JPS6010535B2 - Manufacturing method of heat-resistant silicone oil - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a heat-resistant silicone oil, particularly a colorless to light-colored transparent silicone oil.

Silicone oil has excellent heat resistance, cold resistance, and electrical insulation properties, and as an oil with little change in viscosity due to temperature, it is widely used as insulating oil, hydraulic oil, buffer oil, machine oil, lubricating oil, instrument oil, etc. In addition, silicone grease and silicone compound are produced using this silicone oil as a base oil, and this silicone oil is also added as a heat resistance improver to silicone rubber.However, In the case of pure methyl silicone oil, which is the most standard among silicone oils, the upper limit of the temperature at which it can withstand long-term use is said to be 175°C in air and 20,000°C in vacuum or inert gas. Heat-resistant grade silicone oil has been used for applications that require long-term use at extremely high temperatures. Conventionally, heat-resistant grade silicone oil has been commercially available in two broad categories: One is that the molecular structure of the polyorganosiloxane is made unique, such that phenyl groups account for 20 mol% or more of the organic groups in the polyorganosiloxane, and the other is that the polyorganosiloxane is added with a heat resistance improver. The former has a high viscosity even with a relatively low degree of polymerization due to the presence of many phenyl groups, and in order to exhibit its properties as a silicone oil, it must have a viscosity of at least 25 ratio st at room temperature. This is inconvenient for applications such as insulating oil that require a cooling effect by thermal convection. Also, when circulating with a circulation pump, the pump does not operate at a temperature close to room temperature, especially during startup. There was a dissatisfaction with the fact that one of the advantages of equipment using silicone oil, which is to reduce the size and weight of the equipment due to the heat resistance of the oil, is diminished.

In addition, disadvantages include discoloration when subjected to thermal deterioration, poor cold resistance, large changes in viscosity due to temperature, and high cost. By adding Cu, Zn, etc.) in the form of compounds or by reacting with polysiloxane at high temperatures, the oxidation suppressing effect of these redox metals is used to improve heat resistance, especially in air. In particular, when using methyl silicone oil as a base oil, it has the advantage of being economically advantageous and inheriting the advantages of methyl silicone oil, such as high cold resistance and low viscosity depending on temperature. ``For example, when adding an organic acid salt of iron to methyl silicone oil, there is also a known technique in which iron is introduced into polysiloxane by blowing air into the system at high temperature to further improve heat resistance.'' On the other hand, in the presence of iron, which is the most commonly used Toradox metal, the oil takes on a dark brown color. Because it does not color silicone oil, it is attracting attention as an excellent heat resistance improver.However, cerium compounds are generally insoluble or dissolvable in silicone oil, and are hardly soluble, especially at room temperature. If cerium is simply mixed with silicone oil, the cerium compound will separate and it will not be able to provide sufficient heat resistance.Therefore, bonding cerium to silicone molecules has been considered, but there have been two methods so far. One method is to prepare a cerium chelate compound such as polymethylhydrogensiloxane by blowing air at the reflux temperature of the aromatic hydrocarbon.
One method is to bond cerium to the side chain of polysiloxane via a Si-○-Ce bond by reacting with polyorganosiloxane having a hydrogen atom bonded to a silicon atom. This is a method in which a cerium salt and an alkali metal silanolate having five or more organosiloxane units are reacted with a polyorganosiloxane in the presence of a solvent and a reaction accelerator such as dialkylformamide.

In the former method, since methylhydrogenpoIJ siloxane having an arbitrary number of Si-day bonds can be easily obtained, an arbitrary number of cerium atoms can be bonded to the side chain of the polysiloxane, and the cerium atom On the other hand, it is difficult to completely convert all existing Si-day bonds into Si-○-Ce bonds, and therefore, the remaining Si-day bonds form siloxane chains due to thermal oxidation. The heat resistance decreases due to the presence of cerium, which reduces the effect of improving heat resistance due to the presence of cerium. Furthermore, if Si bonds remain, crosslinking of the siloxane chains will proceed even at room temperature due to the presence of alkaline substances, resulting in extremely poor alkali resistance of the silicone oil. Therefore, it is necessary to strictly control the reaction conditions so that no Si-day bonds remain. Furthermore, in the case of polyorganosiloxanes having special organic groups such as halophenyl groups, there is a problem in that a complicated process is required to introduce Si-day bonds into the siloxane molecules. Furthermore, in the latter method, the number of cerium atoms introduced is limited, and a significant improvement in heat resistance cannot be expected. Furthermore, the alkali metal silanolate used in the reaction is a strong alkali, and trimethylchlorosilane, which is exemplified as being used for neutralization after the reaction, generates hydrogen chloride in the presence of moisture in the air. If the amount of neutralizing agent is too little or too much, or if the mixing is insufficient, residual potassium silanolate or hydrogen chloride will cause siloxane bonds to break during heating, resulting in a significant decrease in heat resistance. vinegar.
Therefore, it is necessary to strictly control the neutralizing agent to prevent such impurities from remaining. In addition, when adding organic acid salts of iron as a heat resistance improver, a method similar to that of heating a mixture of polyorganosiloxane and organic acid salts of iron and blowing air to introduce iron into polyorganosiloxane is used. When applied to a compound, the cerium compound decomposes and cerium is precipitated, making it impossible to introduce a sufficient amount of cerium into the polyorganosiloxane to improve heat resistance.

The present invention solves these problems and uses a cerium compound to create a silicone oil based on ordinary silicone oil.
As a result of investigating ways to obtain colorless to light-colored transparent heat-resistant silicone oil, we arrived at a new manufacturing method that is different from conventional manufacturing methods.

In other words, the present invention combines polyorganosiloxane with a sufficient amount of cerium to impart heat resistance, thereby maintaining the properties of the base polyorganosiloxane while creating a colorless to light-colored transparent product with excellent heat resistance. The present invention provides a heat-resistant silicone oil having the following properties. That is, the present invention provides a polyorganosiloxane represented by the general formula {1} (where RI is a group selected from mutually the same or different monovalent hydrocarbon groups and monovalent halohydrocarbon groups). , a is 1.9-2.2, b is 0-0.
1, a+b is a number from 1.9 to 2.2, n is a number from 10 to 500) and {8) cerium acetylacetonate are dissolved or dispersed in a sieve at a temperature of 10 psi or less. The composition is a polyorganosiloxane represented by the general formula (in which R2 is a group selected from mutually the same or different monovalent hydrocarbon groups and monovalent halohydrocarbon groups, c is 1.9-2.2, b is 0-0.1
, c+d is the number 1.9×2.2, m is 10 to 2,000
The present invention relates to a method for producing a heat-resistant silicone oil, which comprises dropping a composition {q) into a cerium-containing polyorganosiloxane while blowing oxygen at a temperature of 200 to 300 degrees Fahrenheit.

The polyorganosiloxane (3) used in the present invention is represented by the general formula (R1, a, b, and n are as described above), and may be linear or branched, but has excellent heat resistance. In order to get
A straight chain is preferable.

Therefore, a branched type is recommended only when cold resistance up to -100 OO is also required, for example, or when a branched type is more advantageous for synthesis depending on the type of organic group bonded to the silicon atom. RI is a group selected from a monovalent hydrocarbon group and a monovalent halohydrocarbon group, and may be the same or different. Examples include alkyl groups such as methyl, ethyl, propyl, butyl, dodecyl, vinyl, phenyl, 8-phenylethyl,
Examples include chloromethyl group, -chloropropyl group, mono- to polychlorophenyl group, and 3,3,3-trifluoropropyl group. In order to keep the properties of silicone oil in a well-balanced manner, such as excellent electrical insulation and small changes in viscosity due to temperature, it is preferable that all of the RI be methyl groups. A phenyl group may be used as a part of the RI, or a polychlorophenyl group may be used as a part of the RI to improve lubricity. a is between 1.9 and 2.2, and a and b are between 1.9 and 2.2, but if it is less than this, the heat resistance will be poor, and if it is more than this, n will not fall within the desired range. be. b is allowed between 0 and 0.1, but
0 is preferred. This is because heat resistance decreases when the number of hydrogen groups is large. n is on average 10-500, preferably 15-25
0, but this is because if the degree of polymerization is low, the volatilization loss at high temperatures will be large, making it undesirable as a heat-resistant oil, and if the degree of polymerization is high, the viscosity will increase, making it difficult to drip in the step (2). 'Because it's heavy. The cerium acetylacetonate 'B} used in the present invention may be used in the form of a hydrate, or in the form of a mixed acetylacetonate of a rare element containing cerium as a main component.

Cerium (m) acetylacetonate, cerium (W)
Examples include acetylacetonate and cerium (N) basic acetylacetonate, but it is advantageous to use cerium (m) acetylacetonate in the form of a hydrate because of its easy availability. Hereinafter, the hydrate will be referred to as cerium acetylacetonate. The step '1' constituting the present invention is to mix the polyorganosiloxane of wind and the cerium acetylacetonate of {B} and dissolve or disperse the cerium acetylacetonate in the polyorganosiloxane of 100 qo or less. This is the step of making the composition (2). Cerium acetylacetonate is a solid that does not dissolve in polyorganosiloxane at room temperature.
It can be dissolved or dispersed in the polyorganosiloxane by heating to 00° C. or lower, preferably 60 to 80 qC, more preferably 70 to 80 qC.
If this temperature is lower than 6000°C, the amount of cerium dissolved or dispersed will be low, so in order to bond a large amount of cerium to the polyorganosiloxane, it is preferable to heat it to 60°C or higher. When this temperature exceeds 80°C, cerium acetylacetonate begins to decompose. 100o for this decomposition
If the temperature is higher than 0, the cerium component will precipitate and will not dissolve or disperse in the W polyorganosiloxane, so the temperature should be 100°C.
Below, it is necessary to keep it preferably below 80 points. A heating time of 2 hours or less is sufficient. In this step, oxygen may or may not be blown in, but it is effective to blow in oxygen in the form of air to aid dissolution. The amount of cerium acetylacetonate dissolved or dispersed is 0.01 parts by weight of the polyorganosiloxane (1).
~2 parts by weight, preferably between 0.05 and 0.5 parts by weight. This is because if there is too little cerium acetylacetonate, there will be no effect of improving heat resistance, and if there is too much cerium acetylacetonate, the solubility will be insufficient, causing turbidity and sedimentation, which will interfere with the step (2). This is because it causes a decrease in heat resistance. The composition thus prepared (q is yellow to reddish brown and exhibits a transparent liquid or suspension depending on the amount of cerium acetylacetonate. The blood polyorganosiloxane used in the present invention has the general formula ( R2, c, d, and m are as described above), and may be a straight mirror or a branched shape, but a straight mirror is preferable in order to obtain excellent heat resistance.

Therefore, branched products are recommended only when, for example, cold resistance up to 100 qo is required, or when it is more advantageous for synthesis depending on the type of organic group bonded to the silicon atom. R2 is a group selected from a monovalent hydrocarbon group and a monovalent halohydrocarbon group, and may be the same or different. Examples include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, dodecyl group, vinyl group, phenyl group, 6-phenylethyl group, chloromethyl group, y-chloropropyl group, mono- to polychlorophenyl group, 3,3 , 3-trifluoropropyl group, and the like. Excellent electrical insulation,
In order to maintain well-balanced characteristics of the silicone oil, such as small changes in viscosity due to temperature, it is preferable that all of RI be methyl groups, and for example, some of R2 may be a phenyl group to provide cold resistance. Alternatively, a polychlorophenyl group may be used as a part of R2 to improve lubricity. c is between 1.9 and 2.2;
Although c+d is between 1.9 and 2.2, if it is less than this, the heat resistance will be poor, and if it is more than this, m will not fall within the desired range. d is allowed between 0 and 0.1, but 0
is preferred. This is because heat resistance decreases when the number of hydroxyl groups is large. m is in the range of 10 to 2,000 on average, but this is because if the degree of polymerization is less than 10, the volatilization loss will increase at high temperatures, making it undesirable as a heat-resistant oil.
This is because those having a molecular weight of 0.00 or more are difficult to synthesize and have a high viscosity, making them difficult to handle. In the present invention, the base of the cold-resistant silicone oil is blood polyorganosiloxane.

Nagi's polyorganosiloxane plays a role as a solvent or a dispersion agent for cerium acetylacetonate, but as described later, it is dropped into Nagi's polyorganosiloxane and forms part of the heat-resistant silicone oil. do. Therefore, the polyorganosiloxane (2), like the polyorganosiloxane (2), is required not to contain any factors that inhibit heat resistance, and is also required to be compatible with the polyorganosiloxane (3). Therefore, it is preferable to use substantially the same polyorganosiloxane as in ■ and ■, but oils of the same type with different viscosities may be used, as long as they do not lose compatibility. , different types of oil may be used. The '21 process constituting the present invention converts blood polyorganosiloxane into 2
Heat to 0.00~30.00℃ and blow oxygen into 'C}
of the composition.

It is necessary to keep the dropping rate low enough to allow cerium to settle out of the system. This allows a low concentration of cerium to react with the polyorganosiloxane at all times, making it possible to efficiently introduce cerium into the polyorganosiloxane. This process is {11
Unlike the above process, the polyorganosiloxane is oxidized with oxygen and reacts with cerium (m) acetylacetonate contained in } to introduce cerium into the side chains of the polyorganosiloxane, so oxygen is not blown into the polyorganosiloxane. It is essential. Oxygen is usually injected in the form of air, which can be dry or humid air. The temperature is the temperature at which the polyorganosiloxane undergoes oxidation, but at which the polyorganosiloxane is not completely destroyed, that is, 2
The temperature is preferably between 00 and 30°C, preferably between 240 and 280°C. If this temperature is too low, oxidation is difficult to occur and the reaction time becomes longer; if it is too high, the polyorganosiloxane decomposes and the viscosity increases, making it impossible to obtain a product with the desired viscosity, and some polyorganosiloxane is cyclized and exits the system, resulting in a decrease in yield. Even after the addition is completed, in order to cause the cerium to completely react with the polyorganosiloxane, it is preferable to continue blowing oxygen and stirring in the same temperature range as in step (2).

Moreover, during this air blowing, the coloration of the system gradually decreases, and a colorless to pale yellow transparent silicone oil is obtained. The time for blowing oxygen, including the time for dropping the composition 'C', is required to be 2 hours or more, preferably 3 to 8 hours. The end point can be determined by the time when the system becomes almost colorless or pale yellow and transparent. In addition, to remove impurities, it is recommended to carry out heating in the usual way. Unlike the conventionally known cerium forming method, the present invention does not require the use of a large amount of solvent and does not leave impurities such as alkali metals or Si bonds that impede heat resistance, and effectively forms cerium. can be introduced into the polyorganosiloxane.

The heat-resistant silicone oil produced by the production method of the present invention has heat resistance comparable to conventional heat-resistant silicone oils and excellent transparency, and also has cold resistance, lubricity, etc. commensurate with its base oil. It is possible to maintain various properties. That is, the heat-resistant silicone oil produced by the production method of the present invention has better heat resistance in the temperature range of 25 mm or higher than the heat-resistant grade silicone oil obtained by the method of introducing a large amount of phenyl groups into the molecule. When using methyl silicone oil or methyl silicone oil in which a portion of the methyl group is partially substituted with 10 mol% or less of phenyl or halophenyl groups as the base oil, it can have any viscosity and have excellent cold resistance. sex,
Silicone oil with low surface tension can be obtained. Furthermore, when a silicone oil having a halophenyl group or various organic modified groups is used as a base oil, a heat-resistant silicone oil that retains the lubricity of the base oil can be obtained. In addition, compared to heat-resistant grade silicone oils made by adding or bonding iron-based compounds to various silicone oils, heat-resistant silicone oils with superior transparency can be obtained, with no inferiority in heat resistance. . In addition, the heat-resistant silicone oil produced by the production method of the present invention can have superior heat resistance and chemical stability compared to silicone oil into which cerium is introduced by other production methods.

The heat-resistant silicone oil obtained by the present invention is used for hot soot, high-temperature hydraulic bottles, damper oil, etc.

In particular, known heat-resistant silicone oils are used, such as hot soot for oil baths that require low viscosity and need to be able to see through the contents, and heating media that are used in a wide temperature range of 150 to 130 mm. It can be used in areas where conventional methods could not be used. Further, silicone grease or silicone compound can be produced by using the heat-resistant silicone oil obtained according to the present invention as a base oil and adding a thickening agent such as t-metal soap or a filler such as silica.

Moreover, the heat-resistant silicone oil obtained by the present invention can also be added as a heat-resistant improver for silicone rubber. Examples of the present invention will be described below.

In the examples, all parts are by weight. Example 1 Average formula (CH3)3Sio [(CH3)2Si○] Beni S
Polydimethylsiloxane 100 represented by i (C ratio) 3
0.0 parts of cerium (m) acetylacetonate hydrate.
Add 1 part of cerium (
m) Acetylacetonate hydrate was completely dispersed (partially dissolved) in polydimethylsiloxane to prepare a reddish suspension.

Next, a separately prepared base of polydimethylsiloxane 10 similar to the above was heated to 270 qo, and the entire amount of the previously prepared suspension was added dropwise over 2 hours while blowing air. While maintaining the temperature at 270 qo, blowing and air blowing were continued for another 3 hours, and after being allowed to cool, filtering was performed in an oven to obtain a pale yellow transparent cerated polysiloxane oil. This is designated as sample 11. In a similar manner, cerium (m
) The amount of acetylacetonate hydrate added is 0.02 to 0.
．． First, a solution or suspension of cerium (m) acetylacetonate in polydimethylsiloxane was prepared by changing between 3 parts, and then a colorless to slightly yellow transparent cerated polysiloxane was obtained.

However, the addition of cerium (m) in the second stage of the process
0.2 parts of acetylacetonate and 0.2 parts of acetylacetonate. The test using the $100 part took 3 hours. This is sample 12
~15. These samples, the original polydimethylsiloxane (Comparative Example 16), and 0.00% iron octoate were added to the original polydimethylsiloxane (Comparative Example 16).
Iron was introduced into polydimethylsiloxane by adding 15% and performing air oxidation at 270°C (Comparative Example 17)
, average formula (C horse) 3Sj○ [(CH3)2Si○], o
Table 1 shows the color tone, viscosity, and pour point of polymethylphenylsiloxane (Comparative Example 18) represented by [(C6day5)2Si○]6Si(CH3)3.

In addition, 50 liters of each of these samples and the comparative sample were placed in a 100 cc beaker, placed on the table of a rotary table-type thermostat, and heated at 300 qo for 12 to 76 hours.
The viscosity and heating loss at 5°C are also shown in Table 1. Table 1 Example 2 Average formula (CH3)3Si[(CH3)bui○]8.5[
(C6&)2Si0], . Add 0.02 parts of cerium acetylacetonate to 5 parts of polymethylphenylsiloxane represented by 5Si(CH3)3, and heat for 2 hours while maintaining a temperature of 70 to 75°C. and dissolve cerium (m) acetylacetonate, etc.)
A cloudy yellowish solution was obtained.

Separately, the average formula (CH3)3Si [(CH3)2Si○]
False [(C6 day 5) bui○] 2.5Polymethylphenylsiloxane 15 anchor part represented by Si(CH3)3 is 280
1. The previously prepared siloxane solution of cerium (m) acetylacetonate was heated to qo, heated, and while blowing air. I dripped it over time in the morning.

The temperature was lowered to 260 qo, and the mixture was further stirred and blown with air for 3 hours, allowed to cool, and then filtered in an oven to obtain a colorless and transparent cerium-containing polysiloxane. This one (sample 21)
and the average formula (CH3)3Si [(C horse)2Si○]33
[C6 day 5) 2Sj0] 2.5Sj(CH3)3 of polymethylphenylsiloxane (comparative example pine) and 5 each
A heat resistance test of 300 qo was conducted in the same overflow tank as in Example 1 by putting 0 qo in a 100 cc beaker.

That is, the appearance and heat loss of the polysiloxane after 96 hours at 300°C were compared. The results are shown in Table 2. Further, Sample 21 maintained its fluidity even after being left at a low temperature of -68°C for 1 hour. Table 2 Sample Modification
21 Kamidou Wataru 22300℃, 96 Oxidized Sardine Fiber Sardine Gemehi Heating Loss Approximately 14.0
32.8 Example Branched polysiloxane containing 6.5 mol% of 3C6CI4HSi03/g units, the remainder consisting of (CH3)2Sj○ units and (C ratio) i0,/2 units, and having a viscosity of 12&St at 25qo 10 sea breams,
Add 0.02 part of cerium (W) acetylacetonate hydrate and raise the temperature to 70°C while blowing air to completely dissolve cerium (W) acetylacetonate in the branched polysiloxane. A solution was obtained.

The above-mentioned branched polysiloxane 10 base prepared separately was heated to 240 qo while blowing air, and the solution prepared earlier was added dropwise over 1 hour. Further, the mixture was heated at the same temperature for 3 hours, and then filtered in an oven to obtain a pale yellow transparent cerium-containing polysiloxane. 50 pieces of this material (Sample 31) and the branched polysiloxane used as a raw material (Comparative Example 32) were each taken into a 100cc beaker, and heated to 300°C in the same temperature bath as in Example 1.
When the sample 31 was left in the water for 72 hours, the sample 31 maintained a viscosity of 14 pillows at 2yo, whereas the sample 32 had gelled. Example 4 Average formula (CH3)3Si○ [(CH3)2Si○] Group S
Polydimethylsiloxane represented by i (C ratio) 3 5 parts of cerium (m) acetylacetonate hydrate 0.1
of the mixture was heated and kept at a temperature of 75q0 for 1 hour to obtain a reddish-brown suspension.

Separately, the average formula date ○ [(CH3)2Sio]95 hydroxyl group-terminated polydimethylsiloxane shown in rainbow 15
The suspension prepared earlier was added dropwise over 1 hour while heating and heating to 60° C. and blowing air. temperature to 260
While keeping the temperature at ℃, the blowing and air blowing were continued for 2 hours, and after cooling, filtering was performed to obtain a slightly yellow transparent cerium-containing polysiloxane. This was left for 16 hours at 300 oo in a constant temperature bath similar to Example 1, but it still maintained fluidity and its loss on heating was 18.5%. Example 5 Example 1
Under the same conditions as Sample 11, the average formula (C melon) 3Si0 [
A cerium-containing polysiloxane was obtained using polydimethylsiloxane represented by (CH3)2Si○]305Si(CH3)3.

This is designated as sample 51. Same polydimethylsiloxane 1
Comparative Example Sample 52 was obtained by adding 3 parts of ceriumated polysiloxane to 00 parts by a known method. However, this cerium-containing polysiloxane was prepared by the following method. That is, potassium hydroxide and octamethylcyclotetrasiloxane were heated to 150° C. in a nitrogen stream to obtain transparent, semi-occupied potassium silanolate. 2 parts of this potassium silanolate, 3 parts of polydimethylsiloxane with a viscosity of 3 ratio St at 25o0, and 0.2 parts of hexamethylphosphortriamide were mixed, and 1 part of the potassium silanolate was mixed in a nitrogen stream.
Heat to 10° C. for 2 hours, then add 8 parts of dehydrated xylene and 10 parts of cerium octoate, 2. After refluxing for a period of time and cooling, 2 parts of trimethyl silane was added, the solvent was distilled off under reduced pressure, and the solid content formed was removed by filtration to obtain a pale yellow cerated polysiloxane. When sample 51 and comparative sample 52 were left in the same temperature chamber as in Example 1 at 30,000 ℃ for 9 hours, sample 51
was a liquid with a viscosity of 1.18 St at 25o0, but Comparative Example Sample 52 was gelled.

Claims (1)

[Claims] 1 (1) (A) A polyorganosiloxane (in the formula R
^1 is a group selected from the same or different monovalent hydrocarbon groups and monovalent halohydrocarbon groups, a is 1.9 to 2
．． 2, b is a number from 0 to 0.1, a+b is a number from 1.9 to 2.2,
(n is an average number of 10 to 500) and (B) cerium acetylacetonate at a temperature of 100°C or less.
) to obtain a composition (C), (2)
(D) Polyorganosiloxane represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼
2 is the same or different monovalent hydrocarbon group and 1
a group selected from halohydrocarbon groups having a valence of 1.9 to 2.
2, d is a number from 0 to 0.1, c+d is a number from 1.9 to 2.2, m
is an average number of 10 to 2,000) at a temperature of 200 to 300°C while blowing oxygen or air to form a ceriumated polyorganosiloxane. Method of manufacturing silicone oil. 2 The polyorganosiloxane (A) has the general formula R^1
_3SiO [R^1_2SiO]_n_-_2SiR^
1_3 (where R^1 is a group selected from the same or different monovalent hydrocarbon groups and monovalent halohydrocarbon groups, n is a number from 10 to 500 on average) The manufacturing method according to claim 1, which is an organosiloxane. 3 General formula of polyorganosiloxane (A) ▲ Numerical formula,
The manufacturing method according to claim 1, wherein b is 0 in the chemical formula, table, etc. ▼. 4 (A) The polyorganosiloxane has the general formula (CH
_3)_3SiO [(CH_3)_2SiO]_n_-
_2Si(CH_3)_3 (average n is 10-50
The manufacturing method according to claim 1, wherein the manufacturing method is indicated by a number of 0's. 5 (D) The polyorganosiloxane has the general formula R^2
_3SiO [R^2_2SiO]_m_-_2SiR^
A straight chain represented by 2_3 (where R^2 is a group selected from the same or different monovalent hydrocarbon groups and monovalent halohydrocarbon groups, m is a number on average from 10 to 2,000) The manufacturing method according to claim 1, wherein the polyorganosiloxane is a polyorganosiloxane. 6 General formula of polyorganosiloxane (D) ▲ Numerical formula,
The manufacturing method according to claim 1, wherein in the chemical formula, table, etc. ▼, d is 0. 7 (D) The polyorganosiloxane has the general formula (CH
_3)_3SiO [(CH_3)_2SiO]_m_-
_2Si(CH_3)_3 (average 10-2,
000), the manufacturing method according to claim 1. 8. The manufacturing method according to claim 1, wherein the polyorganosiloxane (A) is substantially the same as the polyorganosiloxane (D).