JP4576815B2 - Modified polyallylamine and method for producing the same - Google Patents

Description

  The present invention relates to a modified polyallylamine and a method for producing the same. More specifically, the present invention exhibits excellent color developability, is easily dissolved in water and an organic solvent, and has good stability in a solution containing the water or the organic solvent. The present invention relates to a modified polyallylamine suitably used in the fine chemical field, and a method for efficiently producing the modified polyallylamine.

  Polyallylamine (allylamine polymer) is a linear olefin polymer having an amino group in the side chain, and is a cationic polymer compound that dissolves well in water and is positively charged in water. This polyallylamine has a unique reactive polymer structure and properties, and is therefore used in many fields such as dye fixing agents for reactive dyes, dye fixing agents for direct dyes, and additives in the inkjet recording field. Yes.

  For example, as an application of polyallylamine, there is disclosed an ink jet recording method in which a liquid composition containing polyallylamine and an organic solvent is used together with an ink composition and separately adhered to a recording medium (for example, Patent Document 1 and Patent Document). 2). In such a field, a liquid composition containing polyallylamine is used to improve the storage stability, color developability, and glossiness of a recorded product, and exhibits superior color developability and an ink composition. The liquid mixture (waste liquid) with the liquid composition is required to have good cleaning properties without staying in the cleaning cap.

JP-A-9-207424 JP-A-9-286940

  Under such circumstances, the present invention maintains a useful property of polyallylamine, has a better color developability, is easily dissolved in an organic solvent, and has good stability in an organic solvent. It is an object of the present invention to provide an allylamine polymer copolymer and a method for efficiently producing the polyallylamine polymer copolymer.

  As a result of intensive studies to develop a polyallylamine-based polymer copolymer having the above-mentioned preferable properties, the present inventors have found that a modified polyallylamine having a specific structure can meet the purpose, and It has been found that this modified polyallylamine can be efficiently produced by a specific process, and the present invention has been completed based on this finding.

［式中、Ｒ、Ｒ^１及びＲ^２は、それぞれ独立に炭素数１〜４のアルキル基、Ｘは−ＣＯＮＨ_２、―ＣＯＯＲ^３（ただし、Ｒ^３は炭素数１〜１２のアルキル基又は炭素数６〜１２のアリール基を示す。）又は−ＣＯＲ^４（ただし、Ｒ^４は炭素数１〜１２のアルキル基を示す。）、ｐ及びｒはそれぞれ独立に１以上の整数、ｑ及びｓは０又は１以上の整数を示し、ｑ／ｐは８０／２０〜０／１００、（ｐ＋ｑ）／（ｒ＋ｓ）は２０／８０〜８０／２０である。］
で表される構造を有し、重量平均分子量が２００〜８０００であることを特徴とする変性ポリアリルアミン、
（２） 一般式（Ｉ）において、ｒ／（ｒ＋ｓ）比が０．６〜１である、上記（１）に記載の変性ポリアリルアミン、
That is, the present invention
( 1 ) General formula (I)

[Wherein, R, R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, X is —CONH ₂ , —COOR ³ (where R ³ is an alkyl group having 1 to 12 carbon atoms or carbon 6 represents an aryl group having 6 to 12) or —COR ⁴ (wherein R ⁴ represents an alkyl group having 1 to 12 carbon atoms), p and r are each independently an integer of 1 or more, and q and s are 0 or 1 or more indicates an integer, q / p is 80 / 20~0 / 100, (p + q) / (r + s) is 20/80 to 80/20. ]
Modified polyallylamine have a structure represented by the weight average molecular weight is characterized 200-8000 der Rukoto,
( 2 ) The modified polyallylamine according to (1) above, wherein the general formula (I) has an r / (r + s) ratio of 0.6 to 1.

（式中、Ｒ、Ｒ^１及びＲ^２は、それぞれ独立に炭素数１〜４のアルキル基、ｐ及びｗは、それぞれ独立に１以上の整数、ｑは、０又は１以上の整数を示し、ｑ／ｐは８０／２０〜０／１００、（ｐ＋ｑ）／ｗは２０／８０〜８０／２０である。）
で表され、重量平均分子量が２００〜８０００であるＮ−アルキルジアリルアミンとアリルアミンとの共重合体に、シアン酸を作用させることを特徴とする、
一般式（Ｉ−１）

（式中、ｒは１以上の整数、ｓは０又は１以上の整数を示し、Ｒ、Ｒ^１、Ｒ^２、ｐ及びｑは前記と同じであり、ｑ／ｐは８０／２０〜０／１００、（ｐ＋ｑ）／（ｒ＋ｓ）は２０／８０〜８０／２０である。）
で表される変性ポリアリルアミンの製造方法、
( 3 ) General formula (III)

(Wherein, R, ^{R 1} and ^{R 2} each independently represent an alkyl group having 1-4 carbon atoms, p and w are each independently integer of 1 or more, q is indicates 0 or 1 or more integer Q / p is 80/20 to 0/100, and (p + q) / w is 20/80 to 80/20 .)
In expressed, the weight average molecular weight of the copolymer of Der Ru N- alkyl diallylamine and allylamine 200-8000, characterized in that the action of cyanate,
Formula (I-1)

(Wherein, r is an integer of 1 or more, s represents 0 or an integer of 1 or ^{more, R, R 1, R 2} , p and q Ri same der said, q / p is 80 / 20-0 / 100, (p + q) / (r + s) is Ru 20 / 80-80 / 20 der.)
A method for producing a modified polyallylamine represented by:

（式中、Ｒ、Ｒ^１及びＲ^２は、それぞれ独立に炭素数１〜４のアルキル基、ｐ及びｗは、それぞれ独立に１以上の整数、ｑは０又は１以上の整数を示し、ｑ／ｐは８０／２０〜０／１００、（ｐ＋ｑ）／ｗは２０／８０〜８０／２０である。）
で表され、重量平均分子量が２００〜８０００であるＮ−アルキルジアリルアミンとアリルアミンとの共重合体に、炭素数１〜１２のアルコキシカルボニル化剤又は炭素数６〜１２のアリーロキシカルボニル化剤を作用させることを特徴とする、一般式（Ｉ−２）

（式中、Ｒ^３は炭素数１〜１２のアルキル基又は炭素数６〜１２のアリール基、ｒは１以上の整数、ｓは０又は１以上の整数を示し、Ｒ、Ｒ^１、Ｒ^２、ｐ及びｑは前記と同じであり、ｑ／ｐは８０／２０〜０／１００、（ｐ＋ｑ）／（ｒ＋ｓ）は２０／８０〜８０／２０である。）
で表される変性ポリアリルアミンの製造方法、
( 4 ) General formula (III)

(Wherein, R, ^{R 1} and ^{R 2} each independently represent an alkyl group having 1 to 4 carbon atoms, p and w are each independently an integer of 1 or more, q is indicates 0 or an integer of 1 or more, q / p is 80/20 to 0/100, and (p + q) / w is 20/80 to 80/20 .)
In expressed, the copolymer of weight average molecular weight of Ru der 200-8000 N-alkyl diallylamine and allylamine, the aryloxycarbonylating agent alkoxycarbonyl agent or C6-12 having 1 to 12 carbon atoms General formula (I-2),

(In the formula, R ³ is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, r is an integer of 1 or more, s is 0 or an integer of 1 or more, and R, R ¹ , R ² , p and q Ri same der said, q / p is 80 / 20~0 / 100, (p + q) / (r + s) is Ru 20/80 to 80/20 der.)
A method for producing a modified polyallylamine represented by:

(5) alkoxycarbonyl agent or aryloxycarbonylating ^{agent, R 3 O-CO-OR} 3 ( provided that, ^{R 3} is an alkyl group or an aryl group having 6 to 12 carbon atoms having 1 to 12 carbon atoms.)
( 4 ) The method for producing a modified polyallylamine according to ( 4 ),

（式中、Ｒ、Ｒ^１及びＲ^２は、それぞれ独立に炭素数１〜４のアルキル基、ｐ及びｗは、それぞれ独立に１以上の整数、ｑは０又は１以上の整数を示し、ｑ／ｐは８０／２０〜０／１００、（ｐ＋ｑ）／ｗは２０／８０〜８０／２０である。）
で表され、重量平均分子量が２００〜８０００であるＮ−アルキルジアリルアミンとアリルアミンとの共重合体に、アルキル基の炭素数が１〜１２のアシル化剤を作用させることを特徴とする、一般式（Ｉ−３）

（式中、Ｒ^４は炭素数１〜１２のアルキル基、ｒは１以上の整数、ｓは０又は１以上の整数を示し、Ｒ、Ｒ^１、Ｒ^２、ｐ及びｑは前記と同じである。）
で表される変性ポリアリルアミンの製造方法、
( 6 ) General formula (III)

(Wherein, R, ^{R 1} and ^{R 2} each independently represent an alkyl group having 1 to 4 carbon atoms, p and w are each independently an integer of 1 or more, q is indicates 0 or an integer of 1 or more, q / p is 80/20 to 0/100, and (p + q) / w is 20/80 to 80/20 .)
In expressed, the weight average molecular weight of the copolymer of Der Ru N- alkyl diallylamine and allylamine 200-8000, carbon atoms in the alkyl group, characterized in that the action of 1 to 12 of the acylating agent, generally Formula (I-3)

Wherein R ⁴ is an alkyl group having 1 to 12 carbon atoms, r is an integer of 1 or more, s is 0 or an integer of 1 or more, and R, R ¹ , R ² , p and q are the same as above. is there.)
A method for producing a modified polyallylamine represented by:

( 7 ) The acylating agent has the general formula (IV)
(R ⁴ CO) ₂ O (IV)
(In the formula, R ⁴ represents an alkyl group having 1 to 12 carbon atoms.)
( 6 ) The method for producing a modified polyallylamine according to ( 6 ), which is a carboxylic anhydride represented by
Is to provide.

The modified polyallylamine of the present invention has color developability superior to that of conventional polyallylamine while maintaining the useful properties of polyallylamine, and is easily soluble in water and organic solvents and is stable in organic solvents. Is good.
Therefore, in the method of mixing the liquid composition and the ink composition and performing inkjet recording on the recorded matter, if the modified polyallylamine of the present invention is contained in the liquid composition, printing with good color development becomes possible, and the waste liquid is reduced. The washing operation can be easily performed without stagnation.
That is, when the modified polyallylamine of the present invention is used in such an ink jet recording method, basic performances necessary for ink jet recording such as color developability are highly imparted to the recorded matter, and the liquid composition and the ink are applied to the cleaning cap. The liquid mixture (waste liquid) with the composition is made difficult to accumulate, and a good cleaning operation that cannot be realized conventionally is made possible. The present invention can provide a very useful copolymer in the fine chemical field such as the ink jet recording field.

First, the modified polyallylamine of the present invention will be described.
As described above, the modified polyallylamine of the present invention includes a monomer unit represented by the general formula (M-1) as an essential unit, and optionally includes a monomer unit represented by the general formula (M-2), And as an essential unit, formula (M-3), general formula (M-4), general formula (M-5), general formula (M-6), general formula (M-7), general formula (M-8) ) And at least one monomer unit selected from the monomer units represented by the general formula (M-9), and optionally a monomer unit represented by the formula (M-10) Usually a random copolymer. Preferred embodiments of the modified polyallylamine of the present invention include two embodiments, modified polyallylamine I and modified polyallylamine II.

で表される構造を有する高分子共重合体、通常ランダム共重合体である。 The modified polyallylamine I of the present invention has the general formula (I)

A high molecular copolymer having a structure represented by the formula, usually a random copolymer.

In the general formula (I), ^R, R ¹ and ^{R 2} represents an alkyl group having 1 to 4 carbon atoms. The alkyl group may be linear or branched, and specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert -A butyl group is mentioned. R, R ¹ and R ² may be the same or different from each other, but as R, R ¹ and R ² , a methyl group is particularly preferable.

X represents a -CONH _2, -COOR ³ or -COR ^4. Here, R ³ represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R ⁴ represents an alkyl group having 1 to 12 carbon atoms. The alkyl group having 1 to 12 carbon atoms in R ³ may be linear or branched, but for example, having 1 to 1 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group. Four linear alkyl groups are preferred. Moreover, as a C6-C12 aryl group, a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group etc. are mentioned, for example. On the other hand, the alkyl group having 1 to 12 carbon atoms represented by R ⁴ may be either linear or branched, but for example, methyl group, ethyl group, n-propyl group, isopropyl group, n -Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-nonyl group and the like can be mentioned.

  p and r each independently represent an integer of 1 or more, and q and s each represent 0 or an integer of 1 or more. q / p is usually 90/10 to 0/100, preferably 80/20 to 0/100. The (p + q) / (r + s) ratio is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, and particularly preferably 20/80 to 80/20. Furthermore, the r / (r + s) ratio (degree of modification) is preferably 0.6 to 1 and more preferably 0.9 to 1 in terms of the solubility of the modified polyallylamine I in an organic solvent and the stability of the organic solvent solution. Preferably, substantially 1, ie 0.95-1, is particularly preferred.

  On the other hand, the weight average molecular weight is preferably 12,000 or less, more preferably 200 to 8000, and particularly preferably 300 to 5000. If the molecular weight is too large, the solubility in an organic solvent may be deteriorated, and if it is too small, the performance of a recorded matter may be deteriorated when used in an ink jet recording system. The weight average molecular weight is a value in terms of polyethylene glycol measured by gel permeation chromatography (GPC).

で表される構造を有する高分子共重合体、通常ランダム共重合体である。 On the other hand, the modified polyallylamine II of the present invention has the general formula (II)

A high molecular copolymer having a structure represented by the formula, usually a random copolymer.

In the general formula (II), ^R, R ¹ and ^{R 2} represents an alkyl group having 1 to 4 carbon atoms. This alkyl group is as described R, for R ¹ and R ² in the above modified polyallylamine I.

Y represents —CH ₂ CH (R ⁵ ) —A or —CH ₂ CH (OH) —B. First, _-CH 2 CH ^(R 5) of the Y -A described. R ⁵ represents a hydrogen atom or a methyl group. A represents —CONR ⁶ R ⁷ , —CN or —COOR ⁸ , and R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group, a keto group, or a mono (C 1-4 alkyl) amino group. , A C1-C8 alkyl group which may contain a di (C1-C4 alkyl) amino group or a tri (C1-C4 alkyl) ammonium group; R ⁶ and R ⁷ may be bonded to each other to form a piperidino group or a morpholino group together with a nitrogen atom, R ⁸ represents an alkyl group having 1 to ⁸ carbon atoms, and this alkyl group is a hydroxyl group, a keto group Group, mono (C1-C4 alkyl) amino group, di (C1-C4 alkyl) amino group or tri (C1-C4 alkyl) ammonium group may be contained.

If -A is -CONR ⁶ R _^7, as a ^{-CH 2 CH (R 5) -A} ,
_{-CH 2 CH 2 CONH 2, -CH} 2 CH 2 CONHCH 3, -CH 2 CH 2 CON (CH 3) 2, -CH 2 CH 2 CONHC 2 H 5, -CH 2 CH 2 CON (C 2 H 5) _{2, -CH 2 CH 2 CONH-} nC 3 H 7, -CH 2 CH 2 CON (nC 3 H 7) 2, -CH 2 CH 2 CONH-iC 3 H 7, -CH 2 CH 2 CONHCH 2 O-nC _{4 H 9, -CH 2 CH 2} CONHCH 2 OH, -CH 2 CH 2 CONHCH 2 CH 2 N (CH 3) 2, -CH 2 CH 2 CONHCH 2 CH 2 N (C 2 H 5) 2, -CH 2 _{CH 2 CONHCH 2 CH 2 CH 2} N (CH 3) 2, -CH 2 CH 2 CONHCH 2 CH 2 CH 2 N (C 2 H 5) 2, -CH 2 CH ₂ CONHCH ₂ CH ₂ N ⁺ (CH ₃ ) ₃ , —CH ₂ CH ₂ CONHCH ₂ CH ₂ N ⁺ (C ₂ H ₅ ) ₃ , —CH ₂ CH ₂ CONHCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) _{3 , -CH 2 CH 2 CONHCH 2 CH} 2 CH 2 N + (C 2 H 5) 3, -CH 2 CH 2 CO- morpholino _group, -CH ₂ CH ₂ CO- piperidino _group, -CH 2 _CH (CH 3) _{CONH 2, -CH 2 CH (CH} 3) CONHCH 3, -CH 2 CH (CH 3) CON (CH 3) 2, -CH 2 CH (CH 3) CONHC 2 H 5, -CH 2 CH (CH 3) _{CON (C 2 H 5) 2} , -CH 2 CH (CH 3) CONH-nC 3 H 7, -CH 2 CH (CH 3) CON (nC 3 H 7) 2, -CH 2 CH ( _{CH 3) CONH-iC 3 H} 7, -CH 2 CH (CH 3) CONHCH 2 O-nC 4 H 9, -CH 2 CH (CH 3) CONHCH 2 OH, -CH 2 CH (CH 3) CONHCH 2 CH ₂ N (CH ₃ ) ₂ , —CH ₂ CH (CH ₃ ) CONHCH ₂ CH (CH ₃ ) N (C ₂ H ₅ ) ₂ , —CH ₂ CH (CH ₃ ) CONHCH ₂ CH ₂ CH ₂ N (CH ₃ ) ₂ , —CH ₂ CH (CH ₃ ) CONHCH ₂ CH ₂ CH ₂ N (C ₂ H ₅ ) ₂ , —CH ₂ CH (CH ₃ ) CONHCH ₂ CH ₂ N ⁺ (CH ₃ ) ₃ , —CH ₂ CH ^{_{(CH 3) CONHCH 2 CH 2}} N + (C 2 H 5) 3, -CH 2 CH (CH 3) CONHCH 2 CH 2 CH 2 N + (CH 3) 3, -CH 2 CH ( _{H 3) CONHCH 2 CH 2 CH} 2 N + (C 2 H 5) 3, -CH 2 CH (CH 3) CO- morpholino _group, be exemplified a -CH 2 CH _(CH 3) CO- piperidino it can.

Also, if -A is _CN, as the ^{-CH 2 CH (R 5) -A} , can be exemplified _{-CH 2 CH 2 CN, -CH 2} CH (CH 3) CN. Furthermore, if -A is -COOR _^8, as the ^{-CH 2 CH (R 5) -A} , -CH 2 CH 2 COOCH 3, -CH 2 CH 2 COOC 2 H 5, -CH 2 CH 2 COOC 3 _{H 7, -CH 2 CH 2 COOC} 4 H 9, -CH 2 CH 2 COOCH 2 CH 2 N (CH 3) 2, -CH 2 CH 2 COOCH 2 CH 2 CH 2 N (CH 3) 2, -CH 2 _{CH 2 COOCH 2 CH 2 N (} C 2 H 5) 2, -CH 2 CH 2 COOCH 2 CH 2 CH 2 N (C 2 H 5) 2, -CH 2 CH 2 COOCH 2 CH 2 CH 2 N + (CH _{3) 3, -CH 2 CH 2} COOCH 2 CH 2 N + (C 2 H 5) 3, illustrated and _{-CH 2 CH 2 COOCH 2 CH 2} CH 2 N + (C 2 H 5) 3 Rukoto can. In the case of an ammonium quaternary salt, the counter ion can be exemplified by Cl ⁻ , Br ⁻ and I ⁻ .

Next, a description will be given _-CH 2 CH (OH) -B of Y. B represents an alkyl group having 1 to 8 carbon atoms, and this alkyl group may contain a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms or an alkenyloxy group. Examples of B include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, methoxymethyl group, ethoxymethyl group, propyloxymethyl group, butoxymethyl group, pentoxymethyl group, hydroxymethyl group, (2-propenyloxy) methyl group and the like can be mentioned.

The _{-CH 2 CH (OH) -B,} 2- hydroxypropyl, 2-hydroxybutyl group, 2-hydroxypentyl group, 2-hydroxyhexyl group, 2-hydroxy-heptyl group, 2-hydroxy-octyl group, 3- Methoxy-2-hydroxypropyl group, 3-ethoxy-2-hydroxypropyl group, 3-propoxy-2-hydroxypropyl group, 3- (isopropoxy) -2-hydroxypropyl group, 3-butoxy-2-hydroxypropyl group , 3-pentoxy-2-hydroxypropyl group, 2,3-dihydroxypropyl group, 3- (2-propenyloxy) 2-hydroxypropyl group.

  In this general formula (II), p is an integer of 1 or more, q, t, u and v are each independently 0 or an integer of 1 or more, but at least one of t and u is an integer of 1 or more. is there. q / p is usually 90/10 to 0/100, preferably 80/20 to 0/100. The (p + q) / (t + u + v) ratio is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, and particularly preferably 20/80 to 80/20. Furthermore, the (t + u) / (t + u + v) ratio (degree of modification) is preferably from 0.6 to 1, more preferably from 0.9 to 1, in view of the solubility and stability of the modified polyallylamine. 1 is particularly preferred, ie 0.95 to 1.

  On the other hand, the weight average molecular weight is preferably 12,000 or less, more preferably 200 to 8000, and particularly preferably 300 to 5000. If the molecular weight is too large, the solubility in an organic solvent may be deteriorated, and if it is too small, the performance of a recorded matter may be deteriorated when used in an ink jet recording system. The weight average molecular weight is a value in terms of polyethylene glycol measured by gel permeation chromatography (GPC).

Next, a method for producing the modified polyallylamine of the present invention will be described.
First, the modified polyallylamine I represented by the general formula (I) is represented by the general formula (I-1), the general formula (I-2), and the general formula (I-3) as follows. Modified polyallylamine can be produced.

（ｗは１以上の整数を示し、Ｒ、Ｒ^１、Ｒ^２、ｐ及びｑは前記と同じである。）
で表されるＮ−アルキルジアリルアミンとアリルアミンとの共重合体、通常ランダム共重合体（以下、原料共重合体と称すことがある。）に、Ｎ−カルバモイル化試薬のシアン酸を作用させて、一般式（Ｉ−１）

（式中、Ｒ、Ｒ^１、Ｒ^２、ｐ、ｑ、ｒ及びｓは前記と同じである。）
で表される、一級アミノ基がカルバモイル化された変性ポリアリルアミンを製造する。なお、本明細書において、Ｎ−アルキルジアリルアミンとアリルアミンとの共重合体には、Ｎ−アルキルジアリルアミンとＮ，Ｎ−ジアルキルアリルアミンとアリルアミンとの共重合体も含むものとする。 [Production of Modified Polyallylamine Represented by General Formula (I-1)]
In this case, the general formula (III)

(W represents an integer of 1 or more, and R, R ¹ , R ² , p and q are the same as described above.)
N-carbamoylating reagent cyanic acid is allowed to act on a copolymer of N-alkyldiallylamine and allylamine represented by the formula, usually a random copolymer (hereinafter sometimes referred to as a raw material copolymer), Formula (I-1)

(In the formula, R, R ¹ , R ² , p, q, r and s are the same as above.)
A modified polyallylamine in which the primary amino group is carbamoylated is produced. In the present specification, the copolymer of N-alkyldiallylamine and allylamine includes a copolymer of N-alkyldiallylamine, N, N-dialkylallylamine and allylamine.

  In the raw material represented by the general formula (III), an aqueous solution containing N-alkyldiallylamine and monoallylamine as monomers as essential components and optionally containing N, N-dialkylallylamine in the presence of a polymerization initiator is used. It can be produced by polymerization. In that case, the concentration of the total monomer is usually 10 to 80% by weight, preferably 15 to 70% by weight. As the polymerization initiator, a compound having a water-soluble azo group such as 2,2′-azobis (2-amidinopropane) dihydrochloride is used, and it is preferable to use 0.1 to 30 mol% based on the total amount of monomers. . The polymerization time is 3 to 100 hours, preferably 5 to 70 hours.

  Examples of the monomer that forms the N-alkyldiallylamine unit include N-methyldiallylamine, N-ethyldiallylamine, N-propyldiallylamine, N-butyldiallylamine, etc. N-methyldiallylamine is preferred from the viewpoint of the solubility of the modified product. Is preferred. Examples of monomers that form N, N-dialkylallylamine units include N, N-dimethylallylamine, N, N-diethylallylamine, N, N-dipropylallylamine, N, N-dibutylallylamine, and the like. From the viewpoint of solubility, N, N-dimethylallylamine is preferred.

  The weight average molecular weight (value in terms of polyethylene glycol measured by GPC method) of the raw material copolymer is preferably 12000 or less, more preferably 200 to 8000, and particularly preferably 300 to 5000. If the molecular weight is too large, the modified polyallylamine of the present invention that is produced may be difficult to dissolve, and if it is too small, the performance of the recorded matter may be deteriorated when used for inkjet recording. The unmodified partial monomer ratio q / p is usually 90/10 to 0/100, preferably 80/20 to 0/100. The monomer unit ratio (p + q) / w of the raw material copolymer is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, and particularly preferably 20/80 to 80/20.

  When the modified polyallylamine (I-1) of the present invention is produced by allowing cyanic acid to act on the raw material copolymer, it is preferable to add a cyanate salt to the salt of the raw material copolymer and cause the reaction. A typical production example is shown below.

  The raw material copolymer is dissolved in water or a polar solvent, and an inorganic acid solution such as hydrochloric acid is added thereto to obtain a copolymer salt solution. At this time, the concentration of the raw material copolymer is preferably 5 to 50% by weight. A solution of the raw material copolymer salt is heated to 30 to 80 ° C., and an aqueous solution of cyanate such as sodium cyanate and potassium cyanate is added dropwise thereto and reacted for about 1 to 100 hours. In this reaction, a salt (sodium chloride when the raw material copolymer is hydrochloride and cyanate is sodium cyanate) is by-produced. After completion of the reaction, if necessary, the unreacted hydrochloric acid is neutralized with an alkali such as sodium hydroxide, and then subjected to a desalting operation such as electrodialysis, whereby the modified polyallylamine of the present invention (N-alkyldiallylamine unit and N -Copolymers containing carbamoylated allylamine units, etc.) can be obtained. Cyanate is preferably used in an amount of preferably 0.6 to 1 molar equivalent, more preferably 0.9 to 1 molar equivalent, and particularly preferably 1 molar equivalent relative to the allylamine unit.

（式中、Ｒ、Ｒ^１、Ｒ^２、Ｒ^３、ｐ、ｑ、ｒ及びｓは前記と同じである。）
で表される、一級アミノ基がアルコキシ若しくはアリーロキシカルボニル化された変性ポリアリルアミンを製造する。 [Production of Modified Polyallylamine Represented by General Formula (I-2)]
In this case, an alkoxycarbonylating agent having 1 to 12 carbon atoms or an aryloxycarbonylating agent having 6 to 12 carbon atoms is allowed to act on the raw material copolymer represented by the above general formula (III) to give the general formula (I -2)

(In the formula, R, R ¹ , R ² , R ³ , p, q, r and s are the same as described above.)
A modified polyallylamine in which the primary amino group is alkoxylated or aryloxycarbonylated is produced.

As the alkoxycarbonylating agent or aryloxycarbonylating agent, R ³ O—CO—OR ³ (wherein R ³ is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms) from the viewpoint of reactivity. A carbonic acid diester represented by the formula: Examples of the diester carbonate include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, di (o-tolyl) carbonate, di (m-tolyl) carbonate, and di (p-tolyl) carbonate. it can.

  When producing the modified polyallylamine (I-2) of the present invention by reacting the raw material copolymer with the carbonic acid diester, first, the carbonic acid diester is slowly dropped into a solution such as an aqueous solution of the raw material copolymer. Good. At this time, the carbonic acid diester can be dissolved in a solvent and dropped into the solution of the raw material copolymer. In this case, the solvent for dissolving the carbonic acid diester is usually preferably the same as the solvent for dissolving the raw material copolymer. The reaction between the raw material copolymer and the carbonic acid diester is preferably performed while stirring. The reaction temperature is preferably maintained at 0 to 100 ° C, more preferably 30 to 60 ° C. If the reaction temperature is too high, the produced urethane may be decomposed. The reaction time is usually 1 to 100 hours, preferably 3 to 48 hours, and the modified polyallylamine of the present invention can be obtained as a solution. After the reaction is completed, in order to remove by-produced alcohol, the solution is concentrated to obtain the modified polyallylamine of the present invention (such as a copolymer containing an N-alkyldiallylamine unit and an alkoxycarbonylated allylamine unit). Can be obtained as Concentration is preferably carried out under reduced pressure at a temperature of 25 to 70 ° C., preferably 35 to 60 ° C. when water is used as the solvent and dimethyl carbonate, diethyl carbonate, or dipropyl carbonate is used as the carbonic acid diester. If the temperature is too high, side reactions may occur.

  In this method, the N-alkoxycarbonylation degree (or aryloxycarbonylation degree) depends on the amount of the starting carbonic acid diester. When an equimolar amount of carbonic acid diester is used relative to the amino group of the raw material copolymer, the amino group is usually urethanized. Therefore, the N-alkoxycarbonylation degree (or aryloxycarbonylation degree) of the modified polyallylamine of the present invention to be produced can be adjusted by adjusting the amount of carbonic acid diester used as a raw material.

（式中、Ｒ、Ｒ^１、Ｒ^２、Ｒ^４、ｐ、ｑ、ｒ及びｓは前記と同じである。）
で表される、一級アミノ基がアシル化された変性ポリアリルアミンを製造する。 [Production of Modified Polyallylamine Represented by General Formula (I-3)]
In this case, an acylating agent having 1 to 12 carbon atoms in the alkyl group is allowed to act on the raw material copolymer represented by the general formula (III) to obtain the general formula (I-3)

(In the formula, R, R ¹ , R ² , R ⁴ , p, q, r and s are the same as described above.)
The modified polyallylamine by which the primary amino group was acylated represented by these is manufactured.

As the acylating agent, general formula (IV)
(R ⁴ CO) ₂ O (IV)
(Wherein R ⁴ is the same as described above.)
The carboxylic anhydride represented by these can be used. Examples of the carboxylic anhydride include acetic anhydride, propionic anhydride, n-butyric anhydride, isobutyric anhydride, valeric anhydride, hexanoic anhydride, octanoic anhydride, decanoic anhydride, and lauric anhydride. When acylating 50 mol% or less with respect to the amino group of a raw material copolymer, the amount of carboxylic anhydride may be the same equivalent with respect to the amino group to be acylated. As a solvent for making the raw material copolymer solution, water, an organic solvent, or a mixed solvent of water and an organic solvent can be used. As the organic solvent, a polar solvent is preferable in view of solubility of raw materials, and alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol can be used, and acetonitrile, formamide, N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, 1,4-dioxane and the like can also be used. Of these, water is preferable from the viewpoints of safety and ease of operation.

  In the present invention, when carboxylic anhydride is allowed to act on the raw material copolymer, the carboxylic anhydride is preferably slowly dropped into the copolymer solution. The dropping is usually carried out over 2 to 8 hours, depending on the reaction scale. When the reaction scale is small, it may be less than that, and it may be carried out usually for 1 to 8 hours. The reaction is preferably carried out with stirring. Since this reaction is an exothermic reaction, it is carried out while cooling the reaction vessel with ice or the like, and the reaction solution is preferably maintained at 40 ° C. or lower, more preferably 0 to 10 ° C. After completion of acylation, usually derived from carboxylic anhydride salted on the amino group of the intermediate chain generated after acylation reaction by adding alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate to the reaction solution By neutralizing the carboxylic acid, a free acylated modified polyallylamine solution of the present invention can be produced.

  However, when acylating more than 50 mol% with respect to the primary amino group of the raw material copolymer, the carboxylic acid salted on the amino group in the side chain of the intermediate is converted into sodium hydroxide, potassium hydroxide, carbonic acid. The acylation reaction may proceed while appropriately neutralizing with an alkali such as sodium. In this case, it is preferable to maintain the reaction solution at pH 10-12. When neutralizing, the reaction solution is preferably maintained at 0 to 10 ° C. After completion of neutralization, the resulting solution is dialyzed to remove the neutralized salt and obtain a purified free-form acylated modified polyallylamine solution of the present invention.

  As dialysis for removing the neutralized salt, it is preferable to use electrodialysis described in Japanese Patent Publication No. 7-68289 in view of simplicity of operation. In this case, generally, when the acylated polyallylamine solution being purified is subjected to GPC chromatography, the amount of salt present in the solution can be easily checked. Therefore, the end of purification can be known using GPC chromatography.

  When less than an equivalent amount of carboxylic anhydride is used relative to the primary amino group of the starting copolymer, the carboxylic anhydride is usually almost consumed as an acylating reagent. Therefore, the acylation degree of the modified polyallylamine of the present invention can be adjusted by the amount of carboxylic anhydride.

  Next, with respect to the modified polyallylamine II represented by the general formula (II), the modified polyallylamine represented by the general formula (II-1) and the general formula (II-2) is produced as follows. be able to.

（式中、Ｒ、Ｒ^１、Ｒ^２、Ｙ^１、ｐ、ｑ、ｔ、ｕ及びｖは前記と同じである。）
で表される、一級アミノ基にアクリル化合物がマイケル付加した変性ポリアリルアミンを製造する。 [Production of Modified Polyallylamine Represented by General Formula (II-1)]
In this case, the raw material monomer represented by the general formula (III) is added to the general formula (V).
^{_{CH 2 = C (R 5)}} -A ... (V)
(In the formula, R ⁵ and A are the same as described above.)
Is reacted with an acrylic compound represented by the general formula (II-1)

(In the formula, R, R ¹ , R ² , Y ¹ , p, q, t, u and v are the same as described above.)
A modified polyallylamine in which an acrylic compound is Michael-added to a primary amino group is produced.

This modification is performed by the Michael addition reaction of the acrylic compound to the primary amino group in the raw material copolymer.
As the acrylic compound, a compound having an acrylamide skeleton, a compound having an acrylonitrile skeleton, or a compound having an acrylate skeleton is used. Examples of the compound having an acrylamide skeleton include acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N, N-diethylacrylamide, Nn-propylacrylamide, N, N-di (n-propyl). ) Acrylamide, N-isopropylacrylamide, Nn-butylacrylamide, N-iso-butylacrylamide, N-methylolacrylamide, N, N-dimethylaminoethylacrylamide, N, N-diethylaminoethylacrylamide, N, N-dimethylamino Propylacrylamide, N, N-diethylaminopropylacrylamide, N, N-dimethylaminoethylacrylamide-methyl chloride quaternary salt, N, N-diethylaminoethylacrylamide-methyl Chloride quaternary salt, N, N-dimethylaminopropylacrylamide / methyl chloride quaternary salt, N, N-diethylaminopropylacrylamide / methyl chloride quaternary salt, acroylmorpholine, acroylpiperidine, methacrylamide, N-methylmethacrylamide N, N-dimethylmethacrylamide, N-ethylmethacrylamide, N, N-diethylmethacrylamide, Nn-propylmethacrylamide, N, N-di (n-propyl) methacrylamide, N-isopropylmethacrylamide, Nn-butylmethacrylamide, N-isobutylmethacrylamide, N-methylolmethacrylamide, N, N-dimethylaminoethylmethacrylamide, N, N-diethylaminoethylmethacrylamide, N, N-dimethylaminopro Methacrylamide, N, N-diethylaminopropyl methacrylamide, N, N-dimethylaminoethyl methacrylamide-methyl chloride quaternary salt, N, N-diethylaminoethyl methacrylamide-methyl chloride quaternary salt, N, N-dimethylamino Examples thereof include propyl methacrylamide-methyl chloride quaternary salt, N, N-diethylaminopropyl methacrylamide-methyl chloride quaternary salt, methacryloylmorpholine, and methacryloyl piperidine. Examples of the compound having an acrylonitrile skeleton include acrylonitrile and methacrylonitrile. Examples of the compound having an acrylate skeleton include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, N, N-diethylaminopropyl acrylate, N, N-dimethylaminoethyl acrylate / methyl chloride quaternary salt, N, N-diethylaminoethyl acrylate / methyl chloride quaternary salt, N, N-dimethylaminopropyl acrylate / methyl chloride quaternary salt, Examples thereof include N, N-diethylaminopropyl acrylate / methyl chloride quaternary salt.

  In the present invention, the amount of the acrylic compound used is preferably from 60 to 200 mol%, more preferably from 70 to 120 mol%, particularly preferably from 90 to 105 mol%, based on the primary amino group of the raw material copolymer. The degree of substitution of the amino group with the acrylic compound depends on the acrylic compound to be added. In general, when the amount of the acrylic compound is 100 mol% or less based on the primary amino group, one molecule of the acrylic compound is added to the primary amino group. Units added with acrylic compounds are sequentially produced.

In this invention, when making the said acrylic compound act on a raw material copolymer, it can be as follows, for example.
The raw material copolymer is dissolved in water, methanol, or a mixed solvent of these and a polar solvent. The concentration is about 5 to 60% by weight. The reaction mixture is kept at 30 to 70 ° C., and when the acrylic compound is a liquid, it is dissolved in water or methanol as it is and added dropwise. After completion of dropping, the reaction is allowed to proceed for 0.5 to 48 hours.

（式中、Ｂは前記と同じである。）
で表されるエポキシ化合物を作用させて、一般式（II−２）

（式中、Ｒ、Ｒ^１、Ｒ^２、Ｙ^２、ｐ、ｑ、ｔ、ｕ及びｖは前記と同じである。）
で表される、一級アミノ基にエポキシ化合物が付加した変性ポリアリルアミンを製造する。 [Production of Modified Polyallylamine Represented by General Formula (II-2)]
In this case, the raw material monomer represented by the general formula (III) is substituted with the general formula (VI)

(In the formula, B is the same as described above.)
By acting an epoxy compound represented by the general formula (II-2)

(In the formula, R, R ¹ , R ² , Y ² , p, q, t, u and v are the same as described above.)
The modified polyallylamine which the epoxy compound added to the primary amino group represented by these is manufactured.

  Examples of the epoxy compound represented by the general formula (VI) include 1,2-epoxypropane, 1,2-epoxy-n-butane, 1,2-epoxy-n-pentane, and 1,2-epoxy-n-. Hexane, 1,2-epoxy-n-heptane, 1,2-epoxy-n-octane, methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, isopropyl glycidyl ether, n-butyl glycidyl ether, n-pentyl glycidyl Examples include ether, glycidol, and allyl glycidol ether.

  In the present invention, the amount of the epoxy compound used is preferably from 60 to 200 mol%, more preferably from 70 to 150 mol%, particularly preferably from 90 to 120 mol%, based on the primary amino group of the raw material copolymer. The degree of substitution of the amino group with the epoxy compound depends on the amount of the epoxy compound used.

  The modified polyallylamine (II-2) of the present invention can be produced simply by dissolving the raw material copolymer in a solvent and adding the epoxy compound to the resulting solution and reacting at about 20 to 70 ° C. it can. The solvent used for the reaction is preferably water.

  The reaction temperature when the polyallylamine and the epoxy compound are reacted is usually 20 to 70 ° C, preferably 30 to 60 ° C. The reaction time varies depending on the reaction conditions, but usually 0.5 to 48 hours is sufficient.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples. In addition, the weight average molecular weight of the polymer was measured according to the method shown below.
<Measurement of weight average molecular weight of polymer>
The weight average molecular weight (Mw) of the polymer was measured by gel permeation chromatography (GPC method) using a “Hitachi L-6000 type” high performance liquid chromatograph. The eluent flow path pump is "Hitachi L-6000", the detector is "Shodex RI SE-61" differential refractive index detector, the column is "GS-220HQ" of Asahi Pack's water-based gel filtration type (exclusion limit molecular weight 3 , 000) and “GS-620HQ” (exclusion limit molecular weight 2 million) were used in a double connection. The sample was adjusted to a concentration of 0.5 g / 100 ml with an eluent, and 20 μl was used. A 0.4 mol / L sodium chloride aqueous solution was used as an eluent. The column temperature was 30 ° C. and the flow rate was 1.0 ml / min. A calibration curve was determined using polyethylene glycol having a molecular weight of 106, 194, 440, 600, 1470, 4100, 7100, 10300, 12600, 23000 or the like as a standard sample, and the Mw of the polymer was determined based on the calibration curve.

Production Example 1 Production of N-methyldiallylamine and allylamine copolymer (5/5) In a 2 L four-necked separable flask equipped with a stirrer, Dimroth reflux, and thermometer, the concentration was 69.58 wt%. An N-methyldiallylamine hydrochloride aqueous solution 212.20 g, a 58.80 wt% monoallylamine hydrochloride aqueous solution 159.10 g and distilled water 834.70 g were charged. The monomer aqueous solution was heated to 65 ° C., 54.24 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added as a radical initiator, and polymerization was performed for 48 hours.
After completion of the polymerization, 193.30 g of a 50 wt% sodium hydroxide aqueous solution was added dropwise under ice cooling to neutralize hydrochloric acid. After completion of neutralization, unreacted monomers were distilled off at 50 ° C. under reduced pressure (10.6 kPa).
The solution obtained here was subjected to electrodialysis, desalted, and an aqueous solution of 1055.43 g of a copolymer (copolymerization ratio 5: 5) of free type N-methyldiallylamine and allylamine having a concentration of 14.35 wt%. Got.
A part of the aqueous copolymer solution was converted to hydrochloride and reprecipitated with an isopropanol solvent to obtain copolymer hydrochloride. The results of elemental analysis were C = 50.02, H = 9.01, and N = 11.32. These values agreed with the calculated values C = 49.80, H = 9.19, N = 11.64. In addition, manufacturing conditions of this manufacturing example, a yield, etc. are shown to Table 1-1 with the manufacturing examples 2-3.

Production Example 2 Production of Copolymer (3/7) of N-Methyldiallylamine and Allylamine In Production Example 1, the amount of N-methyldiallylamine hydrochloride aqueous solution was adjusted to a concentration of 69.58 wt%, 127.32 g and monoallylamine hydrochloride. A free type N-methyl diallylamine and allylamine having a concentration of 14.50 wt% were operated in the same manner as in Production Example 1 except that the amount of the aqueous solution was 58.80 wt%, 222.75 g and 747.78 g of distilled water were used. 89.95 g of a copolymer (copolymerization ratio 3: 7) aqueous solution was obtained.

Production Example 3 Production of Copolymer (7/3) of N-Methyldiallylamine and Allylamine In Production Example 1, the amount of N-methyldiallylamine hydrochloride aqueous solution was 69.58 wt%, 297.08 g and monoallylamine hydrochloride. A free type N-methyl diallylamine and allylamine having a concentration of 14.81 wt% were prepared in the same manner as in Production Example 1 except that the amount of the aqueous solution was 95.46 g and 95.46 g of distilled water and 921.66 g of distilled water was used. 1218.26 g of a copolymer (copolymerization ratio 7: 3) aqueous solution was obtained.

Production Example 4 Production of Copolymer (1/1/1) of N-methyldiallylamine, N, N-dimethylallylamine and allylamine 2/1 4-neck separable flask equipped with stirrer, Dimroth reflux and thermometer Among them, 212.20 g of N-methyldiallylamine hydrochloride aqueous solution with a concentration of 69.58 wt%, 191.66 g of N, N-dimethylallylamine hydrochloride aqueous solution with a concentration of 63.45 wt% and monoallylamine hydrochloride aqueous solution with a concentration of 58.80 wt% 159.10 g and distilled water 646.40 g were charged. The monomer aqueous solution was heated to 65 ° C., 54.24 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added as a radical initiator, and polymerization was performed for 48 hours.
After completion of the polymerization, 273.28 g of a 50 wt% sodium hydroxide aqueous solution was added dropwise under ice cooling to neutralize hydrochloric acid. After completion of neutralization, unreacted monomers were distilled off at 50 ° C. under reduced pressure (10.6 kPa).
The solution obtained here was subjected to electrodialysis, desalted, and a free type copolymer of N-methyldiallylamine, N, N-dimethylallylamine and allylamine having a concentration of 14.82 wt% (copolymerization ratio: 1). : 1: 1) 1504.87 g of aqueous solution was obtained.
A part of the aqueous copolymer solution was converted to hydrochloride and reprecipitated with an isopropanol solvent to obtain copolymer hydrochloride. The results of elemental analysis were C = 49.38, H = 9.08, and N = 11.47. These values agreed with the calculated values C = 49.66, H = 9.45, and N = 11.58. In addition, production conditions, yields, and the like of this production example are shown in Table 1-2.

Example 1 Production of Copolymer (5/5) of N-Methyldiallylamine and Carbamoylated Allylamine In a 2 L 4-neck separable flask equipped with a stirrer, Dimroth reflux and thermometer, according to Production Example 1. The produced 586.35 g of an aqueous copolymer solution of free type N-methyl diallylamine and allylamine having a concentration of 14.35 wt% was charged, and 104.17 g of hydrochloric acid having a concentration of 35 wt% was added dropwise under ice cooling. Subsequently, the mixture was heated to 50 ° C., and 455.07 g of a sodium cyanate aqueous solution having a concentration of 7.5% was added dropwise to carry out the reaction for 24 hours.
After completion of the reaction, 42.00 g of sodium hydroxide having a concentration of 50 wt% was added dropwise under ice cooling to neutralize unreacted hydrochloric acid.
The solution obtained here was subjected to electrodialysis, desalted, and an aqueous solution 907 of a copolymer of free type N-methyldiallylamine and carbamoylated allylamine having a concentration of 11.30 wt% (copolymerization ratio 5: 5). 0.000 g (97% yield) was obtained. The copolymer had a weight average molecular weight of 1800.

The copolymer was concentrated to a solid, dissolved in various solvents to prepare a 10 wt% solution, and the solubility in each solution was confirmed. As a result, this copolymer was insoluble in acetone and acetonitrile, but dissolved in methanol, ethanol, isopropanol, DMSO, and DMF. This result shows that the copolymer of the present invention is excellent in solubility in an organic solvent.
A part of the aqueous copolymer solution was converted to hydrochloride and reprecipitated with an isopropanol solvent to obtain copolymer hydrochloride. This result shows that the modified polyallylamine of the present invention can be a cationic polymer.
The results of elemental analysis were C = 53.58, H = 8.92, and N = 16.64. These values agreed with the calculated values C = 53.32, H = 8.95, and N = 16.96. Further, the molar fraction of carbamoylation calculated from neutralization titration of copolymer hydrochloride was 46.76%, which was almost the same as the result of elemental analysis. The IR spectrum is shown in FIG.

Example 2 Production of Copolymer of N-Methyldiallylamine and Carbamoylated Allylamine (3/7) In Example 1, a free type copolymer aqueous solution of N-methyldiallylamine and allylamine produced in Production Example 1 was prepared. Instead, use was made of 505.67 g of an aqueous solution of 14.50% free N-methyldiallylamine and allylamine prepared in Preparation Example 2, 633.710 g of sodium cyanate aqueous solution, and 25.20 g of sodium hydroxide aqueous solution. In the same manner as in Example 1, except for the above, 85.10 g of an aqueous solution of a copolymer (copolymerization ratio 3: 7) of free type N-methyl diallylamine and carbamoylated allylamine having a concentration of 11.52 wt% 95%). The weight average molecular weight of this copolymer was 1500.

Example 3 Production of Copolymer (7/3) of N-Methyldiallylamine and Carbamoylated Allylamine In Example 1, a free type copolymer aqueous solution of N-methyldiallylamine and allylamine produced in Example 1 was prepared. Instead, a 64.18 g aqueous solution (copolymerization ratio 7: 3) of a free type N-methyldiallylamine and allylamine having a concentration of 14.81% produced in Production Example 3 and an aqueous solution of sodium cyanate 273.04 g and water Except for using 58.80 g of an aqueous sodium oxide solution, the same operation as in Example 1 was carried out, and 940.95 g of an aqueous copolymer solution of free type N-methyldiallylamine and carbamoylated allylamine having a concentration of 11.12 wt% 97%). The weight average molecular weight of this copolymer was 2100.

Example 4 Production of Copolymer of N-Methyldiallylamine and Methoxycarbonylated Allylamine (5/5) Production Example 1 was conducted in a 1 L four-necked separable flask equipped with a stirrer, Dimroth reflux, and thermometer. Prepared by charging 586.35 g of an aqueous copolymer solution of free type N-methyldiallylamine and allylamine having a concentration of 14.35 wt% produced by the method, heated to 50 ° C., and dropwise added 47.77 g of dimethyl carbonate having a purity of 99%, The reaction was performed for 24 hours.
After completion of the reaction, methanol produced as a by-product at 50 ° C. was distilled off under reduced pressure (80 mmHg), and a copolymer of free type N-methyldiallylamine and methoxycarbonylated allylamine having a concentration of 22.44 wt% (copolymerization ratio 5). : 5) 494.19 g (yield 98%) of an aqueous solution was obtained. The weight average molecular weight of this copolymer was 1900.
A part of the aqueous copolymer solution was converted to hydrochloride and reprecipitated with an isopropanol solvent to obtain copolymer hydrochloride. The results of elemental analysis were C = 54.69, H = 8.62 and N = 10.37. These values agreed with the calculated values C = 54.85, H = 8.82 and N = 10.66. Moreover, as a result of calculating the methoxycarbonylation mole fraction by neutralization titration of copolymer hydrochloride, it was 49.88%, which almost coincided with the result of elemental analysis.

Example 5 Production of Copolymer (3/7) of N-Methyldiallylamine and Methoxycarbonylated Allylamine In Example 4, a copolymer aqueous solution of free type N-methyldiallylamine and allylamine produced in Production Example 1 The same procedure as in Example 4 was conducted, except that 505.67 g of a free type aqueous solution of N-methyldiallylamine and allylamine having a concentration of 14.50 wt% produced in Production Example 2 and 66.88 g of dimethyl carbonate were used. Thus, 50.27 g (yield 99%) of an aqueous solution (copolymerization ratio 3: 7) of a free type N-methyldiallylamine and a methoxycarbonylated allylamine having a concentration of 22.55 wt% was obtained. The weight average molecular weight of this copolymer was 1500.

Example 6 Production of Copolymer (7/3) of N-Methyldiallylamine and Methoxycarbonylated Allylamine In Example 4, an aqueous copolymer solution of free type N-methyldiallylamine and allylamine produced in Production Example 1 Example 4 was used in the same manner as in Example 4 except that 641.18 g of an aqueous copolymer solution of free type N-methyldiallylamine and allylamine having a concentration of 14.81 wt% produced in Production Example 3 and 28.66 g of dimethyl carbonate were used. Thus, 502.92 g (yield 99%) of an aqueous solution of a free type N-methyldiallylamine and a methoxycarbonylated allylamine (copolymerization ratio 7: 3) having a concentration of 22.12 wt% was obtained. The weight average molecular weight of this copolymer was 2200.

Example 7 Production of Copolymer of N-Methyldiallylamine and Acetylated Allylamine (5/5) In a 1 L 4-neck separable flask equipped with a stirrer, Dimroth reflux and thermometer, according to Production Example 1. 586.35 g of an aqueous copolymer solution of free type N-methyldiallylamine and allylamine having a concentration of 14.35 wt% was prepared. This operation was carried out by adding ½ mol of allylamine dropwise from 54.69 g of acetic anhydride with a purity of 98% under ice-cooling, and neutralizing 42.00 g of sodium hydroxide with a concentration of 50% by the amount of acetic acid by-produced. The whole amount was dropped by repeating the above, and the reaction was performed for 24 hours.
The solution obtained here was subjected to electrodialysis, desalted, and an aqueous solution 695 of a copolymer of free type N-methyldiallylamine and acetylated allylamine having a concentration of 15.12 wt% (copolymerization ratio 5: 5). .50 g (100%) was obtained. The weight average molecular weight of this copolymer was 1900.
A part of the aqueous copolymer solution was converted to hydrochloride and reprecipitated with an isopropanol solvent to obtain copolymer hydrochloride. The results of elemental analysis were C = 58.31, H = 9.16, and N = 11.07. These values agreed with the calculated values C = 58.41, H = 9.40, and N = 11.35. Moreover, as a result of calculating the acetylation molar fraction by neutralization titration of copolymer hydrochloride, it was 50.06%, which almost coincided with the result of elemental analysis.

Example 8 Production of Copolymer of N-Methyldiallylamine and Acetylated Allylamine (3/7) In Example 7, a free type copolymer aqueous solution of N-methyldiallylamine and allylamine produced in Production Example 1 was prepared. Instead of using 50.67 g of an aqueous copolymer solution of 14.50 wt% free type N-methyldiallylamine and allylamine produced in Production Example 2, 76.57 g of acetic anhydride and 58.80 g of an aqueous sodium hydroxide solution were used. Was operated in the same manner as in Example 7, and a copolymer of free type N-methyl diallylamine and acetylated allylamine having a concentration of 15.34 wt% (copolymerization ratio 3: 7) aqueous solution 656.42 g (98%) Got. The weight average molecular weight of this copolymer was 1500.

Example 9 Production of Copolymer (7/3) of N-Methyldiallylamine and Acetylated Allylamine In Example 7, the aqueous copolymer solution of free type N-methyldiallylamine and allylamine produced in Production Example 1 was prepared. Instead of using 64.18 g of an aqueous copolymer solution of free type N-methyldiallylamine and allylamine having a concentration of 14.81 wt% produced in Production Example 3, 32.81 g of acetic anhydride, and 25.20 g of an aqueous sodium hydroxide solution. Was operated in the same manner as in Example 7, and 715.70 g (100%) of an aqueous solution of a free type N-methyldiallylamine and acetylated allylamine having a concentration of 15.03 wt% (copolymerization ratio 7: 3). Got. The weight average molecular weight of this copolymer was 2000.

Example 10 Production of Copolymer of N-Methyldiallylamine and Monocarbamoylethylated Allylamine (5/5) Production Example in a 1 L 4-neck separable flask equipped with a stirrer, Dimroth reflux, and thermometer First, 586.35 g of an aqueous copolymer solution of free type N-methyldiallylamine and allylamine having a concentration of 14.35 wt% prepared according to 1 was charged, heated to 50 ° C., and 74.63 g of acrylamide having a concentration of 50% were dropped. The reaction was performed for 24 hours.
63.93 g (98%) of an aqueous solution (copolymerization ratio 5: 5) of free type N-methyl diallylamine and monocarbamoylethylated allylamine having a concentration of 18.56 wt% was obtained. The copolymer had a weight average molecular weight of 1800.
A part of the aqueous copolymer solution was converted to hydrochloride and reprecipitated with an isopropanol solvent to obtain copolymer hydrochloride. The results of elemental analysis were C = 56.48, H = 8.99, and N = 15.38. These values agreed with the calculated values C = 56.61, H = 9.50, N = 15.24. Moreover, as a result of calculating the monopropyl amidation mole fraction by neutralization titration of the copolymer hydrochloride, it was 49.03%, which almost coincided with the result of elemental analysis.

Example 11 Production of Copolymer (3/7) of N-Methyldiallylamine and Monocarbamoylethylated Allylamine In Example 10, a copolymer of free type N-methyldiallylamine and allylamine produced in Production Example 1 The same as Example 10 except that 50.67 g of an aqueous copolymer solution of free type N-methyl diallylamine and allylamine having a concentration of 14.50 wt% produced in Production Example 2 and 104.49 g of acrylamide were used instead of the aqueous solution. In this way, 588.80 g (97%) of an aqueous solution (copolymerization ratio 3: 7) of a free type N-methyldiallylamine and monocarbamoylethylated allylamine having a concentration of 20.28 wt% was obtained. The weight average molecular weight of this copolymer was 1500.

Example 12 Production of Copolymer (7/3) of N-Methyldiallylamine and Monocarbamoylethylated Allylamine In Example 10, a copolymer of free type N-methyldiallylamine and allylamine produced in Production Example 1 The same as Example 10 except that 641.18 g of an aqueous copolymer solution of free type N-methyldiallylamine and allylamine having a concentration of 14.81 wt% produced in Production Example 3 and 44.78 g of acrylamide were used instead of the aqueous solution. To obtain 687.77 g (98%) of an aqueous solution (copolymerization ratio 7: 3) of a free type N-methyldiallylamine and monocarbamoylethylated allylamine having a concentration of 16.57 wt%. The weight average molecular weight of this copolymer was 2200.

Example 13 Production of Copolymer of N- Methyldiallylamine and Dicarbamoylethylated Allylamine (5/5) In Example 10, the same operation as in Example 10 was carried out except that 149.27 g of acrylamide was used. A 647.03 g (97%) aqueous solution of a free type N-methyldiallylamine and dicarbamoylethylated allylamine having a concentration of 23.27 wt% (copolymerization ratio 5: 5) was obtained. The copolymer had a weight average molecular weight of 1800.
A part of the aqueous copolymer solution was converted to hydrochloride and reprecipitated with an isopropanol solvent to obtain copolymer hydrochloride. The results of elemental analysis were C = 55.18, H = 8.75, and N = 15.81. These values agreed with the calculated values C = 55.40, H = 9.01, N = 16.15. Moreover, as a result of calculating the dipropylamidation molar fraction by neutralization titration of copolymer hydrochloride, it was 48.71% and was almost in agreement with the result of elemental analysis.

Example 14 Production of Copolymer (3/7) of N- Methyldiallylamine and Dicarbamoylethylated Allylamine In Example 11, except that 208.98 g of acrylamide was used, the same operation as in Example 10 was carried out. A 649.28 g (97%) aqueous solution of a copolymer (copolymerization ratio 3: 7) of free type N-methyl diallylamine and dicarbamoylethylated allylamine having a concentration of 25.82 wt% was obtained. The weight average molecular weight of this copolymer was 1500.

Example 15 Production of Copolymer of N- Methyldiallylamine and Dicarbamoylethylated Allylamine (7/3) In Example 12, except that 89.56 g of acrylamide was used, the same operation as in Example 10 was carried out. There was obtained 690.93 g (96%) of an aqueous solution (copolymerization ratio 7: 3) of free type N-methyl diallylamine and dicarbamoylethylated allylamine having a concentration of 19.12 wt%. The weight average molecular weight of this copolymer was 2100.

Example 16 Production of a copolymer of N-methyldiallylamine and monoethoxy-2-hydroxypropylated allylamine (5/5) In a 1 L four-necked separable flask equipped with a stirrer, Dimroth reflux and thermometer Into this, 586.35 g of an aqueous copolymer solution of free type N-methyldiallylamine and allylamine having a concentration of 14.35 wt% produced in Production Example 1 was charged, heated to 50 ° C., and ethyl glycidyl ether 53 having a purity of 100%. .62 g was dropped and the reaction was carried out for 24 hours.
A 614.87 g (100%) aqueous solution of a free type N-methyl diallylamine and monoethoxy-2-hydroxypropylated allylamine having a concentration of 21.99 wt% (copolymerization ratio 5: 5) was obtained. The copolymer had a weight average molecular weight of 1800.
A part of the aqueous copolymer solution was converted to hydrochloride and reprecipitated with an isopropanol solvent to obtain copolymer hydrochloride. The results of elemental analysis were C = 58.50, H = 9.99, and N = 9.08. These values were in agreement with the calculated values C = 58.71, H = 10.18, N = 9.13. Moreover, as a result of calculating the monoethoxy-2-hydroxypropylation mole fraction from neutralization titration of copolymer hydrochloride, it was 50.12%, which almost coincided with the results of elemental analysis.

Example 17 Production of Copolymer (3/7) of N-methyldiallylamine and monoethoxy-2-hydroxypropylated allylamine In Example 16, the free type N-methyldiallylamine and allylamine produced in Production Example 1 Except that 505.67 g of an aqueous copolymer solution of free type N-methyl diallylamine and allylamine having a concentration of 14.50 wt% produced in Production Example 2 and 75.07 g of ethyl glycidyl ether were used instead of the copolymer aqueous solution of By operating in the same manner as in Example 16, a copolymer (copolymerization ratio 3: 7) aqueous solution of free type N-methyldiallylamine and monoethoxy-2-hydroxypropylated allylamine having a concentration of 25.66 wt% 564. 38 g (100%) were obtained. The weight average molecular weight of this copolymer was 1500.

Example 18 Production of Copolymer (7/3) of N-Methyldiallylamine and Monoethoxy-2-hydroxypropylated Allylamine In Example 16, the free type N-methyldiallylamine and allylamine produced in Production Example 1 Except that 641.18 g of an aqueous copolymer solution of free type N-methyldiallylamine and allylamine having a concentration of 14.81 wt% produced in Production Example 3 and 32.17 g of ethyl glycidyl ether were used instead of the copolymer aqueous solution of In the same manner as in Example 16, a copolymer (copolymerization ratio 7: 3) aqueous solution of free type N-methyl diallylamine and monoethoxy-2-hydroxypropylated allylamine having a concentration of 18.74 wt% was obtained in an aqueous solution 670. 22 g (100%) were obtained. The weight average molecular weight of this copolymer was 2100.

Example 19 Production of copolymer (5/5) of N-methyldiallylamine and diethoxy-2-hydroxypropylated allylamine The same as Example 16 except that 107.24 g of ethyl glycidyl ether was used in Example 16. To obtain a 644.36 g (99%) aqueous solution of a free type N-methyl diallylamine and diethoxy-2-hydroxypropylated allylamine having a concentration of 28.62 wt% (copolymerization ratio 5: 5). It was. The copolymer had a weight average molecular weight of 1800.
A part of the aqueous copolymer solution was converted to hydrochloride and reprecipitated with an isopropanol solvent to obtain copolymer hydrochloride. The results of elemental analysis were C = 58.56, H = 9.98, and N = 6.73. These values coincided with the calculated values C = 58.73, H = 10.10, and N = 6.85. Moreover, as a result of calculating the monoethoxy-2-hydroxypropylation mole fraction from neutralization titration of copolymer hydrochloride, it was 49.71%, which was almost the same as the result of elemental analysis.

Example 20 Production of Copolymer (3/7) of N- Methyldiallylamine and Diethoxy- 2-hydroxypropylated Allylamine The same as Example 17 except that 150.13 g of ethyl glycidyl ether was used in Example 17. To obtain a 620.72 g (99%) aqueous solution of a free type N-methyldiallylamine and diethoxy-2-hydroxypropylated allylamine having a concentration of 34.50 wt% (copolymerization ratio 3: 7). It was. The weight average molecular weight of this copolymer was 1600.

Example 21 Production of Copolymer (7/3) of N- Methyldiallylamine and Diethoxy- 2-hydroxypropylated Allylamine The same as Example 18 except that 64.34 g of ethyl glycidyl ether was used in Example 18. To obtain a 680.50 g (99%) aqueous solution of a free type N-methyldiallylamine and diethoxy-2-hydroxypropylated allylamine having a concentration of 22.73 wt% (copolymerization ratio 7: 3). It was. The weight average molecular weight of this copolymer was 2200.

Example 22 Preparation of terpolymer (5/3/2) of N-methyldiallylamine, carbamoylated allylamine and allylamine In Example 1, 273.04 g of sodium cyanate aqueous solution and 58.80 g of sodium hydroxide aqueous solution were added. Except that it was used, the same operation as in Example 1 was carried out, and 817.70 g of a terpolymer aqueous solution of free type N-methyldiallylamine, carbamoylated allylamine and allylamine having a concentration of 11.75 wt% (99% yield) was obtained. ) The copolymer had a weight average molecular weight of 1800.

Example 23 Production of Ternary Copolymer (5/3/2) of N-Methyldiallylamine and Methoxycarbonylated Allylamine and Allylamine Example 4 was used except that 28.66 g of dimethyl carbonate was used. The same operation was performed to obtain 525.35 g (yield 100%) of a terpolymer aqueous solution of free type N-methyldiallylamine having a concentration of 19.33 wt%, methoxycarbonylated allylamine and allylamine. The copolymer had a weight average molecular weight of 1800.

Example 24 Production of terpolymer (5/3/2) of N-methyldiallylamine, acetylated allylamine and allylamine In Example 7, acetic anhydride (32.81 g) and sodium hydroxide aqueous solution (25.20 g) were used. Except for the above, the same operation as in Example 7 was carried out to obtain 704.15 g (100%) of a terpolymer aqueous solution of free-type N-methyldiallylamine, acetylated allylamine and allylamine having a concentration of 13.74 wt%. . The copolymer had a weight average molecular weight of 1800.

Example 25 Production Example of Ternary Copolymer (5/3/2) of N-methyldiallylamine, monocarbamoylethylated allylamine and allylamine In Example 10, except that 44.78 g of acrylamide was used, the ternary co-polymerization of free type N-methyl diallylamine, monocarbamoylethylated allylamine and allylamine with a concentration of 17.26 wt% was carried out in the same manner as in Example 10. 611.07 g (100%) of a combined aqueous solution was obtained. The copolymer had a weight average molecular weight of 1800.

Example 26 Production of terpolymer (5/3/2) of N-methyldiallylamine, monoethoxy-2-hydroxypropylated allylamine and allylamine In Example 16, except that 32.17 g of ethyl glycidyl ether was used. Was operated in the same manner as in Example 16, and 586.51 g (100) of a terpolymer aqueous solution of N-methyldiallylamine having a concentration of 19.57 wt% and monoethoxy-2-hydroxypropylated allylamine and allylamine. %). The copolymer had a weight average molecular weight of 1800.

Example 27 Production of ternary copolymer (1/1/1) of N-methyldiallylamine, N, N-dimethylallylamine and carbamoylated allylamine 4L 2L equipped with stirrer, Dimroth reflux, thermometer Into the mouth-separable flask was charged 570.04 g of a free type ternary copolymer aqueous solution of N-methyldiallylamine, N, N-dimethylallylamine and allylamine having a concentration of 14.82 wt% produced in Production Example 4, and iced. Under cooling, 104.17 g of hydrochloric acid having a concentration of 35 wt% was added dropwise. Subsequently, the mixture was heated to 50 ° C., and 300.35 g of a 7.5% aqueous sodium cyanate solution was added dropwise to carry out the reaction for 24 hours.
After completion of the reaction, 55.44 g of sodium hydroxide having a concentration of 50 wt% was added dropwise under ice cooling to neutralize unreacted hydrochloric acid.
The solution obtained here was subjected to electrodialysis, desalted, and a terpolymer of free type N-methyldiallylamine, N, N-dimethylallylamine and carbamoylated allylamine (concentration 12.13 wt%) ( Copolymerization ratio 1: 1: 1) 782.09 g of aqueous solution (yield 96%) was obtained. The copolymer had a weight average molecular weight of 1700.
A part of the aqueous copolymer solution was converted to hydrochloride and reprecipitated with an isopropanol solvent to obtain copolymer hydrochloride. The results of elemental analysis were C = 51.83, H = 9.13, and N = 14.97. These values agreed with the calculated values C = 52.03, H = 9.28, and N = 15.17. Moreover, as a result of calculating the carbamoylation mole fraction by neutralization titration of copolymer hydrochloride, it was 31.84%, which almost coincided with the result of elemental analysis.

Test example 1
In the ink jet recording using the modified polyallylamine of the present invention (Examples 1 to 27), performance tests of color development and waste liquid retention were performed. This is shown in Table 2. For comparison, the same test was conducted for allylamine homopolymer, a copolymer of N-methyldiallylamine and allylamine (Production Examples 1 to 3), and N-methyldiallylamine homopolymer. This is shown in Table 3. As a result, it has been found that the modified polyallylamine of the present invention exhibits extremely good performance both in terms of color developability and waste liquid retention. The evaluation method and results will be described in detail below.

Preparation of liquid composition A liquid composition comprising the following compositions was prepared.
Liquid composition Modified polyallylamine of the present invention 5.0 wt% (in terms of solid content)
Glycerin (Gly) 25.0% by weight
Triethylene glycol monobutyl ether 3.0% by weight
Olfine E1010 0.3% by weight
Residual amount of water
An ink set ink composition was prepared by the following operation. First, a dispersion with a pigment (styrene-acrylic acid copolymer) is mixed, and the mixture is mixed with glass beads (1.7 mm in diameter, 1.5 times the weight (weight) of the mixture) in a sand mill (Yaskawa Seisakusho) for 2 hours. Dispersed. Thereafter, the glass beads were removed, other additives were added, and the mixture was stirred at room temperature for 20 minutes. Filtration through a 10 μm membrane filter gave a pigment ink.
Ink composition pigment 3.0 parts by weight Styrene acrylic acid copolymer 1.0 part by weight Olphine E1010 0.5 part by weight Gly 15.0 parts by weight TEGmBE 5.0 parts by weight TEA 0.9 part by weight Water remaining amount Total 100 Part by weight As a pigment, yellow is C.I. I. Pigment Yellow 74, magenta is C.I. I. Pigment red 202, cyan is C.I. I. Pigment Blue 15: 3, black was carbon black.
Abbreviations and the like of the ink composition are as follows.
Gly: glycerin TEGmBE: triethylene glycol monobutyl ether TEA: triethanolamine orphine E1010: acetylene glycol surfactant (manufactured by Nissin Chemical Industry)

The print evaluation “duty” is a value calculated by the following equation.
duty (%) = number of actual printing dots / (vertical resolution × horizontal resolution) × 100
(Where “number of actual printing dots” is the number of actual printing dots per unit area, and “vertical resolution” and “horizontal resolution” are resolutions per unit area. 100% duty is a single color for a pixel. Means the maximum ink weight.)
Evaluation 1 Color development test (plain paper)
The liquid composition and the ink set were filled in an ink jet printer (Seiko Epson Corporation; “MC-2000”), and printed on plain paper (Xerox 4024) at 720 × 720 dpi. At this time, the ink composition was printed at 70% duty, and at the same time, the liquid composition was printed at 10% duty.
The optical density of the obtained recorded matter was measured. The optical density was measured using a “Gretag Macbeth SPM50” manufactured by Gretag Co., with a D50 light source, no filter, and a viewing angle of 2 °.
(Evaluation criteria)
S: It is difficult to visually confirm the uncolored portion, and the OD value increases by 0.08 or more than when the liquid composition is not printed.
AA: It is difficult to visually confirm the uncolored portion, and the OD value increases by 0.06 or more than when the liquid composition is not printed.
A: It is difficult to visually confirm the uncolored portion, and the increase in the OD value is 0.03 or more and less than 0.06 as compared with the case where the liquid composition is not printed.
B: The part which is not colored can be easily confirmed by visual observation, and the increase in the OD value is less than 0.03 compared to the case where the liquid composition is not printed.
The evaluation results are shown in Table 3. In the examples, it was difficult to visually confirm the uncolored portion, and the OD value increased by 0.03 or more.

Evaluation 2 Waste Liquid Treatment Performance for Caps with Non-woven Fabric After filling the liquid composition and ink set into an ink jet printer (Seiko Epson Corporation; “MC-2000”), cleaning the recording head (press the printer's cleaning button once) Press) and repeated nozzle check pattern printing. This operation was performed 10 times to evaluate whether the nozzle check pattern was printed normally. Moreover, the state of the waste liquid in a cap (with nonwoven fabric) was observed. Moreover, about the liquid composition whose result was A, this operation | work was performed 90 more times and it was evaluated whether the check pattern was printed normally. Further, for the liquid composition in which the check pattern was normally printed in all 90 test operations and no waste liquid remained in the cap, this test operation was further performed 100 times in an environment of 40 ° C. Evaluated.
Evaluation criteria S: The check pattern is normally printed in all 100 test operations under an environment of 40 ° C., and there is no stagnation of waste liquid in the cap.
AA: The check pattern is normally printed in all 100 test operations under an environment of 20 ° C., and there is no waste liquid remaining in the cap.
A: In an environment of 20 ° C., the check pattern is printed normally in all 10 test operations, and no waste liquid stays in the cap.
B: The check pattern is printed normally in all 10 test operations under an environment of 20 ° C., but there is a slight retention of waste liquid in the cap.
C: The check pattern may not be printed normally under an environment of 20 ° C., and the waste liquid remains in the cap.

  The modified polyallylamine of the present invention exhibits excellent color developability, is easily dissolved in water and an organic solvent, and exhibits good stability in a solution containing the water or the organic solvent. Can be suitably used in the field of fine chemicals.

2 is an infrared absorption (IR) spectrum chart of the modified polyallylamine obtained in Example 1. FIG.

Claims (7)

Formula (I)

[Wherein, R, R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, X is —CONH ₂ , —COOR ³ (where R ³ is an alkyl group having 1 to 12 carbon atoms or carbon 6 represents an aryl group having 6 to 12) or —COR ⁴ (wherein R ⁴ represents an alkyl group having 1 to 12 carbon atoms), p and r are each independently an integer of 1 or more, and q and s are 0 or 1 or more indicates an integer, q / p is 80 / 20~0 / 100, (p + q) / (r + s) is 20/80 to 80/20. ]
Modified polyallylamine have a structure represented by the weight average molecular weight is characterized 200-8000 der Rukoto. The modified polyallylamine according to claim 1, wherein in the general formula (I), the ratio r / (r + s) is 0.6-1. General formula (III)

(Wherein, R, ^{R 1} and ^{R 2} each independently represent an alkyl group having 1 to 4 carbon atoms, p and w are each independently an integer of 1 or more, q is indicates 0 or an integer of 1 or more Q / p is 80/20 to 0/100, and (p + q) / w is 20/80 to 80/20 .)
In expressed, the weight average molecular weight of the copolymer of Der Ru N- alkyl diallylamine and allylamine 200-8000, characterized in that the action of cyanate,
Formula (I-1)

(Wherein, r is an integer of 1 or more, s represents 0 or an integer of 1 or ^{more, R, R 1, R 2} , p and q Ri same der said, q / p is 80 / 20-0 / 100, (p + q) / (r + s) is Ru 20 / 80-80 / 20 der.)
The manufacturing method of modified polyallylamine represented by these. General formula (III)

(Wherein, R, ^{R 1} and ^{R 2} each independently represent an alkyl group having 1 to 4 carbon atoms, p and w are each independently an integer of 1 or more, q is indicates 0 or an integer of 1 or more, q / p is 80/20 to 0/100, and (p + q) / w is 20/80 to 80/20 .)
In expressed, the copolymer of weight average molecular weight of Ru der 200-8000 N-alkyl diallylamine and allylamine, the aryloxycarbonylating agent alkoxycarbonyl agent or C6-12 having 1 to 12 carbon atoms General formula (I-2),

(In the formula, R ³ is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, r is an integer of 1 or more, s is 0 or an integer of 1 or more, and R, R ¹ , R ² , p and q Ri same der said, q / p is 80 / 20~0 / 100, (p + q) / (r + s) is Ru 20/80 to 80/20 der.)
The manufacturing method of modified polyallylamine represented by these. An alkoxycarbonylating agent or an aryloxycarbonylating agent is R ³ O—CO—OR ³ (wherein R ³ represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms).
The method for producing a modified polyallylamine according to claim 4 , wherein the carbonic acid diester is represented by the formula: General formula (III)

(Wherein, R, ^{R 1} and ^{R 2} each independently represent an alkyl group having 1 to 4 carbon atoms, p and w are each independently an integer of 1 or more, q is indicates 0 or an integer of 1 or more, q / p is 80/20 to 0/100, and (p + q) / w is 20/80 to 80/20 .)
In expressed, the weight average molecular weight of the copolymer of Der Ru N- alkyl diallylamine and allylamine 200-8000, carbon atoms in the alkyl group, characterized in that the action of 1 to 12 of the acylating agent, generally Formula (I-3)

Wherein R ⁴ is an alkyl group having 1 to 12 carbon atoms, r is an integer of 1 or more, s is 0 or an integer of 1 or more, and R, R ¹ , R ² , p and q are the same as above. is there.)
The manufacturing method of modified polyallylamine represented by these. The acylating agent is represented by the general formula (IV)
(R ⁴ CO) ₂ O (IV)
(In the formula, R ⁴ represents an alkyl group having 1 to 12 carbon atoms.)
The method for producing a modified polyallylamine according to claim 6 , wherein the carboxylic anhydride is represented by the formula:

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