JPH11124409A - Unsaturated carboxylic acid polymer, its production, biodegradable builder comprising the polymer, detergent composition and dispersant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an unsaturated carboxylic acid polymer having chelating properties and biodegradability free from discoloration, a builder composed of the unsaturated carboxylic acid polymer, a detergent composition composed of the builder and a surfactant and a dispersant composed of the salt of the polymer and to provide a method for producing them. SOLUTION: This unsaturated carboxylic acid polymer contains at least one group of the formula -C(O)X(CH2 )n S- or -C(O)X(CH2 )n SOm - (X is O or NH; (n) is an integer of 1-6) and has 1,000-100,000 number-average molecular weight. The method for producing the unsaturated carboxylic acid polymer comprises polymerizing an unsaturated carboxylic acid in the presence of a hydroxyl group- or amino group-containing thiol compound or both the hydroxyl group- or amino group-containing thiol compound and an inorganic or an organic acid by a nonoxidizing polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel unsaturated carboxylic acid polymer (hereinafter referred to as an unsaturated carboxylic acid polymer including its oligomer), a method for producing the polymer, and a method for preparing the polymer as a main component. A biodegradable builder, a detergent composition and a dispersant. More specifically, the present invention provides a novel unsaturated carboxylic acid polymer having a specific structure in the molecular chain, a method for producing the polymer, a biodegradable detergent builder containing the polymer as a main component, The present invention relates to a detergent composition containing a builder and a dispersant obtained by neutralizing the unsaturated carboxylic acid polymer with an alkali.

[0002]

2. Description of the Related Art Conventionally, detergents containing a surfactant as a main component have been improved in cleaning performance by incorporating a builder as an auxiliary component of the surfactant. As the builder, an inorganic compound showing an alkalinity when added to water, a polymer of an unsaturated aliphatic carboxylic acid, and the like are known. Examples of the former include sodium or potassium carbonates, bicarbonates, phosphates, polyphosphates, silicates and zeolites, and examples of the latter include polyacrylic acid, polymaleic acid, polyitaconic acid. And the like.

[0003] Among these builders, phosphates, polyphosphates and zeolites are used in large amounts from the viewpoints of washing effect, economy and workability. However, phosphates and polyphosphates cause eutrophication of lakes and rivers, and zeolites have various problems in terms of protecting the global environment such as sedimentation. Therefore,
It is not only excellent in at least the performance as a builder (especially, chelating ability) as in the past, but also has the biodegradability important for protecting the global environment and does not remain for a long time, so-called environmentally friendly. In addition, the development of an economically advantageous builder is desired.

Therefore, as a builder polymer having chelating ability and biodegradability, a water-soluble oligomer containing at least a component having a low molecular weight that is biodegradable, although it has little chelating ability by itself, is mainly used. The chains were linked to each other via a biodegradable ester group or amide group by a cross-linking agent such as polyethylene glycol, citric acid, or tartaric acid, to increase the molecular weight, and as a cross-linked polymer, to have chelating ability. A hydrophilic crosslinked polymer is disclosed in JP-A-5-239127.

However, linear polyacrylic acid itself has a low molecular weight but is not easily biodegradable, and contains a considerable amount of high molecular weight polyacrylic acid which does not biodegrade. Biodegradability is not sufficient. Furthermore, since there are two steps of a step of polymerizing the oligomer and a step of cross-linking, and since the specific cross-linking agent is also required, a builder polymer having chelating ability and biodegradability which can be produced in a simpler step, and A manufacturing method is expected.

[0006] Among the above-mentioned conventional builders, unsaturated carboxylic acid polymers such as polyacrylic acid have attracted attention because of their ease of polymerization and high chelating performance with polycarboxylic acids. In the production of the unsaturated carboxylic acid polymer, hydrogen peroxide has usually been used as a polymerization initiator (catalyst), but the hydrogen peroxide is preferable because it hardly remains as a catalyst residue after the polymerization. However, when hydrogen peroxide is used as a polymerization initiator by neutralizing an unsaturated carboxylic acid monomer with a normal base, its efficiency is low. As a countermeasure, a method of adding a metal such as iron, cobalt, or an amine is proposed. However, there is a problem that the polymer is colored, and therefore, its use is limited. Further, when hydrogen peroxide is used as a polymerization initiator after neutralization with a normal base, a large amount of hydrogen peroxide is required as an initiator to synthesize the unsaturated carboxylic acid oligomer. It has been a point.

[0007] In the field of inorganic pigment dispersants, sodium polyacrylate or the like is used to lower the viscosity of the dispersion slurry and to improve the viscosity stability. Therefore, there is a demand for the development of a dispersant which is biodegradable and does not remain for a long period of time, and is economically advantageous.

[0008]

Under such circumstances, the present invention provides an economically advantageous unsaturated carboxylic acid polymer having no coloring, excellent chelating ability, and biodegradability.
A method for efficiently producing the same, and a builder comprising the polymer, which suppresses environmental pollution or destruction, a detergent composition containing the builder component and a surfactant component having excellent cleaning ability, and a dispersant such as an inorganic pigment. It is intended to provide.

[0009]

Means for Solving the Problems As a result of diligent studies to achieve the above object, the present inventors have succeeded in obtaining an unsaturated carboxylic acid polymer having a specific structure in the molecular chain. The polymer of the present invention is colorless and has excellent chelating ability,
It has biodegradability, can be efficiently produced by a simple process, is economically advantageous, and when added to a surfactant as a builder, a useful detergent composition can be obtained. It has been found that alkali salts of polymers are useful as dispersants for inorganic pigments and the like. The present invention has been completed based on such findings.

That is, the present invention is as follows. (1) In a molecular chain, a compound represented by the general formula —C (O) X (CH ₂ ) _n S
— Or —C (O) X (CH ₂ ) _n SO _m — (where X is
Represents O or NH. n is an integer of 1 to 6, and m is 1
Or 2. And a number average molecular weight of from 1,000 to 100,000. (2) The unsaturated carboxylic acid polymer according to (1), wherein the unsaturated carboxylic acid polymer is an alkali metal salt or an ammonium salt. (3) The number average molecular weight after hydrolysis is 500 to 10,000.
The unsaturated carboxylic acid polymer according to (1) or (2), which is 0. (4) A method for producing an unsaturated carboxylic acid polymer, comprising polymerizing an unsaturated carboxylic acid with a non-oxidizing polymerization initiator in the presence of a thiol compound having a hydroxyl group or an amino group. (5) A method for producing an unsaturated carboxylic acid polymer, comprising polymerizing an unsaturated carboxylic acid with a non-oxidizing polymerization initiator in the presence of a thiol compound having a hydroxyl group or an amino group and an inorganic acid or an organic acid. . (6) The method for producing an unsaturated carboxylic acid polymer according to (4) or (5), wherein the polymerization is performed in a solvent-free or non-aqueous solvent. (7) The method for producing an unsaturated carboxylic acid polymer according to any one of (4) to (6), wherein the produced polymer is further oxidized. (8) The unsaturated carboxylic acid is maleic anhydride and (meth) acrylic acid, and maleic anhydride in the total unsaturated carboxylic acid is 10 to 60 mol% (4) to (7).
The method for producing an unsaturated carboxylic acid polymer according to any one of the above. (9) A biodegradable builder comprising the polymer according to any one of (1) to (3) as a main component. (10) A detergent composition containing 1 to 40% by weight of the biodegradable builder described in (8) and 1 to 40% by weight of a surfactant. (11) A dispersant comprising the polymer according to any one of (1) to (3) neutralized with an alkali.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The unsaturated carboxylic acid polymer of the present invention is obtained by polymerizing an unsaturated carboxylic acid monomer such as acrylic acid in the presence of a specific compound. General formula -C (O) X (CH ₂ ) _n S- or-
C (O) X (CH ₂ ) _n SO _m — (wherein X represents O or NH. N is an integer of 1 to 6, and m is 1 or 2
It is. And a number average molecular weight of 1,000 to 100,000. The unsaturated carboxylic acid polymer has the following main constituent units.

[0012]

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Such an unsaturated carboxylic acid polymer having a specific residue in the molecular chain and having a relatively low number average molecular weight has not existed conventionally, and is a substance obtained by the present invention for the first time. The characteristic of this substance is that it is water-soluble and has the unique property of being highly biodegradable.In addition, it has high chelate-forming ability to capture polyvalent metals like ordinary polycarboxylic acid-based polymers, Various uses such as a remover have been considered, particularly as a detergent component that does not cause destruction of the global environment.

[0014] The higher the molecular weight of the conventional unsaturated carboxylic acid polymer, the higher the chelate-forming ability, but the lower the biodegradability. However, the unsaturated carboxylic acid polymer according to the present invention has a specific ester or amide bond and a thioether, sulfone or sulfoxide bond in the molecular chain. It has a great feature that it is not seen.

From these points, the number average molecular weight is 1,000
0 to 100,000 is optimal, and if it is less than 1,000, there is a problem in practicality of chelating performance, and if it exceeds 100,000, there is a problem in biodegradability, and both problems of the present invention can be solved. Disappears. The amount of the specific residue in the molecular chain can be determined by ¹ H-NMR, and the proton of the main chain of the polymer, specifically,

[0016]

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The peaks derived from the underlined protons
(CH of specific residue to area a_Two) _nNo proton
CH adjacent to the ester or amide_TwoThe proton
Ratio of peak area b derived from [(b / a) × 100
(%)], Preferably 3.0% or more, more preferably
It is in the range of 5.0 to 20.0%. This value is less than 3.0%
In the full, even if it has the above specific residue, the main chain of the polymer
Small, i.e. ester or amide opening
The desired biodegradability is obtained because the molecular weight after cleavage is too high
May not be.

The specific residue is -C (O) O (CH_Two)_TwoS-
In the case where is derived from the above-mentioned proton of the polymer,
0 to 3.2 ppm of the specific residue relative to the peak area a
(CH _Two)_TwoOf the protons of C
H_Two4.0 to 4.4 ppm peaks derived from
Calculated as the ratio of the surface area b [(b / a) x 100 (%)]
Can be issued. However, the value of a in the polymer
Complementary to the composition of (meth) acrylic acid, maleic acid, etc.
It is necessary to correct. For example, vinyl of acrylic acid
The peak area of the proton derived from the group is increased by 2/3 times,
2 proton peak areas derived from each monomer unit
Must be corrected to correspond to

In a preferred embodiment of the unsaturated carboxylic acid polymer of the present invention, the polymer obtained by hydrolyzing the polymer under the conditions described below has a number average molecular weight of 500 to 10,000. This is a structure in which a low molecular weight unsaturated carboxylic acid polymer having a number average molecular weight of 500 to 10,000 is connected via an ester or amide bond by employing a production method described later, for example, the following general formula ( It has a structure as shown in I), and it is considered that the site where the ester or amide bond is attached is useful for improving the biodegradability.

[0020]

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The presence of this ester or amide bond is
^{According to 1} H-NMR, 4.0 to 4.4 ppm or -CONH-CH derived from -COO-CH ₂ -protons
₂ - can be grasped from the peak area of 2.9~3.8ppm derived from protons. In a preferred embodiment of the present invention, the number average molecular weight after hydrolysis is 500 to 1
It is an unsaturated carboxylic acid polymer having a molecular weight of 000, more preferably 500 to 5,000, particularly preferably 500 to 2,500. When the number average molecular weight exceeds 10,000, a decrease in biodegradability may be observed.

A more preferred embodiment of the present invention is an unsaturated carboxylic acid polymer having a specific residue of -C (O) O (CH ₂ ) ₂ S-, which has high biodegradability. As the unsaturated carboxylic acid monomer according to the present invention,
Maleic anhydride, maleic acid, fumaric acid, acrylic acid,
Methacrylic acid, maleic acid and the like are preferably used. The unsaturated carboxylic acid polymer of the present invention may be a homopolymer of an unsaturated carboxylic acid or a polymer composed of two or more unsaturated carboxylic acid monomers. In the case of a polymer made by combining two or more kinds, the ratio can be arbitrarily selected depending on the amount of monomer supplied at the time of production.

The unsaturated carboxylic acid polymer of the present invention is preferably prepared from maleic anhydride or maleic anhydride in terms of the amount of monomer supplied during production from the viewpoints of chelating ability and biodegradability and production such as control of molecular weight. 10-6 acids
0 mol%, acrylic acid and / or methacrylic acid
The combination is 0 to 90 mol%. More preferably, the combination is 30 to 50 mol% of maleic anhydride and 50 to 70 mol% of acrylic acid.

It is advantageous from the viewpoint of chelating ability that maleic anhydride or maleic acid be at least 10 mol%, and at most 60 mol% is advantageous in suppressing the increase of unreacted maleic acid. It is. The unsaturated carboxylic acid polymer of the present invention may be a compound represented by the general formula (II) in addition to the above-mentioned unsaturated carboxylic acid monomer.

[0025]

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(Wherein R ⁴ represents a hydrogen atom, a methyl group,-
OH or -COOX ¹ is shown. Y and Z are each a hydrogen atom, a chlorine _{^{atom, -COOX 1, -SO 3 X,}} -
^{OH, -OCOR '', -COR '} ', -CONH 2, -C
OOOH or -CHO is shown. X ¹ represents a hydrogen atom, an alkali metal atom or an ammonium group, and examples of the alkali metal atom include sodium, potassium and lithium. R ^″ represents an alkyl group having 1 to 12 carbon atoms. )) Or a structural unit based on a polymerizable unsaturated compound represented by the formula (1) in the chain or at the terminal.

Examples of the above polymerizable unsaturated compounds include itaconic acid, crotonic acid, α-hydroxyacrylic acid, vinylsulfonic acid, allylsulfonic acid, vinyltoluenesulfonic acid and alkali metal salts, ammonium salts, carbon salts In addition to alcohol esters of formulas 1 to 12, acrylamide, itaconic anhydride, acrolein and the like can be mentioned.

These polymerizable unsaturated compounds may be any of the above unsaturated carboxylic acid monomers 50 to 9 of an unsaturated carboxylic acid polymer.
With respect to 9 mol%, it can be selected in the range of 1 to 50 mol%. The method for producing an unsaturated carboxylic acid polymer according to the present invention is characterized in that a production method characterized by polymerizing an unsaturated carboxylic acid monomer with a non-oxidizing polymerization initiator in the presence of a thiol compound having a hydroxyl group or an amino group and a hydroxyl group Alternatively, a production method characterized by polymerizing an unsaturated carboxylic acid monomer with a non-oxidizing polymerization initiator in the presence of a thiol compound having an amino group and an inorganic acid or an organic acid.

The thiol compound has a general formula (I)
II) X- (CH ₂ ) _n -SH (III) (wherein, X represents an OH group or an NH ₂ group, and n represents 1 to 6)
Is an integer. )) Can be used. Specific examples of the organic thiol compound represented by the general formula (III) include mercaptoethanol, mercaptopropanol, mercaptobutanol, and aminoethanethiol.

Among these organic thiol compounds, a thiol compound having a hydroxyl group can be preferably used. These organic thiol compounds are usually 1 to 30% by weight, preferably 5 to 2% by weight, based on the unsaturated carboxylic acid monomer.
An amount in the range of 5% by weight is used. If this amount exceeds 30% by weight, the chelating ability tends to be insufficient, and
When n exceeds 6, the solubility of the produced polymer in water tends to decrease.

Examples of the inorganic or organic acid include concentrated sulfuric acid, sulfurous acid, boric acid, phosphoric acid, nitric acid, hydrochloric acid, hydrofluoric acid, p-toluenesulfonic acid, p-bromobenzenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. And Bronsted acids such as nonafluorobutanesulfonic acid and 2,2,2-trifluoroethanesulfonic acid, and Lewis acids such as aluminum chloride and boron trifluoride. Among these inorganic or organic acids, Bronsted acids are preferred, and further, concentrated sulfuric acid, sulfurous acid, boric acid,
Phosphoric acid, p-toluenesulfonic acid, and methanesulfonic acid can be suitably used.

These inorganic or organic acids are used in an amount of usually from 0.1 to 10% by weight, preferably from 1 to 5% by weight, based on the unsaturated carboxylic acid monomer. If this amount exceeds 10% by weight, cloudiness tends to occur. Examples of the non-oxidizing polymerization initiator include azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, tetramethylthiuram disulfide and the like.

Further, photopolymerization such as ultraviolet rays can also be mentioned as a polymerization method using a non-oxidizing polymerization initiator. At this time, a photosensitizer may be added as needed. Among these non-oxidizing polymerization initiators, azobisisobutyronitrile can be suitably used. These non-oxidizing polymerization initiators are usually added to the unsaturated carboxylic acid monomer at a ratio of 0.1 to 0.1.
An amount in the range of 1 to 5.0% by weight, preferably 0.5 to 2.0% by weight is used.

The production of the unsaturated carboxylic acid polymer of the present invention is usually carried out using no solvent or a non-aqueous solvent. Examples of the non-aqueous solvent include acetone, dimethylformamide, dimethylacetamide, ethyl acetate, N-methylpyrrolidone, benzene, toluene, xylene, dioxane and the like. Polymerization is preferably carried out without solvent, but when a non-aqueous solvent is used, acetone is preferred.

Further, regarding the reaction conditions, the polymerization pressure is not particularly limited, and is usually from atmospheric pressure to 10 kg / cm ^2.
G, preferably from atmospheric pressure to 5 kg / cm ² G, and the polymerization temperature is appropriately selected in the range of usually 30 to 150 ° C, preferably 50 to 100 ° C. The polymerization time depends on the raw materials, the polymerization temperature and the like, and cannot be determined unconditionally.
The time is from about minutes to 20 hours, preferably about 1 to 4 hours.

The reaction method of the present invention is not particularly limited, and a solution of an unsaturated carboxylic acid monomer, a non-oxidizing polymerization initiator and a non-aqueous solvent, and a solution of an organic thiol compound and a non-aqueous solvent are each heated and stirred. A method of dropping and reacting into a reactor, a solution of an unsaturated carboxylic acid monomer and a non-aqueous solvent is put into the reactor and stirred with heating. A method of reacting a solution of a non-oxidizing polymerization initiator and a non-aqueous solvent by dropping each into a heated and stirred reactor,
A method such as a method in which all the raw materials are charged into a reactor and reacted by heating and stirring may be used.

Further, the produced polymer may be oxidized. By oxidizing the polymer, the general formula -C in the molecular chain _{(O) X (CH 2)} n S- ( wherein, X is O or N
H is shown. n is an integer of 1 to 6, and m is 1 or 2. ) Is a group represented by the general formula -C (O) X (C
H ₂ ) _n SO _m — (wherein, X represents O or NH. N
Is an integer of 1 to 6, and m is 1 or 2. ). Examples of the oxidizing agent include hydrogen peroxide, ozone, and the like, with hydrogen peroxide being preferred. The reaction conditions are not particularly limited and are appropriately selected usually in the range of room temperature to 100 ° C, preferably 40 to 80 ° C. The reaction time depends on the reaction temperature and the like and cannot be determined unconditionally, but is usually about 10 minutes to 10 hours, preferably about 0.5 to 2 hours.

The number average molecular weight of the unsaturated carboxylic acid polymer according to the present invention is 1,000 to 100,000. The number average molecular weight is determined by reaction conditions such as the amount of the thiol compound used, the amount of the inorganic or organic acid used, and the amount of the non-oxidizing polymerization initiator, and is in this range, preferably 1,000 to 25. By taking 3,000, the properties such as biodegradability according to the present invention are exhibited.

In the above polymerization method, the unsaturated carboxylic acid is reacted with a non-oxidizing polymerization initiator in the presence of a thiol compound having a hydroxyl or amino group, or in the presence of a thiol compound having a hydroxyl or amino group and an inorganic or organic acid. Since the acid monomer is polymerized, the structure of the produced polymer is different from that of the conventional method, and the biodegradability can be improved. In addition, these methods facilitated the synthesis of a non-colored, unsaturated carboxylic acid polymer, particularly an oligomer having a low molecular weight. The number average molecular weight is 1,0
Since it is about 100 to 100,000, a high molecular weight substance which does not affect the biodegradability can be formed, and is suitable as a biodegradable builder.

The unsaturated carboxylic acid polymer can be produced by the various methods described above, but after isolating the polymer,
Alternatively, it can be supplied as the biodegradable builder of the present invention in a state in which the polymerization initiator, the residue of the polymerization catalyst, the decomposed product, and the like used in the polymerization are mixed without being isolated. Further, the unsaturated carboxylic acid polymer of the present invention may further comprise, in addition to the above unsaturated carboxylic acid monomer (including an acid anhydride), a compound represented by the general formula (IV):

[0041]

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(Wherein R ⁴ , Y and Z are the same as described above), and polymerized in the same manner as in the above-mentioned method for producing an unsaturated carboxylic acid polymer. It can also be obtained by: Examples of the polymerizable unsaturated compound represented by the general formula (IV) are the same as those described above.

The biodegradable builder of the present invention containing the unsaturated carboxylic acid polymer obtained as described above as a main component is:
It has excellent chelating ability, has biodegradability, is suitably used as a detergent builder, and can be used in combination with a surfactant to obtain a biodegradable detergent composition. The detergent composition according to the present invention is characterized in that the unsaturated carboxylic acid polymer according to the present invention is used as a builder, and a surfactant component is added to the builder to provide a detergent composition having an excellent cleaning function and having biodegradability after use. can get. Examples of the surfactant used include surfactants such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.

The above-mentioned builder and surfactant are preferably incorporated in the detergent composition in an amount of 1 to 40% by weight, and the remaining 20 to 80% by weight is composed of enzymes, bleaching agents, inorganic builders (zeolite). , Sodium carbonate, etc.) are appropriately blended. Examples of the anionic surfactant used in the present invention include fatty acid soap, alkyl ether carboxylate, N-acyl amino acid salt, alkyl benzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, α -Olefin sulfonate, higher alcohol sulfate, alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, fatty acid alkylolamide sulfate, alkyl ether phosphate, alkyl phosphate, and the like. Can be

Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts and the like. As the nonionic surfactant, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, Polyoxyethylene castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene Examples thereof include an alkylamine and an alkylamine oxide.

Examples of the amphoteric surfactant include carboxybetaine-type compounds, aminocarboxylates, and imidazolinium betaines. Further, the unsaturated carboxylic acid polymer of the present invention neutralized with an alkali in a conventional manner is a polymer having an unsaturated carboxylic acid monomer as a main chain and a number average molecular weight of 1,000 to 100,000, Since it has a carboxyl group, it is hydrophilic, and because of the structure described above, it is also biodegradable, and is extremely useful as a dispersant for inorganic pigments such as calcium carbonate and clay used in paper coating. To neutralize the unsaturated carboxylic acid polymer of the present invention, an aqueous solution of NaOH, KOH or the like may be used.

When this dispersant is used, it may be used alone, but another compounding agent such as polyvinyl alcohol may be used in combination as long as the effects of the present invention are not impaired. By adding this dispersant in an amount of 0.05 to 2.0 parts by weight with respect to 100 parts by weight of an inorganic pigment such as calcium carbonate or clay, and dispersing the same in water, the mixture thereof has a low viscosity and It can be highly fluid.

Since the unsaturated carboxylic acid polymer of the present invention has a chelating ability, it is also useful as a scale inhibitor in cooling water systems, boiler water systems and the like. Further, since the unsaturated carboxylic acid polymer of the present invention has good biodegradability, even if wastewater comes out to the outside, it has little effect on the environment.

[0049]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The number average molecular weight, molecular structure, S content, Ca ion chelating ability, biodegradability, detergency and dispersing action of the polymer were determined by the following methods. (1) Number average molecular weight Polyacrylic acid was measured by gel permeation chromatography (GPC) as a standard substance.

The measuring conditions were as follows: ALs manufactured by Waters
C / GPC 150C device (Detector: built-in differential refractometer,
Column: ASAHIPAK (GSM-700 + GS31
Using 0), the mobile phase was acetonitrile / 50 mM sodium acetate = 3/7, the column temperature was 40 ° C., and the flow rate was 0.
7 ml / min and the injection volume was 200 μl. (2) Number-average molecular weight after hydrolysis 1.0 g of a sample was prepared using an aqueous sodium hydroxide solution.
After making the aqueous solution of H13 30 ml, the mixture was placed in a 100 ml flask and heated at 95 ° C. for 10 hours. After completion of the reaction, freeze-drying was performed, and the number-average molecular weight of the obtained hydrolyzate was measured by the GPC method described above. (3) by ¹ H-NMR according to the molecular structure ¹ H-NMR, the amount of such terminal maleic acid residue, the amount and the presence or absence of the ester bond of the end -OH groups were measured.

This measurement was performed using JNM-EX90 manufactured by JEOL Ltd.
Using a device, a solution having a polymer concentration of less than 5% with a heavy methanol solvent was placed in a test tube having a diameter of 5 mmφ, and the solution was cooled to room temperature at 9 ° C.
The measurement was performed by integrating 32 times in a 0 MHz, NON mode. (4) S content This was carried out according to the method of JIS K 0103-1988. (5) Ca ion chelating ability (Ca ²⁺ scavenging ability) In a 200 ml beaker, precisely weighed polymer 20
Then, 100 g of an aqueous solution containing 0.1 N of ammonium chloride, 0.1 N of potassium chloride, and 0.4 N of ammonia and having a Ca ion concentration of 40 ppm was further added and dissolved. Using a Ca ion electrode at 25 ° C., the concentration of divalent Ca ions in the aqueous solution was measured, converted to CaCO ₃ captured by 1 g of the polymer, and the Ca ²⁺ capturing ability (mg
· CaCO ₃ / g). (6) Biodegradation rate The biodegradation rate was measured according to JIS K6950. The biodegradation rate was calculated from TOC (total organic carbon content). (7) Detergency An artificial soil was prepared by mixing the following organic soil components, calcined clay and carbon black at a ratio of 69.7: 29.8: 0.5 (weight ratio).

Oleic acid 28.3 parts by weight Triolein 15.6 parts by weight Cholesterol olein 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 parts by weight 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 reflectance of 38 to 43%. After measuring the surface reflectivity before washing, it was subjected to a washing test under the following conditions.

-Washing conditions- Testing machine Terg-O-Tometer Rotation speed 120 rpm Water hardness 90 ppm (CaCO ₃ conversion) Washing liquid 900 mL Washing temperature 30 ° C Detergent concentration 0.067% Bath ratio 30 times Washing time 10 minutes Rinse Time 3 minutes twice drying Drying iron on paper and then measuring the surface reflectance of the washed cloth (cleaning cloth)
The detergency was determined from the following equation.

Detergency (%) = (K / S of dirty cloth−K / S of cleaning cloth) / (K / S of dirty cloth−K / S of cleaning cloth) × 1
00 [where K / S = (1-R) ² / 2R (Kubelka-Munk
Where R is the surface reflectance of the cloth. (8) Evaluation of dispersing action The dispersing action was determined by adding a calcium salt (manufactured by Kanto Kagaku) and water to a slurry adjusted to have a ratio of 60:40 (weight ratio), and adding a polymer as an Na salt to calcium carbonate. On the other hand, 0.
An amount of 3% by weight was added, stirred for 3 minutes, and allowed to stand for 1 minute, and the viscosity was measured with a B-type rotational viscometer (Viscometer VT-04 manufactured by Rion). In addition, when the polymer was not added, it was 10 dPa · s. Example 1 A separable flask having a capacity of 500 ml and equipped with a stirrer and a thermocouple was heated in a 110 ° C. oil bath. 39.2 g of maleic anhydride, acrylic acid 2
8.8 g and 1.64 g of azobisisobutyronitrile
A solution prepared by adding 20 g of acetone to the solution and a solution of 7.8 g of mercaptoethanol and 20 g of acetone were dropped into the separable flask over 30 minutes with stirring.
After completion of the dropwise addition, heating and stirring were continued for another 3 hours. The properties (including yield and yield; the same applies hereinafter) of the obtained polymer are shown in Table 1.

FIG. 1 shows the results of ¹ H-NMR of the polymer measured using heavy water as a solvent. 4.0 to 4.4 ppm
A methylene group in contact with an ester group, 3.3 to 3.8 pp
m represents a methylene group in contact with the hydroxyl group of mercaptoethanol, and 1.0 to 3.2 ppm confirms absorption by an acrylic acid-maleic acid copolymer. The unsaturated carboxylic acid polymer having a specific residue in the molecular chain. It turned out to be.

The S content was analyzed.
It was 3% by weight. Examples 2 to 7 The same procedure as in Example 1 was carried out except that the amounts of acrylic acid and mercaptoethanol were as shown in Table 1. Table 1 shows the properties of the obtained polymer. Example 8 The same operation as in Example 3 was carried out except that 7.7 g of mercaptoethylamine was used instead of mercaptoethanol. Table 1 shows the properties of the obtained polymer. Comparative Example 1 In the same apparatus as in Example 1, acrylic acid 57.
6 g and 22.6 g of 60% hydrogen peroxide solution
The mixture was dropped into a separable flask heated in a 00 ° C. oil bath over 1 hour with stirring. After completion of the dropwise addition, heating and stirring were continued for another 2 hours. The properties of the obtained polymer are shown in Table 1. Comparative Example 2 Maleic anhydride 3 was added to the same apparatus as in Example 1.
9.2 g and 22.6 g of 60% aqueous hydrogen peroxide
The mixture was stirred at 50 ° C. for 5 minutes to obtain a homogeneous solution. Then, at 20 ° C. or lower, 216.0 g of acrylic acid, 50% hydrogen peroxide solution 4
5.3 g and 1 g of concentrated sulfuric acid were added and stirred. This solution was added dropwise to the separable flask heated in an oil bath at 100 ° C. over 2 hours while stirring. After completion of the dropwise addition, heating and stirring were continued for another 2 hours. The properties of the obtained polymer are shown in Table 1.

[0057]

[Table 1]

Example 9 A 300-ml separable flask equipped with a stirrer and a thermocouple was used. Example 3
50 g of the polymer synthesized in the above and 150 ml of a 30% by weight aqueous hydrogen peroxide solution were added thereto, and the mixture was heated and stirred at 60 ° C. for 1 hour. After the reaction, unreacted hydrogen peroxide was decomposed with sodium hydroxide, and lyophilized to obtain a white solid. The product was a Na salt and the yield was 61.9 g.

¹ H-NMR of the polymer was measured using heavy water as a solvent, and the concentration of -C (O) OCH ₂ was found to be 4.3 to 4.6 ppm.
A methylene group adjacent to an ester group derived from CH ₂ SO ₂ — was confirmed at 2.8 to 3.4 ppm, and a methylene group adjacent to SO ₂ was confirmed. From this result, it was found that sulfide was oxidized to sulfone. The Ca capturing ability of the obtained polymer was 200 mg / g, and the biodegradability was ◎. Example 10 Maleic anhydride 4 was placed in a separable flask of 500 ml capacity equipped with a stirrer and a thermocouple.
9.5 g and 15 g of acetone were added, and the mixture was heated in a 110 ° C. oil bath. Concentrated sulfuric acid was added to 43.2 g of acrylic acid.
A solution prepared by adding 15 g of acetone to 9.8 g of mercaptoethanol and 4.8 g of azobisisobutyronitrile was added dropwise to a separable flask over 30 minutes with stirring over 30 minutes. After dropping, 2 more
Heating and stirring were continued for hours. Table 2 shows the properties (including yield and yield; the same applies hereinafter) of the obtained polymer. Examples 11 and 12 were carried out in the same manner as in Example 10 except that the amounts of mercaptoethanol and concentrated sulfuric acid were as shown in Table 2. Table 2 shows the properties of the obtained polymer. [Examples 13 to 18] The same procedures as in Example 10 were carried out except that the inorganic or organic acids shown in Table 2 were used instead of concentrated sulfuric acid in the amounts shown in the same table. Table 2 shows the properties of the obtained polymer. Example 19 The same operation as in Example 10 was carried out except that concentrated sulfuric acid was not used. Table 2 shows the properties of the obtained polymer.

[0060]

[Table 2]

Example 20 After the polymer of Example 1 was converted to an aqueous solution having a pH of 10 with sodium hydroxide, the detergency of a detergent composition using a solid polymer obtained by freeze-drying as a builder was evaluated. Was. The results are shown in Table 3. Example 21 The polymer of Example 3 was converted into an aqueous solution having a pH of 10 with sodium hydroxide, and then the detergency of a detergent composition using a solid polymer obtained by freeze-drying as a builder was evaluated. The results are shown in Table 3. Comparative Example 3 The procedure of Example 20 was repeated, except that A-type zeolite was used instead of the “polymer of Example 1”. The results are shown in Table 3. Comparative Example 4 The procedure of Example 21 was repeated, except that A-type zeolite was used instead of the “polymer of Example 3”. The results are shown in Table 3.

[0062]

[Table 3]

[Examples 22 to 25] After the polymers of Examples 10 to 13 were converted into an aqueous solution having a pH of 10 with sodium hydroxide, the solid polymer obtained by freeze-drying was used as a builder for a detergent composition. Was evaluated. The results are shown in Table 4.

[0064]

[Table 4]

Examples 26 to 34 The polymers of Examples 1 to 9 were converted into an aqueous solution having a pH of 10 with sodium hydroxide.
Evaluation of the dispersing action of the solid polymer obtained by freeze-drying was performed based on the evaluation method of the dispersing action of (8) above. The results are shown in Table 5. [Comparative Example 5] The polymers obtained in Comparative Example 1 were used in Examples 26 to
In the same manner as in No. 34, Na salts were used, and their dispersing action was evaluated. The results are shown in Table 5.

[0066]

[Table 5]

[0067]

The novel unsaturated carboxylic acid polymer according to the present invention has a molecular structure having a specific structure in the molecular chain, has a relatively low molecular weight, has excellent chelating ability, and is useful as a biodegradable builder. And a suitable detergent composition can be obtained by blending it with various surfactant components. It is also useful as a biodegradable dispersant.

Further, the manufacturing method is simple and economically advantageous.

[Brief description of the drawings]

[1] of the obtained acrylic polymer in Example 1 ¹ H-
NMR chart (deuterated solvent).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 20/06 C08F 20/06 22/02 22/02 22/06 22/06 C11D 3/37 C11D 3/37

Claims (11)

[Claims] 1. A compound of the general formula -C (O) X (CH
_{2) n} S-, or _{-C (O) X (CH 2} ) n SO m -
(In the formula, X represents O or NH. N is an integer of 1 to 6, and m is 1 or 2.) It has at least one group represented by the following formula, and has a number average molecular weight of 1,000 to 100. ,
000 unsaturated carboxylic acid polymers. 2. The unsaturated carboxylic acid polymer according to claim 1, wherein the unsaturated carboxylic acid polymer is an alkali metal salt or an ammonium salt. 3. The number average molecular weight after hydrolysis is 500-1.
The unsaturated carboxylic acid polymer according to claim 1, wherein the molecular weight is 0.000. 4. A process for producing an unsaturated carboxylic acid polymer, which comprises polymerizing an unsaturated carboxylic acid with a non-oxidizing polymerization initiator in the presence of a thiol compound having a hydroxyl group or an amino group. 5. An unsaturated carboxylic acid polymer characterized by polymerizing an unsaturated carboxylic acid with a non-oxidizing polymerization initiator in the presence of a thiol compound having a hydroxyl group or an amino group and an inorganic acid or an organic acid. Production method. 6. The method for producing an unsaturated carboxylic acid polymer according to claim 4, wherein the polymerization is carried out in a solvent-free or non-aqueous solvent. 7. The method for producing an unsaturated carboxylic acid polymer according to claim 4, wherein the produced polymer is further oxidized. 8. The method according to claim 4, wherein the unsaturated carboxylic acid is maleic anhydride and (meth) acrylic acid, and maleic anhydride in the total unsaturated carboxylic acid is 10 to 60 mol%. A method for producing an unsaturated carboxylic acid polymer of the above. 9. A biodegradable builder comprising the polymer according to claim 1 as a main component. 10. The biodegradable builder 1 according to claim 8,
A detergent composition containing 40% by weight and 1 to 40% by weight of a surfactant. 11. A dispersant comprising the polymer according to claim 1 neutralized with an alkali.