JP2002193912A - Production and use for polymer, of amideamineurea compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a water-soluble polymer useful as a water resistance modifier or a printability improver for coated paper. SOLUTION: A branched polyamideaminourea compound contains in its molecule at least 3 groups shown by formula (III) (wherein, R and R1 are each independently hydrogen or methyl; m is an integer of 1-6; n which appear m times are each independently an integer of 2-6; and one of T which appear m times is -CONT1T2 group, while the remainder are each independently hydrogen, methyl or -CONT1T2 group, wherein, T1 and T2 are each independently hydrogen or a 1-4C alkyl), and these groups are combined with nitrogen atoms in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates generally to the preparation of amidoamine urea compounds. More specifically, a method for producing an amidoamine urea compound that can be a water-proofing agent for coated paper or a precursor of a printability improving agent,
The present invention relates to a method for further producing a water-soluble polymer from the amidoamine urea compound, and specific compounds and polymers obtained by these methods.

[0002]

2. Description of the Related Art The reaction product of a polyalkylene polyamine, urea and a dibasic carboxylic acid is added to aldehydes, epihalohydrins and / or α, γ-dihalo-β-.
Water-soluble polymers obtained by reacting hydrins are known, for example, from JP-B-44-11667, JP-B-56-28929, JP-B-61-42931, and JP-A-62-101621. Yes, it is used as a waterproofing agent for coated paper and a printing suitability improving agent. Further, by eliminating the involvement of the dibasic carboxylic acid in this reaction, the condensation reaction product of the polyalkylene polyamine and the urea is reacted with an aldehyde, an epihalohydrin and / or an α, γ-dihalo-β-hydrin. The use of the resulting water-soluble polymer as a resin component of a paper coating composition has also been proposed in JP-A-4-100997.

On the other hand, a polarized α, β-unsaturated monomer such as an acrylic acid compound or a methacrylic acid compound is subjected to a Michael addition reaction with ammonia or a polyamine, and further, a polyamine and an α, β-unsaturated monomer are added. It is possible to obtain highly branched polyamidoamines, so-called starburst dendrimers, by sequentially reacting with the body, respectively, Macromolecules 20 , 1164-1167 (1987),
This is known from Japanese Patent Publication No. 60-500295. The highly branched polyamide polyamine obtained in this way has a larger intramolecular void volume and a higher terminal group density than the ordinary star-branched polymer having the same molecular weight and terminal group, so that it has greater accessibility to chemical reactants. It has the characteristic and the characteristic that the density is relatively low.

[0004] However, in order to produce such highly branched polyamidoamines, it is necessary to carry out successive reactions. Therefore, i) the number of steps is increased, and therefore, the production cost is not sufficiently high. It is not useful, and ii) there is a problem that the number of intramolecular voids increases rapidly as successive reactions are repeated, and it becomes difficult to completely remove the solvent as a reaction medium.

On the other hand, α,
A branched polyamidoamine obtained by sequentially reacting a β-unsaturated carboxylic acid compound with a polyamine is disclosed in Japanese Patent Publication No. 62-7216. It is described that the modified polyamidoamine further modified with epihalohydrin is useful as a wet strength agent in papermaking. However, the epihalohydrin-modified branched polyamidoamine thus obtained is not used as a printability improver for coated paper, which is another chemical for the papermaking industry, because it causes a marked increase in the coating color.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to produce a water-soluble polymer which is useful as a water-proofing agent or a printability improver for coated paper.

Another object of the present invention is to produce a water-soluble polymer which is easy to produce industrially and has excellent properties as a printability improver for coated paper.

Yet another object of the present invention is to produce compounds useful as intermediates for such polymers.

As a result of intensive studies, a compound obtained by reacting a compound having a specific amidoamine structure with a urea or cyanic acid is sufficiently applicable to industrial production, and then is further combined with a crosslinkable compound such as an aldehyde. It has been found that by reacting, excellent properties can be obtained as a waterproofing agent for coated paper or a printability improving agent, and the present invention has been completed.

[0010]

The present invention relates to a compound of the formula (I)

[0011]

Embedded image

Wherein R is hydrogen or methyl; m
Is an integer from 1 to 6; n occurring m times are each independently an integer from 2 to 6; and R ¹ and R ² occurring m times
Are each independently hydrogen or methyl, but at least one of R ¹ and m R ² is hydrogen)

An object of the present invention is to provide a method for producing an amidoamine urea compound by reacting an amide amine compound having a structural unit represented by the following with a urea or cyanic acid.

The compound having the structural unit represented by the formula (I) is generally replaced with an amino compound having an active hydrogen by the formula (II)

[0015]

Embedded image

Wherein R is as defined above;
And Q is CN or COQ ', where Q' is O
H, NH ₂ or lower alkoxy)

Can be produced by subjecting a polarized α, β-unsaturated monomer represented by the formula (1) to a Michael addition reaction and further reacting with a polyamine.

The present invention also provides a water-soluble polymer by reacting a crosslinkable compound selected from aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins with an amidoamine urea compound obtained by the above method. Is provided.

Among the amidoamine urea compounds obtained by the above method, the compound of formula (III)

[0020]

Embedded image

Wherein R, R ¹ , m and n are as defined above; and one of the T occurrences m times is the group —CONT ¹ T ² , and the rest are each independently hydrogen,
A methyl or a group -CONT ¹ T ^2, wherein the T ¹ and T ² are each independently hydrogen or lower alkyl)

A branched polyamidoamine urea compound having at least three groups represented by the following formula in the molecule is particularly important. Therefore, the present invention also provides a compound of the formula (III)
The present invention provides a branched polyamidoamine urea compound having at least three groups represented by the following formulas, and these groups are bonded to a nitrogen atom in the molecule.

The present invention further provides a branched polyamidoamine urea compound having at least three groups represented by the formula (III) in a molecule from an aldehyde, an epihalohydrin and an α, γ-dihalo-β-hydrin. It is intended to provide a water-soluble polymer obtained by reacting with a selected crosslinking compound.

In producing the amidoamine urea compound according to the present invention, it can be obtained by subjecting an α, β-unsaturated monomer represented by the formula (I) to a Michael addition reaction and further reacting with a polyamine.

The amino compound having active hydrogen used here may be a primary monoamine, a secondary monoamine or a polyamine, in addition to ammonia.

As the primary monoamine, generally used are aliphatic amines, and also alkylamines. The alkyl is typically one having 1 to 6 carbon atoms, and more preferably one having 1 to 3 carbon atoms. Specific examples of the primary monoamine include methylamine, ethylamine, propylamine, isopropylamine, butylamine, hexylamine and the like. 2
As the primary monoamine, an aliphatic amine, which is also a dialkylamine, is generally used, and the alkyl is also typically one having 1 to 6 carbon atoms, furthermore one having 1 to 3 carbon atoms. Specific examples of the secondary monoamine include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine and the like.

As the polyamine, a polyamine in which a plurality of amino groups are linked by alkylene is generally used. In particular, in addition to an aliphatic diamine having two primary amino groups and two primary amino groups, Polyalkylene polyamines having one or more secondary amino groups are preferably used. The alkylene linking a plurality of amino groups may have about 2 to 6 carbon atoms, but generally 2 or 3 carbon atoms are sufficient. Therefore, specific examples of the aliphatic diamine include ethylene diamine, propylene diamine, trimethylene diamine, and the like,
Specific examples of the polyalkylene polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, 3-azahexane-1,6-diamine, and 4,7-diazadecane-1,10-diamine. Can be

Among these amino compounds having active hydrogen, ammonia and polyamines are preferably used because they can form branched polyamidoamines.
Among them, ammonia, ethylenediamine, diethylenetriamine, triethylenetetramine and the like are industrially advantageous. Further, these amino compounds having active hydrogen can be used alone or in combination of two or more.

The polarized α, β-unsaturated monomer which undergoes the Michael addition reaction to such an amino compound having active hydrogen is represented by the above formula (II). In other words, the amino group has a carbon-carbon double bond capable of nucleophilic addition, and further has a site capable of reacting with the amino group under different reaction conditions.

In the formula (II), R is hydrogen or methyl; in other words, the compound of the formula (II) comprises acrylic acid,
Methacrylic acid or a derivative thereof. Equation (I
Q in I) is a cyano, carboxy, aminocarbonyl or carboxylic acid lower alkyl ester group.
Here, examples of the lower alkyl include those having about 1 to 4 carbon atoms, and among them, methyl and ethyl are common.

Specific examples of the polarized α, β-unsaturated monomer represented by the formula (II) include α, β-unsaturated carboxylic acids including acrylic acid and methacrylic acid, methyl acrylate, methacrylic acid Esters including methyl, ethyl acrylate, ethyl methacrylate, etc., acid amides including acrylamide and methacrylamide, and nitriles including acrylonitrile and methacrylonitrile.

An amino compound having active hydrogen and a compound of formula (II)
The Michael addition reaction with a polarized α, β-unsaturated monomer represented by
It is carried out at a temperature of about 0 ° C. for about 1 to 48 hours.

The amount of the polarized α, β-unsaturated monomer used depends on the number of active hydrogens in the amino compound, but is usually about 1 mol or 1 mol per 1 mol of the amino compound having active hydrogen. That is all. There is no particular upper limit on the amount used. For example, in order to increase the reaction rate, a large excess of the α, β-unsaturated monomer may be used, and after the reaction is completed, unreacted components may be removed. It is. However, in general, an α, β-unsaturated monomer is used in a range of 2 moles or less of the active hydrogen in the amino compound.

When the amino compound having active hydrogen is a secondary monoamine, the α, β-unsaturated monomer is preferably used in an amount of about 1 to 2 mol per 1 mol of the secondary monoamine. When the amino compound having active hydrogen is a primary monoamine, the α, β-unsaturated monomer is preferably used in an amount of about 1 to 4 mol per 1 mol of the primary monoamine.

When the amino compound having active hydrogen is ammonia or polyamine, that is, a compound having three or more active hydrogens in one molecule, the α, β-unsaturated monomer is used per mole of the amino compound. Is preferably used to give a product having a branched structure. In this case as well, there is no particular upper limit to the amount of the α, β-unsaturated monomer used, but usually about twice or less the amount of active hydrogen in the amino compound is sufficient. More preferably, α,
The β-unsaturated monomer is at least 2.5 moles, more preferably at least 3 moles, per mole of ammonia or polyamine, and 1.5 moles based on active hydrogen in ammonia or polyamine.
It is used about twice or less mole.

As for the order of the reaction, it is preferable to react the polarized α, β-unsaturated monomer with an amino compound having active hydrogen in order to suppress a side reaction.
The reverse is also acceptable. Of course, both can be charged and reacted simultaneously. If desired, the reaction system can be diluted with water or a lower alcohol such as methanol or ethanol.

In this way, a Michael addition product of an α, β-unsaturated monomer to an amino compound having active hydrogen is obtained. The obtained reaction product can be subjected to a reaction with the next polyamine as it is as a mixture.If desired, distillation under reduced pressure or a suitable organic solvent such as dichloromethane, chloroform, ether or the like, and an appropriate pH were adjusted. By common operations such as solvent extraction with water,
It is also possible to purify the main product.

The Michael adduct thus obtained is further reacted with a polyamine. In the Michael addition reaction of an α, β-unsaturated monomer to an amino compound having active hydrogen and the amidation reaction of a polyamine to a Michael adduct, similar conditions are employed. At this time, amidation may occur as a side reaction. Therefore, it is generally preferable to carry out the Michael addition reaction under milder conditions than the subsequent amidation reaction, for example, at a slightly lower reaction temperature.

The polyamine used for the amidation reaction has one primary amino group and one other primary or secondary amino group in the molecule.
Aliphatic diamines having a primary amino group and both of which are linked by alkylene, and one primary amino group and further having at least two primary, secondary or tertiary amino groups; A polyalkylene polyamine in which the groups are linked by alkylene, generally having the formula (Ia)
Indicated by

[0040]

Embedded image NH ₂ (C _n H _2n NR ² ) _m R ¹ (Ia)

Wherein m and n are as defined above, and R ¹ and R ^{2 which} occur m times are each independently hydrogen or methyl, but at least one of R ¹ and m R ² One is hydrogen. In the above formula (Ia), the alkylene represented by C _n H _2n connecting a plurality of amino groups may have 2 to 6 carbon atoms, but generally 2 or 3 carbon atoms are sufficient. Further, m can be an integer of 1 to 6, but generally 1 to 4 is sufficient. When m is 2 or more, alkylene C that appears multiple times corresponding to the value of m
_n H _2n and the group R ² may be the same or different.

Specific examples of such a polyamine include:
Aliphatic diamines such as ethylenediamine, propylenediamine, trimethylenediamine, and diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, 3-azahexane-1,6-diamine, 4,7-diazadecane-1, 1
Examples thereof include polyalkylene polyamines such as 0-diamine and methyliminobispropylamine. Each of these polyamines can be used alone, or 2
Mixtures of more than one species can be used. Further, in addition to such a polyamine, other amines, for example, a primary or secondary monoamine, a diamine having a primary amino group and a tertiary amino group, and the like can be mixed and used.

Α, β to amino compound having active hydrogen
When the polyamine is further reacted with the Michael adduct of the unsaturated monomer, the reaction temperature is usually from 10 to 200, although it depends on the type of the functional group capable of reacting with the amino group remaining in the Michael adduct. ° C, preferably 30 to 18
The reaction is performed at about 0 ° C. for about 3 to 72 hours while removing the alcohol or ammonia generated as necessary outside the system.

The amount of the polyamine to be used is usually about 1 to 20 mol, preferably 3 to 1 mol, per mol of the α, β-unsaturated monomer used in the Michael addition reaction.
It is about 0 mol.

The order of the reaction is as follows:
Preferably, the Michael adduct is reacted, but vice versa. Of course, you can put both together. If desired, the reaction system can be diluted with water or a lower alcohol such as methanol or ethanol. In particular, when nitriles such as acrylonitrile are used as the α, β-unsaturated monomer, the cyano group of the Michael adduct reacts with the polyamine,
Furthermore, since the amide bond is formed by hydrolysis, the reaction between the Michael adduct and the polyamine is usually carried out in the presence of water.

After completion of the reaction, the reaction mixture can be subjected to the subsequent reaction with ureas or cyanic acid. The excess polyamine and the reaction solvent can be separated and removed by distillation under reduced pressure and / or column chromatography. The main product may be isolated.

Although not limited to the above-described reaction, an amidoamine compound having the structural unit represented by the above formula (I) is obtained in this manner. M in the formula (I) can be an integer of 1 to 6, but generally 1 to 4 is sufficient. The alkylene C _n H _2n in the formula (I)
May have 2 to 6 carbon atoms, but generally 2 or 3 carbon atoms are sufficient. When m is 2 or more, the alkylene C _n H _2n and the group R ² appearing a plurality of times corresponding to the value of m may be the same or different. For example, when a polyamine such as 3-azahexane-1,6-diamine or 4,7-diazadecane-1,10-diamine having plural kinds of alkylenes in one molecule is used as the polyamine, the formula (I) The alkylenes that occur more than once in) naturally differ.

In the present invention, an amidoamine compound having a structural unit represented by the formula (I) is further reacted with a urea or cyanic acid to obtain an amidoamine urea compound. The ureas used here are generally represented by the following formula (IV).

[0049]

Embedded image NH ₂ CONT ¹ T ² (IV)

Wherein T ¹ and T ² are each independently hydrogen or lower alkyl. As lower alkyl,
For example, those having 1 to 4 carbon atoms can be mentioned, but methyl or ethyl is generally sufficient. Specific examples of such ureas include urea, N-monoalkyl ureas such as N-methyl urea and N-ethyl urea, and N, N-dialkyls such as N, N-dimethyl urea and N, N-diethyl urea. There are N-mono and N, N-disubstituted ureas such as urea. Urea is preferably used industrially.

Cyanic acid has a structure of HOCN, and is usually sodium cyanate, potassium cyanate,
Cyanates such as ammonium cyanate are used,
Such salts are decomposed under acidic conditions during the reaction, and are used such that cyanic acid is generated in the reaction system. In the reaction with amines, it is known that urea and cyanic acid act almost in the same way.For example, urea is considered to deammonate in the form of ammonium cyanate at the time of the reaction. The product is the same whether urea or cyanic acid is used.

In the reaction between the amidoamine compound having the structural unit represented by the formula (I) and ureas or cyanic acid, the reaction using ureas is usually 100 to 18
At a temperature of about 0 ° C, preferably about 110 to 160 ° C,
It is performed for about 1 to 10 hours. The amount of the urea to be used in this step is preferably about 0.1 to 1.5 mol, more preferably 0. .Five~
It is about 1 mol.

When cyanic acid is used, it is usually 10 to 90
℃, preferably at a temperature of about 30-60 ℃, about 1 ~
The reaction is performed for 5 hours. Usually, a method is employed in which cyanates are added to an acidic reaction system containing an amidoamine compound to thereby cause a reaction while generating cyanic acid in the system.

In the reaction of the urea or cyanic acid with the amidoamine compound, if desired, the reaction can be diluted with a suitable solvent. Reaction solvents that can be used include water,
Lower alcohols such as methanol and ethanol are included.

Thus, an amidoamine urea compound as an intermediate is obtained.
Generally, it has a structural unit represented by the following formula (V).

[0056]

Embedded image

In the formula, R, R ¹ , m, n and T are as defined above.

For example, ammonia is used as an amino compound having active hydrogen, and a sufficient amount of an acrylic compound such as acrylic acid, acrylonitrile, acrylamide, or acrylic ester is used as an α, β-unsaturated monomer, and polyamine is used. When ethylenediamine is used as urea and urea or cyanic acid is used as urea or cyanic acid, a compound having a structure of the following formula (Va) is generated.

[0059]

Embedded image N [CH ₂ CH ₂ CONHCH ₂ CH ₂ NHCONH ₂ ] ₃ (Va)

By appropriately selecting the amount of the acrylic acid compound and the reaction conditions for Michael addition, a mono-adduct or di-adduct to ammonia can be produced.

On the other hand, in the above reaction, a methacrylic acid-based compound such as methacrylic acid, methacrylonitrile, methacrylamide, or methacrylic acid ester is used in place of the acrylic acid-based compound, whereby R in the formula (V) is methyl. Can be manufactured.

Methylamine is used as an amino compound having active hydrogen, a sufficient amount of an acrylic acid compound is used as an α, β-unsaturated monomer, ethylenediamine is used as a polyamine, and urea or cyanide is used as urea or cyanic acid. When an acid is used, a compound having a structure represented by the following formula (Vb) is generated.

[0063]

Embedded image CH ₃ N [CH ₂ CH ₂ CONHCH ₂ CH ₂ NHCONH ₂ ] ₂ (Vb)

In this case, different types of compounds can be produced by appropriately selecting the amount of the acrylic acid compound used, the Michael addition reaction conditions, and the like.

Dimethylamine is used as an amino compound having active hydrogen, an acrylic acid compound is used as an α, β-unsaturated monomer, ethylenediamine is used as a polyamine, and urea or cyanic acid is used as a urea or cyanic acid. In this case, a compound having the structure of the following formula (Vc) is produced.

[0066]

Embedded image (CH ₃ ) ₂ NCH ₂ CH ₂ CONHCH ₂ CH ₂ NHCONH ₂ (Vc)

Ethylene diamine is used as an amino compound having active hydrogen, an acrylic acid compound is used in a sufficient amount as an α, β-unsaturated monomer, ethylene diamine is used as a polyamine, and urea or cyanic acid is used as urea or cyanic acid. In the case where is used, a compound having the structure of the following formula (Vd) is produced.

[0068]

Embedded image CH ₂ N [CH ₂ CH ₂ CONHCH ₂ CH ₂ NHCONH ₂ ] ₂ | (Vd) CH ₂ N [CH ₂ CH ₂ CONHCH ₂ CH ₂ NHCONH ₂ ] ₂

Also in this case, different types of compounds can be produced by appropriately selecting the amount of the acrylic acid compound used, the reaction conditions for Michael addition, and the like.

When another polyamine is used as the amino compound having active hydrogen, when another compound, especially a methacrylic acid-based compound is used as the α, β-unsaturated monomer,
When other compounds, especially polyalkylene polyamines, are used as the polyamine to react with the Michael adduct, and other ureas such as N-
The amidoamine urea compounds obtained when using mono-substituted ureas or N, N-di-substituted ureas will be readily understood by those skilled in the art from the above description.

In particular, when a polyalkylene polyamine is reacted with the Michael adduct, m in the above formula (III) or (V) is 2 or more. Then, by selecting the amount of urea or cyanic acid and the reaction conditions therewith, of T appearing m times in these formulas, except for methyl, all unsubstituted or substituted carbamoyl-
It may be CONT ¹ T ² (where T ¹ and T ² are as defined above), or some T may be left as hydrogen. In addition, a mixture thereof is often obtained.

For example, ammonia is used as an amino compound having active hydrogen, an acrylic acid compound is used as an α, β-unsaturated monomer in a sufficient amount, diethylene triamine is used as a polyamine, and urea is used as urea or cyanic acid. Alternatively, when cyanic acid is used, an amidoamine urea compound represented by the following formula (Ve) or (Vf) or a mixture thereof is obtained.

[0073]

Embedded image

Even if these mixtures are used, or if they further contain an unreacted amidoamine compound, the properties of the polymer obtained by the subsequent reaction with the crosslinkable compound are not significantly affected.

Of the amidoamine urea compounds described above, those having a branched structure with an amino compound having active hydrogen as a nucleus, that is, having at least three groups represented by the above formula (III) in the molecule, and Of particular interest are compounds where the groups are attached to the same or different nitrogen atoms in the molecule. Such a branched polyamidoamine urea compound is generally represented by the following formula (VI).

[0076]

Embedded image

In the formula, p is an integer of 0 to 6; q appearing p times are each independently an integer of 2 to 6;
Is a group represented by the formula (III), which is bonded to a nitrogen atom in the molecule; a is a number of 3 or more; and when a bond coming out of the nitrogen atom is not bonded to the group A, the bond of the nitrogen atom is It is bonded to hydrogen or methyl.

In the above formula (VI), when p is 0,
When p is 1, the compound is branched with an alkylenediamine as a nucleus. When p is 2 or more, the compound is branched with a polyalkylenepolyamine as a nucleus. The value of p can be 0 to 6 depending on the amino compound used as a raw material, but is generally 0.
About 4 is sufficient. The alkylene represented by C _q H _2q can have 2 to 6 carbon atoms, but generally 2 or 3 carbon atoms are sufficient. When p is 2 or more, q appearing a plurality of times corresponding to the value of p may be the same or different. The value of a can be up to 9 corresponding to the value of p, but generally 3 or more and about 7 is sufficient.

The amidoamine urea compound obtained by the present invention can be an intermediate of a water-soluble polymer exhibiting excellent effects when used as a water-proofing agent for coated paper or a printability improving agent. That is, the amidoamine urea compound is further converted to a crosslinkable compound, particularly an aldehyde,
By reacting with epihalohydrins or α, γ-dihalo-β-hydrins, a water-soluble polymer can be obtained.

As aldehydes, there can be used alkyl aldehydes such as formaldehyde, acetaldehyde and propyl aldehyde, and alkyl dialdehydes such as glyoxal, propane dial and butane dial. Industrially, formaldehyde and glyoxal are preferred. Each of these aldehydes can be used alone or as a mixture of two or more.

Epihalohydrins are generally represented by the following formula (VI
Indicated by I).

[0082]

Embedded image

Wherein X is halogen and v is 1, 2 or 3. Preferred examples of epihalohydrins include epichlorohydrin, epibromohydrin and the like. These can be used alone or as a mixture of two or more.

The α, γ-dihalo-β-hydrins are generally represented by the following formula (VIII).

[0085]

Embedded image

In the formula, X and Y are each independently halogen. Specific examples of α, γ-dihalo-β-hydrins include 1,3-dichloro-2-propanol, 1,3
-Dibromo-2-propanol and the like.

The reaction of the amidoamine urea compound with a crosslinkable compound selected from aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins is preferably carried out at a total concentration of about 20 to 80% by weight of each component. It is preferably carried out in an aqueous solution of about 30 to 70% by weight. At this time, the crosslinking compound may be used alone,
Also, two or more kinds may be used in combination. For example, aldehydes and epihalohydrins can be used in combination, or aldehydes and α, γ-dihalo-β
-Hydrins can also be used in combination.

When reacting an amidoamine urea compound with an aldehyde, preferably an acid such as hydrochloric acid, sulfuric acid,
After adjusting the pH to 7 or less, more preferably to pH 3 to 6 with phosphoric acid, formic acid, acetic acid or the like, about 40 to 100 ° C.
The reaction is conducted at a temperature of about 1 to 10 hours. In addition, pH8 ~
First, the reaction was carried out under alkaline conditions of 12 and then the pH was adjusted to 7
Hereinafter, a method in which the pH is adjusted to more preferably 3 to 6 and the reaction is continued is also preferable. In the latter case, the reaction under alkaline conditions is preferably performed at about 40 to 100 ° C. for about 0.5 to 5 hours, and the reaction under acidic conditions is preferably performed at about 40 to 100 ° C. for about 0.5 to 5 hours. The amount of the aldehyde used is 0.1 to 3 aldehyde groups per 1 mol of the amidoamine urea compound.
It is preferable that the amount is about mol, more preferably 0.3 to 1.5 mol.

When the amidoamine urea compound is reacted with epihalohydrins or α, γ-dihalo-β-hydrins, the reaction is preferably carried out at a temperature of about 30 to 100 ° C. under conditions of pH 5 or more, more preferably pH 6 to 9. The reaction is preferably performed at 40 to 90 ° C. for about 1 to 10 hours. The amount of the epihalohydrin or α, γ-dihalo-β-hydrin used is based on 1 mol of the amidoamine urea compound.
The amount is preferably about 0.1 to 3 mol, more preferably 0.3 to 2 mol.
Is a mole.

The reaction between the amidoamine urea compound and the crosslinkable compound is complicated, and it is difficult to express the structure of the resulting polymer in a unified manner. In any case, the crosslinkable compound is represented by the above formula (III). In the structural unit shown, an amino group forming an amide bond, an unsubstituted or substituted urea residue, or an amino group having active hydrogen remaining (hereinafter collectively referred to as reactive nitrogen) In some cases) to form a hydroxyalkyl group or a halohydrin group, and a part thereof is presumed to react with reactive nitrogen in another structural unit to form a crosslinked structure. Of course, since a part of the reactive nitrogen remains as it is, a polymer having these structures complicatedly formed is generated.

For example, when formaldehyde which is a monoaldehyde is used as the crosslinkable compound, the formaldehyde reacts with the reactive nitrogen to form a methylolamino group (= NCH ₂ OH), and a part of the methylolamino group (= NCH ₂ OH) is formed. Reacts with reactive nitrogen in other structural units to form = NCH ₂
It is assumed that a crosslinked structure of N = is formed. When glyoxal, which is a dialdehyde, is used as the crosslinkable compound, it is presumed that the same reaction as in the case of formaldehyde forms a crosslinked structure of = NCH (OH) CH (OH) N =.

When epihalohydrins or α, γ-dihalo-β-hydrins are used as the crosslinkable compound, a halohydrinated amino group as shown in the following formula is formed.

[0093]

Embedded image

Wherein X and v are as defined above. Then, it is presumed that a part of the halohydrinated amino group further reacts with the reactive nitrogen in another structural unit to form a crosslinked structure represented by the following formula.

[0095]

Embedded image

Where v is as defined above.

In actuality, hydrogen remains as it is in a part of the reactive nitrogen, and a part thereof includes a hydroxyalkyl group and a halohydrin group which proceed to a crosslinked structure. Therefore,
A polymer containing these reactive nitrogen, hydroxyalkyl or halohydrin groups and further a crosslinked structure is obtained.

The polymer thus obtained is water-soluble, and has a number average molecular weight in the range of about 800 to 10,000. The number average molecular weight in this case is measured by gel permeation chromatography (GPC). In particular, when used as a waterproofing agent or a printability improving agent for coated paper, those having a number average molecular weight of about 1,000 to 5,000 are preferred. The polymer is usually obtained in the form of an aqueous solution, and the viscosity of the 60% by weight aqueous solution at 25 ° C. is 2%.
It is about 0 to 1,000 cp. Above all, a polymer obtained from a branched polyamidoamine urea compound has a high functional group density and has excellent properties as a printability improving agent for coated paper.

When this polymer is used for coating paper, a composition containing a pigment and an aqueous binder is generally prepared and applied to paper. The paper here is in a broad sense, and includes paper and paperboard in a narrow sense.

The pigment used as a component of the coating composition may be any of those conventionally used in paper coating, and white inorganic pigments and white organic pigments are used. Examples of the white inorganic pigment include kaolin, talc, calcium carbonate (heavy and light), aluminum hydroxide, satin white, titanium oxide, and the like. Examples of the white organic pigment include polystyrene, melamine-formaldehyde resin, and urea. -Formaldehyde resin and the like. These can be used alone or in combination of two or more. Still further, a colored inorganic or organic pigment may be used in combination.

The aqueous binder may be any of those generally used for paper coating, and a water-soluble binder or a water-emulsified binder may be used. Examples of the water-soluble binder include unmodified or modified starches including oxidized starch and phosphorylated ester, polyvinyl alcohol, water-soluble proteins including casein and gelatin, and denaturation including carboxymethyl cellulose. Cellulose and the like.
Examples of the water-emulsifying binder include, for example, a styrene-butadiene resin, a vinyl acetate resin, an ethylene-vinyl acetate resin, and a methyl methacrylate resin.
These aqueous binders can be used alone or in combination of two or more.

In preparing the coating composition for paper, the composition ratio of the pigment and the aqueous binder is determined according to the use and purpose, and there is no particular difference from the composition ratio generally used in the art. . The preferred composition ratio of both is about 5 to 200 parts by weight, more preferably about 10 to 50 parts by weight of the aqueous binder based on 100 parts by weight of the pigment. The water-soluble polymer obtained by the present invention is preferably used in an amount of 0.0
About 5 to 5 parts by weight, more preferably about 0.1 to 2 parts by weight is blended. The solid content concentration in the coating composition varies depending on the type of coater and the application of the paper or composition,
Generally, it is selected from the range of about 20 to 72% by weight.

The water-soluble polymer according to the present invention is usually added and mixed at the time of preparing a paper coating composition, but is previously added and mixed with a pigment slurry or an aqueous binder.
It is also possible to take the method of blending the remaining components with it.

In preparing the paper coating composition, other components such as a dispersant, a viscosity / fluidity regulator, an antifoaming agent, a preservative, a lubricant, a water retention agent, and a dye or a colored pigment may be used. Those conventionally used in paper coating compositions, such as colorants, can be blended as necessary.

The paper coating composition thus obtained can be prepared by a conventionally known method, that is, a blade coater, an air knife coater, a bar coater, a size press coater,
It is applied to a paper substrate by a method using various known coaters such as a gate roll coater and a cast coater. Thereafter, the coated paper is dried and, if necessary, subjected to a smoothing treatment with a super calender or the like, whereby a coated paper can be produced.

[0106]

EXAMPLES Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. All percentages and parts in the examples are by weight unless otherwise indicated. The viscosity is a value measured at 25 ° C.

Example 1 (a) Production of amidoamine urea compound 6.1 g (0.1 mol) of 28% aqueous ammonia was charged into a four-necked flask equipped with a thermometer, a Liebig condenser and a stirring rod, and then charged. Acrylonitrile 13.3 g (0.25
Mol) was added dropwise, and a Michael addition reaction was performed while maintaining the temperature at 20 to 30 ° C for 12 hours. As determined by high performance liquid chromatography, the conversion of acrylonitrile was 77.3%. Thereafter, 61.9 g (0.6 mol) of diethylenetriamine was further added dropwise, and an amidation reaction was performed at a temperature of 120 to 150 ° C. for 24 hours. When analyzed by gas chromatography, the amidation ratio was 68.3%.
Met. 93.1 g of urea (1.55 g) was added to the obtained reaction mixture.
Mol), and a deammonification reaction was performed at a temperature of 120 to 130 ° C. for 5 hours.

The main product of this reaction has the following structure.

[0109]

Embedded image

Here, a, b and c indicate the positions of the corresponding protons in the nuclear magnetic resonance spectrum described later.

Infrared absorption spectrum: 3350-3200 cm ^-1 (NH stretching vibration of -CONH-) 2950 cm ^-1 (Stretching vibration of -CH _2- ) 1650 cm ^-1 (C = O stretching vibration of -CONH- ) ¹ H-NMR (270 MHz, D ₂ O): δ 2.45-2.55 ppm (corresponding to the methylene protons in a) 2.60-2.70 ppm (corresponding to the methylene protons in b) 3.20-3.40 ppm ( Corresponds to the methylene proton of c above)

(B) Preparation of the polymer : 67.5 g of water and 37
% Formalin (43.8 g, 0.54 mol) was added and reacted at 70 ° C. for 4 hours. Thereafter, the pH was adjusted to 6.5 with an aqueous solution of caustic soda to obtain a polymer aqueous solution having a concentration of 60% and a viscosity of 260 cp.

Example 2 (a) Production of amidoamine urea compound A four-necked flask equipped with a thermometer, a Liebig condenser and a stirring rod was charged with 6.1 g (0.1 mol) of 28% aqueous ammonia and then added thereto. 23.2 g of methyl acrylate (0.27 g)
Mol), and kept at a temperature of 30 to 35 ° C. for 9 hours,
A Michael addition reaction was performed. From the results of analysis by liquid chromatography, the reaction rate of methyl acrylate was 85.4.
%Met. Then 61.9 g of diethylenetriamine
(0.6 mol) was added dropwise, and an amidation reaction was performed at a temperature of 110 to 120 ° C. for 6 hours. According to the result of analysis by gas chromatography, the amidation ratio was 91.5%. Subsequently, 31.8 g of water and 93.1 g (1.55 mol) of urea were charged and a deammonification reaction was carried out at a temperature of 110 to 120 ° C. for 6 hours.

The main product of this reaction has the same structure as the compound obtained in Example 1 (a). The infrared absorption spectrum and the nuclear magnetic resonance showed the same results as those of the product obtained in Example 1 (a).

(B) Preparation of the polymer : 56.4 g of water and 37 g of water were added to the reaction mixture obtained in (a).
% Formalin (31.6 g, 0.39 mol) was added and reacted at 70 ° C. for 4 hours. Thereafter, the pH was adjusted to 6.5 with caustic soda to obtain a polymer aqueous solution having a concentration of 60% and a viscosity of 360 cp.

Example 3 (a) Production of amidoamine urea compound A four-necked flask equipped with a thermometer, a reflux condenser and a stirring rod was charged with 6.1 g (0.1 mol) of 28% aqueous ammonia, and acryl was added thereto. 23.2 g (0.27 mol) of methyl acid was added dropwise and reacted at a temperature of 30 to 40 ° C. for 12 hours to complete the Michael addition. At this stage, the reaction rate of methyl acrylate analyzed by liquid chromatography was 8
3.0%. The reaction mixture was subjected to solvent extraction using water and dichloromethane, and the organic phase was concentrated under reduced pressure to isolate a methyl acrylate 3-adduct of ammonia (triscarbomethoxyethylamine).

16.5 g (0.06 mol) of the isolated triscarbomethoxyethylamine was again charged into a four-necked flask equipped with a thermometer, a reflux condenser, and a stirring bar.
Further, 74.3 g (0.72 mol) of diethylenetriamine was added dropwise, and an amidation reaction was performed at a temperature of 140 to 150 ° C. for 10 hours. As a result of analysis by gas chromatography, the amidation ratio was 88.8%. After that, the reflux condenser was replaced with a Liebig condenser, and 1.5 to 3 Torr, 80 to
Distillation was carried out at 100 ° C. for 14 hours to distill off methanol and unreacted diethylenetriamine. Next, the condenser was changed to a reflux condenser again, 37.8 g (0.63 mol) of urea and 15.4 g of water were charged, and a deammonification reaction was carried out at a temperature of 100 to 120 ° C. for 4 hours.

The main product of this reaction has the same structure as the compound obtained in Example 1 (a). The infrared absorption spectrum and the nuclear magnetic resonance showed the same results as those of the product obtained in Example 1 (a).

(B) Preparation of polymer The reaction mixture obtained in (a) was added to 37% formalin 11.4.
g (0.14 mol) and 20.4 g of water were charged and reacted at 70 ° C. for 4 hours. Thereafter, the pH was adjusted to 6.5 with an aqueous solution of caustic soda to obtain a polymer aqueous solution having a concentration of 60% and a viscosity of 260 cp.

Example 4 (a) Production of amidoamine urea compound In a four-necked flask equipped with a thermometer, a reflux condenser and a stirring rod, 10.3 g (0.1 mol) of diethylenetriamine was charged, and methyl acrylate 43 was added thereto. 0.0 g (0.5 mol) was added dropwise, 25 g of water was further charged, and the mixture was reacted at a temperature of 30 to 40 ° C. for 18 hours. When analyzed by high performance liquid chromatography, the Michael addition rate of methyl acrylate was 96.0%. Thereafter, the solvent was extracted using water and dichloromethane, and the organic phase was concentrated under reduced pressure to isolate methyl acrylate pentaadduct of diethylenetriamine (pentakiscarbomethoxyethyldiethylenetriamine).

42.7 g (0.08 mol) of the isolated pentakiscarbomethoxyethyldiethylenetriamine was again charged into a four-necked flask equipped with a thermometer, a reflux condenser and a stirring rod.
3.8 g (1.2 mol) was added dropwise and amidation reaction was carried out at 70 ° C. for 6 hours. When analyzed by gas chromatography, the amidation ratio was 97.8%. After that, the reflux condenser was replaced with a Liebig condenser, and 0.4 Torr, 70 ~
Distillation was carried out at 80 ° C. for 6 hours to remove methanol and unreacted diethylenetriamine. Then 33.0 g of water
And 60.1 g (1 mol) of urea were added.
A deammonification reaction was performed for 0 hours.

The main product of this reaction has the following structure.

[0123]

Embedded image

However, a, b, c and d indicate the positions of the corresponding protons in the nuclear magnetic resonance spectrum described later.

Infrared absorption spectrum: 3350-3200 cm ^-1 (NH stretching vibration of -CONH-) 2950 cm ^-1 (Stretching vibration of -CH _2- ) 1650 cm ^-1 (C = O stretching vibration of -CONH- ) ¹ H-NMR (270 MHz, D ₂ O): δ 2.40-2.50 ppm (corresponding to the methylene protons in a) 2.45-2.55 ppm (corresponding to the methylene protons in b) 2.60-2.70 ppm ( 3.20-3.40 ppm (corresponding to the methylene protons in d above)

(B) Preparation of polymer The reaction mixture obtained in (a) was added to 37% formalin 13.8.
g (0.17 mol) and 41.8 g of water.
Allowed to react for hours. Thereafter, the pH was adjusted to 6.5 with caustic soda to obtain a polymer aqueous solution having a concentration of 60% and a viscosity of 290 cp.

Example 5 The corresponding amidoamine urea compound can be obtained by using equimolar methyl methacrylate instead of acrylonitrile in Example 1 (a).

Example 6 The corresponding polymer aqueous solutions can be obtained by using equimolar glyoxal instead of formalin in each of (b) of Examples 1, 2, 3, and 4.

Reference Example Using the aqueous polymer solutions obtained in Examples 1 to 4, a coating composition for paper was prepared according to the formulation shown in Table 1.

[0130]

[Table 1] ^{* 1} Ultra White 90: Clay manufactured by Engel Hard Minerals, Inc. ^{* 2} Carbital 90: Calcium carbonate manufactured by Fuji Kaolin Co., Ltd. ^{* 3} Sumireze Resin DS-10: Polyacrylic acid pigment dispersant manufactured by Sumitomo Chemical Co., Ltd. ^{* 4} SN-307: Styrene butadiene latex manufactured by Sumitomo Dow Co., Ltd. ^{* 5} MS-4600: Phosphated esterified starch manufactured by Nippon Shokuhin Co., Ltd. ^{* 6 The} mixing ratio is represented by the weight of solid content.

The prepared paper coating composition had a total solid content of 6%.
Water and a 10% aqueous sodium hydroxide solution were used to adjust the pH to 0% and the pH to about 9.0. The physical properties of this composition were measured as follows, and the results are shown in Table 2.

Physical Properties of Coating Composition (a) pH glass electrode type hydrogen ion concentration meter [Toa Denpa Kogyo Co., Ltd.]
The pH of the coating composition immediately after preparation was measured at 25 ° C.

(B) Viscosity Using a B-type viscometer (BL type, manufactured by Tokyo Keiki Co., Ltd.)
The viscosity of the coating composition immediately after preparation was measured at 25 ° C. and rpm.

This coating composition was applied to one or both sides of high quality paper having a basis weight of rice of 83 g / m ² using a wire rod so that the coating amount was 15 g / m ² . Immediately after the application, the resultant was dried with hot air at 120 ° C. for 30 seconds, then conditioned at a temperature of 20 ° C. and a relative humidity of 65% for 16 hours, and further subjected to a super calender treatment twice at a temperature of 60 ° C. and a linear pressure of 60 kg / cm. Thus, a coated paper was obtained.

The coated paper thus obtained was subjected to tests for water resistance, ink acceptability and blister resistance. The test results are shown in Table 2. The test method is as follows.

Water resistance (a) Wet rub method (WR method) Approximately 0.1 ml of ion-exchanged water was dropped on the coated surface and rubbed with a fingertip seven times to transfer the eluted content to black paper, and eluted The amount was determined visually. The judgment criteria were as follows. Water resistance (poor) 1-5 (excellent)

(B) Wet pick method (WP method) Using a RI tester (manufactured by Meiji Seisakusho), the coated surface was wetted with a water supply roll, printed, and the peeling state was visually observed and judged. . The judgment criteria were as follows. Water resistance (poor) 1-5 (excellent)

Ink Acceptability (A) Method A Using a RI tester, the coated surface was wetted with a water supply roll and then printed, and the ink acceptability was visually observed and judged. The judgment criteria were as follows. Ink acceptability (poor) 1-5 (excellent)

(B) Method B Using an RI tester, the ink was printed while water was kneaded into the ink, and the ink receptivity was visually observed and judged. The judgment criteria were as follows. Ink acceptability (poor) 1-5 (excellent)

[0140] Double-sided printing was performed on a double-sided coated paper using an ink for rotary offset printing using a blister-resistant RI tester. After humidity control, the paper was immersed in a heated silicone oil bath to reduce the amount of blisters generated. It was judged with the naked eye. The judgment criteria were as follows. Blister resistance (poor) 1-5 (excellent)

[0141]

[Table 2] ^{* 1} pH at 25 ° C ^{* 2} Viscosity at 25 ° C

[0142]

The amidoamine urea compound obtained according to the present invention is useful as an intermediate of a polymer to be used as a waterproofing agent for coated paper or a printability improving agent. And
A polymer obtained by further reacting a crosslinkable compound such as an aldehyde with the amidoamine urea compound has excellent ink receptivity and water resistance when coated on paper as a paper coating composition, and particularly has a blister resistance. Excellent in nature,
Further, the present invention provides a coated paper having various excellent and effective properties such as almost no formaldehyde odor.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshiyuki Hasegawa 3-1-198, Kasuganaka, Konohana-ku, Osaka-shi Within Sumitomo Chemical Industries Co., Ltd. (72) Munemaro Fujishiro 3-chome, Kasuganaka, Konohana-ku, Osaka-shi No. 98 No. 98 Sumitomo Chemical Co., Ltd. F-term (reference) 4H006 AA01 AB46 4J033 EA01 EA02 EA13 EA14 EA22 EA51 HA08 HB00 HB08 4J043 PA01 PA15 PA18 PB07 QA04 QB47 QB53 RA05 RA08 SA05 SA25 TA38 TB01 YB31 AG33 AG80 AG87 AH02 AH49 AJ04 BE08 EA30 FA15 FA19 GA19

Claims (3)

[Claims] (1) a compound represented by the formula (III): (Wherein, R, R ¹ , m, and n have the same meanings as described above, and one of T appearing m times is a group —CONT ¹ T ² ,
The rest are each independently hydrogen, methyl or group -CONT
¹ T ² , wherein T ¹ and T ² are each independently hydrogen or alkyl having 1 to 4 carbon atoms), and these groups are attached to a nitrogen atom in the molecule. A branched polyamidoamine urea compound characterized by being bonded. 2. A compound of the formula (VI) Wherein p is an integer from 0 to 6; q appearing p times are each independently an integer from 2 to 6; and A is a compound of the formula (III) (Where R and R ¹ are each independently hydrogen or methyl; m is an integer from 1 to 6; n appearing m times are each independently an integer from 2 to 6; of one is a group -CONT ¹ T ^2, hydrogen each remaining independently, a methyl or a group -CONT ¹ T ^2, here at T ¹ and T ² are each independently hydrogen or lower alkyl) A is a number greater than or equal to 3; and when a bond coming out of the nitrogen atom is not bonded to the group A, the bond of the nitrogen atom is bonded to hydrogen or methyl. The branched polyamidoamine urea compound according to claim 1, which is represented by the following formula: 3. A water-soluble compound obtained by further reacting the branched polyamidoamine urea compound according to claim 1 or 2 with a crosslinking compound selected from aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins. polymer.