JP4891553B2 - Terminal-modified polyalkyleneimine alkylene oxide copolymer - Google Patents

Description

  The present invention relates to a terminal-modified polyalkyleneimine alkylene oxide copolymer. More specifically, the present invention is suitable for detergent builders, detergents, water treatment agents, dispersants, and the like. For example, it is used as a detergent builder together with a surfactant. And a terminal-modified polyalkyleneimine alkylene oxide copolymer capable of exhibiting high detergency.

  Polyalkyleneimine alkylene oxide copolymer with polyalkyleneimine as the main chain and ethylene oxide added to the nitrogen atom in polyalkyleneimine is also called polyalkyleneimine ethoxylate modified product, for example, acts as a polymer builder To do. 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 polyalkyleneimine ethoxylate modified product is included in the detergent together with the active agent, the ability to remove dirt from the cloth during washing is improved, and so-called recontamination is prevented in which the dirt removed by washing adheres again to clothing. As a result, high detergency is demonstrated.

A detergent builder composition containing an ethoxylated amine dispersion / anti-redeposition agent has been disclosed for a detergent containing such a modified polyalkyleneimine ethoxylate (see, for example, Patent Document 1). The patent document 1, - ^{[(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 this case, m is 0 to 10 and n is at least 3. These polyoxyalkylene moieties can be mixed to form a block.) Polyamines are disclosed. Terminal structure of alkylene oxide adducts, compatibility nonionic group, anionic group, a mixture of these, as the nonionic group, C ₁ -C ₄ alkyl group, a hydroxyalkyl ester group, an ether group, hydrogen, acetate, methyl Examples include an ether, and examples of the anionic group include PO ₃ ²⁻ and SO ₃ ²⁻ .

In addition, a liquid laundry detergent composition containing a water-soluble or dispersible modified polyamine having a functional main chain portion that exhibits a cotton dirt releasing effect is disclosed (for example, see 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 hydrogen or a sufficient amount of water-soluble cation to satisfy the charge balance. P has a value of 1 to 6 and 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, these prior art polymeric builders have room for further improvements in terms of their ability to remove dirt and prevent recontamination to improve detergency and basic performance in other applications. was there.
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 provides a polyalkyleneimine alkylene oxide copolymer that is suitable for uses such as detergent builders, detergents, water treatment agents, and dispersants, and that can exhibit high basic performance in terms of detergency and the like. It is for the purpose.

The present invention relates to a polyalkyleneimine alkylene oxide copolymer having an alkyleneimine monomer unit having a polyalkylene oxide, wherein some or all of the hydrogen atoms of the terminal hydroxyl groups of the polyalkylene oxide are represented by the following (1) to (8): And a group substituted with two or more groups selected from the group consisting of:
(1) -CO-R ¹ -COOX
(2) —CH ₂ CH (OH) —R ²
(3) —CH ₂ CH (OH) CH ₂ —O—R ³
(4) —CO—NH—R ⁴
(5) —CO—R ⁵ —COOX
(6) —CH ₂ CH (OH) —R ⁶
(7) —CH ₂ CH (OH) CH ₂ —O—R ⁷
(8) —CO—NH—R ⁸
(In the formula, R ¹ represents an alkylene group having 2 to 8 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, or an arylene group having 6 to 14 carbon atoms, and X represents a hydrogen atom, an alkali metal atom, R ² represents an alkyl group having 2 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or carbon, and represents an alkaline earth metal atom, an ammonium group, or an organic ammonium group. R ³ represents a hydrogen atom, an alkyl group having 2 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms. R ⁴ represents an alkyl group having 2 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and R ⁵ represents a sulfoalkylene group having 2 to 8 carbon atoms. The , R ⁶ , R ⁷ and R ⁸ represent a sulfoalkyl group having 2 to 18 carbon atoms.)

When two or more groups are selected from any one of the groups (1) to (8) as terminal groups, that is, even if they belong to the same group, the terminal R ⁿ (n is 1 to 8). Among these, polyalkyleneimine alkylene oxide copolymers in which different integers are present as terminal groups are also included in the present invention.

  It is preferable that at least one of the terminal substituents of the polyalkylene oxide is selected from the group consisting of the above (5) to (8). This is because it has been found that the presence of a sulfoalkyl group increases the detergency. Among these, those having a substituent selected from the above (7) are preferable in terms of high stability against hydrolysis and the like and easy synthesis.

  The other substituent is preferably selected from the group consisting of the above (1) to (4). When a sulfoalkyl group and a different kind of substituent are combined, the improvement in detergency becomes more remarkable. Among these, those having a substituent selected from the above (3) are preferable in terms of high stability against hydrolysis and the like and easy synthesis.

  The present invention also includes detergent builders, detergents, water treatment agents, and dispersants containing the terminal-modified polyalkyleneimine alkylene oxide copolymer as an essential component.

  The terminal-modified polyalkyleneimine alkylene oxide copolymer of the present invention has the above-described configuration, and the effect of improving detergency could be enhanced by introducing terminal groups having two or more different structures. Such a terminal-modified polyalkyleneimine alkylene oxide copolymer can be suitably used in applications such as detergent builders, detergents, water treatment agents, and dispersants.

  The present inventors have found and already filed a polyalkyleneimine alkylene oxide copolymer having a specific terminal structure as a builder for a detergent having higher performance than the prior art (Japanese Patent Application No. 2004-250157). As a result of further investigations, the inventors have found that the detergency of the detergent can be further increased by using two or more types of terminal groups, and have arrived at the present invention. Hereinafter, the present invention will be described in detail.

  The terminal-modified 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 added moles relative to the polyalkyleneimine unit is 1 or 2 or more, and the average number of added moles 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, in the polyalkyleneimine alkylene oxide copolymer, a part or all of the terminal hydroxyl groups of the polyalkylene oxide of the alkyleneimine monomer unit are selected from the group consisting of the above (1) to (8). There must be at least two types of end group structures selected.

In the formula (1), the alkylene group having 2 to 8 carbon atoms in R ¹ 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.

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. When X is an alkaline earth metal, it is -COOX _1/2 . 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. Furthermore, an ammonium group may be sufficient.

In the formula (2) above, the alkyl group having 2 to 18 carbon atoms in R ² is preferably a butyl group, 2-ethylhexyl group or the like, and the alkenyl group having 2 to 18 carbon atoms is an allyl group. , A vinyl group, a propenyl group, and the like are preferable, and a phenyl group, a toluyl group, and the like are preferable as the aryl group having 6 to 14 carbon atoms. As the hydroxyalkyl group having 2 to 6 carbon atoms, a hydroxyethyl group is preferred.

In the formula (3), the alkyl group having 2 to 18 carbon atoms in R ³ is preferably a butyl group, 2-ethylhexyl group or the like, and the alkenyl group having 2 to 18 carbon atoms is an allyl group. , A vinyl group, a propenyl group, and the like are preferable, and a phenyl group, a toluyl group, and the like are preferable as the aryl group having 6 to 14 carbon atoms. The hydroxyalkyl group having 2 to 6 carbon atoms is preferably a hydroxyethyl group.

In the formula (4), the alkyl group having 2 to 18 carbon atoms in R ⁴ is preferably a hexyl group, and the alkenyl group having 2 to 18 carbon atoms is preferably a butenyl group. As the aryl group having 6 to 14 carbon atoms, a phenyl group, a toluyl group and the like are preferable.

As the sulfoalkylene group having 2 to 8 carbon atoms of R ⁵ in the formula (5), a sulfoethylene group, a 1-methylsulfoethylene group and the like are preferable, and R ⁶ in the formulas (6) to (8), As the sulfoalkyl group having 2 to 18 carbon atoms of R ⁷ and R ⁸ , a sulfoethyl group, a sulfopropyl group and the like are preferable.

In the polyalkyleneimine alkylene oxide copolymer of the present invention, a part or all of the terminal hydroxyl groups of the polyalkylene oxide of the alkyleneimine monomer unit are selected from the group consisting of the above (1) to (8). It must be at least two types, but when two or more groups are selected from any one of groups (1) to (8) as end groups, that is, in the same group (for example, group (3)) A polyalkyleneimine alkylene oxide copolymer in which two types having different terminal R ⁿ (n is an integer of any one of 1 to 8) are present as terminal groups. include.

  It is preferable that at least one of the terminal substituents of the polyalkylene oxide is selected from the group consisting of the above (5) to (8). This is because it has been found that the presence of a sulfoalkyl group increases the detergency. Among them, those having a substituent selected from the above (7) are preferable in that they are excellent in stability against hydrolysis and the like and easy to synthesize.

  The other type of substituent is preferably selected from the group consisting of (1) to (4) above. When a sulfoalkyl group and a different kind of substituent are combined, the improvement in detergency becomes more remarkable. Among them, those having a substituent selected from the above (3) are easy to synthesize and, in combination with a sulfoalkyl group, have a significant detergency against both hydrophobic and hydrophilic stains. In order to improve, it is a preferred embodiment of the present invention.

The polyalkyleneimine alkylene oxide copolymer of the present invention has two or more kinds of terminal structures selected from the group consisting of the above (1) to (8) with respect to 100 mol% of all terminal structures of the polyalkylene oxide. It is preferable that they are 5 mol% or more and 100 mol% or less. 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.

  And in the case of combining the terminal structure selected from the above (5) to (8), that is, the terminal structure having a sulfoalkyl group, and the terminal structure selected from the above (1) to (4), When the total of both is 100 mol%, the terminal structure having a sulfoalkyl group is preferably 5 mol% or more and 99 mol% or less. This is because this range is effective for improving the cleaning power. A more preferred lower limit is 10 mol%, a still more preferred lower limit is 20 mol%, a particularly preferred lower limit is 30 mol%, and a most preferred lower limit is 40 mol%. A more preferred upper limit is 97 mol%, a further preferred upper limit is 95 mol%, a particularly preferred upper limit is 93 mol%, and a most preferred upper limit is 90 mol%.

In order to synthesize the terminal-modified polyalkyleneimine alkylene oxide copolymer, the following steps (1) to (6) may be selected.
(1) Step of reacting with an intramolecular cyclic anhydride of polycarboxylic acid (2) Step of reacting with aryl epoxy ethane or epoxy alkene having 2 to 18 carbon atoms (3) Glycidol, alkyl glycidyl ether, alkenyl glycidyl ether or aryl Step of reacting with glycidyl ether (4) Step of reacting with alkyl isocyanate, alkenyl isocyanate or aryl isocyanate (5) Step of reacting with bisulfite and / or sulfite after step (1) (6) Step (2) After (3) or (4), reacting with bisulfite and / or sulfite in the presence of a radical source or oxygen.

  The polyalkyleneimine alkylene oxide copolymer having a terminal hydroxyl group (—OH) derived from alkylene oxide is reacted by at least one step selected from the group consisting of (1) to (6) above. A polyalkyleneimine alkylene oxide copolymer having each terminal structure can be obtained. That is, 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), one or more of a hydroxyl-unmodified polyalkyleneimine alkylene oxide copolymer and an intramolecular cyclic anhydride of polycarboxylic acid can be reacted. 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 alkene having 2 to 18 carbon atoms. As the aryl epoxy ethane, styrene oxide and the like are preferable. As the epoxy alkene having 2 to 18 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, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, and the like are preferable. As the alkenyl glycidyl ether, allyl glycidyl ether and the like are preferable. As the aryl glycidyl ether, phenyl Glycidyl ether and the like are preferred. 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), the polyalkyleneimine alkylene oxide copolymer having the terminal structure of the alkenylene group in (1) obtained in the step (1) is compared with 1 of bisulfite and sulfite. The reaction can be carried out using species or two or more species. As the polyalkyleneimine alkylene oxide copolymer having an alkenylene group terminal structure (1) above, a reaction product of maleic anhydride and a hydroxyl group-unmodified polyalkyleneimine alkylene oxide copolymer is suitable. The polyalkyleneimine alkylene oxide copolymer having the terminal structure of the sulfoalkylene group of (5) can be obtained by the production method including the step (5).

  In the step (6), a polyalkylene having a 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 more of bisulfite and sulfite. As the polyalkyleneimine alkylene oxide copolymer having a terminal structure of alkenyl group (2) above, a reaction product of 3,4-epoxy-1-butene and a hydroxyl group-unmodified polyalkyleneimine alkylene oxide copolymer is suitable. As the polyalkyleneimine alkylene oxide copolymer having a terminal structure of the alkenyl group in (3) above, a reaction product of allyl glycidyl ether and a hydroxyl group-unmodified polyalkyleneimine alkylene oxide copolymer is preferable, As the polyalkyleneimine alkylene oxide copolymer (4) having an alkenyl group terminal structure, a reaction product of allyl isocyanate and a hydroxyl group-unmodified polyalkyleneimine alkylene oxide copolymer is preferable. A polyalkyleneimine alkylene oxide copolymer having the terminal structure of the sulfoalkyl group of (6), (7) or (8) can be obtained by the production method including the step (6). Further, in the step (6), for example, after reacting with an epoxy alkene or alkenyl glycidyl ether having 2 to 18 carbon atoms, it may be reacted with sulfite.

  The method for producing the terminal-modified 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 deriving from the alkylene oxide A step of obtaining a hydroxyl group-unmodified polyalkyleneimine alkylene oxide copolymer having a hydroxyl group at the terminal, and reacting the copolymer by the steps (1) to (6) above, so that a part or all of the hydroxyl group is reacted. A production method including a step of obtaining a terminal-modified polyalkyleneimine alkylene oxide copolymer by substitution with at least two or more substituents is preferred.

  In order to obtain a modified polyalkyleneimine alkylene oxide copolymer having the terminal structure (3) and the terminal structure (7), an alkyl glycidyl ether and an allyl glycidyl ether are reacted in the step (3), The terminal allyl group may be sulfoalkylated in the step (6).

  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 steps (1) to (6), the molar ratio of the hydroxyl group-unmodified polyalkylimine alkylene oxide used in the reaction to the reaction partner raw material (not necessarily one type) of the hydroxyl group-unmodified polyalkylimine alkylene oxide. Is preferably (hydroxyl unmodified polyalkylimine alkylene oxide) / (reaction partner raw material) = 50/1 to 1/50. The molar ratio is more preferably 40/1 to 1/40, further preferably 30/1 to 1/30, particularly preferably 20/1 to 1/20, and 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 into 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 alkenylene group 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. As reaction temperature, 10-60 degreeC is preferable, More preferably, it is 20-40 degreeC.

  A preferred embodiment of the hydroxyl group-unmodified 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 the following general formula (I).

[Wherein, RO 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. In the above general formula, some or all of the polyalkyleneimine polymers are represented by Q ^1- (RO) _x -,-(RO) _z -Q ² and-(RO) _w -Q ^3. Conceptually represents having Q ¹ , Q ² and Q ³ , which are terminal structures of the polyalkylene oxide unit, are either a hydrogen atom or the terminal structures of (1) to (8) above, and conceptually at least two are the above (1 ) To (8). w, x, y, and z are the same or different and represent an integer of 2 or more. ]

In said formula (I), as RO, 1 type may be sufficient and 2 or more types may be sufficient, and ethylene oxide and propylene oxide are preferable. More preferably, it is ethylene oxide. Further, although there are only three terminal structures Q ¹ , Q ² and Q ³ in the above formula (I), when the polyamine moiety is further branched, the number of terminal groups is further increased. The terminal-modified polyalkyleneimine alkylene oxide copolymer has a terminal group having two or more kinds of structures.

  The copolymer represented by the general formula (I) is obtained by substituting a hydrogen atom bonded to the amine nitrogen atom of a polyamine having a structure represented by the following general formula (II) 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 (II) is preferable.

[Wherein, R '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 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 2 or more -N-R'- unit exists in a polyamine.

  In the general formula (II), the other polyamine chain represented by A is preferably bonded to the nitrogen atom via R ′. The polyamine may have one or two or more alkylene groups in R ′, preferably one, and more preferably an ethylene group. In addition, when R '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.

Units derived from the primary amine nitrogen atom are, for example, (H ₂ —N—R ′) — 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 hydroxyl group-unmodified 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 converted into polyalkylene oxide units (polyoxyalkylene groups). It becomes the substituted form.

The polyalkylene oxide unit has the following general formula (III);
-(RO) _a H (III)
(Wherein, RO 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 (III) has a hydroxyl group in the terminal structure. Such a hydroxyl group-unmodified polyalkyleneimine alkylene oxide copolymer is modified by a step selected from the group consisting of (1) to (8) above, thereby modifying the terminal hydroxyl group derived from alkylene oxide. Can do.

  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 is preferably one having at least a moderate branch, that is, one in which the ratio of m to n in the formula (II) is 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 terminal-modified 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 according to 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 (8) above, and has two or more terminal structures of (1) to (8). 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 two terminal structures selected from the group consisting of 1) to (8).

  The terminal-modified polyalkyleneimine alkylene oxide copolymer of the present invention is a builder for detergent, detergent, water treatment agent, dispersant, fiber treatment agent, scale inhibitor (scale inhibitor), cement additive, metal ion sealant. , Thickeners, various binders and the like. Especially, it can use suitably for the builder for detergents, a detergent, a water treatment agent, and a dispersing agent.

  The present invention is also a detergent builder, detergent, water treatment agent or dispersant containing the terminal-modified polyalkyleneimine alkylene oxide copolymer of the present invention as an essential component.

  The detergent builder exhibits an action for preventing dirt from reattaching to the clothes being washed. The terminal-modified polyalkyleneimine alkylene oxide copolymer of the present invention prevents the reattachment of soils, as well as the effect due to the steric structure of the polyalkylene oxide chain, and the affinity for soils is reduced by the hydrophobic terminal structure. This is because the function of causing the contamination is exhibited, and the function of dispersing the soil is sufficiently exhibited by the hydrophilic end structure.

  The terminal-modified polyalkyleneimine alkylene oxide copolymer is excellent in compatibility with a surfactant and can be suitably used as a builder for a liquid detergent because 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 has excellent anti-recontamination ability, has no performance deterioration when stored for a long time, and has extremely high quality, high performance and excellent stability when it does not cause impurity precipitation when kept at a low temperature. It becomes.

  The cleaning ability can be determined by, for example, the cleaning rate measured by the following method.

(Washing rate)
An artificially contaminated cloth is used as a sample. For the artificially contaminated cloth, cloths available from Scientific Service (STC GC C “clay dirt”, EMPA 164 “grass dirt”, EMPA 106 “carbon black / mineral oil dirt”, etc.) are used, and the whiteness is measured by reflectance in advance. . The reflectance can be measured using a colorimetric color difference meter (model number “ND-1001DP” or “SE2000” manufactured by Nippon Denshoku Industries Co., Ltd.). The EMPAs 164 and 106 are standard samples for a cleaning test in which a certain amount of dirt is adhered to the cloth. The EMPA 164 is obtained by attaching grass dirt to a white cotton cloth (EMPA 221). A white cotton cloth (EMPA221) is made by adhering carbon black and mineral oil stains.

  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. Further, 4.8 g of sodium polyoxyethylene lauryl ether sulfate, 0.6 g of polyoxyethylene lauryl ether, 0.6 g of sodium borate, 0.9 g of citric acid and 2.4 g of propylene glycol are added to make 80 g. This solution is adjusted to pH 8.2 with an aqueous sodium hydroxide solution, and then pure water is added to make a total of 100 g to prepare a surfactant solution.

A targot meter is set at 27 ° C., 1000 ml of hard water, 5 ml of an aqueous copolymer solution (concentration 0.55 mass%), 10 ml of an aqueous surfactant solution, about 5 g of an artificially contaminated cloth (EMPA106) and about 5 g of a white cloth, or an artificially contaminated cloth Only (STC GC C and EMPA164) is put into a pot of about 10 g 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 the 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 by the following formula.
Cleaning rate (%) =
100 × (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)

  The cleaning rate is 8.2% or more (more preferably 8.3% or more) when using EMPA164, 19.4% or more (more preferably 19.5% or more) when using EMPA106. More preferably, 19.6% or more).

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

  The present invention also includes detergents. The detergent may be a powder detergent or a liquid detergent, but a liquid detergent is preferred because the terminal-modified polyalkyleneimine alkylene oxide copolymer is excellent in solubility with the liquid detergent. In addition to the terminal-modified polyalkyleneimine alkylene oxide copolymer, additives generally used in detergents can be blended with the detergent. Examples of the additive include surfactants, alkali builders, chelate builders, anti-redeposition agents for preventing re-deposition of contaminants such as sodium carboxymethyl cellulose, and stain 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 terminal modified 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 blended form of the terminal-modified 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 types. Can be used. When using 2 or more types, it is preferable to combine an anionic surfactant and a nonionic surfactant, and the total amount used 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 sulfonate. 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 alkylphenyl 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%, 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. Further, the change (difference) in kaolin turbidity between when the terminal-modified polyalkyleneimine alkylene oxide copolymer of the present invention is added to the 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 air bubbles were removed. Then, a NDU2000 (trade name, turbidimeter) manufactured by Nippon Denshoku Co., Ltd. was used to detect Turbidity at 25 ° C. 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 the 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 detergent has excellent dispersibility, does not deteriorate in performance when stored for a long period of time, does not easily cause precipitation of impurities when held at a low temperature, and can be a detergent with extremely high quality performance and excellent stability.

  The present invention also includes a water treatment agent. A 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 terminal-modified polyalkyleneimine alkylene oxide copolymer may be added as it is, or one containing other components other than the terminal-modified polyalkyleneimine alkylene oxide copolymer may be added. As other composition components and blending ratios other than the terminal-modified polyalkyleneimine alkylene oxide copolymer, various components that can be used in conventionally known water treatment agents are based on the known blending ratios and the effects of the present invention. It can be used as appropriate within the range not damaged.

  The present invention also includes a dispersant. 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 above dispersant can exhibit extremely excellent dispersibility inherently possessed by the terminal-modified polyalkyleneimine alkylene oxide copolymer. In addition, it is possible to obtain a very high quality, high performance, and excellent stability agent that does not deteriorate in performance even when stored for a long period of time and does not cause precipitation of impurities when held at a low temperature. As other composition components and blending ratios other than the terminal-modified polyalkyleneimine alkylene oxide copolymer in the dispersant, various components that can be used in conventionally known dispersants are based on the known blending ratios of the present invention. It can be used as appropriate as long as the effects are not impaired.

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

  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”. Measurement methods in Examples and Comparative Examples are shown below.

(Washing rate-1: hydrophilic stain)
As an artificially contaminated cloth, STC GC C “clay dirt” obtained from Scientific Service was cut into 4.5 cm × 7 cm, and EMPA164 “grass dirt” cut into 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 (model number “SE2000” manufactured by Nippon Denshoku Industries Co., Ltd.) in advance.

  Pure water was added to 1.47 g of calcium chloride dihydrate to 10 kg to prepare hard water. Moreover, pure water was added to polyoxyethylene lauryl ether sodium sulfate 4.8g, polyoxyethylene lauryl ether 0.6g, sodium borate 0.6g, citric acid 0.9g, and propylene glycol 2.4g, and it was set to 80g. This solution was adjusted to pH 8.2 with an aqueous sodium hydroxide solution, and then pure water was added to make a total of 100 g to prepare a surfactant solution.

A targot meter was set at 27 ° C., and 1000 ml of hard water, 5 ml of an aqueous copolymer solution (concentration 0.55% by mass), 10 ml of an aqueous surfactant solution, and artificially contaminated cloth (10 STC GC C cloths, 10 EMPA cloths) It put in the pot and stirred for 10 minutes at 100 rpm. The artificially contaminated cloth was taken out of the pot and the water was squeezed by hand. 1000 ml of hard water was newly added to the pot, an artificially contaminated cloth with squeezed water was added, and the mixture was 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 cloth was applied to the artificially contaminated cloth and dried while stretching the wrinkles with an iron. The whiteness of the dried artificial soiled cloth was measured by reflectance using a colorimetric color difference meter. The cleaning rate (%) was obtained from the value measured by the above method and the following equation.
Cleaning rate (%) =
100 × (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)

(Washing rate-2: hydrophobic stain)
As an artificially contaminated cloth, EMPA106 “carbon black / mineral oil stain” obtained from Scientific Service was cut into 5.0 cm × 5.0 cm. 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 (model number “SE2000” manufactured by Nippon Denshoku Industries Co., Ltd.) in advance.

  Pure water was added to 0.74 g of calcium chloride dihydrate to 10 kg to prepare hard water. Further, a surfactant solution was prepared in the same manner as described above.

  A targot meter was set at 27 ° C., 1000 ml of hard water, 5 ml of aqueous copolymer solution (concentration 0.55 mass%), 10 ml of aqueous surfactant solution, 10 artificially contaminated cloths and 7 white cloths were put in the pot. In the same manner as in the above cleaning rate-1, cleaning, rinsing and drying were performed, the reflectance of the sample was measured, and the cleaning rate was obtained.

Example 1
As a hydroxyl-unmodified copolymer, polyethyleneimine ethylene oxide (PEI) (average molecular weight 600, manufactured by Nippon Shokubai Co., Ltd.) was reacted with ethylene oxide corresponding to 20 moles per mole of nitrogen atoms to ethoxylate the polyethyleneimine ethylene oxide copolymer. A polymer was used.

  A glass reactor equipped with a thermometer and a stirrer was charged with 126 g (0.01 mol) of the hydroxyl-unmodified polyethyleneimine ethylene oxide copolymer, and 10.9 g (0.096 mol) of allyl glycidyl ether while stirring. And 7.6 g (0.041 mol) of 2-ethylhexyl glycidyl ether were added. The mixture was heated to 60 ° C. with stirring and reacted for 6 hours to obtain a water-soluble copolymer (1).

  Formation of the water-soluble copolymer (1) was confirmed as follows. About the obtained water-soluble copolymer (1), an appropriate amount of water was added to prepare about 50 g of an aqueous copolymer solution having a concentration of 30% by mass, 20 g of which was placed in a 40 cm long dialysis membrane and sealed. . As the dialysis membrane, Spectra / Por Membrane MWCO: 1000 fractional molecular weight 1000 (manufactured by SPECTRUM LABORATORIES INC) was used (in the present invention, any membrane 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 copolymer 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 mass change of the dried sample before and after dialysis was considered to be due to unreacted allyl glycidyl ether and 2-ethylhexyl glycidyl ether, the yield of the reaction product was calculated from this value, and was 95%.

Further, the dry sample after the dialysis was dissolved in D ₂ O, was measured by ¹ H-NMR spectrum, signals derived from the double bond of the allyl glycidyl ether epoxy rings are ring-opening addition is, 5.20 ppm and 5. Signals derived from the 2-ethylhexyl group of 2-ethylhexyl glycidyl ether were detected at around 0.65 ppm, 1.12 ppm and 1.38 ppm at around 80 ppm.

  From the above results, the water-soluble copolymer (1) is a terminal-modified polyethyleneimine ethylene oxide copolymer obtained by ring-opening addition of an epoxy ring of allyl glycidyl ether and 2-ethylhexyl glycidyl ether to a hydroxyl group-unmodified polyethylene imine ethylene oxide copolymer. It was confirmed that

  Next, in a glass reaction vessel equipped with a thermometer and a stirrer, 144.5 g (0.01 mol) of the water-soluble copolymer (1) and 288.6 g of pure water were charged and stirred. 10.0 g (0.096 mol) of sodium hydrogen sulfite was added. With the reactor open without being sealed, this aqueous solution was stirred and reacted for 8 hours to obtain a water-soluble copolymer (2). The detergency of the water-soluble copolymer (2) was measured, and the results are shown in Table 1.

Formation of the water-soluble copolymer (2) was confirmed as follows. First, the method for determining the mass reduction before and after dialysis was the same as in the case of the water-soluble copolymer (1). Mass reduction is considered to be the total amount of unreacted sodium bisulfite and allyl glycidyl ether and 2-ethylhexyl glycidyl ether, or low molecular weight compounds derived from these substances. The yield of the reaction product was calculated from the value of mass reduction and found to be 92%. Moreover, when the dried sample after dialysis was dissolved in D ₂ O and the ¹ H-NMR spectrum was measured, a signal derived from the structure in which the double bond of the allyl glycidyl ether having an epoxy ring opened and added was sulfonated was obtained. , Detected at around 1.85 ppm and 2.78 ppm. Furthermore, 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, the water-soluble copolymer (2) was obtained by ring-opening addition of an epoxy group of allyl glycidyl ether and 2-ethylhexyl glycidyl ether to a hydroxyl group-unmodified polyethyleneimine ethylene oxide copolymer, and It was confirmed that the structure was added with a sulfonic acid group.

Example 2
The same polyethyleneimine ethylene oxide copolymer 126 g (0.01 mol) as in Example 1 was charged into a glass reactor equipped with a thermometer and a stirrer, and 9.4 g (0. 082 mol) and 5.1 g (0.027 mol) of 2-ethylhexyl glycidyl ether were added. The mixture was heated to 60 ° C. with stirring and reacted for 6 hours to obtain a water-soluble copolymer (3).

Formation of the water-soluble copolymer (3) was confirmed as follows. First, the method for determining the mass reduction before and after dialysis was the same as in Example 1. The mass decrease was considered to be due to unreacted allyl glycidyl ether and 2-ethylhexyl glycidyl ether, and the yield of the reaction product was calculated from this value, and was 97%. Further, the dry sample after the dialysis was dissolved in D ₂ O, was measured by ¹ H-NMR spectrum, signals derived from the double bond of the allyl glycidyl ether epoxy rings are ring-opening addition is, 5.20 ppm and 5. Signals derived from the 2-ethylhexyl group of 2-ethylhexyl glycidyl ether were detected at around 0.65 ppm, 1.12 ppm and 1.38 ppm at around 80 ppm.

  From the above results, the water-soluble copolymer (3) is a terminal-modified polyethyleneimine ethylene oxide copolymer obtained by ring-opening addition of an epoxy ring of allyl glycidyl ether and 2-ethylhexyl glycidyl ether to a hydroxyl group-unmodified polyethylene imine ethylene oxide copolymer. It was confirmed that

  Next, in a glass reaction vessel equipped with a thermometer and a stirrer, 140.4 g (0.01 mol) of the water-soluble copolymer (3) and 224.7 g of pure water were charged, while stirring. 8.5 g (0.082 mol) of sodium hydrogen sulfite was added. With the reactor open without being sealed, this aqueous solution was stirred and reacted for 8 hours to obtain a water-soluble copolymer (4). The detergency of the water-soluble copolymer (4) was measured, and the results are shown in Table 1.

Formation of the water-soluble copolymer (4) was confirmed as follows. First, the method for determining the mass reduction before and after dialysis was the same as in Example 1. Mass reduction is considered to be the total amount of unreacted sodium bisulfite and allyl glycidyl ether and 2-ethylhexyl glycidyl ether, or low molecular weight compounds derived from these substances. The yield of the reaction product was calculated from the value of mass reduction and found to be 92%. Moreover, when the dried sample after dialysis was dissolved in D ₂ O and the ¹ H-NMR spectrum was measured, a signal derived from the structure in which the double bond of the allyl glycidyl ether having an epoxy ring opened and added was sulfonated was obtained. , Detected at around 1.85 ppm and 2.78 ppm. Furthermore, when the sulfur content of the sample before and after dialysis was compared by inductively coupled plasma emission spectroscopy, 90% sulfur content was contained in the sample after dialysis.

  From the above results, the water-soluble copolymer (4) was obtained by ring-opening addition of an epoxy group of allyl glycidyl ether and 2-ethylhexyl glycidyl ether to a hydroxyl-unmodified polyethyleneimine ethylene oxide copolymer, and It was confirmed that the structure was added with a sulfonic acid group.

Example 3
The same polyethyleneimine ethylene oxide copolymer 126 g (0.01 mol) as in Example 1 was charged into a glass reactor equipped with a thermometer and a stirrer, and 9.4 g (0. 082 mol) and 6.1 g (0.041 mol) of phenyl glycidyl ether were added. The mixture was heated to 60 ° C. with stirring and reacted for 6 hours to obtain a water-soluble copolymer (5).

Formation of the water-soluble copolymer (5) was confirmed as follows. First, the method for determining the mass reduction before and after dialysis was the same as in Example 1. Since the mass decrease is considered to be due to unreacted allyl glycidyl ether and phenyl glycidyl ether, the yield of the reaction product was calculated from this value, which was 94%. Further, the dry sample after the dialysis was dissolved in D ₂ O, was measured by ¹ H-NMR spectrum, signals derived from the double bond of the allyl glycidyl ether epoxy rings are ring-opening addition is, 5.20 ppm and 5. Signals derived from the aromatic ring of phenylglycidyl ether were detected in the vicinity of 80 ppm and in the vicinity of 6.88 ppm and 7.22 ppm.

  From the above results, the water-soluble copolymer (5) is a terminal-modified polyethyleneimine ethylene oxide copolymer obtained by ring-opening addition of an epoxy ring of allyl glycidyl ether and phenyl glycidyl ether to a hydroxyl group-unmodified polyethylene imine ethylene oxide copolymer. It was confirmed.

  Next, in a glass reaction vessel equipped with a thermometer and a stirrer, 143.0 g (0.01 mol) of the water-soluble copolymer (5) and 229.5 g of pure water were charged and stirred. 10.0 g (0.096 mol) of sodium hydrogen sulfite was added. With the reactor open without being sealed, this aqueous solution was stirred and reacted for 8 hours to obtain a water-soluble copolymer (6). The detergency of the water-soluble copolymer (6) was measured, and the results are shown in Table 1.

Formation of the water-soluble copolymer (6) was confirmed as follows. First, the method for determining the mass reduction before and after dialysis was the same as in Example 1. The mass loss is considered to be the total amount of unreacted sodium bisulfite and allyl glycidyl ether and phenylhexyl glycidyl ether, or low molecular weight compounds derived from these substances. When the yield of the reaction product was calculated from the value of mass reduction, it was 93%. Moreover, when the dried sample after dialysis was dissolved in D ₂ O and the ¹ H-NMR spectrum was measured, a signal derived from the structure in which the double bond of the allyl glycidyl ether having an epoxy ring opened and added was sulfonated was obtained. , Detected at around 1.85 ppm and 2.78 ppm. Furthermore, when the sulfur content of the sample before and after dialysis was compared by inductively coupled plasma emission spectroscopy, 90% sulfur content was contained in the sample after dialysis.

  From the above results, the water-soluble copolymer (6) was obtained by ring-opening addition of the epoxy groups of allyl glycidyl ether and phenyl glycidyl ether to the hydroxyl group-unmodified polyethyleneimine ethylene oxide copolymer, and sulfonic acid at the double bond. It was confirmed that the structure was a group added.

Example 4
126 g (0.01 mol) of the same polyethyleneimine ethylene oxide copolymer as in Example 1 was charged into a glass reactor equipped with a thermometer and a stirrer, and 10.9 g of allyl glycidyl ether (0. 096 mol) and 6.1 g (0.041 mol) of phthalic anhydride were added. The mixture was heated to 60 ° C. with stirring and reacted for 6 hours to obtain a water-soluble copolymer (7).

Formation of the water-soluble copolymer (7) was confirmed as follows. First, the method for determining the mass reduction before and after dialysis was the same as in Example 1. The mass decrease is considered to be due to unreacted allyl glycidyl ether and phthalic anhydride, and the yield of the reaction product was calculated from this value, which was 96%. Further, the dry sample after the dialysis was dissolved in D ₂ O, was measured by ¹ H-NMR spectrum, signals derived from the double bond of the allyl glycidyl ether epoxy rings are ring-opening addition is, 5.20 ppm and 5. In the vicinity of 80 ppm, signals derived from the aromatic ring of phthalic acid were further detected in the vicinity of 7.38 ppm, 7.45 ppm and 7.68 ppm.

  From the above results, the water-soluble copolymer (7) is a terminal-modified polyethyleneimine ethylene oxide in which the epoxy ring of allyl glycidyl ether is ring-opened and added to the hydroxyl-unmodified polyethyleneimine ethylene oxide copolymer and phthalic acid is esterified. It was confirmed to be a copolymer.

  Next, in a glass reaction vessel equipped with a thermometer and a stirrer, 143.0 g (0.01 mol) of the water-soluble copolymer (7) and 229.5 g of pure water were charged, while stirring. 10.0 g (0.096 mol) of sodium hydrogen sulfite was added. With the reactor open without being sealed, this aqueous solution was stirred and reacted for 8 hours to obtain a water-soluble copolymer (8). The detergency of the water-soluble copolymer (6) was measured, and the results are shown in Table 1.

Formation of the water-soluble copolymer (8) was confirmed as follows. First, the method for determining the mass reduction before and after dialysis was the same as in Example 1. Mass loss is considered to be the total amount of unreacted sodium bisulfite and allyl glycidyl ether and phthalic acid, or low molecular weight compounds derived from these substances. When the yield of the reaction product was calculated from the value of mass reduction, it was 94%. Moreover, when the dried sample after dialysis was dissolved in D ₂ O and the ¹ H-NMR spectrum was measured, a signal derived from the structure in which the double bond of the allyl glycidyl ether having an epoxy ring opened and added was sulfonated was obtained. , Detected at around 1.85 ppm and 2.78 ppm. Furthermore, when the sulfur content of the sample before and after dialysis was compared by inductively coupled plasma emission spectroscopy, 92% of the sulfur content was contained in the sample after dialysis.

  From the above results, the water-soluble copolymer (8) was obtained by ring-opening addition of the epoxy group of allyl glycidyl ether to the hydroxyl-unmodified polyethyleneimine ethylene oxide copolymer, and further adding a sulfonic acid group to the double bond. It was confirmed that the copolymer was a terminal-modified polyethyleneimine ethylene oxide copolymer having an end group and an end bonded with an ester bond of phthalic acid.

Comparative Example 1
The same polyethyleneimine ethylene oxide copolymer 126 g (0.01 mol) as in Example 1 was charged into a glass reactor equipped with a thermometer and a stirrer, and 12.4 g (0. 109 mol) was added. The mixture was heated to 60 ° C. with stirring and reacted for 6 hours to obtain a water-soluble copolymer (9).

Formation of the water-soluble copolymer (9) was confirmed as follows. First, the method for determining the mass reduction before and after dialysis was the same as in Example 1. Since the mass decrease is considered to be due to unreacted allyl glycidyl ether, the yield of the reaction product was calculated from this value and found to be 96%. Further, the dry sample after the dialysis was dissolved in D ₂ O, was measured by ¹ H-NMR spectrum, signals derived from the double bond of the allyl glycidyl ether epoxy rings are ring-opening addition is, 5.20 ppm and 5. It was detected at around 80 ppm.

  From the above results, it was confirmed that the water-soluble copolymer (9) was a terminal-modified polyethyleneimine ethylene oxide copolymer in which the epoxy ring of allyl glycidyl ether was subjected to ring-opening addition to a hydroxyl group-unmodified polyethyleneimine ethylene oxide copolymer. .

  Next, 138.4 g (0.01 mol) of the water-soluble copolymer (9) and 224.6 g of pure water were charged into a glass reaction vessel equipped with a thermometer and a stirrer, Sodium hydrogen sulfite 11.3 g (0.109 mol) was added. With the reactor open without being sealed, this aqueous solution was stirred and reacted for 8 hours to obtain a water-soluble copolymer (10). The detergency of the water-soluble copolymer (10) was measured, and the results are shown in Table 1.

Formation of the water-soluble copolymer (10) was confirmed as follows. First, the method for determining the mass reduction before and after dialysis was the same as in Example 1. The mass loss is considered to be the total amount of unreacted sodium bisulfite and allyl glycidyl ether and phenylhexyl glycidyl ether, or low molecular weight compounds derived from these substances. The yield of the reaction product was calculated from the value of mass reduction 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, a signal derived from the structure in which the double bond of the allyl glycidyl ether having an epoxy ring opened and added was sulfonated was obtained. , Detected at around 1.85 ppm and 2.78 ppm.

  From the above results, the water-soluble copolymer (10) was obtained by ring-opening addition of an epoxy group of allyl glycidyl ether to a hydroxyl-unmodified polyethyleneimine ethylene oxide copolymer and further adding a sulfonic acid group to the double bond. The structure was confirmed to be a terminal-modified polyethyleneimine ethylene oxide copolymer.

Comparative Example 2
25 g (0.002 mol) of the same polyethyleneimine ethylene oxide copolymer as in Example 1 was charged into a glass reactor equipped with a thermometer and a stirrer, and while stirring, 2.5 g of powdered phthalic anhydride (0.017 mol) was added. The mixture was heated to 60 ° C. with stirring and reacted for 6 hours to obtain a water-soluble copolymer (11). The detergency of this water-soluble copolymer (11) was measured, and the results are shown in Table 1.

  Formation of the water-soluble copolymer (11) was confirmed as follows. First, the method for determining the mass reduction before and after dialysis was the same as in Example 1. Since the mass decrease is considered to be due to unreacted phthalic anhydride, the yield of the reaction product was calculated from this value and found to be 84%.

Moreover, when the dried sample after dialysis was dissolved in D ₂ O and the ¹ H-NMR spectrum was measured, the signals derived from the aromatic ring of half-esterified phthalic acid were 7.38 ppm, 7.45 ppm and 7.68 ppm. Detected nearby.

  From the above results, it was confirmed that the water-soluble copolymer (11) had a terminal structure in which phthalic acid was ester-bonded to a hydroxyl group-unmodified polyethyleneimine ethylene oxide copolymer.

Comparative Example 3
The washing rate was measured with the hydroxyl group-unmodified polyethyleneimine ethylene oxide copolymer used as the starting material in Example 1, and the results are shown in Table 1. In Table 1, “blank” represents the result of measurement in the same manner except that hard water was added in place of the aqueous copolymer solution in the method for measuring the washing rate.

The terminal-modified polyalkyleneimine alkylene oxide copolymer of the present invention has the above-described structure, and has improved ability to peel off dirt and prevent re-contamination by introducing two or more kinds of terminal groups having different structures. In addition, the detergency against both hydrophobic stains and hydrophilic stains could be increased. Such a terminal-modified polyalkyleneimine alkylene oxide copolymer can be suitably used in applications such as detergent builders, detergents, water treatment agents, and dispersants.

Claims (6)

A polyalkyleneimine alkylene oxide copolymer having an alkyleneimine monomer unit having a polyalkylene oxide, wherein some or all of the hydrogen atoms of the terminal hydroxyl groups of the polyalkylene oxide are from the following (1) to (8): And at least one of the terminal substituents of the polyalkylene oxide is selected from the group consisting of the following (1) to (4). A terminal-modified polyalkyleneimine alkylene oxide copolymer , wherein at least one of the terminal substituents of the polyalkylene oxide is selected from the group consisting of the following (5) to (8): Coalescence.
(1) -CO-R ¹ -COOX
(2) —CH ₂ CH (OH) —R ²
(3) —CH ₂ CH (OH) CH ₂ —O—R ³
(4) —CO—NH—R ⁴
(5) —CO—R ⁵ —COOX
(6) —CH ₂ CH (OH) —R ⁶
(7) —CH ₂ CH (OH) CH ₂ —O—R ⁷
(8) —CO—NH—R ⁸
(In the formula, R ¹ represents an alkylene group having 2 to 8 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, or an arylene group having 6 to 14 carbon atoms, and X represents a hydrogen atom, an alkali metal atom, R ² represents an alkyl group having 2 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or carbon, and represents an alkaline earth metal atom, an ammonium group, or an organic ammonium group. R ³ represents a hydrogen atom, an alkyl group having 2 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms. R ⁴ represents an alkyl group having 2 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and R ⁵ represents a sulfoalkylene group having 2 to 8 carbon atoms. The , R ⁶ , R ⁷ and R ⁸ represent a sulfoalkyl group having 2 to 18 carbon atoms.) The terminal-modified polyalkyleneimine alkylene oxide copolymer according to claim 1 , wherein at least one of the terminal substituents of the polyalkylene oxide has a polyalkylene oxide selected from the above (7). The terminal-modified polyalkyleneimine alkylene oxide copolymer according to claim 1 , wherein at least one of the terminal substituents of the polyalkylene oxide is selected from the above (3). Selected from (5) to (8) above with respect to 100 mol% in total of the terminal structure selected from (1) to (4) above and the terminal structure selected from (5) to (8) above The terminal-modified polyalkyleneimine alkylene oxide copolymer according to any one of claims 1 to 3, wherein the terminal structure is 5 mol% or more and 99 mol% or less. Detergent, characterized in that as an essential component terminal-modified polyalkyleneimine alkyleneoxide copolymer according to any one of claims 1-4. Or cleaning rate when using EMPA164 an artificial stained cloth is 8.2% or more, or, in claim 5 cleaning rate when using EMPA106 an artificial stained cloth is 19.4% or more Described detergent .