JP2015140368A - Acid group-containing graft polymer, production method therefor and builder for detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer excellent in more improved re-contamination prevention performance than conventional ones when used for a detergent application, and a production method therefor.SOLUTION: There is provided an acid base-containing graft polymer obtained by a graft polymerization of a polyoxy alkylene compound and an acid group-containing unsaturated monomer in the presence of an organic peroxide polymerization initiator having a half life at 135°C of 1 to 5 hours. The polyoxy alkylene compound has an aryl group having 8 carbon atoms, an alkyl group having 8 carbon atoms and at least one alkenyl group having 8 carbon atoms and an oxyalkylene group, and in the polyoxy alkylene compound, the content of a structure derived from the oxyalkylene group per 1 mole of the polyoxy alkylene compound is 2 to 16 mole and mass ratio of the structure derived from the polyoxy alkylene compound (a) and the structure derived from the acid group-containing unsaturated monomer (b) is (a):(b)=80:20 to 50:50.

Description

  The present invention relates to an acid group-containing graft polymer, a production method thereof, and a builder for a detergent.

  Conventionally, detergents used in apparel have been blended with detergent builders (detergent aids) such as zeolite, carboxymethyl cellulose, and polyethylene glycol for the purpose of improving the cleaning effect of the detergent.

  In addition to the above various detergent builders, in recent years, polymers have been blended in detergent compositions as detergent builders.

  For example, Patent Document 1 discloses a water-soluble / water-dispersible graft having a predetermined amount of graft component and a hydrophobic residue bonded to the graft component via a polyglycol ether chain having a predetermined chain length. The use of the polymer as a detergent builder is disclosed. However, since a large amount of water is used as the polymerization solvent, there is a problem that the graft ratio is not sufficiently improved. If the grafting rate is low, the blending stability into the liquid detergent is lowered, so that a higher grafting rate is required.

  Patent Documents 2 to 4 and 12 disclose that when a polyoxyalkylene compound is graft-polymerized with an acid group-containing unsaturated monomer, the half-life of the polymerization initiator at 135 ° C. is 6 to 60 minutes. A polymer composition obtained using an oxide polymerization initiator is disclosed. However, since the half-life of the polymerization initiator is short, there are problems that the graft initiation point increases and the graft side chain length becomes short.

  Patent Document 5 discloses a polymer obtained by graft polymerization of a monomer component containing a hydrophilic monomer having an anionic group or a hydroxyl group on a polyoxyalkylene compound. However, since the repeating unit of the oxyalkylene group having 2 to 6 carbon atoms is as large as 17 to 200, it is clear from the inventors of the present invention that the ability to prevent recontamination is reduced as compared with the case where the repeating unit is small. It has become.

  Patent Documents 6 and 10 disclose a polymer obtained by graft polymerization of acrylic acid or maleic acid to methoxypolyethylene glycol having a methoxy group at the end of a polyoxyalkylene compound. Since these polymers are difficult to introduce hydrophobic groups due to foaming at the time of polymerization, there is a problem that the cleaning performance against hydrophobic soil is low.

Patent Documents 6 to 11 disclose a polymer obtained by graft polymerization of acrylic acid or maleic acid to phenoxypolyethylene glycol having a phenoxy group at the end of a polyoxyalkylene compound.
These polymers include unreacted phenols and aromatic derivatives obtained by decomposing polymers. Therefore, when a polymer is used for a detergent composition, there is a problem that a substance that may cause harm to the living environment may be discharged into a river or the like.

JP 59-62614 A JP 2010-77427 A JP 2010-209136 A JP 2009-256656 A JP 2007-254679 A JP 2001-294616 A JP2013-155321A JP 2013-1819 A JP 2007-246916 A Japanese Patent Laid-Open No. 11-60652 JP 2001-226441 A JP 2001-247346 A

Thus, although various graft polymers have been reported in the past, development of a detergent builder adapted to the current consumer needs described above has been demanded.
Then, an object of this invention is to provide the polymer excellent in the recontamination prevention ability improved more conventionally than when used for detergent use, and its manufacturing method.

  The present inventors have intensively studied to solve the above problems. As a result, when the present inventors graft-polymerize a polyoxyalkylene compound having an oxyalkylene group of a specific repeating unit and an acid group-containing monomer at a specific ratio using a specific polymerization initiator, The inventors have found that the ability to prevent recontamination of the obtained graft polymer is improved, and have completed the present invention.

  That is, the present invention is obtained by graft polymerization of a polyoxyalkylene compound and an acid group-containing unsaturated monomer in the presence of an organic peroxide polymerization initiator having a half life of 135 ° C. of 1 to 5 hours. The polyoxyalkylene compound is an acid group-containing graft polymer obtained by using at least one of an aryl group having 8 or more carbon atoms, an alkyl group having 8 or more carbon atoms and an alkenyl group having 8 or more carbon atoms, and an oxyalkylene group. The content of the structure derived from the oxyalkylene group per mole of the polyoxyalkylene compound is 2 to 16 moles, and the structure (a) derived from the polyoxyalkylene compound and the acid group-containing unsaturated simple substance It is an acid group containing graft polymer whose mass ratio with the structure (b) derived from a monomer is (A) :( B) = 80: 20 to 50:50.

  The polymer of the present invention has an excellent ability to prevent recontamination. Therefore, if the polymer of the present invention is used as a detergent builder, recontamination of dirt during washing is prevented. Therefore, the polymer of the present invention can be preferably used as a detergent additive.

  Hereinafter, the present invention will be described in detail.

<1> The acid group-containing graft polymer of the present invention is
In the presence of an organic peroxide polymerization initiator having a half-life of 135 ° C. of 1 to 5 hours,
An acid group-containing graft polymer obtained by graft polymerization of a polyoxyalkylene compound and an acid group-containing unsaturated monomer,
The polyoxyalkylene compound has at least one of an aryl group having 8 or more carbon atoms, an alkyl group having 8 or more carbon atoms and an alkenyl group having 8 or more carbon atoms and an oxyalkylene group. The content of the structure derived from the per oxyalkylene group is 2 to 16 mol,
The mass ratio between the structure (a) derived from the polyoxyalkylene compound and the structure (b) derived from the acid group-containing unsaturated monomer is as follows:
(A): (B) = 80: 20 to 50:50,
It is an acid group-containing graft polymer.

<2> The acid group-containing graft polymer of the present invention is
In the presence of water and / or organic solvent,
With respect to the total amount of the polyoxyalkylene compound and the acid group-containing unsaturated monomer,
The total amount of water and organic solvent is 5% by mass or less,
An acid group-containing graft polymer obtained by graft polymerization of a polyoxyalkylene compound and an acid group-containing unsaturated monomer.
The acid group-containing graft polymer according to claim 1.

<3> The acid group-containing graft polymer of the present invention as still another embodiment is
The acid group-containing graft polymer according to claim 1, wherein the acid group-containing unsaturated monomer is acrylic acid.

<4> The acid group-containing graft polymer composition of the present invention comprises:
An acid group-containing graft polymer composition comprising the acid group-containing graft polymer and a polyoxyalkylene compound,
The acid group-containing graft polymer is 50 to 99.9% by mass,
The polyoxyalkylene compound is 0.1 to 50 mass,
The acid group-containing graft polymer; and
The content (I) of an aryl group having 8 or more carbon atoms, an alkyl group having 8 or more carbon atoms, and an alkenyl group having 8 or more carbon atoms constituting the polyoxyalkylene compound,
10 to 35% by mass relative to the total amount of the acid group-containing graft polymer composition,
It is an acid group-containing graft polymer composition.

<5> The method for producing the acid group-containing graft polymer of the present invention comprises:
In the presence of an organic peroxide polymerization initiator having a half-life of 135 ° C. of 1 to 5 hours,
A structure having at least one of an aryl group having 8 or more carbon atoms, an alkyl group having 8 or more carbon atoms and an alkenyl group having 8 or more carbon atoms and an oxyalkylene group, and derived from an oxyalkylene group per mole of a polyoxyalkylene compound A polyoxyalkylene compound (A) having a content of 2 to 16 mol,
The acid group-containing unsaturated monomer (B)
In the ratio (A) :( B) = 80: 20-50: 50 by mass ratio,
In the presence of water and / or organic solvent,
With respect to the total amount of the polyoxyalkylene compound and the acid group-containing unsaturated monomer,
The total amount of the water and the organic solvent is 5% by mass or less,
This is a method for producing an acid group-containing graft polymer having a step of graft polymerization.

  <6> The use of the acid group-containing graft polymer and polymer composition of the present invention is a detergent builder.

[Polyoxyalkylene compounds]
The polyoxyalkylene compound of the present invention has a hydrophobic group selected from at least one of an aryl group having 8 or more carbon atoms, an alkyl group having 8 or more carbon atoms, and an alkenyl group having 8 or more carbon atoms. It contains a group. Here, the content of the structure derived from the oxyalkylene group per mole of the polyoxyalkylene compound (number of added oxyalkylene groups) is 2 to 16 moles.

  Although it does not specifically limit, As a polyoxyalkylene type compound of this invention, what has a structure of the following general formula (1) is specifically mentioned.

  In the general formula (1), R represents an aryl group having 8 or more carbon atoms, an alkyl group having 8 or more carbon atoms, and an alkenyl group having 8 or more carbon atoms. The alkyl group or alkenyl group may be linear or branched. At this time, the carbon number of R is preferably 8 to 20, more preferably 10 to 20, still more preferably 11 to 18, and particularly preferably 12 to 14. If the carbon number of R is less than the lower limit, the interaction between the resulting acid group-containing graft polymer and the hydrophobic soil is weakened, and the ability to prevent recontamination may be reduced. On the other hand, when R has 20 or less carbon atoms, the viscosity is moderate and polymerization can be easily performed. When the carbon number of R is in the above range, the ability to prevent recontamination of the polymer composition is improved.

  The acid group-containing graft polymer preferably does not contain an aromatic ring in its structure. This is because, when the graft polymer of the present invention is discharged into the environment, when the acid group-containing graft polymer is decomposed, the aromatic ring contained in the polymer can cause harmful substances. From such a viewpoint, R is preferably an alkyl group or an alkenyl group. Furthermore, from the viewpoint of relatively low viscosity and easy handling, R is preferably a secondary alkyl group or alkenyl group.

  Examples of the alkyl group having 8 or more carbon atoms include 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, Nonadecyl group, icosyl group, etc. are mentioned.

  Examples of the alkenyl group having 8 or more carbon atoms include octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, and the like. Examples include an icosylene group. Among them, R is preferably 2-ethylhexyl group, dodecyl group, tridecyl group, tetradecyl group, dodecylene group, tridecylene group, tetradecylene group, and is 2-ethylhexyl group, dodecyl group, tridecyl group, tetradecyl group. Is more preferable.

  Examples of the aryl group having 8 or more carbon atoms include phenethyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, biphenylyl group, trityl group, and pyrenyl group. Of these, a phenethyl group, a 2,3- or 2,4-xylyl group, or a naphthyl group is preferable, and a phenethyl group, a 2,3-, or 2,4-xylyl group is more preferable.

  In the general formula (1), X is

  P is 0-1. As described above, the graft polymer of the present invention preferably does not contain an aromatic ring in its structure. Therefore, in the formula (1), when p is 1, X is preferably a carbonyl group. However, it is more preferable that p is 0 (that is, X does not exist).

  In the general formula (1), Y is

Represents one of the following. Here, R _{1 to} R ₄ each independently represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms, and most preferably 2 carbon atoms. R ₅ represents a hydrogen atom or a group represented by the following general formula (2):

It is. In the general formula (2), R ₆ and R ₇ are each independently an alkylene having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms, and most preferably 2 carbon atoms. Represents a group. Moreover, s is 0-200, Preferably it is 0-100, More preferably, it is 0-70, More preferably, it is 0-55. Incidentally, suppose that s is 2 or more, may be present alone by itself as R _7, or two or more may be mixed. Here, Y is preferably —O—R ₁ — from the viewpoint of improving the ability to prevent recontamination.

In the general formula (1), Z represents an oxyalkylene group. At this time, the carbon number of Z is 2 to 20, preferably 2 to 15, more preferably 2 to 10, still more preferably 2 to 5, and particularly preferably 2 to 3. And most preferably 2. Examples of the oxyalkylene group include ethylene oxide (EO), propylene oxide (PO), isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene monooxide, Examples include groups derived from compounds such as octylene oxide, styrene oxide, and 1,1-diphenylethylene oxide. Among these, Z is preferably a group derived from EO or PO (that is, an oxyethylene group or an oxypropylene group), and more preferably an oxyethylene group. In addition, as Z, only 1 type may exist independently and 2 or more types may be mixed. In the said General formula (1), q is 2-16, Preferably it is 3-15, More preferably, it is 5-15, More preferably, it is 7-12.
When q is 2 or less, polymerization may be difficult. Moreover, there exists a possibility that the recontamination prevention ability may also fall with the water solubility fall of a polymer. On the other hand, when q is 16 or more, the viscosity becomes high, and it becomes difficult to polymerize a composition having a high carboxylic acid ratio, or even if the polymerization can be performed, the graft side chain length is shortened so that the capturing ability is lowered. Since the hydrophobic group ratio is lowered, the interaction with the hydrophobic soil is lowered, so that the ability to prevent recontamination may be lowered. In addition, the yield of a graft body improves as q becomes large.

The group formed by the oxyalkylene group (that is, Zq in the general formula (1)) is preferably mainly composed of an oxyethylene group (—O—CH ₂ —CH ₂ —). In this case, “mainly composed of oxyethylene groups” means that when two or more oxyalkylene groups are present in the monomer, the oxyethylene groups occupy most of the total number of oxyalkylene groups present. It means that. Thereby, the superposition | polymerization at the time of manufacture advances smoothly, and the outstanding effect that water solubility and the ability to prevent recontamination improve is acquired.

  In Zq in the general formula (1), when “mainly composed of oxyethylene groups” is expressed by mol% of oxyethylene groups in 100 mol% of all oxyalkylene groups, it is 50 to 100 mol%. preferable. When the content of the oxyethylene group is less than 50 mol%, the hydrophilicity of the group formed from the oxyalkylene group may be lowered. More preferably, it is 60 mol% or more, more preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more.

  In the general formula (1), r is an integer of 1 to 6. When r is 2 or more, the polyoxyalkylene-based compound represented by the general formula (1) has the general formula (1) at a different carbon atom of R (predetermined alkyl group or alkylene group) described above. ) Have a structure in which groups represented by parentheses are bonded to each other, and does not include a repeating structure having a group represented by parentheses of the general formula (1) as a repeating unit. In this case, the groups represented by parentheses in the general formula (1) may be the same or different. R is preferably 1 to 4, more preferably 1 to 2, and most preferably 1.

  Among the compounds represented by the general formula (1), the polyoxyethylene compound most preferably used in the present invention is a compound represented by the following general formula (3).

In the said General formula (3), R, R < ₁ >, Z and q are synonymous with the thing in the said General formula (1). Specifically, it is the same as that described in the column of the general formula (1).

  If such a polyoxyalkylene compound is commercially available, the product may be purchased or may be prepared by itself. Methods for preparing polyoxyalkylene compounds themselves include, for example, 1) strong anion such as alkali metal hydroxides and alkoxides, anionic polymerization using alkylamine or the like as a base catalyst, and 2) halogens of metals and metalloids. Cationic polymerization using fluoride, mineral acid, acetic acid, etc. as a catalyst, 3) Coordination polymerization using a combination of alkoxides of metals such as aluminum, iron, zinc, alkaline earth compounds, Lewis acids, etc. And a method of adding the above-described alkylene oxide to an alcohol, ester, amine, amide, thiol, sulfonic acid or the like containing a hydrocarbon group portion of a polyoxyalkylene compound. Examples of the polyoxyalkylene compound include polyethylene glycol, methoxypolyethylene glycol, butoxyethylene glycol, and phenoxypolyethylene glycol.

[Acid group-containing unsaturated monomer]
In a polymer obtained by graft polymerization of an acid group-containing unsaturated monomer to the polyoxyalkylene compound of the present invention (hereinafter also simply referred to as “graft polymer”), the acid group-containing unsaturated monomer is grafted. By polymerization, a chain grafted to the carbon atom of the polyoxyalkylene chain of the polyoxyalkylene compound described above is formed.

  The acid group-containing unsaturated monomer is a monomer having an acid group. Here, examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphonic acid group. Examples of such acid group-containing unsaturated monomers include monomers having a carboxyl group such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid; 2-acrylamido-2-methyl Monomers having a sulfonic acid group such as propanesulfonic acid, (meth) allylsulfonic acid, vinylsulfonic acid, 2-hydroxy-3-allyloxy-1-propanesulfonic acid, 2-hydroxy-3-butenesulfonic acid; vinyl Examples thereof include monomers having a phosphonic acid group such as phosphonic acid and (meth) allylphosphonic acid. Among them, from the viewpoint of high polymerizability, weak acidity and easy handling, the acid group-containing unsaturated monomer preferably has a carboxyl group, (meth) acrylic acid, maleic acid More preferably, acrylic acid and maleic acid are more preferable, and acrylic acid is particularly preferable. Only one kind of these acid group-containing unsaturated monomers may be used alone, or two or more kinds may be used in combination.

  In addition to the acid group-containing unsaturated monomer, other monomers copolymerizable with the acid group-containing unsaturated monomer may be included. Other monomers are not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Hydroxyl group-containing alkyl (meth) acrylates such as acrylate, 4-hydroxybutyl (meth) acrylate, α-hydroxymethylethyl (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid Alkyl (meth) acrylates obtained by esterification of (meth) acrylic acid such as butyl, cyclohexyl (meth) acrylate and alcohols having 1 to 18 carbon atoms; dimethylaminoethyl (meth) acrylate or a quaternized product thereof Amino group-containing acrylates of Amide group-containing monomers such as acrylamide, dimethylacrylamide, and isopropylacrylamide; Vinyl esters such as vinyl acetate; Alkenes such as ethylene and propylene; Aromatic vinyl monomers such as styrene and styrenesulfonic acid; Maleimide , Phenylmaleimide, cyclohexylmaleimide and other maleimide derivatives; (meth) acrylonitrile and other nitrile group-containing vinyl monomers; (meth) acrolein and other aldehyde group-containing vinyl monomers; methyl vinyl ether, ethyl vinyl ether, butyl And alkyl vinyl ethers such as vinyl ether; vinyl chloride, vinylidene chloride, allyl alcohol: other functional group-containing monomers such as vinyl pyrrolidone; and the like. Also about these other monomers, only 1 type may be used independently and 2 or more types may be used together. In addition, when the monomer component contains other monomers in addition to the acid group-containing unsaturated monomer, in the graft chain composed of these monomer components, the structural unit derived from each monomer component The addition form is not particularly limited, and for example, it may be added in a random form or may be added in a block form. Hereinafter, the acid group-containing unsaturated monomer and other monomers copolymerizable with the acid group-containing unsaturated monomer are also referred to as “monomer component”.

  The ratio of the acid group-containing unsaturated monomer and the acid group-containing unsaturated monomer in the whole other monomers copolymerizable with the acid group-containing unsaturated monomer is not particularly limited, but the present invention The ratio of the acid group-containing unsaturated monomer with respect to the total amount of the monomer components is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, from the viewpoint of sufficiently exerting the operational effects of More preferably, it is 95-100 mol%, Most preferably, it is 100 mol%.

[Acid group-containing graft polymer]
As described above, the acid group-containing graft polymer of the present invention has a structure in which an acid group-containing unsaturated monomer is graft polymerized to a polyoxyalkylene compound.

  The weight average molecular weight of the acid group-containing graft polymer of the present invention is not particularly limited because it can be appropriately set in consideration of the desired performance as a detergent builder, etc., but the weight average of the acid group-containing graft polymer of the present invention is not limited. Specifically, the molecular weight is preferably 300 to 50,000, more preferably 500 to 30,000, and still more preferably 1,000 to 20,000. When the value of the weight average molecular weight is too large, the viscosity becomes high and handling may be complicated. On the other hand, if the value of the weight average molecular weight is too small, the ability to prevent recontamination may not be exhibited. In addition, the value measured by the method as described in the Example mentioned later shall be employ | adopted as a value of the weight average molecular weight of the acid group containing graft polymer of this invention.

  In addition, the number average molecular weight of the acid group-containing graft polymer of the present invention is not particularly limited because it can be appropriately set in consideration of the desired performance as a detergent builder, but the acid group-containing graft polymer of the present invention is not particularly limited. Specifically, the number average molecular weight is preferably 300 to 25,000, more preferably 350 to 15,000, and still more preferably 500 to 10,000. When the value of the number average molecular weight is too large, the viscosity becomes high and handling may be complicated. On the other hand, if the value of the number average molecular weight is too small, the ability to prevent recontamination may not be exhibited. In addition, as a value of the number average molecular weight of the acid group containing graft polymer of this invention, the value measured by the method as described in the Example mentioned later shall be employ | adopted.

In the acid group-containing graft polymer of the present invention, the mass ratio between the structure (a) derived from the polyoxyalkylene compound and the structure (b) derived from the acid group-containing unsaturated monomer is (a): (B) = 80: 20 to 50:50, preferably 78:22 to 50:50, more preferably 77:23 to 55:45, and even more preferably 75:25 to 60:40. is there. If the amount of the structure derived from the acid group-containing unsaturated monomer is too small, the calcium capturing ability and the recontamination preventing ability may be lowered. On the other hand, when the amount of the structure derived from the acid group-containing unsaturated monomer is large, the yield of the graft product tends to be improved, but the dispersibility of the hydrophobic soil tends to be reduced. Preferably there is.
In calculating the mass ratio between the structure derived from the polyoxyalkylene compound and the structure derived from the acid group-containing unsaturated monomer, the mass with the structure derived from the acid group-containing unsaturated monomer corresponds to Calculate the mass of the acid type.

  The graft amount of the acid group-containing unsaturated monomer is not particularly limited, and can be appropriately set in consideration of desired performance as a detergent builder, ease of production, and the like. In particular, the amount of the acid group-containing unsaturated monomer contained in the monomer component may be controlled.

  As described above, the acid group-containing graft polymer of the present invention can disperse hydrophobic soils when used as a detergent builder. That is, it is possible to suppress the hydrophobic dirt from being deposited on the fiber or the like during washing. Accordingly, the acid group-containing graft polymer of the present invention is preferably used as a detergent builder.

[Polymer composition]
The acid group-containing graft polymer of the present invention can be used as a polymer composition. In the polymer composition of the present invention, an acid group-containing graft polymer is essential. In addition, unreacted polyoxyalkylene compounds, by-products derived from acid group-containing unsaturated monomers, unreacted acid group-containing unsaturated monomers, unreacted polymerization initiators, decomposition products of polymerization initiators Further, a polymer composed of an acid group-containing unsaturated monomer may be included.

The mass ratio of the structure (a) derived from the polyoxyalkylene compound present in the polymer composition to the structure (b) derived from the acid group-containing unsaturated monomer is a structure derived from the polyoxyalkylene compound: acid. The ratio of the structure derived from the group-containing unsaturated monomer is (a) :( b) = 80: 20-50: 50, preferably 78: 22-50: 50, more preferably 77. : 23-55: 45, more preferably 75: 25-60: 40. If the amount of the structure derived from the acid group-containing unsaturated monomer is too small, the calcium capturing ability and the recontamination preventing ability may be lowered. On the other hand, when the amount of the structure derived from the acid group-containing unsaturated monomer is large, the yield of the graft product tends to be improved, but the dispersibility of the hydrophobic soil tends to be reduced. Preferably there is.
In calculating the mass ratio between the structure derived from the polyoxyalkylene compound and the structure derived from the acid group-containing unsaturated monomer, the mass with the structure derived from the acid group-containing unsaturated monomer is the corresponding acid. Calculate with the mass of the mold.

  The structure derived from a polyoxyalkylene compound refers to a structure derived from a polyoxyalkylene compound in the acid group-containing graft polymer of the present invention and an unreacted polyoxyalkylene compound (in the case of formation, a polyoxyalkylene compound). The total of (including a polymer of alkylene compounds). Therefore, the mass of the structure derived from the polyoxyalkylene compound is the same as the mass of the polyoxyalkylene compound used in the graft polymerization. Similarly, the structure derived from an acid group-containing unsaturated monomer includes the structure derived from the acid group-containing unsaturated monomer in the acid group-containing graft polymer, the unreacted acid group-containing unsaturated monomer, and the acid. The total of the structure derived from the acid group containing unsaturated monomer in the polymer of group containing unsaturated monomers is pointed out. Therefore, the mass of the structure derived from the acid group-containing unsaturated monomer is the same as the mass of the acid group-containing unsaturated monomer used in the graft polymerization.

  In the present invention, unreacted polyoxyalkylene compounds are reduced by using a specific polymerization initiator described later. Specifically, the reacted polyoxyalkylene compound and the unreacted polyoxyalkylene compound total 100 parts by mass (100 parts by mass of the polyoxyalkylene compound added to the reaction system). The oxyalkylene compound is preferably 45 to 100 parts by mass, more preferably 50 to 100 parts by mass, and still more preferably 55 to 100 parts by mass. The amount of the reacted polyoxyalkylene compound is calculated from the amount of the unreacted polyoxyalkylene compound described in Examples described later.

  The polymer composition referred to in the present application is not particularly limited, but is preferably obtained without a purification step such as impurity removal from the viewpoint of production efficiency. In the polymer composition of the present invention, the remaining polyoxyalkylene compound is reduced, and the yield of the acid group-containing graft polymer (graft) is improved. The effect of improving the ability to prevent pollution can be obtained effectively. Furthermore, after the polymerization step, the obtained mixture is diluted with a small amount of water for convenience of handling (about 1 to 400% by mass with respect to the obtained mixture), and the polymer composition referred to in the present application. include.

  In addition, the term “composition” in the present application essentially includes an acid group-containing graft polymer as a main component, and includes one or more compounds 1-4 described below in addition to the acid group-containing graft polymer. Used to mean a mixture.

The yield of the graft body can be compared with the value calculated by the graft body yield calculation method described later. In general, when the composition ratio of the monomer is increased, a homopolymer of the monomer is formed, and the yield of the graft body is decreased. Even if the composition ratio of the monomer is increased beyond a certain composition, the monomer homopolymer tends to be generated, and therefore, the remaining amount of the unreacted polyoxyalkylene compound is generally reduced. It reaches a peak. However, for example, by using a specific initiator described later, a high graft yield is exhibited even if the monomer composition ratio is increased. In such a case, the polymer composition will contain a residue derived from a specific initiator.
The polymer composition of the present application preferably has at least one of compounds 1 to 4 as a residue derived from an initiator, and exhibits an excellent graft product yield when compared at the same monomer composition ratio. .

  The content of the acid group-containing unsaturated monomer (including the monomer constituting the polymer of the acid group-containing unsaturated monomers) is preferably 1,000 mass ppm or less in the composition, More preferably, it is 100 mass ppm or less, Most preferably, it is 0 mass ppm.

[Compounds 1 to 4]
In the polymer composition of this invention, at least 1 of the compounds 1-4 represented by a following formula may be contained.

  These compounds are decomposition products of an organic peroxide polymerization initiator having a half-life of 135 ° C. of 1 to 5 hours. Therefore, for example, when di-t-butyl peroxide (hereinafter also referred to as PBD) is used, compound 1 is included in the polymer composition. Similarly, for example, when dicumyl peroxide (hereinafter also referred to as PCD) is used as a polymerization initiator, when the compound 2 uses di-t-hexyl peroxide in the polymer composition, In the case where compound 3 uses p-mentahydroperoxide (hereinafter also referred to as PMH) as a polymerization initiator, compound 4 may be included in the polymer composition.

  In addition, a polymerization initiator may be used individually by 1 type, and may be used 2 or more types. Therefore, the polymer composition of the present invention may contain two or more of the compounds 1 to 4.

  Content that the said compounds 1-4 are contained in the polymer composition of this invention is 0.01-5.0 mass% with respect to the whole polymer composition (solid content conversion of a composition). Is preferred. If it is such a range, the polymerization initiator used will be a suitable quantity, and the composition containing the graft polymer excellent in the performance can be obtained. In addition, the said content points out total content, when the said compounds 1-4 are contained 2 or more. Content in the composition of the said compounds 1-4 is measured by the method as described in the below-mentioned Example.

  Moreover, in a polymer composition, the said compounds 1-4 are 0.3-20 mass parts with respect to 100 mass parts of acid group containing unsaturated monomers, Preferably 1-10 mass parts, More preferably, 1 -5 mass parts is contained. If it is such a range, it means that the polymerization initiator used is an appropriate amount, and a polymer composition containing an acid group-containing graft polymer excellent in recontamination prevention ability can be obtained. Here, the amount of the acid group-containing unsaturated monomer refers to the total amount of the acid group-containing unsaturated monomer used when the acid group-containing graft polymer is produced. That is, the amount of the acid group-containing unsaturated monomer is determined based on the structure derived from the acid group-containing unsaturated monomer in the acid group-containing graft polymer in the polymer composition, the unreacted acid group-containing unsaturated monomer. It can also be said that the total amount of the polymer consisting of the polymer and the acid group-containing unsaturated monomer.

  Furthermore, the acid group-containing graft polymer composition of the present invention is an acid group-containing graft polymer composition comprising the acid group-containing graft polymer and a polyoxyalkylene compound, wherein the acid group-containing graft polymer is 50 to 99.9% by mass, the polyoxyalkylene compound is 0.1 to 50% by mass, and the acid group-containing graft polymer and the polyoxyalkylene compound constitute an aryl group having 8 or more carbon atoms The content of the alkyl group having 8 or more carbon atoms and the content of the alkenyl group having 8 or more carbon atoms is 10 to 35% by mass with respect to the total amount of the acid group-containing graft polymer composition. It is a thing.

The ratio of the acid group-containing graft polymer contained in the total amount of the acid group-containing graft polymer composition is preferably 50 to 99.9% by mass. More preferably, it is 55-99.9 mass%, More preferably, it is 60-99.9 mass%, Most preferably, it is 70-99 mass%.
It is preferable that the ratio of the acid group-containing graft polymer contained in the total amount of the acid group-containing graft polymer composition is in the above-described range from the viewpoint of improving the ability to prevent re-contamination of hydrophobic soil. On the contrary, when the ratio of the acid group-containing graft polymer contained in the total amount of the acid group-containing graft polymer composition is smaller than the above range, the ability to prevent re-contamination to hydrophobic soils is reduced. It is not preferable.

  The polyoxyalkylene compound contained in the acid group-containing graft polymer composition is mainly the unreacted and remaining polyoxyalkylene compound, but the polyoxyalkylene compound is added after the polymerization reaction. You may do it.

The ratio of the polyoxyalkylene compound contained in the total amount of the acid group-containing graft polymer composition is preferably 0.1 to 50% by mass. More preferably, it is 0.1-45 mass%, More preferably, it is 0.1-40 mass%, Most preferably, it is 0.1-30 mass%.
When the ratio of the acid polyoxyalkylene compound contained in the total amount of the acid group-containing graft polymer composition is in the above-mentioned range, it is preferable in that stability to a liquid detergent is improved. On the contrary, when the ratio of the polyoxyalkylene compound contained in the total amount of the acid group-containing graft polymer composition is larger than the above range, it is not preferable in that the stability to the liquid detergent is lowered. .

  The acid group-containing graft polymer and the polyoxyalkylene compound constituting the aryl group having 8 or more carbon atoms, the alkyl group having 8 or more carbon atoms and the alkenyl group having 8 or more carbon atoms constitute a polyoxyalkylene compound. It is a hydrophobic end group.

An aryl group having 8 or more carbon atoms, an alkyl group having 8 or more carbon atoms, and an alkyl group having 8 or more carbon atoms constituting the acid group-containing graft polymer and the polyoxyalkylene compound with respect to the total amount of the acid group-containing graft polymer composition. The alkenyl group content is calculated by the following calculation formula.
Content (I) = [Total amount of aryl group having 8 or more carbon atoms, alkyl group having 8 or more carbon atoms and alkenyl group having 8 or more carbon atoms in polyoxyalkylene compound] / acid group-containing graft polymer Composition (g) × 100 [% by mass]
For example, in the case of an alkyl group having 8 carbon atoms which is a hydrophobic group, the molecular formula of the alkyl group having 8 carbon atoms is C8H17, and the molecular weight corresponding to the molecular formula is (12.010) × 8 + (1.0079) × 17. = 113.22, the proportion of the hydrophobic group can be determined from the molecular weight and the molecular weight of the polyoxyalkylene compound, and the weight of the hydrophobic group can be determined from the proportion of the hydrophobic group and the preparation of the polyoxyalkylene compound. .

  The acid group-containing graft polymer and the polyoxyalkylene compound are composed of an aryl group having 8 or more carbon atoms, an alkyl group having 8 or more carbon atoms, and an alkenyl group having 8 or more carbon atoms. It is preferable that it is 10-35 mass% with respect to the total amount of a polymer composition. More preferably, it is 15-30 mass%, More preferably, it is 17-27 mass%, More preferably, it is 18-25 mass%, Most preferably, it is 18-24 mass%.

  The content of the aryl group having 8 or more carbon atoms, the alkyl group having 8 or more carbon atoms and the alkenyl group having 8 or more carbon atoms constituting the acid group-containing graft polymer and the polyoxyalkylene compound is in the above-mentioned range. In view of improving the dispersibility of hydrophobic soil and the ability to prevent re-contamination. On the contrary, the content of the aryl group having 8 or more carbon atoms, the alkyl group having 8 or more carbon atoms and the alkenyl group having 8 or more carbon atoms constituting the acid group-containing graft polymer and the polyoxyalkylene compound is as described above. When it is larger than the range, it is not preferable from the viewpoint that the dispersibility of hydrophobic soil and the ability to prevent re-contamination are lowered.

[Production method]
The acid group-containing graft polymer of the present invention is produced using, for example, a specific polymerization initiator (preferably, an organic peroxide polymerization initiator having a half life of 135 ° C. of 1 to 5 hours).

  The obtained acid group-containing graft polymer and polymer composition are usually diluted and stored with a small amount of water for convenience of handling. The acid group-containing graft polymer and polymer composition of the present invention were found to have very good stability when diluted with water, compared to the graft polymer composition obtained by the conventional production method. did. The reason for this is considered to be that when a specific polymerization initiator is used, the yield of the polymer is improved and the amount of the remaining polyoxyalkylene compound in the polymer composition is reduced. In addition, the said mechanism is estimation and is not limited to this.

  In this invention, there is no restriction | limiting in particular about the manufacturing method of an acid group containing graft polymer, It can manufacture by referring a conventionally well-known knowledge suitably. Preferably, as disclosed in Patent Document 5, in the form of substantially bulk polymerization (bulk polymerization), specifically, as the reaction system of this graft polymerization, the solvent content is set to the total amount of the reaction system. On the other hand, the polymerization is carried out at 5% by mass or less. The specific form of the polymerization is not particularly limited, and conventionally known knowledge relating to bulk polymerization (bulk polymerization) can be referred to as appropriate, and further improved as necessary.

When graft polymerization is performed, first, a polyoxyalkylene compound (A) serving as a trunk of the graft polymer and an acid group-containing unsaturated monomer (B) serving as a branch of the graft polymer are respectively obtained in a desired manner. Prepare only the amount. At this time, the amount of each component to be prepared is (A) :( B) = 80: 20 to 50:50, preferably 78:22 to 50:50, more preferably 77 in terms of mass ratio. : 23-55: 45, more preferably 75: 25-60: 40.
When calculating the mass ratio between the polyoxyalkylene compound and the acid group-containing unsaturated monomer, the mass of the acid group-containing unsaturated monomer is calculated as the mass of the corresponding acid type.

  As a polymerization initiator used when graft polymerization is performed, an organic peroxide polymerization initiator (a specific polymerization initiator of the present invention) having a half-life of 135 ° C. of 1 to 5 hours is preferable. It is preferable to use a polymerization initiator in such a range since the yield of the graft body is further improved.

  In the present invention, the half life of 135 ° C. is measured by the method described in NOF Corporation Organic Peroxide Catalog 10th Edition. Specifically, it refers to the value obtained by the following measurement method.

  First, using a relatively inert solvent (for example, benzene) as a polymerization initiator, a 0.1 mol / L or 0.05 mol / L polymerization initiator solution is prepared and placed in a nitrogen-substituted glass tube. Seal. This is immersed in a thermostat set at 135 ° C. and thermally decomposed. By such a method, the time required for the polymerization initiator concentration to be half of the initial concentration is determined.

  Examples of the organic peroxide polymerization initiator having a half life of 135 ° C. of the present invention of 1 to 5 hours include dicumyl peroxide (half life 1.0 hour), di-t-hexyl peroxide (half life 1. 1 hour), t-butylcumyl peroxide (half-life 1.2 hours), 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (half-life 1.3 hours), di (2 -T-butylperoxyisopropyl) benzene (half-life 1.5 hours), di-t-butyl peroxide (half-life 1.7 hours), p-menta hydroperoxide (half-life 5.0 hours), 2 , 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 (half-life 5.0 hours). Dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide are preferable, and di-t-butyl peroxide is more preferable.

  The organic peroxide polymerization initiator having a half-life of 135 ° C. of the present invention of 1 to 5 hours uses various organic peroxide polymerization initiators including di-t-butyl peroxide disclosed above. Even if it is an organic peroxide polymerization initiator not disclosed above, it can be obtained if it is an organic peroxide polymerization initiator having a half-life of 135 ° C. of 1 to 5 hours. As the acid group-containing graft polymer, the same polymer is obtained.

  This is because the polymerization initiator generally generates a radical at a specific temperature and performs the polymerization reaction with the radical. From the organic peroxide polymerization initiator having a half-life of 135 ° C. of the present invention of 1 to 5 hours, oxygen radicals having various substituents are generated, and the oxygen radicals cause polyoxyalkylene compounds in the polyoxyalkylene compound. An extraction reaction of a hydrogen atom of an oxyalkylene bond and an addition reaction of an unsaturated bond occur. Therefore, it is important that the function required for the organic peroxide polymerization initiator is a specific range having a half-life in a specific temperature range, and the chemical structure is not important.

  Since it is an organic peroxide polymerization initiator having a half-life of 135 ° C. of the present invention of 1 to 5 hours, an acid group-containing graft polymer having a long graft side chain can be obtained. Excellent dispersibility and expresses the ability to prevent recontamination against hydrophobic soils.

  The amount of the organic peroxide polymerization initiator having a half-life of 135 ° C. used for the graft polymerization of 1 to 5 hours is not particularly limited, but is 100% by mass of the acid group-containing unsaturated monomer used for the graft polymerization. On the other hand, it is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, and further preferably 3 to 7% by mass.

  If the amount of the organic peroxide polymerization initiator used is too small, the yield of the grafted monomer component to the polyoxyalkylene chain may be reduced. On the other hand, if the amount of the organic peroxide polymerization initiator used is too large, the reaction between the polyoxyalkylene compounds occurs, making the production difficult due to the increased viscosity during the reaction accompanying the increase in the molecular weight. Since the composition is gelled and an insoluble matter is generated, problems such as the possibility that the quality may be deteriorated and the production cost may be increased.

  In addition to the organic peroxide polymerization initiator having a half-life of 1 to 5 hours at 135 ° C., other polymerization initiators may be used as appropriate. However, in order to obtain the effect of the present invention of reducing the unreacted polyoxyalkylene compound remarkably, the other polymerization initiator is preferably 10% by mass or less of the entire polymerization initiator, and 5% by mass. More preferably, it is 0% by mass (excluding other polymerization initiators). As other polymerization initiators, organic peroxides are preferably used, and known organic peroxides can be appropriately used.

  The addition form of the organic peroxide polymerization initiator having a half-life of 135 ° C. of 1 to 5 hours and optionally other polymerization initiators is not particularly limited. However, it is preferably added at the same time as the monomer component and not previously mixed with the polyoxyalkylene compound. However, a form in which graft polymerization is performed in a state where a polymerization initiator is previously added to at least one of the polyoxyalkylene compound and the monomer component may also be employed.

  In the graft polymerization, in addition to the polymerization initiator described above, a decomposition catalyst for the polymerization initiator or a reducing compound may be added to the reaction system. Examples of the decomposition catalyst for the polymerization initiator include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid, nitric acid and the like. Metal salts of inorganic acids; carboxylic acids such as formic acid, acetic acid, propionic acid, lactic acid, isolacic acid, benzoic acid, their esters and their metal salts; heterocyclic amines such as pyridine, indole, imidazole, carbazole and their derivatives Can be mentioned. These decomposition catalysts may be used alone or in combination of two or more.

  Examples of the reducing compound include organic metal compounds such as ferrocene; iron naphthenate, copper naphthenate, nickel naphthenate, cobalt naphthenate, manganese naphthenate, and the like, such as iron, copper, nickel, cobalt, manganese Inorganic compounds capable of generating metal ions; boron trifluoride ether adducts, potassium permanganate, perchloric acid and other inorganic compounds; sulfur dioxide, sulfite, sulfate, bisulfite, thiosulfate, sulfoxide, Sulfur-containing compounds such as benzenesulfinic acid and its substitutes, homologues of cyclic sulfinic acid such as para-toluenesulfinic acid; octyl mercaptan, dodecyl mercaptan, mercaptoethanol, α-mercaptopropionic acid, thioglycolic acid, thiopropionic acid, α -Sodium thiopropionate sulfopropyl es Tercap, mercapto compounds such as α-thiopropionic acid sodium sulfoethyl ester; nitrogen-containing compounds such as hydrazine, β-hydroxyethylhydrazine, hydroxylamine; formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, isovaleraldehyde Aldehydes such as ascorbic acid and the like. These reducing compounds may also be used alone or in combination of two or more. A reducing compound such as a mercapto compound may be added as a chain transfer agent.

  When the reaction system contains a solvent, the solvent used is not particularly limited, but those having a small chain transfer constant of the monomer component to the solvent, those having a boiling point of 70 ° C. or higher that can be used under normal pressure, and the like are preferable. Water and / or various organic solvents are used. Examples of such solvents include water, isobutyl alcohol, n-butyl alcohol, tert-butyl alcohol, isopropyl alcohol, ethylene glycol, diethylene glycol, glycerin, triethylene glycol, propylene glycol, ethylene glycol monoalkyl ether, propylene glycol mono Alcohols such as alkyl ethers; Diethers such as ethylene glycol dialkyl ether and propylene glycol dialkyl ether; Acetic acid, ethyl acetate, propyl acetate, butyl acetate, acetate ester of ethylene glycol monoalkyl ether, acetate ester of propylene glycol monoalkyl ether, etc. And the like. Only 1 type of these solvents may be used independently, and 2 or more types may be used together. Examples of the alkyl group in the alcohols and diethers include a methyl group, an ethyl group, a propyl group, and a butyl group.

  When graft polymerization is performed in the presence of water and / or an organic solvent, the total amount of the water and the organic solvent is 5% with respect to the total amount of the polyoxyalkylene compound and the acid group-containing unsaturated monomer. %, It is preferable to perform graft polymerization. More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less, Especially preferably, it is 0.5 mass% or less, Most preferably, it does not contain a solvent substantially. “Substantially free of solvent” means a form in which no solvent is positively added during graft polymerization, and it means that mixing of a solvent to the extent of impurities is acceptable.

  The temperature during graft polymerization is preferably 100 ° C. or higher, more preferably 100 to 160 ° C., further preferably 110 to 150 ° C., and most preferably 130 to 140 ° C. If the temperature at the time of polymerization is too low, the viscosity of the reaction solution becomes too high, the graft polymerization hardly proceeds, and the graft ratio of the monomer component may be reduced. On the other hand, if the polymerization temperature is too high, the polyoxyalkylene compound and the resulting acid group-containing graft polymer may be thermally decomposed. Moreover, there exists a possibility that a monomer and an initiator may volatilize. The temperature at the time of graft polymerization does not need to be kept constant during the polymerization reaction. For example, the polymerization is started from room temperature and the temperature is raised to a set temperature at an appropriate temperature raising time or temperature raising rate. Thereafter, the set temperature may be maintained, or the polymerization temperature may be changed (increased or decreased) over time during the course of the polymerization reaction, depending on the dropping method of the monomer component, initiator, and the like. May be.

  The polymerization time is not particularly limited, but is preferably 30 to 420 minutes, more preferably 45 to 390 minutes, still more preferably 60 to 360 minutes, and most preferably 90 to 240 minutes. In the present invention, “polymerization time” represents the time during which a monomer is added.

  The pressure in the reaction system may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure, but from the viewpoint of the molecular weight of the polymer obtained, the reaction system is sealed under normal pressure. However, it is preferably performed under pressure. Moreover, it is preferable to carry out under normal pressure (atmospheric pressure) in terms of equipment such as a pressurizing device, a decompressing device, a pressure-resistant reaction vessel, and piping. The atmosphere in the reaction system may be an air atmosphere, but is preferably an inert atmosphere. For example, the inside of the system is preferably replaced with an inert gas such as nitrogen before the start of polymerization.

  In the graft polymerization, the polymerization may be started in a state where a part or all of the polyoxyalkylene compound serving as a trunk of the graft polymer is charged into the reaction system. For example, a mode in which the entire amount of the polyoxyalkylene compound is charged into the reaction system, the temperature of the reaction system is raised, and then the monomer component and the polymerization initiator are added separately to cause the graft polymerization reaction to proceed is exemplified. . According to such a form, since the molecular weight of the obtained graft polymer can be adjusted easily, it is preferable. In addition, graft polymerization may be performed by a batch type and may be performed by a continuous type.

  The acid group-containing graft polymer of the present invention can be used as a water treatment agent, fiber treatment agent, dispersant, detergent builder (or detergent composition), and the like. As a detergent builder, it can be used by adding to detergents for various uses such as clothing, tableware, residential, hair, body, toothpaste, and automobile.

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

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

<Fiber treatment agent>
The acid group-containing graft polymer of the present invention can be used as a fiber treatment agent. The fiber treatment agent includes at least one selected from the group consisting of a dye, a peroxide and a surfactant, and the acid group-containing graft polymer of the present invention.

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

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

  The blending ratio of the acid group-containing graft polymer of the present invention to at least one selected from the group consisting of a dye, a peroxide, and a surfactant is, for example, the whiteness of the fiber, the color unevenness, and the dyeing tempering degree. For the improvement, at least one selected from the group consisting of a dye, a peroxide, and a surfactant is used per 1 part by weight of the acid group-containing graft polymer of the present invention in terms of a pure amount of the fiber treatment agent. It is preferable to use the composition mix | blended in the ratio of 0.1-100 weight part as a fiber processing agent.

  Any appropriate fiber can be adopted as a fiber that can use the fiber treatment agent. Examples thereof include cellulosic fibers such as cotton and hemp, chemical fibers such as nylon and polyester, animal fibers such as wool and silk, semi-synthetic fibers such as human silk, and woven fabrics and blended products thereof.

  When the fiber treatment agent is applied to the refining process, it is preferable to blend the acid group-containing graft polymer of the present invention with an alkali agent and a surfactant. When applied to the bleaching step, it is preferable to blend the acid group-containing graft polymer of the present invention, a peroxide, and a silicic acid-based agent such as sodium silicate as a decomposition inhibitor for the alkaline bleaching agent.

<Inorganic pigment dispersant>
The acid group-containing graft polymer of the present invention can be used as an inorganic pigment dispersant. If necessary, the inorganic pigment dispersant may contain condensed phosphoric acid and its salt, phosphonic acid and its salt, and polyvinyl alcohol as other compounding agents.

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

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

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

<Detergent composition>
The acid group-containing graft polymer of the present invention can also be added to a detergent composition.

  When the acid group-containing graft polymer of the present invention is used in a detergent composition, the content of the acid group-containing graft polymer in the detergent composition is not particularly limited. However, from the viewpoint that excellent builder performance can be exhibited, the content of the acid group-containing graft polymer is preferably 0.1 to 15% by mass, more preferably, relative to the total amount of the detergent composition. It is 0.3-10 mass%, More preferably, it is 0.5-5 mass%.

  Detergent compositions used in detergent applications usually include surfactants and additives used in detergents. Specific forms of these surfactants and additives are not particularly limited, and conventionally known knowledge can be appropriately referred to in the detergent field. The detergent composition may be a powder detergent composition or a liquid detergent composition.

  The surfactant is one or more selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant. When two or more kinds are used in combination, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 60% by mass with respect to the total amount of the surfactant. It is above, More preferably, it is 70 mass% or more, Most preferably, it is 80 mass% or more.

  Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonate. , Saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, alkenyl phosphate ester or Its salts are preferred. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these anionic surfactants.

  Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters. Esters, alkylamine oxides and the like are preferred. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these nonionic surfactants.

  As the cationic surfactant, a quaternary ammonium salt or the like is suitable. As the amphoteric surfactant, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant, and the like are suitable. The alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may be branched from an alkyl group such as a methyl group.

  The blending ratio of the surfactant is usually 10 to 60% by mass, preferably 15 to 50% by mass, more preferably 20 to 45% by mass, particularly preferably based on the total amount of the detergent composition. Is 25-40 mass%. If the surfactant content is too small, sufficient detergency may not be achieved, and if the surfactant content is too high, the economy may be reduced.

  Additives include anti-redeposition agent to prevent redeposition of contaminants such as alkali builder, chelate builder, sodium carboxymethyl cellulose, stain inhibitor such as benzotriazole and ethylene-thiourea, soil release agent, color transfer Inhibitors, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents, bleaching aids, enzymes, dyes A solvent or the like is preferable. In the case of a powder detergent composition, it is preferable to blend zeolite.

  The detergent composition may comprise other detergent builders in addition to the polymer composition of the present invention. Examples of other detergent builders include, but are not limited to, alkali builders such as carbonates, hydrogen carbonates, and silicates, tripolyphosphates, pyrophosphates, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, Examples thereof include acid salts, (meth) acrylic acid copolymer salts, acrylic acid-maleic acid copolymers, chelate builders such as fumarate and zeolite, and carboxyl derivatives of polysaccharides such as carboxymethylcellulose. Examples of the counter salt used in the builder include alkali metals such as sodium and potassium, ammonium and amine.

  The total blending ratio of the additive and other detergent builder is preferably 0.1 to 50% by mass with respect to 100% by mass of the cleaning composition. More preferably, it is 0.2-40 mass%, More preferably, it is 0.3-35 mass%, Most preferably, it is 0.4-30 mass%, Most preferably, it is 0.5-20 mass% or less. It is. If the additive / other detergent builder content is less than 0.1% by mass, sufficient detergent performance may not be achieved, and if it exceeds 50% by mass, the economy may be reduced.

  In addition, the concept of the detergent composition includes specific uses such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance one of the components. Detergents that are only used are also included.

  When the detergent composition is a liquid detergent composition, the amount of water contained in the liquid detergent composition is usually preferably 0.1 to 75% by mass, more preferably based on the total amount of the liquid detergent composition. Is 0.2 to 70% by mass, more preferably 0.5 to 65% by mass, even more preferably 0.7 to 60% by mass, particularly preferably 1 to 55% by mass, Preferably it is 1.5-50 mass%.

  When the detergent composition is a liquid detergent composition, the detergent composition preferably has a kaolin turbidity of 200 mg / L or less, more preferably 150 mg / L or less, and even more preferably 120 mg / L or less. Especially preferably, it is 100 mg / L or less, Most preferably, it is 50 mg / L or less.

  Further, the change (difference) in kaolin turbidity between when the acid group-containing graft polymer of the present invention is added to the liquid detergent composition as a detergent builder is preferably 500 mg / L or less. Preferably it is 400 mg / L or less, More preferably, it is 300 mg / L or less, Especially preferably, it is 200 mg / L or less, Most preferably, it is 100 mg / L or less. As the kaolin turbidity value, a value measured by the following method is adopted.

<Measurement method of kaolin turbidity>
A sample (liquid detergent) uniformly stirred in a 50 mm square cell having a thickness of 10 mm was removed and air bubbles were removed. Then, a NDU2000 manufactured by Nippon Denshoku Co., Ltd. Kaolin turbidity: mg / L) is measured.

  Proteases, lipases, cellulases, and the like are suitable as enzymes that can be incorporated into the detergent composition. Of these, proteases, alkaline lipases, and alkaline cellulases that are highly active in an alkaline cleaning solution are preferred.

  The amount of the enzyme added is preferably 5% by mass or less with respect to 100% by mass of the cleaning composition. If it exceeds 5% by mass, improvement in detergency cannot be seen, and the economy may be reduced.

  Even when the detergent composition of the present invention is used in an area of hard water (for example, 100 mg / L or more) having a high concentration of calcium ions and magnesium ions, the salt composition hardly precipitates and has an excellent cleaning effect. This effect is particularly pronounced when the detergent composition contains an anionic surfactant such as LAS.

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

Further, the weight average molecular weight, number average molecular weight, quantification of unreacted carboxylic acid monomer, quantification of unreacted polyoxyalkylene compound, polymer (composition) and aqueous polymer solution of the acid group-containing graft polymer of the present invention The solid content was measured according to the following method.
<Weight average molecular weight and measurement conditions (GPC) of unreacted carboxylic acid monomer>
Apparatus: L-7000 series manufactured by Hitachi, Ltd. Detector: RI (weight average molecular weight), UV (residual monomer)
Column: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B manufactured by Showa Denko KK
Column temperature: 40 ° C
Flow rate: 0.5 mL / min
Calibration curve: POLYACRYLIC ACID STANDARD made by Soka Science Co., Ltd.
Eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio)

<Quantification method of unreacted polyoxyalkylene compound>
The unreacted polyoxyalkylene compound in the polymer composition was quantified by high-speed chromatography under the following conditions.
High-performance liquid chromatography measuring device: 8020 series manufactured by Tosoh Corporation Column: CAPCELL PAK C1 UG120 manufactured by Shiseido Co., Ltd.
Temperature: 40.0 ° C
Eluent: 10 mmol / L Disodium hydrogen phosphate.12 hydrate aqueous solution (adjusted to pH 7 with phosphoric acid) / acetonitrile = 45/55 (volume ratio)
Flow rate: 1.0 ml / min
Detector: RI, UV (detection wavelength 215 nm)

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

<Electrophoretic measurement conditions>
Device name: Photo OTSUKA ELECTRONICS CAPI-3300CAPILLARY ELECTROPHORESIS SYSTEM
Column: Otsuka Electronics Co., Ltd. GL capillary tube 75μ × 50cm
Voltage: 15kV
Developing solvent: 50 mmol / L Sodium 4-borate aqueous solution Migration time: 30 minutes Detection: UV 210 nm

<Calcium ion scavenging ability>
50 g of 0.01 mol / L, 0.001 mol / L, 0.0001 mol / L aqueous solution was prepared using calcium chloride dihydrate as a calcium ion standard solution for a calibration curve, and 4.8%
The pH is adjusted within a range of 7 to 8 with an aqueous NaOH solution, and a 4 mol / L potassium chloride aqueous solution (
(Hereinafter abbreviated as 4M-KCl aqueous solution) was added, and the sample was further stirred well using a magnetic stirrer to prepare a sample solution for a calibration curve. In addition, as a calcium ion standard solution for testing, the same amount of 0.001 mol / L aqueous solution using the same calcium chloride dihydrate (
50 g per sample).
Next, 10 mg of the test sample (polymer) in a 100 cc beaker in terms of solid content was weighed,
50 g of the above test calcium ion standard solution was added and sufficiently stirred using a magnetic stirrer. Furthermore, as with the sample for the calibration curve, pH 7 to 4.8% NaOH aqueous solution is used.
A sample solution for test was prepared by adding 1 mL of 4M-KCl aqueous solution.
The calibration curve sample solution and the test sample solution thus prepared were measured with a calcium ion electrode using a titration device COMITE-550 manufactured by Hiranuma Sangyo Co., Ltd.
From the calibration curve and the measured value of the sample solution for the test, the amount of calcium ions captured by the sample (polymer) is obtained by calculation, and the value is expressed in mg of calcium carbonate equivalent of the amount captured per 1 g of polymer solids. This value was defined as the calcium ion scavenging ability value.

<Carbon black dispersibility>
Pure water was added to 67.56 g of glycine, 52.6 g of sodium chloride, and 2.4 g of NaOH.
00 g (this is used as a buffer). To 60 g of buffer, 0.082 g of calcium chloride dihydrate was added, and pure water was further added to make 1000 g (this is used as a buffer). After putting 0.03 g of carbon black into a test tube (made by IWAKI GLASS: diameter 18 mm, height 180 mm), 3 g of 0.1% by weight aqueous solution (in terms of solid content weight) of the copolymer to be measured and 27 g of buffer. Added and sealed. The test tube was shaken to disperse the carbon black. Thereafter, the test tube was left in the dark for 20 hours. After 3 hours, 5 cc of the supernatant of the dispersion was taken and the absorbance was measured with a UV spectrometer (Shimadzu Corporation, UV-1200; 1 cm cell, wavelength 380 nm).

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

<Example 1>
Into a 500 ml glass separable flask equipped with a thermometer, a stirrer, and a reflux condenser, 150% of SOFTANOL 70 (manufactured by Nippon Shokubai Co., Ltd .; 7 mol of ethylene oxide adduct of secondary alcohol (C _12-14 )) 9 g was charged, heated to 128 ° C. while blowing nitrogen, and maintained for 30 minutes. Next, 7.04 g of di-t-butyl peroxide (hereinafter also referred to as PBD) is separated for 220 minutes, and 100.6 g of 100% acrylic acid (hereinafter also referred to as AA) is separately separated over 210 minutes from 20 minutes after the start of PBD dropping. It was dripped continuously. After the completion of 100% AA dropwise addition, the mixture was stirred for 90 minutes at 128 ° C. (ripening), and diluted with water after ripening to obtain a polymer composition 1 of the present invention. The weight average molecular weight of the polymer contained in the polymer composition 1 was 20000, and the solid content was 58.0%. The amount of the unreacted polyoxyalkylene compound was 20% by mass. The results are shown in Table 1.

<Example 2>
A glass separable flask having a capacity of 500 ml equipped with a thermometer, a stirrer, and a reflux condenser was charged with 150.9 g of softanol 70 and 37.7 g of maleic anhydride (hereinafter also referred to as MA), and the temperature was raised to 128 ° C. Maintained for a minute. Next, 7.04 g of PBD was added dropwise continuously for 220 minutes, and 62.9 g of 100% AA was continuously added dropwise over 210 minutes after 20 minutes from the start of PBD addition. After the completion of 100% AA dropwise addition, the mixture was stirred at 128 ° C. for 90 minutes (aging), and diluted with water after completion of aging to obtain a polymer composition 2 of the present invention. The polymer contained in the polymer composition 2 had a weight average molecular weight of 19000 and a solid content of 55.8%. The amount of the unreacted polyoxyalkylene compound was 20% by mass. The results are shown in Table 1.

<Example 3>
150 mL of a 500 ml glass separable flask equipped with a thermometer, a stirrer, and a reflux condenser was added to Softanol 90 (manufactured by Nippon Shokubai Co., Ltd .; 9 mol of ethylene oxide adduct of secondary alcohol (C _12-14 )). 9 g was charged, heated to 128 ° C. while blowing nitrogen, and maintained for 30 minutes. Next, 7.04 g of PBD was added dropwise continuously for 220 minutes, and 100.6 g of 100% AA was continuously added dropwise over 210 minutes after 20 minutes from the start of PBD addition. After the completion of 100% AA dropping, the mixture was stirred for 90 minutes at 128 ° C. (ripening), and diluted with water after the completion of ripening to obtain a polymer composition 3 of the present invention. The polymer contained in the polymer composition 3 had a weight average molecular weight of 20000 and a solid content of 58.4%. The amount of the unreacted polyoxyalkylene compound was 31% by mass. The results are shown in Table 1.

<Example 4>
Into a 500 ml glass separable flask equipped with a thermometer, stirrer and reflux condenser, Softanol 120 (Nippon Shokubai Co., Ltd .; ethylene oxide 12 mol adduct of secondary alcohol (C _12-14 )) 150. 9 g was charged, heated to 128 ° C. while blowing nitrogen, and maintained for 30 minutes. Next, 7.04 g of PBD was added dropwise continuously for 220 minutes, and 100.6 g of 100% AA was continuously added dropwise over 210 minutes after 20 minutes from the start of PBD addition. After the completion of 100% AA dropwise addition, the mixture was stirred at 128 ° C. for 90 minutes (ripening), and diluted with water after completion of ripening to obtain a polymer composition 4 of the present invention. The weight average molecular weight of the polymer contained in the polymer composition 4 was 7100, and the solid content was 71.2%. The amount of the unreacted polyoxyalkylene compound was 18% by mass. The results are shown in Table 1.

<Example 5>
Into a 500 ml glass separable flask equipped with a thermometer, a stirrer, and a reflux condenser, SOFTANOL 150 (manufactured by Nippon Shokubai Co., Ltd .; ethylene oxide 15 mol adduct of secondary alcohol (C _12-14 )) 150. 9 g was charged, heated to 128 ° C. while blowing nitrogen, and maintained for 30 minutes. Next, 7.04 g of PBD was added dropwise continuously for 220 minutes, and 100.6 g of 100% AA was continuously added dropwise over 210 minutes after 20 minutes from the start of PBD addition. After the completion of 100% AA dropping, the mixture was stirred at 128 ° C. for 90 minutes (ripening), and diluted with water after completion of ripening to obtain a polymer composition 5 of the present invention. The weight average molecular weight of the polymer contained in the polymer composition 5 was 6800, and the solid content was 73.1%. The amount of the unreacted polyoxyalkylene compound was 18% by mass. The results are shown in Table 1.
<Example 6>
Into a 500 ml glass separable flask equipped with a thermometer, a stirrer, and a reflux condenser, 150.9 g of New Coal 2305 (manufactured by Nippon Emulsifier Co., Ltd .; ethylene oxide 5 mol adduct of C _12-13 alcohol) was charged, While blowing nitrogen, the temperature was raised to 128 ° C. and maintained for 30 minutes. Next, 7.04 g of PBD was added dropwise continuously for 220 minutes, and 100.6 g of 100% AA was continuously added dropwise over 210 minutes after 20 minutes from the start of PBD addition. After the completion of 100% AA dropping, the mixture was stirred at 128 ° C. for 90 minutes (ripening), and diluted with water after ripening to obtain a polymer composition 6 of the present invention. The weight average molecular weight of the polymer contained in the polymer composition 6 was 30000, and the solid content was 73.1%. The amount of unreacted polyoxyalkylene compound was 22% by mass. The results are shown in Table 1.

<Example 7>
Into a 500 ml glass separable flask equipped with a thermometer, a stirrer, and a reflux condenser, 132.0 g of New Coal 2310 (manufactured by Nippon Emulsifier Co., Ltd .; ethylene oxide 10 mol adduct of C _12-13 alcohol) was charged, While blowing nitrogen, the temperature was raised to 128 ° C. and maintained for 30 minutes. Next, 5.28 g of PBD was added dropwise continuously for 220 minutes, and 88.0 g of 100% AA was continuously added dropwise over 210 minutes after 20 minutes from the start of PBD addition. After the completion of 100% AA dropping, the mixture was stirred for 90 minutes at 128 ° C. (ripening), and diluted with water after ripening to obtain a polymer composition 7 of the present invention. The polymer contained in the polymer composition 7 had a weight average molecular weight of 23,000 and a solid content of 61.6%. The amount of the unreacted polyoxyalkylene compound was 18% by mass. The results are shown in Table 1.

<Example 8>
Into a 500 ml glass separable flask equipped with a thermometer, a stirrer and a reflux condenser was charged 117.3 g of Neucor 1008 (manufactured by Nippon Emulsifier Co., Ltd .; 8-ethyl hexyl alcohol adduct of 2-ethylhexyl alcohol). The temperature was raised to 128 ° C. while blowing nitrogen and maintained for 30 minutes. Next, 7.04 g of PBD was added dropwise continuously for 220 minutes, and 117.3 g of 100% AA was separately added dropwise over 210 minutes after 20 minutes from the start of PBD addition. After the completion of 100% AA dropwise addition, the mixture was stirred at 128 ° C. for 90 minutes (ripening), and diluted with water after completion of ripening to obtain a polymer composition 8 of the present invention. The polymer contained in the polymer composition 8 had a weight average molecular weight of 13,000 and a solid content of 70.3%. The amount of the unreacted polyoxyalkylene compound was 28% by mass. The results are shown in Table 1.

<Comparative Example 1>
Into a 500 ml glass separable flask equipped with a thermometer, a stirrer, and a reflux condenser, 150% of SOFTANOL 200 (manufactured by Nippon Shokubai Co., Ltd .; 15 mol of ethylene oxide adduct of secondary alcohol (C _12-14 )) 9 g was charged, heated to 128 ° C. while blowing nitrogen, and maintained for 30 minutes. Next, 7.04 g of PBD was added dropwise continuously for 220 minutes, and 100.6 g of 100% AA was continuously added dropwise over 210 minutes after 20 minutes from the start of PBD addition. After the completion of 100% AA dropwise addition, the mixture was stirred at 128 ° C. for 90 minutes (ripening), and diluted with water after completion of ripening to obtain a comparative polymer composition 1 of the present invention. The weight average molecular weight of the polymer contained in the comparative polymer composition 1 was 9400, and the solid content was 72.8%. The amount of the unreacted polyoxyalkylene compound was 12% by mass. The results are shown in Table 1.

From the results shown in Table 1, the polymer composition containing the polymer of the present invention has superior scavenging ability, excellent carbon black prevention ability, and excellent recontamination prevention ability as compared with the conventional polymer composition. Is shown to have.
Accordingly, when the polymer or polymer composition of the present invention is used as a detergent builder, and therefore when the polymer or polymer composition of the present invention is used as a detergent builder, it is effective to reattach the hydrophobic soil to the fiber. It is expected that this can be prevented.

Claims (4)

In the presence of an organic peroxide polymerization initiator having a half-life of 135 ° C. of 1 to 5 hours,
An acid group-containing graft polymer obtained by graft polymerization of a polyoxyalkylene compound and an acid group-containing unsaturated monomer,
The polyoxyalkylene compound has at least one of an aryl group having 8 or more carbon atoms, an alkyl group having 8 or more carbon atoms and an alkenyl group having 8 or more carbon atoms and an oxyalkylene group. The content of the structure derived from the per oxyalkylene group is 2 to 16 mol,
The mass ratio between the structure (a) derived from the polyoxyalkylene compound and the structure (b) derived from the acid group-containing unsaturated monomer is as follows:
(A): (b) = 80: 20-50: 50
Acid group-containing graft polymer. An acid group-containing graft polymer composition comprising the acid group-containing graft polymer according to claim 1 and a polyoxyalkylene compound,
The acid group-containing graft polymer is 50 to 99.9% by mass,
The polyoxyalkylene compound is 0.1 to 50 mass,
The acid group-containing graft polymer; and
The content (I) of an aryl group having 8 or more carbon atoms, an alkyl group having 8 or more carbon atoms, and an alkenyl group having 8 or more carbon atoms constituting the polyoxyalkylene compound,
10 to 35% by mass relative to the total amount of the acid group-containing graft polymer composition,
Acid group-containing graft polymer composition. In the presence of an organic peroxide polymerization initiator having a half-life of 135 ° C. of 1 to 5 hours,
A structure having at least one of an aryl group having 8 or more carbon atoms, an alkyl group having 8 or more carbon atoms and an alkenyl group having 8 or more carbon atoms and an oxyalkylene group, and derived from an oxyalkylene group per mole of a polyoxyalkylene compound A polyoxyalkylene compound (A) having a content of 2 to 16 mol,
The acid group-containing unsaturated monomer (B)
In the ratio (A) :( B) = 80: 20-50: 50 by mass ratio,
In the presence of water and / or organic solvent,
With respect to the total amount of the polyoxyalkylene compound and the acid group-containing unsaturated monomer,
The total amount of the water and the organic solvent is 5% by mass or less,
A method for producing an acid group-containing graft polymer comprising a step of graft polymerization. A detergent builder comprising the acid group-containing graft polymer according to claim 1.