JP2005281377A - Detergent and clothing treating agent each containing carboxylic acid polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a carboxylic acid polymer powder excellent in solubility in uses for fiber treating products (e.g., detergents and clothing treating agents). <P>SOLUTION: It has been found out that the detergent and the clothing treating agent each of which contains the carboxylic acid polymer powder satisfying the following requirements (a) and (b) have markedly improved solubility. The above requirements are (a) the viscosity of a 0.2 wt.% aqueous solution is 10 mPa s or higher and/or the pH of a 1 wt.% aqueous solution is below 6, and the viscosity of a 10 wt.% aqueous solution is 300 mPa s or higher and (b) the content of particles which pass a JIS sieve (20 mesh) is 50 wt.% or larger and/or the mean particle diameter is 600 μm or smaller. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a cleaning agent and a treatment agent for clothing comprising a high molecular weight carboxylic acid polymer having excellent solubility.

  In the past, water-soluble polymer substances have been used as a cleaning agent or a polymer that can be used well for non-washed objects during washing to improve the fixability to the surface of the object, or as a polymer that can form a water-soluble or water-dispersible film on textiles. It is disclosed as a blending component of a clothing treatment agent (such as an antifouling agent) (see Patent Documents 1 and 2).

Japanese Patent Laid-Open No. 9-273079 Japanese Patent Laid-Open No. 2003-3198

  By the way, in recent years, washing machines, automatic dishwashers, and the like have become more compact due to problems of energy saving and installation location, and the amount of washing water to be used tends to be reduced, and the washing time tends to be shortened. Therefore, the solubility of various cleaning agents used at the time of cleaning has become very important in order to express the performance of the cleaning agent. However, at the time when the technology of Patent Publication 1 was developed, the problem of solubility was not recognized, and when the technology of Patent Publication 2 was developed, the problem of solubility was recognized. From the viewpoint of solubility, only polyvinyl alcohol was recognized, and was not recognized in carboxylic acid polymers. Furthermore, in order to improve the solubility of polyvinyl alcohol, only a solution has been proposed in which a low viscosity, a so-called low molecular weight is preferable.

  Therefore, the problem to be solved by the present invention is to improve the solubility even with a high molecular weight carboxylic acid polymer, for example, a cleaning agent capable of exhibiting excellent performance in a water-saving type washing machine and The object is to provide a treatment agent for clothing.

  The present inventor has intensively studied to solve the above problems. As a result, the particle size of the carboxylic acid polymer powder is considered to greatly affect the solubility, and it has been found that the solubility is greatly improved when the particle size of the carboxylic acid polymer powder is below a specific value. Completed the invention.

That is, the cleaning agent and the treatment agent for clothing according to the present invention include a carboxylic acid polymer powder that satisfies the following requirements (a) and (b).
(A) The 0.2 wt% aqueous solution viscosity is 10 mPa · s or more and / or the 1 wt% aqueous solution has a pH of less than 6, and the 10 wt% aqueous solution viscosity is 300 mPa · s or more.
(B) 50% by weight or more of JIS sieve having a particle size of 20 mesh pass and / or an average particle size of 600 μm or less.

  According to the present invention, a high molecular weight carboxylic acid polymer powder can be efficiently dissolved. For example, a cleaning agent capable of exhibiting excellent detergency in a water-saving type washing machine, and a wet textile product. A clothing treatment agent to be applied, comprising a polymer capable of forming a water-soluble or water-dispersible film on a dried fiber product after application of the clothing treatment agent. it can.

  Hereinafter, the cleaning agent and the treatment agent for clothing according to the present invention will be described in detail. However, the scope of the present invention is not limited to these explanations, and the scope of the present invention is not impaired except for the following examples. And can be changed as appropriate.

[Carboxylic acid polymer powder and method for producing the same]
Although it does not specifically limit as said carboxylic acid type polymer, Specifically, for example, the homopolymer of the monomer containing a carboxyl group and / or its salt; A carboxyl group and / or its salt And a copolymer of a monomer containing a monomer and other monomers. Among the above-exemplified polymers, a copolymer obtained by polymerizing a monomer component including a monomer containing a carboxyl group and / or a salt thereof is more preferable, and among them, a carboxyl group and / or a salt thereof. A copolymer of a monomer containing a sulfonic acid group and / or a monomer containing a salt thereof is particularly preferred. By introducing the sulfonic acid group, the carboxylic acid polymer powder is less likely to become a spatter, and the dissolution rate of the carboxylic acid polymer powder is improved. Furthermore, the sulfonic acid group has good gelation resistance against polyvalent ions such as calcium ions and magnesium ions contained in the cleaning liquid, and suppresses insolubilization of the carboxylic acid polymer by the polyvalent ions.
The “carboxyl group” in the present invention includes a salt such as an alkali metal salt or an ammonium salt of this functional group in addition to the —COOH group (free carboxyl group). Further, the “sulfonic acid group” in the present invention includes a salt such as an alkali metal salt or an ammonium salt of this functional group in addition to the —SO ₃ H group (free sulfonic acid group).
The above polymer is necessary for, for example, an amide group-containing monomer, a monomer containing a carboxyl group and / or a salt thereof, and a monomer containing a sulfonic acid group and / or a salt thereof. Accordingly, it can be easily obtained by polymerizing a monomer component further containing another monomer copolymerizable with the above monomer (hereinafter simply referred to as other monomer).
The amide group-containing monomer is not particularly limited as long as it is a monomer having an amide group. Specific examples of the amide group-containing monomer include (meth) acrylamide.
The monomer containing a carboxyl group and / or a salt thereof is not particularly limited as long as it is a monomer having a carboxyl group and / or a salt thereof. Specific examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, maleic acid, itaconic acid, mesaconic acid, fumaric acid, citraconic acid, and N- (meth) acryloyl asparagine. An acid etc. are mentioned. Specific examples of the monomer containing a carboxyl group salt include sodium salt, potassium salt, calcium salt, and ammonium salt, but are not particularly limited. Only one kind of these monomers may be used, or two or more kinds may be used in combination. Of the above-exemplified monomers, (meth) acrylic acid and / or a salt thereof is more preferable, and (meth) acrylic acid (meaning acrylic acid and / or methacrylic acid in the present invention) is particularly preferable.
The monomer containing the sulfonic acid group and / or salt thereof is not particularly limited as long as it is a monomer having a sulfonic acid group and / or salt thereof. Specific examples of the sulfonic acid group-containing monomer include 2-acrylamido-2-methylpropanesulfonic acid, (meth) allylsulfonic acid, allyloxybenzenesulfonic acid, 2-hydroxy-3- (2- Propenyloxy) propane sulfonic acid, isopropenyl sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, sulfoethyl (meth) acrylate, sulfonated products of isoprene, and the like. Specific examples of the monomer containing a salt of a sulfonic acid group include a sodium salt, a potassium salt, a calcium salt, and an ammonium salt, but are not particularly limited. Only one kind of these monomers may be used, or two or more kinds may be used in combination. Of the monomers exemplified above, 2-acrylamido-2-methylpropanesulfonic acid, sulfoethyl (meth) acrylate, and alkali metal salts and ammonium salts of these monomers are more preferable, and sulfoethyl (meth) acrylate is more preferable. Particularly preferred is 2-acrylamido-2-methylpropanesulfonic acid.
The other monomers are copolymerized with an amide group-containing monomer, a monomer containing a carboxyl group and / or a salt thereof, and a monomer containing a sulfonic acid group and / or a salt thereof. There is no particular limitation as long as it is a possible monomer. That is, an amide group-containing monomer unit, a monomer unit containing a carboxyl group and / or a salt thereof, and a sulfonic acid group and / or a salt thereof may be contained in the polymer according to the present invention. Structural units other than the monomer units to be contained are not particularly limited.
Examples of other monomers include monoethylenically unsaturated acids such as allyl phosphonic acid, isopropenyl phosphonic acid, vinyl phosphonic acid, and alkali metal salts and ammonium salts of these monomers. An ester of a polyalkylene glycol and a monomer containing the carboxyl group and / or a salt thereof, such as polyethylene glycol (meth) acrylate or methoxypolyethylene glycol (meth) acrylate; methyl (meth) acrylate, ethyl (meth) (Meth) acrylic acid esters such as acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate; vinyl acetate Vinyl esters such as vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, 3 -Unsaturated alcohols such as methyl-2-buten-1-ol and 2-methyl-3-buten-2-ol; Aldehyde group-containing vinyl monomers such as acrolein; Nitrile group-containing vinyl monomers such as (meth) acrylonitrile Amide monomers such as (meth) acrylamide and Nt-butylacrylamide; ethylene oxide adducts of phosphoethyl methacrylate, styrene, allyl alcohol and isoprenol (2 to 18 carbon atoms relative to the unsaturated alcohol) 1 to 3 of alkylene oxide 0 mol, preferably 3 to 100 mol, more preferably 5 to 80 mol added compound), N-vinyl-2-pyrrolidone, N-vinylacetamide, N-vinylformamide, allylamine and other functional groups other than the above. Monomer to contain; etc. are mentioned.
As necessary, these other monomers may be used alone or in combination of two or more. Of the other monomers exemplified above, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, and N-vinyl-2-pyrrolidone are particularly preferred.
The method for producing the polymer, that is, the method for polymerizing the monomer component is not particularly limited. For example, a polymerization method using a polymerization initiator such as a radical polymerization initiator; ionizing radiation, electron beam, etc. Various conventionally known methods such as a polymerization method for irradiating electromagnetic waves such as radiation and ultraviolet rays; a polymerization method by heating; and the like, and two or more of these polymerization methods can be used in combination. .
In addition, the polymerization format in the method of the present invention is solution polymerization in which polymerization is performed in the presence of a solvent. In addition, for example, suspension polymerization can also be employed. Further, these may be either a batch type or a continuous type.
When the obtained carboxylic acid polymer is powdered, after evaporating water from the mixed solution, the obtained carboxylic acid polymer is dried and pulverized, and classified as necessary. Thus, a carboxylic acid polymer having a desired particle size described later can be obtained.
As the radical polymerization initiator, a peroxide-based, redox-based, or azo-based initiator can be used. Specifically, for example, ammonium persulfate, potassium persulfate, hydrogen peroxide, benzoyl peroxide, t -Peroxides suitably used in peroxides and redox systems such as butyl peroxide; redox such as sodium bisulfite, sodium metabisulfate, ferrous ammonium sulfate, L-ascorbic acid, triethanolamine Reducing agent suitably used in the system: 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-aminopropane) dihydrochloride, 2,2′-azobisisobutyramide Azo initiators such as dihydrate, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride; It is not specified. In addition, the usage-amount of a polymerization initiator, the reaction conditions of a polymerization reaction, etc. are not specifically limited.
Hereinafter, in the present embodiment, among the above exemplified polymers, in the present embodiment, among the above exemplified polymers, a homopolymer of a monomer containing a carboxyl group and / or a salt thereof (hereinafter, Homopolymer A) and a copolymer of a monomer containing a carboxyl group and / or a salt thereof and a monomer containing a sulfonic acid group and / or a salt thereof (hereinafter referred to as copolymer B) Will be described.
The copolymer B includes, for example, a monomer containing a carboxyl group and / or a salt thereof, and, if necessary, a monomer containing a sulfonic acid group and / or a salt thereof, or the like. The copolymer B obtained by polymerizing a monomer component further containing the above monomer can also be produced by post-modification by introducing a sulfonic acid group. The manufacturing method will be described in detail later.
As copolymer B according to the present embodiment, among the above examples, copolymer obtained by polymerizing a monomer component containing (meth) acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid Coalescence is most preferred. Since the (meth) acrylic acid is very soluble in water, the dissolution rate is relatively fast. Moreover, 2-acrylamido-2-methylpropanesulfonic acid has a relatively low hygroscopic property. Therefore, the copolymer obtained by copolymerizing the above (meth) acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid can change the compounding ratio and has a relatively high solubility in water. It can be preferably used.
In the present embodiment, the proportion of the monomer containing the carboxyl group and / or salt thereof in the monomer component, that is, the carboxyl group occupying in all the monomer units constituting the copolymer B. And / or the proportion of the monomer unit containing a salt thereof is preferably from 50 mol% to 99.5 mol%, more preferably from 55 mol% to 99 mol%, more preferably from 60 mol% to 98.5 mol%. The following is more preferable, 65 mol% or more and 98 mol% or less is particularly preferable, and 70 mol% or more and 97 mol% is most preferable. When the proportion of the monomer containing the carboxyl group and / or salt thereof is 50 mol% or more, the amount of copolymer B added to the cleaning agent can be further reduced.
In the present embodiment, the proportion of the monomer containing the sulfonic acid group and / or salt thereof in the monomer component, that is, sulfone occupying all the monomer units constituting the copolymer B. The proportion of monomer units containing acid groups and / or salts thereof is preferably 0.5 mol% or more and 90 mol% or less, more preferably 1 mol% or more and 70 mol%, and more preferably 1.5 mol% or more and 50 mol%. Is more preferable, and 2 mol% or more and 40 mol% or less is particularly preferable, and 3 mol% or more and 30 mol% or less is most preferable. If the ratio of the monomer containing the sulfonic acid group and / or salt thereof is 0.5 mol% or more, the dissolution rate of the copolymer B in water can be further improved. Moreover, if the ratio of the monomer containing the sulfonic acid group and / or salt thereof is 90 mol% or less, the blending amount of the copolymer B with respect to the cleaning agent can be further reduced.
That is, the copolymer B according to the present embodiment contains a carboxyl group and a sulfonic acid group, and includes a sulfonic acid group and / or a salt thereof in all the monomer units constituting the copolymer B. The ratio of the monomer unit to be contained is 0.5 mol% or more and 50 mol% or less, or the monomer unit contains a carboxyl group and a sulfonic acid group, and the molar ratio of the carboxyl group to the sulfonic acid group is More preferably, it is within the range of 99.3: 0.5 to 1: 1. In addition, the molar ratio of the carboxyl group to the sulfonic acid group in the copolymer B can be determined, for example, by colloid titration using an aqueous solution adjusted to pH 2 and an aqueous solution adjusted to pH 10 according to a conventional method. This can be easily obtained.
Further, a monomer containing a carboxyl group contained in the homopolymer A and the copolymer B, that is, a carboxyl group constituting the homopolymer A and the copolymer B and / or a salt thereof is provided. The carboxyl group possessed may be present in any state of a free acid or a salt, but it is more preferable that a free carboxyl group is contained. Specific examples of the salt include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as calcium salt and magnesium salt; ammonium salt; amine salt; Sodium salts are preferred.
Among the carboxyl groups contained in the homopolymer A and the copolymer B, the proportion of free carboxyl groups is preferably 5 mol% or more, and preferably 20 mol% or more and 99 mol% or less. More preferably, they are 30 mol% or more and 97 mol% or less, More preferably, they are 40 mol% or more and 95 mol% or less, Most preferably, they are 50 mol% or more and 90 mol% or less.
When the ratio of the free carboxyl group is less than 5 mol%, that is, when the neutralization rate of the homopolymer A and the copolymer B exceeds 95 mol%, there is a possibility that the powder is likely to become a powder. .
The copolymer B according to the present embodiment can be produced by the above-described polymerization method for polymerizing the monomer component, and includes, for example, a monomer containing a carboxyl group and / or a salt thereof. If necessary, it is obtained by polymerizing a monomer component further containing a monomer containing a sulfonic acid group and / or a salt thereof and other monomers (hereinafter referred to as a monomer component for modification). It can also be produced by subjecting the resulting polymer (hereinafter referred to as a modifying polymer) to modification after introducing a sulfonic acid group.
Specific examples of monomers containing carboxyl groups and / or salts thereof, monomers containing sulfonic acid groups and / or salts thereof, and other monomers contained in the monomer component for modification include Examples include the various compounds exemplified above. Examples of the method for obtaining the modifying polymer by polymerizing the modifying monomer component include various methods exemplified above. Specifically, for example, poly (meth) acrylic acid is suitable as the modifying polymer, and polyacrylic acid is most suitable.
As a post-modification method for introducing a sulfonic acid group into a modifying polymer, a method in which a sulfonic acid group-introducing compound is reacted with the modifying polymer is preferable. More specifically, for example, a modification is performed. A method of esterifying a carboxyl group contained in the polymer for polymer and a hydroxyl group contained in sodium isethionate (sodium hydroxyethanesulfonate) as the sulfonic acid group-introducing compound, a carboxyl group contained in the modifying polymer, Sulfonating the modifying polymer using a method of amide-bonding the amino group contained in taurine sodium salt (sodium aminoethanesulfonate) as the sulfone group-introducing compound, fuming sulfuric acid as the sulfonic acid group-introducing compound, etc. Examples of the method include, but are not limited to.
The sulfonic acid group-introducing compound is not particularly limited as long as it is a compound that can introduce a sulfonic acid group into the modifying polymer. Specific examples of the sulfonic acid group-introducing compound include, for example, compounds such as sodium hydroxymethanesulfonate, sodium hydroxyethanesulfonate, sodium hydroxypropanesulfonate, and the like suitable for forming an ester bond; Suitable compounds for formation include compounds such as sodium aminomethanesulfonate, sodium aminoethanesulfonate, sodium aminopropanesulfonate; fuming sulfuric acid; and the like.
As a post-modification reaction method, for example, a modification polymer and a sulfonic acid group-introducing compound may be mixed and heated, but are not particularly limited. The post-modification reaction conditions, such as the amount of the sulfonic acid group-introducing compound used for the modifying polymer, can be set according to the composition of the modifying polymer, the type of the sulfonic acid group-introducing compound, the combination of both, and the like. Well, not particularly limited. Furthermore, in order to increase the ratio of the sulfonic acid group to the copolymer B (copolymer B containing a carboxyl group and a sulfonic acid group) obtained by the above polymerization method for polymerizing the monomer component. If necessary, the above-mentioned post-transformation can also be performed.
The copolymer B according to this embodiment obtained by post-modifying the modifying polymer contains a carboxyl group and a sulfonic acid group, and the sulfone occupying all monomer units constituting the copolymer B. The ratio of the monomer unit containing an acid group and / or a salt thereof is in the range of 0.5 mol% to 50 mol%, or contains a carboxyl group and a sulfone group. The molar ratio with the acid group is more preferably within the range of 99.5: 0.5 to 1: 1.
The unreacted (meth) acrylic acid monomer content of the carboxylic acid polymer blended in the cleaning agent and clothing treating agent of the present invention is 2.0 wt% (mass%) or less in terms of (meth) acrylic acid. It is preferably 1.5% by weight or less, more preferably 1.3% by weight or less, particularly preferably 1.1% by weight or less, and most preferably 1.0% by weight or less. When the content of unreacted (meth) acrylic acid monomer is more than 2.0% by weight, there is a possibility that there is an odor problem.
The viscosity of the carboxylic acid polymer powder blended in the cleaning agent and clothing treating agent of the present invention satisfies the condition (1) and / or (2). Even if the carboxylic acid polymer has the same weight average molecular weight, the viscosity varies depending on the pH. Therefore, the pH measurement method and the viscosity measurement method may be selected depending on the pH of the aqueous solution of the carboxylic acid polymer powder.
The condition (1) is satisfied regardless of the aqueous solution of the carboxylic acid polymer powder. When the condition (1) is not satisfied and the pH (25 ° C.) of the 1 wt% aqueous solution is less than 6, the condition (2) is satisfied.
(1) The viscosity of a 0.2 wt% aqueous solution at 25 ° C. is 10 mPa · s to 10,000 mPa · s, preferably 20 mPa · s to 5,000 mPa · s, more preferably 30 mPa · s to 4,000 mPa. S or less, more preferably 40 mPa · s or more and 3,000 or less, and most preferably 50 mPa · s or more and 2,000 mPa · s or less.
(2) 10% by weight aqueous solution viscosity at 25 ° C. is 300 mPa · s to 5,000 mPa · s, preferably 350 mPa · s to 4,500 mPa · s, more preferably 400 mPa · s to 4,000, Preferably they are 450 mPa * s or more and 3,500 mPa * s or less, Most preferably, they are 500 mPa * s or more and 3,000 mPa * s or less.

  In the case of (1), the 0.2 wt% aqueous solution viscosity is less than 30 mPa · s, and in the case of (2), if the 10 wt% aqueous solution viscosity is less than 300 mPa · s, the molecular weight of the carboxylic acid polymer is low, There is a possibility that the performance as a cleaning agent may not be sufficient, and in the case of (1), when the aqueous solution viscosity of 0.2% by weight is greater than 10,000 mPa · s or in the case of (2), 10% by weight. When the aqueous solution viscosity is larger than 5,000 mPa · s, the viscosity of the cleaning liquid may be too high, and the rinsing efficiency may be deteriorated.

  The weight average molecular weight of the carboxylic acid polymer of the present invention is preferably 200,000 to 10 million, more preferably 250,000 to 9 million, still more preferably 300,000 to 8 million, particularly preferably. It is 400,000 to 7 million, most preferably 500,000 to 5 million. When the weight average molecular weight is less than 100,000, since the molecular weight of the carboxylic acid polymer is low, there is a possibility that the performance as a cleaning agent may not be sufficiently exhibited, and the weight average molecular weight is more than 10 million. If it is too large, the viscosity of the cleaning liquid may become too high, and the efficiency of rinsing may deteriorate.

The particle size of the carboxylic acid polymer powder blended in the cleaning agent and clothing treating agent of the present invention satisfies the condition (3) and / or (4).
(3) JIS sieve containing 20 mesh (750 μm) pass and having a particle size of 300 mesh (30 μm) on is contained 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, and further preferably Contains 75% by weight or more, most preferably 80% by weight or more. The JIS sieve is the one described in JIS Z8801.
(4) The average particle size is preferably from 10 μm to 600 μm, more preferably from 20 μm to 550 μm, further preferably from 30 μm to 500 μm, particularly preferably from 40 μm to 450 μm, and most preferably from 50 μm to 350 μm.

  In the case of (3), when the particle size of 300 mesh on is less than 50% by weight in the 20 mesh pass of the JIS sieve, especially when the number of 20 mesh on increases, it dissolves in the cleaning liquid or water. If the amount of 300-mesh pass increases, spatter increases or powdering may occur at the time of dissolution in cleaning liquid or water. In addition, moisture absorption of the powder is likely to occur.

  In the case of (4), if the average particle diameter is less than 10 μm, there is a risk that the spatter increases or powdering occurs when dissolved in the cleaning liquid or water, and the powder is more likely to absorb moisture. There is a fear. On the contrary, when the average particle size is larger than 600 μm, the solubility in the cleaning liquid or water is lowered, and the insoluble matter may be increased. The average particle diameter used here means the volume average particle diameter described in the examples.

  The carboxylic acid polymer powder of the present invention preferably contains a surfactant as a constituent element, and the surfactant is present when the carboxylic acid polymer is polymerized with one or more monomers. It is preferable to keep it.

  The effect of the presence of the surfactant in the carboxylic acid polymer powder is considered as follows. The water-soluble polymer containing a surfactant can take in water at the same time as the surfactant present on the surface is peeled off and prevent it from becoming a spatter, and the solubility in water is increased.

  By adopting the method of the present invention, it is considered that a particularly excellent effect is obtained for the following reason. The carboxylic acid polymer can be obtained by polymerizing the monomers constituting the carboxylic acid polymer. If this polymerization reaction is carried out in the presence of a surfactant, the water-soluble polymer is added at the end of the polymerization reaction. A mixture of the coalescence and the surfactant is obtained. When the obtained carboxylic acid polymer is powdered, water is evaporated from the mixed solution, and then the obtained carboxylic acid polymer is dried and pulverized. In the evaporation step, the carboxylic acid polymer aggregates as water evaporates. At this time, the surfactant is incorporated between the molecular chains of the carboxylic acid polymer. Therefore, the obtained carboxylic acid polymer has a surfactant not only on its surface but also inside the polymer.

  When such a carboxylic acid polymer is added to the cleaning liquid as described above, the surfactant on the surface peels off and water is taken in at the same time, and the molecular chain begins to loosen. Since the agent is present, it can be dissolved in a washing liquid or the like without adhering and bonding between neighboring molecular chains. Therefore, it is possible to obtain excellent detergency and processing ability without generating spatter.

  The surfactant in the present invention is used to prevent a carboxylic acid polymer from abruptly adhering and bonding to each other in a cleaning solution or a clothing processing solution, thereby preventing a pulverized powder. As the surfactant that can be used in the present invention, in particular, the above-described carboxylic acid-based polymer is not particularly limited as long as it can suppress the adhesion and bonding of the polymers to each other until the carboxylic acid-based polymer is well dissolved in a cleaning liquid or a clothing processing liquid. It is not limited, A well-known surfactant can be used. Specifically, nonionic surfactants are preferred. For example, ether type nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, Polyoxyethylene alkyl ethers such as polyoxyethylene higher alcohol ethers; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, polyoxyethylene derivatives and oxyethyleneoxypropylene block polymers Etc. Ether ester type nonionic surfactants include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate Polyoxyethylene sorbitan mono-, di-, and tri-fatty acid esters such as rate (the same applies to fatty acids having 12 to 18 carbon atoms and the following fatty acids); polyoxyethylene fatty acid esters and the like. Examples of ester-type nonionic surfactants include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan monostearate such as sorbitan tristearate, di, trifatty acid esters; fatty acid monoglycerides; Examples thereof include sugar esters. Among these, sorbitan fatty acid ester is preferable.

[Cleaning agents and clothing treatment agents]
The cleaning agent and the treatment agent for clothing of the present invention contain the carboxylic acid polymer powder. This demonstrates excellent detergency as a cleaning agent, and forms a water-soluble or water-dispersible film on the dried fiber product by applying it to a wet fiber product such as after washing and dehydration. It prevents the soiling of textile products by suppressing the direct adhesion of soiling to the fibers of the textile product, promoting the removal of the soiling in the next washing, or by performing both of these functions. is there.

  The content of the carboxylic acid polymer in the cleaning agent and the clothing treatment agent of the present invention is preferably 0.001 to 10% by weight, and more preferably 0.01 to 8% by weight. 0.02 to 6% by weight is more preferable, 0.03 to 4% by weight is particularly preferable, and 0.04 to 2% by weight is most preferable. If the content of the carboxylic acid polymer is too large, the viscosity of the cleaning agent may increase, and the efficiency of rinsing may be reduced. On the other hand, if the content is too small, sufficient performance may not be exhibited. is there.

  The cleaning agent and the treatment agent for clothing in the present invention may be in any form such as powder, liquid or gel. Hereinafter, as a representative example, a powdery powder cleaning agent and a liquid liquid cleaning agent will be described in detail.

  The cleaning agent of the present invention preferably contains one or more selected from the group consisting of polycarboxylic acid (salt), citrate, zeolite, and layered silicate (hereinafter referred to as “component A”). In particular, when the cleaning agent of the present invention is a powder cleaning agent, the component A is indispensable in order to exhibit an excellent cleaning effect and anti-recontamination ability. On the other hand, when the cleaning agent of the present invention is a liquid cleaning agent, the component A does not necessarily need to be contained, but in this case as well, the cleaning effect and prevention of recontamination can be achieved by containing the component A. Performance can be further improved. In the case where the cleaning agent of the present invention is a liquid cleaning agent and it is desired to make a transparent liquid cleaning agent, among the component A, it is composed of polycarboxylic acid (salt), citrate, and layered silicate. It is preferable to select one or more selected from the group.

  Examples of the polycarboxylic acid (salt) include polyacrylic acid, acrylic acid-maleic acid copolymer, polyglyoxylic acid, aminocarboxylic acid polymer (for example, polyaspartic acid), and salts thereof. It is done. Examples of the salt include sodium salt, potassium salt, ammonium salt and the like. The weight average molecular weight of these polycarboxylic acids (salts) is preferably 500 to 150,000, more preferably 1,000 to 100,000, and 2,000 to 50,000. Is more preferable.

  Examples of the citrate include sodium citrate.

  Examples of the zeolite include hydrated zeolite A, X, B, HS, and the like.

  Examples of the layered silicate include layered sodium silicate.

  When the cleaning agent of the present invention is a powder cleaning agent, the total content of the component A in the cleaning agent is preferably 0.1 to 50% by weight, and preferably 0.5 to 40% by weight. More preferably, it is 1 to 30% by weight. If the total content of component A is too large, the surface activity tends to decrease, while if it is too small, there is a possibility that sufficient cleaning effect and recontamination preventing ability cannot be expressed. In addition, when the cleaning agent of the present invention is a powder cleaning agent, the content of each component A may be appropriately set depending on the type thereof. For example, in the case of polycarboxylic acid (salt) or citrate Is preferably 0 to 30% by weight, and in the case of zeolite or layered silicate, it is preferably 0 to 50% by weight.

  When the cleaning agent of the present invention is a liquid cleaning agent, the total content of the component A in the cleaning agent is preferably 0 to 50% by weight, more preferably 0 to 40% by weight. Preferably, it is 0 to 30% by weight. If the total content of component A is too large, the surface activity tends to decrease, while if it is too small, there is a possibility that sufficient cleaning effect and recontamination preventing ability cannot be expressed. In addition, when the cleaning agent of the present invention is a liquid cleaning agent, the content of each of the components A may be appropriately set depending on the type thereof. For example, polycarboxylic acid (salt), citrate, layered In the case of silicate, it is preferably 0 to 30% by weight, and in the case of zeolite, it is preferably 0 to 20% by weight.

  The cleaning agent of the present invention may further contain a surfactant that is usually blended in the cleaning agent. Specific examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like, and one or more of these are used. can do.

  Specific examples of the anionic surfactant include, for example, 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 salts, 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.

  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 monoester. And alkylamine oxide.

  Examples of the cationic surfactant include quaternary ammonium salts.

  Examples of the amphoteric surfactant include a carboxyl type or sulfobetaine type amphoteric surfactant.

  When the cleaning agent of the present invention is a powder cleaning agent, the content of the surfactant in the cleaning agent is not particularly limited, but is usually preferably 3 to 50% by weight, and preferably 5 to 40% by weight. More preferably, it is more preferably 10 to 35% by weight. If the amount of the surfactant is too large, the economy tends to be lowered. On the other hand, if the amount is too small, there is a possibility that sufficient cleaning agent performance cannot be exhibited.

  When the cleaning agent of the present invention is a liquid cleaning agent, the content of the surfactant in the cleaning agent is preferably 3 to 60% by weight, more preferably 5 to 50% by weight, More preferably, it is 10 to 40 weight%. If the amount of the surfactant is too large, the compatibility tends to be lowered and the economical efficiency is also lowered, which is not preferable. On the other hand, if the amount is too small, there is a possibility that sufficient detergent performance cannot be exhibited.

  The cleaning agent of the present invention may further contain a conventionally known cleaning agent builder. The builder for the detergent is not particularly limited. For example, polyethylene glycol, sodium tripolyphosphate, sodium pyrophosphate, sodium silicate, sodium carbonate, sodium sulfate, sodium nitrilotriacetate, sodium ethylenediaminetetraacetate or potassium, carboxyl of polysaccharide And water-soluble polymers such as fumaric acid (co) polymer salts. In addition, when these detergent builder is also contained, the content rate should just be set suitably in the range which does not impair the effect of this invention.

  The cleaning agent of the present invention may further contain various additives commonly used in cleaning agents. Specifically, for example, sodium carboxymethylcellulose to prevent re-deposition of pollutants, contamination inhibitors such as benzotriazole and ethylene-thiourea, alkali agents (alkaline substances for pH adjustment), fragrances, fluorescent agents , Colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents such as sodium percarbonate and sodium perborate, bleach activators such as nonanoyloxybenzenesulfonate and tetraacetylethylenediamine, enzymes, Examples thereof include solvents such as dyes and water. In addition, what is necessary is just to set the content rate suitably in the range which does not impair the effect of this invention, when these additives are also contained.

  When the cleaning agent of the present invention is a liquid cleaning agent, it is particularly preferable to include an alkali agent among the additives in order to improve the cleaning power, the recontamination prevention ability, and the color transfer prevention ability. The alkali agent is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, alkanolamines such as monoethanolamine and diethanolamine, silicates and carbonates. In this case, the content of the alkaline agent in the cleaning agent is preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, and further preferably 1 to 10% by weight. If the alkali agent is less than 0.1% by weight, there is a tendency that sufficient cleaning effect and re-contamination preventing ability tend to be exhibited. On the other hand, if it exceeds 20% by weight, rough skin occurs when it adheres to the skin. It is not preferable because of fear.

  The cleaning agent of the present invention may be used as a cleaning agent by further blending other components such as enzymes and fragrances necessary for the cleaning agent intermediate, that is, the cleaning agent, or the cleaning agent itself. That is, it may be used as a cleaning agent as it is. The cleaning agent of the present invention is for clothing, shampoo, body soap, washing tub, bath, toilet, floor, carpet, kitchen, tableware, glass, shoes, and automobiles. It can be used as various cleaning agents such as for drain outlets, air conditioners, shavers, toothpastes, and glasses.

As a method for blending the carboxylic acid polymer powder into a powder detergent, various methods can be used. The carboxylic acid polymer powder may be added to the cleaning composition slurry before drying. Another method is to dissolve the carboxylic acid polymer in water and / or another solvent. Then, the solution may be sprayed and mixed with the powder detergent, or may be further mixed with the powder detergent in a dry state as a powder. In any method, the solubility of the carboxylic acid polymer powder is important.
The treatment agent for clothing of the present invention contains the above-described carboxylic acid polymer as an essential component, and the remainder is usually an optional component. Preferably, both the carboxylic acid polymer (a) and the silicone (b) are contained. The carboxylic acid polymer is blended in the above range. Silicone (b) is blended in the clothing treating agent in an amount of 0.002 wt% to 40 wt%, preferably 0.005 wt% to 15 wt%. The combined ratio of both is preferably (a) / (b) = 100/1 to 0.05 / 1 (weight ratio).
The water-soluble organic polymer such as carboxylic acid polymer (a) and silicone (b) used in the present invention is water-soluble and has a water-soluble or water-dispersible film-forming property. Then, a protective film is formed on the fiber surface to prevent dirt from adhering. And since it is water-soluble, even if a dirt adheres to a film, a dirt becomes easy to move to the direction of washing water at the time of the next washing.
In addition, in the treatment agent for clothing of the present invention, a polyhydric alcohol such as a fragrance, an antibacterial agent, a bactericide, a pigment, a pigment, a fluorescent dye, propylene glycol, and ethylene glycol can be optionally added.
The treatment agent for clothing of the present invention is applied to wet textile products (clothing, towels, sheets, etc.) after washing and dehydration. At that time, the composition of the present invention may be dissolved or dispersed in water before use, immersed in a washing machine after washing, or sprayed with a manual spray (eg, pump, trigger, etc.). Alternatively, it may be sprayed together with a high-pressure gas as an aerosol. Moreover, you may apply | coat with the container with a discharge outlet, and may apply | coat through porous substances, such as sponge. Or you may apply | coat using tools, such as a brush and a sponge. The method for applying to clothing and the container for storing the composition of the present invention are not particularly limited.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these. Hereinafter, unless otherwise specified, “parts by weight (parts by mass)” is simply referred to as “parts” and “% by weight (% by mass)” is simply referred to as “%”.

  The volume average particle diameter of the carboxylic acid polymer powder was measured with a particle size distribution meter (manufactured by Nikkiso Co., Ltd .; model name 9200-FRA). And the particle diameter at the time of 50% accumulation by volume distribution (distribution under integrated sieve) was made into the average particle diameter.

The viscosities of the 10 wt% and 0.2 wt% carboxylic acid polymer powders were measured using a B-type viscometer. It measured at 25 degreeC on the conditions of 2 and 30 rpm.
The pH of the 1 wt% and 0.1 wt% carboxylic acid polymer powder was measured at 25 ° C with a pH meter.

  The obtained carboxylic acid polymer weight average molecular weight and unreacted monomer amount were measured by gel permeation chromatography (GPC) analysis.

[Example 1]
In a 1 L stainless steel separable flask (1) equipped with a stirrer, a thermometer and a reflux condenser, 340 g of cyclohexane and sorbitan monostearate (Kao Corporation, trade name “Leodol SP-S10”) 4.59 g (dispersed) Agent), nitrogen was introduced at a rate of 50 ml / min while stirring, and the temperature was raised to 70 ° C.
A 500 ml separable flask (2) equipped with a stirrer, a thermometer and a reflux condenser was placed in 113.05 g of acrylic acid, 36.11 g of 2-acrylamido-2-methylpropanesulfonic acid, and 14.54 g of a 48 wt% aqueous sodium hydroxide solution. Then, 133.71 g of ion-exchanged water was added and dissolved by stirring. Further, nitrogen was introduced into the separable flask (2) solution for 25 minutes while continuing the stirring, and then 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride was reduced to a concentration of 0. 42.62 g of an aqueous solution containing 03 wt%, 4,4′-azobis (4-cyanopentanoic acid) 0.04 wt%, and sodium hypophosphite monohydrate 0.03% wt. In addition to the solution of 2), nitrogen was further introduced for 5 minutes, so that the dissolved oxygen in the solution was 1 mg / L or less. Thereafter, the monomer prepared in the separable flask (2) was added to the separable flask (1) over 2 hours for polymerization, followed by aging for 30 minutes. After dehydration, the mixture was cooled to 30 ° C., the contents were separated into solid and liquid, dried, pulverized, classified, and then the powder (1) of the mixture of copolymer 1 and surfactant was added. Obtained.
Table 1 shows the results.
[Example 2]
Into a 5-liter four-necked flask equipped with a thermometer, a nitrogen inlet tube, a stirrer, and a reflux condenser, was charged 2,540 g of water and the temperature was raised to 100 ° C. Next, 40 g of a 0.7 wt% aqueous ammonium persulfate solution and 920 g of an 80 wt% aqueous acrylic acid solution were continuously added dropwise at a boiling temperature over 1 hour to carry out a polymerization reaction. Further, 160 g of a 0.7 wt% ammonium persulfate aqueous solution was continuously added dropwise at the boiling point for 15 minutes, and after completion of the addition, the mixture was stirred at the boiling point of the system for 30 minutes to complete the polymerization reaction. An aqueous acrylic acid solution was obtained. The obtained polyacrylic acid aqueous solution was dried at 150 ° C. for 2 hours, and then pulverized and classified with a ball mill to obtain a polyacrylic acid homopolymer powder (2).
Table 1 shows the results.
Example 3
In a 1 liter separable flask equipped with a thermometer, a nitrogen inlet tube, a stirrer and a reflux condenser, 973 g of a 37 wt% sodium acrylate aqueous solution with a neutralization rate of 100% (36 wt% vs. total charge) and 17 g of water were added. After charging and cooling the aqueous solution to 10 ± 2 ° C. in an ice bath, nitrogen gas was blown in to remove oxygen dissolved in the aqueous solution. 0.013% by weight (based on the monomer for polymerization) of ammonium persulfate was added to bring the amount of the aqueous solution to 1,000 g. After stirring for 10 minutes, stirring was stopped and immersed in a constant temperature bath at 35 ° C. The aqueous solution started to become cloudy after 20 minutes and gelled. A maximum temperature of 93 ° C. was exhibited 80 minutes after the start of the polymerization. After 4 hours, the transparent gel polymer was taken out, made into small pieces, and dried by ventilation at 190 ° C. for 80 minutes. The obtained polymer was pulverized with a ball mill and classified to obtain a sodium polyacrylate homopolymer powder (3).

[Comparative Example 1]
The powder (1) described in Example 1 was classified to obtain the powder (1 ′) shown in Table 1.

[Comparative Example 2]
The homopolymer powder (2) described in Example 2 was classified to obtain powder (2 ′) shown in Table 1.

[Comparative Example 3]
The homopolymer powder (3) described in Example 3 was classified to obtain the powder (3 ′) shown in Table 1.
<Solubility test>
Pure water is added to 12.5 g of sodium dodecylbenzenesulfonate (LAS), 12.5 g of sodium polyoxyethylene lauryl ether sulfate (AES), and 25 g of sodium carbonate to make a total of 200 g, followed by drying to add a detergent (hereinafter referred to as base) Was prepared). A detergent formulation is prepared by adding 0.5 g of the carboxylic acid polymer powder (1) of Example 1 to the base formulation.
1 L of ultrapure water is put into a 1 L beaker, and after 25 degreeC, it stirs at 80 rpm using a stirrer. 2 g of the above detergent formulation was added to this beaker. Stirring was stopped every minute, and whether or not the carboxylic acid polymer powder was dissolved was visually confirmed to test the solubility. (Table 1)
The carboxylic acid polymer powders of Examples 2 and 3 and Comparative Example 1-3 were similarly tested for solubility. In addition, the dissolution time of the base formulation to which no carboxylic acid polymer powder was added was 4 minutes.

  From the results of Table 1, it is clear that when the carboxylic acid polymer powder described in the present invention is used, it exhibits excellent solubility as a cleaning agent. It can be seen that the function is expressed efficiently.

The cleaning agent and the treatment agent for clothing according to the present invention are blended with a carboxylic acid polymer powder having excellent solubility, and can be dissolved in a small amount of water in a short time. It can be suitably used for washing in a washing machine and processing of clothing.

Claims (3)

A cleaning agent and a treatment agent for clothing, comprising a carboxylic acid polymer powder satisfying the following requirements (a) and (b).
(A) The 0.2 wt% aqueous solution viscosity is 10 mPa · s or more and / or the 1 wt% aqueous solution has a pH of less than 6, and the 10 wt% aqueous solution viscosity is 300 mPa · s or more.
(B) 50% by weight or more of JIS sieve having a particle size of 20 mesh pass and / or an average particle size of 600 μm or less. The cleaning agent for clothes and the treatment agent for clothing according to claim 1, wherein the carboxylic acid polymer powder is a (meth) acrylic acid polymer powder. The cleaning agent and the treatment agent for clothing according to claim 1 or 2, wherein the carboxylic acid polymer powder further contains a surfactant.