JP5660905B2 - Polyalkyleneamine alkylene oxide copolymer - Google Patents

Description

The present invention relates to a polyalkyleneamine alkylene oxide copolymer. More specifically, it is suitable for detergent builders, detergents, water treatment agents, dispersants, and the like. For example, when it is added to a liquid detergent composition as a detergent builder, it exhibits good detergency and good thickening effect. TECHNICAL FIELD The present invention relates to an alkylene amine alkylene oxide copolymer, 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 a property of being dissolved in a liquid detergent, it is indispensable as a component constituting the liquid detergent. When the modified polyethyleneimine ethoxylate is contained in the detergent together with the active agent, recontamination due to dirt removed by washing is prevented, and high detergency is exhibited.

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

Also disclosed is a liquid laundry detergent composition containing a water-soluble and / or dispersible modified polyamine having a functional main chain portion that exerts a cotton soil release effect (see, for example, Patent Document 2). This modified polyamine is represented by — (R ¹ O) _m B (R ¹ is C ₂ -C ₆ alkylene and mixtures thereof, preferably ethylene. M has a value of 4 to about 400). It has an alkylene oxide adduct, and the terminal structure of the alkylene oxide adduct represented by B is hydrogen, C _{1 to} 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 The polymer is M (M is hydrogen or a sufficient amount of a 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 polyalkyleneimine is-(R ¹ O) _m (R ² O) _n R 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 about 1 About 10 and n is about 10 to about 40). The terminal structure of the alkylene oxide adduct is hydrogen, C ₁ -C ₄ alkyl and their It is a polymer to be a mixture.

Patent Document 4 discloses a polyalkyleneimine alkylene oxide copolymer having an alkyleneimine monomer unit having a polyalkylene oxide, and the terminal structure of the polyalkylene oxide has the following (1) to (4): A polyalkyleneimine alkylene oxide copolymer having at least one selected from the group consisting of:
⁽¹⁾ -CO-R 2 -COOX
(2) —CH ₂ CH (OH) —R ³
(3) —CH ₂ CH (OH) CH ₂ —O—R ⁴
(4) -C (O) -NH-R ⁵
(In the formula, R ² represents an alkylene group having 2 to 8 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, an arylene group having 6 to 14 carbon atoms, or a sulfoalkylene group having 2 to 8 carbon atoms. R ³ represents an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a sulfoalkyl group having 2 to 6 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms. ⁴ represents a hydrogen atom, an alkyl group having 2 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a sulfoalkyl group having 2 to 6 carbon atoms. ⁵ represents an alkyl group having 2 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a sulfoalkyl group having 2 to 6 carbon atoms, X being hydrogen Atom, alkali metal atom, alkaline earth Represents a similar metal atom, an ammonium group or an organic ammonium group.)
Patent Document 4 discloses that the copolymer is suitable for uses such as detergent builders, detergents, water treatment agents, and dispersants, and can exhibit high basic performance in terms of detergency and the like. Yes.

  Patent Document 5 discloses a modified polyamine obtained by reacting a polyamine and / or a polyamine derivative with a monoepoxy compound represented by the following general formula.

(In the formula, R is a hydrocarbon group having 28 or less carbon atoms, and n is 0 or an integer of 1 to 30.)
Patent Document 5 discloses that the polyamine has a high surface activity, and can therefore be used as an emulsifier for emulsion polymerization of a wide range of oils, resinous materials, or polymerizable monomers.

Patent Document 6 discloses a polyalkyleneimine alkylene oxide copolymer having an alkyleneimine monomer unit having a polyalkylene oxide, in which part or all of the hydrogen atoms at the terminal hydroxyl groups of the polyalkylene oxide are A terminal-modified polyalkyleneimine alkylene oxide copolymer characterized by being substituted with two or more groups selected from the group consisting of (1) to (8) is disclosed.
(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.)
Patent Document 6 discloses that the copolymer is suitable for uses such as detergent builders, detergents, water treatment agents, dispersants, and can exhibit high basic performance in terms of detergency and the like. Yes.

  By the way, for example, liquid chemicals such as liquid detergents are required to have a certain degree of viscosity in order to prevent dripping. On the other hand, since it is necessary to secure the separation stability of the liquid drug, the liquid drug compounding raw material requires high compatibility with the liquid drug (particularly compatibility with the surfactant). The sticky agent is limited. Further, for example, in the case of a detergent composition, the addition of additives that do not contribute to washing should be minimized in order to avoid a reduction in detergency. For example, it is preferable that a detergent builder or the like has a thickening effect. However, in the above prior art, for example, when used in a detergent application, the structure of the polymer having an alkylene oxide adduct is devised in order to increase the viscosity of the liquid detergent and improve the handleability of the detergent composition. There was room for.

Japanese Patent Publication No.7-116473 Japanese National Patent Publication No. 11-508318 Special table 2002-518585 gazette JP 2005-350640 A JP-A-61-64324 JP 2006-241372 A

Thus, although various copolymers have been reported in the past, there is a demand for the development of a polymer that has the above-described thickening effect of the liquid drug in addition to the detergency.
Then, an object of this invention is to provide the polymer which expresses the thickening effect of a pharmaceutical composition when used for aqueous | water-based uses, such as detergent, and its manufacturing method.

  The present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that a polyalkyleneamine alkylene oxide copolymer having a specific structure has an excellent thickening effect, and completed the present invention.

That is, the present invention is a polyalkyleneamine alkylene oxide copolymer comprising an alkyleneamine structural unit having a polyalkyleneoxide chain, wherein the polyalkyleneamine alkyleneoxide copolymer has a terminal group of the polyalkyleneoxide chain. A polyalkyleneamine alkylene oxide copolymer, characterized in that a part or all thereof is a group represented by the following (1a) and / or (1b).
(1a) —CH ₂ CH (OH) CH ₂ —O—R ₁
(1b) —CH (CH ₂ OH) CH ₂ —O—R ₁
(In the formula, R ₁ represents an alkyl group having 9 to 30 carbon atoms, an alkenyl group having 9 to 30 carbon atoms, or an aryl group having 9 to 30 carbon atoms.)
In another aspect of the present invention, a method for producing a polyalkyleneamine alkylene oxide copolymer is provided. That is, the production method of the present invention includes a step of reacting a polyalkyleneamine alkylene oxide copolymer containing an alkyleneamine structural unit having a polyalkyleneoxide chain with a glycidyl ether compound represented by the following general formula (2). It is a manufacturing method of a polyalkyleneamine alkylene oxide copolymer.

  If the polymer of this invention is used as a detergent builder, the polymer of this invention can provide the detergent composition excellent in the handleability resulting from having a high thickening effect. Moreover, since it has favorable compatibility with surfactant, it can mix | blend preferably with liquid chemicals, such as a liquid detergent.

  Hereinafter, the present invention will be described in detail.

[Polyalkyleneamine alkylene oxide copolymer]
The polyalkyleneamine alkylene oxide copolymer of the present invention is a copolymer containing an alkyleneamine structural unit having a polyalkyleneoxide chain. Such a copolymer has a structure in which an alkylene oxide is added to a nitrogen atom of a polyalkyleneamine polymer composed of an alkyleneamine structural unit or the like.

  The number of moles of alkylene oxide added relative to the polyalkyleneamine is preferably such that the average number of moles added per mole of nitrogen atoms of the polyalkyleneamine polymer is 2 or more and 200 or less (the average number of moles added is This is because the number of moles added usually has a distribution, and since polyalkyleneamines usually contain primary, secondary and tertiary amines, the number of moles to which alkylene oxide is added differs.) More preferably, the average added mole number is 3 or more and 100 or less, further preferably 4 or more and 80 or less, and particularly preferably 5 or more and 70 or less. Some alkylene amine structural units may not have a structure to which a polyalkylene oxide chain is added. However, in order to improve the storage stability of the liquid drug, it is preferable that the amine active hydrogen is substituted with a polyalkylene oxide chain as much as possible. The average added mole number is an average value of the number of moles of oxyalkylene groups added per mole of nitrogen atoms of the polyalkyleneamine polymer.

  In the present invention, the polyalkylene oxide chain is a group containing a structure in which only one oxyalkylene structural unit is present or two or more are continuously formed.

In the present invention, the polyalkyleneamine alkylene oxide copolymer essentially contains the structural unit represented by the above (1a) and / or (1b) in the terminal structure of the polyalkylene oxide chain of the alkyleneamine structural unit. It becomes. That is, part or all of the structure located at the terminal of the group constituted by adding an alkylene oxide to the nitrogen atom contained in the alkyleneamine structural unit is a structure represented by the following (1a) and / or (1b). Become.
In the present invention, for example, when the terminal group of the polyalkylene oxide chain is a group represented by the following (1a), for example, the polyalkylene oxide chain is represented by the following general formula (2).

(In the formula, R ₁ represents an alkyl group having 9 to 30 carbon atoms, an alkenyl group having 9 to 30 carbon atoms, or an aryl group having 9 to 30 carbon atoms, and R ₂ represents an alkylene having 2 to 6 carbon atoms. Represents a group, and n represents a number from 1 to 200.)
As R ₁ in the above (1a), (1b) and the above general formula (2), examples of the alkyl group having 9 to 30 carbon atoms include nonyl group, decanyl group, dodecanyl group, isacosanyl group, etc. The thing of 12-12 is suitable, and as a C9-C30 alkenyl group, a dodecenyl group, an octadecenyl group, etc. are illustrated, A C12-C18 thing is suitable, C9-C9 Examples of the 30 aryl group include a naphthyl group and a nonylphenyl group, and those having 12 to 18 carbon atoms are preferable. When the number of carbon atoms of R ₁ is in the above range, the thickening effect of the liquid drug is improved by hydrophobic interaction with the surfactant and other copolymer molecules. Moreover, since it exists in the tendency for compatibility with surfactant to become favorable if it is the said range, it can mix | blend preferably with a liquid chemical | medical agent.

In the polyalkyleneamine alkylene oxide copolymer of the present invention, the terminal structure represented by the above (1a) and (1b) is 5 mol% or more, 100 mol%, with respect to 100 mol% of all polyalkylene oxide chain terminal structures. It is preferable that it is below mol%. The lower limit tends to improve the detergency and thickening effect, and is more preferably 7 mol% or more, still more preferably 10 mol% or more, particularly preferably 20 mol% or more, and most preferably 30 mol% or more. The upper limit is most preferably 100 mol% in terms of the thickening effect, more preferably 97 mol% or less, still more preferably 94 mol% or less, and particularly preferably 90 mol% in terms of the detergency improving effect. The mol% or less, and most preferably 85 mol% or less. The mol% of the terminal structure can be measured by ¹ H-NMR or the yield after purification of the copolymer.
The preferred form of the polyalkyleneamine alkylene oxide copolymer of the present invention can be represented conceptually by the following general formula (3).

In General Formula (3), R ₃ O is the same or different and represents an oxyalkylene group having 2 to 6 carbon atoms (oxyalkylene structure). AI represents an alkyleneamine structural unit, (AI) _X represents a polyamine main chain, and the alkyleneamine structural unit is a linear, cyclic, branched or combined structure thereof. is there. The general formula (3) conceptually represents that some or all of the alkylene amine structural units have a polyalkylene oxide chain represented by Q ₁ — (R ₃ O) _y —. Q ₁ , which is the terminal structure of the polyalkylene oxide unit, is the same or different and is a hydrogen atom or any one of the terminal structures of (1a) and (1b) above, and at least one of them is the above (1a), ( It is one of the terminal structures of 1b). y is the number of repeating oxyalkylene structures, z is the number of polyalkylene oxide chains of one molecule of the polyalkyleneamine alkylene oxide copolymer, and x, y, and z are the same or different, and one or more Represents a number.

In the above general formula (3), R ₃ O may be one type or two or more types, and oxyethylene because the detergency of the copolymer of the present invention tends to be improved. Group and oxypropylene group are preferred. More preferably, it is an oxyethylene group.

  The polyalkyleneamine alkylene oxide copolymer of the present invention (such as a copolymer represented by the above general formula (3)) is a nitrogen atom of an amino group of a polyamine having a structure represented by the following general formula (4) A copolymer obtained by modifying a part of the terminal hydroxyl group of the polyalkylene oxide chain of a copolymer obtained by adding an alkylene oxide to (a copolymer A) is preferred. Production by modifying a part of the terminal hydroxyl group of the polyalkylene oxide chain of copolymer A is preferable because impurities such as by-products in the production process can be reduced.

In the formula, R ₄ 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. P represents another polyamine chain by branching. l, m and n are the same or different and represent 0 or an integer of 1 or more, and at least one of l, m and n is an integer of 1 or more. In addition, at least two or more —N—R ₄ — units are present in the polyamine.

Examples of the alkylene amine structural unit include H ₂ N—R ₄ —, —NH—R ₄ —, —N (—) — R ₄ —, for example, in the case of the general formula (4). Is done.

In the general formula (4), the other polyamine chain represented by P is preferably bonded to the structure represented by the general formula (4) via R ₄ .
The polyamine may be one kind of alkylene group in R ₄ or two or more kinds, but is preferably one kind, and is preferably an ethylene group. Incidentally, when _{R 4} is a branched alkylene group having 3 to 6 carbon atoms are 1,2-propylene groups are preferred.
Examples of the polyalkyleneamine alkylene oxide copolymer of the present invention (such as a copolymer represented by the above general formula (3)) include a structural unit containing a primary amine nitrogen atom, a structural unit containing a secondary amine nitrogen atom, and three. Polyalkylene oxide of a copolymer (also referred to as copolymer B) obtained by adding alkylene oxide to the nitrogen atom of the amino group of a polyamine having at least one selected from the group consisting of structural units containing a secondary amine nitrogen atom Examples thereof include a copolymer obtained by modifying a part of the terminal hydroxyl group of the chain.
The structural unit containing the primary amine nitrogen atom is represented by the following formula, for example.
_{(H 2 -N-R 6)} -
In some cases, a structural unit represented by the following formula is also included.
-NH ₂
The structural unit containing the secondary amine nitrogen atom is represented by the following formula, for example.

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

_{R 4} in the general formula (5), (6) is the same as _{R 4} in the general formula (4).

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 polyalkyleneamine alkylene oxide copolymer before modification of the terminal hydroxyl group of the polyalkylene oxide chain (also referred to as a hydroxyl group-unmodified polyalkyleneamine alkylene oxide copolymer), the nitrogen atom of the amino group of these starting polyamines A part or all of the bonded hydrogen atoms are substituted with a polyalkylene oxide chain. The polyalkylene oxide chain is represented by the following general formula (7).
- _(R 3 _O) a H Formula (7)
(Wherein R ₃ O is the same as in formula (3). A represents an integer of 1 or more). The polyalkylene oxide chain of the hydroxyl group-unmodified polyalkyleneamine alkylene oxide copolymer has a hydroxyl group in the terminal structure. Such a hydroxyl group-unmodified polyalkyleneamine alkylene oxide copolymer can change the hydroxyl group of the polyalkylene oxide chain end by reacting in the step (I) described later.

  Examples of the polyalkyleneamine (PAA) include polyethyleneamine (PEA), tetrabutylenepentamine, and polyethyleneimine (PEI). 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). Polyethyleneimine is an alkyleneimine having 2 to 6 carbon atoms such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine and the like. Homopolymers and copolymers of these alkyleneimines obtained by polymerization by a conventional method are preferred. These may be used alone or in combination of two or more. More preferred is a homopolymer of ethyleneimine (polyethyleneimine; PEI). In these alkyleneimine homopolymers and copolymers, a polyalkyleneimine chain is formed, and the polyalkyleneimine chain must have a branched structure. PEI having at least moderate branching, that is, in the general formula (4), the ratio of m to n is preferably m / n = 4/1 to 1/4. More preferably, the ratio of m to n is about 3/1 to 1/3, and more preferably 2/1 to 1/2.

  Further, it may be obtained by polymerizing ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the like. Such a polyalkyleneimine usually has a primary amino group or secondary amino group (imino group) in addition to a tertiary amino group in the structure.

  In the present invention, the polyamine main chain is preferably formed mainly of an ethyleneamine structure (ethyleneimine structure). In this case, “main body” means that when the polyamine main chain is formed of two or more types of alkylene amine structures, it occupies most of the number of moles of all alkylene amine structures.

  When the “occupying the majority” is expressed in terms of mol% of ethylene amine structure in 100 mol% of all alkylene amine structures, it is preferably 50 to 100 mol%. If it is less than 50 mol%, the detergency of the polyalkyleneamine alkylene oxide copolymer may decrease. More preferably, it is 60 mol% or more, More preferably, it is 70 mol% or more.

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

  As described above, the hydroxyl group-unmodified polyalkyleneamine alkylene oxide copolymer is preferably obtained by adding an alkylene oxide to the polyalkyleneamine. In this case, the average molecular weight of the polyalkyleneamine is 60 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.

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

In the formula, EO represents an oxyethylene group. Q is the same or different and represents a hydrogen atom or the terminal structure of (1a) or (1b) above. a is an integer of 1 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 — formed by adding polyethylene oxide to amine nitrogen atoms of the PEI main chain, It is a copolymer having a terminal structure represented by 1a) and / or (1b).

[Production method of polyalkyleneamine alkylene oxide copolymer]
The polyalkyleneamine alkylene oxide copolymer of the present invention has (I) a hydroxyl group of a polymer obtained by adding an alkylene oxide to a polyalkyleneamine polymer (for example, the copolymer A and the copolymer B are exemplified). And a step of adding a glycidyl ether compound containing a group selected from an alkyl group having 9 to 30 carbon atoms, an alkenyl group having 9 to 30 carbon atoms, or an aryl group having 9 to 30 carbon atoms. preferable. Examples of the group selected from an alkyl group having 9 to 30 carbon atoms, an alkenyl group having 9 to 30 carbon atoms, and an aryl group having 9 to 30 carbon atoms include the above (1a), (1b), and the above general formula (2 The same as R _{1 in} ) is preferable. The polyalkyleneamine polymer refers to a polymer having an alkyleneamine structural unit. Impurities such as by-products in the production process can be reduced by producing by the production method including the step (I).
In this case, a polymer obtained by adding an alkylene oxide to a polyalkyleneamine polymer changes a part or all of the hydroxyl groups at the terminal of the polyalkylene oxide chain to the above terminal structure. As described above, the polyalkyleneamine alkylene oxide copolymer before the terminal modification reaction is also referred to as a hydroxyl group-unmodified polyalkyleneamine alkylene oxide copolymer.

  What is necessary is just to set reaction conditions which perform the process of said (I) suitably according to the compound used for reaction, the terminal structure of the target copolymer, etc., for example, as reaction temperature, it carries out at 0-200 degreeC. Is preferred. More preferably, they are 5 degreeC or more and 150 degrees C or less, More preferably, they are 20 degreeC or more and 120 degrees C or less, Especially preferably, they are 30 degreeC or more and 110 degrees C or less, Most preferably, it is 40 degrees C or more, It is 100 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.

  The glycidyl ether compound used in the step (I) is preferably 5 mol% or more and 100 mol% or less with respect to 100 mol% of the hydroxyl group of the hydroxyl group-unmodified polyalkyleneamine alkylene oxide copolymer. . The lower limit tends to improve the detergency and thickening effect, and is more preferably 7 mol% or more, still more preferably 10 mol% or more, particularly preferably 20 mol% or more, and most preferably 30 mol% or more. The upper limit is most preferably 100 mol% in terms of the thickening effect, more preferably 97 mol% or less, still more preferably 94 mol% or less, and particularly preferably 90 mol% in terms of the detergency improving effect. The mol% or less, and most preferably 85 mol% or less.

  The step (I) may be performed in an air atmosphere or an inert gas atmosphere. In the step (I), the hydroxyl group-unmodified polyalkyleneamine alkylene oxide copolymer is charged in a reactor, and the glycidyl ether compound may be added all at once or may be added every time. Sequential addition is preferred. In addition, it is preferable not to use a solvent during the reaction, but the reaction can also be performed using a solvent.

  The glycidyl ether compound is represented by the following general formula (8).

In the general formula (8), R ₁ represents an alkyl group having 9 to 30 carbon atoms, an alkenyl group having 9 to 30 carbon atoms, or an aryl group having 9 to 30 carbon atoms. A preferred embodiment of R ₁ is the same as the preferred embodiments R ₁ in the general formula (2).

  Examples of the glycidyl ether compound include nonyl glycidyl ether, decanyl glycidyl ether, dodecanyl glycidyl ether, isacosanyl glycidyl ether, dodecenyl glycidyl ether, octadecenyl glycidyl ether, nonylphenyl glycidyl ether, and naphthyl glycidyl ether. Etc. are exemplified.

  The polymer obtained by adding alkylene oxide to the polyalkyleneamine polymer is preferably produced by the step (II) of adding alkylene oxide to the amino group of the polyalkyleneamine polymer. The polyalkyleneamine polymer used in the step (II) is preferably a polyalkyleneimine, and particularly preferably polyethyleneimine.

[Use of polyalkyleneamine alkylene oxide copolymer]
The polyalkyleneamine alkylene oxide copolymer of the present invention (simply referred to as “the polymer of the present invention” or “the copolymer of the present invention”) is a builder for detergent, detergent, water treatment agent, dispersant, fiber treatment agent. , Scale inhibitors (scale inhibitors), cement additives, metal ion sealants, 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 further includes a builder for detergents, a detergent, and a water treatment, containing the polyalkyleneamine alkylene oxide copolymer of the present invention or the polyalkyleneamine alkylene oxide copolymer produced by the production method of the present invention as an essential component. It is also an agent or a dispersant.

<Detergent builder, detergent composition>
The detergent builder of the present invention exerts an action for preventing dirt from re-adhering to clothes being washed. When the copolymer of the present invention prevents the reattachment of dirt, it exhibits an adsorption action on the dirt component due to the hydrophobic terminal structure as well as the action attributable to the three-dimensional structure of the polyalkylene oxide chain. .
The detergent builder of the present invention is excellent in compatibility with a surfactant and can be suitably used as a builder for 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 detergent builder of the present invention exhibits an excellent thickening effect when blended in a liquid detergent.
Therefore, it is excellent in handleability in order to suppress dripping during use.

  The detergent builder according to the present invention has excellent anti-recontamination ability, and is a detergent with excellent stability and extremely high quality agent performance that is unlikely to cause deterioration in performance when stored for a long period of time or precipitation of impurities when held at low temperatures. Can be a builder.

  The cleaning ability can be determined by the cleaning rate. The cleaning rate can be determined by the following method.

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

The washing rate (%) is obtained from the value measured by the following method and the following formula.
Detergency (%) =
(Whiteness of the artificially contaminated cloth after washing-Whiteness of the artificially contaminated cloth before washing) ÷ (Whiteness of the original white cloth (EMPA221) of the artificially contaminated cloth-Whiteness of the artificially contaminated cloth before washing) × 100
Concerning the above-mentioned washing rate, it is a builder, a detergent, a water treatment agent or a dispersant for a detergent composed of a composition containing a polyalkyleneamine alkylene oxide copolymer, and the washing rate is 7.3 when EMPA164 is used. % Or more, or 17.4% or more when EMPA 106 is used is also one aspect of the present invention. Among these compositions comprising polyalkyleneamine alkylene oxide copolymers, i.e., detergent builders, detergents, water treatment agents or dispersants, these two properties, i.e., the cleaning rate when using EMPA164, and It is preferable to satisfy both of the cleaning rates when the EMPA 106 is used. The cleaning rate when using EMPA 164 is preferably 7.4% or more. The cleaning rate when using the EMPA 106 is preferably 17.5% or more. More preferably, it is 17.6% or more. The artificially contaminated cloths EMPA164 and 106 used for the measurement of the washing rate are standard samples for a dirt test in which a certain dirt is adhered to the cloth. The EMPA164 is used to remove grass dirt on a white cotton cloth (EMPA221). The EMPA 106 is obtained by attaching carbon black and mineral oil to a white cotton cloth (EMPA 221).

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

  The detergent may be a powder detergent or a liquid detergent, but a liquid detergent is preferred because the polyalkyleneamine alkylene oxide copolymer is excellent in solubility with the liquid detergent. In addition to the polyalkyleneamine alkylene oxide copolymer, additives generally used in detergents can be used for the detergent. Examples of the additives include surfactants, alkali builders, chelate builders, anti-redeposition agents for preventing redeposition of contaminants such as sodium carboxymethylcellulose, and dirt inhibitors such as benzotriazole and ethylene-thiourea. , Soil release agent, anti-transfer agent, softener, alkaline substance for pH adjustment, fragrance, solubilizer, fluorescent agent, colorant, foaming agent, foam stabilizer, polish, bactericidal agent, bleaching agent, Bleaching aids, enzymes, dyes, solvents and the like are preferred. In the case of a powder detergent, it is preferable to blend zeolite.

  When used in the detergent, the polyalkyleneamine alkylene oxide copolymer of the present invention is preferably added in an amount of 0.1 to 20% by mass with respect to 100% by mass of the detergent. 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 above detergents include household detergents, textile and other industrial detergents, hard surface cleaners, and detergents used only for specific applications such as bleaching detergents that enhance the function of one of its components. Including.

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

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

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

  In general, the blending ratio of the surfactant is preferably 10 to 60% by mass with respect to 100% by mass of the liquid detergent. More preferably, they are 15 mass% or more and 50 mass% or less, More preferably, they are 20 mass% or more and 45 mass% or less, Especially preferably, they are 25 mass% or more and 40 mass% or less. If the blending ratio of the surfactant is less than 10% by mass, sufficient detergency may not be exhibited, and if it exceeds 60% by mass, the economy may be lowered.

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

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

  The liquid detergent preferably has a kaolin turbidity of 200 mg / L or less. More preferably, it is 150 mg / L or less, More preferably, it is 120 mg / L or less, Especially preferably, it is 100 mg / L or less, Most preferably, it is 50 mg / L or less.

  Further, the change (difference) in kaolin turbidity between when the polyalkyleneamine alkylene oxide copolymer of the present invention is added to a liquid detergent and when it is not added is preferably 500 mg / L or less. More preferably, it is 400 mg / L or less, More preferably, it is 300 mg / L or less, Especially preferably, it is 200 mg / L or less, Most preferably, it is 100 mg / L or less. Kaolin turbidity can be measured, for example, by the following method.

(Measurement method of kaolin turbidity)
A sample (liquid detergent) uniformly stirred in a 50 mm square cell having a thickness of 10 mm was removed, and after removing bubbles, Turbidity at 25 ° C. using NDH2000 (trade name, turbidimeter) manufactured by Nippon Denshoku Co., Ltd. Kaolin turbidity: mg / L) is measured.

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

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

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

<Water treatment agent>
The polymer of the present invention can be used as a water treatment agent. If necessary, the water treatment agent may contain a polymerized phosphate, phosphonate, anticorrosive, slime control agent, and chelating agent as other compounding agents.

  The water treatment agent is useful for scale prevention in a cooling water circulation system, a boiler water circulation system, a seawater desalination apparatus, a pulp digester, a black liquor concentration tank, and the like. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effects.

<Fiber treatment agent>
The polymer of the present invention can be used as a fiber treatment agent. The fiber treatment agent includes at least one selected from the group consisting of a dye, a peroxide, and a surfactant, and the polymer (or polymer composition) of the present invention.

  The content of the polymer of the present invention in the fiber treatment agent is preferably 1 to 100% by weight, more preferably 5 to 100% by weight, based on the entire fiber treatment agent. Further, any appropriate water-soluble polymer may be included as long as the performance and effects are not affected.

  Below, the compounding example of the fiber processing agent which is closer to embodiment is shown. This fiber treatment agent can be used in the steps of refining, dyeing, bleaching and soaping in fiber treatment. Examples of dyeing agents, peroxides and surfactants include those usually used for fiber treatment agents.

  The blending ratio of the polymer of the present invention to at least one selected from the group consisting of a dye, a peroxide, and a surfactant is, for example, for improving the whiteness, color unevenness, and dyeing tempering degree of fibers. Is 0.1 to 100 parts by weight of at least one selected from the group consisting of a dyeing agent, a peroxide and a surfactant with respect to 1 part by weight of the polymer of the present invention in terms of a pure amount of the fiber treatment agent. It is preferable to use the composition mix | blended in a ratio as a fiber processing agent.

  Arbitrary appropriate fiber can be employ | adopted as a fiber which can use the said fiber processing agent. Examples thereof include cellulosic fibers such as cotton and hemp, chemical fibers such as nylon and polyester, animal fibers such as wool and silk, semi-synthetic fibers such as human silk, and woven fabrics and blended products thereof.

When the fiber treatment agent is applied to the refining process, it is preferable to blend the polymer of the present invention with an alkali agent and a surfactant. When applied to the bleaching step, it is preferable to blend the polymer of the present invention, a peroxide, and a silicic acid-based agent such as sodium silicate as a decomposition inhibitor for the alkaline bleaching agent.
<Inorganic pigment dispersant>
The polymer of the present invention can be used as an inorganic pigment dispersant. In the inorganic pigment dispersant, condensed phosphoric acid and its salt, phosphonic acid and its salt, and polyvinyl alcohol may be used as other compounding agents as required.

  The content of the polymer of the present invention in the inorganic pigment dispersant is preferably 5 to 100% by weight with respect to the whole inorganic pigment dispersant. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effect.

  The inorganic pigment dispersant can exhibit good performance as a dispersant for heavy or light calcium carbonate or clay inorganic pigment used in paper coating. For example, by adding a small amount of an inorganic pigment dispersant to an inorganic pigment and dispersing it in water, high concentration calcium carbonate having low viscosity and high fluidity and good aging stability of their performance. High concentration inorganic pigment slurries such as slurries can be produced.

  When the inorganic pigment dispersant is used as a dispersant for an inorganic pigment, the amount of the inorganic pigment dispersant used is preferably 0.05 to 2.0 parts by weight with respect to 100 parts by weight of the inorganic pigment. When the amount of the inorganic pigment dispersant used is within the above range, a sufficient dispersion effect can be obtained, and an effect commensurate with the addition amount can be obtained, which can be economically advantageous.

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

<Analysis of polyalkylene glycol>
Analysis of the polyalkylene glycol of the present invention was performed by confirming the progress of the reaction by analysis by liquid chromatography (disappearance of the raw material glycidyl ether compound) and confirming the structure by ¹ HNMR.
Liquid chromatography measurement conditions:
Measuring device: 8020 series manufactured by Tosoh Corporation Column: CAPCELL PAK C1 UG120 manufactured by Shiseido Co., Ltd.
Temperature: 40.0 ° C
Eluent: 10 mmol / L Disodium hydrogen phosphate.12 hydrate aqueous solution (adjusted to pH 7 with phosphoric acid) / acetonitrile = 45/55 (volume ratio)
Flow rate: 1.0 ml / min
Detector: RI, UV (detection wavelength 215 nm).

<Method for measuring solid content of polymer composition>
In a nitrogen atmosphere, the polymer composition (polymer composition 1.0 g + water 3.0 g) was left to dry for 1 hour in an oven heated to 130 ° C. From the weight change before and after drying, the solid content (%) and the volatile component (%) were calculated.

<Example 1>
A polyalkyleneamine oxide copolymer in which 20 moles of ethylene oxide is added to each NH of polyethyleneimine having a weight average molecular weight of 600 in a 100 mL four-necked flask (an average of 14.7 polyalkylene oxide chains per molecule). 36.4 g) (hereinafter referred to as “PAAO (1)”), and the mixture was heated and stirred at 120 ° C. in a nitrogen atmosphere for dehydration. After 30 minutes, the temperature was lowered to 90 ° C., and 7.1 g of lauryl glycidyl ether (Denacol EX192 (manufactured by Nagase ChemteX)) was added. The mixture was maintained at 90 ° C. and further stirred for 5 hours to obtain a polyalkyleneamine alkylene oxide copolymer (referred to as copolymer (1)) of the present invention.
As a result of analysis by liquid chromatography and ¹ HNMR, the reaction was quantitative. That is, it had a structure in which lauryl glycidyl ether was added to 100 mol% with respect to 100 mol% of the end structure of the polyalkylene oxide chain.

<Example 2>
A polyalkyleneamine oxide copolymer in which 55 moles of ethylene oxide is added to each NH of polyethyleneimine having a weight average molecular weight of 300 in a 100 mL four-necked flask (average of 8.4 polyalkylene oxide chains per molecule). 36.4 g) (hereinafter referred to as “PAAO (2)”), was heated and stirred at 120 ° C. in a nitrogen atmosphere, and dehydrated. After 30 minutes, the temperature was lowered to 90 ° C., and 1.1 g of lauryl glycidyl ether (Denacol EX192 (manufactured by Nagase ChemteX)) was added. The mixture was maintained at 90 ° C. and further stirred for 5 hours to obtain a polyalkyleneamine alkylene oxide copolymer (referred to as copolymer (2)) of the present invention.
As a result of analysis by liquid chromatography and ¹ HNMR, the reaction was quantitative. That is, it had a structure in which lauryl glycidyl ether was added to 35.7 mol% with respect to 100 mol% of the terminal structure of the polyalkylene oxide chain.

<Example 3>
In a 100 mL four-necked flask, 36.4 g of PAAO (2) was charged and dehydrated by heating and stirring at 120 ° C. in a nitrogen atmosphere. After 30 minutes, the temperature was lowered to 90 ° C., and 1.8 g of lauryl glycidyl ether (Denacol EX192 (manufactured by Nagase ChemteX)) was added. The mixture was maintained at 90 ° C. and further stirred for 5 hours to obtain a polyalkyleneamine alkylene oxide copolymer (referred to as copolymer (3)) of the present invention.
As a result of analysis by liquid chromatography and ¹ HNMR, the reaction was quantitative. That is, it had a structure in which lauryl glycidyl ether was added to 59.5 mol% with respect to 100 mol% of the polyalkylene oxide chain terminal structure.

<Example 4>
Polyoxyethylene adduct sulfate sodium salt of lauryl alcohol (Emal 270J (manufactured by Kao Corporation)) and secondary C13 alcohol polyoxyethylene adduct (Softanol 70 (Nippon Shokubai Co., Ltd.)) prepared as a model detergent 50 g of an aqueous solution containing 2% by mass (hereinafter referred to as “A solution”) was weighed into a screw-cap screw tube. 1 mass% (that is, 0.5 g in solid content) of the polyalkyleneamine alkylene oxide copolymer produced in Examples 1 to 3 was added thereto and stirred sufficiently until uniform, and then the viscosity at 25 ° C. was measured. did. The values when the viscosity of the liquid A is the standard (100) are shown in Table 1 as the viscosity increase rate.

From the results shown in Table 1, it has been clarified that the polyalkyleneamine alkylene oxide copolymer of the present invention has an excellent liquid drug thickening effect.

Claims (3)

A polyalkyleneamine alkylene oxide copolymer comprising an alkyleneamine structural unit having a polyalkyleneoxide chain,
Part or all of the end groups of the polyalkylene oxide chain of the polyalkyleneamine alkylene oxide copolymer are the following (1a) and / or (1b) :
(1a) —CH ₂ CH (OH) CH ₂ —O—R ₁
(1b) —CH (CH ₂ OH) CH ₂ —O—R ₁
(In the formula, _{R 1} represents an alkyl group or an alkenyl group having a carbon number of 9 to 30 carbon atoms 9-30.) A group represented by,
The polyalkyleneamine alkylene oxide copolymer is represented by the following general formula (A):

(In the formula, EO represents an oxyethylene group. Q is the same or different and represents a hydrogen atom or the terminal structure of (1a) or (1b) above. A is an integer of 1 or more. The symbol "..." represents that the polymer chain continues in the same manner.) A polyalkyleneamine alkylene oxide copolymer characterized by the following. Following general formula represented by (A '), viewed contains an alkylene amine structural unit having a polyalkylene oxide chain, and a copolymer of a hydroxyl group unmodified glycidyl ether compound represented by the following general formula (8) method for producing a polyalkylene a amine alkylene oxide copolymer which comprises the step of reacting.

(In the formula, EO represents an oxyethylene group. Q ′ represents a hydrogen atom. A is an integer of 1 or more. The symbol “. Represents.)

(In the formula, R ₁ represents an alkyl group having 9 to 30 carbon atoms or an alkenyl group having 9 to 30 carbon atoms.) A detergent composition comprising the polyalkyleneamine alkylene oxide copolymer according to claim 1.