JP5545837B2 - Powder cleaning composition - Google Patents

Description

  The present invention relates to a powder cleaning composition.

  Alkali metal silicates have long been used in builders for cleaning agents. Its feature is that it is soluble in water, unlike builder for detergents of aluminosilicate type such as zeolite. For this reason, there are advantages such as good rinsing properties after washing and low persistence in clothing. Moreover, the point which has an alkali buffering capability is a function which aluminosilicate does not have.

  On the other hand, alkali metal silicates absorb moisture when stored for a long time under high temperature and high humidity conditions. As a result, the particles are deliquescent and the particles are consolidated to cause caking. In addition, when alkali metal silicate particles are blended with a detergent composition containing a water-insoluble component such as aluminosilicate, when stored under high temperature and high humidity, alkali metal silicate and aluminosilicate coalesce, Insoluble coarse particles are formed, which causes residue of the cleaning composition.

  In order to improve this point, Patent Document 1 devises measures to prevent caking by treating the surface of crystalline alkali metal silicate particles with an organic substance that does not substantially contain water.

JP-A-9-208218

  However, although the technique of Patent Document 1 is effective in preventing caking, it has not always been effective in preventing water insolubles due to coalescence of aluminosilicates during storage.

  An object of the present invention is a powder cleaning composition containing an alkali metal silicate and an aluminosilicate, which reduces the generation of water-insoluble matter formed by combining the alkali metal silicate and the aluminosilicate. It is to provide a powder cleaning composition that can be used.

The present invention provides a nonionic organic compound (a2-1) [hereinafter referred to as (a2-1) on the surface of an alkali metal silicate (a1) [hereinafter referred to as component (a1)] having an average particle diameter of 1 to 1000 μm. And a surface treatment agent (a2) [hereinafter referred to as component (a2)] containing a cationic organic compound (a2-2) (hereinafter referred to as component (a2-2)) Alkali metal silicate particles (A) [hereinafter referred to as component (A)],
A powder detergent composition containing an aluminosilicate (B) [hereinafter referred to as component (B)] having an average particle size of 0.1 to 50 μm,
Each of the component (a2-1) or the component (a2-2) has a molecular weight of 200 to 700 and a solubility in 100 g of water at 20 ° C. is 0.5 g or less,
(A2) It is related with the powder cleaning composition whose melting | fusing point of a component is 45 to 90 degreeC, and moisture permeability is 0 to 2%.
In the present invention, “composite” as used in the term “composite” or “composite particle” means that an alkali metal silicate and other compounds, in particular, an organic compound, or an organic compound and an inorganic compound are attached to each other or adsorbed or absorbed. It refers to forming a solid.
In the present invention, the surface of the alkali metal silicate, in some cases from the surface to the inside, mainly refers to the case where the surface treatment agent according to (a2) is attached, adsorbed or absorbed to form one particle.

  ADVANTAGE OF THE INVENTION According to this invention, even if alkali metal silicate particle | grains and aluminosilicate coexist, the powder detergent composition with little production | generation of the water insoluble content by storage can be provided.

<(A1) component>
The alkali metal silicate used in the powder detergent composition of the present invention is an amorphous or crystalline powder having an anhydrous composition represented by the following formula (1) and an average particle diameter of 1 to 1000 μm. Is mentioned.
xM ₂ O.ySiO ₂ .zMeO (1)
(In the formula, M represents Na and / or K, Me represents Ca and / or Mg, y / x = 0.5 to 4.0, z / x = 0 to 1.0, Mg in MeO) / Ca = 0 to 10.)

  The compound of general formula (1) may contain other elements and / or compounds in an amount of up to 1% by weight. Examples of other elements and / or compounds include aluminum, iron, titanium, and oxides thereof.

  The component (a1) is preferably y / x = 1.0 to 3.5 in the general formula (1) from the viewpoint of further improving the ion exchange capacity, alkali buffer capacity, and storage stability. Examples of the alkali metal silicate having such a composition include sodium metasilicate, potassium metasilicate, powder No. 1 sodium silicate, powder No. 2 sodium silicate and the like.

  Further, as a suitable component (a1), a synthetic inorganic builder described in Japanese Patent No. 2525318, which is a crystalline alkali silicate having a high ion exchange capacity, Japanese Patent Application Laid-Open No. 8-26717, And water softeners described in Japanese Patent No. 41116.

  Among these, a crystalline layered silicate having y / x = 2.0 and Z = 0 in the general formula (1) is particularly preferably used. As such a crystalline layered silicate, “Prefeed” marketed by Tokuyama Siltech Co., Ltd. is available and particularly preferably used.

  In this invention, the average particle diameter of (a1) component is 1-1000 micrometers from a soluble viewpoint with respect to water. The lower limit of the average particle diameter is 1 μm or more, preferably 10 μm or more, and more preferably 100 μm or more from the viewpoint of minimizing the amount of the component (a2) to be contacted. Further, the upper limit of the average particle diameter is 1000 μm or less, preferably 800 μm or less, more preferably 600 μm or less, and particularly preferably 200 μm or less from the viewpoint of improving solubility.

  The content of the component (a1) is preferably 0.5% by mass or more, more preferably 2% by mass or more, and still more preferably 4% by mass or more in the composition from the viewpoint of cleaning performance. From the viewpoint of adjusting the pH when the powder detergent composition is dissolved in water, the content in the composition is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less.

<(A2) component>
The surface treatment agent as component (a2) is present on the surface of the alkali metal silicate particles contained in the powder cleaning composition of the present invention, and the surface treatment agent is a hydrophobic nonionic organic compound [( a2-1) component] and / or a hydrophobic cationic organic compound [component (a2-2)]. The melting point of the surface treatment agent (a2) is 45 ° C. to 90 ° C., and the moisture permeability is 0 to 2%. The component (a2) is composed of the component (a2-1) and / or (a2-2), or the component (a2-1) and / or the component (a2-2) and any surfactant described later (a2-3) ).

Moreover, the hydrophobic nonionic organic compound of the component (a2-1) contained in the component (a2) or the hydrophobic cationic organic compound of the component (a2-2) has a molecular weight of 200 to 700, respectively. As the definition of hydrophobicity of the present invention, the solubility in 100 g of water (distilled water) at 20 ° C. is 0.5 g or less.
Furthermore, in order to achieve the regulation of the melting point and moisture permeability of the component (a2), the component (a2-1) and the component (a2-2) preferably have the same properties as the component (a2), and the melting point is 45. The moisture permeability using a moisture-permeable cup is 0 to 2%. In addition, about (a2-1) component, "nonionic" means that it does not have the physical property which melt | dissolves in water and dissociates into ion.
The molecular weight of the component (a2-1) and the component (a2-2) is limited by the formation of a water-insoluble component (hereinafter referred to as unity) in which the aluminosilicate as the component (B) is generated by the alkali metal silicate as the component (A). This molecular weight range is from the viewpoint of compatibility between the suppression of the solubility of the alkali metal silicate particles themselves and the compatibility with the optional surfactant (a2-3) described later. preferable.

For example, when a polymerized hydrocarbon is used as the surface treatment agent, the powder cleaning composition containing the hydrocarbon is improved in the storage stability of the alkali metal silicate, and the aluminosilicate which is the subject of the present invention Although it contributes to the reduction of the water-insoluble matter formed by coalescence with the component, the solubility of the alkali metal silicate itself is remarkably lowered, so that the component (A) itself becomes a water-insoluble matter.
Therefore, in the present invention, it is essential that the component (A) is dissolved in the washing step. For that purpose, the component (a2) is compatible with the surfactant blended in the cleaning composition of the present invention. In the washing process, it must be detached from the surface of the alkali metal silicate and behaved to promote dissolution of the alkali silicate.
Further, the limitation of solubility is meaningful from the viewpoint of the stability of the film formed by the component (a2) when stored under high humidity. When the component (a2) having high solubility is used, the coating dissolves under high humidity, and the defense of the component (a1) becomes incomplete, and the effect of the present invention cannot be obtained.
Moreover, it is preferable that (a2-1) component and (a2-2) component have the same range, when melting | fusing point satisfy | fills the property of (a2) component. By setting to this range, it is possible to suppress the moisture absorption of the alkali metal silicate due to a rapid change in temperature.

  A characteristic of the present invention is the provision of moisture permeability. In the present invention, using a moisture permeable cup having the specifications described in JIS L1099: 2006, the moisture permeability amount that permeates the thinned component (a2) is measured, and the moisture permeability rate is obtained therefrom. Specifically, the evaluation method of an Example can be referred. The method for measuring the moisture absorption is an evaluation method generally known as the measurement of water vapor permeability of fibers, plastic films, etc., and the moisture permeable cup defined by the above JIS is, for example, “ It is marketed as a “wet cup” and can be easily obtained.

The regulation of the moisture permeability of the present invention indicates the degree to which the alkali metal silicate by the component (a2) blocks from moisture in the air, but is not a physical property value determined by the molecular weight or solubility of the component (a2), It is a physical property value determined by the molecular density, the arrangement of hydrophobic groups and submerged groups in the molecule, and packing properties.
Moisture permeability of 2% or less is the minimum value necessary to prevent water insoluble matter due to coalescence of alkali metal silicate and aluminosilicate, which is the subject of the present invention. Because it was set. For example, stearic acid has a molecular weight of 284.5 and a solubility of less than 0.5. However, since the moisture permeability is 2.65%, the water-insoluble matter is not sufficiently suppressed.
The component (a2-1) and the component (a2-2) are hydrophobic low-molecular compounds and have low moisture permeability, so that in combination with the component (a2-3) described later, It is excellent as a detergent composition in which storage stability under high humidity and dispersion solubility during washing are balanced.

  As the component (a2-1) and / or the component (a2-2) contained in the surface treatment agent of the component (a2), it is desirable to use a component that does not substantially contain water. Note that “substantially free of water” means that the water content is 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.1% by mass or less by the Karl Fischer method.

As the component (a2-1) and the component (a2-2), at least one selected from alcohol, fatty acid alcohol ester, ammonium salt and amine is preferably used. Furthermore, at least one selected from alcohols, fatty acid alcohol esters, and amines, and particularly from the viewpoint of reducing the water content after storage, alcohols and / or amines are more preferably used. Since the alkali metal silicate is substantially a base, the amine on the surface exhibits a property close to that of a nonionic organic compound, and is also preferable from the viewpoint of hygroscopicity.
Therefore, the component (a2) is preferably a surface treatment agent containing at least one selected from alcohol, fatty acid alcohol ester and amine, particularly alcohol and / or amine.

  As the alcohol, an aliphatic alcohol having 12 to 22 carbon atoms is preferable, an aliphatic monohydric alcohol having 12 to 22 carbon atoms is more preferable, and stearyl alcohol having 18 carbon atoms is particularly preferably used.

  The fatty acid alcohol ester is preferably an ester of a fatty acid having 12 to 22 carbon atoms and an alcohol having 12 to 22 carbon atoms, particularly an ester of a fatty acid having 18 carbon atoms and an alcohol having 18 carbon atoms, particularly stearyl stearate. Preferably used.

  Examples of the amine include amines in which a hydrocarbon group having 16 to 22 carbon atoms is directly bonded to a nitrogen atom, and primary or 2 in which an alkyl group having 16 to 22 carbon atoms is bonded to one or two nitrogen atoms. A secondary amine is preferably used, and may be a secondary amine in which one alkyl group having 16 to 22 carbon atoms and one hydrocarbon group having less than 16 carbon atoms are bonded to the same nitrogen atom. Among them, alkyl having 18 to 22 carbon atoms may be used. A monoalkylamine having one group (particularly stearylamine) or a dialkylamine having two alkyl groups having 18 to 22 carbon atoms (particularly distearylamine) is preferably used.

  The component (a2-1) and / or the component (a2-2) may be used alone or in combination of two or more.

The proportion of the component (a2-1) and / or the component (a2-2) in the component (a2) is 50% by mass or more, preferably 60% by mass or more, more preferably 65% by mass or more, and most preferably 90% by mass. %, And the upper limit is 100% by mass or less.
Moreover, when it contains the below-mentioned (a2-3) component, the ratio which the (a2-1) and / or (a2-2) component in the (a2) component and the (a2-3) component occupy, 50 mass% or more, preferably 60 mass% or more, more preferably 65 mass% or more, most preferably 90 mass% or more, and the upper limit is 100 mass% or less.

In addition to the component (a2-1) and / or the component (a2-2), the surface treatment agent (a2) may be the component (a2-1) or the component (a2-1) for the purpose of improving the solubility of the powder cleaning composition in water. You may contain surfactant (a2-3) [henceforth (a2-3) component] which does not correspond to (a2-2) component.
The surfactant (a2-3) component is at least one selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. Things.
Of these, anionic surfactants and nonionic surfactants are preferred, and nonionic surfactants that do not contain water and have good compatibility with the components (a2-1) and (a-2). Is more preferable.
Examples of the nonionic surfactant include polyoxyethylene alkyl ethers having 12 to 18 carbon atoms and 3 to 25 addition moles of ethylene oxide, among which 12 to 16 carbon atoms and 8 to 8 ethylene addition moles. 23 is preferably used.

The content of the component (a2-3) in the component (a2) is contained in a range that satisfies the range of the melting point and moisture permeability of the component (a2), but in the present invention, the solubility of the component (a2) From the viewpoint, in the total of the component (a2-1), the component (a2-2) and the component (a2-3), 0.5% by mass or more is preferable, 5% by mass or more is more preferable, and 10% by mass or more is particularly preferable. preferable.
Further, from the viewpoint of maintaining the moisture permeability of the component (a2), the total of the component (a2-1), the component (a2-2) and the component (a2-3) is preferably 50% by mass or less, and 40% by mass or less. Is more preferable, and 35% by mass or less is particularly preferable.

  The component (a2) has a melting point of 45 ° C. to 90 ° C. and has a low moisture permeability. That is, even when the temperature is high, such as in summer, the component (a2) coated on the surface of the component (a1) stably exists without sticking, and the component that does not easily pass through moisture protects the component (a1). From the viewpoint of preventing unification by reaction with aluminosilicate.

  The melting point of the component (a2) is 45 ° C. or higher, more preferably 48 ° C. or higher, and particularly preferably 50 ° C. or higher, from the viewpoint of storage stability at high temperature and solidification. Moreover, from a viewpoint of handling property, it is 90 degrees C or less, 85 degrees C or less is preferable and 80 degrees C or less is especially preferable. The (a2-1) component and the (a2-2) component are also preferably compounds that fall within the same melting point range.

  The component (a2) has a moisture permeability of 0 to 2%, preferably 0.01 to 1.8%, more preferably 0.05 to 1.5% from the viewpoint of storage stability. This moisture permeability is measured by the method of an example described later. The (a2-1) component and the (a2-2) component are preferably compounds that fall within the same moisture permeability range.

  Since the component (a2-1) and / or the component (a2-2) constituting the component (a2) are also suitable for expressing the melting point and moisture permeability as described above, each has a molecular weight. 200 to 700 compounds, preferably 250 to 550.

  The component (a2-1) and / or the component (a2-2), which are constituent components of the component (a2), are hydrophobic compounds having a solubility in 100 g of water (distilled water) at 20 ° C. of 0.5 g or less.

  From the viewpoint of storage stability, the mass ratio of the component (a1) to the component (a2) is (a2) / (a1), preferably 0.01 or more, more preferably 0.1 or more, still more preferably 0.00. It is 2 or more, and 0.3 or more is most preferable. Further, this mass ratio is preferably 0.7 or less, more preferably 0.6 or less, and 0.5 or less from the viewpoint of solubility. Therefore, this mass ratio is preferably 0.01 to 0.7.

<(A) component>
In the alkali metal silicate particles as component (A), component (a2) is present on the surface of alkali metal silicate as component (a1) and is compounded.

The component (A) is obtained by subjecting the component (a1) to a surface treatment with the component (a2). “Surface treatment” refers to bringing the component (a2) into contact with the surface of the component (a1). The component (a2) does not necessarily cover the surface of the component (a1), but the effect is obtained, but from the viewpoint of storage stability, a state in which the surface is completely covered with the component (a2) is preferable.
The state in which the component (a2) is completely covered means a state in which Si or the like, which is a constituent element of the component (a1), is not detected on the surface of the composite particle by a surface analyzer such as ESCA. If the surface of the component (a1) is coated with the component (a2) having a high melting point and low moisture vapor permeability, a storage stability higher than that of the conventional one can be obtained. In the present invention, alkali metal silicate particles in which the (a1) component is coated with the (a2) component can be used as the (A) component.

Even if the (A) component is an aggregate of individual surface-treated particles, the effect of the surface treatment is sufficiently exerted, so such an aggregate is also included in the category of the (A) component of the present invention. Further, particles obtained by surface-treating the component (a2) on the aggregated particles in which the fine particles of the component (a1) are aggregated and collected can also be used as the component (A) of the present invention. In particular, alkali metal silicate particles having a small surface area apparently include a method of surface-treating the component (a2) on an alkali metal silicate granule [component (a1)] obtained by granulating alkali metal silicate fine particles. Since surface treatment can be performed, the storage stability can be improved with a relatively small amount of the component (a2).
Therefore, in the present invention, the component (A) may be alkali metal silicate particles obtained by aggregating the component (a1) with the component (a2).

As a specific surface treatment method, the component (a2) is heated to a melting point or higher and melted, and then the component (a1) is charged and uniformly mixed and cooled, or the melt of the component (a2) is ( a1) It is carried out by a method of uniformly mixing and cooling while spraying the components. Alternatively, a method may be used in which the powder of the component (a2) and the powder of the component (a1) are heated while being mixed, and the treatment is performed while the component (a2) is dissolved.
In order to perform the above treatment, a mixer or a granulator equipped with a heating / cooling device is preferably used. The surface treatment can also be performed by applying mechanical force such as mixing and pulverizing the powder of component (a2) and the powder of component (a1). For such treatment, a pulverizer can be generally used, but a granulator such as a roller compactor that compresses and pulverizes and granulates may be used.

  The average particle size of the obtained component (A) is preferably 1 μm or more, more preferably 10 μm or more, and particularly preferably 100 μm or more, from the viewpoint of preventing powder formation due to fine powder. From the viewpoint of solubility, it is preferably 1000 μm or less, more preferably 800 μm or less, and particularly preferably 500 μm or less.

<(B) component>
Aluminosilicates are likely to react with alkali metal silicates that have absorbed moisture upon storage, resulting in the formation of water insolubles. In powder detergent compositions containing aluminosilicates and alkali metal silicates, when such water-insoluble components are formed, there is a concern about the generation of residues due to a decrease in solubility and a decrease in cleaning power. Therefore, the solution is desired. The present invention solves this problem.

The (B) component aluminosilicate particles may be either amorphous or crystalline. As the composition of the aluminosilicate particles, the general formula of anhydride is xM ₂ O.ySiO ₂ .Al ₂ O ₃ .zMeO (where M represents an alkali metal, Me represents an alkaline earth metal, and x = 0.2 -4, y = 0.5-6, z = 0-0.1). More preferably, M is Na or K in the above composition, and Na is particularly preferable from the viewpoint of easy availability of raw materials and cost. Me is preferably Ca and / or Mg. Moreover, x = 0.6-3 is more preferable. y = 0.9-5 is more preferable. The aluminosilicate particles having the above composition may be either amorphous or crystalline, but are preferably crystalline having low reactivity with the alkali metal silicate (a1) component. Moreover, you may have crystallization water.

  Of these, crystalline aluminosilicate particles represented by the general formula of anhydrides represented by x = 1, y = 2, and z = 0, that is, 4A zeolite are particularly preferably used.

  (B) The average particle diameter of a component is 0.1-50 micrometers, and from a dispersible viewpoint to water, Preferably it is 0.5-20 micrometers. Moreover, content of (B) component is 1-40 mass% in a composition, Furthermore, 10-40 mass% is preferable.

<Powder cleaning composition>
The powder cleaning composition of the present invention can be prepared by a method of mixing the component (A) with the base detergent containing the component (B). The component (A) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 4 parts by mass or more with respect to 100 parts by mass of the base detergent containing the component (B). Further, from the viewpoint of the storage stability of the powder cleaning composition, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 30 parts by mass or less.

  In addition to the (B) component aluminosilicate, the base detergent is a commonly added detergent component such as various surfactants, builders, enzymes, and bleaching agents (percarbonate, perborate, bleach activated) Agent), anti-staining agent (carboxymethyl cellulose and the like), softening agent, reducing agent (sulfite and the like), fluorescent whitening agent, foam suppressant (silicone and the like), fragrance and the like. Further, even a commercially available cleaning agent itself can be used as a base detergent if it contains an aluminosilicate corresponding to the component (B).

  The powder cleaning composition of the present invention preferably contains the component (B) as particles different from the component (A) from the viewpoint of suppressing the reaction between the component (A) and the component (B).

In the powder cleaning composition of the present invention, from the viewpoint of cleaning performance and storage stability, the component (a1) is preferably 0.5 to 40% by mass, more preferably 2 to 35% by mass, and still more preferably 5 to 30%. Contains by mass%. In addition, from the viewpoint of removing the hardness component of the washing water and from the viewpoint of persistence of the component (B) in the clothing, the component (B) is preferably 1 to 40% by mass, more preferably 2 to 35% by mass, and still more preferably. Contains 5-30 mass%.
Moreover, from the viewpoint of storage stability and solubility of the component (a1), the total amount of the component (a2-1), the component (a2-2), and other surfactants is preferably 1 to 60% by mass, more preferably. 2-50 mass%, More preferably, it contains 3-40 mass%. Examples of the surfactant include those used for the surface treatment of the component (A) (for example, the component (a2-3) and those used separately.
Moreover, from a viewpoint of washing | cleaning performance, Preferably it contains 0-60 mass%, More preferably, 2-50 mass%, More preferably, 5-40 mass% of (e) alkali metal carbonate is contained.

  In the powder cleaning composition of the present invention, from the viewpoint of storage stability of the component (a1), the mass ratio of the component (a1) to the component (a2) is (a2) / (a1), preferably 0.01. It is -0.7, Preferably it is 0.2-0.7, More preferably, it is 0.25-0.7.

  The use of the powder cleaning composition of the present invention is not particularly limited, and is suitably used as a detergent for clothing, dish detergent, residential detergent, automobile detergent, body detergent, toothbrush, metal detergent, etc. In particular, it is preferably used as a laundry detergent.

  In the powder detergent compositions prepared in the following Examples and Comparative Examples, the average particle size, melting point, moisture permeability, amount of water insoluble before storage, and amount of water insoluble after storage were measured or calculated by the following methods. .

(1) Average particle diameter In the present invention, the average particle diameter was measured by the following two methods after separating those having a particle diameter of 125 μm or less and those exceeding the average particle diameter with a sieve. When particles are mixed, the average particle size obtained from each is further averaged from the mass ratio divided by whether or not it passes through a 125 μm sieve (passing when passing, turning on when not passing) Was the average particle size.
(1-1) Average particle diameter (in the case of a 125 μm sieve pass particle)
Using a laser diffraction / scattering type particle size distribution measuring apparatus (“LA950” manufactured by Horiba, Ltd.), ethanol having a refractive index of 1.30 is used as a dispersion medium, and the particle size distribution after irradiation with ultrasonic waves for 1 minute is set to a refractive index of 1. The value of the volume median particle size (D50) as measured at 54 was taken as the average particle size.

(1-2) Average particle diameter (in the case of 125 μm sieve on particles)
Using a 9-stage sieve having a mesh size of 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, and 2000 μm and a saucer, the sieves were stacked in order from the sieve with the smallest aperture.
Add 100 g of granules from the top of the top 2000 μm sieve, cover and attach to a low-tap type sieve shaker (manufactured by Hiraiko Seisakusho, tapping 156 times / minute, rolling: 290 times / minute) 5 After vibrating for a minute, the mass of the particles remaining on each sieve and the saucer was measured, and the mass ratio (%) of the particles on each sieve was calculated.
The mass ratio of the particles on the sieve with a small opening was accumulated in order from the saucer, and the particle size at which the total was 50% was defined as the average particle size.

(2) Melting point of surface treatment agent Measured by the method described in item 5.1.4 of JIS K4101: 1993 “General Test Method for Organic Intermediates”. A sample made of hard glass having an inner diameter of 0.8 to 1.2 mm, a thickness of 0.2 to 0.3 mm, a length of about 150 mm, and one end closed. The material used was a 3 mm layer that was dropped into a capillary and bounced and tightly packed. The temperature raising conditions were as described in JIS. The final melting point temperature was rounded to the first decimal place.

(3) Moisture Permeability of Surface Treatment Agent (3-1) Preparation of Sample 20 g of surface treatment agent was placed in a stainless steel bat (20 cm × 16 cm × 3 cm) and melted at 105 ° C. A 105 mm × 150 mm × 84 μm thick paper (basis weight 64 g / m ² , moisture permeability 28%, uncoated PPC paper) was placed on the surface of the melt, and a surface treatment agent was adhered to the paper surface. Thereafter, the paper was separated from the surface treatment agent and left on a flat place until the surface treatment agent solidified.
After the surface treatment agent solidified, the thickness was measured with a micrometer. A surface treatment agent having a film thickness in the range of 80 to 120 μm was selected and cut into a circular shape with a diameter of 70 mm as a test sample. In this case, a test sample having a surface coating amount of 0.35 ± 0.1 g is used. In the present invention, the mount on which the surface treatment agent is applied has a thickness of 70 to 120 μm and a moisture permeability of 25 to 35%. Commercially available PPC paper can be used as such a mount.

(3-2) Measurement of moisture permeability Moisture permeable cup [cylindrical cup with an inner diameter of 60 mm and a depth of 22 mm defined in JIS L 1099: 2006 “Method of Measuring Moisture Permeability of Textile Products” No. 1 which has a ring-shaped plane portion with a width of 15 mm so that a sheet for measuring moisture permeability can be sandwiched between the plane ring and the periphery. A 401 moisture permeable cup (manufactured by Yasuda Seiki Seisakusho) was used. ] 10 g of anhydrous calcium chloride pulverized into powder in a mortar was put in, and a ring-shaped rubber packing was set.
On the rubber packing, the test sample of 70 mm in diameter cut out earlier is placed with the surface treatment film coating side facing down, on which a diameter of 90 mm and an inner diameter of 60 mm for fixing the test sample are mounted. A flat aluminum ring was placed and firmly fixed with screws.
The mass of this was measured and recorded (initial mass). Then, it left still at 50 degreeC and the humidity of 70% for 4.5 hours, and mass was measured again (mass after stationary). And after standing, mass (g)-initial mass (g) was calculated | required as moisture-permeable amount (g).
On the other hand, when the sheet as a test sample was not sandwiched, the moisture permeation amount was determined in the same manner to be 8.4 g. The ratio of moisture permeability of each test sample when the moisture permeability was 100% was defined as moisture permeability.

(4) Water-insoluble part of powder detergent composition (4-1) Water-insoluble part immediately after preparation Tap water made at 5 ° C. is a 1 liter beaker (inner diameter 105 mm, height 150 mm cylindrical type, for example, manufactured by Iwaki Glass Co., Ltd.) In a state where the water temperature of 5 ° C. is kept constant with a water bath, with a stirrer (length 35 mm, diameter 8 mm, for example, model: ADVANTEC, Teflon (registered trademark) round thin type) Stirring was performed at a rotational speed (1000 rpm) at which the spiral depth relative to the water depth was approximately 1/3. The cleaning composition weighed to 0.833 g was added and dispersed in water with stirring, and stirring was continued.
10 minutes after the addition, the dry weight of the cleaning composition dispersion in the beaker was measured in advance (hereinafter sometimes referred to as mass) with a 200-mesh standard sieve (opening 74 μm, sieve diameter 100 mm). The water-containing cleaning composition that was filtered and remained on the sieve was collected together with the sieve in an open container of known mass. The operation time from the start of filtration to the collection of the sieve was 10 ± 2 seconds.
The recovered residue of the recovered detergent composition is dried for 1 hour in an electric dryer heated to 105 ° C together with the sieve and the recovery container, and then cooled by holding for 30 minutes in a desiccator (25 ° C) containing silica gel. did.
After cooling, the total mass of the dissolved residue of the dried cleaning composition, the sieve, and the collection container was measured, and the water-insoluble content (mass%) of the cleaning composition was calculated by the following formula.
Water-insoluble matter (mass%) = (T / S) × 100
S: input mass of cleaning composition (g)
T: When the aqueous solution obtained under the above stirring conditions is applied to the sieve, the dry mass (g) of the residue of the detergent composition remaining on the sieve

(4-2) Water-insoluble matter after storage 12 g of the detergent composition was weighed and stored for 4 days under conditions of a temperature of 50 ° C. and a humidity of 70%. Thereafter, it was stored at a temperature of 25 ° C. and a humidity of 50% for 2 days. Using the cleaning composition after storage, the water-insoluble content after storage was calculated in the same manner as in (5-1).

(Example of preparation of base detergent)
Water was added to a mixing tank having a stirring blade, and after the water temperature reached 55 ° C., sodium chloride (yaki salt, manufactured by Nippon Salt Co., Ltd.) and sodium sulfate were added. After stirring this for 15 minutes, sodium carbonate was added, and after completion of the addition, an aqueous sodium polyacrylate solution (average molecular weight of 15,000, manufactured by Kao Corporation) was added.
This was further stirred for 15 minutes, and then aluminosilicate [Mizusawa Chemical Co., Ltd., trade name: Shilton B (average particle size 5 μm)] was added. This was stirred for 30 minutes to obtain a slurry. The final temperature of this slurry was 60 ° C.

  This slurry was supplied to a spray drying tower, and sprayed from the top of the tower at a spraying pressure of 2.45 MPa, thereby preparing base granule group 1. The composition of the obtained base granule group 1 was composed of 8% by mass of sodium chloride, 12% by mass of sodium polyacrylate, 28% by mass of sodium carbonate, 26% by mass of sodium sulfate, and 26% by mass of aluminosilicate.

  On the other hand, an activator mixed solution at 70 ° C. composed of a nonionic surfactant, an anionic surfactant, polyethylene glycol and water was prepared. The composition was composed of 39% by mass of a nonionic surfactant, 46% by mass of an anionic surfactant, 2% by mass of polyethylene glycol and 13% by mass of water.

Next, detergent particles were obtained by adding a surfactant or the like to the base granules 1. That is, 36 parts by mass of the base granule group 1 was put into a Redige mixer (manufactured by Matsusaka Giken Co., Ltd., capacity 20 L, with jacket), and stirring of the main shaft (100 rpm) was started. Thereto, 20 parts by mass of the above-mentioned activator mixture was added in 3 minutes, and stirred for 5 minutes.
Further, 1 part by mass of palmitic acid [manufactured by Kao Corporation, trade name: LUNAC P-95] was added to this mixer in 30 seconds, and then stirred for 3 minutes.
Further, 24 parts by mass of soda ash and 12 parts by mass of aluminosilicate are added to this mixer, surface coating is performed, the detergent particles are classified using a sieve having an opening of 1180 μm, and the detergent particles having a particle diameter of less than 1180 μm. Got.

  Next, 5 parts by mass of aluminosilicate, 0.4 parts by mass of perfume, and 0.4 parts by mass of enzyme (trade name: Cellulase K, manufactured by Novo Corp., trade name: cannase) 24TK, manufactured by Novo Corp., trade name: Sabinase 6.0T used at a mass ratio of 3: 1: 2) was subjected to after blending with a rotary kiln, and the detergent particles were classified using a sieve having an opening of 2000 μm, and less than 2000 μm A detergent particle group having a particle size of 5 mm was obtained. This was used as a base detergent.

Example 1
4 g of surface treating agent 1 [stearyl allyl alcohol, Calcoal 8098 (manufactured by Kao Corporation)] was added to a 300 mL beaker and dissolved by heating at 105 ° C.
Next, 20 g of a pre-feed (manufactured by Tokuyama Siltec Co., Ltd.) having an average particle diameter of 779 μm composed of particles having an average particle diameter of 12 μm was added and stirred well. When the surface of the pre-feed is uniformly wetted with the surface treatment agent 1 and the surface treatment agent 1 is sufficiently mixed, place the bottom of the beaker in water containing ice, and mix the mixture of the pre-feed and the hydrophobic nonionic organic compound. Stir while cooling.
When the surface treatment agent 1 was solidified and the granules were loosened and the fluidity was sufficient, stirring was stopped, and the particles (average particle size 660 μm) collected between 355 μm and 1000 μm by sieving with sieves were used as composite particles. .
1.2 g of the obtained composite particles and 21.8 g of the base detergent were mixed well to obtain a cleaning composition, and the water-insoluble content was measured immediately after preparation and after storage. The evaluation results are shown in Table 1.

Example 2
A cleaning composition was prepared in the same manner as in Example 1 except that the amount of the surface treatment agent 1 was changed to 6 g, and the water-insoluble component was evaluated. The evaluation results are shown in Table 1.

Example 3
A cleaning composition was prepared in the same manner as in Example 1 except that the amount of the surface treatment agent 1 was changed to 8 g, and the water-insoluble component was evaluated. The evaluation results are shown in Table 1.

Example 4
5.6 g of stearyl alcohol (the same as in Example 1) and 2.4 g of a nonionic surfactant [Emulgen 120 (manufactured by Kao Corporation)] were added to a 300 g beaker, melted at 105 ° C., mixed, and surface-treated. Agent 2 was obtained. A detergent composition was prepared in the same manner as in Example 3 except that this was used as a surface treating agent, and the water-insoluble content was evaluated. The evaluation results are shown in Table 1.

Example 5
A detergent composition was prepared in the same manner as in Example 1 except that the surface treatment agent 3 [stearylamine, Farmin 80 (manufactured by Kao Corporation)] was used as the surface treatment agent, and water insolubles were evaluated. . The evaluation results are shown in Table 1.

Example 6
A detergent composition was prepared in the same manner as in Example 2 except that the surface treatment agent 3 [stearylamine, Farmin 80 (manufactured by Kao Corporation)] was used as the surface treatment agent, and the water-insoluble content was evaluated. . The evaluation results are shown in Table 1.

Example 7
A detergent composition was prepared in the same manner as in Example 3 except that surface treatment agent 3 [stearylamine, Farmin 80 (manufactured by Kao Co., Ltd.)] was used as the surface treatment agent, and water insolubles were evaluated. . The evaluation results are shown in Table 1.

Example 8
5.6 g of stearylamine (same as Example 5) and 2.4 g of nonionic surfactant [Emulgen 120 (manufactured by Kao Corporation)] were added to a 300 g beaker, melted and mixed at 105 ° C., and surface treatment agent 4 was obtained. A detergent composition was prepared in the same manner as in Example 4 except that this was used as a surface treatment agent, and the water-insoluble content was evaluated. The evaluation results are shown in Table 1.

Example 9
A detergent composition was prepared in the same manner as in Example 1 except that the surface treatment agent 5 [stearyl stearate, Exepearl SS (manufactured by Kao Corporation)] was used as the surface treatment agent, and the water-insoluble component was evaluated. It was. The evaluation results are shown in Table 1.

Example 10
A detergent composition was prepared in the same manner as in Example 2 except that the surface treatment agent 5 [stearyl stearate, Exepearl SS (manufactured by Kao Corporation)] was used as the surface treatment agent, and the water-insoluble component was evaluated. It was. The evaluation results are shown in Table 1.

Example 11
A detergent composition was prepared in the same manner as in Example 3 except that the surface treatment agent 5 [stearyl stearate, Exepearl SS (manufactured by Kao Corporation)] was used as the surface treatment agent, and the water-insoluble component was evaluated. It was. The evaluation results are shown in Table 1.

Example 12
5.6 g of stearyl stearate (same as in Example 9) and 2.4 g of nonionic surfactant [Emulgen 120 (manufactured by Kao Corporation)] were added to a 300 g beaker, melted at 105 ° C., mixed, and surface Treatment agent 6 was obtained. A detergent composition was prepared in the same manner as in Example 4 except that this was used as a surface treatment agent, and the water-insoluble content was evaluated. The evaluation results are shown in Table 1.

Example 13
A detergent composition was prepared in the same manner as in Example 1 except that surface treatment agent 7 [distearylamine, Farmin D86 (manufactured by Kao Corporation)] was used as the surface treatment agent, and the water-insoluble component was evaluated. It was. The evaluation results are shown in Table 1.

Example 14
A detergent composition was prepared in the same manner as in Example 2 except that surface treatment agent 7 [distearylamine, Farmin D86 (manufactured by Kao Corporation)] was used as the surface treatment agent, and the water-insoluble component was evaluated. It was. The evaluation results are shown in Table 1.

Example 15
A detergent composition was prepared in the same manner as in Example 3 except that surface treatment agent 7 [distearylamine, Farmin D86 (manufactured by Kao Corporation)] was used as the surface treatment agent, and water-insoluble components were evaluated. It was. The evaluation results are shown in Table 1.

Example 16
5.6 g of distearylamine (the same as Example 1) and 2.4 g of a nonionic surfactant [Emulgen 120 (manufactured by Kao Corporation)] were added to a 300 g beaker, melted at 105 ° C., mixed, and surface Treatment agent 8 was obtained. Except for using this as a hydrophobic nonionic organic compound, composite particles and a detergent composition were obtained in the same manner as in Example 4, and the water-insoluble content was evaluated. The evaluation results are shown in Table 1.

Comparative Example 1
The prefeed was screened to a particle size ranging from 355 μm to 1000 μm. 1.2 g of this product and 21.8 g of the base detergent were mixed well to obtain a cleaning composition, and the water-insoluble content was measured immediately after preparation and after storage. The evaluation results are shown in Table 1.

Comparative Example 2
Cleaning composition as in Example 1 except that comparative surface treating agent 1 [polyethylene glycol (K-PEG6000, manufactured by Kao Corporation, melting point 63 ° C., moisture permeability 3.32%)] was used as the surface treating agent. The product was prepared and the water-insoluble content was evaluated, and the evaluation results are shown in Table 1.

Comparative Example 3
Cleaning composition as in Example 3 except that comparative surface treating agent 1 [polyethylene glycol (K-PEG6000, manufactured by Kao Corporation, melting point 63 ° C., moisture permeability 3.32%)] was used as the surface treating agent. The product was prepared and the water-insoluble content was evaluated, and the evaluation results are shown in Table 1.

Comparative Example 4
A detergent composition as in Example 3 except that comparative surface treatment agent 2 [Lauric acid (Lunac L98, manufactured by Kao Corporation, melting point 43 ° C., moisture permeability 3.27%]] was used as the surface treatment agent. Table 1 shows the evaluation results.

Comparative Example 5
Detergent composition as in Example 1 except that comparative surface treatment agent 3 (palmitic acid, Lunac P95, manufactured by Kao Corporation, melting point 62 ° C., moisture permeability 3.02%) was used as the surface treatment agent. And the water-insoluble content was evaluated. The evaluation results are shown in Table 1.

Comparative Example 6
Detergent composition as in Example 3 except that comparative surface treatment agent 3 (palmitic acid, Lunac P95, manufactured by Kao Corporation, melting point 62 ° C., moisture permeability 3.02%) was used as the surface treatment agent. And the water-insoluble content was evaluated. The evaluation results are shown in Table 1.

Comparative Example 7
Cleaning composition as in Example 3 except that comparative surface treating agent 4 [stearic acid (Lunac S98, manufactured by Kao Corporation, melting point 68 ° C., moisture permeability 3.65%)] was used as the surface treating agent. The product was prepared and the water-insoluble content was evaluated. The evaluation results are shown in Table 1.

Comparative Example 8
Cleaning composition as in Example 3 except that comparative surface treating agent 5 [Laurylamine (Farmin 20D, Kao Corporation, melting point 27 ° C., moisture permeability 21.57%)] was used as the surface treating agent. The product was prepared and the water-insoluble content was evaluated. The evaluation results are shown in Table 1.

Comparative Example 9
A detergent composition as in Example 3 except that comparative surface treatment agent 6 [cetylamine (manufactured by Wako Pure Chemical Industries, Ltd., melting point: 46 ° C., moisture permeability: 8.93%)] was used as the surface treatment agent. And the water-insoluble content was evaluated. The evaluation results are shown in Table 1.

* The amount of treatment is mass% with respect to the alkali metal silicate.
In the table, components not corresponding to the component (a2-1) and the component (a2-2) are also shown in the columns for convenience.

Claims (8)

On the surface of the alkali metal silicate (a1) [hereinafter referred to as component (a1)] having an average particle diameter of 1 to 1000 μm, a nonionic organic compound (a2-1) (hereinafter referred to as component (a2-1)) and Alkaline complexed with the presence of a surface treatment agent (a2) [hereinafter referred to as component (a2)] containing a cationic organic compound (a2-2) [hereinafter referred to as component (a2-2)] Metal silicate particles (A) [hereinafter referred to as component (A)],
A powder detergent composition containing an aluminosilicate (B) [hereinafter referred to as component (B)] having an average particle size of 0.1 to 50 μm,
(A2) component is (a2-1) component or (a2-2) component as stearyl alcohol, ester of fatty acid having 12 to 22 carbon atoms and alcohol having 12 to 22 carbon atoms, alkyl having 18 to 22 carbon atoms Containing at least one compound selected from a monoalkylamine having one group and a dialkylamine having two alkyl groups having 18 to 22 carbon atoms,
Each of the component (a2-1) or the component (a2-2) has a molecular weight of 200 to 700 and a solubility in 100 g of water at 20 ° C. is 0.5 g or less,
The melting point of the component (a2) is 45 ° C. to 90 ° C., and the moisture permeability of the component (a2) according to the following is 0% to 2%.
Powder cleaning composition.
<Moisture permeability of component (a2)>
(1) Sample preparation
A stainless bat (20 cm × 16 cm × 3 cm) is charged with 20 g of component (a2) and melted at 105 ° C. A 105 mm × 150 mm × 84 μm thick paper (basis weight 64 g / m ² , moisture permeability 28%, uncoated PPC paper) is placed on the surface of the melt, and the component (a2) is adhered to the paper surface. Thereafter, the paper is separated from the component (a2) and left on a flat place until the component (a2) is solidified.
(A2) After the component is solidified, the thickness is measured with a micrometer. The component (a2) having a film thickness in the range of 80 to 120 μm is selected, and is cut into a circular shape with a diameter of 70 mm as a test sample. In this case, a test sample having a component (a2) amount of 0.35 ± 0.1 g is used. In addition, the board | substrate which apply | coats (a2) component shall use 70-120 micrometers in thickness, and a moisture permeability of 25-35%.
(2) Measurement of moisture permeability
Moisture permeable cup specified in JIS L 1099: 2006 “Method of measuring moisture permeability of textile products” [cylindrical cup with an inner diameter of 60 mm and a depth of 22 mm, for measuring the moisture permeability on the circumference of the opening. A sheet having a 15 mm-wide ring-shaped plane portion is used so that the sheet can be sandwiched between the plane rings. ] 10 g of anhydrous calcium chloride pulverized into powder in a mortar and set a ring-shaped rubber packing.
A test sample with a diameter of 70 mm cut out earlier is placed on the rubber packing with the side to which the coating of the component (a2) is attached facing down, and a diameter of 90 mm and an inner diameter for fixing the test sample thereon. Place a 60mm flat aluminum ring and fix it firmly with screws.
The mass of this was measured and recorded (initial mass). Then, it leaves still at 50 degreeC and 70% of humidity for 4.5 hours, and measures mass again (mass after standing). And after standing, mass (g)-initial mass (g) is calculated | required as moisture permeability (g).
On the other hand, when the sheet which is the test sample is not sandwiched, the moisture permeability is similarly determined, and the moisture permeability ratio of each test sample when the moisture permeability is 100% is defined as the moisture permeability. The component (a2) does not correspond to the component (a2-1) or the component (a2-2), an anionic surfactant, and poly having 12 to 18 carbon atoms and 3 to 25 added moles of ethylene oxide. containing one or more surfactants selected from polyoxyethylene alkyl ethers (a2-3), the powder detergent composition according to claim 1. (A) The powder cleaning composition of Claim 1 or 2 whose average particle diameter of a component is 1-1000 micrometers. The powder cleaning composition according to claim 3 , wherein the component (A) is alkali metal silicate particles in which the component (a1) is coated with the component (a2). The powder cleaning composition according to claim 3 , wherein the component (A) is alkali metal silicate particles obtained by aggregating the component (a1) with the component (a2). The powder cleaning composition according to any one of claims 1 to 5 , comprising the component (A) and the component (B) as separate particles. Component (a1) 0.5-40% by mass, component (B) 1-40% by mass, component (a2-1), component (a2-2) and other surfactants in total 1-60 % By mass, (e) 0 to 60% by mass of an alkali metal carbonate, and the mass ratio of the (a1) component to the (a2) component is (a2) / (a1) and is 0.01 to 0.7. The powder cleaning composition according to any one of claims 1 to 6 . The powder detergent composition according to any one of claims 1 to 7, wherein a proportion of the component (a2-1) and / or the component (a2-2) in the component (a2) is 50% by mass or more.