JP3363202B2 - Water-soluble polymer having biodegradability, production method thereof and use thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has a chelating action and an action of dispersing a sparingly soluble inorganic substance in an oily substance or water (hereinafter, simply referred to as "dispersing action") and is biodegradable. And a method for producing the same. The present invention further relates to the use of the water-soluble polymer, in particular, a detergent composition, a fiber treatment agent, an inorganic pigment dispersant,
It relates to biodegradable agents in applications such as water treatment agents which may eventually be discharged into the environment.

[0002]

2. Description of the Related Art A water-soluble polymer has an advantage that it can be easily used for various purposes because it can be handled as an aqueous solution. As conventional water-soluble polymers, polymers such as polyacrylic acid salts and polymaleic acid salts are known.
Since these water-soluble polymers have many carboxyl groups, they have excellent chelating action and dispersing action. Therefore, the water-soluble polymer is a detergent additive,
Widely used as dispersants, flocculants, scale inhibitors, chelating agents, fiber treatment agents, cleaning agents, etc.

These drugs are used in large quantities,
It is discharged into the environment after use. Considering the natural environment surrounding us and the impact on the environment of the whole earth, substances discharged in large quantities to the environment must have the characteristic that they can be easily decomposed by the action of organisms such as microorganisms and the natural environment. . However, the above water-soluble polymer is extremely inferior in biodegradability. Moreover, since the water-soluble polymer once dissolves in the environment water and spreads widely,
It is difficult to collect.

In recent years, attempts have been made to impart biodegradability to water-soluble polymers. JP-A-61-31497 discloses a graft polymer obtained by polymerizing a polysaccharide and a water-soluble ethylenically unsaturated monomer such as acrylic acid and maleic acid.
In JP-A-61-31498, a graft polymer obtained by polymerizing a monosaccharide and / or an oligosaccharide and a water-soluble ethylenically unsaturated monomer such as acrylic acid and maleic acid is disclosed.
Canadian Patent No. 2034943 proposes a graft polymer obtained by polymerizing a monosaccharide, an oligosaccharide, a polysaccharide or a modified sugar and a water-soluble ethylenically unsaturated monomer such as acrylic acid or maleic acid.

[0005]

In the above graft polymer, since the sugar moiety is not uniformly introduced between the vinyl polymer moieties of the water-soluble ethylenically unsaturated monomer, the sugar moiety is biodegraded. There is a problem in that the vinyl polymer portion having a large molecular weight is not biodegradable. In addition, the above graft polymer has more saccharide moieties than the vinyl polymer moieties, and the distribution of saccharide moieties in the molecular structure of the graft polymer is biased. For this reason, the graft polymer has a large number of portions having a low density of carboxyl groups, and a chelating action and a dispersing action cannot be sufficiently obtained.

As described above, the conventional water-soluble polymer has a drawback that it is inferior in biodegradability, or inferior in chelating action and dispersing action, and has sufficiently satisfactory performance. Not not. That is, a water-soluble polymer which is excellent in biodegradability and also has a chelating action and a dispersing action has not yet been found. An object of the present invention is to provide a water-soluble polymer which is excellent in biodegradability and also has a chelating action and a dispersing action, and a method for producing the same.

The present invention provides a detergent composition, a fiber treatment agent, an inorganic pigment dispersant, and a water treatment agent which exhibit excellent performances in various applications and which hardly accumulate even when finally discharged into the environment. The challenge is to provide.

[0008]

In order to solve the above-mentioned problems, the present invention provides a biodegradable vinyl polymer unit.
Has a structure linked via a sugar unit, and the bond is
Of the carbon atoms at the end of the main chain of the vinyl polymer unit,
At least one carbon atom of the methylol group of the sugar unit
It is formed by binding to
The polymer unit contains maleic acid and / or its salt 95
Water-soluble ethylenically unsaturated monomer containing
However, the content of maleic acid and / or its salt is 100.
In the case of weight%, contains both maleic acid and its salt
40 to 40% of all acid groups.
90 mol% is neutralized, and the sugar unit is a monosaccharide or
At least one selected from Rigo sugar and derivatives thereof
A water-soluble polymer having biodegradability , which is composed of three sugars .

The present invention also comprises maleic acid and / or a salt thereof in an amount of 95 to 100% by weight and 40 to 9 of all acid groups.
A radical of a water-soluble ethylenically unsaturated monomer component of which 0 mol% has been neutralized and at least one sugar selected from monosaccharides, oligosaccharides and their derivatives, using hydrogen peroxide as a polymerization catalyst. Provided is a method for producing a biodegradable water-soluble polymer that is copolymerized.

The present invention further provides a detergent composition, a fiber treatment agent, an inorganic pigment dispersant, and a water treatment agent, which comprise the water-soluble polymer of the present invention. The water-soluble polymer of the present invention preferably has 90 to 10% by weight of a polymer unit composed of a water-soluble ethylenically unsaturated monomer and 10 to 90% by weight of a sugar unit. 80 to 20% by weight of polymer unit consisting of a polymer and 20 to 8 of sugar unit
More preferred is one having 0% by weight. The polymer unit needs to be neutralized at 40 to 90 mol% of all acid groups, and preferably 50 to 80 mol% is neutralized.
If the neutralization of all the acid groups of the polymer unit is less than the above range, there is a problem that the amount of residual monomer after polymerization increases and the biodegradability decreases due to a decrease in the introduction rate of sugar groups. However, there is a problem that biodegradability is lowered and chelating performance is lowered due to a decrease in the introduction rate. Further, the polymer unit preferably comprises at least one polymer selected from a homopolymer of maleic acid and a copolymer of maleic acid and acrylic acid.

The sugar constituting the sugar unit of the present invention is a monosaccharide,
At least one sugar selected from oligosaccharides and their derivatives, which is obtained by heating at least one selected from polysaccharides, polysaccharide derivatives, and sugar-containing substances in an alkaline aqueous medium. It may be a thing. Here, the saccharide-containing material means a monosaccharide, an oligosaccharide, a polysaccharide,
Modified sugars (here, modified sugars include D-glucose-
Phosphoric acid esters such as 6-phosphoric acid; D-glucose-3-
40% by weight or more of at least one selected from sulfonic acid esters such as sulfuric acid; oxidized sugars such as ketoaldonic acid and uronic acid;

The above-mentioned monosaccharides are, for example, glucose, mannose, galactose, and their derivatives. The oligosaccharides are, for example, disaccharides, trisaccharides, and their derivatives. Specific examples of the disaccharide include sucrose, maltose, cellobiose, lactose, trehalose, gentiobiose, melibiose, turanose, koujiobiose, sophorose, nigerose, laminaribiose, isomaltose, planteobiose, turanose, vicyanose, agarobiose, neo. Examples include agarobiose, silabiose, rutinose, prime broth, xylobiose, and rozimenabiose. In the present invention, at least one selected from sucrose, maltose and lactose is preferably used as the disaccharide. Sucrose is particularly preferable. Examples of the trisaccharide include gentianose trisaccharide.

Specific examples of the above-mentioned polysaccharides include cellulose, amylose, amylopectin, starch and glycogen. In this invention, cellulose is preferably used as the polysaccharide. Cellulose is obtained from a large amount of inexpensive raw materials such as corn core, paper, straw, absorbent cotton, filter paper, and wood chips. These raw materials are generally treated as waste, but can be reused according to the present invention.

Specific examples of the above-mentioned saccharide-containing substances include polysaccharide derivatives such as amino sugars, grain epidermis, grains, algae and the like. In the present invention, at least one selected from amino sugars and grain epidermis is preferably used as the saccharide-containing material. Specific examples of amino sugars include chitosamine, D-galactosamine,
D-mannosamine, D-quinovosamine, D-fucosamine, D-talosamine, muramic acid, chitin, chitosan,
3-amino-3,6-dideoxy-D-glucose, kanamycin B, carbomycin, amisetin, purmycin, hyaluronic acid, teicronic acid and the like. In the present invention, chitin and chitosan are preferably used as the amino sugar.

Specific examples of grain skins include rice bran, bran, millet skin, dwarf skin, black stalk skin, corn skin, and the like, which are available in large quantities at low cost. These grain skins, which are generally treated as waste, can be reused according to the present invention. In the present invention, it is preferable to use disaccharides, amino sugars, grain epidermis and cellulose in order to improve the biodegradability of the water-soluble polymer.

In the present invention, the polysaccharide and the saccharide-containing material are
It is used after being pretreated by heating it under alkaline conditions. The use of polysaccharides and saccharide-containing materials without pretreatment results in water-soluble polymers with very poor biodegradability. The pretreatment under the alkaline condition is, for example, at a temperature of 50 to 200 ° C., preferably by adding an alkaline substance necessary for adjusting the pH to 10 or more in a reaction medium containing a polysaccharide and / or a saccharide-containing substance. Is 80 to 150
The reaction is carried out at 0 ° C for 10 to 120 minutes, preferably 30 to 90 minutes. The alkaline substance is not particularly limited, and examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; organic amines such as ammonia and ethanolamine; and the like, but the water-soluble substances used during polymerization An ethylenically unsaturated monomer that neutralizes an acid group-containing monomer is preferable, and an alkali metal hydroxide is most preferable.

In the present invention, the polysaccharide and the saccharide-containing material may be used after being subjected to pretreatment by heating under acidic conditions. The pretreatment under acidic conditions is, for example, at a temperature of 50 to 200 ° C., preferably at a temperature of 50 to 200 ° C., by adding an acidic substance necessary for adjusting the pH to 2 or less in a reaction medium containing a polysaccharide and / or a saccharide-containing material. Is 80 ~
150 ° C., 10 to 120 minutes, preferably 30 to 90
It is to react for a minute. The acidic substance is not particularly limited, but it may be a mineral acid such as sulfuric acid, hydrochloric acid or nitric acid; an organic acid such as acetic acid, lactic acid, maleic acid, acrylic acid or vinyl sulfonic acid. It is preferable to use a water-soluble ethylenically unsaturated monomer having an acid group, and it is more preferable to use a water-soluble ethylenically unsaturated monomer mainly containing maleic acid.

However, the pretreatment under the above-mentioned alkaline conditions is more effective in improving the biodegradability of the polymer obtained, and is also preferable from the viewpoint of preventing the corrosion of the equipment used. It is preferable to use an aqueous medium as the reaction medium, and it is more preferable to use water alone in the aqueous medium. As the aqueous medium, water alone or a mixed solvent of water and alcohol (water: alcohol = 100: 0-7)
0:30) and the like. As the alcohol, for example, methanol, ethanol, 2-propanol, butanol, ethylene glycol, glycerin or the like is used.

The water-soluble ethylenically unsaturated monomer used in the present invention is not particularly limited as long as it is a water-soluble ethylenically unsaturated monomer and can be used.
Examples of the water-soluble ethylenically unsaturated monomer include unsaturated monocarboxylic acid-based monomers, unsaturated polycarboxylic acid-based monomers, water-soluble vinyl ester-based monomers, and general formula (1):

[0020]

[Chemical 1]

[Wherein R ¹ and R ² each represent hydrogen or a methyl group; R ¹ and R ² do not simultaneously represent a methyl group; R ³ represents —CH ₂ —, — (CH ₂ ) ₂ -,
Or represents —C (CH ₃ ) ₂ —; the total number of carbon atoms in ^two R ¹ , R ² and R ³ is 3; Y represents an alkylene group having 2 to 3 carbon atoms; n is 0 or It is an integer of 1 to 100. ] A hydroxyl group-containing butene-based water-soluble monomer represented by the following general formula (2):

[0022]

[Chemical 2]

[Wherein R ¹ represents hydrogen or a methyl group; a, b, c and d are each independently 0 or 1 to 1;
Represents an integer of 100; a + b + c + d = be 0 to 100; Z when c + d is 0; -OC ₂ H ₄ - - units and -OC ₃ H ₆ unit and may be attached to any order Represents a hydroxyl group, a sulfonic acid group and a (phosphite) group; when c + d is 1 to 100, Z represents a hydroxyl group. ] A (meth) allyloxy water-soluble monomer represented by
(Meth) allyl ether water-soluble monomer, sulfonic acid group-containing water-soluble unsaturated monomer [(meth) allyloxy water-soluble monomer is excluded. ], Alkyl group-containing ester water-soluble unsaturated monomer, monoester water-soluble unsaturated monomer, diester water-soluble unsaturated monomer, and the like,
One or more selected from these groups can be used.

The unsaturated monocarboxylic acid type monomer is, for example, an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, α-hydroxyacrylic acid, crotonic acid or a salt thereof. The unsaturated polycarboxylic acid-based monomer is, for example, an unsaturated polycarboxylic acid such as maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid and salts thereof.

The water-soluble vinyl ester monomer is, for example, vinyl acetate. The hydroxyl group-containing butene water-soluble monomer is, for example, 3-methyl-3-butene-1.
-Ol (isoprenol), 3-methyl-2-buten-1-ol (prenol), 2-methyl-3-buten-2-ol (isoprene alcohol), ethylene oxide and 1 mol of these monomers And / or a monomer to which propylene oxide is added at a ratio of 1 to 100 mol.

The (meth) allyloxy water-soluble monomer is, for example, 3-allyloxy-2-hydroxypropanesulfonic acid and its salt. The above-mentioned (meth) allyl ether-based water-soluble monomer is, for example, glycerol monoallyl ether, and 1 mol of ethylene oxide and / or propylene oxide per 1 mol of this monomer.
It is a monomer added at a ratio of 100 mol.

The sulfonic acid group-containing water-soluble unsaturated monomer [(meth) allyloxy water-soluble monomer is excluded. ] Is, for example, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, sulfoethylmaleimide. is there.

The alkyl group-containing ester-based water-soluble unsaturated monomer is, for example, an alkyl alcohol having 1 to 20 carbon atoms, and 1 mol of ethylene oxide and / or propylene oxide per 1 mol of the alkyl alcohol.
A monoester of the above-mentioned unsaturated monocarboxylic acid and a monoester of the above-mentioned unsaturated polycarboxylic acid, a salt of the monoester, or a diester.

The above monoester water-soluble unsaturated monomer has, for example, ethylene oxide and / or propylene oxide added at a ratio of 1 to 100 mol per 1 mol of the unsaturated monocarboxylic acid monomer. It is a thing. The diester-based water-soluble unsaturated monomer is, for example, a monoester in which ethylene oxide and / or propylene oxide is added at a ratio of 1 to 100 mol per 1 mol of the unsaturated polycarboxylic acid-based monomer, It is a monoester salt or a diester.

The water-soluble ethylenically unsaturated monomer component used in the present invention has a chelating ability for the water-soluble polymer,
In order to improve performance such as dispersibility and improve biodegradability, it is necessary to have at least one selected from maleic acid and salts thereof in an amount of 95% by weight or more when polymerized with a monosaccharide and / or oligosaccharide, When the saccharide-containing material is polymerized with the product obtained by pretreatment, the content of maleic acid (salt) is preferably high, preferably 50% by weight or more,
It is more preferably 5% by weight or more. When the proportion of maleic acid (salt) is less than 95% by weight, a water-soluble polymer having poor chelating ability, dispersing ability or biodegradability is produced.

In the present invention, when the water-soluble ethylenically unsaturated monomer component is polymerized, the polymerization is carried out in the presence of at least one selected from iron ions, vanadium atom-containing ions and copper ions in order to carry out the polymerization in high yield. Is preferably performed. At least one selected from iron ions, vanadium atom-containing ions and copper ions is 0.1 to 5 relative to the total weight of the water-soluble ethylenically unsaturated monomer component.
It is preferable to use it at a ratio of 00 ppm, and 0.1 to 30
0 ppm is more preferable, and 0.1 to 50 ppm is further preferable. If it is less than 0.1 ppm, the polymerization may not occur in a high yield, and if it exceeds 500 ppm, the resulting polymer becomes highly colored, and the performance may be deteriorated when it is used as a detergent.

The iron ion, vanadium atom-containing ion, and copper ion are, for example, Fe ²⁺ , Fe ³⁺ , V ²⁺ , V
³⁺ , VO ²⁺ , VO ₃ ²⁻ , Cu ^{2+ and the} like. Among these, Fe ²⁺ , VO ²⁺ and Cu ²⁺ are preferable. There is no particular limitation on the supply form of the polyvalent metal ion into the polymerization system, and any polyvalent metal compound or simple substance can be used as long as it is ionized in the polymerization system.

Examples of such polyvalent metal compounds or simple substances include, for example, iron acetylacetonate, ammonium iron citrate, ferric ammonium oxalate, ferrous ammonium sulfate, ferric ammonium sulfate, iron citrate, Iron fumarate, iron maleate, ferrous lactate, ferric nitrate, iron pentacarbonyl, ferric phosphate, ferric pyrophosphate, vanadium oxytrichloride, vanadium trichloride, vanadyl oxalate, vanadyl sulfate, Anhydrous vanadic acid, ammonium metavanadate, ammonium sulfate hypovanadas, copper (II) acetate, copper (II) bromide, copper (II) acetylacetonate, cupric chloride ammonium, copper carbonate, copper (II) chloride, citric acid Acid copper (II), copper formate (II), copper hydroxide (II), copper nitrate, naphthene copper, copper oleate, copper maleate, copper phosphate, sulfuric acid Water-soluble polyvalent metal salts such as (II);
Polyvalent metal oxides such as ferrous oxide, ferric oxide, vanadium pentoxide, and copper (II) oxide; iron (III) sulfide, iron sulfide (I
I), polyvalent metal sulfides such as copper sulfide; and simple metals such as copper powder and iron powder.

In the present invention, the polymerization of the water-soluble ethylenically unsaturated monomer component and sugar is carried out at a temperature of 80 to 150 ° C. When the polymerization is performed within this temperature range, the polymerization time can be shortened. In the production method of the present invention, it is necessary to use hydrogen peroxide as a polymerization initiator. The amount of hydrogen peroxide used is preferably 5 to 1 with respect to 1 mol of the water-soluble ethylenically unsaturated monomer component.
The amount is 50 g, more preferably 10 to 100 g, still more preferably 15 to 80 g. If the amount of hydrogen peroxide is less than 5 g, a water-soluble polymer having excellent biodegradability may not be obtained, and if it is used in excess of 150 g, the biodegradability does not decrease. Hydrogen peroxide tends to remain in the obtained water-soluble polymer, and the production cost may increase.

In the present invention, other water-soluble initiators such as ammonium persulfate, persulfates such as sodium persulfate and potassium persulfate; hydrophilic organic peroxides such as tert-butyl hydroperoxide are used as the above-mentioned polymerization initiator. Oxides;
When a water-soluble azo compound such as 2,2'-azobis (2-amidinopropane) hydrochloride is used, a water-soluble polymer having excellent biodegradability as in the production method of the present invention cannot be obtained. The method for supplying hydrogen peroxide into the reaction system is not particularly limited, and for example, initial batch charging may be performed in the reaction system, or continuous charging may be performed during the reaction. It is also possible to throw it in two or more times.

In the present invention, "biodegradable" means
In the biodegradability test described in the section of Examples, it means that the biodegradation rate is 30% or more. The larger the value, the better the biodegradability, and the biodegradation rate is 70% or more. Is more preferable. The water-soluble polymer of the present invention can be used as it is as a detergent, a fiber treatment agent, a water treatment agent, or can be used as a detergent composition by incorporating a surfactant and an enzyme.

The amount of the above water-soluble polymer used in the detergent composition of the present invention is preferably 1 to 50% by weight, more preferably 2 to 30% by weight. Moreover, the surfactant is 5 to 7
It is preferable to add 0% by weight, and more preferably 10 to 30% by weight. As the surfactant, anionic surfactants, nonionic surfactants, amphoteric and cationic surfactants can be preferably used. As the anionic surfactant, alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α
-Sulfo fatty acid salt or ester salt, alkane sulfonate, saturated or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate, amino acid type surfactant,
Examples include N-acyl amino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof, and the like.

As the nonionic surfactant, polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide or alkylene oxide adduct thereof, sucrose fatty acid ester, alkylglycoxide, fatty acid glycerin monoester, Examples thereof include alkylamine oxide.

Examples of the amphoteric surfactant include a carboxy type or sulfobetaine type amphoteric surfactant, and examples of the cationic surfactant include a quaternary ammonium salt. As the enzyme, protease, lipase, cellulase and the like can be used, and particularly protease, alkali lipase, alkaline cellulase and the like which have high activity in an alkaline washing solution are preferable.

To the detergent composition of the present invention, known components such as a known alkali builder, chelate builder, anti-redeposition agent, fluorescent agent, bleaching agent and perfume may be added. Moreover, you may mix | blend a zeolite. As the alkali builder, silicate, carbonate, sulfate and the like can be used. As the chelate builder, diglycolic acid, oxycarboxylic acid salt, EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminehexaacetic acid), citric acid and the like can be used as necessary.

The fiber treatment agent of the present invention can be used in steps such as refining, dyeing, bleaching and soaping in fiber treatment. Although applicable fibers are not particularly limited, for example, cellulosic fibers such as cotton and hemp; chemical fibers such as nylon and polyester; animal fibers such as wool and silk;
Examples include semi-synthetic fibers such as human silk and woven or blended products thereof. When applied to the refining step, it is preferable to add the water-soluble polymer of the present invention, an alkali agent and a surfactant, and in the bleaching step, a silicic acid-based agent such as sodium silicate as a decomposition inhibitor during hydrogen peroxide bleaching. It is advisable to add drugs, etc.

The inorganic pigment dispersant of the present invention exhibits good performance as a dispersant for inorganic pigments such as heavy or light calcium carbonate and clay used for paper coating. A small amount of the inorganic pigment dispersant of the present invention is added to the above-mentioned inorganic pigment instead of the conventional inorganic pigment dispersant (for example, a ratio of 0.05 to 2.0 parts by weight based on 100 parts by weight of the inorganic pigment). By adding and dispersing in water, a high-concentration inorganic pigment slurry (for example, high-concentration calcium carbonate slurry) that has low viscosity and high fluidity and has good stability over time in their performance is obtained. It can be manufactured. In addition, since it has good biodegradability, it is possible to minimize the influence on the environment even when the paper using the inorganic pigment dispersant of the present invention is thrown into the soil as dust.

The water treatment agent of the present invention is useful for preventing scale in a cooling water system, a boiler water system, a seawater desalination apparatus, a pulp digester, a black liquor concentrator, etc., and the water-soluble polymer of the present invention alone. Although it may be used as a water treatment agent, a composition containing a polymeric phosphate, a phosphonate, other anticorrosive agent, a slime control agent, a chelating agent or the like may be used. The water treatment agent of the present invention has a good biodegradability even if waste water is discharged to the outside after use, so that the influence on the environment becomes extremely small.

[0044]

The water-soluble polymer of the present invention is susceptible to biodegradation at the sugar unit portion, and this biodegradation produces a vinyl polymer unit. Such a vinyl-based polymer unit is a compound which has a too low molecular weight to exert a chelating action or a dispersing action, but is very easily biodegradable.

That is, the water-soluble polymer of the present invention has a too low molecular weight for exerting a chelating action and a dispersing action, but is capable of biodegrading a vinyl polymer unit having a structure and a molecular weight which are very easily biodegradable. By linking via a sugar unit, the chelating action and the dispersing action are increased to a molecular weight that is expressed, and biodegradability and
It is possible to achieve both chelating and dispersing effects.

According to the production method of the present invention, once the vinyl-based polymer unit is produced and then the vinyl-based polymer units are bonded to each other via the sugar unit, the molecular weight of the vinyl-based polymer unit is appropriately adjusted. Easy to set to the size of. The detergent composition, the fiber treating agent, the inorganic pigment dispersant, and the water treating agent of the present invention comprise the water-soluble polymer of the present invention described above, and therefore, the dispersing ability, the chelating ability, and the biodegradability. It is excellent and very useful for each application.

[0047]

EXAMPLES Specific examples and comparative examples of the present invention will be shown below, but the present invention is not limited to the following examples.
In the following, "part" means "part by weight" and "%" means "% by weight"
Respectively. Example 1 Maleic anhydride 19 was placed in a 4-liter flask having a capacity of 1 liter equipped with a thermometer, a stirrer and a reflux condenser.
6 parts and 100 parts of water (232 parts as maleic acid), 0.020 parts of iron (III) ammonium sulfate dodecahydrate (10 ppm as Fe ^{3+ with} respect to the weight of maleic acid charged in a four-necked flask) ), And 49 parts of sucrose as a saccharide, and then 48 with stirring.
% Aqueous NaOH solution was added dropwise to make the maleic acid aqueous solution in the four-necked flask a 60% neutralized aqueous solution. Here, 60% is the degree of neutralization with respect to all the carboxyl groups in the four-necked flask. After neutralization, the aqueous solution was heated to boiling temperature under normal pressure with stirring. Then, with stirring, 153.2 parts of 35% hydrogen peroxide solution (1 mole of maleic acid charged in a four-neck flask as H ₂ O ₂
(8 g ratio) was continuously added dropwise over 3 hours to carry out a polymerization reaction. After completion of the dropping, the solution was stirred for another hour at the boiling temperature of the aqueous solution in the four-necked flask to complete the polymerization reaction, and the water-soluble polymer (1) was obtained as an aqueous solution having a solid content of 49.2%.

The molecular weight of the water-soluble polymer (1) thus obtained,
The viscosity, chelating ability and biodegradation rate were measured by the following methods. The results are shown in Table 1. The molecular weight was measured by gel permeation chromatography (GPC) analysis under the following conditions. [GPC analysis conditions] Column: Asahi Pack GFA-7MF (trade name, gel permeation column manufactured by Asahi Kasei Corporation) Eluent: Phosphate buffer flow rate: 0.5 cc / min Detector: Ultraviolet (UV), Wavelength 214 nm Standard sample: Sodium polyacrylate standard sample (manufactured by Sowa Kagaku Co., Ltd.) As for viscosity, a 20 wt% aqueous solution of the obtained water-soluble polymer was used, and a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) type 1 (Manufactured by Seiki Kogyo Kenkyusho) at a temperature of 25 ° C.

The rate of biodegradation was determined by conducting a biodegradability test for 28 days according to the modified MITI method described in the OECD test guideline. Biodegradation rate is TOC measured using an organic carbon analyzer (TOC500 manufactured by Shimadzu Corporation)
[Total organic carbon concentration] was calculated by applying the following equation. In the following formula, the TOC of the test solution at the start is the TOC of the water-soluble polymer excluding the TOC of the unreacted monomer in the test solution. Biodegradation rate after 28 days = [{TOC (ppm) of test solution at the start of biodegradability test-TOC of test solution after 28 days (pp
m)} / TOC (ppm) of test liquid at the start] × 100
[%] For chelating ability, measure the water-soluble polymer in a 50 ml beaker, dissolve in 50 ml of an aqueous solution prepared so that calcium chloride is 1.0 × 10 ⁻³ M and potassium chloride is 0.08 M, and stir the mixture. , The calcium ion concentration in the solution is determined by the divalent cation electrode (Orion Research Ink
MODEL 93-32 manufactured by search INC) is used, and an ion analyzer (Orion Research Inc.
EA920 manufactured by ResearchINC), and the calcium ion chelated by 1 g of the water-soluble polymer is shown in mg converted to calcium carbonate.

The water-soluble polymer (1) obtained in Example 1 was evaluated for its performance as a fiber treatment agent, a water treatment agent, a detergent and an inorganic pigment dispersant by the method described below, and the results are shown in Table 3. It was shown to. [Evaluation as a fiber treatment agent] 1. Dyeability improvement ability and dye dispersibility (evaluation as a dyeing aid) A cotton twill fabric was dyed under the following conditions. A water-soluble polymer was used as a dye improving agent in a ratio of 1 g per 1 liter of water (solid content conversion). (Dyeing conditions) Hardness of used water 30 ° DH (German hardness) Dye (Kayaras Supra Blue 4BL) 1% (Nippon Kayaku Co., Ltd. metal-containing direct dye) Sodium sulfate 10% Bath ratio 1:30 Temperature 95 ° C time The cloth after 30 minutes of dyeing was subjected to color measurement with a SM color computer SM-3 type manufactured by Suga Test Instruments Co., Ltd., and a Hue value (value on the Munsell hue circle) was determined. Pue of Hue value is Purple and Bl
In the meaning of blue-violet between ue (blue), the smaller the value, the closer it is to blue, indicating that the dyeability is excellent. Partial color unevenness of the dyed fabric was visually observed with the naked eye. Further, 300 g of a mixed solution of water, dye (0.1%) and water-soluble polymer (0.1%) used for the above dyeing was prepared, and after standing for 24 hours, it was filtered using 5C filter paper manufactured by Toyo Roshi Kaisha, Ltd. The dye dispersibility was evaluated by ◯ when there was no filtration residue, Δ when there was some filtration residue, and X when there were many filtration residues.

2. Bleaching Performance and Sewing Performance (Evaluation as Bleaching Aid) The refined cotton knitted knitted fabric was bleached under the following conditions. A water-soluble polymer was used as a bleaching aid at a ratio of 1 g per 1 liter of water (in terms of solid content). (Bleaching conditions) Hardness of water used 35 ° DH Bath ratio 1:25 Temperature 85 ° C Time 30 minutes Chemicals used Hydrogen peroxide 10g / l Sodium hydroxide 2g / l Sodium silicate (No. 3) 5g / l For cloth after bleaching The texture is determined by a sensory test method, ○ for soft texture, △ for slightly hard texture,
The very hard ones were marked as x. Further, the whiteness was measured by a SM color computer SM-3 type manufactured by Suga Test Instruments Co., Ltd., and the whiteness W was calculated by the following Lab-based whiteness formula.

W = 100-[(100-L) ² + a ² + b ² ] ^1/2 where L = measured lightness a = measured chromaticness index b = measured chromaticness index Furthermore, after bleaching 4 sheets of cloth are piled up and the needle is sewn with the lockstitch sewing machine.
The number of ground yarn breakage points when sewing 30 cm using 11S was examined.

[Evaluation as Water Treatment Agent] 1. 170g of water is put in a glass bottle with a scale inhibition rate capacity of 225ml, and 1.5
10% 6% calcium chloride dihydrate aqueous solution and 3 g 0.02% aqueous solution of water-soluble polymer as scale inhibitor
(3 pp of water-soluble polymer for the resulting supersaturated aqueous solution)
m) are mixed, and further 3% aqueous sodium bicarbonate solution 10
g and 7 g of water were added to make the total amount 200 g. The resulting supersaturated aqueous solution of calcium carbonate (530 ppm) was sealed and heat-treated at 70 ° C. for 8 hours. After cooling, the precipitate is filtered with a membrane filter having a pore size of 0.1 μm,
The filtrate was analyzed according to JIS K0101. The calcium carbonate scale inhibition rate (%) was calculated by the following formula.

Scale inhibition rate (%) = (C−B) / (A−B) where A: concentration of calcium dissolved in the liquid before the test B: calcium in the filtrate without addition of the scale inhibitor Concentration C: calcium concentration in the filtrate after the test [evaluation as a detergent] An artificial soil having the composition shown below was dispersed in carbon tetrachloride, and a white cotton cloth was passed through the artificial soil solution and dried. Then, by cutting, a stained cloth of 10 cm × 10 cm was prepared. (Dirt composition) Carbon black 0.5% Viscosity 49.75% Myristic acid 8.3% Oleic acid 8.3% Tristearic acid 8.3% Triolein 8.3% Cholesterin 4.38% Cholesterin steer Rate 1.09% Paraffin wax 0.552% Squalene 0.552% A detergent composition was prepared with the following formulation, and the contaminated cloth was washed under the following conditions. After the cloth was washed and dried, the reflectance of the cloth was measured. (Detergent composition) LAS (straight chain 20% average carbon number 11.5 sodium alkylbenzene sulfonate) Polyoxyethylene alkyl ether (average carbon number 15% 12, average degree of polymerization of ethylene oxide (EO) 8) Zeolite 20% Enzyme (protease) 0.5% Water-soluble polymer 20% Sodium carbonate 15% Sodium silicate (JIS K14081 No. 1) 9.5% (Washing conditions) Temperature 20 ° C Bath ratio 1/60 Detergent concentration 0.5% Water quality Water tap Water cleaning device Terg-O-Tometer Cleaning time 10 minutes From the measurement result of reflectance, the cleaning rate was calculated by the following formula to evaluate the cleaning property. Cleaning rate [%] = [(Reflectivity after cleaning-Reflectivity before cleaning)
/ (Reflectance of white cloth-reflectance before washing)] × 100 [Evaluation as an inorganic pigment dispersant] A beaker having a capacity of 1 liter (material SUS 304, inner diameter 90 mm, height 160 mm) is placed in a calcite-based cubic shape. Take 400 parts of filter press dehydrated cake (solid content 65.3%) of light calcium carbonate (primary particle diameter 0.15 μm), and add 3.26 parts of a 40% aqueous solution of a water-soluble polymer (calcium carbonate Water-soluble polymer (0.5% relative to weight) and water (6.9 parts) for adjusting the solid content concentration were added, and the mixture was kneaded with a dissolver stirring blade (50 mmφ) at a low speed for 3 minutes, and then 3000
The dispersion was carried out at rpm for 10 minutes to obtain an aqueous dispersion (1) having a solid content concentration of 64%. The obtained aqueous dispersion (1) was tested for viscosity (viscosity measured at 25 ° C. using a B-type viscometer) and stability over time.

Examples 2 to 4 Water-soluble polymers (2) to (4) were polymerized in the same manner as in Example 1 except that the amount of sucrose used was changed to that shown in Table 4. Got The characteristics and the performance of the obtained water-soluble polymers (2) to (4) were examined in the same manner as in Example 1. The results are shown in Tables 1 and 3.

(Examples 5 and 6) 100 parts of water was added to a four-necked flask having a capacity of 1 liter equipped with a thermometer, a stirrer and a reflux condenser, and the sugars shown in Table 1 are shown in Table 1.
Charge with the amount described in, and stir while stirring 48% NaOH
200 parts of an aqueous solution was added dropwise. The liquid in the flask was heated at 100 ° C. for 1 hour with stirring to pretreat the saccharide.
Then, mix the mixture in the flask with maleic anhydride 196
Parts, 0.02 parts of ammonium iron (III) sulfate dodecahydrate, and 35% hydrogen peroxide water 153.2 with stirring.
(26.8 g of H ₂ O _{2 with} respect to 1 mol of maleic acid charged in a four-necked flask) was continuously added dropwise over 3 hours to carry out a polymerization reaction. After completion of the dropwise addition, the mixture in the four-necked flask was stirred at the boiling temperature for 1 hour to complete the polymerization reaction, and the water-soluble polymer (5),
(6) was obtained. The pretreatment performed here is a pretreatment under alkaline conditions. The obtained water-soluble polymer (5),
For (6), the characteristics were examined and the performance was evaluated in exactly the same manner as in Example 1. The results are shown in Tables 1 and 3.

Examples 7 to 14 In a four-necked flask having a capacity of 1 liter, equipped with a thermometer, a stirrer and a reflux condenser, 100 parts of water, 0.02 part of ammonium ferrous (III) sulfate dodecahydrate (four parts) 10 ppm of Fe ^{3+ based on the} weight of maleic acid charged in the one-necked flask) was added, and 49 parts of bran was added as a saccharide-containing material, and while stirring, 4
200 parts of 8% NaOH aqueous solution was added dropwise. The liquid in the flask was heated at 100 ° C. for 1 hour with stirring to pretreat the saccharide. Then, 196 parts of maleic anhydride was added to the mixture in the flask, and the aqueous solution was heated to boiling temperature under normal pressure with stirring. Next, 35% hydrogen peroxide water 1
53.2 parts (ratio of 26.8 g of H ₂ O ₂ to 1 mol of maleic acid charged in a four-necked flask) and water-soluble ethylenically unsaturated monomers other than maleic acid shown in Tables 1 and 2 Was continuously added dropwise over 3 hours using the amounts shown in Tables 1 and 2 to carry out a polymerization reaction. After completion of the dropping, the mixture in the four-necked flask was stirred at the boiling temperature for another 1 hour to complete the polymerization reaction to obtain water-soluble polymers (7) to (14). The pretreatment performed here is a pretreatment under alkaline conditions. With respect to the obtained water-soluble polymers (7) to (14), the characteristics were examined and the performance was evaluated in exactly the same manner as in Example 1. The results are shown in Tables 1 to 4.

(Examples 15 to 19) Polymerization was carried out in the same manner as in Example 1 except that the amounts of 35% H ₂ O _{2 and} the amount of metal salt used were as shown in Table 2. Union (1
5)-(19) were obtained. Obtained water-soluble polymer (15)
In the same manner as in Example 1 to (19), the characteristics were investigated and the performance was evaluated. The results are shown in Tables 2 and 4.

Example 20 Toilet paper (main component; cellulose) treated with a degrading enzyme as a sugar-containing substance (49 parts of toilet paper and 20 parts of cellulase and 50 parts of water were added thereto and treated at 25 ° C. for 24 hours. Polymerization was performed in the same manner as in Example 1 except that the water-soluble polymer (20) was obtained. The resulting water-soluble polymer (2
0), the characteristics were examined in exactly the same manner as in Example 1,
Performance evaluation was performed. The results are shown in Tables 2 and 4.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

[Table 4]

(Comparative Examples 1 to 3) In Example 7, the type and amount of the saccharides used and the amount of the water-soluble ethylenically unsaturated monomer other than maleic acid were used without pretreatment under alkaline conditions. Comparative water-soluble polymers (1) to (3) were obtained in the same manner as in Example 7 except that the results shown in Table 5 were used. Example 1 of the obtained comparative water-soluble polymers (1) to (3)
The characteristics were examined and the performance was evaluated in exactly the same manner as in. The results are shown in Tables 5 and 6.

Comparative Examples 4 and 5 Comparative water-soluble polymer (4) was prepared in the same manner as in Example 1 except that the neutralization degree in the system at the time of charging was as shown in Table 5. , (5) were obtained. With respect to the obtained comparative water-soluble polymers (4) and (5), the characteristics were examined and the performance was evaluated in exactly the same manner as in Example 1. The results are shown in Tables 5 and 6.

Comparative Example 6 A comparative water-soluble polymer (6) was obtained in the same manner as in Example 1 except that sucrose (sucrose) was not charged as the saccharide. About the obtained comparative water-soluble polymer (6), the characteristics were examined and the performance was evaluated in exactly the same manner as in Example 1. The results are shown in Tables 5 and 6.

[0067]

[Table 5]

[0068]

[Table 6]

As shown in Tables 1 to 4, the water-soluble polymers of Examples had a very good biodegradability of 34% or more, and also had a fiber treatment agent, an inorganic pigment dispersant, a water treatment agent, It also showed good performance as a detergent. On the contrary,
The samples of Comparative Examples were remarkably inferior in biodegradability, and were inferior in performance in various applications such as fiber treatment agents, inorganic pigment dispersants, water treatment agents and detergents.

[0070]

The water-soluble polymer of the present invention has a chelating action and a dispersing action, has good dispersibility in water and is excellent in biodegradability. The production method of the present invention can efficiently produce such a water-soluble polymer at a low cost.

When the water-soluble polymer of the present invention is used in a detergent, it can be blended with the detergent composition regardless of the state of the detergent composition to improve its detergency, and it can be decomposed by organisms such as microorganisms. It is useful as a safe builder that does not cause eutrophication when discharged into lakes and marshes.
When the water-soluble polymer of the present invention is used as a fiber treatment agent, an inorganic pigment dispersant, or a water treatment agent, in the case of a fiber treatment agent, refining,
Dyeing, bleaching, useful for improving the quality of fiber products in each step of soaping, in the case of an inorganic pigment dispersant, useful for lowering the viscosity of the inorganic pigment dispersion slurry and improving the viscosity stability,
In the case of water treatment agents, they are useful for suppressing scale deposition and have the advantage that they are biodegradable even when they are released into the environment to minimize their impact on the environment.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI D06L 3/00 D06L 3/00 // C08L 101/16 C08L 101/16 (56) References JP-A-63-297409 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 61/12 ZBP C08F 22/02 C02F 5/10 620 C11D 3/37 D06L 1/12 D06L 3/00 WPI / L (QUESTEL)

Claims (7)

(57) [Claims] 1. A biodegradable vinyl polymer unit is a sugar unit.
Has a structure bonded via a position, and the bond is a carbon atom at the end of the main chain of the vinyl polymer unit.
Methylol in which at least one of the atoms is the sugar unit
It is formed by bonding to a carbon atom of a group, and the vinyl-based polymer unit comprises maleic acid and / or
Water-soluble ethylenic satiety containing 95-100% by weight of its salt
Sum monomers (provided that maleic acid and / or its salts are included)
If the content is 100% by weight, maleic acid and its salts
Both are included) and all
40 to 90 mol% of the acid groups are neutralized, and the sugar units are monosaccharides, oligosaccharides and their derivatives.
A water-soluble polymer having biodegradability, which comprises at least one sugar selected from the group consisting of: 2. Maleic acid and / or its salt 95
A water-soluble ethylenically unsaturated monomer component containing 100 to 100% by weight and 40 to 90 mol% of all acid groups being neutralized, and a monosaccharide,
The method for producing a water-soluble polymer having biodegradability according to claim 1 , wherein radical copolymerization is carried out with at least one sugar selected from oligosaccharides and their derivatives using hydrogen peroxide as a polymerization catalyst. 3. The method according to claim 2, wherein the saccharide is a product obtained by heating at least one selected from a polysaccharide, a polysaccharide derivative and a saccharide-containing substance in an alkaline aqueous medium. 4. A detergent composition comprising the water-soluble polymer according to claim 1 and a surfactant. 5. The water-soluble polymer according to claim 1,
At least one selected from the water-soluble polymers obtained by the production method according to claim 3 and the water-soluble polymer obtained by the production method according to claim 3, and at least one selected from a dye, a peroxide and a surfactant. A fiber treating agent comprising. 6. The water-soluble polymer according to claim 1, 2.
An inorganic pigment dispersant comprising at least one selected from the water-soluble polymer obtained by the production method according to claim 3 and the water-soluble polymer obtained by the production method according to claim 3. 7. The water-soluble polymer according to claim 1,
A water treatment agent comprising at least one selected from the water-soluble polymer obtained by the production method according to claim 3 and the water-soluble polymer obtained by the production method according to claim 3.