JP2000239322A - Amino polymer compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound having excellent solubility and stability, useful especially for a polymer additive by making the compound include an end group composed of an aromatic group-containing constituent unit, etc., and a specific amino group at the side chain of a repeating unit. SOLUTION: This compound comprises one end group composed of an aromatic group-containing constituent unit and the other end composed of a constituent unit containing a carboxy group or its ester group and one or more of a tertiary amino group, a tertiary ammonium salt and a quaternary ammonium salt at the side chain of a repeating unit. The compound contains preferably a repeating unit of the formula (R1 and R2 are each a 1-3C alkyl or bonded to form a 3-6C oxygen-containing ring; R3 is H or the like; p is 1-5), etc. The compound is obtained by a preferable production method for polymerizing a monomer containing a radical-polymerizable ethylenically unsaturated group and an amino group in the presence of a chain transfer agent containing one or more aromatic groups in the molecule with a polymerization initiator containing a carboxy group, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel amino polymer compound and a method for producing the same.

[0002]

2. Description of the Related Art Amino high molecular compounds are widely used in fiber and paper treatment agents, cosmetics, water treatment agents and the like. However, conventional amino polymer compounds may be limited when used as various additives. That is, the conventional amino polymer compound expresses strong cationicity,
Many of them have a high molecular weight of several tens of thousands to several millions. For example, in a composition that needs to have low viscosity, the amount added is limited due to an increase in viscosity. Further, it is difficult to dissolve in a solvent, and it is difficult to prepare a high concentration. Relatively low molecular weight compounds are commercially available among polyethyleneimines as amino high molecular compounds, but since they have primary amino groups and secondary amino groups in the structure, they can react with them. When used in combination with another composition, a problem arises in its stability. Therefore,
There is a need for an amino polymer compound that solves these problems.

[0003]

An object of the present invention is to provide an amino polymer compound which is excellent in solubility and stability and is useful as various additives, particularly as a polymer additive, and a method for producing the same.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned conventional problems, and as a result, in the polymer, one end group is composed of a structural unit having an aromatic group, The other terminal group is composed of a structural unit having a carboxyl group or an ester group thereof, and the side group of the repeating unit is a tertiary amino group, a tertiary ammonium salt or a quaternary ammonium salt.
It has been found that conventional problems can be solved by using an amino polymer compound having at least one kind of quaternary ammonium salt. Furthermore, the present inventors, in the method for producing an amino polymer compound, a monomer having a radical polymerizable ethylenically unsaturated group and an amino group in the presence of a specific chain transfer agent and / or with a specific polymerization initiator (Co) polymerization method, introduction of the desired terminal group structure using terminal reactive group of reactive polymer, reaction of tertiary amino group of polymer obtained by these methods with acid and desired A method of introducing a tertiary ammonium salt at a ratio (including 100%) and a method of reacting a quaternizing agent to introduce a quaternary ammonium salt at a desired ratio (including 100%), The present invention has been completed. The present invention relates to amino polymer compounds represented by the following (1) to (27) and a method for producing the same.

(1) One terminal group is composed of a constitutional unit having an aromatic group, the other terminal group is composed of a constitutional unit having a carboxyl group or its ester group, and a tertiary amino group is added to the side group of the repeating unit. An amino polymer compound having at least one of a group, a tertiary ammonium salt and a quaternary ammonium salt. (2) The following general formula (1)

Embedded image (Wherein, R ¹ and R ² each independently represent an alkyl group having 1 to 3 carbon atoms, and R ¹ and R ² may form a ring containing an oxygen atom having 3 to 6 carbon atoms. R ³ represents a hydrogen atom or a methyl group, and p represents an integer of 1 to 5.), a repeating unit represented by the following general formula (2)

Embedded image (Wherein, R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ may form a ring containing an oxygen atom having 3 to 6 carbon atoms. R ⁶ represents a hydrogen atom or a methyl group, and q represents an integer of 1 to 5.
X is halogen, R ¹¹ COO, NO ₃ , R ¹² OSO ₃ , B
Represents any one of F ₄ , wherein R ¹¹ and R ¹² each have 1 carbon atom
Represents an alkyl group of 1 to 6. ) Or the following general formula (3)

Embedded image (Wherein, R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 3 carbon atoms, and R ⁷ and R ⁸ may form a ring containing an oxygen atom having 3 to 6 carbon atoms. R ⁹ has 1 carbon atom
To 22 alkyl group, a fluorine-substituted alkyl group, an aralkyl group or a group represented by the general formula ^{(4) - (R 13 -Y} ) s - R 14 (4) ( wherein, R ¹³ may have a substituent Represents an alkyl group, Y is -CONH-, -NHCO-, -NHCOO-, -OCON
H-, -NHCOS-, -SCONH-, -NHCONH-, -S-,
Represents either -O- or -CO-. Also, R
¹⁴ is a carboxyl group, a hydroxyl group, a sulfonic acid group or an alkyl group having 1 to 22 carbon atoms which may have a salt thereof,
Represents a fluorine-substituted alkyl group or an aralkyl group, and s represents an integer of 1 to 5. R ¹⁰ represents a hydrogen atom or a methyl group. R represents an integer of 1 to 5;
Represents the same meaning as described above. R ⁷ , R ⁸ , R ⁹
May be the same or different. In the amino polymer compound having at least one repeating unit represented by the formula (1), one terminal group is composed of a constituent unit having an aromatic group, and the other terminal group is composed of a constituent unit having a carboxyl group or its ester group. The amino polymer compound according to the above (1).

(3) The repeating unit is (1) to (3)
The amino polymer compound according to the above (1) or (2), wherein the repeating unit is represented by the following formula, and the composition ratio of each repeating unit is in the range of 0 to 100%. (4) The amino polymer compound according to any one of the above (1) to (3), wherein the molecular weight of the terminal group comprising the structural unit having an aromatic group is 500 or less. (5) The amino polymer compound according to any one of the above (1) to (4), wherein the molecular weight of the terminal group comprising a structural unit having a carboxyl group or its ester group is 500 or less. (6) The amino polymer compound according to any one of the above (1) to (5), wherein the number average molecular weight is 1,000 to 10,000. (7) The amino polymer compound according to any one of the above (1) to (6), wherein the pH of the aqueous solution of the amino polymer compound is 9 to 11.

(8) In the presence of a chain transfer agent having at least one aromatic group in the molecule, a monomer having a radically polymerizable ethylenically unsaturated group and an amino group is converted to a carboxyl group or an ester thereof. A process for producing an amino polymer compound, comprising (co) polymerizing with a polymerization initiator having a group. (9) In the presence of a chain transfer agent having a carboxyl group or an ester group thereof, a monomer having a radically polymerizable ethylenically unsaturated group and an amino group is reacted with a polymerization initiator having an aromatic group (co). A method for producing an amino polymer compound, comprising polymerizing. (10) One of the terminal groups is composed of a structural unit having a reactive group, the other terminal group is composed of a structural unit having a carboxyl group or an ester group thereof, and the amino group is contained in the side group of the repeating unit. A method for producing an amino polymer compound, comprising reacting a molecule with a compound having at least one aromatic group in the molecule to introduce an aromatic group into a terminal. (11) In the presence of a chain transfer agent in which the reactive polymer has at least one reactive group in the molecule, a monomer having a radically polymerizable ethylenically unsaturated group and an amino group is converted to a carboxyl group. Or (10) which is a polymer obtained by (co) polymerization with a polymerization initiator having the ester group.
3. The method for producing an amino polymer compound according to item 1.

(12) In the presence of a chain transfer agent having at least one carboxyl group or its ester group in the molecule, the reactive polymer has a radical polymerizable ethylenically unsaturated group and an amino group. The method for producing an amino polymer compound according to the above (10), which is a polymer obtained by (co) polymerizing a monomer with a polymerization initiator having a reactive group. (13) a reactive polymer having one end group consisting of a constituent unit having a reactive group, the other end group consisting of a constituent unit having an aromatic group, and having an amino group in a side group of the repeating unit; A method for producing an amino polymer compound, which comprises reacting a compound having at least one carboxyl group or its ester group in a molecule to introduce a carboxyl group or its ester group at a terminal. (14) In the presence of a chain transfer agent in which the reactive polymer has at least one reactive group in the molecule, a monomer having a radically polymerizable ethylenically unsaturated group and an amino group is converted into an aromatic group. (13) The method for producing an amino polymer compound according to the above (13), which is a polymer obtained by (co) polymerization with a polymerization initiator having a group. (15) In the presence of a chain transfer agent in which the reactive polymer has at least one aromatic group in the molecule, a monomer having a radically polymerizable ethylenically unsaturated group and an amino group is reacted with (13) The method for producing an amino polymer compound according to the above (13), which is a polymer obtained by (co) polymerization with a polymerization initiator having a group.

(16) At least one aromatic group in the molecule
The method for producing an amino polymer compound according to the above (8) or (15), wherein the chain transfer agent having at least one compound is benzyl mercaptan or 2,4-diphenyl-4-methyl-1-pentene. (17) When the polymerization initiator having a carboxyl group or its ester group is dimethyl 2,2′-azobis (2-methylpropionate), 4,4′-azobis (4-cyanopentanoic acid) or 2,2 ′ The method for producing an amino polymer compound according to the above (8) or (11), which is -azobis [N- (2-carboxyethyl) -2-methylpropionamidine]. (18) a chain transfer agent having a carboxyl group or an ester group is represented by the following general formula _{(5) HS- (CH 2)} t -COOR 15 (5) ( wherein, R ¹⁵ is 1 to 5 hydrogen atoms or carbon atoms Wherein t represents an integer of 1 to 5.) wherein at least one of the compounds represented by the above (9) or (1
The method for producing an amino polymer compound according to 2). (19) The method for producing an amino polymer compound according to the above (9) or (14), wherein the polymerization initiator having an aromatic group is 1,1′-azobis (1-acetoxy-1-phenylethane).

(20) The above (8), (9), (11), (1) wherein the amino group of the monomer is a tertiary amino group, a tertiary ammonium salt and / or a quaternary ammonium salt.
2) The method for producing an amino polymer compound according to (14) or (15). (21) The above (8), (9), (11), or (1) wherein the monomer is N, N-dialkylaminoalkyl (meth) acrylamide, a salt thereof and / or a quaternary salt thereof.
2) The method for producing an amino polymer compound according to (14), (15) or (20). (22) The tertiary amino group of the amino polymer compound according to any one of (8) to (21) is reacted with an acid, and a part or all of the amino polymer is converted to a tertiary ammonium salt. For producing an amino polymer compound. (23) The method for producing an amino polymer compound according to the above (22), wherein the acid is an organic acid or an inorganic acid having 1 to 6 carbon atoms. (24) The tertiary amino group of the amino polymer compound according to any one of the above (8) to (21) is reacted with a quaternizing agent, and a part or the whole thereof is converted to a quaternary ammonium salt. A method for producing an amino polymer compound.

(25) The method for producing an amino polymer compound according to the above (24), wherein the quaternizing agent is an alkyl halide having 1 to 22 carbon atoms, a halogenated fluorinated alkyl, an aralkyl halide or a sulfate. . (26) reacting the tertiary amino group of the amino polymer compound according to any one of (8) to (21) with an acid and a quaternizing agent simultaneously or separately to form one of the tertiary amino groups; A method for producing an amino polymer compound, wherein part or all of the compound is converted into a tertiary ammonium salt and a quaternary ammonium salt. (27) The above-mentioned (27), wherein the acid is an organic or inorganic acid having 1 to 6 carbon atoms, and the quaternizing agent is an alkyl halide having 1 to 22 carbon atoms, a halogenated fluorine-substituted alkyl, an aralkyl halide, or a sulfate. 26. The method for producing an amino polymer compound according to 26).

That is, the present invention relates to an amino polymer compound which is excellent in solubility and stability and is useful as various additives, especially as a polymer additive, and a method for producing the same.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the amino polymer compound of the present invention will be described. The amino polymer compound of the present invention,
One terminal group is composed of a structural unit having an aromatic group, the other terminal group is composed of a structural unit having a carboxyl group or an ester group thereof, and a third group is a side group of the repeating unit.
No particular limitation is imposed on the amino polymer compound having at least one of a tertiary amino group, a tertiary ammonium salt and a quaternary ammonium salt. General formula (1)

Embedded image (Wherein R ¹ , R ² , R ³ and p have the same meanings as described above), and when the repeating unit has a tertiary ammonium salt in the side group, the following general formula: (2)

Embedded image (Wherein, R ⁴ , R ⁵ , R ⁶ , q and X each have the same meaning as described above), and especially when the repeating unit has a quaternary ammonium salt in the side group. The following general formula (3)

Embedded image (Wherein, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , r, and X each have the same meaning as described above). An amino polymer compound in which the group is composed of a constituent unit having an aromatic group and the other terminal group is composed of a constituent unit having a carboxyl group or its ester group is preferred. The repeating units (1) to (3) have at least one kind, and the composition ratio of each repeating unit is from 0 to 0.
The range may be 100%, and the structures of the repeating units may be different in the same molecule or may be the same. Further, these may be random copolymerization or block polymerization.

[0014] Further, for the purpose of adjusting the cationic strength and the like, other repeating units may be contained. Specific examples of the other repeating units include the following repeating units (6) to (11). Is shown. However, in the formula, R ¹⁶ represents a hydrogen atom or a methyl group, and R ¹⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

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[0015]

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Embedded image These may be random copolymers or block copolymers.

The terminal group consisting of the structural unit having an aromatic group is not particularly limited. Examples of the aromatic group include a substituted or unsubstituted phenyl group or a naphthyl group,
Preferably, a structural unit having a substituted or unsubstituted phenyl group is preferred. The unit molecular weight is preferably 500 or less, and specifically, the following (12) to (2)
The structural unit shown in 3) is exemplified.

[0017]

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[0018]

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[0019]

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[0020]

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The terminal group comprising a structural unit having a carboxyl group or its ester group is not particularly limited. The molecular weight is preferably 500 or less, and specific examples include the structural units shown in the following (24) to (29).

[0022]

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[0023]

Embedded image _{-S-CH 2 CH 2 COOH (} 28) -S-CH 2 CH 2 COOC 2 H 5 (29)

The amino polymer compound preferably has a number average molecular weight (hereinafter abbreviated as Mn) of 1,000 to 10,000. Mn shown here indicates a value determined by gel permeation chromatography (hereinafter abbreviated as GPC). The method of measuring the hydrogen ion concentration index (pH) is not particularly limited, but a method of measuring the pH using a commercially available pH measuring device is simple. A pH measuring device using a glass electrode pH meter is often used. The measurement is usually
The reaction is carried out in an aqueous solution at normal pressure and 25 ° C.

Next, a method for producing the amino polymer compound of the present invention will be described. The method for producing the amino polymer compound of the present invention includes the following two methods (A) and (B). First, the method (A) is a method in which a monomer having a radical polymerizable ethylenically unsaturated group and an amino group is (co) polymerized with a specific polymerization initiator in the presence of a specific chain transfer agent. The above monomer has an amino group as a tertiary amino group,
It has at least one kind of quaternary ammonium salt or quaternary ammonium salt. At this time, when it is desired to introduce a tertiary amino group, a tertiary ammonium salt or a quaternary ammonium salt into the side group of the repeating unit of the amino polymer compound, a radical polymerizable ethylenically unsaturated group and It is only necessary to copolymerize a monomer having an amino group with a desired composition ratio.

Further, a tertiary ammonium salt and / or a quaternary ammonium salt can be introduced into the polymer by the following method (C). That is, the method of (C)
A method in which a tertiary amino group is introduced into a side group of a repeating unit by the method (A) to add an acid to convert the tertiary amino group into a tertiary ammonium salt and / or a quaternizing agent And converting the tertiary amino group into a quaternary ammonium salt, wherein the tertiary amino group can be reacted simultaneously or separately with the acid and the quaternizing agent.
The ratio of the quaternary ammonium salt and / or the quaternary ammonium salt can be adjusted by the amounts of the acid and the quaternizing agent, respectively.

Further, the method (A) includes two methods (A-1) and (A-2) by combining a chain transfer agent and a polymerization initiator. That is, the method (A-1) uses a chain transfer agent having at least one aromatic group in a molecule and a polymerization initiator having a carboxyl group or an ester group thereof, and the method (A-2) The method uses a chain transfer agent having a carboxyl group or its ester group, and a polymerization initiator having an aromatic group.

The method (B) is a method in which a desired terminal group structure is introduced using a terminal reactive group of a reactive polymer having an amino group in a side group of a repeating unit. Is a combination of terminal reactive groups (B-1) and (B-
There are two methods 2). That is, (B-1)
In the method, one end group is composed of a constituent unit having a reactive group, the other terminal group is a reactive polymer consisting of a constituent unit having a carboxyl group or an ester group thereof, and an aromatic group in the molecule at least The method (B-2) is a method of reacting a compound having one or more compounds. One of the terminal groups is composed of a constituent unit having a reactive group, and the other terminal group is composed of a constituent unit having an aromatic group. In this method, a reactive polymer is reacted with a compound having at least one carboxyl group or its ester group in the molecule.

The reactive polymer used in the methods (B-1) and (B-2) is not particularly limited, but can be obtained, for example, by the following method. First, the reactive polymer shown in the production method (B-1) includes two of (B-1-1) and (B-1-2).
It can be synthesized by the following methods. In the method (B-1-1), a monomer having a radically polymerizable ethylenically unsaturated group and an amino group is prepared in the presence of a chain transfer agent having at least one reactive group in the molecule. This is a method of (co) polymerization with a polymerization initiator having a carboxyl group or its ester group, and the method (B-1-2) is a method in which radical polymerization is carried out in the presence of a chain transfer agent having a carboxyl group or its ester group. This is a method of (co) polymerizing a monomer having a functional ethylenically unsaturated group and an amino group with a polymerization initiator having at least one reactive group in a molecule.

Next, the reactive polymer shown in the production method (B-2) can be synthesized by two methods (B-2-1) and (B-2-2). In the method (B-2-1), a monomer having a radically polymerizable ethylenically unsaturated group and an amino group is prepared in the presence of a chain transfer agent having at least one reactive group in a molecule. Polymerization initiator with aromatic group (co)
The method (B-2-2) is a method of polymerizing a radically polymerizable ethylenically unsaturated group and an amino group in the presence of a chain transfer agent having at least one aromatic group in the molecule. This is a method of (co) polymerizing a monomer having the same with a polymerization initiator having a reactive group.

Here, (B-1-1), (B-1-
2), the monomer used in the method (B-2-1) or the method (B-2-2) is such that the amino group is at least one of a tertiary amino group, a tertiary ammonium salt and a quaternary ammonium salt. Have. At this time, the third group is added to the side group of the repeating unit of the reactive polymer.
When it is desired to introduce two or more of a quaternary amino group, a tertiary ammonium salt and a quaternary ammonium salt, a composition having a monomer having a radically polymerizable ethylenically unsaturated group and a target amino group is desired. What is necessary is just to copolymerize in a ratio. Further, according to the method (C), part or all of the tertiary amino groups of the reactive polymer may be converted into a tertiary ammonium salt and / or a quaternary ammonium salt.

Further, (A-1), (A-2), (B-1)
-1), (B-1-2), (B-2-1), (B-2-
When the polymer is obtained by each method of 2), another monomer having a radically polymerizable ethylenically unsaturated group may be copolymerized for the purpose of adjusting the cationic strength or the like.

Hereinafter, each of the manufacturing methods will be described in more detail. The monomer having a radical polymerizable ethylenically unsaturated group and a tertiary amino group is represented by the following general formula (30)

Embedded image It is represented by Here, it is particularly preferable that both R ¹ and R ² are a methyl group having 1 carbon atom and p is 3.

Radical polymerizable ethylenically unsaturated groups and tertiary
The monomer having a quaternary ammonium salt is represented by the following general formula (3)
1)

Embedded image It is represented by Here, it is particularly preferable that both R ⁴ and R ⁵ are a methyl group having 1 carbon atom and q is 3.

Radical polymerizable ethylenically unsaturated groups and quaternary
The monomer having a quaternary ammonium salt is represented by the following general formula (3)
2)

Embedded image It is represented by Here, it is particularly preferable that both R ⁷ and R ⁸ are a methyl group having 1 carbon atom and r is 3.

As the monomers (30) to (32), the same compound may be used, or a plurality of kinds may be used as a mixture at an arbitrary ratio. In the method based on the copolymerization of the method (A), the ratio of the monomers (30) to (32) depends on the polymerization reactivity of the monomers. It must be prepared so that the composition ratio can be obtained in the desired ratio. However, when the methods (A) and (C) are combined, the acid and / or
Alternatively, by adjusting the addition amount of the quaternizing agent, a tertiary amino group of a repeating unit side group of the amino polymer compound,
The ratio between the tertiary ammonium salt and the quaternary ammonium salt can be adjusted.

The chain transfer agent having at least one aromatic group in the molecule is not particularly limited as long as it has the characteristic group. Examples of the aromatic group include a substituted or unsubstituted phenyl group or a naphthyl group, and a compound having a substituted or unsubstituted phenyl group is preferable. For example, benzyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene and the like can be mentioned. These chain transfer agents can be used alone or in combination of two or more kinds at an arbitrary ratio.

The polymerization initiator having a carboxyl group or its ester group is not particularly limited as long as it has the characteristic group, and may have a substituent. For example, dimethyl 2,2′-azobis (2-methylpropionate),
4,4'-azobis (4-cyanopentanoic acid), 2,
2'-azobis [N- (2-carboxyethyl) -2-
Methylpropionamidine]. These polymerization initiators can be used alone or in combination of two or more at an arbitrary ratio.

The chain transfer agent having a carboxyl group or its ester group is not particularly limited as long as it has the characteristic group, and may have a substituent. For example, thioglycolic acid, 3-mercaptopropionic acid, their esters, etc. are mentioned. These chain transfer agents can be used alone or in combination of two or more kinds at an arbitrary ratio.

The polymerization initiator having an aromatic group is not particularly limited as long as it has the characteristic group. Examples of the aromatic group include a substituted or unsubstituted phenyl group or a naphthyl group, and a compound having a substituted or unsubstituted phenyl group is preferable. For example, 1,1′-azobis (1-acetoxy-1-phenylethane), 2,
2′-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2′-azobis [N- (4-
Chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [N- (4-hydroxyphenyl) -2-methylpropionamidine] dihydrochloride,
2,2′-azobis [2-methyl-N- (2-phenylmethyl) -propionamidine] dihydrochloride and the like. These polymerization initiators can be used alone or in combination of two or more at an arbitrary ratio.

The reaction used in the polymer reaction shown in the production methods (B-1) and (B-2) is not particularly limited, but a reaction between a hydroxyl group and an isocyanate group, a reaction between a hydroxyl group and an epoxy group, A preferred example is a reaction between a secondary amino group and a carboxyl group. The reaction between a hydroxyl group and an isocyanate group is particularly preferred because the reaction is easy. At this time, examples of the terminal reactive group of the reactive polymer include a hydroxyl group, a primary amino group, a secondary amino group, and a carboxyl group.

For these polymer reactions, conditions suitable for each reaction can be freely selected from conventionally known methods. Further, it is preferable to carry out the reaction in a solution in order to simplify the reaction operation and to smoothly carry out the reaction. A reaction solvent which is substantially inert to the raw materials during the reaction and which can dissolve or disperse these raw materials can be appropriately selected from conventionally known ones. For example, esters such as ethyl acetate, butyl acetate and amyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane, N, N-dimethylformamide , N-methylformamide, N, N-
Diethylformamide, N-methylacetamide, N,
Amides such as N-dimethylacetamide and N-methylpropionamide; pyrrolidones such as 1-methyl-2-pyrrolidone, 2-pyrrolidone and ε-caprolactam; aromatic hydrocarbons such as benzene, toluene and xylene;
Examples thereof include aliphatic hydrocarbons such as pentane, n-hexane, and cyclohexane, and halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride. These solvents may be used as a mixture of two or more kinds at an arbitrary ratio.

The reactive group of the compound having at least one aromatic group in the molecule shown in the production method (B-1) is
It is selected according to the reactive group of the reactive polymer that reacts with it. When the reactive group on the polymer side is a hydroxyl group, an isocyanate group can be mentioned, and examples of the compound include benzyl isocyanate. The reactive group on the polymer side is a primary amino group or a secondary amino group. In the case of (a), an isocyanate group or an epoxy group is mentioned, and examples of the compound include benzyl isocyanate and 1,2-epoxy-3-phenoxypropane. When the reactive group on the polymer side is a carboxyl group, a primary amino group is mentioned, and examples of the compound include benzylamine.

The reactive group of the compound having at least one carboxyl group or its ester group in the molecule shown in the production method (B-2) is selected depending on the reactive group of the reactive polymer which reacts with the compound. When the reactive group on the polymer side is a hydroxyl group, an isocyanate group is exemplified, and examples of the compound include ethyl isocyanatoacetate. When the reactive group on the polymer side is a primary amino group or a secondary amino group, examples thereof include an isocyanate group and an epoxy group, and examples of the compound include ethyl isocyanatoacetate. When the reactive group on the polymer side is a carboxyl group, a primary amino group is exemplified, and examples of the compound include β-alanine ethyl ester.

The chain transfer agent having at least one reactive group in the molecule is not particularly limited as long as it has reactivity such as a hydroxyl group, a primary amino group, a carboxyl group and the like and can be used as a chain transfer agent. For example, thioglycerol, 2
Mercaptoethanol, thioglycolic acid, 3-mercaptopropionic acid and the like can be mentioned.

The polymerization initiator having at least one reactive group in the molecule is not particularly limited as long as it has reactivity such as a hydroxyl group, a primary amino group and a carboxyl group and can be used as a polymerization initiator. For example, 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis [N-
(2-carboxyethyl) -2-methylpropionamidine], 2,2′-azobis {2-methyl-N- [1,
1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- (2-hydroxybutyl) -propionamide}, 2,2′-azobis {2- Methyl-N- (2-hydroxyethyl) -propionamide {2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2, 2 '
-Azobis (2-methylpropionamidine) dihydrochloride and the like.

The other monomer having a radically polymerizable ethylenically unsaturated group is not particularly limited as long as it can be copolymerized with the aforementioned monomer having a radically polymerizable unsaturated group and an amino group. Specifically, monomers represented by the following (33) to (38) can be mentioned. However, R ¹⁶ and R ¹⁷ represent the same meaning as described above.

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[0048]

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Embedded image These monomers (33) to (38) may use the same compound, or may mix and use a plurality of kinds at an arbitrary ratio.

In the above method (C), an organic acid or an inorganic acid is used as an acid used for converting a tertiary amino group into a tertiary ammonium salt. As the organic acid, for example,
Acetic acid, propionic acid, lactic acid and the like can be mentioned, and inorganic acids include, for example, hydrochloric acid, sulfuric acid, nitric acid and the like. Known conditions can be used for the reaction, and these acids may be used as a mixture of two or more kinds at an arbitrary ratio.

In the method (C), the quaternary amino group used to convert a tertiary amino group to a quaternary ammonium salt is used.
As the grading agent, alkyl halides having 1 to 22 carbon atoms, halogenated fluorine-substituted alkyls, aralkyl halides, sulfates, sodium chloroacetate, propane sultone, and the like can be used, and the reaction is performed under known conditions. Can be. Examples of the alkyl halide include methyl chloride, 1-chloropropane, 1-chlorooctane, 1
-Chlorododecane and the like. As the halogenated fluorine-substituted alkyl, for example, 2- (perfluorobutyl)
Ethyl iodide, 1H, 1H, 5H-octafluoropentyl iodide and the like can be mentioned. Examples of the aralkyl halide include benzyl chloride and 3-phenylpropyl chloride. Examples of the sulfate include dimethyl sulfate and diethyl sulfate. As the quaternizing agent, the same compound may be used, or a plurality of types may be mixed and used at an arbitrary ratio. Also,
When the quaternizing agents react with each other, they may be reacted in multiple stages without mixing.

Production methods (A-1), (A-2), (B-
1-1), (B-1-2), (B-2-1), (B-2)
The method for producing a polymer described in -2) can be performed by a known radical polymerization method. That is, polymerization is carried out by blending a monomer, a polymerization initiator and a chain transfer agent selected under the conditions described above.

For the purpose of lowering the concentration of the reaction residue, for example, the same or different polymerization initiators may be added during the reaction. The amount of addition is 0.1 to the monomer.
1-60% by weight is preferred. The reaction can be performed at normal pressure. Since the reaction is a radical reaction, the reaction is preferably performed in an inert atmosphere (eg, nitrogen, argon, or the like). The reaction temperature is not particularly limited, but may be any temperature at which the polymerization initiator is decomposed, and is usually preferably in the range of 40 to 180 ° C., and may be a method in which the temperature is increased stepwise from a low temperature to a high temperature. When the reaction temperature is lower than 40 ° C., a long time is required for the reaction. When the reaction temperature is higher than 180 ° C., the solvent which can be used is limited. Although the reaction time is not particularly limited, it can be usually performed in the range of 1 to 36 hours.

The polymerization reaction is preferably carried out in a solution for reasons such as simplicity of operation and smoother reaction. The polymerization solvent is substantially inert to the raw materials during the polymerization reaction, and those capable of dissolving or dispersing these raw materials can be appropriately selected from conventionally known ones and used. In addition to the solvents that can be used, methanol, ethanol, isopropanol, butanol, 1,
Alcohols such as 2,6-hexanetriol and glycerin, glycols such as ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol, triethylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol and polyethylene glycol, 2-methoxy Ethanol, 2
-Ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-propoxyethanol, 2-butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, 1-methoxy-2-propanol, Glycol ethers such as 1-ethoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, water and the like are exemplified. These solvents may be used as a mixture of two or more kinds at an arbitrary ratio. However, the production methods (B-1) and (B-
In 2), when a solvent that inhibits the polymer reaction after polymerization is used, it may be replaced with a solvent that does not inhibit the polymer reaction after polymerization. Performing the polymerization reaction with a solvent that does not inhibit the polymerization reaction is convenient and preferable as a production method since it becomes possible to carry out a polymer reaction directly after the polymerization reaction without solvent replacement.

The mixing ratio of the solvent is not particularly limited, and an appropriate ratio may be selected depending on the viscosity and solubility of the obtained polymer and raw materials. Usually 1 to 95
The amount is about 30% by weight, but is preferably 30 to 90% by weight from the viewpoint of the operability of the reaction and the ease of handling of the purification of the product.

The method for adjusting the molecular weight is not particularly limited, but a method for adjusting the amount of the polymerization initiator or the amount of the chain transfer agent can be used. It is advisable to add a large amount to lower the molecular weight, and to add a small amount to increase the molecular weight.
The amount of the chain transfer agent varies depending on the difference in the polymerizability and copolymerizability of the raw material monomers and the content of the polymerization initiator, but is preferably in the range of 0.1 to 60% by weight based on the monomers. . The obtained polymer can be purified by a known method such as solvent evaporation, column chromatography, reprecipitation, or dialysis, if necessary. Depending on the use of the additive, it may be used as a reaction solvent mixture, or may be used after concentration or dilution to adjust the concentration.

[0056]

The present invention will be described in more detail with reference to the following Examples, but the present invention is not limited to these Examples. Example 1 15.0 g of N, N-dimethylaminopropylacrylamide was placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser.
2,4-diphenyl-4-methyl-1-pentene was added to 0.1.
After charging 57 g and 20.0 g of n-butyl acetate, 20.0 g of n-butyl acetate in which 0.44 g of dimethyl 2,2′-azobis (2-methylpropionate) was dissolved was added, and the mixture was stirred under a nitrogen atmosphere. The temperature was raised to 95 ° C. for 4 hours, and the temperature was raised to 95 ° C., and the reaction was continued for another 2 hours. After cooling to room temperature, about 56 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methyl ethyl ketone, and reprecipitation was repeated with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 13.0 g.
Was obtained. As a result of GPC measurement of the product, it was confirmed that the weight average molecular weight was 9400 and the number average molecular weight was 5100 in terms of polyethylene glycol. Also, ¹³ C
From the analysis results of -NMR and ¹ H-NMR, it was found that the ratio of the aromatic ring (benzene ring) to the N, N-dimethylaminopropylamide structure and the methyl ester was about 2.1: 100: 2.4. Further, the pH of the 40 wt% aqueous solution was measured and found to be 10.4.

Example 2 The reaction and purification were carried out in the same manner as in Example 1 except that the amount of 2,4-diphenyl-4-methyl-1-pentene was changed to 1.13 g. The yield after drying was 12.2 g. As a result of GPC measurement of the product,
The weight average molecular weight is 460 in terms of polyethylene glycol.
0, it was confirmed that the number average molecular weight was 2,700. From the analysis results of ¹³ C-NMR and ¹ H-NMR, the ratio of aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure and methyl ester was about 4.1: 100:
It turned out to be 4.5. Further, the pH of the 40 wt% aqueous solution was measured and found to be 10.4.

Example 3 11.8 g of N, N-dimethylaminopropylacrylamide and N- (1,1-dimethyl) were placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. 3.2 g of -3-oxobutyl) acrylamide and 2,4-diphenyl-
After charging 0.56 g of 4-methyl-1-pentene and 20.0 g of n-butyl acetate, n-butyl acetate 20 in which 0.44 g of dimethyl 2,2′-azobis (2-methylpropionate) was dissolved was added. After adding 2.0 g, the temperature was increased while stirring under a nitrogen atmosphere and maintained at 80 ° C. for 4 hours, and then the temperature was increased to 95 ° C. and the reaction was continued for 2 hours. After cooling to room temperature, about 5
6 g of a pale yellow clear solution was obtained. The solvent was distilled off under reduced pressure, the residue was dissolved in acetone, and reprecipitation was repeated in an acetone-hexane system, and the precipitate was dried to obtain 12.5 g of a solid. G
As a result of PC measurement, it was confirmed that the weight average molecular weight was 9300 and the number average molecular weight was 5000 in terms of polyethylene glycol. From the results of ¹³ C-NMR and ¹ H-NMR analysis, the aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure, N- (1,1-dimethyl-3-
The ratio of the oxobutyl) amide structure and the methyl ester was found to be about 2.0: 83: 17: 2.4. When the pH of the 40 wt% aqueous solution was measured,
It was one.

Example 4 15.0 g of N, N-dimethylaminopropyl methacrylamide and 2,4-diphenyl-4 were placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. -Methyl-1-
After charging 0.83 g of pentene and 20.0 g of n-butyl acetate, 20.0 g of n-butyl acetate in which 0.41 g of dimethyl 2,2′-azobis (2-methylpropionate) was dissolved was added, and nitrogen was added. After the temperature was raised while stirring under an atmosphere and kept at 80 ° C. for 4 hours, the temperature was raised to 95 ° C. and the reaction was continued for another 2 hours. After cooling to room temperature, about 56 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 12.9 g of a solid content. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 7000 and the number average molecular weight was 4000 in terms of polyethylene glycol. Also, ¹³ C-NMR and ¹ H-NMR
As a result, it was found that the ratio of the aromatic ring (benzene ring) to the N, N-dimethylaminopropylamide structure and the methyl ester was about 3.0: 100: 3.3. When the pH of the 40 wt% aqueous solution was measured,
It was 3.

Example 5 A 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 5.0 g of the product obtained in Example 2 dissolved in 10.0 g of water. The temperature was raised while stirring under a nitrogen atmosphere and maintained at 80 ° C. for 10 hours, and then cooled to room temperature to obtain about 15 g of a pale yellow transparent solution. The solvent was distilled off under reduced pressure, re-dissolved in methyl ethyl ketone, and re-precipitated repeatedly in a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 4.8 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 4600 in terms of polyethylene glycol, and the number average molecular weight was 27.
00 was confirmed. In addition, ¹³ C-NMR and ¹ H
-NMR analysis results indicate aromatic rings (benzene rings), N, N
Dimethylaminopropylamide structure, the ratio of methyl ester to carboxyl groups is about 4.1: 100: 1.3:
It turned out to be 3.2. The pH of the 40 wt% aqueous solution was measured and found to be 10.2.

Example 6 In a 200 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 15.0 g of N, N-dimethylaminopropylacrylamide and 0.1% of 3-mercaptopropionic acid were added. 50
g, 60.0 g of n-butyl acetate, and
2.00 g of 1'-azobis (1-acetoxy-1-phenylethane) was added and dissolved by stirring. The temperature was raised while stirring under a nitrogen atmosphere and maintained at 80 ° C. for 4 hours, and then the temperature was raised to 95 ° C. and the reaction was continued for another 2 hours. After cooling to room temperature, about 77 g of a pale yellow solution was obtained. 12. The solvent is distilled off under reduced pressure, the remaining highly viscous liquid is dissolved in acetone, and reprecipitation is repeated with an acetone-hexane system, and the precipitate is dried.
5 g of solids were obtained. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 6000 and the number average molecular weight was 2200 in terms of polyethylene glycol. Also, ¹³ C-NM
From the analysis results of R and ¹ H-NMR, the aromatic ring (benzene ring)
The ratio of the N, N-dimethylaminopropylamide structure to the carboxyl group was found to be about 5.5: 100: 5.0. The pH of the 40 wt% aqueous solution was measured and found to be 10.2.

Example 7 15.0 g of N, N-dimethylaminopropylacrylamide and 0.41 g of 2-mercaptoethanol were placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube. ,
After charging 20.0 g of n-butyl acetate, dimethyl 2,2′-azobis (2-methylpropionate) 1.
After adding 20.0 g of n-butyl acetate in which 30 g was dissolved, the temperature was raised while stirring under a nitrogen atmosphere, and the temperature was maintained at 80 ° C. for 4 hours. Then, the temperature was raised to 95 ° C., and the reaction was continued for another 2 hours. After cooling to room temperature, 2.40 g of benzyl isocyanate was gradually added to this solution with stirring, and after adding the whole amount, the temperature was raised to 80 ° C.
After cooling to room temperature for 6 hours, about 58 g of a yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 13.4 g of a solid content. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 7100 and the number average molecular weight was 3000 in terms of polyethylene glycol. Also, ¹³ C-NMR and ¹ H-NMR
As a result, the ratio of the aromatic ring (benzene ring) to the N, N-dimethylaminopropylamide structure and the methyl ester was found to be about 3.6: 100: 4.1. When the pH of the 40 wt% aqueous solution was measured,
It was 4.

Example 8 In a 200 ml flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser, 15.0 g of N, N-dimethylaminopropylacrylamide and 0-ethyl ethyl 3-mercaptopropionate were added. .
After charging 73 g and methanol 20.0 g, 2,
60.0 g of methanol in which 1.65 g of 2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] was dissolved was added, and the temperature was gradually increased while stirring under a nitrogen atmosphere, and the temperature was increased to 12 at reflux temperature. After keeping for a time, it was cooled to room temperature. The solvent was distilled off under reduced pressure, and methyl ethyl ketone 40
g, and the solvent was again distilled off. The remaining highly viscous liquid was dissolved in 40 g of methyl ethyl ketone. Add 1,2
1.8 g of -epoxy-3-phenoxypropane was gradually added, and after the whole amount was added, the temperature was raised and maintained at 80 ° C for 6 hours, followed by cooling to room temperature to obtain about 60 g of a yellow transparent solution. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 14.5 g of a solid content. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 5800 and the number average molecular weight was 2000 in terms of polyethylene glycol. From the analysis results of ¹³ C-NMR and ¹ H-NMR, the ratio of the aromatic ring (benzene ring), the N, N-dimethylaminopropylamide structure and the ethyl ester was about 6.1: 10
0: 5.5 was found. Further, the pH of the 40 wt% aqueous solution was measured and found to be 10.4.

Example 9 15.0 g of N, N-dimethylaminopropylacrylamide and 0.41 g of 2-mercaptoethanol were placed in a 200 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. ,
After charging 60.0 g of n-butyl acetate, 1,1′-
Azobis (1-acetoxy-1-phenylethane) 2.
Then, 00 g was added and dissolved by stirring. The temperature was raised while stirring under a nitrogen atmosphere and kept at 80 ° C. for 4 hours, and then the temperature was raised to 95 ° C. and the reaction was continued for 2 hours. After cooling to room temperature, 0.70 g of ethyl isocyanatoacetate was gradually added to this solution with stirring, the whole amount was added, the temperature was raised, the temperature was maintained at 80 ° C. for 6 hours, and the mixture was cooled to room temperature to obtain about 78 g of a yellow transparent solution. . The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 12.7 g of a solid content. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 7000 and the number average molecular weight was 3000 in terms of polyethylene glycol. From the analysis results of ¹³ C-NMR and ¹ H-NMR, the ratio of the aromatic ring (benzene ring), the N, N-dimethylaminopropylamide structure and the ethyl ester was 4.1: 10.
0: 3.6 was found. Further, the pH of the 40 wt% aqueous solution was measured and found to be 10.6.

Example 10 In a 200 ml flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser, 15.0 g of N, N-dimethylaminopropylacrylamide and 2,4-diphenyl-4-methyl-4-acrylamide were added. After charging 1.20 g of methyl-1-pentene and 70.0 g of methanol, 1.65 g of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] was charged and dissolved by stirring. did. The temperature was gradually raised with stirring under a nitrogen atmosphere, kept at the reflux temperature for 12 hours, and then cooled to room temperature. The solvent was distilled off under reduced pressure, 40 g of methyl ethyl ketone was added, the solvent was again distilled off, and the remaining highly viscous liquid was dissolved in 40 g of methyl ethyl ketone. To this solution, 1.60 g of ethyl isocyanatoacetate was gradually added, and after adding the whole amount, the temperature was raised and maintained at 80 ° C. for 6 hours, followed by cooling to room temperature to obtain about 60 g of a yellow transparent solution. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and re-precipitation was repeated three times with an acetone-hexane system.
g of solids were obtained. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 5900 and the number average molecular weight was 2200 in terms of polyethylene glycol. In addition, ¹³ C-NMR
From the results of ¹ H-NMR analysis, it was found that the ratio of the aromatic ring (benzene ring) to the N, N-dimethylaminopropylamide structure and ethyl ester was about 5.0: 100: 5.5. Further, the pH of the 40 wt% aqueous solution was measured and found to be 10.6.

Example 11 A 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube was charged with 14.0 g of N, N-dimethylaminopropylacrylamide and 75 wt% of trimethylaminopropylacrylamide chloride. 1.3 g of an aqueous solution, 0.90 g of 2,4-diphenyl-4-methyl-1-pentene, N, N-
After charging 20.0 g of dimethylformamide, dimethyl 2,2′-azobis (2-methylpropionate) was added.
1.09 g dissolved N, N-dimethylformamide 2
0.0 g was added, and the temperature was increased while stirring under a nitrogen atmosphere.
After maintaining at 0 ° C for 4 hours, the temperature was raised to 95 ° C and the reaction was continued for another 2 hours. After cooling to room temperature, about 57 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, and the remaining highly viscous liquid was dissolved in methyl ethyl ketone.
Repeat the reprecipitation with hexane, and dry the precipitate
2.3 g of solid was obtained. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 4,200 and the number average molecular weight was 2,800 in terms of polyethylene glycol. In addition, ¹³ C-
From the analysis results of NMR and ¹ H-NMR, the ratio of aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure, trimethylaminopropylamide chloride structure, and methyl ester was about 4.1: 93: 7.0: It turned out to be 4.5. Further, the pH of the 40 wt% aqueous solution was measured and found to be 10.3.

Example 12 2,4-Diphenyl-4-
Methyl-1-pentene was converted to benzyl mercaptan 0.45.
The reaction and purification were carried out in the same manner as in Example 11 except that g was changed to g. The yield after drying was 12.1 g. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 4000 and the number average molecular weight was 2700 in terms of polyethylene glycol. From the results of ¹³ C-NMR and ¹ H-NMR analysis, the ratio of aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure, trimethylaminopropylamide structure, and methyl ester was about 4.0: 93. : 7.0:
It turned out to be 4.5. Further, the pH of the 40 wt% aqueous solution was measured and found to be 10.3.

(Example 13) The same as Example 11 except that dimethyl 2,2'-azobis (2-methylpropionate) was changed to 1.60 g of 4,4'-azobis (4-cyanopentanoic acid). The reaction and purification were carried out. The yield after drying was 12.5 g. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 6000 and the number average molecular weight was 2200 in terms of polyethylene glycol. Also, ¹³ C-N
From the analysis results of MR and ¹ H-NMR, the ratio of the aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure, trimethylaminopropylamide chloride structure, and carboxyl group was about 5.0: 93: 7.0: It turned out to be 5.4. The pH of the 40 wt% aqueous solution was measured and found to be 10.1.

Example 14 Dimethyl 2,2'-azobis (2-methylpropionate) was added to 2.00 g of 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine]. The reaction and purification were carried out in the same manner as in Example 11, except for the change. The yield after drying is 13.5 g
Met. As a result of GPC measurement, the weight average molecular weight was 4500 and the number average molecular weight was 220 in terms of polyethylene glycol.
It was confirmed to be 0. In addition, ¹³ C-NMR and ¹ H-
From the NMR analysis results, the aromatic ring (benzene ring), N, N-
The ratio of the dimethylaminopropylamide structure, trimethylaminopropylamide chloride structure, and carboxyl group was found to be about 5.0: 93: 7.0: 5.3.
When the pH of the 40 wt% aqueous solution was measured,
0.3.

Example 15 2,4-Diphenyl-4-
1. methyl-1-pentene was added to 0.50 g of 3-mercaptopropionic acid, and dimethyl 2,2′-azobis (2-methylpropionate) was 1,1′-azobis (1-acetoxy-1-phenylethane). The reaction and purification were carried out in the same manner as in Example 11 except that the amount was changed to 0 g. The yield after drying was 12.6 g. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 6100 and the number average molecular weight was 2600 in terms of polyethylene glycol. Also, ¹³ C-N
From the results of MR and ¹ H-NMR analysis, the ratio of the aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure, trimethylaminopropylamide chloride structure, and carboxyl group was about 4.3: 93: 7.0: It turned out to be 3.9. Further, the pH of the 40 wt% aqueous solution was measured and found to be 10.3.

Example 16 12.7 g of N, N-dimethylaminopropylacrylamide and 75 wt% of trimethylaminopropylacrylamide chloride were placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. 1.30 g of aqueous solution, 1.35 g of acryloylmorpholine, 0.11 g of 2,4-diphenyl-4-methyl-1-pentene, 1,3-dimethyl-2
After charging 20.0 g of imidazolidinone, dimethyl 2,2′-azobis (2-methylpropionate) 1.
Then, 20.0 g of 1,3-dimethyl-2-imidazolidinone in which 00 g was dissolved was added, the temperature was increased while stirring under a nitrogen atmosphere, and the temperature was maintained at 80 ° C. for 4 hours.
The reaction was continued for hours. After cooling to room temperature, about 56 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methyl ethyl ketone, and reprecipitation was repeated with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 12.0 g of a solid. As a result of GPC measurement, the weight average molecular weight was 6700 in terms of polyethylene glycol,
It was confirmed that the number average molecular weight was 3,800. Also, ¹³
According to the analysis results of C-NMR and ¹ H-NMR, the ratio of aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure, trimethylaminopropylamide chloride structure, morpholino group and methyl ester was about 3.0: 86. : 5.
0: 9.0: 3.2 was found. Also, 40
When the pH of the wt% aqueous solution was measured, it was 10.2.

Example 17 A 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with trimethylaminopropylacrylamide chloride.
20.0 g of a 5 wt% aqueous solution, 2,4-diphenyl-4
-Methyl-1-pentene (2.26 g) and N, N-dimethylformamide (20.0 g) were charged.
2'-azobis (2-methylpropionate) 1.35
g, dissolved in N, N-dimethylformamide 20.0 g
And heated to 80 ° C. while stirring under a nitrogen atmosphere.
After keeping for a time, the temperature was raised to 95 ° C., and the reaction was continued for another 2 hours. After cooling to room temperature, about 63 g of a pale yellow cloudy solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methanol, and reprecipitation was repeated with a methanol-acetone system, and the precipitate was dried to obtain 12.6 g of a solid. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 14,000 and the number average molecular weight was 5,700 in terms of polyethylene glycol. In addition, ¹³ C-NMR and ¹ H-NM
From the analysis results of R, it was found that the ratio of the aromatic ring (benzene ring), trimethylaminopropylamide chloride structure, and methyl ester was about 2.0: 100: 2.2. When the pH of the 40 wt% aqueous solution was measured, it was 9.8.
Met.

Example 18 A 1-liter flask was equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser.
440 g of propanol was charged and the temperature was raised to 80 ° C. while stirring under a nitrogen atmosphere. Here, 560 g of N, N-dimethylaminopropylacrylamide, 25.2 g of 2,4-diphenyl-4-methyl-1-pentene and 575 g of 1-propanol were mixed, and 413 g of 1-propanol and dimethyl 2,2 were added to 413 g of 1-propanol. '-Azobis (2-
Each of the polymerization initiator solutions in which 67.0 g of methyl propionate was dissolved was added over 3 hours while maintaining the solution temperature in the flask at 80 ° C. while stirring under a nitrogen atmosphere, and then the temperature was raised to 95 ° C. The reaction was continued for another 3 hours.
The mixture was cooled to 40 ° C., and 70.8 g of methyl chloride was added over 1 hour while stirring. The reaction was further continued at 40 ° C. for 2 hours, and after cooling to room temperature, about 2150 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methyl ethyl ketone, and reprecipitation was repeated with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 542 g of a solid. As a result of GPC measurement, the weight average molecular weight was 3800 in terms of polyethylene glycol, and the number average molecular weight was 2
It was confirmed to be 300. Also, ¹³ C-NMR and ¹
From the results of H-NMR analysis, the aromatic ring (benzene ring), N,
The ratio of the N-dimethylaminopropylamide structure, trimethylaminopropylamide chloride structure, and methyl ester was found to be about 4.1: 57: 43: 4.5.
When the pH of the 40 wt% aqueous solution was measured,
0.2.

Example 19 A 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 5.0 g of the product obtained in Example 1, 10.0 g of methyl ethyl ketone, methanol Dissolved at 10.0 g. While stirring this solution, benzyl chloride 1.6 was added.
2 g was added slowly. After the addition, the temperature was raised and the reaction was carried out at the reflux temperature for 8 hours. After cooling to room temperature, about 26 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the residue was dissolved in methanol, and reprecipitation was repeated with a methanol-acetone system. The precipitate was dried to obtain 5.0 g of a solid content. As a result of the GPC measurement,
The weight average molecular weight is 970 in terms of polyethylene glycol.
0, the number average molecular weight was confirmed to be 5,500. Also, the ratio of aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure, dimethylbenzylaminopropylamide structure, and methyl ester, except for those derived from benzyl chloride from the results of ¹³ C-NMR and ¹ H-NMR analyses. Was found to be about 2.1: 61: 39: 2.4.
When the pH of the 40 wt% aqueous solution was measured,
0.1.

Example 20 5.0 g of the product obtained in Example 1 was charged into a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and dissolved with 15.0 g of methyl ethyl ketone. did. While stirring this solution, 1.98 g of 3-phenylpropyl chloride was obtained.
Was slowly added. After the addition, the temperature was raised and the reaction was performed at 80 ° C. for 8 hours. After cooling to room temperature, about 22 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, dissolved in acetone, and re-precipitated repeatedly in an acetone-hexane system, and the precipitate was dried to obtain 5.3 g of a solid content. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 9500 and the number average molecular weight was 5200 in terms of polyethylene glycol. In addition, ¹³ C-
Aromatic ring (benzene ring) excluding 3-phenylpropyl chloride derived from NMR and ¹ H-NMR analysis results,
The ratio of the N, N-dimethylaminopropylamide structure, the dimethyl (3-phenylpropyl) aminopropylamide structure, and the methyl ester is about 2.1: 90: 10:
It turned out to be 2.4. The pH of the 40 wt% aqueous solution was measured and found to be 10.1.

Example 21 A 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 5.0 g of the product obtained in Example 2, and dissolved with 15.0 g of methyl ethyl ketone. I do. While the solution was being stirred, 2.63 g of 1-chlorododecane was gradually added, and the temperature was raised to 80 ° C. and reacted for 8 hours. After cooling to room temperature,
About 23 g of a pale yellow clear solution was obtained. The solvent was distilled off under reduced pressure, the residue was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 5.6 g of a solid content. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 9500 and the number average molecular weight was 5300 in terms of polyethylene glycol. Also, ¹³ C-NMR and ¹ H-NMR
According to the analysis result, the ratio of the aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure, dodecyldimethylaminopropylamide structure, and methyl ester is about 2.1: 86: 14: 2.4. Do you get it. When the pH of the 40 wt% aqueous solution was measured,
It was 3.

Example 22 A 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 5.0 g of the product obtained in Example 2, and dissolved with 15.0 g of methyl ethyl ketone. I do. While the solution was stirred, 5.0 g of 2- (perfluorobutyl) ethyl iodide was gradually added, and the temperature was raised to 80 ° C. and the reaction was performed for 8 hours. After cooling to room temperature, about 25 g of a clear yellow solution was obtained.
The solvent was distilled off under reduced pressure, dissolved in acetone, reprecipitated with acetone-hexane system repeatedly, and the precipitate was dried.
3 g of solids were obtained. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 9500 and the number average molecular weight was 5300 in terms of polyethylene glycol. Also, ¹³ C-NM
From the analysis results of R and ¹ H-NMR, the ratio of aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure, dimethyl iodide (perfluorobutylethyl) aminopropylamide structure, methyl ester was about 2.1: 9
It turned out to be 0: 10: 2.4. Also, 40w
When the pH of the t% aqueous solution was measured, it was 10.3.

Example 23 A 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 5.0 g of the product obtained in Example 3, 10.0 g of methyl ethyl ketone, methanol Dissolved at 10.0 g. While stirring this solution, benzyl chloride 3.8
1 g was gradually added, and after the addition, the temperature was raised and the reaction was carried out at reflux temperature for 8 hours. After cooling to room temperature, about 28 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, dissolved in methanol, reprecipitated repeatedly with a methanol-acetone system, and the precipitate was dried to obtain 6.6 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 950 in terms of polyethylene glycol.
0, it was confirmed that the number average molecular weight was 5,100. Further, ¹³ C-NMR and ¹ H-NMR aromatic ring (benzene ring), excluding the derived benzyl chloride The results of analysis of, N, N-dimethylaminopropyl amide structure, dimethylbenzyl aminopropyl amide structure chloride, N-(1 , 1-dimethyl-3-oxobutyl) amide structure and the ratio of methyl ester were found to be about 2.0: 4: 79: 17: 2.4. The pH of the 40 wt% aqueous solution was measured and found to be 10.0.

Example 24 5.0 g of the product obtained in Example 9 was charged into a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and dissolved with 15.0 g of methyl ethyl ketone. did. While stirring this solution, 2.63 g of 1-chlorododecane was gradually added, and the mixture was heated to 80 ° C. and reacted for 8 hours. After cooling to room temperature,
About 23 g of a pale yellow clear solution was obtained. The solvent was distilled off under reduced pressure, the residue was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 6.6 g of a solid content. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 7000 and the number average molecular weight was 3200 in terms of polyethylene glycol. Also, ¹³ C-NMR and ¹ H-NMR
According to the analysis results, the ratio of the aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure, dodecyldimethylaminopropylamide structure, and ethyl ester is about 4.1: 85: 15: 3.6. Do you get it. When the pH of the 40 wt% aqueous solution was measured,
It was 2.

Example 25 5.0 g of the product obtained in Example 10 was charged into a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and 10.0 g of methyl ethyl ketone, methanol Dissolve at 10.0 g. While stirring the solution, methyl iodide.
85 g was gradually added, the temperature was raised to 40 ° C., and the reaction was performed for 8 hours. After cooling to room temperature, about 26 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the residue was dissolved in methanol, and reprecipitation was repeated with a methanol-acetone system. The precipitate was dried to obtain 5.0 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 6,000 in terms of polyethylene glycol,
It was confirmed that the number average molecular weight was 2,400. Also, ¹³
From the results of C-NMR and ¹ H-NMR analysis, the ratio of aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure, trimethylaminopropylamide iodide structure and ethyl ester was about 4.2: 61: 39. : 4.6 was found. The pH of the 40 wt% aqueous solution was measured and found to be 10.1.

Example 26 A 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 5.0 g of the product obtained in Example 7, and dissolved with 20.0 g of methyl ethyl ketone. I do. While stirring the solution, 1.00 g of dimethyl sulfate was gradually added, and 4
The temperature was raised to 0 ° C., and the reaction was performed for 8 hours. After cooling to room temperature, about 26
g of a yellow cloudy solution was obtained. The solvent was distilled off under reduced pressure, dissolved in methanol, and reprecipitated repeatedly in a methanol-acetone system, and the precipitate was dried to obtain 4.3 g of a solid content. G
As a result of PC measurement, it was confirmed that the weight average molecular weight was 7200 and the number average molecular weight was 3300 in terms of polyethylene glycol. From the results of ¹³ C-NMR and ¹ H-NMR analysis, the ratio of aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure, monomethylsulfate trimethylaminopropylamide structure, and methyl ester was about 3.
6: 76: 24: 4.1. Also,
When the pH of the 40 wt% aqueous solution was measured, it was 10.1.

Example 27 5.0 g of the product obtained in Example 8 was charged into a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and dissolved with 15.0 g of methyl ethyl ketone. I do. While stirring this solution, 3.00 g of 1-chlorododecane was gradually added, and the temperature was raised to 80 ° C. and reacted for 8 hours. After cooling to room temperature,
About 23 g of a yellow solution was obtained. The solvent was distilled off under reduced pressure, the residue was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 5.8 g of a solid content. GP
As a result of the C measurement, it was confirmed that the weight average molecular weight was 6100 and the number average molecular weight was 2400 in terms of polyethylene glycol. From the results of ¹³ C-NMR and ¹ H-NMR analysis, the ratio of aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure, dodecyldimethylaminopropylamide structure, and ethyl ester was about 5.3: 8
It turned out to be 5: 15: 5.0. Also, 40w
When the pH of the t% aqueous solution was measured, it was 10.3.

(Effect Example) To 95 parts by weight of the solvents shown in Table 1, 5 parts by weight of the compounds obtained in Examples 1 to 27 were added, and the mixture was stirred at room temperature for 1 hour, and the solubility was evaluated by visual observation. did. As a comparative example, Sunfix 555 (cationic polymer manufactured by Sanyo Chemical Industry Co., Ltd.) was added in an amount of 5 parts by weight to 95 parts by weight of the solvent, and the solubility was similarly evaluated.

[0084]

[Table 1] (Results) The compound of this example had high solubility in general-purpose organic solvents and water, whereas the compound of the comparative example had low solubility.

[0085]

The amino polymer compound of the present invention has excellent solubility and stability and is useful as various additives. Also,
According to the production method of the present invention, the amino polymer compound can be produced easily with good yield in a short time.

Continuation of the front page (72) Inventor Hiroshi Takahashi 1-1-1, Onodai, Midori-ku, Chiba-shi, Chiba Prefecture Showa Denko KK Research Institute (72) Inventor Yoshisumi Nakamura 1-1-1, Onodai, Midori-ku, Chiba-shi, Chiba No. Showa Denko Co., Ltd. (72) Inventor Naoko Ito 1-1-1, Onodai, Midori-ku, Chiba City, Chiba Prefecture Showa Denko Co., Ltd. (72) Inventor Toshio Koshikawa 1, Onodai, Midori-ku, Chiba-shi Chome 1-1 Showa Denko KK Research Laboratory F-term (reference) 4J011 NA25 NB04 4J015 AA02 AA06 AA10 4J100 AM15Q AM17Q AM19Q AM21P AM21Q AN02Q AN04Q AQ07Q AQ08Q BA02P BA02Q BA03P BA12P BA12P BA16P BA16P BAP BAP BA39P BA46Q BA51P BA51Q BA55P BA56P BB07P BC43Q BC49Q CA01 CA04 CA31 FA03 FA04 HA61 JA11 JA13 JA18 JA61

Claims (27)

[Claims] 1. One of the terminal groups comprises a structural unit having an aromatic group, the other terminal group comprises a structural unit having a carboxyl group or an ester group thereof, and a tertiary amino group as a side group of the repeating unit. An amino polymer compound comprising at least one of a tertiary ammonium salt and a quaternary ammonium salt. 2. The following general formula (1): (Wherein, R ¹ and R ² each independently represent an alkyl group having 1 to 3 carbon atoms, and R ¹ and R ² may form a ring containing an oxygen atom having 3 to 6 carbon atoms. R ³ represents a hydrogen atom or a methyl group, and p represents an integer of 1 to 5.), a repeating unit represented by the following general formula (2): (Wherein, R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ may form a ring containing an oxygen atom having 3 to 6 carbon atoms. R ⁶ represents a hydrogen atom or a methyl group, and q represents an integer of 1 to 5.
X is halogen, R ¹¹ COO, NO ₃ , R ¹² OSO ₃ , B
Represents any one of F ₄ , wherein R ¹¹ and R ¹² each have 1 carbon atom
Represents an alkyl group of 1 to 6. ) Or the following general formula (3): (Wherein, R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 3 carbon atoms, and R ⁷ and R ⁸ may form a ring containing an oxygen atom having 3 to 6 carbon atoms. R ⁹ has 1 carbon atom
To 22 alkyl group, a fluorine-substituted alkyl group, an aralkyl group or a group represented by the general formula ^{(4) - (R 13 -Y} ) s - R 14 (4) ( wherein, R ¹³ may have a substituent Represents an alkyl group, Y is -CONH-, -NHCO-, -NHCOO-, -OCON
H-, -NHCOS-, -SCONH-, -NHCONH-, -S-,
Represents either -O- or -CO-. Also, R
¹⁴ is a carboxyl group, a hydroxyl group, a sulfonic acid group or an alkyl group having 1 to 22 carbon atoms which may have a salt thereof,
Represents a fluorine-substituted alkyl group or an aralkyl group, and s represents an integer of 1 to 5. R ¹⁰ represents a hydrogen atom or a methyl group. R represents an integer of 1 to 5;
Represents the same meaning as described above. R ⁷ , R ⁸ , R ⁹
May be the same or different. In the amino polymer compound having at least one repeating unit represented by the formula (1), one terminal group is composed of a constituent unit having an aromatic group, and the other terminal group is composed of a constituent unit having a carboxyl group or its ester group. The amino polymer compound according to claim 1. 3. The amino polymer compound according to claim 1, wherein the repeating unit is a repeating unit of the above (1) to (3), and the composition ratio of each repeating unit is in the range of 0 to 100%. . 4. The amino polymer compound according to claim 1, wherein the molecular weight of the terminal group comprising a structural unit having an aromatic group is 500 or less. 5. The amino polymer compound according to claim 1, wherein a terminal group comprising a structural unit having a carboxyl group or an ester group thereof has a molecular weight of 500 or less. 6. The amino polymer compound according to claim 1, which has a number average molecular weight of 1,000 to 10,000. 7. An aqueous solution of an amino polymer compound having a pH of 9
The amino polymer compound according to any one of claims 1 to 6, wherein 8. In the presence of a chain transfer agent having at least one aromatic group in a molecule, a monomer having a radically polymerizable ethylenically unsaturated group and an amino group is converted into a carboxyl group or an ester group thereof. (Co) with a polymerization initiator having
A method for producing an amino polymer compound, comprising polymerizing. 9. In the presence of a chain transfer agent having a carboxyl group or an ester group thereof, a monomer having a radically polymerizable ethylenically unsaturated group and an amino group is reacted with a polymerization initiator having an aromatic group ( A method for producing an amino polymer compound, which is characterized in that it is copolymerized). 10. A reaction wherein one terminal group comprises a constituent unit having a reactive group, the other terminal group comprises a constituent unit having a carboxyl group or its ester group, and wherein the repeating unit has an amino group in a side group. A method for producing an amino polymer compound, comprising reacting a hydrophilic polymer with a compound having at least one aromatic group in the molecule to introduce an aromatic group into a terminal. 11. A monomer having a radically polymerizable ethylenically unsaturated group and an amino group in the presence of a chain transfer agent in which the reactive polymer has at least one reactive group in the molecule, The method for producing an amino polymer compound according to claim 10, which is a polymer obtained by (co) polymerizing a polymerization initiator having a carboxyl group or an ester group thereof. 12. A monomer having a radically polymerizable ethylenically unsaturated group and an amino group in the presence of a chain transfer agent in which the reactive polymer has at least one carboxyl group or its ester group in the molecule. The method for producing an amino polymer compound according to claim 10, which is a polymer obtained by (co) polymerizing a polymer with a polymerization initiator having a reactive group. 13. A reactive polymer in which one terminal group comprises a constituent unit having a reactive group, the other terminal group comprises a constituent unit having an aromatic group, and wherein the repeating unit has an amino group in a side group. And a compound having at least one carboxyl group or its ester group in the molecule, and introducing a carboxyl group or its ester group into a terminal to produce an amino polymer compound. 14. A monomer having a radically polymerizable ethylenically unsaturated group and an amino group in the presence of a chain transfer agent in which the reactive polymer has at least one reactive group in the molecule. The method for producing an amino polymer compound according to claim 13, which is a polymer obtained by (co) polymerization with a polymerization initiator having an aromatic group. 15. A monomer having a radically polymerizable ethylenically unsaturated group and an amino group in the presence of a chain transfer agent in which the reactive polymer has at least one aromatic group in the molecule, The method for producing an amino polymer compound according to claim 13, which is a polymer obtained by (co) polymerization with a polymerization initiator having a reactive group. 16. The amino group according to claim 8, wherein the chain transfer agent having at least one aromatic group in the molecule is benzyl mercaptan or 2,4-diphenyl-4-methyl-1-pentene. A method for producing a molecular compound. 17. The polymerization initiator having a carboxyl group or its ester group is dimethyl 2,2′-azobis (2-methylpropionate), 4,4′-azobis (4-cyanopentanoic acid) or 2,2′-azobis (4-cyanopentanoic acid). The method for producing an amino polymer compound according to claim 8 or 11, which is 2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine]. 18. A chain transfer agent having a carboxyl group or its ester group is represented by the following general formula (5): HS- (CH ₂ ) _t —COOR ¹⁵ (5) (wherein, R ¹⁵ is a hydrogen atom or a carbon atom having 1 carbon atom). 13. The method for producing an amino polymer compound according to claim 9, wherein the compound is at least one member selected from the group consisting of an alkyl group of from 5 to 5, and t represents an integer of from 1 to 5. 19. The polymerization initiator having an aromatic group, wherein 1,
The method for producing an amino polymer compound according to claim 9 or 14, which is 1'-azobis (1-acetoxy-1-phenylethane). 20. The method according to claim 8, wherein the amino group of the monomer is a tertiary amino group, a tertiary ammonium salt and / or a quaternary ammonium salt.
6. The method for producing an amino polymer compound according to item 5. 21. The method according to claim 8, wherein the monomer is N, N-dialkylaminoalkyl (meth) acrylamide, a salt thereof and / or a quaternary salt thereof.
21. The method for producing an amino polymer compound according to 4, 15 or 20. 22. A reaction between a tertiary amino group of the amino polymer compound according to claim 8 and an acid,
A method for producing an amino polymer compound, wherein a part or all of the compound is converted into a tertiary ammonium salt. 23. The method according to claim 22, wherein the acid is an organic or inorganic acid having 1 to 6 carbon atoms. 24. A reaction of a tertiary amino group of the amino polymer compound according to any one of claims 8 to 21 with a quaternizing agent, and a part or the whole thereof is converted to a quaternary ammonium salt. A method for producing an amino polymer compound, comprising: 25. The method for producing an amino polymer compound according to claim 24, wherein the quaternizing agent is an alkyl halide having 1 to 22 carbon atoms, a halogenated fluorine-substituted alkyl, an aralkyl halide, or a sulfate. 26. A part of the tertiary amino group by reacting the tertiary amino group of the amino polymer compound according to claim 8 with an acid and a quaternizing agent simultaneously or separately. Or a method for producing an amino polymer compound, which comprises converting all of the compound into a tertiary ammonium salt and a quaternary ammonium salt. 27. The acid is an organic or inorganic acid having 1 to 6 carbon atoms, and the quaternizing agent is an alkyl halide having 1 to 22 carbon atoms, a halogenated fluorinated alkyl, an aralkyl halide or a sulfate. A method for producing the amino polymer compound according to claim 26.