JPH10120780A - Amine-modified polyaspartic acid or its salt, and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound or its salt, capable of exhibiting an excellent calcium ion-chelating ability, an excellent moisture-absorbing ability and an excellent moisture-retaining ability and useful as a chelating agent, a moisture-retaining agent for cosmetics, etc., by hydrolyzing a specific amine- modified polysuccimide. SOLUTION: This amine-modified polylaspartic acid or its salt is obtained by subjecting a mixture comprising (A) aspartic acid or polysuccimide, (B) an amine compound having a primary or secondary amino group [preferably a diamino compound having a di(1-6C alkyl) amino group in addition to an amino group related to the reaction from the view point of chelating ability]), and (C) an acidic compound [preferably phosphoric acid (hydrogen salt) or a phosphite ester from the view point of the yield of the amine-modified polysuccimide] to a modification reaction in a solid state and subsequently hydrolyzing the produced amine-modified polysuccimide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an amine-modified polyaspartic acid or a salt thereof, and a method for producing the same.
The amine-modified polyaspartic acid of the present invention or a salt thereof,
Chelating agents, fertilizers, scale inhibitors, detergents, humectants,
It is useful as a pigment and mineral dispersant, and as a water additive for boilers and cooling towers.

[0002]

2. Description of the Related Art Polyaspartic acid has been conventionally used as a chelating agent, fertilizer, scale inhibitor, detergent, humectant, pigment and mineral dispersant, and a water additive for boilers and cooling towers. Usually, it is obtained by hydrolyzing polysuccinimide. Conventionally, as a method for producing polysuccinimide, a method of reacting aspartic acid or maleamic acid in a solid phase at a high temperature of 180 ° C. or higher (US Pat. Nos. 5,057,597 and 5,219,986). A method in which ammonia and maleic anhydride are reacted in a solid phase at a temperature of 120 ° C. or higher (see US Pat. No. 4,839, US Pat. No. 4,839,510). 461, 5,296,578), aspartic acid or maleamic acid in the presence of a solvent such as polyethylene glycol, N-methylpyrrolidone or sulfolane at a temperature of 120 ° C. or higher. (See, for example, JP-A-6-145350 and JP-A-6-211982). However, in these methods, it is necessary to react the raw materials for a long time under high temperature conditions in order to increase the conversion, that is, the yield, and the polyaspartic acid obtained by these methods has a calcium ion chelating ability and a moisturizing property. Performance is low.

As a method of reacting in a short time, aspartic acid is reacted in the presence of a phosphoric acid or polyphosphoric acid catalyst.
A method in which the reaction is carried out in a solid phase at 100 to 250 ° C.
8-20638, U.S. Pat. No. 5,142,062
Is known. However, in this method, it is necessary to use a large amount of a catalyst used to obtain polysuccinimide, so that a complicated process for removing the catalyst used in a large amount in the post-treatment process is required, and the reaction is difficult. In addition to the problem that the equipment used for the above-mentioned method is required to have corrosion resistance, it is difficult to adjust the molecular weight of the obtained polysuccinimide. Furthermore, in these production methods, since the reaction is carried out in a solid phase, there is a problem that the polymer is agglomerated by polymerization during the production, and industrial production is difficult.

As an industrial synthesis method of amine-modified polysuccinimide which is a precursor of amine-modified polyaspartic acid, for example, US Pat. No. 5,286,810
No. 5,391,642 and 5,466,760
And the like, a method of reacting a polyamine with aspartic acid or maleic acid and ammonia in a solid phase at a high temperature of 120 ° C. or higher is known.

However, these methods require a low conversion to polysuccinimide or require a long reaction time at a high temperature, and the amine-modified polysuccinimide formed has a relatively low molecular weight. The amine-modified polyaspartic acid obtained by hydrolyzing the compound had low calcium chelating ability and moisturizing ability, and was insufficient to exhibit the performance as a polymer.

Further, a method for obtaining an amine-modified polysuccinimide by reacting an amine with polysuccinimide,
J. Med. Chem. Vol. 16, No. 8, p. 893 (19
73), U.S. Pat. No. 4,363,797, 5,1
No. 75,285, and JP-B-48-20638. Each of these methods is a method of dissolving polysuccinimide in an aprotic polar solvent and reacting it with an amine to obtain an amine-modified polysuccinimide. However, these methods have problems such as the use of expensive solvents and the necessity of removing the solvent after the reaction.

[0007]

The amine-modified polyaspartic acid is used as a fertilizer, a scale inhibitor, a detergent, a humectant,
It is useful as a pigment and mineral dispersant, and as a water additive for boilers and cooling towers. In addition, amine-modified polyaspartic acid is a biodegradable material, and has attracted attention as an alternative material in applications where polyacrylic acid or the like has been used conventionally. Therefore, a method for easily obtaining an amine-modified polyaspartic acid at a high conversion rate is desired.

[0008]

According to the present invention, aspartic acid and / or polysuccinimide, primary or secondary,
A mixture comprising an amine compound having a secondary amino group and an acidic compound is subjected to a denaturing reaction while maintaining a solid phase state to obtain an amine-modified polysuccinimide, which is then hydrolyzed by a conventional method to obtain a calcium chelating ability and a moisturizing ability. Amine-modified polyaspartic acid with high conversion can be easily obtained at a high conversion.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail. In the present invention, aspartic acid and / or polysuccinimide are reacted with an amine compound in the solid state in the presence of an acidic compound. The reaction in the solid phase state means that the reaction proceeds while the reaction system keeps the solid phase state in appearance, and the liquid phase may be present microscopically.

[0010] The molecular weight of the amine-modified polyaspartic acid or a salt thereof of the present invention is not particularly limited and can be appropriately selected depending on the intended use.
0000, preferably 6,000 to 150,000,
More preferably, it is in the range of 8,000 to 100,000. In addition, in this specification, a molecular weight is a weight average molecular weight and is a polyethylene glycol conversion value measured by gel permeation chromatography.

The amine-modified polyaspartic acid or a salt thereof of the present invention is characterized by having a high calcium ion chelating ability as measured by a calcium ion electrode method using calcium chloride, and is preferably 5.0 (Ca ^++). g /
100 g-polymer), and more preferably 5.3 (Ca ⁺⁺ g / 100 g-polymer) or more. Because of these features, the amine-modified polyaspartic acid or a salt thereof of the present invention is particularly useful as a chelating agent for capturing metal ions such as calcium.

Here, the calcium ion chelating ability in the present invention is based on the description in, for example, JP-A-5-59130 and Oil Chemistry, Vol. 35, No. 3 (1986). After the sample was weighed, dissolved and stirred, the amount of calcium ions in the solution was measured using an ion meter having a calcium ion electrode. Specifically, a 50 ml beaker contains 1.0x calcium chloride.
10 mg of a sample was weighed and dissolved in 50 ml of an aqueous solution adjusted to 10 ^-3 M and 0.08 M potassium chloride, and the mixture was stirred at 30 ° C. for about 10 minutes. Electrode (Orion 93
-20 type) and ion meter (Mode manufactured by Orion)
1 720A) and 100 g of sample polymer
G of calcium ions sequestered by C (unit: C)
a ⁺⁺ g / 100g-polymer).
In addition, the calcium ion chelating ability, in addition to the dye method,
It can also be measured by a measuring method such as a turbidity method.

The amine-modified polyaspartic acid or a salt thereof according to the present invention is characterized by high moisture retention, and preferably has a moisture absorption of 1 to 27% in a moisture absorption / retention test described below.
, The moisture retention is 29% or more, more preferably,
The moisture absorption is 5 to 25%, and the moisture retention is 30% or more. Because of these features, the amine-modified polyaspartic acid or a salt thereof of the present invention is particularly useful as a humectant for use in cosmetics and the like.

The moisture absorption and retention properties in the present invention are described in, for example, JP-A-6-157237 and Fragrance Journal Vol. 47 (1996), etc., about 0.5 g of a sample, which was allowed to stand in a desiccator containing diphosphorus pentoxide to a constant weight and dried sufficiently, was accurately weighed, and was weighed at 25 ° C.
% Relative humidity (RH) for 7 days, the weight was measured, and then, it was further left still in a 25 ° C., 35% RH constant temperature bath for 7 days, and the test was performed by measuring the weight. The moisturizing rate was calculated based on the amount of water (weight) absorbed at 25 ° C. and 65% relative humidity (RH) by 25 ° C. and 35% relative humidity (R).
H) indicates the ratio of the amount of moisture (weight) absorbed, and the moisture absorption indicates the ratio of the amount of moisture (weight) absorbed at 25 ° C. and 35% relative humidity (RH) to the dry weight of the sample. It is a thing.

In the present invention, as a raw material aspartic acid which can be used, any of L-, D-, and DL-aspartic acid or a metal salt thereof can be used. If desired, a polyfunctional compound copolymerizable with aspartic acid can be used in a proportion of 50 mol% or less. As such polyfunctional compounds, hydroxycarboxylic acids such as glycolic acid, lactic acid and 3-hydroxypropionic acid are mainly used, but glycols such as ethylene glycol and dicarboxylic acids such as maleic acid can also be used.

In the present invention, as the raw material polysuccinimide that can be used, one produced by any known method can be used. For example, maleic acid, maleic anhydride or maleic acid ester and ammonia can be used, for example, in German Patent No. 3,626,672, US Pat.
Reaction products obtained by a method described in Nos. 839,461 and 5,286,810 can be used. Since it contains various impurities in addition to polysuccinimide, it is appropriately purified if necessary before use.

Preferably, polysuccinimide obtained by polycondensing aspartic acid under heating is used. Aspartic acid to be subjected to the polycondensation may be any of D-, L- and DL-forms or a metal salt thereof. If desired, the polyfunctional compound copolymer component can be contained in an amount of 50 mol% or less. Such polyfunctional compounds include:
Amino acids such as alanine, leucine, lysine, and glutamic acid, and hydroxycarboxylic acids such as glycolic acid, lactic acid, and 3-hydroxypropionic acid are mainly used, and glycols such as ethylene glycol and dicarboxylic acids such as maleic acid can also be used. it can.

The molecular weight of the polysuccinimide used in the present invention is generally 1,000 to 500,000, preferably 6,000 to 150,000, and more preferably 8,000.
An appropriate value may be selected from the range of 100 to 100,000 depending on the intended use of the amine-modified polyaspartic acid. The molecular weight is a value in terms of polystyrene measured by gel permeation chromatography.

In the present invention, the above-mentioned aspartic acid alone, polysuccinimide alone or a combination thereof can be used as a raw material for production, and it can be selected according to the purpose.
Examples of the amine compound having a primary or secondary amino group include:
Either a monoamine or a polyamine such as a diamine may be used. Further, it may have a functional group other than the primary and secondary amino groups. Some examples are primary alkylamines such as propylamine, laurylamine and stearylamine, secondary alkylamines such as dibutylamine, ethanolamine, propanolamine and 3-amino-.
Hydroxyl-containing amines such as 1,2-propanediol;
N-diethyl-1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, 2-amino-5
Diethylaminopentane, N, N-dibutyl-1,3-
Examples include tertiary amino group-containing amines such as propanediamine, amino acids such as alanine, leucine, lysine, and glutamic acid, and sulfonic acid group-containing amines such as taurine, N-methyltaurine, aminobenzenesulfonic acid, and metal salts thereof. Of these, compounds having a highly reactive primary amino group are preferred. From the viewpoint of the chelating ability of the amino-modified polyaspartic acid or a salt thereof, a diamino compound having a dialkylamino group in which an alkyl group having 1 to 6 carbon atoms is substituted with a nitrogen atom, in addition to the amino group involved in the reaction, is particularly preferred. preferable.

These amine compounds are preferably used in an amount of 0.001 to 0.3 mole times the total mole number of the mole number of aspartic acid and the mole number of the imide ring of polysuccinimide. If this ratio is too small, the modification rate of the finally obtained polyaspartic acid naturally becomes small, and it becomes difficult for the amine-modified polyaspartic acid to exhibit the expected performance. On the other hand, if the ratio is too large, the reactants may become sticky and generate lumps during the denaturation reaction, resulting in a large burden on the stirring or difficulty in maintaining the reactants in the solid state. is there. In addition, when only aspartic acid is used as a raw material, the two carboxylic acids of aspartic acid are both blocked by a compound having an amino group, and the probability that the polymerization reaction is interrupted is increased. The molecular weight of the amine-modified polyaspartic acid may not be sufficiently large. The preferred usage ratio of the amine compound to the imide ring of aspartic acid and polysuccinimide is 0.02 to 0.25 mole times.

In the present invention, when polysuccinimide alone is used as a raw material, a modification reaction takes place. When aspartic acid is used, a polymerization reaction and a modification reaction take place simultaneously. Therefore, in the latter case, the acidic compound also acts as a polymerization catalyst, and condensed water is by-produced in the reaction system. As the acidic compound, usually, hydrochloric acid, sulfuric acid, phosphoric acid,
An inorganic protonic acid such as condensed phosphoric acid is used. Also,
When aspartic acid alone is used as a raw material, phosphorus pentoxide can also be used, and it is considered that this reacts with water produced by the polymerization reaction and exists as phosphoric acid in the reaction system. Also, tin hydrogen phosphate, zinc hydrogen phosphate,
Calcium hydrogen phosphate, sodium hydrogen phosphate, hydrogen phosphate such as potassium hydrogen phosphate, phosphorous acid and its esters and salts, for example, triethyl phosphite, triphenyl phosphite and other phosphite triesters, Phosphorous esters and salts such as diphenyl phosphite, dilauryl phosphite, dioleyl phosphite and other phosphite diesters, phenyl phosphite, methyl phosphite, isopropyl phosphite and other phosphite monoesters Is also used. As the organic acid, sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid, and haloacetic acids such as monochloroacetic acid, trichloroacetic acid, and trifluoroacetic acid are used. Preferred as the acidic compound are phosphoric acid, hydrogen phosphate, phosphite, and the like. When these are used, amine-modified polysuccinimide can be generally obtained in a sufficiently high yield. Also,
Among the phosphites and salts, phosphite triesters are preferred in view of the molecular weight and reaction rate of the produced polymer.
Particularly, triphenyl phosphite is preferred. The amount of the acidic compound used, the fee X of the acidic compound can be represented by the following formula,

[0022]

## EQU2 ## X = A × (mol number of raw material aspartic acid) + B ×
(Number of amino groups of amine compound having primary or secondary amino group)

As A and B in the above formula, A is preferably from 0.001 to 0.3, B is from 0.5 to 3.0, and more preferably A is from 0.02 to 0.25. , B is 0.8-2.5, most preferably, A is 0.02
And B is 1.0 to 2.0. If the amount of the acidic compound used is out of this range, the reaction may be delayed. In addition, the quality of the product may be degraded due to prolonged exposure to high reaction temperatures. Conversely, if the amount used is too large, the reactants become sticky during denaturation and a lump is formed, which may impose a large burden on stirring or make it difficult to maintain the solid state.

In the present invention, the aspartic acid or polysuccinimide used for the reaction, the amine compound and the acidic compound, and the copolymer compound used in some cases are sufficiently mixed in advance and supplied to the reactor as a uniform composition. Is preferred. This allows the denaturation reaction to proceed favorably. Insufficient mixing of each component for the reaction,
If supplied to the reactor in a non-uniform state, the reactants may partially melt in the reactor to form lumps.
The order of mixing the components to be subjected to the reaction is arbitrary, and aspartic acid or polysuccinimide is first mixed with an amine compound, and an acidic compound may be added thereto.
Aspartic acid or polysuccinimide, an amine compound and an acidic compound may be simultaneously mixed. If desired, the amine compound and the acidic compound may be mixed in advance and then mixed with aspartic acid or polysuccinimide. As the equipment used for mixing,
Mills, Henschel mixers, blenders, kneaders, etc.
Any conventional one can be used.

The denaturation reaction is performed at 50 to 300 ° C. If the reaction temperature is too low, the progress of the reaction is significantly delayed. Conversely, if the reaction temperature is too high, there is a risk that a thermal decomposition product is generated or melting occurs. Suitable reaction temperatures are between 100 and 2
60 ° C. The reaction time should be within 10 hours. Exposure of the reactants to elevated temperatures for extended periods of time can result in heat denaturation. From the viewpoint of productivity, a suitable reaction time is within 4 hours, especially within 3 hours.

The reaction can be performed in either a batch mode or a continuous mode. The reaction is preferably performed with stirring,
The reaction is performed using a reactor equipped with a stirrer, for example, a stirring tank or a kneader. In particular, it is preferable to use a horizontal stirring device equipped with a twin-screw stirring blade. Such a stirring device is commercially available as a kneader. "VIVOLAC" manufactured by Sumitomo Heavy Industries, Ltd. "SCR" manufactured by Mitsubishi Heavy Industries, Ltd.
"TEX" manufactured by Japan Steel Works, "TEM" manufactured by Toshiba Machine Co., Ltd. "FCM" manufactured by Kobe Steel, Ltd. and Co., Ltd.
"KRC Kneader" manufactured by Kurimoto Steel Works, and the like. When the reaction is carried out using these stirrers, even if a viscous state appears partially in the middle of the reaction, the polymerization reaction can be carried out while maintaining a substantially solid phase state as a whole. it can.

Since water is generated in the denaturation reaction using aspartic acid, the reaction is preferably carried out under reduced pressure or under normal pressure under an inert gas flow, and the produced water is immediately discharged out of the system. . In the present invention, in a modification reaction using only aspartic acid for the reaction without using polysuccinimide as a raw material, an amine-modified polysuccinimide is obtained in one step, which is an industrially advantageous production method such as cost. . Conversely, in a modification reaction using a large amount of polysuccinimide as a raw material, since the molecular weight of polysuccinimide as a raw material can be maintained, various amine-modified polysuccinimides can be easily produced by selectively using polysuccinimide having various molecular weights. It has the advantage that it can be manufactured.

The reaction product containing the amine-modified polysuccinimide formed by the modification reaction is then hydrolyzed at the imide ring to obtain an amine-modified polyaspartic acid. This hydrolysis can be performed according to a conventional method. For example,
J. Am. Chem. Soc. 80, 3361 (195
8); Org. Chem. 26, 1084 (196
1), US Patent Nos. 5,221,733 and 5,28
No. 8,783, JP-A-60-203636, or the like. In a preferred embodiment,
50 to 1000 parts by weight of water is added to 100 parts by weight of the reaction product, and the amount of alkali metal hydroxide to neutralize the polymerization catalyst in the reaction product and become equimolar to 3 times the mole of the imide ring. The mixture is added and reacted at 0 to 50 ° C. for 10 minutes to 8 hours. As a result, most of the imide ring is opened.

The hydrolysis product thus obtained is an alkali metal salt of an amine-modified polyaspartic acid, and the amine-modified polyaspartic acid according to the present invention includes this. When an acid acts on this alkali metal salt type polyaspartic acid, free polyaspartic acid can be obtained. By adjusting the amount of the acid used, the ratio between the free form and the salt form of the carboxylic acid group of polyaspartic acid can be arbitrarily adjusted.

[0030]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples. The conversion of aspartic acid into a polymer, the weight average molecular weight of polysuccinimide and amine-modified polyaspartic acid, and the amine modification were measured as follows.

Conversion to polymer: The amount of aspartic acid remaining in the amine-modified polysuccinimide was calculated by analysis by liquid chromatography. Weight average molecular weight of polysuccinimide; polystyrene equivalent value obtained by gel permeation chromatography using a differential refractometer Column: PLgel 5 μm MIXED-C column 2
Books (Polymer Laboratory Products)

Eluent: weight average molecular weight of dimethylformamide amine-modified sodium polyaspartate to which 20 mM LiBr was added; value in terms of polyethylene glycol obtained by gel permeation chromatography using a differential refractometer. Column: TSKgel G 6000 PWXL + TSKgel G 3000 PWXL
(Tosoh product) Eluent: 0.4M sodium nitrate aqueous solution

Amine introduction rate: The amine in the amine-modified polyaspartic acid was measured by ¹ H NMR, and the number of amines per aspartic acid unit was defined as the amine introduction rate. Further, as the calcium ion chelating ability, the calcium ion-capturing ability derived from calcium chloride per 100 g of the polymer can be determined based on the description in, for example, JP-A-5-59130 and Oil Chemistry, Vol. 35, No. 3 (1986).
It measured using the ion meter using the calcium ion electrode. Specifically, in a 50 ml beaker, calcium chloride is 1.0 × 10 ⁻³ M and potassium chloride is 0.08 M
10mg sample in 50ml aqueous solution adjusted to
After measuring and dissolving, and stirring at 30 ° C. for about 10 minutes, calcium ions in the solution are measured using a calcium electrode (93-20 type manufactured by Orion) and an ion meter (Model 720A manufactured by Orion). It was measured and indicated by the number of g of calcium ions sequestered by 100 g of the sample polymer (unit: Ca ⁺⁺ g / 100 g-polymer).

The moisture absorption and retention properties are described, for example, in JP-A-6-15.
7237 and Fragrance Journal Vol. 12, p. 47
(1996), and specifically, about 0.5 g of a sample which was allowed to stand in a desiccator containing diphosphorus pentoxide to a constant weight and dried sufficiently was precisely weighed, and was weighed at 25 ° C. and 65% relative humidity. (RH) in a thermostat for 7 days, weigh,
Thereafter, the sample was allowed to stand still in a thermostat at 25 ° C. and 35% RH for 7 days, the weight was measured, and the value was obtained according to the following formula.

[0035]

(Equation 3)

[0036]

(Equation 4)

Production of polysuccinimide (A): Under a nitrogen gas atmosphere, L-aspartic acid powder (5.0 kg) and 85% phosphoric acid (500 g) were mixed with a supermixer (manufactured by Kawata Corporation) for 5 minutes. After mixing, a uniform powdery mixture was obtained. This mixture is called "KRC Kneader" (Co., Ltd.)
(Kurimoto Iron Works, 50φ × 661.5L) was supplied continuously to carry out the polymerization reaction. The operating conditions of the kneader were a heating medium temperature of 260 ° C., a screw rotation speed of 30 rpm, and an average residence time of 16 minutes. The obtained product was a brown powder and had a weight average molecular weight of 17,000.

Production of polysuccinimide (B); 200 mL equipped with cooler, thermometer, stirrer and water separator
25 g of aspartic acid, 2.5 g of 85% phosphoric acid, 56 g of mesitylene and 24 g of sulfolane
Was charged. Subsequently, under normal pressure and under reflux of mesitylene (16
(2 ° C.) for 4.5 hours to carry out the polymerization reaction. The water generated during this time was distilled out of the system together with mesitylene.
After completion of the reaction, the reaction mixture was filtered off, and the product was washed four times with 100 g of pure water and further washed with 100 g of methanol. The product was dried at 80 ° C. under reduced pressure for 24 hours to obtain 17.9 g of yellowish white powder
I got The weight average molecular weight of this product was 66,000.

Example 1 In a nitrogen gas atmosphere, L-aspartic acid powder (1.0 k
g), 85% phosphoric acid (100 g) and taurine sodium salt powder (110.5 g) were added to a “super mixer”
(Kawata Co., Ltd.) for 5 minutes to obtain a uniform mixture. This mixture was continuously supplied to a “KRC kneader” (Kurimoto Iron Works Co., Ltd., 50φ × 661.5 L) to perform a polymerization reaction. The operating condition of the kneader is as follows.
0 ° C., screw rotation speed 30 rpm, average residence time 20
Minutes. The conversion to the polymer was 98.0%.

In a 50 cc beaker equipped with a stirrer, 8 g of water and 0.92 g of sodium hydroxide (purity 93% or more) were added.
And was charged. Under ice-cooling, 2.0 g of the light brown product obtained above was added little by little to the mixture, and the mixture was hydrolyzed by stirring at room temperature for 1 hour. The above hydrolyzed solution was dropped into 100 ml of methanol to obtain 2.6 g of a yellowish white amine-modified sodium polyaspartate precipitated. The weight average molecular weight of this amine-modified sodium polyaspartate was 8,600, and the introduction ratio of taurine was 9.8%. The calcium ion chelating ability is 6.4.
(Ca ⁺⁺ g / 100 g-polymer) and a moisture absorption of 1
It was 6.9% and the moisture retention was 36.4%.

Example 2 Laurylamine (13) instead of taurine sodium salt
The reaction was carried out in the same manner as in Example 1 except that 8.5 g) was used. The conversion to the polymer was 99% or more, and the polymerization reaction product was light brown. The resulting amine-modified sodium polyaspartate was yellow-white, and the yield was 2.5 g. The weight average molecular weight is 1200
0, the introduction ratio of laurylamine was 9.6%. The calcium ion chelating ability was 6.1 (Ca ⁺⁺ g).
/ 100 g-polymer), with a moisture absorption of 13.1% and a moisture retention of 32.6%.

Example 3 40 g of L-aspartic acid powder, 4 g of 85% phosphoric acid and 2.0 g of taurine sodium salt were charged into a mixer (Oster blender) and mixed at room temperature for 15 minutes to obtain a uniform mixture. Labo Plastomill (Toyo Seiki Seisakusho)
Was charged with the mixture obtained above, and the set temperature was 230 ° C.
For 30 minutes to obtain a light brown powder. Conversion to polymer was greater than 99%.

In a 50 cc beaker equipped with a stirrer, 0.46 g of sodium hydroxide (93% or more in purity) and water 4
g. Under ice-cooling, 1.0 g of the product obtained above was added little by little to the mixture, and the mixture was stirred at room temperature for 1 hour to perform hydrolysis. The hydrolyzed solution was dropped into 100 ml of methanol to obtain 1.2 g of precipitated amine-modified sodium polyaspartate. The weight average molecular weight of this amine-modified sodium polyaspartate is 11
000, and the introduction rate of taurine was 4.8%.
The calcium ion chelating ability is 5.9 (Ca ⁺⁺
g / 100 g-polymer), and a moisture absorption rate of 16.8%,
The moisture retention was 31.4%.

Example 4 40 g of L-aspartic acid powder, 4 g of 85% phosphoric acid and 2.0 g of taurine sodium salt were charged into a mixer (Oster blender) and mixed at room temperature for 15 minutes to obtain a uniform mixture. Labo Plastomill (Toyo Seiki Seisakusho)
Was charged with the mixture obtained above, and the set temperature was 200 ° C.
For 30 minutes to obtain a light brown powder. The conversion to the polymer was 93.0%.

In a 50 cc beaker equipped with a stirrer, 0.46 g of sodium hydroxide (93% or more in purity) and water 4
g. Under ice-cooling, 1.0 g of the product obtained above was added little by little to the mixture, and the mixture was stirred at room temperature for 1 hour to perform hydrolysis. The hydrolyzed solution was dropped into 100 ml of methanol to obtain 1.1 g of precipitated amine-modified sodium polyaspartate. The weight average molecular weight of this amine-modified sodium polyaspartate is 10
000, and the introduction rate of taurine was 4.3%.
The calcium ion chelating ability is 5.6 (Ca ⁺⁺
g / 100 g-polymer), and a moisture absorption rate of 16.8%,
The moisture retention was 30.2%.

Example 5 40 g of L-aspartic acid powder, 4 g of 85% phosphoric acid and 1.8 g of ethanolamine were charged into a mixer (Oster blender) and mixed at room temperature for 15 minutes to obtain a uniform mixture. Lab Plastmill (Toyo Seiki Seisakusho)
The mixture obtained above was charged and set at a set temperature of 230 ° C. for 3 hours.
The mixture was stirred for 0 minutes to obtain a light brown powder. Conversion to polymer was greater than 99%.

In a 50 cc beaker equipped with a stirrer, 0.46 g of sodium hydroxide (93% or more in purity) and water 4
g. Under ice-cooling, 1.0 g of the product obtained above was added little by little to the mixture, and the mixture was stirred at room temperature for 1 hour to perform hydrolysis. The hydrolyzed solution was dropped into 100 ml of methanol to obtain 1.2 g of precipitated amine-modified sodium polyaspartate. The weight average molecular weight of this amine-modified sodium polyaspartate is 11
000, and the introduction ratio of ethanolamine was 4.6%. The calcium ion chelating ability is 6.2
(Ca ⁺⁺ g / 100 g-polymer) and a moisture absorption of 1
It was 3.0% and the moisture retention was 32.1%.

Example 6 40 g of L-aspartic acid powder, 4 g of 85% phosphoric acid and 3.3 g of taurine were charged into a mixer (Oster blender) and mixed at room temperature for 15 minutes to obtain a uniform mixture.
The mixture obtained above was charged into Labo Plastmill (manufactured by Toyo Seiki Seisaku-sho, Ltd.), and the mixture was stirred at a set temperature of 230 ° C. for 30 minutes to obtain a light brown powder. Conversion to polymer was greater than 99%.

In a 50 cc beaker equipped with a stirrer, 0.46 g of sodium hydroxide (93% or more in purity) and water 4
g. Under ice-cooling, 1.0 g of the product obtained above was added little by little to the mixture, and the mixture was stirred at room temperature for 1 hour to perform hydrolysis. The hydrolyzed solution was dropped into 100 ml of methanol to obtain 1.2 g of precipitated amine-modified sodium polyaspartate. The weight average molecular weight of this amine-modified sodium polyaspartate is 89
The introduction rate of taurine was 9.6%. The calcium ion chelating ability is 6.5 (Ca ⁺⁺ g).
/ 100 g-polymer), and the moisture absorption was 17.0% and the moisture retention was 36.5%.

Example 7 In a nitrogen gas atmosphere, 1.0 kg of polysuccinimide (A), 118.9 g of 85% phosphoric acid, and 151.4
g of taurine sodium salt was mixed for 5 minutes using a super mixer (manufactured by Kawata Corporation) to obtain a uniform powdery mixture. This mixture is called “KRC Kneader”
(50φ × 661.5L, manufactured by Kurimoto Iron Works Co., Ltd.) to carry out a denaturation reaction to obtain a light brown powder. The operating conditions of the kneader were a heating medium temperature of 200 ° C., a screw rotation speed of 30 rpm, and an average residence time of 20 minutes.

In a 50 cc beaker equipped with a stirrer,
0.92 g of sodium hydroxide (purity 93% or more) and 8
g of water. Under ice-cooling, 2.0 g of the amine-modified polysuccinimide obtained above was added thereto little by little, and then stirred at room temperature for 1 hour to hydrolyze. The hydrolyzed solution was dropped into 100 ml of methanol to obtain 2.5 g of a yellowish white amine-modified sodium polyaspartate precipitated. The weight-average molecular weight of this amine-modified sodium polyaspartate was 12,000, and the introduction ratio of the amine was 8.6%. The calcium ion chelating ability was 5.9 (Ca ⁺⁺ g / 100 g-polymer), the moisture absorption was 15.9%, and the moisture retention was 29.8%.

Example 8 35 g of polysuccinimide (A), 4.15 g of 85
% Phosphoric acid, and 5.30 g of taurine sodium salt,
The mixture was mixed at room temperature for 15 minutes using an Oster blender to obtain a uniform powdery mixture. This mixture was charged into a Labo Plast Mill (manufactured by Toyo Seisakusho), and the temperature was set
After stirring for minutes, a light brown powder was obtained.

2.0 g of this powder was hydrolyzed and post-treated in exactly the same manner as in Example 7 to obtain 2.6 g of a yellowish white amine-modified sodium polyaspartate. The weight average molecular weight of this amine-modified sodium polyaspartate is 1
6,000, and the amine introduction rate was 4.9%.
The calcium ion chelating ability is 5.5 (Ca ⁺⁺
g / 100 g-polymer), with a moisture absorption of 15.6%,
The moisture retention was 29.6%.

Example 9 A 50 ml beaker was charged with 1.40 g of potassium dihydrogen phosphate and 3 g of water. Under ice cooling, 1.52 g of taurine sodium salt was added thereto. This solution and 10 g of polysuccinimide (A) were mixed at room temperature for 15 minutes using an Oster blender to obtain a uniform powdery mixture.

This mixture was subjected to a denaturing reaction in exactly the same manner as in Example 8 to obtain a light brown powder. 2.0 g of this powder was hydrolyzed and post-treated in exactly the same manner as in Example 7 to obtain 2.8 g of a yellowish white amine-modified sodium polyaspartate. The weight-average molecular weight of this amine-modified sodium polyaspartate was 17,000, and the amine introduction rate was 6.4%. The calcium ion chelating ability is 6.2 (Ca ⁺⁺ g / 100g-polymer),
The moisture absorption was 16.2% and the moisture retention was 36.4%.

Example 10 In a 50 ml beaker, 4.15 g of 85% phosphoric acid and 3
g of water. Under ice cooling, 2.2 g of ethanolamine was added dropwise thereto. This solution and 35 g of polysuccinimide (A) were mixed at room temperature for 15 minutes using an Oster blender to obtain a uniform powdery mixture.

This mixture was subjected to a denaturing reaction in exactly the same manner as in Example 8 to obtain a light brown powder. 2.0 g of this powder was hydrolyzed and post-treated in exactly the same manner as in Example 7 to obtain 2.6 g of a yellowish white amine-modified sodium polyaspartate. The weight average molecular weight of this amine-modified sodium polyaspartate was 17,000, and the amine introduction rate was 6.6%. The calcium ion chelating ability is 6.0 (Ca ⁺⁺ g / 100g-polymer),
The moisture absorption was 13.2% and the moisture retention was 32.9%.

Example 11 35 g of polysuccinimide (B), 4.15 g of 85
% Phosphoric acid, and 5.30 g of taurine sodium salt,
The mixture was mixed at room temperature for 15 minutes using an Oster blender to obtain a uniform powdery mixture. This mixture was subjected to a denaturation reaction in exactly the same manner as in Example 8 to obtain a light brown powder.

2.0 g of this powder was hydrolyzed and post-treated in exactly the same manner as in Example 7 to obtain 2.6 g of a yellowish white amine-modified sodium polyaspartate. The weight average molecular weight of this amine-modified sodium polyaspartate is 5
It was 8,000, and the amine introduction rate was 7.2%.
The calcium ion chelating ability is 6.0 (Ca ⁺⁺
g / 100 g-polymer), and a moisture absorption rate of 16.1%.
The moisture retention was 32.1%.

Example 12 A 50 ml beaker was charged with 1.61 g of sodium dihydrogen phosphate dihydrate and 3 g of water. Under ice cooling, 0.63 g of ethanolamine was added thereto. This solution and 10 g of polysuccinimide (A) were mixed at room temperature for 15 minutes using an Oster blender to obtain a uniform powdery mixture.

This mixture was subjected to a denaturing reaction in exactly the same manner as in Example 8 to obtain a light brown powder. 2.0 g of this powder was hydrolyzed and post-treated in exactly the same manner as in Example 7 to obtain 2.6 g of a yellowish white amine-modified sodium polyaspartate. The weight-average molecular weight of this amine-modified sodium polyaspartate was 17,000, and the amine introduction rate was 8.0%. The calcium ion chelating ability is 6.5 (Ca ⁺⁺ g / 100g-polymer),
The moisture absorption was 13.9% and the moisture retention was 33.9%.

Comparative Example 1 The same operation as in Example 3 was carried out except that phosphoric acid was not used. When about 5 minutes had elapsed, the reaction mixture turned black-brown and the stirring was poor, and the reaction had to be stopped. Did not get.

Comparative Example 2 A 50 cc beaker equipped with a stirrer was charged with 10 g of water and 1.4 g of sodium hydroxide (purity of 93% or more). The polysuccinimide (A) obtained above under ice-cooling
3.0 g were added in small portions and then hydrolyzed by stirring at room temperature for 1 hour. The hydrolyzed solution was dropped into 100 ml of methanol to obtain 2.6 g of precipitated yellow-white sodium polyaspartate. The weight average molecular weight of this sodium polyaspartate was 17,000. The calcium ion chelating ability is 5.0 (Ca ⁺⁺ g
/ 100 g-polymer), and the moisture absorption was 11.5% and the moisture retention was 28.9%.

Comparative Example 3 500 equipped with a cooler, a thermometer, a stirrer and a moisture separator
200 g of aspartic acid was charged into a four-necked ml flask. Next, a condensation reaction was carried out for 6 hours while heating in an oil bath maintained at 265 ° C. under a nitrogen stream. After the reaction was completed, 132.2 g of a brown polysuccinimide powder was obtained. The yield based on the theoretical amount was 92%. The weight average molecular weight of the obtained polysuccinimide was 12,000.

In a 50 cc beaker equipped with a stirrer, 10 g of water and 1.4 g of sodium hydroxide (93% or more in purity) were added.
And was charged. Under ice-cooling, 3.0 g of the polysuccinimide obtained above was added little by little, and then stirred at room temperature for 1 hour to hydrolyze. The hydrolyzed solution was dropped into 100 ml of methanol to obtain 2.4 g of precipitated yellow-white sodium polyaspartate. The weight average molecular weight of this sodium polyaspartate was 11,000. The calcium ion chelating ability is 4.2 (C
a ⁺⁺ g / 100 g-polymer) and a moisture absorption of 11.3
% And the moisture retention were 28.5%.

Comparative Example 4 Polysuccinimide (A) 18 was placed in a 2 L eggplant-shaped flask.
8 g and N, N-dimethylformamide (800 g) were charged to dissolve polysuccinimide. Subsequently, 28.4 g of taurine sodium salt was added to the reaction solution, which was then attached to a rotary evaporator set to a bath temperature of 150 ° C., and heated for 3 hours. After completion of the reaction, the reaction solution was added dropwise to 10 L of methanol to crystallize the polymer. After filtering the crystallized product, it was further washed twice with 4 L of methanol,
For 24 hours under reduced pressure to obtain 186 g of a brown solid.

Next, in order to carry out hydrolysis, 76.6 g of 93% sodium hydroxide and 1038 g of ion-exchanged water were charged into a 2 L beaker to dissolve sodium hydroxide.
After cooling the beaker with ice water, the above brown solid 180 g
Was added little by little, and then stirred at room temperature for 1 hour. After the completion of the reaction, 618 g of the reaction solution was added dropwise to 5 L of methanol to crystallize the polymer. After filtering the mixture, the solid was washed twice with 2 L of methanol and dried under reduced pressure at 50 ° C. for 24 hours to obtain 108 g of a yellow-white solid. The weight average molecular weight of this sodium polyaspartate was 3,800, and the amine introduction rate was 12.6%. Met. The calcium ion chelating ability was 3.7 (Ca ⁺⁺ g / 10
0 g-polymer), a moisture absorption of 16.9% and a moisture retention of 2
9.7%.

[0068]

According to the present invention, a modified polyaspartic acid having a high calcium chelating ability, a high moisture retention and a high moisture absorption can be obtained.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI C05C 11/00 C05C 11/00

Claims (14)

[Claims] 1. A mixture comprising aspartic acid and / or polysuccinimide, an amine compound having a primary or secondary amino group, and an acidic compound is subjected to a denaturation reaction while maintaining a solid phase state to obtain an amine-modified polysuccinimide, An amine-modified polyaspartic acid or a salt thereof obtained by hydrolyzing the same. 2. The amine-modified polyaspartic acid or salt thereof according to claim 1, wherein the calcium ion chelating ability measured by a calcium ion electrode method using calcium chloride exceeds 5.0 (Ca ⁺⁺ g / 100 g-polymer). . 3. A chelating agent comprising the amine-modified polyaspartic acid according to claim 2 or a salt thereof. 4. A moisture absorption rate of 1 to 27% and a moisture retention rate of 29%
% Of the amine-modified polyaspartic acid or salt thereof according to claim 1. 5. A humectant comprising the amine-modified polyaspartic acid according to claim 4 or a salt thereof. 6. A mixture comprising aspartic acid and / or polysuccinimide, an amine compound having a primary or secondary amino group, and an acidic compound, is subjected to a polymerization reaction while maintaining a solid phase state to obtain an amine-modified polysuccinimide. A method for producing an amine-modified polyaspartic acid or a salt thereof, which is hydrolyzed. 7. The method according to claim 1, wherein the amine compound is subjected to the polymerization reaction in a ratio of 0.001 to 0.3 mol times to the total number of moles of aspartic acid and the number of moles of imide ring of polysuccinimide. A method for producing the amine-modified polyaspartic acid or a salt thereof according to claim 6. 8. The method for producing an amine-modified polyaspartic acid or a salt thereof according to claim 6, wherein the acidic compound is a protic acid selected from inorganic acids, sulfonic acids and haloacetic acids. 9. The method for producing amine-modified polyaspartic acid or a salt thereof according to claim 6, wherein the acidic compound is selected from phosphoric acid and hydrogen phosphate. 10. The method for producing an amine-modified polyaspartic acid or a salt thereof according to claim 6, wherein the acidic compound is selected from phosphorous acid, esters and salts thereof. 11. The use amount X of the acidic compound is represented by the following formula: X = (0.001 to 0.3) × (mol number of raw material aspartic acid) + (0.5 to 3.0) × (primary or secondary amino group) 11. The method for producing an amine-modified polyaspartic acid or a salt thereof according to any one of claims 6 to 10, wherein the number of amino groups in the amine compound is as follows. 12. The modified polyaspartic acid or modified polyaspartic acid according to claim 6, wherein the polysuccinimide is a copolymer containing 50 mol% or less of a polyfunctional compound as a copolymer component. A method for producing the salt. 13. The production of an amine-modified polyaspartic acid or a salt thereof according to any one of claims 6 to 12, wherein the modification reaction is performed using a horizontal stirring device equipped with a twin-screw stirring blade. Method. 14. The raw material aspartic acid contains a polyfunctional compound copolymerizable with aspartic acid at a ratio of 0.5 mol times or less, wherein the molar ratio is not more than 0.5 mol.
The method for producing an amine-modified polyaspartic acid or a salt thereof according to any one of the above.