JP3162249B2 - Rinse aid for clothes washing and detergent composition containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laundry washing rinse aid suitable for incorporation into a powder detergent for clothing, and a detergent composition for clothing containing the same.

[0002]

2. Description of the Related Art In Europe, drum-type washing machines are mainly used for washing clothes and the like. When a drum-type washing machine is used, foam reduces the washing efficiency, so that an antifoaming agent is generally added to the detergent used for washing.

On the other hand, in Japan, pulsator-type washing machines have conventionally been the mainstream, and foam does not pose a particular problem in terms of washing efficiency. Rather, detergents that generate appropriate foam are preferred by housewives at home due to washing habits. Was.

[0004]

However, in recent years, with the spread of fully automatic washing machines, there has been a change in awareness of foam during washing, and when foam is generated during washing, foam overflows from the lid.
Also, there is a demand for a detergent that suppresses foam formation, for example, because a large amount of foam requires a long rinsing time.

As a defoaming agent for suppressing foam generated during washing, polydimethylsiloxane is well known as disclosed in JP-A-3-186307 and JP-A-4-311800. Polydimethylsiloxane has been found to be effective in eliminating foam during washing when blended into general laundry detergents, but is discharged outside the washing machine during drainage and dehydration after washing, and defoaming during the rinsing process. Cannot be developed, and as a result, the surfactant remaining during the rinsing foams again during the rinsing step, and thus the foaming during the rinsing was insufficient. In addition, removal of turbidity during rinsing was insufficient.

With respect to amino-modified silicones, a foam suppressing composition which is used as a defoaming agent for dyeing which is excellent in dilution stability and defoaming durability and does not cause uneven dyeing is disclosed in JP-A-5-261206. Although it is disclosed in Japanese Patent Application Laid-Open No. 5-285306, there is no description of any action other than the removal of foam, particularly the defoaming property of the rinsing liquid at the time of washing clothes, and even more preferred washing when using the amino-modified silicone. No description is given about the agent composition. Also, JP-A-2-4223,
JP-A-4-4224 discloses a liquid detergent containing an amino-modified silicone, which relates to foaming properties and prevention of felt shrinkage, and makes no mention of the defoaming effect in the rinsing step. Absent.

[0007] Because of these problems, there is a need for a rinse aid that exhibits a defoaming effect in the rinsing step.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have used an aminoalkyl-modified silicone oil having specific physical properties as a silicone constituting a rinsing aid, and having a specific surface area of 100 m ² / g. Inorganic silica and / or
Alternatively, it has been found that a rinsing aid that can solve the above-mentioned problems can be obtained by blending the inorganic silica derivative with the inorganic silica derivative at a specific ratio, and the present invention has been completed.

That is, the present invention provides a rinsing aid for washing clothes which uses the following components (a) and (b) at a weight ratio of (b) / (a) of 0.01 to 0.5, and a detergent containing the same. It provides a composition. (a) Aminoalkyl-modified silicone oil having an amine equivalent of 500 to 50,000 g / mol and a viscosity at 25 ° C of 10 to 100,000 cSt (centistokes). (b) Inorganic having a specific surface area of 100 m ² / g or more by BET method. Silica and / or inorganic silica derivatives.

The aminoalkyl-modified silicone oil which is the component (a) used in the present invention is represented by the general formula (1). _{^{R 1 a R 2 b R 3}} c SiO (4-abc) / 2 ··· (1) [wherein R ¹ is _{^{-R 4 - (NR 5 CH 2}} CH 2) m -NR 6 R 7 ( R ⁴ is a divalent hydrocarbon group having 1 to ⁴ carbon atoms, R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and m is 0 ≦ m is an integer of 4 or less), R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, R ³ is —OR ⁸ (R ⁸ is hydrogen A hydroxyl group or an alkoxy group represented by an atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms), a, b, and c are respectively 0.0001 ≦ a ≦ 1, 1.
1.8 <a + b + c <2.3 for 8 ≤ b ≤ 2.2 and 0 ≤ c ≤ 0.1
Is a number that satisfies ].

In the above (1), the substituent R ¹ is -R ⁴ - (NR ⁵
Is ^{_{CH 2 CH 2) m -NR 6}} R 7. Here, R ⁴ is a divalent hydrocarbon group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group, and a butylene group. R ⁵ , R ⁶ , R ⁷ are each a hydrogen atom or, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, Alkyl groups such as hexadecyl group and octadecyl group,
Vinyl group, alkenyl group such as allyl group, phenyl group, aryl group such as tolyl group, cycloalkyl group such as cyclohexyl group, part or all of the hydrogen atoms bonded to carbon atoms of these groups are halogen atoms, A chloromethyl group substituted with a cyano group or the like, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a halogen substitution such as a cyanoethyl group, a cyano group-substituted hydrocarbon group, but R ⁵ , R ⁶ , It is preferred that 90 mol% or more of all the groups represented by R ⁷ are hydrogen atoms.
Here, m is an integer of 0 ≦ m ≦ 4.

R ² is, for example, a methyl group, an ethyl group,
Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, alkyl group such as octadecyl group, vinyl group, alkenyl group such as allyl group, Aryl groups such as phenyl group and tolyl group, cycloalkyl groups such as cyclohexyl group, and chloromethyl group in which part or all of the hydrogen atoms bonded to carbon atoms of these groups have been substituted with halogen atoms, cyano groups, etc. , 3-chloropropyl group, 3,3,3-trifluoropropyl group, halogen substitution such as cyanoethyl group, the same or different unsubstituted or substituted having 1 to 18 carbon atoms selected from cyano group-substituted hydrocarbon group and the like. Although it is a monovalent hydrocarbon group, 90 mol% of the entire R ² group
The above is preferably a methyl group.

R ³ in the above formula (1) includes a hydroxyl group or an alkoxy group represented by —OR ⁸ . In this case, R ⁸ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Among them, a methyl group or an ethyl group is particularly preferable.

A, b, and c are 0.0001 ≦ a ≦ 1, 1.
1.8 <a + b + c <2.3 with 8 ≤ b ≤ 2.2 and 0 ≤ c ≤ 0.1
Is a number that satisfies 0.001 ≦ a ≦
0.5, 1.9 ≤ b ≤ 2.1, 0 ≤ c ≤ 0.05 and 1.9 <a + b + c
<2.2 is desirable.

The aminoalkyl-modified silicone oil of the above formula (1) is preferably linear, but may be branched. When the amine equivalent of the aminoalkyl-modified silicone oil is less than 500 g / mol or more than 50,000 g / mol, the defoaming effect in the rinsing step is poor. It is required to be within the range, but preferably 1,000
〜10,000 g / mol.

The aminoalkyl-modified silicone oil of the above formula (1) is preferably one having a viscosity as low as possible from the viewpoint of easy dispersibility and workability. The higher the better,
It is required that the viscosity at 25 ° C. is 10 to 100,000 cSt, but if the viscosity is less than 10 cSt, the composition becomes poor in stability, and if the viscosity exceeds 100,000 cSt, the obtained composition is used. This is because there is a problem in workability at the time. Preferably it is in the range of 100 to 20,000 cSt.

The inorganic silica used here and / or
Or, the inorganic silica derivative may be a known one, and may be any of wet silica and dry silica, such as precipitated silica, silica xerogel, fumed silica, and those whose surface is treated with an organic silyl group. Specifically, Aerosil [trade name of Nippon Aerosil Co., Ltd.], nip seal [trade name of Nippon Silica Co., Ltd.],
Cabosil (trade name, manufactured by Cabot Corporation, USA), Santocell (trade name, manufactured by Monsanto Chemical Co., USA), etc., having a specific surface area of 100 m ² / g by the BET method.
That's all. When the specific surface area is less than 100 m ² / g, the adsorption of the aminoalkyl-modified silicone is insufficient and the defoaming effect is poor, so that it is not preferable.

Such silica and / or its derivative is preferably hydrophobized in order to improve the dilution stability and the rinsing property of the desired rinsing aid composition for clothes and laundry. The treatment method is a dry treatment method in which this silica is mixed with an organic silane and a silazane compound, and a heat treatment is performed.
Alternatively, the above-mentioned aminoalkyl-modified silicone oil and the above-mentioned silica, organic silane, and silazane compound may be mixed and heat-treated by any one of wet processing methods.

The organic silane and silazane compound used at this time include trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, dimethylphenylchlorosilane, methylphenyldichlorosilane, diphenyldichlorosilane, phenyltrichlorosilane, dimethyldimethoxysilane, Methyltrimethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, etc. Is exemplified.

The compounding ratio of the aminoalkyl-modified silicone oil as the component (a) and the inorganic silica and / or the inorganic silica derivative as the component (b) constituting the above-mentioned rinsing aid for washing clothes of the present invention is as follows: ) / (A) The weight ratio is required to be 0.01 to 0.5, but if the compounding ratio is less than 0.01, the defoaming performance may be poor, and if it exceeds 0.5, the viscosity of the composition may increase. This is because the water dispersibility and the workability are deteriorated, and it is particularly preferable to be in the range of 0.02 to 0.2.

Further, the above-mentioned rinsing aid for washing clothes is
(a) an aminoalkyl-modified silicone oil as a component;
(b) A predetermined amount of the inorganic silica and / or the inorganic silica derivative as the component is mixed, and the mixture is mixed at room temperature or 50 to 200 if necessary.
It can be produced by heat-treating at a temperature of 1 to 3 hours and optionally removing low-boiling fractions. In order to improve the defoaming continuity and dilution stability during this heat treatment, it is optional to add an inorganic ammonium salt, an organic silicon compound, a siloxane resin, or the like, as is well known (Japanese Patent Publication No. 4-42043). , JP-A-5-261206 and JP-A-5-261207). In addition, if polydimethylsiloxane, which has been conventionally used for clothes washing, is added and used together, it will affect the rinsing effect of the aminoalkyl-modified silicone. 0.1 or less is preferred.

The rinsing aid of the present invention containing an aminoalkyl-modified silicone oil and inorganic silica and / or an inorganic silica derivative is generally granulated or coated to form granules which are not in direct contact with detergent components. From the detergent.

The rinsing aid generally uses a detergent builder substance such as sodium sulfate, sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium tripolyphosphate, etc. as a carrier, onto which the components of the rinsing aid are adsorbed. And used as a granulated product obtained by mixing in the presence of a binder. Further, carboxymethylcellulose, starch or modified starch, dextrin or other starch derivatives, clay, sodium citrate, sodium acetate, sodium sulfate, etc. may be used alone or as a mixture of two or more as a carrier for adsorbing the rinse aid. Good.

Further, in order to improve the solubility of the granules, anionic surfactants such as alkyl sulfates and alkylbenzene sulfonates, and nonionic surfactants such as polyoxyethylene alkyl ethers may be used. Good. Further, in order to improve the powder properties, a polymer such as polyethylene glycol having a melting point of 40 ° C. or more and a water-soluble inorganic compound such as sodium sulfate can be blended. Of course, a fragrance or a coloring agent which does not affect the performance may be blended. For production of granules, JP-A-3-186307 can be referred to.

The rinsing aid of the present invention as described above is particularly used in a detergent composition for clothing using a nonionic surfactant as a main surfactant.

Examples of the nonionic surfactant incorporated in the detergent composition for clothing include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, and polyoxyethylene polyoxy. Examples include propylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene alkylamine, glycerin fatty acid ester, higher fatty acid alkanolamide, alkyl glucoside, and alkylamine oxide. Among them, in particular, as a nonionic surfactant, an ethylene oxide adduct of a linear or branched primary or secondary alcohol having 6 to 22 carbon atoms, and a polyoxyethylene alkyl having an average addition mole number of 3 to 20 It is desirable to use ethers. It is more preferable to use an ethylene oxide adduct of a linear or branched primary or secondary alcohol having 12 to 14 carbon atoms, and to use a polyoxyethylene alkyl ether having an average addition mole number of 6 to 10 .

[0027] The amount of the rinsing aid for clothing laundering incorporated in the detergent composition for clothing is such that the sum of the components (a) and (b) is 0.001 to 0.2 in weight ratio to the nonionic surfactant. , Preferably 0.001 to 0.1. When the weight ratio is less than 0.001, a sufficient rinsing effect cannot be obtained, and when the weight ratio is more than 0.2, foaming does not occur and the function as a detergent is impaired.

As described above, the detergent composition of the present invention is most effective when a nonionic surfactant is used as the main surfactant. The detergent composition contains no anionic surfactant or has no total surfactant. It may be contained at 20% by weight or less in the composition. Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfofatty acid salt or ester salt, alkyl or alkenyl ether carboxylate, Examples thereof include amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphates or salts thereof, and preferably alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate and the like. .
Here, potassium, sodium,
An amine or the like is used, but sodium is preferred. In addition, if the anionic surfactant exceeds 20% by weight, it will interact with the aminoalkyl-modified silicone,
It interferes with the rinsing function. In addition, a cationic surfactant may be used in combination.

The following components can be added to the detergent composition of the present invention in a conventionally known general amount. As the components,
Includes chelating agents, alkali agents, dispersants, etc., for example, non-crystalline alkali agents such as silicates, carbonates and sesquicarbonates, extenders such as sodium sulfate, crystalline aluminosilicates (zeolites), non-crystalline Chelating agents such as aluminosilicate, orthophosphate, pyrophosphate, tripolyphosphate, nitrilotriacetate, ethylenediaminetetraacetate, citrate and isocitrate. Further, usually, for example, dispersants (anti-redeposition agents) such as polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, polyacrylate, etc., as well as enzymes such as protease, esterase, lipase, and cellulase, anti-caking agents, peroxides And small amounts of additional components such as stabilizers, antioxidants, fluorescent dyes, bluing agents and fragrances.

The clothes washing rinse aid and the detergent composition containing the same according to the present invention are used in the form of powder or granules.

The method for producing a detergent composition containing a nonionic surfactant as a main base is not particularly limited. For example, as described in JP-A-5-209200, the following method is used. And a bulk density of 0.6 to 1.2 g / ml
A method of obtaining detergent particles of Step: a step of mixing a detergent raw material containing a nonionic surfactant as a main base. Step: The obtained mixture is stirred and mixed by a stirring mixer having a stirring shaft provided with stirring blades at the center thereof and forming a clearance between the stirring blades and the vessel wall when the stirring blades rotate. Thus, a step of forming an adhesion layer of the detergent raw material on the wall of the stirring type mixer and granulating while increasing the bulk density of the detergent raw material by the stirring blade. Step: mixing the granulated material obtained in the step and the fine powder,
A step of coating the surface of the granulated material with the fine powder. The detergent particles obtained in the above-mentioned steps and the rinse aid obtained by separate granulation are mixed in the mixing ratio as described above, and the non-ionic containing the laundry rinse aid of the present invention is contained. A detergent composition containing a surfactant as a main surfactant is obtained.

[0032]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition,
Parts and% in the examples are based on weight.

Example 1 The composition of the rinse aid used in this example is shown in Table 1.

[0034]

[Table 1]

* (B) Kind of inorganic silica A: Untreated silica (BET specific surface area = 300 m ² / g) B: Organic silyl group-treated silica (BET specific surface area = 200 m ²⁾
/ G).

(1) Preparation of Rinsing Aid Granules After mixing the rinsing aid, dextrin, polyethylene glycol and neutral anhydrous sodium sulfate at 70 ° C. to 80 ° C. with the following composition, extrusion granulation manufactured by Fuji Paudal Co., Ltd. Granulation was performed by a granulator (model EXKS-1). <Ingredient composition>-Rinse aid 20%-Dextrin 40%-Polyethylene glycol 25% (PEG-6000, melting point 58 ° C)-Neutral anhydrous sodium sulfate 15% This granulated product is classified by a 16, 32 mesh sieve. The particle size of the granules was adjusted.・ Average particle size: 800 μm ・ Grain size: 1000 μm or more: 5% ・ Grain size: 250 μm or less: 5% The granulation properties during granulation were evaluated according to the following criteria. …: Yield of 95% or more (500 to 1000 μm) ○: yield of 85% or more and less than 95% ×: yield of less than 85%.

(2) Solubility evaluation method of the rinse aid granules The solubility of the rinse aid granules was evaluated in a 500 ml beaker.
300 ml of water at 10 ° C. was added, and 300 mg of the granulated substance was added while stirring with the degree of rotation with a stirrer, and the time until dissolution was measured. Table 2 shows the results.

[0038]

[Table 2]

Example 2 A detergent having the following composition and a bulk density of 0.7 g / cm ³ was prepared. <Powder detergent composition> ・ Polyoxyethylene alkyl ether 20% (Average carbon number of alkyl group: 12, Ethylene oxide average addition: 6) ・ Zeolite 25% ・ Sodium carbonate 25% ・ Amorphous sodium aluminosilicate 15% ・ Sodium sulfate 10% Water 5% Using the powder detergent obtained above and the granulated rinse aid prepared in Example 1, foaming (height) during washing and rinsing properties were evaluated by the following methods. .

(1) Evaluation of Foaming The rinse aid composition was added to the powder detergent in the amount shown in Table 3, and the laundry was washed under the following washing conditions, and the height of foam after 7 minutes of washing was measured. <Washing conditions> Washing machine… Toshiba Galaxy 2.2kg Water volume… 30 liters Detergent volume… 25g Clothing… 1kg (cotton shirt 600g, T / C shirt)
400g, used for 3 days).

(2) Evaluation of Rinsability After washing by the above method, rinsing was performed under the following conditions, and rinsing properties after 1, 2, 3 times of rinsing were evaluated according to the following criteria. <Rinse conditions> Water injection amount: 20 liter / min Rinse time: Once (after 3 minutes), twice (after 6 minutes), 3
Times (after 9 minutes) <Evaluation criteria for rinsing properties> A: No bubbles remain on the liquid surface. B: About 1/2 bubbles remain on the liquid surface. C: Bubbles remain on the entire liquid surface.

[0042]

[Table 3]

Continued on the front page (72) Inventor Masaki Tsumatori 6-23 Saikazaki, Wakayama-shi, Wakayama Prefecture (72) Inventor Akinari Itagaki 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture 10 Silicone Electronics Materials Technology Research Laboratory (72) Inventor Satoshi Kuwata 1-10 Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture Inside Silicone Electronic Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (56) References JP-A-7-100359 (JP, A) JP-A-5 -271689 (JP, A) Table 9-502746 (JP, A) Table 8-502684 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 1/66 C11D 3/12 C11D 3/16 B01D 19/04 CA (STN) CAOLD (STN) REGISTRY (STN) WPIDS (STN)

Claims (9)

(57) [Claims] (1) an amine equivalent of 500 to 50,000 g / mol;
Aminoalkyl-modified silicone oil having a viscosity at 25 ° C. of 10 to 100,000 cSt. (B) Inorganic silica and / or inorganic silica derivative having a specific surface area of 100 m ² / g or more by BET method. The ratio of the inorganic silica and / or the inorganic silica derivative of the component (b) to the aminoalkyl-modified silicone oil of the component (a) is 0.01 to 0.1.
5 (weight ratio) rinse aid for clothes washing. 2. The composition according to claim 1, wherein the amount of the polydimethylsiloxane is (a)
The rinsing aid for washing clothes according to claim 1, wherein the mixing ratio is 0.1 or less with respect to the aminoalkyl-modified silicone oil as a component. 3. The rinsing aid for washing clothes according to claim 1, wherein the aminoalkyl-modified silicone oil as the component (a) is represented by the following formula (1). _{^{R 1 a R 2 b R 3}} c SiO (4-abc) / 2 ··· (1) [wherein R ¹ is _{^{-R 4 - (NR 5 CH 2}} CH 2) m -NR 6 R 7 ( R ⁴ is a divalent hydrocarbon group having 1 to ⁴ carbon atoms, R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and m is 0 ≦ m is an integer of 4 or less), R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, R ³ is —OR ⁸ (R ⁸ is hydrogen A hydroxyl group or an alkoxy group represented by an atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms), a, b, and c are respectively 0.0001 ≦ a ≦ 1, 1.
1.8 <a + b + c <2.3 for 8 ≤ b ≤ 2.2 and 0 ≤ c ≤ 0.1
Is a number that satisfies ] 4. A nonionic surfactant, and a nonionic surfactant.
A rinsing aid for washing clothes according to any one of the above,
A detergent composition for clothing comprising a nonionic surfactant as a main surfactant. 5. The detergent composition for clothing according to claim 4, comprising 0.001 to 0.2 by weight of the laundry washing rinse aid with respect to the nonionic surfactant. 6. The detergent composition for clothing according to claim 4, wherein the proportion of the anionic surfactant is not more than 20% by weight of the total surfactant. 7. The detergent composition for clothing according to claim 4, further comprising 10 to 90% by weight of a nonionic surfactant. 8. The method according to claim 4, wherein the nonionic surfactant is a polyoxyethylene alkyl ether having an average alkyl group of 6 to 22 carbon atoms and an average ethylene oxide mole number of 3 to 20. Item 14. A detergent composition for clothing according to the above item. 9. The detergent composition for clothing according to claim 4, wherein the form of the detergent composition is powder or granules.