JP2002179743A - Detergent additive and detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent additive having characteristic of a lactam structure-containing polymer such as excellent preventing ability to re-staining and color transferring, and comprising a polymer enhancing washability. SOLUTION: This detergent additive comprises as indispensable components a lactam structure-containing polymer composed of 1 to 55 mol% of hydroxyalkyl(meth)acrylate (monomer A), 30 to 99 mol% of a lactam structure- containing unsaturated monomer (monomer B) and 0 to 50 mol% of a known unsaturated polymer (monomer C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a detergent additive and a detergent composition containing an N-vinyl cyclic lactam polymer having high detergency.

[0002]

2. Description of the Related Art A lactam structure-containing polymer, which is an essential component of the present invention, has been known in the art, for example, see the Chemical Society of Japan, 1977 (1), p. 93-98 and the Chemical Society of Japan, 1977 (7), p. From 1035 to 1040, N
-Vinylpyrrolidone / 2-hydroxyethyl methacrylate random copolymer and the like are known. Meanwhile, US
From 4,655,957, N-vinylpyrrolidone / 2-
Although it is disclosed that particles composed of hydroxyethyl methacrylate / ethylene glycol dimethyl acrylate are useful for contact lenses and body cleansing agents,
Since these polymers are crosslinked, and furthermore the composition ratio of N-vinylpyrrolidone is not sufficient, they are poor in water solubility and adsorptive power, and there is a practical problem in application to a detergent for clothes. Furthermore, since the lactam structure-containing polymer represented by polyvinylpyrrolidone has an excellent ability to prevent re-contamination and color transfer, it is a useful detergent additive from US 3,000,830 and CA994635, respectively. Are known. However, these polymers have a problem that they have poor detergency.

[0003]

Accordingly, an object of the present invention is to provide a polymer having a lactam structure, such as an excellent ability to prevent re-contamination and a color transfer, and to improve detergency. To provide a detergent additive comprising a polymer.

[0004]

Means for Solving the Problems The present inventor has studied to solve the above problems. As a result, they have found that a polymer in which a hydroxyalkyl (meth) acrylate moiety having a specific composition ratio has been introduced into a lactam structure-containing polymer has a high ability to prevent re-contamination and color transfer and has a good detergency. Thus, the present invention has been completed.

[0005] That is, the present invention relates to a structural unit (I) 1 derived from a hydroxyalkyl (meth) acrylate monomer (A).
To 55 mol%, 30 to 99 mol% of a structural unit (II) derived from a lactam structure-containing unsaturated monomer (B), and 0 to 5 of a structural unit (III) derived from another unsaturated monomer (C).
0 mol% (provided that the structural unit (I) and the structural unit (I
The sum of I) and the structural unit (III) is 100 mol
% Of a lactam structure-containing polymer as an essential component.

Further, the production method of the present invention is characterized in that a hydroxyalkyl (meth) acrylate monomer (A)
%, Lactam structure-containing unsaturated monomer (B) 30 to 99 mol
1%, and 0 to 50 mol% of other unsaturated monomer (C)
(However, the monomer component consisting of the monomer (A), the monomer (B), and the monomer (C) is 100 mol%) is polymerized in the presence of a radical initiator to form a lactam. The present invention relates to a method for producing a lactam structure-containing polymer for a detergent additive, which comprises obtaining a structure-containing polymer.

Another process of the present invention relates to a process for producing a lactam structure-containing polymer for a detergent additive, comprising the following steps (I) and (II). (I) Lactam structure-containing unsaturated monomer (B) 30 to 9
9 mol%, and 0 to 50 m of other unsaturated monomers (C)
(II) The polymer obtained in the step (I) is further added to the hydroxyalkyl (meth) acrylate monomer (A) 1-55.
mol%, and 0 to 50 mol of another unsaturated monomer (C)
% Of the monomer (A), the monomer (B), the monomer (C) used in the step (I), and the monomer (C) used in the step (II). Total is 100mo
1%) of the detergent composition of the present invention comprises: a) a structural unit (I) derived from a hydroxyalkyl (meth) acrylate monomer (A), and a structural unit derived from a lactam structure-containing unsaturated monomer (B). A lactam structure-containing polymer comprising (II) and a structural unit (III) derived from another unsaturated monomer (C), b) an anionic or nonionic surfactant, and c) a carboxylic acid group-containing polymer Is a detergent composition comprising as an essential component. The carboxylic acid group-containing polymer (c) preferably has a weight average molecular weight of 2,000 to 70,000.

[0008]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described below in detail.

The lactam structure-containing polymer which is an essential component of the detergent additive of the present invention is a hydroxyalkyl (meth)
Structural unit (I) 1 to 5 derived from acrylate monomer (A)
5 mol%, 30 to 99 mol% of a structural unit (II) derived from a lactam structure-containing unsaturated monomer (B), and 0 to 50 mol of a structural unit (III) derived from another unsaturated monomer (C)
1% (provided that the total of the structural units (I), (II), and (III) is 100 mol%).

The hydroxyalkyl (meth) acrylate monomer (A) used in the lactam structure-containing polymer of the present invention comprises (meth) acrylate structure and an alkyl group having 1 to 20 carbon atoms and 1 to 3 hydroxyl groups. And a compound having a hydroxyalkyl structure bonded with, for example, 2-hydroxyethyl acrylate, 2-acrylate acrylate as a specific compound having such a structure.
Hydroxypropyl, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate are used, and 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferably used.

It is important that the composition ratio of the structural unit (I) derived from the hydroxyalkyl (meth) acrylate monomer (A) in the lactam structure-containing polymer is 1 to 55 mol%, preferably 1 to 35 mol%. And more preferably 5 to 30%. When it is 55 mol% or more, the ability to prevent dye transfer tends to decrease. If the amount is less than 1 mol%, the detergency of a detergent containing a detergent additive containing the lactam structure-containing polymer of the present invention as an essential component tends to decrease.

The lactam structure-containing unsaturated monomer (B) used in the lactam structure-containing polymer of the present invention may be any one having at least an N-vinyl cyclic lactam unit. For example, N-vinylpyrrolidone And N-
Vinyl caprolactam can be used.

It is important that the composition ratio of the structural unit (II) derived from the lactam structure-containing unsaturated monomer (B) in the lactam structure-containing polymer is from 30 to 99 mol%, preferably from 60 to 99 mol%. Yes, more preferably 7
0 to 95 mol%. When the amount is 30 mol% or less, the ability to prevent dye transfer tends to decrease, and when the amount is 99 mol% or more, the detergency of a detergent containing a detergent additive containing the lactam structure-containing polymer of the present invention as an essential component tends to decrease. .

The other unsaturated polymer (C) used in the lactam structure-containing polymer of the present invention may be a lactam structure-containing unsaturated monomer (B) or a hydroxyalkyl (meth) acrylate monomer (A ) May be used as long as it is copolymerizable with, for example, vinyl acetate, (meth) acrylic acid ester, (meth) acrylic acid, maleic acid ester,
Maleic acid, acrylonitrile, styrene, alkyl vinyl ether, N-vinyl imidazole, vinyl pyridine, allyl alcohol, olefins, (meth) acrylamide, and (meth) acrylamide glycolic acid. In addition, as said ester, C1-C20 alkyl ester, aminoalkyl ester, etc. are mentioned. One or two or more of these monomers can be used.

The composition ratio of the structural unit (III) derived from the other unsaturated monomer (C) in the lactam structure-containing polymer can be 0 to 50 mol%. 50
If it is at least mol%, the ability of the detergent containing the detergent additive containing the lactam structure-containing polymer of the present invention as an essential component will tend to reduce the ability to prevent dye transfer.

The lactam structure-containing polymer of the present invention is prepared so that the composition ratio of the structural units (I), (II) and (III) in the polymer falls within the above range. The composition can be obtained by adjusting the composition of A), the lactam structure-containing unsaturated monomer (B), and the other unsaturated monomer (C), and polymerizing in the presence of a radical polymerization initiator. The lactam structure-containing polymer is preferably the following polymer. 1) A hydroxyalkyl (meth) acrylate monomer (A) and a lactam structure-containing unsaturated monomer (B) are essential monomers, and if necessary, a known unsaturated monomer (C)
Obtained by random copolymerization of a polymer in the presence of a radical polymerization catalyst. 2) A lactam structure-containing unsaturated monomer (B) is used as an essential monomer in advance, and a known unsaturated polymer (C) is used as required.
Are randomly copolymerized in the presence of a radical polymerization catalyst, and the obtained polymer is made to contain a hydroxyalkyl (meth) acrylate monomer (A) as an essential monomer, and if necessary, a known unsaturated monomer (C). Is graft-polymerized in the presence of a radical polymerization catalyst.

That is, the production method of the present invention, which can obtain the above-mentioned lactam structure-containing polymer, comprises 1 to 55 mol% of a hydroxyalkyl (meth) acrylate monomer (A),
Lactam structure-containing unsaturated monomer (B) 30 to 99 mol
% And other unsaturated monomer (C) 0 to 50 mol%
(However, the monomer component consisting of the monomer (A), the monomer (B), and the monomer (C) is 100 mol%) is polymerized in the presence of a radical initiator to form a lactam. A method for producing a lactam structure-containing polymer for a detergent additive, comprising obtaining a structure-containing polymer.

Further, another production method of the present invention capable of obtaining the lactam structure-containing polymer is as follows: 30 to 99 mol% of the lactam structure-containing unsaturated monomer (B), and the other unsaturated monomer. (C) In the step (I) of preliminarily polymerizing 0 to 50 mol%, and in the polymer obtained in the step (I),
Step (II) of graft-polymerizing 1 to 55 mol% of a hydroxyalkyl (meth) acrylate monomer (A) and 0 to 50 mol% of another unsaturated monomer (C)
(However, monomer (A), monomer (B), monomer (C) used in step (I), and monomer (C) used in step (II) Is 100mol
%) Is a method for producing a lactam structure-containing polymer for a detergent additive. The lactam structure-containing polymer may be obtained by any known polymerization method as long as it is in the presence of a radical initiator. The radical initiator is not particularly limited as long as a radical is generated by heating or the like.However, when the lactam structure-containing unsaturated monomer is a graft polymer, a peroxide is used from the viewpoint of graft efficiency. Physical initiators are more preferred. As the peroxide initiator, specifically, for example, ammonium persulfate, sodium persulfate, persulfates such as potassium persulfate; hydrogen peroxide; methyl ethyl ketone peroxide, ketone peroxides such as cyclohexanone peroxide; t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,1
Hydroperoxides such as 3,3, -tetramethylbutyl hydroperoxide; di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α'-bis (t-butylperoxy ) Dialkyl peroxides such as p-diisopropylhexine; t-butylperoxyacetate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5
-Dimethyl-2,5-di (benzoylperoxy) hexane, peroxyesters such as t-butylperoxyisopropylcarbonate; n-butyl-4,4-bis (t-butylperoxy) valeate; Peroxy ketals such as 2-bis (t-butylperoxy) butane; diacyl peroxides such as dibenzoyl peroxide; and the like. These initiators may be used alone or 2
More than one species may be used in combination. Further, a redox system using the peroxide initiator and the reducing agent together may be used. Specific examples of the reducing agent include iron (II) salt, sodium dithionite, sodium bisulfite, sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, and ascorbic acid. In the present invention, an azo-based initiator can be used, but when the lactam structure-containing unsaturated monomer of the present invention is a graft polymer, the graft efficiency is higher than that of a peroxide-based initiator. In view of the above, the performance is slightly inferior, so that it is preferable to use it in combination with a peroxide initiator. Preferred azo initiators include, for example, 2-cyano-2-propylazoformamide, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-amidinopropane) dihydrochloride, , 2'-Azobis (2-
Methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-
2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis [2- (5-methyl-2-
Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazoline-2-
Yl) propane] dihydrochloride, 2,2′-azobis (2-methylpropionamidoxime), 2,2′-azobis [2
-(2-imidazolin-2-yl) propane], 2,2 '
-Azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] pyrropionamide}, 2,2′-azobis (N-butyl-2-methylpropionamide) and the like. . The amount of the radical initiator used is not particularly limited, but is preferably 0.01 to 1 based on the monomer component.
00 mol% is preferable, and 0.05 to 20 mol% is more preferable.

The method of adding the initiator is not particularly limited. For example, a method of initial batch charging,
Alternatively, a method of successive addition may be mentioned, but in consideration of the reduction of the residual monomer, the sequential addition is preferred.

The method of the polymerization reaction of the lactam structure-containing polymer is not particularly limited. For example, it can be carried out by a conventionally known polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization and precipitation polymerization. Solution polymerization is particularly preferred.

In the polymerization, the reaction temperature is not particularly limited, but is, for example, 0 to 200 ° C., preferably 50 to 150 ° C.

When the lactam structure-containing polymer is the above-mentioned graft polymer, it is preferable to carry out the polymerization according to the following procedure.

1) Lactam structure-containing unsaturated monomer (B)
Is homopolymerized in the presence of a radical polymerization initiator or, if desired, is copolymerized with a lactam structure-containing unsaturated monomer (B) and another unsaturated monomer (C) in the presence of a radical polymerization catalyst. To obtain a basic polymer in advance.

2) During or after the polymerization of the base polymer, the hydroxyalkyl (meth) acrylate monomer (A) or the hydroxyalkyl (meth) acrylate monomer (A) and the other unsaturated monomer (C) Is added to the polymerization system, and graft polymerization is performed in the presence of a radical polymerization initiator. Here, the graft polymerization may be performed as it is in the polymerization system of step 1), or may be performed after isolating the base polymer from the polymerization system of step 1). The basic polymer may be initially charged in a batch or may be added sequentially. However, in consideration of shortening of reaction time, productivity and the like, it is preferable to use the initial batch charging. On the other hand, the hydroxyalkyl (meth) acrylate monomer (A) is preferably added sequentially in consideration of grafting efficiency and reaction control, but is not limited to this. Can also. Further, the hydroxyalkyl (meth) acrylate monomer (A) may be added after diluting with a solvent. Other monomer (C) used in step 1) above
And the other monomer (C) used in step 2) may be of the same type or different. N-vinylpyrrolidone and N-
Homopolymers or copolymers obtained by polymerizing or copolymerizing vinyl caprolactam are exemplified. As such a homopolymer, specifically, polyvinylpyrrolidone having a weight average molecular weight of 1,000 to 2,500,000 or polyvinylcaprolactam having a weight average molecular weight of 5,000 to 500,000 is preferable. As the copolymer, specifically, N-vinylpyrrolidone or N-vinylcaprolactam, for example, vinyl acetate, (meth) acrylic acid ester, (meth) acrylic acid, maleic acid ester, maleic acid, acrylonitrile, styrene, Alkyl vinyl ether, N-vinyl imidazole, vinyl pyridine, allyl alcohol, olefins, (meth) acrylamide, (meth) copolymer obtained by copolymerization with acrylamide glycolic acid and the like, particularly,
A copolymer obtained by copolymerizing N-vinylpyrrolidone or N-vinylcaprolactam with vinyl acetate is preferred. In addition, as said ester, C1-C20 alkyl ester, aminoalkyl ester, etc. are mentioned. Such a base polymer may be used alone or in combination of two or more.

When the lactam structure-containing polymer is the above graft polymer, it is important that the composition ratio of the lactam structure-containing unsaturated monomer (B) in the base polymer be at least 31 mol%, and the polymer having at least 60 mol% Is more preferable, and most preferably 100 mo
1%. When the composition ratio of the lactam structure-containing unsaturated monomer (B) in the base polymer is less than 31 mol%, the ability of the detergent containing the lactam structure-containing polymer of the present invention containing a detergent additive to decrease the dye transfer-preventing ability is reduced. There is a tendency. The pressure during the synthesis of the lactam structure-containing polymer is not particularly limited, for example, under normal pressure, under reduced pressure,
The reaction may be performed under any pressure. In particular, it is preferable to carry out the reaction while boiling the solvent under normal pressure or reduced pressure, because heat can be effectively removed and the reaction can be easily controlled.
The synthesis of the lactam structure-containing polymer is preferably performed, for example, in an atmosphere of an inert gas such as nitrogen gas, argon gas, or carbon dioxide gas, but is not limited thereto.

The solvent used for the synthesis of the lactam structure-containing polymer is not particularly limited as long as the base polymer having an N-vinyl cyclic lactam unit can be dissolved. Examples thereof include water; alcohols; ethers; Esters; amides; sulfoxides; hydrocarbons; Among these, water, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, t-butyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, acetone, methyl ethyl ketone, tetrahydrofuran, 1,4-dioxane,
1,3-Dioxolan, toluene, ethyl acetate, and a mixed solvent thereof are preferred, and water is particularly preferred. In these solvents, organic amines or ammonia, sodium hydroxide, potassium hydroxide, hydrochloric acid, boric acid, phosphoric acid, acetic acid, carbonic acid, salts thereof, and the like may be added for the purpose of controlling pH. For example, it can be controlled to PH3 to 13. In a solvent containing water, an alkali metal hydroxide can also be used.

When the lactam structure-containing polymer is the above graft polymer, the amount of the solvent used in the polymerization is
It is important to adjust the concentration of the base polymer to be 10% by weight or more. In the case of emulsion polymerization or suspension polymerization, it is necessary to adjust the concentration of the base polymer in the phase in which the base polymer is dissolved to be 10% by weight or more. As described above, by performing the polymerization in a solution in which the concentration of the base polymer is 10% by weight or more, the graft efficiency can be improved and the by-product of the impurity polymer can be suppressed. Specifically, the solvent is used in an amount of 5 to 900 parts by weight, preferably 25 to 400 parts by weight, based on 100 parts by weight of the base polymer. Note that the solvent may be added all at once or may be added sequentially.

The preferred molecular weight of the lactam structure-containing polymer is from 500 to 3, in terms of weight average molecular weight (hereinafter referred to as Mw).
00000, most preferably Mw 1000-
200,000. When it is less than Mw 1000, the ability to prevent dye transfer tends to decrease, and Mw 200,00
If it is 0 or more, it may be difficult to handle as a detergent additive.

The detergent additive of the present invention can be used as it is as a detergent composition. However, as a detergent composition comprising b) an anionic or nonionic surfactant and c) a carboxylic acid group-containing polymer as essential components. It is preferred to use.

That is, the detergent composition of the present invention comprises (a) a structural unit (I) derived from a hydroxyalkyl (meth) acrylate monomer (A) and a structural unit derived from a lactam structure-containing unsaturated monomer (B). A lactam structure-containing polymer comprising units (II) and structural units (III) derived from another unsaturated monomer (C); (b) an anionic or nonionic surfactant (c) containing a carboxylic acid group A detergent composition comprising a polymer as an essential component.

The lactam structure-containing polymer used in the above a) is a structural unit (I) derived from a hydroxyalkyl (meth) acrylate monomer (A) or a structural unit derived from a lactam structure-containing unsaturated monomer (B). It is necessary to be a structural unit (III) derived from (II) and another unsaturated monomer (C), and preferably the lactam structure-containing polymer of the present invention.

As the (b) anionic or nonionic surfactant contained in the detergent composition, examples of the anionic surfactant include sodium and potassium higher fatty acids having 8 to 24 carbon atoms. And alkali metal soaps such as ammonium and alkylol ammonium salts, particularly useful are coconut oil sodium, coconut oil potassium and the like. Other preferred anionic surfactants include water-soluble salts of organic sulfuric acid reaction products having alkyl groups having from 10 to 20 carbon atoms, and sulfonic or sulfate groups, preferably alkali metals, ammonium or alkyl. Roll ammonium salts. Particularly useful are the sodium or potassium alkyl benzene sulfonates wherein the alkyl group has about 9 to 15 carbon atoms in a linear or branched configuration, wherein the average number of carbon atoms in the alkyl group is from about 11 to 1 carbon atoms.
C ₁₁ having a linear alkyl group having 3 to ₁₃ intended to be abbreviated as LAS.

Preferred nonionic surfactants are, for example, condensation products of alcohols having 12 to 15 carbon atoms with about 5 to 50 moles of ethylene oxide per mole of alcohol;
Alternatively, polyhydroxysulfuric amides such as N-methyl N-1-deoxyglucityl cocoamide and the like can be mentioned, and these can be used alone or in combination of two or more.

The detergent composition of the present invention may contain a generally known zwitterionic, amphoteric or cationic surfactant.

When these surfactants are contained, their proportion in the detergent composition of the present invention is preferably from 1 to 70% by weight, particularly preferably from 15 to 60% by weight. Further, the ratio of the surfactant to the lactam structure-containing polymer is preferably 0.01 to 700 parts, more preferably 0.1 to 1 part, per part of the lactam structure-containing polymer.
More preferably, it is 50 parts.

The (c) carboxylic acid group-containing polymer contained in the detergent composition includes (meth) acrylic acid,
One or more monomers selected from fumaric acid, maleic acid, itaconic acid, acrylamide glycolic acid, and their alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts were polymerized in the presence of a radical initiator. Polymers. These polymers are preferably any of homopolymers, random copolymers, block copolymers, and graft copolymers. Also,
The molecular weight of the carboxylic acid group-containing polymer is preferably from 2,000 to 70,000. When such a carboxylic acid group-containing polymer is contained, its proportion in the cleaning composition of the present invention is preferably 0.1 to 80% by weight, particularly preferably, the cleaning composition of the present invention is supplied in a liquid state. 1 to 10% by weight, when supplied in granular form,
５０50% by weight. It is also possible to use a detergent composition containing only a) and b) as essential components.

The detergent composition of the present invention may contain a generally known inorganic builder.

Examples of the inorganic builder include silicates, aluminosilicates, borates and carbonates. Particularly preferred are aluminosilicates such as sodium and potassium carbonates, bicarbonates and silicates and zeolites. Acid salt.

The cleaning composition of the present invention may contain 0.1 to 10% by weight of a generally known color transfer inhibitor.
Preferred examples include polyvinylpyrrolidone, polyvinylimidazole, polyvinylpyridine N-oxide and the like having a molecular weight of 1,000 to 2,000,000.

The cleaning composition of the present invention may further comprise a generally known fluorescent brightener, a foaming agent, a foam inhibitor, a corrosion inhibitor, a rust inhibitor, a soil suspending agent, a soil releasing agent, and a pH control. Agents, bactericides, chelating agents, viscosity modifiers, enzymes, enzyme stabilizers, fragrances, fiber softeners, peroxides, may contain conventionally known additives such as peroxide stabilizers, preferably 0.005% by weight
~ 10% by weight is added.

The cleaning composition of the present invention may further contain a generally known solvent in addition to the above-mentioned N-vinyl cyclic lactam-based graft polymer, and water, alcohols such as ethanol, isopropanol and ethylene. Glycol, propylene glycol, alkanolamines such as monoethanolamine, esters such as ethyl acetate, methyl glycolate, ketones such as acetone, etc.

[0042] The cleaning composition of the present invention can be in the form of a liquid, a paste, or a granule.

The detergent additive and the detergent composition of the present invention comprise:
It is preferably used for washing fibers, cloths and clothing, but is also used for washing metals, plastics, ceramics, wood, hair, skin, nails and the like.

[0044]

EXAMPLES [Production Example 1-1] In a 200 ml separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube,
Distilled water (77.3 g) was charged, the inside of the flask was replaced with nitrogen, and the temperature was adjusted to 80 ° C. 5.2 g of 2-hydroxyethyl methacrylate, vinylpyrrolidone 1
7.8 g of the mixture was fed over 2 hours, during which 4.5 wt% of V-50 (2,2-azobis (2-amidinopropane) dihydrochloride, manufactured by Wako Pure Chemical Industries, Ltd.) as an initiator. 12 g of a 10% aqueous solution was added in 10 portions. After completion of the mixed drop, aging was continued for 2 hours. During this time, V
6 g of a 4.5% by weight aqueous solution of -50 (2,2-azobis (2-amidinopropane) dihydrochloride, manufactured by Wako Pure Chemical Industries, Ltd.)
Was added in two portions. After the reaction, the residual monomer in the reaction solution was analyzed by liquid chromatography, and it was found that N-vinylpyrrolidone 10 p
pm, 0 ppm of 2-hydroxyethyl methacrylate,
It was 630 ppm of 2-pyrrolidone as a by-product.
When the molecular weight of the obtained copolymer was measured by gel permeation chromatography, Mw = 3.
It was 0,400 (polyethylene glycol conversion).
The obtained reaction liquid was designated as detergent additive 1. [Production Example 1-2] In a 200 ml separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser, 33.3 g of polyvinylpyrrolidone K-15 (manufactured by Tokyo Chemical Industry) and 33.3 g of distilled water were charged, and the inside of the flask was charged. Was replaced with nitrogen, and then dissolved by stirring to obtain a uniform solution. Thereafter, the temperature was raised until the temperature inside the flask reached 85 ° C. Then, into this flask, 45.2 g (0.128 mol) of a 37% by weight aqueous solution of 2-hydroxyethyl methacrylate was dropped over 90 minutes, and at the same time, 6.3 ammonium persulfate was used as an initiator.
23.4 g (6.4 mmol) of a weight% aqueous solution were added in 15 portions over a period of 90 minutes. After dropping of 2-hydroxyethyl methacrylate, aging was continued for 2 hours. During this period, 4.7 (1.3 mmol) of a 6.3% by weight aqueous solution of ammonium persulfate was further added in two portions. After the reaction, the residual amount of the 2-hydroxyethyl methacrylate monomer in the reaction solution was analyzed by liquid chromatography, and was found to be 0.1% by weight or less based on the amount of the 2-hydroxyethyl methacrylate added dropwise. The molecular weight of the thus obtained graft copolymer was measured and found to be Mw = 24,500 (in terms of polyethylene glycol). The obtained reaction liquid was designated as detergent additive 2. [Production Example 3] A detergent composition of the present invention was prepared with the following composition.

[0045]

[Table 1]

The ability of the detergent compositions 1 to 3 of the present invention to prevent dye transfer was evaluated in the following manner.

<Dye Transfer Prevention Ability> A cotton test cloth obtained from the Laundry Science Association was 5 cm ×
The pieces were cut into 5 cm pieces to make 10 white cloths. The whiteness (Z value) of each white cloth is measured in advance by a colorimetric colorimeter (Nippon Denshoku Industries Co., Ltd., N
D-1001DP type) and the average value was taken as (A0). When measuring the whiteness, the remaining nine sheets were superimposed on the cloth to be measured (on the surface opposite to the measurement surface), and the measurement was performed.

Pure water was added to 4.41 g of calcium chloride dihydrate to make 15 kg and hard water was prepared. Hard water and tap water for rinsing were placed in a thermostat at 25 ° C.

The turgot meter was set at 60 ° C., and 500 mL of hard water and 10 white cloths were added and stirred at 100 rpm for 1 minute.

7.7% aqueous 5% by weight sodium carbonate solution
g, zeolite 0.7 g, and the detergent composition of the present invention 7.0 g.
(However, 10.5 g of the detergent composition 2) was put in a pot and stirred at 100 rpm for 1 minute.

Dye (Direct Fast Red 3B,
4 g of a 0.125% by weight aqueous solution of (Tokyo Kasei) is placed in a pot and stirred for 30 minutes.

The water on the white cloth was drained by hand, and 500 mL of tap water heated to 60 ° C. was put into a pot and stirred at 100 rpm for 2 minutes. This was done twice.

Apply a patch to each of the ten white cloths,
After drying while stretching wrinkles with an iron, the whiteness (Z value) of each white cloth was measured by reflectance using the above colorimetric colorimeter, and the average value was defined as (A1).

From (A1) and (A0) obtained as described above, the following formula is used.

Color transfer prevention ability (%) = (A1) / (A0) × 100 The color transfer prevention ability was evaluated. That is, the higher the numerical value, the better the color transfer prevention ability.

The detergency of the detergent compositions 1 to 3 of the present invention was evaluated in the following manner.

<Detergency Test> A cotton test cloth obtained from the Laundry Science Association was 5 cm ×
The pieces were cut into 5 cm pieces to make five white cloths. In addition, wet artificially stained cloth was also obtained from the Laundry Science Association. The whiteness (Z value) of the wet artificially stained cloth was measured in advance using a colorimetric color difference meter (ND-1001DP, manufactured by Nippon Denshoku Industries Co., Ltd.), and the average value was defined as (A0). did.

Pure water was added to 4.41 g of calcium chloride dihydrate to make 1500 g, and hard water was prepared. Hard water and tap water for rinsing were placed in a thermostat at 25 ° C.

A turgot meter was set at 25 ° C., 500 ml of hard water, 5 wet artificially stained cloths and 5 white cloths were put in a pot, and stirred at 100 rpm for 1 minute.

2 g of a 5% by weight aqueous solution of sodium carbonate, 0.075 g of zeolite, and 4 g of the detergent composition of the present invention (however, 6 g of the detergent composition 2) were placed in a pot, and the mixture was stirred at 100 rpm.
and stirred for 10 minutes.

The water on the white cloth was drained by hand, and 500 ml of tap water heated to 25 ° C. was placed in a pot, followed by stirring at 100 rpm for 2 minutes. This was done twice.

Was repeated three times.

A white cloth was placed on the cloth and dried while the wrinkles were being stretched with an iron, and then the whiteness of the white cloth was measured again by the reflectance using the above colorimeter.

From the above measurement results, the ability to prevent re-contamination was determined by the following equation.

Cleaning rate (%) = (whiteness of contaminated cloth after cleaning−whiteness of contaminated cloth before cleaning) / (whiteness of original white cloth−whiteness of contaminated cloth before cleaning) × 100 The higher the value, the better the ability to prevent color transfer.

[0066]

Example 1 The composition to which the detergent composition 1 of the present invention was added was evaluated as Example 1 in the procedure of <Dye transfer prevention ability>. According to the procedure of <detergency test>, the composition to which the detergent composition 1 of the present invention was added was evaluated as Example 1. Table 1 shows the results.

[0067]

Example 2 The composition to which the detergent composition 2 of the present invention was added was evaluated as Example 2 in the procedure of <Dye transfer prevention ability>. According to the procedure of <detergency test>, the composition to which the detergent composition 2 of the present invention was added was evaluated as Example 2. Table 1 shows the results.

[0068]

Example 3 A sample to which the detergent composition 3 of the present invention was added was evaluated as Example 3 in the procedure of <Dye transfer preventing ability>. According to the procedure of <detergency test>, the composition to which the detergent composition 3 of the present invention was added was evaluated as Example 3. Table 1 shows the results.

[0069]

COMPARATIVE EXAMPLE 1 Comparative Example 1 was evaluated by the procedure of <Dye transfer prevention ability> in which the detergent composition of the present invention was not added. In the procedure of the <detergency test>, a composition without the detergent composition of the present invention was evaluated as Comparative Example 1. Table 1 shows the results.

[0070]

COMPARATIVE EXAMPLE 2 Comparative Example 2 was evaluated by the procedure of <Dye transfer prevention ability> in which Comparative Composition 1 was added instead of the detergent composition of the present invention. In the procedure of <detergency test>, a composition to which Comparative Composition 1 was added instead of the detergent composition of the present invention was evaluated as Comparative Example 2. Table 1 shows the results.

[0071]

[Table 2]

[0072]

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H003 AB19 DA01 EB28 EB30 ED02 FA06 FA08 4J026 AA11 AA17 AA31 AA38 AA45 AA49 AA50 AA55 AA61 BA01 BA05 BA14 BA15 BA20 BA27 BA30 BA31 BA32 BA36 BA40 BB03 DA02 DA07 GA08 A08 GA08 A08 AB02R AD03R AE02R AG04R AJ02R AJ09R AL01R AL09Q AL34R AM02R AM15R AQ06P AQ08P AQ12R AQ19R CA05 JA57

Claims (7)

[Claims] 1. A structural unit (I) derived from a hydroxyalkyl (meth) acrylate monomer (A) in an amount of 1 to 55 mol%, and a structural unit (I) derived from a lactam structure-containing unsaturated monomer (B).
I) 30 to 99 mol%, and 0 to 50 mol% of the structural unit (III) derived from another unsaturated monomer (C) (provided that the structural unit (I), the structural unit (II), and the structural unit (III) Is a total of 100 mol%), comprising a lactam structure-containing polymer as an essential component. 2. The lactam structure-containing unsaturated monomer (B) is N
The detergent additive according to claim 1, which is -vinylpyrrolidone. 3. The detergent additive according to claim 1, which is used for clothing. 4. A detergent composition comprising the detergent additive according to claim 1 and an anionic or nonionic surfactant. 5. A hydroxyalkyl (meth) acrylate monomer (A) (1 to 55 mol%), a lactam structure-containing unsaturated monomer (B) 30 to 99 mol%, and another unsaturated monomer (C) 0 ~ 50 mol% (however, monomer (A),
The total of the monomer (B) and the monomer (C) is 100 mo
1%) in the presence of a radical initiator to obtain a lactam structure-containing polymer, which is a method for producing a lactam structure-containing polymer for a detergent additive. 6. A method for producing a lactam structure-containing polymer for a detergent additive, comprising the following steps (I) and (II). (I) Lactam structure-containing unsaturated monomer (B) 30 to 9
9 mol%, and 0 to 50 m of other unsaturated monomers (C)
(II) The polymer obtained in the step (I) is further added to the hydroxyalkyl (meth) acrylate monomer (A) 1-55.
mol%, and 0 to 50 mol of another unsaturated monomer (C)
% Of the monomer (A), the monomer (B), the monomer (C) used in the step (I), and the monomer (C) used in the step (II). The total is 100 mol%) 7. A detergent composition comprising the following a), b) and c) as essential components. a) Structural unit (I) derived from hydroxyalkyl (meth) acrylate monomer (A), structural unit (II) derived from lactam structure-containing unsaturated monomer (B), and other unsaturated monomers ( C) Lactam-structure-containing polymer comprising structural unit (III) derived from b) Anionic or nonionic surfactant c) Carboxylic acid group-containing polymer