JPH10245592A - Additive for chlorine-containing detergent and chlorine-containing detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an additive which makes the chlorine-releasing substance in a chlorine-containing detergent to difficultly decomposable by selecting a copolymer of an α,β-ethylenically unsaturated carboxylic acid or its alkali metal salt, comprising structural units derived from 2-acrylamido-2- methylpropanesulfonic acid or an alkali salt thereof and having a specified weight-average molecular weight. SOLUTION: This additive comprises a copolymer comprising 5-95wt.% 2- acrylamido-2-methylpropanesulfonic acid or an alkali salt thereof and an α,β-unsaturated carboxylic acid (e.g. (meth)acrylic acid) or an alkali salt thereof. The additive should have a weight-average molecular weight of 5,000-250,000. Its average molecular weight depends on the kinds of the unsaturated carboxylic acid used. It is 15,000 or above when (meth)acrylic acid is used, is 6,000 or above when maleic acid is used, and is 10,000 or above when a combination of maleic acid and (meth)acrylic acid is used. The formulating amount of the additive used is 0.2-30wt.%, based on the chlorine-containing detergent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an additive for a chlorine-based detergent, and more particularly to an additive called a builder or a sequestering agent. The present invention relates to an additive that does not promote the decomposition of a chlorine-releasing substance contained in a system cleaning agent.

[0002]

2. Description of the Related Art Generally, a detergent contains a surfactant and / or an alkali agent as a main agent, and a builder or a sequestering agent of an α, β-ethylenically unsaturated carboxylic acid or a salt thereof as a sequestering agent. A polymer or copolymer of an alkali salt (hereinafter, also collectively referred to as an unsaturated carboxylic acid (salt)) is blended. For example, polyacrylic acid,
BACKGROUND ART Unsaturated carboxylic acid polymers such as polymaleic acid are compounds having a function of capturing metal ions such as Ca ions, and it is known that the detergency is improved by blending them in a detergent. . On the other hand, so-called chlorine-based cleaning agents contain a chlorine-releasing substance such as sodium hypochlorite for the purpose of sterilization or bleaching.

However, unsaturated carboxylic acid polymers such as polyacrylic acid and polymaleic acid have a property of rapidly decomposing this chlorine releasing substance when coexisting with the chlorine releasing substance. For this reason, in chlorine-based cleaning agents,
It has been difficult to add and use these unsaturated carboxylic acid polymers as builders and the like.

Japanese Unexamined Patent Publication No. 8-13995 discloses an unsaturated carboxylic acid-based polymer which does not easily decompose a chlorine releasing substance. Maleic acid is used as a metal ion sequestering agent in liquid detergents for automatic dishwashers containing the chlorine releasing substance. It is disclosed that a copolymer of an acid or acrylic acid and a sulfonated styrene is used. However, although the decomposition of the chlorine-releasing substance can be suppressed to some extent by the copolymer, the effect is still insufficient, and the sulfonated styrene having a benzene ring is copolymerized. The copolymer has low compatibility with water, anionic and nonionic surfactants, and in detergents containing a surfactant as a main component, when a high concentration detergent solution is used, turbidity may occur, and in some cases, the solution may become turbid. The problem of separation exists.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to prevent the decomposition of chlorine-releasing substances contained in a chlorine-based cleaning agent, and to improve the compatibility with water, anionic and nonionic surfactants. An object of the present invention is to provide a chlorine-based detergent additive that functions well as a builder or a sequestering agent.

[0006]

Means for Solving the Problems The present inventors have proposed an unsaturated carboxylic acid (salt) copolymer containing 2-acrylamido-2-methylpropanesulfonic acid as a constituent monomer,
The inventors have found that it is less likely to decompose chlorine releasing substances than the copolymer disclosed in JP-B-8-13995, and that it has excellent compatibility with water, anionic and nonionic surfactants, and completed the present invention. .

The present invention consists of two inventions, and the first invention is 2-
It contains acrylamide-2-methylpropanesulfonic acid or an alkali salt thereof as a constituent monomer, and has a weight average molecular weight of 5,000 to 250,000, and a copolymer of an α, β-ethylenically unsaturated carboxylic acid and an alkali salt thereof. The present invention relates to a chlorine-based additive for a cleaning agent comprising a polymer.

[0008] A second invention relates to a chlorine-based detergent containing the additive of the first invention.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The unsaturated carboxylic acid (salt) as a copolymer component constituting the additive for a chlorine-based cleaning agent of the present invention is a component for exhibiting the original performance as a builder of a cleaning agent, that is, a metal ion capturing ability. In the past, the polymers have been widely used as additives for detergents, and specific examples of the unsaturated carboxylic acids (salts) include acrylic acid,
Examples include methacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid and itaconic acid, and alkali salts thereof. Examples of the alkali salt include alkali metal salts such as Na and K, alkaline earth metal salts such as Ca and Mg, and amine salts such as ethylamine. Preferred in the present invention are the alkali metal salts. One kind of these unsaturated carboxylic acids (salts) may be used alone, or two or more kinds thereof may be used in combination. These unsaturated carboxylic acids (salts)
Among them, it is preferable to use one or more selected from acrylic acid (salt), methacrylic acid (salt) and maleic acid (salt) because of excellent metal ion capturing ability, and maleic acid (salt) It is particularly preferred to use

The polymer of the unsaturated carboxylic acid (salt), which decomposes the chlorine releasing component as described above, is obtained by converting the unsaturated carboxylic acid (salt) into 2-acrylamido-2-methylpropanesulfonic acid or the same. Alkaline salt (hereinafter ATBS)
(Salt) is copolymerized to give the function of suppressing the decomposition of chlorine-releasing components without impairing the ability of unsaturated carboxylic acids (salts) to trap metal ions (hereinafter referred to as chlorine stabilization function). Wherein ATBS (salt) is a compound represented by the following structural formula (1) or an alkali salt thereof. The alkali salt is the same as the above-mentioned unsaturated carboxylate.

[0011]

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Due to the fact that the ATBS (salt) does not have a benzene ring and has an amide bond, the additive of the present invention comprising a copolymer of the ATBS (salt) and an unsaturated carboxylic acid (salt) is: Compared to the case of using sulfonated styrene, the compatibility with water and the solubility in water are high, and the ability to dissolve or disperse a hydrophobic substance in water is excellent, so that dirt is re-adhered to the object to be cleaned. Effectively prevents the scale from adhering to scales and cleaning equipment, and furthermore has good compatibility with anionic and / or nonionic surfactants. This also has the advantage that the liquid is difficult to be turbid or separated.

In the copolymer of ATBS (salt) and unsaturated carboxylic acid (salt), the copolymerization ratio of ATBS (salt) is preferably 5 to 95% by weight, more preferably 10 to 90% by weight. % By weight, particularly preferably 10 to 40
% By weight. When the copolymerization ratio of ATBS (salt) is less than the above range, the chlorine stabilizing function becomes insufficient. On the other hand, when the copolymerization ratio of ATBS (salt) exceeds the above range, the copolymerization ratio of the unsaturated carboxylic acid (salt) decreases, and the metal ion trapping ability decreases. , The function as a builder becomes insufficient. Generally, only ATBS (salt) and unsaturated carboxylic acid (salt) are used as the constituent monomers of the copolymer. However, in order to adjust the viscosity and compatibility as an additive, a third compound is used. Polymerizable monomers, such as alkyl acrylate, hydroxyalkyl acrylate, alkylene glycol acrylate, vinyl acetate, styrene, alkyl methacrylate, etc., in place of the above components, within a range that does not impair the effects of the present invention. It can be used as a copolymer component.

The copolymer has a weight average molecular weight of 5,0.
When the weight average molecular weight is less than 5,000, the chlorine stabilizing function is degraded. When the weight average molecular weight exceeds 250,000, the copolymer has a weight average molecular weight of more than 250,000. Since the viscosity is too high, the handleability during production and use is poor, and the solubility in water and surfactants is low. In addition, the weight average molecular weight in this specification is a molecular weight in terms of polyethylene oxide determined by aqueous gel permeation chromatography.

The more preferable range of the weight average molecular weight of the copolymer depends on the kind of the unsaturated carboxylic acid (salt) used. For example, as the unsaturated carboxylic acid (salt), acrylic acid (salt) or methacrylic acid (salt) is used. )), A weight-average molecular weight of 15,
It is preferably at least 000, more preferably at least 80,000. In contrast, when maleic acid (salt) is used as the unsaturated carboxylic acid (salt),
A high chlorine stabilizing function can be obtained in a weight average molecular weight range of 6,000 or more. When maleic acid (salt) and acrylic acid (salt) or methacrylic acid (salt) are used in combination, the weight average molecular weight of the copolymer is preferably 10,000 or more.

[0016] The copolymer according to the present invention is ATBS.
(Salt) and an unsaturated carboxylic acid (salt) are obtained by polymerizing a monomer selected from conventional methods, and more generally, the carboxyl group present in the copolymer is partially or The whole is blended in the detergent as an alkali salt, that is, an alkali salt type copolymer. As a method for obtaining an alkali-salt-type copolymer, an acid is selected for both the above-mentioned ATBS (salt) and unsaturated carboxylic acid (salt), and they are copolymerized. Any of a method of neutralizing a part or the whole with an alkali metal hydroxide or the like and a method of copolymerizing an alkali salt of each component may be used, but a method of neutralizing after copolymerization is preferable. Examples of the chlorine-based detergent containing the additive of the present invention include various chlorine-based detergents for automatic dishwashers, clothes, toilets, kitchens, furniture, and the like. These cleaning agents contain hypochlorite, chlorite, chlorinated isocyanuric acid, and the like as chlorine releasing substances. The amount of the additive of the present invention in the chlorine-based cleaning agent is generally 0.2 to 30% by weight, preferably 0.5 to 1% by weight, based on the entire chlorine-based cleaning agent.
0% by weight. If the compounding amount is less than the above range, sufficient metal ion capturing ability cannot be obtained, and the function as a builder may be insufficient.On the other hand, even if the compounding amount exceeds the above range, the effect tends to be saturated. Not economical.

The chlorine-based detergent containing the additive of the present invention contains, in addition to a chlorine releasing substance, an inorganic builder such as a surfactant, an alkali agent, a phosphate and a silicate, an enzyme, a fluorescent agent, Conventionally known components such as a solubilizer, a foam inhibitor, an oxygen bleach, and a softener are blended as necessary. The additive of the present invention can be added to any type of chlorine-based detergent such as powder and liquid. When added to a liquid chlorine-based detergent, the additive of the present invention has a high compatibility with anionic and nonionic surfactants, so that there is an advantage that a detergent solution having good transparency and difficult to separate can be obtained. .

[0018]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. In the monomer compositions shown in Table 1 below, after performing aqueous solution polymerization by a usual radical polymerization method, the copolymers of Examples 1 to 10 and Comparative Examples 1 to 9 were completely neutralized with sodium hydroxide or A polymer was obtained. Table 1 shows the weight average molecular weight of each polymer.

[0019]

[Table 1]

The abbreviations in Table 1 have the following meanings. ATBS; 2-acrylamido-2-methylpropanesulfonic acid SSS; styrenesulfonic acid MAS; methallylsulfonic acid AA; acrylic acid MLA; maleic acid MAA; methacrylic acid

These polymers were evaluated by the following methods. (1) Chlorine stabilizing function Each polymer was dissolved in water with the following composition to prepare a chlorine-based cleaning agent. [Blending composition] 2% by weight of polymer (builder) 5% by weight of potassium pyrophosphate 2.5% by weight of sodium metasilicate 5% by weight of potassium hydroxide 2% by weight of sodium hypochlorite

The obtained cleaning agent was evaluated for "effective chlorine remaining rate (%)" which is a measure of the stability of the chlorine releasing substance (sodium hypochlorite) during storage. The effective chlorine remaining rate (%) was determined as a ratio of the effective chlorine remaining immediately after adjustment and after storage at 35 ° C. for 5 days. Table 1 shows the measurement results. In addition, the effective chlorine residual amount was measured by the following method. [Measurement of Effective Chlorine Residual] Take 5 g of each detergent in a 100 ml conical beaker,
5 ml of a 10% KI solution and 3 ml of a 50% acetic acid solution are added. Titration is performed with a 0.1 N sodium thiosulfate solution, and the effective chlorine remaining amount (% by weight; converted to chlorine atoms) is calculated by the following formula (I).

[Calculation formula of residual effective chlorine amount] Effective chlorine (%: as Cl) = (0.3545 × A) × f / S (I) In the above formula (I), A is required for titration. The amount of the sodium thiosulfate solution, S is the amount of the sample, and f is the factor of the sodium thiosulfate solution.

(2) Capability of Capturing Metal Ions The detergent prepared in (1) above was evaluated for its ability to capture Ca ions by the following method. The results are shown in Table 1 above. [Measurement of Ca ion capturing ability] 100 ml of 800 ppm calcium chloride solution was adjusted to pH
After adjusting to 8.5, 1 ml of a 4M potassium chloride solution was added, and each detergent was further added to a pure concentration of 400 ppm. After leaving this solution at 30 ° C. for 10 minutes, the concentration of Ca remaining in the solution was measured with a Ca ion meter to determine the amount of Ca ions captured by the detergent.

(3) Compatibility with Surfactant (3-1) Compatibility with Nonionic Surfactant Example 3 was prepared in a 40% aqueous solution of polyoxyethylene lauryl ether (8 moles of ethylene added). , 4, 6, 8
The polymers of Comparative Examples 4 and 6 were added at a pure concentration of 3 to 7%, and the turbidity of the liquid was visually evaluated. The evaluation results were as follows: ○; no turbidity; Δ; some turbidity; ×;
In three stages. The results are shown in Table 2 below. The test was performed at a liquid temperature of 25 ° C.

[0026]

[Table 2]

(3-2) Compatibility with anionic surfactant The polymers of Examples 3, 4, 6, 8 and Comparative Examples 4, 6 were purely dissolved in a 25% aqueous solution of sodium dodecylbenzenesulfonate. The solution was added at a concentration of 1 to 4%, and the turbidity of the solution was visually evaluated. The evaluation results were expressed in three stages: ；: no turbidity, Δ: slight turbidity, ×: clear turbidity. The results are shown in Table 3 below. The test was performed at a liquid temperature of 25 ° C.

[0028]

[Table 3]

As can be seen from Tables 1 to 3, all of the samples using the polymers of Examples 1 to 8 have an effective chlorine residual ratio of 20% or more and a Ca ion trapping ability of 170 CaCo ₃ mg / g or more. It was good. Further, it showed relatively high compatibility with both nonionic and anionic surfactants.

On the other hand, polyacrylic acid (Comparative Examples 1 and 2), which is preferably used in cleaning agents other than chlorine-based ones, has a high Ca ion trapping ability but an extremely low effective chlorine remaining rate. According to the copolymer of styrene sulfonic acid and maleic acid or acrylic acid (Comparative Examples 3 to 6), the effective chlorine residual ratio is improved to some extent, but is not necessarily sufficient. Further, as compared with the polymers of the examples, they had low compatibility with the surfactant, and even when added in a small amount, they produced turbidity. In the copolymer using methallyl sulfonic acid instead of styrene sulfonic acid (Comparative Examples 8 and 9), the effective chlorine residual ratio was further reduced as compared with the case where styrene sulfonic acid was used. Comparative Example 7 is an example in which the molecular weight of the copolymer was too low, and both the effective chlorine remaining rate and the Ca ion trapping ability were insufficient.

In Example 9, the copolymer of ATBS and acrylic acid had a small copolymerization ratio of ATBS and a small effect of suppressing the decomposition of chlorine-releasing substances. In Example 10, the copolymerization ratio of acrylic acid was small. Although it is excellent in the effect of suppressing the decomposition of chlorine-releasing substances, it has low Ca ion trapping ability and leaves a problem in its original function as a builder.

[0032]

The additive of the present invention has sufficient metal ion-capturing ability, is hardly decomposed even when coexisting with a chlorine releasing substance, and has a high compatibility with water and a surfactant. Having. Therefore, it is very useful as an additive for chlorine-based cleaning agents.

Continuation of the front page (51) Int.Cl. ⁶ identification code FI C11D 3: 065 3:08 3:04 3:39) (72) Inventor Minoru Okada One of 1 Funamicho, Minato-ku, Nagoya-shi, Aichi 1 Nagoya Research Institute

Claims (2)

[Claims] An α, β-ethylenically unsaturated carboxylic acid containing 2-acrylamido-2-methylpropanesulfonic acid or an alkali salt thereof as a constituent monomer and having a weight average molecular weight of 5,000 to 250,000. An additive for a chlorine-based detergent, comprising a copolymer of an acid or an alkali salt thereof. 2. A chlorine-based cleaning agent comprising the additive according to claim 1.