JP2013155321A - Polymer and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer having excellent storage stability and re-contamination prevention ability.SOLUTION: A polymer has a structural unit (p) originating from a polyoxyalkylene based compound (P) and a structural unit (a) originating from a carboxylic acid based monomer as essential ingredients and the ratio by mass of the unit structure (p) to the structural unit (a) is 60:40-90:10, the ratio of a structural unit originating from acrylic acid (salt) to 100 mol% structural unit (a) originating from the carboxylic acid based monomer is 85-100 mol%, the polyoxyalkylene based compound (P) has a group selected from ≤7C aryl group, alkyl group, alkenyl group at least in a main chain terminal and has 25-100 pieces of oxyalkylene groups per one molecule of the polyoxyalkylene based compound (P), the polymer is obtained by including a step of polymerizing a monomer containing polyoxy alkylene based compound (P) and the carboxylic acid based monomer in the presence of an organic peroxide having a 10-180 min half-life at 135°C, and the quantity of the organic peroxide to be used is 0.1-8 mass% to the carboxylic acid based monomer.

Description

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

  Conventionally, polymers obtained by graft polymerization of carboxylic acid monomers to polyalkylene glycols are known.

  For example, Patent Document 1 discloses a hydrophilic graft polymer in which a monomer component containing an unsaturated monocarboxylic acid is grafted onto a polyalkylene oxide, and a side chain portion derived from the unsaturated monocarboxylic acid. A hydrophilic graft polymer is disclosed in which the molar ratio is 90 mol% or more based on the total side chain, and the residual amount of unsaturated monocarboxylic acid is less than 200 ppm by mass relative to the total mass of the hydrophilic graft polymer. Has been. Patent Document 1 discloses that the hydrophilic graft polymer has a reduced amount of residual unsaturated monocarboxylic acid and good stability over time.

International Publication No. 2008/020556

Thus, various polymers obtained by graft polymerization of a carboxylic acid monomer to a polyalkylene glycol compound have been reported. However, there is a demand for a smaller change in molecular weight during storage of the graft polymer.
Furthermore, in the detergent field, for example, energy-saving washing machines that wash with a small amount of water are widely used, and washing using remaining hot water in the bath has been widely performed. The effect of adhesion is increasing. Therefore, there is a demand for a polymer that is superior in performance of suppressing these (pre-contamination preventing ability).
Then, an object of this invention is to provide the polymer which has favorable storage stability and recontamination prevention ability.

The present inventors have intensively studied to solve the above problems. As a result, the present inventors have developed a polymer having a structural unit derived from a polyoxyalkylene compound having a specific structure and a structural unit (a) derived from a monocarboxylic acid monomer. The present invention was completed by finding that it has good storage stability and ability to prevent recontamination.

  That is, the polymer of the present invention is a polymer having as essential the structural unit (p) derived from the polyoxyalkylene compound (P) and the structural unit (a) derived from the carboxylic acid monomer. The mass ratio of the structural unit (p) and the structural unit (a) contained in the polymer is 60:40 to 90:10, and the structural unit (a) derived from the carboxylic acid monomer is 100 mol%. The ratio of the structural unit derived from acrylic acid (salt) to 85 to 100 mol% of the polyoxyalkylene compound (P) is an aryl group or alkyl group having 7 or less carbon atoms at the end of at least one main chain. The polyoxyalkylene compound (P) has 25 to 100 oxyalkylene groups per molecule, and the polymer comprises the polyoxyalkylene compound (P) A polymer obtained by polymerizing a monomer containing the carboxylic acid monomer in the presence of an organic peroxide having a half-life at 35 ° C. of 10 to 180 minutes. It is a polymer whose usage-amount of a thing is 0.1-8 mass% with respect to this carboxylic acid-type monomer.

  Since the polymer of the present invention has good storage stability and anti-recontamination ability, it can be preferably used, for example, as an additive in a detergent composition.

Hereinafter, the present invention will be described in detail.
<Polyoxyalkylene compound (P)>
The polymer of the present invention is characterized by containing a structural unit (p) derived from a specific polyoxyalkylene compound (also referred to as polyoxyalkylene compound (P)) within a predetermined range. The “polymer of the present invention” also includes a (typically unreacted) polyoxyalkylene compound (P). Further, the polyoxyalkylene compound (P) itself corresponds to the “structural unit (p) derived from the polyoxyalkylene compound (P)”. On the other hand, the polyoxyalkylene compound not having the structural unit (p) derived from the polyoxyalkylene compound (P) does not fall under the “polymer of the present invention”.

The polyoxyalkylene compound (P) is characterized by having a group selected from an aryl group having 7 or less carbon atoms, an alkyl group, and an alkenyl group at at least one main chain terminal.
Specific examples of the aryl group having 7 or less carbon atoms include a phenyl group and a methylphenyl group. Examples of the alkyl group having 7 or less carbon atoms include a methyl group, an n-propyl group, an isopropyl group, t- Examples include a butyl group, an n-hexyl group, a cyclohexyl group, and the like, and examples of the alkenyl group having 7 or less carbon atoms include a propenyl group and a butenyl group. Among these, it is preferable that the polymer of the present invention has a phenyl group and a methylphenyl group because the ability to prevent recontamination of the polymer of the present invention is improved.
The polyoxyalkylene compound (P) may have at least one main chain terminal having a group selected from an aryl group, alkyl group, and alkenyl group having 7 or less carbon atoms. You may have in the chain end.

The polyoxyalkylene compound (P) is characterized by having 25 to 100 oxyalkylene groups per molecule of the polyoxyalkylene compound (P). Among these, it is preferable that the polymer of the present invention has 27 to 80 alkylene oxide groups, and more preferably 30 to 60 alkylene oxide groups, since the ability to prevent recontamination of the polymer of the present invention is improved.
The oxyalkylene group is preferably a oxyalkylene group having 2 to 6 carbon atoms because it tends to improve the recontamination prevention ability and storage stability of the polymer of the present invention, and includes an oxyethylene group, an oxypropylene group, More preferred is an oxybutylene group. In addition, as an oxyalkylene group, you may have only 1 type and may have 2 or more types.
The polyoxyalkylene compound (P) contains an oxyethylene group (—O—CH ₂ —CH ₂ —) because it tends to improve the recontamination prevention ability and storage stability of the polymer of the present invention. It is preferable that the oxyethylene group is contained in an amount of 50 to 100 mol%, more preferably 80 mol% or more, and more preferably 90 mol% or more with respect to 100 mol% of all oxyalkylene groups contained. It is particularly preferable that it contains 100 mol%, and most preferably.

  The number average molecular weight of the polyoxyalkylene compound (P) is preferably 1000 or more, and more preferably 1200 or more. When the number average molecular weight is less than 1,000, the graft ratio tends to decrease and the number of unreacted polyoxyalkylene compounds tends to increase. The upper limit of the number average molecular weight is preferably 5000 or less. When the number average molecular weight exceeds 5000, the viscosity tends to be high, and it may be difficult to handle during polymerization.

The polyoxyalkylene compound (P) can be obtained, for example, by polymerizing an alkylene oxide by a known method in the presence of a compound serving as a polymerization starting point (production method (P-1)). Examples of the compound that serves as a starting point for the polymerization include alcohols and amines having at least one group selected from an aryl group having 7 or less carbon atoms, an alkyl group, and an alkenyl group. Used above. Of these, alcohol is preferred.
Examples of the alkylene oxide include ethylene oxide (EO), propylene oxide (PO), butylene oxide, and the like.
Examples of the alcohol or amine having a group selected from at least one aryl group having 7 or less carbon atoms, alkyl group, and alkenyl group include alcohols having 7 or less aryl groups such as phenol and methylphenol; methanol, n-propyl alcohol, isopropyl alcohol, t-butyl alcohol, n-hexyl alcohol, cyclohexyl alcohol and the like having an alkyl group having 7 or less carbon atoms; propenyl alcohol, butenyl alcohol and the like having 7 or less carbon atoms. An alcohol having an aryl group having 7 or less carbon atoms such as aniline; an amine having an alkyl group having 7 or less carbon atoms such as isopropylamine or t-butylamine; an alkenyl having 7 or less carbon atoms such as propenylamine or butenylamine; Amines having Le group and the like, which are used alone or in combination.
Another method for producing the polyoxyalkylene compound (P) is to polymerize alkylene oxide by a known method in the presence of a compound having two or more polymerization starting points such as ethylene glycol and glycerin. A part or all of the terminal hydroxyl groups of the polyoxyalkylene compound and the polyoxyalkylene compound (P) obtained by the production method (P-1), an aryl group having 7 or less carbon atoms, an alkyl group, Examples thereof include a method of reacting with a compound having a group selected from an alkenyl group and a group selected from a carboxyl group, an ester group, an isocyanate group, an amino group, a halogen group and the like.

  The method for polymerizing alkylene glycol in the presence of the compound that is the starting point of the polymerization is not particularly limited, and (i) a strong alkali such as an alkali metal hydroxide or alcoholate, or an alkylamine or the like as a base catalyst. Anionic polymerization used as (ii) cationic polymerization using metal and metalloid halides, mineral acids, acetic acid and the like as catalysts, and (iii) alkoxides of metals such as aluminum, iron and zinc, alkaline earth compounds, Lewis Coordination polymerization using a combination of acids or the like can be used.

<Structural unit (p) derived from polyoxyalkylene compound (P)>
The polymer of the present invention is a structural unit (p) derived from the polyoxyalkylene compound (P) (among structural units contained in a copolymer of a monomer and a polyoxyalkylene compound (P), It has a structural part other than the structural unit derived from the monomer, and an unreacted polyoxyalkylene compound (P)).
In the polymer of the present invention, the structural unit (p) derived from the polyoxyalkylene compound (P) is compared with the structural unit (p) derived from the carboxylic acid monomer described later. ): The structural unit (a) has a mass ratio of 60:40 to 90:10. Preferably it is 65: 35-85: 15, More preferably, it is 70: 30-80: 20. By having the content within the above range, the ability of the polymer of the present invention to prevent recontamination and storage stability tend to be improved.

<Structural Unit (a) Derived from Carboxylic Acid Monomer>
The polymer of the present invention has a structural unit (a) derived from a carboxylic acid monomer.
The structural unit (a) derived from a carboxylic acid monomer is a structure formed by polymerizing a monomer having one or more carboxyl groups, and the polymerizable carbon carbon of the monomer. A double bond is a carbon-carbon single bond. For example, when the carboxylic acid monomer is sodium acrylate, the structural unit (a) can be represented by —CH ₂ —CH (COONa) —. The polymer of the present invention has “structural unit (a) derived from a carboxylic acid monomer” means that the finally obtained polymer is a polymerizable carbon-carbon dimer of a carboxylic acid monomer. It is meant to include structural units in which a heavy bond is replaced with a carbon-carbon single bond. The carboxylic acid monomer itself is not included in the structural unit (a) derived from the carboxylic acid monomer.

  The composition amount of the structural unit (a) derived from the carboxylic acid monomer in the polymer of the present invention is as described above, but when the mass ratio of the structural unit (p): structural unit (a) is calculated. Is calculated in terms of acid type. Acid type conversion means that a structural unit derived from a monomer containing an acid group (here, a carboxylic acid monomer) (or a monomer containing an acid group) is an acid group salt (here, a carboxyl group salt) ) Is calculated as the corresponding acid. Specifically, when the structural unit derived from the carboxylic acid monomer is a structural unit derived from sodium acrylate, the mass ratio is calculated as a structural unit derived from acrylic acid which is the corresponding acid.

  Specific examples of the carboxylic acid monomer include monocarboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, α-hydroxyacrylic acid, and salts thereof; maleic acid, itacon Examples include dicarboxylic acid monomers such as acid, fumaric acid, 2-methyleneglutaric acid, and salts thereof (including the case where only one carboxyl group is in a salt form). As for these carboxylic acid-type monomers, only 1 type may be used independently and 2 or more types may be used together. The said salt represents a metal salt, ammonium salt, and an amine salt.

  The polymer of this invention has 85-100 mol% of structural units derived from acrylic acid (salt) with respect to 100 mol% of structural units (a) derived from carboxylic acid monomers. Preferably it is 87-100 mol%, More preferably, it is 90-100 mol%. By having the content within the above range, the recontamination preventing ability and the storage stability of the polymer of the present invention tend to be improved.

<Structural unit derived from other monomer (e)>
The polymer of the present invention may have a structural unit (e) derived from another monomer as an optional component, if desired. In the present invention, the other monomer is a monomer other than the carboxylic acid monomer (when the monomer is a polyoxyalkylene compound (P), the monomer is also a single monomer). The structural unit (e) derived from the other monomer is a structure formed by polymerizing the other monomer, and the polymerizable carbon carbon of the monomer. A double bond is a carbon-carbon single bond. Other monomers themselves are not included in the structural unit (e) derived from other monomers.

The polymer of the present invention has a structural unit (e) derived from other monomers in an amount of 0 to 25% by mass with respect to 100% by mass in total of the structural unit (p) and the structural unit (a). You may do it. More preferably, it is 0-20 mass%, More preferably, it is 0-15 mass%.
In addition, when calculating the mass ratio (% by mass) of the structural unit (e) derived from the other monomer, when it has an acid group, it is calculated in terms of acid type, and when it has an amino group Calculated in terms of amine. In terms of amine conversion, when a structural unit derived from another monomer (or other monomer) contains an amino group salt, it is calculated as the corresponding amine. Specifically, when the structural unit (e) derived from another monomer is a structural unit derived from vinylamine hydrochloride, the mass ratio is calculated as a structural unit derived from vinylamine which is the corresponding amine. When the structural unit (e) derived from other monomers exceeds the above range, it is not preferable because the ability to prevent recontamination of the polymer tends to decrease.

  Specific examples of the other monomers include vinyl sulfonic acid, 1-acrylamide-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, and 2- (meth) acrylamide-2-methyl-1. -Propanesulfonic acid, (meth) allyloxybenzenesulfonic acid, styrenesulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, (meth) allylsulfonic acid, isoprenesulfonic acid, 3-allyloxy-2-hydroxy- 1-propanesulfonic acid and sulfonic acid group-containing monomers such as salts thereof; N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-N- N-biphenyl such as methylacetamide and N-vinyloxazolidone Monomer; amide monomers such as (meth) acrylamide, N, N-dimethylacrylamide and N-isopropylacrylamide; allyl ether monomers such as (meth) allyl alcohol; isoprene monomers such as isoprenol Mer: (meth) acrylic acid alkyl ester monomers such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate; hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, α-hydroxymethylethyl (meth) acrylate, hydroxypentyl (meta ) (Meth) acrylic acid hydroxyalkyl monomers such as acrylate, hydroxyneopentyl (meth) acrylate, hydroxyhexyl (meth) acrylate; vinylaryl monomers such as styrene, indene, vinylaniline, isobutylene, vinyl acetate; Vinyl aromatic amino group-containing monomers having a heterocyclic aromatic hydrocarbon group and an amino group, such as vinyl pyridine and vinyl imidazole, and quaternized products and salts thereof; dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethyl Aminoalkyl (meth) acrylates such as aminopropyl acrylate and aminoethyl methacrylate and quaternized products and salts thereof; allylamines such as diallylamine and diallyldimethylamine and quaternized products and salts thereof; (i) ( (Ii) epoxy ring of allyl glycidyl ether, isoprenyl glycidyl ether, vinyl glycidyl ether, (ii) dialkylamine such as dimethylamine, diethylamine, diisopropylamine, di-n-butylamine, alkanolamine such as diethanolamine, diisopropanolamine, morpholine And monomers obtained by reacting amines such as cyclic amines such as pyrrole, and quaternized products and salts thereof. Moreover, the said other monomer may be used individually by 1 type, or may be used with the form of a 2 or more types of mixture.

<Molecular weight of polymer>
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 in each application, but the number average molecular weight of the polymer of the present invention is specifically preferably Is 1500-20000, More preferably, it is 1800-18000, More preferably, it is 2000-15000. If it is the said range, it exists in the tendency for the recontamination prevention capability and storage stability of the polymer of this invention to improve. 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.

<Organic peroxide>
The polymer of the present invention comprises a monomer (carboxyl) containing a carboxylic acid monomer in the presence of a polyoxyalkylene compound (P) and an organic peroxide having a half-life at 135 ° C. of 10 to 180 minutes. It is characterized by being obtained by including a step (also referred to as “polymerization step”) of polymerizing an acid-based monomer and other monomers if necessary. In the polymerization step, the organic peroxide having a half-life at 135 ° C. of 10 to 180 minutes mainly acts as a polymerization initiator. By producing by including the above polymerization step, the ability of the polymer of the present invention to prevent recontamination and storage stability tend to be improved.
Organic peroxides having a half-life at 135 ° C. of 10 to 180 minutes include t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5- Dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di- (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl4,4- Di- (t-butylperoxy) valerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, etc. It is exemplified.
The half-life at 135 ° C. can be measured by a usual method, but specifically, it can be measured by the method described in the catalog (10th edition) of NOF Corporation Organic Oxide. .

The use amount of the organic peroxide having a half-life at 135 ° C. of 10 to 180 minutes is 0.1 to 8% by mass, preferably 0.3 to 7% by mass, based on the carboxylic acid monomer. Yes, more preferably 0.5 to 6% by mass.
In the production of the polymer of the present invention, a part of the organic peroxide having a half-life of 10 to 180 minutes at 135 ° C. can be used in steps other than the polymerization step. It is preferable that the total use amount of the organic peroxide having a half-life at 135 ° C. of 10 to 180 minutes is 0.1 to 8% by mass (more preferably 0.3 to 7% by mass, More preferably 0.5 to 6% by mass).

The organic peroxide having a half-life at 135 ° C. of 10 to 180 minutes mainly acts as a polymerization initiator, but other polymerization initiators can be used in combination in the polymerization step. Examples of usable polymerization initiators include organic peroxides other than organic peroxides having a half-life at 135 ° C. of 10 to 180 minutes, hydrogen peroxide, persulfates, azo compounds, and the like.
The amount of all polymerization initiators used in the polymerization step (including the amount of organic peroxide used at 135 ° C. is 10 to 180 minutes) The half life at 135 ° C. is 10 to 180 minutes with respect to 100% by mass. The amount of the organic peroxide used is preferably 90 to 100% by mass.

<Polymer composition of the present invention>
The polymer composition of the present invention essentially contains the polymer of the present invention. In addition, raw material residues and by-products of the polymerization reaction such as unreacted carboxylic acid monomers and other monomers, unreacted polymerization initiators, and polymerization initiator decomposition products may be included.
The polymer of the present invention essentially contains a copolymer of a monomer and the polyoxyalkylene compound (P), and if present, the (unreacted) polyoxyalkylene compound ( P) and a polymer in which a monomer is polymerized irrespective of the polyoxyalkylene compound (P). The copolymer of the monomer and the polyoxyalkylene compound (P) mainly has a structure formed by polymerizing the monomers with the polyoxyalkylene compound (P) as a trunk. The graft polymer.

  The polymer composition of this invention contains a solvent as needed. As a solvent, what contains water as an essential thing is preferable, and it is more preferable that it is water. When the polymer composition of the present invention contains a solvent such as water, the content of the solvent may be 10% by mass to 99% by mass with respect to 100% by mass of the polymer composition from the viewpoint of handleability. preferable.

It is preferable that content of a polyoxyalkylene type compound (P) is 1-40 mass% with respect to 100 mass% of polymer compositions (solid content conversion) for the polymer composition of this invention. When the content of the polyoxyalkylene compound (P) is in the above range, the storage stability (particularly the separation stability when stored as an aqueous solution) is improved.
The content of the polyoxyalkylene compound (P) with respect to 100% by mass of the polymer composition (in terms of solid content) is more preferably 3 to 37% by mass, and further preferably 5 to 35% by mass. The copolymer of the polyoxyalkylene compound (P) and the monocarboxylic acid monomer does not correspond to the “polyoxyalkylene compound (P)”.

<Storage stability of polymer (composition)>
The polymer (composition) of the present invention is characterized by little change in the number average molecular weight during storage. Specifically, it is characterized in that the change in molecular weight is 15% or less after being adjusted to a 50% by mass aqueous solution and maintained at 40 ° C. for 14 days.

[Production Method of Polymer (Composition)]
The method for producing a polymer of the present invention comprises a monomer comprising a carboxylic acid monomer in the presence of a polyoxyalkylene compound (P) and an organic peroxide having a half-life at 135 ° C. of 10 to 180 minutes. It is characterized by being obtained including a step (polymerization step) of polymerizing a body (a carboxylic acid monomer and, if necessary, other monomers).

<Amount of raw material used>
The method for producing a polymer of the present invention uses a polyoxyalkylene compound (P), a carboxylic acid monomer, and an organic peroxide having a half-life of 10 to 180 minutes at 135 ° C. Mandatory. As for the usage-amount of the said polyoxyalkylene type compound (P) and the carboxylic acid-type monomer in the manufacturing method of the polymer of this invention, it is preferable that mass ratio (acid type conversion) is 60: 40-90: 10. . More preferably, it is 65: 35-85: 15, More preferably, it is 70: 30-80: 20. By having the content within the above range, the ability of the polymer of the present invention to prevent recontamination and storage stability tend to be improved.
Moreover, it is preferable that the usage-amount of acrylic acid (salt) is 85-100 mol% among the total usage-amount 100 mol% of the said carboxylic acid-type monomer. More preferably, it is 87-100 mol%, More preferably, it is 90-100 mol%. By having the content within the above range, the recontamination preventing ability and the storage stability of the polymer of the present invention tend to be improved.
Furthermore, although the manufacturing method of the polymer of this invention is arbitrary, it is also possible to use another monomer as needed. The amount of the other monomer used is 0% by mass or more and 25% by mass or less with respect to 100% by mass of the total amount of the polyoxyalkylene compound (P) and the carboxylic acid monomer used. preferable. More preferably, it is 0-20 mass%, More preferably, it is 0-15 mass%.
The amount of the organic peroxide used in the polymer production method of the present invention having a half-life at 135 ° C. of 10 to 180 minutes is as described above.

<Addition of raw materials>
In the production method of the polymer (composition) of the present invention, the polymerization is preferably started in a state where a part or all of the polyoxyalkylene compound (P) is charged into the reaction system. From the viewpoint of facilitating the graft polymerization based on the polyoxyalkylene compound (P), the polymerization is started in a state where the entire amount of the polyoxyalkylene compound (P) used is charged in the reaction system. It is particularly preferred.

In the production method of the polymer (composition) of the present invention, the polymerization may be carried out while adding a part or all of the monomer and the polymerization initiator to the reaction system (that is, added to the reaction system after the start of polymerization). preferable. Specifically, when maleic acid (salt) is used as the carboxylic acid monomer, it is preferable to add the entire amount of maleic acid (salt) to the reaction system before starting the polymerization (also referred to as initial charge). However, it is preferable that the carboxylic acid monomer other than maleic acid (salt) (for example, acrylic acid (salt)) is polymerized while adding the entire amount thereof to the reaction system.
The polymerization initiator is preferably polymerized while adding the entire amount to the reaction system.
In addition, superposition | polymerization may be performed by a batch type and may be performed by a continuous type.

  In addition, the manufacturing method of the polymer (composition) of this invention is the said polyoxyalkylene type compound (P), a monomer (except a carboxylic acid type monomer), and the half life in 135 degreeC is 10 to 180 minutes. It is preferable to add the total amount of the organic peroxide to the reaction solution before the polymerization step is completed, from the viewpoint of improving the recontamination prevention ability and storage stability of the polymer obtained, but a part of the polymerization step It is also possible to add after completion.

  In the method for producing a polymer (composition) of the present invention, the polymerization step is a step between the start of polymerization and the end of polymerization. Here, the polymerization start point is (i) part or all of the polyoxyalkylene compound (P), (ii) part or all of the carboxylic acid monomer, and (iii) 135 ° C. This is the time when all or part of the organic peroxide having a half-life of 10 to 180 minutes is added to the reaction system (reaction vessel). When the polymerization is completed while adding a part or all of the carboxylic acid monomer, the polymerization completion time is the time when the addition of the entire amount of the carboxylic acid monomer is completed. When the polymerization is carried out while adding a part or all of the organic peroxide having a half-life at 135 ° C. of 10 to 180 minutes at the same time, the half-life at 135 ° C. is 10 to 180 minutes. When the addition of the entire amount of the organic peroxide is completed, the reaction system is used when polymerization is performed by adding together the carboxylic acid monomer and the organic peroxide having a half-life of 10 to 180 minutes at 135 ° C. The time when the heating of is finished.

<Polymerization temperature>
In the method for producing a polymer (composition) of the present invention, the polymerization temperature is preferably set to 100 ° C. or higher and 150 ° C. or lower.
Polymerization in the above temperature range tends to improve the yield of the polymer. Further, the ability to prevent recontamination of the polymer and the storage stability tend to be improved.
The lower limit of the polymerization temperature is preferably 105 ° C or higher, more preferably 110 ° C or higher, and the upper limit of the polymerization temperature is preferably 145 ° C or lower, more preferably 140 ° C or lower.
The polymerization step (polymerization step) may be set so as to be within the above temperature range during a part of the time, but it is 50% or more of the polymerization time (refers to the time from the polymerization start point to the polymerization end point). It is preferable to keep the temperature range in the time zone, more preferably to keep the temperature range in the time zone of 80% or more, and more preferably to keep the temperature range in the time zone of 100% of the polymerization time. .
In addition, you may set to the said temperature range also in time slots (before polymerization start or after polymerization start) other than polymerization time.

<Polymerization time>
In the method for producing a polymer (composition) of the present invention, the polymerization time is not particularly limited, but is preferably 30 to 420 minutes, more preferably 45 to 390 minutes, and further preferably 60 to 360 minutes. Most preferably, it is 90 to 300 minutes. In the present invention, the “polymerization time” is as described above.

<Pressure during polymerization>
In the method for producing a polymer (composition) of the present invention, the pressure in the reaction system may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure, but the molecular weight of the obtained polymer. In this point, it is preferable to carry out the reaction under normal pressure or under pressure while the reaction system is sealed. 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.

<Polymerization solvent>
In the polymerization step of the method for producing the polymer (composition) of the present invention, the amount of the solvent used is preferably 10% by mass or less based on the total amount of the reaction system. The amount of the solvent used is more preferably 7% by mass or less, further preferably 5% by mass or less, and particularly preferably 3% by mass or less. From the viewpoint of improving the graft ratio of the resulting polymer, Most preferably, it is 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. The polyoxyalkylene compound (P), monomer, and polymerization initiator are not included in the solvent.
On the other hand, by carrying out the polymerization reaction under the reflux of an organic solvent, it is possible to suppress the adhesion of gel deposits to the wall surface or upper part in the reactor. From such a viewpoint, it is preferable to use a small amount of an organic solvent.

  In the above polymerization step, when the reaction system contains a solvent, the solvent to be used is not particularly limited. However, the monomer component has a small chain transfer constant to the solvent or has a boiling point of 70 ° C. or higher that can be used under normal pressure. Etc. are 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.

<Other additives>
In the method for producing a polymer (composition) of the present invention, 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.

<Aging process>
In the method for producing a polymer (composition) of the present invention, an aging step may be provided in addition to the polymerization step.
The aging step can be carried out, for example, by aging after completion of dropping of the monomer while maintaining the polymerization temperature or changing the polymerization temperature. By including the aging step, the residual monomer can be reduced. On the other hand, the color tone of the polymer (composition) tends to deteriorate. Considering the economical aspect, it is better that the aging time is short. For example, the aging step is preferably 30 minutes to 6 hours, and more preferably 1 to 3 hours.

The method for producing a polymer (composition) of the present invention may be provided with a post-treatment step in which the polymer composition is further dissolved in water and a peroxide is added in addition to or in place of the aging step. good. By providing the post-treatment step, it is possible to reduce the residual monomer.
The peroxide added in the post-treatment step is hydrogen peroxide; inorganic peroxide (peroxodisulfate (sodium persulfate, potassium persulfate, ammonium persulfate, etc.), peroxoborate, dithionite, sulfurous acid. Hydrogen peroxide, disulfite, etc.); organic peroxides (those exemplified as polymerization initiators, peracetic acid, peracetates (such as sodium peracetate), percarbonates (such as sodium percarbonate)) Water-soluble ones are preferable, water-soluble weak oxides are more preferable, and hydrogen peroxide is most preferable.
In the post-treatment step, it is preferable to use together with a peroxide a decomposition accelerator that can accelerate the decomposition of the peroxide. Examples of the decomposition accelerator include reducing agents such as amines, ascorbic acid and iron, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. One or more of these are used. be able to. As the decomposition accelerator, a reducing agent is preferable, and ascorbic acid is most preferable.
When using a peroxide or its decomposition accelerator in the post-treatment step, the total is preferably 0.01 to 10% by mass with respect to 100% by mass of the polymer. More preferably, it is 0.05-5 mass%, More preferably, it is 0.1-2 mass%.

  The method for producing a polymer (composition) of the present invention may further include a neutralization step, a dilution step, a concentration step, and a drying step.

[Use of polymer (composition)]
The polymer (or polymer composition) of the present invention comprises a water treatment agent, a scale inhibitor (scale inhibitor), a fiber treatment agent, a dispersant, a metal ion sealant, a thickener, various binders, an emulsifier, and skin care. It can be used as an agent, hair care agent, detergent composition and the like.

<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 reverse osmosis membrane treatment 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 mass and more preferably 5 to 100% by mass with respect to 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 a fiber treatment agent in terms of a pure component, 0.1 to 100 parts by mass of at least one selected from the group consisting of a dye, a peroxide and a surfactant with respect to 1 part by mass of the polymer of the present invention. 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. In the inorganic pigment dispersant, condensed phosphoric acid and its salt, phosphonic acid and its salt, and polyvinyl alcohol may be used as other compounding agents as required.
The content of the polymer of the present invention in the inorganic pigment dispersant is preferably 5 to 100% by mass 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 mass with respect to 100 parts by mass 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 (composition) of the present invention can also be added to a detergent composition (also referred to as the detergent composition of the present invention).
Although the polymer (composition) of the present invention includes the above-described polymer, the content of the polymer is preferably relative to the total amount of the detergent composition from the viewpoint that excellent builder performance can be exhibited. Is 0.1 to 15% by mass, more preferably 0.3 to 10% by mass, and still more preferably 0.5 to 5% by mass.
The detergent composition of the present invention usually contains 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. Salt, 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 salt etc. are suitable. The alkyl groups and alkenyl groups in these anionic surfactants are branched by alkyl groups such as methyl groups. Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkylphenyls. Ethers, higher fatty acid alkanolamides or their alkylene oxide adducts, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters, alkyl amine oxides and the like are suitable. 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 70% by mass, more preferably 20 to 60% by mass, and 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.

  Examples of the additives include alkali builder, chelate builder, anti-redeposition agent for preventing redeposition of contaminants such as sodium carboxymethyl cellulose, stain inhibitor such as benzotriazole and ethylene-thiourea, soil release agent, color Anti-transfer agent, softener, alkaline substance for pH adjustment, fragrance, solubilizer, fluorescent agent, colorant, foaming agent, foam stabilizer, glossing agent, 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 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%.

  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”.

<Molecular weight of polymer>
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer were measured using gel permeation chromatography (GPC).
GPC measurement conditions:
Device: HLC-2320GPC manufactured by Tosoh Corporation
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: Polyethylene Oxide STANDARD made by GL Sciences Inc.
Eluent: 0.1 M aqueous sodium acetate solution / acetonitrile = 75/25 (wt / wt).

<Measurement of residual monomer>
The residual monomer was quantified using liquid chromatography.
Measurement conditions for liquid chromatography:
Measuring device: 8020 series manufactured by Tosoh Corporation Column: CAPCELL PAK C1 UG120 250 mm 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: UV for carboxylic acid monomers (detection wavelength 254 nm), RI for polyoxyalkylene compounds.

<Measurement of graft ratio>
The content (mass%) of the graft polymer in the polymer composition (in terms of solid content) was taken as the graft yield. That is, it is the ratio of the mass of the graft polymer contained in the polymer composition to the mass of the solid content of the polymer composition, and is calculated by the following formula.
100 (%)-(content of unreacted polyoxyalkylene compound (%) in solid in polymer composition + monomer content (%) in solid in polymer composition).

<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.

<Measurement method of recontamination prevention rate>
(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 SE2000 type manufactured by Nippon Denshoku Industries Co., Ltd. in advance.
(2) Pure water was added to 11.0 g of calcium chloride dihydrate to make 15 kg, and hard water was prepared.
(3) Pure water was added to 4.0 g of sodium dodecylbenzenesulfonate, 6.0 g of sodium carbonate, and 2.0 g of sodium sulfate to make 100.0 g to prepare an aqueous surfactant solution.
(4) Set targot meter at 28 ° C., put 1 L of hard water and 5 g of surfactant aqueous solution, 1 g of 5.0% polymer composition aqueous solution in terms of solid content, and 1.0 g of carbon black in a pot, at 150 rpm Stir 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 at 28 ° C. was placed in the pot, and the mixture was stirred at 100 rpm for 2 minutes. This was done twice.
(6) A white cloth was applied and dried while stretching the wrinkles with an iron, and then the whiteness of the white cloth was again measured by reflectance using the colorimetric color difference meter.
(7) The recontamination prevention rate was calculated | required by the following numerical formula from the above measurement result. In addition, it means that it is excellent in the recontamination prevention capability, so that the recontamination prevention rate is high.

<Number of molecular weight change rate calculation method>
A 50% by mass aqueous solution of the polymer composition obtained in Examples and Comparative Examples was prepared, and the number average molecular weight after holding for 14 days under the condition of holding at 40 ° C. was measured. The change rate of the number average molecular weight before and after the retention was calculated using the following formula.

<Example 1>
A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was obtained by adding phenoxypolyethylene glycol having a number average molecular weight of 2300 (average 50 mol of ethylene oxide to phenol. Hereinafter referred to as PH500). .) 192.0 parts by weight were charged. The charge was dissolved by heating under a nitrogen stream, and the temperature was raised to 128 ° C. with stirring. Next, while maintaining the temperature at 128 ° C., 6.83 parts by mass of perbutyl I as an organic peroxide (containing 75% of tert-butyl peroxyisopropyl monocarbonate, manufactured by NOF Corporation, hereinafter referred to as PBI)) It was dripped continuously over 250 minutes. Twenty minutes after starting the dropping of PBI, 64.0 parts by mass of acrylic acid was added dropwise over 240 minutes. Stirring was continued for another 55 minutes after the dropping of acrylic acid was completed to obtain a polymer.
After adding 137.8 parts by mass of ion-exchanged water to the obtained polymer, 1.05 parts by mass of 35% H ₂ O ₂ (manufactured by ADEKA Corporation) is added and aged at 50 to 70 ° C. for 30 minutes. As a result, a polymer composition (1) containing the polymer of the present invention was obtained. The graft yield of the polymer in the obtained polymer composition was 93%, and the number average molecular weight was 3219.
Moreover, content of acrylic acid of a polymer composition (1) was 0 ppm with respect to 100 mass% of polymer compositions (solid content conversion).

<Example 2>
In a glass reactor equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a reflux condenser, 204.8 parts by mass of PH500 was charged. The charge was dissolved by heating under a nitrogen stream, and the temperature was raised to 128 ° C. with stirring. Next, while maintaining the temperature at 128 ° C., 4.55 parts by mass of PBI as an organic peroxide was continuously added dropwise over 250 minutes. 20 minutes after the start of dropping of PBI, 68.2 parts by mass of acrylic acid was dropped over 240 minutes. Stirring was continued for another 55 minutes after the dropping of acrylic acid was completed to obtain a polymer.
After adding 146.6 parts by mass of ion-exchanged water to the obtained polymer, 1.11 parts by mass of 35% H ₂ O ₂ (manufactured by ADEKA Co., Ltd.) is added and aged at 50 to 70 ° C. for 30 minutes. As a result, a polymer composition (2) containing the polymer of the present invention was obtained. The graft yield of the polymer in the obtained polymer composition was 87%, and the number average molecular weight was 3208.
Moreover, content of acrylic acid of a polymer composition (2) was 0 ppm with respect to 100 mass% of polymer compositions (solid content conversion).

<Example 3>
In a glass reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a reflux condenser, 213.3 parts by mass of PH500 was charged. The charge was dissolved by heating under a nitrogen stream, and the temperature was raised to 128 ° C. with stirring. Next, 2.84 parts by mass of PBI as an organic peroxide was continuously added dropwise over 250 minutes while maintaining the temperature at 128 ° C. 20 minutes after the start of dropping of PBI, 71.1 parts by mass of acrylic acid was dropped over 240 minutes. Stirring was continued for another 55 minutes after the dropping of acrylic acid was completed to obtain a polymer.
After adding 152.4 parts by mass of ion-exchanged water to the obtained polymer, 1.15 parts by mass of 35% H ₂ O ₂ (manufactured by ADEKA Corporation) is added and aged at 50 to 70 ° C. for 30 minutes. As a result, a polymer composition (3) containing the polymer of the present invention was obtained. The polymer graft yield in the obtained polymer composition was 82%, and the number average molecular weight was 6063.
Moreover, content of acrylic acid of a polymer composition (3) was 0 ppm with respect to 100 mass% of polymer compositions (solid content conversion).

<Example 4>
As polyethylene glycol, except that 213.3 parts by mass of a phenoxy polyethylene glycol having a number average molecular weight of 1850 (obtained by adding 40 mol of ethylene oxide to phenol in average; hereinafter referred to as PH400) was charged in a glass reactor. Then, the reaction was carried out according to the procedure of Example 3 to obtain a polymer composition (4) containing the polymer of the present invention. The polymer graft yield in the obtained polymer composition was 77%, and the number average molecular weight was 4970.
Moreover, content of acrylic acid of a polymer composition (4) was 15 ppm with respect to 100 mass% of polymer compositions (solid content conversion).

<Example 5>
As polyethylene glycol, except that 213.3 parts by mass of phenoxypolyethylene glycol having a number average molecular weight of 1410 (obtained by adding ethylene oxide in an average of 30 moles to phenol, hereinafter referred to as PH300) was charged in a glass reactor. Then, the reaction was carried out according to the procedure of Example 3 to obtain a polymer composition (5) containing the polymer of the present invention. The graft yield of the polymer in the obtained polymer composition was 72%, and the number average molecular weight was 4287.
Moreover, content of acrylic acid of a polymer composition (5) was 12 ppm with respect to 100 mass% of polymer compositions (solid content conversion).

<Example 6>
In a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser, 192.0 parts by mass of PH500, 5.1 parts by mass of maleic acid, and 1.3 parts by mass of isopropyl alcohol were charged. The charge was dissolved by heating under a nitrogen stream, and the temperature was raised to 128 ° C. with stirring. Next, while maintaining the temperature at 128 ° C., 6.82 parts by mass of PBI as an organic peroxide was continuously added dropwise over 250 minutes. Twenty minutes after starting the dropping of PBI, 58.9 parts by mass of acrylic acid was added dropwise over 240 minutes. Stirring was continued for another 55 minutes after the dropping of acrylic acid was completed to obtain a polymer.
After adding 137.8 parts by mass of ion-exchanged water to the obtained polymer, 1.05 parts by mass of 35% H ₂ O ₂ (manufactured by ADEKA Corporation) is added and aged at 50 to 70 ° C. for 30 minutes. As a result, a polymer composition (6) containing the polymer of the present invention was obtained. The graft yield of the polymer in the obtained polymer composition was 90%, and the number average molecular weight was 3614.
The monomer content of the polymer composition (6) was 0 ppm maleic acid and 8 ppm acrylic acid based on 100% by mass of the polymer composition (in terms of solid content).

<Example 7>
In a glass reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a reflux condenser, 192.0 parts by mass of PH500, 12.8 parts by mass of maleic acid, and 1.3 parts by mass of isopropyl alcohol were charged. The charge was dissolved by heating under a nitrogen stream, and the temperature was raised to 128 ° C. with stirring. Next, while maintaining the temperature at 128 ° C., 6.83 parts by mass of PBI as an organic peroxide was continuously added dropwise over 250 minutes. 20 minutes after the start of dropping of PBI, 51.2 parts by mass of acrylic acid was dropped over 240 minutes. Stirring was continued for another 55 minutes after the dropping of acrylic acid was completed to obtain a polymer.
After adding 137.8 parts by mass of ion-exchanged water to the obtained polymer, 1.05 parts by mass of 35% H ₂ O ₂ (manufactured by ADEKA Corporation) is added and aged at 50 to 70 ° C. for 30 minutes. As a result, a polymer composition (7) containing the polymer of the present invention was obtained. The graft yield of the polymer in the obtained polymer composition was 87%, and the number average molecular weight was 8828.
The monomer content of the polymer composition (7) was 31 ppm maleic acid and 227 ppm acrylic acid based on 100% by mass of the polymer composition (in terms of solid content).

<Example 8>
A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 204.8 parts by mass of PH500, 5.5 parts by mass of maleic acid, and 1.4 parts by mass of isopropyl alcohol. The charge was dissolved by heating under a nitrogen stream, and the temperature was raised to 128 ° C. with stirring. Next, while maintaining the temperature at 128 ° C., 4.55 parts by mass of PBI as an organic peroxide was continuously added dropwise over 250 minutes. Twenty minutes after starting the dropping of PBI, 62.8 parts by mass of acrylic acid was added dropwise over 240 minutes. Stirring was continued for another 55 minutes after the dropping of acrylic acid was completed to obtain a polymer.
After adding 146.6 parts by mass of ion-exchanged water to the obtained polymer, 1.11 parts by mass of 35% H ₂ O ₂ (manufactured by ADEKA Co., Ltd.) is added and aged at 50 to 70 ° C. for 30 minutes. As a result, a polymer composition (8) containing the polymer of the present invention was obtained. The polymer graft yield in the resulting polymer composition was 85%, and the number average molecular weight was 6695.
The monomer content of the polymer composition (8) was 0 ppm maleic acid and 84 ppm acrylic acid based on 100% by mass of the polymer composition (in terms of solid content).

<Example 9>
A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 215.6 parts by mass of PH500 and 4.9 parts by mass of maleic acid. The charge was dissolved by heating under a nitrogen stream, and the temperature was raised to 128 ° C. with stirring. Next, 0.95 parts by mass of PBI as an organic peroxide was continuously dropped over 250 minutes while maintaining the temperature at 128 ° C. Twenty minutes after starting the dropping of PBI, 66.1 parts by mass of acrylic acid was added dropwise over 240 minutes. Stirring was continued for another 55 minutes after the dropping of acrylic acid was completed to obtain a polymer.
After adding 153.3 parts by mass of ion-exchanged water to the obtained polymer, 1.15 parts by mass of 35% H ₂ O ₂ (manufactured by ADEKA Co., Ltd.) is added and aged at 50 to 70 ° C. for 30 minutes. As a result, a polymer composition (9) containing the polymer of the present invention was obtained. The graft yield of the polymer in the obtained polymer composition was 70%, and the number average molecular weight was 1,0027.
The monomer content of the polymer composition (9) was 25 ppm for maleic acid and 60 ppm for acrylic acid with respect to 100% by mass of the polymer composition (in terms of solid content).

<Example 10>
A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 213.3 parts by weight of PH500, 5.7 parts by weight of maleic acid, and 1.4 parts by weight of isopropyl alcohol. The charge was dissolved by heating under a nitrogen stream, and the temperature was raised to 128 ° C. with stirring. Next, 2.84 parts by mass of PBI as an organic peroxide was continuously added dropwise over 250 minutes while maintaining the temperature at 128 ° C. 20 minutes after the start of dropping of PBI, 65.4 parts by mass of acrylic acid was dropped over 240 minutes. Stirring was continued for another 55 minutes after the dropping of acrylic acid was completed to obtain a polymer.
After adding 152.4 parts by mass of ion-exchanged water to the obtained polymer, 1.15 parts by mass of 35% H ₂ O ₂ (manufactured by ADEKA Corporation) is added and aged at 50 to 70 ° C. for 30 minutes. As a result, a polymer composition (10) containing the polymer of the present invention was obtained. The graft yield of the polymer in the obtained polymer composition was 76%, and the number average molecular weight was 8695.
The monomer content of the polymer composition (10) was 0 ppm for maleic acid and 137 ppm for acrylic acid with respect to 100% by mass of the polymer composition (in terms of solid content).

<Example 11>
A reaction was carried out according to the procedure of Example 10 except that PH400 was used as polyethylene glycol to obtain a polymer composition (11) containing the polymer of the present invention. The graft yield of the polymer in the obtained polymer composition was 71%, and the number average molecular weight was 7229.
The monomer content of the polymer composition (11) was 0 ppm for maleic acid and 74 ppm for acrylic acid with respect to 100% by mass of the polymer composition (in terms of solid content).

<Example 12>
Except that PH300 was used as polyethylene glycol, the reaction was performed according to the procedure of Example 10 to obtain a polymer composition (12) containing the polymer of the present invention. The graft yield of the polymer in the obtained polymer composition was 68%, and the number average molecular weight was 5471.
The monomer content of the polymer composition (12) was 0 ppm for maleic acid and 68 ppm for acrylic acid with respect to 100% by mass of the polymer composition (in terms of solid content).

<Example 13>
A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 213.3 parts by weight of PH500, 5.7 parts by weight of maleic acid, and 1.4 parts by weight of isopropyl alcohol. The charge was dissolved by heating under a nitrogen stream, and the temperature was raised to 128 ° C. with stirring. Next, while maintaining the temperature at 128 ° C., 2.84 parts by mass of perbutyl D as an organic peroxide (di-tert-butyl peroxide, manufactured by NOF Corporation, hereinafter referred to as PBD) is continued for 250 minutes. Dripped. Twenty minutes after starting the dropping of PBD, 65.4 parts by mass of acrylic acid was added dropwise over 240 minutes. Stirring was continued for another 55 minutes after the dropping of acrylic acid was completed to obtain a polymer.
After adding 152.4 parts by mass of ion-exchanged water to the obtained polymer, 1.15 parts by mass of 35% H ₂ O ₂ (manufactured by ADEKA Corporation) is added and aged at 50 to 70 ° C. for 30 minutes. As a result, a polymer composition (13) containing the polymer of the present invention was obtained. The graft yield of the polymer in the obtained polymer composition was 63%, and the number average molecular weight was 9895.
The monomer content of the polymer composition (13) was 35 ppm for maleic acid and 170 ppm for acrylic acid with respect to 100% by mass of the polymer composition (in terms of solid content).

<Comparative Example 1>
A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was obtained by adding phenoxypolyethylene glycol having a number average molecular weight of 970 (average 20 mol of ethylene oxide to phenol; hereinafter referred to as PH200). .) 192.0 parts by weight were charged. The charge was dissolved by heating under a nitrogen stream, and the temperature was raised to 128 ° C. with stirring. Next, 3.22 parts by mass of PBD as an organic peroxide was continuously dropped over 195 minutes while maintaining the temperature at 128 ° C. Twenty minutes after starting the dropping of PBD, 74.7 parts by mass of acrylic acid was added dropwise over 225 minutes. Stirring was continued for an additional 70 minutes after the dropping of acrylic acid was completed to obtain a polymer.
After adding 110.2 parts by mass of ion-exchanged water to the obtained polymer, 0.99 parts by mass of 35% H ₂ O ₂ (manufactured by ADEKA Corporation) is added and aged at 50 to 70 ° C. for 60 minutes. As a result, a comparative polymer composition (1) was obtained. The graft yield of the polymer in the obtained comparative polymer composition was 47%, and the number average molecular weight was 5809.
Moreover, content of acrylic acid of a comparative polymer composition (1) was 0 ppm with respect to 100 mass% of polymer compositions (solid content conversion).

<Comparative example 2>
In a glass reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a reflux condenser, 192.0 parts by mass of PH500, 12.8 parts by mass of maleic acid, and 1.3 parts by mass of isopropyl alcohol were charged. The charge was dissolved by heating under a nitrogen stream, and the temperature was raised to 128 ° C. with stirring. Next, while maintaining the temperature at 128 ° C., 8.53 parts by mass of PBI as an organic peroxide was continuously added dropwise over 250 minutes. 20 minutes after the start of dropping of PBI, 51.2 parts by mass of acrylic acid was dropped over 240 minutes. Stirring was continued for another 55 minutes after the dropping of acrylic acid was completed to obtain a polymer.
After adding 136.1 parts by mass of ion-exchanged water to the obtained polymer, 1.05 parts by mass of 35% H ₂ O ₂ (manufactured by ADEKA Corporation) is added and aged at 50 to 70 ° C. for 30 minutes. As a result, a comparative polymer composition (2) was obtained. The graft yield of the polymer in the obtained comparative polymer composition was 90%, and the number average molecular weight was 8722.
The content of the monomer in the comparative polymer composition (2) was 0 ppm for maleic acid and 12 ppm for acrylic acid with respect to 100% by mass of the polymer composition (in terms of solid content).

<Comparative Example 3>
In a glass reactor equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a reflux condenser, 58.5 parts by mass of PH500 was charged. The charge was dissolved by heating under a nitrogen stream, and the temperature was raised to 128 ° C. with stirring. Next, while maintaining the temperature at 128 ° C., 4.39 parts by mass of perbutyl Z as an organic peroxide (tert-butyl peroxybenzoate, manufactured by NOF Corporation, hereinafter referred to as PBZ), 87.7 acrylic acid Mass parts were dropped from separate nozzles. PBZ was 210 minutes, and acrylic acid was 210 minutes from 20 minutes after the start of dropping PBZ. Stirring was continued for another 55 minutes after the dropping of acrylic acid was completed to obtain a polymer.
After adding 74.3 parts by mass of ion-exchanged water to the obtained polymer, 1.05 parts by mass of 35% H ₂ O ₂ (manufactured by ADEKA Corporation) is added and aged at 50 to 70 ° C. for 30 minutes. As a result, a comparative polymer composition (3) was obtained.

<Comparative example 4>
In a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser, 192.0 parts by mass of PH500 and 16.5 parts by mass of maleic acid were charged. The charge was dissolved by heating under a nitrogen stream, and the temperature was raised to 128 ° C. with stirring. Next, 3.01 parts by mass of PBD as an organic peroxide was continuously added dropwise over 195 minutes while maintaining the temperature at 128 ° C. Twenty minutes after starting the dropping of PBD, 46.7 parts by mass of acrylic acid was added dropwise over 225 minutes. Stirring was continued for an additional 70 minutes after the dropping of acrylic acid was completed to obtain a polymer.
After adding 136.3 parts by mass of ion-exchanged water to the obtained polymer, 1.05 parts by mass of 35% H ₂ O ₂ (manufactured by ADEKA Corporation) is added and aged at 50 to 70 ° C. for 60 minutes. As a result, a comparative polymer composition (4) was obtained. The graft yield of the polymer in the obtained comparative polymer composition was 89%, and the number average molecular weight was 9431.
The content of the monomer in the comparative polymer composition (4) was 800 ppm maleic acid and 200 ppm acrylic acid with respect to 100% by mass of the polymer composition (in terms of solid content).

  Next, for the polymer compositions (1) to (13) obtained in Examples 1 to 13 and the comparative polymer compositions (1) to (4) obtained in Comparative Examples 1 to 4, According to the method, the graft body yield (%), storage stability, and anti-recontamination rate were evaluated. The results of the graft yield (%) are summarized in Table 1, the storage stability results are summarized in Table 2, and the results of the recontamination prevention rate are summarized in Table 3. In addition, the polymer composition immediately after superposition | polymerization was used for the measurement of the recontamination prevention rate.

  From the above results, it has been clarified that the polymer of the present invention is superior in storage stability (storage stability) and has a good ability to prevent recontamination as compared with conventional polymers.

Claims (2)

It is a polymer having as essential the structural unit (p) derived from the polyoxyalkylene compound (P) and the structural unit (a) derived from the carboxylic acid monomer,
The mass ratio of the structural unit (p) and the structural unit (a) contained in the polymer is 60:40 to 90:10,
The ratio of the structural unit derived from acrylic acid (salt) to 100 mol% of the structural unit derived from the carboxylic acid monomer (a) is 85 to 100 mol%,
The polyoxyalkylene compound (P) has a group selected from an aryl group, alkyl group, and alkenyl group having 7 or less carbon atoms at at least one main chain terminal, and one molecule of the polyoxyalkylene compound (P) 25 to 100 oxyalkylene groups per
The polymer polymerizes a monomer containing the carboxylic acid monomer in the presence of the polyoxyalkylene compound (P) and an organic peroxide having a half-life at 135 ° C. of 10 to 180 minutes. The polymer obtained by including the process to perform, and the usage-amount of this organic peroxide is 0.1-8 mass% with respect to this carboxylic acid-type monomer. A method for producing a polymer comprising a step of polymerizing a monomer containing a carboxylic acid monomer in the presence of a polyoxyalkylene compound (P) and an organic peroxide,
The polyoxyalkylene compound (P) has at least one main chain terminal having a group selected from an aryl group having 7 or less carbon atoms, an alkyl group, and an alkenyl group,
The polyoxyalkylene compound (P) has 25 to 100 oxyalkylene groups per molecule,
The organic peroxide has a half-life at 135 ° C. of 10 to 180 minutes,
The carboxylic acid monomer has an acrylic acid (salt) ratio of 85 to 100 mol%,
A method for producing a polymer, wherein the polyoxyalkylene compound (P) and the carboxylic acid monomer are used in a mass ratio of 60:40 to 90:10.