JP5282353B2 - Granular silicone antifoam composition and powder detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a granular silicone defoaming agent composition capable of efficiently suppressing foams in washing (including rinsing) and also high in preservation stability in a detergent composition, and to provide such a powdery detergent composition containing the above defoaming agent composition. <P>SOLUTION: The granular silicone defoaming agent composition comprises (A) a silicone defoaming agent, (B) an excipient material, (C) organowaxes and (D) either one or both of a polyoxyalkylene-modified organosiloxane with a melting point of 35&deg;C or higher and a siloxane-polyoxyalkylene block copolymer with a melting point of 35&deg;C or higher. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to detergent compositions, in particular granular silicone antifoam compositions and powder detergent compositions suitable for powder detergent compositions.

  Conventionally, pulsator-type washing machines have been the mainstream in Japan, and foam generated during washing has not been a problem in terms of washing efficiency. Rather, detergents that foam moderately tend to be preferred by housewives in the home rather than a washing habit that moderate foaming has a better cleaning effect. However, in recent years, with the widespread use of fully automatic washing machines, there has been a demand for detergents that have low foaming properties and good rinsing properties so that rinsing can be completed within a predetermined program time.

  Furthermore, in recent years, the spread of washing machines equipped with dryers (washing dryers) has become widespread, but many of these laundry dryers are drum-type, and if foam is generated during washing, the washing efficiency deteriorates and the washing effect decreases. Or a foam overflowing from the lid of the washing machine, there is a demand for a detergent that suppresses the generation of foam.

  Silicone antifoaming agents are known as antifoaming agents that suppress foam generated during washing. However, when silicone antifoaming agents are added directly to powdered detergents, they exhibit an antifoaming effect immediately after addition, but are stored for a while. Then, it is known that antifoaming performance will fall remarkably by the influence of the alkali agent contained in detergent. Therefore, after granulating and coating the silicone antifoaming agent, it is also mixed with detergent components, but if stored at high temperatures, it cannot suppress the bleeding of the silicone antifoaming agent and defoaming performance It is not possible to prevent a decrease in

Therefore, in Patent Document 1, a granular antifoam composition comprising a silicone antifoam, carrier particles, water-insoluble fatty acid or fatty alcohol is used, and in Patent Document 2, a silicone antifoam, carrier particles, and a monoester of fatty acid and glycerol. Patent Document 3 proposes a granular antifoaming composition in which a silicone antifoaming agent is adsorbed on gelatinized water-swellable hydrophilic starch, each of which is water-soluble. Due to its poor properties, the defoamer component is not released into the water when the water temperature is low, and sufficient defoaming effect cannot be obtained, or it takes a long time to be effective, and it remains undissolved. There is also a problem that adheres to clothes.
JP-A-62-27496 JP-A-62-27497 JP-A-62-57616

  An object of the present invention is to efficiently suppress foam during washing (that is, from washing to rinsing), and further contain a granular silicone antifoam composition having excellent storage stability in a detergent composition, and An object of the present invention is to provide a powder detergent composition.

  As a result of intensive studies to achieve the above problems, the present inventors have found that a silicone antifoaming agent, a carrier material, an organic wax, a polyoxyalkylene-modified organosiloxane having a predetermined structure and a melting point of 35 ° C. or higher, and A granular silicone antifoam composition comprising one or both of a siloxane-polyoxyalkylene block copolymer having a predetermined structure and a melting point of 35 ° C. or higher has an effective defoaming effect during washing And has been found to be excellent in storage stability in a detergent composition, leading to the present invention.

That is, the present invention
(A) silicone antifoaming agent,
(B) a carrier material,
(C) organic waxes, and (D) the following general formula (I):

［式中、Ｒ^１は同一または異種の非置換もしくは置換の１価炭化水素基であり、Ｒ^２は下記一般式（ＩＩＩ）：
−Ｒ^３−Ｏ−（Ｒ^４Ｏ）_ｄ−Ｒ^５ （ＩＩＩ）
（式中、Ｒ^３及びＲ^４のおのおのは２価炭化水素基であり、Ｒ^５は水素原子または１価の有機基であり、ｄは１以上の整数であり、ただし、ｄ≧２のとき、Ｒ^４は同一でも異なっていてもよい。）
で表される基であり、ａは０または１であり、ｂはｂ≧０を満たす整数であり、ｃはｃ≧０を満たす整数であり、ただし、ａ＋ｃ≧１であり、上記一般式（Ｉ）中にＲ^２が複数含まれる場合、Ｒ^２は同一でも異なっていてもよい］
で示される３５℃以上の融点を有するポリオキシアルキレン変性オルガノシロキサンおよび下記一般式（ＩＩ）：

[Wherein, R ¹ represents the same or different unsubstituted or substituted monovalent hydrocarbon group, and R ² represents the following general formula (III):
—R ³ —O— (R ⁴ O) _d —R ⁵ (III)
(In the formula, each of R ³ and R ⁴ is a divalent hydrocarbon group, R ⁵ is a hydrogen atom or a monovalent organic group, d is an integer of 1 or more, provided that d ≧ 2 , R ⁴ may be the same or different.)
A is 0 or 1, b is an integer satisfying b ≧ 0, c is an integer satisfying c ≧ 0, provided that a + c ≧ 1, and the above general formula ( I) When R ² is contained in plural, R ² may be the same or different.
And a polyoxyalkylene-modified organosiloxane having a melting point of 35 ° C. or higher represented by the following general formula (II):

［式中、Ｒ^６は同一または異種の非置換もしくは置換の１価炭化水素基であり、Ｒ^７は同一または異種の２価炭化水素基であり、Ｒ^８は２価炭化水素基であり、ｅはｅ≧１を満たす整数であり、ｆはｆ≧１を満たす整数であり、ｇはｇ≧１を満たす整数であり、ただし、ｆ≧２のとき、Ｒ^８は同一でも異なっていてもよい］
で示される３５℃以上の融点を有するシロキサン−ポリオキシアルキレンブロック共重合体のどちらか一方または両方
を含有することを特徴とする粒状シリコーン消泡剤組成物、ならびに、この粒状シリコーン消泡剤組成物を含有することを特徴とする粉末洗剤組成物を提供するものである。

[Wherein R ⁶ is the same or different unsubstituted or substituted monovalent hydrocarbon group, R ⁷ is the same or different divalent hydrocarbon group, and R ⁸ is a divalent hydrocarbon group, e is an integer that satisfies e ≧ 1, f is an integer that satisfies f ≧ 1, and g is an integer that satisfies g ≧ 1, provided that when f ≧ 2, R ⁸ may be the same or different. Good]
A granular silicone defoamer composition comprising either or both of a siloxane-polyoxyalkylene block copolymer having a melting point of 35 ° C. or higher represented by the formula: The present invention provides a powder detergent composition characterized by containing a product.

  The granular silicone antifoam composition of the present invention effectively suppresses foam during washing and is excellent in storage stability in a detergent composition, and therefore is used in a detergent composition, particularly a powder detergent composition. It is useful as a granular silicone antifoaming agent. The powder detergent composition comprising the granular silicone antifoam composition of the present invention efficiently suppresses the generation of foam during washing, and the antifoaming effect is unlikely to deteriorate even when stored for a long period of time.

  The present invention will be described in detail below. In the present invention, the viscosity is a value measured with an Ostwald viscometer at 25 ° C.

[(A) component]
(A) A component is a silicone antifoamer. The silicone antifoaming agent is not particularly limited, but is composed of a silicone oil compound composed of an organopolysiloxane and finely divided silica, or the silicone oil compound and a polyoxyalkylene-modified organosiloxane that is liquid at 25 ° C. Silicone mixtures are preferred. (A) The silicone antifoamer of a component may be used individually by 1 type, or may use 2 or more types together.

(Silicone oil compound)
Organopolysiloxane The organopolysiloxane may be linear or branched, and may be used alone or in combination of two or more. Viscosity at 25 ° C. This organopolysiloxane is preferably 10~100,000mm ² / s, defoaming property, from the viewpoint of workability, more preferably 50~50,000mm ² / s. Examples of the organopolysiloxane include an average composition formula (IV):
R ⁹ _h SiO _{(4-h) / 2} (IV)
(Wherein R ⁹ is independently a hydroxyl group or an unsubstituted or substituted monovalent hydrocarbon group, and h is a number from 1.9 to 2.2)
The thing represented by is mentioned.

In this general formula (IV), the unsubstituted or substituted monovalent hydrocarbon group represented by R ⁹ is preferably one having 1 to 20 carbon atoms, specifically, for example, a methyl group, Alkyl groups such as ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl; and the like; cyclohexyl A cycloalkyl group; an alkenyl group such as a vinyl group and an allyl group; an aryl group such as a phenyl group and a tolyl group; an aralkyl group such as a styryl group; or a part or all of the hydrogen atoms of these hydrocarbon groups are halogen atoms, cyano A group substituted with a group, amino group, etc., for example, chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropylene Group, cyanoethyl group, 3-aminopropyl group, N-(beta-aminoethyl)-.gamma.-and aminopropyl group but can be mentioned, in terms of defoaming and economy, 90 to 100 mol% of all R ⁹ Is preferably a methyl group.

  H in the general formula (IV) needs to be a number from 1.9 to 2.2. When h is less than 1.9, the viscosity of the organopolysiloxane tends to be high, and workability and emulsification characteristics may be deteriorated. When h is larger than 2.2, the molecular weight of the organopolysiloxane becomes small, and the resulting composition may not exhibit sufficient antifoaming properties.

  Preferable specific examples of the organopolysiloxane represented by the general formula (IV) include dimethylpolysiloxane, diethylpolysiloxane, methylphenylpolysiloxane, dimethylsiloxane-diphenylsiloxane copolymer, methyl (3,3,3-trifluoro). Propyl) polysiloxane, α, ω-dihydroxydimethylpolysiloxane and the like.

-Fine powder silica The fine powder silica may be a known one, and may be either hydrophilic silica or hydrophobic silica. The fine powdered silica preferably has a specific surface area by the BET method of 100 m ² / g or more, more preferably 150 to 500 m ² / g. Fine powder silica may be used alone or in combination of two or more. Examples of the hydrophilic silica include wet silica such as precipitated silica and gel silica, and dry silica such as silica xerogel and fumed silica. Specific examples thereof include Aerosil (registered trademark) (trade name, manufactured by Nippon Aerosil Co., Ltd.), Nipsil, Nipgel (both trade names, manufactured by Tosoh Silica Co., Ltd.), Siricia (registered trademark) (trade name, Fuji Silysia Chemical Co., Ltd.). Examples of the hydrophobic silica include fine powder silica obtained by hydrophobizing the surface of hydrophilic silica with a compound having an organic silyl group. The hydrophobizing treatment can be performed by a conventionally known method, that is, by treating hydrophilic silica with an organosilicon compound such as organochlorosilane, organoalkoxysilane, organodisilazane, organopolysiloxane, organohydrogenpolysiloxane or the like. it can.

-Preparation of silicone oil compound For example, the silicone oil compound is prepared by mixing a predetermined amount of the above-mentioned organopolysiloxane and finely divided silica, treating the mixture at room temperature (25 ° C) to 200 ° C, and then lowering the boiling point if necessary. Can be manufactured by removing the minutes. In this silicone oil compound, for example, as described in JP-B-4-42043, JP-A-5-261206, and the like, an inorganic ammonium salt, an organosilicon compound, a siloxane resin, and the like are further used for defoaming, high temperature. You may add for improvement of a characteristic, dilution stability, etc.

  In addition, it is preferable to make the addition amount of fine powder silica into the range of 2-30 mass parts with respect to 100 mass parts of said organopolysiloxane, More preferably, it is the range of 3-20 mass parts. When the amount is less than 2 parts by mass, the defoaming performance of the resulting composition may be inferior. When the amount exceeds 30 parts by mass, the viscosity of the silicone oil compound may increase and workability may deteriorate.

(Silicone mixture)
-Polyoxyalkylene-modified organosiloxane Further, a liquid polyoxyalkylene-modified organosiloxane at 25 ° C may be added to the silicone oil compound to form a silicone mixture. These polyoxyalkylene-modified organosiloxanes may be used alone or in combination of two or more. Viscosity at 25 ° C. This polyoxyalkylene-modified organosiloxane is preferably in terms of emulsifying dispersing action and workability in an aqueous is 10~10,000mm ² / s, more preferably 100~7,000mm ² / s It is. Examples of the polyoxyalkylene-modified organosiloxane include the following general formula (V):

［式中、Ｒ^１０は同一または異種の非置換もしくは置換の１価炭化水素基であり、Ｒ^１１は下記一般式（ＶＩ）：
−Ｒ^１２−Ｏ−（Ｒ^１３Ｏ）_Ｌ−Ｒ^１４ （ＶＩ）
（式中、Ｒ^１２及びＲ^１３のおのおのは２価炭化水素基であり、Ｒ^１４は水素原子または１価の有機基であり、Ｌは１以上の整数であり、ただし、Ｌ≧２のとき、Ｒ^１３は同一でも異なっていてもよい。）
で表される基であり、ｉは０または１であり、ｊはｊ≧０を満たす整数であり、ｋはｋ≧０を満たす整数であり、ただし、ｉ＋ｋ≧１であり、上記一般式（Ｖ）中にＲ^１１が複数含まれる場合、Ｒ^１１は同一でも異なっていてもよい］
で示され、25℃にて液状であるものが挙げられる。

[Wherein R ¹⁰ represents the same or different unsubstituted or substituted monovalent hydrocarbon group, and R ¹¹ represents the following general formula (VI):
—R ¹² —O— (R ¹³ O) _L —R ¹⁴ (VI)
(In the formula, each of R ¹² and R ¹³ is a divalent hydrocarbon group, R ¹⁴ is a hydrogen atom or a monovalent organic group, L is an integer of 1 or more, provided that L ≧ 2 , R ¹³ may be the same or different.)
I is 0 or 1, j is an integer satisfying j ≧ 0, k is an integer satisfying k ≧ 0, provided that i + k ≧ 1, and the above general formula ( In the case where a plurality of R ¹¹ are contained in V), R ¹¹ may be the same or different.
And is liquid at 25 ° C.

In the general formula (V), the unsubstituted or substituted monovalent hydrocarbon group represented by R ¹⁰ is preferably one having 1 to 20 carbon atoms, and specifically, for example, in R ⁹ Specific examples of the unsubstituted or substituted monovalent hydrocarbon group represented are listed. In particular, from the viewpoint of the defoaming effect and economy, it is preferable that 90 to 100 mol% of all R ¹⁰ is a methyl group.

  In the general formula (V), j is preferably an integer of 5 to 300, more preferably an integer of 10 to 200, and k is an integer of 0 to 50, from the viewpoint of emulsification and dispersion action and workability. Preferably, it is an integer of 1-30.

In the general formula (VI), the divalent hydrocarbon group represented by R ¹² and R ¹³ preferably has 2 to 6 carbon atoms. Specific examples of R ¹² include an ethylene group and a trimethylene group. And an alkylene group having no branch such as a tetramethylene group. Specific examples of R ¹³ include ethylene group, methylethylene group, 1,2-butylene group, 1,3-butylene group, and 2,3-butylene. And alkylene groups such as a tetramethylene group.

In the general formula (VI), examples of the monovalent organic group represented by R ¹⁴ include alkyl having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Group, acetyl group, isocyano group and the like.

  In the general formula (VI), L is preferably an integer of 1 to 100, more preferably an integer of 5 to 80.

  As a preferable specific example of the polyoxyalkylene-modified organosiloxane represented by the general formula (V),

等が挙げられる。

Etc.

・ Preparation This polyoxyalkylene-modified organosiloxane is intended to enhance the dispersibility of the silicone oil compound in water, and the amount added must be at most 200 parts by mass with respect to 100 parts by mass of the silicone oil compound. However, it is more preferably 180 parts by mass or less. If the amount added exceeds 200 parts by mass, the defoaming effect of the resulting composition may be reduced.

  In addition, a predetermined amount of silicone oil compound and polyoxyalkylene-modified organosiloxane at a temperature of 15 to 60 ° C., for example, propeller mixer, anchor mixer, paddle mixer, gate mixer, homomixer, line mixer, colloid mill, homogenizer, It is preferable to prepare the silicone mixture by uniformly mixing with a stirring mixer such as a homodisper.

[Component (B)]
(B) Component carrier material has (A) component silicone antifoaming agent, (C) component organic wax, and (D) component polyoxyalkylene-modified organosiloxane and siloxane-polyoxyalkylene block on the surface thereof. One or both of the copolymers are attached so that they can be handled as particulates. Component (B) may be used alone or in combination of two or more. The component (B) may be a known component, and examples thereof include zeolite, granular sodium tripolyphosphate, sodium sulfate, sodium carbonate, sodium citrate, carboxymethylcellulose, starch, modified starch, dextrin, clay mineral and the like. .

[Component (C)]
The component (C) is an organic wax, the action of making the silicone antifoaming agent of the component (A) easy to adhere to the carrier material of the component (B), and preventing the defoaming performance from being deteriorated by the alkali component contained in the detergent. It is responsible for the action. Although (C) component may be used individually by 1 type, it is preferable to use combining 2 or more types. The (C) component organic wax may be generally known, and examples thereof include polyethylene glycol having a molecular weight of 2000 to 40,000, higher fatty acids having 8 or more carbon atoms, higher alcohols, sorbitan fatty acid esters, glycerin. Fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene hydrogenated castor oil , Polyoxyethylene lanolin alcohol, polyoxyethylene sorbit beeswax and the like, preferably polyethylene glycol having a molecular weight of 3000 to 30000 and Higher fatty acids having 10 or more elementary atoms, higher aliphatic alcohols and esters thereof, more preferably polyethylene glycol having a molecular weight of 3000 to 20000, and higher fatty acids, higher alcohols and esters thereof having 12 or more carbon atoms It is kind.

[(D) component]
Component (D) is a polyoxyalkylene-modified organosiloxane having a melting point of 35 ° C. or higher represented by the following general formula (I) and a siloxane-polyoxyalkylene having a melting point of 35 ° C. or higher represented by the following general formula (II) Either or both of the block copolymers, strengthening the interaction between the silicone antifoaming agent of component (A) and the organic waxes of component (C), and bleeding of the silicone antifoaming agent during long-term storage Not only prevents the defoaming effect from decreasing, but also imparts an effect of uniformly dispersing the silicone antifoaming agent in water. Each of the polyoxyalkylene-modified organosiloxane and the siloxane-polyoxyalkylene block copolymer may be used alone or in combination of two or more.

(Polyoxyalkylene-modified organosiloxane)
Formula (I):

［式中、Ｒ^１は同一または異種の非置換もしくは置換の１価炭化水素基であり、Ｒ^２は下記一般式（ＩＩＩ）：
−Ｒ^３−Ｏ−（Ｒ^４Ｏ）_ｄ−Ｒ^５ （ＩＩＩ）
（式中、Ｒ^３及びＲ^４のおのおのは２価炭化水素基であり、Ｒ^５は水素原子または１価の有機基であり、ｄは１以上の整数であり、ただし、ｄ≧２のとき、Ｒ^４は同一でも異なっていてもよい。）
で表される基であり、ａは０または１であり、ｂはｂ≧０を満たす整数であり、ｃはｃ≧０を満たす整数であり、ただし、ａ＋ｃ≧１であり、上記一般式（Ｉ）中にＲ^２が複数含まれる場合、Ｒ^２は同一でも異なっていてもよい］

[Wherein, R ¹ represents the same or different unsubstituted or substituted monovalent hydrocarbon group, and R ² represents the following general formula (III):
—R ³ —O— (R ⁴ O) _d —R ⁵ (III)
(In the formula, each of R ³ and R ⁴ is a divalent hydrocarbon group, R ⁵ is a hydrogen atom or a monovalent organic group, d is an integer of 1 or more, provided that d ≧ 2 , R ⁴ may be the same or different.)
A is 0 or 1, b is an integer satisfying b ≧ 0, c is an integer satisfying c ≧ 0, provided that a + c ≧ 1, and the above general formula ( I) When R ² is contained in plural, R ² may be the same or different.

In the general formula (I), the unsubstituted or substituted monovalent hydrocarbon group represented by R ¹ preferably has 1 to 20 carbon atoms, and specifically includes, for example, methyl group, ethyl Group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group and other alkyl groups; cyclohexyl group and other cyclo groups Alkyl groups; alkenyl groups such as vinyl groups and allyl groups; aryl groups such as phenyl groups and tolyl groups; aralkyl groups such as styryl groups; or some or all of the hydrogen atoms of these hydrocarbon groups are halogen atoms, cyano groups A group substituted with an amino group, such as a chloromethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, Anoechiru group, 3-aminopropyl group, N-(beta-aminoethyl)-.gamma.-amino although a propyl group, from the standpoint of the defoaming property and economy, 90 to 100 mol% of all R ¹ is methyl It is preferably a group.

In the general formula (III), the divalent hydrocarbon group represented by R ³ and R ⁴ preferably has 2 to 6 carbon atoms. Specific examples of R ³ include an ethylene group and a trimethylene group. And an alkylene group having no branch such as a tetramethylene group. Specific examples of R ⁴ include an ethylene group, a methylethylene group, a 1,2-butylene group, a 1,3-butylene group, and a 2,3-butylene group. And alkylene groups such as a tetramethylene group. In order for the polyoxyalkylene-modified organosiloxane to have a melting point of 35 ° C. or higher, it is desirable that 80 to 100 mol% of the entire R ⁴ is an ethylene group.

  Furthermore, in the above general formula (III), if d is less than 20, the melting point of the polyoxyalkylene-modified organosiloxane tends to be low, so d is preferably an integer of 20 or more, more preferably 20 to 200. It is an integer, and even more preferably an integer of 25-100.

In the general formula (III), examples of the monovalent organic group represented by R ⁵ include alkyl having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Group, acetyl group, isocyano group and the like.

  In the above general formula (I), b is preferably an integer of 5 to 200, more preferably an integer of 10 to 150, and c is preferably an integer of 0 to 100, more preferably 1 to An integer of 50.

  The polyoxyalkylene-modified organosiloxane represented by the above general formula (I) is, for example, an organohydrogensiloxane having a hydrogen atom bonded to a silicon atom and an aliphatic unsaturated group such as an allyl group at the molecular chain end according to a conventional method. It can be obtained by addition reaction with a polyoxyalkylene compound having a hydrogen atom in the presence of a catalyst such as platinum.

  As preferable examples of the polyoxyalkylene-modified organosiloxane,

等が挙げられる。

Etc.

(Siloxane-polyoxyalkylene block copolymer)
General formula (II):

［式中、Ｒ^６は同一または異種の非置換もしくは置換の１価炭化水素基であり、Ｒ^７は同一または異種の２価炭化水素基であり、Ｒ^８は２価炭化水素基であり、ｅはｅ≧１を満たす整数であり、ｆはｆ≧１を満たす整数であり、ｇはｇ≧１を満たす整数であり、ただし、ｆ≧２のとき、Ｒ^８は同一でも異なっていてもよい］

[Wherein R ⁶ is the same or different unsubstituted or substituted monovalent hydrocarbon group, R ⁷ is the same or different divalent hydrocarbon group, and R ⁸ is a divalent hydrocarbon group, e is an integer that satisfies e ≧ 1, f is an integer that satisfies f ≧ 1, and g is an integer that satisfies g ≧ 1, provided that when f ≧ 2, R ⁸ may be the same or different. Good]

In the above general formula (II), the unsubstituted or substituted monovalent hydrocarbon group represented by R ⁶ is preferably one having 1 to 20 carbon atoms, specifically, for example, in R ¹ Specific examples of the unsubstituted or substituted monovalent hydrocarbon group represented are listed. In particular, from the viewpoint of the defoaming effect and economy, it is preferable that 90 to 100 mol% of all R ⁶ is a methyl group.

In the general formula (II), the divalent hydrocarbon group represented by R ⁷ and R ⁸ preferably has 2 to 6 carbon atoms, and specific examples of R ⁷ include an ethylene group and a trimethylene group. And an alkylene group having no branch such as a tetramethylene group. Specific examples of R ⁸ include ethylene group, methylethylene group, 1,2-butylene group, 1,3-butylene group, and 2,3-butylene. And alkylene groups such as a tetramethylene group. In order for the block copolymer to have a melting point of 35 ° C. or higher, 90 to 100 mol% of the entire R ⁸ is desirably an ethylene group.

  Furthermore, in the general formula (II), if f is smaller than 20, the melting point of the block copolymer tends to be low, so f is preferably an integer of 20 or more, more preferably an integer of 20 to 200. And even more preferably an integer from 25 to 100.

  In the said general formula (II), it is preferable that e is an integer of 1-150, More preferably, it is an integer of 5-100. In consideration of workability, g is preferably an integer of 1 to 100, more preferably an integer of 3 to 50.

  The siloxane-polyoxyalkylene block copolymer represented by the general formula (II) is, for example, an α, ω-dihydrogenorganosiloxane and an aliphatic unsaturated group such as an allyl group at both ends of the molecular chain according to a conventional method. It can be obtained by addition reaction with a polyoxyalkylene compound having a hydrogen atom in the presence of a catalyst such as platinum.

  As a preferable example of the siloxane-polyoxyalkylene block copolymer,

等が挙げられる。

Etc.

[Granular silicone antifoam composition]
In the granular silicone antifoaming agent composition of the present invention, the preferred blending amount of each component is, for example, (A) silicone antifoaming agent of component: 100 parts by mass,
(B) Component carrier material: 50-2000 parts by mass, more preferably 100-1000 parts by mass,
(C) Component organic wax: 5 to 600 parts by mass, more preferably 30 to 500 parts by mass, and (D) Component polyoxyalkylene-modified organosiloxane and copolymer, or both: 5 It is -500 mass parts, More preferably, it is 10-300 mass parts.

  Examples of the method for producing the granular silicone antifoam composition of the present invention include known granulation methods such as extrusion granulation method, stirring granulation method, rolling granulation method, and fluidized bed granulation method. Preferably, (A) a silicone antifoam is added to (B) the carrier material while mixing, then (C) an organic wax and (D) a polyoxyalkylene modified organosiloxane and a siloxane-polyoxyalkylene block copolymer One of or both of them may be mixed under heating, and a granulated product may be obtained by extrusion granulation, or a method in which each component is stirred and granulated under heating by a stirring and mixing granulator. Although it depends on the kind of these components, the temperature may be any temperature that moderately softens the mixture so that it can be easily stirred, and examples thereof include 30 to 100 ° C. In order to ensure that the granular silicone antifoam composition of the present invention has a particle size distribution within a desired range, the above granulated composition is passed through a first sieve having a larger mesh size, The sieved fraction may be applied to a second sieve having a smaller mesh opening to obtain a sieved fraction, and the sieved fraction may be used as the granular silicone antifoam composition of the present invention. As the first sieve, for example, a sieve having an opening of 2800 to 710 μm as defined in JIS Z 8801-1 can be used. As the second sieve, for example, a sieve having an aperture of 600 to 150 μm of the same standard can be used. The average particle size of the granular silicone antifoaming agent composition of the present invention is preferably 100 to 2000 μm, more preferably 150 to 1500 μm from the viewpoints of fluidity, water dispersibility, and antifoaming properties. In the present invention, the average particle diameter can be determined as a volume-based cumulative average diameter by a laser diffraction method or the like.

[Powder detergent composition]
Furthermore, the present invention provides a low-foaming powder detergent composition. The constituents of the powder detergent composition are not particularly limited as long as the powder detergent composition contains the detergent component and the granular silicone antifoam composition of the present invention and functions effectively as a detergent. Examples of the detergent component include surfactants and detergent builders. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. Examples of the anionic surfactant include alkali metal salts of higher fatty acids, linear alkylbenzene sulfonates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, α-olefin sulfonates, and the like. Examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts. Examples of nonionic surfactants include polyoxyalkylene alkyl ethers and polyethylene glycol fatty acid esters. Examples of amphoteric surfactants include imidazoline compounds and betaine compounds. Examples of detergent builders include zeolites, carbonates, bicarbonates, silicates, phosphates, sulfates and the like.

  In addition, in the powder detergent composition of the present invention, as other components, bleach components such as perborate and percarbonate; anti-redeposition agents such as carboxymethylcellulose and polyethylene glycol; enzymes such as lipase and protease; fluorescence Brighteners; softeners; fragrances and the like may be added.

In the powder detergent composition of the present invention, the preferred blending amount of each component is, for example,
Anionic surfactant: 10-60 parts by mass,
Detergent builder: 20-100 parts by weight,
Nonionic surfactant, cationic surfactant, amphoteric surfactant: 0 to 50 parts by mass in total,
Other ingredients: 1 to 10 parts by mass when added
Granular silicone antifoam composition of the present invention: 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these Examples.

[(A) Silicone antifoaming agent]
・ Silicone oil compound (1)
100 parts by weight of dimethylpolysiloxane having a viscosity of 1,000 mm ² / s as a hydrophobic organopolysiloxane, and hydrophilic wet silica as a fine powder silica (trade name: Nipsil HD-2, manufactured by Tosoh Silica Co., Ltd., BET A silicone oil compound (1) was obtained by heating and mixing 10 parts by mass (specific surface area: 300 m ² / g) in a nitrogen gas atmosphere at 150 ° C. for 3 hours.
・ Silicone oil compound (2)
As a hydrophobic organopolysiloxane, the viscosity is 5,000 mm ² / s, and 100 parts by mass of branched dimethylpolysiloxane containing 1 mol% of CH ₃ SiO _3/2 units with respect to all siloxane units, and fine powder silica 5 parts by mass of hydrophobized silica (trade name: AEROSIL200, Nippon Aerosil Co., Ltd., BET specific surface area: 200 m ² / g) prepared by surface treatment with hexamethyldisilazane, Under a nitrogen gas atmosphere, the mixture was heated and mixed at 160 ° C. for 3 hours to obtain a silicone oil compound (2).
・ Silicone mixture (3)
Silicone oil compound (1) 100 parts by weight and the following formula:

で表されるポリオキシアルキレン変性オルガノシロキサン(4)（粘度：2000mm^２／s）40質量部をＴＫホモミキサー（プライミクス株式会社製）にて混合することによりシリコーン混和物(3)を得た。

A silicone admixture (3) was obtained by mixing 40 parts by mass of polyoxyalkylene-modified organosiloxane (4) (viscosity: 2000 mm ² / s) represented by TK using a TK homomixer (manufactured by Primics Co., Ltd.).

[(D) A polyoxyalkylene-modified organosiloxane having a melting point of 35 ° C. or higher represented by the general formula (I) and a siloxane-polyoxyalkylene block having a melting point of 35 ° C. or higher represented by the general formula (II) One or both of the polymers]
・ Polyoxyalkylene-modified organosiloxane (5) (melting point: 48 ℃)

・ポリオキシアルキレン変性オルガノシロキサン(6)（融点：45℃）

・ Polyoxyalkylene-modified organosiloxane (6) (melting point: 45 ℃)

・シロキサン−ポリオキシアルキレンブロック共重合体(7)（融点：46℃）

Siloxane-polyoxyalkylene block copolymer (7) (melting point: 46 ° C)

[Granular silicone antifoam composition]
Each component (unit: part by mass) shown in Table 1 is put in Hibismix (Primics Co., Ltd.), stirred and mixed at a temperature of 60-80 ° C. It was granulated and further sized with a power mill (Fuji Paudal Co., Ltd.). The obtained particles were passed through an 18 mesh sieve (mesh size 850 μm) defined in JIS Z 8801-1. The obtained under-sieving fraction is further passed through a 36-mesh sieve of the same standard (mesh size: 425 μm), so that the average particle size of 700 μm with a particle size distributed in the range of about 425 to 850 μm is obtained as the top-sieving fraction. A silicone antifoam composition was obtained.

[Powder detergent composition]
-Linear alkyl (C12-C13) sodium benzenesulfonate 25 parts by mass-Sodium lauryl sulfate 10 parts by mass-Polyoxyethylene alkyl (C12-C13) ether 5 parts by mass-Zeolite 25 parts by mass-Sodium carbonate 10 parts by mass-Kei A powder detergent composition having a bulk density of 0.7 g / cm ³ consisting of 15 parts by weight of acid soda, 5 parts by weight of sodium sulfate, and one part of granular silicone antifoam composition 1 to 8 parts by weight of 0.8 parts by weight and 4.2 parts by weight of water. These components were prepared by mixing with a power mill (Fuji Paudal Co., Ltd.). However, in Comparative Example 4, no granular silicone antifoam composition was added.

  Foaming and rinsing properties during washing of the powder detergent composition prepared above were evaluated as follows.

[Evaluation of foaming]
Washing was performed under the following conditions, and the foam height after 7 minutes of washing was measured. The results are shown in Table 2.
・ Washing conditions
Washing machine: Toshiba Galaxy 2.2kg
Amount of water: 30 liters Amount of powder detergent composition: 25 g
Clothing: 1kg (600g cotton shirt, 400g T / C shirt, each worn for 3 days)

[Rinse evaluation]
After washing by the above method, rinsing was performed under the following conditions, and the amount of foam remaining after rinsing was evaluated according to the following criteria. The results are shown in Table 2.
・ Rinse condition Water injection volume: 20 liters / minute Rinse time: 3 minutes / once
A: No bubbles remain on the liquid surface
B: Bubbles remain in less than 1/4 of the entire liquid level
C: Foam remains in 1/4 or more and less than 3/4 of the entire liquid level
D: Bubbles remain on more than 3/4 of the entire liquid surface

  The powder detergent composition was stored at 40 ° C. for 3 weeks, and foaming and rinsing were evaluated again. The results are shown in Table 2.

As can be seen from Table 2, the powder detergent composition comprising the granular silicone antifoaming agent of the present invention is low in foaming properties and has good defoaming at the time of rinsing. Absent.

Claims (2)

(A) silicone antifoaming agent,
(B) a carrier material,
(C) organic waxes, and (D) the following general formula (I):

[Wherein, R ¹ represents the same or different unsubstituted or substituted monovalent hydrocarbon group, and R ² represents the following general formula (III):
—R ³ —O— (R ⁴ O) _d —R ⁵ (III)
(In the formula, each of R ³ and R ⁴ is a divalent hydrocarbon group, R ⁵ is a hydrogen atom or a monovalent organic group, d is an integer of 1 or more, provided that d ≧ 2 R ⁴ may be the same or different, and 80 to 100 mol% of R ⁴ is an ethylene group.
A is 0 or 1, b is an integer satisfying b ≧ 0, c is an integer satisfying c ≧ 0, provided that a + c ≧ 1, and the above general formula ( I) When R ² is contained in plural, R ² may be the same or different.
And a polyoxyalkylene-modified organosiloxane having a melting point of 35 ° C. or higher represented by the following general formula (II):

[Wherein R ⁶ is the same or different unsubstituted or substituted monovalent hydrocarbon group, R ⁷ is the same or different divalent hydrocarbon group, and R ⁸ is a divalent hydrocarbon group, e is an integer that satisfies e ≧ 1, f is an integer that satisfies f ≧ 1, and g is an integer that satisfies g ≧ 1, provided that when f ≧ 2, R ⁸ may be the same or different. Good]
A granular silicone defoamer composition comprising either or both of a siloxane-polyoxyalkylene block copolymer having a melting point of 35 ° C. or higher represented by:
A powder detergent composition comprising the granular silicone antifoam composition according to claim 1.