JP2685691B2 - Foam suppressor composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention provides a foam inhibitor composition, and particularly excellent dilution stability and defoaming durability, and causes uneven dyeing even in high-temperature processing in the dyeing industry and the like, and processing using dyes. The present invention relates to a suds suppressor composition that is useful as an antifoaming agent for dyeing.

[0002]

2. Description of the Related Art Silicone defoaming agents containing dimethylpolysiloxane as a main component have various excellent properties as compared with other defoaming agents, so that they can be used in general chemical industries involving foaming. Widely used in the process. However, since this dimethylpolysiloxane is essentially hydrophobic, it is used as an emulsion type defoaming agent in which it is dispersed in water using a surfactant. When the liquid to be treated is at a high temperature or is subject to high shear, the desired defoaming effect cannot be expected because the emulsion is destroyed, and sometimes foaming is promoted. Can not be used in a non-aqueous system, and also has the disadvantage that the emulsion separates during long-term storage, and in the dyeing industry, the repellency of the separated dimethylpolysiloxane causes uneven dyeing on the object to be treated. There was also.

[0003]

For this reason, it has been proposed to use an organopolysiloxane modified with a polyoxyalkylene group as the defoaming agent (see US Pat. No. 3,233,986). Has a disadvantage of having a small bubble breaking and defoaming effect. A hydrophilic polysiloxane represented by polyoxyalkylene-modified dimethylpolysiloxane is used as a base oil, and an oil compound composed of dimethylpolysiloxane and fine powder silica is used in combination. It has also been proposed to improve the defoaming effect (Japanese Patent Publication Nos. 52-19836, 52-22638, and 55).
No. 23084), a base oil containing a long-chain alkyl group and a polyoxyalkylene co-modified organopolysiloxane has also been proposed (see Japanese Patent Publication No. 58-58126).

However, when these are also used in the dyeing industry, high temperature or mechanically strong shearing force is applied for a long time, so that the hydrophobic oil compound component causes agglomeration, which causes the object to be treated. Has the disadvantage of uneven dyeing. Therefore, regarding the defoaming agent used in the dyeing step which is usually performed at a high temperature, in the polyoxyalkylene group-containing organopolysiloxane used here, the molar fraction of ethyleneoxy groups in the polyoxyalkylene group is increased to Although it is also proposed to prevent the agglomeration in the above, increasing the mole fraction of the ethyleneoxy group reduces the dispersibility of the diorganopolysiloxane and the finely divided silica, and this dilute stability, The mechanical stability and high temperature stability are also reduced, so that it becomes impractical.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a suds suppressor which solves these disadvantages, which comprises A) the general formula

Embedded image [Wherein G ¹ is a group selected from R ¹ , G ² or G ³ , G ² , G ³
Is a formula (CH ₂ ) _r —O (R ² O) _s Q having a molecular weight of 500 to 3,000 (R ² is an ethylene group and a propylene group, Q is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, an acetyl group, isocyanate Monovalent organic group selected from acid groups, r is 2 to 6 and s is 5 to 50)
In the group represented by, G ² is an ethyleneoxy group in the (R ² O) group.
10 to 30 mol%, G ³ has an ethyleneoxy group of 65 in the (R ² O) group.
Is of 85 mol%, G ² / G ³ (molar ratio) is 0.3 / 1 to 3 /
1, R ¹ is a monovalent hydrocarbon group having 3 to 20 carbon atoms, a is 0 or 1, m and n are positive numbers from 1 to 30, p is 10 to 100, and q is 1
Polyoxyalkylene-modified silicone oil 30 to 80% by weight B) 100 parts by weight of dimethylpolysiloxane having a viscosity of 10 to 100,000 cS at 25 ° C. and 1 to 40 parts by weight of finely divided silica. From 5 to 50% by weight, C) having a molecular weight range of 500
To 3,000 and 5 to 50% by weight of a polyoxyethylene-polyoxypropylene copolymer having an ethyleneoxy group of 10 to 85 mol%, D) the viscosity at 25 ° C is 10 to 500 cS, and both ends of the molecular chain are mono It is characterized by comprising 2 to 20% by weight of dimethylpolysiloxane blocked with a hydroxydimethylsilyl group.

That is, the inventors of the present invention have made various investigations on various methods for solving the disadvantages of the defoaming agent containing a conventionally known polyoxyalkylene-modified organopolysiloxane as a main component, and as a result, the polyoxyalkylene-modified organopolysiloxane The amount of ethyleneoxy groups and propyleneoxy groups contained in and the molar ratio thereof are specified, and the amount of ethyleneoxy groups and the compound of conventionally known dimethylpolysiloxane and fine powder silica are added thereto. When the specified polyoxyethylene-polyoxypropylene copolymer and dimethylpolysiloxane whose both molecular chain terminals are blocked with monohydroxydimethylsilyl groups are added, the foam suppressor thus obtained has dilution stability and defoaming. It has been found that it has excellent durability and high temperature stability.

Further, as compared with a polysiloxane modified with a single polyoxyalkylene, when a polysiloxane containing two kinds of polyoxyalkylene in the same molecule as described above is used, this polysiloxane has excellent properties. In addition to exhibiting foam sustainability and foam breaking properties, the emulsion is not broken even under high temperature and high shear, and there are no oil spots or aggregates. It was confirmed that there was nothing to do, and the present invention was completed by conducting research on the types and mixing ratios of the above-mentioned components. This will be described in more detail below.

[0008]

The present invention relates to a foam inhibitor composition which is particularly useful in the dyeing industry and the like because of its excellent dilution stability, defoaming durability and high temperature stability, and this foam inhibitor composition Is A) a polyoxyalkylene-modified silicone oil represented by the above general formula (1), B) a blend consisting of dimethylpolysiloxane and finely divided silica, C) a polyoxyethylene-polyoxypropylene copolymer, D). It is prepared by mixing a predetermined amount of dimethylpolysiloxane whose both molecular chain ends are blocked with monohydroxydimethylsilyl groups.

The polyoxyalkylene-modified silicone oil as the component A) constituting the foam control composition of the present invention has the general formula

Embedded image , Where G ¹ is selected from R ¹ , G ² or G ³ ,
G ^2, G ³ is represented by the formula _{(CH 2) r -O (R} 2 O) s -Q, R 2 is an ethylene group and a propylene group, Q is 1-8 hydrogen atoms or carbon atoms
A monovalent organic group selected from an alkyl group, an acetyl group and an isocyanic acid group, r is 2 to 6, preferably 2 to 3, s
Is 5 to 50, preferably 15 to 45, and G ² is
The ethyleneoxy group in the (R ² O) group is 10 to 30 mol%, and G ³ is (R
It is required that the ethyleneoxy group in the ² O) group be 65 to 85 mol%.

When the average molecular weight of G ² and G ³ is less than 500, the effect of the alkyleneoxy group as a hydrophilic group is not sufficiently exerted, and when it exceeds 3,000, the viscosity becomes too high and the dispersibility,
Since the workability becomes poor, it is necessary to set it in the range of 500 to 3,000, preferably 1,000 to 2,000. Also this
Regarding G ² and G ³ , if G ² / G ³ (molar ratio) in the formula is less than 0.3, the defoaming property becomes poor, and if it exceeds 3, the hydrophobic part increases and the dispersibility becomes poor. It must be in the range of 3.

In the above, Q is selected from a hydrogen atom, an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and an octyl group, an acetyl group and an isocyanic acid group. R ¹ is a monovalent hydrocarbon group, but R ¹ is a monovalent hydrocarbon group, but if the carbon number exceeds 20, the defoaming property and the water dispersibility deteriorate, so the carbon number is 3 to 20.
When m and n are positive numbers of 1 to 30 and m + n is 3 to 40, preferably 3 to 20, and p is less than 10, the defoaming property becomes poor and the viscosity of The storage stability deteriorates due to the decrease, and when it exceeds 100, the viscosity at the time of dilution becomes high and the workability deteriorates, so 10 to 100, preferably 20
-60, and q is a positive number from 1 to 10, and this has a content of a hydrophobic moiety represented by siloxane in the molecule, that is, from the total molecular weight to G ² , G ³ The amount excluding the molecular weight of is preferably 5 to 30% by weight.

This polyoxyalkylene-modified silicone oil can be synthesized by a conventionally known method. For example, there are two types of methylpolysiloxane containing ≡SiH group and vinyl group or allyl group at the terminal of the molecular chain. The above polyoxyalkylene compound and an unsaturated olefin having 3 to 20 carbon atoms are subjected to an addition reaction in the presence of a platinum catalyst, or an organopolysiloxane containing an ≡SiH group and an R ¹ group is added with a vinyl group or The foam inhibitor composition of the present invention can be easily obtained by addition reaction of two or more polyoxyalkylene compounds having an allyl group and the like.
If the content of component (A) in 00% by weight is less than 30% by weight, the water dispersibility is poor, and if it is more than 80% by weight, a uniform and stable self-emulsifying emulsion is unlikely to be formed, so
The amount may be 80% by weight, and more preferably 50 to 70% by weight.

Next, the foam control composition of the present invention is constituted.
The composition as the component (B) is a main component for imparting defoaming persistence to the foam inhibitor composition of the present invention, which is composed of dimethylpolysiloxane and fine powder silica. .

The dimethylpolysiloxane used here may be linear or branched, but it is preferable that the terminal of the molecular chain is blocked with a trimethylsilyl group. This dimethylpolysiloxane should have a viscosity as low as possible from the viewpoint of ease of dispersion and workability, and it is better that the viscosity is high from the viewpoint of defoaming durability.
When the viscosity is less than 10 cS, the resulting composition has poor stability, and when the viscosity is more than 100,000 cS, the resulting composition becomes significantly thickened when diluted with water before being used as a suds suppressor composition. There is a difficulty in sex, so 10 to 10
It may be in the range of 0,000 cS, preferably 100 to 5,000 cS.

The finely divided silica used here may be a known one, and may be either wet silica or dry silica. Therefore, precipitated silica, silica xerogel, fumed silica, and further its surface may be used. Those treated with an organic silyl group are shown. Specifically, Aerosil [trade name of Nippon Aerosil Co., Ltd.], Nipsil [trade name of Nihon Silica Co., Ltd.], Cabosil [trade name of Cabot Co., USA], Examples include Santocell [trade name of Monsanto Chemical Co., USA], and it is preferable that the specific surface area by BET method is 100 m ² / g or more. When the amount of this finely divided silica is less than 1 part by weight with respect to 100 parts by weight of dimethylpolysiloxane in component B), the defoaming performance becomes poor, and when it exceeds 40 parts by weight, the viscosity of the composition increases. Since the water dispersibility and workability are deteriorated, it is necessary to set it to 1 to 40 parts by weight, and more preferably 5 to 20 parts by weight.

The blend used as the component B) in the present invention is prepared by blending the above-mentioned dimethylpolysiloxane and finely divided silica, heat-treating at room temperature to 200 ° C., and removing low-boiling fractions if necessary. Although it can be produced, the composition of the component B) in 100% by weight of the foam inhibitor composition of the present invention is less than 5% by weight, and the defoaming performance cannot be sufficiently exhibited.
When it is more than 50% by weight, the viscosity of this system is increased and workability is deteriorated.
It may be in the range of 10 to 30% by weight.

It also constitutes the suds suppressor composition of the present invention.
The polyoxyethylene-polyoxypropylene copolymer as the component C) serves as an emulsification aid for emulsifying and dispersing the components A), B) and the component D) described below.
If the molecular weight is less than 500, the resulting composition has poor stability over time, and if it exceeds 3,000, the viscosity increases and the dispersibility is affected.
It is required to be in the range of 3,000 to 3,000, preferably 1,500 to 2,500.

Further, when the ethyleneoxy group contained in the component C) is less than 10 mol%, the hydrophobicity becomes strong and the function as an emulsification aid becomes insufficient, and when it exceeds 85 mol%, the HLB becomes large. In this case too, the function as an emulsification aid will not be fully exerted, so it is necessary that the content of ethyleneoxy groups is in the range of 10 to 85 mol%, preferably 30 to 70 mol%. However, if the blending amount of this product in 100% by weight of the suds suppressor composition is less than 5% by weight, the storage stability will be poor, and if it is more than 50% by weight, the dilution stability of the composition will be poor. Is 5
It may be in the range of up to 50% by weight, more preferably 10 to 30% by weight.

The dimethylpolysiloxane as the component D) constituting the foam control composition of the present invention is one in which both ends of the molecular chain are blocked with monohydroxydimethylsilyl groups. This is A) as described above in the foam control composition of the present invention.
It is said to be effective as a compatibilizer for the component and B) component,
Originally little compatibility with monohydroxydimethylsilyl group
It has the function of lowering the interfacial tension between the components A) and B) and improves the compatibility of these components, but this one causes oil spots when the viscosity is less than 10 cS, and 500 cS
If the viscosity is higher, the viscosity cannot be lowered, and the effect of its addition becomes insufficient.Therefore, the viscosity is 10 to 500 cS, preferably 30 to 20 in order not to increase the viscosity of the foam inhibitor composition.
It is required to be 0cS.

The foam inhibitor composition of component D) is 100% by weight.
If the compounding amount is less than 2% by weight, the above-mentioned effect is not sufficiently exhibited, and if it exceeds 20% by weight, the viscosity becomes too low and the silica content precipitates, which deteriorates the storage stability over time. -20% by weight, more preferably 5-
It may be in the range of 15% by weight.

The foam control composition of the present invention has the above A) to D).
It can be obtained by mixing predetermined amounts of the components, but this may be achieved by uniformly mixing each of these components using a mixer such as a homomixer, and the mixing order is not particularly limited, but at the time of mixing You may heat in the range of 40-150 degreeC.

The foam inhibitor composition of the present invention thus obtained imparts an excellent low foaming property to the liquid to which it is added for a long period of time, and it has excellent dispersion stability and high temperature, It has excellent mechanical stability under high shear and does not cause agglomeration, so it is useful as a defoaming agent for high-temperature dyeing. According to this, uneven dyeing caused by defoaming agents in various dyeing processes occurs. The advantage of being able to avoid such troubles is given. It should be noted that this product has excellent stability, and its dispersibility is not impaired even when used in combination with various chemicals, so it is also suitable for use as an antifoaming agent for internal addition of various oil agents, or for general paints and aqueous cutting oils. can do.

[0023]

EXAMPLES Examples of the present invention and comparative examples will now be described.
The viscosity in the examples is a value measured at 25 ° C.

(Dilution Stability Test Method) 10 of foam control composition
Add 100 g of 100% aqueous dispersion to a 200 ml glass beaker and add 25
The stability over time after storage at 1 ° C for 1 day was visually evaluated as follows. ⊚: Good emulsion and oil floating are not observed. ◯: There is some oil floating or silica sedimentation. Δ: A lot of oil floats and a lot of silica sedimentation. × ・ ・ ・ Separation

(Test method for defoaming property) 100 g of 0.2% sodium oleate aqueous solution was put into a 1,000 cc measuring cylinder,
2.0 g of 10% aqueous dispersion of suds suppressor composition (as an active ingredient, 2,
000ppm) is added, and air is blown through the glass diffuser stone at 1,000cc / min by the air bubbling method.
The amount of foam (foam amount + liquid amount) after 20 minutes was measured at 25 ° C.

(Dyeing test method) Dye / S-BGU [trade name of HOECHST] 0.1 g, dyeing aid / Emer NC-35 [trade name of Kao Corporation] 4 g, acetic acid 4 g, suds suppressor Composition 10g
Using 2,000 cc of aqueous solution with added, 10 g of polyester cloth was heated at 135 ° C for 10 min with a high temperature dyeing machine (JF type) manufactured by Matisse.
And the unevenness of dyeing was visually evaluated as follows. A: No uneven dyeing is observed. A: Same as blank but slightly uneven in dyeing. Δ: There is a little dark color or white blemishes. X: Dark color or white spots are noticeable.

Examples 1 to 4, Comparative Examples 1 to 3 Average composition formula

Embedded image , A polyoxyalkylene-modified silicone oil having a viscosity of 950 cS (hereinafter abbreviated as A-1), an average composition formula

Embedded image (G ² and G ³ are the same as above), the viscosity is 920 cS
Polyoxyalkylene-modified silicone oil (hereinafter A
-2), average composition formula

Embedded image (G ² and G ³ are the same as above), the viscosity is 900 cS
Polyoxyalkylene-modified silicone oil (hereinafter A
-3), average composition formula

Embedded image (G ² and G ³ are the same as above), the viscosity is 1,080c
Polyoxyalkylene-modified silicone oil of S (hereinafter abbreviated as A-4), average composition formula

Embedded image (G ² and G ³ are the same as above), the viscosity is 1,020c
Polyoxyalkylene-modified silicone oil of S (hereinafter abbreviated as A-5), average composition formula

Embedded image (G ² and G ³ are the same as above), the viscosity is 1,550c
Polyoxyalkylene-modified silicone oil of S (hereinafter abbreviated as A-6), average composition formula

Embedded image (G ² and G ³ are the same as above), the viscosity is 2,670c
A polyoxyalkylene-modified silicone oil of S (hereinafter abbreviated as A-7) was prepared.

The average composition formula

Embedded image , A polyoxyalkylene-modified silicone oil having a viscosity of 1,050 cS (hereinafter abbreviated as B-1), an average composition formula

Embedded image (G ² and G ³ are the same as above), the viscosity is 980 cS
Polyoxyalkylene-modified silicone oil (hereinafter B
-2), average composition formula

Embedded image (G ² and G ³ are the same as above), the viscosity is 1,030c
Polyoxyalkylene-modified silicone oil of S (hereinafter abbreviated as B-3), average composition formula

Embedded image (G ⁴ is the same as above) and has a viscosity of 2,330 cS and is a polyoxyalkylene-modified silicone oil (hereinafter referred to as B-4).
Abbreviated).

Next, to each of 650 g of these 11 kinds of polyoxyalkylene-modified silicone oil, 67.5 g of dimethylpolysiloxane having a viscosity of 1,150 cS and dimethylpolysiloxane having a viscosity of 100 cS, in which both ends of the molecular chain were blocked with trimethylsilyl groups. Siloxane 67.5g and fine powder silica Nipsil 9019
[Nippon Silica Co., Ltd. product name] Silicone consisting of 15g
Oil compound 150 g, average composition formula

Embedded image The polyoxyethylene-polyoxypropylene copolymer having a viscosity of 250 cS (150 g) and the dimethylpolysiloxane having a viscosity of 50 cS and having both ends of the molecular chain blocked with monohydroxydimethylsilyl groups are added. Was thoroughly kneaded with a homomixer to prepare 11 types of foam suppressing compositions, and the dilution stability, defoaming property and dyeing property of these were investigated, and the results shown in Table 1 were obtained.

[0030]

[Table 1]

[0031]

The present invention relates to a suds suppressor composition, which comprises A) a polyoxyalkylene-modified silicone oil represented by the general formula (1) and B) a dimethylpolysiloxane oil and a fine powder as described above. A compound comprising silica, C) a polyoxyethylene-polyoxypropylene copolymer, and D) a dimethylpolysiloxane having both ends of the molecular chain blocked with monohydroxydimethylsilyl groups. However, this product is superior in dilution stability, defoaming persistence and high temperature characteristics to the conventionally known silicone-based defoaming agents, and even when used in the dyeing industry, dyeing unevenness does not occur. Therefore, it has an industrial advantage of being useful as an antifoaming agent for dyeing.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 83/12 LRX C08L 83/12 LRX D06P 1/52 D06P 1/52 // (C08L 83/12 71:02 83:06) (72) Kunihiro Yamada, Kunihiro Yamada, No. 1 Hitomi, Osamu Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Hiroshi Ohashi Matsui, Usui-gun, Gunma Prefecture Tamachi Oji Hitomi 1-10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Nobuyuki Terae 2-6-1 Otemachi, Chiyoda-ku, Tokyo Shin-Etsu Chemical Co., Ltd. In-house (72) Invention Satoshi Kuwata 1 Hitomi, Oita, Matsuida-cho, Usui-gun, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (56) Document JP-flat 3-157106 (JP, A)

Claims (1)

(57) [Claims] 1. A) General formula: [G ¹ is a group selected from R ¹ , G ² or G ³ , and G ² and G ³ are of the formula (CH ₂ ) _r -O (R ² O) _s -Q (R ² is Ethylene group and propylene group, Q is a hydrogen atom or a carbon number of 1 to
8 is a monovalent organic group selected from an alkyl group, an acetyl group and an isocyanic acid group, r is 2 to 6 and s is 5 to 50), and G ² is a group in the (R ² O) group. 10 to 30 ethyleneoxy groups
Mol%, G ³ is the ethyleneoxy group in the (R ² O) group is 65 to 85 mol%, G ² / G ³ (molar ratio) is 0.3 / 1 to 3/1, R ¹
Is a monovalent hydrocarbon group having 3 to 20 carbon atoms, a is 0 or 1,
m and n are positive numbers of 1 to 30, p is 10 to 100, and q is a positive number of 1 to 10] 30 to 80% by weight of polyoxyalkylene-modified silicone oil, B) the viscosity at 25 ° C. is 10 to A blend consisting of 100 parts by weight of 100,000 cS dimethylpolysiloxane and 1 to 40 parts by weight of finely divided silica 5 to 50% by weight, C) Molecular weight range of 500 to 3,000 and ethyleneoxy groups of 10 to 85% by mole A polyoxyethylene-polyoxypropylene copolymer of 5 to 50% by weight, D) a viscosity of 10 to 500 cS at 25 ° C. dimethylpolysiloxane whose molecular chain ends are blocked with monohydroxydimethylsilyl groups 2 to 20 %, And a foam suppressor composition.