JP6270585B2 - Modified alkyleneimine polymer - Google Patents

Description

The present invention relates to a modified alkyleneimine polymer. More specifically, it is suitable for water treatment agents, fiber treatment agents, inorganic pigment dispersants, detergent builders, detergent compositions, and the like. For example, when used together with an activator as a detergent builder, it exhibits high detergency. The present invention relates to a modified alkyleneimine polymer, a production method thereof, and an application.

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

In addition, as a polymer in which an unsaturated carboxylic acid is added to a polyalkyleneimine chain, an N-alkylcarboxylic acid-ethyleneimine polymer in which the amino group of polyethyleneimine is alkylated with a carboxylic acid is disclosed as a blending component of a detergent. ing. (Patent Documents 1 to 3)

Furthermore, an example in which an alkyleneimine polymer introduced with a hydrophobic group by reacting a polyalkyleneimine with an epoxy compound having a hydrophobic group composed of an organic group having 5 to 20 carbon atoms is incorporated in a dispersant is disclosed. Has been. (Patent Document 4)

JP 2003-286344 A JP 2005-248144 A JP 2005-104999 A JP 2005-170977 A

However, in these prior arts, when used in a detergent application, it is more suitable as a polymer builder, so that not only hydrophilic particles and water-soluble soils but also hydrophobic soils can be recycled. In order to sufficiently prevent contamination and improve detergency, and to improve basic performance in other applications, a polymer in which an unsaturated carboxylic acid is added to the amino group of polyethyleneimine has a hydrophobic group. There was room for ingenuity to introduce.

In addition, in an alkyleneimine polymer in which a hydrophobic group is introduced by reacting a polyalkyleneimine with an epoxy compound having a hydrophobic group composed of an organic group having 5 to 20 carbon atoms, the ability to prevent recontamination of hydrophobic soils. However, there is a problem that the ability to prevent re-contamination against hydrophilic soils is reduced.

Therefore, the present invention has been made in view of the present situation, odor can be reduced to a level that does not cause a problem, the cleaning ability of hydrophobic dirt can be improved, a builder for cleaning agents, a cleaning agent, The purpose is to provide a modified alkyleneimine polymer that is suitable for use in water treatment agents, dispersants, etc., and that can exhibit high basic performance in terms of detergency, etc., and a method for producing the same. To do.

The present inventors have made various studies on modified alkyleneimine polymers having hydrophobic groups. In such polymers, by introducing carboxyl groups and hydrophobic groups, conventional polyalkyleneimine polymers can be obtained. It paid attention to exhibiting the effect different from a polymer.
Then, when a part of the nitrogen atom of polyalkyleneimine has a specific structure of 1) a carboxylalkyl group and 2) a hydrophobic group, the inventors have conceived that the above problems can be solved brilliantly. For example, when used in the field of detergents, such a polymer is considered to adhere to hydrophilic particles such as hydrophilic dirt and mud having an anionic property due to the cationic property due to polyethyleneimine. Moreover, when it is set as the polymer which has a specific hydrophobic group, it is thought that it adsorb | sucks to hydrophobic dirt. Moreover, it is thought that the polymer which adsorb | sucked these dirt by the carboxyl group is disperse | distributed. These actions are exhibited synergistically to improve basic performance such as cleaning power. Furthermore, it has been found that when the polymer is produced by reacting a polyalkyleneimine polymer with a specific compound, the above-mentioned effects are exhibited. Also, such a polymer is water treatment agent, fiber treatment agent, inorganic agent. The present invention has also been found to be suitable for use in pigment dispersants, detergent builders, and detergent compositions.

<1>
That is, the polymer of the present invention is
A modified alkyleneimine polymer having an alkyleneimine structural unit,
In the nitrogen atom of the modified polyalkyleneimine polymer,
It has a structure of carboxylalkyl represented by the following general formula (1-1), and
A modified alkyleneimine polymer having the following structure (2) or (3):

(In General Formula (1-1), R ¹ is represented by one selected from a hydrogen atom, a methyl group, and a carboxyl group, and R ² represents a hydrogen atom or a methyl group.)
(2) —CH ₂ CH (OH) CH ₂ —O—R ³
(3) —CH ₂ CH (OH) —R ⁴
(In the formula, R ³ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ⁴ represents 2 to 20 carbon atoms. And an aryl group having 6 to 20 carbon atoms.)

<2>
Moreover, as a preferable form of the polymer of the present invention, the modified alkyleneimine polymer has a weight average molecular weight of 300 to 1,000,000.

<3>
Furthermore, as another preferable form of the polymer of the present invention,
The structure of the general formula (1-1) of the polyalkyleneimine polymer is 0.2 to 0.98 mol with respect to 1 mol of the nitrogen atom,
The structure of (2) or (3) of the polyalkyleneimine polymer is 0.001 to 0.9 mol with respect to 1 mol of a nitrogen atom, and
The carbon atom contained in said (2) or said (3) of the said polyalkyleneimine polymer is 0.001-4 mol with respect to 1 mol of nitrogen atoms.
<4>
The method for producing the polymer of the present invention comprises:
A polyalkyleneimine polymer;
An unsaturated carboxylic acid compound represented by the following general formula (1-2);
At least one compound selected from the group consisting of the following (a) and (b):
A process for producing a modified alkyleneimine polymer characterized by reacting.

(In General Formula (1-2), R ¹ is represented by one selected from a hydrogen atom, a methyl group, and a carboxyl group, and R ² represents a hydrogen atom or a methyl group.)
(A) a glycidyl ether having an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, or an aryl glycidyl ether having 6 to 20 carbon atoms (b) an epoxy alkene having 2 to 20 carbon atoms Or an aryl group-containing epoxy alkane having 6 to 20 carbon atoms

<5>
The use of the modified alkyleneimine polymer of the present invention is at least one selected from a water treatment agent, a fiber treatment agent, an inorganic pigment dispersant, a detergent builder, and a detergent composition.

According to the present invention, it is possible to efficiently disperse particles, for example, a novel modified alkyleneimine polymer capable of exhibiting excellent performance in uses such as a cleaning agent and a water treatment agent, a method for producing the same, and a method for producing the same Applications can be provided.

Hereinafter, the modified ethyleneimine polymer according to the present invention, its production method and its use will be described in detail. However, the scope of the present invention is not limited to these explanations, and the present invention is not limited to the following examples. Changes can be made as appropriate without departing from the spirit of the invention.

[Modified alkyleneimine polymer]
The modified alkylene imine polymer of the present invention is obtained by adding an unsaturated carboxylic acid compound and an epoxy compound having a hydrophobic group to a polyalkylene imine chain. The modified alkylene imine polymer of the present invention can be easily obtained by the production method of the modified alkylene imine polymer of the present invention described later, but the one obtained by the production method of the present invention is used. It is not limited.

Examples of the polyalkyleneimine chain in the present invention include polyalkyleneimines such as polyethyleneimine and polypropyleneimine. These polyalkyleneimines are preferably branched, and in particular, the proportion of tertiary amines among primary amine, secondary amine and tertiary amine present in the branched polyalkyleneimine is 1 to 50 mol%. It is preferable that it is 5 to 45 mol%, more preferably 10 to 40 mol%. The proportion of tertiary amine in the branched polyalkyleneimine can be measured by NMR analysis or the like. The polyalkyleneimine chain may be only one type or two or more types.

The modified alkyleneimine polymer has a structure of the following general formula (1-1) on the nitrogen atom of the polyalkylene polymer having an alkyleneimine structural unit.

(In General Formula (1-1), R ¹ is represented by one selected from a hydrogen atom, a methyl group, and a carboxyl group, and R ² represents a hydrogen atom or a methyl group.)
As a preferable form of the general formula (1-1), for example,
A) a structure in which R ¹ and R ² are hydrogen atoms;
A) a structure in which R ¹ is a hydrogen atom and R ² is a methyl group;
C) A structure in which R ¹ is a carboxyl group and R ² is a hydrogen atom.

In the case of a), acrylic acid is a structure obtained by Michael addition reaction to the NH group of the polyalkyleneimine chain,
In the case of i), methacrylic acid is a structure obtained by Michael addition reaction to the NH group of the polyalkyleneimine chain,
In the case of (c), maleic acid has a structure obtained by Michael addition reaction with the NH group of the polyalkyleneimine chain.

The structure of the general formula (1-1) of the polyalkyleneimine polymer is preferably 0.2 to 0.98 mol, more preferably 0.2 to 0.95 mol with respect to 1 mol of the nitrogen atom, 0.25 to 0.93 mol is more preferable, 0.3 to 0.9 mol is particularly preferable, and 0.4 to 0.9 mol is most preferable in view of water solubility.

The modified alkyleneimine polymer has the following structure (2) or (3) on the nitrogen atom of the polyalkylene polymer having an alkyleneimine structural unit.
(2) —CH ₂ CH (OH) CH ₂ —O—R ³
(3) —CH ₂ CH (OH) —R ⁴
In the formula (2), R ³ is preferably an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 2 to 18 carbon atoms, more preferably an alkyl group having 3 to 15 carbon atoms, An alkyl group having a number of 4 to 10 is more preferable, a butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, and an octyl group are particularly preferable, and a butyl group and a 2-ethylhexyl group are most preferable.
The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 3 to 15 carbon atoms, more preferably an alkenyl group having 4 to 12 carbon atoms, and particularly preferably an alkenyl group having 4 to 10 carbon atoms.
The aryl group having 6 to 20 carbon atoms (which may contain an alkyl group) is preferably an aryl group having 6 to 15 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and a phenyl group or a toluyl group. A naphthyl group is particularly preferred, and a phenyl group is most preferred.

In the formula (3), R ⁴ is preferably an alkenyl group having 2 to 20 carbon atoms, more preferably an alkenyl group having 4 to 12 carbon atoms, as an alkenyl group having 2 to 20 carbon atoms. The aryl group having 6 to 20 carbon atoms (which may contain an alkyl group) is preferably an aryl group having 6 to 15 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and a phenyl group or a toluyl group. A naphthyl group is particularly preferred.
The structures of the formulas (2) and (3) are introduced into the NH group of the polyalkyleneimine chain by a ring-opening addition reaction of an epoxy group.

The (2) or (3) structure of the polyalkyleneimine polymer is preferably 0.001 to 0.9 mol, more preferably 0.002 to 0.7 mol, relative to 1 mol of the nitrogen atom. 0.004 to 0.5 mol is more preferable, 0.005 to 0.4 mol is particularly preferable, and 0.01 to 0.2 mol is most preferable from the viewpoint of water solubility.

The carbon atom contained in (2) or (3) of the polyalkyleneimine polymer is preferably 0.001 to 4 mol, more preferably 0.01 to 3 mol, relative to 1 mol of nitrogen atom, 0.02 to 2 mol is more preferable, 0.03 to 2 mol is particularly preferable, and 0.04 to 1 mol is most preferable from the viewpoint of water solubility.

The modified alkyleneimine polymer of the present invention is specifically represented by the following general formula X.

In the general formula (X), ^{R 1} and, ^{R 2} is Formula (1-1), and, ^{R 1} in the general formula (1-2), and is identical to ^{R 2.}
Y is a structure derived from the formulas (2) and (3), and is at least one selected from —CH ₂ —O—R ³ or —R ⁴ . R ³ and, ^{R 4,} said (2), and, ^{R 3} of the above (3), and is identical to ^{R 4.}
l is 4.9-79.9 mol%, m is 20-95 mol%, and n is 0.1-90 mol%.

The formulas (2) and (3) may be of one type or two or more types, but preferably one type. In addition, when selecting 2 or more types of alkyl groups etc., the ratio of each alkyl group in 2 or more types of alkyl groups is not specifically limited. As a preferable combination when selecting two or more alkyl groups, a combination selected from a decyl group, an undecyl group, a dodecyl group, a tridecyl group, and a pentadecyl group is preferable from the viewpoint of easiness of synthesis. At this time, the ratio of the two or more alkyl groups is preferably 1 to 99 mol% for each alkyl group, more preferably 2 to 98 mol%, still more preferably 3 to 97 mol%. Is good.

The weight average molecular weight of the modified alkyleneimine polymer of the present invention is preferably 300 to 1,000,000, more preferably 500 to 500,000, still more preferably 1,000 to 200,000, and particularly preferably. Is preferably 3,000 to 50,000. If the weight average molecular weight is too large, handling may be complicated.On the other hand, if it is too small, the performance as a polymer is difficult to be expressed. For example, it has excellent performance in applications such as cleaning agents and water treatment agents. There is a possibility that it cannot be expressed.

The number average molecular weight of the modified alkyleneimine polymer of the present invention is preferably 200 to 750,000, more preferably 300 to 300,000, still more preferably 700 to 100,000. If the number average molecular weight is too large, handling may be complicated, while if it is too small, the performance as a polymer is difficult to be expressed. For example, it has excellent performance in applications such as cleaning agents and water treatment agents. There is a possibility that it cannot be expressed.

The modified alkyleneimine polymer of the present invention may be further modified. For example, the molecular weight can be increased by bonding polymers with a polyfunctional compound.

[Method for producing modified alkyleneimine polymer]
The method for producing the modified alkyleneimine polymer of the present invention includes a polyalkyleneimine polymer,
An unsaturated carboxylic acid compound represented by the following general formula (1-2);

(In General Formula (1-2), R ¹ is represented by one selected from a hydrogen atom, a methyl group, and a carboxyl group, and R ² represents a hydrogen atom or a methyl group.)
Specific examples of the unsaturated carboxylic acid represented by the general formula (1-2) are acrylic acid, methacrylic acid, maleic acid, crotonic acid, and isocrotonic acid.
Among these, acrylic acid and maleic acid are preferable because they have a high carboxylic acid modification rate and an excellent ability to disperse dirt.

A modified alkyleneimine polymer is obtained by reacting with at least one compound selected from the group consisting of the following (a) and (b).
(A) Glycidyl ether having an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms (which may have an alkyl group) glycidyl ether, etc. Glycidyl ether compound (b) epoxy-containing compound not containing an ether bond such as an epoxy alkene having 2 to 20 carbon atoms or an aryl group-containing epoxy alkane having 6 to 20 carbon atoms

The glycidyl ether having an alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 2 to 18 carbon atoms, more preferably an alkyl group having 3 to 15 carbon atoms, and still more preferably an alkyl group having 4 to 10 carbon atoms. A butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, and an octyl group are particularly preferable, and a butyl group and a 2-ethylhexyl group are most preferable.
The glycidyl ether having an alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 3 to 15 carbon atoms, more preferably an alkenyl group having 4 to 12 carbon atoms, and particularly preferably an alkenyl group having 4 to 10 carbon atoms. . The aryl having 6 to 20 carbon atoms (which may have an alkyl group) glycidyl ether is preferably an aryl group having 6 to 15 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, a phenyl group, A toluyl group and a naphthyl group are particularly preferable, and a glycidyl ether having a phenyl group is most preferable.

Moreover, as a C2-C20 epoxy alkene, a C3-C15 epoxy alkene is preferable and a C4-C12 epoxy alkene is more preferable.
The aryl group-containing epoxy alkane having 6 to 20 carbon atoms is preferably an aryl group-containing epoxy alkane having 6 to 15 carbon atoms, more preferably an aryl group-containing epoxy alkane having 6 to 12 carbon atoms, a phenyl group, a toluyl group, An aryl group-containing epoxy alkane having a naphthyl group is more preferred, and styrene oxide is particularly preferred.

The unsaturated carboxylic acid compound represented by the general formula (1-2) is introduced into the NH group of the polyalkyleneimine chain by a Michael addition reaction.
On the other hand, the epoxy compounds (a) and (b) are introduced into the NH group of the polyalkyleneimine chain by a ring-opening addition reaction of an epoxy group.

In the method for producing a modified alkyleneimine polymer of the present invention, the polyalkyleneimine polymer before modification preferably has a weight average molecular weight of 300 to 500,000, more preferably 400 to 200,000. 000, more preferably 600 to 100,000, and particularly preferably 1,000 to 50,000. If the weight average molecular weight of the polyalkyleneimine polymer is too large, the addition amount of the glycidyl ether compound and the epoxy-containing compound that does not contain an ether bond in the resulting modified alkyleneimine polymer tends to decrease, whereas it is too small. In addition, there is a risk that the re-contamination preventing ability, the cleaning effect, and the like that can be exhibited by the resulting modified alkyleneimine polymer are insufficient.

In the method for producing a modified alkyleneimine polymer of the present invention, the number average molecular weight of the polyalkyleneimine polymer before modification is preferably 200 to 400,000, more preferably 300 to 150, 000, more preferably 400 to 80,000. If the number average molecular weight of the polyalkyleneimine polymer is too large, the addition amount of the glycidyl ether compound and the epoxy-containing compound not containing an ether bond in the resulting modified alkyleneimine polymer tends to decrease, whereas it is too small. In addition, there is a risk that the re-contamination preventing ability, the cleaning effect, and the like that can be exhibited by the resulting modified alkyleneimine polymer are insufficient.

In the ring-opening addition reaction when the glycidyl ether compound or an epoxy-containing compound not containing an ether bond is added to the polyalkyleneimine, the polyalkyleneimine and the glycidyl ether compound or an epoxy-containing compound not containing an ether bond to be used The ratio of the polyalkyleneimine polymer to be used may be appropriately set so that the amount introduced into the nitrogen atom of the polyalkyleneimine polymer obtained is within the range described above in the section of [Polyalkyleneimine polymer]. The use ratio of the glycidyl ether compound and the epoxy-containing compound not containing an ether bond is preferably 0.1 to 2.0 parts by weight, and 0.05 to 1.0 part by weight with respect to 1 part by weight of the polymer. More preferably, 0.03 to 0.6 parts by weight is more preferable, and 0.02 to 0.4 parts by weight is particularly preferable. Preferably, most preferably 0.01 to 0.2 parts by weight.

The addition method for adding the glycidyl ether compound or the epoxy-containing compound not containing an ether bond to the polyalkyleneimine polymer is not particularly limited, but a solventless reaction is preferable. Any of the above may be used, but it is preferable to carry out the stirring.

When adding a solvent during the solution reaction, an aqueous solvent is preferable, and water is more preferable. In addition, a solvent other than the aqueous solvent may be appropriately added within a range of 10% by weight or less. Specifically, as the aqueous solvent, one or more kinds are appropriately selected from lower alcohols such as methanol, ethanol and isopropyl alcohol; amides such as dimethylformamide; ethers such as diethyl ether and dioxane; Can be used.

The raw material concentration at the time of performing the solution reaction is not particularly limited, but from the viewpoint of shortening the reaction time, the total amount of the polyalkyleneimine and the glycidyl ether compound or the epoxy-containing compound not containing an ether bond is It is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, and even more preferably 30 to 70% by weight.

When the glycidyl ether compound or an epoxy-containing compound not containing an ether bond is added to the polyalkyleneimine polymer, all of the polyalkyleneimine polymer and the unsaturated carboxylic acid may be charged all at once. However, either one of them may be initially charged and the rest may be dropped, or all may be dropped, but the glycidyl ether compound or an epoxy-containing compound containing no ether bond is added to the polyalkyleneimine polymer. It is more preferable to dripping. When adding the glycidyl ether compound or an epoxy-containing compound not containing an ether bond to the polyalkyleneimine polymer, a catalyst is basically unnecessary, but it does not adversely affect the reaction if necessary. If present, it may be used as appropriate, and a tertiary amine is preferred.

When the glycidyl ether compound or an epoxy-containing compound not containing an ether bond is added to the polyalkyleneimine polymer, a polymerization inhibitor may be used. In particular, when a highly polymerizable glycidyl ether compound or an epoxy-containing compound that does not contain an ether bond is used, a polymerization inhibitor is preferably used.

Although the reaction temperature at the time of adding the said glycidyl ether compound and the epoxy-containing compound which does not contain an ether bond to the said polyalkyleneimine type polymer is not restrict | limited, It is preferable to set it as 20-120 degreeC. In particular, in order to suppress side reactions, a slightly lower temperature is preferable, for example, preferably 30 to 110 ° C, more preferably 40 to 100 ° C, and further preferably 50 to 90 ° C. preferable.

The reaction time for adding the glycidyl ether compound or the epoxy-containing compound not containing an ether bond to the polyalkyleneimine polymer is not particularly limited, but is preferably 10 minutes to 50 hours, preferably 15 minutes to 40 More preferably, the time is set, and more preferably 30 minutes to 30 hours.

When adding the glycidyl ether compound or the epoxy-containing compound not containing an ether bond to the polyalkyleneimine polymer, it is preferable to perform the reaction in a nitrogen atmosphere in order to suppress coloring of the resulting derivative. What is necessary is just to set the atmosphere in this case suitably according to the intended purpose of the derivative | guide_body obtained. The reaction may be performed at normal pressure (atmospheric pressure), pressurization, or reduced pressure.

In addition, after adding the glycidyl ether compound or an epoxy-containing compound not containing an ether bond to the polyalkyleneimine polymer, the resulting modified alkyleneimine polymer may be further modified, for example, unsaturated Carboxylic acid can be reacted to impart hydrophilicity, or the molecular weight can be increased by combining polymers with a polyfunctional compound.

[Cleaning agent, cleaning agent builder]
The cleaning agent and cleaning agent builder of the present invention are characterized by containing the modified alkyleneimine polymer as an essential component.
As a result, dirt can be efficiently dispersed and the dirt can be prevented from re-adhering to the object to be cleaned, and excellent performance as a cleaning agent can be exhibited.

The content of the modified alkyleneimine polymer in the cleaning agent of the present invention is preferably 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, More preferably, it is ˜5% by weight. If the content of the modified alkyleneimine polymer is too large, the cleaning agent may be colored. On the other hand, if the content is too small, sufficient cleaning ability may not be exhibited.

The cleaning agent in the present invention may be in any form such as powder, liquid or gel. Hereinafter, as a representative example, a powdery powder cleaning agent and a liquid liquid cleaning agent will be described in detail.

When the cleaning agent of the present invention is a powder cleaning agent, the weight average molecular weight of the modified alkyleneimine polymer is preferably 300 to 1,000,000, more preferably 500 to 500,000, still more preferably. Is preferably from 1,000 to 200,000, particularly preferably from 10,000 to 50,000. On the other hand, when the cleaning agent of the present invention is a liquid cleaning agent, the weight average molecular weight of the modified alkyleneimine polymer is preferably 300 to 500,000, more preferably 1,000 to 100,000, More preferably, it is 2,000-50,000.

The cleaning agent of the present invention preferably contains one or more selected from the group consisting of polycarboxylic acid (salt), citrate, zeolite, and layered silicate (hereinafter referred to as “component A”). In particular, when the cleaning agent of the present invention is a powder cleaning agent, the component A is indispensable in order to exhibit an excellent cleaning effect and anti-recontamination ability. On the other hand, when the cleaning agent of the present invention is a liquid cleaning agent, the component A does not necessarily need to be contained, but in this case as well, the cleaning effect and prevention of recontamination can be achieved by containing the component A. Performance can be further improved. In the case where the cleaning agent of the present invention is a liquid cleaning agent and it is desired to make a transparent liquid cleaning agent, among the component A, it is composed of polycarboxylic acid (salt), citrate, and layered silicate. It is preferable to select one or more selected from the group.

Examples of the polycarboxylic acid (salt) include polyacrylic acid, acrylic acid-maleic acid copolymer, polyglyoxylic acid, aminocarboxylic acid polymer (for example, polyaspartic acid), and salts thereof. It is done. Examples of the salt include sodium salt, potassium salt, ammonium salt and the like. The weight average molecular weight of these polycarboxylic acids (salts) is preferably 500 to 200,000, more preferably 1,000 to 100,000, and 2,000 to 50,000. Is more preferable.

Examples of the citrate include sodium citrate.

Examples of the zeolite include hydrated zeolite A, X, B, HS, and the like.

Examples of the layered silicate include layered sodium silicate.

When the cleaning agent of the present invention is a powder cleaning agent, the total content of the component A in the cleaning agent is preferably 0.1 to 50% by weight, and preferably 0.5 to 40% by weight. More preferably, it is 1 to 30% by weight. If the total content of component A is too large, the surface activity tends to decrease, while if it is too small, there is a possibility that sufficient cleaning effect and recontamination preventing ability cannot be expressed. In addition, when the cleaning agent of the present invention is a powder cleaning agent, the content of each component A may be appropriately set depending on the type thereof. For example, in the case of polycarboxylic acid (salt) or citrate Is preferably 0 to 30% by weight, and in the case of zeolite or layered silicate, it is preferably 0 to 50% by weight.

When the cleaning agent of the present invention is a liquid cleaning agent, the total content of the component A in the cleaning agent is preferably 0 to 50% by weight, more preferably 0 to 40% by weight. Preferably, it is 0 to 30% by weight. If the total content of component A is too large, the surface activity tends to decrease, while if it is too small, there is a possibility that sufficient cleaning effect and recontamination preventing ability cannot be expressed. In addition, when the cleaning agent of the present invention is a liquid cleaning agent, the content of each of the components A may be appropriately set depending on the type thereof. For example, polycarboxylic acid (salt), citrate, layered In the case of silicate, it is preferably 0 to 30% by weight, and in the case of zeolite, it is preferably 0 to 20% by weight.

The cleaning agent of the present invention may further contain a surfactant that is usually blended in the cleaning agent. Specific examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like, and one or more of these are used. can do.

Specific examples of the anionic surfactant include, for example, alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonate. Examples thereof include salts, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof.

Examples of the nonionic surfactant include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycoxide, fatty acid glycerin monoester. And alkylamine oxide.

Examples of the cationic surfactant include quaternary ammonium salts.

Examples of the amphoteric surfactant include a carboxyl type or sulfobetaine type amphoteric surfactant.

When the cleaning agent of the present invention is a powder cleaning agent, the content of the surfactant in the cleaning agent is not particularly limited, but is usually preferably 5 to 70% by weight, and preferably 10 to 60% by weight. More preferably, it is more preferably 15 to 50% by weight. If the amount of the surfactant is too large, the economy tends to be lowered. On the other hand, if the amount is too small, there is a possibility that sufficient cleaning agent performance cannot be exhibited.

When the cleaning agent of the present invention is a liquid cleaning agent, the content of the surfactant in the cleaning agent is preferably 5 to 70% by weight, more preferably 10 to 65% by weight, More preferably, it is 15-60 weight%. If the amount of the surfactant is too large, the compatibility tends to be lowered and the economical efficiency is also lowered, which is not preferable. On the other hand, if the amount is too small, there is a possibility that sufficient detergent performance cannot be exhibited.

The cleaning agent of the present invention may further contain a conventionally known cleaning agent builder. The builder for the detergent is not particularly limited. For example, polyethylene glycol, sodium tripolyphosphate, sodium pyrophosphate, sodium silicate, sodium carbonate, sodium sulfate, sodium nitrilotriacetate, sodium ethylenediaminetetraacetate or potassium, carboxyl of polysaccharide And water-soluble polymers such as derivatives and fumaric acid (co) polymer salts. In addition, when these detergent builder is also contained, the content rate should just be set suitably in the range which does not impair the effect of this invention.

The cleaning agent of the present invention may further contain various additives commonly used in cleaning agents. Specifically, for example, sodium carboxymethylcellulose to prevent re-deposition of pollutants, contamination inhibitors such as benzotriazole and ethylene-thiourea, alkali agents (alkaline substances for pH adjustment), fragrances, fluorescent agents , Colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents such as sodium percarbonate and sodium perborate, bleach activators such as nonanoyloxybenzenesulfonate and tetraacetylethylenediamine, enzymes, Examples thereof include solvents such as dyes and water. In addition, what is necessary is just to set the content rate suitably in the range which does not impair the effect of this invention, when these additives are also contained.

In the case where the cleaning agent of the present invention is a liquid cleaning agent, it is particularly preferable that an alkaline agent is included among the additives in order to improve the cleaning power and the ability to prevent recontamination. The alkali agent is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, alkanolamines such as monoethanolamine and diethanolamine, silicates and carbonates. In this case, the content of the alkaline agent in the cleaning agent is preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, and further preferably 1 to 10% by weight. If the alkali agent is less than 0.1% by weight, there is a tendency that sufficient cleaning effect and re-contamination preventing ability tend to be exhibited. On the other hand, if it exceeds 20% by weight, rough skin occurs when it adheres to the skin. It is not preferable because of fear.

The cleaning agent of the present invention may be used as a cleaning agent by further blending other components necessary as an intermediate of the cleaning agent, that is, the cleaning agent, or the cleaning agent itself, that is, as it is. It may be used as a cleaning agent. Further, the cleaning agent of the present invention is for clothing, tableware, residential, automobile, body, pet, outer wall, electronic component, medical, textile industry, glasses, food, plant, It can be used as various cleaning agents for dentures, toothpastes, and the like, and also includes cleaning agents used only for specific applications such as bleaching cleaning agents that enhance the function of one of its components.

(Water treatment agent)
The water treatment agent of the present invention contains the modified alkyleneimine polymer as an essential component.
This makes it possible to suppress the formation of scales such as calcium carbonate, calcium phosphate, zinc phosphate and silica, and to efficiently disperse particles such as scale-generating substances, and to exhibit excellent scale prevention ability as a water treatment agent. It becomes. It can also be used as an anticorrosive.
The water treatment agent of the present invention is used in a desalination process such as cooling water, boiler water, geothermal power generation, brine such as seawater.

The content of the modified alkyleneimine polymer in the water treatment agent of the present invention is preferably 1 to 100% by weight, more preferably 5 to 95% by weight, and 10 to 90% by weight. More preferably it is. If the content of the modified alkyleneimine polymer is less than 1% by weight, sufficient performance cannot be exhibited.

The water treatment agent of the present invention preferably adds 0.01 to 1,000 ppm to cooling water or the like, more preferably 0.02 to 800 ppm, more preferably 0.03 to 500 ppm, and 0.05 to 300 ppm. Particularly preferred is 0.1 to 100 ppm.

The weight average molecular weight of the modified alkyleneimine polymer in the water treatment agent of the present invention is preferably 500 to 500,000, more preferably 1,000 to 300,000, still more preferably 2,000 to 100. 000.

The water treatment agent of the present invention may contain a polymer other than the modified alkyleneimine polymer as necessary, as long as the effects of the present invention are not impaired. The polymer other than the modified alkyleneimine polymer is not particularly limited, and examples thereof include acrylic acid polymers and sulfonic acid polymers.
As other composition components and blending ratios other than the modified alkyleneimine polymer in the water treatment agent, various components such as bactericides and oxygen scavengers that can be used in conventionally known water treatment agents, and blending ratios thereof Based on the above, it can be appropriately used within a range not impairing the effects of the present invention.

[Dispersant]
The dispersant of the present invention is characterized by containing the modified alkylene imine polymer as an essential component.
The dispersant may be an aqueous dispersant such as a pigment dispersant, a cement dispersant, a calcium carbonate dispersant, a kaolin dispersant, an iron particle dispersant such as iron oxide, and an alumina silica such as zeolite. Suitable for acid salt dispersant, alumina dispersant, gypsum dispersant and the like.

The dispersant can express extremely excellent dispersibility inherent in the modified alkyleneimine polymer. In addition, it is possible to obtain a very high quality, high performance, and highly stable dispersant that does not cause deterioration in performance or precipitation of impurities when kept at a low temperature even when stored for a long period of time.

The content of the modified alkyleneimine polymer in the dispersant of the present invention is preferably 1 to 100% by weight, more preferably 5 to 95% by weight, and 10 to 90% by weight. More preferably. If the content of the modified alkyleneimine polymer is less than 1% by weight, sufficient performance cannot be exhibited.

The dispersant of the present invention is preferably added in an amount of 0.01 to 10%, more preferably 0.02 to 8%, more preferably 0.03 to 5%, and more preferably 0.05 to 3% with respect to the dispersed particles. % Is particularly preferable, and 0.1 to 1% is most preferable.

The weight average molecular weight of the modified alkyleneimine polymer in the dispersant of the present invention is preferably 500 to 500,000, more preferably 1,000 to 300,000, still more preferably 2,000 to 100,000. 000 should be good.

As other composition components and blending ratios other than the modified alkyleneimine polymer in the dispersant, various components such as bactericides that can be used in conventionally known dispersants, and blending ratios of the present invention are used. It can be used as appropriate as long as the effects are not impaired.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these. Hereinafter, unless otherwise specified, “parts by weight” is simply referred to as “parts”, and “% by weight” is simply referred to as “%”.
Gel permeation chromatography (GPC) analysis of the obtained polyethyleneimine derivative was measured under the following conditions.
Equipment: HLC-8320GPC manufactured by Tosoh Corporation
Detector: RI, UV (214 nm)
Column: “TSK-GEL α” + “TSK-GEL α-M” “TSK-GEL α-2500” manufactured by Tosoh Corporation
Column temperature: 40 ° C
Calibration curve: Created by approximating the relationship between the logarithm (logMp) of the peak top molecular weight (Mp) and the retention time by a cubic equation using “molecular weight standard PolyethyleneGlycol” and “molecular weight standard PolyethyleneOxide” manufactured by GL Sciences Inc. : 100 mM boric acid (pH 9.2) / acetonitrile = 80/20 (wt / wt)
Flow rate: 0.8mL / min

<Clay dispersibility>
Pure water was added to 67.56 g of glycine, 52.6 g of sodium chloride, and 2.4 g of NaOH.
00 g (this is used as a buffer). To 60 g of buffer, 0.082 g of calcium chloride dihydrate was added, and pure water was further added to make 1000 g (this is used as a buffer). After putting 3.0 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 weight aqueous solution (in terms of solid content weight) of the copolymer to be measured, and a buffer 27 g was added and sealed. The test tube was shaken to disperse the clay. Thereafter, the test tube was left in the dark for 16 hours. After 16 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).

<Carbon black (CB) dispersibility>
Pure water was added to 67.56 g of glycine, 52.6 g of sodium chloride, and 2.4 g of NaOH.
00 g (this is used as a buffer). To 60 g of buffer, 0.082 g of calcium chloride dihydrate was added, and pure water was further added to make 1000 g (this is used as a buffer). After putting 0.03 g of carbon black into a test tube (made by IWAKI GLASS: diameter 18 mm, height 180 mm), 3 g of 0.1% by weight aqueous solution (in terms of solid content weight) of the copolymer to be measured and 27 g of buffer. Added and sealed. The test tube was shaken to disperse the carbon black. Thereafter, the test tube was left in the dark for 20 hours. After 20 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).

<Evaluation of ability to prevent re-contamination of clay>
(1) A cotton cloth obtained from Test fabric was cut into 5 cm × 5 cm to prepare a white cloth. The whiteness of the white cloth was measured by reflectance using a colorimetric color difference meter SE6000 manufactured by Nippon Denshoku Industries Co., Ltd. in advance.
(2) Pure water was added to 7.5 g of calcium chloride dihydrate to 17 kg to prepare hard water.
(3) Pure water was added to 4.0 g of polyoxyethylene (8) lauryl ether to make 100.0 g to prepare a surfactant aqueous solution. The pH was adjusted to 8.5 with sodium hydroxide.
(4) A targot meter was set at 25 ° C., 1 L of hard water, 1 g of a surfactant aqueous solution, 1 g of a 5% polymer aqueous solution in terms of solid content, and 1 g of JIS 11 seed clay were placed in a pot and stirred at 100 rpm for 1 minute. Then, 5 white cloths were put and stirred at 100 rpm for 10 minutes.
(5) The white cloth was drained by hand, 1 L of hard water adjusted to 25 ° C. was placed in the pot, and stirred at 100 rpm for 2 minutes.
(6) A white cloth was applied and dried while stretching the wrinkle with an iron. Then, the whiteness of the white cloth was measured again with the colorimetric color difference meter.
(7) From the above measurement results, the ability to prevent recontamination was determined by the following equation.
(8) Recontamination preventing ability (%) = [(whiteness after washing) / (whiteness of raw white cloth)] × 100.

<Evaluation of ability to prevent carbon black (CB) recontamination>
(1) A polyester cloth obtained from Test fabric was cut into 5 cm × 5 cm to prepare a white cloth. The whiteness of the white cloth was measured by reflectance using a colorimetric color difference meter SE6000 manufactured by Nippon Denshoku Industries Co., Ltd. in advance.
(2) Pure water was added to 7.5 g of calcium chloride dihydrate to 17 kg to prepare hard water.
(3) Pure water was added to 4.0 g of polyoxyethylene (8) lauryl ether to make 100.0 g to prepare a surfactant aqueous solution. The pH was adjusted to 8.5 with sodium hydroxide.
(4) A targot meter was set at 25 ° C., 1 L of hard water, 1 g of an aqueous surfactant solution, 1 g of a 5% polymer aqueous solution in terms of solid content, and 0.1 g of carbon black were placed in a pot and stirred at 100 rpm for 1 minute. . Then, 5 white cloths were put and stirred at 100 rpm for 10 minutes.
(5) The white cloth was drained by hand, 1 L of hard water adjusted to 25 ° C. was placed in the pot, and stirred at 100 rpm for 2 minutes.
(6) A white cloth was applied and dried while stretching the wrinkle with an iron. Then, the whiteness of the white cloth was measured again with the colorimetric color difference meter.
(7) From the above measurement results, the ability to prevent recontamination was determined by the following equation.
(8) Recontamination preventing ability (%) = [(whiteness after washing) / (whiteness of raw white cloth)] × 100.

<Example 1>
A glass 500 ml separable flask equipped with a reflux condenser, a thermometer and a stirrer was charged with 54.0 g of polyethyleneimine A (molecular weight 10,000) and dissolved by adding 81.6 g of pure water to obtain a polyethyleneimine aqueous solution. . This polyethyleneimine aqueous solution was heated to 80 ° C., and 51.3 g of an 80% acrylic acid aqueous solution was added dropwise over 30 minutes with stirring. After completion of the dropwise addition, the reaction was further continued for 8 hours to obtain polyethyleneimine derivative 1.
46.8 g of polyethyleneimine derivative 1 was charged into a glass 100 ml separable flask equipped with a reflux condenser, a thermometer, and a stirrer, and the temperature was raised to 80 ° C. 1.8 g of butyl glycidyl ether was added and reacted for 4 hours with stirring to obtain a polymer (1).

<Example 2>
46.8 g of polyethyleneimine derivative 1 was charged into a glass 100 ml separable flask equipped with a reflux condenser, a thermometer, and a stirrer, and the temperature was raised to 80 ° C. 7.2 g of butyl glycidyl ether was added and reacted for 6 hours with stirring to obtain a polymer (2).

<Example 3>
46.8 g of polyethyleneimine derivative 1 was charged into a glass 100 ml separable flask equipped with a reflux condenser, a thermometer, and a stirrer, and the temperature was raised to 80 ° C. 0.24 g of Denacol EX-121 (2-ethylhexyl glycidyl ether; manufactured by Nagase ChemteX Corporation) was added and reacted for 8 hours with stirring to obtain a polymer (3).

<Example 4>
Polyethyleneimine derivative 1 was charged into a glass 100 ml separable flask equipped with a reflux condenser, a thermometer, and a stirrer, and the temperature was raised. Denacol EX-121 (2-ethylhexyl glycidyl ether; manufactured by Nagase ChemteX Corporation) was added and reacted for several hours with stirring to obtain a polymer (4).

<Example 5>
Polyethyleneimine derivative 1 was charged into a glass 100 ml separable flask equipped with a reflux condenser, a thermometer, and a stirrer, and the temperature was raised. Denacol EX-192 (C11-C15 alkyl glycidyl ether; manufactured by Nagase ChemteX Corporation) was added and reacted for several hours with stirring to obtain a polymer (5).
When various evaluations were performed, satisfactory results were obtained.

<Example 6>
A glass 500 ml separable flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 54.0 g of polyethyleneimine A (molecular weight 10,000) and dissolved by adding 97.3 g of pure water to obtain a polyethyleneimine aqueous solution. . The polyethyleneimine aqueous solution was heated to 80 ° C., and 101.7 g of an 80% aqueous acrylic acid solution was added dropwise over 30 minutes with stirring. After the completion of dropping, 37.7 g of 48% aqueous sodium hydroxide solution was added dropwise over 10 minutes with stirring, and the reaction was further continued for 8 hours to obtain polyethyleneimine derivative 2.
48.3 g of polyethyleneimine derivative 2 was charged into a glass-made 100 ml separable flask equipped with a reflux condenser, a thermometer, and a stirrer, and the temperature was raised to 80 ° C. 0.7 g of butyl glycidyl ether was added and reacted for 8 hours with stirring to obtain a polymer (6).

<Example 7>
Polyethyleneimine B (molecular weight 70,000) was charged into a glass 500 ml separable flask equipped with a reflux condenser, a thermometer, and a stirrer, and pure water was added and dissolved to obtain a polyethyleneimine aqueous solution. The polyethyleneimine aqueous solution was heated, and an 80% aqueous acrylic acid solution was added dropwise over 30 minutes with stirring. After completion of the dropwise addition, the reaction was continued for several hours to obtain polyethyleneimine derivative 3.
Polyethyleneimine derivative 3 was charged into a glass 100 ml separable flask equipped with a reflux condenser, a thermometer, and a stirrer, and the temperature was raised. Butyl glycidyl ether was added and reacted with stirring for several hours to obtain a polymer (7).
When various evaluations were performed, satisfactory results were obtained.

<Example 8>
Polyethyleneimine C (molecular weight 1,800) was charged into a glass-made 500 ml separable flask equipped with a reflux condenser, a thermometer, and a stirrer, and pure water was added and dissolved to obtain a polyethyleneimine aqueous solution. The polyethyleneimine aqueous solution was heated, and an 80% aqueous acrylic acid solution was added dropwise over 30 minutes with stirring. After completion of the dropping, a 48% aqueous sodium hydroxide solution was added dropwise over 10 minutes with stirring, and the reaction was continued for several hours to obtain polyethyleneimine derivative 4.
The polyethyleneimine derivative 4 was charged into a glass 100 ml separable flask equipped with a reflux condenser, a thermometer, and a stirrer, and the temperature was raised. Butyl glycidyl ether was added and reacted for several hours with stirring to obtain a polymer (8).
When various evaluations were performed, satisfactory results were obtained.

<Comparative Example 1>
Various evaluations were performed using polyethyleneimine A as the comparative polymer 1.

<Comparative example 2>
Various evaluations were performed using the polyethyleneimine derivative 1 as a comparative polymer 2.

<Comparative Example 3>
A glass 500 ml separable flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 54.0 g of polyethyleneimine A (molecular weight 10,000) and dissolved by adding 88.4 g of pure water to obtain a polyethyleneimine aqueous solution. . The polyethyleneimine aqueous solution was heated to 80 ° C. 7.4 g of butyl glycidyl ether was added and reacted for 8 hours with stirring to obtain a comparative polymer (3).

From the results shown in Table 1, the modified alkyleneimine polymers of the polymers (1) to (3) are more excellent in clay dispersibility and carbon than the comparative polymers (1) to (3) in which the terminal structure is not changed. Black dispersibility was improved at the same time.

From the results in Table 2, the modified alkyleneimine polymers of the polymers (1), (3) and (6) are more clay-based than the comparative polymers (1) to (3) in which the terminal structure is not changed. Dispersibility and carbon black dispersibility were simultaneously improved.

The polymers described in JP 2003-286344 A, JP 2005-248144 A, and JP 2005-104999 A correspond to the comparative polymer (1), and JP 2005-170977 A. The polymer described in the publication corresponds to the comparative polymer (3).

Claims (3)

A modified alkyleneimine polymer having an alkyleneimine structural unit,
In the nitrogen atom of the modified polyalkyleneimine polymer,
It has a structure of carboxylalkyl represented by the following general formula (1-1), and
A modified alkyleneimine polymer having the following structure (2) or (3):
(In the general formula (1-1), R ¹ is represented by one selected from a hydrogen atom, a methyl group, and a carboxyl group, and R ² represents a hydrogen atom or a methyl group.)
(2) —CH ₂ CH (OH) CH ₂ —O—R ³
(3) —CH ₂ CH (OH) —R ⁴
(In the formula, R ^3, .R ⁴ is -C 4-20 represents an alkyl group, an alkenyl group having a carbon number of 4-20, an aryl group having 6 to 20 carbon atoms carbon atoms 4-20 And an aryl group having 6 to 20 carbon atoms.) A polyalkyleneimine polymer;
An unsaturated carboxylic acid compound represented by the following general formula (1-2);
At least one compound selected from the group consisting of the following (a) and (b):
A method for producing a modified alkyleneimine polymer characterized by reacting ,
The unsaturated carboxylic acid compound represented by the general formula (1-2) is introduced into the NH group of the polyalkyleneimine chain of the polyalkyleneimine polymer by a Michael addition reaction,
A method for producing a modified alkyleneimine polymer, wherein the compounds (a) and (b) are introduced into the NH group of the polyalkyleneimine chain of the polyalkyleneimine polymer by a ring-opening addition reaction of an epoxy group .
(In the general formula (1-2), R ¹ is represented by one selected from a hydrogen atom, a methyl group, and a carboxyl group, and R ² represents a hydrogen atom or a methyl group.)
(A) glycidyl ethers having an alkyl or alkenyl group having a carbon number of 4-20 carbon atoms 4-20, or aryl glycidyl ethers having 6 to 20 carbon atoms (b) carbon atoms 4-20 epoxy alkenes Or an aryl group-containing epoxy alkane having 6 to 20 carbon atoms A water treatment agent, a fiber treatment agent, an inorganic pigment dispersant, a detergent builder, or a detergent composition comprising the modified alkyleneimine polymer according to claim 1.