JPH0230734B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention provides a self-emulsifying silicone composition, in particular, which is self-emulsifying even when diluted with water, and the diluted solution also exhibits excellent high temperature stability and mechanical stability, and is free from cissing. The present invention relates to a self-emulsifying silicone composition that does not cause problems such as oil spots and is useful as an antifoaming agent, a mold release agent, a fiber treatment agent, a cosmetic additive, and a foam stabilizer for polyurethane production. (Prior art) Polyoxyalkylene-modified polysiloxane is water-soluble and has excellent physical and chemical stability, so it is used as an antifoaming agent, mold release agent, fiber treatment agent, cosmetic additive, and in the production of foamed polyurethane. It is widely used as a foam stabilizer. However, this product is inferior in antifoaming properties, mold release properties, water repellency, and gloss properties compared to those based on ordinary diorganopolysiloxanes. It has the disadvantage of not exhibiting a foaming effect. For this reason, antifoam compositions have been proposed in which polyoxyalkylene-modified polysiloxanes are blended with dimethylpolysiloxane, or in which silica fillers and siloxane resins are further blended. It is used in applications that require paintability, such as defoaming foam and water-based cutting oils, paints, and inks. If the addition ratio is increased, the water dispersibility in water and the mechanical stability after dilution will deteriorate.
On the other hand, increasing the addition ratio of polyoxyalkylene-modified polysiloxane improves dilution stability, but has the disadvantage that the antifoaming effect deteriorates. Therefore, in order to improve these shortcomings,
A base composition consisting of a foam suppressing component consisting of dimethylpolysiloxane, a silica filler, and a siloxane resin, and a polyoxyalkylene-modified polysiloxane is subjected to a condensation reaction of a silicone resin and polyoxyethylene or polyoxypropylene as a dispersion aid. It can be added to compositions that are effective for defoaming in jet dyeing processes that require high-temperature properties and mechanical stability (see Japanese Patent Application Laid-Open No. 49-25283), and also to the above-mentioned base compositions. Foam-inhibiting composition for carpet dyeing process containing dimethylpolysiloxane whose molecular chain ends are blocked with hydroxyl groups (Tokuko Showa)
52-19836), and further a composition in which a polyoxyalkylene-modified siloxane resin is added as a dispersant to the above base composition (Japanese Patent Publication No. 52-22638).
(see Japanese Patent Application Laid-open No. 149388/1983), and a composition using two types of polyoxyalkylene-modified polysiloxanes as dispersants (see Japanese Patent Application Laid-Open No. 149388/1983). In addition, polyoxyalkylene-modified polysiloxanes include those with improved mechanical stability and storage stability by combining low and high HLB materials (see Japanese Patent Publication No. 1983-43015), polyoxyalkylene-modified polysiloxanes with α -Olefin-modified polysiloxanes have been proposed to improve storage stability (see Japanese Patent Application Laid-Open No. 149388/1988), but in all of these, the components tend to aggregate with each other, resulting in layer separation. Attention has been focused on how to solve the drawback of causing However, in the conventional method, each component is adjusted separately and finally dispersed and mixed using a dispersion machine such as a homomixer or homogenizer to obtain a composition, which results in poor storage stability and mechanical stability after dilution. It naturally had its limits. (Structure of the Invention) The present invention relates to a self-emulsifying silicone composition that solves these disadvantages, and has the following formula: (1) General formula R ¹ (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _n [( _CH3 )HSiO] _o
Si(CH ₃ ) ₂ R ¹ (where R ¹ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, m,
n is a positive integer, n=1~70, m+n=5~
500) 2 to 35 parts by weight of methylhydrodiene polysiloxane, (2) general formula (Here, R ² is a divalent organic group having 1 to 16 carbon atoms, R ³
is a group selected from a hydroxyl group, an acetyl group, an alkoxy group having 1 to 20 carbon atoms, and an isocyanate group, R ⁴ is a hydrogen atom or a methyl group, a = 4 to 60, b = 0 to
60, the average molecular weight represented by a+b=4-75) is
Oxyalkylene compounds that are 200-6000 20-80
Parts by weight, (3) 0 to 10 parts by weight of an unsaturated hydrocarbon compound having 5 to 20 carbon atoms having a vinyl group at the end of the molecular chain, (4)
1 to 35 parts by weight of a foam suppressor consisting of 85 to 98 parts by weight of liquid dimethylpolysiloxane having a viscosity of at least 20 cS at 25°C and 15 to 2 parts by weight of finely powdered silica; (5) 0.00001 to 0.5 parts by weight of a platinum-based catalyst; It is characterized by the following. In other words, the present inventors have developed a self-emulsifying product that is self-emulsifying even when diluted with water, that the diluted liquid exhibits excellent high-temperature stability and mechanical stability, and that does not cause problems such as cissing and oil spots. As a result of various studies on emulsifying silicone compositions, we found that the polyoxyalkylene component that acts as a dispersant in this type of composition is the addition of the above-mentioned methylhydrodiene polysiloxane as the first component and an oxyalkylene compound as the second component. When the reaction product is a polyoxyalkylene-polysiloxane block copolymer, if this copolymer is composed of dimethylpolysiloxane and finely divided silica, it forms an intimate mixture with the foam suppressant and is itself shelf-stable. Moreover, it self-emulsifies easily even when diluted with water, and when used in foaming systems, it improves dilution stability without reducing the antifoaming effect and prevents the occurrence of oil spots. Moreover, this block copolymer is easily formed from the first component and the second component in the presence of the fifth component during the production of the above-mentioned composition, so there is no need to synthesize it separately and the process is large. In addition, this block copolymer is compatible with dimethylpolysiloxane, and the generation of repellency and oil spots due to organic groups present in this processing solution can be avoided by introducing hydrocarbon groups that have an affinity for this. Based on this finding, the present invention was completed by conducting research on the composition and blending ratio of each component constituting the composition of the present invention. The methylhydrodiene polysiloxane as the first component constituting the composition of the present invention has the general formula R ¹
(CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _n [(CH ₃ )HSiO] _o Si
( _CH3 ) _2R1 ^, and this ^R1 is bonded to a hydrogen atom or an alkyl group such as a methyl group, ethyl group, propyl group, butyl group, an aryl group such as a phenyl group, or a carbon atom of these groups. 1 carbon number selected from chloromethyl group, trifluoropropyl group, cyanomethyl group, etc. in which some or all of the hydrogen atoms are substituted with halogen atoms, cyano groups, etc.
~6 unsubstituted or substituted monovalent hydrocarbon groups, m, n
is a known positive integer, but if m+n is a low polymerization degree of 5 or less, antifoaming properties will be poor and dispersion stability will not be good.
If it is more than 500, the viscosity will be too high and it will be difficult to mix and disperse each component, and the reaction with the second and third components will not proceed well.
It is necessary to keep the n value in the range of 500, and if the n value exceeds 70, the reaction system becomes unstable and gels easily, and the amount of hydrogen generated in the reaction increases and there is a risk of ignition and explosion. Must be in the range 1-70. Next, this oxyalkylene compound as the second component has the general formula ^R2 is an alkylene group having 1 to 16 carbon atoms such as methylene, ethylene, propylene, butylene, etc., a divalent organic group such as -CO-, -CONH-, and ^R3 is a hydroxyl group or an acetyl group. , a terminal capping group exemplified by an alkoxy group having 1 to 20 carbon atoms, an isocyanate group, etc., R ⁴ is a hydrogen atom or a methyl group,
a is an integer of 4 to 60, preferably 8 to 30, b is an integer of 0 to 60, preferably 0 to 30, and a + b = 4 to 75, and the presence of a platinum-based catalyst as the fifth component to be described later. Since it undergoes an addition reaction with the ≡SiH bond in the methylhydrodiene polysiloxane as the first component described above to form a polyoxyalkylene-polysiloxane block copolymer,
As shown in the above formula, it is necessary to have an aliphatic unsaturated group at the end of its molecular chain. If the molecular weight is less than 200, the composition will not show sufficient hydrophilicity and the antifoaming performance will be poor, and if it is more than 6000, the viscosity will increase and the workability will be poor. , a, b, and R ² must be appropriately selected to have a molecular weight in the range of 200 to 6,000. Further, the hydrocarbon compound as the third component is added to the first component in the presence of the fifth component together with the second component described above.
The vinyl group that reacts with the ≡SiH bond of the first component is added to produce a hydrocarbon-modified siloxane that imparts lipophilicity and paintability to the composition. It is necessary to have it at the end of the molecular chain, and if the number of carbon atoms is 5 or less, there is no paintability imparting effect, and 20
If the above is used, the antifoaming properties will be deteriorated, so it is necessary to use a carbon number of 5 to 20. However, it is not necessary to add this third component, and although the composition of the present invention exhibits excellent stability, antifoaming properties, and dispersibility without adding this third component, it is not necessary to add this third component. If it is contained, stability and paintability will be further improved, and this preferred range is
The amount is 0.5 to 10 parts by weight, but addition of 10 parts by weight or more is not preferable because storage stability tends to deteriorate. In addition, the above-mentioned first component to third component cause an addition reaction between the ≡SiH bond in the first component and the unsaturated group in the second and third components, but the If the amount of unsaturated groups is less than 0.8 per ≡SiH bond in the first component, there will be too many ≡SiH bonds and gelation will occur easily, and if it is more than 2.0, antifoaming properties will deteriorate, so this should be 0.8 to 2.0. It is preferable that the range is within the range of Next, the foaming inhibitor as the fourth component constituting the composition of the present invention is a known one, and is made from dimethylpolysiloxane and finely powdered silica, and this dimethylpolysiloxane has a sufficient antifoaming effect. In order to exhibit this, the viscosity at 25°C must be at least 20cS.
There is no upper limit to the viscosity of this dimethylpolysiloxane, and it may be up to 1,000,000 cS or higher, but from the standpoint of workability and dispersibility, it is best to keep it below 5,000 cS. It can be either. Further, the fine powder silica used here may be either dry silica or wet silica,
These include precipitated silica, silica xerogel, fumed silica, and silica whose surface has been treated with organic silyl groups. Specifically, Erosil (trade name manufactured by Nippon Aerosil Co., Ltd.), Nipsil (trade name manufactured by Nippon Silica Co., Ltd.) , Kyabosil (trade name manufactured by Kyabot Corporation, USA), Santocel (trade name manufactured by Monsanto Corporation, USA), and Degutsusa (trade name manufactured by Degutsusa Corporation, USA), etc. These have a specific surface area of 50 m ² / It is preferable that it is more than g. This foaming inhibitor can be obtained by blending 15 to 2 parts by weight of the above-mentioned silica to 85 to 98 parts by weight of the above-mentioned dimethylpolysiloxane. Moreover, this platinum-based catalyst as the fifth component is
It is used as a catalyst to cause an addition reaction between the ≡SiH bonds in the components and the terminal unsaturated groups in the second and third components. and even chloroplatinic acid,
Examples include alcohol compounds or aldehyde compounds of chloroplatinic acid, and complex salts of chloroplatinic acid and various olefins and vinyl siloxanes. The amount is 0.00001 to 0.5 part by weight, which is 0.1 ppm or more, preferably 1 to 50 ppm, based on the total amount. The composition of the present invention can be obtained by mixing predetermined amounts of the first to fifth components described above, and the composition is then heated at 40 to 250°C, preferably at 60°C.
2-60 hours, preferably 4-20 hours at a temperature of ~180℃
It is preferable to perform the heat treatment while stirring and mixing for a period of time.
In addition, if necessary, this material may be uniformly mixed using a mixer such as a colloid mill or a homomixer. Fatty acid esters of oxyalkylene compounds, ethylene oxide-propylene oxide block copolymers, and the like may be optionally used within the scope of the invention. Note that in the above heat treatment, the reaction between the first component and the second and third components can be made more effective if the above composition is dissolved in an organic solvent and then heat treated. Examples of organic solvents include aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, ether solvents, and alcohol solvents, specifically benzene, toluene, xylene, n-paraffin, ethanol, isopropyl alcohol,
Examples include petroleum ether. Next, examples of the present invention will be given. Parts in the examples are parts by weight, and viscosity is a value measured at 25°C. The properties, mechanical stability, etc. are the results of tests conducted using the methods described below. (Defoaming test using latex) Weigh out 100g of SBR latex (50% active ingredient) into a 200ml cylinder with a stopper, and add antifoaming agent to it.
Changes in the foaming height over time were measured when shaking for 30 seconds by hand within 30 seconds after adding 1000 ppm. (Paintability test using latex) The latex tested in the defoaming test above was applied to glassine paper using a wire bar, dried, and marked with red marker ink to observe the degree of repellency. Evaluation method ◎...Same as blank (no antifoaming agent added), 〇...Some cissing is observed, △...Many cissing is present, ×...Innumerable cissing is present. (Anti-foaming test using staining liquid) Weigh out 100g of staining liquid (composition - 0.25 parts of Tetrosin R, 0.1 part of Demol RNL, 0.1 part of Toho Salt A-10N, 99.5 parts of water) into a 1000ml measuring cylinder. After adding 100 ppm of an antifoaming agent as a sample to this, the temperature was raised to 80°C, and the amount of foaming was measured when air was passed through a glass ball filter at a rate of 1.0/min. (Oil spot test) Add 5% antifoaming agent as a sample to the above dyeing solution and disperse it in a 300ml glass beaker.
g was weighed out, heated to 130°C for 30 minutes, cooled to room temperature, and observed for the presence or absence of oil spots. Evaluation method: Almost no oil spots are observed. △...A few small oil spots are observed. ×...Large oil spots are observed. (Storage Stability Test) 100 g of the sample was weighed into a glass bottle, placed in a constant temperature bath at 40°C, and the storage status of each bottle was observed after 10, 20, and 30 days. Evaluation method ◎...No separation after 30 days or more, 〇...Separation within 20-30 days, △...Separation within 10-20 days, ×...Separation within 10 days. (High temperature stability test of diluted solution) Dilute and disperse 10 g of sample in 90 g of water, put it in a 200 ml beaker, and heat it in a high temperature sterilizer at 130℃ for 30 minutes.
After heating for a minute, the mixture was allowed to cool to room temperature, and this state was observed.At the same time, the state after redispersion by stirring gently with a spatula was observed. Evaluation method: ◎...There is no oil floating or dirt on the wall surface, and it is easily redispersed. 〇...There is some oil floating or dirt on the wall surface, but it is easily redispersed. △...There is oil floating or dirt on the wall surface, and it is easy to redistribute. Does not re-disperse, ×...There is oil floating and dirt on the wall surface, so there is almost no re-dispersion. (Mechanical stability test of diluted solution) Dilute and disperse 20 g of sample in 180 g of water, put it in a 300 ml beaker, and mix at 7000 rpm using a homomixer.
After stirring at high speed for 10 minutes, the state was observed. Evaluation method ◎...There is almost no oil floating or dirt on the wall surface, 〇...There is no oil floating but the wall surface is a little dirty, △...There is some oil floating and the wall surface is also dirty, ×...There is a large amount of oil floating. (Anti-foaming test at room temperature) After weighing out 100 ml of 0.2% sodium oleate aqueous solution into a graduated cylinder with an internal volume of 1000 ml, 1 ml of the 10% dispersion of the composition obtained in the example was added thereto, and then Air was continuously introduced into the solution at a rate of 1/min through a glass ball filter, and the change over time in the amount of foaming was observed. (Anti-foaming test at high temperature) 200 ml of an aqueous solution of 0.3% polyoxyethylene nonyl phenyl ether Emulgen 909 (trade name, manufactured by Kao Soap Co., Ltd.) was weighed into a measuring cylinder with an inner volume of 1000 ml, and the sample was added to the sample according to the example. 0.02 ml (10 ppm) of a 10% aqueous dispersion of the obtained composition was added, and this was then heated to 80°C.
After raising the temperature to , air was continuously introduced at a rate of 1/min through a glass ball filter.
At this time, changes in the amount of foaming over time were investigated. Example 1, Comparative Example 1 The following three types of methylhydrodiene polysiloxane were used as the first component, As the second component, the following three types of polyoxyalkylene compounds POA-1 CH ₂ = CHCH ₂ O(C ₂ H ₄ O) ₂₁ (C ₃ H ₆ O) ₂₁ COCH ₃ , POA-2 CH ₂ = CHCH ₂ O( C ₂ H ₄ O) ₆ (C ₃ H ₆ O) ₂₄ H, and using 1-octene (C ₈ H ₁₆ ) or 1-decene (C ₁₀ H ₂₀ ) as the third component,
The fourth component is dimethylpolysiloxane (DMS-(1)) with a viscosity of 1000cS whose molecular chain ends are capped with trimethylsilyl groups or dimethylpolysiloxane (DMS-2) with a viscosity of 500cS whose molecular chain ends are capped with monohydroxydimethylsilyl groups (DMS-2). ) and finely powdered Silica Nipsil LP (trade name manufactured by Nippon Silica Co., Ltd.) or Aerosil-300 (trade name manufactured by Nippon Aerosil Co., Ltd.) in the amounts shown in Table 1. Pour into a flask and heat to 80°C while stirring and mixing, then add the alcohol compound of chloroplatinic acid (platinum amount: 2% by weight).
0.5 part was added, the temperature was raised to 120°C, and the reaction was carried out by heating for 8 hours. Then, this reaction composition was dispersed and mixed for 30 minutes at a rotation speed of 5500 rpm using a homogenizer, resulting in a light brown opaque color shown in Table 1. liquid A~
F was obtained.

[Table] Also, for comparison, methylhydrodiene polysiloxane MHS-1 used in the above example
~3 and polyoxyalkylene compounds/POA1~3
and 1-decene in the amounts shown in Table 2 into a three-necked flask, and to this were added 800 parts of isopropyl alcohol, 1.0 part of potassium acetate, and 0.5 part of an alcohol compound of chloroplatinic acid, and the mixture was heated to a temperature of 80 to 90°C. After reacting under reflux, the reaction was conducted under reduced pressure of 10 mmHg.
The solvent was removed at a temperature of 120°C to produce polyoxyalkylene-modified opolysiloxane~, and the dimethylpolysiloxane (DMS-1~2) used in the above examples and finely powdered silica were added to it as shown in Table 3. After heating at 60°C, the mixture was mixed and dispersed by rotating at 5500 rpm for 30 minutes using a homomixer to prepare compositions A' to E' shown in Table 3.

【table】

【table】

[Table] Next, 11 of compositions A to F and A' to E' obtained above are shown.
When we investigated the antifoaming properties, paintability, and dispersibility of seeds using latex, we obtained the results shown in Table 4. When we investigated the antifoaming properties and oil spot properties of these seeds using staining solutions, we obtained results shown in Table 5. The results shown in the table were obtained.

【table】

[Table] Example 2, Comparative Example 2 The following three types of methylhydrodiene polysiloxane were used as the first component, The polyoxyalkylene compounds POA-1 to 3 used in Example 1 were selected as the second component, and the dimethylpolysiloxane DMS-1 to 2 used in Example 1 and the molecular chain terminals were monopolized as the fourth component. Dimethylpolysiloxane (DMS) with a viscosity of 100 cS capped with hydroxydimethylsilyl groups
-3) A foaming suppressor made by adding the finely powdered silica Nipsil LP or Aerosil 300 used in Example 1 to dimethylpolysiloxane (DMS-4) with a viscosity of 50 cS and whose molecular chain ends are capped with monoethoxydimethylsilyl groups. The mixture was heated to 80°C while blending them in the amounts shown in Table 6, and then 0.5 part of an alcohol compound of chloroplatinic acid (platinum amount: 2% by weight) was added thereto, and the temperature was raised to 120°C. The reaction composition was then heated and reacted for 8 hours, and then this reaction composition was dispersed and mixed for 30 minutes at a rotation speed of 5500 rpm using a homomixer, and light brown opaque liquids G to M shown in Table 6 were obtained. .

【table】

[Table] For comparison, the methylhydrodiene polysiloxane MHS- used in Example 2 above is also shown.
4, 5 and polyoxyalkylene compound POA-1
-3 in the amounts shown in Table 7 and charged into a three-necked flask (3), to which were added isopropyl alcohol, 1.0 part of potassium acetate, and 0.5 part of an alcohol compound of chloroplatinic acid (platinum amount: 2% by weight). , 80
After reacting under reflux at a temperature of ~90℃, 10mm
Polyoxyalkylene-modified polysiloxane ~ is prepared by removing the solvent at 120°C under reduced pressure of Hg, and this is mixed with the dimethylpolysiloxane (DMS-1 to 4) used in Example 2 above and finely powdered silica. Add the foam suppressor shown in Table 8 in the amount shown in Table 8,
After heating to ℃, using a homo mixer at 5500 rpm.
The mixture was mixed and dispersed by spinning for 30 minutes to prepare compositions F' to J' shown in Table 8.

【table】

[Table] Next, the storage stability, high temperature stability, mechanical stability, and antifoaming property at room temperature of the 12 compositions G to M and F' to J' obtained above were investigated. The results are shown in Table 9, and when we investigated the antifoaming properties of these at high temperatures, we found that
The results shown in Table 10 were obtained.

【table】

【table】

【table】

Claims (1)

[Claims] 1 (1) General formula R ¹ (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _n [(CH ₃ )
HSiO〕 _o Si(CH ₃ ) ₂ R ¹ (where R ¹ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, m and n are positive integers, where n = 1 to 70,
m+n=5-500) 2-35 parts by weight of methylhydrodiene polysiloxane, (2) General formula (Here, R ² is a divalent organic group having 1 to 16 carbon atoms,
R ³ is a group selected from a hydroxyl group, an acetyl group, an alkoxy group having 1 to 20 carbon atoms, and an isocyanate group, R ⁴ is a hydrogen atom or a methyl group, a = 4 to
60, b = 0 to 60 and a + b = 4 to 75) 20 to 80 parts by weight of an oxyalkylene compound with an average molecular weight of 200 to 6000, (3) a carbon number of 5 to 20 having a vinyl group at the end of the molecular chain
0 to 10 parts by weight of an unsaturated hydrocarbon compound, (4) a foam suppressor comprising 85 to 98 parts by weight of liquid dimethylpolysiloxane having a viscosity of at least 20 cS at 25°C and 15 to 2 parts by weight of finely powdered silica.
1 to 35 parts by weight, and (5) 0.00001 to 0.5 parts by weight of a platinum-based catalyst.