JP2014047265A - Builder particle for cleaning agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a builder particle for cleansing that can effectively suppress reattachment of contamination, and further can obtain excellent detergency even when cleaning water is a little; and a detergent composition including the same.SOLUTION: Provided is a builder particle for cleansing that has a carboxy group, and the builder particle for cleansing is that a median size in deionized water of 20°C is at least 5 μm and at most 1,000 μm.

Description

  The present invention relates to a cleaning builder particle and a cleaning composition containing the same.

In recent years, due to growing environmental awareness, drum-type water-saving washing machines that can be washed with less washing water have become widespread, and many consumers tend to pack more than a specified amount of laundry into the washing machine Therefore, the amount of water for clothes at the time of washing is decreasing. Although reduction of the amount of water at the time of washing is desirable from the viewpoints of the environment and economy, the clothes become darkened, so-called redeposition of dirt occurs.
This re-adhesion of dirt is caused by dirt such as mud and soot detached from clothing and fibers detached from clothing again adhering to the clothing. When the amount of washing water decreases, the concentration of dirt in the washing water is reduced. Therefore, the problem of redeposition of dirt is more likely to occur.

  Techniques for preventing the reattachment of dirt include the technique of preventing dirt from reattaching by dispersing the dirt in the wash water using a dispersing agent such as a polymer, or by adsorbing smectite-type clay minerals to the fibers. Examples thereof include a technique for preventing reattachment of dirt, and a technique for preventing the dirt by a cleaning composition composed of a polymer flocculant made of an ultra-high molecular weight acrylic polymer (for example, Patent Documents 1 to 3).

JP-A-62-253694 JP 56-167798 A JP 7-216389 A

  In the cleaning builders described in Patent Documents 1 to 3, the problem of soil reattachment can be suppressed to some extent, but in the wash water with a high soil concentration, soil reattachment cannot be sufficiently prevented. Therefore, improvement is strongly desired.

  The present invention provides a cleaning builder particle capable of effectively suppressing the reattachment of dirt even when the amount of washing water is small and capable of obtaining an excellent cleaning power, and a cleaning composition containing the cleaning builder particle Offer things.

That is, this invention makes the following a summary.
[1] Cleaning builder particles having a carboxy group, the cleaning builder particles having a median diameter in deionized water at 20 ° C. of 5 μm or more and 1000 μm or less.
[2] A cleaning composition containing the builder particles.

  According to the present invention, builder particles for cleaning that can effectively suppress the reattachment of dirt even when the amount of washing water is small and can obtain further excellent cleaning power, and cleaning containing the same An agent composition can be provided.

[Builder particles for cleaning]
The cleaning builder particles of the present invention have a carboxy group and have a median diameter in deionized water at 20 ° C. of 5 μm or more and 1000 μm or less, so that dirt in washing water can be effectively aggregated and separated. And reattachment of dirt to clothing can be efficiently suppressed. The median diameter of the cleaning builder in deionized water can be determined from the volume particle size distribution by a scattered light method, which will be described later.

<Shape of builder particles for cleaning>
In the present invention, the median diameter in deionized water is 5 μm or more and 1000 μm or less.
The median diameter in deionized water is 5 μm or more, preferably 7 μm or more, more preferably 10 μm or more, and even more preferably 15 μm or more from the viewpoint of improving the cleaning performance. Cleaning builder particles having a median diameter that is too small tend to penetrate between fibers of the fiber product and prevent improvement in cleaning power. In addition, the median diameter in deionized water is 1000 μm or less, preferably 500 μm or less, more preferably 350 μm or less, even more preferably 200 μm or less, and even more preferably 100 μm or less, from the viewpoint of improving dirt aggregation performance. When cleaning builder particles having a large median diameter are used, it is necessary to increase the amount of cleaning builder used to obtain an effect, which adversely affects cleaning efficiency.
More specifically, the median diameter in deionized water is 5 to 1000 μm, preferably 5 to 500, more preferably 7 to 350 μm, and still more preferably 10 to 200 μm, from the viewpoint of improving the cleaning performance.
In addition, when water-insoluble and high-molecular cleaning builder particles having a constitutional unit derived from the carboxy group-containing monomer of the present invention are used in an environment with high ionic strength such as hardness water, the cleaning builder particles are sufficiently obtained. It may shrink without swelling, and in this case, a sufficient effect cannot be obtained.
In the present invention, from the viewpoint of obtaining sufficient recontamination prevention and cleaning properties, the median diameter ratio [20 ° C., 4 ° DH, 2 mM, median diameter in Na ₂ CO ₃ water] / [20 ° C. deionized water] The median diameter is preferably 1/10 or more, more preferably 1/8 or more, further preferably 1/4 or more, more preferably 5/4 or less, and even more preferably 1/1 or less.
More specifically, the median diameter ratio is preferably 1/10 to 5/4, and more preferably 1/4 to 1/1.

Measurement of the median diameter in water is performed using 20 ° C. deionized water. Deionized water is obtained by ion exchange of tap water with an ion exchange resin. The median diameter was measured using a laser diffraction / scattering particle size measuring apparatus (manufactured by Horiba Ltd., model number “LA-920”), using deionized water as a dispersion medium, and a relative refractive index of 1.12. Can be measured.
Also, 4 ° DH, the median diameter in 2mMNa ₂ CO ₃ water, using a 4 ° DH, 2mMNa ₂ CO ₃ water as a dispersion medium, the relative refractive index 1.12, others can be determined in the same manner as the Can do.

  The builder particles for washing are preferably those that swell in water because the larger the surface area, the easier it is to adsorb dirt, and the median diameter in water is preferably at least twice the median diameter at the time of drying, more preferably at least 3 times, And 75 times or less are preferable, 50 times or less are more preferable, 40 times or less are more preferable, 30 times or less are more preferable, 20 times or less are still more preferable, and 10 times or less are still more preferable. Specifically, the median diameter in water is preferably 2 to 75 times, more preferably 3 to 50 times the median diameter when dried.

In the present invention, the median diameter during drying of the cleaning builder particles is preferably 1 μm or more, more preferably 2 μm or more, and further preferably 3 μm or more from the viewpoint of improving the cleaning performance. Further, the median diameter at the time of drying is preferably 200 μm or less, and more preferably 100 μm or less, from the viewpoint of improving the effect of aggregating dirt.
Incidentally, the median diameter of the dry cleaning builder particles as defined in the present invention is smaller than the median diameter in deionized water at 20 ° C., 4 ° DH, smaller than the median diameter in 2mMNa ₂ CO ₃ in water.
The cleaning builder particles are insoluble in water, and the amount of water-soluble components in the cleaning builder particles measured by the method described in the section of carboxy group-containing polymer particles described later is 10% by mass or less. The content is preferably 8% by mass or less, and more preferably 5% by mass or less.

<Configuration of builder particles for cleaning>
Cleaning builder particles having a carboxy group are particles composed of a polymer having a carboxy group, polymer particles obtained by crosslinking this polymer, inorganic particles such as silica, alumina, bentonite and zeolite, and organic materials such as cellulose as core particles. And particles obtained by complexing the core particles with a polymer having a carboxy group, and particles obtained by modifying the surface of a natural polymer compound such as cellulose with an organic compound having a carboxy group. In these, the particle | grains comprised by the polymer which bridge | crosslinked the polymer which has a carboxy group, or the polymer which has a carboxy group are preferable. Examples of the core particles include those described in JP-B-4-820401.

[Cleaning builder particles composed of a polymer containing a carboxy group]
The polymer having a carboxy group (hereinafter also referred to as a carboxy group-containing polymer) is preferably a polymer of a monomer having a carboxy group (hereinafter also referred to as a carboxy group-containing monomer). That is, the builder particles for cleaning are preferably polymer particles having a carboxy group, and more preferably water-swellable polymer particles having a carboxy group.

(Carboxy group-containing monomer)
Examples of the monomer having a carboxy group constituting the cleaning builder include (meth) acrylic acid and salts thereof, styrene carboxylic acid and salts thereof, maleic acid monomers and salts thereof, and itaconic acid and salts thereof. Among these, from the viewpoint of ease of polymerization, (meth) acrylic acid and salts thereof, styrene carboxylic acid and salts thereof are preferable, (meth) acrylic acid and salts thereof are more preferable, and acrylic acid is more preferable. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.
The monomer may be used as a salt group by neutralizing a part or all of the carboxy group with a basic substance.
In addition, (meth) acrylic acid refers to acrylic acid, methacrylic acid or a mixture thereof, and maleic acid type is composed of maleic anhydride, maleic acid, maleic acid monoester, and maleic acid monoamide or two or more of them. Refers to a mixture.
The carboxy group-containing polymer particles in the present invention may be a random polymer of these monomers, or may be a block polymer.

The carboxy group may have a counter ion. Examples of the counter ion include a metal ion, an ammonium ion, an alkyl or alkenyl ammonium ion having 1 to 22 carbon atoms, an alkyl or alkenyl substituted pyridinium ion having 1 to 22 carbon atoms. And alkanol ammonium ions having 1 to 22 carbon atoms in total. Among these, alkali metal ions such as sodium ions and potassium ions, or ammonium ions are preferable, and sodium ions and potassium ions are more preferable.
The content of the structural unit derived from the carboxy group-containing monomer is preferably 25 mol% or more, more preferably 30 mol% or more, and even more preferably 35 mol% or more as a proportion of the total monomer derived from the structural unit of the carboxy group-containing polymer particle. Preferably, 99.9 mol% or less is preferable, 95 mol% or less is more preferable, and 92 mol% or less is still more preferable. The specific content is preferably 25 to 99.9 mol%, more preferably 30 to 95 mol%, still more preferably 35 to 92 mol%.
In addition, the said content is the value computed from the compounding ratio at the time of reaction of the monomer which has a carboxy group, the arbitrary other monomers mentioned later, and a crosslinking agent. The polymer particles having a carboxy group are composed of a structure derived from a monomer having a carboxy group, a structure derived from any other monomer, and a structure derived from a crosslinking agent, and the sum of these monomers is substantially 100 mol%. .

(Other monomers)
In the present invention, the cleaning builder particle may be constituted by a homopolymer of a monomer having a carboxy group, but the cleaning builder particle is constituted by a copolymer of a monomer having a carboxy group and another monomer. May be. In this specification, “crosslinking agent” is excluded from “other monomers” for technical explanation.
Examples of the other monomer include a monomer having at least one substituent selected from the group consisting of a sulfonic acid group and a salt type group thereof, a sulfuric acid group and a salt type group thereof. Specifically, 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acrylamide-2-alkyl (C1-4) propanesulfonic acid, vinylsulfone Examples include acid, allyl sulfonic acid, styrene sulfonic acid, and vinyl sulfuric acid. By using such a strong electrolyte monomer, the swellability of the cleaning builder particles in water can be improved.
Among these, 2- (meth) acryloyloxyethane sulfonic acid, 2- (meth) acryloyloxypropane sulfonic acid, 2- (meth) acrylamide-2- Alkyl (1 to 4 carbon atoms) propanesulfonic acid and styrenesulfonic acid are preferable, 2-acrylamido-2-methylpropanesulfonic acid and styrenesulfonic acid are more preferable, and 2-acrylamido-2-methylpropanesulfonic acid is more preferable. preferable. Here, examples of the counter ion in the case where the monomer forms a salt include the counter ion described above.

The other monomer may be a monomer having at least one substituent selected from the group consisting of a phosphoric acid group and a salt type group thereof, a phosphonic acid group and a salt type group thereof. Specifically, (meth) acryloyloxyalkyl (C1-C4) phosphoric acid, vinylphosphonic acid, etc. are mentioned. Here, when the monomer forms a salt, examples of the counter ion include the counter ions described above.
Alternatively, (meth) acrylamides in which a hydrogen atom on nitrogen is substituted with a saturated or unsaturated alkyl group having 1 to 4 carbon atoms or an aralkyl group may be used as another monomer. Specifically, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, (meth) acryloyl Morpholine, 2- (N, N-dimethylamino) ethyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide N-butoxymethyl (meth) acrylamide and the like.
Moreover, (meth) acrylic acid esters can also be used. For example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2- (meth) acrylic acid 2- Examples include methoxyethyl, polyethylene glycol mono (meth) acrylic acid ester and the like.

The content of the structural unit derived from the other monomer is an amount excluding the content of the structural unit derived from the carboxy group-containing monomer and the content of the structural unit derived from the crosslinking agent described later in the carboxy group-containing polymer. is there. Specifically, 0.1 mol% or more is preferable, 1 mol% or more is more preferable, 2 mol% or more is further preferable, 70 mol% or less is preferable, and 60 mol% or less is more preferable.
In addition, the said content is the value computed from the compounding ratio at the time of reaction of the monomer which has a carboxy group, another monomer, and a crosslinking agent.

(Crosslinking of carboxy group-containing polymer)
The carboxy group-containing polymer particle may be adjusted so that the particle has a specific median diameter in deionized water by manipulating the type and degree of polymerization of the monomer copolymerized with the monomer having a carboxy group, In particular, it preferably has a crosslinked structure. Therefore, in the present invention, it can also be said to be a crosslinked water-swellable polymer particle containing a carboxy group. If the carboxy group-containing polymer particle has a crosslinked structure, it swells without dissolving in water, and it becomes easy to prepare particles having a specific median diameter in water.
A method for preparing a crosslinked carboxy group-containing polymer includes a method of crosslinking in the presence of a crosslinking agent at the time of polymerization of a monomer, or a crosslinking between polymers or oligomers by later crosslinking a polymer or oligomer composed of the monomer. A method of forming a structure is mentioned.

Examples of the crosslinking agent include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, 1,2-butylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) (Meth) acrylic acid ester compounds of polyhydric alcohols such as acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate; N-methyl Acrylamide compounds such as allylacrylamide, N-vinylacrylamide, N, N′-methylenebis (meth) acrylamide, bisacrylamideacetic acid; divinyl compounds such as divinylbenzene, divinylether, divinylethyleneurea; diallyl phthalate, diallyl malate, diallylamine, Polyallyl compounds such as triallylamine, triallylammonium salt, allyl etherified pentaerythritol, allyl etherified sucrose having at least two allyl ether units in the molecule; vinyl (meth) acrylate, allyl (meth) acrylate And (meth) acrylic acid esters of unsaturated alcohols such as 2-hydroxy-3-acryloyloxypropyl (meth) acrylate.
Among these cross-linking agents, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, divinylbenzene, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, and N, N′-methylenebis (meth) acrylamide 1 type or 2 types or more chosen from are preferable.

  The amount of the crosslinking agent when performing the crosslinking treatment is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, as a proportion of the total amount of the monomer and the crosslinking agent derived from the constituent units of the polymer particles. And, 10 mol% or less is preferable, 5 mol% or less is more preferable, and 1 mol% or less is more preferable. The specific amount of the crosslinking agent is preferably 0.05 to 10 mol%, more preferably 0.05 to 5 mol%, as a proportion of the total amount of monomers and crosslinking agents derived from the structural units of the polymer particles. 0.1-1 mol% is more preferable.

In the present invention, crosslinking may be performed using an epoxy compound such as 1,2-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, and polymerization. Self-crosslinking, cross-linking reaction between polymers, covalent cross-linking by methods such as radiation irradiation, ion-bond cross-linking through metal ions, cross-linking through hydrogen bonding, cross-linking derived from a partial crystal structure It may be a bridge derived from a helix structure.
In the present invention, the carboxy group-containing monomer is acrylic acid, the other monomer is at least one selected from 2-acrylamido-2-methylpropanesulfonic acid, N, N-dimethylacrylamide, and acrylamide, and the crosslinking agent is More preferred is methylene bisacrylamide. The other monomer is more preferably 2-acrylamido-2-methylpropanesulfonic acid. Moreover, it is preferable that it is in the above-mentioned range about content of a carboxy group containing monomer, another monomer, a crosslinking agent, and each median diameter.

(Method for synthesizing carboxy group-containing polymer particles)
There is no restriction | limiting in particular in the method to synthesize | combine a carboxyl group-containing polymer particle, It can synthesize | combine by a well-known method. For example, the monomer having a carboxy group may be homopolymerized, or the monomer having a carboxy group may be copolymerized with the other monomer. The monomer may be additionally polymerized to a monomer having a carboxy group or an oligomer derived from another monomer. Moreover, you may superpose | polymerize so that the quantity of the monomer which has a carboxy group may be 25 mass% or more with respect to arbitrary polymers. When using a cross-linking agent, the addition timing of the cross-linking agent is considered from the viewpoint of the structural design of the builder particles, but it is usually added when the monomer having a carboxy group and any other monomer are polymerized. Polymerization is mentioned.

There is no particular limitation on the polymerization mode, and synthesis may be performed by bulk polymerization or precipitation polymerization. However, from the viewpoint of easy control of the polymerization reaction, it is preferable to synthesize by a reverse phase suspension polymerization method.
Moreover, a well-known method can be used for the polymerization method, and radical polymerization, anionic polymerization, and cationic polymerization can be mentioned.
Examples of radical polymerization initiators that can be used for radical polymerization include potassium persulfate, ammonium persulfate, sodium persulfate, t-butyl hydroperoxide, peroxide initiators such as hydrogen peroxide, and 2,2′-azobis. (2-amidinopropane) azo-based initiators such as dihydrochloride, redox-type initiator based initiators using these in combination with reducing agents such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfate, L-ascorbic acid Can be mentioned. Further, the polymerization may be initiated by irradiation with ultraviolet rays, electron beams, γ rays or the like.
The amount of the polymerization initiator that can be used for radical polymerization is preferably 0.0001 mol% or more, more preferably 0.001 mol% or more, still more preferably 0.01 mol% or more, based on the total amount of monomers used as a raw material, And 5 mol% or less is preferable, 1.5 mol% or less is more preferable, and 0.5 mol% or less is still more preferable. Specifically, 0.0001-5 mol% is preferable, 0.001-1.5 mol% is more preferable, and 0.01-0.5 mol% is still more preferable.

As a polymerization initiator in the case of synthesis by anionic polymerization, an aromatic complex of an alkali metal such as naphthyl sodium, an alkali metal such as lithium, sodium or potassium, n-butyllithium, t-butyllithium, methyllithium or fluorenyl An organic lithium compound (alkyl lithium compound) such as lithium can be used. Further, organic magnesium compounds, specifically, Grignard compounds such as phenyl magnesium bromide and butyl magnesium bromide, and diorgano magnesium compounds such as dibenzyl magnesium, dibutyl magnesium and benzyl picolyl magnesium may be used.
The amount of polymerization initiator used in the synthesis by anionic polymerization is preferably 0.0001 mol% or more, more preferably 0.001 mol% or more, still more preferably 0.01 mol% or more, based on the total amount of monomers used as a raw material. 5 mol% or less is preferable, 1.5 mol% or less is more preferable, and 0.5 mol% or less is still more preferable. Specifically, 0.0001-5 mol% is preferable, 0.001-1.5 mol% is more preferable, and 0.01-0.5 mol% is still more preferable.

As a polymerization initiator in the case of synthesis by cationic polymerization, Bronsted acids such as trifluoroacetic acid, trichloroacetic acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, water-boron trifluoride, water-boron trichloride, water -Bronsted acid-Lewis acid mixtures such as aluminum chloride, water-aluminum bromide, water-tin tetrachloride, trichloroacetic acid-tin tetrachloride, hydrogen chloride-boron trichloride, hydrogen chloride-aluminum trichloride . Moreover, the mixture which produces | generates oxocarbenium ions, such as organic cations, such as a trityl cation and a tropylium cation, an acetyl chloride- silver hexafluoroantimonate, and an acetyl chloride- silver perchlorate, is also mentioned.
The amount of the polymerization initiator used in the synthesis by cationic polymerization is preferably 0.0001 mol% or more, more preferably 0.001 mol% or more, still more preferably 0.01 mol% or more, based on the total amount of monomers used as a raw material. 5 mol% or less is preferable, 1.5 mol% or less is more preferable, and 0.5 mol% or less is still more preferable. Specifically, 0.0001-5 mol% is preferable, 0.001-1.5 mol% is more preferable, and 0.01-0.5 mol% is still more preferable.

  The carboxy group-containing polymer particles in the present invention may be a condensation polymer such as polyester, polyamide, polyurethane, or polyimide, or may be a polyether polymer. Moreover, you may introduce | transduce and use a carboxyl group and its salt-type group in the ratio of 10 mass% or more with respect to arbitrary condensation polymers and polyether polymers.

In the carboxy group-containing polymer particle, the amount of the water-soluble component in the polymer particle is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less. preferable. Since the carboxy group-containing polymer particles exhibit water-insoluble properties, they can adsorb and agglomerate dirt in the wash water, and when the water-soluble content increases, it acts on the dirt on the clothes and removes the dirt. Adversely affect. It is possible to prevent the laundry from being soiled by the soluble components of the cleaning builder particles. In the present invention, water-insoluble means that the amount of water-soluble components in the polymer particles is 10% by mass or less.
The method for measuring the amount of water-soluble component is as follows.

(Method for measuring water-soluble content)
100 mL of a 10% by mass dispersion of builder particles for cleaning is prepared using deionized water under a temperature condition of 20 to 30 ° C., and mixed for 2 hours at 1500 rpm with a stirrer. Then, when a water insoluble component and a water soluble component isolate | separate, let a supernatant liquid be a water soluble component solution.
When separation is difficult and the median diameter of the cleaning builder particles is 5 μm or more, the dispersion is filtered using a 0.45 μm filter, and the filtrate is used as a water-soluble component solution.
When filtration is difficult, you may perform centrifugation for 1 hour at 10,000 rpm ("CR21GIII" by Hitachi, Ltd.).
The amount of solid content in the separated water-soluble component solution was measured in an automatic moisture measurement mode at 120 ° C./30 seconds using an infrared moisture meter, manufactured by Kett Scientific Laboratory, model number “FD-240”. Let the amount of solid content be soluble amount.
When the carboxy group-containing polymer particles have a crosslinked structure, the water-soluble content may be measured by the following method.
First, a 0.1% by weight aqueous solution of builder particles for cleaning was filtered through a 0.45 μm cellulose acetate type membrane filter (Advantech Co., Ltd.), and the TOC (total organic carbon content) of the filtrate was manufactured by Shimadzu Corporation. It can be determined by measuring with the model number “TOC-VPCN” and comparing it with the value of the uncrosslinked polymer particles. If it is difficult to perform filtration, centrifugation may be performed by the method described above.
The builder particles for washing of the present invention may be used after being dispersed in water and then sedimented by centrifugation to remove soluble components of the supernatant.

[Cleaning builder particles having core particles]
As described above, the cleaning builder particles having a carboxy group may be particles in which inorganic particles such as silica and organic particles such as cellulose are used as core particles, and the core particles and a polymer having a carboxy group are combined. Good.
As a method of obtaining a cleaning builder having such core particles, a method of reacting a compound having a carboxy group after treating the surface of the core particles as necessary, an oligomer having a carboxy group and a core particle or A method of complexing with a polymer can be mentioned.
The term “composite” means that the core particles and the polymer are physically or chemically adsorbed or bonded. Specifically, a method of physically adsorbing a core particle and a carboxy group-containing polymer by ionic bond or hydrophobic interaction, by reacting a carboxy group-containing monomer with a functional group introduced on the surface of the core particle A method of chemically fixing can be mentioned.
Moreover, the method of making it composite by making a carboxy-group containing polymer adhere to the core particle surface and drying is also mentioned.

  When the monomer is polymerized on the surface of the core particle, the polymer formed on the surface of the core particle is a polymer made of polyacrylic acid having a mass average molecular weight of 5 to 5 million or a salt thereof, and the mass average molecular weight is 5 to 5 million. A polymer comprising an acrylic acid-maleic acid copolymer or a salt thereof is preferred.

  In addition, when the carboxy group-containing monomer is polymerized on the particle surface, for example, when the core particles are silica-based particles, for example, the silica particles and trimethoxymercaptopropylsilane are reacted to synthesize mercapto-modified silica particles. And a method of polymerizing acrylic acid by radical polymerization.

  The particle shape of the water-insoluble particles is not particularly limited, and may be, for example, a spherical shape, a plate shape, or a fiber shape. The shape of the water-insoluble particles is determined by the shape of the later-described core particles constituting the water-insoluble particles. Since the shape of the core particle is preferably spherical from the viewpoint of ease of production, the particle shape of the water-insoluble particle is preferably spherical.

<Nuclear particles>
As the core particles, organic particles, inorganic particles, or the like can be used.
Organic particles include crosslinked (meth) acrylate resins such as crosslinked polymethyl (meth) acrylate and crosslinked polyethyl (meth) acrylate, crosslinked polystyrene, polydivinylbenzene, polyimide, epoxy resin, polyurethane, polytetrafluoroethylene and its derivatives, polysulfene And particles composed of polyethersulfone, thermoplastic polyimide, polyamideimide, polyetherketone, and the like.
Examples of inorganic particles include inorganic oxides such as silica, zinc oxide (ZnO ₂ ), titanium oxide (TiO ₂ ), aluminum oxide (Al ₂ O ₃ ), calcium carbonate (CaCO ₃ ), barium titanate (BaTiO ₃ ), and talc. Such as physical particles.
As silica-based inorganic particles, it is preferable to use particles that have been surface-treated with a known silane compound such as trimethoxymercaptopropylsilane in order to react the carboxy group-containing monomer on the surface. In the present invention, these may be referred to as modified silica.

These nuclear particles may be used alone or in combination of two or more. The median diameter of the nuclear particles in deionized water at 20 ° C. is preferably 2 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more, in preparing a cleaning builder having the effects of the present invention. 150 μm or less is preferable, 100 μm or less is more preferable, and 50 μm or less is even more preferable. Specifically, the median diameter of the core particles in deionized water is preferably 2 to 150 μm, more preferably 3 to 100 μm, and even more preferably 5 to 50 μm.
As the core particles, inorganic particles having a large specific gravity are preferable from the viewpoint of sedimentation of aggregates, and silica particles having a high surface reactivity are preferable.

  Of the cleaning builder formed by combining the core particles and the carboxy group-containing polymer, the content ratio of the carboxy group-containing polymer is preferably 0.2% by mass or more, more preferably 1% by mass or more, and 1.5% % By mass or more is still more preferred, 30% by mass or less is preferred, 20% by mass or less is more preferred, and 15% by mass or less is even more preferred. Specifically, the content of the carboxy group-containing polymer of the cleaning builder when using the core particles is preferably 0.2 to 30% by mass, more preferably 1 to 20% by mass, and 1.5 to 15% by mass. Is even more preferred. The carboxy group-containing polymer used for complexing with the core particles may contain the cross-linking agent, or may fix the surface of each particle by using a cross-linking agent. It is preferable that the usage-amount of the crosslinking agent in that case is the ratio shown with the said carboxyl group-containing polymer particle.

  The cleaning builder particles formed by combining the core particles and the carboxy group-containing polymer are insoluble in water.

  The composite ratio of the carboxy group-containing polymer may be calculated from the reaction rate at the time of the composite, but when the core particle is a heat-resistant substance such as silica, it is measured from the weight loss rate at 100 to 600 ° C. May be.

[Other cleaning builder particles]
Other builder particles include particles in which a carboxy group-containing compound is introduced by a known method on the surface of particles made of natural polymers such as cellulose particles. The median diameter of the natural polymer is preferably 5 μm or more, more preferably 7 μm or more, even more preferably 10 μm or more, and preferably 150 μm or less, preferably 100 μm or less, in preparing a cleaning builder having the effects of the present invention. Is more preferable, and 50 μm or less is even more preferable.

[Cleaning composition]
The cleaning composition of the present invention contains the builder particles for cleaning, and can effectively suppress the reattachment of dirt during cleaning.
<Amount of cleaning builder>
The cleaning composition of the present invention only needs to contain at least the cleaning builder particles of the present invention, and the content is preferably 0.01% by mass or more from the viewpoint of improving the anti-redeposition performance. 0.05 mass% or more is more preferable, and 0.1 mass% or more is still more preferable. Moreover, 3 mass% or less is preferable from a viewpoint of rinsing property and the powder physical property of a cleaning composition, 2 mass% or less is more preferable, and 1 mass% or less is still more preferable.

The cleaning composition may contain the following components in addition to the cleaning builder particles.
<Surfactant>
As surfactants, those commonly used in cleaning agents can be used, and from the viewpoint of improving cleaning performance, anionic surfactants and nonionic surfactants should be used as main surfactants. Is preferred.
Examples of the anionic surfactant include linear alkyl or alkenyl benzene sulfonate having alkyl or alkenyl chain having 10 to 18 carbon atoms, alkyl or alkenyl sulfate ester salt, polyoxyalkylene alkyl or alkenyl ether sulfate, and alpha sulfo fatty acid. Alkali metal salts such as methyl ester salts, N-acyl amino acid type surfactants, alkyl or alkenyl ether carboxylates, amino acid type surfactants, alkyl or alkenyl phosphates or salts thereof are preferred, derived from beef tallow and palm oil It is more preferable to blend a fatty acid salt. Among these, alkyl or alkenyl benzene sulfonate, alkyl or alkenyl sulfate ester salt, polyoxyalkylene alkyl or alkenyl ether sulfate are preferable, and it is more preferable to use these anionic surfactant and fatty acid salt in combination. preferable. In particular, it is preferable to contain sodium alkyl or alkenylbenzenesulfonate and fatty acid salt.

The content of the anionic surfactant in the cleaning composition is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and more preferably 5 to 15% from the viewpoint of efficiently removing mud from the fiber product. % Is more preferable.
In addition, at least one selected from the group consisting of alkyl or alkenyl benzene sulfonate, alkyl or alkenyl sulfate ester salt, and polyoxyalkylene alkyl or alkenyl ether sulfate is converted into sodium salt in an anionic surfactant. It is preferable to occupy 50 to 100% by mass, and the fatty acid salt in terms of sodium occupies 0 to 20% by mass in the anionic surfactant and preferably does not exceed 10% by mass in the composition.

As the nonionic surfactant, polyoxyalkylene alkyl ether is preferable, and polyoxyethylene alkyl ether and polyoxypropylene alkyl ether are more preferable. Polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, alkyl glycoside, fatty acid glycerin monoester can also be used.
Nonionic surfactants have good resistance to hard water, and have a remarkable detergency for oily dirt such as sebum dirt.
The nonionic surfactant in the cleaning composition is preferably 1 to 20% by mass and more preferably 5 to 15% by mass from the viewpoint of foamability and rinsability.

  In the cleaning composition of the present invention, a surfactant such as a betaine amphoteric surfactant and a cationic surfactant can be appropriately blended. However, the content of the cationic surfactant is 5% by mass or less, preferably 1% by mass or less, in order to sufficiently exhibit the builder effect of the component (a).

<Alkaline agent>
As an alkali agent, the general thing used for a detergent composition can be used, and from a viewpoint of detergency, alkali metal carbonates, such as sodium carbonate collectively called dense ash and light ash, and JIS No. 1, Examples include amorphous alkali metal silicates such as No. 2 and No. 3 sodium silicates, and alkali metal salts such as crystalline alkali metal silicates.
The content of the alkali metal salt in the cleaning composition is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 7% by mass or more, more preferably 10% by mass or more, and more preferably 12% by mass or more. More preferably, 15% by mass or more is further preferable, and 20% by mass or more is even more preferable. Moreover, from a viewpoint of the balance of a mixing | blending, 40 mass% or less is preferable, and 35 mass% or less is more preferable.

<Metal ion sequestering agent>
A metal ion sequestering agent may be included in the cleaning composition. The sequestering agent captures the hardness component in the wash water, and is therefore very effective in improving the washability.
As sequestering agents, crystalline aluminosilicate, crystalline sodium silicate, acrylic polymer and acrylic acid-maleic acid copolymer other than builder particles for cleaning, sodium tripolyphosphate, ethylenediaminetetraacetic acid, methylglycine diacetic acid Etc.
However, in the present invention, sodium carbonate and amorphous sodium silicate are not included in the sequestering agent.
The content of the sequestering agent in the cleaning composition is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and more preferably 20% by mass or more from the viewpoint of improving the detergency. Is even more preferable. Moreover, from a viewpoint of the balance of a mixing | blending, 50 mass% or less is preferable, 40 mass% or less is more preferable, and 35 mass% or less is still more preferable.

<Inorganic salt releasing hydrogen peroxide>
In the present invention, a hydrogen peroxide-releasing inorganic salt that releases hydrogen peroxide in water may be contained. Examples of the hydrogen peroxide releasing inorganic salt include sodium percarbonate and sodium perborate. The hydrogen peroxide releasing inorganic salt is preferably coated with sodium silicate, polyethylene glycol, or boric acid compound in order to improve stability.
The content of the hydrogen peroxide-releasing inorganic salt in the cleaning composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more from the viewpoint of improving detergency. From the viewpoint of obtaining sufficient detergency and the relationship with other components, it is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and even more preferably 2.5% by mass or less. .

<Other polymers>
The detergent composition may contain a chain organic polymer having a mass average molecular weight of less than 500,000, preferably 1,000 to 100,000, and a water-soluble organic polymer for the purpose of enhancing dispersibility of solid particle dirt. it can.
Specific examples of the polymer include carboxylic acid polymers and nonionic polymers.

The carboxylic acid-based polymer other than the cleaning builder particles having a carboxyl group of the present invention includes known acrylic acid and methacrylic acid from the viewpoint of sequestering metal ions and assisting dispersibility of the solid particle soil in the washing bath. A homopolymer or copolymer such as acid or itaconic acid is preferred, and the copolymer may contain a copolymer of the above monomer and maleic acid as long as the effects of the present invention are not impaired.
Moreover, as a carboxylic acid-type polymer, carboxymethylcellulose which has the effect | action which disperse | distributes solid particle | grain dirt in a washing bath can also be used.

  Examples of the nonionic polymer include polyalkylene glycol having an oxyalkylene group having 2 to 3 carbon atoms such as polyethylene glycol, polypropylene glycol, or polyethylene glycol-polypropylene glycol copolymer. Polyalkylene glycol and polyethylene glycol have the effect of dispersing nonionic solid particle soil such as carbon in the washing bath. The weight average molecular weight is preferably 1000 to 20,000.

  The mass average molecular weight of water-soluble polyalkylene glycol and polyacrylic acid type polymer was determined by gel permeation chromatography using a mixed solution of acetonitrile and water (phosphate buffer) as a developing solvent and polyethylene glycol as a standard substance. Can be measured. If measurement by this method is difficult, the light scattering method is used. Specifically, it can be measured by a dynamic light scattering photometer (manufactured by Otsuka Electronics Co., Ltd., DLS-8000 series).

<Other additives>
In the cleaning composition of the present invention, enzymes, fragrances, fluorescent dyes, bluing agents, coloring dyes, pigments, and the like can be appropriately blended.

<Form of cleaning composition>
The form of the cleaning composition is not particularly limited, but is preferably in the form of a powder because of easy blending of builder particles.

  When the cleaning composition of the present invention is manufactured according to a general powder detergent manufacturing process, the present invention is a step of adding a fluorescent dye, enzyme, fragrance, antifoaming agent, bleach, bleach activator, etc. The cleaning builder particles may be added, may be added in the surface modification step, the granulation step, or may be added in the slurry blending step.

In relation to the above-described embodiment, the present invention discloses the following cleaning builder particles and cleaning composition.
<1> Cleaning builder particles having a carboxy group, wherein the cleaning builder particles have a median diameter in deionized water at 20 ° C. of 5 μm or more and 1000 μm or less.
<2> The cleaning builder particle according to <1>, wherein the cleaning builder particle is a water-swellable polymer particle having a carboxy group.

<3> The cleaning builder particles according to <2>, wherein the polymer particles have a crosslinked structure.
<4> The cleaning builder particle according to <2> or <3>, wherein the polymer particle includes a structural unit having a carboxy group and a structural unit derived from a 2-acrylamido-2-methylpropanesulfonic acid monomer.

<5> The builder particle for cleaning according to <4>, wherein the structural unit having a carboxy group is a structural unit derived from acrylic acid.
<6> The cleaning builder particle according to any one of <2> to <5>, wherein the water-swellable polymer particle having a carboxy group has a water-soluble component content of 10% by mass or less.
<7> The cleaning builder particle according to <1>, wherein the cleaning builder particle is a particle in which a core particle and a polymer having a carboxy group are combined.

<8> The cleaning builder particle according to <7>, wherein the polymer having a carboxy group includes a structural unit having a carboxy group and a structural unit derived from 2-acrylamido-2-methylpropanesulfonic acid monomer.
<9> The cleaning builder particle according to <8>, wherein the structural unit having a carboxy group is a structural unit derived from acrylic acid.

<10> The median diameter in deionized water is preferably 7 μm or more, more preferably 10 μm or more, further preferably 15 μm or more, and preferably 500 μm or less, more preferably 350 μm or less, more preferably 200 μm or less, More preferably, it is 100 micrometers or less, Specifically, Preferably it is 5-500 micrometers, More preferably, it is 7-350 micrometers, More preferably, it is 10-200 micrometers, For washing | cleaning in any one of <1>-<9> Builder particles.
<11> Median diameter ratio [20 ° C., 4 ° DH, 2 mM, median diameter in Na ₂ CO ₃ water] / [median diameter in 20 ° C. deionized water] is preferably 1/10 or more Preferably it is 1/8 or more, more preferably 1/4 or more, and preferably 5/4 or less, more preferably 1/1 or less, specifically, preferably 1/10 to 5/4. The builder particles for cleaning according to any one of <1> to <10>, more preferably 1/4 to 1/1.

<12> The median diameter at the time of drying of the builder particles for washing is preferably 1 μm or more, more preferably 2 μm or more, further preferably 3 μm or more, and preferably 200 μm or less, more preferably 100 μm or less. The builder particles for cleaning according to any one of 1> to <11>.
<13> The median diameter in water is preferably 2 times or more, more preferably 3 times or more of the median diameter at the time of drying, and preferably 75 times or less, more preferably 50 times or less, more preferably 40 times. Times or less, more preferably 30 times or less, still more preferably 20 times or less, even more preferably 10 times or less, specifically preferably 2 to 75 times, more preferably 3 to 50 times, < The builder particle | grains for washing | cleaning in any one of 1>-<12>.

<14> The content of the structural unit derived from the monomer having a carboxy group (carboxy group-containing monomer) in the polymer having a carboxy group (carboxy group-containing polymer) is preferably 25 mol% or more, more preferably 30 mol% or more, and further Preferably, it is 35 mol% or more, and preferably 99.9 mol% or less, more preferably 95 mol% or less, still more preferably 92 mol% or less, specifically, preferably 25 to 99.9 mol%, more preferably Is a builder particle for cleaning according to any one of <7> to <13>, which is 30 to 95 mol%, more preferably 35 to 92 mol%.
<15> The carboxy group-containing monomer constituting the carboxy group-containing polymer is acrylic acid, and the other monomer is one or more selected from 2-acrylamido-2-methylpropanesulfonic acid, N, N-dimethylacrylamide and acrylamide. The cleaning builder particle according to any one of <7> to <14>, which is preferably 2-acrylamido-2-methylpropanesulfonic acid and the cross-linking agent is methylenebisacrylamide.

<16> The amount of the crosslinking agent is preferably 0.05 mol% or more, more preferably as a proportion of the total amount of the monomer and the crosslinking agent derived from the carboxy group-containing polymer particles or the constituent unit of the carboxy group-containing polymer. Is 0.1 mol% or more, and preferably 10 mol% or less, more preferably 5 mol% or less, more preferably 1 mol% or less, specifically preferably 0.05 to 10 mol%, more preferably The cleaning builder particles according to <3> or <15>, which are 0.05 to 5 mol%, more preferably 0.1 to 1 mol%.
<17> Core particles are crosslinked (meth) acrylate resins such as crosslinked polymethyl (meth) acrylate and crosslinked polyethyl (meth) acrylate, crosslinked polystyrene, polydivinylbenzene, polyimide, epoxy resin, polyurethane, polytetrafluoroethylene and derivatives thereof. The builder particles for cleaning according to any one of <7> to <16>, which are particles composed of polysulfene, polyethersulfone, thermoplastic polyimide, polyamideimide, and polyetherketone.

<18> The core particles are silica, zinc oxide (ZnO ₂ ), titanium oxide (TiO ₂ ), aluminum oxide (Al ₂ O ₃ ), calcium carbonate (CaCO ₃ ), barium titanate (BaTiO ₃ ), and talc. <7>-<16> The cleaning builder particle | grains in any one of <16>.
<19> The builder particle for cleaning according to <18>, wherein the core particle is silica.

The median diameter of <20> core particles in deionized water at 20 ° C. is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 5 μm or more, and preferably 150 μm or less, more preferably 100 μm or less. More preferably, it is 50 μm or less, specifically, preferably 2 to 150 μm, more preferably 3 to 100 μm, still more preferably 5 to 50 μm, <7> to <19> Builder particles for cleaning.
The amount of the water-soluble component in the <21> carboxy group-containing polymer is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, <7> to <20 > The builder particle for washing | cleaning in any one of.

The content ratio of the <22> carboxy group-containing polymer is preferably 0.2% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, and preferably 30% by mass or less. More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less, Specifically, Preferably it is 0.2-30 mass%, More preferably, it is 1-20 mass%, More preferably, it is 1.5. The builder particle for washing | cleaning in any one of <7>-<21> which is -15 mass%.
<23> A cleaning composition containing the builder particles according to any one of <1> to <22>.

<24> The content of builder particles for cleaning is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 3% by mass. Hereinafter, the cleaning composition according to <23>, more preferably 2% by mass or less, and still more preferably 1% by mass or less.
<25> The cleaning composition according to <23> or <24>, further containing a surfactant.

<26> The cleaning composition according to any one of <23> to <25>, further containing an alkali agent.
<27> The alkali agent is an alkali metal salt, and the content of the alkali metal salt is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 7% by mass or more, more preferably 10% by mass. Or more, more preferably 12% by mass or more, further preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, <26 > Cleaning composition.

Example 1: Synthesis of builder particles for washing composed of a crosslinked carboxy group-containing polymer First, the following aqueous solutions (1) to (3) were prepared.
(Aqueous solution (1))
A 100 ml beaker was charged with 20.2 g of a 48 mass% aqueous sodium hydroxide solution and 38.5 g of ion-exchanged water and stirred with a stirrer in an ice bath with 2-acrylamido-2-methylpropanesulfonic acid (Toa Gosei Co., Ltd.) ) 50.2 g added in 5 portions and neutralized aqueous solution. During the neutralization reaction, the reaction solution temperature was controlled not to exceed 15 ° C.
(Aqueous solution (2))
An aqueous solution in which methylene bisacrylamide (MBA, Kanto Chemical Co., Inc .: 0.147 g; 0.12 mol% with respect to monomer) was added to 2.80 g of ion-exchanged water and dissolved.
(Aqueous solution (3))
An aqueous solution in which sodium persulfate (NaPS, Wako Pure Chemical Industries, Ltd .: 0.190 g; monomer 0.10 mol%) was added to 3.00 g of ion-exchanged water and dissolved.

(Synthesis procedure)
A 500 ml eggplant-shaped flask was charged with 50.0 g of an 80% by weight acrylic acid aqueous solution (Toagosei Co., Ltd.) and 65.2 g of ion-exchanged water, and 32.4 g of a 48% by weight aqueous sodium hydroxide solution while stirring at 200 rpm in an ice bath. Was slowly added dropwise to neutralize the acrylic acid. The aqueous solutions (1) to (3) were added thereto to prepare an aqueous monomer solution as a raw material.
In a 2 L beaker, 1050.5 g of cyclohexane (Wako Pure Chemical Industries, Ltd.) and 1.05 g of sugar ester (manufactured by Mitsubishi Chemical Foods Co., Ltd., model number “S-770”) are charged and heated in a hot water bath (60 ° C.). To obtain a homogeneous solution. After cooling to 30 ° C. or lower, the monomer aqueous solution was added and the mixed reaction solution was made into fine droplets (9000 rpm / 4 min) with a homogenizer. A 12 cm crescent moon stirring blade and a cooling tube were attached to a 2 L separable flask, and the reaction liquid made into fine droplets was added. While stirring at 100 rpm, the nitrogen was replaced with nitrogen at a flow rate of 150 ml / min for 30 minutes, and then the temperature of the oil bath was heated from 25 ° C. to 1 ° C./min for polymerization.
After completion of the polymerization, when about 90 to 95% by mass of the water in the reaction solution was removed, the dehydration operation was terminated, and after cooling and decantation, the generated particles were No. Filtered under reduced pressure using 5 filter paper. Then, the builder particle | grains for washing | cleaning were obtained by making it dry overnight at 100 degreeC conditions with a dryer.
The median diameter of the obtained cleaning builder particles was measured with a laser diffraction / scattering particle size measuring device (manufactured by Horiba, Ltd., model number “LA-920”). The median diameter at the time of drying was measured with a dispersion medium of cyclohexane and a relative refractive index of 1.12. The median diameter at the time of swelling with water was measured with a dispersion medium of deionized water and a relative refractive index of 1.12. The median diameter at 4 ° dh / 2 mM was measured with a dispersion medium of 4 ° DH hardness water and an aqueous solution having a Na ₂ CO ₃ concentration of 2 mM and a relative refractive index of 1.12.
The amount of the soluble component was obtained by filtering a 0.1% by weight aqueous solution of cleaning builder particles with a 0.45 μm cellulose acetate type membrane filter (manufactured by Advantech), and calculating the TOC (total organic carbon content) of the filtrate by Shimadzu Corporation. The measurement was made according to the model number “TOC-VPCN” manufactured by Seisakusho.

Examples 2-7, Comparative Example 1
Cross-linked cleaning builder particles were produced in the same manner as in Example 1 except that the reaction was performed according to the formulation shown in Table 1. In addition, when the builder particle | grains for washing | cleaning of the comparative example 1 were added to water, since it melt | dissolved, the median diameter was not measured.

Example 8: Synthesis of washed builder particles having core particles As core particles, silica particles “H-201” (manufactured by AGC S-Tech Co., Ltd.) dried at 105 ° C. under reduced pressure overnight were used. After adding 400 g of toluene (Wako Pure Chemical Industries, Ltd.) to a 1 L separable flask, 150 g of the silica particles and 5.05 g of trimethoxymercaptopropylsilane (Shin-Etsu Chemical Co., Ltd.) are added, and the mixture is stirred by Teflon crescent. After purging with nitrogen at a flow rate of 150 mL / min for 30 minutes while stirring at 200 rpm using a blade (60 mm), the reaction solution was heated to the toluene reflux temperature (oil bath temperature 110 ° C.). The mixture was heated for 5 hours while maintaining the temperature. Thereafter, it was cooled to room temperature. Filtration was performed with 5C filter paper, and the obtained particles were washed with 200 mL of ethanol and further dried at 100 ° C./reduced pressure overnight to obtain mercapto-modified silica particles.

After charging 530.7 g of ion-exchanged water and 30.0 g of the above mercapto-modified silica particles into a 500 mL separable flask and purging with nitrogen for 30 minutes while stirring at 300 rpm using a Teflon crescent stirring blade (60 mm), The temperature was raised to 85 ° C. (oil bath temperature 95 ° C.), 37.5 g (0.52 mol) of 80% by mass acrylic acid aqueous solution, 0.36 g (1.6 mmol) of 20% by mass NaPS (sodium persulfate) aqueous solution, ions A mixture of 1.45 g of exchange water was added in 15 portions and added every 15 minutes. After completion of the addition, the reaction was terminated by aging at 85 ° C. for 3 hours. Centrifugation (3000 rpm, 30 min) was performed to remove the polyacrylic acid not forming a bond with the silica particles, and the supernatant was removed. After removing the supernatant, 300 g of ion-exchanged water is added, and sonication is performed for 5 minutes at an output of 100% using an ultrasonic machine (“UT-205” manufactured by SHARP), and then centrifuged again at 3000 rpm for 30 minutes. Washing was performed by removing the supernatant. This washing with ion-exchanged water was further carried out four times, and the concentration of polyacrylic acid in the supernatant produced by the final centrifugation was measured. The concentration was 0.4% by mass. Thereafter, 1N-NaOH was added to neutralize the polyacrylic acid, and the pH was adjusted to around 7 to obtain cleaning builder particles.
The median diameter of the obtained particles in deionized water was measured with a laser diffraction / scattering particle size measuring device (manufactured by Horiba, Ltd., model number “LA-920”). The polymer content in the builder particles was calculated from the weight loss from 100 to 600 ° C. by heating to 700 ° C. with a TGA measuring device TG-DTA (manufactured by Shimadzu Corporation).

Example 9: Synthesis of washed builder particles having core particles The mercapto-modified silica obtained in Example 8 was used. The cleaning builder was prepared by the following method.
After charging 501.4 g of ion-exchanged water and 20.0 g of the above mercapto-modified silica particles into a 500 mL separable flask, the mixture was purged with nitrogen (150 mL / min) for 30 min while stirring at 300 rpm using a Teflon crescent stirring blade (60 mm). The reaction solution was heated to 85 ° C. (oil bath temperature 95 ° C.), 75.0 g (1.04 mol) of an 80% by mass aqueous acrylic acid solution, and 0.75 g (3. 2 mmol) and 2.90 g of ion-exchanged water were added in four portions and added every 15 minutes. After completion of the addition, the reaction was terminated by aging at 85 ° C. for 3 hours. Centrifugation (3000 rpm / 30 min) was performed to remove the polyacrylic acid not forming a bond with the silica particles, and the supernatant was removed. After removing the supernatant, 300 g of ion-exchanged water is added, and sonication is performed for 5 minutes at an output of 100% using an ultrasonic machine (“UT-205” manufactured by SHARP), and then centrifuged again at 3000 rpm for 30 minutes. Washing was performed by removing the supernatant. This washing with ion-exchanged water was further carried out four times, and the concentration of polyacrylic acid in the supernatant produced by the final centrifugation was measured. The concentration was 0.4% by mass. Thereafter, 1N-NaOH was added to neutralize the polyacrylic acid, and the pH was adjusted to around 7 to obtain cleaning builder particles.
By the measuring method described in Example 8, the median diameter of the obtained particles in deionized water and the polymer content in the builder particles were measured.

Example 10
Washing builder particles were produced in the same manner as in Example 8, except that silica particles “H-51” (manufactured by AGC S-Tech Co., Ltd.) were used as the core particles.
By the measuring method described in Example 8, the median diameter of the obtained particles in deionized water and the polymer content in the builder particles were measured.

[Evaluation of detergency]
<Preparation of treatment cloth for evaluation>
0.067% by mass of clothing detergent (powdered new beads (without fluorescent dye)) was used as a pretreatment for the test cloth (cotton knitted fabric (non-dyed fluorescent dye)) obtained from Tanigami Shoten Co., Ltd. A test cloth cut into 4 cm × 5 cm was subjected to a washing process 5 times according to a standard course of a fully automatic washing machine to obtain a treatment cloth for evaluation.
<Preparation of mud-contaminated cloth for evaluation>
Kanuma Horticultural Akadama purchased at Kokusaien Co., Ltd. was dried at 120 ° C. ± 5 ° C. for 4 hours and then pulverized, and 150 mesh (100 μm) passes were dried at 120 ° C. ± 5 ° C. for 2 hours. ± 150 g was dispersed in 1000 L of parkren to obtain a dispersion. After bringing the gold width # 2023 cloth into contact with the obtained dispersion liquid, the cloth surface is brushed to remove the dispersion liquid, and then the mud adhered to the cloth surface is further removed to obtain a dirt cloth for evaluating mud dirt. Obtained. When the obtained mud-stained cloth is observed with a microscope, it is confirmed that many of the fibers adhere to the fibers in a shape in which mud particles are embedded, and it is confirmed that there is a thing close to the state of dirt adhesion in daily life. It was done.

<Detergency test>
According to the composition shown in Tables 1 and 2, 100 ml of a 4 ° DH test solution was prepared, and placed in a 1 L cap-made polypropylene container (manufactured by Sampratec Co., Ltd., product number “2046”). After putting 15 steel balls of 15 μm in diameter into this, 5 sheets of the evaluation mud-contaminated cloth (4 cm × 5 cm) and 5 sheets of the evaluation processing cloth (4 cm × 5 cm) were put and covered.
Set the water level to “low” with a drum-type washing machine (National “NA-VR1100”), put the polypropylene container into the drum-type washing machine with water at 20 ° C., and stir for 5 minutes in the washing process. did. After stirring, the lid of the polypropylene container was opened, the treated cloth and mud-contaminated cloth were taken out, rinsed with 5 L of tap water, and then subjected to an iron press treatment.
Next, the reflectance at 460 nm of each cloth was measured with a spectral color difference meter “SE2000” manufactured by Nippon Denshoku Industries Co., Ltd., and the washing rate (%) and the recontamination prevention rate (%) were calculated from the following equations. The results are shown in Tables 1 and 2.
Cleaning rate (%) = [(Reflectivity of mud-contaminated cloth for evaluation after test--of mud-contaminated cloth for evaluation before washing
Reflectivity) / (Reflectivity of treated cloth for evaluation-anti-mud cloth for evaluation before washing)
Emissivity)] × 100
Recontamination prevention rate (%) = [reflectance of evaluation treated cloth after cleaning / reflectance of evaluation treated cloth on line]
] × 100

Details in the table are as follows.
AA (Na): Sodium acrylate AMPS: Sodium 2-acrylamido-2-methylpropanesulfonate DMAAm: N, N-dimethylacrylamide AAm: Acrylamide NaPS: Sodium persulfate V-50: Water-soluble azo polymerization initiator (Wako Pure) Yakuhin Kogyo Co., Ltd.)
MBA: Methylenebisacrylamide sodium carbonate: Wako Pure Chemical Industries, Ltd.
G-15: Sodium alkylbenzene sulfonate
Product name “Neopelex G-15” manufactured by Kao Corporation

Core particle (A): H-201 (manufactured by AGC S-Itech)
Nuclear particle (B): H-51 (manufactured by AGC S-Tech)
Nuclear particle (C): H-121 (manufactured by AGC S-Tech)

Examples 11 and 12, Comparative Example 2
A cleaning composition was prepared according to the description in Table 3, and the performance of the cleaning builder particles was evaluated by the following test. The results are shown in Table 3.
<Recontamination prevention test>
The recontamination prevention property was evaluated using a round ohmmeter (manufactured by Suga Test Instruments Co., Ltd.). Using the builder particles of Example 1, 40 mL of calcium hard water having a hardness of 72 mg / L (calculated as CaCO ₃ ) in mud (200 mesh sieve) in a glass cup for a round ohmmeter. Sono) It adjusted so that it might become 2.5 g / L, it melt | dissolved each cleaning composition of Table 3, and it prepared so that a density | concentration might be 0.133 mass%.

Five evaluation cloths (4 cm × 5 cm) and a cotton knitted cloth (4 cm × 5 cm) as appropriate as a bath ratio adjusting cloth are put into the solution in the cup, and the pot rotation speed is 40 ± 2 times at 20 ° C. for 30 minutes. Washing was performed with a round ohmmeter at / min. After rinsing with 5 L of tap water, an iron press treatment was performed. Next, the reflectance at 550 nm of the evaluation treatment cloth before washing and the evaluation treatment cloth after washing was measured with a spectral color difference meter manufactured by Nippon Denshoku Industries Co., Ltd., model number “SE2000”. The rate (%) was calculated. The results are shown in Table 3.
Recontamination prevention rate (%) = (reflectance of treated cloth after washing / reflectance of treated cloth before washing) × 100

The details of the compounds described in the table are as follows.
Anionic surfactant: linear alkylbenzene having 12 to 14 carbon atoms in the alkyl group
Sodium sulfonate / nonionic surfactant: Ethylene oxide is added to C ₁₂ -C ₁₄ primary alcohol.
Polyoxya added on average 6 moles per mole of alcohol
Lucylene alkyl ether ("Emulgen 106" (Kao
(Made by Co., Ltd.)
-Sodium polyacrylate: weight average molecular weight 15,000
(Measurement by GPC, polyethylene glycol conversion)
・ Soda ash: Sodium carbonate ・ Crystalline silicate: Pre-feed granule (manufactured by Tokuyama Siltech Co., Ltd.)
・ Zeolite: Zeobuilder (Zeobuilder)
・ Sola salt: Sodium sulfate

  From the results of Examples and Comparative Examples, it can be seen that the cleaning builder and the cleaning composition of the present invention have both excellent cleaning performance and anti-redeposition performance of dirt.

Claims (11)

  A cleaning builder particle having a carboxy group, the cleaning builder particle having a median diameter in deionized water at 20 ° C. of 5 μm or more and 1000 μm or less.   The cleaning builder particle according to claim 1, wherein the cleaning builder particle is a water-swellable polymer particle having a carboxy group.   The cleaning builder particle according to claim 2, wherein the polymer particle has a crosslinked structure.   The builder particle | grain for washing | cleaning of Claim 2 or 3 in which a polymer particle contains the structural unit which has a carboxy group, and the structural unit derived from 2-acrylamido-2-methylpropanesulfonic acid monomer.   The builder particle | grain for washing | cleaning of Claim 4 whose structural unit which has a carboxy group is a structural unit derived from acrylic acid.   The cleaning builder particle according to claim 1, wherein the cleaning builder particle is a particle in which a core particle and a polymer having a carboxy group are combined.   The builder particle | grain for washing | cleaning of Claim 6 in which the polymer which has a carboxy group contains the structural unit which has a carboxy group, and the structural unit derived from 2-acrylamido-2-methylpropanesulfonic acid monomer.   The builder particle | grain for washing | cleaning of Claim 7 whose structural unit which has a carboxy group is a structural unit derived from acrylic acid.   The builder particle for cleaning according to any one of claims 6 to 8, wherein the core particle is silica.   The cleaning composition containing the builder particle in any one of Claims 1-9.   The detergent composition according to claim 10, further comprising a surfactant.