JP3494261B2 - N-allyl urethane polymer and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel N-allyl.
The present invention relates to a urethane polymer and a method for producing the same. More specifically, it relates to a novel N-allyl urethane polymer having a small number of amino groups and having a reactive side chain, and a simple production method thereof.

[0002]

2. Description of the Related Art Polyallylamine polymers such as polyallylamine and poly (N-alkylallylamine) are
It is a straight-chain olefin polymer containing an amino group in its side chain, and is a cationic polymer that dissolves well in water and is positively charged in water. Such a polyallylamine-based polymer has a unique reactive polymer structure and properties, and therefore is used as a dye fixing agent for reactive dyes, a dye fixing agent for direct dyes, a food preservative and an anchor coating agent. There is. Further, it has been proposed to use a polyallylamine-based polymer in the fields of silver halide photographic light-sensitive materials, sustained-release pharmaceutical compositions, ion exchange resins, functional membranes and the like. However, "Synthesis and Applications of Reactive Polymers" published by CMC, pp. 80-92 (1
989), generally speaking,
The number of reactive groups of the reactive polymer does not need to be too large, and if it is too large, it may be inconvenient. On the other hand, although it is possible to synthesize a polymer having reduced amino groups by copolymerization, monoallylamine-based monomers such as monoallylamine and mono (N-alkylallylamine) are ordinary vinyl-based monomers. Since it does not copolymerize with, it is difficult to synthesize a polyallylamine derivative having a low cation density by copolymerization. Therefore, a method of reacting the amino group of the polyallylamine-based polymer with another compound to convert it into an inactive group has also been studied. An allylurea polymer (Japanese Patent Publication No. 63-43403) is known as a polyallylamine derivative produced by such a method. But,
This polyallylamine-based derivative is problematic in that it is difficult to purify, so that it is rarely used in practice.

On the other hand, a polyallylamine-based polymer dissolves well in water, and therefore, a water-based anchor coating agent as an alternative to an organic solvent-based anchor coating agent (JP-A-4-2926).
No. 40) and other applications in the adhesive field are known. However, the laminated film produced by using these anchor coating agents has a practical problem of lacking water resistance. Therefore, there has been a demand for the development of a novel polyallylamine-based derivative in which a crosslinking reaction easily occurs by heat treatment to make it insoluble and, as a result, the water resistance is improved.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention, fewer amino group and having a reactive side chain, may be further insolubilized readily occur crosslinking reaction by heat treatment Poria
It is an object of the present invention to provide a rilamine-based derivative, more specifically, an N- allylurethane- based polymer and a method for easily producing the same.

[0005]

The present inventors have developed a novel N-ary having a small number of amino groups and a reactive side chain.
As a result of earnestly researching a urethane polymer and a method for easily producing the same, as a result of reacting a specific polyallylamine polymer with a specific carbonic acid diester, it is possible to reduce the number of amino groups and block isocyanate groups. It has been found that a novel N-allyl urethane polymer having the above can be easily produced, and the present invention has been completed based on this finding. In the present specification, urethanization means that an amino group (NH) is an alkyloxycarbonylamino group or an aryloxycarbonylamino group (NC).
O-OR ² ).

The present invention has the general formula

[0007]

[Formula 4] (In the formula, m represents an integer of 10 or more, j represents a number satisfying 0 <j ≦ 1, R ¹ represents hydrogen, an n- and iso-alkyl group having 1 to 8 carbon atoms, and 5 carbon atoms. To a cycloalkyl group having 12 to 12 carbon atoms, R ² represents a substituent selected from an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms). It is a polymer or its addition salt .

The N-allyl urethane polymer of the present invention is
It has a blocked isocyanate group. Therefore, usually
Under heating conditions, urethane becomes isocyanate, so that the reactivity becomes high.

INDUSTRIAL APPLICABILITY The N-allyl urethane polymer and its addition salt of the present invention are stable in a solution, particularly in an acidic solution, moderately soluble in water, and easily available as a raw material. Therefore, it is preferable that R ¹ is hydrogen and R ² is an n- or iso-alkyl group having 1 to 12 carbon atoms.

In the present invention, m represents the degree of polymerization of the N-allyl urethane polymer of the present invention. m is 10 or more,
It is preferably 10 to 5000.

In the present invention, j represents the degree of urethane formation. j is 0 <j ≦ 1, but from the degree of decrease in the cation density of the N-allyl urethane polymer of the present invention,
0.05 ≦ j ≦ 1 is preferable.

In the present invention, R ¹ is hydrogen and has 1 to 1 carbon atoms.
8 n- and iso-alkyl groups and 5 to 1 carbon atoms
2 represents a substituent selected from the cycloalkyl group of 2. From a practical viewpoint of solubility in water and availability of raw materials, R ¹ is preferably hydrogen for practical purposes.

In the present invention, R ² has 1 to 12 carbon atoms.
Shows a substituent selected from an alkyl group of and an aryl group having 6 to 12 carbon atoms . In this case, examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl and propyl. Examples of the aryl group having 6 to 12 carbon atoms for R ² include a phenyl group, an o-tolyl group, an m-tolyl group, and a p-tolyl group. In the N-allyl urethane polymer of the present invention, R ² is an n-alkyl group having 1 to 12 carbon atoms or an iso-alkyl group because of its stability in solution, particularly stability in acidic solution. It is preferably a group.

[0014] The force of the N- allyl urethane-based polymer of the present invention
Salting is an addition salt to a side chain amino group in a non-urethaned monomer unit. Such addition salts include hydrochloride, hydrobromide, hydroiodide, sulfate,
Carboxylates such as phosphates, phosphonates and acetates,
Examples thereof include oxycarboxylates such as methanesulfonate, p-toluenesulfonate, citrate and tartrate, and benzoate.

Generally, the N-allyl urethane polymer of the present invention may become unstable in a solution state when made into a salt. Therefore, the N-allyl urethane polymer of the present invention is preferably free in a solution state.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The N-allyl urethane polymer or its addition salt of the present invention can be produced by reacting a specific polyallylamine polymer with a specific carbonic acid diester. That is, the N-allyl urethane polymer of the present invention has the general formula

[0017]

[Formula 5] (In the formula, m represents an integer of 10 or more, and R ¹ represents a substituent selected from hydrogen, an n- and iso-alkyl group having 1 to 8 carbon atoms, and a cycloalkyl group having 5 to 12 carbon atoms). In the polyallylamine-based polymer represented by the formula, R ² O—CO—OR ² (wherein R ² is an alkyl group having 1 to 12 carbon atoms and a carbon atom).
It can be produced by reacting a carbonic acid diester represented by the formula (6 to 12 represents a substituent selected from an aryl group). The raw material polyallylamine-based polymer for producing the N-allyl urethane-based polymer of the present invention has the general formula

[0018]

[Formula 6] (In the formula, m represents an integer of 10 or more, and R ¹ represents a substituent selected from hydrogen, an n- and iso-alkyl group having 1 to 8 carbon atoms, and a cycloalkyl group having 5 to 12 carbon atoms) It is represented by.

Further, as such a raw material, a partial salt of the polyallylamine polymer can also be used. Such partial salts are

[0020]

[Formula 7] (In the formula, m represents an integer of 10 or more, k represents a number satisfying 0 <k <1, R ¹ represents hydrogen, an n- and iso-alkyl group having 1 to 8 carbon atoms, and 5 carbon atoms. ~ 12 represents a substituent selected from a cycloalkyl group , X is a partial salt
It expresses in forming salts for). The acid for forming this part partial salts, as long as it is an acid capable of forming an amino group and salts of the side chain of polyallylamine-based polymer is not particularly limited. Examples of such acids include carboxylic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, phosphonic acid, acetic acid, methanesulfonic acid, p-toluenesulfonic acid,
Examples thereof include oxycarboxylic acids such as citric acid and tartaric acid, and benzoic acid.

The raw material polyallylamine polymer is R ¹
When is hydrogen, it is polyallylamine. The polyallylamine is preferably a free type. The free type, but the salts of known polyallylamine may be used that is neutralized with an alkali, a commercially available concentration of 15% polyallylamine (about 10,000 molecular weight) aqueous solution (Nitto Boseki Co.,
Ltd., PAA-15), concentration of 10% polyallylamine
(Molecular weight about 10,000) Aqueous solution (Nitto Boseki Co., Ltd., PAA-
10C), concentration of 20% polyallylamine (molecular weight of about 1
50,000) solution (Nitto Boseki Co., PAA-L) and concentrated <br/> of 20% of the polyallylamine (molecular weight: about 100,000) aqueous solution (Nitto Boseki Co., Ltd., the PAA-H), etc. You can use it as it is.

In the polyallylamine polymer as a raw material, when R ¹ is a substituent selected from n- and iso-alkyl groups having 1 to 8 carbon atoms and cycloalkyl groups having 5 to 12 carbon atoms, Publication 63-43402 Patent Publication No.
Report , Japanese Patent Publication No. 6-2779, Japanese Patent Publication No. 2-57084
A salt of poly (N-alkylallylamine) is prepared by a method as described in Japanese Patent Application Publication No. 2003-53242, and an aqueous solution of the salt of poly (N-alkylallylamine) is then diluted with an alkali such as sodium hydroxide. After neutralization, a neutralized salt produced as a by-product such as sodium chloride removed by dialysis can be used.

Water, an organic solvent, or a mixed solvent of water and an organic solvent can be used as a solvent for forming the raw material polyallylamine polymer into a solution. As the organic solvent, polar solvents are preferable from the solubility of the raw materials, and alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetonitrile, formamide, N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran. , 1,4-dioxane and the like can be exemplified. The amount of the solvent for polyallylamine polymers of the raw material to the solution, compared polyallylamine polymer 1 weight of the feed, preferably from 0.5 to 100 wt.

The carbonic acid diester as a raw material for producing the N-allyl urethane polymer of the present invention has the general formula R ² O.
-CO-OR ² (wherein, R ² represents a substituent selected from alkyl groups and aryl groups having 6 to 12 carbon atoms having 1 to 12 carbon atoms) represented by. Examples of carbonic acid diesters include dimethyl carbonate, diethyl carbonate and diphenyl carbonate. The amount of carbonic acid diester to be reacted is usually N
-A stoichiometrically calculated amount required for the degree of urethanization of the allyl urethane polymer can be used.

When the raw material polyallylamine-based polymer and the carbonic acid diester are reacted to produce the N-allyl urethane-based polymer of the present invention, first, the carbonic acid diester is slowly added to the solution of the raw material polyallylamine-based polymer. It is good to drip. At this time, the carbonic acid diester can be dissolved in a solvent and added dropwise to the solution of the raw material polyallylamine polymer. In this case, the solvent for dissolving the carbonic acid diester is usually the same as the solvent for dissolving the raw material polyallylamine-based polymer. The reaction of the polyallylamine-based polymer and the carbonic acid diester is preferably performed with stirring. The reaction temperature is preferably 0-10.
It is good to maintain at 0 ° C, and more preferably at 30 to 60 ° C. If the reaction temperature is too high, the generated urethane may decompose. The reaction time is usually 12 to 48 hours, preferably at 12 to 25 hours to give a solution of the allyl urethane polymer of the present invention. After the reaction is completed, the reaction solution is removed in order to remove by-produced alcohol and reaction solvent.
The N-allyl urethane polymer of the present invention can be obtained as a solid by vacuum drying. The vacuum drying is carried out at a temperature of 25 to 70 ° C., preferably 35 to 60, when water is used as a solvent and dimethyl carbonate, diethyl carbonate, or dipropyl carbonate is used as a carbonic acid diester.
It is preferred to carry out at a suitable vacuum condition at ° C. If the temperature is too high, side reactions may occur. In addition, the N-
The addition salt of the allyl urethane polymer is obtained by using a partial salt of the polyallylamine polymer as a raw material, and reacting this with a carbonic acid diester in the same manner as in the case of using the free polyallylamine polymer. , Can be manufactured. Usually, when a partial salt of a polyallylamine-based polymer as a raw material is reacted with a carbonic acid diester, N in the polyallylamine-based polymer does not form a salt with NH in the polyallylamine-based polymer.
H is preferentially urethanized. After completion of the reaction, the resulting salt solution of the N-allyl urethane polymer is added to a solvent such as acetone and reprecipitated to take out the addition salt of the N-allyl urethane polymer of the present invention as a solid. It becomes possible.

The degree of urethanization (mol%) of the N-allyl urethane polymer of the present invention depends on the amount of the carbonic acid diester used as the starting material. When an equimolar amount of carbonic acid diester is used with respect to the amino group of the raw material polyallylamine-based polymer, most of the amino group is usually urethanized. Therefore, the cation density of the N-allyl urethane polymer of the present invention can be adjusted by adjusting the amount of carbonic acid diester used as a raw material. The hydrophobicity of the N-allyl urethane polymer of the present invention can be changed depending on the type of carbonic acid diester used.
Therefore, when the N-allyl urethane polymer of the present invention is used in various applications, it is possible to select a polymer having an appropriate cation density and an appropriate hydrophobicity.

Furthermore, since the N-allyl urethane polymer of the present invention is also a polyallylamine having a blocked isocyanate group, the dissociation temperature of the blocked isocyanate group can be selected by selecting the urethane group to be introduced. it can.

The N-allyl urethane polymer of the present invention and the method for producing the same are shown below in Examples. Of course, the present invention is not limited to these examples.

Example 1 20 mol% methoxycarbonyl
Polyallylamine (N-allyl urethane type heavy polymer of the present invention
Preparation of Combined I with j = 0.2, R ¹ = H, R ² = CH ₃ ) 3 equipped with stirrer, dropping funnel, thermometer and reflux condenser
0 separable flask 100 ml, (manufactured by Nitto Boseki (Ltd.), PAA-10C) concentration of 10.1% of the Po <br/> Riariruamin (about 10,000 molecular weight) aqueous solution of 200 g (in a monomer unit of polyallylamine. 35 mol), and the temperature is 50
The temperature was maintained at 0 ° C., and 6.38 g (0.07 mol) of dimethyl carbonate (manufactured by Mitex Co., Ltd.) was added dropwise to the aqueous solution over 15 minutes. While maintaining the temperature at 50 ° C after the dropping,
It continued for 2 hours to obtain a reaction solution of transparency, light yellow. PH of the solution was 10.84. Next, 1 g of this reaction solution was placed in a weighing bottle and vacuum-dried at room temperature for 24 hours, and then phosphoric anhydride was used as a desiccant and vacuum-dried at 50 ° C. for 48 hours to obtain 20 mol% methoxycarbonylated polyallylamine. It was The result of elemental analysis is C = 58.97%, H =
10.93% and N = 19.76%. These values are calculated C = 59.44%, H = 10.86%, N = 2
It almost coincided with 0.39%.

Example 2 60 mol% methoxycarbonyl
Polyallylamine (N-allyl urethane type heavy polymer of the present invention
J = 0.6 coalescence ^{I, R 1 = H, R} 2 = CH 3 in the same reaction vessel as in Production Example 1 of) concentration of 10.1% of polyallylamine (molecular weight: about 10,000) solution (Nitto Spinning Co., Ltd.
PAA-10C) (200 g, 0.35 mol of polyallylamine monomer unit) was added, the temperature was kept at 50 ° C., and dimethyl carbonate (manufactured by Mitex Co., Ltd.) was added to the aqueous solution.
19.14 g (0.21 mol) was added dropwise over 40 minutes. Keeping After completion of the dropwise addition the temperature to 50 ° C., it continued for 12 hours to obtain a reaction solution of transparency, light yellow. The pH of this solution was 9.78. Next, 1 g of this reaction solution was placed in a weighing bottle and dried under the same conditions as in Example 1 to obtain 60 mol% methoxycarbonylated polyallylamine. The results of elemental analysis are C = 54.32%, H = 9.17%, N =
It was 14.75%. These values are calculated C = 54.
88%, H = 8.99%, was almost the same as the N = 15.24%.

FIG. 1 shows the infrared absorption spectrum of 60 mol% methoxycarbonylated polyallylamine in the KBr method . The absorption spectrum shows 1580 cm ⁻¹ based on the primary amino group (—NH ₂ ) and a urethane group (N—CO—O—).
Absorption of 1700 cm ^-1 based on the C = O of R) was observed
It was

Example 3 100 mol% methoxycarboni
Polyallylamine (N-allyl urethane type of the present invention
In Polymer ^{I j = 1, R 1 =} H, in the same reaction vessel as in Production Example 1 of R ² = CH _3), about 10,000 concentration of 10.1% of polyallylamine (molecular weight) aqueous solution (Nitto Boseki (stock)
PAA-10C) (200 g, 0.35 mol of polyallylamine monomer unit) was added, the temperature was kept at 50 ° C., and dimethyl carbonate (manufactured by Mitex Co., Ltd.) was added to the aqueous solution.
33.50 g (0.37 mol) was added dropwise over 1 hour. Keeping After completion of the dropwise addition the temperature to 50 ° C., it continued for 12 hours to obtain a reaction solution of transparency, light yellow. The pH of this solution was 7.85. Next, 1 g of this reaction solution was placed in a weighing bottle and dried under the same conditions as in Example 1 to obtain 100 mol% methoxycarbonylated polyallylamine. The results of elemental analysis are C = 51.68%, H = 7.94%, N
= 11.83%. These values are calculated values C = 5
It was almost in agreement with 2.16%, H = 7.88%, and N = 12.17%.

Example 4 20 mol% ethoxycarbonyl
Polyallylamine (N-allyl urethane type heavy polymer of the present invention
J = 0.2 coalescence ^{I, R 1 = H, R} 2 = C 2 H 5 in the same reaction vessel as in Production Example 1 of) concentration of 10.1% of polyallylamine (molecular weight: about 10,000) solution (Nitto Boseki Co., Ltd.
PAA-10C) (200 g, 0.35 mol in terms of monomer unit of polyallylamine) was added, the temperature was kept at 50 ° C., and diethyl carbonate (special grade, manufactured by Nacalai Tesque, Inc.) 8.37 g (0. (07 mol) was added dropwise over 15 minutes. After maintaining the temperature at 50 ° C after the dropping, 2
It continued for 4 hours to obtain a reaction solution of transparency, light yellow. PH of the solution was 10.88. Next, 1 g of this reaction solution was placed in a weighing bottle and dried under the same conditions as in Example 1,
20 mol% ethoxycarbonylated polyallylamine was obtained. The results of elemental analysis are C = 59.94% and H = 10.7.
9% and N = 19.32%. These values are calculated values C = 60.47%, H = 11.00%, N = 19.59.
It almost coincided with%.

Example 5 60 mol% ethoxycarbonyl
Polyallylamine (N-allyl urethane type heavy polymer of the present invention
J = 0.6 coalescence ^{I, R 1 = H, R} 2 = C 2 H 5 in the same reaction vessel as in Production Example 1 of) concentration of 10.1% of polyallylamine (molecular weight: about 10,000) solution (Nitto Boseki Co., Ltd.
(Manufactured by PAA-10C) (200 g, 0.35 mol of polyallylamine monomer unit) was added, the temperature was kept at 50 ° C., and 25.10 g of diethyl carbonate (special grade, manufactured by Nacalai Tesque, Inc.) (0. (21 mol) was added dropwise over 40 minutes. After the dropping, keep the temperature at 50 ° C,
It continued for 24 hours to obtain a reaction solution of transparency, light yellow.
The pH of this solution was 9.55. Next, 1 g of this reaction solution was placed in a weighing bottle and dried under the same conditions as in Example 1,
60 mol% ethoxycarbonylated polyallylamine was obtained. The results of elemental analysis are C = 56.98% and H = 9.41.
%, N = 13.52%. These values are calculated values C
= 57.46%, H = 9,44%, N = 13.96%
Almost matched.

FIG. 2 shows an infrared absorption spectrum of 60 mol% ethoxycarbonylated polyallylamine. The absorption spectrum, based on the primary amino group (-NH ₂₎ 1
C = of 580 cm ⁻¹ and urethane group (N—CO—O—R)
Absorption at 1700 cm ^-1 based on O was observed .

Example 6 100 mol% ethoxycarboni
Polyallylamine (N-allyl urethane type of the present invention
In Polymer ^{I j = 1, R 1 =} H, in the same reaction vessel as in Production Example 1 of _{^{R 2 = C 2 H 5)}} , 10,000) aqueous solution concentration of 10.1% of polyallylamine (molecular weight ( Nitto Boseki Co., Ltd.
PAA-10C) (200 g, 0.35 mol of polyallylamine monomer unit) was added, the temperature was kept at 50 ° C., and diethyl carbonate (special grade, manufactured by Nacalai Tesque, Inc.) 43.93 g (0. (37 mol) was added dropwise over 1 hour. After the dropping, keep the temperature at 50 ° C,
The reaction is continued for 24 hours, and the clear reaction solution separated into two layers is added .
Got The upper layer of pH of the solution was 7.81. Next, 1 g of the lower layer reaction solution was placed in a weighing bottle and dried under the same conditions as in Example 1 to obtain 100 mol% ethoxycarbonylated polyallylamine. The result of elemental analysis is C = 55.3
It was 7%, H = 8.42%, and N = 10.51%. These values are calculated values C = 55.80%, H = 8.58%,
It almost coincided with N = 10.84%.

[0037]

Effects of the Invention N- allyl urethane-based polymer of the present invention, by urethanization an amino group of a particular polyallylamine polymer, those obtained by changing the cation density of the polyallylamine polymer There is . What slave, N- allyl urethane polymer of the present invention is now in the field polyallylamine is used, and is intended to provide a very effective material in the field of low cationic density are desired. Further, N- allyl urethane polymer of the present invention, anti
Introducing a blocked isocyanate group having responsiveness
Therefore, it provides an extremely effective material in the field of utilizing the reactivity of the blocked isocyanate group. For example, dye fixing agent for reactive dyes, dye fixing agent for direct dyes,
It is proposed to use it in the field where it is desired to improve the adhesiveness or water resistance of an anchor coating agent for extrusion lamination. The N-allyl urethane polymer of the present invention is manufactured by
It is extremely easy to make. In addition, cation density and reactive groups
Easily control the degree of substitution of blocked isocyanate groups
it can.

[Brief description of drawings]

FIG. 1 shows an infrared absorption spectrum of 60 mol% methoxycarbonylated polyallylamine (N-allyl urethane polymer of Example 2).

FIG. 2 shows an infrared absorption spectrum of 60 mol% ethoxycarbonylated polyallylamine (N-allyl urethane polymer of Example 5). The horizontal axis represents wave number (cm ⁻¹ ) and the vertical axis represents transmittance (%) or absorbance.

Continuation of front page (56) References JP-A-9-169821 (JP, A) JP-A-4-110313 (JP, A) JP-A-62-256801 (JP, A) JP-A-62-187719 (JP , A) JP 62-10104 (JP, A) JP 60-108405 (JP, A) JP 60-106801 (JP, A) JP 61-233007 (JP, A) JP 60-106804 (JP, A) JP-A 5-132513 (JP, A) JP-A 63-228053 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 8/00 -8/50 C08F 26/02

Claims (3)

(57) [Claims] 1. A general formula [Formula 1] (In the formula, m represents an integer of 10 or more, j represents a number satisfying 0 <j ≦ 1, R ¹ represents hydrogen, an n- and iso-alkyl group having 1 to 8 carbon atoms, and 5 carbon atoms. A C-C12 alkyl group and R ² represents a C1-C12 alkyl group and a C6-C12 aryl group). Polymer, or its addition salt . 2. R ¹ is hydrogen and R ² has 1 carbon atom.
2. The N-allyl urethane polymer according to claim 1, which is a substituent selected from the n- and iso-alkyl groups of to 12, or an addition salt thereof . 3. A general formula [Formula 2] (In the formula, m represents an integer of 10 or more, and R ¹ represents a substituent selected from hydrogen, an n- and iso-alkyl group having 1 to 8 carbon atoms and a cycloalkyl group having 5 to 12 carbon atoms). The polyallylamine-based polymer represented by the formula or a partial salt thereof has a general formula R ² O—CO—OR ² (wherein R ² is selected from an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms). A general formula [formula 3] characterized by reacting a carbonic acid diester represented by (In the formula, m represents an integer of 10 or more, j represents a number satisfying 0 <j ≦ 1, R ¹ represents hydrogen and n having 1 to 8 carbon atoms.
-And an iso-alkyl group and a substituent selected from a cycloalkyl group having 5 to 12 carbon atoms, R ² represents a substituent selected from an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms. The method for producing an N-allyl urethane polymer or its addition salt represented by