JPH08104892A - Detergent composition - Google Patents

Abstract

PURPOSE: To provide the subject inexpensive composition having a polyvalent metal sequestering capability and a biodegradability and containing a surfactant and a builder composed of a polymer of an unsaturated carboxylic acid monomer obtained by the catalytic oxidization of a hydroxyl compound in the presence of a specific supported catalyst and an oxidizing agent. CONSTITUTION: A monomer having carboxyl group is produced by the catalytic oxidization of a hydroxyl compound (e.g. glycerol) in the presence of an oxidizing agent and a supported catalyst composed of (i) the 1st catalyst component consisting of one or more elements such as Pd, Pt, Rh and Ru and the 2nd catalyst component consisting of one or more elements such as Bi, Te, Sn, Pb, Sb or Se, (ii) the 1st catalyst component and the 3rd catalyst component consisting of one or more elements selected from rare earth metal elements, (iii) all of the 1st, the 2nd and the 3rd catalyst components or (iv) exclusively the 1st catalyst component. The objective detergent composition having high detergency and producible at a low cost is produced by compounding (A) a surfactant with (B) a builder consisting of a carboxyl-containing polymer produced by polymerizing the above carboxyl-containing monomer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to detergent compositions.
More specifically, it relates to a detergent composition containing a polymer builder, which has a high ability to capture divalent metal ions and biodegradability and can be produced using an inexpensive raw material.

[0002]

BACKGROUND OF THE INVENTION In the past, phosphate compounds such as sodium tripolyphosphate have been used as builders in detergent compositions. However, the use of phosphate compounds in detergent compositions has been administratively regulated or banned because they promote eutrophication of lakes and rivers.

At present, aluminosilicate is widely used as a substitute for phosphate compounds in powder detergent compositions. However, aluminosilicate has drawbacks such as a low rate of capturing divalent metal ions, and in order to compensate for it, a polycarboxylic acid represented by a copolymer with polyacrylic acid or maleic acid is used in combination. In many cases However, since these polycarboxylic acids have low biodegradability, their environmental impact has become a problem.

In view of such a situation, US Monsanto Co., Ltd. conducted a synthetic research on a polycarboxylic acid salt (polyglyoxylic acid, Builder U), which is a biodegradable polymer, using glyoxylic acid ester as a raw material, and published Japanese Patent Publication No. Sho 62-37044. Japanese Patent Publication (USP 4,144,226). This builder U has an excellent biodegradability and a high divalent metal ion capturing ability because the polymer main chain is formed by an acetal bond, and is an excellent detergent builder. However, since the raw material monomer glyoxylic acid ester is expensive and the synthetic route of the monomer and the polymer is complicated, there remains a problem in terms of practicality. So, as a builder for cleaning agents,
An inexpensive biodegradable polymer having a high divalent metal ion-capturing ability has been earnestly desired.

In order to solve the above problems, an object of the present invention is to efficiently produce a polymer having a high divalent metal ion-capturing ability and biodegradability using an inexpensive raw material, and use this as a detergent builder. It is intended to provide a detergent composition which has a high detergency and is excellent in economic and environmental aspects.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that glycerin, glyceric acid, ethylene glycol, propylene glycol, hydroxyacetone, lactic acid or a salt thereof, a salt of glyceric acid, etc. A cleaning composition containing a polymer having a carboxyl group obtained by catalytic oxidation in the presence of an inexpensive raw material, a predetermined catalyst composition and an oxidizing agent is equal to or more than a cleaning composition containing an aluminosilicate. It was found that the detergency of the present invention is shown, and the present invention has been completed. That is, the gist of the present invention is as follows: (1) In a detergent composition containing a surfactant and a builder, the builder catalytically oxidizes a hydroxyl compound in the presence of a catalyst composition and an oxidizing agent described below. A detergent composition characterized by being a polymer having a carboxyl group obtained by polymerizing the monomer having a carboxyl group, and a catalyst composition: consisting of palladium, platinum, rhodium and ruthenium One or more elements selected from the group as the catalyst first component, one or more elements selected from the group consisting of bismuth, tellurium, tin, lead, antimony, and selenium as the catalyst second component, one selected from the rare earth elements The above elements are used as a catalyst third component, and (a) a catalyst first component and a catalyst second component (b) a catalyst first component and a catalyst third component (c) Medium first component, the catalyst second component and catalyst third component,
Alternatively, (d) a supported catalyst consisting of only the catalyst first component. (2) The cleaning composition according to (1) above, wherein the hydroxyl group compound is glycerin, glyceric acid or a salt of glyceric acid, (3) The hydroxyl group compound is tartronic acid or a salt thereof. (1) The detergent composition according to (1), wherein the hydroxyl compound is ethylene glycol, glycolic acid or a salt of glycolic acid, (5) The hydroxyl group The compound is propylene glycol, hydroxyacetone, lactic acid or a salt of lactic acid, (6) The detergent composition according to the above (1), wherein the hydroxyl compound is a mixture of glycerin and ethylene glycol. The detergent composition according to (1) above, (7) The catalyst composition of the catalyst composition (c) has a catalyst first component of palladium and platinum, and a catalyst second component of bismuth. Or tellurium,
The cleaning composition according to any one of (1) to (6), wherein the third component of the catalyst is cerium and / or lanthanum, (8) the reaction is carried out in a fixed bed reactor filled with the catalyst composition. (9) The detergent composition according to any one of (1) to (7), (9) The catalyst composition is diluted with 0.5 to 20 parts by weight of a diluent per 1 part by weight and filled. (8) The detergent composition according to (8), (10) the polymer having a carboxyl group has a weight average molecular weight of 500 to 1, measured by gel permeation chromatography.
(1) The detergent composition according to any one of (1) to (9), wherein the polymer having a carboxyl group has a calcium capturing ability of 100 to 600 mg-CaCO ₃ / g. The cleaning composition according to any one of (1) to (10) above.

The detergent composition of the present invention is a detergent composition comprising a surfactant and a builder, wherein the builder catalytically oxidizes a hydroxyl compound in the presence of the following catalyst composition and oxidant. To produce a monomer having a carboxyl group and polymerize the monomer to obtain a polymer having a carboxyl group. Therefore, first, the method for producing the polymer will be described below based on the reaction scheme shown in FIG.

The polymerization in the present invention is mainly oxidative dehydrogenation polymerization. That is, active hydrogen at the polymerization site of a precursor of a monomer (hereinafter sometimes abbreviated as a monomer precursor) which is a reaction raw material catalytically reacts with oxygen supplied from the bulk on the catalyst surface to generate water. That is, a monomer having an aldehyde group or a carbonyl group directly involved in the polymerization (hereinafter sometimes abbreviated as a monomer) is generated on the catalyst surface, and the polymerization reaction of the monomer proceeds.

The monomer precursor in the present invention is
(1) Glycerin, glyceric acid, or a salt of glyceric acid, (2) tartronic acid or a salt thereof, (3) ethylene glycol, glycolic acid, or a salt of glycolic acid,
(4) Propylene glycol, hydroxyacetone, lactic acid or a salt of lactic acid is used.

Glyceric acid and tartronic acid are oxides of glycerin, and glycolic acid is a decarboxylated decomposition product of tartronic acid or an oxide of ethylene glycol. These are glycerin, as shown in the reaction scheme of FIG.
Glycerin, ethylene glycol, and propylene glycol are the cheapest initial raw materials because they are sequentially produced by catalytic oxidation of ethylene glycol and propylene glycol.

Further, as the monomer directly involved in the polymerization, tartronic aldehyde, ketomalonic acid, glyoxylic acid, pyruvic acid or their obtained by catalytic oxidation of glyceric acid, tartronic acid, glycolic acid, lactic acid or their salts, respectively. Although they are salts, these monomers may be those synthesized by a separate synthesis method.

Although the reaction mechanism of further polymerizing the monomers produced by using these monomer precursors to produce the polymer of the present invention has not been completely clarified, it has been found from the conventional knowledge about catalytic oxidation that the reaction mechanism shown in FIG. Is estimated as. That is, the reaction of the present invention is as follows: (1) an oxidation reaction part for producing a monomer precursor and a monomer;
It is roughly classified into three parts, (2) a polymerized portion into a polymer having a carboxyl group, and (3) a decarboxylation decomposition portion of the polymer.

As an oxidation reaction part for producing a monomer precursor and a monomer, for example, catalytic oxidation of glycerin starts and glyceric acid is produced via glyceraldehyde. Glyceric acid is further oxidized to form tartronic aldehyde, one of the monomers in the present invention. Alternatively, the tartronic aldehyde is further oxidized to form tartronic acid, which in turn forms one of the monomers in the present invention, ketomalonic acid.
In addition, tartronic acid produces glycolic acid by decarboxylation and further produces glyoxylic acid, which is one of the monomers in the present invention.

When ethylene glycol is used as the starting material, it is oxidized to glycolic acid via the corresponding aldehyde, which is the same as that produced by decarboxylation of tartronic acid. Glycolic acid is further oxidized to produce the monomer glyoxylic acid.

When propylene glycol is used as a starting material, pyruvic acid, which is one of the monomers in the present invention, is produced via hydroxyacetone or lactic acid.

The polymerized portion into the polymer having a carboxyl group is roughly classified into the following four routes ((a) to (d)) corresponding to the above oxidation reaction route.

(A) In the case of using tartronic acid or a salt thereof as a monomer precursor, in this route, a polymerization reaction using ketomalonic acid as a monomer proceeds while the secondary hydroxyl group undergoes oxidative dehydrogenation ( Route 1). As a result, polyketomalonic acid (I) or a salt thereof is produced as a polymer.

(B) when glycerin, glyceric acid, or a salt of glyceric acid is used as a monomer precursor,
In this route, tartronic acid aldehyde or its salt, which is a monomer, is generated by the oxidation of the primary hydroxyl group of glyceric acid or its salt, which is the monomer precursor immediately before it, and the aldehyde group is converted into an ether bond to proceed the polymerization reaction. (Route 2). It is presumed that as a result, polytartronic acid aldehyde (III) or a salt thereof is produced as a polymer, and the secondary hydroxyl group is further oxidized to produce polymesoxalaldehyde acid (IV) or a salt thereof which is a polymer.

(C) Tartronic acid or its salt itself undergoes decarboxylation as described above to become glycolic acid or its salt. In this case, glycolic acid or a salt thereof which is a monomer precursor is further oxidized to proceed a polymerization reaction using glyoxylic acid or a salt thereof as a monomer (route 3). As a result, polyglyoxylic acid (II) or a salt thereof is produced as a polymer. Also, when ethylene glycol is used as a monomer precursor, polyglyoxylic acid (II) is similarly produced via glycolic acid and glyoxylic acid.

(D) In the case of using propylene glycol, hydroxyacetone, lactic acid or a salt of lactic acid as a monomer precursor, both produce polypyruvic acid (V) via pyruvic acid (route 4).

As the decarboxylative decomposition portion of the polymers ((I) and (IV)), polyketomalonic acid (I), polymesoxalaldehyde acid (IV) or their salts are thermodynamically unstable. Therefore, it is presumed that it is easily decarboxylated at high temperature and decomposed into polyglyoxylic acid (II) or its salt. As is clear from such a reaction scheme, it is effective to suppress the disappearance of the carboxyl group due to the decarboxylation of the polymer as much as possible in order to produce a polymer having a large amount of the carboxyl group.

When a mixture of glycerin and ethylene glycol (for example, an equimolar mixture) is used as a starting material in the present invention, the same polymerization reaction proceeds according to Routes 1-3. In this case, a random copolymer of ketomalonic acid and glyoxylic acid is formed, as compared with the homopolymer of ketomalonic acid of Route 1, so that the copolymerization is good and the copolymer having good thermal stability is formed.

As the hydroxyl group compound in the present invention, glycerin, ethylene glycol, glyceric acid,
In addition to raw materials such as tartronic acid or glycolic acid or salts thereof, for example, 1,2-propylene glycol, 1,
Polyhydric alcohols such as 3-propylene glycol, monohydric alcohols such as methanol, ethanol, propyl alcohol and isopropyl alcohol, or aldehydes such as formaldehyde and acetaldehyde can be made to coexist. Also in this case, the polyhydric alcohol, the corresponding aldehyde or ketone which is an oxide of a monohydric alcohol, or the structural unit of the aldehyde is incorporated in the main chain of the polymer having a carboxyl group of the present invention (random copolymerization. ), Because of the thermodynamic stability of the produced polymer, it may be more effective as a polymer builder for detergent than when glycerin or its oxide is used as a starting material.

A platinum-based noble metal catalyst is effective as the catalyst composition used in the present invention. That is, one or more elements selected from the group consisting of palladium, platinum, rhodium, and ruthenium as the catalyst first component, one or more elements selected from the group consisting of bismuth, tellurium, tin, lead, antimony, and selenium. When the catalyst second component is one or more elements selected from rare earth elements and the catalyst third component is (a) a catalyst composition in which a catalyst first component and a catalyst second component are combined, (b) a catalyst first component And a catalyst composition in which a catalyst third component is combined, (c) a catalyst first component, a catalyst composition in which a catalyst second component and a catalyst third component are combined,
(D) A catalyst composition comprising only the catalyst first component is used.

Since the polymer having a carboxyl group of the present invention is thermally unstable and easily undergoes decarboxylation decomposition, it has a low temperature activity that allows oxidative polymerization to proceed under mild conditions. Noble metal catalysts are particularly effective.
However, other general oxidation catalysts, or oxidation by an inorganic or organic reagent (hydrogen peroxide, peracetic acid, etc.) and oxidative polymerization can also be used together.

The catalyst composition (a) in which the catalyst first component and the catalyst second component are combined is a preferable catalyst composition from the viewpoint of suppressing a decrease in catalyst activity due to oxygen poisoning. As the second component of the catalyst, bismuth, tellurium, tin,
Examples include lead, antimony, and selenium, with no particular limitation, antimony, bismuth, tellurium, and lead being particularly effective. For example, by complexing palladium with bismuth or tellurium, oxygen poisoning can be avoided and the oxidation reaction rate and the raw material conversion rate can be greatly improved. Also known as Lindlar catalyst is Pb / Pd /
CaCO ₃ catalyst can also be used as the catalyst of the present invention. Bismuth, tellurium and antimony are particularly useful.

In the present invention, since the polymerization reaction occurs concurrently with the production of the monomer, the effect of mass transfer is large, and as a result, the poisoning of the product derived from the produced polymer becomes an important problem. In order to promote mass transfer, three methods such as the combined use of a diluent described below, an outer layer supporting method, and control of the oxygen supply amount are proposed, but these are not direct methods. In order to suppress the poisoning of polymer-derived products at the atomic / molecular level, it is necessary to consider the physicochemical interaction between the produced polymer and the catalyst surface on the solid catalyst surface. Taking this into consideration, by eliminating the product poisoning derived from the produced polymer, it is possible to provide an unprecedented new method of applying the fixed bed reactor to the polymerization reaction.

[0028] As a concrete method, the idea of modifying the solid surface based on surface science is required. To achieve this effect, how to add the catalyst second component to the surface of the main catalyst element of the underlying layer. It is determined by whether or not it is possible to carry the highly dispersed particles effectively. This is determined by the physical properties of the base metal and the second component of the catalyst, but depends largely on the catalyst preparation method. The liquid phase equilibrium adsorption step supporting method used in the present invention is an extremely effective method and can be applied to mass production of catalysts. Here, the liquid phase equilibrium adsorption step supporting method is as follows. When loading the catalyst components, the loading process for each component is provided independently, or the difference in solubility is used to make the loading process of the catalyst components proceed stepwise, and after the loading is completed, water as a solvent is separated by filtration. Then, a slight amount of excess catalyst component is removed, or the reduction treatment is carried out as it is in the liquid phase (in water) without evaporating the solvent containing the catalyst component to dryness as in the usual impregnation method.
For example, in the case of the Pt / Bi catalyst, which is a typical catalyst of the present invention, a homogeneous hydrochloric acid aqueous solution of chloroplatinic acid and bismuth chloride is prepared in advance as a supporting catalyst raw material solution. Chloroplatinic acid is supported as a uniform aqueous solution due to the difference in solubility between the two components in the loading step, but bismuth chloride having a low solubility becomes water-insoluble once and becomes cloudy, and the cloudy component remains for 10 to 60 minutes. After that, it is gradually dissolved and supported. That is, a stepwise loading process is carried out in which platinum is first loaded and then bismuth is loaded. Alternatively, it also includes a method in which Pt and Bi are independently prepared as supporting materials and each is independently supported in two stages.

From these findings, bismuth is particularly effective as the second component of the catalyst in the present invention. That is, bismuth has an ad-atom structure or an ad-layer structure on the surface of the main catalytic element typified by palladium or platinum, especially on the (111) plane, as compared with other catalyst second components.
It is considered that the structure is easy to take, and as a result, the adsorption of the produced polymer is greatly suppressed. This peculiarity of bismuth depends on the measurement of the CO adsorption amount of a two-component catalyst with palladium or platinum. In the case of bismuth, the adsorption amount of the produced polymer is Compared with the case of platinum alone, it is drastically reduced to 1/5 to 1/6, and the atomic ratio of Pd / Bi and Pt / Bi on the catalyst surface obtained from the dispersity of palladium or platinum and the surface area is 3 I understand.

The catalyst composition (b) in which the catalyst first component and the catalyst third component are combined is a combination of the catalyst third component from the viewpoint of achieving high-speed reactivity. Lanthanum, cerium, praseodymium, neobidium and the like are effective as the rare earth element. This is because the addition of the rare earth element, which is a basic element, causes the catalyst first component, such as palladium, to be in a highly dispersed state and imparts basicity to the catalyst surface, and as a result, high-speed reactivity is achieved. .

The catalyst composition (C) obtained by combining the catalyst first component, the catalyst second component and the catalyst third component is the above-mentioned (A).
It is a composition having both the properties of the catalyst composition of (2) and (2), and it is possible to obtain the effect of suppressing the decrease in catalyst activity due to oxygen poisoning and achieving high-speed reactivity. The catalyst composition is not particularly limited, but may be, for example, Ce.Bi.
・ Pd, Ce ・ Te ・ Pd, Se ・ Bi ・ Pd, Ce ・
Bi / Se / Pd, Ce / Bi / Te / Pd, Bi / P
Examples are t.Pd, Ce.Bi, Pt, Pd, and the like.
Among them, as the catalyst composition of (C), one in which the catalyst first component is palladium and platinum, the catalyst second component is bismuth and / or tellurium, and the catalyst third component is cerium and / or lanthanum is preferably used. . Further, as described above, in the present invention, by using a plurality of catalyst first components, in particular platinum as a co-catalyst, it is possible to reform to a low temperature active catalyst system. In particular, the four-component catalyst of Ce, Bi, Pt, and Pd has remarkable low-temperature activity and polymerization activity, and gives a polycarboxylic acid having a high Ca-capturing ability.

That is, Ce, Bi, P using two kinds of palladium and platinum in combination as the first catalyst component, bismuth as the second catalyst component and cerium as the third catalyst component.
The t-Pd four-component catalyst (catalyst composition (c)) is one of the high-performance low-temperature active catalysts in which the functions of the individual elements are highly complexed, and each element mainly has the following functions. Ce: High dispersant for Pd and Pt, basicity imparting agent Bi: Oxygen poisoning inhibitor, product poisoning inhibitor Pt: Low temperature activator Pd: Primary hydroxyl group oxidizing ability (under basicity), mainly Catalytic element Bi / Pt: Secondary hydroxyl group oxidizing ability (under acidic condition)

This four-component catalyst is composed of a composite of a Ce.Bi.Pd catalyst system which mainly exhibits a primary hydroxyl group oxidizing ability and a Bi.Pt catalyst system which mainly exhibits a secondary hydroxyl group oxidizing ability. Therefore, for example, when glycerin is used as the starting material, the primary hydroxyl group of glycerin is Ce · Bi · P.
The Bi · Pt catalyst efficiently oxidizes the secondary hydroxyl group of tartronic acid generated by oxidation with the d catalyst to induce ketomalonic acid. The catalyst performance and the composition of the product can be largely controlled by the composition of other components (Pt, Bi, Ce) with respect to palladium as the main catalyst element.

In the catalyst composition of the present invention, for example, palladium can be used alone as shown in the catalyst composition (d). However, preferably, it is combined with the catalyst second component (catalyst composition (a)), with the catalyst third component (catalyst composition (b)), and further with the catalyst second component and the catalyst third component. By compounding (catalyst composition (C)),
Further, by using two or more kinds of each catalyst component in combination, the catalytic activity and selectivity can be dramatically improved.

The composition of the multi-component catalyst in the present invention is important and has a great influence on the catalytic activity. Therefore, the atomic ratio of the bulk of the catalyst second component to the catalyst first component (R1)
The following range is selected depending on the type of the catalyst second component. When the second catalyst component is selenium, R1 is 0.05 to
It is 0.3, preferably 0.05-0.10. When the second component of the catalyst is tellurium, bismuth, antimony or tin, R1 is 0.05 to 1.5, preferably 0.1 to 0.5.
Is. When the second component of the catalyst is bismuth or tellurium, the optimum R1 is 0.2 and the surface structure is √3 × √
It is presumed to have a 3R30 ° structure.

The amount of catalyst supported has an influence on the molecular weight of the polymer to be produced, and the lower the amount of carrier, the larger the molecular weight tends to be. The supported amount of the catalyst first component is usually 0.1 to 10% by weight, preferably 0.1 to 10%, based on the total supported catalyst (including the catalyst carrier).
-5% by weight, particularly preferably 0.1-3% by weight.
Among them, when the catalyst first component is palladium, when it is used alone or when it is used in combination with the catalyst second component and the catalyst third component, 0.5 to 10% by weight is preferable, and 1 to 6% by weight is more preferred. 0.5% by weight
If it is less than 10%, the reaction rate is slow, and if it exceeds 10% by weight, there is a problem in terms of cost. The supported amount of the second component of the catalyst is R1 described above.
From the viewpoint of catalytic activity, it is usually 0.1 to 10% by weight, preferably 0.1 to 5% by weight, and particularly preferably 0.5 to 3% by weight.

From the viewpoint of catalytic activity, the atomic ratio (R2) of the bulk of the catalyst third component to the catalyst first component is usually 0.01.
˜1.0, preferably 0.05 to 0.5, and more preferably 0.1 to 0.3. The loading amount of the third component of the catalyst is
From the viewpoint of catalytic activity, it is usually 0.1 to 5% by weight, preferably 0.3 to 3% by weight, and particularly preferably 0.3 to 1.5% by weight.

In the catalyst composition of the present invention, the catalyst component is supported on the catalyst carrier in water by a conventional impregnation method, co-impregnation method, dipping method or co-precipitation method, and formalin, hydrazine, sodium borohydride, hydrogen, Lower alcohol (methanol, ethanol, glycerin, ethylene glycol, etc.)
It can be easily prepared by an ordinary method such as a reduction treatment by the above. In particular, when a catalyst component is supported on a catalyst carrier in an aqueous solution, a highly active catalyst can be prepared by carrying out a reduction treatment in water in a dispersed state without dehydrating and drying the catalyst precursor after supporting.

In preparing the catalyst, an outer layer supporting (egg shell) in which the catalyst component is mainly supported on the outer layer of the catalyst carrier is used.
The type) is very effective for mass transfer because the reaction of the present invention is a polymerization reaction. As the effect of supporting the outer layer, bismuth, which is the second component of the catalyst used as the oxygen poisoning inhibitor, is particularly effective. This is because the bismuth has an ad-atom structure or an ad-atom structure as compared with other second catalyst components as described above.
It is considered that this is because the layer structure is easily obtained, and as a result, the adsorption of the produced polymer is largely suppressed.
This peculiarity of bismuth is different from that of other second catalyst components, tellurium and lead, in the case of bismuth by measuring the CO adsorption amount of a two-component catalyst with palladium, as compared with the case of palladium alone. It can also be understood from the drastic decrease as described above. The surface structure of the outer layer supported catalyst is
Although it largely depends on the preparation method, it basically depends on the surface properties of the main catalyst element, palladium, and the catalyst second component. When preparing the outer layer supported catalyst, the supporting time is also an important factor. In the liquid phase equilibrium adsorption stage supporting method used in the present invention, the supporting time should be 5 hours or less, preferably 2 hours or less.

Examples of the catalyst carrier include activated carbon, carbon black, calcium carbonate, silica, alumina, molecular sieve, asbestos, oxides of rare earth elements, and the like. Activated carbon having a high surface area, carbon black, alumina and silica are more preferable. preferable. Of these, activated carbon is particularly effective.

The activated carbon as a catalyst carrier used in the present invention may be derived from any raw material such as coconut shell, wood-based, coal-based, beet carbon-based or petroleum pitch-based materials.
In particular, coconut shells, woods and petroleum pitches having a low ignition residue or low ash content are effective. The activated carbon may be activated by either steam activation or chemical activation, but the steam activated product may be more effective as a carrier. The activated carbon as the catalyst carrier used in the present invention may be a commercially available product as it is, but may be used after a suitable pretreatment such as acid treatment to adjust the pore distribution or reduce the ash content. . As the commercially available granular and powdered activated carbon used in the present invention, those for general water treatment and water-soluble food refining are used, for example, granular Shirasagi series (WH, Sx, KL) and carborafine manufactured by Takeda Pharmaceutical Co., Ltd. Powdered activated carbon represented by Norit and granular activated carbon (RO
X, RAX, DARCO, C, ELORIT, etc.) and powder products (AZO
, PN, ZN, etc.), beaded activated carbon (BAC) manufactured by Kureha Chemical Co., Ltd.
Is mentioned.

Commercially available carbon black is also effective as a catalyst carrier when carrying out the reaction of the present invention,
For example, carbon black manufactured by Cavrac Co., Ltd. may be mentioned. However, the activated carbon and carbon black used in the present invention are not particularly limited to these activated carbon and carbon black.

The reaction temperature for synthesizing the polymer of the present invention is an extremely important factor and greatly affects the yield of the polymer having a carboxyl group of the present invention. That is, in order to suppress the decomposition of the carboxyl group in the polymer by decarboxylation as much as possible, it is desirable to carry out the reaction in both the oxidation reaction section and the polymerization section of the reaction scheme as low as possible.
The reaction temperature can be carried out at -30 to 100 ° C, but is preferably -10 to 60 ° C, more preferably 0 to prevent decarboxylation decomposition of the produced polymer.
It is good to carry out at -50 ° C, particularly preferably at 20-40 ° C.

That is, in the synthesis of the polymer according to the present invention, the lower the reaction temperature is, the more easily the polymer is produced, and the by-product of sodium carbonate due to decarboxylation can be kept at several% or less. In addition, the optimum reaction temperatures for the monomer production step and the polymer production step are different, the former being 60 ° C. or lower and the latter being 30 ° C. or lower. . Furthermore, the low temperature is more advantageous in terms of the solubility of oxygen. Therefore, by using the low temperature active catalyst composition of the present invention, oxidative polymerization at room temperature can be efficiently progressed. The reaction time largely depends on the reaction temperature, the type of catalyst and its concentration, etc., but is usually preferably 1 to 30 hours.

In the reaction for synthesizing the polymer in the present invention, the step of producing a carboxyl group is carried out in an aqueous solution in a basic atmosphere, and thus the polymer produced is generally a carboxylic acid salt. Therefore, it is preferable to set the concentration of the starting material in consideration of the solubility of the polymer formed at the applied reaction temperature.
That is, the raw material concentration is usually preferably 1 to 80% by weight,
50% by weight is more preferred. If the raw material concentration is less than 1% by weight, the concentration of the obtained polymer is too low to be practical.
If it exceeds 0% by weight, the viscosity becomes too high and the mass transfer rate decreases, resulting in a large decrease in the reaction rate. Further, it is effective to use water as the reaction solvent from the viewpoint of productivity and efficiency.

In the polymer synthesis reaction of the present invention,
Sodium hydroxide is used as an alkali agent required for synthesizing a monomer precursor and a monomer by an oxidation reaction and for promoting an oxidative polymerization reaction in a basic atmosphere.
Alkali metal hydroxides such as potassium hydroxide and lithium hydroxide, amines such as monoethanolamine and diethanolamine, and ammonia are used.

In this case, the alkali excess serves as an important reaction factor to control the pH during the reaction and has a great influence on the structure and the degree of polymerization of the polymer in the present invention, and as a result, the Ca-trapping ability as a builder for detergents. Have a great influence on. For example, when synthesizing a polymer according to the present invention using glycerin as a starting material as shown in the following formula, sodium hydroxide, for example, as an alkaline agent is used in an amount twice that of glycerin.

[0048]

Embedded image

As a result, sodium hydroxide is consumed up to polyketomalonic acid, but polyketomalonic acid is thermodynamically unstable, so that part of the carboxyl is easily decarboxylated. As a result, the glyoxylic acid skeleton is present in the polymer chain and excess sodium hydroxide is produced. This excess sodium hydroxide usually reacts with carbon dioxide that has been decarboxylated and decomposed to produce sodium hydrogen carbonate and sodium carbonate.

Therefore, when the starting material is glycerin, the equivalence ratio of sodium hydroxide charged to the glycerin is 0.
50 to 0.90 is preferable. Further, when ethylene glycol is used as a raw material, sodium hydroxide may be 0.5 equivalent or less, and when a mixture of glycerin and ethylene glycol is used as a raw material, sodium hydroxide may be used in consideration of the above points. Adjust the excess and adjust the pH of the aqueous reaction mixture.
Is preferably set so as to meet the conditions of the present invention.

The pH during the reaction is such that when a polymer is produced,
At the time of monomer formation, it is preferable to have a basicity of 7 to 13. On the other hand, during polymerization, the pH is preferably 7 or less, preferably 6.0 to 2.5, and particularly preferably 4.5 to 3.0.

For example, in the case of producing a polymer using a stirred tank reactor, the pH is adjusted to 7 to 10 at the time when the monomer production in the initial stage of the reaction is the main, and the time when the polymerization reaction from the middle to the end of the reaction is the main time. Then, it is preferable to control the feed rate of the raw materials (alkali agent, oxidizing agent) so that the pH becomes 7 or less.

Further, the polymer is more preferably produced by using a fixed bed reactor filled with a catalyst composition. In this case, the fixed bed reactor used is preferably a downward cocurrent trickle bed reactor. Monomer production mainly proceeds in the upper stage of the reaction tower of this apparatus, and polymerization reaction mainly proceeds in the middle and lower stages of the reaction tower. In this case, the pH in the height direction of the reaction tower tends to greatly drop from the upper stage to the lower stage, and if necessary, the raw materials are supplied (alkaline agent, oxidizing agent) from a plurality of places in the middle stage of the reaction column, The pH of the outlet reaction mixture is preferably maintained at 6.5-2.0.

As the oxidant used in the present invention, pure oxygen, a mixed gas of pure oxygen and nitrogen, or air can be used, and air is economical although it is not particularly limited.

In the reaction of the present invention, a monomer which is an oxide of glycerin is mainly produced in the initial stage of the reaction, but a polymerization reaction using these monomers as a raw material proceeds in the middle stage to the final stage of the reaction. Therefore, the influence of mass transfer becomes significant in the process of polymer production, and as a result, the reactivity is greatly reduced due to the poisoning of the product, and therefore the oxygen supply amount may be insufficient. The amount of oxygen supplied should be increased with an increase in the molecular weight of the produced polymer, preferably not more than 3 times the equivalent amount, particularly preferably 0.5 to 2 equivalents.
It is better to set it to double. On the contrary, excessive increase of oxygen supply causes concomitant self-poisoning of the catalyst by oxygen.

The reaction in the present invention may be either a stirred tank reactor or a fixed bed reactor (trickle bed) depending on the form of the catalyst composition. When using a fixed bed reactor, it is preferable to dilute and fill the catalyst composition of the present invention with a diluent (reactive inert granules). At this time, the catalyst composition was 0.5 with respect to 1 part by weight of the catalyst composition.
It is preferably diluted with 20 to 20 parts by weight of a diluent, more preferably 4 to 15 parts by weight. By diluting with a diluent, the product poisoning resulting from the adsorption of the produced polymer is remarkably alleviated, and high productivity can be achieved. If it is not diluted with a diluent, the polymer stays on the surface of the catalyst to a large extent and the mass transfer rate is greatly reduced, which may cause a drastic decrease in the reaction rate.

Further, when the catalyst is packed in the fixed bed reactor as described above, the catalyst effective coefficient is increased by mixing the catalyst with the diluent, and as a result, the catalyst activity is increased by a factor of 2 to 3. Sometimes.

Any material may be used as the diluent as long as it does not adversely affect the reaction of the present invention, and examples thereof include porcelain, ceramics, polymer, glass or metal which is inert to the reaction. The particle size of the diluent is not particularly limited,
A particle size of 1/2 to 5 times that of the catalyst carrier is preferred.

The selection of the reactor is not particularly limited, but when the weight average molecular weight of the obtained polymer is 100,000 or more, and a highly viscous polymer is produced, the stirring tank reactor is preferably applied. . However, the weight average molecular weight is 500
In the case of about 100,000, application of a fixed bed reactor is preferable. In this case, there is an advantage that the catalyst separation step can be simplified.

Next, regarding the reaction method in the present invention,
An example of using an aqueous glycerin solution as a starting material will be described. When carrying out the reaction using a stirred tank reactor, a glycerol aqueous solution is added to a stirred tank batch reactor equipped with a stirrer, a thermometer, a pH meter, a raw material gas (oxygen, air, etc.) introduction pipe, and a waste gas line. The catalyst composition is charged and set to a predetermined temperature, oxygen or air as an oxidant is bubbled into the solution, and an aqueous sodium hydroxide solution is continuously added so as to maintain a predetermined pH. By reacting for a predetermined time, the polymerization reaction proceeds along with the formation of the monomer by the oxidation reaction to produce the polymer having a carboxyl group of the present invention.

When a trickle bed type fixed bed reactor is used, for example, a molded catalyst composition is mixed with a diluent and charged into a reaction column, and the packed catalyst is added before carrying out the oxidation reaction of the present invention. It is preferable to carry out the reactivation treatment of. The reason for this is that the surface of the catalyst reduced during the preparation of the catalyst may be oxidized during the storage period and the catalytic activity may be reduced. In carrying out reactivation, 5 to 20% by weight of a hydroxyl compound such as glycerin or ethylene glycol, which is a starting material, is supplied without supplying a basic substance (sodium hydroxide, etc.), which is one of the starting materials for this reaction. It is achieved by supplying the aqueous solution to the reaction tower at a temperature of room temperature to 50 ° C. under air supply overnight. After the catalyst reactivation, the aqueous glycerin solution, the aqueous sodium hydroxide solution, and oxygen or air as an oxidizing agent may be supplied in a downward cocurrent flow from the top of the reaction tower. In this case, the liquid hourly space velocity based on the total of both raw material aqueous solutions is 0.5 to 0.01 h ⁻¹ , preferably 0.1.
Set to 2 to 0.05 h ^-1 .

The composition of the product is 40 to 60% by weight of the monomer and the polymer component is 60 to 40% by weight from 24 to 48 hours after the start of the raw material supply, but the monomer content decreases with the passage of time. In parallel with this, the Ca trapping ability of the polymer obtained in parallel with this greatly increases. The time course of the monomer content in the reaction product can be monitored by HPLC (High Performance Liquid Chromatography) and GPC (Gel Permeation Chromatography), but the baseline of HPLC is usually greatly disturbed due to polymer formation.

The obtained polymer is separated from the reaction mixture by dehydration by freeze-drying, dialysis using a membrane filter or separation by an ultrafiltration membrane, and solvent reprecipitation using a solvent such as isopropyl alcohol, ethanol or methanol. Can be done by law. When the reaction mixture is freeze-dried or reprecipitated by a solvent reprecipitation method, the polymer of the present invention can be obtained as a white powder by drying after solvent separation. However, when the polymer of the present invention is used as a builder for detergent, the aqueous solution of the oxidative polymerization reaction mixture discharged from the reaction tower should be blended into the detergent slurry and spray-dried without separating the polymer. You can

The weight average molecular weight of the thus obtained polymer reached 500 to 1,000,000 by gel permeation chromatography (GPC) analysis, and that of conventional polyglycerin (molecular weight of 500 to 1000). It is far beyond. However, when it is used as a builder for detergents, it is 1000 in view of its ability to capture divalent metal ions.
˜200,000 is preferable, and 2,000 to 100,000 is particularly preferable. In the GPC measurement of the polymer obtained in the present invention, when the terminal stabilization treatment is not particularly performed, the polymer may be easily adsorbed in the column or may be decarboxylated depending on the kind of the packing material. Needs to select the optimal column system.

From the infrared absorption spectrum of the polymer of the present invention, absorption peaks of carbonyl vibrational vibration of carboxylate and vibrational vibration of ether bond were obtained,
From the proton NMR and C ¹³ NMR spectra, absorption peaks of the proton bonded to the etheric carbon and the etheric carbon are obtained, respectively. From this, it has been found that the polymer in the present invention is a polymer having a large amount of carboxyl groups. Further, the polymer in the present invention exhibits biodegradability because the polymer main chain has an acetal bond.

Its structure is represented by formula (i), formula (ii), formula (ii)
i), any one of the formulas (iv) and (v), or a structure containing two or more types of structural units is presumed. This is because the polymerization reaction proceeds under the oxidation reaction, and is one of the features of the production method of the present invention.

[0067]

Embedded image

The polymer obtained by removing the monomer component from the reaction mixture in the present invention has a high calcium ion-trapping ability of 100 to 600 mg-CaCO ₃ / g as measured by the method described in the following examples, and therefore, it is used as a detergent. Useful as a builder.

The polymer of the present invention is added to the detergent composition in an appropriate amount within the range where the desired effect is obtained. Specifically, it is usually 0.1 to 90% by weight in the entire detergent composition. Preferably 0.5 to 50% by weight is blended. If it is less than this range, the washing performance tends to be insufficient because the effect of the builder cannot be obtained, and if it is more than this range, the blending amount of other components such as a surfactant becomes small and it is difficult to obtain sufficient washing performance. Tend.

The detergent composition of the present invention contains the above-mentioned polymer as a builder, contains the following surfactant as an essential component, and may optionally contain various components shown below. However, these are not particularly limited and may be blended according to the purpose.

(1) Surfactant Generally, all the surfactants to be added for detergents can be used. For example, anionic surfactants such as alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, α-sulfo fatty acid salts or esters, higher fatty acid salts, poly Oxyalkylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or their alkylene oxide adducts, alkylamine oxides, nonionic surfactants such as alkyl glycosides, amino acid type or betaine type carboxylate type Examples thereof include amphoteric surfactants, sulfonate-type amphoteric surfactants such as sulfobetaine, and cationic surfactants typified by quaternary ammonium surfactants.

These surfactants are usually added in an amount of 1 to 99% by weight, preferably 5 to 90% by weight, based on the total detergent composition. If it is less than this range, the cleaning performance tends to be insufficient, and if it is more than this range, the physical properties of the powder or the stability of the solution tend to deteriorate.

(2) Builder As a builder component, in addition to the above-mentioned carboxyl group-containing polymer, for example, one or more of the following various alkali metal salts can be used. That is, condensed polyphosphates such as tripolyphosphate, pyrophosphate, metaphosphate, nitrilotriacetate, ethylenediaminetetraacetate, aminopolyacetate such as diethylenetriaminepentaacetate, citrate, malate, glycolic acid, etc. And polyacrylic acid and salts thereof, acrylic acid-maleic anhydride copolymers and salts thereof, and polyelectrolytes such as polyglyoxylic acid and salts thereof. Further, as the water-insoluble substance, talc, finely powdered silica, clay, silicate, and crystalline or amorphous zeolite having divalent metal ion exchange ability can be blended if necessary.

(3) Alkaline Agent or Inorganic Electrolyte As the alkaline agent or inorganic electrolyte, for example, one kind or two or more kinds of various alkali metal salts such as silicate, carbonate and sulfate can be used. In addition, alkanolamines represented by triethanolamine, diethanolamine, monoethanolamine, triisopropanolamine and the like can also be used as the organic alkali agent.

(4) Anti-staining Agent As the anti-staining agent, one or more kinds of polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose and the like can be used.

(5) Bleaching agents, fluorescent dyes, enzymes, etc. Sodium percarbonate, sodium perborate, sodium sulfate / sodium chloride hydrogen peroxide adducts and the like as bleaching agents, and commercially available fluorescent dyes as brightening agents, Fragrance, protease,
Enzymes such as amylases, lipases and cellulases, bluing agents, bleach activators and the like can be added as required. In addition, as a solubilizer used in the liquid detergent, lower alcohols such as ethanol and isopropanol, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin and sorbitol, p-toluenesulfonic acid salt, m-xylenesulfonic acid salt and the like Can also be used.

The detergent composition of the present invention can be produced by a generally known production method, for example, a spray drying method, a spray mix method, a crushing granulation method, a method of impregnating beads containing an inorganic builder, a method of producing a high-density granular detergent, tablets. It can be produced by a method for producing a detergent such as a mold, a flake or a rod, or a method for producing a liquid detergent such as a batch-type mixing method or a continuous-type mixing method.

[0078]

The present invention will be described in detail below with reference to synthesis examples and examples, but the present invention is not limited to these examples. In the following examples and the like,% indicated with respect to the amount of supported catalyst means% by weight. Further, the conversion rate of the hydroxyl compound represents the ratio of the number of moles consumed in the oxidation reaction to the charged hydroxyl compound. In addition,% of conversion rate is
All are weight percent. Further, the polymer yield is a value excluding the molar-based residual ratio of the hydroxyl group compound, the monomer and the monomer precursor remaining in the reaction mixture.

[0079]

[Equation 1]

The various analyzes and evaluations performed in the synthesis examples and examples were carried out by the following methods.

(Analysis of Polymer) The reaction mixture was reprecipitated by the solvent reprecipitation method using ethyl alcohol, and the solvent was separated and dried. The hygroscopic white powder thus obtained was analyzed by infrared absorption spectrum, NMR spectrum and gel permeation chromatography (GPC). The GPC measurement conditions are shown below. Column: G 2000SW-G 4000SW (Toso-manufactured silica gel packed column) Before the analysis of the polymer, an aqueous solution of the sodium formalin condensate of naphthalene sulfonate is passed through the column, and the condensate is silica gel. It is necessary to be adsorbed on. -Solvent: 0.1 M-NaCl aqueous solution / acetonitrile = 7 / 3-Flow rate: 0.8 ml / min-Temperature: 25 ° C-Detector: UV-8011 (manufactured by Toso), 210 nm
Measured at ・ Sample concentration: 0.1% aqueous solution

(Quantitative analysis by HPLC) The conditions of HPLC are shown below.・ High performance liquid chromatography: D-2500 / L-6
Type 000 manufactured by Hitachi, Ltd.-Detector: L-3300 type (RI monitor) -Column: C-61OS-Eluent: 0.5% phosphoric acid aqueous solution 0.5 ml /
min ・ Pressure: 10kg / cm ²・ Temperature ： 50 ℃

(Ca ion scavenging ability) Polymers collected in the following synthesis examples were freeze-dried, and the Ca ion scavenging ability was measured by the following method using the dried polymer. To prepare a standard Ca ion solution using first _{0.1M-NH 4 Cl-NH 4} OH buffer (pH 10),
The potential of the standard Ca ion solution is measured using an ion analyzer (model 920A, manufactured by Orion Co.) equipped with a Ca ion electrode, and a calibration curve showing the relationship between the logarithm of the Ca ion concentration and the potential as shown in FIG. 2 is created. Next, 0.1 g of the dried polymer is weighed in a 100 ml volumetric flask, and the volume is adjusted with the above buffer solution. 20,000ppm to this
(CaCO ₃ equivalent) CaCl ₂ solution (pH 1
0) is dropped from the buret (a blank is also measured). Dropping is performed by adding 0.1 to 0.2 ml of CaCl ₂ solution, the potential at that time is read, and the calcium ion concentration is determined from the calibration curve in FIG. The Ca ion concentration at the dropping amount A of the sample in FIG. 3 is the Ca ion trapping ability of the sample.

(Preparation of catalyst composition) Takeda Pharmaceutical Co., Ltd.
Wood-based activated carbon, WH ₂ C (specific surface area: 1200 m ² /
g, bulk density: 500 / liter, pore volume: 0.8 ml
/ G) as a catalyst carrier 0.9% Ce.3.0%
A three-component catalyst composed of Bi · 3.0% Pd / C was prepared by the following method. 93 g of activated carbon dried with hot air at 120 ° C. was dispersed in 1250 ml of ion-exchanged water overnight. Meanwhile, cerium chloride _{(CeCl 3 · 7H 2 O)} 2.
4 g, 4.5 g of bismuth chloride (BiCl ₃ ) and 5.0 g of palladium chloride (PdCl ₃ ) were uniformly dissolved under stirring in a hydrochloric acid aqueous solution in which 26 ml of concentrated hydrochloric acid was added to 150 ml of ion-exchanged water. The obtained brown homogeneous solution of the catalyst component was added to an aqueous dispersion of activated carbon, and the mixture was stirred for 5 hours.
The catalyst component was loaded at room temperature. The supernatant liquid became colorless and transparent. In order to carry out the reduction treatment of the obtained catalyst precursor, the pH of the aqueous dispersion of the catalyst precursor was maintained at about 12 with 20% sodium hydroxide aqueous solution, and 20 ml of 37% formalin aqueous solution was added. While stirring, raise the temperature to 80 ° C and
The reduction treatment was performed at 30 ° C for 30 minutes. The resulting catalyst was allowed to cool to room temperature, washed 3 times with 1500 ml of deionized water, and filtered under reduced pressure. By the above operation, the water content of about 50% of 0.
100 g of a 9% Ce / 3.0% Bi / 3.0% Pd / C catalyst was obtained as a dry product. The other catalyst compositions in the synthesis examples were prepared by the same operation.

(Washing evaluation) -Mud dirt-contaminated cloth (artificial-contaminated cloth) Deer mud horticultural red ball soil was dried for 4 hours at 120 ° C ± 5 ° C, then crushed, and a 150-mesh (100 µm) pass was used for 120
After drying for 2 hours at ℃ ± 5 ℃, about 150g is dispersed in 1 liter Perkren, and a cloth # 2023 is contacted with this solution and brushed to remove the dispersion and remove excess adherent dirt (JP-A-55-55). 26473).

-Sebum-dirt-contaminated cloth (artificial-contaminated cloth) * Model sebum-dirt composition Cotton seed oil 60% Cholesterol 10% Oleic acid 10% Palmitic acid 10% Liquid and solid paraffin 10% 10 cm x 10 cm Composed of 2 g of the above composition on cotton cloth Apply the model sebum stain evenly.

Washing condition and evaluation method 5 l of 10 cm × 10 cm cotton mud-dirt-contaminated cloth or sebum-contaminated cloth (artificial-contaminated cloth) was added to 1 liter of the detergent aqueous solution for evaluation.
Sheets were put in and washed with a tergotometer at 100 rpm under the following conditions. The washing conditions are as follows. <Washing conditions> Washing time 10 minutes Washing concentration 0.083% Water hardness 4 ° DH Water temperature 20 ° C Susugi 5 minutes with tap water Detergency is 460n of original cloth before and before and after cleaning
The reflectance at m was measured with a self-recording colorimeter (manufactured by Shimadzu Corp.), and the cleaning rate (%) was calculated by the following formula (the table shows the average value of 5 sheets measured).

[0088]

[Equation 2]

Synthesis Example 1 0.9% Ce · 3.0% prepared in the catalyst composition preparation example
Inner diameter 2 with jacket of Bi / 3.0% Pd / C catalyst
A 200 ml fixed bed reaction tower made of Pyrex having a height of 0 mm and a height of 700 mm was packed with 100 g as a dry product. The reaction temperature was set to 50 ° C., 100 parts of 50% glycerin aqueous solution and 30% sodium hydroxide aqueous solution were added from the top of the reaction tower.
0 parts of the mixed solution, the liquid hourly space velocity (LHSV) 0.07h
Oxygen gas was supplied at a flow rate of r ⁻¹ and a downward cocurrent flow rate of 5 N liter / hr. After 40 hours, a colorless transparent viscous liquid (pH 10 to 11) was distilled from the outlet of the reaction tower. When this liquid was analyzed by high performance liquid chromatography (HPLC), conversion of glycerin was 100%, residual tartronic acid selectivity was 30%, and glyceric acid selectivity was 25%.
Met. On the other hand, analyze this viscous liquid with GPC (Fig. 4)
As a result, a polymer having a weight average molecular weight of 4.503 × 10 ^{4 based on} sodium polystyrene sulfonate was found to be 5.
It was confirmed that 2 wt% and 7.324 × 10 ³ polymer were present in 6.8 wt% (total 12 wt%). The viscous liquid was dialyzed to separate the polymer component. From the infrared absorption spectrum of the obtained polymer, the presence of carboxylate and ether bond was confirmed.
The presence of carbon and hydrogen having an ether bond was confirmed by MR and C ¹³ NMR spectra. From these results, it was estimated that the structure of the obtained polymer was composed of the structural units of the above-mentioned formulas (i) to (iv).

Synthesis Example 2 The reaction was carried out under the same conditions as in Synthesis Example 1, except that a mixed solution of 100 parts of 50% glyceric acid aqueous solution and 130 parts of 26% sodium hydroxide aqueous solution was used. According to GPC measurement of the reaction mixture, 16% of the polymer having a weight average molecular weight of 62,000 based on sodium polystyrene sulfonate was used.
It turned out to exist. It was estimated from the infrared absorption spectrum and the NMR spectrum that the structure of the polymer component obtained by dialysis separation consisted of the structural units of formulas (i) to (iv).

Synthesis Example 3 The catalyst composition is 0.9% Ce.1.5% Te.3.0% P.
d / C and 50% tartronic acid aqueous solution 100
Parts, and the reaction was performed under the same conditions as in Synthesis Example 1 except that a mixed solution of 23 parts of a 23% aqueous sodium hydroxide solution was used. From the GPC measurement of the reaction mixture, it was found that 19% of the polymer having a weight average molecular weight of 47,000 based on sodium polystyrenesulfonate was present. It was estimated from the infrared absorption spectrum and the NMR spectrum that the structure of the polymer component obtained by dialysis-separating the polymer component was composed of the structural units of formulas (i) to (iv).

Synthesis Example 4 The catalyst composition of the first reaction column (the same reactor as used in Synthesis Example 1) was 0.8% Ce.1.5% Bi.0.75%.
Pt.3.0% Pd / C, the catalyst composition of the second reaction column (reactor similar to that used in Synthesis Example 1) was 0.6% Bi.
Using 3.0% Pt / C, 100 parts of 25% aqueous solution of glycerin and ethylene glycol mixed at a molar ratio of 1: 1 and 145 parts of 15% sodium hydroxide, a reaction temperature of 25 ° C was used. The reaction was performed in the same manner as in Synthesis Example 1 except that the above was performed. The reaction mixture leaving the first reaction column was introduced into the second reaction column at the same flow rate as it was. The pH of the distillate at the outlet of the reaction tower was 3.5. Polymer yields are summarized in Table 1. The structure of the polymer component is an infrared absorption spectrum,
It was estimated from the NMR spectrum that it was composed of the structural units of formulas (i) to (iv).

[0093]

[Table 1]

Synthesis Example 5 0.8% Ce / 1.5% Bi / 0.75% Pt / 3.0
% Of Pd / C was diluted with glass beads having a diameter of 0.8 mm as a diluent by a factor of 4 by weight to fill the reaction tower used in Synthesis Example 1 with 100 parts of 25% glycerin aqueous solution. The reaction was performed in the same manner as in Synthesis Example 1 except that a mixed aqueous solution of 145 parts of 15% sodium hydroxide was used. The pH of the distillate at the outlet of the reaction tower was 5.4. Polymer yields are summarized in Table 1. The structure of the polymer component is
From the infrared absorption spectrum and the NMR spectrum, the formula (i)-
It was estimated to consist of the structural unit of formula (iv).

Synthesis Example 6 A mixed aqueous solution of 100 parts of 25% ethylene glycol aqueous solution and 145 parts of 15% sodium hydroxide was used, and 0.8% Ce.1.5% Bi.0.75% Pt was used as a catalyst composition.
-A reaction was performed in the same manner as in Synthesis Example 1 except that it was 3.0% Pd / C. The polymer yields are summarized in Table 1. The pH of the distillate at the outlet of the reaction tower was 5.3. The structure of the polymer component was estimated to consist of the structural unit of formula (ii) from the infrared absorption spectrum and the NMR spectrum.

Synthesis Example 7 A reaction was performed in the same manner as in Synthesis Example 6 except that the starting material was glycolic acid. The polymer yields are summarized in Table 1. The pH of the distillate at the outlet of the reaction tower was 5.3. The structure of the polymer component was estimated to consist of the structural unit of formula (ii) from the infrared absorption spectrum and the NMR spectrum.

Synthesis Example 8 Synthesis Example 6 except that the raw material is propylene glycol
The reaction was performed in the same manner as in. The polymer yields are summarized in Table 1. The pH of the distillate at the outlet of the reaction tower was 5.7. The structure of the polymer component was estimated to consist of the structural unit of formula (v) from the infrared absorption spectrum and the NMR spectrum.

Synthesis Example 9 The reaction was performed in the same manner as in Synthesis Example 6 except that the raw material was hydroxyacetone. The polymer yields are summarized in Table 1.
The pH of the distillate at the outlet of the reaction tower was 6.2. The structure of the polymer component was estimated to consist of the structural unit of formula (v) from the infrared absorption spectrum and the NMR spectrum.

Synthesis Example 10 A reaction was performed in the same manner as in Synthesis Example 6 except that the raw material was lactic acid. The polymer yields are summarized in Table 1. The pH of the distillate at the outlet of the reaction tower was 5.7. The structure of the polymer component was estimated to consist of the structural unit of formula (v) from the infrared absorption spectrum and the NMR spectrum.

Example 1 With respect to the polymers obtained in Synthesis Examples 1 to 10, the Ca ion trapping ability was measured. Table 1 shows the results. The values are also shown for the builders used for comparison products.

Example 2 With respect to the detergent composition having the composition shown in Table 2, the cleaning performance for the artificially contaminated cloth was evaluated. The detergent composition is produced by crushing and granulating particles obtained by spray-drying the slurry with a high speed mixer. Table 2 shows the results.

[0102]

[Table 2]

In Table 2, LAS: straight chain alkylbenzene sulfonate sodium (C ₁₂
-C ₁₃₎ AS: alkyl sulfate sodium (C ₁₄ ~C ₁₅₎ AES: polyoxyethylene alkyl sulfate sodium (C ₁₄
To C ₁₅ , ethylene oxide average added mole number 1.5) Nonionic surfactant: polyoxyethylene alkyl ether (C _{12 to} C ₁₃ , ethylene oxide average added mole number 10), and B is 100 in total. Is an abbreviation for the balance amount (the same applies to Table 3).

Example 3 With respect to the liquid detergent composition having the composition shown in Table 3, the cleaning performance was evaluated in the same manner as in Example 2. However, of the cleaning conditions, only the cleaning concentration was 0.133%. The liquid detergent composition was produced by batch blending using a propeller shaft agitator. Table 3 shows the results.

[0105]

[Table 3]

As shown by the above results, the detergent composition of the present invention using a polymer having a high divalent metal ion-capturing ability was excellent in both model sebum stain cleaning ability and mud stain cleaning ability. In contrast, the comparative products using zeolite and low-molecular-weight carboxylate were inferior in both model sebum stain and mud stain cleaning power.

[0107]

EFFECT OF THE INVENTION The detergent composition of the present invention is a detergent containing a conventional aluminosilicate or the monomer of the present invention, which uses a polymer having a carboxyl group obtained by a specific production method as a builder. It exhibits a higher divalent metal ion capturing ability and higher detergency than the agent composition. Further, the polymer in the present invention can be produced inexpensively using inexpensive raw materials, and since it contains an acetal bond involved in biodegradability in the polymer main chain, by using this polymer, economically It is possible to provide a detergent composition which is excellent in terms of environment.

[Brief description of drawings]

FIG. 1 shows a schematic diagram of a reaction scheme in the present invention.

FIG. 2 is a calibration curve showing the relationship between the logarithm of Ca ion concentration and the potential.

[Fig. 3] Fig. 3 shows Ca when measuring Ca ion capturing ability.
It is a graph showing the relationship between the dropping weight and the Ca ion concentration of Cl ₂ solution.

FIG. 4 is a GPC of the reaction mixture obtained in Synthesis Example 1.
The chart of (gel permeation chromatography) is shown. In the figure, peak 1 (area 3.05%) is the polymer of the present invention (weight average molecular weight 4.503 × 10 ⁴ ), peak 2 (area 3.98%) is the polymer of the present invention (weight average). Molecular weight: 7.324 × 10 ³ ), peak 3 (area: 46.06%)
Is a raw material / low molecular weight oxide (weight average molecular weight 3.826 ×
10 ² ), peak 4 (area 46.77%) represents the eluent.

Claims (11)

[Claims] 1. A detergent composition comprising a surfactant and a builder, wherein the builder catalytically oxidizes a hydroxyl compound in the presence of a catalyst composition and an oxidizing agent described below to form a monomer having a carboxyl group. A detergent composition, which is a polymer having a carboxyl group obtained by polymerizing the monomer while being produced. Catalyst composition: One or more elements selected from the group consisting of palladium, platinum, rhodium, and ruthenium as the catalyst first component, and one or more elements selected from the group consisting of bismuth, tellurium, tin, lead, antimony, and selenium. An element is used as a catalyst second component, one or more elements selected from rare earth elements is used as a catalyst third component, and (a) catalyst first component and catalyst second component (b) catalyst first component and catalyst third component (ha) ) A catalyst first component, a catalyst second component and a catalyst third component,
Alternatively, (d) a supported catalyst consisting of only the catalyst first component. 2. The cleaning composition according to claim 1, wherein the hydroxyl compound is glycerin, glyceric acid or a salt of glyceric acid. 3. The detergent composition according to claim 1, wherein the hydroxyl compound is tartronic acid or a salt thereof. 4. The cleaning composition according to claim 1, wherein the hydroxyl group compound is ethylene glycol, glycolic acid or a salt of glycolic acid. 5. The hydroxyl compound is propylene glycol,
The cleaning composition according to claim 1, which is hydroxyacetone, lactic acid or a salt of lactic acid. 6. The cleaning composition according to claim 1, wherein the hydroxyl compound is a mixture of glycerin and ethylene glycol. 7. The catalyst first component of the catalyst composition of (c) is palladium and platinum, the catalyst second component is bismuth and / or tellurium, and the catalyst third component is cerium and / or lanthanum. The cleaning composition according to any one of claims. 8. The cleaning composition according to claim 1, wherein the cleaning composition is reacted in a fixed bed reactor filled with the catalyst composition. 9. 0.5-2 based on 1 part by weight of the catalyst composition.
The cleaning composition according to claim 8, wherein the cleaning composition is diluted with 0 part by weight of a diluent and then filled. 10. The polymer having a carboxyl group has a weight average molecular weight of 500 by gel permeation chromatography.
The cleaning composition according to any one of claims 1 to 9, wherein the cleaning composition is from 1,000,000 to 1,000,000. 11. The calcium-capturing ability of a polymer having a carboxyl group is 100 to 600 mg-CaCO ₃ / g.
The cleaning composition according to any one of claims 1 to 10, wherein