JP2007177129A - Soil release polymer-containing particle, method for producing soil release polymer-containing particle and granular detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide soil release polymer-containing particles suppressed in solidification and improved in particle strength and to provide a method for producing the particles and to provide a granular detergent composition using the soil release polymer-containing particles. <P>SOLUTION: The soil release polymer-containing particles comprise (A) a soil release polymer, (B) an organic compound having ≤50°C melting point, (C) oil-absorbing inorganic powder and (D) a water-soluble inorganic substance, and pH at 25°C indicated when the particles are treated as 1 mass% aqueous dispersion is 4-8. The method for producing the particles comprise mixing (A) soil release polymer with (B) an organic compound having ≤50°C melting point at temperatures not lower than both melting points to prepare a melt mixture, mixing the mixture with (C) oil-absorbing inorganic powder and (D) a water-soluble inorganic substance and granulating the mixture. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a soil release polymer-containing particle, a method for producing the soil release polymer-containing particle, and a granular detergent composition containing the soil release polymer-containing particle.

In recent years, there is an increasing number of cases where washing is performed in a situation where mechanical force is difficult to be applied due to a decrease in mechanical force, a reduction in bath ratio, and use of a laundry net accompanying an increase in the size of a washing machine. Therefore, it has become difficult to drop hydrophobic stains to a satisfactory level in normal washing.
As a means for removing such hydrophobic stains, for example, a soil release polymer (water-soluble polymer having a soil-release) also called an SR agent has been studied.
As main soil release polymers, polyesters based on dicarboxylic acids such as terephthalic acid, polyalkylene glycols and monomeric glycols are known.

The soil release polymer is known to be able to impart an effect to the fiber surface to repel dirt and prevent re-contamination of clothing, and application to a detergent is being studied.
When the soil release polymer is used in a granular detergent composition for clothing or the like, it is usually made into particles containing the soil release polymer by granulation, and other components (for example, surfactant, builder (organic builder, inorganic builder), Various types of soil release polymer-containing particles and production methods thereof have been studied so far (see, for example, Patent Documents 1 to 4). For example, Patent Document 4 describes a method in which a soil release polymer is melted, mixed with an inorganic solid, and crushed.
JP 2000-345200 A JP 2000-352000 A JP 2000-26492 A Japanese National Patent Publication No. 10-508895

However, the soil release polymer-containing particles have a problem that they are easily solidified during storage. In addition, the soil release polymer-containing particles have a problem of low particle strength.
Such problems include, for example, granular detergents that become agglomerated after storage, have poor fluidity, break up particles and generate fine powder, and become miscible with other particles used in the granular detergent composition. Since the application to a composition becomes difficult, the improvement is calculated | required.
Accordingly, an object of the present invention is to provide a soil release polymer-containing particle in which solidification is suppressed and particle strength is improved, a method for producing the same, and a granular detergent composition using the soil release polymer-containing particle.

  A first aspect of the present invention that solves the above problems is (A) a soil release polymer, (B) an organic compound having a melting point of 50 ° C. or lower, (C) an oil-absorbing inorganic powder, and (D) a water-soluble inorganic substance. And a soil release polymer-containing particle having a pH of 4 to 8 at 25 ° C. when it is made into a 1% by mass aqueous dispersion.

  The second aspect of the present invention is a mixture prepared by mixing (A) a soil release polymer and (B) an organic compound having a melting point of 50 ° C. or lower at a temperature equal to or higher than both melting points, and (C) an oil absorption. It is a manufacturing method of the soil release polymer containing particle | grains characterized by mixing and granulating water-soluble inorganic powder and (D) water-soluble inorganic substance.

The third aspect of the present invention is a granular detergent composition containing the soil release polymer-containing particles of the first aspect.
The fourth aspect of the present invention is a granular detergent composition containing soil release polymer-containing particles produced by the method for producing soil release polymer-containing particles of the second aspect.

  According to the present invention, it is possible to provide a soil release polymer-containing particle which is suppressed in solidification and has improved particle strength, a method for producing the soil release polymer-containing particle, and a granular detergent composition using the soil release polymer-containing particle.

<Soil release polymer-containing particles>
The soil release polymer-containing particles of the present invention (hereinafter sometimes referred to as (S) particles) contain the following components (A), (B), (C) and (D) as essential components. .
[(A) component (soil release polymer)]
The component (A) used in the present invention may be what is generally referred to as a soil release polymer, an SR agent or the like. In the present invention, the component (A) is preferably a polymer having an alkylene terephthalate unit and / or an alkylene isophthalate unit and an oxyalkylene unit.
“Having an alkylene terephthalate unit and / or an alkylene isophthalate unit and an oxyalkylene unit” means having the following (a1) unit and the following (a2) unit.
(A1) Unit: One or both of an alkylene terephthalate unit and an isophthalate unit.
(A2) Unit: An oxyalkylene unit.

  Here, “unit” refers to a monomer unit constituting the polymer.

-(A1) unit An alkylene terephthalate unit is represented by the following general formula (I).

（式中、Ｒは低級アルキレン基である。）

(In the formula, R is a lower alkylene group.)

In formula (I), the lower alkylene group of R is an alkylene group having 1 to 6 carbon atoms, preferably having 4 or less carbon atoms, and particularly preferably having 2 to 4 carbon atoms.
Specific examples of alkylene terephthalate units include ethylene terephthalate units, propylene terephthalate units, isopropylene terephthalate units, n-butylene terephthalate units, isobutylene terephthalate units, sec-butylene terephthalate units, tert-butylene terephthalate units, and mixtures thereof. Among them, ethylene terephthalate units and / or isopropylene terephthalate units are preferable.

  The alkylene isophthalate unit is represented by the following general formula (II).

（Ｒは低級アルキレン基である。）

(R is a lower alkylene group.)

In the formula (II), examples of the lower alkylene group for R include the same alkylene groups as those for R in the formula (I).
Specific examples of alkylene isophthalate units include ethylene isophthalate units, propylene isophthalate units, isopropylene isophthalate units, n-butylene isophthalate units, sec-butylene terephthalate units, tert-butylene isophthalate units, and these Among them, ethylene isophthalate units and / or isopropylene isophthalate units are preferable.

In the component (A), one selected from the units (a1) may be contained alone or in combination.
The alkylene terephthalate unit and the isophthalate unit are usually obtained as a mixture.

-(A2) unit An oxyalkylene unit can be represented by general formula-(R'O) n-.
In the formula, R ′ is a lower alkylene group, and examples of the lower alkylene group of R include the same alkylene groups as R in formula (I), and an ethylene group, a propylene group, or a mixture thereof is preferable. .
n is an integer greater than or equal to 1, Preferably it is 5-200, More preferably, it is 10-150.
Examples of the oxyalkylene unit include an oxyethylene unit of n = 1, an oxypropylene unit; a polyoxyethylene unit where n is 2 or more, a polyoxypropylene unit, a polyoxyethylene polyoxypropylene unit, and the like, and in particular, an oxyethylene unit. Or a polyoxyethylene unit is preferable.
In the component (A), one selected from the units (a2) may be contained alone or in combination of two or more.

  The component (A) includes units other than these essential units (the (a1) unit and the (a2) unit), for example, a unit derived from a polymerization initiator, a polymerization terminator and the like, and other copolymerizable units. However, it is preferable that 80 mol% or more, preferably 90 mol% or more of the total of all units constituting the component (A) is constituted by these essential units.

The component (A) preferably has a weight average molecular weight of 2000 to 50000, more preferably 2000 to 20000. When it is at least the lower limit value, the soil release property is excellent. Moreover, handling property is favorable in it being below an upper limit.
Here, the weight average molecular weight is a value obtained by converting a value measured by GPC (gel permeation chromatography) with a solvent: THF (tetrahydrofuran) using PEG (polyethylene glycol) as a calibration curve.

  The component (A) is, for example, preferably a polymer compound in which the (a1) unit and the (a2) unit are polymerized randomly or in blocks, and in particular, those in which the units are polymerized in blocks are preferred.

As the method for producing the component (A), any method disclosed in various documents, textbooks, patents and the like can be used.
For example, using the method described in Journal of Polymer Science, Vol. 3, pages 609 to 630 (1948), Journal of Polymer Science, Vol. 8, pages 1 to 22 (1951), Japanese Patent Application Laid-Open No. 61-218699. Alternatively, other methods may be used.

  Specific examples of the component (A) include trade name TexCare SRN-200 (manufactured by Clariant GmbH, Germany, weight average molecular weight 6000) (hereinafter abbreviated as SRN-200), trade name TexCare SRN-300 (Germany, Clarant GmbH). SR agent commercially available as “Made in Japan” (weight average molecular weight 7000) (hereinafter abbreviated as SRN-300).

  As a suitable component (A), the specific structure of the SR agent corresponding to SRN-200 and SRN-300 is shown in the following general formula (III).

In formula (III), A and B are each independently a hydrogen atom or a methyl group, preferably a methyl group.
R ¹ is an alkylene group having 2 to 4 carbon atoms.
R ² is a methyl group and / or a hydrogen atom, and a methyl group is preferable.
x is preferably 0 to 15, more preferably 0.5 to 13, and particularly preferably 1 to 10.
y is 1 to 200, preferably 1 to 150, particularly preferably 1 to 130.
When x and y are within the above ranges, the performance of the anti-staining property is sufficiently reduced when blended into the granular detergent composition and the performance is sufficiently exhibited.

  In the above general formula (III), those having terephthalate units are shown, but the component (A) may have isophthalate units, and those having terephthalate units and those having isophthalate units. A mixture with may also be used. That is, as the component (A), in the general formula (III), the partial structure shown in parentheses with the subscript X is represented by the following general formula (IV), (V), or (VI). Those substituted in the structure may be included.

^{R 2} and x in the formula (IV) ~ (VI) are the same as ^{R 2} and x in the formula (III).

  In (S) particles, the amount of component (A) is not particularly limited, but is usually preferably 5 to 60% by mass, and 10 to 50% by mass with respect to the total mass of (S) particles. More preferably, 20-40 mass% is still more preferable. When the blending amount of the component (A) is equal to or higher than the lower limit, the soil release performance is favorably exhibited, and when it is equal to or lower than the upper limit, the cost can be reduced.

[Component (B) (organic compound having a melting point of 50 ° C. or lower)]
Component (B) is an organic compound having a melting point of 50 ° C. or lower. The component (B), together with the components (C) and (D), contributes to suppression of solidification of the (S) particles and improvement of particle strength, and is particularly effective in improving particle strength. The melting point is preferably 50 ° C. or lower. Although there is no restriction | limiting in particular as a lower limit, Considering the exudation of (B) component, 0 degreeC or more is preferable and 15 degreeC or more is more preferable.

  The “melting point” in the present specification and claims is a value that can be measured by the melting point measurement method described in JIS K0064-1992 “Method for measuring the melting point and melting range of chemical products”.

In this invention, as (B) component, it is a well-known organic compound as a detergent component, Comprising: A compound whose melting | fusing point is 50 degrees C or less is used suitably.
Specifically, nonionic surfactants exemplified below include those having a melting point of 50 ° C. or lower, polyethylene glycol (PEG) having a melting point of 50 ° C. or lower, and the like.

Examples of nonionic surfactants include the following.
(1) Polyoxyalkylene alkyl (or alkenyl) obtained by adding an average of 3 to 30 moles, preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms ether.
Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable.
Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) Fatty acid alkyl ester alkoxylate represented by, for example, the following general formula (1), in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
R ¹ CO (OA) _n OR ² (1)
(In the formula, R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA represents an alkylene having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms such as ethylene oxide and propylene oxide. Represents an addition unit of oxide, and n represents the average number of moles of alkylene oxide added, and is generally a number of 3 to 30, preferably 5 to 20. R ² may have a substituent of 1 to 3 carbon atoms. A good lower (C1-C4) alkyl group is shown.)
(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbite fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.
(9) Polyoxyalkylamine

Among the nonionic surfactants described above, the above-described nonionic surfactants (1) and (3) are preferable. In particular, an average of 5 to 5 alkylene oxides having 2 to 4 carbon atoms are added to aliphatic alcohols having 8 to 18 carbon atoms. Polyoxyalkylene alkyl (or alkenyl) ether added with 20 moles is preferred.
Polyoxyethylene alkyl (or alkenyl) ether having an HLB value of 9 to 16, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, fatty acid methyl ester ethoxylate in which ethylene oxide is added to fatty acid methyl ester, ethylene in fatty acid methyl ester Fatty acid methyl ester ethoxypropoxylate added with oxide and propylene oxide is also preferably used.
In addition, the HLB value of the nonionic surfactant in this specification is a value calculated | required by the method of Griffin (Yoshida, Shindo, Ogaki, Yamanaka co-edition, "New edition surfactant handbook", Kogyoshosho, 1991). Year, page 234).

As PEG, that whose weight average molecular weight is 380-1600 is preferable, and what is 570-1600 is more preferable.
Examples of commercially available products of PEG include PEG # 600 (melting point: 19 to 23 ° C., weight average molecular weight: 570 to 630), PEG # 1000 (melting point: 35 to 39 ° C., weight average molecular weight: 950 to 1050) manufactured by Lion Chemical Co., Ltd. ), PEG # 1540 (melting point: 43 to 47 ° C., weight average molecular weight: 1300 to 1600) and the like.

These (B) components can be used individually by 1 type or in combination of 2 or more types as appropriate. Among these, at least one selected from the group consisting of AE and MEE used in Examples described later and PEG is preferable.
(S) The content of the component (B) in the particles is preferably 5 to 30% by mass, more preferably 5 to 20% by mass, and still more preferably 10 to 20% by mass. When the content of the component (B) is not less than the lower limit of the above range, the effect of the present invention is improved, and when it is not more than the upper limit of the above range, the solidification resistance during storage of the soil release polymer-containing particles is good. Good particle handling.

[(C) component (oil-absorbing inorganic powder)]
The “oil-absorbing inorganic powder” is a water-insoluble inorganic powder having fine irregularities on the surface and pores in the particles and capable of absorbing and carrying a liquid such as oil in the irregularities and pores. The component (C) contributes to the suppression of solidification of the (S) particles and the improvement of particle strength together with the components (B) and (D), and is particularly effective for suppressing the solidification.
As the component (C), the oil absorption measured in accordance with JIS-K5101-13-2 [Pigment Test Method-Part 13: Oil Absorption-Section 2: Boiled Apricot Oil Method] is 80 mL / 100 g or more. A substance having the oil-absorbing property is preferable. When the oil supply amount is 80 mL / 100 g or more, the handling property is good. Moreover, particle strength improves that it is 600 mL / 100g or less, and handling property is also favorable. The oil absorption is more preferably 100 to 600 mL / 100 g.

In order to obtain good stability of the component (A), the component (C) preferably has a pH of 8 or less at 25 ° C. when a 1% by mass aqueous dispersion is prepared. The lower limit of the pH is preferably 4 or more. (C) The more preferable range of pH of a component is 5-8. When the pH is within the above range, the soil release performance is good.
The pH value of the component (C) in the present invention is the pH value at 25 ° C. of the aqueous solution or dispersion obtained when the component (C) is dissolved or dispersed in water so that the concentration becomes 1% by mass. Value.

  The bulk density of the component (C) is preferably 0.005 to 0.2 g / mL, more preferably 0.02 to 0.1 g / mL.

Specific examples of the component (C) are given below.
Amorphous silicic acid (oil absorption: 250 mL / 100 g, bulk density: 0.06 g / mL, pH 7.5) (Tokuyama “Toceal NR”, Nippon Aerosil “Aerosil”, Nippon Silica “Nip Seal” ).
Amorphous calcium silicate (oil absorption: 450 mL / 100 g, bulk density: 0.03 g / mL) (“FLORITE” manufactured by Toxo Corporation, “Tixorex” manufactured by Cochrane Chemical Co.).
Amorphous aluminosilicate (oil absorption: 150 mL / 100 g, bulk density: 0.08 g / mL).
Magnesium silicate (oil absorption: 180 mL / 100 g, bulk density: 0.08 g / mL).
Magnesium carbonate (oil absorption: 150 mL / 100 g, bulk density: 0.08 g / mL).
Calcium carbonate (oil absorption: 110 mL / 100 g, bulk density: 0.09 g / mL).
Spinel (oil absorption amount: 600 mL / 100 g, bulk density: 0.008 g / mL).
Cordierite (oil absorption: 600 mL / 100 g, bulk density: 0.008 g / mL).
・ Mullite (oil absorption: 560 mL / 100 g, bulk density: 0.009 g / mL).
Diatomaceous earth (oil absorption: 100 mL / 100 g, pH 7.0) (“Silica 100S” manufactured by Chuo Silica Co.)

These oil-absorbing inorganic powders may be used alone, or a mixture of two or more kinds may be used as the component (C).
(S) As for content of (C) component in particle | grains, 5-70 mass% is preferable, 10-60 mass% is more preferable, 10-50 mass% is further more preferable. (C) By making content of a component more than the lower limit of the said range, the favorable stability of (A) component in detergent solution is obtained, and it is favorable by making it below the upper limit of the said range. The effect of preventing recontamination can be obtained.

[(D) component (water-soluble inorganic substance)]
The component (D) contributes to the suppression of solidification of the (S) particles and the improvement of the particle strength together with the components (B) and (C), and is particularly effective for improving the particle strength.
Here, the “water-soluble inorganic substance” is an inorganic substance exhibiting solubility in water.
“Showing solubility in water” means that 1 g of the inorganic substance is completely dissolved when added to 1 L (25 ° C.) of water.

Examples of component (D) include salts of strong acids such as sulfuric acid and hydrochloric acid with strong bases such as sodium hydroxide, potassium hydroxide and magnesium hydroxide.
In the present invention, the component (D) is preferably one in which the aqueous solution exhibits neutrality (pH within the range of 4 to 8 at 25 ° C.) when the aqueous solution is prepared. Specifically, sodium sulfate, potassium sulfate, Examples include neutral salts such as sodium chloride and potassium chloride. Among these, sodium sulfate is preferable.
Sodium sulfate may be a hydrate or an anhydride. For example, anhydrous mirabilite is commercially available and is easily available, and therefore an anhydride is preferably used.

  (S) As for content of (D) component in particle | grains, 5-70 mass% is preferable, 5-60 mass% is more preferable, 10-55 mass% is further more preferable. By setting the content of the component (D) to be equal to or higher than the lower limit of the above range, the particle strength of the (S) particles is improved. Moreover, the balance with another component is favorable by setting it as below the upper limit of the said range.

[Other optional ingredients]
In addition to the component (A), the component (B), the component (C), and the component (D), the (S) particles are other optional components (hereinafter referred to as (E), as long as the effects of the present invention are not impaired. May be referred to as a component).
The (S) particle | grains of this invention may contain the cellulose and raw starch which play an oil-absorbing support | carrier as (E) component.
As the component (E) other than the above, for example, a component known as a component of a detergent composition (for example, a component known as a builder of a detergent composition, a component known as a bulking agent, an anionic surfactant, and The acid precursor thereof can be used. Specific examples of such components include acrylic acid polymers, acrylic acid maleic acid copolymers, fatty acids, linear alkylbenzene sulfonates (LAS), polyoxyethylene alkyl ether sulfates (AES), and the like.
(E) It is preferable that an alkaline component is not contained in a component.

[(S) particles]
The (S) particles have a pH of 4 at 25 ° C. of 4% in terms of suppressing the solidification of the (S) particles and obtaining a good stability of the component (A) at 1% by mass aqueous dispersion. Must be in the range of ~ 8. When the pH is within the above range, the soil release performance is good. The pH is more preferably in the range of 5-8.
In addition, the value of “pH at 25 ° C. when a 1% by mass aqueous dispersion is used” of (S) particles in the present invention is the value obtained by dissolving or dispersing (S) particles in water so that the concentration becomes 1% by mass. This can be determined by measuring the pH at 25 ° C. of the liquid (aqueous dispersion) obtained when the liquid is made.
The pH can be adjusted using, for example, a pH adjusting agent or the like as described in the method for producing the soil release polymer-containing particles of the present invention described later.

(S) The average particle diameter of the particles is preferably 150 to 2000 μm, more preferably 200 to 1500 μm, and still more preferably 300 to 700 μm. When it is above the lower limit, when (S) particles are blended in the granular detergent composition, they are mixed uniformly and classification is suppressed. When it is below the upper limit, the dissolution rate of the (S) particles is high, and the performance of the (S) particles is exhibited well.
The bulk density of (S) particles is preferably 0.4 g / mL or more, more preferably 0.5 to 1.0 g / mL, and still more preferably 0.5 to 0.95 g / mL.
(S) The average particle diameter and bulk density of the particles can be measured in accordance with, for example, JIS K3362: 1998.

Further, the mass ratio (A / B) of the component (A) and the component (B) contained in the (S) particles is preferably 95/5 to 50/50, more preferably 80/20 to 50/50. . (B) By making the ratio of a component more than the lower limit of the said range, the solubility with respect to the water of (S) particle | grains is favorable, and it is favorable by making the ratio of (A) component more than the lower limit of the said range. Re-contamination prevention effect can be obtained.
(S) The total content of the component (A) and the component (B) in the particles is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass. By setting the total content of the component (A) and the component (B) within the above range, a good recontamination preventing effect can be obtained.

  Although the (S) particle | grains of this invention can be manufactured with a well-known manufacturing method, it is preferable to manufacture with the manufacturing method of the (S) particle | grain of the following this invention.

<Method for producing soil release polymer-containing particles>
In the method for producing the soil release polymer-containing particles (hereinafter referred to as (S) particles) of the present invention, the (S) particles were prepared by mixing the components (A) and (B) at a temperature equal to or higher than their melting points. The molten mixture, the component (C), and the component (D) are mixed and granulated.
(S) particle | grains with high particle | grain intensity | strength are obtained by melt | dissolving (A) component and (B) component previously, and making it a uniform mixture. Moreover, the soil release polymer containing particle | grains which express recontamination prevention ability efficiently are obtained by melt | dissolving beforehand and setting it as a uniform mixture.
At this time, when the molten mixture, the component (C) and the component (D) are mixed, or before or after mixing, other optional components may be mixed.

  As the component (A), the component (B), the component (C), the component (D) and other optional components, the component (A), component (B), The same thing as (C) component, (D) component, and other arbitrary components ((E) component)) is mentioned.

  The “temperature above the melting point of both the component (A) and the component (B)” means a temperature equal to or higher than the higher melting point of the melting point of the component (A) and the melting point of the component (B). By mixing the component (A) and the component (B) at such a temperature, the molten mixture can be made into a uniform mixture.

The melting point (fluidization point) of the molten mixture of component (A) and component (B) can be measured as follows.
The prepared molten mixture is filled to a height of about 1/3 of a glass container having a diameter of 5 cm and a height of 10 cm, and is left to solidify by being left at 5 ° C. for about 12 hours. The glass container is immersed in a water bath so that the water surface reaches the level of the contents, and the temperature at which the molten mixture fluidizes is obtained while raising the temperature by 5 ° C., and the temperature is taken as the melting point. The fluidization of the molten mixture is confirmed by checking whether or not the angle formed between the surface (liquid level) and the horizontal plane is 45 ° or less by flowing the molten mixture within 1 minute after the glass container is turned over. .

Mixing of the molten mixture prepared by mixing the component (A) and the component (B) at a temperature equal to or higher than the melting point of the component, the component (C), and the component (D) is +5 of the melting point of the molten mixture. It is preferable to carry out at a temperature (mixing temperature) of -20 ° C. By mixing each component at such a mixing temperature, it is possible to produce particles that are uniformly mixed with the components (C) and (D), have excellent solidification resistance, and excellent particle strength.
The mixing temperature is more preferably +5 to + 20 ° C., more preferably +5 to + 15 ° C., which is the higher melting point of the melting points of both the component (A) and the component (B).
The adjustment of the mixing temperature is, for example, a method of setting the temperature in the mixer to be used (for example, the kneader in the following method (1), the stirring granulator in the method (2)), the component (C), The component (D) and the optional (E) component are adjusted so as to have an appropriate temperature when mixed with the component (A) and the component (B), and the component (C), the component (D) and the optional component (E) There is a method of preheating. Temperature regulation is not limited by these methods.

The preparation of the molten mixture and the mixing of the molten mixture with the component (C) and the component (D) may be performed by one apparatus or may be performed by another apparatus.
As a method for preparing the molten mixture and mixing the component (C) and the component (D) with one apparatus (kneader), for example, first, the component (A) and the component (B) are mixed in a kneader. There is a method in which the components are charged and mixed at a temperature equal to or higher than the melting point of both, and then the components (C) and (D) are charged and mixed.
In the case of using a continuous kneader, first, the components (A) and (B) are charged at the inlet of the continuous kneader, and then the components (C) and ( D) Component may be added and mixed.

  The granulation after mixing the molten mixture, the component (C) and the component (D) is a general granulation method such as extrusion granulation method, compression granulation method, stirring granulation method, rolling granulation method. A fluidized bed granulation method can be used.

In the present invention, it is preferable to perform granulation of the molten mixture by the following method (1) or (2).
Method (1): The molten mixture, the component (C), and the component (D) are charged into a kneader and mixed to prepare a kneaded mixture at a temperature equal to or higher than the melting point of the molten mixture, or The component (A) and the component (B) are charged into a kneader, mixed at a temperature equal to or higher than the melting point of both, and then the component (C) and the component (D) are charged to obtain a kneaded product. A method in which the prepared kneaded product is extruded and granulated in an environment below the melting point of the molten mixture.
Method (2): The component (C) and the component (D) are fluidized in a stirring granulator, the molten mixture is added thereto, and the melting point of the molten mixture is −20 to + 20 ° C. Granulation method at particle surface temperature.

Hereinafter, each of these methods (1) and (2) will be described in more detail.
In method (1), the molten mixture, the component (C), and the component (D) are charged into a kneader and mixed to prepare a kneaded material at a temperature equal to or higher than the melting point of the molten mixture. When extruding and granulating in an environment below the melting point of the molten mixture, it is preferable to produce the (S) particles as follows.
First, (A) component and (B) component are mixed at the temperature more than both melting | fusing point, and a molten mixture is obtained. At this time, water may be added. If necessary, heat and melt. The heating temperature is preferably about 40 to 80 ° C.
Next, the obtained molten mixture, the component (C), the component (D) and other optional components are kneaded in an extruder, and the obtained kneaded product is extruded by the extrusion method (A) and (B). Extruded under an environment below the melting point of the molten mixture of, to obtain a pellet-shaped or noodle-shaped molded product.
At this time, the temperature of the kneaded product is preferably +1 to 20 ° C., more preferably +1 to 10 ° C. of the melting point of the molten mixture. When the temperature of the kneaded material is within the above range, the extrusion resistance from the extruder is small and the production efficiency is excellent.
“Environment below the melting point of component (A) and component (B)” means a temperature environment lower than the melting point of component (A) and the melting point of component (B). By extruding the kneaded product in such a temperature environment, the kneaded product is solidified and a molded product is obtained.
At this time, a part of the component (C) may be used as a surface treatment agent and used for the surface treatment of the kneaded product.
Next, the obtained molded product is pulverized to obtain granular (S) particles.

In the method (1), the components (A) and (B) are charged into a kneader, mixed at a temperature equal to or higher than the melting point of both, and then the components (C) and (D) are charged. A kneaded material may be prepared in this manner, and the kneaded material may be extruded and granulated in an environment below the melting point of the molten mixture. That is, the component (C) and the component (D) may be mixed in a state where the component (A) and the component (B) are not completely melted and mixed.
In this case, the (S) particles are prepared by, for example, putting the component (A) and the component (B) into a kneader and mixing them at a temperature equal to or higher than their melting points, and then mixing the component (C) and the component (D). ) Component is prepared by continuous kneading and mixing, and the mixture is granulated in the same manner as described above. In addition, the components (A) and (B) are mixed in the kneading machine at a temperature equal to or higher than the melting point of both, and then the components (C) and (D) are added to the same kneading machine and mixed. The kneaded product may be prepared by doing so.

  In the method (1), it is preferable to prepare the molten mixture in advance, and charge and mix the molten mixture, the component (C), and the component (D).

In the method (2), it is generally preferable to produce the (S) particles as follows.
In advance, the component (A) and the component (B) are mixed at a temperature equal to or higher than their melting points to obtain a molten mixture. At this time, water may be added. Melt by heating if necessary. The heating temperature is preferably about 40 to 80 ° C.
And (C) component, (D) component, and other arbitrary components are thrown in in a stirring granulator, and stirring is started (fluidized). After making it into a fluidized state, the previously prepared molten mixture is added into a stirring granulator and granulated to obtain (S) particles.
At this time, a part of the component (C) may be used as a surface treatment agent and used for the surface treatment of the granulated product.
At this time, the granulation is performed at a particle surface temperature of −20 to + 20 ° C. of the mixing temperature of the molten mixture, preferably −20 to + 5 ° C. of the mixing temperature of the molten mixture, more preferably −10 to + 5 ° C. Thereby, adhesion in the stirring granulator can be suppressed, the particle size is excellent in average, and the obtained (S) particles are hardly solidified and have high particle strength.
“Particle surface temperature” is the surface temperature of particles present in the agitation granulator after the addition of the molten mixture, and is measured using a surface thermometer (HA-100 manufactured by Anritsu Keiki Co., Ltd.). Can do. The particle surface temperature can be adjusted by the jacket temperature and the preparation temperature of the component (C) and the component (D).

Since the (S) particles obtained by the method for producing (S) particles of the present invention have improved particle strength and solidification is suppressed, the pH at 25 ° C. when a 1% by mass aqueous dispersion is obtained. It is preferably within the range of 4-8, and more preferably within the range of 5-8. Moreover, stability of (A) component also improves that it is pH within the said range.
The pH can be adjusted by appropriately selecting a pH adjusting agent and adding an appropriate amount.
Examples of the pH adjuster include organic acids such as citric acid and malic acid and salts thereof, potassium dihydrogen phosphate, sodium dihydrogen phosphate and the like.

The (S) particles of the present invention and the (S) particles produced by the production method of the present invention are those in which solidification is suppressed and particle strength is improved. Easy to mix with other particles in the production of granular detergent compositions because solidification is difficult to occur after storage, and because particle strength is high and it is difficult to break, resulting in less variation in particle size. It is.
Further, the (S) particles of the present invention and the (S) particles produced by the production method of the present invention have good solubility in water, for example, good for low-temperature water of about 15 ° C. Shows solubility.
In addition, since a soil release polymer usually tends to decompose when it comes into contact with an alkaline component, there is a problem that stability in a detergent solution is poor and it is difficult to sufficiently exert a recontamination preventing effect. The (S) particles and the (S) particles produced by the production method of the present invention are also excellent in the stability of the soil release polymer in a mixed state with particles containing alkaline components (detergent particles). Even when used in combination, a good anti-recontamination effect can be obtained.
Accordingly, the (S) particles of the present invention and the (S) particles produced by the production method of the present invention are suitable for a granular detergent composition.

<Granular detergent composition>
The granular detergent composition of the present invention contains (S) particles of the present invention or (S) particles produced by the method for producing (S) particles of the present invention.
The content of (S) particles is preferably 0.1 to 10% by mass and more preferably 0.5 to 5% by mass with respect to the total amount of the granular detergent composition from the viewpoint of cleaning performance.

The granular detergent composition of the present invention may contain particles other than (S) particles. Examples of such particles include known particles as constituent particles of the granular detergent composition. Examples of such particles include the following (1) to (6). Any of these particles can be produced by a known method, or can be obtained from a commercial product.
(1) Anionic surfactant-containing particles The content of the anionic surfactant in the anionic surfactant-containing particles is preferably 10 to 50% by mass, and more preferably 15 to 40% by mass.
The average particle size is preferably 200 to 1000 μm, more preferably 300 to 700 μm. The bulk density is preferably 0.65 g / mL or more, more preferably 0.7 to 1.0 g / mL.
When the anionic surfactant-containing particles are contained in the granular detergent composition, the content thereof is preferably 10 to 99 mass%, more preferably 20 to 99 mass%, based on the total amount of the granular detergent composition, from the viewpoint of detergency. %.
Components other than the anionic surfactant contained in the anionic surfactant-containing particles are not particularly limited. For example, nonionic surfactant, cationic surfactant, amphoteric surfactant, inorganic compound, water-soluble polymer compound, inorganic Examples include builders, organic builders, fluorescent agents, fragrances, and dyes.
In particular, it is more preferable from the viewpoint of cleaning performance that both the anionic surfactant and the nonionic surfactant are contained in the same particle.

(2) Nonionic surfactant-containing particles The content of the nonionic surfactant in the nonionic surfactant-containing particles is preferably about 10 to 50% by mass, and more preferably about 10 to 30% by mass.
The average particle size is preferably 200 to 1000 μm, more preferably 300 to 700 μm.
The bulk density is preferably 0.65 g / mL or more, and more preferably 0.7 to 1.0 g / mL.
When nonionic surfactant-containing particles are included in the granular detergent composition, the content thereof is preferably 5 to 95 mass%, more preferably 10 to 50 mass%, based on the total amount of the granular detergent composition, from the viewpoint of detergency. %.
Components other than the nonionic surfactant contained in the nonionic surfactant-containing particles are not particularly limited. For example, anionic surfactant, cationic surfactant, amphoteric surfactant, inorganic compound, water-soluble polymer compound, inorganic Examples include builders, organic builders, fluorescent agents, fragrances, and dyes.

(3) Alkali builder-containing particles The alkali builder content in the alkali builder-containing particles is preferably about 50 to 95% by mass, more preferably about 70 to 90% by mass.
The alkali builder-containing particles are preferably subjected to a surface treatment for solubility in water having a low water temperature. As the surface treatment agent, for example, a water-soluble polymer, a higher fatty acid, or the like is used.
The average particle diameter of the coated alkali builder-containing particles is preferably 200 to 700 μm, and more preferably 300 to 500 μm. The bulk density is preferably 0.6 to 1.4 g / mL, and more preferably 0.7 to 1.3 g / mL.
When alkali builder-containing particles are contained in the granular detergent composition, the content thereof is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, based on the total amount of the granular detergent composition, from the viewpoint of cleaning performance. is there.
As alkali builder-containing particles, carbonates such as sodium carbonate and potassium carbonate, bicarbonates such as sodium bicarbonate and potassium bicarbonate, sesqui carbonates such as sodium sesquicarbonate, sulfites such as sodium sulfite and potassium sulfite, layered Coated inorganic particles obtained by coating (surface treatment) particles having silicates such as silicate as a main component are preferably used.

(4) Bleach component (inorganic peroxide) -containing particles The content of the bleach component in the bleach component-containing particles is preferably about 8 to 15% by mass, more preferably about 10 to 13% as the amount of effective oxygen. preferable.
When moisture or other detergent components come into contact with the surface of the bleach component-containing particles, the inorganic peroxide may be decomposed. Therefore, it is preferable to perform a treatment such as coating to prevent this.
As the bleaching-component-containing particles in a coated form, oxygen-based bleaching particles that have already been proposed can be used. Examples thereof include bleaching particles described in Japanese Patent No. 2918991. The bleaching agent particles are a granulated product obtained by spraying and drying sodium borate particles maintained in a fluidized state separately with a boric acid aqueous solution and an alkali metal silicate aqueous solution. In addition to the above, a conventionally known stabilizer such as a chelating agent may be used in combination with the coating agent.

The average particle size of the coated bleach component-containing particles (preferably sodium percarbonate particles) is preferably from 100 to 2,000 μm, more preferably from 200 to 2,000 μm, from the viewpoint of the stability and solubility of the bleach component-containing particles. It is 1,000 μm, more preferably 300 to 800 μm.
For example, SPC-D manufactured by Mitsubishi Gas Chemical Co., Ltd. can be cited as such sodium percarbonate particles. The bulk density of the bleach component-containing particles is preferably 0.5 to 1.0 g / mL, more preferably 0.7 to 0.9 g / mL.
When the granular detergent composition contains bleach component-containing particles, the content thereof is preferably 0.5 to 30% by mass, more preferably 1 with respect to the total amount of the granular detergent composition from the viewpoint of bleaching performance and efficiency. ˜20 mass%.

(5) Bleach activator-containing particles As the bleach activator, known compounds can be used, but organic peracid precursors are preferred.
The content of the bleach activator in the bleach activator-containing particles is preferably 30 to 95% by mass, more preferably 50 to 90% by mass. If the blending amount is outside this range, the effect of granulation may not be sufficiently obtained.
The bleach activator-containing particles are desirably granulated together with a binder material such as PEG and a surfactant, and the blending amount of the binder material is 0.5 to 30% by mass in the granulated product, preferably 1 to 20%. The blending amount of the surfactant powder is preferably 0 to 50% by weight, more preferably 3 to 40% by weight, particularly preferably 5 to 5% by weight in the granulated product. 30% by mass.
The average particle size of the bleach activator-containing particles is preferably 200 to 1,500 μm, more preferably 300 to 1,000 μm, from the viewpoints of solubility and storage stability.
The bulk density is preferably 0.4 to 1.0 g / mL, and more preferably 0.5 to 0.8 g / mL.
When the granular detergent composition contains bleach activator-containing particles, the content thereof is preferably from 0.1 to 15 mass%, particularly preferably from 0.3 to 10 mass%, based on the total amount of the granular detergent composition.

(6) Enzyme particles Commercially available enzyme particles can be used as appropriate. The average particle size of the enzyme particles is preferably 200 to 1,000 μm, more preferably 300 to 700 μm, from the viewpoint of solubility and storage stability.
When enzyme particles are contained in the granular detergent composition, the content thereof is preferably 0.1 to 5 mass%, particularly preferably 0.5 to 4 mass%, based on the total amount of the granular detergent composition.

The granular detergent composition can be prepared, for example, by mixing (S) particles and other particles.
As a mixing method, for example, dry mixing is preferably used. Any mixer may be used as long as various particles can be sufficiently mixed. As the mixer, a horizontal cylindrical type, a double cone type, a V type, a rotation / revolution type, or the like can be suitably used. Moreover, you may use a stirring granulator and a rolling granulator.

  Among the components blended in the granular detergent composition of the present invention, the alkali component is granulated separately, and (S) particles and (X) particles containing an alkali component (for example, the alkali builder-containing particles of (3) above) ) And are preferably blended separately. Thereby, the stability of the soil release polymer in the (S) particles before being dissolved in water is good. Moreover, the solubility of the granular detergent composition in water is good, for example, it shows good solubility in low-temperature water of about 15 ° C. The dispersibility of the (S) particles when the granular detergent composition is dissolved in water is also good. Furthermore, even in a detergent solution in which an alkali component is dissolved, the stability of the soil release polymer in the (S) particles is excellent, and a good anti-recontamination effect can be obtained.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, “%” represents mass%, and the ratio represents mass ratio.
Measurement methods used in Examples and Comparative Examples are shown below.
<Measurement of melting point of molten mixture>
The melting point (fluidization point) of the molten mixture of component (A) and component (B) was measured as follows.
The prepared molten mixture was filled to a height of about 1/3 of a glass container having a diameter of 5 cm and a height of 10 cm, and allowed to stand at 5 ° C. for about 12 hours to solidify. The glass container was immersed in a water bath so that the water surface reached the level of the contents, and the temperature at which the molten mixture fluidized was determined while increasing the temperature by 5 ° C., and the temperature was taken as the melting point. The fluidization of the molten mixture was confirmed by checking whether or not the angle formed between the surface (liquid level) and the horizontal plane was 45 ° or less by flowing the molten mixture within 1 minute after the glass container was turned over. .

<Measurement of average particle diameter>
In the following examples and comparative examples, the average particle diameter of the particles was measured by the following method.
First, the prepared particles were classified using a sieve having an opening of 2,000 μm, and (S) particles that passed through the sieve having an opening of 2,000 μm were used as samples.
Next, a classification operation was performed using a 9-stage sieve having a mesh opening of 1,680 μm, 1,410 μm, 1,190 μm, 1,000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm and a tray. In the classification operation, a sieve with a small opening is stacked on a tray in the order of a sieve with a large opening, and the above sample is put on the top 1,680 μm sieve at a rate of 100 g / turn, and a lid is put on a low-tap type sieve shaker. Attaching to (made by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute), vibrating for 10 minutes, and then collecting the particles remaining on each sieve and tray for each sieve. Went.
By repeating this operation, 1,410 to 1,680 μm (1,410 μm.on), 1,190 to 1,410 μm (1,190 μm.on), 1,000 to 1,190 μm (1,000 μm.on) 710-1000 μm (710 μm.on), 500-710 μm (500 μm.on), 350-500 μm (350 μm.on), 250-350 μm (250 μm.on), 149-250 μm (149 μm.on), dish- A classified sample having a particle size of 149 μm (149 μm.pass) was obtained, the mass of each classified sample was measured, and the mass frequency (%) was calculated.
Next, the mass frequency of each classified sample is accumulated from the saucer side, the initial sieve opening with an accumulated mass frequency of 50% or more is defined as a μm, and the sieve opening one step larger than a μm is defined as b μm. The average particle size (mass 50%) is obtained by the following equation, where c is the cumulative mass frequency from the tray to the sieve with the aperture of a μm, and d is the mass frequency of the classified sample on the sieve with the aperture of a μm. It was.

<Measurement of bulk density>
The bulk density of the particles was measured according to JIS K3362-1998.

(Examples 1, 2, 3 and Comparative Example 1)
According to the composition shown in Table 1 (the numerical value of each component indicates the blending amount (%)), the component (C) and the component (D) were uniformly mixed, and this was heated and melted at 80 ° C. and mixed in advance. While supplying the molten mixture of the component (A) and the component (B), the mixture was mixed by a kneader (KRC S-1: manufactured by Kurimoto Steel Works) whose jacket temperature was adjusted to 80 ° C. A perforated plate having a hole diameter of 0.8 mm with zigzag 60 ° was attached to the discharge port to obtain a noodle-like extruded granulated product. This is cooled with cold air at 5 ° C., and New Speed Mill (Okada Seiko Co., Ltd.) is used as a grinding aid by using Toxeal NP, which has previously been separated by 2% of the total mass of (S) particles. ).

  The melting points of the molten mixtures of the components (A) and (B) in each of the above Examples 1 to 3 and Comparative Example 1 were Example 1: 40 ° C., Example 2: 45 ° C., and Example 3: 45 ° C., respectively. Comparative Example 1 was 40 ° C. The melting point of each of the component (A) and the component (B) is described in the raw material section of Table 1 described later.

(Examples 4 and 5, Comparative Examples 2 and 3)
Of the compositions shown in Table 1, all components except the component (A) and the component (B)) are equipped with a blade-shaped excavator at 25 ° C. and a shovel-wall clearance is 5 mm. (Matsubo Co., Ltd., M20 type) was charged (filling rate: 50% by volume), and stirring was started under conditions of a main shaft of 200 rpm and a chopper of 6000 rpm. Thirty seconds after the start of stirring, a molten mixture in which the components (A) and (B) were previously heated and melted to 70 ° C. and uniformly mixed was added over 2 minutes, and stirring granulation was performed at a jacket temperature of 30 ° C. The stirring granulation was continued until the average particle size shown in Table 1 was reached.

The melting points of the molten mixture of the component (A) and the component (B) in each of Examples 4 and 5 and Comparative Examples 2 and 3 are as follows: Example 4: 40 ° C., Example 5: 40 ° C., Comparative Example 2: 40 ° C., Comparative Example 3: 35 ° C. The melting point of each of the component (A) and the component (B) is described in the raw material section of Table 1 described later.
In Examples 4 and 5 and Comparative Examples 2 and 3, the particle surface temperature during stirring granulation was measured with a surface thermometer (manufactured by Anritsu Keiki Co., Ltd., product name: HA-100). Example 4: 37 ° C, Example 5: 44 ° C, Comparative Example 2: 32 ° C, Comparative Example 3: 40 ° C.

The following evaluation was performed about the (S) particle | grains obtained above. The results are also shown in Table 1.
<PH at 25 ° C. when 1% by mass aqueous solution>
(S) The pH (1% pH) at 25 ° C. when the particles were dissolved in water to form a 1% aqueous dispersion was measured with a pH meter (manufactured by Toa Denpa Kogyo Co., Ltd .: HM-11P).

<Stability evaluation>
(S) particles were added to a detergent composition (manufactured by Lion Corporation, product name “Top”) so that the content of component (A) was 1%, and mixed uniformly. The obtained (S) particle-containing detergent composition was stored for 1 month under cycle conditions of 45 ° C., 16 hours, followed by 25 ° C., 8 hours, and the obtained sample A was used as an evaluation target.
An aqueous solution or dispersion dissolved or dispersed in 900 mL of 25 ° C. tap water so that the concentration of sample A is 667 ppm is added to Terg-O-Tometer (manufactured by Testing, USA), and dirt oil (Tristearin / (Oleic acid / carbon = 100/100/1 mixture) After adding 0.3 mL, stirring was performed at 120 rpm for 1 minute, stirring was stopped, and a recontamination evaluation cloth was introduced. After introducing the recontamination evaluation cloth, the recontamination evaluation cloth was taken out by further stirring for 10 minutes.
The reflectance (Z value) of the recontamination evaluation cloth before and after the experiment was measured using a reflectometer, and the difference in reflectance (ΔZ) before and after the experiment was defined as the recontamination property of the recontamination evaluation cloth.
As a calibration curve, a detergent composition having a composition obtained by removing only the component (A) from the sample A to be evaluated, and a predetermined ratio (0%, 25%, 50 to the content of the component (A) in the sample A to be evaluated %, 75%, and 100%) were used in place of the sample A, and the same experiment as described above was performed to determine the recontamination ΔZ, and a calibration curve was prepared. The soil release polymer was added as a 1% by mass aqueous dispersion.
From the obtained calibration curve, the recontamination ΔZ when using the sample A to be evaluated is calculated as a value when the content of the component (A) is contained. The percentage of the initial content (1%) was calculated, and from the results, the stability of the component (A) in the (S) particles was evaluated according to the following evaluation criteria.
<Evaluation criteria>
○: 60% or more.
Δ: 40% or more and less than 60%.
X: Less than 40%.

<Particle strength evaluation>
Samples were prepared by removing particles passing through a sieve having an opening of 355 μm from the prepared (S) particles.
On the rotating shaft of the Tokyo Science Instruments Co., Ltd. Stirrer Magella Z-1300 (fixed position: 40 cm height from the bottom of the stand) Attached. Next, the cylindrical longitudinal direction center part of the polystyrene cylindrical container (container inner height 123 mm, bottom inner diameter 75 mm) was sandwiched by the above-mentioned clamp so as not to be loosened, and adjusted so that the rotational surface of the cylindrical container was vertical. After the adjustment, 30 ± 0.2 g of alumina balls having a diameter of 4 mm and 10 g of the sample were put into the cylindrical container and stirred at 100 rpm for 10 minutes.
After the completion of stirring, the contents in the cylindrical container were discharged from the top of the sieve in the order of 3350 μm, 355 μm, 250 μm, and a tray in the order of opening and sieved.
After the completion of the above test, the 250 μm sieve particle generation rate [%] was calculated by the following formula (1).
Formula (1) ((A + (BC)) ÷ D) × 100
[In the formula (1), A is the mass of particles that passed through a sieve having an opening of 250 μm after the test was completed; B was a cylindrical container after the contents were discharged after the test was completed (the fine powder that was not discharged remained C is the mass of the empty cylindrical container before the test; D is the mass (10 g) of the sample used in the test. ]
The particle strength was evaluated based on the following evaluation criteria from the generation rate [%] of particles passing through a 250 μm sieve.
<Evaluation criteria>
○: 250 μm sieve passing particle generation rate [%] is less than 30%.
Δ: 250 μm sieve passing particle generation rate [%] is 30% or more and less than 60%.
X: 250 μm sieve passing particle generation rate [%] is 60% or more.

<Evaluation of solidification>
A cylindrical cylinder having a diameter of 5 cm and a height of 5 cm was filled with (S) particles. In a 45 degreeC high temperature tank, the load of 3.0 kgf / cm < ² > was added for 3 minutes with respect to (S) particle | grains, and the cylindrical molded object was obtained. The obtained compact is left on the electronic balance, the pressure arm is lowered under the condition of 3 cm / min, the load is gradually applied to the entire bottom surface of the cylinder, and the maximum load applied until the compact collapses. (Kg) was measured.
The maximum load (kg) applied until the molded body collapsed was evaluated based on the following evaluation criteria.
<Evaluation criteria>
A: Maximum load applied until the molded body collapses: 0.01 kg or more and less than 1 kg.
○: Maximum load applied until the molded body collapses: 1 kg or more to less than 3 kg.
Δ: Maximum load applied until the molded body collapses: 3 kg or more to less than 5 kg.
X: Maximum load applied until the molded body collapses: 5 kg or more.
Here, in view of the blocking property when the (S) particles are stored in the storage tank, the maximum load in the evaluation is preferably less than 3 kg (Δ or more), more preferably less than 1 kg (◯ or more).

The raw materials shown in Table 1 were as follows.
SRN-300: Soil release polymer (manufactured by Clariant, melting point 60-70 ° C.).
-AE: Same as nonionic surfactant A below (melting point: 26-29 ° C).
-MEE: Same as the following nonionic surfactant B (melting point: 34 to 36 ° C).
Tokushir NP: White carbon (manufactured by Tokuyama Corporation, pH 6.0, oil absorption of about 260 mL / 100 g).
Silica 100S: Diatomaceous earth (Chuo Silica Co., Ltd., pH 7.0, oil absorption of about 100 mL / 100 g).
A-type zeolite: Shilton B (manufactured by Mizusawa Chemical Co., Ltd., pure content 80%).
・ Solalite: Neutral anhydrous sodium sulfate (manufactured by Shikoku Kasei Kogyo, Na ₂ SO ₄ )
Cellulose: ARBOCEL FD-600 / 30 (manufactured by J. RETTENMIER & SOEHNE, average fiber length: 45 μm, average fiber thickness (diameter): 25 μm).
Raw starch: Raw tapioca starch (manufactured by Nippon Corn Starch, pH 5.4, oil absorption of about 40 mL / 100 g).

As shown in the results of Table 1, the (S) particles of Examples 1 to 5 had low solidification properties and high particle strength. The stability of the component (A) in the (S) particles was also good.
On the other hand, the (S) particles of Comparative Examples 1 and 2 that did not contain the component (D) were easy to solidify and had low particle strength. Further, in Comparative Example 3 in which 1% pH was 10.3, the (S) particles were easily solidified. Moreover, the stability of the component (A) in the (S) particles was also poor.

(Examples 6 to 10, Comparative Examples 4 to 6)
A granular detergent composition was prepared using the (S) particles produced in Examples 1-5 and Comparative Examples 1-3 and the other particles listed in Table 5.

First, prior to the preparation of the granular detergent composition, (a) anionic surfactant-containing particles, (b) nonionic surfactant-containing particles, and (c) coated inorganic particles as alkali builder-containing particles are produced by the following methods, respectively. did.
<(A) Preparation Method 1 of Anionic Surfactant-Containing Particles>
According to the composition shown in Table 2 below, anionic surfactant-containing particles a1 were prepared by the following procedure.
First, water was put into a jacketed mixing tank equipped with a stirring device, and the temperature was adjusted to 60 ° C. To this, surfactant excluding α-SF-Na and nonionic surfactant was added and stirred for 10 minutes. Subsequently, MA1 (acrylic acid / maleic acid copolymer sodium salt) and a fluorescent agent were added. After further stirring for 10 minutes, a part of the powder A-type zeolite (2.0% equivalent amount (vs. each particle, the same applies hereinafter) for the addition during kneading, 3.2% equivalent amount for the grinding aid, Sodium carbonate, potassium carbonate, and sodium sulfite were added except 5% equivalent amount of each type A zeolite for surface coating. The slurry was further stirred for 20 minutes to prepare a slurry for spray drying having a moisture content of 38%, and then spray dried using a countercurrent spray drying tower at a hot air temperature of 280 ° C. to obtain an average particle size of 320 μm and a bulk density of 0.30 g / Spray-dried particles with cm ³ and 5% moisture were obtained.
On the other hand, an aqueous slurry of α-SF-Na (moisture concentration 25%) obtained by sulfonating and neutralizing the fatty acid ester of the raw material was mixed with a part of the nonionic surfactant (25 relative to α-SF-Na). %) Was added and concentrated under reduced pressure with a thin film dryer until the water content was 11% to obtain a mixed concentrate of α-SF-Na and a nonionic surfactant.

The above-mentioned spray-dried particles, this mixed concentrate, 2.0% equivalent of type A zeolite, 0.5% equivalent of the remaining nonionic surfactant and water except for spray addition, and continuous kneader (Kurimoto Co., Ltd.) (Kakosho, KRC-S4 type) was kneaded under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C. to obtain a surfactant-containing kneaded product. This surfactant-containing kneaded product was cut with a cutter while extruding it with a pelleter double (Fuji Paudal Co., Ltd., EXDFJS-100 type) equipped with a die having a hole diameter of 10 mm (cutter peripheral speed was 5 m / s) A pellet-shaped surfactant-containing molded product having a length of about 5 to 30 mm was obtained.
Next, 3.2% equivalent amount of particulate A-type zeolite (average particle size: 180 μm) as a grinding aid was added to the obtained pellet-shaped surfactant-containing molded product, and coexisting with cold air (10 ° C., 15 m / s) The powder was pulverized using a Fitz mill (manufactured by Hosokawa Micron Co., Ltd., DKA-3) arranged in series at the bottom (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation Number: 1st stage / 2nd stage / 3rd stage are all 4700 rpm). Finally, filled with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, the inner wall surface of the drum of the container 131.7L has two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm) Rolling for 1 minute while spraying 0.5% equivalent of nonionic surfactant and fragrance, adding 1.5% equivalent of fine powder A-type zeolite under the conditions of rate 30 volume%, rotation speed 22rpm, 25 ° C Then, the surface was modified to obtain particles.
In order to color a part of the obtained particles, the surfactant-containing particles are transported at a speed of 0.5 m / s on the belt conveyor (the height of the surfactant-containing particle layer on the belt conveyor is 30 mm, the layer width) 300 mm) A 20% aqueous dispersion of a pigment was sprayed on the surface to obtain surfactant-containing particles a1 (average particle size of 500 μm).

  Surfactant-containing particles a3 (average particle diameter and bulk density are listed in Table 2) were obtained in the same manner as the preparation method of the surfactant-containing particles a1.

<(A) Preparation Method 2 of Anionic Surfactant-Containing Particles>
According to the composition shown in Table 2 below, surfactant-containing particles a2 were prepared by the following procedure. First, water was put into a jacketed mixing tank equipped with a stirring device, and the temperature was adjusted to 50 ° C. To this, sodium sulfite and a fluorescent agent were added and stirred for 10 minutes. Subsequently, after adding sodium carbonate, MA2 (polyacrylic acid sodium salt) was added, and after stirring for another 10 minutes, a part of the powder A-type zeolite was added. Furthermore, the slurry for spray drying was prepared by stirring for 30 minutes.
The temperature of the obtained slurry for spray drying was 50 ° C. This slurry was spray-dried with a counter-current spray dryer equipped with a pressure spray nozzle to obtain spray-dried particles having a water content of 3%, a bulk density of 0.50 g / cm ³ , and an average particle size of 250 μm.
Separately, a nonionic surfactant and an anionic surfactant were mixed at a temperature of 80 ° C. to prepare a surfactant composition having a water content of 10%. LAS-Na was used as a solution neutralized with an aqueous sodium hydroxide solution.

Then, the obtained spray-dried particles were put into a Roedige mixer (M20 type, manufactured by Matsubo Co., Ltd.) equipped with a blade-shaped excavator and having a clearance between the shovel and the wall surface of 5 mm (filling rate 50% by volume). The stirring of the main shaft (150 rpm) and the chopper (4000 rpm) was started while flowing 80 ° C. warm water through the jacket at a flow rate of 10 L / min. The surfactant composition prepared above was added thereto over 2 minutes and then stirred for 5 minutes, and then a layered silicate (SKS-6, average particle size 5 μm) and a part of the powder A-type zeolite (10 % Equivalent amount) and stirred for 2 minutes to obtain particles.
In order to color a part of the surfactant-containing particles after mixing the obtained particles and a part of powder A-type zeolite (equivalent to 2%) with a V blender and spraying a fragrance, an anionic surfactant A 20% aqueous dispersion of the dye was sprayed in the same manner as in Preparation Method 1 of Containing Particles to obtain surfactant-containing particles a2 (average particle size 300 μm, bulk density 0.78 g / cm ³ ).

<(B) Method for preparing nonionic surfactant-containing particles>
According to the composition shown in Table 3 below, nonionic surfactant-containing particles b1 to b2 were prepared by the following procedure.
Of the composition components shown in Table 3 below, all components (temperature 25 ° C.) except the surfactant are equipped with a blade-shaped excavator, and a Roedige mixer (Matsubo Co., Ltd.) having a shovel-wall clearance of 5 mm. (Molding, M20 type) (filling rate 50% by volume), and stirring was started under the conditions of a main shaft of 200 rpm and a chopper of 6000 rpm. After 30 seconds from the start of stirring, a surfactant (nonionic surfactant is heated to 60 ° C. and uniformly mixed) and water (temperature 60 ° C.) are added in 2 minutes, and the jacket temperature is 30 ° C. Under the conditions, the stirring granulation was continued until the average particle size became 1000 μm to obtain particles.

<Preparation of (c) coated inorganic particles>
Coated inorganic particles were obtained by the following production method.
Among the compositions shown in Table 4, sodium carbonate was put into a Ladige mixer (M20 type, manufactured by Matsubo Co., Ltd.) equipped with a blade-shaped shovel and a shovel-wall clearance of 5 mm (filling rate: 30 volumes) %), Stirring of the spindle at 200 rpm was started (the chopper was stopped). After 10 seconds from the start of stirring, a water-soluble polymer compound aqueous solution (MA1) was added in 30 seconds to perform granulation / coating operation.
Subsequently, lauric acid (manufactured by NOF Corporation, NAA-122, melting point 43 ° C.) was added in 30 seconds while continuing stirring of the Leedige mixer.

The raw materials shown in Tables 2 to 4 were as follows.
Α-SF-Na: 14 carbon atoms: sodium salt of α-sulfo fatty acid methyl ester having carbon number 16 = 18: 82 (manufactured by Lion Corporation, AI = 70%, the remainder is unreacted fatty acid methyl ester, sodium sulfate , Methyl sulfate, hydrogen peroxide, water, etc.).
LAS-Na: linear alkyl (C10-14) benzenesulfonic acid. A product obtained by neutralizing Lion LH-200 (LAS-H pure content 96%) manufactured by Lion Co., Ltd. with a 48% aqueous sodium hydroxide solution when preparing the surfactant composition. The compounding quantity in Table 2 shows the mass% as LAS-Na.
LAS-K: linear alkyl (C10-14) benzenesulfonic acid. A product obtained by neutralizing Lipon LH-200 (manufactured by Lion Corporation LAS-H 96%) with a 48% aqueous potassium hydroxide solution when preparing the surfactant composition. The compounding quantity in Table 2 shows the mass% as LAS-K.
Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 40 to 45 ° C., fatty acid composition: C ₁₂ : 11.7%, C ₁₄ : 0.4%, C ₁₆ : 29.2%, C ₁₈ F0 (stearic acid): 0.7%, C ₁₈ F1 (oleic acid): 56.8%, C ₁₈ F2 (linoleic acid): 1.2%, molecular weight: 289 ).
Nonionic surfactant A: LMAO-90 (manufactured by Lion Chemical Co., Ltd., alcohol having an alkyl group having 12 to 14 carbon atoms) an average 15 mol of ethylene oxide adduct (pure 90%).
Nonionic surfactant B: 15 mol of ethylene oxide average adduct of Pastel M-181 (manufactured by Lion Chemical Co., Ltd.)
A-type zeolite: Same as A-type zeolite in Table 1.
MA1: acrylic acid / maleic acid copolymer Na salt, Aqualic TL-400 (manufactured by Nippon Shokubai Co., Ltd., pure 40% aqueous solution)
MA2: acrylic acid / maleic acid copolymer Na salt: Sokalan CP45 (manufactured by BASF) diluted with water to a pure content of 40%.
-Sodium sulfite: anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.).
Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd., average particle size 490 μm, bulk density 1.30 g / cm ³ ).
Sodium carbonate: granular ash (Asahi Glass Co., Ltd. average particle size 320 μm, bulk density 1.07 g / cm ³ ).
Fluorescent agent: Chinopearl CBS-X (manufactured by Ciba Specialty Chemicals) / Chinopearl AMS-GX (manufactured by Ciba Specialty Chemicals) = 3/1 (mass ratio).
Fragrance A: Fragrance composition A shown in JP-A-2002-146399 [Table 11] to [Table 18].
Fragrance B: Fragrance composition B shown in JP-A-2002-146399 [Table 11] to [Table 18].
Fragrance C: Fragrance composition C shown in JP-A-2002-146399 [Table 11] to [Table 18].
Fragrance D: Fragrance composition D shown in JP-A-2002-146399 [Table 11] to [Table 18].
Pigment A: Ultramarine (Daiichi Seika Kogyo Co., Ltd., Ultramarine Blue).
-Dye B: Pigment Green 7 (manufactured by Dainichi Seika Kogyo Co., Ltd.).
Cellulose: Same as cellulose in Table 1.
White carbon: Same as Tokuseal NP in Table 1.

<Preparation of granular detergent composition>
Next, according to the composition of Table 5, a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, baffle plate having a clearance of 20 mm from the inner wall surface and a height of 45 mm on the drum inner wall surface of the container 131.7 L Each particle was mixed for 5 minutes under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. to obtain a granular detergent composition.

  About the obtained granular detergent composition, the granular detergent composition obtained by the test method which changed "sample A" in the soil release polymer stability test about the said (S) particle | grains into "the granular detergent composition of evaluation object" Soil release polymer stability in the product was evaluated. The results are shown in Table 5.

The raw materials shown in Table 5 were as follows.
-Sodium percarbonate particle | grains: SPC-D (Mitsubishi Gas Chemical Co., Ltd. make, sodium percarbonate, effective oxygen amount 13.2%, average particle diameter of 760 micrometers).
Bleach activator granulated product: Organic peracid precursor particles produced by the following method.
As an organic peracid precursor, 70 parts by mass of 4-decanoyloxybenzoic acid (manufactured by Mitsui Chemicals), 20 parts by mass of PEG [polyethylene glycol # 6000M (manufactured by Lion Corporation)], and an α-olefin having 14 carbon atoms Sodium sulfonate powder product (Liporan PJ-400 (manufactured by Lion Corporation)) is put into Hosokawa Micron's Extrude Ohmic EM-6 so that the total amount is 5000 g at a ratio of 5 parts by mass, and kneaded and extruded. Thus, a noodle-like extruded product having a diameter of 0.8 mmφ was obtained. This extruded product (60 ° C.) was introduced into Fitzmill DKA-3 manufactured by Hosokawa Micron Co., Ltd., and 5 parts by mass of A-type zeolite powder was similarly supplied as an auxiliary agent and pulverized to obtain an average particle size of about 900 μm and a bulk density. 0.5 g / mL organic peracid precursor particles (granulated material) were obtained.
Enzyme particles A: Sabinase 12T (Novozymes) / LIPEX100T (Novozymes) / Termamyl 60T (Novozymes) / Celzyme 0.7T (Novozymes) = 5/2/1/2 (mass ratio) mixture (average particle) Diameter 700 μm, bulk density 0.85 g / mL).
Enzyme particles B: Sabinase 12TW (Novozymes) / LIPEX100T (Novozymes) / Stainzyme 12T (Novozymes) = 4/5/1 (mass ratio) mixture (average particle size 700 μm, bulk density 0.85 g / mL) ).

Claims (6)

  (A) Soil release polymer, (B) an organic compound having a melting point of 50 ° C. or less, (C) an oil-absorbing inorganic powder, and (D) a water-soluble inorganic substance. A soil release polymer-containing particle having a pH of 4 to 8 at 25 ° C.   A molten mixture prepared by mixing (A) a soil release polymer and (B) an organic compound having a melting point of 50 ° C. or lower at a temperature equal to or higher than the melting point of both, (C) an oil-absorbing inorganic powder, and (D) A method for producing soil release polymer-containing particles, characterized by mixing and granulating a water-soluble inorganic substance.   The molten mixture, the component (C) and the component (D) are charged into a kneader and mixed to prepare a kneaded material at a temperature equal to or higher than the melting point of the molten mixture, or (A) The component and the component (B) were charged into a kneader, mixed at a temperature equal to or higher than the melting point of the two, and then the component (C) and the component (D) were charged to prepare a kneaded product. The method for producing soil-release polymer-containing particles according to claim 2, wherein the kneaded product is extruded and granulated in an environment below the melting point of the molten mixture.   The component (C) and the component (D) are fluidized in a stirring granulator, the molten mixture is added thereto, and the mixture is granulated at a particle surface temperature of −20 to + 20 ° C. of the melting point of the molten mixture. The manufacturing method of the soil release polymer containing particle | grains of Claim 2 granulated.   The granular detergent composition containing the soil release polymer containing particle | grains of Claim 1. The granular detergent composition containing the soil release polymer containing particle manufactured by the manufacturing method of the soil release polymer containing particle as described in any one of Claims 2-4.