WO2020241734A1 - (poly)alkylene glycol-containing compound - Google Patents

Abstract

The present invention provides a poly(alkylene) glycol-containing compound that has excellent detergency to combined dirt in which hydrophilic dirt and hydrophobic dirt are combined. The present invention is a poly(alkylene) glycol-containing compound which is characterized by having (A) a structure having an alkylene group and two or more nitrogen atoms, (B) a poly(alkylene) glycol structure, and (C) a lactam ring-containing structure.

Description

(Poly) alkylene glycol-containing compound

The present invention relates to (poly) alkylene glycol-containing compounds. More specifically, the present invention relates to a (poly) alkylene glycol-containing compound useful for detergents and the like.

A compound having a (poly) alkylene glycol chain is endowed with properties such as hydrophilicity, hydrophobicity, flexibility and steric repulsion by appropriately adjusting the chain length and the alkylene oxide constituting the compound. It is used in various applications such as treatment agents, anti-scale agents, and dispersants.
For example, Patent Document 1 describes a polyalkyleneimine alkylene oxide copolymer having an alkyleneimine monomer unit having a polyalkylene oxide, and the terminal structure of the polyalkyleneimine is at least one selected from a predetermined structure. A polyalkyleneimine alkylene oxide copolymer characterized by requiring one is disclosed.
Patent Document 2 describes a polyalkyleneimine alkylene oxide copolymer having an alkyleneimine monomer unit having a polyalkylene oxide, and the polyalkyleneimine alkylene oxide copolymer uses an ethylene oxide unit as the alkylene oxide unit. The terminal structure of the polyalkylene oxide requires at least one selected from a predetermined structure, and the ratio of the terminal structure selected from the predetermined structure to 100 mol% of the terminal structure of the polyalkylene oxide is 20. A polyalkyleneimine alkylene oxide copolymer characterized by being mol% or more and 98 mol% or less is disclosed.
Patent Document 3 discloses a polyalkylene glycol represented by a specific structure used as an antiscale agent, a detergent composition, and a pigment dispersant.
Patent Document 4 describes a hydrophobically modified polymer containing a vinylamine unit or an ethyleneimine unit, wherein the polymer comprises (a) a polymer containing a vinylamine unit or an ethyleneimine unit and (b) a compound having a predetermined structure. A hydrophobically modified polymer containing a vinylamine unit or an ethyleneimine unit, which can be obtained by the reaction of the above, is disclosed.

Japanese Unexamined Patent Publication No. 2005-350640 JP-A-2010-168592 Japanese Unexamined Patent Publication No. 2012-149185 Japanese Unexamined Patent Publication No. 2006-501319

As described above, Patent Documents 1 to 4 disclose compounds having various (poly) alkylene glycol structures. However, for example, in detergent applications, it will be mixed with various other additives, so further compounds may be added so that the type of additive that exerts detergency can be selected according to the additive to be used in combination. It was required to develop. In particular, among the detergency, there was room to develop a further compound having excellent detergency against composite stains in which hydrophilic stains and hydrophobic stains are compounded.

The present invention has been made in view of the above situation, and an object of the present invention is to provide a (poly) alkylene glycol-containing compound having excellent detergency against composite stains in which hydrophilic stains and hydrophobic stains are combined.

The present inventor has made various studies on (poly) alkylene glycol-containing compounds, and found that compounds having a structure having an alkylene group and two or more amino groups, a (poly) alkylene glycol structure, and a lactam ring-containing structure were found. We have found that it is excellent in detergency against composite stains in which hydrophilic stains and hydrophobic stains are combined, and have arrived at the idea that the above problems can be solved brilliantly, and have reached the present invention.

That is, the present invention is a (poly) alkylene glycol-containing compound having a structure (A) having an alkylene group and two or more nitrogen atoms, a (poly) alkylene glycol structure (B), and a lactam ring-containing structure (C). Is.

The structure (A) having the above alkylene group and two or more nitrogen atoms has the following formulas (1) and / or (2);

(In the formulas (1) and (2), R ¹ represents the same or different alkylene group having 2 to 6 carbon atoms. * Indicates a nitrogen atom in the (poly) alkylene glycol-containing compound to which the nitrogen atom is bonded. In formula (1), m1 represents a number of 2 or more. In formula (2), m2 represents a number of 1 or more).

The (poly) alkylene glycol-containing compound preferably has an oxyalkylene group directly bonded to at least one nitrogen atom in the above formulas (1) and / or (2).

It is preferable that the oxygen atom at the terminal of the alkylene glycol structure (B) and the nitrogen atom of the lactam ring structure are bonded via a hydrocarbon group having 1 to 50 carbon atoms which may have a hetero atom.

The lactam ring is preferably a pyrrolidone ring.

The above (poly) alkylene glycol-containing compound has the following formula (3);

(In the formula, R ¹ represents the same or different alkylene group having 2 to 6 carbon atoms. R ² represents the same or different alkylene group having 2 to 20 carbon atoms. R ³ represents a hetero. It represents a divalent hydrocarbon group having 1 to 50 carbon atoms, which may have an atom. N represents a number of 1 to 100. K represents a number of 1 to 3). It is preferable to have such a structure.

It said R ³ may have a branched chain, the branched chain, may have a hetero atom is preferably a hydrocarbon group having 1-49 carbon atoms.

The above R ³ is expressed by the following equation (4);

(In the formula, R ⁴ represents a hydrocarbon group having 1 to 47 carbon atoms which may have a hydrogen atom or a hetero atom. R ⁵ represents an alkylene group having 2 to 20 carbon atoms. p is preferably a divalent group represented by (representing a number from 0 to 20).

The content ratio of the structure (A) having the alkylene group and two or more nitrogen atoms is preferably 1 to 60% by mass with respect to 100% by mass of the (poly) alkylene glycol-containing compound.

The content ratio of the (poly) alkylene glycol structure (B) is preferably 30 to 98% by mass with respect to 100% by mass of the (poly) alkylene glycol-containing compound.

The content ratio of the lactam ring-containing structure (C) is preferably 1 to 60% by mass with respect to 100% by mass of the (poly) alkylene glycol-containing compound.

The content ratio of the lactam ring-containing structure (C) is 1 with respect to a total of 100 mol% of the nitrogen atom having active hydrogen in the structure (A) and the nitrogen atom of the structure (A) to which the structure (B) is bonded. It is preferably ~ 50 mol%.

The content ratio of the lactam ring-containing structure (C) is preferably 10 to 100 mol% with respect to 100 mol% of oxygen atoms at the terminal of the structure (B).

The (poly) alkylene glycol-containing compound may have a structure (D) containing an organic group in addition to the structures (A) to (C), and the content ratio of the structure (D) containing an organic group is , (Poly) alkylene glycol-containing compound is preferably 0 to 60% by mass with respect to 100% by mass.

The (poly) alkylene glycol-containing compound may have a structure (E) other than the structures (A) to (D), and the content ratio of the other structure (E) is (poly) alkylene. It is preferably 0 to 30% by mass with respect to 100% by mass of the glycol-containing compound.

The (poly) alkylene glycol-containing compound preferably has a number average molecular weight of 1000 to 500,000.

The present invention is also a detergent additive containing the above (poly) alkylene glycol-containing compound.

The present invention is also a detergent composition containing the above (poly) alkylene glycol-containing compound and a detergent additive other than the compound.

The (poly) alkylene glycol-containing compound of the present invention has excellent detergency against composite stains in which hydrophilic stains and hydrophobic stains are combined, and therefore can be suitably used for detergents and the like.

The preferred embodiments of the present invention will be specifically described below, but the present invention is not limited to the following description, and can be appropriately modified and applied without changing the gist of the present invention. A form in which two or three or more of the individual preferred forms of the present invention described below are combined also falls under the preferred form of the present invention.

≪ (Poly) alkylene glycol-containing compound≫
The (poly) alkylene glycol-containing compound (hereinafter, also referred to as PAG compound) of the present invention has a structure (A) having an alkylene group and two or more nitrogen atoms (hereinafter, also referred to as a structure (A)) and (poly). ) An alkylene glycol structure (B) (hereinafter, also referred to as structure (B)) and a lactam ring-containing structure (C) (hereinafter, also referred to as structure (C)). The PAG compound may have other structures as long as it has at least one structure (A), (B), and (C).
By having the above-mentioned specific structure, the PAG compound of the present invention exhibits excellent detergency against composite stains in which hydrophilic stains and hydrophobic stains are combined.
The PAG compound of the present invention is amphipathic with the hydrophilic (poly) alkylene glycol structure (B), which has excellent adsorptivity to the fiber surface due to the cationic property derived from the nitrogen atom of the structure (A). Therefore, by having a lactam ring that interacts with a carboxyl group or an ester group contained in stains such as sebum, the interaction with a composite stain in which hydrophilic stains and hydrophobic stains are combined is strengthened, so that the interaction with the composite stain is strengthened. It is presumed that excellent detergency can be exhibited. However, the present invention is not limited to this mechanism. In addition, the PAG compound of the present invention has the above-mentioned structure and is excellent in the ability to prevent recontamination against complex stains.

<Structure having an alkylene group and two or more amino groups (A)>
The structure (A) of the PAG compound is not particularly limited as long as it has an alkylene group and two or more nitrogen atoms, but the nitrogen atom is preferably a nitrogen atom constituting an amino group or a quaternary ammonium group. .. More preferably, it is a nitrogen atom constituting an amino group.
The amino group may be any of the primary to tertiary amino groups.
The structure (A) preferably has an alkylene group and two or more amino groups, and has the following formulas (1) and / or (2);

(In the formulas (1) and (2), R ¹ represents the same or different alkylene group having 2 to 6 carbon atoms. * Indicates a nitrogen atom in the (poly) alkylene glycol-containing compound to which the nitrogen atom is bonded. In formula (1), m1 represents a number of 2 or more. In formula (2), m2 represents a number of 1 or more.) It is more preferable to have a structure represented by. ..
Specific examples of the alkylene group include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, and an n-hexylene group.
The number of carbon atoms of the alkylene group is preferably 2 to 4, more preferably 2 to 3, and most preferably 2.

In the above formulas (1) and (2), m1 and m2 represent the number of alkyleneimine structural units possessed by the structure (A), m1 is a number of 2 or more, and m2 is a number of 1 or more.
The PAG compound of the present invention may have at least one structure represented by the above formula (1) or (2) as the structure (A), and may have a plurality of these. The total of m1 and / or m2 in the PAG compound is preferably 1 to 300, more preferably 1 to 100, still more preferably 2 to 75, still more preferably 3 to 50, even more preferably 4 to 4. It is 30, particularly preferably 4 to 20. The structure A may be linear or branched.

* In the formulas (1) and (2) represents an atom other than the nitrogen atom in the (poly) alkylene glycol-containing compound to which the nitrogen atom is bonded. The atom other than the nitrogen atom in the (poly) alkylene glycol-containing compound is not particularly limited, and for example, a hydrogen atom, a carbon atom of a hydrocarbon group contained in the structures (A) to (E), a carboxyl group, a hydroxyl group, and a carbonyl. Examples include atoms of functional groups such as groups, alkoxy groups, acyl groups, sulfonic acid groups, and phosphoric acid groups.
It is preferable that at least one of * is bonded to a carbon atom in the structure (B).

Examples of the form in which the structure (A) has only the structure represented by the formula (2) and m2 is 1, include structures derived from alkylenediamine such as ethylenediamine and propylenediamine.
The structure (A) preferably has a structure in which two or more structural units consisting of an alkylene group and an amino group are continuous, and more preferably a structure derived from a polyalkylene polyamine or a polyalkyleneimine.
Examples of the polyalkylene polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like.
Examples of the polyalkyleneimine include polyethyleneimine, polypropyleneimine, polybutyleneimine and the like, and carbon such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine and 1,1-dimethylethyleneimine. It can be obtained by polymerizing one or more of alkyleneimines having 2 to 6 atoms by a commonly used method.
The structure derived from polyalkylene polyamine or polyalkylene imine means a structure excluding at least one hydrogen atom bonded to a nitrogen atom of alkylene polyamine or polyalkylene imine.

<(Poly) alkylene glycol structure (B)>
The PAG compound of the present invention has a (poly) alkylene glycol structure (B), and the alkylene groups constituting the structure (B) have the same or different carbon atoms of 2 to 20.
The alkylene group has 2 to 20 carbon atoms "same or different", which means that when a plurality of alkylene groups are present in the (poly) alkylene glycol, the alkylene group has the same carbon number. It means that it may or may not be different.

The (poly) alkylene glycol structure (B) has the following formula (5);
-(R ² O) n- (5)
(In the formula, R ² is the same or different and represents an alkylene group having 2 to 20 carbon atoms. N represents a number of 1 to 100.) It is preferable that the structure is represented by.
R ² represents "same or different" as an alkylene group having 2 to 20 carbon atoms, which may be the same for all n alkylene groups of R ² present in the (poly) alkylene glycol. , Means that they can be different.

Oxyalkylene group represented by R 2 ^O is an alkylene oxide adduct, as such alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, styrene oxide Examples thereof include alkylene oxides having 2 to 8 carbon atoms. More preferably, it is an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide and butylene oxide, and even more preferably ethylene oxide and propylene oxide.
When the polyalkylene glycol is any two or more types of alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like, any of random addition, block addition, alternating addition and the like. It may be in the form. In order to secure a balance between hydrophilicity and hydrophobicity, it is preferable to have an oxyethylene group as an essential component as the oxyalkylene group in the (poly) alkylene glycol, and 50 mol% or more is the oxyethylene group. More preferably, 90 mol% or more is an oxyethylene group.

In the above formula (5), n is the average number of moles of oxyalkylene group added and represents a number from 1 to 100. n is preferably 2 to 90, more preferably 3 to 85, still more preferably 5 to 80, still more preferably 6 to 75, particularly preferably 7 to 70, and most preferably 9 ~ 60.
The PAG compound of the present invention may have a plurality of (poly) alkylene glycol chains, but the above n represents the average number of moles of oxyalkylene groups added per (poly) alkylene glycol chain.

The structure (B) is preferably bonded to one or more structures (A) directly or via a linking group. The linking group is not particularly limited, but is preferably an organic group having 1 to 20 carbon atoms, which is -CH _2- CH _2- C (= O)-, -CH _2- CH (-CH ₃ ). _{-C (= O) -, -} CH 2 -CH 2 -CH 2 -O -, - CH 2 -CH (-CH 3) -CH 2 -O -, - CH 2 -CH 2 -CH 2 -CH 2 _{-O -, - CH 2 -CH (} -CH 3) -CH-CH 2 -O -, - CH 2 -CH (OH) -CH 2 -, - CH (CH 2 OH) -CH 2 - and the like illustrated Will be done.

<Lactam ring-containing structure (C)>
The lactam ring-containing structure (C) in the above PAG compound is not particularly limited as long as it has a lactam ring, but the following formula (6);

(In the formula, R ⁶ represents a trivalent hydrocarbon group having 2 to 50 carbon atoms, which may have the same or different heteroatoms. K represents a number of 1 to 3.) The structure represented by is preferable.
K in the above formula (6) represents a number of 1 to 3, preferably 1 or 2, and more preferably 1.
In the PAG compound of the present invention, the form in which the lactam ring is a pyrrolidone ring is one of the preferred embodiments of the present invention.
Preferably 2 to 40 as the number of carbon atoms in the hydrocarbon group represented by ^{R 6,} more preferably 2 to 30, more preferably from 2 to 20, more preferably 2 to 10, particularly preferably from 2 to It is 7, and more preferably 2 to 5.
R ⁶ in the above formula (6) is the following formula (7) or (7');

(In the formula, x represents 0 or 1. R ⁷ represents an alkylene group having 1 to 8 carbon atoms which may have a direct bond or an ether structure.) Is preferable.
The carbon number of the alkylene group in R ⁷ is preferably 1 to 7, more preferably 1 to 5, and even more preferably 1 to 3.
Is more preferably the ^{R 6,} the following formula (8);

(In the formula, R ⁵ represents an alkylene group having 2 to 20 carbon atoms. P represents a number of 0 to 20; x represents 0 or 1.).
Specific examples and preferable examples of the above R ⁵ are the same as those of the above R ² .
The p represents a number of 0 to 20, preferably 0 to 10, more preferably 0 to 5, still more preferably 0 to 3, and particularly preferably 0 or 1. The form in which p is 0 is one of the preferred embodiments of the present invention.
In the above formulas (7), (7') and (8), x represents 0 or 1, and is preferably 1.
In the above formulas (7), (7') and (8), the oxygen atom represented by-(O) x- may have a hydrogen atom or a hetero atom, and has 1 to 47 carbon atoms. It is preferable that it is bonded to the hydrocarbon group of. When the oxygen atom is bonded to a hydrogen atom, the structure (C) has a hydroxyl group, and such a form is one of the preferred embodiments of the present invention.
The hydrocarbon group having 1 to 47 carbon atoms, which may have the heteroatom, is preferably a group derived from the structure (D), and the structure (C) has a structure (D) via the oxygen atom. ) Is also one of the preferred embodiments of the present invention, which may have a heteroatom derived from) and is bonded to a hydrocarbon group having 1 to 47 carbon atoms. The hydrocarbon group having 1 to 47 carbon atoms, which may have the above heteroatom, is more preferably a hydrocarbon group containing a hydroxyl group and / or an ether group.
<Structure containing organic groups (D)>
The PAG compound may have a structure (D) containing an organic group in addition to the structures (A) to (C), and the form having the structure (D) is one of the preferred embodiments of the present invention. It is one. The structure (D) is a structure derived from an organic compound which may have a hetero atom, and does not correspond to the structures (A) to (C). The structure derived from an organic compound means a structure obtained by extracting one or more hydrogen atoms from an organic compound.
The structure (D) is preferably a structure derived from an organic compound exhibiting hydrophobicity. Since the PAG compound of the present invention has a hydrophobic structure (D) in addition to the structures (A), (B) and (C), the hydrophobicity of the PAG compound is in a more preferable range. The interaction with hydrophobic stains is strengthened, and the detergency against compound stains is further improved.

The organic compound preferably has an insoluble content of 9.5 g or more when 10 g of the organic compound is dissolved in 100 g of water at 25 ° C.
The organic compound is preferably a hydrocarbon compound having 1 to 50 carbon atoms which may have a hetero atom. The number of carbon atoms of the hydrocarbon compound is preferably 3 to 30. It is more preferably 4 to 21, still more preferably 8 to 18, and particularly preferably 10 to 14. Examples of the hydrocarbon compound include an acyclic hydrocarbon compound, a cyclic saturated hydrocarbon compound, and an aromatic compound.

The hydrocarbon compound which may have a heteroatom may be a hydrocarbon compound having a heteroatom or a hydrocarbon compound having no heteroatom. A hydrocarbon compound having a heteroatom means a hydrocarbon compound in which at least a part of carbon atoms or hydrogen atoms constituting the hydrocarbon compound is substituted with a heteroatom or a substituent having a heteroatom.
The hydrocarbon compound which may have a hetero atom is a hetero atom such as a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom and a halogen atom as long as the hydrophobic structure (D) in the PAG compound is hydrophobic. It may also have a substituent such as a hydroxyl group, an alkoxy group, a carboxyl group, an acyl group, a sulfonic acid group, an amino group, or a phosphoric acid group.
The carbon number of the above hydrocarbon compound shall include the carbon number of the substituent.
The same applies to the hydrocarbon group which may have a hetero atom described later.

Examples of the acyclic hydrocarbon compound include alkanes, alkenes and alkynes having 1 to 50 carbon atoms.
Alkanes with 1 to 50 carbon atoms include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonan, decane, undecane, dodecane, tridecan, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, and icosan. Examples thereof include alkanes having a linear or branched chain such as henikosan, tetracosane, triacontane, tetracontane, and pentacontane.

Alkenes with 2 to 50 carbon atoms include ethylene, propene, butene, pentene, hexene, heptene, octene, nonen, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, icosene, and henikosen. Examples thereof include alkenes having a straight chain or a branched chain such as tetracocene, triacene, tetracontene, and pentacontene.

Alkynes with 2 to 50 carbon atoms include acetylene, propyne, butine, pentyne, hexyne, heptin, octyne, nonyne, decine, undecine, dodecin, tridecine, tetradecine, pentadecine, hexadecine, heptadecine, octadecine, nonadesin, icocin, henicocin, Examples thereof include alkynes having a straight chain or a branched chain such as tetracosine, triacontin, tetracontin, and pentacontin.

Examples of the cyclic saturated hydrocarbon compound having 3 to 50 carbon atoms include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like, and those having one or more alkyl groups.
Aromatic compounds having 6 to 50 carbon atoms include benzene, naphthalene, anthracene, toluene, o-xylene, m-xylene, p-xylene, ot-butyltoluene, mt-butyltoluene, and pt-. Butyltoluene, 1-ethyl-4-methylbenzene, 1-ethyl-3-methylbenzene, 1-isopropyl-4-methylbenzene, 1-t-butyl-4-methylbenzene, mesitylene, pseudocumene, durene, methylnaphthalene, Examples thereof include dimethylnaphthalene, methylanthracene, 4,4'-dimethylbiphenyl, ethylbenzene, propylbenzene, butylbenzene, 1,4-diethylbenzene and the like, and other compounds having one or more alkyl groups on the aromatic ring.

As the organic compound, a compound having a functional group capable of reacting with a hydroxyl group is preferable. As the functional group, a hydroxyl group, an epoxy group, an ester group, an isocyanate group, a halogeno group, an aldehyde group and the like are preferable. The organic compounds are more preferably alkylene oxides, glycidyl ethers, isocyanates, halogen compounds, ester compounds, aldehydes and the like. When butylene oxide is used as the organic compound, the structure (D) has a group represented by -CH ₂ CH (-C ₂ H ₅ )-.
By introducing the structure (D) into the PAG compound of the present invention, desired properties can be added to the (poly) alkylene glycol-containing compound of the present disclosure.

As long as the PAG compound of the present invention has at least one structure (A), (B) and (C), these positions are not particularly limited, but at least one nitrogen atom in the structure (A). , It is preferable that the oxyalkylene group of the structure (B) is bonded.
That is, it is preferable that the oxyalkylene group is directly bonded to at least one nitrogen atom in the above formulas (1) and / or (2).
Further, in the above PAG compound, the oxygen atom at the (poly) alkylene glycol terminal of the structure (B) and the nitrogen atom of the lactam ring structure of the structure (C) may have a hetero atom and have 1 to 50 carbon atoms. It is preferable that the compound is bonded via the hydrocarbon group of.
More preferably, the oxyalkylene group of the structure (B) is bonded to at least one nitrogen atom in the structure (A), and the oxygen atom at the (poly) alkylene glycol terminal of the structure (B) and the lactam of the structure (C). It is a form in which a nitrogen atom having a ring structure is bonded via a hydrocarbon group having 1 to 10 carbon atoms which may have a hetero atom.

As described above, the PAG compound of the present invention may have a hydrophobic structure (D), in which case the position of the structure (D) in the PAG compound is not particularly limited, and for example, the structure (A). The structure (D) may be bonded to the amino group or the alkylene group of the structure (B), the alkylene group of the structure (B), or the lactam ring of the structure (C), but at the connecting portion between the structure (B) and the structure (C). The form in which the structure (D) is located is preferable.

The above (poly) alkylene glycol-containing compound has the following formula (3);

(In the formula, R ¹ represents the same or different alkylene group having 2 to 6 carbon atoms. R ² represents the same or different alkylene group having 2 to 20 carbon atoms. R ³ represents a hetero. It represents a divalent hydrocarbon group having 1 to 50 carbon atoms, which may have an atom. N represents a number of 1 to 100. K represents a number of 1 to 3). It is preferable to have such a structure.

The above R ¹ , R ² , n, and k are as described above.

The above-mentioned R ³ is a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a hetero atom, and a form having a hydrophobic structure (D) in R ³ is a preferred embodiment of the present invention. It is one of the forms. In R ^3, the structure may have a hydrophobic structure (D) and the terminal nitrogen atom of oxygen and structure (C) as a main chain connecting the (B), but the structure (B) ( A form in which the main chain connecting C) has a branched chain and the branched chain has a structure (D) is preferable.
That is, the above R ³ has a branched chain, and the branched chain is preferably a hydrocarbon group having 1 to 49 carbon atoms, which may have a hetero atom.
The above is more preferably R ^3, which may have a hetero atom, in the main chain of the divalent hydrocarbon group having 1 to 10 carbon atoms, which may have a hetero atom, 49 It is a form in which the hydrocarbon groups of the above are bonded as a branched chain.

More preferably, the following formula as the ^{R 3} (4);

(In the formula, R ⁴ represents a hydrocarbon group having 1 to 47 carbon atoms which may have a hydrogen atom or a hetero atom. R ⁵ represents an alkylene group having 2 to 20 carbon atoms. Is a divalent group represented by (representing a number from 0 to 20).
Specific examples and preferable examples of the above R ⁵ are the same as those of the above R ² .
The preferable range of p is as described in the formula (8).
Preferably an oxygen atom as a hetero atom in the R ^4.
Examples of the preferred R ^4, a hydrogen atom, a hydrocarbon group having a carbon number of 1-47 having no heteroatom, or a hydrocarbon group having a carbon number of 1-47 having a hydroxyl group and / or ether groups.

The number of carbon atoms of the hydrocarbon group having 1 to 47 carbon atoms is preferably 1 to 40, more preferably 3 to 30, still more preferably 4 to 21, still more preferably 8 to 18, and particularly preferably. Is 12-14.

Examples of alkyl groups having 1 to 47 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group (amyl group), n-hexyl group, n-heptyl group, and n-. Octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n- Octadecyl group, n-nonadecil group, n-eicosanyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i -Amil group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2 -Ethyl-2-methylpropyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, pentatria Aliphatic alkyl groups such as contyl group, tetracontyl group, pentatetracontyl group, heptatetracontyl group; cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl Group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group (C7), adamantyl group (C10), cyclopentylethyl group, cyclopropyloctadecyl group, cyclobutylheptadecyl group, cyclopentylhexadecyl group, Examples thereof include alicyclic alkyl groups such as cyclohexylpentadecyl group, cycloheptyltetradecyl group and cyclooctyl redesyl group.

Examples of the alkenyl group having 2 to 47 carbon atoms include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group and a dodecenyl group. Octadesenyl group, icosenyl group, eicosenyl group, henicosenyl group, docosenyl group, tricosenyl group, tetracosenyl group, pentacosenyl group, hexacosenyl group, heptacosenyl group, octacosenyl group, nonacocenyl group, triacontenyl group, pentatrioacontenyl group, tetracontenyl group Examples thereof include a group, a pentatetracontenyl group, a heptatetracontenyl group and the like.

Examples of the alkynyl group having 2 to 47 carbon atoms include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, and a dodecynyl group. Octadesinyl group, icocinyl group, eicocinyl group, henicocinyl group, docosinyl group, tricosynyl group, tetracosynyl group, pentacocinyl group, hexacocinyl group, heptacosynyl group, octacocinyl group, nonacocynyl group, triacocynyl group, pentatriachynyl group, tetracontinyl group Examples include a group, a pentatetracontynyl group, a heptatetracontynyl group and the like.

Examples of the aryl group having 6 to 47 carbon atoms include a phenyl group; a naphthyl group; a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 3-phenylpropyl group, a 4-phenylbutyl group, and a styryl group (Ph). -CH = C- group), cinnamyl group (Ph-CH = CHCH _2- group), 1-benzocyclobutenyl group, 1,2,3,4-tetrahydronaphthyl group, quarter-phenyl group, kinkphenyl group, etc. In addition, these groups, phenyl groups, naphthyl groups, fluorenyl groups, anthracenyl groups, phenanthryl groups, biphenyl groups, terphenyl groups, distyreneized phenyl groups, etc., and other aromatic rings such as benzene and naphthalene, alkyl groups, etc. Examples include bonded groups.

Examples of the heterocyclic group having 2 to 47 carbon atoms include a pyrrole group, a furan group, a thiophene group, an imidazole group, a pyrazole group, an oxazole group, an isooxazole group, a thiazole group, an isothiazole group, a tetrazole group, a pyridinyl group and a pyrimidinyl group. Group, pyridadinyl group, pyrazinyl group, 1,2,3-triazinyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, phthalazinyl group, buteridinyl group, cummarinyl group, chromonyl group, 1,4-benzodiazepinyl group, indol group , Benzimidazole group, benzofuranyl group, prynyl group, acridinyl group, phenoxazinyl group, phenothiazinyl group and the like, and those having the above alkyl group in the aromatic heterocycle and the like can be mentioned. As the heterocyclic group, an aromatic heterocyclic group having aromaticity is preferable, and a tetrazole group and an imidazole group are more preferable.

The alkyl group, alkenyl group, and alkynyl group preferably have 2 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, still more preferably 8 to 20 carbon atoms, and particularly preferably 10 to 18 carbon atoms. Most preferably, it is 12 to 14.
The aryl group preferably has 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and even more preferably 6 to 25 carbon atoms.
The heterocyclic group preferably has 2 to 40 carbon atoms, more preferably 2 to 30, and even more preferably 2 to 20 carbon atoms.

The hydrocarbon group is preferably an alkyl group, more preferably an aliphatic alkyl group having a straight chain or a branched chain.

Preferably the following formula as a hydrocarbon group having 1-47 carbon atoms having a hydroxyl group and / or ether group in the R ⁴ (9);

(In the formula, R ⁸ represents a hydrocarbon group having 1 to 47 carbon atoms. Q represents 0 or 1.) It is preferable that the group is represented by.
Specific examples of the hydrocarbon groups having 1 to 47 carbon atoms of R ⁸ and preferable ranges of carbon atoms are as described in R ⁴ .
q represents 0 or 1, preferably 1. when q is 1, will be hydrophilic structure (B), amphipathic structure (C), a hydrocarbon group having a carbon number of 1 to 47 in the R ⁸ which exhibits hydrophobic positioned in this order, It is presumed that a wetting gradient that gradually changes from hydrophilic to hydrophobic is formed in the compound. Therefore, it is presumed that the interfacial tension between the washing water and the hydrophobic component in the composite stain can be effectively reduced, thereby exhibiting a better detergency against the composite stain. However, the present invention is not limited to this mechanism.

The content ratio of the structure (A) in the PAG compound is preferably 1 to 60% by mass with respect to 100% by mass of the (poly) alkylene glycol-containing compound. As a result, the adsorptivity of the PAG compound to the fiber is further improved. It is more preferably 2 to 50% by mass, further preferably 3 to 40% by mass, still more preferably 4 to 30% by mass, still more preferably 4 to 20% by mass, and particularly preferably 4 to 4 to 20% by mass. It is 10% by mass.

The content ratio of the structure (B) in the PAG compound is preferably 30 to 98% by mass with respect to 100% by mass of the (poly) alkylene glycol-containing compound. It is more preferably 40 to 98% by mass, further preferably 50 to 98% by mass, further preferably 60 to 97% by mass, further preferably 70 to 96% by mass, and particularly preferably 80 to 80 to 90% by mass. It is 96% by mass.
The structure (B) refers to a structure derived from a raw material used for introducing (poly) alkylene glycol into a PAG compound. For example, when an alkylene oxide described later is used in the production of the PAG compound, the structure derived from the alkylene oxide is the structure (B).
The content ratio of the structure (B) in the PAG compound is 100 mol% in total of the nitrogen atom having active hydrogen in the structure (A) and the nitrogen atom of the structure (A) to which the structure (B) is bonded. It is preferably 10 to 100 mol%. It is more preferably 20 to 100 mol%, further preferably 30 to 100 mol%, and particularly preferably 40 to 100 mol%.

The content ratio of the structure (C) in the PAG compound is preferably 1 to 60% by mass with respect to 100% by mass of the (poly) alkylene glycol-containing compound. It is more preferably 3 to 50% by mass, further preferably 4 to 40% by mass, still more preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass.
The structure (C) refers to a structure derived from a raw material used for introducing a lactam ring-containing structure into a PAG compound. For example, when a lactam skeleton-containing compound described later is used in the production of the PAG compound, the structure derived from the lactam skeleton-containing compound becomes the structure (C).
The content ratio of the structure (C) in the PAG compound is 100 mol% in total of the nitrogen atom having active hydrogen in the structure (A) and the nitrogen atom of the structure (A) to which the structure (B) is bonded. It is preferably 1 to 50 mol%. It is more preferably 5 to 30 mol%, still more preferably 10 to 20 mol%.
Further, the content ratio of the structure (C) in the PAG compound is preferably 10 to 100 mol% with respect to 100 mol% of oxygen atoms at the terminal of the structure (B). It is more preferably 30 to 100 mol%, still more preferably 40 to 100 mol%, and particularly preferably 50 to 100 mol%.

The mass ratio of the lactam ring in the PAG compound is preferably 1 to 60% by mass with respect to 100% by mass of the (poly) alkylene glycol-containing compound. It is more preferably 3 to 50% by mass, further preferably 4 to 40% by mass, still more preferably 5 to 30% by mass, still more preferably 5 to 20% by mass, and particularly preferably 5 to 5 to 20% by mass. It is 10% by mass.

The content ratio of the structure (D) in the PAG compound is preferably 0 to 60% by mass with respect to 100% by mass of the (poly) alkylene glycol-containing compound. It is more preferably 3 to 50% by mass, further preferably 5 to 40% by mass, still more preferably 8 to 30% by mass, and particularly preferably 10 to 20% by mass. The structure (D) refers to a structure derived from a raw material used for introducing a hydrophobic structure (D) into a PAG compound. For example, when a hydrophobic group-containing compound described later is used in the production of the PAG compound, the structure derived from the hydrophobic group-containing compound becomes the structure (D).
The content ratio of the structure (D) in the PAG compound is preferably 0 to 100 mol% with respect to 100 mol% of the structure (C). It is more preferably 20 to 100 mol%, further preferably 40 to 100 mol%, and particularly preferably 60 to 100 mol%.

The PAG compound may have a structure (E) other than the structures (A), (B), (C) and (D). The content ratio of the other structure (E) is preferably 0 to 30% by mass with respect to 100% by mass of the (poly) alkylene glycol-containing compound. It is more preferably 0 to 25% by mass, further preferably 0 to 20% by mass, and particularly preferably 0 to 10% by mass.

The number average molecular weight of the PAG compound is not particularly limited, but is preferably 1000 to 500,000. As a result, the detergency against complex stains is further improved. The number average molecular weight is more preferably 3000 to 100,000, still more preferably 5,000 to 50,000, and particularly preferably 10,000 to 30,000. The number average molecular weight of the PAG compound can be calculated based on the molecular weight of each structure constituting the PAG compound and the number of each structure.

The PAG compound preferably has a detergency (%) of 35.5% or more as measured by the method described in Examples. It is more preferably 36% or more, further preferably 36.5% or more, and particularly preferably 37% or more.

<< Method for Producing PAG Compound of the Present Invention >>
The method for producing the PAG compound of the present invention is not particularly limited, and for example, a first step of synthesizing a precursor having an alkylene group and two or more amino groups, and an alkylene oxide are added to the precursor obtained in the first step. Examples thereof include a method of performing a second step of addition and a third step of reacting the alkylene oxide adduct obtained in the second step with a lactam skeleton-containing compound. For example, a commercially available polyalkyleneimine, (poly) alkylene polyamine, or the like can be used as a precursor having an alkylene group and two or more amino groups. As the alkylene oxide adduct obtained in the second step, commercially available products such as the alkylene oxide adduct of polyalkyleneimine and the alkylene oxide adduct of (poly) alkylene poly can also be used. Therefore, for example, when a commercially available alkylene oxide adduct of polyalkyleneimine is used, only the third step may be performed.
Further, when the PAG compound of the present invention has a structure (D) containing an organic group in addition to the structures (A) to (C), the fourth step of reacting the reactant obtained in the third step with the organic compound. By performing the above, a PAG compound having the structure (D) can be obtained.
When the PAG compound of the present invention has a hydrophobic structure (D), the hydrophobic structure (D) is obtained by performing the fourth step of reacting the reactant obtained in the third step with the hydrophobic group-containing compound. A PAG compound having D) can be obtained.
In the following, as a typical method for producing a PAG compound of the present invention, a commercially available polyalkyleneimine as a precursor having an alkylene group and two or more amino groups or a commercially available alkylene oxide adduct of polyalkyleneimine is used. The second and subsequent steps will be described.

<Second step>
In the second step, an alkylene oxide adduct of polyalkyleneimine can be obtained by carrying out a reaction of adding alkylene oxide to polyalkyleneimine.
The amount of the alkylene oxide used in the second step is preferably 1 to 100 mol with respect to 1 mol of the nitrogen atom having the active hydrogen of the polyalkyleneimine. It is more preferably 3 to 80 mol, still more preferably 5 to 60 mol, and particularly preferably 10 to 50 mol.
In the second step, it is preferable to use a catalyst from the viewpoint of reaction rate. Examples of the catalyst include mineral acids such as sulfuric acid and phosphoric acid, acid catalysts such as Lewis acid such as tin tetrachloride and boron trifluoride; and basic catalysts such as hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide. And so on.

The reaction temperature in the second step is not particularly limited, but is preferably 80 to 160 ° C, more preferably 100 to 150 ° C. As the reaction pressure is preferably not more than 20 Kg / cm ² G from atmospheric pressure, and more preferably 1 ~ 10Kg / cm ² G.

<Third step>
The third step is a step of reacting a lactam skeleton-containing compound with an alkylene oxide adduct of polyalkyleneimine obtained in the second step or commercially available.
The above-mentioned lactam skeleton-containing compound is not particularly limited as long as it has a lactam skeleton and can react with an alkylene oxide adduct of polyalkyleneimine, but the following formula (10);

(In the formula, R ⁹ represents an organic group having 2 to 10 carbon atoms having a reactive functional group. K represents a number of 1 to 3.) The compound represented by is preferable.
The preferable range of k is as described in the formula (6).
The number of carbon atoms of the organic group is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 5.
Examples of the reactive functional group in R ⁹ include an epoxy group, a halogen atom, a hydroxyl group, a carboxyl group, an amino group and the like. It is preferably an epoxy group.

The following formula (11) is more preferable as the lactam skeleton-containing compound;

(In the formula, R ¹⁰ represents an oxyalkylene group having 1 to 20 carbon atoms, which is the same or different. R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R represents 0 to 20. Represents a number. K represents a number from 1 to 3).
The r in the above formula (11) is preferably 0 to 10, more preferably 0 to 5, and even more preferably 0 or 1.
The oxyalkylene group in R ¹⁰ is preferably an oxyalkylene group having 2 to 4 carbon atoms. When the p is 1 or more, 50 mol% or more of R ¹⁰ is preferably an oxyethylene group (−CH ₂ CH ₂ O−), and more preferably 80 mol% or more is an oxyethylene group.
When R ¹¹ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms and is an alkyl group having 1 to 12 carbon atoms, the PAG compound of the present invention is hydrophobic without performing the fourth step described later. Will have a group.
The number of carbon atoms of the alkyl group in R ¹¹ is preferably 1 to 8, and more preferably 1 to 4.
The R ¹¹ is preferably a hydrogen atom.

The compound represented by the above formula (10) is a functional group having the above reactivity with a lactam compound such as 1- (2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, 2-piperidone or ε-caprolactam. Can be manufactured by introducing. A compound represented by the above formula (10) by reacting a lactam compound with a compound having a functional group capable of reacting with a hydroxyl group or a nitrogen atom in the lactam compound, in addition to the above reactive functional group. It is preferable to obtain.
Examples of the functional group capable of reacting with the hydroxyl group and the nitrogen atom in the lactam compound include an epoxy group, a halogen atom, a hydroxyl group, a carboxyl group, an amino group and the like, and a halogen atom is preferable. Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like, and a chlorine atom is preferable.
For example, the compound represented by the above formula (11) is N-hydroxyethylpyrrolidone, N-hydroxypropylpyrrolidone, N-hydroxybutylpyrrolidone, N-hydroxypentylpyrrolidone, N-hydroxyhexylpyrrolidone, 2-pyrrolidone, 2-. It can be obtained by reacting piperidone or ε-caprolactam with a compound having an epoxy group and a halogen atom.
The compound having an epoxy group and a halogen atom is preferably epichlorohydrin, more preferably epichlorohydrin, epibromohydrin, 2- (chloromethyl) -1,2-epoxypropane, 2- (chloromethyl)-. It is 1,2-epoxybutane, most preferably epichlorohydrin.

The amount of the lactam skeleton-containing compound used in the third step is not particularly limited, but is preferably 10 to 100 mol% with respect to 100 mol% of the hydroxyl groups of the alkylene oxide adduct of polyalkyleneimine. It is more preferably 30 to 100 mol%, still more preferably 40 to 100 mol%, still more preferably 50 to 100 mol%.
In the third step, it is preferable to use a catalyst from the viewpoint of reaction rate. Examples of the catalyst include the above-mentioned acid catalyst and basic catalyst. It is preferably a basic catalyst, and more preferably an alkali metal hydroxide.
The reaction temperature in the third step is not particularly limited, but is preferably 50 to 180 ° C, more preferably 50 to 150 ° C, and even more preferably 60 to 120 ° C. As the reaction pressure is preferably not more than 20 Kg / cm ² G from atmospheric pressure, and more preferably 1 ~ 10Kg / cm ² G.

<4th process>
In the fourth step, a PAG compound having a hydrophobic structure (D) can be obtained by reacting the reactant obtained in the third step with a hydrophobic group-containing compound.
The hydrophobic group-containing compound is not particularly limited as long as it has a hydrophobic group and can react with the reactant obtained in the third step, but the following formula (12);
R ⁸ -X (12)
(In the formula, R ⁸ represents a hydrocarbon group having 1 to 47 carbon atoms which may have a hetero atom. X represents a reactive functional group.) preferable.
Specific examples and preferred examples of R ⁸ in the formula (12) are as described for formula (9).

X in the above formula (12) is not particularly limited as long as it is a functional group having reactivity with the reactant obtained in the third step, but for example, a halogen atom, an epoxy group, a glycidyl group, a glycidyl ether group, or a carboxyl group. , Amino group, isocyanate group and the like. The X is preferably a hydrogen atom, a halogen atom, a glycidyl group, a glycidyl ether group, or an isocyanate group.
Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like, and chlorine is preferable.

Specific examples of the hydrophobic group-containing compound represented by the above formula (12) include a hydrophobic group-containing compound having a hydroxyl group such as an alkyl alcohol having 1 to 47 carbon atoms; an alkyl halide having 1 to 47 carbon atoms and the like. Hydrophobic group-containing compound having a halogen atom; a hydrophobic group-containing compound having a glycidyl ether group such as an alkylglycidyl ether having 1 to 47 carbon atoms; a hydrophobic group having an isocyanate group such as an alkylisocyanate having 1 to 47 carbon atoms. Examples include contained compounds. Among these, a hydrophobic group-containing compound having a glycidyl ether group, a hydrophobic group-containing compound having a hydroxyl group, and a hydrophobic group-containing compound having a halogen atom are preferable.

The alkyl alcohol having 1 to 47 carbon atoms is preferably methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol and tri. Decyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecil alcohol, icosyl alcohol and the like.

The alkyl halide having 1 to 47 carbon atoms is preferably methyl halide, ethyl halide, propyl halogenated, butyl halide, pentyl halide, hexyl halogenated, heptyl halogenated, octyl halogenated, nonyl halogenated, halogen Decyl halide, undecyl halogenated, dodecyl halogenated, tridecyl halogenated, tetradecyl halogenated, pentadecyl halogenated, hexadecyl halogenated, heptadecyl halogenated, octadecyl halogenated, nonadecil halogenated and icosyl halogenated.

The alkyl glycidyl ether having 1 to 47 carbon atoms is preferably methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl. Glycyzyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, heptadecyl glycidyl ether, octadecyl glycidyl ether, nonadecil glycidyl ether and icosyl glycidyl ether And so on.

The alkyl isocyanate having 1 to 47 carbon atoms is preferably methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, pentyl isocyanate, hexyl isocyanate, heptyl isocyanate, octyl isocyanate, nonyl isocyanate, decyl isocyanate, undecyl isocyanate, dodecyl isocyanate, tridecyl. Isocyanate, tetradecyl isocyanate, pentadecyl isocyanate, hexadecyl isocyanate, heptadecyl isocyanate, octadecyl isocyanate, nonadecil isocyanate, icosyl isocyanate and the like.

The reaction temperature in the fourth step is not particularly limited, but is preferably 50 to 180 ° C, more preferably 50 to 150 ° C. As the reaction pressure is preferably not more than 20 Kg / cm ² G from atmospheric pressure, and more preferably 1 ~ 10Kg / cm ² G.

<< Composition containing the PAG compound of the present invention >>
A composition containing the PAG compound of the present invention as an essential is also one of the present inventions. In addition to the PAG compound of the present invention, the composition may contain other components such as unreacted raw materials, by-products, catalyst residues, and solvents.

The content of the PAG compound of the present invention in the above composition is preferably 1 to 99.9% by mass with respect to 100% by mass of the composition. More preferably, it is 1 to 99% by mass.
That is, the composition containing the (poly) alkylene glycol-containing compound of the present invention contains the (poly) alkylene glycol-containing compound and other components other than the compound, and the content of the (poly) alkylene glycol-containing compound is the composition. It is preferably 1 to 99.9% by mass with respect to 100% by mass of the compound. The content of the (poly) alkylene glycol-containing compound is more preferably 30 to 99.9% by mass, and further preferably 50 to 99.9% by mass.

<< Applications of the PAG compound of the present invention >>
The (poly) alkylene glycol-containing compound of the present invention is used for various purposes such as detergent additives, detergents, water treatment agents, scale inhibitors, dispersants, etc., but is preferably used as detergent additives and the like. Is preferable. A method of adding the (poly) alkylene glycol-containing compound of the present invention to a detergent and using it, and a method of using it as an additive for a detergent are also one of the present inventions. Furthermore, a method for producing a detergent, which comprises a step of mixing the (poly) alkylene glycol-containing compound of the present invention with other additives for detergent, is also one of the present inventions.
The additive for detergent is not particularly limited as long as it is an additive used for detergent, and examples thereof include a detergent builder. A detergent builder containing the (poly) alkylene glycol-containing compound of the present invention is also one of the present inventions.

<Detergent composition>
The present invention is also a detergent composition containing the (poly) alkylene glycol-containing compound of the present invention and a detergent additive other than the compound.
The detergent additive other than the (poly) alkylene glycol-containing compound is not particularly limited as long as it is an additive used in a surfactant or a normal detergent, and conventionally known findings in the detergent field can be appropriately referred to.
Further, the detergent composition may be a powder detergent composition or a liquid detergent composition.

The surfactant is preferably one or more selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants.

Examples of anionic surfactants include alkylbenzene sulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, α-olefin sulfonates, α-sulfo fatty acids or ester salts, and alkane sulfonates. , Saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acylamino acid type surfactant, alkyl phosphate ester or its salt, alkenyl phosphate ester or The salt or the like is suitable. Alkyl groups such as methyl groups may be branched into the alkyl groups and alkenyl groups in these anionic surfactants.

Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycolides, and fatty acid glycerin mono. Esters, alkylamine oxides and the like are suitable. Alkyl groups such as methyl groups may be branched into the alkyl groups and alkenyl groups in these nonionic surfactants.

As the cationic surfactant, a quaternary ammonium salt or the like is suitable. Further, as the amphoteric surfactant, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant and the like are suitable. Alkyl groups such as methyl groups may be branched in the alkyl groups and alkenyl groups of these cationic surfactants and amphoteric surfactants.

The blending ratio of the surfactant is usually 10 to 60% by mass, preferably 15 to 50% by mass, more preferably 20 to 45% by mass, and particularly preferably 20 to 45% by mass, based on the total amount of the detergent composition. Is 25 to 40% by mass. If the blending ratio of the surfactant is too small, sufficient detergency may not be exhibited, and if the blending ratio of the surfactant is too large, the economic efficiency may be lowered.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".

<Evaluation of detergency of complex stains (oil / protein / mud / carbon black)>
(1) The whiteness of a 5 cm × 5 cm wet artificially contaminated cloth (distributed by the Laundry Science Association) was measured in advance by the reflectance using a colorimetric color difference system SE6000 manufactured by Nippon Denshoku Kogyo Co., Ltd.
(2) Pure water was added to 7.34 g of calcium chloride dihydrate to make 20 kg, and hard water was prepared.
(3) 10 g of a 2% solid content aqueous solution of each evaluation sample was prepared in a 20 mL screw tube.
(4) As detergent components, 0.25 g of linear sodium alkylbenzene sulfonate (LAS), 0.25 g of polyoxyethylene lauryl ether (average number of moles of ethylene oxide added), 2 g of sodium sulfate, and 0.5 g of sodium carbonate are added to the beaker. Weighed.
(5) The beaker of (4) was added with the hard water of (2) to adjust the weight to 2 kg to prepare a cleaning solution.
(6) The turgot meter was set to 25 ° C., 500 mL of the cleaning solution of (5) and 1.0 mL of the sample aqueous solution of (3) were added to each pot, and the mixture was stirred at 100 rpm for 2 minutes. Then, 5 sheets of contaminated cloth and 14.6 g of cotton cloth (5 cm × 5 cm manufactured by Test fabrics) for adjusting the bath ratio were added, and the mixture was stirred at 100 rpm for 10 minutes. (As a reference, the one to which pure water was added instead of the sample aqueous solution of (3) was also evaluated.)
(7) The contaminated cloth was taken out from each pot, the water was drained by hand, 500 mL of the hard water of (2) was put into the pot, the temperature was adjusted to 25 ° C., and the mixture was stirred at 100 rpm for 4 minutes.
(8) The contaminated cloth was taken out from each pot, drained by hand, dried overnight at room temperature, and then the whiteness of the contaminated cloth was measured again by the reflectance with the above colorimetric color difference meter.
(9) Similar to (8), the whiteness of CW98 was measured by the reflectance as an uncontaminated cloth (hereinafter, also referred to as white cloth).
(10) From the above measurement results, the cleaning rate (detergency) was determined by the following formula, and the cleaning rate improvement rate was determined from the cleaning rate of the comparative sample.
Cleaning rate (%) = ((whiteness of contaminated cloth before cleaning)-(whiteness of contaminated cloth after cleaning)) / ((whiteness of contaminated cloth before cleaning)-(whiteness of white cloth)) × 100
Cleaning rate improvement rate (%) = (cleaning rate of the compound of the present invention-cleaning rate of the comparative compound (1)) / (cleaning rate of the comparative compound (1)) × 100
The larger the number, the better the cleaning effect than the comparative compound (1).

<Composite stain (clay-carbon black) recontamination prevention ability evaluation>
(1) A cotton cloth (manufactured by Test fabrics) was cut into a size of 5 cm × 5 cm to prepare a white cloth. The whiteness of this white cloth was measured in advance by the reflectance using a colorimetric color difference system SE6000 type manufactured by Nippon Denshoku Kogyo Co., Ltd.
(2) Pure water was added to 1.47 g of calcium chloride dihydrate to make 20 kg, and hard water was prepared.
(3) 10 g of a 1% solid content aqueous solution of each evaluation sample was prepared in a 20 mL screw tube.
(4) 100 g of a 4% linear alkylbenzene sulfonate sodium (LAS) aqueous solution was prepared and used as a surfactant aqueous solution.
(5) Set the turgot meter to 25 ° C., and put 1 L of hard water of (2), 5.0 g of the sample aqueous solution of (3), 5.0 g of the surfactant aqueous solution of (4), and carbon black (Mitsubishi carbon) in each pot. 0.25 g of black # 10) and 0.50 g of clay (1-11 kinds of powder for JIS test) were placed in a pot and stirred at 100 rpm for 1 minute. Then, 5 cotton cloths were put in and stirred at 100 rpm for 10 minutes. (As a reference, the one to which pure water was added instead of the sample aqueous solution of (3) was also evaluated.)
(6) Drain the water from the white cloth by hand, put 1 L of the hard water of (2) in a pot, adjust the temperature to 25 ° C., and stir at 100 rpm for 2 minutes.
(7) After applying a cloth to a white cloth and drying it while smoothing out wrinkles with an iron, the whiteness of the cotton cloth was measured again by the reflectance with the above colorimetric color difference meter.
(8) From the above measurement results, the recontamination prevention rate (recontamination prevention ability) was calculated by the following formula.
Recontamination prevention rate (%) = (whiteness after cleaning) / (whiteness before cleaning) x 100
The larger the value of the recontamination prevention rate, the better the recontamination prevention ability.

<Synthesis example 1>
In a glass four-necked eggplant flask reaction vessel with a capacity of 2 L equipped with a thermometer, a stirrer, and a reflux tube, 2-pyrrolidone (hereinafter, also referred to as 2Py) 297.89 g (3.50 mol), epichlorohydrin 971. 46 g (10.50 mol) was charged and heated to 45 ° C. with stirring with a stirrer. Then, while maintaining 50 ° C. or lower, 140.0 g (3.50 mL) of granular sodium hydroxide was added in 10 portions. Then, 21.0 g (0.53 mL) of granular sodium hydroxide was added in two portions, and the mixture was stirred for 1 hour while maintaining 50 ° C. Then, the reaction solution was allowed to cool to room temperature, and the salt produced was removed by suction filtration. Subsequently, residual epichlorohydrin was largely removed from the crude product obtained by evaporation. Then, the residual epichlorohydrin was completely removed by vacuum distillation to obtain a pyrrolidone compound having an epoxy ring (hereinafter, also referred to as pyrrolidone compound (1) or 2Py-ECH (ECH-2Py)).

<Example 1>
It was obtained by adding ethylene oxide corresponding to 20 mol per 1 mol of all active hydrogen of polyethyleneimine (average molecular weight 600) to a glass four-necked eggplant flask reaction vessel equipped with a thermometer, a stirrer and a nitrogen introduction tube. Polyethyleneimine Polyethylene oxide compound (hereinafter, also referred to as comparative compound (1)) 61.40 g (5.0 mmоl) and potassium hydroxide 0.39 g (7.0 mmol) as a catalyst were charged, and nitrogen was charged in the reaction vessel under stirring. The mixture was replaced, heated to 120 ° C. under a nitrogen atmosphere, and maintained at that temperature for 1 hour under normal pressure. Then, the temperature was lowered to 80 ° C., and 9.85 g (70 mmоl) of the pyrrolidone compound (1) obtained in Synthesis Example 1 was added to the reaction vessel at 0.1 mL / min with a syringe at that temperature for 4 hours under a nitrogen atmosphere. (Hereinafter, the crude product at this time is referred to as the crude product (1)). Then, ion-exchanged water was added and the mixture was stirred well. The obtained aqueous solution was transferred into a dialysis membrane having a molecular weight cut off of 10000, left overnight in ion-exchanged water, and the aqueous solution in the dialysis membrane was recovered to add ECH-Py to the comparative compound (1). The compound (1) of the present invention was obtained. The compound (1) of the present invention was a compound in which ECH-Py was added to all (100 mol%) of the hydroxyl groups at the ends of the comparative compound (1).

<Example 2>
In a glass reaction vessel equipped with a thermometer, a stirrer and a nitrogen introduction tube, 12.28 g (1.0 mmоl) of the comparative compound (1) and 0.0056 g (0.1 mmol) of potassium hydroxide as a catalyst were charged and stirred. The inside of the reaction vessel was replaced with nitrogen, heated to 155 ° C. under a nitrogen atmosphere, and kept at that temperature for 1 hour under normal pressure. Then, 1.58 g (1.1 mmоl) of the pyrrolidone compound (1) obtained in Synthesis Example 1 was added to the reaction vessel at 0.1 mL / min with a syringe, and the temperature was maintained for 6 hours under a nitrogen atmosphere. Then, ion-exchanged water was added and the mixture was stirred well. The obtained aqueous solution was transferred into a dialysis membrane having a molecular weight cut off of 8000, left overnight in ion-exchanged water, and the aqueous solution in the dialysis membrane was recovered to add ECH-Py to the comparative compound (1). The compound (2) of the present invention was obtained. The compound (2) of the present invention was a compound in which ECH-Py was added to 80 mol% of the hydroxyl group at the terminal of the comparative compound (1).

<Example 3>
8.54 g of the crude product (1) obtained in Example 1 was charged in a glass reaction vessel equipped with a thermometer, a stirrer and a nitrogen introduction tube, heated to 60 ° C. under stirring and a nitrogen atmosphere, and butyl. 0.87 g (6.7 mmоl) of glycidyl ether was added. Then, it heated to 80 degreeC in a nitrogen atmosphere and kept the temperature for 5 hours. Ion-exchanged water was added and the mixture was stirred well. The obtained aqueous solution was transferred into a dialysis membrane having a molecular weight cut off of 8000, left overnight in ion-exchanged water, and the aqueous solution in the dialysis membrane was recovered to obtain the compound (3) of the present invention. The compound (3) of the present invention was a compound in which butyl glycidyl ether was added to 80 mol% of the hydroxyl groups derived from ECH-Py of the compound (1) of the present invention.

<Example 4>
9.97 g of the crude product (1) obtained in Example 1 was charged in a glass reaction vessel equipped with a thermometer, a stirrer and a nitrogen introduction tube, heated to 60 ° C. under stirring and a nitrogen atmosphere, and butyl. 1.27 g (9.8 mmоl) of glycidyl ether was added. Then, it heated to 80 degreeC in a nitrogen atmosphere and kept the temperature for 5 hours. Ion-exchanged water was added and the mixture was stirred well. The obtained aqueous solution was transferred into a dialysis membrane having a molecular weight cut off of 8000, left overnight in ion-exchanged water, and the aqueous solution in the dialysis membrane was recovered to obtain the compound (4) of the present invention. The compound (4) of the present invention was a compound in which butyl glycidyl ether was added to all (100 mol%) of the hydroxyl groups derived from ECH-Py of the compound (1) of the present invention.

<Example 5>
In a glass reaction vessel equipped with a thermometer, a stirrer and a nitrogen introduction tube, 5.00 g (0.34 mmol) of the compound (1) of the present invention obtained in Example 1 was charged under stirring and in a nitrogen atmosphere. Further, 5.0 g of tetrahydrofuran was added to dissolve the compound (1) of the present invention. Then, 0.06 g of sodium hydride was further added to the solution of the compound (1) of the present invention, the mixture was stirred at room temperature for 30 minutes, and the temperature was raised to 65 ° C., Denacol EX-192 (manufactured by Nagase Chemtech Co., Ltd.). 1.20 g (4.70 mmol) of a glycidyl ether mixture of an alcohol having 11-15 carbon atoms was added, and the reaction was continued at 65 ° C. for 30 hours. After completion of the reaction, tetrahydrofuran was distilled off at 60 ° C. under reduced pressure to obtain compound (5) of the present invention. The compound (5) of the present invention was a compound in which glycidyl ether of an alcohol having 11-15 carbon atoms was added to all (100 mol%) of the hydroxyl groups derived from ECH-Py of the compound (1) of the present invention.

The detergency of composite stains was evaluated for the compounds (1), (3) to (5) of the present invention obtained in Examples 1, 3 to 5 and the comparative compound (1) as Comparative Example 1. The results are shown in Table 1.

Claims (18)

1. A (poly) alkylene glycol-containing compound having a structure (A) having an alkylene group and two or more nitrogen atoms, a (poly) alkylene glycol structure (B), and a lactam ring-containing structure (C). ..
2. The structure (A) having the alkylene group and two or more nitrogen atoms has the following formulas (1) and / or (2);
   

   

   (In the formulas (1) and (2), R ¹ represents the same or different alkylene group having 2 to 6 carbon atoms. * Indicates a nitrogen atom in the (poly) alkylene glycol-containing compound to which the nitrogen atom is bonded. In the formula (1), m1 represents a number of 2 or more. In the formula (2), m2 represents a number of 1 or more). The (poly) alkylene glycol-containing compound according to claim 1.
3. The (poly) according to claim 2, wherein the (poly) alkylene glycol-containing compound has an oxyalkylene group bonded to at least one nitrogen atom in the formulas (1) and / or (2). An alkylene glycol-containing compound.
4. In the (poly) alkylene glycol-containing compound, the oxygen atom at the terminal of the alkylene glycol structure (B) and the nitrogen atom of the lactam ring structure may have a hetero atom via a hydrocarbon group having 1 to 50 carbon atoms. The (poly) alkylene glycol-containing compound according to claim 2 or 3, wherein the compound is bonded to the compound.
5. The (poly) alkylene glycol-containing compound according to any one of claims 1 to 4, wherein the lactam ring is a pyrrolidone ring.
6. The (poly) alkylene glycol-containing compound has the following formula (3);
   

   

   (In the formula, R ¹ represents the same or different alkylene group having 2 to 6 carbon atoms. R ² represents the same or different alkylene group having 2 to 20 carbon atoms. R ³ represents a hetero. It represents a divalent hydrocarbon group having 1 to 50 carbon atoms, which may have an atom. N represents a number of 1 to 100. K represents a number of 1 to 3). The (poly) alkylene glycol-containing compound according to any one of claims 1 to 5, which has a structure such as
7. The sixth aspect of claim 6 is characterized in that R ³ has a branched chain, and the branched chain is a hydrocarbon group having 1 to 49 carbon atoms, which may have a hetero atom. ) Hydrocarbon-containing compound.
8. Wherein ^{R 3} is represented by the following formula (4);
   

   

   (In the formula, R ⁴ represents a hydrocarbon group having 1 to 47 carbon atoms which may have a hydrogen atom or a hetero atom. R ⁵ represents an alkylene group having 2 to 20 carbon atoms. The (poly) alkylene glycol-containing compound according to claim 6 or 7, wherein p is a divalent group represented by (0 to 20).
9. Claim 1 is characterized in that the content ratio of the structure (A) having the alkylene group and two or more nitrogen atoms is 1 to 60% by mass with respect to 100% by mass of the (poly) alkylene glycol-containing compound. The (poly) alkylene glycol-containing compound according to any one of 8 to 8.
10. The content ratio of the (poly) alkylene glycol structure (B) is 30 to 98% by mass with respect to 100% by mass of the (poly) alkylene glycol-containing compound, according to any one of claims 1 to 9. The (poly) alkylene glycol-containing compound described.
11. The content of any of claims 1 to 10, wherein the content ratio of the lactam ring-containing structure (C) is 1 to 60% by mass with respect to 100% by mass of the (poly) alkylene glycol-containing compound. (Poly) alkylene glycol-containing compound.
12. The content ratio of the lactam ring-containing structure (C) is 1 with respect to a total of 100 mol% of the nitrogen atom having active hydrogen in the structure (A) and the nitrogen atom of the structure (A) to which the structure (B) is bonded. The (poly) alkylene glycol-containing compound according to any one of claims 1 to 11, which is characterized in that it is in an amount of about 50 mol%.
13. Any one of claims 1 to 12, wherein the content ratio of the lactam ring-containing structure (C) is 10 to 100 mol% with respect to 100 mol% of oxygen atoms at the terminal of the structure (B). (Poly) alkylene glycol-containing compound according to.
14. The (poly) alkylene glycol-containing compound may have a structure (D) containing an organic group in addition to the structures (A) to (C), and the content ratio of the structure (D) containing the organic group is The (poly) alkylene glycol-containing compound according to any one of claims 1 to 13, wherein the content is 0 to 60% by mass with respect to 100% by mass of the (poly) alkylene glycol-containing compound.
15. The (poly) alkylene glycol-containing compound may have a structure (E) other than the structures (A) to (D), and the content ratio of the other structure (E) is (poly) alkylene. The (poly) alkylene glycol-containing compound according to any one of claims 1 to 14, wherein the content is 0 to 30% by mass with respect to 100% by mass of the glycol-containing compound.
16. The (poly) alkylene glycol-containing compound according to any one of claims 1 to 15, wherein the (poly) alkylene glycol-containing compound has a number average molecular weight of 1000 to 500,000.
17. An additive for a detergent, which comprises the (poly) alkylene glycol-containing compound according to any one of claims 1 to 16.
18. A detergent composition comprising the (poly) alkylene glycol-containing compound according to any one of claims 1 to 16 and a detergent additive other than the compound.