WO2000077074A1

WO2000077074A1 - Polymer of unsaturated carboxylic acid, process for producing the same, and use

Info

Publication number: WO2000077074A1
Application number: PCT/JP2000/003548
Authority: WO
Inventors: Shigeru Matsuo; Shinji Ito
Original assignee: Idemitsu Petrochemical Co., Ltd.
Priority date: 1999-06-11
Filing date: 2000-06-01
Publication date: 2000-12-21

Abstract

An unsaturated carboxylic acid polymer which comprises repeating units consisting of a residue of acrylic acid and ones consisting of a residue of glyoxal or formaldehyde and/or maleic acid and has a number-average molecular weight of 500 to 1,000,000; a crosslinked object obtained by crosslinking the polymer; processes for producing these; a builder comprising the polymer; a solid particulate or liquid detergent composition comprising the builder and a surfactant as the main components; a dispersant comprising the polymer; a process for producing a crosslinked polymer of an unsaturated carboxylic acid which comprises copolymerization and crosslinking; and the crosslinked object which combines high water absorption with biodegradability. The unsaturated carboxylic acid polymer is highly useful as a builder excellent in the ability to trap calcium ions and in biodegradability. The detergent composition dispersant comprises this builder and a surfactant as the main components.

Description

Specification

Unsaturated carboxylic acid polymer, its production method and application

Technical field

The present invention relates to an unsaturated carboxylic acid polymer, a crosslinked product thereof, a production method thereof, and a use thereof. More specifically, an unsaturated carboxylic acid polymer having excellent biodegradability and excellent performance as a builder for detergents, an efficient production method thereof, and a builder using this polymer as a constituent component And detergents.

Background art

Conventionally, in detergents containing a surfactant as a main component, the washing ability has been enhanced by blending a builder as an auxiliary component of the surfactant. As the builder, inorganic compounds exhibiting an alkaline property when added to water, and polymers of unsaturated aliphatic carboxylic acids are known. Examples of the former include sodium or potassium carbonates, bicarbonates, phosphates, polyphosphates, silicates and zeolites, and examples of the latter include polyacrylics. Acids, polymeriic acid, polyitaconic acid and the like.

Among these builders, phosphates, polyphosphates and zeolites are used in large quantities in terms of cleaning effect, economy and workability. However, phosphates and polyphosphates have various problems in terms of environmental protection, such as the enrichment of lakes and rivers and the accumulation of zeolite.

Therefore, it has at least the same performance as a builder, especially the chelating ability (calcium ion trapping ability), as well as the excellent biodegradability, which is important in terms of environmental protection. Eco-friendly and economical that does not remain in nature for a long time There is a demand for the development of a builder that is advantageous to the above.

In response to such demands, Japanese Patent Application Laid-Open No. 5-239127 discloses a polymer suitable for use as a builder having chelating ability and biodegradability, and the polymer itself contains chelate. Almost no ability, but water-soluble oligomer backbones containing biodegradable low molecular weight components can be biodegradable by cross-linking agents such as polyethylene glycol, citric acid and tartaric acid. Crosslinked polymers having an increased molecular weight by bonding through groups have been proposed. However, this crosslinked polymer has improved biodegradability by reducing the molecular weight, but linear polyacrylic acid itself is difficult to biodegrade, and high-molecular-weight linear polyacrylic acid is difficult to biodegrade. Biodegradability is not high enough because it contains a considerable amount of luic acid. In addition, in the process of producing the crosslinked polymer, it is necessary to carry out in two stages, a process of polymerizing the oligomer and a process of crosslinking, and the production process is complicated since it is necessary to use a specific crosslinking agent. There is a drawback that there is.

Also, Japanese Patent Application Laid-Open No. 50-80777 proposes that a copolymer obtained by copolymerizing acrolein with atalylic acid is used as a builder. And biodegradability are not sufficient, and they are not satisfactory in terms of economics, so they have not been put to practical use.

On the other hand, in the field of detergents, liquid detergents are used as more suitable for fully automatic washing machines because they have the advantage that they can be applied directly to contaminated parts such as clothes, compared to powder detergents that have been used frequently. ing. By the way, in this liquid detergent, there is a problem of stability of the liquid detergent, such as phase separation and sedimentation of each component, which are not present in the powder detergent. In order to solve these problems, the types and combinations of surfactants used, Precise control of the type of lukari agent and water content is required. In addition, the incorporation of water-insoluble substances such as zeolite and builder substances such as sequestering agents and polymer dispersants will further impair the stability of this liquid detergent. In order to solve such problems, it has been proposed to add a hydrotrope such as p-toluenesulfonate and a solvent such as ethylene glycol, propylene glycol and ethanol. However, it was difficult to mix in a sufficient amount in comparison with the mixing ratio to the powder detergent. In addition, attempts have been made to increase the concentration of surfactants to make products more compact.For such concentrated liquid detergents, the builders that have been used in the past have been used to improve the detergency. There is a problem that it is difficult to mix them in a sufficient amount.

Therefore, there is a demand for the development of a builder which has excellent chelating ability and high biodegradability, and can be stably compounded in a sufficient mixing ratio with both detergents such as powder detergent and liquid detergent. . In the field of inorganic pigment dispersants, sodium polyacrylate and the like are used to reduce the viscosity of dispersion liquid and to improve the viscosity stability.However, since polyacrylic acid does not have biodegradability, Like the above-mentioned builder, development of a dispersant which is biodegradable, does not remain for a long time, and is economically advantageous is desired. In the agricultural field, superabsorbent resins are used as soil conditioners and water retention agents; in the civil engineering field, water-blocking agents and excavated sludge compositions; in the daily necessities field, disposable diapers and sanitary products; It is used in various fields such as sensors. As the superabsorbent resin, unsaturated carboxylic acid polymers and copolymers such as polyacrylic acid have been widely used. Materials and articles made of these unsaturated carboxylic acid polymers are incinerated after use or buried in soil. However, when materials and articles made of unsaturated carboxylic acid polymers are incinerated, smoke emissions have a large adverse effect on the environment, and alkaline incineration ash is generated, damaging the incinerator and causing soil damage. There was a problem that any disposal would adversely affect the natural environment, for example, if buried, it would remain in the soil as it was, causing problems.

For this reason, there has been an increasing demand for the development of biodegradable superabsorbent resins as materials for materials and articles that do not adversely affect the natural environment during disposal. Such resins having both biodegradability and high water absorbency include starch-based water-absorbent resins, hyalponic acid-based water-absorbent resins, and polyglutamic acid-based crosslinked products (Japanese Patent Laid-Open Publication No. (See Japanese Unexamined Patent Application Publication No. 7-300563, Japanese Unexamined Patent Application Publication No. 10-250142). By the way, these resins are more complicated in their production method than conventionally used unsaturated carboxylic acid-based polymers and copolymers such as polyacrylic acid, and can sufficiently satisfy water absorption. Therefore, there is a demand for the development of a resin that is easy to produce and that has both sufficiently high biodegradability and high water absorption.

The present invention relates to an economically advantageous unsaturated carboxylic acid polymer having excellent chelating ability and biodegradability, an efficient production method thereof, a builder containing this polymer as a constituent component, It is an object of the present invention to provide a detergent composition, a liquid detergent, and a dispersant such as an inorganic pigment, which contain a surfactant and a surfactant. It is another object of the present invention to provide a crosslinked unsaturated carboxylic acid polymer having both high biodegradability and water absorption, and an efficient production method by a simple process.

Disclosure of the invention

The present inventors have conducted intensive studies to achieve the above object, and as a result, an unsaturated carboxylic acid polymer having a specific chemical structure in a molecular chain has been Found that it has excellent biodegradability, is biodegradable, and is economically advantageous because it can be produced efficiently by a simple process, and this polymer is also useful as a builder. Highly useful as a detergent composition and dispersant, and a crosslinked unsaturated carboxylic acid polymer has both high biodegradability and water absorption, and is efficiently manufactured through simple processes And found that the present invention was completed based on such findings.

That is, the gist of the present invention is as follows.

(1) (a) the following general formula (1),

R

C 0 0 X [1]

Wherein (1), X represents a hydrogen atom, an alkali metal atom or an Anmoniumu radical, R represents a hydrogen atom or a methyl group] and橾返and single position 5 0-9 7 mole ^_0/0 expressed by, (B) The following general formula [2],

[In the formula (2), n represents 1 or 2 are shown] made of repeating units 3-5 0 mole ^_0/0 Metropolitan represented by a number average molecular weight of 5 0 0-1 0 0 0 0 0 0 And an unsaturated carboxylic acid polymer.

(2) (a) the following general formula (1), R

C 00 X [1]

Wherein (1), X represents a hydrogen atom, an alkali metal atom or an Anmoniumu radical, R represents a hydrogen atom or a methyl group] and repeating units of 3-9 0 mole ^_0/0 represented by, (b ) The following general formula [2],

[In the formula [2], n represents 1 or 2.] 3 to 50 mol of a repeating unit represented by the following formula: /. , And (c) the following general formula [3],

-{~ C H- C H ten

C 00 X C 00 X [3]

[In the formula (3), X has the same meaning as X in the formula [1]] consists repeating units from 0.1 to 50 mole ^_0/0 Metropolitan being Table, the number average molecular weight of 5 00- An unsaturated carboxylic acid polymer having a molecular weight of 1,000,000.

[3] (a) The following general formula [4],

CH2 = CR

[Four]

C00X (Wherein, R represents hydrogen or a methyl group, and X represents hydrogen, an alkali metal, or an ammonium group.) An acrylic acid compound represented by the formula: The method for producing an unsaturated carboxylic acid polymer according to the above [1], wherein the polymerization is carried out at 30 to 120 ° C. in the presence of the polymer.

[4] (a) The following general formula [4],

CH2 = CR

I [4]

C00X

(Wherein, R represents hydrogen or a methyl group, X represents hydrogen, an alkali metal or an ammonium group.) And (b) a compound represented by the following general formula [5]:

C H = C H

C 00 X C O O X [5]

(In the formula, X represents hydrogen, an alkali metal or an ammonium group.) A glyoxal or formaldehyde represented by the formula: is reacted at 30 to 120 ° C in the presence of a radical initiator. The method for producing an unsaturated carboxylic acid polymer according to the above [2], wherein the polymerization is carried out in the following.

[5] A biodegradable builder containing the unsaturated carboxylic acid polymer according to [1] or [2] as a constituent component. [6] A detergent composition containing the unsaturated carboxylic acid polymer according to [1] or [2] and a surfactant as constituent components.

[7] A liquid detergent composition comprising the unsaturated carboxylic acid polymer according to [1] or [2], a surfactant and water as constituent components.

[8] A dispersant comprising a polymer obtained by neutralizing the unsaturated carboxylic acid polymer according to [1] or [2] with alkali.

[9] The following general formula [4],

CH ₂ two CR

I [4]

C00X

(Wherein, R represents hydrogen or a methyl group, and X represents hydrogen, an alkali metal, or an ammonium group.) The acrylic acid-based compound represented by the following formula is cross-linked with daryoxal or formaldehyde. Crosslinked unsaturated carboxylic acid polymer produced by copolymerization and crosslinking at 0 to 120 in the presence of an initiator and a radical initiator.

[10] The following general formula [4],

CH ₂ = CR

I [4]

C00X

(Wherein, R represents hydrogen or a methyl group, and X represents hydrogen, an alkali metal, or an ammonium group.) A process for producing a crosslinked unsaturated carboxylic acid polymer, which comprises copolymerizing and crosslinking oxal or formaldehyde at 0 to 120 ° C in the presence of a crosslinking agent and a radical initiator.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is an NMR chart of the compound obtained in Example 23.

BEST MODE FOR CARRYING OUT THE INVENTION

The unsaturated carboxylic acid polymer of the present invention has a repeating unit of 50 to 97 mol represented by the general formula [1]. / ₀ and a repeating unit 3-5 0 Monore% represented by the general formula (2) and the force Rannahli, number average molecular weight of 5 0 0-1 0 0 0 0 0 is 0-unsaturated carboxylic acid polymer It is. Furthermore, unsaturated force carboxylic acid polymer of the present invention, the repeating unit 3-5 0 represented by the repeating unit represented by formula (1) 3-9 0 mole ^_0/0 and general formula [2] Mole. / ₀ and an unsaturated carboxylic acid having a repeating unit represented by the general formula [3] of 0.1 to 50 mol% and having a number average molecular weight of 500 to 1,000,000. It is an acid polymer. Examples of the alkali metal represented by X in the repeating unit represented by the general formula (13) include lithium, sodium potassium, and rubidium, and sodium and potassium are preferable. Al Li metal.

Next, in the unsaturated carboxylic acid polymer of the present invention, the content of the repeating unit represented by the above general formula!: 1] and the general formula [2] is 50% of the repeating unit represented by the general formula [1]. to 9 7 mole ^_0/0, preferably 5 0-7 0 mol. / By _0, the general formula (2) repeat units 3-5 0 mole ^_0/0 expressed in, preferably 3 0-5 0 mol ^_0/0. This means that the content of the repeating unit represented by the general formula [2] is 3 mol. This is because an unsaturated carboxylic acid polymer having a ratio of less than / ₀ causes a decrease in biodegradability, and the content of the repeating unit represented by the general formula [2] is 50 mol. / More than ₀ unsaturated carboxylic acid This is because the polymer has a reduced molecular weight and is inferior in function as a builder.

The content of the unsaturated carboxylic acid polymer comprising the repeating unit represented by the general formula [1], the general formula [2] and the general formula [3] is represented by the general formula [1]. Table, the total of the repeating units represented by the repeating unit and the formula [3], 5 0-9 5 mol ^_0/0, with respect to preferably 5 0-7 0 mol%, the general formula (2) that repeat units 3-5 0 molar% being, preferably 3 0-5 0 mol ^_0/0. Here, the content ratio of the repeating unit represented by the general formula [1] and the repeating unit represented by the general formula [3] is as follows: the former: the latter are represented by a molar ratio of 40 to 90: 10 to 6; It is preferably 0. Further, the content of the repeating unit represented by the general formula [2] in the ternary unsaturated carboxylic acid polymer is determined for the same reason as in the case of the binary unsaturated carboxylic acid polymer. However, it is desirable that the content ratio of each repeating unit be within the above range.

The number average molecular weight of the unsaturated carboxylic acid polymer is in the range of 500 to 1, 000, 0000, preferably in the range of 1, 000 to 100, 000, More preferably, it is in the range of 1,000 to 500,000. If the number average molecular weight is less than 50,000, sufficient chelating ability cannot be obtained when it is used as a builder. On the other hand, if it is more than 1, 000, 000 This is because the biodegradability is reduced.

Further, the unsaturated carboxylic acid polymer of the present invention contains the repeating unit represented by the general formula [1] and the general formula [2] or further the general formula [3] in a specific ratio. Furthermore, structural units other than the repeating units represented by these general formulas may be introduced as long as the object of the present invention is not impaired. Unsaturated compounds capable of introducing such structural units For example, itaconic acid, crotonic acid, α-hydroxyacrylic acid, vinylsulfonic acid, arylsulfonic acid, vinyltoluenesulfonic acid, vinylinole acetate, acrylinoleamide, acrolein, and hydroquinone , Resonoresinol, catechol, benzoquinone and the like.

Next, the method for producing the unsaturated carboxylic acid polymer is a method of polymerizing atalylic acid or methacrylic acid with dalioxal or formaldehyde at 30 to 120 ° C in the presence of a radical initiator. It can be based on When the above ternary unsaturated carboxylic acid polymer is produced, acrylic acid or methacrylic acid, maleic acid or fumaric acid and dalioxal or formaldehyde are reacted in the presence of a radical initiator. The polymerization may be performed at a temperature of 0 to 120 ° C. The use ratio of these acrylic acid or methacrylic acid to maleic acid or fumaric acid is preferably in the range of 40 to 90: 10 to 60 in molar ratio. Further, these acrylic acid, methacrylic acid, maleic acid, and fumaric acid may be in the form of an acid, an anhydride thereof may be used, and further, an alkali metal salt gammonium salt may be used. Glyoxal or formaldehyde may be used in the reaction as an aqueous solution, in which case the concentration is 10 to 40% by weight, more preferably about 40% by weight. . Further, as the glyoxal, a cyclic trimer may be used.

The liquid property of the polymerization system at the time of performing this reaction is desirably in the range of pH 4 to 10, and a base is preferably used for the adjustment. Examples of such a base include sodium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate. Preferred is sodium hydroxide.

Also, acrylic acid or methacrylic acid and glyoxal or phoric acid As the radical initiator used for the polymerization reaction with aldehyde, for example, a radical initiator composed of a combination of hydrogen peroxide and a reducing agent is suitably used. Examples of the reducing agent include divalent iron ions, copper ions, metal ions such as zinc ion and cobalt ion, ascorbic acid, and reducing sugar. The proportion of the radical initiator used is 0.1 to 100% by weight, preferably 0.1 to 100% by weight, based on the whole raw material obtained by adding acrylic acid or methacrylic acid and glyoxal, formaldehyde, maleic acid or fumaric acid. 0.5 to 50 weight. / ₀ .

In addition, as the radical initiator used here, azobisisobutyronitrile linole, azobis-1,2,4-dimethinolevalerone trinole, azobissic hexancarboditriol, tetramethylthidimethyldisulfide, or the like may be used. Good. The use ratio of these compounds is 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the whole raw materials. If the use ratio of these radical initiators is less than the above range, unreacted monomers may remain, and if it exceeds the above range, the effect corresponding thereto cannot be obtained.

Further, in the production of the unsaturated carboxylic acid polymer, usually, no solvent or an aqueous solvent is used. A non-aqueous solvent may be used as the solvent. As the non-aqueous solvent, acetone, dimethylformamide, dimethylacetamide, ethyl acetate, N-methylpyrrolidone, benzene, toluene, xylene, dioxane and the like are used. In this reaction, polymerization is preferably carried out in a solvent-free solvent, but when a non-aqueous solvent is used, acetone is preferred.

The reaction conditions in this case are as follows: at atmospheric pressure to 0.98 MPa, preferably at atmospheric pressure to 0.49 MPa, 30 to 120 ° C., preferably 40 to 12 ° C. It can be appropriately selected from the range of 0. Also, during polymerization The time depends on the type of the starting compound and the polymerization temperature, but is usually 1 to 24 hours, preferably 3 to 12 hours.

The biodegradable builder of the present invention comprising the unsaturated carboxylic acid polymer obtained in this way has excellent chelating ability, has biodegradability, and can be suitably used as a detergent builder.

In addition, by using this unsaturated carboxylic acid polymer together with a surfactant, a detergent composition having biodegradability can be obtained. As such a surfactant, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant and the like can be used.

Examples of the anionic surfactant include fatty acid soap, alkyl ether carboxylate, N-acyl amino acid salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, and dialkyl sulfosuccinate. , _Α -olefin sulphonate, higher alcohol sulphate, alkyl ether sulphate, polyoxyethylene alkyl unyl ether sulphate, ester sulphate of fatty acid alkyl amide, sulphate Esters / phosphates of phosphoric acid, ester of anorex / esters of phosphoric acid and the like are preferably used.

Further, as the cationic surfactant, an aliphatic amine salt, an aliphatic quaternary ammonium salt, a benzalkonium salt, a benzotonium chloride, a pyridinium salt, an imidazolinium salt and the like are suitable.

Examples of nonionic surfactants include polyoxyethylene alkynoleate, polyoxyethylene phenol / lefeninoleate, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene. Nglycerin fatty acid ester, polyoxyethylene castor oil, polio Xylethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, luster fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, fatty acid alcohol amide, polyoxyethylene fatty acid Amides, polyoxyethylene alkylamines, alkylamine oxides and the like are preferred.

As the amphoteric surfactant, for example, carboxybetaine-type compounds, aminocarboxylates, imidazolinidum betaine and the like are suitable.

The mixing ratio of the builder and the surfactant in this detergent composition is such that the builder is 2 to 20% by weight based on the total amount of the detergent composition when a solid powdery detergent composition is produced. The surfactant is 20 to 60% by weight. / ₀ , and the remaining 20 to 78% by weight is suitably used by appropriately mixing enzymes, bleaching agents, inorganic builders (for example, zeolite, sodium carbonate) and the like.

Further, in the production of liquid detergent compositions, for the whole amount of the detergent composition, builder 0.1 to 2 0% by weight, preferably 1 to 1 0 weight ^_0/0, surfactant 2 0 - 80% by weight, preferably 30 to 60% by weight, and water is 10 to 60% by weight. / ₀ , preferably 20 to 50% by weight, and those obtained by blending these main components with various additives are suitably used.

Such additives include, for example, polymers such as polyethylene glycol and carboxymethyl cellulose, color transfer inhibitors such as polybutylpyrrolidone, and metals such as citric acid, diglycolic acid, and phosphoric acid. Scavengers, alkaline agents such as alkali metal carbonates, alkali metal silicates, and alkanolamines; enzymes such as proteases, cellulases, and lipases; Enzyme stabilizers such as calcium chloride, formic acid, and boric acid; antifoaming agents such as silicone; lower alcohols such as ethanol and benzenesulfonate; Salts, glycols such as propylene glycol and polyethylene glycol, solubilizers such as benzoic acid and urea, oxidation prevention such as butylhydroxytoluene, distyrenated cresol, sodium sulfite, and sodium bisulfite Agents, fluorescent dyes, fragrances, antibacterial preservatives and the like. Further, the unsaturated carboxylic acid polymer of the present invention can be obtained by neutralizing an unsaturated carboxylic acid monomer by an ordinary method, for example, by neutralizing with an aqueous solution of an alkali such as sodium hydroxide or a hydroxylic power. It is obtained as a hydrophilic polymer having a number-average molecular weight of 1,000 to 100,000, whose main chain is a polymer. This polymer is also highly biodegradable due to its chemical structure, and is highly useful as a dispersant for inorganic pigments such as calcium carbonate and clay used in coating agents such as paper. is there.

In preparing such a coating agent, this dispersant is added in a proportion of 0.05 to 2.0 parts by weight based on 100 parts by weight of an inorganic pigment such as calcium carbonate and the like. This can be obtained by dispersing this in water. By using this dispersant, the coating agent can have low viscosity and high fluidity. In this case, the dispersant may be used alone, or another compounding agent, such as polyvinyl alcohol, may be used in combination.

Further, since the unsaturated carboxylic acid polymer of the present invention has excellent chelating ability, it is highly useful as a scale adhesion inhibitor in cooling water systems, boiler water systems and the like.

The crosslinked unsaturated carboxylic acid polymer of the present invention is produced by copolymerizing acrylic acid with daloxal or formaldehyde and crosslinking. It is an unsaturated carboxylic acid polymer crosslinked product. More specifically, a cross-linked unsaturated carboxylic acid polymer produced by adding a cross-linking agent and a radical initiator to acrylic acid and dalioxal or formaldehyde and simultaneously performing copolymerization and cross-linking, or It is a crosslinked unsaturated carboxylic acid polymer produced by adding a crosslinking agent and a radical initiator to acrylic acid and glyoxal or formaldehyde, copolymerizing the resultant, and then performing crosslinking. Further, it may be a crosslinked unsaturated rubonic acid polymer produced by copolymerizing atalylic acid and daloxal or formaldehyde with a radical initiator and then adding a crosslinking agent to crosslink.

Among the structural units constituting the crosslinked product of the unsaturated carboxylic acid polymer, the content ratio of the repeating unit based on the residue of acrylic acid and the repeating unit based on the residue of the above aldehydes is particularly limited. Although there is no restriction, those having a monore ratio in the range of 0.5 to 0.9: 0.1 to 0.5 are preferable because they have both high biodegradability and high water absorption.

Further, as the structural units constituting the crosslinked unsaturated carboxylic acid polymer, the basic structural units are the above-mentioned repeating unit based on the residue of acrylic acid and the above-mentioned aldehydes Is a repeating unit based on the residue of maleic acid, fumaric acid, methacrylic acid, vinyl acetate, alkyl acrylate, alkyl methacrylate, etc. It may be introduced as long as the object of the present invention is not hindered.

Next, the method for producing the crosslinked unsaturated carboxylic acid polymer can be a method for producing a copolymer of acrylic acid and daryoxal or formaldehyde and crosslinking them. More specifically, a method in which a crosslinking agent and a radical initiator are added to acrylic acid and dalioxal or formaldehyde together to form a crosslink at the same time as copolymerization, or After that, it may be produced by any method of crosslinking. Alternatively, it may be produced by a method in which acrylic acid and glyoxal or formaldehyde are copolymerized in the presence of a radical initiator, and then a crosslinking agent is added for crosslinking.

The raw material acrylic acid used here may be acrylic acid itself, or an alkali metal salt or an ammonium salt thereof. In addition, the above aldehydes may be used as they are, or may be used as an aqueous solution. When dalioxal is used, an aqueous solution having a concentration of about 10 to 40% by mass is preferable. Further, as the dalioxal, a cyclic trimer may be used.

Next, as the crosslinking agent, a water-soluble compound having two or more functional groups capable of reacting with a carboxyl group in one molecule, or two or more carbon-carbon unsaturated bonds in one molecule is used. Compounds are preferably used. Of these, water-soluble compounds having two or more functional groups capable of reacting with a carboxyl group in one molecule include ethylene glycol diglycidyl ether, glyceryl triglycidyl ether, and polyethylene glycol. Core diglycidyl ether, dipropylene glycol diglycidyl ether, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, diethanolamine, triethanolamine, polyoxypropylene Examples include len, polyvinyl alcohol, pentaerythritol, sorbite, sonolebitan, glucose, mannite, and mannitan. Compounds having two or more carbon-carbon unsaturated bonds in one molecule include N, N-methylenebisacrylamide, ethylene glycol dimethacrylate, and polyethylene glycol ^^ diethanol. And trimethylolpropane triatrate. The use ratio of these crosslinking agents is 0.05 to 5% by mass, preferably 0.1 to 1% by mass, based on the whole raw materials. / ₀ . If the amount of the crosslinking agent used is less than 0.05% by mass, the degree of crosslinking of the resulting unsaturated carboxylic acid polymer crosslinked product may not be sufficiently improved. When the content exceeds 5% by mass, the degree of crosslinking of the resulting unsaturated carboxylic acid-based polymer crosslinked product becomes too high, which causes a decrease in water absorption.

Further, as the radical initiator used in the present invention, for example, a radical initiator composed of a combination of hydrogen peroxide and a reducing agent is suitably used. As the reducing agent, metal ions such as divalent iron ion, copper ion, zinc ion and cobalt ion, ascorbic acid, reducing sugar and the like are used. The content of the radical initiator, with respect to the entire raw materials, 0.1 to 1 0 0 mass ^_0/0, preferably from 0.5 to 5 0 wt. / ₀ .

Further, the radical initiators used herein include azobis (2,4-dimetholene / renox erythritol), azobis (2,4-dimetholone), azobis (cyclohexyl) carboxytritol, tetramethylthiuramidine / sulfide, etc. May be used. The use ratio of these compounds is from 0.5 to 10% by mass, and preferably from 0.5 to 5% by mass, based on the whole raw materials. / ₀ . If the use ratio of these radical initiators is less than the above range, unreacted monomers may remain, and if the use ratio exceeds the above range, no effect corresponding thereto can be obtained.

The reaction conditions for producing the crosslinked unsaturated carboxylic acid polymer are as follows: from atmospheric pressure to IMP a (G), preferably from atmospheric pressure to 0.5 MPa (G); 120 ° C., preferably in the range of 40 to: L 20 °. The polymerization time depends on the type of the raw material compound and the polymerization temperature, but is usually 1 to 24 hours, preferably 3 to 24 hours. ~ 12 hours.

Since the unsaturated carboxylic acid polymer crosslinked product thus obtained has high water absorption, it can be used as a soil conditioner, a water retention agent, a water stopping agent, a drilling sludge composition, a disposable diaper, a sanitary product, and oil-water separation. It can be used as a material for materials and articles in a wide range of industrial fields such as chemicals and various sensors. Next, the present invention will be described in more detail with reference to examples.

(Example 1)

(1) Production of unsaturated carboxylic acid polymer

In a 500 milliliter separable flask equipped with a stirrer and thermocouple, 72.0 g of acrylic acid, 40.0 g of sodium hydroxide, and 40% by weight of glyoxal An aqueous solution having a concentration of 29.02 g (16.7 mol%), ferrous chloride tetrahydrate 50 mg and water 50 g were added. Next, the flask was heated to 1 ° C and stirred, and 56.6 g of a hydrogen peroxide solution having a concentration of 60% by weight was added dropwise thereto over 8 hours with stirring. After completion of the dropwise addition, the reaction was further continued for 1 hour with stirring under heating.

After completion of the reaction, the obtained reaction product was freeze-dried to obtain 114 g of a solid polymer (yield: 97%).

The number average molecular weight of the obtained polymer measured by gel permeation chromatography (GPC) using polyacrylic acid as a standard substance was 13,700. The weight average molecular weight of this polymer was 87,800.

In addition, in the measurement result of ¹³ C-NMR of this polymer, absorption derived from diketone was observed at 180 ppm. Absorption based on the main coalescence of the coalescence and absorption derived from the methine group proton that is synergistic with the diketone at 3.1 ppm were confirmed. These results and From the charge ratio, it was confirmed that the chemical structure of this polymer was as follows. -CH: -CH— ^ ~

COON a 0.8

C

B I

O 0 0.2

(2) Evaluation of calcium ion scavenging ability

20 mg of the polymer obtained in the above (1) was put into a beaker having a volume of 100 milliliters, and then 0.1N of calcium chloride, 0.1N of potassium chloride, ammonia 100 g of an aqueous solution containing 0.4 N and having a calcium ion concentration of 40 ppm was added and dissolved. Next, using a calcium ion electrode, the concentration of divalent calcium ions in the aqueous solution was measured, converted to calcium carbonate (unit: mg) captured by 1 g of the polymer, and this value was calculated. Ability.

As a result of the measurement, the polymer obtained in the above (1) had a calcium ion trapping ability of 165 mgZg.

(3) Evaluation of biodegradability

For the polymer obtained in (1) above, the decomposition rate between 28 B by activated sludge of the polymer was measured according to JIS K6950, and calculated from TOC (total organic carbon content). .

As a result of the measurement, the biodegradation rate of the polymer obtained in the above (1) was 40. /. Met.

Table 1 summarizes these results. (Example 2)

(1) Production of unsaturated carboxylic acid polymer

A 500-milliliter separable flask with stirrer, thermocouple, 98 g of maleic anhydride, 72.0 g of acrylic acid, and 80 g of sodium hydroxide. O g, 50 g of water, 50 mg of ferrous chloride tetrahydrate and 40 weight of dalioxal. /. 58.04 g (16.7 mol./.) Of the aqueous solution having a concentration was added, and the mixture was stirred at room temperature for 30 minutes, and then heated to 100 ° C. on an oil bath.

Then, while stirring the liquid in the flask, 56.6 g of a hydrogen peroxide solution having a concentration of 60% by weight was added dropwise thereto over 8 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour with stirring under heating.

After the completion of the reaction, the obtained reaction product was freeze-dried to obtain 2 18 g of a solid polymer (92% yield).

The number average molecular weight of the obtained polymer measured by gel permeation chromatography (GPC) using polyacrylic acid as a standard substance was 2,830. The weight average molecular weight of this polymer was 42,600.

In addition, in the measurement result of ¹³ C-NMR of this polymer, absorption derived from diketone was recognized at 180 ppm, and in the measurement result of _NMR, it was 1.2 to 3.0 ppm. Absorption based on the main chain of the polymer and absorption derived from the proton of the methine group interacting with the diketone at 3.1 ppm were confirmed. From these results, it was confirmed from the raw material charge ratio that the chemical structure of this polymer was as follows. CH: One CH

COON a 0.41

CH CH ~-

C 00 N a C 00 N a 0.41

(2) Evaluation of calcium ion scavenging ability

The calcium ion trapping ability of the polymer obtained in (1) was measured in the same manner as in (2) of Example 1, and as a result, it was 270 mgZg.

(3) Evaluation of biodegradability

The biodegradation rate of the polymer obtained in (1) above was measured in the same manner as in (3) of Example 1, and as a result, it was 40%.

Table 1 shows the results.

(Example 3)

(1) Production of unsaturated carboxylic acid polymer

Example 2 (1) except that the amount of the 40% by weight aqueous solution of glyoxal added in (1) of Example 2 was changed to 29.0 g (9.1 mol./ο). In the same manner as in the above, an unsaturated carboxylic acid polymer was obtained.

The number average molecular weight of the polymer obtained here was 4,550. The weight average molecular weight of this polymer was 31,780.

The measurement results of ¹³ C-NMR and ¹ H-NMR of this polymer were the same as those of (1) of Example 2.

(2) Evaluation of calcium ion trapping ability

The calcium ion-trapping ability of the polymer obtained in the above (1) was determined in Examples. As a result of measurement in the same manner as in (2) of 1, the result was 255 mg / g.

(3) Evaluation of biodegradability

The biodegradation rate of the polymer obtained in (1) was measured in the same manner as in (3) of Example 1, and as a result, it was 31%.

Table 1 shows the results.

(Example 4)

(1) Production of unsaturated carboxylic acid polymer

The amount of aqueous solution of 4 0 wt% concentration of glyoxal added in (1) of Example 2, 1 1 6 g (2 8. 5 mol. / ₀₎ was replaced by the Example 2 (1) In the same manner as in the above, an unsaturated carboxylic acid polymer was obtained.

The number average molecular weight of the obtained polymer was 2,650. The weight average molecular weight of this polymer was 25,500.

Further, the measurement results of ¹³ C-NMR and ¹ H-NMR of this polymer were the same as those of (1) of Example 2.

(2) Evaluation of calcium ion scavenging ability

The calcium ion trapping ability of the polymer obtained in the above (1) was measured in the same manner as in (2) of Example 1, and as a result, it was 230 mg / g.

(3) Evaluation of biodegradability

The biodegradation rate of the polymer obtained in (1) above was measured in the same manner as in (3) of Example 1, and as a result, was 51%.

Table 1 shows the results.

(Example 5)

(1) Production of unsaturated carboxylic acid polymer

In a 500 milliliter separable flask with stirrer and thermocouple, 980.0 g of maleic anhydride, 80.0 g of sodium hydroxide, 50 g of water, and ferrous chloride 10 mg of the tetrahydrate salt was added. Next, this hula The mixture was heated to 100 ° C. and stirred, while stirring, to 56.6 g of a 60% by weight aqueous hydrogen peroxide solution, 72.O g of acrylic acid and 40% by weight of darixol. 58.04 g (16.7 mol./.) Of a 1% aqueous solution was added dropwise over 5 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour with stirring under the heat of force B.

After the completion of the reaction, the obtained reaction product was lyophilized to obtain 228 g (yield: 96%) of a solid polymer.

The number average molecular weight of the obtained polymer measured by gel permeation chromatography (GPC) using polyacrylic acid as a standard substance was 1,750. The weight average molecular weight of this polymer was 10,300.

(2) Evaluation of calcium scavenging ability

The calcium ion scavenging ability of the polymer obtained in the above (1) was measured in the same manner as in (2) of Example 1, and as a result, it was 230 mg / g.

(3) Evaluation of biodegradability

The biodegradation rate of the polymer obtained in (1) was measured in the same manner as in (3) of Example 1, and as a result, it was 46%.

Table 1 shows the results.

(Example 6)

(1) Production of unsaturated carboxylic acid polymer

In a 500-milliliter separaprene flask equipped with a stirrer, thermocouple, and reflux condenser, 98.0 g of maleic anhydride, 72.O g of acrylic acid, and Sodium 80.0 g, water 50 g, ferrous chloride tetrahydrate 50 mg, glyoxal 40% by weight aqueous solution 29.02 g (16.7 moles ⁰ / o) and 1.1 g of hydroquinone were added and stirred at room temperature for 30 minutes. Next, the flask was heated to 100, and 56.6 g of a hydrogen peroxide solution having a concentration of 60% by weight was added dropwise thereto over 8 hours while stirring. After the completion of the dropwise addition, the reaction was further continued for 1 hour with stirring under heating.

After completion of the reaction, the obtained reaction product was freeze-dried to obtain 219 g (yield: 92%) of a solid polymer.

The number average molecular weight of the obtained polymer measured by gel permeation chromatography (GPC) using polyacrylic acid as a standard substance was 2,260. The weight average molecular weight of this polymer was 10,500.

In addition, the measurement results of ¹³ C-NMR and ¹ H-NMR of this polymer showed the same absorption as (1) in Example 1 and also confirmed the absorption derived from a benzene ring.

(2) Evaluation of calcium scavenging ability

The calcium ion scavenging ability of the polymer obtained in (1) was measured in the same manner as in (2) of Example 1, and as a result, it was 240 mg / g.

(3) Evaluation of biodegradability

The biodegradation rate of the polymer obtained in (1) was measured in the same manner as in (3) of Example 1, and as a result, it was 32%.

Table 1 shows the results.

(Example 7)

(1) Production of unsaturated carboxylic acid polymer

In a 500 milliliter separable flask equipped with a stirrer, thermocouple, and reflux condenser, 98.O g of maleic anhydride, 72.O g of acrylic acid, and sodium hydroxide Lithium 80.Og, water 50g, ferrous chloride tetrahydrate 100 mg of salt, 40 weight of glyoxal. /. An aqueous solution having a concentration of 14.5 g (1.0 mol) was added, and the mixture was stirred at room temperature for 30 minutes. Next, this flask was heated to 100 ° C., and 56.6 g of a hydrogen peroxide solution having a concentration of 60% by weight was added dropwise thereto over 8 hours while stirring. After completion of the dropwise addition, the reaction was further continued for 1 hour with stirring under heating.

After the completion of the reaction, the obtained reaction product was freeze-dried to obtain a solid polymer (306 g, yield: 100%).

The number average molecular weight of the obtained polymer measured by gel permeation chromatography (GPC) using polyacrylic acid as a standard substance was 1,880. The weight average molecular weight of this polymer was 21,700.

In the measurement results of ¹³ C-NMR and ¹ H-NMR of this polymer, the same absorption as (1) in Example 2 was observed.

(2) Evaluation of calcium capture ability

The calcium ion scavenging ability of the polymer obtained in (1) was measured in the same manner as in (2) of Example 1, and as a result, it was 240 mg Z g.

(3) Evaluation of biodegradability

The biodegradation rate of the polymer obtained in (1) was measured in the same manner as in (3) of Example 1, and as a result, was 52%.

Table 1 shows the results.

(Example 8)

(1) Preparation of detergent composition

After the polymer obtained in (1) of Example 1 was converted to an aqueous solution, sodium hydroxide was added to adjust the solution to pH 10 and this was used as a builder.

Then, 20 parts by weight of this builder was directly used as a surfactant. Sodium alkyl benzene sulfonate (abbreviated as LAS in Table 2) 20 parts by weight and sodium alkylsulfate (abbreviated as AS in Table 2) 5 parts by weight, sodium silicate as another additive 10 parts by weight, polyethylene glycol (abbreviated as PEG in Table 2) 2 parts by weight, 15 parts by weight of sodium carbonate, 5 parts by weight of sodium sulfate, and 23 parts by weight of water A composition was prepared.

(2) Detergency evaluation of detergent composition

Next, an evaluation test of the detergency of the detergent composition obtained in the above (1) was performed. As the artificial soil used here, one having the following composition was prepared. Organic soil components: 69.7 parts by weight

Firing viscosity: 29.8 parts by weight

Power Bon Black: 0.5 parts by weight

As the organic dirt component, those containing the following substances at a predetermined ratio were used.

Oleic acid: 0.28.3 parts by weight

Triolein: 15.6 weight parts

Cholesterol monolein: 12.2 parts by weight

Liquid paraffin: 2.5 parts by weight

Squalene: 2.5 parts by weight

Cholesterol: 1.6 parts by weight

Gelatin: 7.0 parts by weight

69.7 weight parts in total

Next, using this artificial soil, a contaminated cloth is prepared from a clean cloth by a water-solvent-based wet method and cut into 5 cm x 5 cm to produce a cloth having a reflectivity of 38 to 43%. After measuring the surface reflectance before cleaning, a cleaning test was performed under the following conditions. Testing machine: Terg-O-Tometer

Number of rotations: 1 2 0 r p m

Water hardness: 9 0 ppm (C a C0 3 conversion)

Wash volume: 900 milliliters

Washing temperature: 30 ° C

Detergent concentration: 0.0 6 7%

Bath ratio: 30 times

Washing time: 10 minutes

Rinse time: 3 minutes twice

Drying: Dry the mouth with filter paper

Next, the surface reflectivity of the washed cloth (cleaning cloth) was measured, and the cleaning power was calculated from the following equation.

Detergency (%) = [(KZS of dirty cloth-KZS of cleaning cloth) Z (K / S of dirty cloth-K / S of cleaning cloth)] X100

[In this equation, KS = (1 - R) is a ² Z ² R (Kubelka- formula Munk), R represents a surface reflectance of the fabric. ]

As a result of evaluating the detergency of the detergent composition as described above, the detergency of the detergent composition obtained in the above (1) was 66%.

Table 2 shows the composition of the detergent composition and the evaluation results of the cleaning power.

(Examples 9 to 13)

(1) Preparation of detergent composition

A detergent composition was prepared in the same manner as in Example 8, (1) except that the polymers obtained in Examples 2 to 6 were used.

(2) Detergency evaluation of detergent composition

Next, the detergent composition obtained in the above (1) was subjected to an evaluation test of its detergency in the same manner as in the item (2) of Example 8. Table 2 shows the compositions of these detergent compositions and the evaluation results of the cleaning power.

(Comparative Example 1)

(1) Preparation of detergent composition

20 parts by weight of A-type zeolite was used as a builder, whereas 20 parts by weight of sodium linear alkyl benzene sulfonate and 10 parts by weight of sodium alkyl sulfate were used as surfactants. The other additives were 10 parts by weight of sodium silicate, 2 parts by weight of polyethylene dalicol, 15 parts by weight of sodium carbonate, 5 parts by weight of sodium sulfate and 18 parts by weight of water. A detergent composition was prepared by blending.

(2) Detergency evaluation of detergent composition

Next, the detergent composition obtained in the above (1) was subjected to an evaluation test of its detergency in the same manner as in the item (2) of Example 8.

[Example 14 to: I 6]

(1) Preparation of liquid detergent composition

The polymer obtained in Example 7 as a builder, polyoxetylene alkynoleate / le and sodium linear olenoquinolebenzenesnolephonate as surfactants, and sodium solubiliser Monoethanolamine and ethanol, propylene glycol, sodium sulfite and water as antioxidants were used in the proportions shown in Table 3 and mixed to prepare a liquid detergent composition. did.

(2) Evaluation of liquid detergent composition

The liquid detergent composition obtained in (1) above was evaluated for its storage stability and detergency.

The storage stability was evaluated by placing each of the above liquid detergent compositions in a glass bottle with a content volume of 100 milliliters and sealing the bottle. The glass bottle was placed in a constant temperature bath at 10 ° C and allowed to stand. After the 7-day storage period, the liquid detergent composition in the glass bottle was visually observed and evaluated according to the following criteria.

No separation, sedimentation or cloudiness; 〇

Slightly cloudy, with precipitation; △

With separation, sedimentation and cloudiness; X

The detergency was evaluated in the same manner as in Example 8 (2). Table 3 shows the compositions of these liquid detergent compositions and the evaluation results of the cleaning power. (Comparative Examples 2-3)

Each component was blended as shown in Table 3 to prepare a liquid detergent composition, which was evaluated in the same manner as in Examples 14 to 16 described above. In these comparative examples, an acrylic acid-maleic acid copolymer (abbreviated as PAM in Table 3) was used as an organic builder.

Table 3 shows the compositions of these liquid detergent compositions and the evaluation results of the cleaning power. (Example 17)

(1) Preparation of dispersion

The concentration of the polymer obtained in (1) of Example 1 was 10 ppm, and the concentration of activated clay was 1 weight. A dispersion was prepared in which both were dissolved in water so as to be / ₀ .

(2) Evaluation of dispersion performance

The dispersion was stirred in 100 milliliters for 10 minutes, then placed in a 100-milliliter graduated cylinder and allowed to stand for 14 hours. Next, 5 milliliters of the supernatant of this dispersion was sampled, the absorbance was measured using a light source having a wavelength of 400 nm, and the value was evaluated as an index of the dispersion performance of the polymer. did.

When this polymer is used as a dispersant, the absorbance is 0.128. Was. In the blank test, the absorbance was 0.000. Table 4 shows the evaluation results of the dispersion performance.

(Example 18 to 22)

(1) Preparation of dispersion

A dispersion was prepared in the same manner as (1) of Example 17 except that the polymer obtained in (1) of Example 2 to (1) of Example 6 was used as a dispersant. .

(2) Evaluation of dispersion performance

With respect to the dispersion prepared in the above (1), the dispersant dispersion performance was evaluated in the same manner as in Example 17, (2). Table 4 shows the evaluation results.

Example 23

In a 500 ml separable flask equipped with stirrer, thermocouple and reflux condenser, 98.0 g of maleic anhydride, 40 g of sodium hydroxide, 50 g of water and 50 g of ferrous chloride tetrahydrate 100 mg of the salt was collected and stirred. A mixed solution of 72.0 g of acrylic acid and 78.9 g of a 38% aqueous solution of formaldehyde, an aqueous solution containing 40 g of sodium hydroxide, and 60% hydrogen peroxide solution 84.9 g were added dropwise over 8 hours while stirring at 100 ° C. After completion of the dropwise addition, the mixture was further heated and stirred for 1 hour. After the completion of the polymerization reaction, the mixture was freeze-dried to obtain a white solid polymer.

The obtained polymer was as follows.

Yield: 26 2 g (Yield: 100%)

Number average molecular weight: 2 6 8 0

Weight average molecular weight: 7 5 8 0

Calcium scavenging ability: 250 mgg Biodegradation rate: 80% (Polymerization occurs in a 100 ml glass cylinder Take 100 mg of activated sludge, 100 mg of activated sludge, and 20 Om1 of an aqueous solution containing salt as described in JISK 6950, and continue blowing air through a diffuser for 28 days. The aqueous solution was freeze-dried, and the biodegradation rate was determined by GPC based on the peak areas before and after the decomposition. The same applies hereinafter. )

This polymer was identified by nuclear magnetic resonance spectrum ( ^13C- NMR) measurement and elemental analysis.

Figure 1 shows the NMR chart.

In the NMR chart of Fig. 1, the absorption derived from the carboxy group was found at 182-187 ppm, the absorption derived from the carbonyl group at 180 ppm, and the binding of the carboxyl group at 45-60 ppm. Absorption derived from methine carbon and absorption derived from methylene carbon with a carboxyl group bonded at 36 to 45 ppm were confirmed.

From this NMR chart and elemental analysis, the polymer was

Equation (6)

CHz one CH

(6)

COONa equation (2)

One C

II (2)

0 and equation (7) — CH CH—

I I (7)

COONa COOH

It was found that the mole fraction of (6) was 0.33, the mole fraction of (2) was 0.33, and the mole fraction of (7) was 0.33.

Example 2 4

In a 500 ml separable flask equipped with a stirrer, thermocouple and reflux condenser, 98.0 g of maleic anhydride, 72.0 g of acrylic acid, 80 g of sodium hydroxide, 50 g of water g and ferrous chloride tetrahydrate 100 mg were collected and stirred. After 20 minutes, 3 8 <½ aqueous solution of formaldehyde 3

Add 1.6 g, stir at room temperature for 30 minutes, then raise the temperature to 100 ° C and, while stirring, add 56.6 g of 60% aqueous hydrogen peroxide dropwise over 8 hours. Was. After completion of the dropwise addition, the mixture was further heated and stirred for 1 hour, and a polymer was obtained in the same manner as in Example 23.

The obtained polymer was as follows.

Yield: 24.4 g (Yield: 100%)

Number average molecular weight: 2 8 8 0

Weight average molecular weight: 5 7 0 0

Calcium trapping capacity: 2 9 6 1118 8

Biodegradation rate: 46%

By measurement of nuclear magnetic resonance spectrum ( ¹³ C-NMR) and elemental analysis, the polymer was obtained by using the above formula (6), the above formula (2) and the above formula (7) as constituent units, and the mole fraction of (6) It was found that the mole fraction was 0.42, the mole fraction of (2) was 0.16, and the mole fraction of (7) was 0.42.

Example 2 5 The procedure was performed in the same manner as in Example 23, except that 118% of a 38% aqueous solution of formaldehyde was used and 113.2 g of a 60% aqueous hydrogen peroxide solution was used. The obtained polymer was as follows.

Yield: 277 g (Yield: 100%)

Number average molecular weight: 1 2 3 0

Weight average molecular weight: 4 1 4 0

Calcium capture capacity: 190 mg / g

Biodegradation rate: 85%

By measurement of nuclear magnetic resonance spectrum ( ¹³ C-NMR) and elemental analysis, the polymer was obtained by using the above formula (6), the above formula (2) and the above formula (7) as constituent units, and The mole fraction is 0.28, the mole fraction of (2) is 0.44,

The molar fraction of (7) was found to be 0.28.

Example 26

Example 23 was carried out except that 157.8 g of a 38% aqueous solution of formaldehyde and 141.5 g of a 60% aqueous hydrogen peroxide solution were used. The obtained polymer was as follows.

Yield: 292 g (Yield: 100%)

Number average molecular weight: 1 1 0 0

Weight average molecular weight: 6 3 6 0

Calcium trapping capacity: 1 4 5 mg Z g

Biodegradation rate: 85%

By measurement of nuclear magnetic resonance spectrum ( ¹³ C-NMR) and elemental analysis, the polymer was obtained by using the above formula (6), the above formula (2) and the above formula (7) as constituent units. It was found that the mole fraction was 0.25, the mole fraction of (2) was 0.50, and the mole fraction of (7) was 0.25.

Example 2 7 In a 500 ml separable flask equipped with stirrer, thermocouple and reflux condenser, 72.0 g of acrylic acid, 40.0 g of sodium hydroxide,

39.5 g of a 38% aqueous solution of formaldehyde and 30 g of water were collected and stirred. Then, with the temperature being raised to 100 ° C. and stirring, 60% hydrogen peroxide solution (28.3 g) was added dropwise over 8 hours, and the polymer was prepared in the same manner as in Example 23. I got

The obtained polymer was as follows.

Yield: 105.7 g (Yield: 97%)

Number average molecular weight: 2 3 8 0 0

Weight average molecular weight: 1 9 7 2 0 0

Calcium trapping capacity: 140 m gZ g

Biodegradation rate: 55%

By measurement of nuclear magnetic resonance spectrum ( ¹³ C_NMR) and elemental analysis, the polymer was obtained by using the above formula (6) and the above formula (2) as constituent units, and the mole fraction of (6) was 0.67. It was found that the mole fraction of (2) was 0.33.

Example 2 8

The following detergent composition containing the polymer obtained in Example 23 was prepared.

Polymer obtained by Builder Example 23 20 wt%

Surfactant Sodium Alkyl Benzene Sulfonate 25 wt% Surfactant Sodium Alkyl Sulfate 10 wt%

Soil deflocculant sodium silicate 10 wt%

Recontamination inhibitor polyethylene glycol 2 wt%

PH adjuster Sodium carbonate 15 wt%

Extender sodium sulfate 5 wt% Water 13 wt%

The detergency of this detergent composition was evaluated by the method described in Example 8.

As a result, the detergency of this detergent composition was 61%.

Example 2 9

The following detergent composition containing the polymer obtained in Example 24 was prepared.

Builder 20 Polymer obtained according to Example 24 0 wt%

Surfactant Sodium Alkylbenzenesulfonate 20 w.t% Surfactant Sodium Alkyl Sulfate 10 w.t%

Surfactant Nonionic surfactant 5 wt%

Soil deflocculant Sodium sodium silicate 10 wt%

Anti-recontamination agent Polyethylene glycol 2 wt%

PH adjuster Sodium carbonate 15 wt%

Extender sodium sulfate 5 wt%

Water 13 w t%

The detergency of this detergent composition was evaluated in the same manner as in Example 8.

As a result, the detergency of this detergent composition was 63%.

Example 30

The following detergent composition containing the polymer obtained in Example 25 was prepared.

Polymer obtained by builder example 25 20 wt%

Surfactant Sodium Alkylbenzenesulfonate 25 wt% Surfactant Sodium Alkyl Sulfate 10 wt%

Soil deflocculant Sodium sodium silicate 10 wt%

Anti-recontamination agent Polyethylene glycol 2 wt%

PH adjuster Sodium carbonate 15 wt% Extender sodium sulfate 5 wt%

Water 13 w t%

As a result, the detergency of this detergent composition was 59%.

Example 3 1

The following detergent composition containing the polymer obtained in Example 26 was prepared.

Builder 1 Polymer obtained according to Example 26 20 wt%

Surfactant Sodium Alkyl Benzene Sulfonate 20 wt% Surfactant Sodium Alkyl Sulfate 10 wt%

Surfactant Nonionic surfactant 5 wt%

Soil deflocculant Sodium sodium silicate 10 wt%

Anti-recontamination agent Polyethylene glycol 2 wt%

PH adjuster Sodium sodium carbonate 15 wt%

Extender sodium sulfate 5 wt%

Water 13 w t%

As a result, the detergency of this detergent composition was 58%.

Example 3 2

The following detergent composition containing the polymer obtained in Example 27 was prepared.

20 wt% of the polymer obtained according to Builder Example 27

Surfactant Sodium Sodium Benzoate ^^ 25 wt% Surfactant Sodium Sodium Alkyl Sulfate 10 wt%

Soil deflocculant sodium silicate 10 wt%

Recontamination inhibitor polyethylene glycol 2 wt% PH adjuster Sodium carbonate 15 wt%

Extender sodium sulfate 5 wt%

Water 1 3 wt ⁰ / ο

The detergency of this detergent composition was evaluated in the same manner as in Example 8. As a result, the detergency of this detergent composition was 64%. Comparative Example 4

The following detergent composition was prepared.

Builder type 1 zeolite 2 0 w t%

Soil deflocculant Sodium sodium silicate 10 wt%

Anti-recontamination agent Polyethylene glycol 2 wt%

PH adjuster Sodium sodium carbonate 15 wt%

Extender sodium sulfate 5 wt%

Water 13 w t%

The detergency of this detergent composition was evaluated in the same manner as in Example 8. As a result, the detergency of this detergent composition was 50. /. Met. Comparative Example 5

The following detergent composition was prepared.

Builder _ Type A zeolite 20 wt%

Surfactant Nonionic surfactant 5 wt%

Soil deflocculant sodium silicate 10 wt%

Anti-recontamination agent Polyethylene glycol 2 wt%

PH adjuster Sodium carbonate 15 wt% Extender sodium sulfate 5 wt%

Water 13 w t%

As a result, the detergency of this detergent composition was 52%.

Example 3 3

In a 500 ml separable flask equipped with stirrer, thermocouple and reflux condenser, 98.0 g of maleic anhydride, 72.O g of acrylic acid, 80.O g of sodium hydroxide, 50 g of water and 100 mg of ferrous chloride tetrahydrate were collected and stirred. Then, after 20 minutes, add 79 g of a 38% aqueous solution of formaldehyde, stir at room temperature for 30 minutes, then raise the temperature by 100 ° to 60% hydrogen peroxide 56.6. g was added dropwise over 8 hours. After completion of the dropwise addition, the mixture was further heated and stirred for 1 hour. After the completion of the polymerization reaction, the mixture was freeze-dried to obtain a white solid polymer.

The obtained polymer was as follows.

Yield: 303 g (Yield: 100%)

Number average molecular weight: 2 2 0 0

Weight average molecular weight: 2 3 1 0 0

Calcium capturing capacity: 255 mg gZg

According to NMR chart and elemental analysis, the polymer has the above formula (6), the above formula (2) and the above formula (7) as constituent units, and the mole fraction of (6) is 0.33, (2 ) Was 0.33, and that of (7) was 0.33.

Example 3 4

Example 33 The following detergent composition containing the polymer obtained in Example 3 was prepared. -Builder-polymer obtained according to Example 33 2.0 wt% Surfactant Polyoxyethylene alkyl ether 5.0 wt% Surfactant Sodium linear alkylbenzene sulfonate 6.0 wt% Solubilizer monoethanolamine 4.0 wt%

Solubilizer ethanol 3.0 wt%

Solubilizer propylene glycol 3.0 w t%

Antioxidant sodium sulfite 0. L wt%

Water 3 1.9 w t%

The detergent composition was collected in a 100-ml glass container, sealed, and allowed to stand in a thermostat at 5 ° C. for 7 days. The stability was evaluated (the same applies hereinafter). No precipitation or turbidity occurred.

The detergency was 62%.

Example 3 5

Example 33 The following detergent composition containing the polymer obtained in Example 3 was prepared.

Builder Polymer obtained by Example 3 3.0 wt%

Surfactant Polyoxyethylene alkyl ether 5.0 wt% Surfactant Sodium linear alkylbenzene sulfonate 6.0 wt% Solubilizer monoethanolamine 4.0

Solubilizer ethanol 3.0 wt%

Solubilizer propylene glycol 3.0 w t%

Antioxidant sodium sulfite 0.1 wt%

Water 30.9 wt%

When the stability was evaluated, no separation, sedimentation or cloudiness occurred.

The detergency was 62%.

Example 3 6

The following detergent composition containing the polymer obtained in Example 33 was prepared. Was.

Builder—Polymer obtained according to Example 33 3.0 wt%

Surfactant Polyoxyethylene alkyl ether 6.0 wt% Surfactant Sodium linear alkylbenzene sulfonate 6.0 wt% Solubilizer monoethanolamine 4.0 wt%

Solubilizer ethanol 3.0 wt%

Solubilizer propylene glycol 3.0 w t%

Antioxidant sodium sulfite 0. L wt%

Water 20.9 wt%

The detergency was 65%.

Comparative Example 6

The following detergent composition was prepared.

Builder acrylic acid-maleic acid copolymer 3.0 wt%

Surfactant Polyoxetylene alkyl ether '50 · 0 wt% Surfactant Sodium linear alkylbenzene sulfonate 6.0 wt% Solubilizer monoethanolamine 4.0 wt%

Solubilizer ethanol 3.0 wt%

Solubilizer propylene glycol 3.0 / w 3.0%

Antioxidant sodium sulfite 0. L wt%

Water 30.9 wt%

When the stability was evaluated, separation, sedimentation, and cloudiness were observed.

The detergency was 58%.

Comparative Example 7

The following detergent composition was prepared.

Builder acrylic acid-maleic acid copolymer 3.0 wt% Surfactant polyoxyethylene alkyl ether 60.0 wt% Surfactant sodium linear alkylbenzene sulfonate 6.0 wt% Solubilizer monoethanolamine 4.0 wt%

Solubilizer ethanol 3.0 wt%

Solubilizer propylene glycol 3.0 w t%

Antioxidant sodium sulfite 0.l wt%

Water 2 0.9 w t%

The detergency was 60%.

(Example 3 7)

(1) Production of crosslinked unsaturated carboxylic acid polymer

Stirrer, a capacitor 5 0 0 Mi Separaburufura score of Li Li Tsu Torr equipped with a thermocouple, placed the accession acrylic acid 7 2. O g, the aqueous solution 1 4 5. lg concentration 4 0 mass ^_0/0 of glyoxal And stirred. Next, 500 mg of glycerin as a cross-linking agent and 30 mg of ferrous chloride tetrahydrate as a radical initiator were added and dissolved to form a homogeneous solution. It was adjusted. Then, the flask was immersed in an oil bath to maintain the content at 100 ° C., and 40.0 g of an aqueous solution containing 64 mg of hydrogen peroxide was added dropwise over 3 hours. After the completion of the dropping of the hydrogen peroxide solution, the polymerization reaction was further carried out for 1 hour with stirring while maintaining the temperature at 100.

Next, sodium hydroxide was added to the reaction product after the completion of the polymerization reaction to adjust the pH to 7, and a part of the reaction product was transferred to a stainless steel bag. The mixture was heated to 0 ° C. and dried for 90 minutes. During this time, a crosslinking reaction (dehydration reaction) of the unsaturated carboxylic acid polymer was performed to obtain a crosslinked product of unsaturated rubonic acid polymer.

(2) Evaluation of water absorption Using the powder obtained by crushing the unsaturated carboxylic acid polymer crosslinked product obtained in the above (1) with a vibrating crusher, water absorption of a 0.9% by mass saline solution (physiological saline solution). The magnification was measured to evaluate the water absorption of the crosslinked product of unsaturated carboxylic acid polymer.

0.3 g of the powder of the crosslinked unsaturated carboxylic acid polymer is placed in a nonwoven fabric bag of 80 mm long and 60 mm wide, and the bag is immersed in physiological saline for 30 minutes. Drained for 1 minute on a wire net inclined at 30 degrees, and the mass was measured. The mass of the blank was subtracted from the mass measured here, and further converted to a value per 1 g of the mass of the sample to obtain a water absorption capacity. Table 1 shows the results.

(3) Evaluation of biodegradability

Using 0.1 g of the powder of the crosslinked unsaturated carboxylic acid polymer obtained in the above (1), and putting it in a nonwoven fabric bag of 80 mm long and 60 mm wide, Activated sludge collected at a sewage treatment plant was immersed in an aqueous solution with a concentration of 1, OOO ppm (mass), and a biodegradability test was performed for 24 hours with aeration.

After the completion of this test, the sample was taken out of the nonwoven fabric bag, and the mass after drying was measured. The biodegradation rate was determined from the difference in mass between the sample before and after the test. Table 5 shows the results.

(Example 38)

(1) Production of crosslinked unsaturated carboxylic acid polymer

Unsaturation was performed in the same manner as in Example 37 (1), except that the amount of the aqueous solution having a concentration of 40% by mass of glyoxal added in (1) of Example 37 was changed to 72.6 g. A carboxylic acid polymer crosslinked product was obtained.

(2) Evaluation of water absorption

The powder of the crosslinked unsaturated carboxylic acid polymer obtained in (1) above was used as a sample. The water absorption was evaluated in the same manner as in Example 37 (2), except that the water absorption was used. Table 1 shows the results.

(3) Evaluation of biodegradability

The biodegradability was evaluated in the same manner as in (3) of Example 37, except that the crosslinked unsaturated carboxylic acid polymer obtained in (1) was used as a sample. . Table 5 shows the results.

(Example 3 9)

(1) Production of crosslinked unsaturated carboxylic acid polymer

Stirrer, a capacitor 5 0 0 Mi Separaburufura score of Li Li Tsu Torr equipped with a thermocouple, placed the accession acrylic acid 7 2. O g, the aqueous solution 1 4 5. lg concentration 4 0 mass ^_0/0 of glyoxal And stirred. Then, 30 mg of ferrous chloride tetrahydrate was added and dissolved as a radical initiator to obtain a homogeneous solution, and the pH was adjusted to 3. Then, the flask was immersed in an oil bath, the content liquid was maintained at 80 ° C., and 40.0 g of an aqueous solution containing 64 mg of hydrogen peroxide was added dropwise thereto over 3 hours. After the completion of the addition of the hydrogen peroxide solution, the polymerization reaction was further performed at 80 ° C. for 1 hour with stirring. Next, sodium hydroxide was added to the reaction product after the polymerization reaction to adjust the pH to 7, and then ethylene glycol diglycidyl ether was added to the reaction product as a crosslinking agent. After adding 260 mg of 1 ter and uniformly dispersing, a part of the reaction product containing the crosslinking agent was transferred to a stainless steel bag, which was heated to 70 ° C and held for 2 hours. In the meantime, a crosslinking reaction (addition reaction) of the unsaturated carboxylic acid polymer was performed to obtain a crosslinked unsaturated carboxylic acid polymer.

(2) Evaluation of water absorption

Evaluation of water absorption in the same manner as in (2) of Example 37, except that the powder of the crosslinked unsaturated carboxylic acid polymer obtained in (1) above was used as a sample. Did. Table 5 shows the results.

(3) Evaluation of biodegradability

(Example 40)

(1) Production of crosslinked unsaturated carboxylic acid polymer

Unsaturation was carried out in the same manner as (1) of Example 39, except that the amount of the aqueous solution having a concentration of 40% by mass of dalioxal added in (1) of Example 39 was changed to 72.6 g. A carboxylic acid polymer crosslinked product was obtained.

(2) Evaluation of water absorption

The water absorption was evaluated in the same manner as in (2) of Example 37, except that the powder of the crosslinked unsaturated carboxylic acid polymer obtained in (1) was used as a sample. Table 5 shows the results.

(3) Evaluation of biodegradability

(Comparative Example 8)

(1) Production of crosslinked unsaturated carboxylic acid polymer

A crosslinked acrylic acid polymer was obtained in the same manner as (1) of Example 37 except that dalioxal was not added.

(2) Evaluation of water absorption

The water absorption was evaluated in the same manner as in (2) of Example 37, except that the crosslinked acrylic acid polymer obtained in (1) was used as a sample. Table 5 shows the results. (3) Evaluation of biodegradability

Biodegradability was evaluated in the same manner as in (3) of Example 37, except that the powder of the crosslinked acrylic acid polymer obtained in (1) was used as a sample. Table 5 shows the results.

Table 1

Table 2 Example (Comparative Example) 8 9 1 0 1 1 1 2 1 3 (1) Builder (Polymer) 2 0 2 0 2 0 2 0 2 0 2 0-Wash LAS 2 0 2 5 2 0 2 0 2 5 2 5 2

Pair

A S 5 1 0 5 5 1 0 1 0 1 0

object

Adult type A zeolite 20 min

(Sodium sodium silicate 10 1 0 1 0 1 0 1 0 1 0 1 0

Quantity

P E G 2 2 2 2 2 2 2

%

)

Sodium carbonate 1 5 1 5 1 5 1 5 1 5 1 5 1 5 Sodium sulfate 5 5 5 5 5 5 5 5 Water 2 3 1 3 2 3 2 3 1 3 1 3 1 8 Detergency (%) 6 6 6 4 6 5 5 9 6 1 6 0 5 2

Table 3 Example (Comparative Example) 14 15 15 16 (2) (3) Builder (polymer) 2.0 3.0 3.0--Polyoxyethylene 505 0 6 0 5 0 6 0 washing

Anorekinoreetenore

Agent

Pair

LAS 6.0 6.0 6.0 6.0 6.0

object

Monoethanolamine 4.0 4.0 4.0 4.0 4.0 min

(

Ethanol 3.0 3.0 3.0 3.00 3.0

■ Single-

%

Propylene glycol 3.0 3.0 3.0 3.0 3.0

)

No. Sodium sulfite o.i 0.1 0.1 0.1 0.1

P AM 3.0 3.0 Remaining Remaining Remaining Remaining Remaining Remaining storage stability 〇〇 OXX Detergency (%) 6 0 6 1 6 5 5 8 6 0 Table 4

Examples Polymers used Absorbance Example 1 重合 Polymer of Example 1 0.1 2 8 Example 18 Polymer of Example 2 0.12 0 Example 1 9 Polymer of Example 3 0.1 1 1 Example 20 Polymer of Example 4 0.09 8 Example 21 Polymer of Example 5 0.087 Example 22 2 Polymer of Example 6 0.093

Table 5

Example Water absorption ratio Biodegradation rate

(Comparative example) (times) (%) Example 3 7 7 0 3 0 Example 3 8 6 3 2 2 Example 3 9 6 8 3 5 Example 4 0 6 2 2 0 Comparative example 8 6 5 1

Industrial applicability

The unsaturated carboxylic acid polymer of the present invention is excellent in calcium ion trapping ability and excellent in biodegradability, so that it is highly useful as a detergent builder, and has a detergency by being incorporated into a surfactant component. Thus, a solid powder or liquid detergent composition having high biodegradability and a biodegradable dispersant can be obtained. Crosslinked unsaturated carboxylic acid polymers have high water absorbency, so they are highly useful as materials and articles in the fields of agriculture, civil engineering construction, sanitary goods, etc., and have excellent biodegradability. There is no danger to the natural environment when disposing after use.

Claims

(a) the following general formula [1],

R

C H, C-

C 00 X [1]

of

[In the formula (1), X represents a hydrogen atom, an alkali metal atom, or an ammonium group.

And R represents a hydrogen atom or a methyl group.)

(B) the following general formula [2]:

[In the formula [2], n represents 1 or 2.] A repeating unit represented by the following formula: 3 to 50 mol%, having a number average molecular weight of 500 to 1, 000, 0000 Certain unsaturated carboxylic acid polymers.

2. (a) The following general formula [1],

R

C H C-

C 00 X [1]

(In the formula (1), X is a hydrogen atom, an alkali metal atom, or an ammonium atom. Represents a group, R represents a repeating unit of 3-9 0 mole ^_0/0, represented by a hydrogen atom or a methyl group], (b) the following formula. [2],

[In the formula (2), n represents 1 or 2] repeat units 3-5 0 mole ^_0/0 expressed by, and (c) the following general formula [3],

~ (~ C H C H ——)

C O O X C O O X [3]

[In the formula (3), X has the same meaning as X in the formula [1]] consists repeating units from 0.1 to 5 0 mole ^_0/0 Metropolitan being Table, the number average molecular weight of 5 0 An unsaturated carboxylic acid polymer having a molecular weight of 0 to 1,000,000;

3. (a) The following general formula [4],

CH2 = CR

I [4]

C00X

(Wherein, R represents hydrogen or a methyl group, and X represents hydrogen, an alkali metal or an ammonium group.) The acrylic acid compound represented by the formula The method for producing an unsaturated carboxylic acid polymer according to claim 1, wherein the polymerization is carried out at a temperature of 30 to 120 ° C.

4. (a) The following general formula [4], CH ₂ = CR

I C4]

coox

(Wherein, R represents hydrogen or a methyl group, X represents hydrogen, an alkali metal or an ammonium group); and (b) a compound represented by the following general formula [5]:

C C H

C O O X C O O X [5]

(Wherein, X represents hydrogen, an alkali metal or an ammonium group.) A maleic acid compound represented by the formula and glyoxal or formaldehyde are polymerized at 30 to 120 ° C in the presence of a radical initiator. The method c for producing an unsaturated carboxylic acid polymer according to claim 2,

5. A biodegradable builder comprising the unsaturated carboxylic acid polymer according to claim 1 as a constituent.

6. A detergent composition comprising the unsaturated carboxylic acid polymer according to claim 1 and a surfactant as constituents.

7. A liquid detergent composition comprising the unsaturated carboxylic acid polymer according to claim 1 or 2, a surfactant, and water as constituents.

8. A dispersant comprising a polymer obtained by neutralizing the unsaturated carboxylic acid polymer according to claim 1 or 2 with an alcohol.

9. The following general formula [4], CH ₂ = CR

I [4]

coox

(Wherein, R represents hydrogen or a methyl group, and X represents hydrogen, an alkali metal, or an ammonium group.) An acrylic acid compound represented by the formula A crosslinked unsaturated carboxylic acid polymer produced by copolymerization and crosslinking at 0 to 120 ° C in the presence of an initiator.

10. The following general formula [4],

CH ₂ = CR

I [4]

COOX

(In the formula, R represents hydrogen or a methyl group, and X represents hydrogen, an alkali metal or an ammonium group.) An acrylic acid-based compound represented by A method for producing a crosslinked unsaturated carboxylic acid polymer, characterized by copolymerization and crosslinking at 0 to 120 in the presence of a radical initiator.