JP2009035574A - Water-soluble polymer and its manufacturing method, and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-soluble polymer exhibiting excellent performances for deterging hydrophobic stains and hydrophilic stains, and to provide an efficient manufacturing method of the polymer, and a builder for a detergent and a detergent composition using the polymer. <P>SOLUTION: The water-soluble polymer is prepared by copolymerizing 1-80 mass% of a hydrophobic group-containing polyalkylene oxide (a) represented by general formula (1) and 20-99 mass% of a cationic monomer (b) containing at least one nitrogen atom. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a water-soluble polymer, a method for producing the same, and uses thereof. More specifically, a water-soluble polymer obtained by copolymerizing a hydrophobic group-containing polyalkylene oxide (a) and a cationic monomer (b) containing at least one nitrogen atom, a method for producing the polymer, The present invention relates to a detergent builder and a detergent composition using a polymer.

  The polyalkylene oxide copolymer is a useful polymer used in various industrial fields. For example, the polymer is useful for aqueous applications such as a dispersant and a cleaning composition.

  When the polyalkylene oxide copolymer is used for the above-mentioned aqueous application, it is necessary to consider the influence of the water quality of the aqueous system used, the influence of the interaction with other components used together, and the like. For example, water hardness varies depending on the country or region. For this reason, even if it is a polyalkylene oxide type copolymer which can exhibit various effects in a low hardness aqueous system, sufficient effects may not be exhibited in a high hardness aqueous system. Moreover, when a surfactant is contained in the cleaning composition, the cleaning effect may not be sufficiently exhibited depending on the degree of interaction between the polyalkylene oxide polymer and the surfactant.

  Furthermore, when a polyalkylene oxide copolymer is used in a cleaning composition, the degree of interaction between the soil to be cleaned and the polyalkylene oxide copolymer affects the cleaning effect.

  In addition, when used as a cleaning agent, the polyalkylene oxide copolymer is required to exhibit a cleaning power against both hydrophobic soil and hydrophilic soil.

  In addition to structural units derived from specific unsaturated carboxylic acid monomers and structural units derived from specific unsaturated polyalkylene glycol monomers, polyalkylene oxide copolymers with improved detergency against hydrophobic soils A structural unit derived from a (meth) acrylic acid monomer and / or a (meth) acrylamide monomer having 1 to 3 amino groups, and 1 to 3 in all structural units Water-soluble copolymers in which the content of structural units derived from (meth) acrylic acid monomers and / or (meth) acrylamide monomers having an amino group of 1 to 80% by weight have been proposed (Patent Document 1). Further, it is a water-soluble amphoteric copolymer obtained by copolymerizing a cationic monomer and an anionic monomer with an unsaturated polyalkylene glycol monomer, and uses a molar ratio of monomer components. A water-soluble amphoteric copolymer identified according to the type of anionic monomer has been proposed (Patent Document 2). However, it is desired that these polyalkylene oxide copolymers further improve the detergency against hydrophobic soils.

Other polyalkylene oxide copolymers include a polymer obtained by polymerizing a quaternary nitrogen-containing radical polymerizable monomer in the presence of polyalkylene oxide (Patent Document 3), and dimethylaminoethyl acrylate and vinyl pyrrolidone to polyethylene glycol. A polyalkylene oxide-based cationic copolymer such as a graft copolymerized polymer (Patent Document 4) has been proposed. However, these polyalkylene oxide-based cationic copolymers are not sufficient with respect to the performance of the water-based application.
JP 2005-350516 A JP 2007-39676 A JP-T-2005-531517 Japanese Patent Laid-Open No. 51-144741

  An object of the present invention is to provide a water-soluble polymer capable of exhibiting high performance for both washing of hydrophobic soils and hydrophilic soils in aqueous applications. Another object of the present invention is to provide an efficient method for producing the polymer, a detergent builder using the polymer, and a cleaning composition.

式（１）中、Ｒ_１は水素原子、炭素数１〜２４の直鎖状若しくは分岐状のアルキル基、または炭素数６〜２４の置換または非置換のアリール基であり、Ｒ_２は炭素数２〜４の直鎖状もしくは分岐状のアルキレン基であり、Ｒ_３は炭素数１〜２４の直鎖状若しくは分岐状のアルキル基、または炭素数６〜２４の置換または非置換のアリール基であり、ｎは５〜２００の整数を表す。 The water-soluble polymer of the present invention comprises 1 to 80% by mass of a hydrophobic group-containing polyalkylene oxide (a) represented by the general formula (1) and a cationic monomer (b) 20 containing at least one nitrogen atom. It is obtained by copolymerizing with ˜99% by mass.

In Formula (1), R ₁ is a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, and R ₂ is a carbon number. A linear or branched alkylene group having 2 to 4 carbon atoms, and R ₃ is a linear or branched alkyl group having 1 to 24 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms. Yes, n represents an integer of 5 to 200.

  In a preferred embodiment, the cationic monomer (b) containing at least one nitrogen atom is dialkylaminoalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylamide, vinylimidazole, diallylalkylamine, and these At least one monomer selected from the group consisting of quaternized compounds.

  In a preferred embodiment, the water-soluble polymer of the present invention is a graft copolymer.

  According to another aspect of the present invention, a polymer composition is provided. This polymer composition is a water-soluble polymer of the present invention, a hydrophobic group-containing polyalkylene oxide (a) represented by the general formula (1), a cationic monomer (b) containing at least one nitrogen atom, Including a homopolymer of the cationic monomer (b), and a copolymer of the cationic monomer (b) and other monomers when other monomers are used, Thus, the water-soluble polymer is contained in an amount of 45% by mass or more.

  According to another aspect of the invention, a detergent builder is provided. This detergent builder contains the water-soluble polymer of the present invention.

  According to another aspect of the present invention, a cleaning composition is provided. This cleaning composition contains the water-soluble polymer of the present invention.

  According to another aspect of the present invention, a method for producing a water-soluble polymer is provided. This production method is a method for producing the water-soluble polymer of the present invention, wherein the hydrophobic group-containing polyalkylene oxide (a) represented by the above formula (1) is 1 to 80% by mass, and at least one nitrogen atom. The cationic monomer (b) containing 20 to 99% by mass is copolymerized at a temperature of 120 ° C. or higher in the presence of an organic peroxide containing at least an aliphatic group.

  According to the present invention, water-solubility capable of exhibiting high performance in cleaning hydrophobic and hydrophilic soils by copolymerizing a hydrophobic group-containing polyalkylene oxide and a cationic monomer containing at least one nitrogen atom. A polymer can be provided. Moreover, the efficient manufacturing method of this polymer, the builder for detergents using this polymer, and a cleaning composition can be provided.

式（１）中、Ｒ_１は水素原子、炭素数１〜２４の直鎖状若しくは分岐状のアルキル基、または炭素数６〜２４の置換または非置換のアリール基であり、
Ｒ_２は炭素数２〜４の直鎖状もしくは分岐状のアルキレン基であり、
Ｒ_３は炭素数１〜２４の直鎖状若しくは分岐状のアルキル基、または炭素数６〜２４の置換または非置換のアリール基であり、
ｎは５〜２００の整数である。 (Water-soluble polymer)
The water-soluble copolymer of the present invention is obtained by copolymerizing a hydrophobic group-containing polyalkylene oxide (a) represented by the general formula (1) and a cationic monomer (b) containing at least one nitrogen atom. Can be obtained.

In Formula (1), R ₁ is a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms,
R ₂ is a linear or branched alkylene group having 2 to 4 carbon atoms,
R ₃ is a linear or branched alkyl group having 1 to 24 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms,
n is an integer of 5 to 200.

When R ₁ or R ₃ is a substituted aryl group, the substituent preferably does not have an unsaturated double bond such as an alkenyl group. Since the substituent of the aryl group does not have an unsaturated double bond, the graft ratio can be increased.

R ₁ is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms. And particularly preferably a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, and particularly preferably a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. And most preferably a hydrogen atom.

R ₂ is preferably a linear or branched alkylene group having 2 to 3 carbon atoms, and more preferably an ethylene group (—CH ₂ CH ₂ —).

R ₃ is preferably a linear or branched alkyl group having 6 to 18 carbon atoms, or a substituted or unsubstituted benzyl group, and more preferably a linear or branched alkyl group having 8 to 18 carbon atoms. Most preferably a linear or branched alkyl group having 12 to 16 carbon atoms. By using a polyalkylene oxide having a hydrophobic group at the terminal in this way, a water-soluble polymer having high adsorptivity to hydrophobic soil and excellent detergency against hydrophobic soil can be obtained. When R ₃ is a substituted benzyl group, the substituent is preferably an alkyl group having 1 to 16 carbon atoms, and preferably has no unsaturated double bond such as an alkenyl group. Since the substituent of R ₃ does not have an unsaturated double bond, the graft ratio can be increased.

  n is preferably an integer of 10 to 100, more preferably an integer of 15 to 50.

  The hydrophobic group-containing polyalkylene oxide (a) can be prepared by any appropriate method. For example, it can be obtained by adding a cyclic ether in the presence of a compound to be reacted that becomes the starting point of polymerization. Only one cyclic ether may be used, or two or more cyclic ethers may be used in combination.

  Any appropriate monomer can be used as the cationic monomer (b) containing at least one nitrogen atom. Examples include dialkylaminoalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylamide, vinylimidazole, vinylpyridine, diallylalkylamine, and quaternized products thereof, and diallylamine. Dialkylaminoalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylamide, vinylimidazole, and diallylalkylamine are preferable. If these tertiary amines are used as the cationic monomer, a water-soluble polymer having superior detergency against hydrophilic dirt such as mud particles and water-soluble coloring substances can be obtained as compared with the case of using these quaternized products. When the water-soluble polymer is blended with a detergent, excellent detergency can be obtained. As said cationic monomer, only 1 type may be used and 2 or more types may be used together.

  Examples of the dialkylaminoalkyl (meth) acrylate include dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dipropylaminoethyl (meth) acrylate. Dimethylaminobutyl (meth) acrylate, diethylaminobutyl (meth) acrylate, dimethylaminohexyl (meth) acrylate, dimethylaminooctyl (meth) acrylate, and dimethylaminododecyl (meth) acrylate. Of these, dimethylaminoethyl (meth) acrylate is preferably used.

    Examples of the dialkylaminoalkyl (meth) acrylamide include dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminobutyl (meth) acrylamide, dimethylaminooctyl (meth) acrylamide, and dimethylaminododecyl (meth). Examples include acrylamide and diethylaminopropyl (meth) acrylamide.

  Examples of vinylimidazole include vinylimidazole, 3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methyl sulfate, 3-ethyl-1-vinylimidazolium ethyl sulfate, and 3-ethyl-1. -Vinyl imidazolium chloride 3-Benzyl-1-vinyl imidazolium chloride is mentioned. Of these, vinylimidazole is preferably used.

  Examples of diallylalkylamine include diallylmethylamine, diallylethylamine, diallyldimethylammonium chloride, diallyldiethylammonium chloride, diallylmethylethylammonium chloride, diallyldipropylammonium chloride. Preferably, diallyldialkylammonium chloride is used.

  The content of the hydrophobic group-containing polyalkylene oxide (a) in the water-soluble polymer of the present invention is 1 to 80% by mass, preferably 40 to 80% by mass, and more preferably 40 to 75% by charge ratio. The mass% is more preferably 45 to 70 mass%, particularly preferably 50 to 68 mass%. Similarly, the content of the cationic monomer (b) containing at least one nitrogen atom is 20 to 99% by mass, preferably 20 to 60% by mass, and more preferably 25 to 60% by mass. %, More preferably 30 to 55% by mass, particularly preferably 32 to 50% by mass. Thus, since there is much content of the cationic monomer (b) containing at least 1 nitrogen atom, the water-soluble polymer excellent in the detergency with respect to hydrophilic dirt, such as a mud particle and a water-soluble coloring substance, is obtained. be able to.

  The water-soluble polymer of the present invention may further be polymerized containing other monomers. Examples of other monomers include unsaturated monocarboxylic acid monomers such as (meth) acrylic acid and crotonic acid, and unsaturated dicarboxylic acid monomers such as maleic acid, itaconic acid, citraconic acid, and fumaric acid. , Unsaturated monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, glyceryl (meth) acrylate, 3-allyloxy-1,2-propanediol, methyl (meth) acrylate, (meth) (Meth) acrylic acid esters such as ethyl acrylate, monomers having an amide group such as (meth) acrylamide, monomers having a sulfonic acid group such as vinyl sulfonic acid, polyalkylene glycols having no hydrophobic portion System monomers, vinyl acetate, styrene, acrylonitrile, and isobutylene. Examples of the polyalkylene glycol monomer having no hydrophobic portion include, for example, an alkylene glycol ester of an unsaturated carboxylic acid such as an alkylene glycol ester of (meth) acrylic acid; 1 mol of an unsaturated alcohol such as isoprenol or allyl alcohol In contrast, an adduct obtained by adding 1 to 200 mol, preferably 10 to 100 mol, more preferably 10 to 50 mol, of an alkylene oxide having 2 to 20 carbon atoms; These other monomers may be used alone or in combination of two or more.

  The content of the other monomer is preferably 30% by weight or less, more preferably 10% by weight or less, particularly preferably in the monomer composition comprising the cationic monomer and the other monomer. Is 5% by weight or less, most preferably 0% by weight. However, the composition ratio is calculated for the cationic monomer in terms of the corresponding amine and for the carboxylic acid monomer in terms of the corresponding acid.

  Arbitrary appropriate polymerization methods can be employ | adopted for the polymerization method for obtaining the water-soluble polymer of this invention. Of these, graft copolymerization is preferred. By using the graft copolymerized water-soluble polymer, a polymer composition excellent in recontamination prevention ability and clay dispersion ability can be obtained.

  In producing the graft copolymer in the present invention, first, the above-mentioned hydrophobic group-containing polyalkylene oxide (a) which becomes the main chain of the graft copolymer, and at least one nitrogen which becomes the side chain of the graft copolymer. A desired amount of each of the cationic monomer (b) containing atoms and, if necessary, the other monomer is prepared, and graft copolymerization is performed.

  The graft copolymer is preferably the cationic monomer (b) containing at least one nitrogen atom in the presence of the hydrophobic group-containing polyalkylene oxide (a) and, if necessary, the other monomer. The polymer can be obtained by radical polymerization at a suitable polymerization temperature under a suitable polymerization initiator. This is because it is simple and has a high detergency against the hydrophobic soil of the obtained graft copolymer.

  When performing the graft copolymerization, any appropriate radical polymerization initiator can be used as a polymerization initiator. Examples of the radical polymerization initiator include organic peroxides containing at least an aliphatic group, and preferably di-tert-butyl peroxide (PBD), tert-butyl peroxybenzoate (PBZ), and tert-butyl peroxy. Isopropyl monocarbonate (PBI), more preferably di-tert-butyl peroxide (PBD). These organic peroxides may be used alone or in combination of two or more.

  As the amount of the radical polymerization initiator used in the graft copolymerization, any appropriate amount can be adopted as long as the object of the present invention can be achieved. For example, it is preferably 0.1 to 10% by weight, more preferably 0.5 to 8% by weight, still more preferably 1 to 6% based on the total amount of the components used for graft copolymerization excluding the hydrophobic group-containing polyalkylene oxide. % By weight. If the amount of the radical polymerization initiator used is too small, the graft ratio may decrease. When the amount of the radical polymerization initiator used is too large, there is a risk that it may be disadvantageous in terms of cost, or the initiator fragment may affect the physical properties of the graft copolymer.

  As the addition form of the radical polymerization initiator, any appropriate form can be adopted as long as the object of the present invention can be achieved.

  In the graft copolymerization, in addition to the radical polymerization initiator, a decomposition catalyst for the radical polymerization initiator or a reducing compound may be added to the reaction system.

  Examples of the decomposition catalyst for the radical 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 and nitric acid. Metal salts of inorganic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, benzoic acid and the like, esters thereof and metal salts thereof; heterocyclic amines such as pyridine, indole, imidazole, carbazole and derivatives thereof; Etc. These cracking catalysts may be used independently and 2 or more types may be used together.

  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; ascorbic acid; and the like. These reducing compounds may be used independently and 2 or more types may be used together.

  Any appropriate solvent may be used in the graft copolymerization. A solvent having a small chain transfer constant to the solvent of the cationic monomer (b) containing at least one nitrogen atom, a solvent having a boiling point of 80 ° C. or higher, and the like are preferably used. Examples of such a solvent include water; alcohols such as isobutyl alcohol, n-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol monoalkyl ether, and propylene glycol monoalkyl ether. Diethers such as ethylene glycol dialkyl ether and propylene glycol dialkyl ether; acetic acid compounds such as acetic acid, ethyl acetate, propyl acetate, butyl acetate, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate; Etc. Preferably, it is water. The amount of the solvent used is, for example, preferably 10% by weight or less, more preferably 7% by weight or less, still more preferably 5% by weight or less, particularly preferably substantially the content of the solvent with respect to the total amount of the reaction system. 0. “Substantially 0” means a form in which no solvent is positively added at the time of graft copolymerization, and it means that mixing of a solvent of an impurity level is acceptable. By setting the amount of the solvent used within the above range, the graft copolymerization is carried out substantially in the form of bulk polymerization (bulk polymerization), enabling efficient grafting, and cationic containing at least one nitrogen atom. It is possible to suppress a decrease in builder performance caused by the impurities derived from the monomer (b).

  Any appropriate temperature can be adopted as the temperature during the graft copolymerization within the range in which the object of the present invention can be achieved. For example, it is preferably 120 ° C or higher, more preferably 120 ° C to 150 ° C, still more preferably 120 to 140 ° C, and most preferably 130 to 140 ° C. When the temperature at the time of graft copolymerization is too low, the viscosity of the reaction solution becomes too high, and the graft copolymerization is difficult to proceed, and the graft ratio may be lowered. That is, the graft ratio can be increased by setting the temperature during graft copolymerization to the above range. As a result, the content of the cationic monomer can be increased, and a water-soluble polymer having excellent detergency against hydrophilic dirt such as mud particles and water-soluble coloring substances can be obtained. If the temperature during the graft copolymerization is too high, the polyalkylene oxide and the resulting graft copolymer may be thermally decomposed.

  The temperature at the time of the graft copolymerization need not always be kept constant during the progress of the polymerization reaction. For example, depending on the dropping method of the monomer component, initiator, etc. The polymerization temperature may be varied (temperature increase or decrease).

  As the polymerization time at the time of the graft copolymerization, any appropriate time can be adopted as long as the object of the present invention can be achieved. Preferably it is 60-420 minutes, More preferably, it is 90-390 minutes, More preferably, it is 120-360 minutes. In the present invention, the time when the initiator is charged is 0 minute (polymerization start time).

  As the reaction pressure at the time of the graft copolymerization, any appropriate pressure can be adopted as long as the object of the present invention can be achieved. For example, it may be under normal pressure (atmospheric pressure), reduced pressure, or increased pressure. In view of the molecular weight of the obtained polymer, it is preferably carried out under normal pressure or under pressure. From the point of simplicity of equipment, it is preferable to carry out under normal pressure (atmospheric pressure). As the atmosphere of the reaction system, any appropriate atmosphere of the reaction system can be adopted as long as the object of the present invention can be achieved. An inert atmosphere is preferable. For example, it is preferable to replace the inside of the system with an inert gas such as nitrogen before the start of polymerization.

  Any appropriate form can be adopted as the form of the graft copolymer as long as the object of the present invention can be achieved. Preferably, the polymerization is started in a state where a part or all of the hydrophobic group-containing polyalkylene oxide (a) serving as the main chain of the graft copolymer is charged into the reaction system. Specifically, for example, the entire amount of the hydrophobic group-containing polyalkylene oxide (a) is charged into the reaction system, the temperature of the reaction system is raised, and then the cationic monomer (b) containing at least one nitrogen atom and the necessary The radical copolymerization initiator is separately added according to the above, and the graft copolymerization reaction is allowed to proceed. According to such a form, the molecular weight of the obtained graft copolymer can be easily adjusted. In addition, graft copolymerization may be performed by a batch type, and may be performed by a semibatch type or a continuous type.

  In the graft copolymerization, after the polymerization time has elapsed, the reaction may be continued while maintaining the polymerization temperature for the purpose of reducing the residual monomer. As reaction time in this case, Preferably it is 20 to 360 minutes, More preferably, it is 20 to 180 minutes, More preferably, it is 20 to 120 minutes.

  For the purpose of further reducing the residual monomer, a post-treatment of adding a peroxide and / or an azo compound may be performed on the reaction product obtained by the graft copolymerization.

  In the post-treatment, considering the actual use, the graft copolymer is preferably an aqueous solution. The concentration of the aqueous solution of the graft copolymer is preferably higher from the viewpoint of the economical efficiency (transportation cost) of the product form, preferably 40% by weight or more, more preferably 50% by weight or more, and still more preferably 60%. % By weight or more.

  The reactant obtained as described above includes the water-soluble polymer of the present invention (typically a graft copolymer), the remaining polyalkylene oxide (a), the remaining cationic monomer (b), It is a polymer composition comprising a homopolymer of a cationic monomer (b) and a copolymer of the cationic monomer (b) and another monomer when another monomer is used. . In the composition, the water-soluble polymer is preferably 45% by mass or more, more preferably 55% by mass or more, further preferably 60% by mass or more, and particularly preferably 65% by mass with respect to the total amount of the obtained reactants. % Or more. When the content ratio of the water-soluble polymer is in the above range, a polymer composition excellent in recontamination prevention ability and clay dispersibility can be obtained. In the present invention, the content of the water-soluble polymer can be measured by capillary electrophoresis. That is, the content ratio of the water-soluble polymer is calculated from the ratio of the peak area attributed to the water-soluble polymer to the total area of the peak attributed to each composition of the reactant in the capillary electrophoresis measurement chart. Can do.

  The water-soluble polymer of the present invention can exhibit high performance in aqueous applications and has high hardness resistance, detergency, ability to prevent recontamination, clay dispersibility, interaction with surfactants, etc. When used as an agent, detergent builder, detergent composition, cleaning agent, or water treatment agent, particularly excellent performance can be exhibited.

  The water-soluble polymer of the present invention has a recontamination preventing ability (details of the measuring method will be described later), preferably 82.0% or more, more preferably 83.0% or more, and further preferably 85.0% or more. .

  The water-soluble polymer of the present invention has a weight average molecular weight of preferably 1000 to 1000000, more preferably 2000 to 200000, and further preferably 2000 to 50000. If the weight average molecular weight is out of the above range, the recontamination prevention ability and the clay dispersibility may be inferior.

[Detergent builder]
The detergent builder of the present invention contains the water-soluble polymer. Specifically, the detergent builder of the present invention may be composed of only the water-soluble polymer or a mixture with any other suitable detergent builder.

  The content of the water-soluble polymer in the detergent builder according to the present invention is preferably 0.1 to 80% by weight, more preferably 1 to 70% with respect to 100% by weight of the detergent builder according to the present invention. % By weight, more preferably 5 to 65% by weight. If the content of the water-soluble polymer is less than 0.1% by weight, the cleaning power when used as a cleaning composition may be insufficient. If the content of the water-soluble polymer exceeds 80% by weight, it may be uneconomical.

  Other suitable detergent builders include, for example, sodium tripolyphosphate, sodium pyrophosphate, sodium silicate, pour glass, sodium carbonate, sodium nitrilotriacetate, sodium or potassium ethylenediaminetetraacetate, zeolite, carboxyl carboxylate Examples thereof include water-soluble polymers such as derivatives, (meth) acrylic acid (co) polymer salts, and fumaric acid (co) polymer salts.

  The detergent builder of the present invention may be for liquid detergent or powder detergent. The detergent builder of the present invention is excellent in compatibility with a surfactant. For this reason, the liquid detergent is preferred in that it can be a highly concentrated liquid detergent composition.

  The detergent builder of the present invention can be set to any appropriate type and blending ratio of the other components other than the water-soluble polymer as long as the type and blending ratio do not impair the effects of the present invention. .

  The detergent builder of the present invention can cope with various types of dirt such as hydrophilic and hydrophobic dirt, and is excellent in properties such as anti-staining ability.

[Cleaning composition]
The cleaning composition of the present invention contains the water-soluble polymer of the present invention. Preferably, the detergent builder of the present invention is included.

  The cleaning composition of the present invention may be a powder cleaning composition or a liquid cleaning composition. The cleaning composition of the present invention may contain any appropriate additive that can be used in a detergent. Examples of the additive include an anti-redeposition agent for preventing re-deposition of contaminants such as alkali builder, chelate builder, sodium carboxymethyl cellulose, anti-fouling agent such as benzotriazole and ethylene-thiourea, and a soil release agent. , Anti-transfer agent, softener, alkaline substance for pH adjustment, fragrance, solubilizer, fluorescent agent, colorant, foaming agent, foam stabilizer, polish, bactericidal agent, bleaching agent, bleaching aid, Enzymes, dyes, solvents and the like are preferred. In the case of a powder detergent composition, it is preferable to blend zeolite.

  The content ratio of the detergent builder of the present invention in the cleaning composition of the present invention is preferably 0.1 to 20% by weight, more preferably 0.2% with respect to 100% by weight of the cleaning composition of the present invention. -15% by weight, more preferably 0.3-10% by weight, particularly preferably 0.4-8% by weight, most preferably 0.5-5% by weight. If the content of the detergent builder according to the present invention is less than 0.1% by weight, sufficient cleaning performance may not be exhibited. When the content ratio of the builder for detergents of the present invention exceeds 20% by weight, the economy may be lowered.

  In the cleaning composition of the present invention, the water-soluble polymer or the builder for detergent according to the present invention may be mixed in liquid form or solid form. What is necessary is just to determine according to the form (for example, liquid substance or solid substance) at the time of sale of a detergent. Moreover, you may mix | blend with the form of the aqueous solution after superposition | polymerization, you may mix | blend in the state which reduced the water | moisture content of the aqueous solution to some extent, and may mix | blend in the state which dried and solidified.

  In addition, the detergent composition of the present invention is used for specific applications such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface detergents, and bleaching detergents that enhance one of the components. Also includes detergents that are only used. Since the water-soluble polymer is excellent in chelating ability, it can be suitably used because it can stabilize hydrogen peroxide by capturing trace metals, and is excellent in stabilizing ability of the bleach.

  The cleaning composition of the present invention preferably contains a surfactant in addition to the water-soluble polymer.

  The surfactant preferably contained in the cleaning composition of the present invention is at least one selected from an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. These surfactants may be used alone or in combination of two or more.

  When two or more surfactants are used in combination, the combined use amount of the anionic surfactant and the nonionic surfactant is preferably 50% by weight or more, more preferably 100% by weight based on the total surfactant. Is 60% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more.

  Specific examples of the anionic surfactant include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonate, Examples thereof include saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof. Further, an alkyl group such as a methyl group may be branched between the alkyl group and alkenyl group of these anionic surfactants.

  Specific examples of the nonionic surfactant include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycoxide, fatty acid glycerin mono Examples thereof include esters and alkylamine oxides. Further, an alkyl group such as a methyl group may be branched between the alkyl group and alkenyl group of these nonionic surfactants.

  Specific examples of the cationic surfactant include quaternary ammonium salts. An alkyl group such as a methyl group may be branched between the alkyl group and alkenyl group of the cationic surfactant.

  Specific examples of the amphoteric surfactant include a carboxyl type or sulfobetaine type amphoteric surfactant. An alkyl group such as a methyl group may be branched between the alkyl group and alkenyl group of the amphoteric surfactant.

  The blending ratio of the surfactant contained in the cleaning composition of the present invention is preferably 10 to 60% by weight, more preferably 12 to 50% by weight, and further preferably 15 to 15% in the cleaning composition. It is 45% by weight, particularly preferably 15 to 40% by weight. If the blending ratio of the surfactant is less than 10% by weight, sufficient detergent performance may not be exhibited. On the other hand, if it exceeds 60% by weight, the economy may be lowered.

  When the cleaning composition of the present invention is a liquid cleaning composition, the amount of water contained in the liquid cleaning composition is preferably 0.1 to 75 with respect to 100% by weight of the liquid cleaning composition. % By weight, more preferably 0.2 to 70% by weight, still more preferably 0.5 to 65% by weight, still more preferably 0.7 to 60% by weight, particularly preferably 1 to 55% by weight, most preferably 1.5 to 50% by weight.

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

  The change (difference) in kaolin turbidity with and without adding the water-soluble polymer of the present invention as a detergent builder to the liquid detergent composition is preferably 500 mg / L or less, more preferably 400 mg / L. Hereinafter, it is more preferably 300 mg / L or less, particularly preferably 200 mg / L or less, and most preferably 100 mg / L or less.

  The kaolin turbidity is measured by, for example, using a turbidimeter (NDH2000) manufactured by Nippon Denshoku Co., Ltd. after a uniformly stirred sample (liquid detergent) is charged into a 10 mm thick 50 mm square cell to remove bubbles. Measure Tubidity (Kaolin Turbidity: mg / L) at ° C.

  Proteases, lipases, cellulases and the like are suitable as enzymes that can be blended in the detergent composition. Of these, protease, alkaline lipase, and alkaline cellulase, which are highly active in the alkaline cleaning solution, are preferable. The amount of the enzyme added is preferably 5% by weight or less with respect to 100% by weight of the cleaning composition. If it exceeds 5% by weight, there is a possibility that the improvement of the detergency cannot be seen, and the economic efficiency may be lowered.

  As the alkali builder that can be blended in the cleaning composition, silicate, carbonate, sulfate and the like are suitable.

  Preferred chelate builders that can be incorporated into the detergent composition include diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), STPP (sodium tripolyphosphate), citric acid, and the like. is there. You may add what contains other components other than the water-soluble polymer in this invention.

  The cleaning composition of the present invention may be used for liquid detergents or powder detergents, but has excellent compatibility with surfactants and can be a highly concentrated liquid cleaning composition. Then, the liquid detergent is preferable.

  The cleaning composition of the present invention is of any appropriate component within the range that does not impair the effects of the present invention, with respect to the other components other than the water-soluble polymer or the detergent builder of the present invention. Types and blending ratios can be set.

  The cleaning composition of the present invention can cope with various types of stains such as hydrophilic and hydrophobic stains, and is excellent in properties such as the ability to prevent recontamination.

[Other uses]
The water-soluble polymer can also be used for pigment dispersants and scale inhibitors. It can also be widely applied in the fields of body detergents such as shampoos, rinses, body soaps, fiber processing, building material processing, paints, ceramics and the like.

  The water-soluble polymer can also be used for water treatment agents and fiber treatment agents.

  When the water treatment agent is added to a water system such as a cooling water system or a boiler water system, there is a possibility that it may be advantageous for, for example, a scale prevention property such as calcium carbonate or silica, or a metal corrosion prevention property.

  The above-mentioned fiber treatment agent may be advantageous for water absorption, flexibility, abrasion resistance, dirt prevention, touch, etc., for example, by treating various fibers.

  In the water treatment agent and the fiber treatment agent, the water-soluble polymer may be added as it is, or may be added together with other components other than the water-soluble polymer of the present invention.

  The water treatment agent and the fiber treatment agent have any appropriate type and blending ratio, as long as the types and blending ratios of the other components other than the water-soluble polymer do not impair the effects of the present invention. Can be set.

  The water treatment agent and the fiber treatment agent can cope with various kinds of stains such as hydrophilic and hydrophobic stains, and are excellent in properties such as anti-recontamination ability.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Unless otherwise specified, parts and% in the examples are based on weight.

[Example 1]
In a 500 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer, 80.0 g of SOFTANOL 200 (manufactured by Nippon Shokubai Co., Ltd .: ethylene oxide 20 mol adduct of secondary alcohol (C12-14)) A polymerization reaction system was prepared by charging, blowing nitrogen, and raising the temperature to 135 ° C. with stirring. Next, in a polymerization reaction system maintained at 135 ° C. with stirring, 40.0 g of 100% dimethylaminoethyl acrylate (hereinafter, 100% DAA), 2.2 g of di-ter-butyl peroxide (hereinafter, PBD) Were dropped from separate nozzles. The dropping time of each solution was 200 minutes for PBD 2.0 g and 180 minutes for 100% DAA 20 minutes after the start of dropping PBD. Further, 30 minutes after the completion of the 100% DAA addition, 0.2 g of PBD was added dropwise over 5 minutes. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. Thereafter, the polymerization was terminated by maintaining (aging) at 135 ° C. for another 25 minutes. After completion of the polymerization, 118.0 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. In this way, an aqueous solution of polymer (1) having a solid content concentration of 50% was obtained.

[Example 2]
A SUS separable flask having a capacity of 500 ml equipped with a reflux condenser, a thermometer, and a stirrer was charged with 120.0 g of softanol 200, blown with nitrogen, and heated to 135 ° C. with stirring to obtain a polymerization reaction system. Next, 100% DAA; 48.0 g and PBD; 2.64 g were dropped from separate nozzles into the polymerization reaction system maintained at 135 ° C. with stirring. The dropping time of each solution was 200 minutes for PBD 2.4 g, and 180 minutes for 100% DAA 20 minutes after the start of dropping PBD. Further, 30 minutes after the completion of 100% DAA dropping, 0.24 g of PBD was dropped over 5 minutes. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. Thereafter, the polymerization was terminated by maintaining (aging) at 135 ° C. for another 25 minutes. After the polymerization was completed, the polymerization reaction solution was allowed to cool and stirred, and 165.5 g of pure water was gradually added dropwise to dilute the polymerization reaction solution. In this way, an aqueous solution of polymer (2) having a solid concentration of 50% was obtained.

Example 3
A SUS separable flask having a capacity of 500 ml equipped with a reflux condenser, a thermometer, and a stirrer was charged with 200.160.0 g of softanol, blown with nitrogen, and heated to 125 ° C. with stirring to obtain a polymerization reaction system. Next, 100% DAA; 48.0 g, PBD; 2.64 g were dropped from separate nozzles into the polymerization reaction system maintained at 125 ° C. with stirring. The dropping time of each solution was 200 minutes for PBD 2.4 g, and 180 minutes for 100% DAA 20 minutes after the start of dropping PBD. Further, 30 minutes after the completion of 100% DAA dropping, 0.24 g of PBD was dropped over 5 minutes. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. Thereafter, the polymerization was terminated by maintaining (aging) at 125 ° C. for another 25 minutes. After completion of the polymerization, while the polymerization reaction solution was allowed to cool and stirred, 205.6 g of pure water was gradually added dropwise to dilute the polymerization reaction solution. In this way, an aqueous solution of polymer (3) having a solid concentration of 50% was obtained.

[Comparative Example 1]
Softanol 200 was prepared as a comparative polymer (C1).

[Evaluation]
The obtained polymers (1), (2) and (3) and the comparative polymer (C1) were evaluated for weight average molecular weight and ability to prevent recontamination.

<Weight average molecular weight>
The weight average molecular weight (Mw) is a value measured by GPC (gel permeation chromatography).
Measuring device: Hitachi "L-7000 series"
Detector: RI, UV (detection wavelength: 254 nm)
Column: Showa Denko “SHODEX SB-G”, “SHODEX SB-804HQ”, “SHODEX SB-803HQ”, “SHODEX SB-802.5HQ” connected in this order Temperature: 40 ° C.
Flow rate: 0.8 mL / minute calibration curve: prepared using a polyethylene oxide standard sample (manufactured by GL Sciences Inc.) Eluent: 0.5 M acetic acid + 0.5 M sodium acetate

<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) Hard water was prepared by adding pure water to 2.94 g of calcium chloride dihydrate to 10 kg.
(Iii) Pure water was added to 4.0 g sodium linear alkylbenzene sulfonate and 4.0 g sodium carbonate to make 100.0 g to prepare an aqueous surfactant solution.
(Iv) A targot meter is set at 25 ° C., 1 L of hard water, 5 g of an aqueous surfactant solution, 1 g of a 2% polymer aqueous solution in terms of solid content, 0.15 g of zeolite, and 0.25 g of carbon black are put in a pot, and 100 rpm For 1 minute. Then, 10 white cloths were put and stirred at 100 rpm for 10 minutes.
(V) The white cloth was drained by hand, 1 L of hard water adjusted to 25 ° C. was put 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.
Recontamination prevention ability (%) = [(whiteness after washing) / (whiteness of raw white cloth)] × 100

The evaluation results are shown in Table 1.

  The water-soluble polymer of the present invention has high resistance to hard water, dispersibility of dirt and clay, interaction with a surfactant, and the like. Therefore, when it uses for a dispersing agent, a builder for detergents, a cleaning composition, a cleaning agent, and a water treatment agent, the especially outstanding performance can be exhibited.

Claims (7)

1 to 80% by mass of a hydrophobic group-containing polyalkylene oxide (a) represented by the general formula (1) and 20 to 99% by mass of a cationic monomer (b) containing at least one nitrogen atom, Water-soluble polymer obtained by:

In Formula (1), R ₁ is a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, and R ₂ is a carbon number. A linear or branched alkylene group having 2 to 4 carbon atoms, and R ₃ is a linear or branched alkyl group having 1 to 24 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms. Yes, n represents an integer of 5 to 200.   The cationic monomer (b) containing at least one nitrogen atom is dialkylaminoalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylamide, vinylimidazole, vinylpyridine, diallylalkylamine, and quaternized compounds thereof. And at least one monomer selected from the group consisting of diallylamine.   The water-soluble polymer according to claim 1 or 2, wherein the water-soluble polymer is a graft copolymer.   A water-soluble polymer according to any one of claims 1 to 3, a hydrophobic group-containing polyalkylene oxide (a), a cationic monomer (b) containing at least one nitrogen atom, a cationic monomer (b ), And a polymer composition comprising a cationic monomer (b) and a copolymer of another monomer when other monomer is used, the water-soluble polymer The water-soluble polymer, the hydrophobic group-containing polyalkylene oxide (a), the cationic monomer (b) containing at least one nitrogen atom, a homopolymer of the cationic monomer (b), And 45% by mass or more of the polymer composition with respect to the total of the copolymer of the cationic monomer (b) and other monomers when other monomers are used.   A detergent builder comprising the water-soluble polymer according to any one of claims 1 to 3.   A cleaning composition comprising the water-soluble polymer according to claim 1. 1 to 80% by mass of a hydrophobic group-containing polyalkylene oxide (a) represented by the general formula (1) and 20 to 99% by mass of a cationic monomer (b) containing at least one nitrogen atom A method for producing a water-soluble polymer, wherein copolymerization is carried out at a temperature of 120 ° C. or higher in the presence of an organic peroxide containing a group.