JPH0867896A - Rinsing aid for laundry for laundry and detergent composition containing the same - Google Patents

Abstract

(57) [Summary] [Structure] (a) Amine equivalent is 500 to 50,000 g / mol, 25
An aminoalkyl-modified silicone oil having a viscosity of 10 to 100,000 cSt at 0 ° C., and (b) an inorganic silica and / or an inorganic silica derivative having a specific surface area of 100 m ² / g or more by the BET method, (b) / (a) = 0.01 to 0.5 (weight ratio), a rinsing aid for clothes washing, and a detergent composition for clothes, which comprises a nonionic surfactant containing the same as a main surfactant. [Effect] In the washing process, generation of bubbles is appropriately suppressed, and a sufficient defoaming effect is exhibited in the rinsing process.

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 clothes, and a laundry detergent composition containing the same.

[0002]

2. Description of the Related Art In European countries, 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, and therefore, a detergent used for washing is generally mixed with an antifoaming agent.

On the other hand, in Japan, a pulsator-type washing machine has been the mainstream in the past, and foam is not a problem in terms of washing efficiency. Rather, a detergent that produces an appropriate foam is favored by housewives at home due to their washing habits. It was

[0004]

However, the change in consciousness of foam during washing with the spread of fully automatic washing machines in recent years, and the foam overflowing from the lid when foam is generated during washing,
Further, there is a demand for a detergent in which foam generation is suppressed because the rinse time is long if the foam is large.

Polydimethylsiloxane is well known as an antifoaming agent for suppressing foams generated during washing, as disclosed in JP-A-3-186307 and JP-A-4-311800. Polydimethylsiloxane has been found to have the effect of eliminating bubbles during washing when blended with general clothing detergents, but is discharged to the outside of the washing machine during the drainage and dehydration processes after washing, and has a defoaming effect during the rinsing process. As a result, the surfactant remaining during the rinsing re-foams during the rinsing step, resulting in insufficient defoaming during rinsing. Moreover, the removal of turbidity during rinsing was insufficient.

With respect to amino-modified silicone, it is used as a defoaming agent for dyeing which is excellent in dilution stability and defoaming durability and does not cause uneven dyeing, and a foam suppressing composition containing this is disclosed in JP-A-5-261206, Although disclosed in JP-A-5-285306, there is no description about effects other than defoaming, in particular, defoaming properties of rinsing liquid at the time of washing clothes, let alone washing preferred when using the amino-modified silicone. No description is given regarding the agent composition. Further, JP-A-2-4223,
Japanese Patent Application Laid-Open No. 4-4224 discloses a liquid detergent containing an amino-modified silicone, but these are related to foaming properties and prevention of felt shrinkage, and nothing is said about the defoaming effect in the rinsing step. Absent.

Because of these problems, there is a demand for a rinse aid which exhibits a defoaming effect in the rinse 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 have a specific surface area of 100 m ² / g. Or more inorganic silica and /
Alternatively, they have found that a rinsing aid that can solve the above problems can be obtained by blending the inorganic silica derivative with a specific ratio, and have completed the present invention.

That is, the present invention provides a rinsing aid for laundry for clothes, which comprises the following components (a) and (b) at a ratio of (b) / (a) by weight of 0.01 to 0.5, and a detergent containing the same. A composition is provided. (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 BET specific surface area of 100 m ² / g or more 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), 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. Atomic groups or hydroxyl groups or alkoxy groups represented by C1 to C6 monovalent hydrocarbon groups), a, b and c are 0.0001 ≦ a ≦ 1 and 1.
1.8 <a + b + c <2.3 when 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
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 and R ⁷ are each a hydrogen atom or 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 groups, alkenyl groups such as allyl groups, phenyl groups, aryl groups such as tolyl groups, cycloalkyl groups such as cyclohexyl groups, halogen atoms for some or all of the hydrogen atoms bonded to the carbon atoms of these groups, 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, R ⁵ , R ⁶ , It is preferable that 90 mol% or more of all groups of R ⁷ are hydrogen atoms.
In addition, m is an integer of 0 ≦ m 2 ≦ 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, octadecyl group and other alkyl groups, vinyl group, allyl group and other alkenyl groups, Aryl group such as phenyl group, tolyl group, cycloalkyl group such as cyclohexyl group, chloromethyl group in which some or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. , A 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a halogen substitution such as a cyanoethyl group, a cyano group-substituted hydrocarbon group of the same or different type, which is unsubstituted or substituted Monovalent hydrocarbon group, but 90 mol% of the total R ² group
The above is preferably a methyl group.

Examples of R ³ in the above formula (1) include 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 when 8 ≤ b ≤ 2.2 and 0 ≤ c ≤ 0.1
However, 0.001 ≤ a ≤ from the viewpoint of defoaming property.
0.5, 1.9 ≤ b ≤ 2.1, 0 ≤ c ≤ 0.05, 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. Further, the amine equivalent of this aminoalkyl-modified silicone oil is less than 500 g / mol, and if it exceeds 50,000 g / mol, the defoaming effect in the rinsing step will be poor, so 500-50,000 g / mol. Range is required, but preferably 1,000
Is in the range of up to 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 ease of dispersion and workability, and from the viewpoint of defoaming durability. Considering that higher is better,
Viscosity at 25 ° C is required to be 10-100,000cSt, which means that the composition becomes unstable when the viscosity is less than 10cSt, and the composition obtained when it exceeds 100,000cSt is used. This is because there is a problem in workability at the time. It is preferably in the range of 100 to 20,000 cSt.

The inorganic silica and / or
Alternatively, the inorganic silica derivative may be a known one, and either wet silica or dry silica may be used, and therefore, precipitated silica, silica xerogel, fumed silica, and those whose surface is treated with an organic silyl group may be used. Specifically, Aerosil [trade name of Nippon Aerosil Co., Ltd.], nip seal [trade name of Nippon Silica Co., Ltd.],
Examples include Cabosil [trade name of American Cabot Corporation] and Santocell [trade name of Monsanto Chemical Company of the United States], which have a BET specific surface area of 100 m ² / g.
That is all. Those having a specific surface area of less than 100 m ² / g are not preferable because the adsorption of aminoalkyl-modified silicone is insufficient and the defoaming effect is poor.

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

The organic silanes and silazane compounds 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 blending ratio of the aminoalkyl-modified silicone oil which is the component (a) and the inorganic silica and / or the inorganic silica derivative which is the component (b) constituting the rinse aid for clothes washing of the present invention described above is (b) ) / (A) It is required that the weight ratio 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 workability are deteriorated, and it is particularly preferable to set it in the range of 0.02 to 0.2.

Further, the above-mentioned rinsing aid for clothes washing is
(a) component, an aminoalkyl-modified silicone oil,
(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, if necessary, 50 to 200
It can be produced by heat-treating at a temperature of [deg.] C. for 1 to 3 hours, and optionally removing a low boiling point fraction. Incidentally, it is optional to add an inorganic ammonium salt, an organic silicon compound, a siloxane resin, etc., as is well known, in order to improve the defoaming durability, dilution stability and the like during this heat treatment (Japanese Patent Publication No. 4-42043). Japanese Patent Laid-Open No. 5-261206 and Japanese Patent Laid-Open No. 5-261207). If polydimethylsiloxane, which has been used for laundry for clothes, is added and used together, it will affect the rinsing effect of aminoalkyl-modified silicone. 0.1 or less is preferable.

The rinsing aid of the present invention containing an aminoalkyl-modified silicone oil and an inorganic silica and / or an inorganic silica derivative is generally granulated or coated to give granules, which are not in direct contact with detergent ingredients. Blended into the detergent from.

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

Further, in order to improve the solubility of the granulated product, an anionic surfactant such as alkyl sulfate or alkylbenzene sulfonate, or a nonionic surfactant such as polyoxyethylene alkyl ether may be used. Good. Further, in order to improve the physical properties of the powder, a polymer having a melting point of 40 ° C. or higher such as polyethylene glycol or a water-soluble inorganic compound such as mirabilite can be added. Of course, you may mix | blend the fragrance | flavor and coloring agent which do not affect performance. Regarding the production of the granulated product, reference can be made to JP-A-3-186307.

The rinsing aid of the present invention as described above is particularly used for a detergent composition for clothes which contains a nonionic surfactant as a main surfactant.

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

The amount of the rinsing aid for clothes washing to be added to the detergent composition for clothes is such that the total amount of the components (a) and (b) is 0.001 to 0.2 by weight with respect to the nonionic surfactant. , Preferably 0.001 to 0.1. If this weight ratio is less than 0.001, sufficient rinsing effect cannot be obtained, and if it exceeds 0.2, no foaming occurs and the function as a detergent is impaired.

As described above, the detergent composition of the present invention is most effective when the nonionic surfactant is the main surfactant, and the anionic surfactant is not contained or the total surfactant is not present. It may be contained in the agent at 20% by weight or less. As the anionic surfactant, alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty 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 phosphate esters or salts thereof, preferably alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate. .
Here, the salt serving as the counterion includes potassium, sodium,
An amine or the like is used, but sodium is preferable. Further, when the anionic surfactant exceeds 20% by weight, it interacts with the aminoalkyl-modified silicone,
It impairs the rinsing function. Other cationic surfactants may be used together.

The detergent composition of the present invention may contain the following components in the conventional amounts known in general. As an ingredient,
Contains chelating agents, alkaline agents, dispersants, etc., for example, non-crystalline silicates, carbonates, sesquicarbonates, etc. alkali agents, Glauber's salt etc., extenders, crystalline aluminosilicates (zeolites), non-crystalline And a chelating agent such as an aluminosilicate, an orthophosphate, a pyrophosphate, a tripolyphosphate, a nitrilotriacetate, an ethylenediaminetetraacetate, a citrate and an isocitrate. Usually, for example, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, polyacrylic acid dispersants (recontamination inhibitors), in addition, enzymes such as protease, esterase, lipase, cellulase, anti-caking agents, peroxides. A small amount of additional components such as a stabilizer, an antioxidant, a fluorescent dye, a bluing agent, and a fragrance can also be added.

The rinsing aid for laundry of the present invention and the detergent composition containing the same 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, but, for example, as shown in JP-A-5-209200, the following method is used. Consisting of the steps from ~ to a bulk density of 0.6 to 1.2 g / ml
The method for obtaining the detergent particles is Step: A step of mixing a detergent raw material containing a nonionic surfactant as a main base. Step: Stir and mix the obtained mixture with a stirring shaft having a stirring blade in the center of the inside and forming a clearance between the stirring blade and the vessel wall when the stirring blade rotates. Thereby, a step of forming an adhering 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. Process: The granulated product obtained in the process and fine powder are mixed,
A step of coating the surface of the granulated product with the fine powder. The detergent particles obtained in the above steps to and the rinsing aid obtained by separate granulation are mixed in the mixing ratio as described above, and the nonionic ionic liquid containing the rinsing aid for clothes washing of the present invention is mixed. 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 Table 1 shows the composition of the rinse aid used in this example.

[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 Rinse Aid Granules Rinse aid, dextrin, polyethylene glycol and neutral anhydrous Glauber's salt having the following composition were mixed at 70 ° C. to 80 ° C., and then extrusion granulated by Fuji Paudal Co., Ltd. A granulation product was obtained by granulating with a machine (model EXKS-1). <Ingredient composition> -Rinse aid 20% -Dextrin 40% -Polyethylene glycol 25% (PEG-6000 melting point 58 ° C) -Neutral anhydrous Glauber's salt 15% Classify and granulate this granule with a 16 or 32 mesh sieve. The particle size of the granules was adjusted. -Average particle size: 800 μm-Particle size of 1000 μm or more: 5% -Particle size of 250 μm or less: 5% The granulation property during granulation was evaluated according to the following criteria. A: Yield 95% or more (500 to 1000 μm) O: Yield 85% or more and less than 95% X ... Yield less than 85%.

(2) Solubility Evaluation Method of Rinse Aid Granules The solubility evaluation of rinse aid granules was carried out in a 500 ml beaker.
300 ml of water at 10 ° C. was added, 300 mg of the granulated product was added with stirring while rotating 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 having a bulk density of 0.7 g / cm ³ was prepared. <Powder detergent composition> Polyoxyethylene alkyl ether 20% (Average carbon number of alkyl group is 12, ethylene oxide average addition mole number is 6) Zeolite 25% Sodium carbonate 25% Amorphous sodium aluminosilicate 15% Sodium sulfate 10% water 5% Using the powder detergent obtained above and the rinse aid granules prepared in Example 1 above, the foaming (height) at the time of washing and the rinsability were evaluated by the following methods. .

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

(2) Evaluation of rinsability After washing by the above method, rinsing was carried out under the following conditions, and the rinsability after 1, 2 and 3 times of rinsing was evaluated according to the following criteria. <Rinse conditions> Water injection rate: 20 liters / min Rinse time: 1 time (after 3 minutes), 2 times (after 6 minutes), 3
Time (after 9 minutes) <Evaluation criteria for rinsability> A ... No bubbles remain on the liquid surface. B ... About 1/2 of bubbles remain on the liquid surface. C ... Bubbles remain on the entire liquid surface.

[0042]

[Table 3]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaki Tsumadori 6-23 Saikazaki, Wakayama City, Wakayama Prefecture (72) Inventor Akinari Itagaki 1 Hitomi, Osamu Matsuida Town, Usui District, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Inside the Technical Research Center (72) Inventor Satoshi Kuwata 1 Hitomi, Oita, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd.

Claims (9)

[Claims] 1. An amine equivalent of 500 to 50,000 g / mol,
Aminoalkyl-modified silicone oil having a viscosity of 10 to 100,000 cSt at 25 ° C (b) Inorganic silica and / or inorganic silica derivative having a BET specific surface area of 100 m ² / g or more (a) component and (b) 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.
A rinsing aid for clothes washing that is 5 (weight ratio). 2. The compounding amount of polydimethylsiloxane is (a).
The rinsing aid for clothes washing according to claim 1, which has a compounding ratio of 0.1 or less with respect to the component aminoalkyl-modified silicone oil. 3. The rinsing aid for laundry according to claim 1, wherein the aminoalkyl-modified silicone oil of 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), 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. Atomic groups or hydroxyl groups or alkoxy groups represented by C1 to C6 monovalent hydrocarbon groups), a, b and c are 0.0001 ≦ a ≦ 1 and 1.
1.8 <a + b + c <2.3 when 8 ≤ b ≤ 2.2 and 0 ≤ c ≤ 0.1
Is a number that satisfies. ] 4. A nonionic surfactant and claims 1-3.
Containing a rinse aid for clothes washing according to any one of
A laundry detergent composition comprising a nonionic surfactant as a main surfactant. 5. The laundry detergent composition according to claim 4, wherein the rinse aid for laundry for clothes is contained in a weight ratio of 0.001 to 0.2 with respect to the nonionic surfactant. 6. The laundry detergent composition according to claim 4, wherein the proportion of the anionic surfactant is 20% by weight or less based on the total amount of the surfactants. 7. The detergent composition for clothes according to claim 4, which contains 10 to 90% by weight of a nonionic surfactant. 8. The nonionic surfactant is a polyoxyethylene alkyl ether having an alkyl group having an average carbon number of 6 to 22 and an ethylene oxide average addition mole number of 3 to 20. The detergent composition for clothes according to the item. 9. The detergent composition for clothes according to claim 4, wherein the detergent composition is in the form of powder or particles.