JPH0528740B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention provides a flame-retardant silicone oil composition, in particular, its flame retardance is reduced without impairing its electrical properties and heat resistance, and its self-extinguishing property is also excellent.
The present invention relates to a flame-retardant silicone oil composition which has the advantage of exhibiting high safety when used as an electrical equipment melting insulating oil. (Prior technology) Various types of insulating oils have been used for electrical equipment such as power cables, capacitors, and transformers, including mineral oils, phosphate ester oils, aromatic hydrocarbon oils, chlorinated synthetic oils, silicone oils, and fluorine oils. However, mineral oil, aromatic hydrocarbon oil, and low viscosity silicone oil are flammable and
Chlorinated synthetic oils have toxicity problems, and fluorine oils have high specific gravity, which increases the weight of equipment and is expensive. In addition, medium to high viscosity silicone oil is said to be flame retardant, but this is also achieved using the glass tape method (JIS
Since C2101) is flammable, it has been proposed to add a flame retardant or non-combustible agent that is compatible with silicone oil (JP-A-49-39173, JP-A-51-20720, JP-A-59 -Refer to Publication No. 226408)
However, all of these are non-silicone-based, and some of them are compounds such as fluorine oil, so they have the disadvantage of being highly volatile and making it difficult to obtain stable performance over a long period of time. Bromine compounds and phosphorus-containing compounds have problems with corrosivity and electrical properties, and also lack long-term stability, so improvements in this area have long been sought. (Structure of the Invention) The present invention relates to a flame-retardant silicone oil composition that does not have the disadvantages described above and is made of flame-retardant silicone oil, which has the following general formula: (1)

100 parts by weight of an organopolysiloxane represented by the formula: (wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group of the same or different type, 0.1 to 30 mol% thereof is a vinyl group, and a is 1.8 to 2.3) , (2) an organic solvent-soluble platinum compound containing 0.0001 to 0.1 parts by weight of platinum, (3) (a) cerium, a rare earth metal mixture containing cerium as a main component, and a metal element selected from titanium, zirconium, or hafnium. (b) an organosilane compound or organopolysiloxane compound containing one or more aromatic amine structures in its molecular structure; (c) an organosilane containing one or more hindered phenol structures in its molecular structure. 0.01 to 10 parts by weight of an organosilicon compound selected from compounds or organopolysiloxane compounds. That is, as a result of various studies on methods of making silicone oil itself flame retardant, the inventors of the present invention determined that the silicone oil, which is the main material, contains a vinyl group and added an organic solvent-soluble platinum compound thereto. As a result, this silicone oil becomes self-extinguishing and has excellent flame retardancy, and in addition, specific metallosiloxanes, organosilanes or organopolymers containing an aromatic amine structure in the molecular structure are used as heat resistance improvers. When an organosilicon compound selected from siloxane or organosilane or organopolysiloxane containing a hindered phenol structure in its molecular structure is added, it has good heat resistance and excellent electrical properties, so it is suitable for electrical equipment. We have discovered that when used as an insulating oil, it is more stable than conventional silicone oil, and we have developed information on the type of silicone oil used, the platinum compound, the type of heat resistance improver, and the amount added. The research progressed and the present invention was completed. The silicone oil as the first component constituting the flame retardant silicone oil composition of the present invention has the general formula

[Formula], R ¹ is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group, an alkenyl group such as an allyl group, a phenyl group,
Selected from aryl groups such as tolyl groups, or chloromethyl groups, trifluoropropyl groups, cyanoethyl groups, etc. in which some or all of the hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. It is an unsubstituted or substituted monovalent hydrocarbon group, and a is 1.8 to 2.3,
A part of this R ¹ group must be a vinyl group, and the amount of vinyl groups is 0.1 mol%.
Below this, the silicone oil will not be flame retardant, and if it exceeds 30 mol%, the heat resistance will decrease.
There is a risk that the viscosity will increase during use.
It needs to be in the range of 0.1 to 30 mol%. In addition,
The viscosity of this silicone oil does not need to be particularly specified, but since it is used as an insulating oil for electrical equipment, it is preferable that the viscosity at 25° C. be 5 to 1000 cS. In addition, as the organic solvent soluble platinum compound added to the silicone oil as the second component, chloroplatinic acid, US Pat. No. 3,159,601, US Pat.
Examples include platinum compounds used in hydrosilylation reactions, such as [Pt(PPh ₃ )], which are described in No. 3775452.
This may be, for example, a complex compound of vinyl siloxane and a platinum compound, or an alcohol-denatured compound thereof, and these may be added by dissolving it in the silicone oil as the main material mentioned above. . In addition, if the amount of platinum compound added is less than 0.0001 parts by weight of platinum per 100 parts by weight of the silicone oil described above, it is too small and no flame retardant effect can be obtained, and even if it is added more than 0.1 parts by weight, flame retardancy is hardly achieved. Therefore, it is necessary to set it in the range of 0.0001 to 0.1 part by weight, but this preferred range is 0.001 to 0.01 part by weight. Next, the third component added to this silicone oil is
The heat resistance improver as a component is metallosiloxane,
It is selected from organosilanes or organopolysiloxanes containing an aromatic amine structure in its molecular structure, or organosilanes or organopolysiloxanes containing a hindered phenol structure in its molecular structure. This metallosiloxane has the general formula

[Formula], R ² is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, or a carbon group of these groups. Unsubstituted or substituted, identical or different monovalent carbons selected from chloromethyl groups, trifluoropropyl groups, cyanoethyl groups, etc. in which all or part of the hydrogen atoms bonded to atoms are substituted with halogen atoms, cyano groups, etc. Hydrogen group, b is 1.8 to 2.3 Organopolysiloxane containing 1 selected from cerium or a rare earth metal element mixture containing cerium as a main component, titanium, zirconium, and hafnium.
It is said to contain a species or two or more metal atoms, but if the metal content exceeds 5%, it becomes difficult to manufacture, and if it is less than 0.05%, the amount added to obtain the effect of improving heat resistance increases. Since it becomes impractical, it is preferably in the range of 0.05 to 5% by weight. For example, this metallosiloxane is made by adding 100 parts by weight of dimethylpolysiloxane with a viscosity of 100 cS, 10 parts by weight of a turpentine solution (rare earth metal element content: 6% by weight) of 2-ethylhexanoate, which is a rare earth metal mixture containing cerium as the main component, and - A mixture with 2.1 parts by weight of n-butyl titanate was added with sufficient stirring, heated while passing a small amount of nitrogen gas to distill out turpentine, and then heated to 300°C for 1 hour.
When heated for a period of time, it is obtained as a dark reddish-brown transparent liquid, and this production is known, for example, in US Pat. No. 3,008,900.
Specification, Special Publication No. 12541, Publication No. 12541, Special Publication No. 12541
Publication No. 50970, Japanese Patent Publication No. 57-57501, Japanese Patent Application Publication No. 1983
The method described in JP-A-65400 and JP-A-60-163966 may be used. In addition, organosilane or organopolysiloxane formulas containing this aromatic amine structure in their molecular structure

【formula】 【formula】

, R ² is the same as above, R ³ is

【formula】

[expression] or

[Formula] is assumed to be. In addition, if the m value exceeds 50, the amount added to obtain the desired heat resistance improvement effect increases, making it impractical, so it is set to 1 to 50, and the p value is also set to 1 to 50. If it exceeds 47, p+q also increases to 48. If it exceeds it, it becomes impractical for the same reason, so p is 0 to 47, p
+q must be between 1 and 48, and regarding the q value
If the number is greater than 10, the solubility in the silicone oil as the first component will decrease, making it difficult to obtain a uniform composition, so it is necessary to set the number in the range of 1 to 10. In addition, this one can be expressed as, for example, the formula The aminophenol represented by and an alkylsilane or alkylpolysiloxane having a reactive group, such as a chlorinated alkylsilane or a chlorinated alkylpolysiloxane, are mixed in equimolar amounts, and ammonia, pyridine, and ammonia as a hydrochloric acid scavenger are mixed in a toluene solvent. It can be obtained by a method in which the product is reacted with stirring at room temperature or under heating in the presence of triethylamine, etc., the hydrochloride is removed from the product, and then the product is stripped under reduced pressure and heating. It may be made by the method described in Japanese Patent Publication No. 55-18457, Japanese Patent Publication No. 61-21591, and Japanese Patent Application Laid-Open No. 60-106891. Furthermore, organosilanes or organopolysiloxanes containing the above-mentioned hindered phenol structure in their molecular structure, for example, have the formula

【formula】

, R ² , m, p, and q are the same as above, and R ⁴ is

【formula】

【formula】

【formula】

[Formula] is assumed to be. This one is for example

[Heat aging operation]

(1) Collect 30g of sample oil into a clean 50ml hard glass ampoule, (2) Bubble dry nitrogen using a clean hard glass capillary, degas and dry at room temperature, (3) Finish bubbling. Immediately after that, it is melt-sealed and left in a hot air circulation constant temperature bath at 150°C or 180°C for 8 days. Examples 1-4, Comparative Examples 1-2 The average composition formula is The vinyl group content is 9.5 mol% and the viscosity is
30.4cS methylvinylpolysiloxane (hereinafter abbreviated as polysiloxane A), a vinylpolysiloxane-platinum complex (platinum content 30% by weight), cerium 0.3% by weight, and titanium 0.3% by weight. Polysiloxane A, metallopolysiloxane B containing 3.0% by weight of zirconium,
formula Aromatic amine group-containing dimethylpolysiloxane (hereinafter abbreviated as aromatic amine modified polysiloxane A) represented by the formula A flame-retardant silicone oil composition is prepared by adding dimethylpolysiloxane containing a hindered phenol group (hereinafter abbreviated as hindered phenol-modified polysiloxane A) shown in Table 1. Heat aging at 150℃
The flame test was carried out for 8 days at 180° C. and for 8 days at 180° C., and the flame-extinguishing time was measured by conducting a combustion test before and after aging, and the results were obtained as shown in Table 1. However, for comparison, 0.01 part of the vinyl polysiloxane-platinum complex used above was added to 100 parts of the above-mentioned polysiloxane A, but a composition V was prepared without adding any heat resistance improver. When a similar test was conducted, in this case, as shown in Table 1, the flame retardancy before heat aging was good, but after heat aging
The extinguishing time significantly increased at 150°C for 8 days, and at 180°C
The flame retardance was significantly reduced without extinguishing the flame after 8 days. In addition, for comparison, the above polysiloxane A
When a combustion test was conducted on this product without adding anything to it, no extinguishment of flame was observed and the product burned continuously, as noted in Section 1.

[Table] Examples 5 to 7, Comparative Examples 3 to 4 Average composition formula The vinyl group content is 4.9 mol% and the viscosity is
To 100 parts of methylvinylpolysiloxane (hereinafter abbreviated as polysiloxane B) of 51.0 cS, the vinylpolysiloxane-platinum complex used in Example 1 and the metallopolysiloxane A used in Example 1, formula Aromatic amine group-containing dimethylpolysiloxane (hereinafter abbreviated as aromatic amine modified polysiloxane B) represented by the formula A flame-retardant silicone oil composition is prepared by adding a hindered phenol group-containing dimel polysiloxane (hereinafter abbreviated as hindered phenol-modified polysiloxane B) shown in Table 2 in the amount shown in Table 2. Heat aging these at 150℃
Flame retardancy tests were carried out for 8 days and at 180° C. for 8 days before and after aging, and the flame retardation time was measured, and the results shown in Table 2 were obtained. However, for comparison, the polysiloxane mentioned above
A composition was prepared by adding 0.01 part of the vinyl polysiloxane-platinum complex used above to 100 parts of B, but without adding any heat resistance improver, and the above test was conducted on this composition. As shown in Table 2, the flame retardancy before heat aging was good, but after heat aging, the flame-out time increased significantly at 150°C for 8 days, and no flame retardation occurred at 180°C for 8 days. , the flame retardancy significantly decreased. In addition, for comparison, the above polysiloxane B
When this product was subjected to a combustion test without adding anything, no extinguishing of flame was observed as shown in Table 1, and continuous combustion occurred.

[Table] When the electrical properties of the compositions of the present invention were examined, they exhibited the physical properties shown in Table 3 below, and all were found to be excellent as electrical insulating oils.

【table】 [Brief explanation of the drawing]

FIG. 1 shows a perspective view of a silicone oil combustion test method.

Claims (1)

[Claims] 1 (1) General formula [Formula] (where R ¹ is an unsubstituted or substituted monovalent hydrocarbon group of the same or different type, 0.1 to 30 mol% of it is a vinyl group, and a is 1.8 ~
Organopolysiloxane shown in 2.3)
100 parts by weight, (2) an organic solvent-soluble platinum compound containing 0.0001 to 0.1 parts by weight of platinum (3) (a) a metal element selected from cerium, a rare earth metal mixture containing cerium as a main component, titanium, zirconium, or hafnium; (b) an organosilane compound or organopolysiloxane compound containing one or more aromatic amine structures in its molecular structure; (c) a metallosiloxane compound containing one or more hindered phenol structures in its molecular structure; A flame-retardant silicone oil composition comprising 0.01 to 10 parts by weight of an organosilicon compound selected from organosilane compounds and organopolysiloxane compounds. 2 Metallosiloxane is an organopolysiloxane represented by the general formula [Formula] (where R ² is an unsubstituted or substituted monovalent hydrocarbon group of the same or different type, and b is 1.8 to 2.3). The flame-retardant silicone oil composition according to claim 1, which contains 0.05 to 5% by weight of a metal element selected from rare earth metal mixtures, titanium, zirconium, and hafnium. 3 An organosilane compound or organosiloxane compound containing one or more aromatic amine structures in its molecular structure has the general formula R ² ₃ Si-OR ³ , [Formula] or (Here, R ² is the same as above, R ³ is [Formula] [Formula] or [Formula] m is 1 to 50, p is 0 to 47, q is an integer of 1 to 10, and p+q is an integer of 1 to 48. Flame retardant silicone oil composition. 4 Hindered phenol structure in the molecular structure
_The ^organosilane _compound or _{organosiloxane} compound containing more ^than
[Formula] or (Here, R ² , m, p, and q are the same as above, and R ⁴ is [Formula] [Formula] [Formula] or [Formula]) Flammable silicone oil composition.