JPH1135989A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent which has a higher detergency by blending, with a surfactant, a specific amt. of an acrylic acid copolymer of a specific mol.wt. obtd. using a redox initiation system as a polymerization initiator. SOLUTION: One to 10 wt.% of an acrylic acid copolymer with a wt. average mol.wt. of 15,000-80,000 and 20-60 wt.% of a surfactant are blended. As an acrylic acid copolymer a copolymer of acrylic acid and an unsaid. mono- or dicarboxylic acid (salt or anhydride) can be used. Particularly pref. is a copolymer of acrylic acid and maieic acid. Acrylic acid/maleic acid (molar ratio) ranges pref. from 40/60 to 80,20. As a surfactant an anionic or a nonionic surfactant is pref.. Further blending 1-10 wt.% of a crystalline silicate is pref. A silicate having formula I (wherein M is a group 1a metal; Me is a group IIa, IIb, IIIa, IVa or VIII metal; or the like) or formula II (wherein M is an alkali metal; etc.), is suited as a crystalline silicate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cleaning composition. More specifically, the present invention relates to a detergent composition having a high detergency and containing an acrylic acid copolymer using a redox initiation system as a polymerization initiator.

[0002]

2. Description of the Related Art Carboxylic acid-based polymers such as polyacrylic acid (salt) are known as components to be incorporated in detergents as dispersants, chelating agents and the like. For this reason, various studies have been made on the production of copolymers for detergents. Specifically, as a method of generating radicals in an aqueous system and polymerizing a monomer, a method of generating radicals by thermal decomposition, or a method of generating radicals by a redox initiator using an oxidizing agent and a reducing agent together (a method using a redox polymerization method) Is mainly reported). As methods utilizing thermal decomposition, Japanese Patent Publication No. Sho 56-54005 reports the combined use of hydrogen peroxide and persulfate, and Japanese Patent Publication No. 3-14046 reports a polymerization method using hydrogen peroxide. As a method using a redox initiator, Japanese Patent Application Laid-Open No. 3-9905 is reported in which a polymer having a molecular weight of less than 10,000 is obtained.

[0003]

However, the thermal decomposition method using hydrogen peroxide as the polymerization initiator has a problem that the reaction time is prolonged in order to obtain a high polymerization rate. When coalescing is used as a cleaning agent,
It did not exhibit sufficient performance in its detergency. Further, the polymer disclosed in Japanese Patent Application Laid-Open No. 3-9905 is not sufficient in terms of improving the detergency.

[0004] Accordingly, an object of the present invention is to find a high molecular weight polymer which gives more excellent detergency as a component of a detergent, and to provide a detergent composition showing more excellent detergency.

[0005]

Under these circumstances, the present inventors have closely examined the relationship between the difference in polymerization initiator and the cleaning performance of the copolymer, and as a result, as a polymerization initiator, redox was used. By blending the acrylic acid copolymer having a specific molecular weight obtained using the starting system into a system based on a surfactant, it has been found that a detergent composition having a higher detergency can be obtained. It was completed.

That is, the present invention relates to (a) an acrylic acid copolymer having a weight average molecular weight of 15,000 to 80,000 obtained by using a redox initiation system as a polymerization initiator.
The present invention provides a detergent composition containing 1 to 10% by weight (b) 20 to 60% by weight of a surfactant. Less than,
The cleaning composition of the present invention will be described in detail.

In the present invention, the acrylic acid copolymer as the component (a) has a weight average molecular weight of 15,000 to 80,000, and is incorporated in the composition at 1 to 10% by weight, preferably 3 to 8% by weight. You.
As the component (a), those having the above-mentioned weight average molecular weight range have excellent detergency, and those out of this range do not show any improvement in detergency.

The acrylic acid copolymer of the component (a) is a copolymer of acrylic acid and a monomer copolymerizable therewith. As the monomer copolymerizable with acrylic acid, unsaturated dicarboxylic acid or unsaturated Monocarboxylic acids and their salts or anhydrides. Specifically, examples of the unsaturated dicarboxylic acid include maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, methylenemalonic acid, mesaconic acid, and salts or anhydrides thereof.
Examples of unsaturated monocarboxylic acids include methacrylic acid, dimethylacrylic acid, vinyl acetic acid, allyl acetic acid, propylidene acetic acid, ethylidene propionic acid, and salts or anhydrides thereof.

As the component (a), a copolymer of acrylic acid and maleic acid is particularly preferred. In this case, the molar ratio of acrylic acid to maleic acid is acrylic acid / maleic acid = 40/60.
It is preferable that acrylic acid / maleic acid is 45 / 55-55 / 45 and the weight average molecular weight is 15,000-50,000 acrylic acid / maleic acid is 55 / 45-65 / 35. Those having a weight average molecular weight of 15,000 to 60,000 acrylic acid / maleic acid = 65/35 to 75/25 and a weight average molecular weight of 30,000 to 80,000 are particularly excellent in detergency.

The acrylic acid copolymer which is the component (a) of the present invention is obtained by using a redox initiator which generates a free radical by redox. The redox initiator is a combination of an oxidizing agent and a reducing agent. Examples of the oxidizing agent include hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, t-butyl hydroperoxide, perroyl SA, and the like. Examples of the reducing agent include sodium bisulfite, sodium sulfite, ascorbic acid, Rongalit, sodium diotinate, triethanolamine and the like. These oxidizing agents and reducing agents are used alone or in combination of two or more. Of these, redox initiation systems such as hydrogen peroxide and Rongalit, and ammonium persulfate and sodium bisulfite are preferred from the viewpoint of obtaining a high reaction rate. Also effective in combination with a metal promoter, for example, iron salts,
Copper salt, zinc salt, cobalt salt, cerium salt, nickel salt,
A manganese salt, a molybdenum salt, a zirconium salt, a vanadium salt and the like are raised, and one or two or more of them are used in combination.

The method for synthesizing component (a) of the present invention using a redox initiator may be in accordance with a known method, but the obtained acrylic acid copolymer has a weight average molecular weight of 15,000 to 80,000. It is necessary to select such conditions.

As the surfactant of the component (b), anionic surfactants, nonionic surfactants, amphoteric surfactants and cationic surfactants are used, and preferably, anionic surfactants and nonionic surfactants are used. It is an ionic surfactant.

[0013] As the anionic surfactant, a compound having 10 to 10 carbon atoms is used.
Sulfate of 18 linear or branched primary or secondary alcohols, sulfate of ethoxylated alcohol having 8 to 20 carbon atoms, alkylbenzene sulfonate, paraffin sulfonate, α-olefinsulfonic acid Salts, α-sulfofatty acid salts, α-sulfofatty acid alkyl ester salts or fatty acid salts are preferred. In the present invention,
A straight-chain alkylbenzene sulfonate having 12 to 14 carbon atoms in the alkyl chain and an alkyl sulfate having 12 to 18 carbon atoms are preferred. As the counter ion, alkali metals are preferred, and sodium and / or potassium are particularly preferred.

As the nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, and polyoxyethylene polyoxypropylene block polymer are preferable. Particularly, as the nonionic surfactant, an HLB value obtained by adding 4 to 20 mol of an alkylene oxide such as ethylene oxide or propylene oxide to a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms (Griffin method) Are preferably 10.5 to 15.0, preferably 11.0 to 14.5.

In the present invention, the surfactant of the component (b) is
20 to 60% by weight, preferably 30 to 50% by weight is blended.

In the present invention, it is preferable to further add a crystalline silicate as the component (c). The crystalline silicate has a maximum pH of 11 or more when dispersed in ion-exchanged water at 20 ° C. in 0.1% by weight, and a 0.1N HCl aqueous solution is added to 1 liter of the above dispersion to adjust the pH to 10. It is excellent in alkali ability that requires 5 ml or more and is distinguished from crystalline aluminosilicate.

Particularly preferred as crystalline silicates are those having the following composition: _{x (M 2 O) · y} (SiO 2) · z (Me m O n) · w (H 2 O) (I) ( wherein, M is Group Ia elements of the periodic table (particularly preferably K and / Or Na), and Me is an element of group IIa of the periodic table, II
One or a combination of two or more selected from group b elements, group IIIa elements, group IVa elements or group VIII elements (preferably M
g / Ca), y / x = 0.5-2.6, z / x = 0.01-
0.9, w = 0 to 20, and n / m = 0.5 to 2.0. For the method for producing the crystalline silicate represented by the general formula (I), JP-A-7-89712 can be referred to.

Further, a crystalline silicate having the following composition can also be suitably used. _{M 2 O · x '(SiO} 2) · y' (H 2 O) (II) ( wherein, M represents an alkali metal (particularly preferably K and / or Na), x '= 1.5~2.6, y '= 0 to 20 (particularly preferably substantially 0). The crystalline silicate of the general formula (II) is disclosed in JP-A-60-227895 and Phys. Chem. Glasses. 7, 127-138 ( 1966), Z. Kristall
ogr., 129, 396-404 (1969). In addition, a powdery or granular product is available from Hoechst under the trade name “Na-SKS-6” (δ-Na ₂ Si ₂ O ₅ ). In the present invention, the crystalline silicate of the component (c) is preferably 1
-10% by weight, especially 3-8% by weight.

The cleaning composition of the present invention contains the above (a)
The component (b) and optional components other than the component (c) can be blended. For example, sequestering agents such as crystalline aluminosilicate which is a zeolite, organic sequestering agents such as ethylenediaminetetraacetic acid (EDTA) and citrate, and carboxyls other than the component (a) of the present invention such as polyacrylic acid. Acid-based polymers, alkali metal carbonates such as carboxymethylcellulose and soda ash, alkali metal silicates such as JIS No. 1, No. 2 and No. 3, sodium silicate and the like, extenders such as sodium sulfate, polyethylene glycol (PEG), Dispersants or color transfer inhibitors (PVP) such as polyvinylpyrrolidone (PVP) and polyvinyl alcohol (PVA), bleaching agents such as sodium percarbonate, bleaching described in JP-A-6-316700 and bleaching such as tetraacetylethylenediamine (TAED) Activators, proteases, cellulases, amylases and lipases Enzymes such as zero,
Conventionally known components such as boron compounds and enzyme stabilizers such as sodium sulfite, biphenyl-type and stilbene-type fluorescent dyes, defoamers such as silicone / silica, antioxidants, bluing agents and fragrances are known. It can be blended in a blending amount. Specific examples of the above components include those described in JP-A-8-218093.

The cleaning composition of the present invention comprises the above (a) to (b)
It is a high-density granular detergent composition comprising a component, furthermore, a component (c) and optional components optionally blended, preferably having a bulk density of 0.6 to 1.2 g / ml. As a method for producing such a high-density granular detergent composition, a conventionally known production method can be used, and as for the production conditions, those skilled in the art can easily select the exact conditions according to the composition.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

<Preparation of Acrylic Acid Copolymer> Samples 1 to 16 of acrylic acid copolymer were prepared by the following method.

(A) Preparation of Sample 5 Raw material supply of the monomer solution and the initiator solution to a glass reactor equipped with a stirrer, a thermometer, a reflux condenser, an inlet for dropping the monomer solution and the initiator solution, and a heating jacket. In a polymerization apparatus equipped with a tank, maleic acid salt 4 previously partially neutralized with a 48% aqueous sodium hydroxide solution at a neutralization degree of 50% was used.
A reactor is charged with 350 g of a 0% aqueous solution, and 550 g of a 40% aqueous acrylate salt partially neutralized with a 48% aqueous sodium hydroxide solution at a neutralization degree of 28% is charged into a monomer supply tank. Also, 18 g of a 40% aqueous solution of sodium bisulfite,
44 g of a 40% aqueous solution of ammonium persulfate was prepared and charged in each initiator supply tank. Warm water is passed through the jacket of the reactor to adjust the polymerization temperature to 80 ± 3 ° C. A 40% aqueous solution of an acrylate, a 40% aqueous solution of sodium bisulfite, and a 40% aqueous solution of ammonium persulfate were continuously dropped through the inlet and stirred. Dropping is performed in 1 hour, and then 1
Stayed for a time. At this time, although a little heat was generated, the polymerization temperature was maintained at 80 ± 3 ° C. while adjusting the jacket warm water. By performing these series of operations, a copolymer (sample 5) having a polymerization rate of acrylic acid and maleic acid of 95% or more and a weight average molecular weight of 70,000 was obtained. 48% copolymer
The pH was adjusted to 7 and the concentration was adjusted to 40% using an aqueous sodium hydroxide solution.

(B) Preparation of Samples 1-4, 6-14 The monomer composition ratio of acrylic acid and maleic acid was as shown in Table 1, and the initiator concentration was 2-30% by weight (based on the total amount of acrylic acid and maleic acid). ) And the same operation as that of Sample 5 was carried out, and samples 1 to 4, 6 to
14 was obtained. The weight average molecular weights are shown in Table 1.

(C) Preparation of Sample 15 In a polymerization apparatus similar to that of Sample 5, 350 g of a 40% aqueous maleate solution partially neutralized with a 48% aqueous sodium hydroxide solution at a neutralization degree of 40% in advance was placed in a reactor. Then, 250 g of an 80% aqueous solution of acrylic acid is charged into the monomer supply tank. Also, 40 g of 35% hydrogen peroxide solution was charged into the initiator supply tank. Hot water is passed through the jacket of the reactor to adjust the polymerization temperature to 100 ± 3 ° C. Acrylic acid 8 there
A 0% aqueous solution and a 35% aqueous hydrogen peroxide solution were continuously dropped through the inlet and stirred. The dropping was performed in 6 hours, and thereafter, the solution was retained for 2 hours. At this time, although a little heat was generated, the polymerization temperature was maintained at 100 ± 3 ° C. while adjusting the jacket warm water. By performing these series of operations, a copolymer (sample 15) having a polymerization rate of acrylic acid and maleic acid of 95% or more and a weight average molecular weight of 70,000 was obtained. 48 copolymers
PH to 7 using aqueous sodium hydroxide solution, and
The concentration was adjusted to 40%.

(D) Preparation of Sample 16 The monomer composition ratio of acrylic acid and maleic acid was set to the ratio shown in Table 1, and the initiator concentration (to the total amount of acrylic acid + maleic acid) was changed, and the procedure of Sample 15 was repeated. As a result, a sample 16 of an acrylic acid-based copolymer was obtained. Table 1 shows the weight average molecular weight.

<Measurement of polymerization rate> Samples 1 to 16
Was calculated by high-performance liquid chromatography under the following conditions. Column: Tosoh Corp. TSK-GEL SAX Mobile phase: water / acetonitrile = 97/3 0.05M sodium dihydrogen phosphate dihydrate 0.03M sodium perchlorate (anhydrous) Neutralized to pH 2.5 with phosphoric acid.

<Method for Measuring Molecular Weight> Samples 1 to 1 above
The weight average molecular weight of No. 6 was measured using gel permeation chromatography under the following conditions and converted using a calibration curve of polyethylene glycol. Column: Tosoh Corporation G400PWXL + G2500PWXL Mobile phase: 0.2 M phosphate buffer / acetonitrile = 90/10

[0029]

[Table 1]

Example 1 Detergency Test of Eri Aka Cloth
Performed according to JIS K 3362-1990. Prepare a detergent for determination of the composition shown below, wash under the following conditions, JIS K 33
The detergency was evaluated by the method of 62-1990. The detergency of two detergents (detergents A and B for convenience) was compared by the combination of Table 2 and the detergent A contained 1% of the detergent B. In the case where the detergent A is superior in the order of magnitude, it is expressed as "B @ A", and in the case where the detergent A is superior to the detergent B in the order of 5%, it is expressed as "B <A";
When there is no difference between the detergent A and the detergent B, "A = B" is represented.

(Washing conditions) Washing time 10 minutes Washing agent concentration 0.067% Water hardness 4 ° DH Water temperature 20 ° C. Rinsing 5 minutes in tap water (Blending of detergent for judgment) ・ Acrylic acid copolymer (Samples 1 to 16) 5% by weight ・ LAS: linear alkyl (C ₁₂ ) sodium salt of benzenesulfonic acid 25% by weight ・ AS: 5% by weight of sodium salt of dodecyl alcohol sulfate ester ・ AE: polyoxyethylene dodecyl ether (HLB = 10.0 to 16.0) 5 % By weight ・ FA: Na salt of palmitic acid 4% by weight ・ Crystalline silicate 5% by weight [Composition M ₂ O ・ 1.8SiO ₂・ 0.02M′O (where M: Na, K, K / Na = 0.03, M ′ = Ca, Mg, Mg / Ca = 0.01), average particle size 15 μm] ・ Crystalline aluminosilicate 20% by weight [composition M ₂ O ・ Al ₂ O ₃・ 2SiO ₂・ 2H ₂ O, average particle size 4 μm Amorphous silicate; JIS No. 1 amorphous sodium silicate 10% by weight ・ Sodium carbonate 10% by weight ・ Common component: PEG 1% by weight (polyethylene glycol having a weight average molecular weight of 13,000), an enzyme [Sabinase 12.0TW (protease, manufactured by Novo Nordisk), lipase 100T (lipase, manufactured by Novo Nordisk), KAC500 (cellulase, Kao Corporation) 1% by weight) and Termamil 60T (amylase, manufactured by Novo Nordisk) in a ratio of 2: 1: 1: 1 (weight ratio)] and a fluorescent dye [compounding ratio: Tinopal CBS (manufactured by Ciba Geigy) ) / WHITEX SA (manufactured by Sumitomo Chemical Co., Ltd.) = 1/1 (weight ratio)] 0.5% by weight and sodium sulfate, and the total amount of sodium sulfate was adjusted to 100%.

[0032]

[Table 2]

Example 2 Various cleaning compositions shown in Table 3 were prepared, and a cleaning test of the artificially stained cloth was performed by the following method. Table 3 shows the results.

<Test for Detergency of Artificially Contaminated Cloth> (Preparation of Artificially Contaminated Cloth) An artificially contaminated cloth was prepared by attaching an artificially contaminated liquid having the following composition to the cloth. The artificial contaminant was attached to the cloth by printing the artificial contaminant on the cloth using a gravure roll coater. The process of adhering the artificially contaminated liquid to the cloth to produce the artificially contaminated cloth is based on the cell capacity of the gravure roll.
The drying was performed at 8 cm ³ / cm ² , a coating speed of 1.0 m / min, a drying temperature of 100 ° C., and a drying time of 1 minute. The cloth used was a cotton gold cloth 2003 (manufactured by Tanito Shoten).

[Composition of artificial contaminated liquid] Lauric acid 0.44% by weight Myristic acid 3.09% by weight Pentadecanoic acid 2.31% by weight Palmitic acid 6.18% by weight Heptadecanoic acid 0.44% by weight Stearic acid 1.57% by weight Oleic acid 7.75% by weight 13.06% by weight N-Hexadecyl palmitate 2.18% by weight Squalene 6.53% by weight Egg white lecithin liquid crystal 1.94% by weight Kanuma red clay 8.11% by weight Carbon black 0.01% by weight Tap water balance (Washing conditions and evaluation method) Five pieces of the prepared artificially contaminated cloth of 10 cm × 10 cm were put and washed at 100 rpm with a tergotometer. The washing conditions are as follows.

Cleaning conditions Cleaning time 10 minutes Cleaning agent concentration 0.067% Water hardness 4 ° DH Water temperature 20 ° C. Rinse for 5 minutes in tap water Detergency is the reflectance at 550 nm of the original cloth before contamination and the contaminated cloth before and after cleaning. Was measured with a self-recording colorimeter (manufactured by Shimadzu Corporation), the cleaning rate (%) was determined by the following equation, and the measured average value of the five sheets was shown as the cleaning power.

[0037]

(Equation 1)

[0038]

[Table 3]

AA / MA copolymer: acrylic acid-maleic acid copolymer of sample 4 LAS: straight-chain alkyl (C ₁₂ ) sodium salt of benzenesulfonic acid AS: sodium salt of dodecyl alcohol sulfate ester AE: polyoxyethylene dodecyl ether (HLB = 1
・ FA: Na salt of palmitic acid ・ Crystalline silicate: Composition M ₂ O ・ 1.8SiO ₂・ 0.02M′O (where M: Na, K, K / Na = 0.03, M ′ = Ca) , Mg, Mg / Ca =
0.01), average particle size 15μm ・ Crystalline aluminosilicate: Composition M ₂ O ・ Al ₂ O ₃・ 2SiO ₂・ 2H
₂ O, average particle diameter 4 μm ・ Common component: 1% by weight of PEG (polyethylene glycol having a weight average molecular weight of 13,000) and an enzyme [Sabinase 12.0 TW
(Protease, Novo Nordisk), Lipolase
100T (Lipase, Novo Nordisk), KAC500
(Cellulase, manufactured by Kao Corporation), Termamyl 60T (Amylase, manufactured by Novo Nordisk) in 2: 1: 1: 1
(Weight ratio)] and 1% by weight of a fluorescent dye [compounding ratio: Tinopearl CBS (manufactured by Ciba-Geigy) / Whitetex SA (manufactured by Sumitomo Chemical) = 1/1 (weight ratio)]
It was 0.5% by weight and sodium sulfate, and the total amount of sodium sulfate was adjusted to 100%.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Seiji Tamaki 1334 Minato, Wakayama City, Wakayama Pref.

Claims (4)

[Claims] (1) 1 to 10% by weight of an acrylic acid copolymer having a weight average molecular weight of 15,000 to 80,000 obtained by using a redox initiator system as a polymerization initiator (b) Surfactant 20 to 60 % Detergent composition comprising: 2. The cleaning composition according to claim 1, further comprising (c) 1 to 10% by weight of a crystalline silicate. 3. The acrylic acid copolymer of component (a) is a copolymer of acrylic acid and maleic acid, wherein the ratio of acrylic acid to maleic acid is acrylic acid / maleic acid = 40 / 60-80 /
The cleaning composition according to claim 1, wherein the composition is 20. 4. The crystalline silicate of the component (c) comprises the following (I)
The cleaning composition according to claim 2 or 3, which is a crystalline silicate represented by the formula or / and (II). _{x (M 2 O) · y} (SiO 2) · z (Me m O n) · w (H 2 O) (I) ( wherein, M represents a Group Ia elements of the periodic table, Me represents the periodic One or a combination of two or more elements selected from the group IIa element, IIb element, IIIa element, IVa element or VIII element shown in the table, y / x = 0.5 to 2.6, z / x = 0.01 to 0.9 ,
w = 0 to 20, and n / m = 0.5 to 2.0. ) M ₂ O · x ′ (SiO ₂ ) · y ′ (H ₂ O) (II) (wherein M represents an alkali metal, x ′ = 1.5 to 2.6, y ′)
= 0 to 20. )