JP4176595B2 - Cleaning composition - Google Patents

Description

  The present invention relates to a powdery or granular detergent composition. More specifically, the present invention relates to a powdery or granular detergent composition having excellent solubility in cold water and suitable for textile products.

  Powdered or granular detergent compositions are strongly directed to higher bulk density and lower usage for the convenience of consumers. However, it is known that higher bulk density and lower usage tend to lower the dissolution rate of the particles constituting the composition. In addition, recent trends in washing machines, such as lowering the temperature of washing water, shortening operating time, and lowering of washing machine power based on environmental / energy issues and economic efficiency, are all powdery or granular detergents. This causes a delay in dissolution of the composition, and as a result, the cleaning ability of the cleaning composition is significantly reduced. Moreover, it is mentioned as a serious subject that the concern that the undissolved residue of the powdery or granular detergent composition remains in the clothing at the end of washing increases.

  On the other hand, depending on the method of charging the powdery or granular detergent composition into the washing machine, the particle aggregate that is partially dissolved and agglomerated only at the surface of the particles, such as during water injection, where mechanical force is difficult to be applied, cannot be fully dispersed into a paste. As a result, there is a problem that inconveniences remaining in the clothes occur. This phenomenon tends to be prominent particularly at low water temperatures of 10 ° C. or less, particularly 5 ° C. or less, where the paste once is difficult to dissolve.

  The residue in the previous garment is due to the slow dissolution rate of the particles, whereas the residue in the later garment has a relatively high dissolution rate, which causes the particles to aggregate under low mechanical force. This is due to pasting.

  Problems due to such residues include damages due to partial exposure of clothing to high concentrations of alkali, bleach, or enzyme, particularly when it remains in paste form.

  Furthermore, the powder or granular detergent composition can be stored in a detergent net in order to avoid residue on clothing due to the slow dissolution rate of the powder or granular detergent composition, or water can be used for convenience. When a single use amount of detergent is packaged and packaged with a natural packaging material, there is a problem that the cleaning composition is present in a collective state, creating a situation under low mechanical force and causing paste formation. was there.

As an attempt to improve the dispersibility and solubility at such a low water temperature, for example, it is known to make the particle size distribution of the cleaning composition a specific distribution (see, for example, Patent Documents 1, 2, and 3). .) It is also known to control the dissolution rate of the entire particle by specifying the composition of the cleaning composition (see, for example, Patent Documents 4, 5, and 6). It is also known to add alkaline filler particles to granular detergent dough (see, for example, Patent Documents 7, 8, and 9).
Re-published WO00 / 42162 Japanese Patent Laid-Open No. 11-35998 JP 2000-351996 A JP-A-8-218093 JP 2001-262194 A JP 2000-336399 A Japanese Patent Laid-Open No. 62-167399 JP-A-62-253699 JP 7-509267 A

  However, the techniques of Patent Documents 1 to 9 require a great deal of effort to adjust the particle size distribution, and significantly reduce the compositional freedom of the cleaning composition. For this reason, it has not reached the technique which distribute | circulates the cleaning composition which improved the solubility in cold water to a market.

  An object of the present invention is to provide a powdery or granular detergent composition which is excellent in solubility in cold water and has a small amount of detergent particles remaining on an object to be cleaned.

The present invention is a cleaning composition containing a surfactant [hereinafter referred to as component (a)] and a non-deliquescent neutral salt [hereinafter referred to as component (b)], comprising the following particles (A): The present invention relates to a detergent composition containing 15 to 80% by mass and 1 to 30% by mass of particles (B).
Particle (A): The component (a) is contained in the particle in an amount of 5% by mass or more, and the particle size (B): the component (b) is contained, and the component (a) is substantially contained. Particles that do not contain and have a particle size of 500 to 1000 μm

  In the present invention, particles having a predetermined particle size range can be obtained by classifying detergent particles with a classifier comprising a sieve having a mesh size of 125 μm, 500 μm, and 1000 μm according to JIS Z 8801.

  According to the present invention, a powdery or granular detergent composition excellent in solubility and dispersibility in cold water can be obtained.

<Particle (A) and component (a)>
The composition of the present invention contains 5% by mass or more of the component (a) in the particles and 15 to 80% by mass of particles (A) having a particle size of 125 to 1000 μm. 18-70 mass% is preferable at the point of washing | cleaning performance and low temperature solubility, 18-60 mass% is more preferable, 20-50 mass% is still more preferable, and 20-40 mass% is especially preferable. Hereinafter, particles containing 5% by mass or more of the component (a) may be collectively referred to as surfactant particles. Further, the component (b) may be contained in the particles (A).

  The composition of the present invention may contain surfactant particles having a particle size of less than 125 μm, but is preferably 10 parts by mass or less, preferably 8 parts by mass or less per 100 parts by mass of the particles (A) in terms of low-temperature solubility. Is more preferable, and 5 mass parts or less is still more preferable. Moreover, although surfactant particle | grains exceeding a particle size of 1000 micrometers may be contained, 15 mass parts or less are preferable per 100 mass parts of particle | grains (A) at a low temperature solubility point, 12 mass parts or less are more preferable, 10 More preferred is less than or equal to parts by weight.

  In the present invention, from the viewpoint of cleaning performance and solubility, the surfactant particles preferably contain 5 to 99% by mass of surfactant, more preferably 10 to 95% by mass, and further 20 to 90% by mass. preferable.

  Examples of the component (a) surfactant include anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants.

  Examples of the anionic surfactant include a sulfate ester salt of an alcohol having 10 to 18 carbon atoms, a sulfate ester salt of an alkoxylated product of an alcohol having 8 to 20 carbon atoms, an alkyl (preferably having 8 to 14 carbon atoms) benzenesulfonate, Paraffin sulfonate (preferably 8 to 18 carbon atoms), α-olefin (preferably 10 to 20 carbon atoms) sulfonate, α-sulfo fatty acid salt (preferably 8 to 18 carbon atoms), α-sulfo fatty acid ( Preferably it is C8-C18) alkyl (preferably C1-C3) ester salt or fatty acid salt (preferably C10-20). In the present invention, a linear alkylbenzene sulfonate having an alkyl chain having 10 to 14 carbon atoms, more preferably 12 to 14 carbon atoms is preferred, and alkali metals and amines are preferred as the counter ion. Or potassium, monoethanolamine, and diethanolamine are preferable.

  Nonionic surfactants include polyoxyalkylene alkyl (8 to 20 carbon atoms) ether, alkyl (preferably 8 to 18 carbon atoms) polyglycoside, polyoxyalkylene alkyl (8 to 20 carbon atoms) phenyl ether, polyoxy Examples include alkylene sorbitan fatty acid (carbon number 8 to 22) ester, polyoxyalkylene glycol fatty acid (carbon number 8 to 22) ester, polyoxyethylene polyoxypropylene block polymer, fatty acid alkanolamide, alkyl polyglycoside and the like. Among these, polyoxyalkylene alkyl ethers obtained by adding an average of 4 to 20 moles of alkylene oxide such as ethylene oxide and propylene oxide to alcohol having 10 to 18 carbon atoms are preferable. These nonionic surfactants preferably have an HLB value (calculated by the Griffin method) of 10.5 to 15.0, more preferably 11.0 to 14.5.

  Examples of the amphoteric surfactant include alkyl (preferably having 8 to 20 carbon atoms) betaine, imidazolinium betaine, amine oxide (preferably having an alkyl group having 8 to 20 carbon atoms), alkyl (preferably having 8 to 20 carbon atoms). 20) Alanine etc. are mentioned.

  Examples of the cationic surfactant include quaternary mono long chain alkyls and di long chain alkyl ammonium salts. These long-chain alkyl groups preferably have 8 to 18 carbon atoms.

  Especially, it is preferable to contain anionic surfactant and nonionic surfactant by the mass ratio of 100 / 0-30 / 70, the mass ratio of 100 / 0-40 / 60 is more preferable, and 100 / 0-50 A mass ratio of / 50 is more preferred.

  From the viewpoint of cleaning performance and solubility, it is preferable that the surfactant particles such as the particles (A) contain one or more selected from water-insoluble inorganic substances, water-soluble polymers, and water-soluble salts. 10-80 mass% is preferable, as for the water-insoluble inorganic substance in surfactant particle | grains, such as particle | grains (A), 20-70 mass% is more preferable, and 30-60 mass% is the most preferable. Moreover, 10-80 mass% is preferable, as for the water-soluble component in surfactant particle | grains, such as particle | grains (A), 20-70 mass% is more preferable, and 30-60 mass% is the most preferable. Moreover, 0.5-20 mass% is preferable, as for the water-soluble polymer in surfactant particle | grains, such as particle | grains (A), 1-15 mass% is more preferable, and 2-10 mass% is the most preferable.

  As the water-insoluble inorganic substance, those having an average primary particle diameter of 0.1 to 20 μm are preferable. For example, crystalline or amorphous aminosilicate, silicon dioxide, hydrated silicate compound, perlite, bentonite, etc. Among these, crystalline or amorphous aluminosilicates, silicon dioxide, and hydrated silicate compounds are preferred. Among these, crystalline aluminosilicates are preferred in terms of sequestering ability and supporting ability of surfactants. Silicates are preferred.

  Examples of water-soluble polymers include carboxylic acid-based polymers, carboxymethyl cellulose, soluble starch, saccharides, etc. Among them, the weight average molecular weight in terms of sequestering ability, dispersibility of solid dirt / particle dirt and recontamination prevention ability. Thousands (specifically 2000) to 100,000 carboxylic acid polymers are preferred. Particularly preferred are salts of acrylic acid-maleic acid copolymers and polyacrylates. Here, examples of the salt include sodium salt, potassium salt, and ammonium salt.

  Water-soluble salts include carbonates, bicarbonates, sulfates, sulfites, hydrogen sulfates, hydrochlorides, phosphates, and other alkali metal salts, ammonium salts, amine salts, and other water-soluble inorganic salts, Low molecular weight water-soluble organic acid salts such as citrate and fumarate are listed. By blending the water-soluble salts, the bubbles generated from the detergent particles are thermally expanded by the heat of hydration and the heat of dissolution generated by the reaction of the water-soluble salts and water, thereby promoting the disintegration of the particles. More preferable in terms.

  In addition, the surfactant particles such as the particles (A) can contain a fragrance, a fluorescent dye, a colorant, and the like.

  Surfactant particles such as particles (A) are, for example, spray drying methods described in “Patent Office Gazette, Known and Conventional Techniques (Powder Detergent for Clothing)” (issued on March 26, 1998, Patent Office), It can be obtained by a neutralization method, a dry granulation method, a dry granulation method, a wet granulation / drying method, a dry blend method or the like. The surfactant particles such as the particles (A) are preferably granulated products.

  Surfactant particles such as particles (A) are preferably surface-modified with a surface coating agent in terms of fluidity and non-caking properties. 1-30 mass% is preferable in surfactant particle | grains in a surface coating agent, 2-25 mass% is more preferable, and 5-25 mass% is still more preferable. Examples of the surface coating agent include aluminosilicates, calcium silicates, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, crystalline silicate compounds such as silicate compounds, metal soaps, powder surfactants, etc. Water-soluble polymers such as fine powders, carboxymethylcellulose, polyacrylic acid soda, polycarboxylic acid salts such as copolymers of acrylic acid and maleic acid or salts thereof; fatty acids. Of these, water-insoluble inorganic substances are preferred, and crystalline aluminosilicates, amorphous aluminosilicates, and crystalline silicate compounds are particularly preferred.

  In terms of cleaning performance, solubility, and productivity, the surfactant particles such as particles (A) may be two or more types depending on the physical properties of the surfactant.

<Particle (B) and component (b)>
The composition of the present invention contains 1 to 30% by mass of particles (B) having a particle size of 500 to 1000 μm, which contains component (b) and does not substantially contain component (a). 5-30 mass% is preferable at the point of washing | cleaning performance and low-temperature solubility, 5-25 mass% is more preferable, 5-20 mass% is still more preferable, 10-20 mass% is especially preferable. Hereinafter, the particles containing the component (b) and substantially not containing the component (a) may be referred to as non-deliquescent neutral salt particles. Further, “substantially free of component (a)” means that the amount of component (a) in the particles is less than 1% by mass, preferably 0% by mass.

  The composition of the present invention may contain non-deliquescent neutral salt particles having a particle size of less than 500 μm, but is preferably 30 parts by mass or less per 100 parts by mass of the particles (B) from the viewpoint of low-temperature solubility. The amount is more preferably at most 10 parts by mass, and still more preferably at most 10 parts by mass. Further, although non-deliquescent neutral salt particles having a particle size exceeding 1000 μm may be contained, in terms of low-temperature solubility, it is preferably 10 parts by mass or less, more preferably 7 parts by mass or less per 100 parts by mass of the particles (B). Preferably, 5 parts by mass or less is more preferable.

  The non-deliquescent neutral salt particles of the particles (B) may be a granulated product, but it is preferable from the viewpoint of low-temperature solubility to use crystal particles as they are. In terms of low-temperature solubility, the non-deliquescent neutral salt content in the non-deliquescent neutral salt particles of the particles (B) is preferably 99 parts by mass or more with respect to 100 parts by mass of the non-deliquescent neutral salt particles. Substantially more preferably 100 parts by mass.

  The non-deliquescent neutral salt of the particles (B) may be an organic salt, but an inorganic salt is preferred from the viewpoint of low-temperature solubility. Non-deliquescent neutral inorganic salts include sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, magnesium sulfate and the like. Of these, magnesium sulfate and sodium sulfate are preferred from the viewpoint of low-temperature solubility.

  In terms of cleaning performance, solubility, and productivity, the non-deliquescent neutral salt particles of the particles (B) may be two or more types depending on the physical properties of the non-deliquescent neutral salt.

  In the present invention, the mass ratio (A) / (B) of the particles (A) to the particles (B) is preferably 1 to 20, more preferably 2 to 12 in terms of cleaning performance and solubility. In terms of cleaning performance, the total content of the particles (A) and the particles (B) is preferably 30% by mass or more, more preferably 40% by mass or more in the composition.

<Component (c)>
In terms of washing performance and low-temperature solubility, the composition of the present invention preferably contains 5 to 40% by mass of a builder other than the component (b) [hereinafter referred to as component (c)], and 5 to 30% by mass. Is more preferable, 5-20 mass% is still more preferable, and 5-15 mass% is especially preferable.

  The component (c) can be contained in the surfactant particles or non-deliquescent neutral salt particles, but granulation having a particle size of 250 to 1400 μm containing the component (c) as particles other than those particles. It can also be blended as a product. Hereinafter, particles other than the non-deliquescent neutral salt particles containing the component (c) and the surfactant of less than 5% by mass may be referred to as builder particles.

  The composition of the present invention may contain builder particles having a particle size of less than 250 μm, but in terms of low-temperature solubility, it is preferably 7 parts by mass or less, more preferably 5 parts by mass or less, 2 parts by mass or less is more preferable. Further, although builder particles having a particle size exceeding 1400 μm may be contained, it is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, more preferably 5 parts by mass or less, in terms of low-temperature solubility. preferable.

In terms of cleaning performance and low-temperature solubility, the component (c) in the builder particles is preferably 70% by mass or more, and more preferably 80% by mass or more.

  In the present invention, the builder itself has no detergency or is not so remarkably present, but when it is incorporated into a detergent composition, it significantly improves the detergency. As an action, it has at least one action of capturing a polyvalent metal cation, a dirt dispersing action and an alkali buffering action. Examples of such builders include water-soluble inorganic compounds, water-insoluble inorganic compounds, and organic compounds.

  Examples of the water-soluble inorganic compound include phosphates (tripolyphosphate, pyrophosphate, metaphosphate, trisodium phosphate, etc.), silicates, carbonates, and the like. Among these, phosphate is preferable in that it has all the three actions.

  Examples of the water-insoluble inorganic compound include aluminosilicate (A-type zeolite, P-type zeolite, X-type zeolite, amorphous aluminosilicate, etc.), crystalline silicate, and the like. Among these, A-type zeolite having a particle size of 3 μm or less (more preferably 1 μm or less) is preferable.

  Organic compounds include carboxylates (aminocarboxylates, hydroxyaminocarboxylates, hydroxycarboxylates, cyclocarboxylates, maleic acid derivatives, oxalates, etc.), organic carboxylic acid (salt) polymers (acrylic acid) Polymer and copolymer, polyvalent carboxylic acid polymer and copolymer, glyoxylic acid polymer, polysaccharides and salts thereof, and the like. Of these, organic carboxylic acid (salt) polymers are preferred.

  In the builder salt, the counter ion is preferably an alkali metal salt or an amine, and particularly preferably sodium and / or potassium, monoethanolamine, or diethanolamine.

  In the present invention, these components (c) can be used alone or in combination of two or more in the builder particles. In particular, in the present invention, the water-soluble inorganic compound is preferably contained as the component (c), more preferably a water-soluble inorganic compound and an organic compound are used in combination, and the water-soluble inorganic compound, the organic compound and the water-insoluble inorganic compound are used. It is more preferable to use together.

  In terms of cleaning performance, solubility, and productivity, the builder particles may use two or more kinds of particles depending on the physical properties of the component (c). The builder particles are preferably a granulated product.

  The builder particles can be colored with dyes, pigments and the like. Coloring can give a high-class feeling to the cleaning composition, which is preferable.

<Component (d)>
The cleaning composition of the present invention preferably contains 0.1 to 10% by mass of an enzyme [hereinafter referred to as component (d)] in terms of cleaning performance, and is 0.2 to 8% by mass. Is more preferable, and 0.3-5 mass% is still more preferable.

  Examples of the component (d) enzyme include protease, amylase, peptinase, lipase, cellulase and the like, and a combination of protease and cellulase is particularly preferable. The component (d) can be blended as particles containing the component (d), such as a granulated product, and the particle size is not particularly limited, but the average particle size is preferably 100 to 2000 μm, more preferably 150 to 1500 μm. In addition, when an enzyme granulated material contains 5 mass% or more surfactant and a particle size is 125-1000 micrometers, the said enzyme granulated material is handled as particle | grains of particle | grains (A). In addition, when the enzyme granule is a particle containing the component (b) and substantially not containing the component (a) and having a particle size of 500 to 1000, the enzyme granule is a particle (B ). Hereinafter, all particles containing the enzyme may be referred to as enzyme particles.

  The enzyme particles preferably contain a surfactant from the viewpoints of shape retention and dispersibility. The amount of the surfactant is preferably from 0.1 to 20% by mass, more preferably from 0.2 to 10% by mass in the enzyme particles.

  The enzyme particles can be mixed with a diluent (for example, a bulking agent, a filler, etc.), a drying accelerator, a buffering agent, and the like for keeping the specific activity of the preparation particles constant. Moreover, a coloring agent, a stabilizer, etc. can be used suitably, Furthermore, a fragrance | flavor, a deodorant, an antistatic agent, etc. can be used.

The bulk density of the enzyme particle, 0.5~2.0g / cm ^3, further is 0.7~1.5g / cm ³ preferred. The particle bulk density is measured by a method defined by JIS K 3362.

  In terms of washing performance, solubility, and productivity, two or more types of component (d) may be used depending on the physical properties of the enzyme.

  The content of the component (d) in the enzyme particles is preferably 0.5 to 20% by mass, more preferably 0.8 to 15% by mass, in terms of granulation property, solubility and cleaning performance, and more preferably 1 to 10%. More preferred is mass%.

  A known granulated product can be used as the enzyme particle, but the granulated product of (I) and / or (II) shown below is preferable, and low-temperature solubility and low dusting properties More preferably, the granulated product of (II).

  The granulated product (I) is obtained by granulating an enzyme together with a core material composed of water-soluble particles having an average particle diameter of 200 to 1200 μm and a water-soluble organic binder having a melting point of 35 to 70 ° C. It is a granulated product whose diameter is 1 to 2 times the average particle size of the nuclear material.

  Examples of the nuclear material include water-soluble particles such as sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, and sugar. Among them, sodium chloride is preferable. The average particle size of the nuclear material is preferably 200 to 1200 μm, more preferably 250 to 1000 μm, from the viewpoints of solubility, the appearance of the final final enzyme particles mixed with detergent particles, and the non-classification property. preferable. The average particle size of the nuclear material can be determined from the mass fraction according to the size of the mesh after vibrating for 5 minutes using a standard sieve of JIS Z 8801.

  The content of the nuclear material is preferably 30 to 80% by mass and more preferably 40 to 70% by mass in the granulated product (I) from the viewpoint of granulation property and solubility.

  Examples of the water-soluble organic binder include polyethylene glycol, nonionic surfactants (polyoxyethylene-polyoxypropylene glycol, polyoxyethylene / alkyl ether, etc.), among which polyethylene glycol is preferable. In terms of productivity, the amount of the water-soluble organic binder is preferably 5 to 60% by mass in the granulated product.

  The melting point of the water-soluble organic binder is preferably 35 to 70 ° C, more preferably 40 to 70 ° C, still more preferably 45 to 68 ° C. The melting point can be measured by a visual method defined in JIS K 0064: 1992.

  The method for producing the granulated product (I) by granulating an enzyme together with a nuclear substance and a water-soluble organic binder may be any known method, for example, the granulation described in JP-A-62-257990. The method is preferred.

  The average particle size of the granulated product (I) obtained as described above is preferably 1 to 2 times the average particle size of the core material from the viewpoint of solubility and non-classification, and is preferably 1.05 to 1. 5 times is more preferable.

  The granulated product of (II) contains 45% by mass or more of an enzyme, a water-insoluble substance, and 5 to 40% by mass of a water-soluble binder, and has a structure having more water-soluble binder near the surface than inside. It is a grain.

  Examples of water-insoluble substances include organic substances such as cellulose powder, inorganic substances such as zeolite, talc, clay, alumina, kaolin, titania, calcium carbonate, and barium sulfate, and inorganic substances are preferred from the viewpoint of heat stability. Of these, zeolite and kaolin are particularly preferred from the viewpoint of dispersibility. In terms of uniformity, the water-insoluble substance has an average primary particle size of preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 0.1 to 5 μm. The content of the water-insoluble substance in the granulated product (II) is preferably 45% by mass or more, more preferably 50% by mass or more, from the viewpoint of promoting rapid elution of the enzyme. On the other hand, 90 mass% or less is preferable, 80 mass% or less is more preferable, and 70 mass% or less is especially preferable at the point of the undissolved residue prevention.

  Examples of the water-soluble binder include polyethylene glycol and derivatives thereof, polyvinyl alcohol and derivatives thereof, water-soluble cellulose derivatives, carboxylic acid polymers, starch, saccharides and the like. Examples of the derivatives include ether compounds. Among them, carboxylic acid polymers and saccharides are preferable from the viewpoint of productivity and high-speed solubility, and salts of acrylic acid-maleic acid copolymers and polyacrylates are more preferable. As the salt, sodium salt, potassium salt, and ammonium salt are preferable. Mixing the water-soluble binder is preferable in terms of improving the particle strength and promptly disintegrating the particles. The content of the water-soluble binder in the granulated product (II) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more from the viewpoint of low dust generation. Moreover, 40 mass% or less is preferable at the point of high-speed solubility, 35 mass% or less is more preferable, and 30 mass% or less is still more preferable.

  The granulated product of (II) has a structure in which more water-soluble binder exists near the surface than inside the particle. For example, the enzyme, the water-insoluble substance, and the water-soluble binder are mixed, It is obtained by forming a slurry having a water content of 30 to 60% by mass and then spray drying the slurry. The temperature of the hot air during spray drying is preferably 140 to 180 ° C. from the viewpoint of enzyme stability and productivity. Other spray drying conditions are not particularly limited. In addition, the confirmation of uneven distribution of the water-soluble binder in the enzyme particles is performed by using, for example, a method (FT-IR / PAS) in combination with Fourier transform infrared spectroscopy (FT-IR) or photoacoustic spectroscopy (PAS). It can be carried out. These can be found in Applied Spectroscopy vol. 47, 1311-1316 (1993), which is a method for analyzing the distribution state of substances in the depth direction from the surface of the particles, whereby the uneven distribution of water-soluble components can be confirmed.

<Component (e)>
The cleaning composition of the present invention preferably contains 0.1 to 10% by mass of bleach (hereinafter referred to as component (e)) in terms of cleaning performance, and further 0.5 to 8% by mass. Preferably, 1-6 mass% is the most preferable.

  Component (e) includes a compound that releases hydrogen peroxide in an aqueous solution. In terms of low-temperature solubility and cleaning performance, the compound that releases hydrogen peroxide in the aqueous solution in the component (e) is preferably 50% by mass or more, more preferably 60 to 95% by mass, and further 70 to 90% by mass. preferable.

  The component (e) can be blended as particles containing the component (e), for example, a granulated product, and the particle size is not particularly limited, but the average particle size is preferably 200 to 1500 μm, more preferably 500 to 1300 μm. In addition, when a bleaching agent granule contains a 5 mass% or more component (a) and a particle size is 125-1000 micrometers, the said bleaching agent granule is handled as particle | grains of particle | grains (A). Moreover, when the bleaching agent granule contains the component (b) and does not substantially contain the component (a) and has a particle diameter of 500 to 1000 μm, the bleaching agent granule is a particle. Treat as (B) particles. Hereinafter, particles containing a bleaching agent may be referred to as bleaching agent particles.

  Compounds that release hydrogen peroxide in aqueous solution include carbonate / hydrogen peroxide adduct, borate / hydrogen peroxide adduct, tripolyphosphate / hydrogen peroxide adduct, pyrophosphate / hydrogen peroxide adduct. And urea / hydrogen peroxide adducts. Of these, carbonate / hydrogen peroxide adduct and borate / hydrogen peroxide adduct are preferable, sodium carbonate / hydrogen peroxide adduct and sodium borate / hydrogen peroxide adduct are more preferable. Sodium / hydrogen peroxide adduct is more preferred.

  The bleaching agent particles can be further improved in storage stability by coating with inorganic salts and / or polymers. Of these, coating with borate, silicate, sulfate, and carbonate is more preferable. The coating amount is preferably 5 to 20% by mass in the bleaching particles in terms of stability and solubility. Further, conventionally known stabilizers, dissolution accelerators, chelating agents, and the like may be included. Of these, chlorides, urea, anionic surfactants, and nonionic surfactants are preferable from the viewpoint of solubility, and it is preferable that one or more of these are contained in the bleaching particles in an amount of 0.1 to 5% by mass.

  In terms of cleaning performance, solubility, and productivity, two or more types of component (e) may be used depending on the physical properties of the compound that releases hydrogen peroxide in an aqueous solution. Component (e) is preferably blended as a granulated product.

<Component (f)>
The cleaning composition of the present invention preferably contains 0.1 to 10% by mass of a bleach activator [hereinafter referred to as component (f)] in terms of cleaning performance, and preferably 0.5 to 8% by mass. Is more preferable, and 1 to 6% by mass is most preferable.

  The component (f) can be blended as particles containing the component (f), for example, a granulated product, and the particle size is not particularly limited, but the average particle size is preferably 200 to 2000 μm, more preferably 500 to 1500 μm. In addition, when a bleaching activator granule contains 5 mass% or more of component (a) and a particle size is 125-1000 micrometers, the said bleaching activator granule is particle | grains (A). Treat as particles. In addition, when the bleaching activator granule is a particle containing the component (b) and substantially not containing the component (a) and having a particle size of 500 to 1000 μm, Granules are handled as particles of particles (B). Hereinafter, the particles containing the bleach activator may be referred to as bleach activator particles.

  Examples of the component (f) include compounds that react with hydrogen peroxide in an aqueous solution to generate an organic peracid. In terms of low-temperature solubility and cleaning performance, the compound that reacts with hydrogen peroxide in an aqueous solution to generate organic peracid in the bleach activator particles is preferably 40% by mass or more, more preferably 50 to 90% by mass, 60-80 mass% is still more preferable.

  Compounds that react with hydrogen peroxide in an aqueous solution to generate organic peracids include glucose pentaacetate, triacetin, N, N, N ′, N′-tetraacetyl, which are commonly used in oxygen-based bleach-containing detergents. Although bleach activators such as ethylenediamine and tetraacetylglycolyluril can be used, the compounds represented by the general formulas (1) to (4) are particularly preferable in terms of effects.

[Wherein, R ₁ is preferably an alkyl group having 4 to 13 carbon atoms (more preferably 10 to 13), R ₂ is preferably an alkyl group having 5 to 13 carbon atoms (more preferably 7 to 11), and M is A hydrogen atom or an alkali metal, an alkaline earth metal, ammonium or alkanolamine is shown. ]

_{Wherein, R 3, R 4, R} 5, R 6, R 7, R 9, R 10 are each independently a methyl group, an ethyl group, a hydroxyethyl group, R ₈ is 2 carbon atoms 10 is an alkylene group, X ^- represents an anion (preferably a halogen ion, alkyl sulfate ion having 1 to 3 carbon atoms, fatty acid ion having 1 to 12 carbon atoms, phosphate ion, sulfate ion) a. ]

  The bleach activator particles preferably contain a surfactant and a binder in terms of solubility and granulation. As the surfactant, an anionic surfactant is more preferable, and an alkyl sulfate having 10 to 18 carbon atoms, particularly sodium lauryl sulfate, sodium myristyl sulfate, or polyoxyethylene having 10 to 18 carbon atoms [ethylene Oxide average added mole number (hereinafter referred to as EOp) 1 to 10, especially 1 to 5] alkyl ether sulfate, especially polyoxyethylene (EOp 2 to 5) sodium lauryl ether sulfate, polyoxyethylene (EOp 2 to 5) sodium myristyl ether sulfate Blending is more preferred. As the binder, polyethylene glycol having a weight average molecular weight of 2000 to 20000 and a fatty acid having 8 to 20 carbon atoms are more preferable, and the weight average molecular weight of polyethylene glycol is preferably 4000 to 10000, more preferably 4000 to 8000. Moreover, carbon number of a fatty acid becomes like this. Preferably it is 10-18, More preferably, it is 12-18. The fatty acid may be in the form of sodium or potassium soap. In the component (f), the surfactant is preferably 1 to 40% by mass, and the binder is preferably 0.5 to 30% by mass. Further, an acidic substance may be blended for the purpose of further improving the stability. Examples of the acidic substance include one or more organic carboxylic acids selected from succinic acid, maleic acid, fumaric acid, citric acid, glycolic acid, and p-hydroxybenzoic acid.

  In terms of cleaning performance, solubility, and productivity, two or more types of component (f) may be used depending on the physical properties of the compound that releases hydrogen peroxide in an aqueous solution. Component (f) is preferably blended as a granulated product.

<Cleaning agent composition>
The cleaning composition of the present invention may contain a fragrance, a foam modifier, a softener, a colorant, a chlorine scavenger, a fluorescent dye, a soil release agent, etc. in addition to the components (a) to (f). it can. In addition, also about these components, when mix | blending as particle | grains, the particle | grains which contain the component (a) 5 mass% or more and whose particle size is 125-1000 micrometers shall be handled as particle | grains of particle | grains (A). Moreover, the particle | grains which are 500-1000 micrometers in particle size which contain a component (b) and do not contain a component (a) substantially are handled as a particle | grain of particle | grains (B).

  In terms of low-temperature solubility, stability, and cleaning performance, the apparent density (bulk density) of the cleaning composition of the present invention measured by the method described in JIS K 3362: 1998 is preferably 400 to 1000 g / L, and 600 to 950 g. / Ml is more preferable, and 700-950 g / ml is still more preferable.

  In terms of low-temperature solubility and detergency, the average particle size of the cleaning composition of the present invention obtained from the mass fraction according to the size of the sieve mesh is 150 to 150 after being vibrated for 5 minutes using a standard sieve of JIS Z 8801. 750 micrometers is preferable, More preferably, it is 150-700 micrometers, More preferably, it is 180-600 micrometers.

  In the cleaning composition of the present invention, the pH of the 0.05% by mass aqueous solution measured at 20 ° C. described in JIS K3362: 1998 is preferably 8 to 12, more preferably 9 to 11.5 in terms of cleaning performance. 9.5 to 11 are more preferable, and 10 to 11 are particularly preferable.

  The equilibrium relative humidity at 40 ° C. of the cleaning composition of the present invention is preferably 15 to 35%, more preferably 18 to 32%, and still more preferably 20 to 30% in terms of storage stability. Equilibrium relative humidity is measured in a 2.4 liter moisture-proof container with 600 g of detergent composition and polymer film humidity sensor (preferably a combination of T & D's Thermo Recorder Ondori RH TR-72S and TR-3110 temperature / humidity sensor. ) And seal. This is maintained at 40 ° C. and stored for 24 hours. Humidity readings were read every 30 minutes, and the value at which there was no change was taken as the equilibrium relative humidity.

  In terms of cleaning performance and low-temperature solubility, the surfactant equivalent of the cleaning composition of the present invention described in JIS K3362: 1998 is preferably 10 to 60% by mass, more preferably 15 to 45% by mass, and 18 to 40%. % By mass is more preferable, and 20 to 35% by mass is particularly preferable.

  In terms of cleaning performance and low-temperature solubility, the total amount of the water-soluble inorganic salt in the cleaning composition of the present invention is preferably 30 to 70% by mass, more preferably 35 to 60% by mass, and 40 to 55% by mass. Further preferred.

  In terms of cleaning performance and low temperature solubility, the total amount of the water-insoluble inorganic salt in the cleaning composition of the present invention is preferably 10 to 35% by mass, more preferably 15 to 30% by mass, and more preferably 10 to 25% by mass. Further preferred.

  In terms of cleaning performance and low-temperature solubility, the mass ratio of the organic compound / inorganic compound in the cleaning composition of the present invention is preferably 50/50 to 15/85, more preferably 45/55 to 20/80, More preferably, 40/60 to 20/80.

The particles used in the following examples and comparative examples were prepared by the following method.
<Surfactant particle I-1>
Sodium dodecylbenzene sulfate (manufactured by Kao Corporation, Neoperex GS) 40 parts by mass, beef tallow fatty acid sodium (manufactured by Kao Corporation, Lunac TD-2) 1.5 parts by mass, anhydrous sodium carbonate (manufactured by Central Glass Co., Ltd.) , Dense ash) 30 parts by mass, fluorescent dye (Ciba Specialty Chemicals, Inc., Chino Pearl CBS-X) 4.5 parts by mass, zeolite (Zeobuilder, 4A type, average particle size: 3.5 μm) 10 parts by mass An aqueous slurry having a solid content of 40% by mass was prepared and spray-dried using a drying tower to obtain a dry dough having a moisture content of 3% by mass. 84 parts by mass of this spray-dried dough, 5 parts by mass of anhydrous sodium carbonate (Dense Ash, manufactured by Central Glass Co., Ltd.), polyoxyethylene alkyl ether (manufactured by Kao Corporation, Emulgen 108KM (EOp: 8.5, alkyl chain) Carbon number: 12-14)) 1.5 parts by mass and agitation granulation with water for water adjustment, surface using zeolite (Zeobuilder, 4A type, average particle size: 3.5 μm) 9 parts by mass Coating was performed to obtain surfactant particles I-1 having an average particle diameter of 560 μm and an apparent density of 820 g / L. In the obtained particles, particles having a particle size of less than 125 μm accounted for 3.5% by mass of all particles, and particles having a particle size of more than 1000 μm accounted for 2.5% by mass of all particles. Contains 94% by mass of particles (A)].

<Surfactant particle I-2>
Surfactant particle I-1 was classified to obtain particle I-2 having an average particle diameter of 1050 μm. In the obtained particles, particles having a particle size of less than 125 μm accounted for 0.1% by mass in all particles, and particles having a particle size of more than 1000 μm accounted for 57.2% by mass in all the particles. 42.7% by mass of the particles (A) is contained].

<Surfactant particle II>
Alkyl sulfate ester salt (Kao Co., Ltd., Emar 40 paste) 25 parts by mass, soda ash (Central Glass Co., Ltd., dense ash) 48 parts by mass, zeolite (Zeobuilder, 4A type, average particle size: 3.5 μm) 20 parts by mass with stirring and granulated, and surface-coated with 6 parts by mass of zeolite (Zeobuilder, 4A type, average particle size: 3.5 μm), average particle size 420 μm, apparent density 850 g / L Surfactant particles II were obtained. In the obtained particles, particles having a particle size of less than 125 μm accounted for 4.2% by mass in all particles, and particles having a particle size of more than 1000 μm accounted for 5.3% by mass in all particles. In which 90.5 mass% of particles (A) are contained].

<Non-deliquescent neutral salt particles I>
Sodium sulfate produced by recrystallization was sieved with a 1400 μm JIS standard sieve, and the amount passed through the sieve was designated as non-deliquescent neutral salt particles I. The particles were 11% by mass of particles having a particle size of more than 1000 μm, 72% by mass of particles having a particle size of 500 μm or more, and the average particle size was 602 μm. In the obtained particles, the particles having a particle size of less than 250 μm accounted for 5.8% by mass in all the particles (therefore, the particles (B) were contained in 61% by mass).

<Non-deliquescent neutral salt particles II>
Anhydrous sodium sulfate (manufactured by Shikoku Kasei Co., Ltd., neutral anhydrous sodium sulfate average particle size 106 μm) was used as non-deliquescent neutral salt particles II. Among the particles, particles having a particle size of less than 500 μm accounted for 96% by mass of all particles, and particles having a particle size of more than 1000 μm were not included. [Thus, the particles contained 4% by mass of particles (B). ]

<Builder particles I>
The pre-feed granule product (manufactured by Tokuyama Siltec Co., Ltd.) was sieved with a 1400 μm JIS standard sieve, and the part passing through the sieve was designated as builder particle I.

<Builder particle II>
85 parts by weight of anhydrous sodium carbonate (light ash made by Tokuyama Co., Ltd.) and 10 parts by weight of polyethylene glycol having a molecular weight of 4000 are put into a readyge mixer (Matsuzaka Giken Co., Ltd., capacity 130L, with jacket) to a total of 30 kg The main shaft (rotation speed: 60 rpm, peripheral speed: 1.6 m / s) was stirred for 5 minutes. Warm water at 80 ° C. was passed through the jacket at 10 L / min. The obtained particles were sieved with JIS standard sieves of 1400 μm and 125 μm, and the coarse and fine fractions were removed to obtain builder particles II. The average average particle diameter of the particles was 570 μm, and the ratio of particles having a particle diameter of less than 125 μm was 0.1% by mass or less.

<Enzyme particles>
Protease granules (Novazyme Cannase 24TK) were used.

<Bleach particles>
According to Example 1 of JP-A-59-196399, 5% sodium metaborate tetrahydrate coated on sodium percarbonate was removed with a 125 μm JIS standard sieve to remove small particles. The bleach particles were obtained. The particles had an average particle size of 421 μm and the proportion of particles having a particle size of less than 125 μm was 0.1% by mass or less.

<Bleaching activator particles I>
10 parts by weight of sodium lauryl sulfate, 2 parts by weight of sodium polyoxyethylene lauryl ether sulfate (Emal E-70C manufactured by Kao Corporation), 20 parts by weight of polyethylene glycol (molecular weight 8000, melting point 62 ° C.), sodium lauroyloxybenzenesulfonate 60 A high speed mixer (FS-GC-10 manufactured by Fukae Kogyo Co., Ltd.) is charged with 5 parts by mass and 8 parts by mass of succinic acid, jacket temperature is 80 ° C., spindle speed is 200 rpm, and crushing blade speed is 1500 rpm. Then, the mixture was heated up and extracted when the temperature of the powder reached 70 ° C. Next, this was extruded through a screen having a pore diameter of 800 μm by an extrusion granulator (Pelleter Double EXD-100 type manufactured by Fuji Powder Co., Ltd.). After the obtained extrudate was cooled with a vibration cooler (Fuji Paudal Vibro / Flow Dryer VDF / 6000 type) and then crushed with a granulator (Fuji Paudal knife cutter FL-200 type), Small particles were removed with a 350 μm JIS standard sieve to obtain bleach activator particles I. The particles had an average particle size of 900 μm, particles having a particle size of more than 1000 μm were 1.1% by mass, and particles having a particle size of less than 125 μm were 0.1% by mass [therefore, particles (A) in the particles Is 98.8% by mass.

<Bleaching activator particles II>
Instead of sodium lauroyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate was used, and bleaching activator particles II were obtained by the same preparation method as bleaching activator particle I. The average particle diameter and particle size distribution of the particles II were the same as those of the bleach activator particle I [therefore, the particles (A) are contained in 98.8% by mass in the particles).

<Preparation of cleaning composition>
When the above particles were put into a rotary kiln and mixed, the fragrance was sprayed and scented to prepare a cleaning composition having the composition shown in Table 1. The bulk density of the resulting cleaning composition was 834 to 929 g / L, and the average particle size was 562 to 630 μm.

<Low temperature dispersibility>
Place 25.0 g of the detergent composition shown in Table 1 in an assembled state near one outer periphery of the fan-shaped depression of the pulsator of the Matsushita Electric Industrial washing machine "Aizuma No. NA-F42Y1" 1.5 kg of clothing was put into a washing tub, and 22 L of tap water of 10 ° C. was poured at a flow rate of 10 L / min so that the detergent would not be directly exposed to water. Three minutes after the start of water injection, stirring was started with a weak water flow (hand washing mode), and after stirring for 3 minutes, the water was drained, and the state of the detergent remaining in the clothes and the washing tub was visually determined according to the following evaluation criteria. In addition, the stirring force of this evaluation is extremely weaker than the standard, and evaluation criteria I and II indicate excellent dispersibility. The “aggregate” described below refers to a lump having a diameter of 3 mm or more in which detergent particles are aggregated.

〔Evaluation criteria〕
I: There is no aggregate.
II: Almost no aggregates (1 to 5 lumps having a diameter of about 3 mm are observed).
III: A small amount of aggregate remains (a lump having a diameter of about 6 mm is observed, and 10 or less lump having a diameter of 3 to 10 mm is recognized).
IV: A large amount of agglomerates remains (a large number of lumps exceeding 6 mm in diameter are observed)

<Low temperature solubility>
1 liter of hard water (Ca / Mg molar ratio 7/3) corresponding to 71.2 mg CaCO ₃ / liter cooled to 5 ° C. in a 1 liter beaker (inner diameter 105 mm, height 150 mm cylindrical type, for example, manufactured by Iwaki Glass Co., Ltd. 1 In a state where the water temperature of 5 ° C. is kept constant in a water bath, the water depth is increased with a stirrer (length 35 mm, diameter 8 mm, for example, model: ADVANTEC, Teflon round thin type). Stirring is performed at a rotational speed (800 rpm) at which the depth of the vortex is approximately 1/3. The detergent composition that has been reduced and weighed to 1.000 ± 0.0010 g is added to and dispersed in water under stirring, and stirring is continued. 60 seconds after charging, the cleaning composition dispersion in the beaker was filtered through a standard sieve (diameter 100 mm) with a known opening of 74 μm according to JIS Z 8801 (corresponding to ASTM No. 200), and remained on the sieve. The water-containing cleaning composition is collected together with a sieve in an open container of known mass. The operation time from the start of filtration until the sieve is collected is 10 ± 2 seconds. The recovered residue of the detergent composition recovered is dried for 1 hour in an electric dryer heated to 105 ° C., and then cooled by being held in a desiccator (25 ° C.) containing silica gel for 30 minutes. After cooling, the total mass of the dissolved residue, sieve and collection container of the dried cleaning composition is measured, and the dissolution rate (%) of the cleaning composition is calculated by the following formula. The mass is measured using a precision balance.

Dissolution rate (%) = {1- (T / S)} × 100 (1)
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

  In addition, all the compositions in Table 1 had a cleaning power equivalent to that of a standard detergent in the cleaning power evaluation method of JIS K3362.

Claims (6)

A detergent composition containing a surfactant [hereinafter referred to as component (a)] and a non-deliquescent neutral salt [hereinafter referred to as component (b)], wherein 15 to 80 mass of the following particles (A) are contained. %, and particles (B) from 1 to detergent compositions containing 25% by weight.
Particle (A): The component (a) is contained in the particle in an amount of 5% by mass or more, and the particle size (B): the component (b) is contained, and the component (a) is substantially contained. Particles having a particle size of 500 to 1000 μm that are not contained, and the content of component (b) is 99 parts by mass or more with respect to 100 parts by mass of the particles (B) The ratio of the particles (B ′) containing the component (b) and substantially not containing the component (a) and having a particle size of less than 500 μm is 30 parts by mass or less per 100 parts by mass of the particles (B). Item 2. A cleaning composition according to Item 1. The cleaning composition according to claim 1 or 2, further comprising (c) 5 to 40% by mass of a builder. The cleaning composition according to any one of claims 1 to 3, further comprising (d) an enzyme. The cleaning composition according to any one of claims 1 to 4, further comprising (e) a bleaching agent and (f) a bleaching activator. The total amount of water-soluble inorganic salt in the cleaning composition is 30 to 70% by mass.