JP6609151B2 - Polyalkyleneimine derivatives - Google Patents

Description

The present invention relates to a polyalkyleneimine derivative. More specifically, the present invention relates to polyalkyleneimine derivatives useful for detergent builders, detergents, water treatment agents, dispersants and the like.

Polyalkyleneimine is a water-soluble polymer obtained by polymerizing alkyleneimine, and is used as an anchoring agent for laminate, a heavy metal chelating agent, a metal plating additive, a fiber flocculant, an adhesive, an industrial dispersant, and the like.
In addition, polyalkyleneimine has been studied to be derivatized. For example, derivatives obtained by adding unsaturated carboxylic acid or alkylene oxide to polyalkyleneimine are disclosed (see, for example, Patent Documents 1 and 2). ). Furthermore, Patent Document 3 discloses a polymeric antibacterial agent produced by substituting a nitrogen atom in the skeleton of an ethyleneimine polymer.

JP 2004-002589 A JP 2005-350640 A JP 2009-524719 A

As described above, various polyalkyleneimine derivatives have been studied. However, the polyalkylenimine derivatives have not been sufficiently studied, and there is room for further development of derivatives.

The present invention has been made in view of the above situation, and an object thereof is to provide a novel polyalkyleneimine derivative.

As a result of various studies on the novel polyalkyleneimine derivatives, the present inventors have succeeded in producing a polyalkylenimine derivative having a structure in which a specific substituent having an amide structure is bonded to the nitrogen atom of the polyalkyleneimine. Furthermore, the present inventors have found that this polyalkyleneimine derivative is excellent in clay dispersibility and carbon black dispersibility, and have reached the present invention.

That is, the present invention provides a polyalkyleneimine derivative having a structure in which a substituent is bonded to a nitrogen atom of polyalkyleneimine, wherein the derivative is at least one hydrogen atom of a primary or secondary amino group of polyalkyleneimine. Is the following formula (1);

(In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom or an organic group. X represents a divalent linking group.) It is an imine derivative.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

<Polyalkyleneimine derivative>
The polyalkyleneimine derivative of the present invention has a structure in which at least one hydrogen atom of a primary or secondary amino group of the polyalkyleneimine is substituted with a group represented by the above formula (1). That is, the polyalkyleneimine derivative has a structure in which a group represented by the formula (1) is bonded to at least one nitrogen atom of a primary or secondary amino group of the polyalkyleneimine. The polyalkyleneimine derivative is not particularly limited as long as it has at least one such structure.
When the polyalkyleneimine derivative of the present invention has such a structure, the dispersibility of both hydrophilic clay and hydrophobic carbon black is excellent. The reason is estimated as follows.
Since clay is negatively charged, in addition to being easy to interact with a positively charged polyalkyleneimine skeleton, the clay molecule itself has a charge and has a highly planar molecular structure. The polyalkyleneimine derivative of the present invention has a long π-conjugated system that is easy to interact electronically, and the introduction of an amide skeleton with high planarity improves the interaction with clay, It is estimated that the dispersibility of clay is improved.
In addition, the unshared electron pair of the amino group in the amide skeleton flows toward the carbonyl group and is delocalized, so that the amide group becomes less polar than the amino group of the polyalkyleneimine, so that the hydrophobicity is reduced. It is thought to increase. It is presumed that this facilitates interaction with highly hydrophobic carbon black and improves the dispersibility of carbon black.

The organic group for R ¹ and R ² in the formula (1) is not particularly limited, for example, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, an amino structure and / or imino structure A group having a carboxyl group, a carboxyl group, a hydroxyl group, a cyano group, and the like.
The hydrocarbon group preferably has 1 to 16 carbon atoms. More preferably, it is 1-12.
The hydrocarbon group is not particularly limited, and examples thereof include chain hydrocarbon groups such as alkyl groups and alkenyl groups, and cyclic hydrocarbon groups such as aryl groups and cycloalkyl groups. The hydrocarbon group is preferably a chain hydrocarbon group, and more preferably an alkyl group.
The substituent that the hydrocarbon group may have is not particularly limited, and examples thereof include an amino group, an imino group, a carboxyl group, a hydroxyl group, and a cyano group. The substituent is preferably an amino group, an imino group or a cyano group.
Moreover, it is preferable that the polyalkyleneimine derivative of this invention has a hydrophobic group at the terminal of the structure represented by the above formula (1). By having such a structure, the dispersibility of carbon black is further improved. That is, it is preferable that at least one end of the organic groups represented by R ¹ and R ² in the above formula (1) is a hydrophobic group. Although it does not restrict | limit especially as a hydrophobic group, For example, a cyano group, a hydrocarbon group, etc. are mentioned. The hydrophobic group is preferably a cyano group.

The organic group is preferably a group having an amino structure and / or an imino structure.
The group having an amino structure and / or an imino structure has the following formula (2):

(In the formula, R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. R ⁴ may have a hydrogen atom, an amino group or a substituent. Represents a good hydrocarbon group having 1 to 18 carbon atoms, p is an integer of 0 to 6) or the following formula (3);

(Wherein, R ⁵ are the same or different, an amino group, a hydrogen atom or a substituted 1-18 carbon atoms which may hydrocarbon group. Provided that at least one of R ⁵ is An amino group, q is an integer of 0 to 6).

The specific example of the C1-C18 hydrocarbon group which may have a substituent in R < ³ > or R < ⁴ > of the said Formula (2) may have a substituent in the said Formula (1). This is the same as the hydrocarbon group having 1 to 18 carbon atoms. As a substituent which the said hydrocarbon group has, an amino group is preferable.
The p is preferably an integer of 0 to 3, more preferably 0.
R ³ is preferably a hydrogen atom. R ⁴ is preferably a hydrogen atom, an amino group, or a hydrocarbon group having an amino group as a substituent, and more preferably an amino group.

Specific examples and preferred examples of the hydrocarbon group having 1 to 18 carbon atoms which may have a substituent in R ⁵ of the above formula (3) may have a substituent in the above formula (2). This is the same as the hydrocarbon group having 1 to 18 carbon atoms. Q is preferably an integer of 0 to 3, more preferably 0.

The amino group in R ⁴ of the above formula (2), the amino group of the hydrocarbon group having an amino group as a substituent, and the amino group in R ⁵ of the formula (3) may be any of 1 to 3 grades. Although it is good, it is preferably a secondary amino group. Examples of the amino group or the hydrocarbon group having an amino group include the following formula (4):

(In the formula, R ⁶ represents a hydrogen atom. R ⁷ represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms or a cyano group. R is an integer of 0 to 6. Is preferred.)
Specific examples of the hydrocarbon group having 1 to 18 carbon atoms which may have a substituent in R ⁷ of the above formula (4) include 1 carbon atom which may have a substituent in the above formula (1). It is the same as the hydrocarbon group of -18.
R ⁷ is preferably a cyano group. R is preferably an integer of 0 to 3, more preferably 0.

In the polyalkyleneimine derivative of the present invention, it is preferable that at least one of R ¹ and R ² in the above formula (1) is an organic group, and the organic group has an amino structure and / or an imino structure.
When the polyalkyleneimine derivative of the present invention has such a structure, the dispersibility of clay and carbon black is further improved.
In the polyalkyleneimine derivative of the present invention, it is more preferable that at least one of R ¹ and R ² in the formula (1) has an amino structure and an imino structure.
More preferably, at least one of R ¹ and R ² in the formula (1) is a group represented by the above formula (2), and R ⁴ is an amino group. That is, in the polyalkyleneimine derivative of the present invention, it is more preferable that at least one of R ¹ and R ² in the formula (1) has a guanidino group.
Particularly preferably, ^one of R ¹ and R ² is a guanidino group and the other is a hydrogen atom.

The polyalkyleneimine derivative of the present invention has a substituent on the nitrogen atom derived from the amino group of the polyalkyleneimine as described above, but a part of the substituent of the polyalkyleneimine derivative is at the terminal end of the substituent, You may couple | bond with the primary or secondary amino group derived from the polyalkyleneimine of the same or different molecule | numerator. Thus, the polyalkyleneimine derivative may form a crosslinked structure within the molecule or between the molecules. For example, when one end of R ¹ and R ² in Formula (1) is a cyano group, the cyano group may react with a primary or secondary amino group derived from polyalkyleneimine to form a crosslinked structure. Can be mentioned.

X in the above formula (1) is a divalent linking group. Although it does not restrict | limit especially as a bivalent coupling group, For example, a bivalent hydrocarbon group etc. are mentioned.
Examples of the divalent hydrocarbon group include an alkylene group having 1 to 18 carbon atoms and an alkenyl group having 2 to 18 carbon atoms, preferably an alkylene group having 1 to 12 carbon atoms, more preferably an ethylene group. It is.

The polyalkyleneimine derivative of the present invention preferably has 1 to 70 mol% of the group represented by the above formula (1) with respect to 100 mol% of the nitrogen atom derived from polyalkyleneimine.
When the polyalkyleneimine derivative has the group represented by the formula (1) in such a ratio, the dispersibility of the clay and the carbon black is further improved, and the viscosity of the polyalkyleneimine derivative is within a suitable range. Therefore, it will be excellent in handling. The ratio of the group represented by the formula (1) is more preferably 1 to 60 mol%, and further preferably 1 to 50 mol%.

The polyalkyleneimine derivative of the present invention preferably has a structure in which at least one hydrogen atom of the primary amino group of the polyalkyleneimine is substituted with a group represented by the formula (1).
In the polyalkyleneimine derivative of the present invention, the content ratio of the structure in which the hydrogen atom of the primary amino group derived from polyalkyleneimine is substituted with the group represented by the formula (1) is It is preferable that it is 1-90 mol% with respect to 100 mol% of groups. More preferably, it is 1-80 mol%, More preferably, it is 1-70 mol%. When the polyalkyleneimine derivative of the present invention is obtained by bonding the group represented by the above formula (1) to the nitrogen atom of the primary or secondary amino group of the polyalkyleneimine as described later, it is caused by steric hindrance. Thus, the group represented by the above formula (1) is preferentially bonded to the primary amino group of the polyalkyleneimine. Therefore, the content ratio of the structure in which the hydrogen atom of the primary amino group derived from the polyalkyleneimine is substituted with the group represented by the formula (1) is determined based on the polyethyleneimine used in the production of the present invention and the formula (1). It shall calculate from the ratio of the compound which has group represented by these.

The polyalkyleneimine structure in the polyalkyleneimine derivative of the present invention may be any of a linear structure, a branched structure, and a three-dimensionally crosslinked structure. The polyalkyleneimine structure is preferably a branched structure.

The alkylene group derived from polyalkyleneimine in the polyalkyleneimine derivative of the present invention is not particularly limited, but is preferably the same or different and is an alkylene group having 2 to 6 carbon atoms. More preferred is an alkylene group having 2 to 4 carbon atoms, and still more preferred is an ethylene group. That is, the polyalkyleneimine in the polyalkyleneimine derivative of the present invention is preferably polyethyleneimine.
The alkylene group in the polyalkyleneimine derivative is preferably 50 to 100 mol% of ethylene groups with respect to 100 mol% of all alkylene groups. More preferably, it is 70-100 mol%, More preferably, it is 90-100 mol%, Most preferably, it is 100 mol%.

The viscosity of the 8% by mass aqueous solution of the polyalkylenimine derivative of the present invention is not particularly limited, but is preferably 0.5 to 50, more preferably 0.8 to 40, still more preferably 1.0 to 35.
The viscosity of the polyalkyleneimine derivative can be measured with a viscometer.

<Method for producing polyalkyleneimine derivative>
The method for producing the polyalkyleneimine derivative of the present invention is not particularly limited as long as the group represented by the above formula (1) can be bonded to the nitrogen atom of the primary or secondary amino group of the polyalkyleneimine. And polyalkyleneimine represented by the following formula (5):

(In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom or an organic group. R ⁸ is an unsaturated hydrocarbon group having 2 to 18 carbon atoms or a halogenated alkyl group having 2 to 18 carbon atoms. Or represents an epoxy-containing group) is preferred. Thus, when the compound represented by the above formula (5) is added to the polyalkyleneimine, the primary amino group of the polyalkyleneimine is preferentially represented by the above formula (5) due to steric hindrance. It is thought that the compound will add.

The halogenated alkyl group is not particularly limited, and examples thereof include an alkyl chloride group, an alkyl bromide group, and an alkyl iodide group.
Although it does not restrict | limit especially as said epoxy-containing group, For example, a glycidyl group, a glycidyl ether group, etc. are mentioned.
R ⁸ is preferably an unsaturated hydrocarbon group having 2 to 18 carbon atoms.
The number of carbon atoms of the unsaturated hydrocarbon group having 2 to 18 carbon atoms of the ^{R 8,} 2 to 16, more preferably from 2 to 12, particularly preferably 2. The unsaturated hydrocarbon group for R ⁸ is preferably an alkenyl group. More preferably, it is a vinyl group.
When the compound represented by the above formula (5) is an α, β-unsaturated carbonyl compound, the above formula (1) is added to the nitrogen atom of the primary or secondary amino group of the polyalkyleneimine by a Michael addition reaction. ) Can be bonded.
Specific examples and preferred examples of ^{R 1} and ^{R 2} in the compound represented by the formula (5) is the same as ^{R 1} and ^{R 2} in the formula (1).

Examples of the compound represented by the above formula (5) include dicyandiamide acrylic acid amide. As the compound represented by the formula (5), dicyandiamide acrylic acid amide is preferable.

The addition method for Michael addition of the compound represented by the formula (5) to the polyalkyleneimine is not particularly limited, but a solution reaction is preferable, and in this case, either stirring or standing may be used.
As the solvent for the addition reaction, a commonly used solvent can be used, and one or more selected from the group consisting of water; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol; It is preferable to use a solvent or a mixed solvent in which 0 to 50% by mass of water is water based on all solvents. More preferred are alcohols, and still more preferred is methyl alcohol.

It is preferable that the usage-amount of the compound represented by Formula (5) in the said addition reaction is 14-42000 mol% with respect to 100 mol% of polyalkyleneimines. More preferably, it is 14-10000 mol%, More preferably, it is 14-7000 mol%.
Moreover, it is preferable that the usage-amount of the compound represented by Formula (5) in the said addition reaction is 1-70 mol% with respect to 100 mol% of nitrogen atoms derived from polyalkyleneimine. More preferably, it is 1-65 mol%, More preferably, it is 1-60 mol%.
Furthermore, the usage-amount of the compound represented by Formula (5) in the said addition reaction shall be 1-95 mol% with respect to a total of 100 mol% of the primary and secondary amino group which polyalkyleneimine has. preferable. More preferably, it is 1-93 mol%, More preferably, it is 1-90 mol%.

The pH of the reaction solution in the addition reaction is not particularly limited, but is preferably 7 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 14 or less.
The pH is adjusted, for example, by alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, ammonia, ethanolamine and triethylamine. It is preferable to use an organic amine or the like, and it is more preferable to use an alkali metal hydroxide.

In the above addition reaction, all of the polyalkyleneimine and the compound represented by the formula (5) may be charged all together, or one of them may be initially charged and the rest may be dropped, or all may be dropped. May be.

The reaction temperature in the addition reaction is not particularly limited, but is preferably 20 to 90 ° C. More preferably, it is 30-85 degreeC, More preferably, it is 40-80 degreeC.
The reaction time is not particularly limited, but is preferably 3 to 40 hours, and more preferably 5 to 30 hours.
The atmosphere of the reaction system in the addition reaction is not particularly limited, and may be any of an air atmosphere, a nitrogen atmosphere, and the like. From the viewpoint of suppressing coloring of the obtained polymer, a nitrogen atmosphere is preferable.
The reaction may be performed at normal pressure (atmospheric pressure), pressurization, or reduced pressure.

The polyalkyleneimine used for producing the polyalkyleneimine derivative of the present invention is not particularly limited, and may be any of a linear structure, a branched structure, and a three-dimensionally crosslinked structure. A branched structure is preferred. Preferred examples of the alkylene group in the polyalkyleneimine are as described in the polyalkyleneimine derivative of the present invention.

In the polyalkyleneimine, the total ratio of primary and secondary amino groups may be 60 to 95 mol% with respect to 100 mol% of all amino groups (1st to 3rd amino groups) of the polyalkyleneimine. preferable. When the total ratio of the primary and secondary amino groups is within such a range, the compound represented by the above formula (5) is more sufficiently reacted with the primary or secondary amino group derived from polyalkyleneimine. Can do. More preferably, it is 65-93 mol% as a ratio of the sum total of a primary and secondary amino group, More preferably, it is 68-90 mol%.
The ratio of the primary to tertiary amino groups in the polyalkyleneimine can be measured by NMR.

In the polyalkyleneimine, the proportion of primary amino groups is preferably 10 to 60 mol% with respect to 100 mol% of all amino groups (1st to 3rd amino groups) of the polyalkyleneimine. When the ratio of the primary amino group is within such a range, the compound represented by the formula (5) can be more sufficiently reacted with the primary amino group derived from polyalkyleneimine. More preferably, it is 15-55 mol% as a ratio of a primary amino group, More preferably, it is 20-50 mol%.

The weight average molecular weight of the polyalkyleneimine is not particularly limited, but is preferably 100 to 100,000, more preferably 150 to 90,000, and still more preferably 200 to 80,000.
The weight average molecular weight of the polyalkyleneimine can be measured by gel permeation chromatography (GPC) under the following conditions.
Detector: Suggested refractometer (manufactured by Shimadzu Corporation)
Column: asahipak column GF-310, 510, 710 HQ (3 in series)
Calibration curve: Shodex standard P-82 (Pullan) (manufactured by Wako Pure Chemical Industries)
Eluent: 0.2M MEA (monoethanolamine) aqueous solution pH adjusted to 5.1 (pH adjusted with acetic acid)

The polyalkyleneimine used in the production of the polyalkyleneimine derivative can be obtained by polymerizing one or more of the alkyleneimines by a commonly used method.

Examples of the compound represented by the formula (5) used in the production of the polyalkyleneimine derivative include acrylic acid halide and the following formula (6);

(Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom or an organic group) and can be produced by reacting with an amine compound.
Specific examples and preferred examples of the ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the formula (1).

Examples of the compound represented by the above formula (6) include dicyandiamide, alkylamine, aromatic amine and the like. In Example 3 of Patent Document 3 described above, cyanamide is reacted with polyethyleneimine to produce a guanidine-substituted polyethyleneimine. However, cyanamide is in equilibrium with highly reactive carbodiimide and stored at 40 ° C. or higher. Since cyanamide and carbodiimide react with each other to form a dimer (dicyandiamine), the thermal stability is poor, and there is a problem as a raw material for industrial production. On the other hand, the dicyandiamide, alkylamine, and aromatic amine are excellent in stability due to heat and the like, and can be suitably used for producing the polyalkyleneimine derivative of the present invention. As the compound represented by the formula (6), dicyandiamide and alkylamine are preferable, and dicyandiamide is more preferable.

Examples of the acrylic acid halide include fluorinated acryl, chlorinated acryl, acryl bromide, acryl iodide, etc., preferably acryl chloride and bromo bromide, more preferably acryl chloride.

The amount of the amine compound represented by the formula (6) in the reaction between the acrylic acid halide and the amine compound represented by the formula (6) is 1 to 2.0 mol with respect to 1 mol of the acrylic acid halide. It is preferable. More preferably, it is 1-1.5 mol.

The reaction between the acrylic acid halide and the amine compound represented by the formula (6) is not particularly limited, but is preferably a solution reaction. As the solvent used in the solution reaction, a commonly used solvent can be used, which is selected from the group consisting of water; ketones such as acetone and methyl ethyl ketone, or 5 or more for all solvents. It is preferable to use a mixed solvent in which ˜70 mass% is water. A mixed solvent with water and ketones is more preferable, and a mixed solvent with water and acetone is still more preferable.

In the reaction of the acrylic acid halide with the amine compound represented by the formula (6), it is preferable to use a catalyst. As the catalyst, a basic compound is preferable. Although it does not restrict | limit especially as a basic compound, For example, the hydroxide of alkali metals, such as potassium and sodium, etc. are mentioned, Preferably they are potassium hydroxide and sodium hydroxide, More preferably, it is potassium hydroxide.

The reaction temperature of the reaction between the acrylic acid halide and the amine compound represented by formula (6) is preferably -20 to 20 ° C, and the reaction time is preferably 0.5 to 24 hours.

In the production of the compound represented by the above formula (5), a purification step may be performed. Although the said refinement | purification process is not restrict | limited in particular, For example, it can carry out by filtering, recrystallization, crystallization, distillation, washing with water, etc. The purification step is preferably performed by crystallization.

<Detergent Builder>
The polyalkyleneimine derivative of the present invention comprises detergent builder, detergent, water treatment agent, dispersant, fiber treatment agent, scale inhibitor (scale inhibitor), cement additive, metal ion sealant, thickener, various binders. It can use suitably for etc. Especially, it can use suitably for detergent builder, detergent, water treatment agent, and a dispersing agent.
The present invention is also a detergent builder comprising the polyalkylenimine derivative of the present invention.

As a content rate of the polyalkyleneimine derivative in the said detergent builder, it is preferable that it is 0.1-80 mass% with respect to 100 mass% of detergent builder, for example. When it is 0.1% by mass or more, the cleaning power when used as a cleaning composition is more sufficient, and when it is 80% by mass or less, it is economically excellent. As a content rate of a polyalkyleneimine derivative, More preferably, it is 1 mass% or more, More preferably, it is 5 mass% or more. Moreover, More preferably, it is 70 mass% or less, More preferably, it is 65 mass% or less.

<Cleaning agent composition>
The present invention is also a cleaning composition containing the detergent builder.
The blending ratio of the detergent builder in the cleaning composition is preferably 0.1 to 20% by mass with respect to 100% by mass of the cleaning composition. More preferably, it is 0.2-15 mass%, More preferably, it is 0.3-10 mass%, More preferably, it is 0.4-8 mass%, Most preferably, it is 0.5- 5 mass. If the blending ratio of the detergent builder is 0.1% by mass or more, sufficient detergent performance can be exhibited, and if it is 20% by mass or less, the economy is excellent.
The cleaning composition may be a powder detergent composition or a liquid detergent composition.

In addition to the detergent builder, surfactants and additives used in detergents can be used in the cleaning composition.
The surfactant is one or more selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant.
The above additives include alkali builder, chelate builder, anti-redeposition agent for preventing redeposition of contaminants such as sodium carboxymethyl cellulose, anti-fouling agent such as benzotriazole and ethylene-thiourea, soil release agent, color Anti-transfer agent, softener, alkaline substance for pH adjustment, fragrance, solubilizer, fluorescent agent, colorant, foaming agent, foam stabilizer, glossing agent, bactericidal agent, bleaching agent, bleaching aid, enzyme, Dyes, solvents and the like are preferred. In the case of a powder detergent composition, it is preferable to blend zeolite.

The polyalkyleneimine derivative of the present invention is a polyalkyleneimine derivative having a new structure having a structure in which a specific substituent is bonded to the nitrogen atom of the polyalkyleneimine, which is preferably used for detergent builders and the like. be able to.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

<Method for measuring clay dispersibility>
(1) Pure water was added to 67.56 g of glycine, 52.6 g of sodium chloride, and 2.4 g of NaOH to make 600 g (this is used as a buffer).
(2) 0.082 g of calcium chloride dihydrate was added to 60 g of buffer, and pure water was further added to make 1000 g (this is used as a buffer).
(3) After putting 0.3 g of JIS11 type clay into a test tube (made by IWAKI GLASS: diameter 18 mm, height 180 mm), 3 g of a 0.1% by mass aqueous solution (in terms of solid content) of the polyalkylenimine derivative to be measured Then, 27 g of buffer was added and sealed.
(4) The test tube was shaken to disperse the clay. Thereafter, the test tube was left in the dark for 2 hours. After 2 hours, 5 cc of the supernatant of the dispersion was taken and the absorbance was measured with a UV spectrometer (Shimadzu Corporation, UV-1200; 1 cm cell, wavelength 380 nm).

<Measurement method of carbon black dispersibility>
(1) A glycine buffer solution was prepared by adding ion-exchanged water to 60 ml of glycine 67.6 g, sodium chloride 52.6 g and 1 mol / L NaOH aqueous solution to make 600 g.
(2) A dispersion was prepared by adding pure water to 0.082 g of calcium chloride dihydrate and 60.0 g of glycine buffer prepared in (1) to make 1000 g.
(3) A 0.1% by mass polyalkylenimine derivative aqueous solution in terms of solid content was prepared.
(4) In a general test tube having a capacity of about 30 cc, 0.1 g of carbon black (obtained from the Laundry Science Association), 28.5 g of the dispersion of (2), 1.5 g of the polyalkyleneimine derivative aqueous solution of (3) Was added. At this time, the calcium concentration of the test solution was 50 ppm in terms of calcium carbonate.
(5) The test tube was sealed with a rubber stopper and then shaken up and down 60 times. The test tube was allowed to stand in a place not exposed to direct sunlight for 2 hours, and then the dispersion was visually observed.
(6) After 2 hours, 5 cc of the supernatant of the dispersion was taken and the absorbance was measured with a UV spectrometer (Shimadzu Corporation, UV-1200; 1 cm cell, wavelength 380 nm).

<Measurement method of viscosity>
The viscosity of the polyalkyleneimine derivative was measured under the following conditions.
Apparatus: TV25 viscometer manufactured by Toki Sangyo Co., Ltd. Measurement temperature: 25.0 ° C
Rotor: 01 type 1 ° 34 '× R24
Rotation speed: 20rpm

<Example 1>
Polyethyleneimine (Mw600): 7.809 g manufactured by Nippon Shokubai Co., Ltd. and methanol: 100 mL were added to an eggplant flask equipped with a reflux condenser, and stirring using a magnetic stirrer was started. To the reaction solution, 2.518 g of dicyandiamide acrylic acid amide was added in small portions and then stirred at room temperature for 1 hour. Subsequently, the reaction solution was heated to 50 ° C. using a water bath, and stirred at that temperature for 14 hours. After cooling to room temperature, the mixture was filtered using a Toyo Filter Paper 5B type 110 mm filter paper, and concentrated using a rotary evaporator. Then, the target polyalkyleneimine derivative: 9.420g was obtained by performing vacuum drying. It was 2.0 mPa * s when the 8 mass% aqueous solution viscosity of this compound was measured.
The polyethyleneimine has 14 nitrogen atoms in one molecule, and among the nitrogen atoms contained, the primary and secondary amines are 35% and tertiary amines are 30%, respectively. In the above reaction, it is considered that dicyandiamide acrylic acid amide is preferentially added to the primary amine of polyethyleneimine due to steric hindrance, and therefore 29% of the primary amine of polyethyleneimine is considered to be guanidinoylated. .
The obtained polyethyleneimine derivative was measured for clay dispersibility and carbon black dispersibility by the methods described above, and the results are shown in Tables 1 and 2.

<Comparative Example 1>
The clay dispersibility and the carbon black dispersibility were measured in the same manner as in Example 1 except that 3 g of pure water was used instead of 3 g of the 0.1% by mass aqueous solution of the polyalkyleneimine derivative. The value of each dispersibility was confirmed. The results are shown in Tables 1 and 2.

<Comparative Example 2>
In the same manner as in Example 1, except that 3 g of 0.1% by weight aqueous polyethyleneimine (SP-006 Mw = 600) manufactured by Nippon Shokubai was used instead of 3 g of 0.1% by weight aqueous solution of the polyalkyleneimine derivative. The dispersibility and the carbon black dispersibility were measured, and the value of each dispersibility of the polyalkyleneimine before derivatization was confirmed. The results are shown in Tables 1 and 2.

It can be said that the larger the absorbance (K * Abs), which is the measured value of the clay dispersibility, is, the higher the dispersibility of the clay by the polymer sample, and the easier it is to remove mud stains when blended in a detergent. As can be seen from the comparison between Example 1 and Comparative Examples 1 and 2 in Table 1, the polyalkyleneimine derivative of the present invention is significantly more than the case of no addition of the polymer, compared to the polyethyleneimine before derivatization. A significant improvement in clay dispersibility is observed. From this, it can be said that the polyalkylenimine derivative of the present invention has a high possibility of exhibiting high mud stain dispersibility when blended in a detergent.

As the absorbance (K * Abs), which is a measured value of carbon black dispersibility, is larger, the dispersibility of carbon black by the polymer sample is higher, and it can be said that oil stains tend to fall off when blended in a detergent. As can be seen from the comparison between Example 1 and Comparative Examples 1 and 2 in Table 2, the polyalkyleneimine derivative of the present invention is not added to the polymer, but compared to polyethyleneimine before derivatization. A significant improvement in carbon black dispersibility is observed. From this, it can be said that the polyalkyleneimine derivative of the present invention has a high possibility of exhibiting high oil stain dispersibility when blended in a detergent.

Since the polyalkyleneimine derivative of the present invention has a high detergency against both mud dirt and oil dirt, it can be said to be suitable for applications such as detergent builders, detergent compositions, and cleaning agents.

Claims (3)

A polyalkyleneimine derivative having a structure in which a substituent is bonded to a nitrogen atom of the polyalkyleneimine,
In the derivative, at least one hydrogen atom of the primary or secondary amino group of the polyalkyleneimine is represented by the following formula (1):

(In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom or an organic group. X represents a divalent linking group, provided that at least one of R ¹ and R ² has the following formula: (2);

(In the formula, R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. R ⁴ represents a hydrogen atom, a primary to tertiary amino group , the following formula (4 );

(In the formula, R ⁶ represents a hydrogen atom. R ⁷ represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms or a cyano group. R is an integer of 0 to 6. And a hydrocarbon group having 1 to 18 carbon atoms which may have a structure represented by or a substituent. p is 0 . ). A polyalkylenimine derivative characterized by having a structure substituted with a group represented by The said polyalkyleneimine derivative has 1-70 mol% with respect to 100 mol% of nitrogen atoms derived from polyalkyleneimine as the group represented by said Formula (1). Polyalkyleneimine derivative. A detergent builder comprising the polyalkyleneimine derivative according to claim 1 or 2.