferred as a sulfonating agent and sulfonating reaction is normally carried out at 0-80 deg.C (preferably at 10-50 deg.C) under anhydrous conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to polyelectrolyte builders and detergent compositions. [Prior art] Conventionally, phosphates, particularly tripolyphosphates, have been widely used as polymer electrolyte builders, but due to water quality issues, Since it has the disadvantage of eutrophication, polyelectrolyte pilders have been studied to replace phosphates. As a builder to replace phosphate, a polymer builder consisting of sodium styrene sulfonate alone or a copolymer with methacrylic acid is known (for example, JP-A No. 11i2-108997).

[Problems to be Solved by the Invention] However, the conventional polymer builders described above do not have sufficient ability to prevent oil stains from re-adhering to cloth, and do not meet all the requirements of cleaning power comparable to that of phosphoric acid builders. It was not a contentious struggle.

[Means for Solving the Problems] The present inventors have conducted intensive studies on a polymer builder that has sufficient ability to prevent oil stains from re-adhering to cloth and has a cleaning power comparable to or greater than that of phosphoric acid builders. As a result, we have arrived at the present invention.

That is, the present invention is a detergent composition comprising a polymer electrolyte builder comprising a sulfonated aromatic vinyl polymer and/or a salt thereof, and the polymer builder and surfactant according to claim 1 or 2.

The aromatic vinyl monomer in the present invention includes styrene,
Examples include alkyl group-substituted styrene (α-methylstyrene, p-methylstyrene, vinyltoluene, etc.), vinylnaphthalene, and the like. Preferred is styrene.

Monomers copolymerized with aromatic vinyl monomers include carboxylic acid group-containing ethylenically unsaturated monomers [unsaturated monocarboxylic acids (acrylic acid, methacrylic acid, etc.), unsaturated dicarboxylic acids (maleic acid, fumaric acid and itaconic acid), acid anhydrides of the unsaturated mono- or dicarboxylic acids (maleic anhydride, itaconic anhydride, etc.)], hydroxyl group-containing ethylenically unsaturated monomers {hydroxy lower alkyl (meth)acrylates [ Hydroxyethyl (meth)acrylate, hydroxyprobyl (meth)acrylate, etc., polyethylene glycol (meth)acrylate [triethylene glycol (meth)acrylate, etc.], unsaturated alcohol [(meth)allyl alcohol, etc.], ( Meth)acrylic acid alkyl ester [methyl (meth)acrylate, ethyl (meth)acrylate,
Butyl (meth)acrylate, (meth)acrylic acid-2
- Ethylhexyl, (meth)stearyl acrylate, etc., fatty acid vinyl [vinyl acetate, vinyl blobionate, etc.], aromatic hydrocarbon vinyl monomers [p-methylstyrene, etc., (chlorinated) olefins [α-olefin] , isoprene, imbutylene, diisobutylene, butadiene, chloroprene, etc.], nitrile group-containing vinyl monomers [(meth)acrylonitrile, etc.].

Preferred among these are ethylenically unsaturated monomers having carboxylic acid (acid anhydride) groups and/or hydroxyl groups.

The styrene content of the styrene copolymer is 30 mol%
The above amount is preferably 50 mol% or more.

The sulfonated product can be produced using a conventional sulfonating agent in a solvent by a known method. As the solvent, those inert to the sulfonating agent are usually used, such as aliphatic hydrocarbons having 1 to 2 carbon atoms and nitrated aliphatic hydrocarbons having 1 to 3 carbon atoms.

Specific examples of aliphatic halogenated hydrocarbons include 1.2-
Dichloroethane, methylene dichloride, ethyl chloride, carbon tetrachloride, t,i-dichloroethane, l. ! ,2,2-
Examples include tetrachloroethane, chloroform, and ethylene dibromide. As nitrated aliphatic hydrocarbons,
Nitromethane, nitroethane, l-nitropropane, 2
, 12 Troprono{annato b4. Preferred are aliphatic/X-logenated hydrocarbons.

Dissolution of the aromatic vinyl polymer depends on the molecular weight of the polymer, but the aromatic vinyl polymer is usually dissolved in 1 to 100 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the solvent.

As the sulfonating agent, sulfuric anhydride, Chronoresulfuric acid, etc. are used. Preferred is sulfuric anhydride.

Liquid sulfuric anhydride, liquid sulfuric anhydride with nitrogen, inert gas such as dry air, and 1,2-dichloroethane, salt {? ．． Sulfuric anhydride diluted with an inert solvent to a sulfonating agent such as an aliphatic halogenated hydrocarbon having 1 to 2 carbon atoms such as ethyl can also be used. The concentration of anhydrous sulfuric acid diluted with an inert gas is usually 1 to 15% by volume, preferably 3 to 5% by volume. The concentration of sulfuric anhydride diluted with an inert solvent is usually 1 to 50% by weight, preferably 5 to 20% by weight.

Moreover, a complex of sulfuric anhydride and Lewis base can also be used. Examples of the Lewis base include trialkyl phosphates such as triethyl phosphate and trimethyl phosphate, fatty acid alkyl esters such as ethyl acetate and ethyl nolumitate, and ethers or thioethers such as dioxane, thioxane and diethyl ether. Preferred Lewis bases are trialkyl phosphates and fatty acid alkyl esters.

The amount of the sulfonating agent used is usually 0.4 to 2 monooles per mole of aromatic ring units in the aromatic vinyl polymer.

The sulfonation reaction is usually carried out at 0 to 80°C, preferably at 1
It is carried out at 0-50°C and in anhydrous conditions.

The sulfonate is neutralized with Tong'er's neutralizing agent.

The solvent is removed by a conventional method such as separation, filtration, or distillation to obtain a water-dispersible or water-soluble aqueous liquid or powder sulfonated aromatic vinyl polymer or a salt thereof.

Patent application No. 1-1 for which the present applicant has applied for a patent for a method other than the above-mentioned method.
Sulfonation can also be carried out by the methods described in Japanese Patent Application No. 81189, Japanese Patent Application No. 1-114593, and Japanese Patent Application No. 1-117832.

Among the above sulfonate salts, the salts include sodium salt,
Examples include alkali metal salts such as potassium salts and lithium salts, alkaline earth metal salts such as calcium salts and magnesium salts, and amine salts such as ethanolamine salts and triethanolamine salts. Preferred are sodium, potassium, lithium, calcium, and magnesium salts. Two or more of these may be used in combination.

In the case of combined salts, one having two or more types of salts in one molecule of the copolymer is preferable, but a mixture of two or more types of salts may be used.

The polymer electrolyte builder of the present invention is used as a builder for detergents.

The detergent composition of the present invention comprises the polyelectrolyte builder of the present invention (
A) and a surfactant (B).

As the surfactant (B), anionic surfactants (alkylbenzene sulfonate, α-olefin sulfonate, alkanesulfonate, alkyl sulfate ester salt,
Nonionic surfactants (polyethylene glycol alkyl ether, polyethylene glycol alkyl phenyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyethylene glycol sorbitan fatty acid ester, Coconut oil fatty acid diethanolamide)
; Cationic surfactants (alkyltrimethylammonium chloride, dialkynoredimethylammonium chloride, etc.); Ampholytic surfactants (alkyldimethylaminoacetic acid betaine, etc.).

Other builders (sodium tripolyphosphate, sodium metasilicate, sodium aluminosilicate, nitrilotriacetate, citrate, laurate, triethanolamine hydrochloride, etc.); inorganic compounds (monite, urea, etc.); alkalis (Caustic soda, soda carbonate, sodium silicate, triethanolamine, etc.): Acids (hydrochloric acid, citric acid, etc.); Solvents (ethanol, isopropyl alcohol, butyl alcohol, ethylene glycol, etc.); Water;
Oxidizing agents (hydrogen peroxide, sodium percarbonate, etc.); Reducing agents (sodium bisulfite, etc.); Chelating agents (ethylenediaminetetraacetate, etc.); Anti-recontamination agents (carboxymethylcellulose, etc.); Abrasives (talc, finely powdered silica, etc.) Components such as clouding agents; perfumes; colorants; preservatives; foaming agents; foam stabilizers; polishing agents; enzymes; fluorescent dyes; hydrotope agents, etc.) can be blended.

In the detergent composition of the present invention, the polymer builder of the present invention (
The amount of A) is usually 0.05 based on the weight of the detergent composition.
-50%, preferably 1-15%. If the amount of (A) is less than this range, the ability to soften hard water and the ability to prevent recontamination will be insufficient, resulting in a decrease in detergency.

Moreover, exceeding the upper limit is uneconomical. In addition, surfactant (B
) is usually 3-60% based on the weight of the detergent composition.
, preferably 1O~40%, and the amount of other components is usually 30%
~90%, preferably 50-70%.

The detergent composition of the present invention can be prepared in the form of solid, powder, liquid, paste, slurry, etc. by a conventional method.

The method of using the detergent composition of the present invention is not particularly limited, and it is usually diluted with water to about 100 to ,000 times.

The composition of the present invention can be preferably used as a detergent composition for textile products. Textile products include natural fibers such as cotton, wool, and silk, recycled fibers such as cotton and rayon, semi-synthetic fibers such as acetate, synthetic fibers such as nylon, acrinole, polyester, and polypropylene, and various fibers that are a mixture of these fibers. These include textile products such as knitted and woven fabrics, especially household textile products (underwear, diapers, lingerie, sweaters, etc.).

tam&! The method for applying it to products is, for example, diluting it with water to prepare a cleaning bath, immersing the textile product in it, stirring it,
After rinsing, you can wring it out to dry.

[Examples] The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Parts and percentages in the examples are based on ffi quantity.

Builders of the present invention (Examples 1-5) and comparative builders (Comparative Examples 1-2) are shown below.

Example 1 As a sulfonation reactor, 1,2-dichloroethane 1 was placed in a 3 L four-necked flask equipped with a stirrer and a thermometer.
040 g and triethyl phosphate 9.1 g (0.0
5 mol) was added. In addition, in advance, 104 g of polystyrene (molecular weight 20,000) (1.
Solution A was obtained by dissolving 0 mol) in 938 g of 1,2-dichloroethane.

The temperature in the reactor was maintained at 20 to 25° C., and 4 g (0.05 mol) of liquid sulfuric anhydride was gradually added dropwise. Next, 040 g of solution AI and 80 g of liquid sulfuric anhydride (1.
0 mol) was added dropwise at the same time. The dropping rate is 4
The rate was adjusted to 16 g/hour and sulfuric anhydride at a rate of 32 g/hour. During the dropping process, cool the temperature to 18-2
It was kept at 2°C.

The sulfonated polystyrene precipitated as it formed. After the sulfonation was completed, the dispersion slurry of sulfonated polystyrene was gradually added to 481 g of an aqueous solution containing 44 g of sodium hydroxide at a temperature of 30° C. while stirring. Furthermore, h2-dichloroethane was removed by distillation until the odor of 1,2-dichloroethane in the aqueous solution of the sulfonated product disappeared. Next, add sodium hydroxide to pH 8.0.
and water was added to obtain a 30% concentration sodium salt of sulfonated polystyrene (builder of the present invention). 'The polymeric sulfonic acid-containing plate has a viscosity of 42% by weight and an aqueous solution.
It was 70cp3. Examples 2 to 5 Various polystyrenes were reacted in the same manner as in Example 1 to obtain sodium salts of sulfonated polystyrenes (builders of the present invention). The results are shown in Table-1.

body. (Molecular ffi 30,000) Example 8-10
(Detergent composition of the present invention) and Comparative Examples 3 to 4 (Comparative detergent composition) Powder detergent compositions having the following formulations were obtained using the builders of Examples 1 to 5 and Comparative Example 1.2. The details are shown in Table-2.

(Unit parts by weight) LAS (linear alkylbenzene sulfonate sodium salt): 20 Builder 20 Sodium silicate 8 Sodium carbonate 8 Sodium sulfate
43 Comparative Example Polymer of styrene sulfonic acid sodium salt (molecular weight 50
．． 000> Comparative Example 2 Copolymerization of sodium styrene sulfonate (20 mol%) and sodium methacrylate (80 mol%)
Total
100 The detergency of this detergent composition was also measured by the following method. The results are shown in Table-2.

(Cleaning power test method) An artificial dirt was prepared by mixing the following organic dirt components, fired clay, and carbon plaque at a ratio of 89.7:29.8:0.5 (weight ratio).

One organic stain component (unit, parts by weight) Oleic acid: 2B. 3 trio rain
: 15.8 Cholesterol Ole}: 1
2.2 Liquid paraffin: 2.5 Squalene = 2.5 Cholesterol: 1.8 Gelatin = 7.0 Total 69.7 Using this artificial soil, a soil collection cloth was created using a water solvent wet method, and this was 5c
The test piece was cut into a size of m×5 cm and had a reflectance of 0±2%. In the test, 10 pieces of this contaminated cloth and 3 pieces of cotton knitted cloth to which organic dirt of [i0B was attached per cloth were used, and cleaning was carried out under the following conditions.

-Cleaning conditions -Testing machine: Terg-0-Toseter rotation speed
: 120 rpm Water hardness: 90 ppm (CaCOs conversion) Washing liquid ff
i: 90hl Washing temperature: 30''C Washing concentration: 0.1O% for powder, 0.OG7% for liquid Bath ratio: 30 times (adjusted with clean cotton knitted cloth) Washing time: 0 minutes Rinse time: 3 minutes Drying twice: Cloth was sandwiched between filter papers and ironed to dry.The surface reflectance of the cloth was measured before and after washing, and the cleaning power was calculated from the following formula.

K/S=(1-R)”/2R-Kubelk
a-Hunk's formula where R represents the surface reflectance of the cloth.

Table 2 It can be seen that the detergent compositions of the invention exhibit better detergency than detergent compositions containing comparative builders.

[Effects of the Invention] The polymer electrolyte builder and cleaning composition of the present invention have excellent ability to prevent oil stains from re-deposition to cloth, have a high cleaning rate, and are safe in terms of water quality conservation.

Claims (1)

[Scope of Claims] 1. A polymer electrolyte builder comprising a sulfonated aromatic vinyl polymer and/or a salt thereof. 2. The aromatic vinyl polymer has an aromatic vinyl monomer and one or more ethylenically unsaturated monomers having a carboxylic acid (acid anhydride) group and/or a hydroxyl group as essential constituent units. The polymer electrolyte builder according to claim 1, which is a copolymer of 3. A detergent composition comprising the polymer builder (A) and surfactant (B) according to claim 1 or 2.