JP5574678B2 - NOVEL POLYMER AND PROCESS FOR PRODUCING THE SAME - Google Patents

Description

  The present invention relates to a novel polymer and a method for producing the same.

  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 obtained by graft polymerization of various monomers to polyalkylene glycol are blended in detergent compositions as detergent builders.

  For example, Patent Document 1 discloses a graft obtained by grafting vinyl acetate to polyalkylene oxide in a weight ratio of 1: 0.2 to 1:10, and saponifying the acetate group to 15% if desired. It is disclosed that the polymer can be used as an anti-graying agent during washing.

  Furthermore, Patent Document 2 discloses that the number of carbon atoms constituting the structural unit located at the end of the main chain of a graft polymer obtained by grafting an unsaturated carboxylic acid such as (meth) acrylic acid on polyalkylene glycol is different from a certain value. It is disclosed that by mixing a graft polymer of more than one species, the builder performance and the compatibility with a liquid detergent are excellent.

Here, as a recent market trend, liquid detergents tend to prefer highly concentrated types (low water composition ratio), and consumers prefer a liquid detergent with high transparency and no turbidity. It is in. Therefore, compatibility with other liquid detergent components typified by surfactants and the like required for polymers has become very strict as compared with conventional ones.
In addition, with regard to builder performance, it has become well established that consumers use the remaining hot water from the bath for washing, as consumers have become more aware of environmental problems in recent years. In order to cope with the problem of having to wash under conditions of high hardness due to the concentration of calcium components and conditions with a lot of soil components by using the remaining hot water, the soil components can be reattached to the fibers being washed. There is a need for an agent that has a further improved ability to prevent so-called recontamination, and an agent that has further improved the dispersibility of hydrophobic / hydrophilic composite soil.

JP-A-62-95399 JP 2002-332391 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.
Accordingly, the present invention provides a polymer having both improved anti-contamination ability and improved dispersibility of hydrophobic / hydrophilic composite soil when used in detergent applications, and a method for producing the same. For the purpose.

  The present inventors have intensively studied to solve the above problems. As a result, the present inventors have the ability to prevent recontamination of a polymer having a predetermined structure obtained by polymerizing a carboxyl group-containing monomer and a hydrophobic group-containing monomer in the presence of a polyoxyalkylene compound. In addition, the present inventors have found that the dispersibility of the hydrophobic / hydrophilic composite soil is improved and have completed the present invention.

  That is, the present invention is a polymer obtained by polymerizing an acid group-containing unsaturated monomer and a hydrophobic group-containing monomer as essential components in the presence of a polyoxyalkylene compound, The total mass of the structure derived from the polyoxyalkylene compound and the structure derived from all monomers (carboxyl group-containing monomer, hydrophobic group-containing monomer, other monomers) is 100% by mass. On the other hand, the mass ratio of the structure derived from the polyoxyalkylene compound is 50 to 98 mass%, the mass ratio of the structure derived from the carboxyl group-containing monomer is 1 to 49 mass%, and the hydrophobic group-containing simple substance is The mass ratio of the structure derived from the monomer is 1 to 49% by mass, and the polymer has a site mainly composed of a carboxyl group-containing monomer and a site mainly composed of a hydrophobic group-containing monomer. Is a polymer.

  In another aspect of the present invention, a method for producing a polymer is provided. That is, the production method of the present invention is a polymer obtained by polymerizing a carboxyl group-containing monomer and a hydrophobic group-containing monomer in the presence of a polyoxyalkylene compound. And (i) a step of adding a carboxyl group-containing monomer as a main component to the polymerization vessel, and (ii) a step of adding a hydrophobic group-containing unsaturated monomer as a main component to the polymerization vessel, the polyoxyalkylene The polyoxyalkylene compound is 50 to 98% by mass with respect to 100% by mass of the total mass of the compound and all monomers (carboxyl group-containing monomer, hydrophobic group-containing monomer, and other monomers). A polymer production method comprising polymerizing a carboxyl group-containing monomer in an amount of 1 to 49% by mass and a hydrophobic group-containing monomer in an amount of 1 to 49% by mass. Monomer composition If a manufacturing method, the polymer is characterized by adding a monomer component mainly the hydrophobic group-containing monomer separately to the reaction system.

  When the polymer of the present invention is used as a detergent builder, the polymer of the present invention has high re-contamination prevention ability and excellent dispersibility (dispersion ability) of hydrophobic / hydrophilic composite soil. Thus, the ability of the detergent composition to prevent re-contamination and the dispersibility of the hydrophobic / hydrophilic composite soil are remarkably improved. Moreover, if the polymer of the present invention is used as a builder for liquid detergents, the transparency of the liquid detergent composition results from the fact that the polymer of the present invention has excellent compatibility with surfactants. The stability over time is remarkably improved.

  Hereinafter, the present invention will be described in detail.

The polymer of the present invention is a polymer obtained by polymerizing a carboxyl group-containing monomer and a hydrophobic group-containing monomer as essential components in the presence of a polyoxyalkylene compound.
Specifically, a structure derived from a side chain (graft chain) including a structure derived from a carboxyl group-containing monomer in a structure derived from a polyoxyalkylene compound and a structure derived from a hydrophobic group-containing monomer by the above polymerization. It is a polymer including a graft polymer having a side chain (graft chain).

[Polyoxyalkylene compounds]
The polymer of the present invention is characterized by having a structure derived from a polyoxyalkylene compound (referred to as structure a). The structure a derived from the polyoxyalkylene compound is a structure derived from the polyoxyalkylene compound as a polymerization raw material, but the polymer of the present invention usually contains an unreacted polyalkylene compound (that is, The polymer of the present invention is usually a mixture (composition) containing a copolymer and an unreacted polyalkylene compound.) Therefore, the structure a derived from the polyoxyalkylene compound is a polyoxyalkylene compound, Derived from a polyoxyalkylene compound contained in a polymer obtained by polymerizing a carboxyl group-containing monomer, a hydrophobic group-containing monomer, a carboxyl group-containing monomer, and, if necessary, other monomers And the structure of the unreacted polyoxyalkylene compound itself.
The polyoxyalkylene compound used in the present invention is a compound obtained by polymerizing ethylene oxide and other alkylene oxides with water or alcohol as a starting point by a known method. Examples of the starting alcohol include primary alcohols having 1 to 22 carbon atoms such as methanol, ethanol, n-propanol, and n-butanol; secondary alcohols having 3 to 18 carbon atoms; and tertiary alcohols such as t-butanol. Diols such as ethylene glycol, diethylene glycol, propanediol, butanediol, and propylene glycol; triols such as glycerin and trimethylolpropane; polyols such as sorbitol are exemplified. Other alkylene oxides that can be copolymerized with ethylene oxide are not particularly limited, but propylene oxide and butylene oxide are preferred. Further, the polyoxyalkylene compound used in the present invention has a structure derived from ethylene oxide (-CH2CH2O-) as a structural unit of 80 mol% or more with respect to 100 mol% of the structure derived from all alkylene oxide, and is copolymerized with ethylene oxide. A compound having 0 to 20 mol% of a structure derived from another possible alkylene oxide is preferable. When the structure derived from other alkylene oxide exceeds 20 mol%, the graft ratio of the resulting graft polymer tends to be lowered. Furthermore, as a polyoxyalkylene compound, all or some of the hydroxyl groups at the end of the compound obtained as described above are substituted with fatty acids having 2 to 22 carbon atoms, succinic acid, succinic anhydride, maleic acid, anhydrous Examples thereof include those esterified with a dicarboxylic acid such as maleic acid and adipic acid.
The molecular weight of the polyoxyalkylene compound used in the present invention is 200 or more, preferably 500 or more, more preferably 1000 or more. The upper limit of the molecular weight is not particularly limited, but is preferably 20000 or less, and is preferably 6000 or less when the polyether has two or more hydroxyl groups. When the molecular weight is smaller than 200, the number of polyoxyalkylene compounds not involved in polymerization increases.

  When the product is commercially available, the polyoxyalkylene compound may be one obtained by purchasing the product or one 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, methoxy polyethylene glycol, and phenoxy polyethylene glycol. In addition, the compound which has a radically polymerizable carbon carbon double bond does not correspond to the polyoxyalkylene type compound of this invention.

  The polymer of the present invention has a structure derived from a polyoxyalkylene compound (structure a), a structure derived from the polyoxyalkylene compound, and all monomers (carboxyl group-containing monomer, hydrophobic group-containing). Monomers and other monomers) are contained in an amount of 50 to 98% by mass with respect to 100% by mass of the total structure derived from the structure. From the viewpoint of further improving the compatibility of the polymer with the surfactant, it is preferably 60 to 96% by mass, more preferably 65 to 94% by mass, further preferably 68 to 92% by mass, Most preferably, it is 70-90 mass%.

[Carboxyl group-containing monomer]
The polymer of the present invention is characterized by having a structure derived from a carboxyl group-containing monomer (referred to as structure b). Here, the structure derived from the carboxyl group-containing monomer is a structure formed by polymerization of the carboxyl group-containing monomer. For example, the carboxyl group-containing monomer is acrylic acid (CH ₂ = CHCOOH). In some cases, the structure derived from a carboxyl group-containing monomer can be represented by —CH ₂ —CH (COOH) —. In addition, when the carboxyl group-containing monomer is a salt, the carboxyl group-containing monomer for the structure derived from all raw materials (the structure derived from the polyoxyalkylene compound (structure a) and the structure derived from all monomers) is used. When calculating the mass ratio of the structure derived from the monomer, it is calculated as the corresponding acid conversion. For example, if it is sodium acrylate, a mass ratio (mass%) is calculated as acrylic acid which is a corresponding acid. Furthermore, in the present invention, a compound corresponding to both a polyoxyalkylene compound and a carboxyl group-containing monomer is calculated as a carboxyl group-containing monomer when calculating the mass ratio to the structure derived from other raw materials. To do.
Since the polymer of the present application has a structure derived from a carboxyl group-containing monomer, it has good hydrophilic dirt dispersibility.

  The carboxyl group-containing monomer is a monomer having a carboxyl group and a carbon-carbon unsaturated double bond. Examples thereof include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 2-methyleneglutaric acid, and salts thereof. Of these, (meth) acrylic acid, maleic acid, and salts thereof are more preferable, acrylic acid and maleic acid are more preferable, and acrylic acid is particularly preferable. These carboxyl group-containing monomers may be used alone or in combination of two or more.

  The polymer of the present invention comprises a structure derived from a carboxyl group-containing monomer (structure b), a structure derived from a polyoxyalkylene compound (structure a), and all monomers (carboxyl group-containing monomers, 1 to 49% by mass with respect to 100% by mass of the total mass of the structure derived from the hydrophobic group-containing monomer and other monomers). From the viewpoint of further improving the re-contamination prevention ability of the polymer, it is preferably 2-38% by mass, more preferably 3-32% by mass, still more preferably 4-28% by mass, and most preferably 5 to 25% by mass.

[Hydrophobic group-containing monomer]
The polymer of the present invention is characterized by having a structure derived from a hydrophobic group-containing monomer (referred to as structure c). Here, the structure derived from the hydrophobic group-containing monomer (structure derived from the hydrophobic group-containing monomer) is a structure formed by polymerization of the hydrophobic group-containing monomer. When the functional group-containing monomer is butyl acrylate (CH ₂ ═CHCOOC ₄ H ₉ ), the structure derived from the hydrophobic group-containing monomer is represented by —CH ₂ —CH (COOC ₄ H ₉ ) —. be able to. In the present invention, the compound corresponding to both the polyoxyalkylene compound and the hydrophobic group-containing monomer is a hydrophobic group-containing monomer when calculating the mass ratio with respect to the structure derived from other raw materials. Calculate.
The hydrophobic group-containing monomer is a monomer having an alkyl group having 3 or more carbon atoms, an aryl group, an alkenyl group, and a carbon-carbon unsaturated double bond, isopropyl (meth) acrylate, N-propyl (meth) acrylate, isopropyl (meth) acrylate, tertiary butyl (meth) acrylate, secondary butyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate Hydrophobic group-containing alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate; styrene, vinyl naphthalene, vinyl toluene, Vinyl aryl such as indene; isopropyl vinyl ether, tertiary butyl vinyl Hydrophobic group-containing vinyl ethers such as ether; hexene, hydrophobic group-containing alkenes such as octene; phenylmaleimide, hydrophobic group-containing maleimides such as cyclohexyl maleimide, acrylamide, hydrophobic group-containing amides such as isobutyl acrylamide, and the like. Among these, alkyl (meth) acrylate and styrene having an alkyl group having 4 to 12 carbon atoms are more preferable, and alkyl (meth) acrylate having an alkyl group having 4 to 8 carbon atoms is more preferable. Is particularly preferably formed of only carbon and hydrogen atoms.

  Since the polymer of the present application has a structure derived from a hydrophobic group-containing monomer, it has a good ability to prevent recontamination as the adsorptivity of the polymer to the hydrophobic component is improved.

  In addition, by using alkyl (meth) acrylate or styrene having an alkyl group having 4 to 12 carbon atoms as a raw material for the polymer, the monomer remaining after polymerization can be kept low, so it is mixed with a liquid detergent. The transparency can be particularly improved. Furthermore, the polymer of the present invention has a balanced structure derived from a carboxyl group-containing monomer and a structure derived from a hydrophobic group-containing monomer, thereby improving the dispersibility of hydrophobic / hydrophilic composite soil. Play.

  The polymer of the present invention comprises a structure derived from a hydrophobic group-containing monomer (structure c), a structure derived from a polyoxyalkylene compound (structure a), and all monomers (carboxyl group-containing monomers). 1 to 49% by mass with respect to 100% by mass of the total mass derived from the structure derived from (hydrophobic group-containing monomer, other monomer). From the viewpoint of further improving the compatibility of the polymer with the surfactant and the ability to prevent recontamination, it is preferably 2 to 38% by mass, more preferably 3 to 32% by mass, and still more preferably 4 to 28%. % By mass, most preferably 5 to 25% by mass.

[Other monomers]
In addition to the structure derived from a carboxyl group-containing monomer or a hydrophobic group-containing monomer, the polymer of the present invention has a structure derived from another monomer (called a structural unit e) as necessary. May be included. The other monomer is not particularly limited as long as it has a polymerizable carbon-carbon unsaturated double bond (of course, the above polyoxyalkylene compound, the above carboxyl group-containing monomer, the above hydrophobic group). Those corresponding to the group-containing monomer are not included in other monomers.), For example, 2-acrylamido-2-methylpropanesulfonic acid, (meth) allylsulfonic acid, vinylsulfonic acid, 2- Monomers having a sulfonic acid group such as hydroxy-3-allyloxy-1-propanesulfonic acid and 2-hydroxy-3-butenesulfonic acid; monomers having a phosphonic acid group such as vinylphosphonic acid and (meth) allylphosphonic acid Hydroxyl-containing alkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and α-hydroxymethylethyl (meth) acrylate Salts; alkyl (meth) acrylates other than the hydrophobic group-containing monomers such as methyl (meth) acrylate and ethyl acrylate; amino groups such as dimethylaminopropyl (meth) acrylate or quaternized products thereof Acrylates; Amide group-containing monomers such as (meth) acrylamide and dimethylacrylamide; Vinyl esters such as vinyl acetate and vinyl propionate; Alkenes such as ethylene and propylene; Maleimide derivatives such as maleimide and methylmaleimide; ) Nitrile group-containing vinyl monomers such as acrylonitrile; Aldehyde group-containing vinyl monomers such as (meth) acrolein; Alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; Vinyl chloride, vinylidene chloride, allyl alcohol: Vinyl pyrrolidone, etc. Other functional group-containing monomers: monomers having a structure in which an alkylene oxide is added to an unsaturated alcohol such as allyl alcohol or isoprenol, an alkylene glycol chain-containing monomer such as an alkoxyalkylene glycol of (meth) acrylate, etc. Is mentioned. Also about these other monomers, only 1 type may be used independently and 2 or more types may be used together.

  In the polymer of the present invention, a structure (structure a) derived from a polyoxyalkylene compound and a structure derived from another monomer which is an optional component (structure e), and all monomers (carboxyl group-containing monomer) The ratio of the structure derived from the other monomer to the total mass of 100 mol% of the structure derived from the monomer, the hydrophobic group-containing monomer, and the other monomer) is sufficient for the effects of the present invention. From the viewpoint of exhibiting, it is preferably 0 to 10% by mass, more preferably 0 to 8% by mass, still more preferably 0 to 5% by mass, and most preferably 0% by mass.

[Polymer of the present invention]
The polymer of the present invention is a polymer obtained by polymerizing a carboxyl group-containing monomer and a hydrophobic group-containing monomer as essential components in the presence of a polyoxyalkylene compound. Since the dispersibility of dirt is improved, the polymer of the present invention mainly comprises a structure derived from a polyoxyalkylene compound (structure a) and a structure derived from a carboxyl group-containing monomer (structure b). It is preferable to have a site and a site mainly composed of a structure (structure c) derived from a hydrophobic group-containing monomer, and specifically, a main structure composed of a polyoxyalkylene compound (structure a) A side chain mainly composed of a chain, a structure derived from a carboxyl group-containing monomer (structure b) (graft chain), and a side chain mainly composed of a structure derived from a hydrophobic group-containing monomer (structure c) Heavy with (graft chain) It is further preferable to include the body.

Here, the “side chain (graft chain) mainly composed of a carboxyl group-containing monomer (structure b)” means that the structure (structure b) derived from a carboxyl group-containing monomer A chain having 50% by mass or more of a structure (structure b) derived from a carboxyl group-containing monomer with respect to 100% by mass of the structure derived from all monomers constituting the chain. Similarly, “a side chain mainly composed of a structure derived from a hydrophobic group-containing monomer (structure c) (graft chain)” means that the structure derived from all monomers constituting the side chain is 100% by mass. On the other hand, the chain which has 50 mass% or more of structures (structure c) derived from a hydrophobic group-containing monomer is meant. Thus, when the polymer contains both the side chain mainly composed of structure b and the side chain mainly composed of structure c, the ability to prevent recontamination of the polymer is remarkably improved.
A graft polymer having both a side chain mainly composed of structure b and a side chain mainly composed of structure c is, for example, (i) in the presence of a polyoxyalkylene compound and a polymerization initiator capable of hydrogen abstraction. Separately, the time for dropping the monomer component mainly comprising a carboxyl group-containing monomer and (ii) the monomer component mainly comprising a monomer component mainly comprising a hydrophobic group-containing monomer And it can manufacture by adding to a reaction container (polymerization container) and superposing | polymerizing.
"Side chain mainly composed of structure derived from carboxyl group-containing monomer (structure b) (graft chain)", "Side chain mainly composed of structure derived from hydrophobic group-containing monomer (structure c)" (Graft chain) ”preferably has 80% by mass or more and 100% by mass or less of structure b and structure c, respectively, particularly preferably 90% by mass or more and 100% by mass or less, and most preferably 100% by mass. .

As described above, the polymer of the present invention is usually a mixture (composition) containing a copolymer and an unreacted polyalkylene compound. From the viewpoint of improving the ability to prevent recontamination, it is preferable to reduce unreacted polyalkylene compounds as much as possible.
The site mainly composed of the structure derived from the carboxyl group-containing monomer is a monomer component (one type or two or more types) mainly composed of the carboxyl group-containing monomer in the presence of the polyalkylene compound. It is preferably a site formed by polymerizing the monomer, and the site mainly composed of the structure derived from the hydrophobic group-containing unsaturated monomer is in the presence of a polyalkylene compound. Thus, it is preferably a site formed by polymerizing a monomer component mainly composed of a hydrophobic group-containing unsaturated monomer. The “mainly comprising a carboxyl group-containing monomer” and the “mainly comprising a hydrophobic group-containing unsaturated monomer” are as described later.

  The weight average molecular weight of the 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. Preferably it is 100-50000, More preferably, it is 500-30000, More preferably, it is 1000-20000. 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 is lowered, and there is a possibility that sufficient performance as a detergent builder may not be exhibited. In addition, as a value of the weight average molecular weight of the polymer of this invention, the value measured by the method as described in the Example mentioned later shall be employ | adopted.

  In addition, the number average molecular weight of the 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 number average molecular weight of the polymer of the present invention is specifically Is preferably 100 to 40000, more preferably 200 to 25000, and even more preferably 500 to 15000. 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 is lowered, and there is a possibility that sufficient performance as a detergent builder may not be exhibited. In addition, as a value of the number average molecular weight of the polymer of this invention, the value measured by the method as described in the Example mentioned later shall be employ | adopted.

[Polymer composition]
The polymer of the present application is included as essential in the polymer composition. In addition, unreacted polyoxyalkylene compounds, unreacted carboxyl group-containing monomers, unreacted hydrophobic group-containing monomers, other unreacted monomers, unreacted polymerization initiators, polymerization initiation An agent decomposition product, a polymer composed of a carboxyl group-containing monomer and a hydrophobic group-containing monomer may be included.

  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. 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.

[Method for producing polymer of the present invention]
The production method of the present invention is a method for polymerizing a monomer having a carboxyl group-containing monomer and a hydrophobic group-containing monomer as essential components in the presence of a polyoxyalkylene compound. And 100 to 100 mol% of the total mass of all monomers (carboxyl group-containing monomer, hydrophobic group-containing monomer, and other monomers), 50 to 98 mass% of polyoxyalkylene compound, carboxyl A polymer production method comprising polymerizing a group-containing monomer in an amount of 1 to 49% by mass and a hydrophobic group-containing monomer in an amount of 1 to 49% by mass.

Polyoxyalkylene compound based on a total of 100% by mass of the polyoxyalkylene compound, carboxyl group-containing monomer, hydrophobic group-containing monomer, and other monomers (sometimes referred to as all raw materials) in the production method of the present invention The amount of the compound used is 50 to 98% by mass, preferably 60 to 96% by mass, more preferably 65 to 94% by mass, still more preferably 68 to 92% by mass, and most preferably 70. It is -90 mass%.
If it is in the said range, the polymer obtained will express compatibility with favorable surfactant.

Use of carboxyl group-containing monomer with respect to 100% by mass in total of polyoxyalkylene compound, carboxyl group-containing monomer, hydrophobic group-containing monomer, and other monomers (all raw materials) in the production method of the present invention The amount is 1 to 49% by mass, preferably 2 to 38% by mass, more preferably 3 to 32% by mass, further preferably 4 to 28% by mass, and most preferably 5 to 25% by mass. %.
If it is in the said range, the polymer obtained will express the favorable recontamination prevention ability.

  Hydrophobic group-containing monomer with respect to a total of 100% by mass of the polyoxyalkylene compound, carboxyl group-containing monomer, hydrophobic group-containing monomer, and other monomers (all raw materials) in the production method of the present invention The amount used is 1 to 49% by mass, preferably 2 to 38% by mass, more preferably 3 to 32% by mass, still more preferably 4 to 28% by mass, and most preferably 5 to 25%. % By mass. If it is in the said range, the polymer obtained will express compatibility with a favorable surfactant, and recontamination prevention ability.

In the production method of the present invention, the polyoxyalkylene compound, the carboxyl group-containing monomer, the hydrophobic group-containing monomer, and other single quantities that are optional components with respect to a total of 100% by mass of other monomers (total raw materials) The amount of the body used is preferably 0 to 10% by mass, more preferably 0 to 8% by mass, still more preferably 0 to 5% by mass, and most preferably 0% by mass. The production method of the present invention is a method for polymerizing a monomer having a carboxyl group-containing monomer and a hydrophobic group-containing monomer as essential components in the presence of a polyoxyalkylene compound. In the presence, (i) a monomer component mainly composed of a carboxyl group-containing monomer and (ii) a monomer component mainly composed of a hydrophobic group-containing unsaturated monomer are separately polymerized. It is preferable to manufacture. As a method of separately polymerizing and manufacturing, a monomer component mainly composed of a carboxyl group-containing monomer and a monomer component mainly composed of a hydrophobic group-containing unsaturated monomer are reacted at different times. In the production method to be added to the container (polymerization vessel), the carboxyl group-containing monomer, the hydrophobic group-containing unsaturated monomer, and the other monomer as required, separately added, Examples of the production method include changing the concentration of each monomer contained in the polymerization system during the polymerization by changing the addition amount of the monomer during the polymerization (including adjusting the addition rate to 0).
That is, the production method of the present invention is a method in which a monomer is polymerized in the presence of a polyoxyalkylene compound, (i) a step of mainly adding a carboxyl group-containing monomer to a polymerization vessel, and (ii) A step of adding a hydrophobic group-containing unsaturated monomer as a main component to the polymerization vessel. By including these steps, during the polymerization, polymerization mainly composed of carboxyl group-containing monomers and polymerization mainly composed of hydrophobic group-containing unsaturated monomers are performed.

  “Mainly containing a carboxyl group-containing monomer” means that the carboxyl group-containing monomer is 50% by mass or more with respect to 100% by mass of all monomers, and has 80% by mass or more and 100% by mass or less. More preferably, it is particularly preferably 90% by mass or more and 100% by mass or less, and most preferably 100% by mass. The same applies to “mainly comprising a hydrophobic group-containing unsaturated monomer”. For example, if the carboxyl group-containing monomer is 50% by mass or more with respect to 100% by mass of all monomers added to the polymerization vessel at a certain point in the polymerization, the “mainly added carboxyl group-containing monomer” Or “a step of adding a carboxyl group-containing monomer mainly”. Since there is a tendency that the amount of unreacted polyoxyalkylene compound is further reduced, and since there is a tendency that the washing performance of the obtained polymer is improved, polymerization mainly composed of a carboxyl group-containing monomer is performed. It is preferably performed before the polymerization mainly comprising a hydrophobic group-containing unsaturated monomer.

<Polymerization initiator>
The polymer of the present invention is preferably polymerized in the presence of an organic oxide as a polymerization initiator. By using an organic oxide as a polymerization initiator, it is possible to efficiently produce a graft polymer (that is, a polyoxyalkylene compound containing a carboxyl group-containing monomer or a hydrophobic group-containing unsaturated monomer). A graft chain consisting of a body can be formed). For this reason, the compatibility with the surfactant of the polymer of the present invention is improved. An organic oxide is preferable because it is relatively excellent in the ability to extract a hydrogen atom of a polyoxyalkylene compound.
Usable organic peroxides include benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,1′-di-t-butylperoxy-3, 3,5-trimethylenecyclohexane, 1,3-di- (t-butylperoxy) -diisopropylbenzene, di-t-butyl peroxide, t-butyl hydroperoxide, t-butylperoxy-2-ethylhexanoate, t -Butyl peroxypivalate, t-amyl peroxy-2-ethylhexanoate, t-amyl hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl monocarbonate, n-butyl 4,4'-di ( t-butylperoxy) valerate and the like. These organic peroxides may be used alone or in combination of two or more. Among these organic peroxides, di-t-butyl peroxide (abbreviated as PBD), t-butyl peroxybenzoate (abbreviated as PBZ), t-butyl peroxyisopropyl monocarbonate (abbreviated as PBI), n-butyl 4,4′-di (t-butylperoxy) valerate (abbreviated as PHV) is preferred.

  Other usable polymerization initiators include hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; and azo compounds. However, from the viewpoint of producing a graft polymer efficiently, it is preferable to use an organic peroxide in combination even when these polymerization initiators are used.

The amount of the polymerization initiator used in the polymerization reaction may be appropriately adjusted according to the amount of the monomer component used, and is not particularly limited. 0.001 mass part or more and 20 mass parts or less, More preferably, it is 0.01 mass part or more and 15 mass parts or less, More preferably, it is 1 mass part or more and 10 mass parts or less.
If the amount of the polymerization initiator, particularly the organic peroxide, is too small, the yield of the graft product in which the monomer is grafted onto the polyoxyalkylene compound may be lowered. On the other hand, if the amount of the organic peroxide polymerization initiator used is too large, the quality may be deteriorated and the production cost may be increased.

  In the method for producing a polymer of the present invention, in the polymerization, in addition to the above-described polymerization initiator, 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; metals such as iron, copper, nickel, cobalt, and manganese, such as iron naphthenate, copper naphthenate, nickel naphthenate, cobalt naphthenate, and manganese naphthenate. Inorganic compounds capable of generating ions; inorganic compounds such as boron trifluoride ether adduct, potassium permanganate, perchloric acid; sulfur dioxide, sulfite, sulfate, bisulfite, thiosulfate, sulfoxide, benzene Sulfuric acid and its substitution products, sulfur-containing compounds such as 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 ester , Mercapto compounds such as α-thiopropionic acid sodium sulfoethyl ester; nitrogen-containing compounds such as hydrazine, β-hydroxyethyl hydrazine, 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.

  In the method for producing a polymer of the present invention, when a polymerization reaction is carried out, an arbitrary chain transfer agent, pH adjuster, buffering agent and the like can be used as required in addition to the polymerization initiator.

<Polymerization solvent>
In the method for producing a polymer of the present invention, the polymerization reaction is preferably substantially in the form of bulk polymerization (bulk polymerization), and specifically, the solvent content is used as a reaction system for this graft polymerization. Polymerization is carried out at 10% by mass or less based on the polyoxyalkylene compound. 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.

  The amount of the solvent used is preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass with respect to the polyoxyalkylene compound to be used. % Or less, most preferably substantially free of solvent. “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.

  When the polymerization reaction system includes a solvent at the time of polymerization, the solvent used is not particularly limited, but those having a small chain transfer constant to the solvent of the monomer component, those having a boiling point of 70 ° C. or higher that can be used under normal pressure, etc. Is preferred. Examples of such solvents include 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 monoalkyl ether. Alcohols such as ethylene glycol dialkyl ethers, diethers such as propylene glycol dialkyl ethers; acetic acid such as acetic acid, ethyl acetate, propyl acetate, butyl acetate, acetates of ethylene glycol monoalkyl ether, acetates of propylene glycol monoalkyl ether, etc. System compounds; 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.

  The obtained polymer (polymer composition) may be diluted with a small amount of water and stored for convenience of handling.

<Polymerization temperature>
In the method for producing a polymer of the present invention, the polymerization temperature is preferably 100 ° C. or higher, more preferably 100 to 160 ° C., further preferably 110 to 150 ° C. If the polymerization temperature is within the above range, the graft polymerization occurs efficiently, so the compatibility of the resulting polymer with a surfactant and the ability to prevent recontamination tend to be good.
The temperature at the time of polymerization does not need to be kept constant constantly during the polymerization reaction. Thereafter, the set temperature may be maintained, or the polymerization temperature may be varied (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. Also good.

<Polymerization time>
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.

<Polymerization pressure>
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.

<Addition of raw materials>
In the method for producing a polymer of the present invention, at the time of polymerization, the polymerization may be started with a part or all of the polyoxyalkylene compound being charged into the reaction system. By doing so, the yield of the graft polymer is improved. 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 polymerization reaction to proceed is exemplified. Such a form is preferable because, in addition to improving the yield of the graft polymer, the molecular weight of the obtained polymer can be easily adjusted. In addition, superposition | polymerization may be performed by a batch type and may be performed by a continuous type.

In the production method of the present invention, as described above, there may be a step of adding mainly a carboxyl group-containing monomer and a step of adding mainly a hydrophobic group-containing unsaturated monomer during polymerization. In this case, the step of adding the carboxyl group-containing monomer as the main component may be the first step, or the step of adding the hydrophobic group-containing unsaturated monomer as the main component may be the first step. Preferably, the step of adding the carboxyl group-containing monomer as a main component is first.
In the polymerization method of the present invention, when the polymerization conditions of the carboxyl group-containing monomer and the polymerization conditions of the hydrophobic group-containing unsaturated monomer are completely different (for example, the reaction temperature and the type of polymerization initiator), Even if the monomer is added at a constant rate, a structure derived from a side chain (graft chain) mainly composed of a structure derived from a carboxyl group-containing monomer (structure b) and a hydrophobic group-containing unsaturated monomer ( Side chains (graft chains) mainly composed of structure c) will be formed separately.

  A polymerization initiator, a carboxyl group-containing monomer, a hydrophobic group-containing unsaturated monomer, and if necessary, other monomers may be dissolved in a solvent and added to the polymerization vessel, but as described above In terms of improving the yield of the graft polymer, it is preferable to set the amount of the solvent used to a minimum, and it is more preferable not to use the solvent.

[Use of polymer and polymer composition]
The polymer (or polymer composition) of the present invention comprises a water treatment agent, fiber treatment agent, dispersant, detergent builder (or detergent composition), scale inhibitor (scale inhibitor), metal ion encapsulant, It can be used as a sticking agent, various binders, emulsifiers, skin care agents, hair care agents 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 polymer (or polymer composition) of the present invention can be used as a water treatment agent. If necessary, the water treatment agent may contain a polymerized phosphate, phosphonate, anticorrosive, slime control agent, and chelating agent as other compounding agents.

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

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

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

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

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

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

When the fiber treatment agent is applied to the refining process, it is preferable to blend the polymer of the present invention with an alkali agent and a surfactant. When applied to the bleaching step, it is preferable to blend the polymer of the present invention, a peroxide, and a silicic acid-based agent such as sodium silicate as a decomposition inhibitor for the alkaline bleaching agent.
<Inorganic pigment dispersant>
The polymer (or polymer composition) 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 polymer of the present invention in the inorganic pigment dispersant is preferably 5 to 100% by weight with respect to the whole inorganic pigment dispersant. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effect.

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

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

<Detergent composition>
The polymer (or polymer composition) of the present invention can also be added to a detergent composition.

  The content of the polymer of the present invention in the detergent composition is not particularly limited. However, from the viewpoint that excellent builder performance can be exhibited, the content of the polymer of the present invention is preferably 0.1 to 15% by mass, more preferably 0, based on the total amount of the detergent composition. 0.3 to 10% by mass, and more preferably 0.5 to 5% by 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 80% by mass, preferably 15 to 75% by mass, more preferably 20 to 70% by mass, and particularly preferably based on the total amount of the detergent composition. Is 25-65 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 alkali builders, chelate builders, other anti-redeposition agents to prevent redeposition of contaminants such as sodium carboxymethyl cellulose, soil inhibitors such as benzotriazole and ethylene-thiourea, soil release agents, Color transfer inhibitor, softener, alkaline substance for pH adjustment, fragrance, solubilizer, fluorescent agent, colorant, foaming agent, foam stabilizer, polish, bactericidal agent, bleaching agent, bleaching aid, enzyme , Dyes, solvents and the like are preferred. In the case of a powder detergent composition, it is preferable to blend zeolite.

  The detergent composition may contain other detergent builders in addition to the polymer (or 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 builder for detergent is usually 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 above-mentioned detergent composition includes specific detergents 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.
Proteases, lipases, cellulases, and the like are suitable as enzymes that can be incorporated into the cleaning 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.
As the alkali builder, silicate, carbonate, sulfate and the like are preferable. As the chelate builder, diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), STPP (sodium tripolyphosphate), citric acid and the like are preferable. Other water-soluble polycarboxylic acid-based polymers other than the copolymer in the present invention may be used.
The above detergent composition has excellent anti-recontamination ability, and is a highly stable detergent with extremely high quality agent performance that is unlikely to cause deterioration in performance when stored for a long period of time or precipitation of impurities when held at low temperatures. can do.

  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, polymer composition and solid content of the polymer aqueous solution of the present invention were measured according to the following method. The formation of the polymer was confirmed by analysis using GPC, capillary electrophoresis, or the like.

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

<Measurement conditions of weight average molecular weight and number average molecular weight (GPC)>
Apparatus: L-7000 series detector manufactured by Hitachi, Ltd. Detector: RI
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: POLYETHYLENGLYCOL STANDARD made by Soka Science Co., Ltd.
Eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio).

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

<Electrophoretic measurement conditions>
The distribution (uneven distribution) of the acid groups of the unreacted polyoxyalkylene compound and graft polymer was examined under the following conditions. An uncharged polyoxyalkylene compound is detected early, a graft polymer having a large charge is slow, and an ungrafted polymer having a larger charge is detected later.
Device name: Photo OTSUKA ELECTRONICS CAPI-3300
CAPILLARY 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.

<Clay dispersibility>
(I) 67.6 g of glycine, 52.6 g of sodium chloride, and 60 ml of 1 mol / l NaOH aqueous solution were added with ion exchange water to prepare a glycine buffer solution to 600 g.
(Ii) Pure water was added to 0.074 g of calcium chloride dihydrate, 0.20 g of polyoxyethylene (20) lauryl ether, and 54 g of glycine buffer solution to make 900 g, thereby preparing a dispersion. Moreover, 0.1% polymer aqueous solution was adjusted in conversion of solid content.
(Iii) In a general test tube used for an experiment of about 30 cc, 0.30 g of JIS test powder I, 11 types (Kanto loam, fine particles: Japan Powder Industry Technology Association) is placed, and the dispersion of (ii) 27 g and 3 g of an aqueous polymer solution were added. At this time, the calcium concentration of the test solution is 50 ppm in terms of calcium carbonate.
(Iv) The test tube was sealed with a rubber stopper, and then shaken up and down 60 times so that the clay was dispersed throughout. The test tube was allowed to stand in a place not exposed to direct sunlight for 2 hours, and then 5 ml of the supernatant of the dispersion was collected with a whole pipette.
(V) Absorbance (ABS) was measured with a cell of 1 cm under the condition of a wavelength of 380 nm using a UV spectrometer, and this value was defined as a clay dispersibility value (also simply referred to as clay dispersibility).

<Carbon black dispersibility>
(I) 67.6 g of glycine, 52.6 g of sodium chloride, and 60 ml of 1 mol / l NaOH aqueous solution were added with ion exchange water to prepare a glycine buffer solution to 600 g.
(Ii) 0.074 g of calcium chloride dihydrate, 0.20 g of polyoxyethylene (20) lauryl ether, 1.0 g of carbon black (obtained from Laundry Science Association), 54 g of glycine buffer solution, and 900 g by adding pure water. And the dispersion was adjusted. Further, a 0.05% polymer aqueous solution in terms of solid content was prepared.
(Iii) To a general test tube used for an experiment of about 30 cc, 27 g of the dispersion liquid (ii) and 3 g of the polymer aqueous solution were added. At this time, the calcium concentration of the test solution is 50 ppm in terms of calcium carbonate.
(Iv) The test tube was sealed with a rubber stopper and then shaken up and down 60 times. The test tube was allowed to stand in a place not exposed to direct sunlight for 20 hours, and then 5 ml of the supernatant of the dispersion was collected with a whole pipette.
(V) Absorbance (ABS) was measured in a 1 cm cell using a UV spectrometer at a wavelength of 380 nm, and this value was defined as a carbon black dispersibility value (also simply referred to as carbon black dispersibility).

<Recontamination prevention capability>
(I) 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 SE2000 type manufactured by Nippon Denshoku Industries Co., Ltd. in advance.
(Ii) Pure water was added to 1.1 g of calcium chloride dihydrate to 15 kg to prepare hard water.
(Iii) Pure water was added to 4.0 g of polyoxyethylene (20) lauryl ether to make 100.0 g to prepare a surfactant aqueous solution. The pH was adjusted to 8.5 with sodium hydroxide.
(Iv) 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 1.0 g of carbon black were placed in a pot and stirred at 150 rpm for 1 minute. . Then, 5 white cloths were put and stirred at 100 rpm for 10 minutes.
(V) The white cloth was drained by hand, and 1 L of tap water adjusted to 25 ° C. was placed in the pot and stirred at 100 rpm for 2 minutes.
(Vi) A white cloth was applied and dried while stretching the wrinkle with an iron, and then the whiteness of the white cloth was measured again with the colorimetric color difference meter.
(Vii) From the above measurement results, the ability to prevent recontamination was determined by the following equation.
(Viii) Recontamination preventing ability (%) = [(whiteness after washing) / (whiteness of raw white cloth)] × 100.

<Example 1-1>
Into a 300 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer, 119.4 g of methoxypolyethylene glycol (obtained by adding an average of 25 mol of ethylene oxide to methanol) was charged, and nitrogen was blown. While stirring, the temperature was raised to 128 ° C. to obtain a polymerization reaction system. Next, 25.6 g of 100% acrylic acid (hereinafter abbreviated as 100% AA) and 100% butyl acrylate (hereinafter abbreviated as 100% BA) in a polymerization reaction system maintained at 128 ° C. with stirring. ) 25.6 g and 2.6 g of tert-butylperoxyisopropyl monocarbonate (hereinafter abbreviated as PBI) were dropped from separate nozzles. The dropping time of each solution was 250 minutes for PBI, 100 minutes for 100% AA from 20 minutes after the start of dropping PBI, and 140 minutes for 100% BA after 120 minutes from the start of dropping PBI. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After completion of the dropwise addition of 100% BA, the reaction solution was kept at 128 ° C. (ripening) for 60 minutes to complete the polymerization. After completion of the polymerization, 17.6 g of pure water was gradually added dropwise while the polymerization reaction solution was allowed to cool and stirred to dilute the polymerization reaction solution. Thus, an aqueous solution of polymer 1 having a solid content concentration of 90% and a weight average molecular weight of 6,300 was obtained.
The content of acrylic acid and butyl acrylate in the aqueous solution of the polymer was less than 1000 ppm, and the ratio of unreacted methoxypolyethylene glycol was 18%.

<Example 1-2>
In Example 1-1, the dropping time was 100 minutes AA for 140 minutes from 120 minutes after the start of PBI dropping, and 100% BA was 100 minutes after the start of dropping PBI for 100 minutes. Polymerization was carried out in the same manner as in Example 1-1 except that the reaction solution was kept at 128 ° C. for 1 minute (ripening) to terminate the polymerization.
Thus, an aqueous solution of polymer 2 having a solid content concentration of 88% and a weight average molecular weight of 4,300 was obtained.
The content of acrylic acid and butyl acrylate in the aqueous polymer solution was less than 1000 ppm, and the proportion of unreacted methoxypolyethylene glycol was 28%.

<Example 1-3>
Into a 300 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer, 119.4 g of methoxypolyethylene glycol (obtained by adding an average of 25 mol of ethylene oxide to methanol) was charged, and nitrogen was blown. While stirring, the temperature was raised to 128 ° C. to obtain a polymerization reaction system. Next, in a polymerization reaction system maintained at 128 ° C. with stirring, 25.6 g of 100% AA, 25.6 g of 100% BA, and 2.6 g of di-tert-butyl peroxide (hereinafter abbreviated as PBD). Were dropped from separate nozzles. The dropping time of each solution was 180 minutes for PBD, 100 minutes for 100% AA from 20 minutes after the start of dropping PBD, and 140 minutes for 100% BA after 120 minutes from the start of dropping PBD. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After completion of the dropwise addition of 100% BA, the reaction solution was kept at 128 ° C. (ripening) for 60 minutes to complete the polymerization. After completion of the polymerization, 17.6 g of pure water was gradually added dropwise while the polymerization reaction solution was allowed to cool and stirred to dilute the polymerization reaction solution. Thus, an aqueous solution of polymer 3 having a solid content concentration of 91% and a weight average molecular weight of 10,000 was obtained.
The content of acrylic acid and butyl acrylate in the aqueous solution of the polymer was less than 1000 ppm, and the ratio of unreacted methoxypolyethylene glycol was 21%.

<Example 1-4>
Into a 300 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer was charged 119.4 g of methoxypolyethylene glycol (obtained by adding 10 mol of ethylene oxide to methanol on average), and nitrogen was blown into the flask. While stirring, the temperature was raised to 128 ° C. to obtain a polymerization reaction system. Next, 25.6 g of 100% AA, 25.6 g of 100% BA, and 2.6 g of PBI were added dropwise from separate nozzles to the polymerization reaction system maintained at 128 ° C. with stirring. The dropping time of each solution was 250 minutes for PBI, 100 minutes for 100% AA from 20 minutes after the start of dropping PBI, and 140 minutes for 100% BA after 120 minutes from the start of dropping PBI. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After completion of the dropwise addition of 100% BA, the reaction solution was kept at 128 ° C. (ripening) for 60 minutes to complete the polymerization. After completion of the polymerization, 17.6 g of pure water was gradually added dropwise while the polymerization reaction solution was allowed to cool and stirred to dilute the polymerization reaction solution. Thus, an aqueous solution of polymer 4 having a solid content concentration of 89% and a weight average molecular weight of 4,200 was obtained.
The content of acrylic acid and butyl acrylate in the aqueous solution of the polymer was less than 1000 ppm, and the proportion of unreacted methoxypolyethylene glycol was 37%.

<Example 1-5>
Into a 300 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer, 119.4 g of methoxypolyethylene glycol (obtained by adding an average of 25 mol of ethylene oxide to methanol) was charged, and nitrogen was blown. While stirring, the temperature was raised to 128 ° C. to obtain a polymerization reaction system. Next, 10.2 g of 100% AA, 41.0 g of 100% BA and 2.6 g of PBI were dropped from separate nozzles into the polymerization reaction system maintained at 128 ° C. with stirring. The dropping time of each solution was 250 minutes for PBI, 60 minutes after 180 minutes from the start of dropping PBI for 100% AA, and 180 minutes after 20 minutes from the start of dropping PBI for 100% BA. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After the completion of the addition of 100% AA, the reaction solution was kept at 128 ° C. (ripening) for another 60 minutes to complete the polymerization. After completion of the polymerization, 17.6 g of pure water was gradually added dropwise while the polymerization reaction solution was allowed to cool and stirred to dilute the polymerization reaction solution. Thus, an aqueous solution of polymer 5 having a solid content concentration of 88% and a weight average molecular weight of 3,700 was obtained.
The content of acrylic acid and butyl acrylate in the aqueous polymer solution was less than 1000 ppm, and the proportion of unreacted methoxypolyethylene glycol was 16%.

<Example 1-6>
Into a 300 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer was charged 119.4 g of methoxypolyethylene glycol (obtained by adding an average of 25 mol of ethylene oxide to methanol), and nitrogen was blown into the flask. While stirring, the temperature was raised to 128 ° C. to obtain a polymerization reaction system. Next, 41.0 g of 100% AA, 10.2 g of 100% BA and 2.6 g of PBI were dropped from separate nozzles into the polymerization reaction system maintained at 128 ° C. with stirring. The dropping time of each solution was 250 minutes for PBI, 160 minutes for 100% AA from 20 minutes after the start of dropping PBI, and 80 minutes for 100% BA after 180 minutes from the start of dropping PBI. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After completion of the dropwise addition of 100% BA, the reaction solution was kept at 128 ° C. (ripening) for 60 minutes to complete the polymerization. After completion of the polymerization, 17.6 g of pure water was gradually added dropwise while the polymerization reaction solution was allowed to cool and stirred to dilute the polymerization reaction solution. Thus, an aqueous solution of polymer 6 having a solid content concentration of 90% and a weight average molecular weight of 6,700 was obtained.
The content of acrylic acid and butyl acrylate in the aqueous solution of the polymer was less than 1000 ppm, and the proportion of unreacted methoxypolyethylene glycol was 25%.

<Example 1-7>
Into a 300 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer, 119.4 g of methoxypolyethylene glycol (obtained by adding an average of 25 mol of ethylene oxide to methanol) was charged, and nitrogen was blown. While stirring, the temperature was raised to 128 ° C. to obtain a polymerization reaction system. Next, 41.0 g of 100% AA, 10.2 g of 100% 2-ethylhexyl acrylate (hereinafter abbreviated as 100% EHA), and 2.6 g of PBI were placed in a polymerization reaction system maintained at 128 ° C. with stirring. Each was dropped from a separate nozzle. The dropping time of each solution was 250 minutes for PBI, 160 minutes for 20% after starting PBI dropping for 100% AA, and 80 minutes for 180% after starting PBI dropping for 100% EHA. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After completion of the dropwise addition of 100% EHA, the reaction solution was kept at 128 ° C. (ripening) for another 60 minutes to complete the polymerization. After completion of the polymerization, 17.6 g of pure water was gradually added dropwise while the polymerization reaction solution was allowed to cool and stirred to dilute the polymerization reaction solution. Thus, an aqueous solution of polymer 7 having a solid content concentration of 89% and a weight average molecular weight of 7,900 was obtained.
The content of acrylic acid and 2-ethylhexyl acrylate in the aqueous solution of the polymer was less than 1000 ppm, and the ratio of unreacted methoxypolyethylene glycol was 27%.

<Example 1-8>
Into a 300 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer, 119.4 g of methoxypolyethylene glycol (obtained by adding an average of 25 mol of ethylene oxide to methanol) was charged, and nitrogen was blown. While stirring, the temperature was raised to 128 ° C. to obtain a polymerization reaction system. Next, 25.6 g of 100% AA, 25.6 g of 100% EHA, and 2.6 g of PBI were added dropwise from separate nozzles to the polymerization reaction system maintained at 128 ° C. with stirring. The dropping time of each solution was 250 minutes for PBI, 100 minutes for 100% AA from 20 minutes after the start of dropping PBI, and 100 minutes for 140% EHA after 120 minutes from the start of dropping PBI. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After completion of the dropwise addition of 100% EHA, the reaction solution was kept at 128 ° C. (ripening) for another 60 minutes to complete the polymerization. After completion of the polymerization, 17.6 g of pure water was gradually added dropwise while the polymerization reaction solution was allowed to cool and stirred to dilute the polymerization reaction solution. Thus, an aqueous solution of polymer 8 having a solid content concentration of 88% and a weight average molecular weight of 5,200 was obtained.
The content of acrylic acid and 2-ethylhexyl acrylate in the aqueous polymer solution was less than 1000 ppm, and the proportion of unreacted methoxypolyethylene glycol was 13%.

<Reference Example 1-1>
Into a 300 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer, 119.4 g of methoxypolyethylene glycol (obtained by adding an average of 25 mol of ethylene oxide to methanol) was charged, and nitrogen was blown. While stirring, the temperature was raised to 128 ° C. to obtain a polymerization reaction system. Next, 25.6 g of 100% AA, 25.6 g of 100% BA, and 2.6 g of PBI were dropped from separate nozzles into the polymerization reaction system maintained at 128 ° C. with stirring. The dropping time of each solution was 250 minutes for PBI, 240 minutes after 20 minutes from the start of dropping PBI for 100% AA, and 180 minutes after 20 minutes from the start of dropping PBI for 100% BA. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After the completion of the addition of 100% AA, the reaction solution was kept at 128 ° C. (ripening) for another 60 minutes to complete the polymerization. After completion of the polymerization, 17.6 g of pure water was gradually added dropwise while the polymerization reaction solution was allowed to cool and stirred to dilute the polymerization reaction solution. Thus, an aqueous solution of Reference Polymer 1 having a solid content concentration of 90% and a weight average molecular weight of 3,700 was obtained.
The content of acrylic acid and butyl acrylate in the aqueous solution of the polymer was less than 1000 ppm, and the proportion of unreacted methoxypolyethylene glycol was 25%.

<Comparative Example 1-1>
Into a 300 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer, 119.4 g of methoxypolyethylene glycol (obtained by adding an average of 25 mol of ethylene oxide to methanol) was charged, and nitrogen was blown. While stirring, the temperature was raised to 128 ° C. to obtain a polymerization reaction system. Next, 51.2 g of 100% AA and 2.6 g of PBI were dropped from separate nozzles into the polymerization reaction system maintained at 128 ° C. with stirring. The dropping time of each solution was 250 minutes for PBI and 240 minutes for 100% BA from 20 minutes after the start of PBI dropping. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After the completion of the addition of 100% AA, the reaction solution was kept at 128 ° C. (ripening) for another 60 minutes to complete the polymerization. After completion of the polymerization, 14.0 g of pure water was gradually added dropwise while the polymerization reaction solution was allowed to cool and stirred to dilute the polymerization reaction solution. Thus, an aqueous solution of Comparative Polymer 1 having a solid content concentration of 90% and a weight average molecular weight of 7,200 was obtained.

<Example 2>
Next, the clay dispersibility of the said polymers 1-8 and the comparative polymer 1 was evaluated in accordance with the said evaluation method. The results are as shown in Table 1 below.

＜実施例３＞
次に、上記重合体１〜８、比較重合体１の、カーボンブラック分散能を上記評価方法に従って評価した。結果は以下の表２の通りである。

<Example 3>
Next, the carbon black dispersibility of the said polymers 1-8 and the comparative polymer 1 was evaluated according to the said evaluation method. The results are as shown in Table 2 below.

<Example 4>
Next, the recontamination preventing ability of the polymer and comparative polymer 1 was evaluated according to the evaluation method. The results are as shown in Table 3 below.

From the results shown in Tables 1 to 3, the polymer of the present invention has superior anti-recontamination ability, hydrophobic dirt and hydrophilic dirt dispersibility compared to conventional polymer compositions. Is shown.
Therefore, when the polymer composition of the present invention is used as a detergent builder, recontamination of dirt can be effectively prevented even if washing is performed using remaining hot water in a bath.

Claims (3)

A graft polymer obtained by polymerizing a carboxyl group-containing monomer and a hydrophobic group-containing monomer as essential components in the presence of a polyoxyalkylene compound (but not having a polymerizable unsaturated double bond). There,
Polyoxyalkylene compound with respect to 100% by mass of the total mass of the structure derived from the polyoxyalkylene compound (however, having no polymerizable unsaturated double bond) and the structure derived from all monomers The mass ratio of the structure derived from (but not having a polymerizable unsaturated double bond) is 50 to 98 mass%, and the mass ratio of the structure derived from the carboxyl group-containing monomer is 1 to 49 mass%. And the mass proportion of the structure derived from the hydrophobic group-containing monomer is 1 to 49 mass%,
The graft polymer has a site mainly composed of a structure derived from a carboxyl group-containing monomer and a site mainly composed of a structure derived from a hydrophobic group-containing monomer.
Graft polymer. In the method of polymerizing a monomer having a carboxyl group-containing monomer and a hydrophobic group-containing monomer as essential components in the presence of a polyoxyalkylene compound (but not having a polymerizable unsaturated double bond). There,
The polymerization method is
(I) adding a carboxyl group-containing monomer as a main component to the polymerization vessel;
(Ii) adding a hydrophobic group-containing monomer as a main component to the polymerization vessel,
The content of the solvent is 10% by mass or less based on the polyoxyalkylene compound used, and
The polyoxyalkylene compound (provided that the polymerizable unsaturated double bond does not have a polymerizable unsaturated double bond) and the total mass of all the monomers is 100 mol%. Graft polymer characterized by polymerizing 50 to 98% by mass of non-bonded), 1 to 49% by mass of carboxyl group-containing monomer, and 1 to 49% by mass of hydrophobic group-containing monomer Manufacturing method. A detergent composition comprising the graft polymer according to claim 1.