JP5117887B2 - Cationic copolymer and use thereof - Google Patents

Description

  The present invention relates to a cationic copolymer and use thereof. Specifically, the cationic copolymer obtained by copolymerizing a monomer composition containing a hydrophobic group-containing polyalkylene oxide monomer and a cationic monomer containing at least one nitrogen atom in a predetermined ratio. The present invention relates to a polymer, a detergent builder and a detergent composition using the cationic copolymer.

  The polyalkylene oxide copolymer is a useful polymer used in various industrial fields. For example, the copolymer is useful for aqueous applications such as a dispersant and a detergent 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. When the detergent composition contains a surfactant, the cleaning effect may not be sufficiently exhibited depending on the degree of interaction between the polyalkylene oxide copolymer and the surfactant.

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

  In addition, when used in a detergent composition, the polyalkylene oxide copolymer is required to exhibit detergency against both hydrophobic soil and hydrophilic soil.

  Until now, as a polyoxyalkylene copolymer, a copolymer of a polyoxyalkylene monomer and a quaternized nitrogen-containing monomer (Patent Document 1), a polyoxyalkylene monomer and a quaternary are known. A copolymer with a cationic group-containing monomer (Patent Document 2) and the like have been proposed.

However, the polyalkylene oxide copolymers proposed so far are not sufficient with respect to the performance of the above-mentioned aqueous applications.
Special table 2007-510806 gazette JP 2001-181354 A

  An object of the present invention is to provide a copolymer capable of exhibiting high performance for washing both hydrophobic soils and hydrophilic soils, particularly in aqueous applications. Another object of the present invention is to provide a detergent builder and a detergent composition using the copolymer.

（式（１）中、
Ｘは、Ｒ_４、または、一般式（２）、もしくは−ＯＣＨ_２ＣＨ_２−で表される構造であり、

Ｙは、酸素原子、または、一般式（３）で表される構造であり、

Ｒ_１は、水素原子またはメチル基であり、
Ｒ_２は、炭素数２〜４の直鎖または分岐アルキレン基であり、
Ｒ_３は、炭素数６〜２４の直鎖もしくは分岐アルキル基、または炭素数６〜２４の置換もしくは無置換アリール基であり、
Ｒ_４は、炭素数１〜２のアルキレン基であり、
Ｒ_５は、炭素数１〜２のアルキレン基であり、
ｎ１は、５〜２００の整数である。） The cationic copolymer of the present invention is a cationic monomer containing 1 to 55% by weight of the hydrophobic group-containing polyalkylene oxide monomer (a) represented by the general formula (1) and at least one nitrogen atom. It is obtained by copolymerizing a monomer composition containing 45 to 99% by weight of body (b).

(In the formula (1),
X is a structure represented by R ₄ , the general formula (2), or —OCH ₂ CH ₂ —.

Y is an oxygen atom or a structure represented by the general formula (3),

R ₁ is a hydrogen atom or a methyl group,
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 6 to 24 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms,
R ₄ is an alkylene group having 1 to 2 carbon atoms,
R ₅ is an alkylene group having 1 to 2 carbon atoms,
n1 is an integer of 5 to 200. )

（式中、Ｒ_６は、水素原子またはメチル基であり、Ｒ_７は、炭素数１〜２のアルキレン基であり、Ｒ_８は、炭素数６〜２４の直鎖もしくは分岐アルキル基、または炭素数６〜２４の置換もしくは無置換アリール基であり、ｎ２は、５〜２００の整数である。）

（式中、Ｒ_９は、水素原子またはメチル基であり、Ｒ_１０は、炭素数１〜２のアルキレン基であり、Ｒ_１１は、炭素数６〜２４の直鎖もしくは分岐アルキル基、または炭素数６〜２４の置換もしくは無置換アリール基であり、ｎ３は、５〜２００の整数である。） In a preferred embodiment, the hydrophobic group-containing polyalkylene oxide monomer (a) is selected from the group consisting of a compound represented by the general formula (4) and a compound represented by the general formula (5). At least one monomer.

(In the formula, R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 1 to 2 carbon atoms, R ₈ is a linear or branched alkyl group having 6 to 24 carbon atoms, or carbon. (It is a substituted or unsubstituted aryl group of formulas 6 to 24, and n2 is an integer of 5 to 200.)

(In the formula, R ₉ is a hydrogen atom or a methyl group, R ₁₀ is an alkylene group having 1 to 2 carbon atoms, R ₁₁ is a linear or branched alkyl group having 6 to 24 carbon atoms, or carbon. (It is a substituted or unsubstituted aryl group of formulas 6 to 24, and n3 is an integer of 5 to 200.)

  In a preferred embodiment, the cationic monomer (b) is dialkylaminoalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylamide, vinylimidazole, vinylpyridine, diallylalkylamine, and a quaternized product thereof. And at least one monomer selected from the group consisting of diallylamine.

  According to another aspect of the invention, a detergent builder is provided. This detergent builder contains the cationic copolymer.

  According to another aspect of the invention, a detergent composition is provided. This detergent composition contains the cationic copolymer.

  According to the present invention, by copolymerizing a monomer composition containing a polyalkylene oxide monomer containing a hydrophobic group and a cationic monomer containing at least one nitrogen atom in a predetermined ratio. In particular, it is possible to provide a cationic copolymer capable of exhibiting high performance for washing both hydrophobic soils and hydrophilic soils in aqueous applications.

  Moreover, the builder and detergent composition for detergents using this cationic copolymer can be provided.

  In particular, the cationic copolymer of the present invention has high hard water resistance, detergency, ability to prevent recontamination, clay dispersibility, interaction with a surfactant, and the like.

（式（１）中、
Ｘは、Ｒ_４、または、一般式（２）、もしくは−ＯＣＨ_２ＣＨ_２−で表される構造であり、

Ｙは、酸素原子、または、一般式（３）で表される構造であり、

Ｒ_１は、水素原子またはメチル基であり、
Ｒ_２は、炭素数２〜４の直鎖または分岐アルキレン基であり、
Ｒ_３は、炭素数６〜２４の直鎖もしくは分岐アルキル基、または炭素数６〜２４の置換もしくは無置換アリール基であり、
Ｒ_４は、炭素数１〜２のアルキレン基であり、
Ｒ_５は、炭素数１〜２のアルキレン基であり、
ｎ１は、５〜２００の整数である。） [Cationic copolymer]
The cationic copolymer of the present invention is a cationic monomer containing 1 to 55% by weight of the hydrophobic group-containing polyalkylene oxide monomer (a) represented by the general formula (1) and at least one nitrogen atom. It is obtained by copolymerizing a monomer composition containing 45 to 99% by weight of the body (b).

(In the formula (1),
X is a structure represented by R ₄ , the general formula (2), or —OCH ₂ CH ₂ —.

Y is an oxygen atom or a structure represented by the general formula (3),

R ₁ is a hydrogen atom or a methyl group,
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 6 to 24 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms,
R ₄ is an alkylene group having 1 to 2 carbon atoms,
R ₅ is an alkylene group having 1 to 2 carbon atoms,
n1 is an integer of 5 to 200. )

X is preferably a structure represented by R ₄ , the general formula (2) or —OCH ₂ CH ₂ —, and more preferably a structure represented by R ₄ or the general formula (2). If X is a structure represented by R ₄ , the general formula (2) or —OCH ₂ CH ₂ —, when used in a detergent composition, under neutral to weak alkaline conditions that are suitably used as a detergent, Stable and high detergency, clay dispersibility, recontamination prevention ability, etc. can be exhibited. By having this structure, it is highly stable against changes in pH and temperature, so it is extremely difficult to decompose even under harsh conditions during monomer synthesis or polymerization, or under each application, for example, during the manufacture of detergents. Has characteristics. Therefore, for example, when blended in a detergent or the like, high performance can be exhibited and variation in product quality can be suppressed. When a hydrophobic group-containing polyalkylene oxide monomer other than the structure is used, for example, in the hydrophobic group-containing polyalkylene oxide monomer, the unsaturated double bond and the polyalkylene glycol chain are bonded via an ester bond. In the case of having the structure, the ester bond is subject to hydrolysis in the above step. In general, a polyalkylene oxide monomer having a hydrophobic group has a high molecular weight, and even if a small amount of ester bond undergoes hydrolysis, it has a great influence on the physical properties of the polymer. Therefore, the dispersion of the performance of the polymer obtained becomes large. In addition, for example, when the unsaturated double bond site has a structure such as a vinyl ether bond, since the copolymerization is low, the amount of residual monomer varies, resulting in a large variation in the performance of the resulting polymer. End up. With the hydrophobic group-containing polyalkylene oxide monomer in the present invention, it is possible to substantially avoid the occurrence of the above problems.

  Y is preferably an oxygen atom or a structure represented by the general formula (3).

R ₁ is preferably a hydrogen atom.

R ₂ is preferably an 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 24 carbon atoms, more preferably a linear or branched alkyl group having 8 to 18 carbon atoms, and particularly preferably a linear chain having 12 to 16 carbon atoms. Or it is a branched alkyl group. In the present invention, R ₃ functions as a hydrophobic group. By having a hydrophobic group, the cationic copolymer of the present invention can exhibit high detergency, clay dispersibility, recontamination preventing ability and the like when used in a detergent composition.

R ₄ is preferably a methylene group (—CH ₂ —).

R ₅ is preferably a methylene group (—CH ₂ —).

  n1 is preferably an integer of 10 to 100, more preferably an integer of 15 to 50.

  In the general formula (1), different alkylene oxide groups may be arranged in a random structure or a block structure.

  The hydrophobic group-containing polyalkylene oxide monomer represented by the general formula (1) is preferably a compound represented by the general formula (4) and a compound represented by the general formula (5). It is done. As said hydrophobic group containing polyalkylene oxide type monomer, only 1 type may be used and 2 or more types may be used together.

（式中、Ｒ_６は、水素原子またはメチル基であり、Ｒ_７は、炭素数１〜２のアルキレン基であり、Ｒ_８は、炭素数６〜２４の直鎖もしくは分岐アルキル基、または炭素数６〜２４の置換もしくは無置換アリール基であり、ｎ２は、５〜２００の整数である。）

(In the formula, R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 1 to 2 carbon atoms, R ₈ is a linear or branched alkyl group having 6 to 24 carbon atoms, or carbon. (It is a substituted or unsubstituted aryl group of formulas 6 to 24, and n2 is an integer of 5 to 200.)

R ₆ is preferably a hydrogen atom. R ₇ is preferably a methylene group (—CH ₂ —). R ₈ is preferably a linear or branched alkyl group having 6 to 24 carbon atoms, more preferably a linear or branched alkyl group having 8 to 18 carbon atoms, and particularly preferably a linear chain having 12 to 16 carbon atoms. Or it is a branched alkyl group.

（式中、Ｒ_９は、水素原子またはメチル基であり、Ｒ_１０は、炭素数１〜２のアルキレン基であり、Ｒ_１１は、炭素数６〜２４の直鎖もしくは分岐アルキル基、または炭素数６〜２４の置換もしくは無置換アリール基であり、ｎ３は、５〜２００の整数である。）

(In the formula, R ₉ is a hydrogen atom or a methyl group, R ₁₀ is an alkylene group having 1 to 2 carbon atoms, R ₁₁ is a linear or branched alkyl group having 6 to 24 carbon atoms, or carbon. (It is a substituted or unsubstituted aryl group of formulas 6 to 24, and n3 is an integer of 5 to 200.)

R ₉ is preferably a methyl group. R ₁₀ is preferably an ethylene group (—CH ₂ CH ₂ —). R ₁₁ is preferably a linear or branched alkyl group having 6 to 24 carbon atoms, more preferably a linear or branched alkyl group having 8 to 18 carbon atoms, and particularly preferably a linear chain having 12 to 16 carbon atoms. Or it is a branched alkyl group.

  n2 and n3 are each independently preferably an integer of 10 to 100, more preferably an integer of 15 to 50.

  The hydrophobic group-containing polyalkylene oxide monomer (a) represented by the general formula (1) can be prepared by any appropriate method.

  For example, the compound represented by the general formula (4) is obtained by adding an allyl glycidyl ether to a hydrophobic group-containing polyalkylene oxide, or an ethylenically unsaturated polyalkylene oxide (for example, an alkylene oxide adduct of allyl alcohol or isoprenol). It can be prepared, for example, by adding an alkyl or aryl glycidyl ether containing an alkylene oxide.

  For example, the compound represented by general formula (5) can be prepared by adding an alkyl or aryl glycidyl ether to an ethylenically unsaturated polyalkylene oxide (eg, an alkylene oxide adduct of allyl alcohol or isoprenol). it can.

  Any appropriate monomer can be used as the cationic monomer containing at least one nitrogen atom. For example, dialkylaminoalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylamide, vinylimidazole, vinylpyridine, diallylalkylamine, and quaternized products thereof, and diallylamine are preferably used. By using these cationic monomers, a copolymer excellent in detergency against hydrophilic dirt such as mud particles and water-soluble coloring substances 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 quaternized product of dialkylaminoalkyl (meth) acrylate include quaternized dialkylaminoalkyl (meth) acrylate with any appropriate quaternizing agent. Specifically, for example, trimethylammonium ethyl (meth) acrylate chloride, trimethylammonium ethyl (meth) acrylate sulfate, dimethylethylammonium ethyl (meth) acrylate sulfate, trimethylammonium propyl (meth) acrylate chloride, trimethylammonium propyl (meth) Examples thereof include acrylate sulfate, dimethylethylammonium propyl (meth) acrylate sulfate, trimethylammonium butyl (meth) acrylate chloride, trimethylammonium butyl (meth) acrylate sulfate, and dimethylethylammonium butyl (meth) acrylate sulfate. Among these, trimethylammonium ethyl (meth) acrylate chloride, trimethylammonium ethyl (meth) acrylate sulfate, and dimethylethylammonium ethyl (meth) acrylate sulfate are preferable, and trimethylammonium ethyl (meth) acrylate chloride is more preferably used.

  Any appropriate quaternizing agent is used. For example, alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide, benzyl chloride and the like can be mentioned.

  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. In addition, examples of the quaternized product include a quaternized dialkylaminoalkyl (meth) acrylamide with any appropriate quaternizing agent. Specific examples include (meth) acrylamidoethyltrimethylammonium chloride, (meth) acrylamidopropyltrimethylammonium chloride, and (meth) acrylamidobutyltrimethylammonium chloride. As the quaternizing agent, the same ones as described above can be used.

  Examples of vinyl imidazole and quaternized compounds thereof include vinyl imidazole, 3-methyl-1-vinyl imidazolium chloride, 3-methyl-1-vinyl imidazolium methyl sulfate, 3-ethyl-1-vinyl imidazolium ethyl sulfate, An example is 3-ethyl-1-vinylimidazolium chloride 3-benzyl-1-vinylimidazolium chloride. Of these, vinylimidazole is preferably used.

  Examples of vinyl pyridine and quaternized products thereof include vinyl pyridine, 1-methyl-4-vinylpyridinium chloride, 1-methyl-4-vinylpyridinium methyl sulfate, and 3-benzyl-1-vinylpyridinium chloride.

  Examples of diallylalkylamines and quaternized products thereof include diallylmethylamine, diallylethylamine, diallyldimethylammonium chloride, diallyldiethylammonium chloride, diallylmethylethylammonium chloride, and diallyldipropylammonium chloride. Preferably, diallyldialkylammonium chloride is used.

  In the monomer composition used in the present invention, the content of the hydrophobic group-containing polyalkylene oxide monomer (a) represented by the general formula (1) is 1 to 55% by weight, preferably 5 It is -55 weight%, More preferably, it is 10-55 weight%, Especially preferably, it is 15-50 weight%, Most preferably, it is 20-50 weight%. Similarly, the content of the cationic monomer (b) containing at least one nitrogen atom is 45 to 99% by weight, preferably 45 to 95% by weight, more preferably in the monomer composition. It is 45 to 90% by weight, particularly preferably 50 to 85% by weight, and most preferably 50 to 80% by weight. When the content of the hydrophobic group-containing polyalkylene oxide monomer is less than 5% by weight, the amount of hydrophobic groups contained in the copolymer is not sufficient, so that the adsorptivity to hydrophobic soils is reduced. Detergency against sexual soil may be reduced. If the content of the cationic copolymer is less than 50% by weight, the adsorptivity to hydrophilic dirt may be reduced, and the detergency against the hydrophilic dirt may be reduced.

  The monomer composition may further contain other monomers. Examples of other monomers include unsaturated monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, glyceryl (meth) acrylate, 3-allyloxy-1,2-propanediol, (meth ) (Meth) acrylic acid esters such as methyl acrylate and ethyl (meth) acrylate, monomers having an amide group such as (meth) acrylamide, monomers having a sulfonic acid group such as vinyl sulfonic acid, hydrophobicity Examples include polyalkylene glycol monomers having no moiety, 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 in the monomer composition is preferably 30% by weight or less, more preferably 10% by weight or less, particularly preferably 5% by weight or less, and most preferably 0% by weight. is there.

  Any appropriate polymerization method can be adopted as the polymerization method for obtaining the cationic copolymer of the present invention. For example, radical polymerization is mentioned. The radical polymerization can be performed by any appropriate method. For example, a solution polymerization method and an emulsion polymerization method, preferably a solution polymerization method.

  Any appropriate solvent can be adopted as the solvent used in the solution polymerization. Preferably, aqueous solvents, such as water, alcohol, glycol, glycerin, polyethylene glycols, are mentioned, More preferably, water is mentioned. The said solvent may use only 1 type and may use 2 or more types together. Further, in order to improve the solubility of the monomer in the solvent, an organic solvent may be appropriately added within a range that does not adversely affect the polymerization reaction.

  Any appropriate organic solvent can be adopted as the organic solvent. For example, lower alcohols such as methanol and ethanol; amides such as dimethylformaldehyde; ethers such as diethyl ether and dioxane; As for the said organic solvent, only 1 type may be used and 2 or more types may be used together.

  The amount of the solvent used is preferably 40 to 300 parts by weight, more preferably 45 to 200 parts by weight, and still more preferably 50 to 150 parts by weight with respect to 100 parts by weight of the monomer composition. When the amount of the solvent used is less than 40 parts by weight relative to 100 parts by weight of the monomer composition, the molecular weight of the resulting polymer may be too high. On the other hand, when the amount of the solvent used exceeds 300 parts by weight with respect to 100 parts by weight of the monomer composition, the concentration of the obtained polymer is lowered, and in some cases, the solvent may be required to be removed.

  In solution polymerization, typically, a solution containing the monomer and a solution containing an initiator are dropped into a solvent charged in advance in the reaction system. Any appropriate concentration can be adopted as the concentration of each solution. For example, 50 to 100% by weight of the total amount of the hydrophobic group-containing polyalkylene oxide monomer represented by the general formula (1) is previously charged in the reaction system together with a solvent, and the remaining monomer (0 ˜50% by weight of the hydrophobic group-containing polyalkylene oxide monomer represented by the general formula (1), a cationic monomer containing at least one nitrogen atom, and, if necessary, the above-mentioned other monomer Body), an initiator component, and other additives are each dissolved in a solvent, and polymerized by adding (dropping) appropriately into the reaction system during the polymerization. By performing polymerization by adding in this way, the remaining hydrophobic group-containing polyalkylene oxide monomer represented by the general formula (1) can be reduced. In addition, for example, in the above, the total amount of the hydrophobic group-containing polyalkylene oxide monomer represented by the general formula (1) may be appropriately added dropwise to the reaction system during the polymerization.

  In the polymerization reaction, the addition of the hydrophobic group-containing polyalkylene oxide monomer is preferably completed earlier than the addition of the cationic monomer, and the addition of the hydrophobic group-containing polyalkylene oxide monomer is completed. Furthermore, it is more preferable that 5 to 100% by weight of the total amount of the cationic monomer is not added. Specifically, when a monomer represented by the general formula (4) or (5) having relatively low polymerizability is used as the hydrophobic group-containing polyalkylene oxide monomer, the addition of the monomer Is completed, it is preferable that 10 to 100% by weight, preferably 30 to 100% by weight, and more preferably 50 to 100% by weight of the total amount of the cationic monomer is not added. By adding and polymerizing in this way, the copolymerizability of the hydrophobic group-containing polyalkylene oxide monomer having a different polymerizability and the cationic monomer can be improved. This is preferable since the clay dispersibility of the coalescence, the ability to prevent recontamination and the like are improved.

  Any appropriate initiator can be adopted as the initiator. For example, hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; bisulfites such as sodium bisulfite, potassium bisulfite, and ammonium bisulfite; sulfites, pyrosulfites, and phosphites Hypophosphite; 2,2′-azobis (2-amidinopropane) hydrochloride, 4,4′-azobis-4-cyanovaleric acid, azobisisobutyronitrile, 2,2′-azobis (4- Azo compounds such as methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide and cumene hydroperoxide; . An azo compound is preferred, and 2,2'-azobis (2-amidinopropane) hydrochloride is more preferred. These initiators may be used alone or in combination of two or more.

  The amount of the initiator used can be appropriately set according to the type and concentration of the monomer. The usage-amount of an initiator is 0.1-20g normally with respect to 1 mol of monomer compositions, Preferably it is 0.5-15g, More preferably, it is 1-10g.

  In the polymerization reaction, an additive such as a chain transfer agent may be included in the reaction system. Any appropriate additive can be adopted as the additive. For example, additives such as mercaptoethanol, thioglycolic acid and sodium disulfite can be added during the polymerization.

  The amount of the additive used can be appropriately set according to the type and concentration of the monomer. For example, 0.1 to 5 parts by weight of the additive may be used with respect to 100 parts by weight of the monomer composition.

  The time required for the dropping (dropping time) is preferably 60 minutes to 420 minutes, more preferably 60 minutes to 300 minutes, and particularly preferably 90 minutes to 240 minutes. The dropping time may be different depending on the monomer to be dropped and the type of initiator. If the dropping time is less than 60 minutes, the copolymer may have a high molecular weight, so that the detergency may be reduced, and a homopolymer of a cationic monomer is easily formed. As a result, the cleaning power may be reduced. When the dropping time exceeds 420 minutes, a problem may occur in terms of productivity of the obtained polymer.

  Arbitrary appropriate temperature can be employ | adopted for the polymerization temperature in the said polymerization reaction with an initiator. The polymerization temperature is usually 25 to 200 ° C, preferably 50 to 150 ° C, more preferably 60 to 120 ° C, and particularly preferably 80 to 110 ° C. If the polymerization temperature is too low, the weight average molecular weight of the resulting polymer may increase or the amount of impurities generated may increase. The polymerization temperature refers to the temperature of the reaction solution for the polymerization reaction. Any appropriate method or means can be adopted as a method for measuring or controlling the polymerization temperature. For example, the measurement may be performed using a generally used apparatus.

  In the polymerization reaction, any appropriate pressure can be adopted as the pressure during the polymerization. For example, the pressure may be any of normal pressure, reduced pressure, and increased pressure. The atmosphere in the reaction system may be an air atmosphere, but may be an inert gas atmosphere. For example, the inside of the reaction system can be replaced with an inert gas such as nitrogen before the start of polymerization. Thereby, atmospheric gas (for example, oxygen gas etc.) in a reaction system melt | dissolves in a liquid phase, and acts as a polymerization inhibitor.

  The solid content concentration in the reaction solution (copolymer solution) at the time when the dropping is completed and the polymerization reaction in the reaction system is completed is preferably 35% by weight or more. If it is less than 35% by weight, the productivity of the resulting polymer may not be significantly improved. More preferably, it is 40-70 weight%, More preferably, it is 45-65 weight%. Thus, if the solid content concentration at the end of the polymerization reaction is 35% by weight or more, the polymerization can be carried out at a high concentration and in one stage. Therefore, a polymer can be obtained efficiently. For example, the concentration step can be omitted, the productivity of the polymer is greatly improved, and an increase in manufacturing cost can be suppressed. The time point at which the polymerization reaction is completed may be a time point at which the dropping of all of the dropping components is completed, but preferably refers to a time point at which a predetermined aging time has elapsed (the time point at which the polymerization is completed). .

  The solid content concentration may be calculated as the solid content of the non-volatile content after processing for 1 hour with a 130 ° C. hot air dryer.

  The aging time is preferably 1 to 120 minutes, more preferably 5 to 60 minutes, and still more preferably 10 to 30 minutes. When the aging time is less than 1 minute, the monomer component may remain because the aging is insufficient, and impurities due to the residual monomer may be formed, leading to performance degradation. If the aging time exceeds 120 minutes, the polymer solution may be colored.

  The cationic copolymer of the present invention that can be preferably produced by the above method can exhibit high performance in aqueous applications, hard water resistance, detergency, recontamination prevention ability, clay dispersibility, surface activity. Since the interaction with the agent is high, particularly excellent performance can be exhibited when used in a dispersant, a detergent builder, a detergent composition, a cleaning agent, or a water treatment agent.

  The cationic copolymer of the present invention has a recontamination prevention rate of hydrophobic soil (details of the measurement method will be described later), preferably 65.0% or more, more preferably 68.0% or more, and still more preferably 70. 0% or more.

  The cationic copolymer of the present invention has a weight average molecular weight of preferably 1000 to 1000000, more preferably 2000 to 200000, and particularly preferably 4000 to 100000. 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 above cationic copolymer. Specifically, the detergent builder of the present invention may be composed of only the above cationic copolymer, or may be composed of a mixture with any other suitable detergent builder.

  The content of the cationic copolymer in the detergent builder according to the present invention is preferably 0.1 to 80% by weight, more preferably 1 to 80% by weight with respect to 100% by weight of the detergent builder according to the present invention. 70% by weight, more preferably 5 to 65% by weight. If the content of the cationic copolymer is less than 0.1% by weight, the cleaning power when used as a detergent composition may be insufficient. If the content of the cationic copolymer is more than 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 is set to any appropriate type and blending ratio within the range that does not impair the effects of the present invention, with regard to the other components other than the cationic copolymer. obtain.

  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.

[Detergent composition]
The detergent composition of the present invention contains the above cationic copolymer. Preferably, the detergent builder of the present invention is included.

  The detergent composition of the present invention may be a powder detergent composition or a liquid detergent composition. The detergent 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 of the builder for detergent of the present invention in the detergent composition of the present invention is preferably 0.1 to 20% by weight, more preferably 0.2 to 15% with respect to 100% by weight of the detergent composition of the present invention. % By weight, more preferably 0.3 to 10% by weight, particularly preferably 0.4 to 8% by weight, and most preferably 0.5 to 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 detergent composition of the present invention, the cationic copolymer or the builder for a detergent of the present invention may be blended in a liquid form or a 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 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 only for specific applications such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface cleaners, and bleach detergents that enhance one of the components. Also includes the detergent used. Since the cationic copolymer is excellent in chelating ability, it can be suitably used because it can stabilize hydrogen peroxide by capturing a trace amount of metal and is excellent in stabilizing ability of a bleaching agent.

  The detergent composition of the present invention preferably contains a surfactant in addition to the cationic copolymer.

  The surfactant preferably contained in the detergent composition of the present invention is at least one selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. 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 detergent composition of the present invention is preferably 10 to 60% by weight, more preferably 12 to 50% by weight, and further preferably 15 to 45% by weight in the detergent composition. %, 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 detergent composition of the present invention is a liquid detergent composition, the amount of water contained in the liquid detergent composition is usually preferably 0.1 to 75% by weight and more preferably 100% by weight to 100% by weight of the liquid detergent composition. Preferably it is 0.2 to 70% by weight, 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 preferably has a kaolin turbidity of 200 mg / L or less, more preferably 150 mg / L or less, more preferably 120 mg / L or less, particularly Preferably it is 100 mg / L or less, most preferably 50 mg / L or less.

  The change (difference) in kaolin turbidity with and without adding the cationic copolymer as a detergent builder to the liquid detergent composition is preferably 500 mg / L or less, more preferably 400 mg / L or less, More preferably, it is 300 mg / L or less, Especially preferably, it is 200 mg / L or less, Most preferably, it is 100 mg / L or less.

  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 into 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 detergent 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 detergent composition, silicate, carbonate, sulfate and the like are suitable.

  As the chelate builder that can be blended in the detergent composition, diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), STPP (sodium tripolyphosphate), citric acid and the like are suitable. . You may add what contains other components other than the polyalkylene glycol type polymer in this invention.

  The detergent composition of the present invention may be used for liquid detergents or powder detergents, but is liquid in that it is excellent in compatibility with a surfactant and can be made into a highly concentrated liquid detergent composition. For detergents.

  In the detergent composition of the present invention, the other components other than the cationic copolymer or the detergent builder of the present invention may be of any appropriate type within the range that does not impair the effects of the present invention. Types and blending ratios can be set.

  The detergent 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 anti-recontamination ability.

[Other uses]
The cationic copolymer 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 cationic copolymer 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 cationic copolymer may be added as it is, or may be added together with other components other than the cationic copolymer.

  The water treatment agent and the fiber treatment agent are other appropriate components and blending ratios in addition to the cationic copolymer as long as the types and blending ratios 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.

Preparation Example 1 Preparation of Hydrophobic Group-Containing Polyalkylene Oxide Monomer A glass reactor equipped with a reflux condenser, a thermometer, and a stirrer was charged with SOFTanol 200 (manufactured by Nippon Shokubai Co., Ltd .; carbon number 12-14) 22.8 g of a secondary alcohol ethylene oxide adduct) was maintained at 60 ° C. To the reactor, 22.8 g of allyl glycidyl ether was added little by little and stirred until uniform. While stirring the resulting mixture, 1.0 ml of boron trifluoride diethyl ether complex was further added and reacted at 60 ° C. for 36 hours. As a result, an allyl glycidyl ether-modified product of softanol 200 (hereinafter abbreviated as “AGE-SFT200”) was obtained.

[Example 1] Preparation of copolymer (1) Into a 500 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer, 22.6 g of AGE-SFT200 was charged and stirred. The temperature was raised to 0 ° C. to obtain a polymerization reaction system. Next, 120.0 g of 75% trimethylammonium ethyl acrylate chloride (hereinafter abbreviated as “75% 4DAM”), 15% 2,2′-azobis (2) in a polymerization reaction system maintained at 90 ° C. with stirring. -Amidinopropane) Dihydrochloride aqueous solution (hereinafter abbreviated as “15% V-50”) 30.2 g and pure water 22.4 g were added dropwise from separate nozzles. The dropping time of 75% 4DAM was 180 minutes, and the dropping time of 15% V-50 and pure water was 190 minutes. The dropping speed of each solution was constant, and each solution was continuously dropped. After completion of the dropwise addition of 75% 4DAM, the reaction solution was aged at 90 ° C. for another 30 minutes to complete the polymerization. After completion of the polymerization, 97.6 g of pure water was gradually added dropwise while the polymerization reaction solution was allowed to cool and stirred to dilute the polymerization reaction solution. In this way, an aqueous solution of the copolymer (1) having a solid concentration of 40% was obtained.

[Example 2] Preparation of copolymer (2) In a 500 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer, 57.0 g of AGE-SFT200 was charged and stirred. The temperature was raised to 0 ° C. to obtain a polymerization reaction system. Next, 76.0 g of 75% 4DAM, 21.4 g of 15% V-50, and 41.0 g of pure water were dropped from separate nozzles into the polymerization reaction system maintained at 90 ° C. with stirring. did. The dropping time of 75% 4DAM was 240 minutes, and the dropping time of 15% V-50 and pure water was 250 minutes. The dropping speed of each solution was constant, and each solution was continuously dropped. After completion of the dropwise addition of 75% 4DAM, the reaction solution was aged at 90 ° C. for another 30 minutes to complete the polymerization. After completion of the polymerization, 97.6 g of pure water was gradually added dropwise while the polymerization reaction solution was allowed to cool and stirred to dilute the polymerization reaction solution. In this way, an aqueous solution of the copolymer (2) having a solid content concentration of 40% was obtained.

[Example 3] Preparation of copolymer (3) 21.6 g of AGE-SFT200 was charged into a 500 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer while stirring. The temperature was raised to 0 ° C. to obtain a polymerization reaction system. Next, 86.0 g of 100% dimethylaminoethyl methacrylate (hereinafter abbreviated as “100% DAM”), 37.8 g of 15% V-50, in a polymerization reaction system maintained at 90 ° C. with stirring. 5.9 g of pure water and 15.8 g of 100% acetic acid were added dropwise from separate nozzles. The dropping time of 100% DAM and 100% acetic acid was 240 minutes, and the dropping time of 15% V-50 and pure water was 250 minutes. The dropping speed of each solution was constant, and each solution was continuously dropped. After the completion of the dropwise addition of 100% DAM, the reaction solution was kept at 90 ° C. for aging for 30 minutes to complete the polymerization. After completion of the polymerization, 80.0 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 the copolymer (3) having a solid content concentration of 40% was obtained.

[Example 4] Preparation of copolymer (4) Into a 500 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer, 21.6 g of AGE-SFT200 was charged and stirred. The temperature was raised to 0 ° C. to obtain a polymerization reaction system. Next, 86.0 g of 100% dimethylaminoethyl acrylate (hereinafter abbreviated as “100% DAA”), 41.2 g of 15% V-50, in a polymerization reaction system maintained at 90 ° C. with stirring. 40.6 g of pure water and 16.2 g of 100% acetic acid were added dropwise from separate nozzles. The dropping time of 100% DAA and 100% acetic acid was 240 minutes, and the dropping time of 15% V-50 and pure water was 250 minutes. The dropping speed of each solution was constant, and each solution was continuously dropped. After the addition of 100% DAA was completed, the reaction solution was aged at 90 ° C. for an additional 30 minutes to complete the polymerization. After completion of the polymerization, 49.6 g of pure water was gradually dropped while the polymerization reaction solution was allowed to cool and stirred to dilute the polymerization reaction solution. In this way, an aqueous solution of the copolymer (4) having a solid content concentration of 40% was obtained.

[Example 5] Preparation of copolymer (5) In a glass reactor equipped with a reflux condenser, a thermometer, a stirrer and a nitrogen inlet, 212.8 g of softanol 200 and 4.4 g of KOH were added. The mixture was stirred and stirred at 120 ° C. for 1 hour while flowing nitrogen to remove moisture. The liquid temperature was lowered to 90 ° C., 22.8 g of allyl glycidyl ether was added over 30 minutes, and the mixture was stirred until uniform. After completion of the addition of allyl glycidyl ether, the mixture was further reacted for 240 minutes to obtain an allyl glycidyl ether-modified product (2) of softanol 200 (hereinafter abbreviated as AGE-SFT200 (2)).
A 3.5 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 13.5 g of pure water and heated to 90 ° C. with stirring to form a polymerization reaction system. Then, 57.0 g of 100% DAM, 17.8 g of 80% AGE-SFT200 (2), 7.6 g of 15% V-50, 3 in a polymerization reaction system maintained at 90 ° C. with stirring. 8 g of pure water and 20.9 g of 100% acetic acid were added dropwise from separate nozzles. The dropping time of each solution was 180 minutes for 100% DAM and 100% acetic acid, 120 minutes for 80% AGE-SFT200 (2), and 210 minutes for 15% V-50 and pure water. The dropping speed of each solution was constant, and each solution was continuously dropped. After the addition of 100% DAM was completed, the reaction solution was aged at 90 ° C. for another 60 minutes to complete the polymerization. After completion of the polymerization, 60.3 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 the copolymer (5) having a solid concentration of 40% was obtained.

[Example 6] Preparation of copolymer (6) 13.5 g of pure water was charged into a 500 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer and stirred at 90 ° C. The temperature was raised to a polymerization reaction system. Next, 57.0 g of 100% DAM, 17.8 g of 80% AGE-SFT200 (2), 12.7 g of 15% V-50, 20. 9 g of 100% acetic acid was added dropwise from a separate nozzle. The dropping time of each solution was 100 minutes for 100% DAM and 100% acetic acid, 90 minutes for 80% AGE-SFT200 (2), and 150 minutes for 15% V-50. The dropping speed of each solution was constant, and each solution was continuously dropped. After the addition of 100% DAM was completed, the reaction solution was aged at 90 ° C. for another 60 minutes to complete the polymerization. After completion of the polymerization, 61.0 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 the copolymer (6) having a solid content concentration of 40% was obtained.

[Example 7] Preparation of copolymer (7) A 500 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 13.3 g of pure water and stirred at 90 ° C. The temperature was raised to a polymerization reaction system. Then, 35.0 g of 100% DAM, 43.8 g of 80% AGE-SFT200 (2), 5.3 g of 15% V-50, 7. In a polymerization reaction system maintained at 90 ° C. with stirring. 8 g of pure water and 12.8 g of 100% acetic acid were added dropwise from separate nozzles. The dropping time of each solution was 120 minutes for 100% DAM and 100% acetic acid, 60 minutes for 80% AGE-SFT200 (2), and 150 minutes for 15% V-50 and pure water. The dropping speed of each solution was constant, and each solution was continuously dropped. After the addition of 100% DAM was completed, the reaction solution was aged at 90 ° C. for another 60 minutes to complete the polymerization. After completion of the polymerization, 59.0 g of pure water was gradually dropped while the polymerization reaction solution was allowed to cool and stirred to dilute the polymerization reaction solution. In this way, an aqueous solution of the copolymer (7) having a solid content concentration of 40% was obtained.

[Example 8] Preparation of copolymer (8) In a glass reactor equipped with a reflux condenser, thermometer, stirrer and nitrogen inlet, 296.5 g of isoprenol ethylene oxide 25 mol adduct and 7 .2 g of KOH was charged, and the mixture was stirred at 120 ° C. for 1 hour while flowing nitrogen to remove moisture. The liquid temperature was lowered to 90 ° C., and 62.5 g of C12-13 alkyl glycidyl ether (hereinafter abbreviated as LGE) was added over 30 minutes, followed by stirring until uniform. After completion of the addition of LGE, the reaction was further continued for 240 minutes to obtain an LGE-modified product (hereinafter abbreviated as IPN25-LGE) of an isoprenol ethylene oxide 25 mol adduct.
A 3.5 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 13.5 g of pure water and heated to 90 ° C. with stirring to form a polymerization reaction system. Next, 57.0 g of 100% DAM, 17.8 g of 80% IPN25-LGE aqueous solution (hereinafter abbreviated as 80% IPN-LGE), 7.6 g in a polymerization reaction system maintained at 90 ° C. with stirring. 15% V-50, 3.8 g of pure water, and 20.9 g of 100% acetic acid were dropped from separate nozzles. The dropping time of each solution was 120 minutes for 100% DAM and 100% acetic acid, 90 minutes for 80% IPN25-LGE, and 150 minutes for 15% V-50 and pure water. The dropping speed of each solution was constant, and each solution was continuously dropped. After the addition of 100% DAM was completed, the reaction solution was aged at 90 ° C. for another 60 minutes to complete the polymerization. After completion of the polymerization, 60.3 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 the copolymer (8) having a solid content concentration of 40% was obtained.

[Comparative Example 1] Preparation of Comparative Copolymer (C1) 50.0 g of pure water was charged into a 500 ml SUS separable flask equipped with a reflux condenser, a thermometer, and a stirrer while stirring. The temperature was raised to 0 ° C. to obtain a polymerization reaction system. Next, 120.0 g of 75% 4DAM, 37.6 g of 60% allyl alcohol ethylene oxide 20 mol adduct (hereinafter abbreviated as “60% PEA25”) in a polymerization reaction system maintained at 90 ° C. with stirring. 30.2 g of 15% V-50 and 22.4 g of pure water were added dropwise from separate nozzles. The dropping time of 75% 4DAM was 180 minutes, the dropping time of 60% PEA 25 was 150 minutes, and the dropping time of 15% V-50 and pure water was 190 minutes. The dropping speed of each solution was constant, and each solution was continuously dropped. After completion of the dropwise addition of 75% 4DAM, the reaction solution was aged at 90 ° C. for another 30 minutes to complete the polymerization. After the polymerization, the polymerization reaction solution was allowed to cool and stirred, and 32.8 g of pure water was gradually added dropwise to dilute the polymerization reaction solution. In this way, an aqueous solution of the copolymer (C1) having a solid concentration of 40% was obtained.

[Evaluation]
About the obtained copolymer (1), (2), (3), (4), (5), (6), (7), (8), and the comparative copolymer (C1), the weight average The molecular weight and the ability to prevent recontamination were evaluated. The results are shown in Table 1.

<Weight average molecular weight>
The weight average molecular weight (Mw) is a value measured by GPC (gel permeation chromatography).
Measuring device: "L-7000 series" manufactured by Hitachi
Detector: RI, UV (detection wavelength: 254 nm)
Column: "SHODEX SB-G", "SHODEX SB-804HQ", "SHODEX SB-803HQ", and "SHODEX SB-802.5HQ" manufactured by Showa Denko KK in this order Temperature: 40 ° C
Flow rate: 0.8 mL / min Calibration curve: Prepared using polyethylene oxide standard sample (manufactured by GL Sciences) 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 of sodium linear alkylbenzene sulfonate and 4.0 g of 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 and 5 g of an aqueous surfactant solution, 1 g of a 2% copolymer 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 stirred at 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 recontamination prevention rate was determined by the following equation.
Recontamination prevention rate (%) = [(whiteness after washing) / (whiteness of raw white cloth)] × 100

The cationic copolymer of the present invention can exhibit high detergency, clay dispersibility, ability to prevent recontamination, and the like. Therefore, when it uses for a dispersing agent, a builder for detergents, a detergent composition, a cleaning agent, and a water treatment agent, the especially outstanding performance can be exhibited.

Claims (3)

A sparse water-based polyalkylene oxide monomer (a) 1 to 55 wt%, a monomer composition comprising 45 to 99% by weight cationic monomer (b) containing at least one nitrogen atom A cationic copolymer obtained by copolymerization ,
The hydrophobic group-containing polyalkylene oxide monomer (a) is at least one unit selected from the group consisting of a compound represented by the general formula (4) and a compound represented by the general formula (5). Including masses,
The cationic monomer (b) is selected from the group consisting of dialkylaminoalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylamide, vinylimidazole, vinylpyridine, diallylalkylamine, and quaternized products thereof, and diallylamine. Comprising at least one selected monomer,
Cationic copolymer .

(In the formula, R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 1 to 2 carbon atoms, R ₈ is a linear or branched alkyl group having 6 to 24 carbon atoms, or carbon. (It is a substituted or unsubstituted aryl group of formulas 6 to 24, and n2 is an integer of 5 to 200.)

(In the formula, R ₉ is a hydrogen atom or a methyl group, R ₁₀ is an alkylene group having 1 to 2 carbon atoms, R ₁₁ is a linear or branched alkyl group having 6 to 24 carbon atoms, or carbon. (It is a substituted or unsubstituted aryl group of formulas 6 to 24, and n3 is an integer of 5 to 200.) A detergent builder comprising the cationic copolymer according to claim 1 . A detergent composition comprising the cationic copolymer according to claim 1 .