JP4549135B2 - Polyalkyleneimine alkylene oxide copolymer - Google Patents

Description

The present invention relates to a polyalkyleneimine alkylene oxide copolymer. More specifically, it is suitable for detergent builders, detergents, water treatment agents, dispersants, etc., for example, a polyalkyleneimine alkylene oxide copolymer that exhibits high detergency when used with an activator as a detergent builder, The present invention relates to a manufacturing method and an application.

A polymer having a polyalkyleneimine as a main chain and ethylene oxide or the like added to a nitrogen atom in the polyalkyleneimine is also referred to as a modified polyethyleneimine ethoxylate, and can function as, for example, a polymer builder. . Since such a polymer has a property of being dissolved in a liquid detergent, it is indispensable as a component constituting the liquid detergent. When the modified polyethyleneimine ethoxylate is contained in the detergent together with the active agent, recontamination due to dirt removed by washing is prevented, and high detergency is exhibited.

A detergent builder composition containing an ethoxylated amine dispersion / anti-redeposition agent has been disclosed for a detergent containing such a modified polyethyleneimine ethoxylate (see, for example, Patent Document 1). The ethoxylated amine, - _{^{[(R 5 O) m (CH}} 2 CH 2 O) n ] -. ^{(R 5} is _C 3 -C ₄ alkylene or hydroxyalkylene, preferably propylene polyamines and amine polymers In the case, m is 0 to 10 and n is at least 3. These polyoxyalkylene moieties can be mixed to form a block. The alkylene oxide adduct is a polymer in which the terminal structure of the adduct is a compatible nonionic group, anionic group, or a mixture thereof. Nonionic groups include C ₁ -C ₄ alkyl groups, hydroxyalkyl ester groups, ether groups, hydrogen, acetate, and methyl ether, and anionic groups include PO ₃ ²⁻ and SO ₃ ⁻ .

Also disclosed is a liquid laundry detergent composition containing a water-soluble and / or dispersible modified polyamine having a functional main chain portion that exerts a cotton soil release effect (see, for example, Patent Document 2). The modified polyamine is an alkylene represented by — (R ¹ O) mB (R ¹ is C ₂ -C ₆ alkylene and a mixture thereof, preferably ethylene. M has a value of 4 to about 400). are those having oxide adducts, the terminal structure of the alkylene oxide adduct represented by B is _hydrogen, C 1 -C _{6 alkyl, - (CH 2) q SO} 3 M, - (CH 2) p CO 2 _{M, - (CH 2) q} (CHSO 3 M) CH 2 SO 3 M, - (CH 2) q (CHSO 2 M) CH 2 SO 3 M, - (CH 2) p PO 3 M, -PO 3 M (M is a sufficient amount of water-soluble cations to satisfy hydrogen or charge balance. P has a value of 1 to 6. q has a value of 0 to 6.)

Furthermore, a laundry detergent composition comprising an alkoxylated polyalkyleneimine is disclosed (for example, see Patent Document 3). The alkoxylated polyalkylenimine is — (R ¹ O) m (R ² O) nR ³ (R ¹ is 1,2-propylene, 1,2-butylene and mixtures thereof, preferably 1,2- Propylene, R ² is ethylene, R ³ is hydrogen, C ₁ -C ₄ alkyl and mixtures thereof, preferably hydrogen or methyl, more preferably hydrogen, m is from about 1 to about. 10 and n is from about 10 to about 40), and the terminal structure of the alkylene oxide adduct is hydrogen, C ₁ -C ₄ alkyl, and a mixture thereof. Is a polymer.

However, in these prior arts, when used in a detergent application, by making it more suitable as a polymer builder, recontamination is sufficiently prevented to improve cleaning power, and other uses In order to improve the basic performance of the polymer, there is room for improvement in the structure of the polymer having an alkylene oxide adduct.
Japanese Patent Publication No.7-116473 (pages 8 to 10) JP 11-508318 A (pages 46-55) Japanese translation of PCT publication No. 2002-518585 (pages 11-16)

The present invention has been made in view of the above situation, and is suitable for uses such as detergent builders, detergents, water treatment agents, and dispersants, and can exhibit high basic performance in terms of detergency and the like. It is an object of the present invention to provide a polyalkyleneimine alkylene oxide copolymer, a production method and use thereof.

The inventors of the present invention have made various studies on modified polyethyleneimine ethoxylates having an alkylene oxide adduct. In such a polymer, the terminal structure is usually derived from the terminal structure of the alkylene oxide, resulting in a hydroxyl group (—OH However, when this is used as another hydrophilic group, or conversely, a hydrophobic group, attention has been paid to the fact that it exhibits different effects from the conventional one. The inventors have conceived that the above problem can be solved brilliantly when a part or all of the terminal structure is a specific structure other than a hydroxyl group. For example, when used in the detergent field, such a polymer is considered to adhere to the surface of a cloth such as cotton due to the cationic property attributable to polyethyleneimine. In this case, dirt such as mud is prevented from re-adhering to the cloth due to the three-dimensional structure of the alkylene oxide adduct, but if the terminal structure of the polymer is a specific hydrophobic group, mud etc. Since the soil is hydrophilic, it is difficult for the soil to adhere to the cloth, and these actions are synergistically exhibited to improve basic performance such as cleaning power. Furthermore, it has been found that when the above-mentioned polymer is produced by reacting a polyalkyleneimine alkylene oxide copolymer with a specific compound, the above-mentioned effects are exhibited, and such a polymer is also used as a cleaning builder, detergent, water. It has also been found that it is suitable for uses such as treating agents and dispersants, and has reached the present invention.

That is, the present invention is a polyalkyleneimine alkylene oxide copolymer having an alkyleneimine monomer unit having a polyalkylene oxide, wherein the terminal structure of the polyalkylene oxide is a group consisting of the following (1) to (4): It is a polyalkyleneimine alkylene oxide copolymer having at least one selected from the above.
⁽¹⁾ -CO-R 2 -COOX
(2) —CH ₂ CH (OH) —R ³
(3) —CH ₂ CH (OH) CH ₂ —O—R ⁴
(4) -C (O) -NH-R ⁵
In the formula, R ² represents an alkylene group having 2 to 8 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, an arylene group having 6 to 14 carbon atoms, or a sulfoalkylene group having 2 to 8 carbon atoms. R ³ represents an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a sulfoalkyl group having 2 to 6 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms. R ⁴ represents a hydrogen atom, an alkyl group having 2 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a sulfoalkyl group having 2 to 6 carbon atoms. R ⁵ represents an alkyl group having 2 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a sulfoalkyl group having 2 to 6 carbon atoms. X represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or an organic ammonium group.
The present invention is described in detail below.

The polyalkyleneimine alkylene oxide copolymer of the present invention is a copolymer having an alkyleneimine monomer unit having a polyalkylene oxide as an essential repeating unit. Such a copolymer has a structure in which an oxyalkylene group is added to a nitrogen atom of a polyalkyleneimine unit composed of an alkyleneimine.
The oxyalkylene group preferably has an average addition mole number of 2 to 200 with respect to the polyalkyleneimine unit, and usually the addition mole number is distributed. That is, the number of moles added to the polyalkyleneimine unit is 1 or 2 or more, and the average number of moles added is preferably 2 or more and 200 or less. More preferably, they are 3 or more and 100 or less, More preferably, they are 4 or more and 80 or less, Especially preferably, they are 5 or more and 50 or less. Some of the plurality of polyalkyleneimine units may not have a structure to which an oxyalkylene group is added.
The average number of moles added is the average value of the number of moles of oxyalkylene groups added per mole of polyalkyleneimine unit.

In the present invention, the polyalkyleneimine alkylene oxide copolymer comprises at least one selected from the group consisting of (1) to (4) above in which the terminal structure of the polyalkylene oxide that the alkyleneimine monomer unit has. It will be mandatory. That is, part or all of the structure located at the terminal of the group constituted by adding an oxyalkylene group is one or more groups of the above (1) to (4).

In the formula (1), the alkylene group having 2 to 8 carbon atoms in R ² is preferably an ethylene group, trimethylene group, hexamethylene group or the like, and the alkenylene group having 2 to 8 carbon atoms as An ethenylene (vinylene) group, a propenylene group, and the like are preferable. As the arylene group having 6 to 14 carbon atoms, an o-phenylene group, an m-phenylene group, a p-phenylene group, and the like are preferable. Moreover, as a C2-C8 sulfoalkylene group, a sulfoethylene group, 1-methylsulfoethylene group, etc. are suitable.
The alkali metal atom in X is preferably an alkali metal such as a lithium atom, a sodium atom, or a potassium atom, and the alkaline earth metal atom is preferably an alkaline earth metal such as calcium or magnesium. As the organic ammonium group (organic amine group), an alkanolamine group such as an ethanolamine group, a diethanolamine group, or a triethanolamine group, or a triethylamine group is preferable. Further, it may be an ammonium group.

In the formulas (2) to (4) above, as the alkenyl group having 2 to 6 carbon atoms in R ³ , a vinyl group, a propenyl group, and the like are preferable, and as the aryl group having 6 to 14 carbon atoms, A phenyl group, a toluyl group and the like are preferable. As the sulfoalkyl group having 2 to 6 carbon atoms, a sulfoethyl group is preferable, and as the hydroxyalkyl group having 2 to 6 carbon atoms, a hydroxyethyl group is preferable.
The alkyl group having 2 to 8 carbon atoms in R ⁴ is preferably a butyl group, 2-ethylhexyl group or the like, and the alkenyl group having 2 to 6 carbon atoms is preferably an allyl group or the like, As the aryl group of formulas 6 to 14, a phenyl group, a toluyl group and the like are preferable. As the sulfoalkyl group having 2 to 6 carbon atoms, a sulfoethyl group is preferable, and as the hydroxyalkyl group having 2 to 6 carbon atoms, a hydroxyethyl group is preferable.
The alkyl group having 2 to 8 carbon atoms in R ⁵ is preferably a hexyl group or the like, and the alkenyl group having 2 to 8 carbon atoms is preferably a butenyl group or the like, having 6 to 14 carbon atoms. As the aryl group, a phenyl group, a toluyl group and the like are preferable. Moreover, as a C2-C6 sulfoalkyl group, a sulfoethyl group, a sulfopropyl group, etc. are suitable.

In the polyalkyleneimine alkylene oxide copolymer of the present invention, the terminal structure selected from the group consisting of the above (1) to (4) is 5 mol% or more with respect to 100 mol% of all terminal structures of the polyalkylene oxide. 100 mol% or less is preferable. More preferably, they are 10 mol% or more and 99 mol% or less, More preferably, they are 20 mol% or more and 98 mol% or less, Most preferably, they are 30 mol% or more and 97 mol% or less, Most preferably. Is 40 mol% or more and 95 mol% or less. If it is less than 5 mol%, for example, there is a possibility that basic performance such as detergency when the polyalkyleneimine alkylene oxide copolymer is used in the detergent field cannot be sufficiently improved. The mol% of the terminal structure can be measured by ¹ H-NMR or the yield after purification of the copolymer.

The present invention is also a method for producing a polyalkyleneimine alkylene oxide copolymer in which a polyalkyleneimine alkylene oxide copolymer is reacted by at least one step selected from the group consisting of the following (1) to (6).
(1) A step of reacting with an intramolecular cyclic anhydride of polycarboxylic acid.
(2) A step of reacting with aryl epoxy ethane or epoxy alkylene having 2 to 6 carbon atoms.
(3) A step of reacting with glycidol, alkyl glycidyl ether, alkenyl glycidyl ether or aryl glycidyl ether.
(4) A step of reacting with an alkyl isocyanate, alkenyl isocyanate or aryl isocyanate.
(5) A step of reacting with bisulfite and / or sulfite after step (1).
(6) A step of reacting with hydrogen sulfite and / or sulfite in the presence of a radical generation source or oxygen after step (2), (3) or (4).
In the present invention, the reaction can be carried out by at least one of the steps (1) to (4), but the reaction can be carried out by the step (5) or by the step (6). You can also. That is, as an embodiment of the present invention, the reaction is performed by at least one of the steps (1) to (4), or at least two steps such as the steps (5) and (6). The form made to react can be mentioned.

In the above step, the polyalkyleneimine alkylene oxide copolymer having a hydroxyl group (—OH) derived from alkylene oxide at the terminal is reacted in at least one step selected from the group consisting of the above (1) to (6). Thus, it is preferable to obtain the above-described polyalkyleneimine alkylene oxide copolymer of the present invention. In this case, a part or all of the hydroxyl group which the copolymer has at the terminal of the polyalkylene oxide is changed to the above terminal structure. Hereinafter, the polyalkyleneimine alkylene oxide copolymer before being used in the reaction is also referred to as a hydroxyl group-unmodified polyalkyleneimine alkylene oxide copolymer.

In the step (1), the reaction can be carried out using one or more of the intramolecular cyclic anhydrides of polycarboxylic acid. As the intramolecular cyclic anhydride of polycarboxylic acid, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, cis-Δ4-tetrahydrophthalic anhydride, itaconic anhydride and the like are suitable. By the production method including the step (1), a polyalkyleneimine alkylene oxide copolymer having the terminal structure (1) can be obtained.

In the step (2), the reaction can be performed using one or more of aryl epoxy ethane and epoxy alkylene having 2 to 6 carbon atoms. As the aryl epoxy ethane, styrene oxide and the like are preferable. As the epoxy alkylene having 2 to 6 carbon atoms, 3,4-epoxy-1-butene and the like are preferable. By the production method including the step (2), a polyalkyleneimine alkylene oxide copolymer having the terminal structure (2) can be obtained.

In the step (3), the reaction can be carried out using one or more of glycidol, alkyl glycidyl ether, alkenyl glycidyl ether and aryl glycidyl ether. As the alkyl glycidyl ether, butyl glycidyl ether and the like are preferable, as the alkenyl glycidyl ether, allyl glycidyl ether and the like are preferable, and as the aryl glycidyl ether, phenyl glycidyl ether and the like are preferable. By the production method including the step (3), a polyalkyleneimine alkylene oxide copolymer having the terminal structure (3) can be obtained.

In the step (4), the reaction can be carried out using one or more of alkyl isocyanate, alkenyl isocyanate and aryl isocyanate. As the alkyl isocyanate, hexyl isocyanate and the like are preferable, and as the aryl isocyanate, phenyl isocyanate and the like are preferable. By the production method including the step (4), a polyalkyleneimine alkylene oxide copolymer having the terminal structure (4) can be obtained.

In the step (5), a bisulfite and a sulfite are obtained with respect to the polyalkyleneimine alkylene oxide copolymer having the terminal structure of the alkenylene group (1) obtained in the step (1). It can be made to react using 1 type or 2 types of. As the polyalkyleneimine alkylene oxide copolymer having an alkenylene group terminal structure (1), a reaction product of maleic anhydride and a polyalkyleneimine alkylene oxide copolymer is suitable. The polyalkyleneimine alkylene oxide copolymer having the terminal structure of the sulfoalkylene group of (1) can be obtained by the production method including the step (5).

In the step (6), the polyalkylene having the terminal structure of the alkenyl group (2), (3) or (4) obtained in the step (2), (3) or (4) The imine alkylene oxide copolymer can be reacted with one or two of bisulfite and sulfite. As the polyalkyleneimine alkylene oxide copolymer having a terminal structure of the alkenyl group (2) above, a reaction product of 3,4-epoxy-1-butene and a polyalkyleneimine alkylene oxide copolymer is preferable, As the polyalkyleneimine alkylene oxide copolymer having a terminal structure of the alkenyl group of (3) above, a reaction product of allyl glycidyl ether and a polyalkyleneimine alkylene oxide copolymer is preferable, and the alkenyl of (4) above. As a polyalkyleneimine alkylene oxide copolymer having a terminal structure of a group, a reaction product of allyl isocyanate and a polyalkyleneimine alkylene oxide copolymer is suitable. The polyalkyleneimine alkylene oxide copolymer having the terminal structure of the sulfoalkyl group of (2), (3) or (4) can be obtained by the production method including the step (6).
In the step (6), for example, after reacting with an epoxy alkylene or alkenyl glycidyl ether having 2 to 6 carbon atoms, a reaction with a sulfite can be performed.

The method for producing the polyalkyleneimine alkylene oxide copolymer includes a step of polymerizing an alkyleneimine to obtain a polyalkyleneimine having a polyamine main chain, adding an alkylene oxide to the polyalkyleneimine, and then a hydroxyl group derived from the alkylene oxide. And a polyalkyleneimine alkylene oxide copolymer having a terminal, and the polyalkyleneimine alkylene oxide copolymer is reacted in at least one step selected from the group consisting of (1) to (6) above. Thus, a production method including a step of obtaining a polyalkyleneimine alkylene oxide copolymer is preferable.
What is necessary is just to set suitably the reaction conditions which perform the process of said (1)-(6) according to the compound used for reaction, the terminal structure of the target copolymer, etc. For example, as reaction temperature, it is 0-200. It is preferable to carry out at ° C. More preferably, they are 5 degreeC or more and 150 degrees C or less, More preferably, they are 10 degreeC or more and 120 degrees C or less, Especially preferably, they are 15 degreeC or more and 100 degrees C or less, Most preferably, it is 20 degrees C or more, It is 80 degrees C or less. The reaction time is preferably 1 to 100 hours. More preferably, they are 2 hours or more and 50 hours or less, More preferably, they are 3 hours or more and 30 hours or less, Especially preferably, they are 4 hours or more and 25 hours or less.

In the above steps (1) to (6), the molar ratio between the polyalkylimine alkylene oxide used in the reaction and the raw material to be reacted with the polyalkylimine alkylene oxide is (polyalkylimine alkylene oxide) / (polyalkylimine). The raw material to be reacted with the alkylene oxide) is preferably 50/1 to 1/50. The molar ratio is more preferably 40/1 to 1/40, still more preferably 30/1 to 1/30, and particularly preferably 20/1 to 1/20, most preferably. Is 15/1 to 1/15.

The steps (1) to (6) may be performed in an air atmosphere or in an inert gas atmosphere. However, in the case of the step (6), it is more preferable to carry out in an air atmosphere.
In the steps (1) to (4), a polyalkyleneimine alkylene oxide is charged in a reactor, and raw materials to be reacted with the polyalkylimine alkylene oxide may be added all at once or each time. Although it is good, addition at every time is preferable. In addition, it is preferable not to use a solvent during the reaction, but the reaction can also be performed using a solvent.
In the step (5), for example, a polyalkyleneimine alkylene oxide copolymer having an alkenylene group terminal structure may be charged in a reactor, and bisulfite and / or sulfite may be added all at once. These may be added sequentially, but sequential addition is preferred. The solvent is preferably an aqueous solvent such as water, alcohol, glycol, glycerin, or polyethylene glycol, and particularly preferably water. These may be used individually by 1 type and may use 2 or more types together. The pH of the reaction solution at 25 ° C. is preferably 6 to 10, more preferably 7 to 9. As reaction temperature, 10-60 degreeC is preferable, More preferably, it is 20-40 degreeC.

In the step (6), for example, a polyalkyleneimine alkylene oxide copolymer having an alkenyl terminal structure may be charged into a reactor, and bisulfite and / or sulfite may be added all at once. These may be added sequentially, but sequential addition is preferred. As the radical generating source, persulfate is preferable. These may be added all at once or sequentially, but sequential addition is preferred. In the case of oxygen, air or oxygen may be bubbled, or the reaction may be performed only in an air atmosphere. The solvent is preferably an aqueous solvent such as water, alcohol, glycol, glycerin, or polyethylene glycol, and particularly preferably water. These may be used individually by 1 type and may use 2 or more types together. The pH of the reaction solution at 25 ° C. is preferably 4 to 10, more preferably 6 to 10. More preferably, it is 7-10. As reaction temperature, 10-60 degreeC is preferable, More preferably, it is 20-40 degreeC.

A preferred form of the polyalkyleneimine alkylene oxide copolymer of the present invention will be described.
If the preferable form of the said copolymer is represented notionally, it can represent with following General formula (1).

In the formula, R ¹ O is the same or different and represents an alkylene oxide having 2 to 6 carbon atoms. AI represents an alkyleneimine monomer unit, (AI) _y represents a polyamine main chain, and a structure in which an alkyleneimine monomer unit is bonded in a linear, cyclic, branched or complex state. It has become. Above general formula, some or all of the polyalkylene imine polymer ^{Q 1 - (R 1 O)} x- or ^- (R 1 O) concept that having a polyalkylene oxide unit represented by the ^{z-Q 2} It expresses. Q ¹ and Q ² which are terminal structures of the polyalkylene oxide unit are the same or different, and are either a hydrogen atom or the terminal structures of (1) to (4) above, and at least one of the terminal structures of (1 ) To (4). x, y, and z are the same or different and represent an integer of 2 or more.
In the general formula (1), R ¹ O may be one type or two or more types, and ethylene oxide and propylene oxide are preferable. More preferably, it is ethylene oxide.

The copolymer represented by the general formula (1) is obtained by substituting the hydrogen atom bonded to the amine nitrogen atom of the polyamine having the structure represented by the following general formula (2) with a polyalkylene oxide unit. A copolymer obtained by adding an alkylene oxide to an amine nitrogen atom of a polyamine having a structure represented by the general formula (2) is preferable.

Wherein, R ⁶ are the same or different, a straight-chain alkylene group having 2 to 6 carbon atoms, or represents a branched alkylene group having 3 to 6 carbon atoms. A represents another polyamine chain due to branching. l, m, and n are the same or different and represent 0 or an integer of 1 or more. In addition, at least two or more —N—R ⁶ — units are present in the polyamine.
In the general formula (2), the other polyamine chain represented by A is preferably bonded to the structure represented by the general formula (2) via R ⁶ .
The polyamine may have one kind of alkylene group in R ⁶ or two or more kinds, but is preferably one kind, and more preferably an ethylene group. When R ⁶ is a branched alkylene group having 3 to ⁶ carbon atoms, a 1,2-propylene group is preferable.

The polyamine has at least one selected from the group consisting of a unit derived from a primary amine nitrogen atom, a unit derived from a secondary amine nitrogen atom, and a unit derived from a tertiary amine nitrogen atom.
The unit derived from the primary amine nitrogen atom is represented by the following formula, for example.
^{_{(H 2 -N-R 6)}} -
And -NH ₂
The unit derived from the secondary amine nitrogen atom is represented by the following formula, for example.

The unit derived from the tertiary amine nitrogen atom is represented by the following formula, for example.

In the polyamine, the presence form of the unit is not particularly limited, and for example, the unit is randomly included. The amine nitrogen atom may be quaternized or oxidized.
In the polyalkyleneimine alkylene oxide copolymer, in some or all of these amine nitrogen atoms, some or all of the hydrogen atoms of the amine nitrogen atoms are substituted with polyalkylene oxide units (polyoxyalkylene groups). It becomes a form.

The polyalkylene oxide unit has the following general formula (3):
-(R ¹ O) _a H (3)
(Wherein R ¹ O is the same as described above. A represents an integer of 2 or more). The polyamine main chain having the polyalkylene oxide unit of the general formula (3) has a hydroxyl group in the terminal structure. Such a hydroxyl group-unmodified polyalkyleneimine alkylene oxide copolymer is reacted with at least one step selected from the group consisting of the above (1) to (6) to thereby convert the terminal hydroxyl group derived from alkylene oxide. Can be changed.

As the polyamine capable of forming the polyamine main chain, polyalkyleneamine (PAA) and polyalkyleneimine (PAI) are suitable.
Examples of the polyalkyleneamine (PAA) include polyethyleneamine (PEA) and tetrabutylenepentamine. PEA can be obtained by reacting ammonia and ethylene dichloride, followed by fractional distillation. PEA obtained by such a method is triethylenetetramine (TETA) and tetraethylenepentamine (TEPA).

Examples of the polyalkyleneimine include one or two alkyleneimines having 2 to 6 carbon atoms such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and 1,1-dimethylethyleneimine. Homopolymers and copolymers of these alkyleneimines obtained by polymerizing more than one species by conventional methods are preferred. These may be used alone or in combination of two or more. More preferred is a homopolymer of ethyleneimine (polyethyleneimine; PEI). In these alkyleneimine homopolymers and copolymers, a polyalkyleneimine chain is formed, and the polyalkyleneimine chain must have a branched structure. PEI having at least moderate branching, that is, a ratio of m to n is preferably m / n = 4/1 to 1/4. More preferably, the ratio of m to n is about 3/1 to 1/3, and more preferably 2/1 to 1/2.
Further, it may be obtained by polymerizing ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the like. Such a polyalkyleneimine usually has a primary amino group or secondary amino group (imino group) in addition to a tertiary amino group in the structure.

In the present invention, the polyamine main chain is preferably formed mainly of ethyleneimine. In this case, the “main body” means that when the polyamine main chain is formed of two or more types of alkyleneimines, it occupies most of the total number of moles of alkyleneimines.
When the above “occupying the majority” is expressed in terms of mol% of ethyleneimine in 100 mol% of all alkyleneimines, it is preferably 50 to 100 mol%. If it is less than 50 mol%, the detergency of the polyalkyleneimine alkylene oxide copolymer may be reduced. More preferably, it is 60 mol% or more, More preferably, it is 70 mol% or more.

The relative proportions of units derived from primary, secondary and tertiary amine nitrogen atoms in the polyamine main chain can be appropriately selected depending on the production method, particularly in the case of PEI. PEI can be produced by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid and the like.

As described above, the hydroxyl group-unmodified polyalkyleneimine alkylene oxide copolymer is preferably obtained by adding an alkylene oxide to a polyalkyleneimine. In this case, the average molecular weight of the polyalkyleneimine is 200 to 20000. It is preferable that More preferably, it is 300 or more and 10,000 or less, More preferably, it is 400 or more and 5000 or less, Especially preferably, it is 500 or more and 2000 or less. Moreover, as an average addition mole number of an oxyalkylene group, 2 or more and 200 or less are preferable. More preferably, they are 3 or more and 100 or less, More preferably, they are 4 or more and 80 or less, Especially preferably, they are 5 or more and 50 or less.
As the alkylene oxide unit, ethylene oxide, propylene oxide, and butylene oxide are preferable. More preferably, it is ethylene oxide.

A preferred form of the polyalkyleneimine alkylene oxide copolymer of the present invention is represented by the following general formula.

In the formula, EO represents ethylene oxide. Q is the same or different and represents a hydrogen atom or the terminal structure of (1) to (4) above. a is an integer of 2 or more. In addition, the symbol of "..." in a formula represents that a polymer chain continues similarly.
The copolymer represented by the above general formula has a plurality of polyoxyethylene groups — (CH ₂ CH ₂ O) _a H formed by adding polyethylene oxide to amine nitrogen atoms of the PEI main chain, It is a copolymer having at least one terminal structure selected from the group consisting of 1) to (4).

The polyalkyleneimine alkylene oxide copolymer is a detergent builder, detergent, water treatment agent, dispersant, fiber treatment agent, scale inhibitor (scale inhibitor), cement additive, metal ion sealing agent, thickener. It can be suitably used for various binders. Especially, it can use suitably for the builder for detergents, a detergent, a water treatment agent, and a dispersing agent.

The present invention further includes a builder for detergents, a detergent, and a water treatment, containing the polyalkyleneimine alkylene oxide copolymer of the present invention or the polyalkyleneimine alkylene oxide copolymer produced by the production method of the present invention as an essential component. It is also an agent or a dispersant.
The detergent builder exhibits an action for preventing dirt from reattaching to the clothes being washed. In the case where the polyalkyleneimine alkylene oxide copolymer prevents the reattachment of dirt, the action resulting from the three-dimensional structure of the polyalkylene oxide chain and the action of reducing the affinity for dirt when having a hydrophobic terminal structure, or When it has a hydrophilic terminal structure, it is preferable to sufficiently exhibit the function of dispersing dirt.
The detergent builder can be suitably used as a builder for liquid detergents because it has excellent compatibility with surfactants and the resulting detergent becomes a highly concentrated liquid detergent. By being excellent in compatibility with the surfactant, transparency when used in a liquid detergent is improved, and the problem of separation of the liquid detergent caused by turbidity can be prevented. Moreover, it can be set as a highly concentrated liquid detergent by being excellent in compatibility, and the washing | cleaning capability of a liquid detergent can be improved.
The above-mentioned detergent builder is excellent in re-contamination prevention ability, and is a detergent builder with excellent stability and extremely high quality agent performance that is less likely to cause performance degradation when stored for a long period of time and precipitation of impurities when held at low temperatures. be able to.

The cleaning ability can be determined by the cleaning rate. The cleaning rate can be determined by the following method.
(Washing rate)
An artificially contaminated cloth is used as a sample. As an artificially contaminated cloth, a cloth (STC GC C “clay dirt”, EMPA 164 “grass dirt”, EMPA 106 “carbon black / mineral oil dirt”) obtained from Scientific Service is used, and the whiteness is measured by reflectance in advance. For the measurement, a colorimetric color difference meter ND-1001DP type (manufactured by Nippon Denshoku Industries Co., Ltd.) or the like can be used.
Pure water is added to 1.47 g of calcium chloride dihydrate (0.74 g when EMPA106 is used as a sample) to make 10 kg, and hard water is prepared.
Add pure water to polyoxyethylene lauryl ether sodium sulfate (AES) 4.8g, polyoxyethylene lauryl ether (AE) 0.6g, sodium borate 0.6g, citric acid 0.9g, propylene glycol 2.4g The total weight is 80 g. After adjusting the pH to 8.2 with an aqueous sodium hydroxide solution, pure water is added to make a total of 100 g to prepare a surfactant aqueous solution.
A targot meter is set at 27 ° C., 1000 mL hard water, 5 mL polymer aqueous solution (concentration 0.50% (concentration 0.60% when using EMPA106 as a sample)), 10 mL surfactant aqueous solution, artificially contaminated cloth 5.4 g and 5.4 g of white cloth or 10.8 g of artificially contaminated cloth alone are put in a pot and stirred at 100 rpm for 10 minutes.
Remove the artificially contaminated cloth and white cloth from the pot and squeeze the water by hand. Place 1000 mL of hard water in the pot, put artificially contaminated cloth and white cloth with squeezed water into the pot, and stir at 100 rpm for 2 minutes. Remove the artificially contaminated cloth and white cloth from the pot, squeeze the moisture by hand, apply the cloth to the artificially contaminated cloth, and dry it while stretching the wrinkles with an iron. The whiteness of the dried artificially contaminated cloth is measured by a colorimetric colorimeter with reflectance.
The washing rate (%) is obtained from the value measured by the following method and the following formula.
Cleaning rate (%) =
(Whiteness of the artificially contaminated cloth after washing-Whiteness of the artificially contaminated cloth before washing) ÷ (Whiteness of the original white cloth (EMPA221) of the artificially contaminated cloth-Whiteness of the artificially contaminated cloth before washing) × 100

With regard to the above-mentioned cleaning rate, a detergent builder, a detergent, a water treatment agent or a dispersant composed of a composition containing a copolymer having a polyalkyleneimine alkylene oxide structure, when the cleaning rate is EMPA164 One of the present inventions is 7.3% or more, or 17.4% or more when EMPA 106 is used. Among these compositions containing a copolymer having a polyalkyleneimine alkylene oxide structure, that is, a detergent builder, a detergent, a water treatment agent, or a dispersant, these two characteristics, that is, a cleaning rate when using EMPA164 And those satisfying both of the cleaning rates when EMPA 106 is used are preferable. The cleaning rate when using EMPA 164 is preferably 7.4% or more. The cleaning rate when using the EMPA 106 is preferably 17.5% or more. More preferably, it is 17.6% or more. The artificially contaminated cloths EMPA164 and 106 used for the measurement of the washing rate are standard samples for a dirt test in which a certain dirt is adhered to the cloth. The EMPA 106 is obtained by attaching carbon black and mineral oil to a white cotton cloth (EMPA 221).

As other composition components and blending ratios other than the polyalkyleneimine alkylene oxide copolymer in the detergent builder, various effects that can be used in conventionally known detergent builders, and the effects of the present invention based on the blending ratios. Can be used as long as the above is not impaired.

The detergent may be a powder detergent or a liquid detergent, but a liquid detergent is preferred because the polyalkyleneimine alkylene oxide copolymer is excellent in solubility with the liquid detergent. In addition to the polyalkyleneimine alkylene oxide copolymer, additives commonly used in detergents can be used for the detergent. Examples of the additives include surfactants, alkali builders, chelate builders, anti-redeposition agents for preventing redeposition of contaminants such as sodium carboxymethylcellulose, and dirt inhibitors such as benzotriazole and ethylene-thiourea. , Soil release agent, anti-transfer agent, softener, alkaline substance for pH adjustment, fragrance, solubilizer, fluorescent agent, colorant, foaming agent, foam stabilizer, polish, bactericidal agent, bleaching agent, Bleaching aids, enzymes, dyes, solvents and the like are preferred. In the case of a powder detergent, it is preferable to blend zeolite.
When using for the said detergent, it is preferable to add 0.1-20 mass% of polyalkyleneimine alkylene oxide copolymers with respect to 100 mass% of detergents. If it is less than 0.1% by mass, the cleaning power of the detergent may be insufficient, and if it exceeds 20% by mass, it may be uneconomical.

The blending form of the polyalkyleneimine alkylene oxide copolymer in the detergent may be either liquid or solid, and is determined according to the form at the time of sale of the detergent (for example, liquid or solid). Can do. You may mix | blend with the form of the aqueous solution after superposition | polymerization, you may mix | blend in the state which reduced the water | moisture content of the aqueous solution to some extent, and may mix | blend in the state solidified dry.
The above detergents include household detergents, textile and other industrial detergents, hard surface cleaners, and detergents used only for specific applications such as bleaching detergents that enhance the function of one of its components. Including.

The surfactant is at least one selected from anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants, and these surfactants include one or more. Can be used. When using 2 or more types, the combined use amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more with respect to 100% by mass of the total surfactant. More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more, Most preferably, it is 80 mass% or more.

Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonic acid. Salt, saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, alkenyl phosphate ester Or its salt etc. are suitable.
The alkyl group or alkenyl group in the anionic surfactant may have a branched alkyl group such as a methyl group.

Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, alkyl glycoxide, fatty acid glycerin. Monoesters, alkylamine oxides and the like are preferred. The alkyl group or alkenyl group in the nonionic surfactant may have a branched alkyl group such as a methyl group.
As the cationic surfactant, a quaternary ammonium salt or the like is suitable.
As the amphoteric surfactant, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant and the like are suitable.
The alkyl group and alkenyl group in the cationic surfactant and amphoteric surfactant may be branched from an alkyl group such as a methyl group.

In general, the blending ratio of the surfactant is preferably 10 to 60% by mass with respect to 100% by mass of the liquid detergent. More preferably, they are 15 mass% or more and 50 mass% or less, More preferably, they are 20 mass% or more and 45 mass% or less, Especially preferably, they are 25 mass% or more and 40 mass% or less. If the blending ratio of the surfactant is less than 10% by mass, sufficient detergency may not be exhibited, and if it exceeds 60% by mass, the economy may be lowered.
The blending ratio of the liquid detergent builder is usually preferably 0.1 to 20% by mass with respect to 100% by mass of the liquid detergent. More preferably, it is 0.2 mass% or more and 15 mass% or less, More preferably, it is 0.3 mass% or more, 10 mass% or less, More preferably, it is 0.4 mass% or more, 8 mass% Or less, and particularly preferably 0.5% by mass or more and 5% by mass or less. If the blending ratio of the builder for liquid detergent is less than 0.1% by mass, sufficient detergent performance may not be exhibited, and if it exceeds 20% by mass, the economy may be lowered.

The water content contained in the liquid detergent is usually preferably 0.1 to 75% by mass with respect to 100% by mass of the liquid detergent. More preferably, it is 0.2 mass% or more and 70 mass% or less, More preferably, it is 0.5 mass% or more and 65 mass% or less, Especially preferably, it is 0.7 mass% or more, 60 mass% Or less, more preferably 1% by mass or more and 55% by mass or less, and most preferably 1.5% by mass or more and 50% by mass or less.

The liquid detergent preferably has a kaolin turbidity of 200 mg / L or less. More preferably, it is 150 mg / L or less, More preferably, it is 120 mg / L or less, Especially preferably, it is 100 mg / L or less, Most preferably, it is 50 mg / L or less.
Moreover, the change (difference) in kaolin turbidity between when the polyalkyleneimine alkylene oxide copolymer of the present invention is added to a liquid detergent and when it is not added is preferably 500 mg / L or less. More preferably, it is 400 mg / L or less, More preferably, it is 300 mg / L or less, Especially preferably, it is 200 mg / L or less, Most preferably, it is 100 mg / L or less. Kaolin turbidity can be measured, for example, by the following method.
(Measurement method of kaolin turbidity)
A sample (liquid detergent) uniformly stirred in a 50 mm square cell having a thickness of 10 mm was removed, and after removing bubbles, Turbidity at 25 ° C. using NDH2000 (trade name, turbidimeter) manufactured by Nippon Denshoku Co., Ltd. Kaolin turbidity: mg / L) is measured.

Proteases, lipases, cellulases and the like are suitable as enzymes that can be incorporated into the detergent of the present invention. Of these, proteases, alkaline lipases, and alkaline cellulases that are highly active in an alkaline cleaning solution are preferred.
The amount of the enzyme added is preferably 5% by mass or less with respect to 100% by mass of the detergent. If it exceeds 5% by mass, improvement in detergency cannot be seen, and the economy may be reduced.

As the alkali builder, silicate, carbonate, sulfate and the like are preferable. As the chelate builder, diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), citric acid and the like are preferable. A water-soluble polycarboxylic acid polymer may be used.

The above-mentioned detergent has excellent dispersibility, and can be a highly stable detergent with extremely high quality agent performance that is unlikely to cause deterioration in performance when stored for a long period of time or precipitation of impurities when held at a low temperature.

The said water treatment agent is added to water systems, such as a cooling water system and a boiler water system, for example. In this case, the polyalkyleneimine alkylene oxide copolymer may be added as it is, or one containing other components other than the polyalkyleneimine alkylene oxide copolymer may be added.

As other composition components and blending ratios other than the polyalkyleneimine alkylene oxide copolymer in the water treatment agent, various components that can be used in conventionally known water treatment agents and the blending ratios of the present invention. It can be used as appropriate as long as the effects are not impaired.

The dispersant may be an aqueous dispersant, and for example, a pigment dispersant, a cement dispersant, a calcium carbonate dispersant, a kaolin dispersant, and the like are suitable.
The dispersant can express the extremely excellent dispersibility inherent in the polyalkyleneimine alkylene oxide copolymer. In addition, it is possible to obtain a very high quality, high performance, and highly stable dispersant that does not cause deterioration in performance or precipitation of impurities when kept at a low temperature even when stored for a long period of time.

As other composition components and blending ratios other than the polyalkyleneimine alkylene oxide copolymer in the above-mentioned dispersant, various components that can be used in conventionally known dispersants and the effects of the present invention based on the blending ratios. Can be used as long as the above is not impaired.

The polyalkyleneimine alkylene oxide copolymer of the present invention is thus suitable for use in detergent builders, detergents, water treatment agents or dispersants, but also in other uses. In applications where the copolymer is used, various properties exhibited by the copolymer can be improved and used suitably.

The polyalkyleneimine alkylene oxide copolymer of the present invention has the above-described structure, and has a high basic performance in terms of detergency and the like by making the terminal structure of the alkylene oxide other hydrophilic group and / or hydrophobic group. Can be exhibited. Such a polyalkyleneimine alkylene oxide copolymer can be suitably used in applications such as detergent builders, detergents, water treatment agents, and dispersants.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited by these. “%” Indicates “% by mass”.
A method for measuring the cleaning rate in Examples and Comparative Examples is shown below.
(Washing rate (1) hydrophilic stain)
As an artificially contaminated cloth, a cloth obtained from Scientific Service (STC GC C “clay dirt” cut to 4.5 cm × 7.0 cm, EMPA164 “grass dirt” cut to 5.0 cm × 5.0 cm) ) Was used. For the artificially contaminated cloth, the whiteness was measured by reflectance using a colorimetric color difference meter SE2000 (manufactured by Nippon Denshoku Industries Co., Ltd.).
Pure water was added to 1.47 g of calcium chloride dihydrate to 10 kg to prepare hard water.
Add pure water to polyoxyethylene lauryl ether sodium sulfate (AES) 4.8g, polyoxyethylene lauryl ether (AE) 0.6g, sodium borate 0.6g, citric acid 0.9g, propylene glycol 2.4g The total weight was 80 g. After adjusting the pH to 8.2 with an aqueous sodium hydroxide solution, pure water was added to make a total of 100 g to prepare a surfactant aqueous solution.
Set targot meter at 27 ° C, 1000 mL of hard water, 5 mL of aqueous polymer solution (concentration 0.55%), 10 mL of aqueous surfactant solution, artificially contaminated cloth (STC GC C cloth: 10 sheets, EMPA cloth: 5 sheets) It put into the pot and stirred for 10 minutes at 100 rpm.
The artificially contaminated cloth was taken out of the pot, and the moisture of the artificially contaminated cloth was squeezed by hand. 1000 mL of hard water was put into the pot, and an artificially contaminated cloth with the water squeezed was put into the pot and stirred at 100 rpm for 2 minutes.
The artificially contaminated cloth was taken out from the pot, and after water was squeezed by hand, the artificially contaminated cloth was applied to the artificially contaminated cloth and dried while stretching the wrinkles with an iron. The whiteness of the dried artificially contaminated cloth was measured by reflectance with a colorimetric colorimeter.
The cleaning rate (%) was obtained from the value measured by the above method and the following equation.
Cleaning rate (%) =
(Whiteness of the artificially contaminated cloth after washing-Whiteness of the artificially contaminated cloth before washing) ÷ (Whiteness of the original white cloth (EMPA221) of the artificially contaminated cloth-Whiteness of the artificially contaminated cloth before washing) × 100

(Washing rate (2) hydrophobic stain)
EMPA106 ("carbon black / mineral oil stain" cut to 5.0 cm x 5.0 cm) was used as the artificially contaminated cloth. As a white cloth, a JIS L0803 cotton cloth cut to 5.0 cm × 5.0 cm was used. For the artificially contaminated cloth, the whiteness was measured by reflectance using a colorimetric color difference meter SE2000 (manufactured by Nippon Denshoku Industries Co., Ltd.).
Pure water was added to 0.74 g of calcium chloride dihydrate to 10 kg to prepare hard water.
Add pure water to polyoxyethylene lauryl ether sodium sulfate (AES) 4.8g, polyoxyethylene lauryl ether (AE) 0.6g, sodium borate 0.6g, citric acid 0.9g, propylene glycol 2.4g. The total weight was 80 g. After adjusting the pH to 8.2 with a sodium hydroxide aqueous solution, pure water was added to make a total of 100 g to prepare a surfactant aqueous solution.
Set the tartometer at 27 ° C., put 1000 mL of hard water, 5 mL of polymer aqueous solution (concentration 0.60%), 10 mL of surfactant aqueous solution, 7 artificially contaminated cloths and 7 white cloths into a pot, and stir at 100 rpm for 10 minutes. did.
The artificially contaminated cloth and white cloth were taken out from the pot and the water was squeezed by hand. The pot was filled with 1000 mL of hard water, and the artificially contaminated cloth and white cloth with squeezed water were put into the pot and stirred at 100 rpm for 2 minutes. The artificially contaminated cloth and the white cloth were taken out from the pot, and after the water was squeezed by hand, the artificially contaminated cloth was applied to the cloth and dried while stretching the wrinkles with an iron. The whiteness of the dried artificially contaminated cloth was measured by reflectance with a colorimetric colorimeter.
The cleaning rate (%) was determined from the value measured by the following method and the following formula.
Cleaning rate (%) =
(Whiteness of the artificially contaminated cloth after washing-Whiteness of the artificially contaminated cloth before washing) ÷ (Whiteness of the original white cloth (EMPA221) of the artificially contaminated cloth-Whiteness of the artificially contaminated cloth before washing) × 100

Polymer (1)
As the polymer (1), a polyethyleneimine ethylene oxide copolymer obtained by ethoxylating polyethyleneimine (PEI) (average molecular weight 600, manufactured by Nippon Shokubai Co., Ltd.) with ethylene oxide corresponding to 20 moles per mole of nitrogen atom is used. It was.

Example 1
25 g of polymer (1) was charged into a glass reactor equipped with a thermometer and a stirrer, and 2.5 g of powdered maleic anhydride was added while stirring. This polymer mixture was heated to 60 ° C. with stirring and reacted for 6 hours to obtain a water-soluble polymer (1). Formation of the water-soluble polymer (1) was confirmed as follows.

About the obtained water-soluble polymer (1), an appropriate amount of water was added to prepare about 50 g of a polymer aqueous solution having a concentration of 30% by mass, 20 g of which was placed in a 40 cm long dialysis membrane and sealed. For the dialysis membrane, Spectra / Por Membrane MWCO: 1000 fractional molecular weight 1000 (manufactured by SPECTRUM LABORATORIES INC) was used. (In the present invention, any material having a fractional molecular weight comparable to that of the dialysis membrane may be used.) This was immersed in 2000 g of water in a 2 liter beaker and stirred with a stirrer. After 3 hours, the dialysis membrane was taken out of the beaker and the outside of the dialysis membrane was thoroughly washed with water, and then the contents of the dialysis membrane were taken out. The taken-out contents were concentrated with an evaporator and then left to stand in a desiccator under reduced pressure for 12 hours to be dried.
For comparison, 20 g of a 30% by weight polymer aqueous solution before dialysis was concentrated with an evaporator, then allowed to stand in a desiccator under reduced pressure for 12 hours and dried.
Since the weight change of the dried sample before and after dialysis was considered to be due to unreacted maleic anhydride, the yield of the reaction product was calculated from this value and found to be 86%.
Moreover, when the dried sample after dialysis was dissolved in D ₂ O and measured for ¹ H-NMR spectrum, signals derived from the half-esterified maleic acid double bond were detected at around 5.90 ppm and 6.48 ppm. It was.
From the above results, the water-soluble polymer (1) was confirmed to be a copolymer obtained by esterifying a polyethyleneimine ethylene oxide copolymer with maleic acid.
The detergency of the water-soluble polymer (1) was measured. The results are shown in Table 1.

Example 2
A glass reaction vessel equipped with a thermometer and a stirrer was charged with 25 g of the polymer (1), and 2.5 g of powdered succinic anhydride was added with stirring. This polymer mixture was heated to 60 ° C. with stirring and reacted for 24 hours to obtain a water-soluble polymer (2). Formation of the water-soluble polymer (2) was confirmed as follows.

About the obtained water-soluble polymer (2), an appropriate amount of water was added to prepare about 50 g of a polymer aqueous solution having a concentration of 30% by mass, 20 g of which was placed in a dialysis membrane having a length of 40 cm and sealed. For the dialysis membrane, Spectra / Por Membrane MWCO: 1000 fractional molecular weight 1000 (manufactured by SPECTRUM LABORATORIES INC) was used. (In the present invention, any material having a fractional molecular weight comparable to that of the dialysis membrane may be used.) This was immersed in 2000 g of water in a 2 liter beaker and stirred with a stirrer. After 3 hours, the dialysis membrane was taken out of the beaker and the outside of the dialysis membrane was thoroughly washed with water, and then the contents of the dialysis membrane were taken out. The taken-out contents were concentrated with an evaporator and then left to stand in a desiccator under reduced pressure for 12 hours to be dried.
For comparison, 20 g of a 30% by weight polymer aqueous solution before dialysis was concentrated with an evaporator, then allowed to stand in a desiccator under reduced pressure for 12 hours and dried.
The weight reduction after dialysis relative to the weight of the charged polymer was considered to be the weight of unreacted succinic anhydride, and the yield of the reaction product was calculated from this value, and was 81%.
Further, when the dried sample after dialysis was dissolved in D ₂ O and measured for ¹ H-NMR spectrum, a signal derived from ethylene of half-esterified succinic acid was detected at around 2.42 ppm and 2.48 ppm.
From the above results, the water-soluble polymer (2) was confirmed to be a copolymer obtained by esterifying a polyethyleneimine ethylene oxide copolymer with succinic acid.
The detergency of the water-soluble polymer (2) was measured. The results are shown in Table 1.

Example 3
25 g of the polymer (1) was charged into a glass reactor equipped with a thermometer and a stirrer, and 2.5 g of powdered phthalic anhydride was added while stirring. This polymer mixture was heated to 60 ° C. with stirring and reacted for 24 hours to obtain a water-soluble polymer (3). Formation of the water-soluble polymer (3) was confirmed as follows.

About the obtained water-soluble polymer (3), an appropriate amount of water was added to prepare about 50 g of a polymer aqueous solution having a concentration of 30% by mass, 20 g of which was placed in a 40 cm long dialysis membrane and sealed. For the dialysis membrane, Spectra / Por Membrane MWCO: 1000 fractional molecular weight 1000 (manufactured by SPECTRUM LABORATORIES INC) was used. (In the present invention, any material having a fractional molecular weight comparable to that of the dialysis membrane may be used.) This was immersed in 2000 g of water in a 2 liter beaker and stirred with a stirrer. After 3 hours, the dialysis membrane was taken out of the beaker and the outside of the dialysis membrane was thoroughly washed with water, and then the contents of the dialysis membrane were taken out. The taken-out contents were concentrated with an evaporator and then left to stand in a desiccator under reduced pressure for 12 hours to be dried.
For comparison, 20 g of a 30% by weight polymer aqueous solution before dialysis was concentrated with an evaporator, then allowed to stand in a desiccator under reduced pressure for 12 hours and dried.
The weight reduction after dialysis relative to the weight of the charged polymer is considered to be the weight of unreacted phthalic anhydride, and the yield of the reaction product was calculated from this value, and was found to be 84%.
Further, the dry sample after the dialysis was dissolved in _{D 2} ^O, 1 was measured 1 H-NMR spectrum, signals from the aromatic ring of the half esterified phthalic acid 7.38Ppm, 7.45 ppm, around 7.68ppm Detected.
From the above results, the water-soluble polymer (3) was confirmed to be a copolymer obtained by esterifying a polyethyleneimine ethylene oxide copolymer with phthalic acid.
The detergency of the water-soluble polymer (3) was measured. The results are shown in Table 1.

Example 4
25 g of the polymer (1) was charged into a glass reactor equipped with a thermometer and a stirrer, and 2.5 g of allyl glycidyl ether was added while stirring. This polymer mixture was heated to 60 ° C. with stirring and reacted for 24 hours to obtain a water-soluble polymer (4). Formation of the water-soluble polymer (4) was confirmed as follows.

About the obtained water-soluble polymer (4), an appropriate amount of water was added to prepare about 50 g of a polymer aqueous solution having a concentration of 30% by mass, 20 g of which was placed in a 40 cm-long dialysis membrane and sealed. For the dialysis membrane, Spectra / Por Membrane MWCO: 1000 fractional molecular weight 1000 (manufactured by SPECTRUM LABORATORIES INC) was used. (In the present invention, any material having a fractional molecular weight comparable to that of the dialysis membrane may be used.) This was immersed in 2000 g of water in a 2 liter beaker and stirred with a stirrer. After 3 hours, the dialysis membrane was taken out of the beaker and the outside of the dialysis membrane was thoroughly washed with water, and then the contents of the dialysis membrane were taken out. The taken-out contents were concentrated with an evaporator and then left to stand in a desiccator under reduced pressure for 12 hours to be dried.
For comparison, 20 g of a 30% by weight polymer aqueous solution before dialysis was concentrated with an evaporator, then allowed to stand in a desiccator under reduced pressure for 12 hours and dried.
The weight loss after dialysis with respect to the weight of the charged polymer is considered to be the weight of unreacted allyl glycidyl ether, and the yield of the reaction product was calculated from this value and found to be 90%.
Moreover, when the dried sample after dialysis was dissolved in D ₂ O and the ¹ H-NMR spectrum was measured, the signal derived from the double bond of the allyl glycidyl ether added by the epoxy ring was around 5.20 ppm and 5.80 ppm. was detected.
From the above results, it was confirmed that the water-soluble polymer (4) was a copolymer obtained by adding an epoxy ring of allyl glycidyl ether to a polyethyleneimine ethylene oxide copolymer.
The detergency of the water-soluble polymer (4) was measured. The results are shown in Table 2.

Example 5
25 g of the polymer (1) was charged into a glass reactor equipped with a thermometer and a stirrer, and 1.25 g of allyl glycidyl ether was added with stirring. This polymer mixture was heated to 60 ° C. with stirring and reacted for 24 hours to obtain a water-soluble polymer (5). Formation of the water-soluble polymer (5) was confirmed as follows.
About the obtained water-soluble polymer (5), an appropriate amount of water was added to prepare about 50 g of a polymer aqueous solution having a concentration of 30% by mass, 20 g of which was placed in a 40 cm long dialysis membrane and sealed. For the dialysis membrane, Spectra / Por Membrane MWCO: 1000 fractional molecular weight 1000 (manufactured by SPECTRUM LABORATORIES INC) was used. (In the present invention, any material having a fractional molecular weight comparable to that of the dialysis membrane may be used.) This was immersed in 2000 g of water in a 2 liter beaker and stirred with a stirrer. After 3 hours, the dialysis membrane was taken out of the beaker and the outside of the dialysis membrane was thoroughly washed with water, and then the contents of the dialysis membrane were taken out. The taken-out contents were concentrated with an evaporator and then left to stand in a desiccator under reduced pressure for 12 hours to be dried.
For comparison, 20 g of a 30% by weight polymer aqueous solution before dialysis was concentrated with an evaporator, then allowed to stand in a desiccator under reduced pressure for 12 hours and dried.
Since the weight reduction after dialysis with respect to the weight of the charged polymer is considered to be the weight of unreacted allyl glycidyl ether, the yield of the reaction product was calculated from this value and found to be 96%.
Moreover, when the dried sample after dialysis was dissolved in D ₂ O and the ¹ H-NMR spectrum was measured, the signal derived from the double bond of the allyl glycidyl ether added by the epoxy ring was around 5.20 ppm and 5.80 ppm. was detected.
From the above results, it was confirmed that the water-soluble polymer (5) was a copolymer obtained by adding an epoxy ring of allyl glycidyl ether to a polyethyleneimine ethylene oxide copolymer.

Example 6
25 g of the polymer (1) was charged into a glass reactor equipped with a thermometer and a stirrer, and 2.5 g of phenylglycidyl ether was added while stirring. This polymer mixture was heated to 60 ° C. with stirring and reacted for 24 hours to obtain a water-soluble polymer (6). Formation of the water-soluble polymer (6) was confirmed as follows.

About the obtained water-soluble polymer (6), an appropriate amount of water was added to prepare about 50 g of a polymer aqueous solution having a concentration of 30% by mass, 20 g of which was placed in a 40 cm long dialysis membrane and sealed. For the dialysis membrane, Spectra / Por Membrane MWCO: 1000 fractional molecular weight 1000 (manufactured by SPECTRUM LABORATORIES INC) was used. (In the present invention, any material having a fractional molecular weight comparable to that of the dialysis membrane may be used.) This was immersed in 2000 g of water in a 2 liter beaker and stirred with a stirrer. After 3 hours, the dialysis membrane was taken out of the beaker and the outside of the dialysis membrane was thoroughly washed with water, and then the contents of the dialysis membrane were taken out. The taken-out contents were concentrated with an evaporator and then left to stand in a desiccator under reduced pressure for 12 hours to be dried.
For comparison, 20 g of a 30% by weight polymer aqueous solution before dialysis was concentrated with an evaporator, then allowed to stand in a desiccator under reduced pressure for 12 hours and dried.
The weight reduction after dialysis relative to the weight of the charged polymer is considered to be the weight of unreacted phenyl glycidyl ether, and the yield of the reaction product was calculated from this value, which was 93%.
Moreover, when the dried sample after dialysis was dissolved in D ₂ O and the ¹ H-NMR spectrum was measured, signals derived from the aromatic ring of phenylglycidyl ether added with an epoxy ring were detected at around 6.88 ppm and 7.22 ppm. It was done.
From the above results, it was confirmed that the water-soluble polymer (6) was a copolymer obtained by adding an epoxy ring of phenylglycidyl ether to a polyethyleneimine ethylene oxide copolymer.
The detergency of the water-soluble polymer (6) was measured. The results are shown in Tables 1 and 2.

Example 7
25 g of the polymer (1) was charged into a glass reactor equipped with a thermometer and a stirrer, and 1.25 g of phenylglycidyl ether was added while stirring. This polymer mixture was heated to 60 ° C. with stirring and reacted for 24 hours to obtain a water-soluble polymer (7). Formation of the water-soluble polymer (7) was confirmed as follows.
About the obtained water-soluble polymer (7), an appropriate amount of water was added to prepare a polymer aqueous solution having a concentration of 30% by mass, and 20 g of this was put in a dialysis membrane having a length of 40 cm and sealed. For the dialysis membrane, Spectra / Por Membrane MWCO: 1000 fractional molecular weight 1000 (manufactured by SPECTRUM LABORATORIES INC) was used. (In the present invention, any material having a fractional molecular weight comparable to that of the dialysis membrane may be used.)
This was immersed in 2000 g of water in a 2 liter beaker and stirred with a stirrer. After 3 hours, the dialysis membrane was taken out of the beaker and the outside of the dialysis membrane was thoroughly washed with water, and then the contents of the dialysis membrane were taken out. The extracted contents were concentrated with an evaporator and then left to stand in a desiccator under reduced pressure for 12 hours to be completely dried.
For comparison, 20 g of a 30% by mass polymer aqueous solution before dialysis was concentrated with an evaporator and then allowed to stand for 12 hours in a desiccator under reduced pressure and dried.
The weight loss after dialysis relative to the weight of the charged polymer is considered to be the weight of unreacted phenyl glycidyl ether, and the yield of the reaction product was calculated from this value, which was 97%.
Moreover, when the dried sample after dialysis was dissolved in D ₂ O and the ¹ H-NMR spectrum was measured, signals derived from the aromatic ring of phenylglycidyl ether added with an epoxy ring were detected at around 6.88 ppm and 7.22 ppm. It was done.
From the above results, it was confirmed that the water-soluble polymer (7) was a copolymer obtained by adding an epoxy ring of phenylglycidyl ether to a polyethyleneimine ethylene oxide copolymer.
The detergency of the water-soluble polymer (7) was measured. The results are shown in Table 2.

Example 8
A glass reactor equipped with a thermometer and a stirrer was charged with 22 g of the water-soluble polymer (4) synthesized in Example 4 and 35.7 g of pure water, and 1.8 g of sodium bisulfite was added with stirring. Under stirring, this aqueous polymer solution was allowed to react at room temperature for 5 hours in an open state without sealing the reactor to obtain a water-soluble polymer (8). Formation of the water-soluble polymer (8) was confirmed as follows.
About the obtained water-soluble polymer (8), an appropriate amount of water was added to prepare a polymer aqueous solution having a concentration of 30% by mass, and 20 g of this was put in a dialysis membrane having a length of 40 cm and sealed. For the dialysis membrane, Spectra / Por Membrane MWCO: 1000 fractional molecular weight 1000 (manufactured by SPECTRUM LABORATORIES INC) was used. (In the present invention, any material having a fractional molecular weight comparable to that of the dialysis membrane may be used.)
This was immersed in 2000 g of water in a 2 liter beaker and stirred with a stirrer. After 3 hours, the dialysis membrane was taken out of the beaker and the outside of the dialysis membrane was thoroughly washed with water, and then the contents of the dialysis membrane were taken out. The taken out contents were concentrated with an evaporator and then left to stand in a desiccator under reduced pressure for 12 hours to be completely dried.
For comparison, 20 g of a 30% by mass polymer aqueous solution before dialysis was concentrated with an evaporator, and then allowed to stand for 12 hours in a desiccator under reduced pressure and dried.
The weight loss after dialysis relative to the weight of the charged polymer is considered to be the total weight of unreacted sodium bisulfite and allyl glycidyl ether, or low molecular weight compounds derived from these substances. The yield was calculated to be 90%.
Moreover, when the dried sample after dialysis was dissolved in D ₂ O and measured for ¹ H-NMR spectrum, the signal derived from the structure in which the double bond of allyl glycidyl ether added with an epoxy ring was sulfonated was 1.85 ppm. It was detected at around 2.78 ppm.
Moreover, when the sulfur content of the sample before and after dialysis was compared by inductively coupled plasma (ICP) emission spectroscopic analysis, 90% of the sulfur content was contained in the sample after dialysis.
From the above results, it was confirmed that the water-soluble polymer (8) had a structure in which an epoxy ring of allyl glycidyl ether was added to a polyethyleneimine ethylene oxide copolymer and a sulfonic acid group was further added to the double bond portion. .
The detergency of the water-soluble polymer (8) was measured. The results are shown in Table 2.

Example 9
A glass reactor equipped with a thermometer and a stirrer was charged with 21 g of the water-soluble polymer (5) synthesized in Example 5 and 32.8 g of pure water, and 0.9 g of sodium bisulfite was added with stirring. Under stirring, this aqueous polymer solution was allowed to react at room temperature for 5 hours in an open state without sealing the reactor to obtain a water-soluble polymer (9). Formation of the water-soluble polymer (9) was confirmed as follows.
About the obtained water-soluble polymer (9), an appropriate amount of water was added to prepare an aqueous polymer solution having a concentration of 30% by mass, and 20 g of this was put in a dialysis membrane having a length of 40 cm and sealed. For the dialysis membrane, Spectra / Por Membrane MWCO: 1000 fractional molecular weight 1000 (manufactured by SPECTRUM LABORATORIES INC) was used. (In the present invention, any material having a fractional molecular weight comparable to that of the dialysis membrane may be used.)
This was immersed in 2000 g of water in a 2 liter beaker and stirred with a stirrer. After 3 hours, the dialysis membrane was taken out of the beaker and the outside of the dialysis membrane was thoroughly washed with water, and then the contents of the dialysis membrane were taken out. The extracted contents were concentrated with an evaporator and then left to stand in a desiccator under reduced pressure for 12 hours to be completely dried.
For comparison, 20 g of a 30% by mass polymer aqueous solution before dialysis was concentrated with an evaporator and then allowed to stand for 12 hours in a desiccator under reduced pressure and dried.
The weight loss after dialysis relative to the weight of the charged polymer is considered to be the total weight of unreacted sodium bisulfite and allyl glycidyl ether, or low molecular weight compounds derived from these substances. The yield was calculated to be 93%.
Moreover, when the dried sample after dialysis was dissolved in D ₂ O and measured for ¹ H-NMR spectrum, the signal derived from the structure in which the double bond of allyl glycidyl ether added with an epoxy ring was sulfonated was 1.85 ppm. It was detected at around 2.78 ppm.
Moreover, when the sulfur content of the sample before and after dialysis was compared by inductively coupled plasma (ICP) emission spectroscopic analysis, 90% of the sulfur content was contained in the sample after dialysis.
From the above results, it was confirmed that the water-soluble polymer (9) had a structure in which an epoxy ring of allyl glycidyl ether was added to a polyethyleneimine ethylene oxide copolymer and a sulfonic acid group was further added to the double bond portion. .

Example 10
A glass reactor equipped with a thermometer and a stirrer was charged with 22 g of the water-soluble polymer (1) synthesized in Example 1 and 36.9 g of pure water, and 2.6 g of sodium sulfite was added with stirring. This aqueous polymer solution was reacted at room temperature for 1 hour with stirring to obtain a water-soluble polymer (10). Formation of the water-soluble polymer (10) was confirmed as follows.
About the obtained water-soluble polymer (10), an appropriate amount of water was added to prepare an aqueous polymer solution having a concentration of 30% by mass, and 20 g of this was put in a dialysis membrane having a length of 40 cm and sealed. For the dialysis membrane, Spectra / Por Membrane MWCO: 1000 fractional molecular weight 1000 (manufactured by SPECTRUM LABORATORIES INC) was used. (In the present invention, any material having a fractional molecular weight comparable to that of the dialysis membrane may be used.)
This was immersed in 2000 g of water in a 2 liter beaker and stirred with a stirrer. After 3 hours, the dialysis membrane was taken out of the beaker and the outside of the dialysis membrane was thoroughly washed with water, and then the contents of the dialysis membrane were taken out. The extracted contents were concentrated with an evaporator and then left to stand in a desiccator under reduced pressure for 12 hours to be completely dried.
For comparison, 20 g of a 30% by weight polymer aqueous solution before dialysis was concentrated with an evaporator, and then allowed to stand for 12 hours in a desiccator under reduced pressure and dried.
The weight loss after dialysis relative to the weight of the charged polymer is considered to be the total weight of unreacted sodium sulfite and maleic acid, or low molecular weight compounds derived from these substances. The rate was calculated to be 89%.
Moreover, when the dried sample after dialysis was dissolved in D ₂ O and the ¹ H-NMR spectrum was measured, the signal derived from the structure in which the double bond of the half-esterified maleic acid was sulfonated was 2.88 ppm, 3 Detected at around .85 ppm and 4.15 ppm.
Moreover, when the sulfur content of the sample before and after dialysis was compared by inductively coupled plasma (ICP) emission spectroscopic analysis, 90% of the sulfur content was contained in the sample after dialysis.
From the above results, it was confirmed that the water-soluble polymer (10) had a structure in which a polyethyleneimine ethylene oxide copolymer was esterified with maleic acid and a sulfonic acid group was added to the double bond.
The detergency of the water-soluble polymer (10) was measured. The results are shown in Table 2.

Example 11
25 g of the polymer (1) was charged into a glass reactor equipped with a thermometer and a stirrer, and 2.5 g of powdered cis-Δ4-tetrahydrophthalic anhydride was added while stirring. This polymer mixture was heated to 80 ° C. with stirring and reacted for 3 hours to obtain a water-soluble polymer (11). Formation of the water-soluble polymer (11) was confirmed as follows.
About the obtained water-soluble polymer (11), an appropriate amount of water was added to prepare about 50 g of a polymer aqueous solution having a concentration of 30% by mass, 20 g of which was placed in a 40 cm long dialysis membrane and sealed. For the dialysis membrane, Spectra / Por Membrane MWCO: 1000 fractional molecular weight 1000 (manufactured by SPECTRUM LABORATORIES INC) was used. (In the present invention, any material having a fractional molecular weight comparable to that of the dialysis membrane may be used.) This was immersed in 2000 g of water in a 2 liter beaker and stirred with a stirrer. After 3 hours, the dialysis membrane was taken out of the beaker and the outside of the dialysis membrane was thoroughly washed with water, and then the contents of the dialysis membrane were taken out. The taken-out contents were concentrated with an evaporator and then left to stand in a desiccator under reduced pressure for 12 hours to be dried.
For comparison, 20 g of a 30% by weight polymer aqueous solution before dialysis was concentrated with an evaporator, then allowed to stand in a desiccator under reduced pressure for 12 hours and dried.
Since the weight change of the dried sample before and after dialysis was considered to be due to unreacted cis-Δ4-tetrahydrophthalic anhydride, the yield of the reaction product was calculated from this value, which was 96%.
Moreover, when the dried sample after dialysis was dissolved in D ₂ O and measured for ¹ H-NMR spectrum, the signal derived from half-esterified cis-Δ4-tetrahydrophthalic acid was 2.26 ppm, 2.90 ppm, 5 Detected around .58 ppm.
From the above results, the water-soluble polymer (11) was confirmed to be a copolymer obtained by esterifying a polyethyleneimine ethylene oxide copolymer with cis-Δ4-tetrahydrophthalic acid.

Example 12
A glass reactor equipped with a thermometer and a stirrer was charged with 22 g of the water-soluble polymer (11) and 35.1 g of pure water, and 1.4 g of sodium bisulfite was added while stirring. Under stirring, this aqueous polymer solution was allowed to react at room temperature for 8 hours in an open state without sealing the reactor to obtain a water-soluble polymer (12). Formation of the water-soluble polymer (12) was confirmed as follows.
About the obtained water-soluble polymer (12), an appropriate amount of water was added to prepare a polymer aqueous solution having a concentration of 30% by mass, and 20 g of this was put in a dialysis membrane having a length of 40 cm and sealed. For the dialysis membrane, Spectra / Por Membrane MWCO: 1000 fractional molecular weight 1000 (manufactured by SPECTRUM LABORATORIES INC) was used. (In the present invention, any material having a fractional molecular weight comparable to that of the dialysis membrane may be used.)
This was immersed in 2000 g of water in a 2 liter beaker and stirred with a stirrer. After 3 hours, the dialysis membrane was taken out of the beaker and the outside of the dialysis membrane was thoroughly washed with water, and then the contents of the dialysis membrane were taken out. The extracted contents were concentrated with an evaporator and then left to stand in a desiccator under reduced pressure for 12 hours to be completely dried.
For comparison, 20 g of a 30% by weight polymer aqueous solution before dialysis was concentrated with an evaporator, then allowed to stand in a desiccator under reduced pressure for 12 hours and dried.
The weight loss after dialysis relative to the weight of the charged polymer is considered to be the total weight of unreacted sodium bisulfite and cis-Δ4-tetrahydrophthalic acid or low molecular weight compounds derived from these substances. From the above, the yield of the reaction product was calculated to be 92%.
Moreover, when the dried sample after dialysis was dissolved in D ₂ O and measured for ¹ H-NMR spectrum, a signal derived from a structure in which the double bond of half-esterified cis-Δ4-tetrahydrophthalic acid was sulfonated was obtained. It was detected in the vicinity of 1.35 ppm, 1.68 ppm and 3.20 ppm.
Moreover, when the sulfur content of the sample before and after dialysis was compared by inductively coupled plasma (ICP) emission spectroscopic analysis, 90% of the sulfur content was contained in the sample after dialysis.
From the above results, it was confirmed that the water-soluble polymer (12) had a structure in which a polyethyleneimine ethylene oxide copolymer was esterified with cis-Δ4-tetrahydrophthalic acid and a sulfonic acid group was added to the double bond. It was.
The detergency of the water-soluble polymer (12) was measured. The results are shown in Table 2.

Table 1 shows the results for the cleaning rate (1) for hydrophilic soil, and Table 2 shows the results for the cleaning rate (2) for hydrophobic soil. In Tables 1 and 2, “Polymer 1” represents the result of measuring the detergency using the polymer (1). “Blank” represents the result of measurement in the same manner except that hard water was added instead of the polymer aqueous solution in the method of measuring the washing rate.

From the results of Tables 1 and 2, the polyethyleneimine ethylene oxide copolymers of Examples 1, 2, 3, 4, 6, 7, 8, 10 and 12 were changed to the polymer (1) whose terminal structure was not changed. In comparison, the cleaning rate was improved.

Claims (3)

Reacting the polyalkyleneimine alkylene oxide copolymer by at least one step selected from the group consisting of the following (1) to (6);
The alkylene oxide unit has an ethylene oxide unit, and the proportion of the terminal structure formed by at least one step selected from the group consisting of the following (1) to (6) is 20 mol% or more and 98 mol% or less. A process for producing a polyalkyleneimine alkylene oxide copolymer, which comprises producing a polyalkyleneimine alkylene oxide copolymer.
(1) A step of reacting with an intramolecular cyclic anhydride of polycarboxylic acid.
(2) A step of reacting with aryl epoxy ethane or epoxy alkylene having 2 to 6 carbon atoms.
(3) A step of reacting with glycidol, alkyl glycidyl ether, alkenyl glycidyl ether or aryl glycidyl ether.
(4) A step of reacting with an alkyl isocyanate, alkenyl isocyanate or aryl isocyanate.
(5) A step of reacting with bisulfite and / or sulfite after step (1).
(6) A step of reacting with hydrogen sulfite and / or sulfite in the presence of a radical generation source or oxygen after step (2), (3) or (4). The polyalkyleneimine alkylene oxide copolymer has the following general formula (2):

Wherein R ⁶ is the same or different and represents a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms. A represents another polyamine chain by branching. L, m and n are the same or different and each represents 0 or an integer of 1 or more, wherein at least 2 —N—R ⁶ — units are present in the polyamine. A copolymer obtained by adding an alkylene oxide to an amine nitrogen atom of a polyamine having the structure: wherein in the above general formula (2), m / n = 4/1 to 1/4. A process for producing a polyalkyleneimine alkylene oxide copolymer according to claim 1 . In the steps (1) to (6), the molar ratio of the polyalkylimine alkylene oxide used in the reaction to the raw material to be reacted with the polyalkylimine alkylene oxide is (polyalkylimine alkylene oxide) / (polyalkylimine alkylene). 3. The process for producing a polyalkyleneimine alkylene oxide copolymer according to claim 1 or 2 , wherein the raw material to be reacted with oxide is 50/1 to 1/50.