JPS63284296A - Detergent composition - Google Patents

Abstract

PURPOSE:To provide a detergent compsn. which is excellent in detergency, biodegradability and safety to human bodies and does not cause eutrophication of a lake or a swamp and which comprises a builder salt of a terpolymer of an alkylene, CO and maleic anhydride and a surfactant as essential components thereof. CONSTITUTION:In the presence of an olefin (a) (e.g., ethylene), CO (b) and maleic anhydride (c) are radical-copolymerized so as to obtain a terpolymer having an average MW of 500-5,000. The terpolymer is saponified, thereby obtaining a builder salt (B) selected from an alkali (earth) metal salt, ammonium salt and amine salt of a terpolymer having an alkylene component content of 5-80mol.%, a CO component content of 0.1-40mol.% and a maleic component content of 10-90mol.% (the total of the moles of the three components being 100%). 5-60wt.% surfactant pref. selected from nonionic and anionic surfactants is mixed with 0.05-50wt.% component (B), together with an optional component selected from an alkalinizing agent, an inorg. acid salt, a solvent, a solubilizing agent, an abrasive, a bleaching agent, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field] The present invention relates to detergent compositions containing a surfactant and a novel copolymer builder salt. The compositions of the present invention are particularly useful as laundry detergents.

[Conventional technology]

Detergents are generally used as compositions containing surfactants, builders, and other additives.

Furthermore, various studies have been made to improve the detergency of surfactants in detergent compositions through interaction with builders.

Conventionally, condensed phosphate compounds such as sodium tripolyphosphate (STPP) have been widely used as builders due to their performance and cost. Due to the environmental problems that have arisen due to this, the use of substitutes for noodles is rapidly progressing.

For example, zeolite, an inorganic compound that has no problems in terms of eutrophication or safety, has come to be used, but since zeolite is water-insoluble, it acts like an ion exchange and sequesters metal ions. Detergent compositions containing this have the drawbacks of inferior detergency compared to those containing 5TPP, which has chelating ability, and that they cannot be blended into liquid detergents.

For this reason, compounds such as 5TPP that have the ability to chelate metal ions are being investigated, and polycarboxylic acids such as citric acid and succinic acid, N-containing carboxylic acids such as nitrotriacetic acid, polyacrylic acid and anhydride are being investigated. Maleic acid-ethylene copolymer (Japanese Patent Publication No. 39-29447), maleic anhydride-long-chain alkylene copolymer (Japanese Patent Publication No. 1987-29447)
Polymer electrolytes such as those disclosed in Japanese Patent No. 12807) have been proposed.

[Problem that the invention seeks to solve]

However, the above-mentioned polyhydric carboxylic acid has a cleaning power of 5T.
Inferior to PP, N-containing carboxylic acids have problems with eutrophication and safety for the human body due to the N content they contain, and the polymer electrolytes proposed so far have the problem of poor biodegradability. Therefore, these compounds have not been widely used.

The present invention can be formulated with commonly used surfactants.
The present invention aims to provide a detergent composition containing a novel builder that exhibits detergency equivalent to or higher than 1'pp, does not cause eutrophication of lakes and marshes, is biodegradable, and has fewer safety problems for the human body. It is something to do.

[Means to solve problems]

The present invention provides a composition in which a surfactant is blended with a novel copolymer builder salt having a structure containing CO groups in the main chain.
It was discovered that the cleaning power is equivalent to or higher than that using P.

That is, the present invention provides at least one surfactant;
The present invention provides a detergent composition containing alkylene, carbon monoxide, and a builder salt of a terpolymer of maleic anhydride.

The surfactants used in the present invention include linear or branched alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or H-fulkenyl sulfates,
alpha sulfo fatty acid group or urx chill salt, alkane or alkene sulfonate, saturated or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate, amino acid type surfactant, ``alkyl or alkenyl phosphate ester or salt thereof, etc. Anionic surfactants, nonionic surfactants such as polyalkylene glycol alkyl ether, polyalkylene glycol alkyl phenyl ether, polyalkylene glycol fatty acid ester, sorbitan fatty acid ester, purkyl polyglycol, fatty acid dialkanolamide, alkyltrimethylammonium chloride , cationic surfactants such as dialkyldimethylammonium chloride, and amphoteric surfactants such as alkyldimethylamine oxide and alkyldimethylsulfopropyl betaine. Among these, it is preferable to use at least one type of nonionic and anionic surfactants, and for clothing, nonionic and anionic surfactants preferably range from 10 to 40.

The ternary copolymer of alkylene, carbon monoxide, and maleic anhydride used as a builder salt in the present invention is a polymer electrolyte consisting of three structural units with missing main chains (in the formula, Fb, R1 , R8 represents a hydrogen atom, a methyl group, or an ethyl group, and ■, ME is a cation derived from an alkali metal, an alkaline earth metal, ammonium, or an amine.) The builder salt used in the present invention is ethylene, Propylene, 1-butene, 2-butene, isoptene, pentene,
It can be obtained by saponifying a terpolymer obtained by radical copolymerization of carbon monoxide and maleic anhydride in the presence of an olefin such as hexene by a conventional method.

Among them, a copolymer using ethylene as the olefin is most preferable in terms of yield and reactivity. The molar ratio of the constituent units of the copolymer is such that the alkylene component is 5 to
80%, preferably 10-70%, carbon monoxide content is 0
．． The maleic acid component is in the range of 1 to 40, preferably 0.5 to 25, and the maleic acid component is in the range of 10 to 90, preferably 20 to 80, so that the total of the three components is 100. The average molecular weight of the copolymer is 500 to 50,000, preferably soo to 30,000 as a terpolymer before saponification.
@The builder salt of the present invention has c in the polymer main chain.
.

Because it has a group, it is easily cleaved and decomposed by light or microorganisms, and during eutrophication of rivers and lakes, the concentration is 50%, preferably 1 to 25%. If the amount is too small, the recontamination prevention effect will be insufficient and the cleaning power will be reduced, which is not preferable.

In addition to the above-mentioned surfactant and builder salt of alkylene/Co/maleic anhydride ternary copolymer, the detergent composition of the present invention contains a substance that imparts alkalinity in order to effectively exhibit the performance of the builder salt. It is made into a wo. The alkalizing agent may be any book that makes the pH of the aqueous detergent solution alkaline, such as caustic soda, inorganic builders such as soda carbonate, sodium silicate, and sodium borate, and triethanol to 401 or the above-mentioned ternary copolymers. The combined builder salt and alkalizing agent are blended so that the total amount is S* or more.

In addition, the cleaning composition of the present invention can be in various forms such as powder or liquid, and can be formulated in various ways depending on the type of object to be cleaned or the type of contamination, and various ingredients can be further added as necessary. It is used as Specifically, the inorganic acid salt is mirabilite, the solvent is water, ethanol, impropatol, ethylene glycol, hexaronlube, calpitol, etc., the solubilizer is urea, p-toluenesulfonic acid, etc., and the abrasive is talc,
Micropowdered silica, etc., oxidizing bleaching agents such as hydrogen peroxide, percarbonate), reducing bleaching agents such as sodium bisulfite, recontamination prevention agents such as carboxymethyl cellulose, etc., enzymes, fluorescent dyes, fragrances, etc. Examples include components such as colorants, preservatives, and chelating agents.

The method of using the detergent composition of the present invention is not particularly limited, but it is usually used after being diluted with water about 50 times to 10,000 times. Although it can be used to clean dishes, household items, etc., it is particularly preferable to use it as a detergent for textile products.

Specifically, fiber products such as natural fibers such as cotton, wool, and linen, synthetic fibers such as polyester, nylon, and acrylic, and blended fabrics thereof are exemplified.

〔Example〕

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these experimental examples.

Example 1 100 ml of a toluene solution containing 20 f of maleic anhydride was placed in an autoclave. Hydroxylation of the terpolymer obtained by radical polymerization at 95°C by introducing 100 kg/-G of ethylene and 400~/ctlG of carbon monoxide (calculated as a pressure gauge) Using a builder salt obtained by neutralization with an aqueous sodium solution, a detergent composition having the following formulation was prepared, and its detergency was measured using an artificially contaminated cloth at a washing water temperature of 25°C.

LAS 15 parts by weight builder salt 17
1 ol Soda carbonate 31 Glauber's salt 58 parts by weight CMC1# Example 2 The cleaning power was measured in the same manner as in Example 1 except that the cleaning temperature was 60°C.

Comparative Example 1 In Example 1, a composition in which the terpolymer builder salt was not used and the 75-layer stationary part was made of Glauber's salt was used. It was measured.

Comparative Example 2 The detergency was measured in the same manner as in Example 1, except that a composition using 5TPP instead of the terpolymer builder salt was used.

The results of the detergency test are summarized in Table 1.

Table 1: The detergency test was carried out using the following method. 90 (1) Artificially contaminated fabric Artificial dirt with the following composition was dispersed in water, and contaminated fabrics were prepared using a water-solvent wet method. was cut into 5 pieces x 5 rms, and a piece with a reflectance of 42±2 inches was used as a test cloth.

Composition of artificial dirt (weight) Organic content (69,7) Oleic acid 28.3 Triolein
15.6 Cholesterol oleate 12.2 Liquid paraffin 2.5 Squalene 2.5 Cholesterol
1.6 gelatin
7.0 inorganic content (3
1,3) Red yellow ± 29.8 carbon 0.5 Also, in the detergency test, a piece of cotton knitted cloth with 60q of organic dirt attached was used as a sebum cloth for adjusting the bath ratio.

(2) Cleaning Power Test Using Terg-0-Tometer, cleaning was carried out under the following cleaning conditions. The cleaning power was determined by measuring the surface reflectance of the cloth after washing and using the following formula.

However, K/S = (1-R)”/2 R-・Kube
In the formula lKa-Munk, R is the surface reflectance of each cloth.

Rotation speed 12 Orpm Dirty cloth 10 pieces Cleaning liquid fIkg00PILe Water hardness 3HD Detergent me 0. o a 7 wt4 bath ratio
Washing time: 10 minutes Rinse time: 3 minutes x 2 times Drying After air drying, iron drying Reference example Builder salt incorporated in Example 1 and average molecular weight: 11,700
As a result of a biodegradability experiment using a disodium salt of a binary copolymer of ethylene and maleic anhydride, the builder salt used in Example 1 was found to be a disodium salt of a binary copolymer of ethylene and maleic anhydride. The decomposition rate was about twice that of the previous one. The same test was conducted using a closed system oxygen consumption measuring device, adjusting the test substance at 100 ppm and activated sludge at 6 Qppm, and measuring the change in oxygen consumption over time while stirring thoroughly at 25±1°C.

Claims (3)

[Claims] (1) at least one surfactant and alkylene,
A detergent composition comprising carbon monoxide and a builder salt of a terpolymer of maleic anhydride. (2) The surfactant is selected from nonionic and anionic surfactants, and the builder salt of the terpolymer is an alkali metal salt, an alkaline earth metal salt,
The composition according to claim (1), which is at least one of an ammonium salt and an amine salt. (3) The alkylene component constituting the terpolymer is 5 to 8
0%, carbon monoxide component ranges from 0.1 to 40%, and maleic anhydride component ranges from 10 to 90% (however, if the total of the three components is 1
00%. ), and the average molecular weight of the polymer is in the range of 500 to 50,000.