JP4827132B2 - Washing method - Google Patents

Description

  The present invention relates to a washing method and a granular cleaning composition. More specifically, the present invention relates to a washing method and a granular detergent composition that are excellent in preventing mud particle recontamination while improving labor load during hand washing.

  In general, powdered laundry detergents are composed of surfactants, hardness component capture builders, pH buffering agents, other auxiliary agents (cleaning enzymes, fluorescent whitening agents, bleaching systems, etc.), etc. Therefore, various improvements have been attempted from the viewpoints of higher performance, improved environmental suitability, lower cost, improved formulation suitability, and the like. In addition, the manufacturing method has been repeatedly improved from the viewpoints of labor saving, cost reduction, quality stability and improvement. Thus, at present, high-performance powder clothing detergents are efficiently supplied by mass production.

  On the other hand, as a method of use by general users (consumers) of clothing detergents, washing machine washing and hand washing can be generally mentioned. Compared to washing with a washing machine, hand-washed washing enables fine washing according to the situation, such as the degree of dirt removal and the type of object to be washed. Accompanied by. In addition, “rubbing”, which rubs objects to be cleaned, is one of the most natural hand-washing methods because it is easy to apply mechanical force to the parts to be cleaned. Cause a great deal of physical and mental fatigue.

  Microscopically, objects to be cleaned such as cloth are not smooth, and resistance is generated when these are actually rubbed together. This resistance is perceived as an unpleasant factor such as “roughness” and “squeak” for those who are washing, and also increases the burden on the body from the viewpoint of exhaustion of physical strength due to the rice washing exercise. In addition, local friction that occurs during fir washing causes hand scratches and cuts in the case of humans, and in the case of an object to be cleaned, it appears as abrasion of fibers, so-called “scratches of cloth”. The fiber damage not only shortens the service life of the garment, but also serves as an accelerating factor in terms of dirt adhesion, and further increases the physical burden required for cleaning.

  On the other hand, with the exception of technological improvements in manufacturing methods, technical development related to dosage forms, technical improvements that solve problems at the distribution stage, such as storage stability, etc. Conventionally, it has been proposed to improve the cleaning power of detergents, prevent redeposition of dirt on the object to be cleaned, and prevent migration due to pigments detached from other objects to be cleaned. "How to remove the object to be cleaned and prevent new contamination", "How to clean the object after washing," such as adding flexibility to clothes after washing and preventing wrinkling of clothes Technical development focused on the aspect of “finished” was the main (see, for example, Patent Documents 1 to 4). Considering such discomfort factors and physical loads that occur during hand-washing as described above, that is, “mental and physical burdens for those who do laundry”, technological development focused on the improvement has been made so far. It wasn't.

Patent Document 4 discloses a technology for preventing color migration using an acrylamide alkylene sulfonic acid polymer. However, this technique is also not an approach for improving the mental and physical burden as described above for hand-washing launders, but provides slipping to clothes during washing to reduce friction, and clothes in washing liquid It is not intended to give a smooth feel to the skin and thereby to make hand washing comfortable. In addition, the anti-recontamination property for mud particles was not sufficient.
Japanese National Patent Publication No. 5-508889 JP-A-1-98697 JP 7-216389 A JP-A-6-179893

  Therefore, the problem to be solved by the present invention is to improve unpleasant factors and physical load generated during hand-washing, that is, "mental and physical burden for those who do laundry", and is excellent in preventing mud particle recontamination. An object of the present invention is to provide a washing method and a granular detergent composition suitable for the method.

  In response to the above problems, the present inventors have found that a specific sulfonic acid-based polymer imparts an appropriate garment slipperiness during hand washing and washing, and has the effect of reducing labor load. The present inventors have found that by changing the relative action sequence with the cleaning component, the mud particle recontamination prevention property can be dramatically improved, and the present invention has been completed.

That is, the present invention
[1] A method for washing an object to be washed in a washing bath comprising an anionic surfactant, a hardness component trapping builder, an alkaline substance, and a sulfonic acid polymer, wherein the sulfonic acid polymer is represented by the following formula (I Is a sulfonic acid polymer having a weight average molecular weight of 1,000,000 to 30,000,000 in a ratio of 50 to 100 mol% in all the constituent monomer units, and all or one in the washing bath. A method for washing an object to be cleaned, wherein the object to be cleaned is brought into contact with an anionic surfactant in which a part is dissolved, and then the sulfonic acid polymer is post-contacted, and

(In the formula, A represents a hydrogen atom or an alkali metal, R ¹ represents a hydrogen atom or a methyl group, and X represents any one of the following formulas (II) to (IV).)

(In the formula, Ph represents a phenylene group.)

(In the formula, m represents 1 to 6.)

(Wherein R ² represents a linear or branched alkylene group having 2 to 8 carbon atoms),
[2] A base detergent particle group containing individually prepared anionic surfactants and a monomer unit represented by the formula (I) described in [1] above in a constituent monomer of 50 to 100 mol% A granular detergent composition obtained by mixing a particle group containing a sulfonic acid polymer having a weight average molecular weight of 1,000,000 to 30,000,000 in a ratio of 70% by weight or more, and [3] 70% by weight of a sulfonic acid polymer having a monomer unit represented by the formula (I) described in [1] in a ratio of 50 to 100 mol% in all the constituent monomer units and having a weight average molecular weight of 100 to 30 million. An additive for a cleaning agent containing the above, having an average particle size of 50 to 500 μm, a mesh opening of 63 μm and a sieve passage of 20% by weight or less, and a sieve residue having a mesh opening of 1400 μm and a residue of 10% by weight or less about The

  According to the washing method of the present invention, it is possible to improve the smoothness between washing clothes at the time of hand-washing and to reduce the labor load of the hand-washing laundry, while further improving the prevention of mud particle recontamination. In addition, by using the granular detergent composition of the present invention, the effect of being able to naturally enjoy the above improvement for hand-washed washers is achieved.

  In the washing method of the present invention, prior to the dissolution of the sulfonic acid polymer, all or a part of the base detergent component including the anionic surfactant, the hardness component trapping builder, and the alkaline substance is dissolved in the washing water. It is characterized by.

  As a method of washing in this way, a method of keeping the above-described order and introducing each into washing water individually may be used. As a more specific example of such a method, for example, a method in which an aqueous solution containing a required amount of an anionic surfactant and a required amount of a sulfonic acid polymer individually is prepared in advance, and sequentially added to washing water, And a method in which a solid or particulate base detergent particle group is introduced directly into washing water, and after partially or completely dissolved, a solid or particulate sulfonic acid polymer is then introduced.

  Further, for example, when using a composition in which a particulate base detergent particle group and a particulate sulfonic acid polymer are mixed together, the washing of the present invention is performed by dissolving the polymer particles. There is a method of performing the process more slowly or gradually than the dissolution of the particle group.

  In short, the washing method of the present invention is not limited to simply adding the anionic surfactant in the cleaning component and the sulfonic acid polymer individually and stepwise into the cleaning water, Even if the anionic surfactant and the sulfonic acid polymer are dissolved, the dissolution progress of the anionic surfactant is higher than the dissolution progress of the sulfonic acid polymer due to the difference in the dissolution rate of the solid or granular material composed of the anionic surfactant and the sulfonic acid polymer. If the dissolution conditions are realized, the effect of the present invention can be obtained even if the dissolution in water starts and progresses at the same time.

  According to the washing method of the present invention, it is possible to improve the smoothness between washing clothes at the time of hand-washing and to reduce the labor load of the hand-washing laundry, and further improve the prevention of mud particle recontamination.

  The present invention is not limited by theory, but these effects in the washing method of the present invention exist between the sulfonic acid polymer of the present invention and a cleaning component such as an anionic surfactant. It is considered that due to some interaction, the affinity of the sulfonic acid polymer itself with the dirt particles is reduced or lost, and the dispersibility of the mud particles is improved. Originally, the order of addition of the components to be cleaned, the dirt particles and the detergent components may be considered not to define the stable state of the composite system formed by them. Although it may be considered that it does not change due to the action sequence of the agent, the time required for the steady state of the adsorption / desorption of the cleaning base, the fibers to be cleaned, and the dirt particles is the time required for general washing If it is interpreted as exceeding the scale of the above, it explains the effect that the action sequence of the cleaning base, which has occurred as described above, can lead to the improvement of the prevention of mud particle recontamination. That is, it is considered that the difference in timing at which the substantial action is caused by each component is contrary to expectation and has a great influence on the cleaning result.

<Sulfonic acid polymer>
The sulfonic acid polymer used in the present invention is a vinyl monomer unit having a sulfonic acid residue in the side chain, that is, the formula (I):

(In the formula, A represents a hydrogen atom or an alkali metal, R ¹ represents a hydrogen atom or a methyl group, and X represents any one of the following formulas (II) to (IV).)

(In the formula, Ph represents a phenylene group.)

(In the formula, m represents 1 to 6.)

(In the formula, R ² represents a linear or branched alkylene group having 2 to 8 carbon atoms.)
Is a sulfonic acid polymer having a weight average molecular weight of 1,000,000 to 30,000,000 in a monomer unit at a ratio of 50 to 100 mol%. The ratio of the constituent monomer units in the polymer is 50 mol% or more from the viewpoint of mud particle dispersibility, but is preferably 70 mol% or more, more preferably 80 mol% or more because of better mud particle dispersibility. Is more preferable, 85 mol% or more is still more preferable, and 90 mol% or more is still more preferable. In addition, those substantially free of other constituent monomers are also suitable as the sulfonic acid-based polymer used in the present invention.

A in the formula (I) represents a hydrogen atom or an alkali metal, and R ¹ represents a hydrogen atom or a methyl group. Preferably, R ¹ is a hydrogen atom. X in the formula (I) is preferably a group that does not impair the high polymerizability of the monomer unit represented by the above formula (I), such as a phenylene group, an ester alkylene group, or an amidoalkylene group. X in I) is preferably any group of formulas (II) to (IV).

(In the formula, Ph represents a phenylene group.)

(In the formula, m represents 1 to 6.)

(In the formula, R ² represents a linear or branched alkylene group having 2 to 8 carbon atoms.)

  In the monomer unit represented by the formula (I) constituting the sulfonic acid polymer, X in the formula (I) may be any one of the above formulas (II) to (IV), and these are mixed. You may do it.

  When X is a group represented by the formula (III), m in the formula (III) is 1-6.

When X is an amide alkylene group represented by the formula (IV), R ² in the formula (IV) is an alkylene group having 2 to 8 carbon atoms, and the alkylene group is either a straight chain or a branched chain It may be. Among these, those in which R ² is an alkylene group having a branched chain are preferable because they are easily available. Furthermore, the monomer unit of the formula (I) is preferably a group in which X in the formula (I) is a group represented by any one of the following formulas (V) to (VII) because the polymerizability is good. More preferably, the monomer unit of the formula (I), wherein X in the formula (I) is a group represented by the following formula (V) is a highly versatile material and has extremely good polymerizability. Therefore, it is preferable.

As the monomer unit represented by the formula (I), those in which R ¹ in the formula (I) is a hydrogen atom and X is an amide alkylene group represented by the formula (V) It is more suitable not only from general versatility but also from the standpoint of clothing slippage after polymerization into a sulfonic acid polymer and prevention of mud particle recontamination.

  The monomer units represented by the formula (I) in the constituent monomers may be all in the acid form, or may be in the salt form in which all or a part thereof is neutralized. When a part or all of the monomer units represented by the formula (I) in the constituent monomer is a neutral salt form, a monovalent cation is preferable as a counter ion for neutralizing the sulfonic acid residue. is there. More specifically, alkali metal ions are preferred, and among these, salt forms neutralized in the form of Na and K salts are more preferred.

  As a constituent monomer other than the monomer unit represented by the formula (I), any vinyl comonomer can be used for copolymerization while closely examining the effects of the present invention.

  As the comonomer that can be used in the present invention, acrylic acid, methacrylic acid, acrylamide, N-vinylacetamide, maleic monomer (maleic anhydride, maleic acid, maleic acid monoester, maleic acid monoamide, or two or more kinds thereof) And a salt thereof, itaconic acid and a salt thereof, and the like, and one or more selected from these may or may not be contained as a comonomer. Preferred comonomers include those having high copolymerizability with the monomer unit represented by formula (I). For example, acrylic acid or a salt thereof is suitable as a comonomer constituting the sulfonic acid polymer of the present invention. . In the sulfonic acid-based polymer of the present invention, the molar ratio of acrylic acid or a salt thereof is 30 mol% or less, more preferably 20 mol% or less, more preferably 10 mol% or less, more preferably from the viewpoint of preventing mud particle recontamination. Preference is given to 5 mol% or less. For example, a copolymer composed of 70 to 100 mol% of a monomer unit represented by the formula (I) and 0 to 30 mol% of acrylic acid or a salt thereof is suitable as the sulfonic acid-based polymer used in the present invention.

  When the sulfonic acid polymer of the present invention contains acrylamide as a constituent comonomer, the molar ratio of acrylamide used in the present invention is preferably 10 mol% or less, more preferably 8 from the viewpoint of preventing mud particle recontamination. The mol% or less, more preferably 6 mol% or less, and further preferably 4 mol% or less.

  When the sulfonic acid polymer contains N-vinylacetamide as a constituent comonomer, the molar ratio of N-vinylacetamide is preferably 10 mol% or less, more preferably 8 mol, from the viewpoint of mud recontamination prevention. % Or less, more preferably 6 mol% or less, still more preferably 4 mol% or less.

  The sulfonic acid-based polymer expresses a comfortable sliding property when washing by hand. From the viewpoint of this effect, the weight average molecular weight is 1,000,000 or more, but since it can impart high smoothness, it is preferably 1.2 million or more, more preferably 1.5 million or more, still more preferably 2 million or more, and further preferably. Is 3 million or more, more preferably 5 million or more, and more preferably 6 million or more. The average molecular weight is preferably 30 million or less, more preferably 25 million or less, and still more preferably 20 million or less from the viewpoint of availability.

  The molecular weight is measured by gel permeation chromatography (hereinafter referred to as GPC method) under the following measurement conditions, and the molecular weight in terms of polyethylene oxide (PEO) is used as the measurement value.

[GPC method measurement conditions]
Column is PW / GMPWXL / GMPWXL (manufactured by Tosoh Corporation), 0.2M phosphate buffer (KH ₂ PO ₄ , Na ₂ HPO ₄ , pH = 7) / CH ₃ CN = 9/1 (weight ratio) ), Column temperature: 40 ° C., flow rate: 1 mL / min, and sample concentration of 10 to 100 μg / mL. The detector uses RALLS (Right Angle Laser Light Scattering).

  In order to obtain sufficient smoothness during hand washing, the ratio of the sulfonic acid polymer in the total cleaning composition is 0 on the basis of the total cleaning agent after mixing the sulfonic acid polymer-containing particles composed of the polymer. 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.3% by weight or more, still more preferably 0.5% by weight or more, and 0.8% by weight or more, still more preferably 1. 0% by weight or more, more preferably 1.2% by weight or more is suitable. Moreover, from the point of giving an appropriate feel during hand washing, the ratio of the sulfonic acid polymer is 10% by weight or less, preferably 8% by weight or less, more preferably 5% by weight or less, still more preferably 4% by weight or less, More preferably, it is 3.5% by weight or less, more preferably 3% by weight or less, and particularly preferably 2.5% by weight or less. Furthermore, since the smoothness is sufficient and appropriate at the time of hand washing, the ratio of the sulfonic acid-based polymer of the present invention in the total detergent composition is preferably 0.05 to 5 on the basis of the total detergent containing the polymer. 10% by weight, more preferably 0.1 to 8% by weight, still more preferably 0.3 to 5% by weight, still more preferably 0.5 to 4% by weight, still more preferably 1.2 to 3% by weight. .

  Further, when the particle group containing a sulfonic acid polymer is used as an additive for a cleaning agent, the amount of the polymer used at the time of cleaning is the same as that of the sulfonic acid polymer of the present invention in the entire cleaning composition described above. The ratio is preferably the same.

  The method for synthesizing the sulfonic acid polymer used in the present invention is not particularly limited. Examples of such sulfonic acid-based polymers include cross-linked polymers and non-cross-linked polymers, but those having a lower degree of cross-linking are preferred from the standpoint of developing smoothness. A method in which formation of a crosslinked structure hardly occurs is more preferable.

  The sulfonic acid polymer used in the present invention can be synthesized by a method such as radical polymerization, anionic polymerization, or cationic polymerization.

  When synthesizing by radical polymerization, a peroxide initiator such as potassium persulfate, ammonium persulfate, sodium persulfate, t-butyl hydroperoxide, or hydrogen peroxide may be used as the radical polymerization initiator. Azo initiators such as 2,2'-azobis (2-amidinopropane) dihydrochloride may be used, and these may be reduced with sodium sulfite, sodium bisulfite, ferrous sulfate, L-ascorbic acid, etc. A redox initiator system may be used in combination with an agent, or polymerization may be initiated by irradiation with ultraviolet rays, electron beams, γ rays, or the like. In addition, the usage-amount of these polymerization initiators is preferably 0.0001 to 5 mol%, more preferably 0.001 to 1.5 mol%, and still more preferably based on the monomer used for polymerization or copolymerization. 0.01 to 0.5 mol%.

  In addition, when synthesized by an anionic polymerization method, as a polymerization initiator, an alkali metal aromatic complex such as naphthyl sodium, an alkali metal such as lithium, sodium or potassium, n-butyllithium, t-butyllithium, methyllithium Alternatively, an organic lithium compound (alkyl lithium compound) such as fluorenyl lithium may be used, or an organic magnesium compound, preferably a Grignard compound such as phenyl magnesium bromide or butyl magnesium bromide, or dibenzyl magnesium, dibutyl magnesium or Diorganomagnesium compounds such as benzylpicolylmagnesium may be used. In addition, the usage-amount of these polymerization initiators is 0.0001-5 mol% with respect to the monomer with which it uses for superposition | polymerization or copolymerization, More preferably, it is 0.001-1.5 mol%, More preferably 0.01 to 0.5 mol%.

  On the other hand, in the case of synthesizing by a cationic polymerization method, a Bronsted acid such as trifluoroacetic acid, trichloroacetic acid, sulfuric acid, methanesulfonic acid trifluoromethanesulfonic acid, or a water / boron trifluoride may be used as a polymerization initiator. Bronsted acids such as water / boron trichloride, water / aluminum chloride, water / aluminum bromide, water / tin tetrachloride, trichloroacetic acid / tin tetrachloride, hydrogen chloride / boron trichloride or hydrogen chloride / aluminum trichloride / Lewis acid mixtures may be used, organic cations such as trityl cation and tropylium cation, or mixtures producing oxocarbenium ions such as acetyl chloride / silver hexafluoroantimonate or acetyl chloride / silver perchlorate. It is done. In addition, the usage-amount of these polymerization initiators is 0.0001-5 mol% with respect to the monomer with which it uses for superposition | polymerization or copolymerization, More preferably, it is 0.001-1.5 mol%, More preferably 0.01 to 0.5 mol%.

  As a polymerization method for obtaining the sulfonic acid-based polymer used in the present invention, bulk polymerization or precipitation polymerization can be performed, but in order to obtain a polymer having higher slip performance, the polymerization can be easily controlled. From the viewpoint, aqueous solution polymerization or reverse phase suspension polymerization is preferred.

<Sulfuric acid polymer-containing particles>
The sulfonic acid-based polymer-containing particles used in the granular detergent composition of the present invention or used as an additive for detergent are base detergent particles containing an anionic surfactant, a hardness component capturing builder, and an alkaline substance. A detergent composition is formed together with the group, and after being put into water, it exhibits smoothness by dissolving. Therefore, in order to develop the smoothness, it is preferable to dissolve within the washing time. On the other hand, compared with the base detergent particles containing an anionic surfactant, hardness component trapping builder, and alkaline substance, the mud particle recontamination prevention property is improved when the dissolution of the sulfonic acid polymer-containing particles is slow or gradual. Improved. That is, the sulfonic acid-based polymer-containing particle group preferably has a low dissolution rate as a relative relationship with the base detergent particle group, while having sufficient particle solubility for detergent use. Thus, as a method of obtaining a sulfonic acid polymer-containing particle group having a preferable dissolution rate, a method of adjusting the molecular weight of the sulfonic acid polymer from the above-mentioned preferable range to a specific molecular weight, the sulfonic acid polymer containing A method of adjusting the particle size of the particle group or a treatment such as a processing on the particle surface, and examining the species / amount of components other than the sulfonic acid polymer constituting the particle group together with the sulfonic acid polymer Examples include a method for controlling dissolution of the entire group. Among them, as a method for obtaining a sulfonic acid polymer-containing particle group having a preferable dissolution rate, the method of adjusting the molecular weight of the sulfonic acid polymer and the method of adjusting the particle size of the sulfonic acid polymer-containing particle group have simple steps. It is preferable from the point of being.

  The method for obtaining a sulfonic acid polymer-containing particle group having a preferred particle size is not particularly limited, and any method can be used as long as the particle group having a particle size giving the preferred dissolution rate as described above can be obtained. . As a method for obtaining a sulfonic acid polymer-containing particle group having a preferable particle size, for example, a method of fractionating using a sieve, a method of performing rolling drying granulation while spraying the aqueous polymer solution using means such as fluid drying When the polymer is polymerized in a reversed-phase suspension system, in the polymerization process, the suspension system to be used as a polymerization field and / or stirring conditions such as a stirring blade and a stirring speed are adjusted to generate the polymer. Examples thereof include a method for controlling the particle size and particle size distribution of the polymer particle group, and a method for combining these methods. Among these, particle size control in the polymerization stage of the polymer is preferable from the point that a new process is not included or the polymer can be used effectively.

  As the sulfonic acid polymer-containing particle group used in the granular detergent composition of the present invention or used as an additive for detergent, it was obtained as particles having a high polymer content as in the above-mentioned reverse phase suspension polymerization. From the standpoint that no undissolved particles are produced during washing, the average particle size is 500 μm or less, preferably 400 μm or less, more preferably 350 μm or less, and even more preferably 300 μm or less.

  The average particle size is preferably 50 μm or more, more preferably 70 μm or more, still more preferably 90 μm or more, and even more preferably 110 μm or more, for the reason that the dissolution is slow and the mud particle recontamination prevention property is excellent. .

  The average particle diameter is preferably 50 to 500 μm, more preferably 70 to 400 μm, and still more preferably 90 to 350 μm.

  Even if the average particle size is the same, the dissolution of the entire particle group is slower if the proportion of the finer portion is smaller in the distribution of the fraction located on the finer side than the average particle size. From this, the 63 μm sieve passage of the sulfonic acid polymer-containing particles used in the granular detergent composition of the present invention or used as an additive for the detergent is preferably 20% by weight or less, more preferably It is 15% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less.

  Even if the average particle size is the same, if the proportion of the coarse particle size fraction is small, the undissolved particles will not be produced during washing. From this, the 1400 μm sieve residue of the sulfonic acid polymer-containing particles used in the granular detergent composition of the present invention or as an additive for detergent is preferably 10% by weight or less, more preferably It is 8% by weight or less, more preferably 6% by weight or less, more preferably 4% by weight or less, and further preferably 2% by weight or less.

Particle size and particle size measurement method Using a twelve-stage sieve and a tray with a mesh opening of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 180 μm, 125 μm, 90 μm, 63 μm and 45 μm (made by HEIKO SEISAKUSHO) ), And 100 g of the sample is shaken for 10 minutes (tapping: 156 times / minute, rolling: 290 times / minute), and then the weight of particles remaining on the saucer and each sieve is measured. The sieve opening with a cumulative weight ratio of 50% or more (from the fine particle side) is set to a μm, the sieve opening one step larger than a μm is set to b μm, and the integrated weight ratio from the tray to the a μm sieve is c %, And when the weight ratio on the a μm sieve is d%,
(Average particle size) = 10 ^A
A = (50- (cd / (log b-log a) x log b)) / (d / (log b-log a))
Calculate according to

(63 μm sieve passage) = weight ratio on the 45 μm sieve + weight ratio on the tray (1400 μm sieve residue) = the ratio of the total weight on the sieve having a sieve opening of 2000 μm and 1400 μm

  The sulfonic acid polymer-containing particle group may or may not contain one or more components other than the sulfonic acid polymer as long as the effects of the present invention are not impaired.

  For the trace components such as unreacted monomers, polymerization initiators, dispersants, solvents and by-products resulting from them carried over from the sulfonic acid polymer polymerization step, moisture, etc., the effect of the present invention is achieved. There is no particular limitation as long as it is not lost.

  The content of the sulfonic acid-based polymer in the sulfonic acid-based polymer particle group is originally preferably a high content rate from the viewpoint of reducing the amount added as the particle group, and the ratio of the sulfonic acid-based polymer contained in the particle group is Is 70% by weight or more, preferably 75% by weight or more, more preferably 80% by weight or more, still more preferably 85% by weight or more, and still more preferably 90% by weight or more. In the case of a sulfonic acid polymer having a weight average molecular weight of 1 million or more, the higher the content ratio of the polymer in the particle group, the slower the dissolution rate. Also excellent in terms of sex.

  However, in mixing the particles of the sulfonic acid polymer-containing particles of the present invention and the base detergent particles, according to the specified amount ratio of both, according to the purpose such as mixing both accurately, Use the sulfonic acid polymer-containing particles that are mixed and added only in a small amount after being diluted in advance by mixing with the third granular material, or add other components during the preparation of the sulfonic acid polymer-containing particles. In some cases, the measurement accuracy may be improved by diluting the polymer ratio. More preferably, in the latter case, the polymer ratio in the sulfonic acid-based polymer-containing particle group is lowered, but may be arbitrarily implemented as long as the original effect of the present invention is not impaired.

<Base detergent particles>
The base detergent particle group used in the granular detergent composition of the present invention contains at least an anionic surfactant, and preferably further contains a hardness component trapping builder and an alkaline substance. It may contain a cleaning base of the kind / amount necessary to exhibit the minimum functions as a cleaning agent for clothing alone, and one additional cleaning agent for clothing It may be necessary to add or add the above components.

  In order to obtain the effects of the present invention, the base detergent particle group used together with the sulfonic acid polymer-containing particle group has high solubility.

  Since the dissolution rate is rapid, the average particle size of the base cleaning agent particle group is preferably 600 μm or less, and more preferably 550 μm or less. Further, it is more preferably 500 μm or less, further preferably 450 μm or less, and further preferably 400 μm or less.

  Further, from the viewpoint of the physical properties of the powder, the average particle size of the base cleaning agent particle group is preferably 100 μm or more, more preferably 125 μm or more, further preferably 150 μm or more, further preferably 175 μm or more, and further preferably 200 μm or more. is there.

  The range of the average particle size of the base detergent particle group is preferably 100 to 600 μm, more preferably 125 to 550 μm, still more preferably 150 to 500 μm, still more preferably 175 to 450 μm, still more preferably 200 to 400 μm. .

  The particle size is measured using a rot tap machine as in the case of the sulfonic acid polymer-containing particles.

  The method for preparing the base detergent particles is not particularly limited as long as it is a known method such as a spray drying method or a tumbling granulation method. Among these, the spray drying method is a production method that tends to be hollow particles, and is therefore a preferable preparation method in that the dissolution rate of the base detergent composition particles is sufficiently high.

  Moreover, since the base detergent particle group used in the granular detergent composition of the present invention has a high dissolution rate, the bulk specific gravity measured by the method described in JISK3362 is preferably 1.0 or less, more preferably 0.9 or less, more preferably 0.8 or less, more preferably 0.7 or less, and still more preferably 0.65 or less. On the other hand, from the viewpoint of ease of portability, ease of storage, ease of measurement, etc. in the distribution stage as a commercial product of granular detergent compositions and in situations where consumers actually use, the granular detergent composition The product preferably has a high bulk specific gravity, preferably 0.25 or more, more preferably 0.3 or more, still more preferably 0.4 or more, still more preferably 0.45 or more, and 0.3 to 0 .9 is more preferable, and 0.4 to 0.8 is more preferable.

<Anionic surfactant>
Examples of the anionic surfactant used in the washing method and granular detergent composition of the present invention include alkylbenzene sulfonate, higher alcohol sulfate ester salt, α-olefin sulfonate salt, α-sulfo fatty acid short chain alkyl ester salt And those having an anionic hydrophilic group having a sulfuric acid-based structure and a sulfonic acid-based structure such as a polyalkoxylated higher alcohol sulfate ester salt. More preferably, alkylbenzene sulfonate can be mentioned as an anionic surfactant suitable for this invention from the point of economical efficiency and versatility.

  The anionic surfactant contained in the cleaning composition of the present invention is preferably 8% by weight or more, more preferably 10% by weight or more, and further preferably 12% by weight or more from the viewpoint of cleaning performance and foaming. More preferably, it is 14% by weight or more, more preferably 16% by weight or more, and further preferably 18% by weight or more.

  On the other hand, the anionic surfactant contained in the total cleaning composition is 50% by weight in the total cleaning composition for the purpose of avoiding excessive foam formation and ensuring the freedom of blending of the entire composition. The content is preferably 45% by weight or less, more preferably 40% by weight or less, still more preferably 37% by weight or less, and still more preferably 35% by weight or less.

  The content of the anionic surfactant is preferably 8 to 50% by weight, more preferably 10 to 45% by weight, and still more preferably, in the cleaning composition contained in the washing method and the granular cleaning composition of the present invention. It is 12 to 40% by weight, more preferably 14 to 37% by weight, and further preferably 16 to 35% by weight.

<Alkylbenzene sulfonate>
Examples of the alkylbenzene sulfonate used in the present invention include a hard type in which an alkyl chain has a branched structure, a soft type in which a linear structure is used, and the like. From the viewpoint of biodegradability, the alkylbenzene sulfonate is preferably a straight-chain type (soft type). The alkylbenzene sulfonate is obtained by sulfonating alkylbenzene. In this case, the alkylbenzene used as a raw material is synthesized by various synthesis methods. However, the content of phenyl isomers varies depending on the synthesis method, and the physical properties as a surfactant after being derived into alkylbenzene sulfonates. To affect. From the viewpoint of detergency and productivity, alkylbenzene sulfonates using alkylbenzene synthesized by an α-olefin method as a raw material are preferable.

  Also, from the viewpoint of detergency and hard water resistance, alkylbenzene sulfonates such as methyl branched alkyl type and methyl-substituted benzene type can be suitably used.

  The alkylbenzene sulfonate is obtained by sulfonating the above alkylbenzene with sulfurous acid gas or fuming sulfuric acid and neutralizing with an alkaline component such as sodium hydroxide or potassium hydroxide. The salt used is not particularly limited as long as it is a monovalent cation such as an ammonium salt or an amine salt in addition to an alkali metal salt such as a lithium salt, a potassium salt, or a sodium salt. Alkaline earth metal salts such as calcium and magnesium have the effect of precipitating alkylbenzene sulfonic acid, and therefore are preferably as small as possible. About a counter ion, an alkali metal salt is preferable from a viewpoint of storage stability and cost, and a sodium salt is still more preferable especially.

  The alkylbenzene sulfonate contained in the laundry method and granular detergent composition of the present invention is blended in the range described as the anionic active agent.

<Hardness component capture builder>
The hardness component trapping builder used in the present invention traps polyvalent metal cations such as Ca ²⁺ and Mg ²⁺ in cleaning water that inhibits the cleaning action and the like by the surfactant, thereby improving the cleaning performance. It is blended with.

  Examples of hardness component capturing builders suitable for the present invention include crystalline aluminosilicates such as zeolite A type, X type, Y type and P type, condensed phosphates such as tripolyphosphate and pyrophosphate, Water-soluble organic acid salts represented by low-molecular carboxylates such as acid salts and fumarate are exemplified. As the water-soluble organic acid salt, a base having a large cation exchange capacity and / or a large pKCa is preferable, and more specifically, methyliminodiacetate, iminodisuccinate, ethylenediamine disuccinate, taurine diacetate, hydroxyethyl Iminodiacetate, β-alanine diacetate, hydroxyiminodisuccinate, methylglycine diacetate, glutamate diacetate, asparagine diacetate, serine diacetate, and the like are preferable from the viewpoint that high detergency can be expected.

  Of these hardness component trapping builders, condensed phosphates, crystalline aluminosilicates, and mixtures thereof are preferred from the standpoint of economy.

  Condensed phosphates are preferred because they can be easily blended into the aqueous slurry when the detergent particles are prepared by spray drying the aqueous slurry. Furthermore, tripolyphosphate is preferable in that it has a high cation exchange capacity. More preferred as the condensed phosphate is sodium tripolyphosphate.

  Crystalline aluminosilicates are preferred because they can exhibit the effects of formulation aids such as surface modification of the detergent particles, or particle property modifiers. More preferable as the crystalline aluminosilicate is the zeolite A type, and among them, the primary particle diameter of the crystal having an average particle diameter of 0.5 to 10 μm has a hardness component capturing ability and / or a particle property modifying ability. It is preferable from the point.

  The hardness component capture builder content contained in the washing method and granular detergent composition of the present invention is preferably 5% by weight or more, more preferably 8% by weight from the viewpoint of securing a sufficient hardness capture capacity. As mentioned above, More preferably, it is 10 weight% or more, and it is still more preferable that it is 12 weight% or more. In addition, the hardness component capture builder content is preferably 50% by weight or less, more preferably 40% by weight in the sense that the blending freedom of the entire granular detergent composition including other cleaning bases is ensured. Hereinafter, it is more preferably 35% by weight or less, further preferably 30% by weight or less, and further preferably 25% by weight or less. Further, the blending amount of the hardness component capturing builder in the whole granular detergent composition is preferably 5 to 40% by weight, more preferably 8 to 35% by weight, and further preferably 10 to 30% by weight.

<Alkaline substances>
The alkaline substance used in the present invention is not particularly limited, and a known alkaline substance can be used. The alkaline substance of the present invention refers to a group of compounds that increase the pH of washing water. In the cleaning system, the soil (more preferably, fatty acid) is soaped to self emulsify and disperse to remove and remove the soil from the substrate. A cleaning effect such as action can be obtained.

  Examples of the alkaline substance include hydroxides, carbonates, hydrogen carbonates, and silicates. Examples of the counter ion include alkali metals such as lithium, potassium, and sodium.

  As the alkaline substance used in the present invention, a weak acid-strong base salt is preferable because it has a large function of buffering the washing system in a pH range suitable for washing, and as an inorganic compound, carbonate, bicarbonate, silicate and These mixtures are preferred. The counter ion is not particularly limited, but potassium salt and sodium salt are preferable from the viewpoint of storage stability and cost, or from the viewpoint of improving the ionic strength of the washing liquid and favorably acting on sebum dirt cleaning, etc. Preferred is the sodium salt.

  Sodium carbonate, sodium hydrogen carbonate, sodium silicate and a mixture thereof are more preferably used as the alkaline substance from the viewpoint of having a preferable pH buffer range, a high cleaning effect, and economical efficiency.

  The content of the alkaline substance contained in the washing method and granular detergent composition of the present invention is preferably 7% by weight or more, more preferably 7% by weight or more in the granular detergent composition from the viewpoint that a high cleaning effect is obtained. Is 8% by weight or more, more preferably 10% by weight or more, more preferably 12% by weight or more, and still more preferably 15% by weight or more. In addition, from the viewpoint of skin irritation and safety for the laundry during hand washing, the content of the alkaline substance is 40% by weight or less, preferably 35% by weight or less, more preferably 31% by weight or less, Preferably it is 27 weight% or less.

  The more preferable range of the content of the alkaline substance contained in the washing method and granular detergent composition of the present invention is 7 to 40% by weight, preferably 8 to 35% by weight, more preferably in the granular detergent composition. Is 10 to 31% by weight, more preferably 12 to 27% by weight.

<Other cleaning ingredients>
As other cleaning components used in the present invention, arbitrary components can be blended as long as the effects of the present invention are not impaired.

(Other surfactants)
The cleaning method and / or cleaning composition of the present invention may contain a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like as the surfactant other than the anionic surfactant.

  Examples of the cationic surfactant include monoalkylammonium quaternary salts and dialkylammonium quaternary salts.

  Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene glycol represented by Pluronic (trade name), polyoxyethylene alkylamine, and higher fatty acids. Examples include alkanolamides, polyoxyalkylene higher fatty acid alkanolamides, alkyl glucosides, alkyl glucose amides, alkyl amine oxides, higher fatty acid alkylene diamine-N-amide-N′-dialkyl oxides, and the like.

  Examples of amphoteric surfactants include betaine, amidopropyl betaine, sulfobetaine and the like.

(Distributed system)
The cleaning method and / or cleaning composition of the present invention may contain any dispersion system. Examples of the dispersion system include polyethylene glycol, polycarboxylic acid polymer, polyvinyl alcohol, polyvinyl pyrrolidone, and dispersant systems such as carboxymethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, hydroxyethylcellulose and the like, and mixed systems thereof. Can be mentioned.

(enzyme)
The cleaning method and / or cleaning composition of the present invention may contain any enzyme. Examples of the enzyme include protease, lipase, cellulase, amylase, mannanase and the like. Furthermore, from the viewpoint of washing performance, the combined use of cellulase and protease is preferable.

(Fluorescent brightener)
The cleaning method and / or cleaning composition of the present invention may contain any fluorescent whitening agent. Examples of the optical brightener include biphenyl type and aminostilbene type.

(Bleaching system)
The cleaning method and / or cleaning composition of the present invention may contain an optional bleaching system in order to reinforce the function of recovering stain stains and recovering yellowing of clothes. As the bleaching system, an oxygen-based bleaching system that hardly causes discoloration of the colored pattern dye is preferable. As such a bleaching system, a system containing a peroxide compound typified by sodium percarbonate or sodium perborate as a hydrogen peroxide generation source, or tetraacetylethylenediamine, nonanoyloxybenzenesulfonate or decanoyloxybenzenesulfonate is used. And a bleaching system comprising a bleach activating species represented by an organic peracid precursor such as

(Other ingredients)
The cleaning method and / or cleaning composition of the present invention preferably contains an inorganic salt such as sulfate in order to adjust the ionic strength of the cleaning liquid. Furthermore, inexpensive sodium sulfate is preferably used because it can exhibit functions such as a particulate agent and a bulking agent.

  In addition, sulfite, thiosulfate, etc., as a reducing agent for active chlorine that may be present in tap water, white carbon and amorphous silica compounds as surface modifiers for detergent particles, clay minerals such as bentonite, You may use as a clothing softening agent using a solid lubrication effect | action.

Disclosure of test method <Evaluation of prevention of recontamination of detergent>
The recontamination prevention evaluation not particularly described was carried out by the following method.
Mud particles (Kanuma red clay for gardening that passed through a 200 mesh sieve in a beaker containing 1000 mL of water used at 20 ° C. (CaCl ₂ : 55.42 mg / L, MgCl ₂ .6H ₂ O: 43.51 mg / L) Purchased from Kuniyukien Co., Ltd. (10, Zenshocho, Izumi City, Osaka)] 2.5 g was added and dispersed uniformly, and then this dispersion was transferred to a sample cup of Terg-O-Tometer at 20 ° C. Next, 5.0 g of the detergent composition and 5 pieces of white cotton cloth cut into a 6 cm × 6 cm square (standard product selected by the Japan Oil Chemistry Association, # 2023 cloth sold by the Laundry Science Association) are put in at the same time. After stirring and washing for 10 minutes at a rotational speed of 100 ± 5 r / min, the white cotton cloth was taken out and lightly squeezed by hand so that the water content was 200% by weight or less. CaC _{2: 55.42mg / L, MgCl 2} · 6H 2 O: 43.51mg / L) placed in a 1000 mL, rinsed for three minutes with a Terg-O-Tometer (rotational speed 100 ± 5r / min), the rinsing operation The white cloth taken out was air-dried and ironed, and the reflectance at 460 nm was measured (manufactured by Nippon Denshoku Industries Co., Ltd., colorimetric color difference meter). The rate (%) was determined.
Recontamination prevention rate (%) = [(reflectance of white cotton cloth after test) / (reflectance of white cotton cloth before test)] × 100

<Slip property evaluation method>
In a washbasin made of polypropylene (made by Yazaki) of 2 L of hard water (Ca / Mg molar ratio 7/3) corresponding to 8.9 mg CaCO ₃ / L adjusted to 25 ° C. with a diameter of 30 cm, a depth of 13 cm and a capacity of 8.2 L After putting 15 g of the cleaning composition into water, stirring was continued by hand to such an extent that water did not scatter from the basin. After 30 seconds from the start of stirring, a 100% cotton T-shirt (Gunze white, L size) was soaked in the washing solution in the wash basin so that the entire T-shirt was sufficiently wet. Grip with both hands and rub the chests of the T-shirts together. At this time, the parts to be rubbed were taken out from the washing liquid. Every time 3 to 5 times of rubbing, the portion to be rubbed against the washing solution was immersed. The ease of rubbing at the time of rubbing is determined as smoothness, and it is set to 1 to 5 ranks. When this evaluation was carried out using only the above-mentioned adjustment water, the wrinkles of the T-shirt hindered the smoothness, and since there were no bubbles in the rubbing part, it was very difficult to rub and the smoothness was poor. At this time, the smoothness was set to 1. The status of each rank is shown below.

Rank 1: The slipperiness is very low, there is a squeaky feeling, and hand washing is very difficult.
Rank 2: Low smoothness, squeaky feeling, and difficult to wash by hand.
Rank 3: The smoothness is moderate and there is no feeling of squeezing, and hand washing can be performed.
Rank 4: High smoothness, no squeaky feeling and easy to wash by hand.
Rank 5: Very smooth, no squeaky feeling, and easy to wash by hand.

  In the above test, the average value of the evaluation results by six professional panelists was obtained and used as the evaluation value.

<Solubility evaluation>
In a 1 L beaker, 1000 mL of tap water adjusted to 10 ° C. and a stirrer made of fluororesin having a diameter of about 8 mm and a length of about 35 mm were added, and a magnetic stirrer (manufactured by Shimadzu Corporation, product name: SST-172 type). Was used so that the indicated value of the rotational speed was maintained at 800 ± 10 rpm. Thereto, 1 g of the detergent composition was added, and stirring was continued for 10 minutes after the addition. After completion of the stirring, the residue was collected by filtering the water in the beaker with a 200-mesh wire mesh. The obtained residue was dried together with a wire mesh at 105 ° C. for 30 minutes, and the residue weight was obtained from the difference between the wire mesh weight measured in advance and the weight after drying. [%] Was calculated.
Water-insoluble content [%] = [(residue weight) / (test detergent weight)] × 100

Preparation example 1 of sulfonic acid polymer-containing particle group
When sugar ester (Mitsubishi Chemical Foods Co., Ltd., product name: S-770) 6.00 g was dissolved in cyclohexane 800 g and heated to 70 ° C. in a nitrogen atmosphere, 2-acrylamido-2-methylpropanesulfonic acid was obtained. Ion exchange 600 g, sodium hydroxide 160 g, acrylic acid 10 g, 2,2′-azobis (2-methylpropionamidine) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd., product name: V-50)] A solution dissolved in 510 g of water was dropped and dispersed over 1 hour, and the mixture was further stirred for 30 minutes. Only the aqueous phase is separated from the azeotropic reflux liquid, and the mixture is allowed to cool when the water content is reduced to 30% by weight. The obtained solid granular material is sufficiently dried under reduced pressure to give colorless particles as sulfonic acid polymer-containing particles. Group A, 672 g (99.4%) was obtained.

  The polymer of the particle group A had a weight average molecular weight of 5 million as measured by the method described in the present application. In addition, the average particle size of the particle group A was 197 μm, the passing through 63 μm sieve was 0.7% by weight, and the remaining 1400 μm sieve was 0.6% by weight.

Preparation Example 2
When sugar ester (Mitsubishi Chemical Foods Co., Ltd., product name: S-770) 6.00 g was dissolved in cyclohexane 800 g and heated to 70 ° C. in a nitrogen atmosphere, 2-acrylamido-2-methylpropanesulfonic acid 622 g, sodium hydroxide 160 g, 2,2′-azobis (2-methylpropionamidine) dihydrochloride (Wako Pure Chemical Industries, Ltd., product name: V-50) 24 g dissolved in ion-exchanged water 510 g Was added dropwise over 1 hour to disperse and stirred for an additional 30 minutes. Only the aqueous phase was separated from the azeotropic reflux liquid, allowed to cool when the water content was reduced to 30% by weight, and the resulting solid particulate matter was sufficiently dried under reduced pressure to give a sulfonic acid polymer-containing particle group G as colorless particulate matter. 681 g (99.0%) were obtained.

  The polymer of the particle group G had a weight average molecular weight of 1,200,000 measured by the method described in the present application. In addition, the average particle size of the particle group G was 145 μm, the passing through 63 μm sieve was 1.6 wt%, and the remaining 1400 μm sieve was 0.5 wt%.

Preparation Example 3
Except that 24 g of 2,2′-azobis (2-methylpropionamidyne) dihydrochloride in Preparation Example 2 was changed to 36 g, the same operation as in Preparation Example 2 was performed to obtain sulfonic acid polymer-containing particles as colorless particulates. Group H, 684 g (99.4%) was obtained.

  The polymer of particle group H had a weight average molecular weight of 700,000 measured by the method described in the present application. In addition, the average particle size of the particle group H was 132 μm, the amount passing through the 63 μm sieve was 1.7% by weight, and the remaining part of the 1400 μm sieve was 0.6% by weight.

Preparation Example 4
Except that 10 g of acrylic acid in Preparation Example 1 was changed to 12 g of N-vinylacetamide, the same operation as in Preparation Example 1 was performed to obtain a sulfonic acid polymer-containing particle group I.D. 667 g (98.7%) were obtained.

  The polymer of particle group I had a weight average molecular weight of 5 million as measured by the method described herein. In addition, the average particle size of the particle group I was 188 μm, the amount passing through the 63 μm sieve was 0.8% by weight, and the amount remaining on the 1400 μm sieve was 0.8% by weight.

Example of preparation of base detergent particle group 210 kg of 50% by weight sodium dodecylbenzenesulfonate aqueous solution, 87.5 kg of 40% by weight No. 2 sodium silicate aqueous solution, 50 kg of sodium carbonate, 50 kg of sodium tripolyphosphate, 152 kg of sodium sulfate, 60% by weight of polyethylene 1.67 kg of an aqueous solution of glycol (average molecular weight 13000), 5 kg of 40 wt% acrylic acid / maleic acid copolymer aqueous solution, 1 kg of DM type fluorescent dye, 1 kg of carboxymethylcellulose and water were mixed to prepare a uniform slurry of 50 wt% water. . The slurry was then dried by spray drying to obtain a detergent fabric. Furthermore, 90 parts by weight of the obtained detergent dough and 10 parts by weight of zeolite were mixed using a concrete mixer (manufactured by Koyo Machine Industry Co., Ltd.) to obtain a base detergent particle group A containing 10% by weight of water. . The average particle diameter was 251 μm, and the bulk specific gravity of JISK3362 was 0.45. The composition of the obtained cleaning agent particle group A is shown in Table 1.

Recontamination prevention test example 1
The sulfonic acid polymer-containing particle group A obtained in the sulfonic acid polymer preparation example 1, the base detergent particle group A obtained in the base detergent particle group preparation example, and mud particles (horticulture through a 200-mesh sieve) Kanuma Akado [purchased from Kokusaien Co., Ltd. (10, Zenshocho, Izumi, Osaka)] and white cloth (Laundry Science Association # 2023 cloth) were used in combination with the following steps to conduct a recontamination prevention test.

Step 1: Add 2.5 g of mud particles into a beaker, add 800 mL of hard water (CaCl ₂ : 55.42 mg / L, MgCl ₂ · 6H ₂ O: 43.51 mg / L) at 20 ° C., and mud lumps disappear Step 2: Disperse uniformly while confirming that: Step 100: Add 100 mL of the base detergent particle group aqueous solution (4.9 g / 100 mL (the above hard water)) into the beaker Step 3: 6 cm × in the beaker Step 4 of adding 5 pieces of white cloth cut to 6 cm Step 4: Adding 100 mL of the sulfonic acid polymer-containing particle group aqueous solution (0.1 g / 100 mL (the above hard water)) into the beaker Step 5: Cloth in the beaker And all of the solution, etc. are transferred to a Terg-o-meter cleaning tank and immediately washed at 20 ° C., 100 ± 5 r / min for 10 minutes. The cloth, squeezed out by hand lightly so as to 200% by weight or less, 20 ° C. of water used _{(CaCl 2: 55.42mg / L,} MgCl 2 · 6H 2 O: 43.51mg / L) placed in a 1000mL , Rinse for 3 minutes using a Terg-o-meter (rotation speed 100 ± 5 r / min), and this rinsing operation is performed twice in total. Step 7: Air-drying of the taken-out white cloth, ironing, and reflection at 460 nm Step of measuring the rate (made by Nippon Denshoku Industries Co., Ltd., colorimetric color difference meter). Process for obtaining recontamination prevention rate [%] according to the following formula: Recontamination prevention rate [%] = [(reflectance of white cotton cloth after test) / (reflectance of white cotton cloth before test)] × 100

Each experiment was performed by changing the combination order of the above steps.
Experiment 1 Step 1 → 2 → 3 → 4 → 5 → 6 → 7
Experiment 2 Step 1 → 4 → 3 → 2 → 5 → 6 → 7
Experiment 3 Step 1 → 3 → 2 and 4 (at the same time) → 5 → 6 → 7

  Table 2 shows the measurement results of the recontamination prevention rate. A good anti-recontamination rate was obtained by contacting the sulfonic acid polymer after the base detergent.

<Example of particle size adjustment of sulfonic acid polymer-containing particles>
Each particle size fraction of the particle group A obtained in the particle group preparation example 1 using a JIS standard sieve (2000, 1400, 1000, 710, 500, 355, 250, 180, 125, 90, 63, 45 μm). After the fractionation, each particle size fraction was reconstituted to the ratio shown in Table 3, and each particle group A to F having different average particle size and particle size distribution was obtained as shown in the table.

  The particle distributions of the particle groups A to F are shown in FIGS. From the results shown in each figure, the average particle diameter of the particle group A is 197 μm (FIG. 1), the average particle diameter of the particle group B is 74 μm (FIG. 2), and the average particle diameter of the particle group C is 467 μm (FIG. 3). The average particle size of the particle group D was 180 μm (FIG. 4), the average particle size of the particle group E was 96 μm (FIG. 5), and the average particle size of the particle group F was 681 μm (FIG. 6).

Examples 1-5 and Comparative Examples 1-4
98 parts by weight of the base cleaning agent particle group A and 2 parts by weight of each of the sulfonic acid polymer-containing particle groups A to I were uniformly mixed to obtain cleaning compositions A to I. Using this composition, anti-staining property, slipperiness and solubility were measured. The obtained results are shown in Tables 3 and 4 below.

Examples 6 to 9 and Comparative Example 5
Furthermore, by mixing the base cleaning agent particle group A and the sulfonic acid polymer-containing particle group A, the ratio of the sulfonic acid polymer-containing particle group A is 0.04% by weight, 0.06% by weight, Compositions J to N that were 2 wt%, 4 wt%, and 8 wt% were obtained. Using this composition, anti-staining property, slipperiness and solubility were measured. The results obtained are shown in Table 5.

  From the results shown in Table 5, each of the compositions J-M obtained in Examples 6 to 9 is excellent in re-contamination prevention property, excellent in slip property evaluation and solubility evaluation, and has very low insoluble content. On the other hand, the composition N obtained in Comparative Example 5 exhibits unpleasant sensation due to excessive slipperiness of all the panelists.

  The laundry method and granular detergent composition of the present invention are intended to improve the labor load during hand washing, and the composition is particularly applied to a granular detergent for hand washing.

FIG. 1 is a view showing the particle size distribution of the particle group A obtained in the particle size preparation example of the sulfonic acid-based polymer particle group, FIG. 2 is a diagram showing the particle size distribution of the particle group B obtained in the particle size preparation example of the sulfonic acid polymer particle group, FIG. 3 is a diagram showing the particle size distribution of the particle group C obtained in the particle size preparation example of the sulfonic acid polymer particle group, FIG. 4 is a view showing the particle size distribution of the particle group D obtained in the particle size preparation example of the sulfonic acid polymer particle group, FIG. 5 is a diagram showing the particle size distribution of the particle group E obtained in the particle size preparation example of the sulfonic acid-based polymer particle group, and FIG. 6 is a diagram showing the particle size distribution of the particle group F obtained in the particle size preparation example of the sulfonic acid polymer particle group.

Claims (3)

A method of washing to be washed in washing濯浴,
Contacting an object to be cleaned with cleaning water in which all or a part of a base cleaning agent component including an anionic surfactant, a hardness component capturing builder, and an alkaline substance is dissolved; and
A sulfonic acid polymer containing a monomer unit represented by the following formula (I) in the washing water at a ratio of 50 to 100 mol% in all the constituent monomer units and having a weight average molecular weight of 1,000,000 to 30,000,000 is dissolved. , The process of contacting with the object to be cleaned
A method for washing an object to be cleaned.
(In the formula, A represents a hydrogen atom or an alkali metal, R ¹ represents a hydrogen atom or a methyl group, and X represents any one of the following formulas (II) to (IV).)
(In the formula, Ph represents a phenylene group.)
(In the formula, m represents 1 to 6.)
(In the formula, R ² represents a linear or branched alkylene group having 2 to 8 carbon atoms.)   The washing method according to claim 1, wherein the anionic surfactant is an alkylbenzene sulfonate.   The washing method according to claim 1 or 2, wherein the object to be cleaned is an object to be cleaned contaminated with mud particles.