JP2001226441A - Hydrophilic graft polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrophilic graft polymer having slight color and decreased residual monomer content and provide a method for producing a hydrophilic graft polymer having slight color and decreased residual monomer content. SOLUTION: The objective hydrophilic graft polymer is produced by the graft polymerization of a monomer component composed of 10-90 mol% monoethylenic unsaturated monocarboxylic acid, 10-90 mol% monoethylenic unsaturated dicarboxylic acid and 0-80 mol% other copolymerizable monoethylenic unsaturated monomer to a polyalkylene glycol. The hydrophilic graft polymer contains <=900 ppm of the monoethylenic unsaturated monocarboxylic acid and has a hue (b-value) of <=10 in the form of 50 wt.% aqueous solution. The method for the production of the hydrophilic graft polymer comprises the graft-polymerization of the monomer component to the polyalkylene glycol and the post-treatment of the produced graft polymer in the state of an aqueous solution in the presence of an additive.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a hydrophilic graft polymer. More specifically, the present invention relates to a hydrophilic graft polymer useful as a detergent builder, a water treatment agent, a fiber treatment agent, a dispersant, a cement dispersant, and the like.

[0002]

2. Description of the Related Art A hydrophilic graft polymer obtained by graft polymerization of a monoethylenically unsaturated monomer such as (meth) acrylic acid to a polyalkylene glycol is used as a detergent builder, a scale inhibitor, a lubricant, a dyeing aid. Agent, fiber treatment agent,
They are used for applications such as dispersants for organic and inorganic particles.
For example, JP-A-55-71710, JP-A-59-71710
JP-A-62614 and JP-A-7-53645 disclose a hydrophilic graft polymer and a method for producing the same. The production method described in these publications is a method in which polymerization is carried out substantially without using a solvent, and a polyalkylene glycol and a part of a monoethylenically unsaturated monomer are charged into a reactor, if necessary, In general, a method of dropping all or a part of the monoethylenically unsaturated monomer and the polymerization initiator after the temperature is raised, and continuing the ripening while maintaining the polymerization temperature for several hours after the completion of the dropping has been generally employed. This aging step is considered to be an indispensable step in terms of reducing residual monomers such as monoethylenically unsaturated monocarboxylic acids, and in order to further reduce the residual monomers, it is conceivable to extend the aging time. . However, when the monomer component to be grafted contains a monoethylenically unsaturated dicarboxylic acid, it has been found that there is a problem that the color of the polymer becomes darker as the aging time is extended, and the quality is deteriorated. did.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a hydrophilic graft polymer in which the coloring of the polymer is small and the residual monomer is reduced.
Another object of the present invention is to provide a method for producing a hydrophilic graft polymer in which the coloring of the polymer is small and the residual monomer is reduced.

[0004]

Means for Solving the Problems In order to solve the above problems, the present invention provides the following configurations. The hydrophilic graft polymer of the present invention is obtained by adding 10 to 90 mol% of a monoethylenically unsaturated monocarboxylic acid, 10 to 90 mol% of a monoethylenically unsaturated dicarboxylic acid and another copolymerizable monoethylenically unsaturated polyalkylene glycol. Monomer 0-8
In a hydrophilic graft polymer obtained by graft-polymerizing a monomer component consisting of 0 mol%, the content of a monoethylenically unsaturated monocarboxylic acid is 900 ppm or less,
The color (b value) of the 50% by weight aqueous solution is 10 or less.

In the method for producing a hydrophilic graft polymer of the present invention, a hydrophilic graft polymer obtained by graft-polymerizing a monomer component to a polyalkylene glycol is obtained by polymerization, and then the polymer is prepared in the form of an aqueous solution of the polymer. Post-treatment is performed in the presence of the additive. In the method for producing a water-soluble polymer of the present invention, after performing a polymerization in a non-aqueous system to obtain a water-soluble polymer, the polymer is dissolved in water to form an aqueous solution, and in the state of the aqueous solution in the presence of an additive. To perform post-processing.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The polyalkylene glycol used in the hydrophilic graft polymer of the present invention has an alkylene oxide as a constitutional unit. As the alkylene oxide, ethylene oxide, propylene oxide,
Isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylethylene oxide, butadiene monoxide, styrene oxide, 1,1-diphenylethylene oxide, epifluorohydrin, epichlorohydrin, epicubromodrin, glycidol , Butyl glycidyl ether,
Hexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, 2-chloroethyl glycidyl ether, o-chlorophenyl glycidyl ether, ethylene glycol diglycidyl ether, bisphenyl A diglycidyl ether, methacryl chloride epoxide, cyclohexene oxide, dihydronaphthalene oxide, vinyl Cyclohexene monoxide, oxetane, tetrahydrofuran, 1,4-epoxycyclohexane and the like can be mentioned, and one or more of these are used. Among them, ethylene oxide and / or
Alternatively, it is preferable to have propylene oxide as a constituent unit in an amount of 50 mol% or more. When the proportion of ethylene oxide and / or propylene oxide is less than 50 mol%, the graft ratio of the monoethylenically unsaturated monomer decreases.

The polyalkylene glycol can be obtained by polymerizing an alkylene oxide in the presence of a compound to be a starting point of the polymerization by a known method or the like. There is no particular limitation on the type, molecular weight, etc. of the compound to be reacted. As the compound to be reacted, for example, water; hydrogen; oxygen; carbon dioxide; alcohol;
Ammonia; amine; hydroxylamine; carboxylic acid; acid halide; lactone; aldehyde; benzene and the like, and one or more of these can be used. Among them, at least one selected from water, alcohol and amine is preferable.

Examples of the alcohol include primary aliphatic alcohols having 1 to 22 carbon atoms, such as methanol, ethanol, n-propanol and n-butanol; phenol, iso-propylphenol, octylphenol, tert-butylphenol, nonylphenol and the like.
Aromatic alcohols such as naphthol; secondary alcohols having 3 to 18 carbon atoms such as iso-propyl alcohol and alcohols obtained by oxidizing n-paraffin; tertiary alcohols such as tert-butanol; ethylene glycol, diethylene glycol, propanediol And diols such as butanediol and propylene glycol; triols such as glycerin and trimethylolpropane; and polyols such as sorbitol. These may be used alone or in combination of two or more.

Examples of the amine include aniline, naphthylamine, ethylenediamine and the like, and one or more of these are used. There is no particular limitation on the reaction mode of the polymerization of the alkylene oxide, and there is no particular limitation.
Any of cationic polymerization using a mineral acid, acetic acid or the like as a catalyst and coordination polymerization using a combination of alkoxides of metals such as aluminum, iron and zinc, alkaline earth compounds, Lewis acids and the like may be used.

[0010] The polyalkylene glycol may be a derivative derived from the polyalkylene glycol obtained by the above polymerization. Examples of such a derivative include a terminal group converter in which a terminal functional group of polyalkylene glycol is converted, a polyalkylene glycol, and a crosslinking agent having a plurality of groups such as a carboxyl group, an isocyanate group, an amino group, and a halogen group. And a crosslinked product obtained by reacting the above. As the terminal group converter,
At least one terminal hydroxyl group of the above polyalkylene glycol is esterified with a dicarboxylic acid such as a fatty acid having 2 to 22 carbon atoms such as acetic acid or acetic anhydride, an acid anhydride thereof, succinic acid, succinic anhydride, and adipic acid. Is preferred.

The number average molecular weight of the polyalkylene glycol is preferably 100 or more, more preferably 200 or more. When the number average molecular weight is less than 100, there is a problem that the graft ratio decreases and unreacted polyalkylene glycol increases. The upper limit of the number average molecular weight is not particularly limited, but is preferably 1
00000 or less. When the number average molecular weight exceeds 100,000, the viscosity tends to increase, and it becomes difficult to handle during polymerization. The number of repeating units in the polyalkylene glycol is not particularly limited, and is preferably 2 or more, more preferably 3 or more in the polyether compound.

The monomer components used in the hydrophilic graft polymer of the present invention include 10 to 90 mol% of a monoethylenically unsaturated monocarboxylic acid, 10 to 90 mol% of a monoethylenically unsaturated dicarboxylic acid and other copolymerizable monomers. Of monoethylenically unsaturated monomers of from 0 to 80 mol%. More preferably, monoethylenically unsaturated monocarboxylic acid 30 to 9
0 mol%, monoethylenically unsaturated dicarboxylic acid 10
50 mol% and 0-20 mol% of other copolymerizable monoethylenically unsaturated monomers. When the amount of the monoethylenically unsaturated dicarboxylic acid is less than 10 mol%, the carboxylic acid density of the obtained hydrophilic graft polymer is low, and various performances such as polyvalent metal ion chelating ability and dispersing ability are satisfactory. Not done. Alternatively, there is a problem that the rate of introduction of the monoethylenically unsaturated dicarboxylic acid into the hydrophilic graft polymer is reduced and the amount of the remaining monomer is increased. On the other hand, the amount of the monoethylenically unsaturated monocarboxylic acid is 10 m
ol%, residual monoethylenically unsaturated dicarboxylic acid (unreacted monoethylenically unsaturated dicarboxylic acid)
There is a problem that is increased.

Examples of the monoethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid and the like. One or more of these are used, and among them, acrylic acid is preferred. Examples of the monoethylenically unsaturated dicarboxylic acid include (anhydride) maleic acid, fumaric acid, and itaconic acid. One or more of these are used, and (maleic anhydride) is particularly preferred. In addition, (anhydride) maleic acid means maleic acid and / or maleic anhydride. Other monoethylenically unsaturated monomers copolymerizable with monoethylenically unsaturated monocarboxylic acid and monoethylenically unsaturated dicarboxylic acid include alkyl esters of acrylic acid such as methyl acrylate; methyl methacrylate and the like. Alkyl esters of methacrylic acid;
Alkyl esters of maleic acid such as monomethyl maleate, dimethyl maleate, monoethyl maleate and diethyl maleate; alkyl esters of fumaric acid such as monomethyl fumarate, dimethyl fumarate, monoethyl fumarate and diethyl fumarate; hydroxyethyl (Meta)
Acrylates; hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate; alkenyl acetates such as vinyl acetate; aromatic vinyls such as styrene; vinylamides such as N-vinylpyrrolidone; alkyl vinyl ethers such as ethyl vinyl ether A nitrile group-containing monomer such as (meth) acrylonitrile; an amide group-containing monomer such as (meth) acrylamide;
Dialkylaminoethyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate; 2-acrylamido-2-methylpropanesulfonic acid and the like;
One or more of these can be used.

These monomer components are preferably graft-polymerized at a ratio of 20% by weight or more to polyalkylene glycol, more preferably at least 40% by weight. If the proportion of the monomer component to be graft-polymerized is less than 20% by weight, the carboxylic acid density of the obtained graft polymer is low, and various properties such as polyvalent metal ion chelating ability and dispersing ability are not satisfied. The graft ratio of the hydrophilic graft polymer of the present invention is preferably 20% or more, more preferably 30% or more, as calculated by the Soxhlet extraction method described in Examples below. Yes, more preferably at least 40%, and most preferably at least 50%. When the graft ratio is less than 20%, various performances such as a scale inhibitor,
Performance when used as a detergent builder or the like is reduced.

In the embodiment, the hydrophilic graft polymer of the present invention may be a polymer composition containing at least a specific amount of the graft polymer, as can be seen from the above expression of the graft ratio. is there. As described above, the content of the graft polymer in the polymer composition is preferably 20% or more, more preferably 30% or more, and still more preferably 40%, in consideration of the builder performance and the like.
Or more, and most preferably 50% or more. Also,
The acid value of the hydrophilic graft polymer of the present invention is 40 mg KOH.
/ G or more, more preferably 100
mgKOH / g or more. Acid value is 40mgKOH / g
When the value is less than the above range, the carboxylic acid density of the obtained graft polymer is low, and various performances such as polyvalent metal ion chelating ability and dispersing ability are not satisfied.

The hydrophilic graft polymer of the present invention is characterized in that the content of the monoethylenically unsaturated monocarboxylic acid is small. Specifically, it is 900 ppm or less, more preferably 800 ppm or less, and most preferably 5 ppm or less.
It is not more than 00 ppm. Further, the hydrophilic graft polymer of the present invention is characterized by little coloring,
Specifically, the hue (b value) of the 50% by weight aqueous solution is 10 or less, more preferably 9 or less, and most preferably 8 or less. As a method for producing the hydrophilic graft polymer of the present invention having a low content of the monoethylenically unsaturated monocarboxylic acid and little coloring, the method for producing the hydrophilic graft polymer of the present invention is preferable. That is,
After obtaining by polymerization a hydrophilic graft polymer obtained by graft-polymerizing a monomer component to a polyalkylene glycol,
It is preferable to carry out post-treatment in the presence of an additive in the state of an aqueous solution of the polymer. By this specific post-treatment (aging step), the content of residual monomers (especially monoethylenically unsaturated monocarboxylic acids) is small, or the polymer can be decolorized, and preferably the monoethylenically unsaturated monocarboxylic acids are used. Content as low as 900 ppm or less, 50% by weight
A hydrophilic graft polymer (a graft polymer component or a graft polymer composition obtained by graft-polymerizing a monomer component to polyalkylene glycol) having a hue (b value) of an aqueous solution as small as 10 or less is obtained. be able to.

Hereinafter, the method for producing the hydrophilic graft polymer of the present invention will be described in detail. At the time of graft polymerization, a polymerization initiator is usually used. As the polymerization initiator, a known radical polymerization initiator can be used, and an organic peroxide is particularly preferable. Examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide,
Hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl hydroperoxide;
t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α′-bis (t
-Butylperoxy) p-diisopropylbenzene,
dialkyl peroxides such as α, α′-bis (t-butylperoxy) p-diisopropylhexyne;
Butyl peroxyacetate, t-butyl peroxy laurate, t-butyl peroxybenzoate, di-t
-Butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-
Peroxyesters such as butylperoxyisopropyl carbonate; peroxyketals such as n-butyl-4,4-bis (t-butylperoxy) valate and 2,2-bis (t-butylperoxy) butane; And diacyl peroxides such as dibenzoyl peroxide. Considering that the polymerization temperature is preferably 100 ° C. or higher, and more preferably 110 to 160 ° C., as described later, among these organic peroxides, those having a 10-hour half-life of 90 to 150 ° C. are preferable, and Those having a time half life of 100 to 140 ° C are more preferably used.

The amount of the polymerization initiator is not particularly limited, but is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on the monomer components. If the amount is smaller or larger, the grafting efficiency of the monomer to the polyalkylene glycol decreases. The polymerization initiator can be added to the polyalkylene glycol in advance, but it can also be added simultaneously with the monomer component. The graft polymerization is preferably performed in a non-aqueous system. Further, it is preferable not to use an organic solvent other than water, such as alcohol and toluene. When water or an organic solvent is used, the grafting efficiency of the monomer to the polyalkylene glycol decreases. When an organic solvent is used for the addition of a polymerization initiator or a monomer, the amount thereof is as small as possible, preferably 5% by weight or less based on the total amount, or it is immediately distilled off from the reaction system after the addition. Is preferred.

The polymerization temperature is preferably 100 ° C. or higher, more preferably 110-160 ° C. When the temperature is lower than 100 ° C., the grafting efficiency of the monomer to the polyalkylene glycol decreases. At a temperature higher than 160 ° C., thermal decomposition of the polyalkylene glycol and the obtained graft polymer may occur. At the time of graft polymerization, it is preferable to initially or partially charge the polyalkylene glycol. The monomer component may be added dropwise in its entirety, or a part or all of the monomer component may be initially charged. Of the monomer components, the monoethylenically unsaturated dicarboxylic acid is preferably initially charged with at least half of the amount used together with the polyalkylene glycol, and the monoethylenically unsaturated monocarboxylic acid is preferably dripped in its entirety. . It is preferable that the remaining monomers and the polymerization initiator be separately dropped after heating the polyalkylene glycol to 100 ° C. or higher. At this time, when a part of the polyalkylene glycol is initially charged, the remaining polyalkylene glycol can be mixed with a polymerization initiator or a monomer and dropped.

After completion of the dropwise addition, aging may be performed, if necessary, while maintaining the polymerization temperature. However, as described above, the residual monomer can be reduced by aging, but the color of the polymer becomes darker. Also, in consideration of economy, it is better that the aging time is short. Therefore, the ripening time should be set in consideration of the target monoethylenically unsaturated monocarboxylic acid content and the hue, but from 30 minutes to
Six hours is preferred, and one to three hours is more preferred. Subsequently, the obtained hydrophilic graft polymer (graft polymer component or graft polymer composition obtained by graft-polymerizing a monomer component to polyalkylene glycol) is dissolved in water to form an aqueous solution, Post-treatment is performed in the state of the aqueous solution in the presence of an additive. When the polymerization of the hydrophilic graft polymer is performed in an aqueous solution, the post-treatment is performed as it is in the state of the aqueous solution. By this step, the content of the residual monomer (particularly, monoethylenically unsaturated monocarboxylic acid) can be reduced, or the polymer can be decolorized.

The concentration of the aqueous solution of the hydrophilic graft polymer is not particularly limited from the viewpoint of the reactivity of the post-treatment, but the concentration is preferably higher from the viewpoint of the economics of the product form (transportation cost). It is preferably at least 40% by weight, more preferably at least 50% by weight, further preferably at least 80% by weight, and most preferably at least 90% by weight. As the additive used in the post-treatment, at least one selected from peroxides and azo compounds is preferably used. Further, an oxidizing agent other than the peroxide and the azo compound may be used in combination.

As the peroxide, hydrogen peroxide; inorganic peroxides (peroxodisulfate (sodium persulfate, potassium persulfate, ammonium persulfate, etc.), peroxoborate, dithionite, bisulfite, Disulfite, etc.);
Organic peroxides (such as those exemplified as the polymerization initiator, peracetic acid, peracetates (such as sodium peracetate), and percarbonates (such as sodium percarbonate)) may be mentioned. A weak oxide is more preferred, and hydrogen peroxide is most preferred. As the azo compound, 1,
1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile,
2'-azobis (2,4-dimethylvaleronitrile),
Azonitrile compounds such as 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile); 2,2 '
-Azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride,
Azoamidine compounds such as 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride and 2,2'-azobis [2- (2-imidazolin-2-yl) propane]; 2 , 2'-Azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-
[Hydroxyethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (2-methyl-
Azoamide compounds such as propionamide) dihydrate; 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpentane)
Azoalkyl-based compounds such as 2-cyano-2-propylazoformamide; 4,4'-azobis (4-cyanovaleric acid); dimethyl 2,2'-azobis (2
-Methylpropionate); 2,2'-azobis (2-
Hydroxymethylpropionitrile),
Water-soluble (2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2-
(5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2-
(2-imidazolin-2-yl) propane] dihydrochloride, 2-cyano-2-propylazoformamide) is preferred.

When a peroxide is used as an additive in the post-treatment, the peroxide is preferably different from the polymerization initiator used in the polymerization. The polymerization temperature is preferably 100 ° C or higher, more preferably 110 to 160 ° C.
However, since the post-treatment is performed in the state of an aqueous solution, the temperature is at most 100 ° C., and the compounds suitable for each temperature range are naturally different. Specifically, those which are preferable as the polymerization initiator have a 10-hour half-life of 100 ° C. or more, and those which are preferable as the peroxide used for the post-treatment have a 10-hour half-life of less than 100 ° C. From another viewpoint, an organic peroxide is preferable as a polymerization initiator, and an inorganic peroxide is preferable as a peroxide used in the post-treatment.

When a peroxide is used as an additive in the post-treatment, it is preferable to use a decomposition accelerator which can accelerate the decomposition of the peroxide together with the peroxide. Examples of the decomposition accelerator include amines, reducing agents such as ascorbic acid and iron, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. One or more of these are used. be able to. As the decomposition accelerator, a reducing agent is preferable, and ascorbic acid is most preferable. The amount of the additive used in the post-treatment is preferably 0.01 to 50% by weight based on the weight of the graft polymer.
More preferably, it is from 0.05 to 10% by weight. Even if the amount exceeds the above range, the effect of addition corresponding to the amount is hard to appear. If the amount is less than the above range, the effect of reducing the residual monoethylenically unsaturated monocarboxylic acid and improving the color tone may not be sufficiently exhibited. When a reducing agent is used in combination with the peroxide, the amount of the reducing agent is preferably 1 to 500% by weight based on the peroxide, and 10% by weight.
It is more preferable that the content be 200 to 200% by weight.

The method of adding the additives in the post-treatment is not particularly limited, and may be in the form of a powder or a liquid. However, a liquid is preferred from the viewpoint of ease of production. When used as a liquid, it is most preferably used as an aqueous solution, and its concentration is not particularly limited, and can be appropriately set in consideration of economy, stability of the liquid, and the like. When two or more kinds of additives are used, they may be added dropwise at the same time or may be added in two or more steps. The temperature of the post-treatment is not particularly limited as long as the additive reacts, but is preferably room temperature or higher. It may be performed under reflux. The post-treatment time depends on the reaction temperature and the type of additive used, but is preferably 10 minutes or more.

Since the hydrophilic graft polymer of the present invention is very excellent in dispersing action of solid particles, it can be used as a detergent builder,
It is useful as a water treatment agent, a fiber treatment agent, a dispersant, a cement dispersant, and the like. The hydrophilic graft polymer of the present invention can be used as it is dissolved in a solvent such as water or alcohol, or can be used by adding a base. Examples of the base include a monovalent metal salt such as a sodium salt and a potassium salt, a divalent metal salt such as a calcium salt, a trivalent metal salt such as an aluminum salt, an ammonium salt, and an organic amine salt such as monoethanolamine and triethanolamine. Can be mentioned. In that case, water is preferable as the solvent.

The detergent builder of the present invention contains the hydrophilic graft polymer of the present invention, and may further contain other components as necessary. The detergent builder of the present invention
It can be used as a detergent composition containing a surfactant and, if necessary, an enzyme. The detergent composition may be any of a liquid detergent composition and a powder detergent composition. The ratio of the hydrophilic graft polymer of the present invention in the detergent composition is preferably from 0.1 to 15% by weight. As surfactants, anionic surfactants, nonionic surfactants,
Amphoteric and cationic surfactants can be used.

Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate,
α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonate, saturated or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, Examples thereof include an alkyl or alkenyl phosphate or a salt thereof. Examples of the nonionic surfactant include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycooxide, fatty acid glycerin monoester, and alkyl. Amine oxide and the like can be mentioned.

Examples of the amphoteric surfactant include a carboxy type or a sulfobetaine type amphoteric surfactant. Examples of the cationic surfactant include a quaternary ammonium salt. The amount of these surfactants is preferably 5 to 70% by weight in the detergent composition, more preferably 20 to 60% by weight. However, when a nonionic surfactant is used, the concentration of the nonionic surfactant is preferably 50% by weight or more for the purpose of compacting the detergent and improving the detergency, and more preferably 60% by weight or more. It is preferably at least 70% by weight.

As the enzyme, protease, lipase, cellulase and the like can be used. Particularly, protease, alkaline lipase, alkaline cellulase and the like having high activity in an alkaline washing solution are preferable. The amount of the enzyme is preferably 0.01 to 5% by weight in the detergent composition.
If the ratio is out of this range, the balance with the surfactant is lost, and the cleaning power cannot be improved. The detergent composition containing the hydrophilic graft polymer of the present invention, if necessary, is commonly used in known detergent compositions such as known alkali builders, chelate builders, anti-redeposition agents, fluorescent agents, bleaching agents, and fragrances. Components may be blended. Further, zeolite may be blended. Silicates, carbonates, sulfates and the like can be used as the alkali builder. Chelate builders include diglycolic acid, oxycarboxylate, ED
TA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminehexaacetic acid), citric acid and the like can be used.

The washing rate of the detergent composition (the measuring method is defined in Examples described later) is preferably 60% or more, more preferably 65% or more. The water treatment agent of the present invention contains the hydrophilic graft polymer of the present invention, and may further contain other components as necessary. Other components include, for example, organic sulfonic acids; phosphoric acid compounds such as polymerized phosphates and phosphonates; metal salts such as zinc, chromium and manganese; corrosion inhibitors; slime control agents; chelating agents; Antioxidant; sludge dispersant; scale dissolution remover; carryover inhibitor; canning agent; ion exchange resin detergent; OSR type detergent; These other components may be used alone or in combination of two or more. The amount is not particularly limited.

The water treatment agent of the present invention may be added as it is to water systems such as a cooling water system, a boiler water system, a seawater desalination apparatus, an oil feed, a pulp dissolving pot, and a black liquor concentrating pot.
The addition amount is usually 1 to 100 ppm. When the water treatment agent of the present invention contains components other than the hydrophilic graft polymer of the present invention, they can be added separately. The water treatment agent of the present invention includes calcium carbonate, calcium phosphate, zinc hydroxide, barium sulfate, calcium sulfate, calcium sulfite, calcium silicate, magnesium silicate, magnesium hydroxide, zinc phosphate, zinc hydroxide, and basic zinc carbonate. , Silicate, silica, iron and the like can be used to prevent and remove scale.

The scale suppression ratio (defined by the measuring method in the examples described later) of the water treatment agent of the present invention is preferably 30% or more, more preferably 40% or more. The fiber treating agent of the present invention contains the hydrophilic graft polymer of the present invention, and may further contain other components as necessary. Other components include at least one component selected from the group consisting of a dye, a peroxide, and a surfactant. The dyes, peroxides and surfactants are not particularly limited, and for example, those used in known fiber treatment agents can be diverted.

The blending ratio of at least one component selected from the group consisting of a dye, a peroxide and a surfactant in the fiber treating agent of the present invention and the hydrophilic graft polymer of the present invention is not particularly limited. However, in order to improve the whiteness of the fiber, the unevenness of the color, the degree of dyeing and the like, the dye is composed of a dye, a peroxide and a surfactant with respect to 1 part by weight of the hydrophilic graft polymer of the present invention. It is preferable that at least one component selected from the group is in a ratio of 0.1 to 100 parts by weight. Fibers that can use the fiber treatment agent of the present invention are not particularly limited, for example, cotton,
Cellulose fibers such as hemp; synthetic fibers such as nylon and polyester; animal fibers such as wool and silk; semi-synthetic fibers such as human silk; and woven and blended products using these fibers.

The fiber treating agent of the present invention can be used in any of the steps of refining, dyeing, bleaching and soaping in fiber treatment. For example, when the fiber treating agent of the present invention is applied to a scouring step, the fiber treating agent preferably contains an alkali agent and a surfactant in addition to the hydrophilic graft polymer of the present invention. When the fiber treating agent of the present invention is applied to the bleaching step, the fiber treating agent may be, in addition to the hydrophilic graft polymer of the present invention, peroxide and sodium silicate which is a decomposition inhibitor of an alkaline bleaching agent. And the like. The fiber treatment agent of the present invention is preferably 70 or more, and more preferably 75 or more, in the evaluation of whiteness by a whiteness test (the measurement method is defined in Examples described later).

The dispersant of the present invention contains the hydrophilic graft polymer of the present invention, and may contain other components as necessary. Examples of the other components include at least one compound selected from the group consisting of polymerized phosphoric acid, polymerized phosphate, phosphonic acid, phosphonate, polyvinyl alcohol, and anionized modified polyvinyl alcohol. The dispersant of the present invention is useful as an inorganic or organic dispersant, but exhibits particularly good performance as a dispersant for inorganic pigments such as heavy or light calcium carbonate and clay used for paper coating. For example, by adding a small amount of the dispersant of the present invention to an inorganic pigment and then dispersing it in water, it has a low viscosity and high fluidity, and a stable high-concentration inorganic material that does not change with time in these properties. Pigment slurries (eg, high-concentration calcium carbonate slurries) can be produced.

The amount of the dispersant used in the present invention is 10
0.05 to 2.0 parts by weight per 0 parts by weight is preferred.
If the amount of the inorganic pigment dispersant is too small, a sufficient dispersing effect may not be exhibited. On the other hand, if the amount is too large, improvement of the dispersing effect commensurate with the added amount can no longer be expected, and this may be economically disadvantageous. The cement dispersant of the present invention contains the hydrophilic graft polymer of the present invention, and may further contain other components as necessary. When the cement dispersant of the present invention is used for a cement composition such as cement mortar or concrete, the dispersibility is improved by the hydrophilic graft polymer of the present invention, and high flowability is obtained without causing a large hardening retardation due to the addition. Since the mortar works and the concrete works are significantly improved, the workability of the mortar work and the concrete work is remarkably improved. Therefore, the cement dispersant of the present invention,
For example, it can be used as a fluidizer for concrete including ready-mixed concrete. In particular, the production of ready-mixed concrete with a high water reduction ratio as a high-performance AE water reducing agent added simultaneously with a plant can be easily realized.

The cement dispersant of the present invention can be used for dispersing hydraulic cement such as portland cement, alumina cement, various types of mixed cement, and other hydraulic materials other than cement such as gypsum. The blending amount of the cement dispersant of the present invention with respect to the cement is not particularly limited.
It is preferably from 1 to 1.0 part by weight. Examples of the method of using the cement dispersant of the present invention include, for example, a method of dissolving in kneading water and then adding it to the kneading water at the time of adjusting the cement composition, or a method of adding to the already kneaded cement composition. . The cement dispersant of the present invention can also be used as a high-performance water reducing agent for the production of secondary concrete products, which reduces water and increases strength.

In the present invention, after a water-soluble polymer is obtained by performing polymerization in a non-aqueous system, the polymer is dissolved in water to form an aqueous solution, and the aqueous solution is subjected to post-treatment in the presence of an additive. And a method for producing a water-soluble polymer. This is an extended application of the method for producing a hydrophilic graft polymer described above to a whole water-soluble polymer obtained by performing polymerization in a non-aqueous system. The amount can be reduced and the polymer can be decolorized. The post-treatment can be performed under the same treatment conditions using the same additives as in the post-treatment step of the hydrophilic graft polymer. The same is true for aging after polymerization, if necessary.

The water-soluble polymer targeted by the production method of the present invention is not particularly limited as long as it is a water-soluble polymer which can be polymerized in a non-aqueous system. The hydrophilic graft polymer is preferably composed of 10 to 90 mol% of a monoethylenically unsaturated monocarboxylic acid, 10 to 90 mol% of a monoethylenically unsaturated dicarboxylic acid and another copolymerizable monoethylenically unsaturated polyalkylene glycol. Monomer 0-80mo
A hydrophilic graft polymer obtained by graft-polymerizing a monomer component of 1% is particularly preferred.

[0041]

EXAMPLES The present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. <Method for measuring carboxylic acid value> 1 g of a polymer was diluted to be a 1% by weight aqueous solution (in the case of a polymer aqueous solution, concentrated, and 1 g of the obtained polymer was diluted to be a 1% by weight aqueous solution). Stir well. While stirring the aqueous solution,
An aqueous solution of potassium hydroxide of N is added dropwise to perform acid-base titration. The measurement was made using a Hiranuma Sangyo Co., Ltd. Hiranuma automatic titrator (CO
MTITE-550) and Hiranuma Sangyo Co., Ltd. G
Using E101 and Hiranuma Sangyo RE201 for the glass electrode,
B-900 is used as a burette. pH 5 to 9
PH change is the largest with respect to the amount of drop between 0.1N
Of the aqueous potassium hydroxide solution is determined. The weight of potassium hydroxide in the amount of the dropped liquid is determined in mg.
This value is defined as a carboxylic acid value (KOH mg / g).

<Method of measuring hue (b value)> The polymer (or aqueous polymer solution) is diluted or concentrated with pure water to adjust the polymer concentration to 50% by weight. The b value of Lab value was measured by performing transmission measurement of the adjusted aqueous solution using a colorimetric colorimeter ND-1001DP manufactured by Nippon Denshoku Industries Co., Ltd. The larger the b value is in the positive direction, the deeper the yellow color of the aqueous solution. <Method for Measuring Monoethylenically Unsaturated Monocarboxylic Acid Content> As a method for measuring the monoethylenically unsaturated monocarboxylic acid content, acrylic acid will be described below as an example.

The acrylic acid content was measured by GPC. Using G3000PWXL (manufactured by Tosoh Corporation) for the column, the measurement was performed at a column temperature of 35 ° C., a mobile phase of a 0.1% by weight phosphoric acid aqueous solution, a flow rate of 1.0 ml / min, a detector of UV, and a wavelength of 200 nm. . The acrylic acid used for the polymerization was used as a calibration curve, and the residual acrylic acid in the polymer was determined in terms of the acid type. <Method for measuring graft ratio (Soxhlet extraction method)> In order to remove the esterified product in the polymer, an aqueous sodium hydroxide solution is added, and the mixture is stirred at 70 ° C. That is, the polymer (or polymer aqueous solution) is diluted or concentrated to a 50% by weight aqueous solution,
Add sodium hydroxide 1.2 times the amount (mol number) of the carboxylic acid in the polymer calculated from the carboxylic acid value obtained by the method described above, and stir at 70 ° C for 2 hours. The polymer aqueous solution is dried (condition: 110 ° C., 2 hours), and the dried product from which water has been removed is ground in a mortar.

Using 10 times the weight of chloroform with respect to the prepared polymer, Soxhlet extraction is performed for 2 hours.
The extract is dried, chloroform is removed, and the weight is measured. The weight obtained by dividing the weight by the weight of the polyalkylene glycol in the original polymer is subtracted from 1, and the result obtained by multiplying by 100 and expressed as a percentage is defined as the graft ratio. [Example A-1] A phenoxy polyethylene glycol having a number average molecular weight of 910 (phenol was obtained by adding 20 moles of ethylene oxide on average to a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser). thing)
100 parts by weight and 17.5 parts by weight of maleic acid were charged, and the charged substance was dissolved by heating under a nitrogen stream, and stirred for 120 minutes.
The temperature was raised to ° C. Next, while maintaining the temperature at 117 to 123 ° C., 25.3 parts by weight of acrylic acid and perbutyl I (t
2.1 parts by weight of tert-butyl peroxyisopropyl monocarbonate (manufactured by NOF CORPORATION) were separately added dropwise continuously over 2 hours, and then stirred for 1 hour to obtain a graft polymer. Was.

While keeping 100 parts by weight of the obtained 80% by weight aqueous solution of the graft polymer at 90 ° C., 4.0 parts by weight of a 10% by weight aqueous sodium persulfate solution was continuously dropped over 30 minutes, and then stirred for 30 minutes. To obtain a graft polymer aqueous solution. The graft ratio of the graft polymer in the obtained aqueous graft polymer solution was 41%, the carboxylic acid value was 230 KOH mg / g, the residual acrylic acid concentration was 560 ppm, and the b value of the 50 wt% aqueous graft polymer solution was (Nippon Denshoku Industries color difference meter Z-1001DP) was 11. [Example A-2] Polypropylene glycol having a number average molecular weight of 580 (produced by adding an average of 10 mol of propylene oxide to water) in a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser. ) 100 parts by weight,
Maleic acid (17.5 parts by weight) was charged, and the charged material was dissolved by heating under a nitrogen stream, and the temperature was increased to 130 ° C. with stirring. Next, while maintaining the temperature at 127 to 133 ° C, 25.3 parts by weight of acrylic acid and perbutyl D (di-tert-
Contains 98% butyl peroxide, manufactured by NOF Corporation
2.1 parts by weight were separately dropped continuously over 2 hours, and thereafter, stirring was continued for 1 hour to obtain a graft polymer.

While keeping 100 parts by weight of the obtained 80% by weight aqueous solution of the graft polymer at 90 ° C., 1.1 parts by weight of a 35% by weight aqueous hydrogen peroxide solution were continuously dropped over 30 minutes, and then stirred for 30 minutes. To obtain a graft polymer aqueous solution. The graft ratio of the graft polymer in the obtained aqueous graft polymer solution was 45%, the carboxylic acid value was 230 KOHmg / g, and the residual acrylic acid concentration was 200%.
0 ppm, and 50% by weight of the aqueous graft polymer solution
The value was 9. Example A-3 A phenoxy polyethylene glycol having a number average molecular weight of 910 (a phenol obtained by adding 20 moles of ethylene oxide on average to a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser). thing)
100 parts by weight and 3.5 parts by weight of maleic acid were charged, and the charged material was dissolved by heating under a nitrogen stream, and the mixture was stirred at 130 ° C.
Temperature. Next, while maintaining the temperature at 127 to 133 ° C, 5.7 parts by weight of acrylic acid and methyl methacrylate 3 were added.
3.6 parts by weight and 4.3 parts by weight of perbutyl D (containing 98% of di-tert-butyl peroxide, manufactured by NOF Corporation) were separately dropped continuously over 2 hours, and then stirred for 1 hour. Was continued to obtain a graft polymer.

While maintaining 100 parts by weight of a 50% by weight aqueous solution of the obtained graft polymer at 50 ° C., 0.3 parts by weight of a 35% by weight aqueous hydrogen peroxide solution and 1.0 parts by weight of a 10% by weight aqueous ascorbic acid solution were added. Separately, the mixture was dropped continuously over 30 minutes, and thereafter, stirring was continued for 30 minutes to obtain an aqueous graft polymer solution. The graft ratio of the graft polymer in the obtained aqueous graft polymer solution was 46%, the carboxylic acid value was 230 KOH mg / g, and the residual acrylic acid concentration was 2%.
It was 80 ppm, and the b value of the 50% by weight aqueous graft polymer solution was 9. Example A-4 100 parts by weight of triethylene glycol and 40.6 parts by weight of maleic acid were charged into a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser.
Heat and dissolve the charge in a nitrogen stream, and stir
The temperature was raised to 0 ° C. Next, while maintaining the temperature at 127 to 133 ° C., 58.8 parts by weight of acrylic acid, perbutyl D
5.0 parts by weight (containing 98% of di-tert-butyl peroxide, manufactured by NOF CORPORATION) were separately added dropwise continuously over 2 hours, and then stirred for 1 hour to obtain a graft polymer. Was.

While maintaining 100 parts by weight of a 90% by weight aqueous solution of the obtained graft polymer at 80 ° C., 0.8 parts by weight of a 35% by weight aqueous hydrogen peroxide solution and 2.7 parts by weight of a 10% by weight ascorbic acid aqueous solution were added. Separately, the mixture was dropped continuously over 30 minutes, and thereafter, stirring was continued for 30 minutes to obtain an aqueous graft polymer solution. The graft ratio of the graft polymer in the obtained aqueous graft polymer solution was 40%, the carboxylic acid value was 370 KOH mg / g, and the residual acrylic acid concentration was 8%.
It was 00 ppm, and the b value of the 40% by weight aqueous graft polymer solution was 9. [Example A-5] A methoxypolyethylene glycol having a number average molecular weight of 470 (an average of 10 moles of ethylene oxide was added to methanol was obtained in a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser). Thing) 1
The mixture was heated under a nitrogen stream and heated to 130 ° C. with stirring. Next, the temperature was set to 127 to 1
While maintaining the temperature at 33 ° C., 11.1 parts by weight of acrylic acid and 0.6 parts by weight of perbutyl D (containing 98% of di-tert-butyl peroxide, manufactured by NOF CORPORATION) were separately and continuously fed for 2 hours. Then, stirring was continued for 1 hour to obtain a graft polymer.

While keeping 100 parts by weight of the obtained 50% by weight aqueous solution of the graft polymer at 30 ° C., 0.1 parts by weight of a 35% by weight aqueous hydrogen peroxide solution and 0.5 parts by weight of a 10% by weight aqueous ascorbic acid solution were added. Separately, the mixture was dropped continuously over 30 minutes, and thereafter, stirring was continued for 30 minutes to obtain an aqueous graft polymer solution. The graft rate of the graft polymer in the obtained aqueous graft polymer solution was 51%, the carboxylic acid value was 67 KOH mg / g, and the residual acrylic acid concentration was 31%.
0 ppm, and 50% by weight of the aqueous graft polymer solution
The value was 8. [Example A-6] A methoxypolyethylene glycol having a number average molecular weight of 470 (an average of 10 moles of ethylene oxide was added to methanol was obtained in a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser). Thing) 1
Then, 00 parts by weight, 34.3 parts by weight of maleic anhydride and 6.3 parts by weight of water were charged, and the charged substance was dissolved by heating under a stream of nitrogen and heated to 130 ° C. with stirring.
Next, while keeping the temperature at 127 to 133 ° C., 58.8 parts by weight of acrylic acid and perbutyl Z (containing 98% of tert-butylperoxybenzoate, manufactured by NOF Corporation)
5.0 parts by weight were separately added dropwise continuously over 2 hours, and thereafter stirring was continued for 1 hour to obtain a graft polymer.

While maintaining 100 parts by weight of the obtained 80% by weight aqueous solution of the graft polymer at 50 ° C., 11.4 parts by weight of a 35% by weight aqueous hydrogen peroxide solution and 40.0 parts by weight of a 10% by weight aqueous ascorbic acid solution were added. Separately, the mixture was dropped continuously over 30 minutes, and thereafter, stirring was continued for 30 minutes to obtain an aqueous graft polymer solution. The graft ratio of the graft polymer in the obtained aqueous graft polymer solution was 51%, the carboxylic acid value was 370 KOH mg / g, the residual acrylic acid concentration was 870 ppm, and the b value of the 50% by weight aqueous graft polymer solution was Was 8. [Example A-7] A phenoxy polyethylene glycol having a number average molecular weight of 530 (an average of 10 mol of ethylene oxide added to phenol was added to a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser). thing)
100 parts by weight, 19.8 parts by weight of maleic anhydride were charged, and the charge was dissolved by heating under a nitrogen stream.
The temperature was raised to 130 ° C. with stirring. Next, the temperature was set to 127 to 1
While maintaining the temperature at 33 ° C., 1.6 parts by weight of acrylic acid and perbutyl Z (tert-butylperoxybenzoate 98)
% By weight, manufactured by Nippon Oil & Fats Co., Ltd.)
The solution was continuously dropped over 2 hours, and thereafter, stirring was continued for 1 hour to obtain a graft polymer.

While maintaining 100 parts by weight of the obtained 50% by weight aqueous solution of the graft polymer at 50 ° C., 0.7 parts by weight of a 35% by weight aqueous hydrogen peroxide solution and 2.5 parts by weight of a 10% by weight ascorbic acid aqueous solution were added. Separately, the mixture was dropped continuously over 30 minutes, and thereafter, stirring was continued for 30 minutes to obtain an aqueous graft polymer solution. The graft ratio of the graft polymer in the obtained aqueous graft polymer solution was 42%, the carboxylic acid value was 168 KOH mg / g, and the residual acrylic acid concentration was 2%.
It was 00 ppm, and the b value of the 50% by weight aqueous graft polymer solution was 8. Example A-8 A methoxypolyethylene glycol having a number average molecular weight of 470 (an average of 10 moles of ethylene oxide was added to methanol was obtained in a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser). Thing) 1
Then, 00 parts by weight and 1.5 parts by weight of maleic acid were charged, and the charged substance was dissolved by heating under a nitrogen stream, and the temperature was increased to 130 ° C. with stirring. Next, the temperature is set to 127 to 133 ° C.
8.5 parts by weight of acrylic acid, perbutyl Z
1.0 part by weight (containing 98% of tert-butyl peroxybenzoate, manufactured by NOF CORPORATION) was separately dropped continuously over 2 hours, and then stirred for 1 hour to obtain a graft polymer. . 5 of the obtained graft polymer
While maintaining 100 parts by weight of the 0% by weight aqueous solution at 80 ° C.,
0.7 parts by weight of a 5% by weight aqueous hydrogen peroxide solution and 2.5 parts by weight of a 10% by weight ascorbic acid aqueous solution were separately dropped continuously over 5 minutes, and then stirring was continued for 5 minutes to remove the graft polymer aqueous solution. Obtained.

The graft ratio of the graft polymer in the obtained aqueous graft polymer solution was 40%, the carboxylic acid value was 65 KOH mg / g, and the residual acrylic acid concentration was 400 pp.
m and the b value of the 50% by weight aqueous graft polymer solution is 8
Met. [Example A-9] A phenoxy polyethylene glycol having a number average molecular weight of 530 (an average of 10 moles of ethylene oxide was added to phenol was added to a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser). thing)
100 parts by weight were charged, 17.5 parts by weight of maleic acid was charged, and the charged substance was dissolved by heating under a nitrogen stream, and the temperature was raised to 120 ° C. with stirring. Next, the temperature was adjusted to 117 to 123.
25.3 parts by weight of acrylic acid, perbutyl D (containing 98% of di-tert-butyl peroxide,
2.1 parts by weight (manufactured by Nippon Oil & Fats Co., Ltd.) were separately added dropwise continuously over 2 hours, and then stirring was continued for 1 hour to obtain a graft polymer.

While maintaining 100 parts by weight of the obtained 80% by weight aqueous solution of the graft polymer at 90 ° C., 1.1 parts by weight of a 35% by weight aqueous hydrogen peroxide solution and 0.4 parts by weight of triethylamine were separately added for 30 minutes. , And the mixture was continuously stirred for 30 minutes to obtain an aqueous graft polymer solution. The graft ratio of the graft polymer in the obtained aqueous graft polymer solution was 42%, and the carboxylic acid value was 235 KO.
Hmg / g, the residual acrylic acid concentration was 1980 ppm, and the b value of the 50% by weight aqueous graft polymer solution was 9. Example A-10 A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with a number average molecular weight of 530.
100 parts by weight of phenoxy polyethylene glycol (obtained by adding an average of 10 moles of ethylene oxide to phenol), and 17.5 parts by weight of maleic acid, and the charged substance was dissolved by heating under a nitrogen stream.
The temperature was raised to 130 ° C. with stirring. Next, the temperature was set to 127 to 1
While maintaining the temperature at 33 ° C., 25.3 parts by weight of acrylic acid and 2.1 parts by weight of perbutyl D (containing 98% of di-tert-butyl peroxide, manufactured by NOF CORPORATION) were separately and continuously fed for 2 hours. Then, stirring was continued for 1 hour to obtain a graft polymer.

While maintaining 100 parts by weight of an 80% by weight aqueous solution of the obtained graft polymer at 90 ° C., 1.1 parts by weight of a 35% by weight aqueous hydrogen peroxide solution and 0.8 parts by weight of a 48% by weight aqueous sodium hydroxide solution were added. , Separately and continuously for 30 minutes, followed by continuous stirring for 30 minutes to obtain an aqueous graft polymer solution. The graft ratio of the graft polymer in the obtained aqueous graft polymer solution was 41%, the carboxylic acid value was 235 KOH mg / g, the residual acrylic acid concentration was 2120 ppm, and the b value of the 50 wt% aqueous graft polymer solution was Was 9. Example A-11 A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with a number average molecular weight of 530.
100 parts by weight of phenoxy polyethylene glycol (obtained by adding an average of 10 moles of ethylene oxide to phenol), and 17.5 parts by weight of maleic acid, and the charged substance was dissolved by heating under a nitrogen stream.
The temperature was raised to 130 ° C. with stirring. Next, the temperature was set to 127 to 1
While maintaining the temperature at 33 ° C., 25.3 parts by weight of acrylic acid and 2.1 parts by weight of perbutyl D (containing 98% of di-tert-butyl peroxide, manufactured by NOF CORPORATION) were separately and continuously fed for 2 hours. Then, stirring was continued for 1 hour to obtain a graft polymer.

While keeping 100 parts by weight of an aqueous solution of the obtained graft polymer at 90 ° C., 1.1 parts by weight of a 35% by weight aqueous hydrogen peroxide solution and 4.0 parts by weight of a 10% by weight aqueous sodium persulfate solution were added. , Separately and continuously for 30 minutes, followed by continuous stirring for 30 minutes to obtain an aqueous graft polymer solution. The graft ratio of the graft polymer in the obtained aqueous graft polymer solution was 45%, the carboxylic acid value was 230 KOH mg / g, the residual acrylic acid concentration was 570 ppm, and the b value of the 50 wt% aqueous graft polymer solution was Was 9. [Example A-12] A number average molecular weight of 530 was added to a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser.
100 parts by weight of phenoxy polyethylene glycol (obtained by adding an average of 10 moles of ethylene oxide to phenol), and 17.5 parts by weight of maleic acid, and the charged substance was dissolved by heating under a nitrogen stream.
The temperature was raised to 130 ° C. with stirring. Next, the temperature was set to 127 to 1
While maintaining the temperature at 33 ° C., 25.3 parts by weight of acrylic acid and 2.1 parts by weight of perbutyl D (containing 98% of di-tert-butyl peroxide, manufactured by NOF CORPORATION) were separately and continuously fed for 2 hours. Then, stirring was continued for 1 hour to obtain a graft polymer.

While 100 parts by weight of the obtained 80% by weight aqueous solution of the graft polymer was kept at 90 ° C., 0.5 parts by weight of benzoyl peroxide containing 25% of water was added thereto all at once, and then stirring was continued for 1 hour. Thus, a graft polymer aqueous solution was obtained. The graft ratio of the graft polymer in the obtained aqueous graft polymer solution was 45%, and the carboxylic acid value was 230 KO.
Hmg / g, the residual acrylic acid concentration was 1960 ppm, and the b value of the 50% by weight aqueous graft polymer solution was 9. Example A-13 A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with a number average molecular weight of 530.
100 parts by weight of phenoxy polyethylene glycol (obtained by adding an average of 10 moles of ethylene oxide to phenol), and 17.5 parts by weight of maleic acid, and the charged substance was dissolved by heating under a nitrogen stream.
The temperature was raised to 130 ° C. with stirring. Next, the temperature was set to 127 to 1
While maintaining the temperature at 33 ° C., 25.3 parts by weight of acrylic acid and 2.1 parts by weight of perbutyl D (containing 98% of di-tert-butyl peroxide, manufactured by NOF CORPORATION) were separately and continuously fed for 2 hours. Then, stirring was continued for 1 hour to obtain a graft polymer.

While maintaining 100 parts by weight of an 80% by weight aqueous solution of the obtained graft polymer at 90 ° C., V50 (2,
2'-Azobis (2-amidinopropane) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto all at once, and then stirring was continued for 1 hour to obtain an aqueous graft polymer solution. The graft ratio of the graft polymer in the obtained aqueous graft polymer solution was 45%, the carboxylic acid value was 230 KOH mg / g, the residual acrylic acid concentration was 890 ppm, and the b value of the 50 wt% aqueous graft polymer solution was Was 11. [Comparative Example A-1] A phenoxy polyethylene glycol having a number average molecular weight of 910 (phenol was obtained by adding 20 moles of ethylene oxide on average to a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser). thing)
100 parts by weight and 17.5 parts by weight of maleic acid were charged, and the charged substance was dissolved by heating under a nitrogen stream, and the resulting mixture was stirred for 130 minutes.
The temperature was raised to ° C. Next, while maintaining the temperature at 127 to 133 ° C., 25.3 parts by weight of acrylic acid and 2.1 parts by weight of perbutyl D (containing 98% of di-tert-butyl peroxide, manufactured by NOF Corporation) were separately added. The mixture was continuously dropped for 2 hours, and then stirred for 1 hour to obtain a graft polymer.

The graft ratio of the obtained graft polymer was 4
5%, the carboxylic acid value was 230 KOH mg / g, the residual acrylic acid concentration was 2130 ppm, and 50% by weight.
The b value of the aqueous graft polymer solution was 11. [Comparative Example A-2] A phenoxy polyethylene glycol having a number average molecular weight of 910 (an average of 20 moles of ethylene oxide was added to phenol was obtained in a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser). thing)
100 parts by weight and 17.5 parts by weight of maleic acid were charged, and the charged substance was dissolved by heating under a nitrogen stream, and the resulting mixture was stirred for 130 minutes.
The temperature was raised to ° C. Next, while maintaining the temperature at 127 to 133 ° C., 25.3 parts by weight of acrylic acid and 2.1 parts by weight of perbutyl D (containing 98% of di-tert-butyl peroxide, manufactured by NOF Corporation) were separately added. Then, the mixture was continuously dropped over 2 hours, and thereafter, stirring was continued for 5 hours to obtain a graft polymer.

The graft ratio of the obtained graft polymer was 4
The carboxylic acid value was 218 KOH mg / g, the residual acrylic acid concentration was 980 ppm, and the b value of the 50% by weight aqueous graft polymer solution was 13. [Comparative Example A-3] A phenoxy polyethylene glycol having a number average molecular weight of 530 (an average of 10 moles of ethylene oxide was added to phenol was added to a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser). thing)
100 parts by weight and 17.5 parts by weight of maleic acid were charged, and the charged material was dissolved by heating under a nitrogen stream, and the mixture was stirred at 80 ° C.
Temperature. Next, while maintaining the temperature at 77 to 83 ° C, 25.3 parts by weight of acrylic acid and perbutyl D (di-t
2.1 parts by weight of tert-butyl peroxide (98% containing, manufactured by NOF CORPORATION) were separately added dropwise continuously over 2 hours, followed by stirring for 1 hour to obtain a graft polymer.

The graft ratio of the obtained graft polymer was 1
0%, the carboxylic acid value was 241 KOHmg / g, the residual acrylic acid concentration was 9800 ppm, and the
The b value of the aqueous graft polymer solution was 8. [Comparative Example A-4] A phenoxy polyethylene glycol having a number average molecular weight of 530 (an average of 10 moles of ethylene oxide was added to phenol was obtained in a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser). thing)
100 parts by weight and 17.5 parts by weight of maleic acid were charged, and the charged substance was dissolved by heating under a nitrogen stream, and then 100 parts by weight was stirred.
The temperature was raised to ° C. Next, while maintaining the temperature at 97 to 103 ° C., 25.3 parts by weight of acrylic acid and 6.1 parts by weight of 35% sodium persulfate were separately dropped continuously over 2 hours, and then stirred for 1 hour. Subsequently, a polymer was obtained.

The graft ratio of the obtained polymer was 0%, the carboxylic acid value was 246 KOH mg / g, the residual acrylic acid concentration was 890 ppm, and the b value of the 50% by weight aqueous polymer solution was 10. . Examples A-1 to A-13,
Comparative Examples A-1 to A-4 are summarized in Tables 1 and 2 below.
The polymers of Examples A-1, 2, 5, 9, 10, 12, and 13 are examples in which a water-soluble polymer was produced by the method for producing a water-soluble polymer according to the present invention. Does not produce such a hydrophilic graft polymer. In other examples, the hydrophilic graft polymer according to the present invention was produced by the method for producing a water-soluble polymer according to the present invention.

[0062]

[Table 1]

[0063]

[Table 2]

[Examples B-1 to B-5, Comparative Examples B-1 to B-4] (Evaluation of detergency) Examples A-1, 2, 4, 8, 11, and Comparative Examples A-1, 2, and 4 Using sodium salt of each polymer as a sample builder, sodium alkylbenzene sulfonate 2
A detergent composition was obtained by mixing 0% by weight, sample builder 20% by weight, No. 2 sodium silicate 10% by weight, anhydrous sodium carbonate 10% by weight, and anhydrous sodium sulfate 40% by weight.
In addition, water was added instead of the sample builder having the above composition to obtain a detergent composition to which no builder was added.

The detergency of each of the above detergent compositions was examined. Detergency was determined as follows. Water used is 4 ゜ D
Using water having a hardness of H (Ca ²⁺ / Mg ²⁺ = ^3/1 (molar ratio)), 0.1% by weight of the detergent composition obtained by the above blending was used.
A washing solution was prepared so as to have a concentration of 1. Using a tergotometer (manufactured by Koa Shokai Co., Ltd.), four artificially contaminated cloths of 10 cm × 10 cm were washed at a temperature of 25 ml in 500 ml of the washing solution.
Washing was performed at 100 rpm for 5 minutes at 100C. After rinsing for 5 minutes, the cloth was dried, and the state of stain removal of the cloth was measured for surface reflectance using a surface reflectance meter, and the cleaning rate was calculated according to the following equation.

Washing rate (%) = (RW−RS) / (RO−RS) × 100 RO: Surface reflectance of the present white cloth of the artificially stained cloth RS: Surface reflectance of the artificially stained cloth RW: Artificial contamination after washing The surface reflectance of the cloth The results are shown in Table 3. Those using the hydrophilic graft polymer of the present invention exhibited good builder performance. The hydrophilic graft polymers of Comparative Examples A-1 and A-2 only had poor hue, and thus had no problem in builder performance.

[0067]

[Table 3]

[Examples C-1 to C-5, Comparative Examples C-1 to C-3] (Evaluation as a water treatment agent) Examples A-1, 2, 4, 8,
11, the scale prevention performance was evaluated using each polymer of Comparative Examples A-1, 2, and 4 as a water treatment agent. 170 g of water is placed in a glass bottle having a capacity of 225 ml, 10 g of a 1.56% by weight aqueous solution of calcium chloride dihydrate, and 0.0 g of each polymer.
3 g of a 2% by weight aqueous solution was mixed, and 10 g of a 3% by weight aqueous solution of sodium bicarbonate and 7 g of water were added to make the total amount 20%.
0 g. The obtained 530 ppm supersaturated aqueous solution of calcium carbonate was sealed and heated at 70 ° C. for 3 hours.
After cooling, the precipitate was filtered through a membrane filter having a pore size of 0.1 μm, and the filtrate was analyzed according to JIS K0101 to determine the scale inhibition rate (%) according to the following equation. The results are shown in Table 4.

Scale inhibition rate (%) = (CB) / (A
-B) × 100 A: The concentration of calcium dissolved in the solution before the test B: The concentration of calcium in the filtrate tested without the addition of a scale inhibitor C: The concentration of calcium in the filtrate after the test It is described in Table 4. Those using the hydrophilic graft polymer of the present invention showed a good scale inhibition rate. In addition,
Since the hydrophilic graft polymers of Comparative Examples A-1 and A-2 only had poor hue, there was no problem with the scale inhibition rate.

[0070]

[Table 4]

[Examples D-1 to D-4, Comparative Examples D-1 to D-4] (Evaluation as a fiber treatment agent) Examples A-1, 2, 4, 1
1. Each of the polymers of Comparative Examples A-1, 2, and 4, and a conventionally known compound, having a weight average molecular weight of 5,000 and a molar ratio of maleic acid structural unit to acrylic acid structural unit of 3: 7 in molar ratio. Certain maleic acid-acrylic acid copolymer sodium salts were used to evaluate their performance as fiber treatment agents. That is, a fiber treating agent was formed as a composition containing 2 g / L (in terms of solid content) of each polymer. The various components and the amounts blended in the fiber treatment agent are shown below. The fiber treating agent is an aqueous solution.

(Components of Fiber Treatment Agent) Each polymer 2 g / L hydrogen peroxide 10 g / L sodium hydroxide 2 g / L No. 3 sodium silicate 5 g / L A bleaching test was conducted using the obtained fiber treatment agent. Was. As a test cloth, a scoured cotton sheet knit was used.
The bleaching conditions are shown below. (Bleaching conditions) Hardness of used water 35 DH (German hardness) Bath ratio 1:25 Temperature 85 ° C Time 20 minutes Then, the texture of the bleached cloth was determined by a sensory inspection method. The whiteness is 3M manufactured by Suga Test Instruments Co., Ltd.
Color measurement using a color computer SM-3
b-based whiteness formula W = 100 − [(100−L) ² + a ² + b ² ] ^1/2 L: measured lightness a: measured red chromaticness index b: measured blue chromaticness The degree of whiteness (W value) was determined by an index and evaluated. Further, the sewability was evaluated by the number of broken ground yarns when four cloths were piled up and 30 cm of empty sewing was performed with a needle # 11S on a lockstitch sewing machine.

The results are shown in Table 5. Those using the hydrophilic graft polymer of the present invention are superior in texture and whiteness, and greatly reduce the number of ground yarn breaks, as compared with the case where a conventionally known compound is used as a fiber treatment agent. You can see that it is. Since the hydrophilic graft polymers of Comparative Examples A-1 and A-2 only had poor hue, there was no problem with the scale suppression rate.

[0074]

[Table 5]

[Example E-1, Comparative Example E-1] (Evaluation as Dispersant) The performance of each polymer of Example A-6 and Comparative Example A-4 as a dispersant was evaluated. Light viscosity calcium carbonate (Brilliant # 1500: trade name, manufactured by Shiraishi Industry Co., Ltd.) / Water = 60/40 (weight ratio), each polymer was added to the slurry, and the viscosity of the slurry was adjusted by stirring. Was measured with a B-type rotational viscometer and expressed in units of centipoise. When each polymer was not added, the slurry had almost no fluidity, and viscosity measurement was impossible.

The results are shown in Table 6. The graft polymer of the present invention exhibited better performance as a dispersant than the polymer of Comparative Example A-4, and the viscosity of the calcium carbonate slurry was reduced at a low addition amount.

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[Table 6]

[0078]

The hydrophilic graft polymer of the present invention is a polymer in which the coloring of the polymer is small and the residual monomer (particularly, monoethylenically unsaturated monocarboxylic acid) is reduced.
ADVANTAGE OF THE INVENTION According to the manufacturing method of the hydrophilic graft polymer of this invention, the coloring of a polymer is small, and the hydrophilic graft polymer in which the residual monomer was reduced can be manufactured. According to the method for producing a water-soluble polymer of the present invention, it is possible to produce a water-soluble polymer in which the coloring of the polymer is small and the residual monomer is reduced.

Continued on the front page (72) Inventor Yoshikazu Fujii 5-8, Nishiobari-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Inventor Shigeru Yamaguchi 5-8, Nishiobari-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. F-term (reference) 4H003 EB30 EB32 FA04 4J026 AB19 AB20 AB21 BA04 BA20 BA25 BA27 BA29 BA30 BA31 BA32 BA34 BA35 BA36 BA39 BA40 DA04 DA15 DB04 EA02 GA01 GA06

Claims (6)

[Claims] 1. A polyalkylene glycol comprising 10 to 90 mol% of a monoethylenically unsaturated monocarboxylic acid, 10 to 90 mol% of a monoethylenically unsaturated dicarboxylic acid and 0 to 10 other monoethylenically unsaturated monomers copolymerizable. 80m
ol% of the hydrophilic graft polymer obtained by graft polymerization of the monomer component, the content of the monoethylenically unsaturated monocarboxylic acid is 900 ppm or less;
A hydrophilic graft polymer, wherein the hue (b value) of the aqueous solution by weight is 10 or less. 2. A hydrophilic graft polymer obtained by polymerizing a hydrophilic graft polymer obtained by graft-polymerizing a monomer component to a polyalkylene glycol, and performing a post-treatment in the presence of an additive in the state of an aqueous solution of the polymer. A method for producing a graft polymer. 3. The method for producing a water-soluble polymer according to claim 2, wherein a peroxide different from the polymerization initiator used in the polymerization is used as the additive. 4. A detergent builder comprising the hydrophilic graft polymer according to claim 1. 5. A detergent builder comprising the hydrophilic graft polymer produced by the production method according to claim 2. 6. A non-aqueous polymerization is carried out to obtain a water-soluble polymer, and the polymer is dissolved in water to form an aqueous solution, and the aqueous solution is subjected to post-treatment in the presence of an additive. Method for producing functional polymer.