JP3199227B2 - Acylated polyallylamine and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel polyallylamine derivative and a method for producing the same. More specifically, the present invention relates to a novel polyallylamine derivative having a small amount of cation and a simple method for producing the same.

[0002]

2. Description of the Related Art Polyallylamine is a linear olefin polymer containing a primary amino group (-NH ₂ ) in a side chain, and is a cationic polymer that is well soluble in water and is positively charged in water. Polyallylamine has a unique reactive polymer structure and properties, and is therefore used in an extremely large number of fields such as dye fixatives for reactive dyes, dye fixatives for direct dyes, and food preservatives. It has also been proposed to use polyallylamine in the fields of silver halide photographic materials, sustained release pharmaceutical compositions, ion exchange resins, functional films and the like. However, as described in “Synthesis and Application of Reactive Polymers” published by CMC, pp. 80-92 (1989), generally speaking, the number of reactive groups in a reactive polymer is:
There is no need to be too many, and even too many may be inconvenient. On the other hand, it is conceivable to synthesize a polymer in which amino groups are reduced by copolymerization.However, since monoallylamine monomer does not copolymerize with a normal vinyl monomer, cation density is reduced by copolymerization. It is difficult to synthesize a small polyallylamine-based polymer.

Therefore, a method of reacting the —NH ₂ group of polyallylamine with another compound to form an inactive group has been studied. For example, poly- (N-allyl urea) (Japanese Patent Publication No. Sho 6)
Polyallylamine derivatives such as a polymer compound modified with a fluorine-containing group (Japanese Patent Application Laid-Open No. 1-207312, Japanese Patent Application Laid-Open No. 2-64114) are known. However, these polyallylamine derivatives have many problems in that the reagents used for their production are toxic, and, since an organic solvent is used as a reaction solvent, there are problems such as difficulty in purification, and practical At present, it is rarely used.

[0004]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a novel polyallylamine-based polymer having a low cation density and a method for easily producing the same.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on a novel polyallylamine-based polymer having a small cationic group content and a method for easily producing the same. It has been found that a novel polyallylamine-based polymer having a low cation density can be easily produced by treating with carboxylic anhydride, and the present invention has been accomplished based on this finding.

The present invention provides a compound represented by the general formula

Embedded image (Wherein, m represents an integer of 10 or more, j represents a number satisfying 0 <j <1, and R represents n- or i having 1 to 17 carbon atoms.
(indicating a so-alkyl group)) or a salt of the acylated polyallylamine.

Further, the present invention provides a compound represented by the following general formula:

Embedded image (Wherein m represents an integer of 10 or more) to a polyallylamine represented by the general formula (RCO) ₂ O (wherein, R represents an n- or iso-alkyl group having 1 to 17 carbon atoms)
The carboxylic anhydride represented by is then treated, the carboxylic acid by-produced is neutralized with an alkali, and if necessary, further treated with an organic acid or an inorganic acid to obtain a compound represented by the general formula

Embedded image (Wherein, m represents an integer of 10 or more, j represents a number satisfying 0 <j <1, and R represents n- or i having 1 to 17 carbon atoms.
(indicating a so-alkyl group)) or a salt of the acylated polyallylamine.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polymerization degree m of the raw material polyallylamine is 10 or more, preferably 10 to 5000. The raw material polyallylamine is preferably a free type. As the free type, after neutralizing a known polyallylamine salt and dialyzing to remove the neutralized salt, a commercially available 15% aqueous solution of polyallylamine having a molecular weight of about 10,000 (Nitto Boseki Co., Ltd.) can be used. PAA-15), a 10% aqueous solution of polyallylamine having a molecular weight of about 10,000 (PAA-10C manufactured by Nitto Boseki Co., Ltd.), a 20% aqueous solution of polyallylamine having a molecular weight of about 10,000 (PAA-L manufactured by Nitto Boseki Co., Ltd.),
A 20% aqueous solution of polyallylamine having a molecular weight of about 100,000 (PAA-H manufactured by Nitto Boseki Co., Ltd.) or the like may be used as it is.

The starting carboxylic anhydride has the general formula (RC)
O) ₂ O (where R is n- or is having 1 to 17 carbon atoms)
an acetic anhydride, propionic anhydride, n-butyric anhydride, isobutyric anhydride, valeric anhydride, hexanoic anhydride, octanoic anhydride, decanoic anhydride,
Examples thereof include lauric anhydride, stearic anhydride, and palmitic anhydride. From the viewpoint of solubility, the starting carboxylic acid anhydride is represented by n in the above general formula wherein n is 1 to 11 carbon atoms.
Carboxylic anhydrides which are-or iso-alkyl groups are preferred. 50 mol% based on amino groups of polyallylamine
When performing the following acylation, the amount of carboxylic anhydride is
The same amount may be used for the amino group to be acylated. As a solvent for preparing a polyallylamine solution, water, an organic solvent, or a mixed solvent of water and an organic solvent can be used.
As the organic solvent, a polar solvent is preferable in view of the solubility of the raw materials, and alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol can be used. In addition, acetonitrile, formamide, N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, 1,
4-Dioxane can also be used. Among them, water is preferred as a solvent for preparing a polyallylamine solution from the viewpoint of safety and easiness of operation.

In the present invention, when treating polyallylamine with carboxylic anhydride, it is preferable to slowly drop carboxylic anhydride into the polyallylamine solution. The dropping is usually performed over 2 to 8 hours, depending on the reaction scale. If the reaction scale is small, it may be smaller,
Usually, it may be performed over 1 to 8 hours. The reaction is preferably performed with stirring. Since this reaction is an exothermic reaction, the reaction is preferably carried out while cooling the reaction vessel with ice or the like, and the reaction solution is preferably maintained at 40 ° C. or lower, more preferably 0 to 10 ° C. After completion of the acylation, the reaction solution is usually
By adding an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, and sodium carbonate, and neutralizing the carboxylic acid derived from carboxylic anhydride formed into an amino group of the side chain of the intermediate formed after the acylation reaction, A free type acylated polyallylamine solution of the present invention can be produced.

However, when acylation exceeding 50 mol% with respect to the amino group of polyallylamine is carried out, the carboxylic acid formed into the amino group of the side chain of the intermediate is converted into sodium hydroxide, potassium hydroxide, sodium carbonate. The acylation reaction may be allowed to proceed while appropriately neutralizing with an alkali such as. In this case, it is preferable to maintain the reaction solution at pH 10 to 12. When neutralizing, add 0 to 1
It is preferable to keep the temperature at 0 ° C. After completion of the neutralization, the resulting solution is dialyzed to remove the neutralized salt, and a purified free type acylated polyallylamine solution of the present invention can be obtained.

As the dialysis for removing the neutralized salt, it is preferable to use the electrodialysis described in Japanese Patent Publication No. 7-68289 from the viewpoint of easy operation. In this case,
When the acylated polyallylamine solution during purification is subjected to GPC chromatography, the amount of salt present in the solution can be easily checked. Therefore, GPC
Chromatography can be used to determine the end of purification.

The inorganic acid of the acylated polyallylamine is added to a purified free type acylated polyallylamine solution of the present invention by adding an appropriate amount, preferably an equivalent amount of an inorganic acid or an organic acid, to the free amino group. Or an organic acid salt can be produced. In this case, examples of the inorganic acid include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid and the like. Further, as the organic acid, acetic acid, propionic acid, n-butyric acid,
Examples thereof include isobutyric acid, n-valeric acid, isovaleric acid, methylethylacetic acid, trimethylacetic acid, caproic acid, heptonic acid, caprylic acid, capric acid, undecylic acid, lauric acid, palmitic acid, stearic acid, and benzoic acid.

By adding the acylated polyallylamine salt solution of the present invention to a solvent such as acetone and reprecipitating,
An inorganic acid or an organic acid salt of an acylated polyallylamine,
Often it can be taken out as a solid. The degree of acylation of the acylated polyallylamine of the present invention depends on the amount of the starting carboxylic anhydride used. When a carboxylic anhydride in an amount less than the equivalent to the amino group of polyallylamine as a raw material is used, the carboxylic anhydride is generally almost consumed as an acylating reagent. Therefore, it can be produced by adjusting the cation density of the acylated polyallylamine of the present invention depending on the amount of the carboxylic anhydride. The acylation degree of the acylated polyallylamine of the present invention can be measured by NMR measurement or colloid titration. The hydrophobicity of the acylated polyallylamine of the present invention can be changed depending on the type of the carboxylic anhydride used. Therefore, when the acylated polyallylamine of the present invention is used for various applications, it is possible to select an acylated polyallylamine having an appropriate cation density and an appropriate hydrophobicity.

[0015]

【Example】

Example 1 Synthesis of 30 mol% acetylated polyallylamine
Adult stirrer, Dimroth condenser reflux condenser, a dropping funnel, a four-necked 51 round bottomed separable flask equipped with a thermometer, a 10% aqueous solution of polyallylamine having a molecular weight of about 10,000 (Nitto Boseki Co.,
3443 g (6.0 mol per PAA monomer unit) were charged, and the flask was cooled with ice water to obtain 200 ml.
While stirring at rpm, 189.54 g of acetic anhydride (1.
80 mol) was slowly added dropwise, and the whole amount was added dropwise over 4 hours. The temperature during the reaction was kept at 0 to 5 ° C. Subsequently, while maintaining the same temperature by stirring while cooling the flask, 1
511.13 g of a 4.83% aqueous sodium hydroxide solution
(1.90 mol) was added dropwise to neutralize the by-produced acetic acid.

[0016] The obtained neutralized liquid is washed with JP-B 7-682.
89, electrodialysis, desalting for 44 hours, and free-type 30 mol% acetylated polyallylamine, that is, 30 mol% acetylated poly (amine) of the raw material polyallylamine. A coalescence was obtained. NMR was measured by changing the water in this aqueous solution to heavy water. The results are shown in FIG. In the NMR method, the degree of acetylation of the acetylated polyallylamine was found to be 31% based on the area ratio between the hydrogen of the methylene group bonded to the amino group and the hydrogen of the methylene group bonded to the amide group.

FIG. 2 shows the results of GPC chromatography of the acetylated polyallylamine solution before and after electrodialysis. In the GPC chromatography measurement, the eluent flow path pump was L-6000, the detector was a Shodex RISE-61 differential refractive index detector, and the column was Asahi Pack's aqueous gel filtration type GS-220HQ.
(Exclusion limit molecular weight 3000) and GS-620HQ (exclusion limit molecular weight 2,000,000) were used in a double connection. The sample was adjusted to a concentration of 0.5 g / 100 ml,
20 μl was used. A 0.4 mol / l aqueous solution of sodium chloride was used as an eluent. The column temperature was 30 ° C. and the flow rate was 1.0 ml / min. When the acetylated polyallylamine aqueous solution after electrodialysis is measured by GPC,
It was confirmed that the peak at 17.6 min derived from sodium acetate disappeared.

Example 2 30 mol% acetylated polyallylamine hydrochloride
Synthesis of Salt Hydrochloric acid was added to the free type aqueous solution of 30 mol% acetylated polyallylamine produced in Example 1, and reprecipitated with an acetone solvent to obtain 30 mol% acetylated polyallylamine hydrochloride. Elemental analysis of this hydrochloride gave C, 44.75%; H, 9.78%; N, 1
It was 4.57%. On the other hand, the calculated value of 30 mol% acetylated polyallylamine hydrochloride is C, 45.41%;
H, 8.79%; N, 14.71%. Since the analytical and calculated values are close, it is supported that the resulting acetylated polyallylamine hydrochloride has 30% of the amino groups acetylated. The colloid titration method supported a structure in which 30 mol% of the amino groups were acetylated. In the colloid titration, toluidine blue was used as a titration indicator, an N / 400 aqueous solution of polyvinyl potassium sulfate was used as a colloid titration reagent, and a concentration of 0.2380 was used as a sample solution.
g / l of 5 ml was used. Further, the IR spectrum of 30 mol% acetylated polyallylamine hydrochloride is shown in FIG.
Shown in 1650 cm ^-1 in the amide carbonyl (-NH
It shows absorption derived from CO- ) and supports the structure of the acetylated product.

Example 3 Synthesis of 50 mol% acetylated polyallylamine
The amount of adult acetic anhydride 315.77g (3.00 moles), the amount of 18.41% aqueous sodium 667.31g (3.07 moles) hydroxide sodium hydroxide, except for using the same manner as in Example 1 To obtain a free type 50 mol% acetylated polyallylamine. The NMR is shown in FIG. The calculated value of the degree of acetylation was found to be 51 mol%.

Example 4 50 mol% acetylated polyallylamine hydrochloride
Using a sample obtained in Example 3 of salts, performs substantially the same procedure as in Example 2 to obtain 50 mol% acetylated polyallylamine hydrochloride. Elemental analysis of this hydrochloride gave C, 49.40.
%; H, 9.87%; N, 14.05%. On the other hand, the calculated value of 30 mol% acetylated polyallylamine hydrochloride is C, 49.87%; H, 8.89%; 14.5.
Since the analytical value and the calculated value are close to 4%, the obtained acetylated polyallylamine hydrochloride supports that 50 mol% of the amino groups are acetylated. The IR spectrum is shown in FIG. 5 and shows the amide carbonyl (—NH 2 CO 3) at 1650 cm ^−1.
It shows absorption derived from-), and supports the structure of the acetylated product.

Example 5 50 mol% high molecular weight acetylation
As polyallylamine as a raw material for the synthesis of polyallylamine, 20 having a molecular weight of about 100,000
% Polyallylamine aqueous solution (PAA- manufactured by Nitto Boseki Co., Ltd.)
H) 1,722 g (6.0 mol in PAA monomer units)
The procedure of Example 1 was repeated, except that 1722 g of water was added, to obtain 50 mol% of a free type acetylated polyallylamine.

Example 6 50 mol% high molecular weight acetylation
Synthesis of polyallylamine hydrochloride Using 50 mol% acetylated polyallylamine obtained in Example 5, the same operation as in Example 2 was performed to obtain 50 mol% acetylated polyallylamine hydrochloride. Elemental analysis of this hydrochloride gave C, 49.32%; H, 10.07
%; N, 14.06%. Also, the IR spectrum, 1650 cm ^-1 in the amide carbonyl (-NH C
It shows absorption derived from O- ) and supports the structure of the acetylated product.

Example 7 40 mol% propionylated polyallylamine
And a 10% aqueous solution of polyallylamine having a molecular weight of about 10,000 (Nitto Boseki Co., Ltd.) in a four-necked 31 round bottom separable flask equipped with a stirrer, a Dimroth condenser, a dropping funnel, and a thermometer.
1763 g (3.0 mol per PAA monomer unit) was charged into the flask, and the flask was cooled with ice water to obtain 200 μg.
While stirring at rpm, propionic anhydride 161.00
g (1.20 mol) was slowly dropped, and the whole amount was dropped over 6 hours. The temperature during the reaction was kept at 0 to 5 ° C. Subsequently, while maintaining the same temperature by stirring while cooling the flask, a 11.25% aqueous sodium hydroxide solution 447.
97 g (1.26 mol) was added dropwise to neutralize the by-produced propionic acid. The obtained neutralized solution was subjected to electrodialysis in the same manner as in Example 1, desalted for 28 hours, and obtained as a free type 40 mol% propionylated polyallylamine, that is, the amino group of the raw material polyallylamine. To obtain a polymer which was 40 mol% propionylated.

Hydrochloric acid was added to the polymer aqueous solution and reprecipitated with an acetone solvent to obtain 40 mol% propionylated polyallylamine hydrochloride. Elemental analysis of this hydrochloride gave C, 49.54%; H, 10.58%;
N, 13.26%. On the other hand, the calculated value of 40 mol% propionylated polyallylamine hydrochloride is C, 49.
75%; H, 9.15%; N, 13.81%.
Since the analytical and calculated values are close, it is supported that the resulting propionylated polyallylamine hydrochloride is one in which 40 mol% of the amino groups are propionylated. Further, from the IR spectrum of 40 mol% propionylated polyallylamine hydrochloride, 1650 cm ⁻¹
Shows the absorption derived from amide carbonyl (-NHCO-), which supports the structure of the propionylated product.

Example 8 Highly concentrated aqueous solution of polyallylamine
Preparation of a 10% aqueous solution of polyallylamine having a molecular weight of about 10,000 (PAA-10 manufactured by Nitto Boseki Co., Ltd.) in a rotary evaporator.
C) was added thereto and concentrated to prepare a 35% aqueous solution of polyallylamine.

Examples 9 to 11 20 mol% acylated polyallylamine
Synthesis of Hydrochloride A 35% polyallylamine aqueous solution prepared in Example 8 was placed in a four-necked 300 ml round bottom separable flask equipped with a stirrer, a Dimroth condenser, a dropping funnel, and a thermometer.
8.40 g (0.3 mol per PAA monomer unit) was charged, and 65.80 g of isopropyl alcohol was added.
% Polyallylamine solution. Cool the flask 20
While stirring at 0 rpm, n
-Using butyric acid (Example 9), n-valeric anhydride (Example 10) or n-caproic anhydride (Example 11), prepare a 0.06 mol dropping funnel as shown in Table 1, and slowly add dropwise. The whole amount was dropped over 1.5 hours. The temperature during the reaction is 0
It was kept at 5 ° C. Thereafter, the mixture was concentrated at a bath temperature of 30 ° C., hydrochloric acid was added while cooling the flask with ice water, and immediately reprecipitated with an acetone solvent to obtain a 20 mol% acylated polyallylamine hydrochloride. Elemental analysis of this hydrochloride and 2
Table 1 shows the calculated values of the 0 mol% acylated polyallylamine hydrochloride. From Table 1, the analytical values and the calculated values are close to each other, and it is supported that the obtained acylated polyallylamine hydrochloride is an acylated polyallylamine hydrochloride in which 40 mol% of amino groups are acylated. You. Also,
From the IR spectrum of 20 mole% acylated polyallylamine hydrochloride, the amide carbonyl 1650 cm ^-1 (-
It shows absorption derived from NHCO-) and supports the structure of the acylated product.

Examples 12-16 40 mol% acylated polyallylaminate
Synthesis of hydrochloride salt A 48% aqueous solution of polyallylamine prepared in Example 8 was placed in a four-necked 300 ml round bottom separable flask equipped with a stirrer, a Dimroth condenser, and a dropping funnel thermometer.
40 g (0.3 mol per PAA monomer unit) was charged, and 65.80 g of isopropyl alcohol was added to obtain a 15% polyallylamine solution. Cool the flask 200rpm
While stirring at m, n-butyric anhydride (Example 12), n-valeric anhydride (Example 13) or n-caproic anhydride (Example 14) as a carboxylic anhydride, iso-butyric anhydride (Example 15) ) Or iso-valeric anhydride (Example 1)
Using 6), the mixture was charged into a 0.12 mol dropping funnel as shown in Table 1, slowly dropped, and the whole amount was dropped over 3 hours. The temperature during the reaction was kept at 0 to 5 ° C. After that, bath temperature 3
The mixture was concentrated at 0 ° C., hydrochloric acid was added while cooling the flask with ice water, and immediately reprecipitated with an acetone solvent.
Acylated polyallylamine hydrochloride was obtained. Table 1 shows the elemental analysis value of this hydrochloride and the calculated value of 40 mol% acylated polyallylamine hydrochloride. From Table 1, the analytical values and the calculated values are close to each other, and it is supported that the obtained acylated polyallylamine hydrochloride is an acylated polyallylamine hydrochloride in which 40 mol% of amino groups are acylated. You. Also, from the IR spectrum of the 40 mol% acylated polyallylamine hydrochloride, it shows an absorption derived from amide carbonyl (—NHCO—) at 1650 cm ⁻¹ ,
It supports the structure of the acylated form.

Example 17 20 mol% n-butyrylated polyallylaminate
Obtained in Example 9 of emissions hydrochloride, 20 mol% n-butyryl polyallylamine hydrochloride, water was added dissolved to give a polymer concentration of 5% aqueous solution. To this polymer solution was added the same amount of sodium hydroxide as the part where the amino group and hydrochloric acid formed a salt,
The hydrochloric acid was neutralized. The obtained neutralized solution was subjected to electrodialysis and desalted in the same manner as in Example 1 to obtain a free type of 20 mol%.
An n-butyrylated polyallylamine, that is, a polymer in which n-butyryl was 20 mol% with respect to the amino group of the raw material polyallylamine was obtained.

Table 1 shows the amount of carboxylic anhydride treated, the elemental analysis value of the acylated polyallylamine obtained, and the degree of acylation.

[0030]

[Table 1]

[0031]

The acylated polyallylamine of the present invention is
The cation density of polyallylamine is changed by acylating the amino group structure of polyallylamine. The acylated polyallylamine of the present invention is very easy to produce and can easily control the cation density, and is extremely useful in fields where polyallylamine is currently used and where low cation density is desired. It is believed to provide an effective material. The acylated polyallylamine of the present invention is proposed to be used in the fields of dye fixatives for reactive dyes, dye fixatives for direct dyes, and the like.

[Brief description of the drawings]

FIG. 1 is an NMR spectrum of 30 mol% acetylated polyallylamine synthesized in Example 1.

FIG. 2 shows the results of GPC chromatography of 30 mol% acetylated polyallylamine synthesized in Example 1 before and after electrodialysis.

FIG. 3 is an IR spectrum of 30 mol% acetylated polyallylamine hydrochloride synthesized in Example 2.

FIG. 4 is an NMR spectrum of a 50 mol% acetylated polyallylamine synthesized in Example 3.

FIG. 5 is an IR spectrum of a 50 mol% acetylated polyallylamine hydrochloride synthesized in Example 4.

FIG. 6 is an IR spectrum of 40 mol% propionylated polyallylamine hydrochloride synthesized in Example 7.

FIG. 7 is an IR spectrum of 20 mol% n-butyrylated polyallylamine hydrochloride synthesized in Example 9.

FIG. 8 shows 20 mol% n- synthesized in Example 10.
It is an IR spectrum of pentanoylated polyallylamine hydrochloride.

FIG. 9 shows 20 mol% n-synthesized in Example 11.
It is an IR spectrum of hexanoylated polyallylamine hydrochloride.

FIG. 10 shows 40 mol% synthesized in Example 12.
It is an IR spectrum of n-butyryl polyallylamine hydrochloride.

FIG. 11 shows 40 mol% synthesized in Example 13.
It is an IR spectrum of n-pentanoylated polyallylamine hydrochloride.

FIG. 12 shows 40 mol% synthesized in Example 14.
It is an IR spectrum of n-hexanoylated polyallylamine hydrochloride.

FIG. 13 shows 40 mol% synthesized in Example 15.
It is an IR spectrum of iso-butyrylated polyallylamine hydrochloride.

FIG. 14 shows 40 mol% synthesized in Example 16.
IR of iso-pentanoylated polyallylamine hydrochloride
It is a spectrum.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Tadao Endo 31-9 Shimogawara, Kubota-machi, Tokuyama-cho, Koriyama-shi, Fukushima (56) References JP-A-63-170405 (JP, A) JP-A-7-82320 ( JP, A) JP-A-6-26326 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 8/10

Claims (4)

(57) [Claims] 1. A compound of the general formula (Wherein, m represents an integer of 10 or more, j represents a number satisfying 0 <j <1, and R represents n- or i having 1 to 17 carbon atoms.
an acylated polyallylamine or a salt of the acylated polyallylamine. 2. R is n- or iso having 1 to 11 carbon atoms.
The acylated polyallylamine of claim 1, which is an alkyl group, or a salt of the acylated polyallylamine. 3. R is n- or iso- having 1 to 5 carbon atoms.
The acylated polyallylamine according to claim 1, which is an alkyl group, or a salt of the acylated polyallylamine. 4. A compound of the general formula (Wherein m is an integer of 10 or more) represented by the general formula (RCO) ₂ O (where R is n having 1 to 17 carbon atoms)
-Or an iso-alkyl group) is treated, the carboxylic acid by-produced is neutralized with an alkali, and if necessary, further treated with an organic acid or an inorganic acid to obtain a compound represented by the general formula: Chemical formula 3] (Wherein, m represents an integer of 10 or more, j represents a number satisfying 0 <j <1, and R represents n- or i having 1 to 17 carbon atoms.
(indicating a so-alkyl group) or a salt of the acylated polyallylamine.