[2]The present invention relates to silicone compositions smectically, more specifically, relates to can contains larger amount of thickening agent, and has the polysiloxane composition smectically good heat resistance.
[4]Liquid organopolysiloxane with the zinc oxide powder or alumina powder of the thickening agent, such as by, for example, polysiloxane composition smectically, opens illustriously especially 50-105573 of communiques, opens illustriously especially 51-55870 of communiques, opens illustriously especially 61-157587, the proposed, but a large number of these composition containing a thickener or smectically does not present the decentralization of the high temperature consistency after the problem is obviously reduced or cured.
[5]The present inventors to the above-mentioned subject concentre of the results of the study has finished this invention.
[6]In other words, the purpose of this invention to provide a containing thickening agent, and has the polysiloxane composition smectically good heat resistance.
[7]Content of the invention
[8]Polysiloxane composition smectically of this invention, which is characterized in that at least the (A) type: R2 SiO2/2 siloxane units expressed 80-96.5 mol %, type: RSiO3/2 said siloxane units of 1.0-10.0 mol % formula: R3 SiO1/2 siloxane units expressed by the 0.25-10.0 mol % a liquid organopolysiloxane (in the formula, R is the same or different monovalent hydrocarbyl), and the (B) thickening agent composition.
[9]The best plan for implementation of the invention
[10]The following, detail represents said polysiloxane composition smectically of the invention.
[11](A) component is the main ingredient of the composition, is at least represented by formula: R2 SiO2/2 siloxane units expressed by the, type: RSiO3/2 siloxane units expressed by the formula: R3 SiO1/2 of the siloxane units expressed by the branched, or with a portion of a branched linear liquid organopolysiloxane. R in the formula is the same or different monovalent hydrocarbyl, for example, can be enumerated methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, alkyl; cyclopentyl, cyclohexyl, cycloalkyl; vinyl, allyl, butenyl, pentenyl, enyl base and so on alkenyl; phenyl, naphthyl, tolyl, xylyl, etc. aryl; benzyl, phenethyl, aralkyl; chloromethyl, 3-chloro-propyl, 3, 3, 3-trifluoropropyl and the like, such as alkyl halide, preferably an alkyl, alkenyl, aryl, most preferably methyl, ethyl, vinyl, phenyl.
[12]The liquid organopolysiloxane, characterized in that type: R2 SiO2/2 said siloxane unit content is 80-96.5 within the range of molar %, type: RSiO3/2 said siloxane unit content is 1.0-10.0 mol % in the range of, type: R3 SiO1/2 said siloxane unit content is 0.25-10.0 mol % range. This is because formula: RSiO3/2 of the content of siloxane units expressed by the lack of the lower limit of the above-mentioned range of liquid organopolysiloxane degree of branching of small, containing no (B) component, the heat resistance of the resulting polysiloxane composition smectically tendency is reduced, the above-mentioned range exceeds the upper limit of the degree of branching of the large liquid organic polysiloxane, the polysiloxane composition smectically the operability of the tendency or fluidity is obviously reduced.
[13]This liquid organic polysiloxane viscosity is not limited, but preferably in the 25 is of degree of viscosity under [...] 10-100, in the range of 000 MPa. s, re-is preferably 100-100, in the range of 000 MPa. s. This is because the viscosity of the liquid organic polysiloxane is less than the lower limit of the above-mentioned range, worried that is easy to volatilize, and when exceeding the upper limit of the above-mentioned range, the operability of the lubrication to qualify or siloxane the shape gathers the tendency of fluidity is reduced.
[14]This kind of liquid organopolysiloxane modulation method is not limited, for example, the following method can be cited: formula: RSiCl3, R2 SiCl2 and R3 SiCl of said organic halo silane together prepared by hydrolysis and condensation reaction formula: RSiO3/2 siloxane units expressed by the formula: R2 SiO2/2 siloxane units expressed by the formula: R3 SiO1/2 said organic siloxane unit of the poly-siloxane, in sodium hydroxide, potassium hydroxide, potassium silicate (potassium silanolate) balanced reaction of compound in the presence of the catalyst, the general formula: R3 SiO (R2 SiO)m SiR3 the diorganopolysiloxane and/or formula : (R2 SiO)n the cyclic two organo-siloxane balancing is carried out after the reaction, carbon dioxide is used, the acid phosphoric acid and the like, or R2 SiCl2, R3 SiCl halogen silicon hydride and the like. Furthermore, in the formula, R is the same or different monovalent hydrocarbyl, can be enumerated with the same group.
[15](B) ingredient is in order to enable the use of a thickening agent forming smectically, the inorganic powder or organic powder. The particle size of the thickener is not limited, but the average particle size is preferably 0.1-100 the within the range of m. This is because the average particle size is smaller than the lower limit of the above-mentioned range, can not be fully [...] role that, and, when exceeding the upper limit of the above-mentioned range, it is difficult to uniformly dispersed in (A) in the composition. This thickening agent of the shape is not limited, can enumerate spherical, multidimensional, needle, amorphous. As this kind of thickening agent can also be the shape of two or more kinds combined use of a thickening agent, for example, can be the spherical thickening agent used in combination with the amorphous thickening agent.
[16]As this type of thickening agent, for example, can be enumerated alumina, silicon carbide, aluminum nitride, boron nitride, quartz powder, powder heat; carbon black, graphite, metal powder or the like of a conductive powder; Mn-Zn ferrite based magnetic powder, Ni-Zn ferrite based magnetic powder, -permanent Ni alloy powder, powder alloy Fe-Al-Si, Fe-Si-B series of nano-crystalline soft magnetic powder and other electromagnetic interference suppressing soft magnetic powder; fumed silica, hydrophobic fumed silicon dioxide, silicon oxide impregnat, hydrophobization settling silica, molten silica, diatomaceous earth, talc, calcium carbonate, zinc oxide, titanium dioxide, iron oxide, manganese carbonate, inorganic powder cerium and so on hydroxide; also glass fiber, glass bead, glass ball, tetrafluoroethylene powder. These can also be two or more in combination is used as the thickening agent.
[17]In the composition (B) component content is not limited, however, relative to the (A) ingredient 100 parts by weight is preferably 10-2,000 parts by weight of the range, and then is preferably 10-1,500 the range of parts by weight, most preferably 10-1,000 parts by weight of the range. This is because (B) content is less than the lower limit of the above-mentioned range, the composition obtained will probably not presenting smectically, and, when exceeding the upper limit of the above-mentioned range, that the operability of the resulting composition or flow properties reduce, or do not exhibit smectically.
[18]The compositions, as any other component, also may contain a methyl trimethoxy silane, nhexyl trimethoxy silane, is decyl trimethoxy silane, methyl trichlorosilane, hexa alkane and so on second surface treatment agent of silicon ammonia; in addition can also contain pigment, dye, fluorescent dye, a plasticizer, heat-resistance improving agent, antioxidant, anti-mildew agent, organic solvent or the like.
[19]By adopting this composition is the mixing device (A) component, (B) component, according to the needs of other optional component but modulation of mixing uniformly. As this kind of mixing device, can enumerate well the Company seisakusho on three mixes the type , double-mixing type or planetary mixer, super high speed mixer for industrial Juisui the Company, T.K special machine chemical to the Company. High-dispersion type mixer, and the like. Furthermore, at this moment can also be according to the need for cooling or heating. Furthermore, using these mixing device modulation smectically the polysiloxane composition, in order to make it more uniform, trigeminy roller can also be used for, colloid mill, mixing such as grinding.
[20]The use of the composition with a portion of a branched chain branched or straight liquid organopolysiloxane as (A) ingredient, leakage can be suppressed, the electric contact can be avoided the undesirable powerups, miniature motor running the bad fault such as, in addition, because even the long-term is not solidified even in a high-temperature environment, therefore, suitable for use as a transistor, IC, diode, temperature sensitive resistor, grease.
[22]The following, detail by embodiments of the invention represents smectically said polysiloxane composition. Viscosity is 25 the value of under [...] , in addition, the consistency of the silicone composition smectically in accordance with JIS K 2220 measuring process. Furthermore, the heat resistance of the silicone composition smectically, is to measure the composition in the 200 [...] placed in the oven 24 hours after the consistency of the, back and forth through the heat resistance test of changes in the consistency of the evaluation.
[24]Input planetary mixer to a viscosity of 800 MPa the s, by formula (CH3)2 SiO2/2 siloxane units expressed 94.0 mole %, type: CH3 SiO3/2 siloxane units expressed by the 3.3 mol % formula : (CH3)3 SiO1/2 siloxane units expressed by 2.7 mol % a liquid organopolysiloxane (I) 100 parts by weight, and an average particle size of 11.5 the spherical alumina powder m of 930 parts by weight, after stirring, the stirring at room temperature under reduced pressure for 30 minutes, the prepared polysiloxane composition smectically.
[26]Embodiment 1 in, in addition to the average grain size for the 2.5 m of the amorphous alumina powder 600 weight parts instead of an average particle size of 11.5 the aluminum oxide powder m of 930 parts by weight of other than, other embodiment 1 similarly modulation smectically polysiloxane composition.
[28]Embodiment 1 in, except using an average particle size of 5.0 the quartz powder crushing m 350 weight parts instead of an average particle size of 11.5 the aluminum oxide powder m of 930 parts by weight of other than, other embodiment 1 similarly modulation smectically polysiloxane composition.
[30]Embodiment 1 in, except using an average particle size of 0.6 the zinc oxide powder m 200 weight parts instead of an average particle size of 11.5 the aluminum oxide powder m of 930 parts by weight of other than, other embodiment 1 similarly modulation smectically polysiloxane composition.
[32]Embodiment 1 in, except using an average particle size of 5.0 the powder of silicon carbide m 500 weight parts instead of an average particle size of 11.5 the aluminum oxide powder m of 930 parts by weight of other than, other embodiment 1 similarly modulation smectically polysiloxane composition.
[34]Embodiment 1 in, in addition to the average grain size for the 2.5 m of the aluminum nitride powder 600 weight parts instead of an average particle size of 11.5 the aluminum oxide powder m of 930 parts by weight of other than, other embodiment 1 similarly modulation smectically polysiloxane composition.
[36]Embodiment 1 in, in addition to the viscosity for the 600 MPa s, by formula : (CH3)2 SiO2/2 siloxane units expressed 94.0 mole %, type: CH3 SiO3/2 siloxane units expressed 2.5 mol %, type : (CH3)3 SiO1/2 siloxane units expressed by the 3.5 mol % a liquid organopolysiloxane instead of liquid organopolysiloxane (I) other than, other embodiment 1 similarly modulation smectically polysiloxane composition.
[38]Embodiment 1 in, in addition to the viscosity for the 800 MPa s, by formula : (CH3)2 SiO2/2 siloxane units expressed 94.0 mole %, type: CH3 SiO3/2 siloxane units expressed by the 3.3 mol %, type : (CH3)3 SiO1/2 siloxane units expressed by the 2.0 mol %, of the formula : (CH3)2 (CH2 =CH) SiO1/2 said siloxane units of 0.7 mol % a liquid organopolysiloxane instead of liquid organopolysiloxane (I) other than, other embodiment 1 similarly modulation smectically polysiloxane composition.
[39][Comparative example 1]
[40]Embodiment 1 in, in addition to the viscosity for the 110 MPa s, the end of the molecular chain with trimethyl silyl oxygen radical sealed end linear dimethyl polysiloxane instead of liquid organopolysiloxane (I) other than, other embodiment 1 similarly, but can't make smectically polysiloxane composition.
[41][Comparative example 2]
[42]Embodiment 1 in, in addition to the viscosity for the 350 MPa s, the end of the molecular chain with trimethyl silyl oxygen radical sealed end linear dimethyl polysiloxane instead of liquid organopolysiloxane (I) other than, other embodiment 1 similarly, but can't make smectically polysiloxane composition.
[43][Comparative example 3]
[44]Embodiment 1 in, in addition to the viscosity for the 1,000 MPa s, the end of the molecular chain with trimethyl silyl oxygen radical sealed end linear dimethyl polysiloxane instead of liquid organopolysiloxane (I) other than, other embodiment 1 similarly to, but can't make smectically polysiloxane composition.
[45][Comparative example 4]
[46]Embodiment 2 in, in addition to the viscosity for the 110 MPa s, the end of the molecular chain with trimethyl silyl oxygen radical sealed end linear dimethyl polysiloxane instead of liquid organopolysiloxane (I) other than, other embodiment 2 similarly, but can't make smectically polysiloxane composition.
[47][Comparative example 5]
[48]Embodiment 2 in, in addition to the viscosity for the 1,000 MPa s, the end of the molecular chain with trimethyl silyl oxygen radical sealed end linear dimethyl polysiloxane instead of liquid organopolysiloxane (I) other than, other embodiment 2 similarly, but can't make smectically polysiloxane composition.
[49][Comparative example 6]
[50]In the embodiment 2 in, in addition to the viscosity for the 900 MPa s, by formula : (CH3) (C12 H25) SiO2/2 siloxane units expressed 48.0 mol %, type : (CH3) (C14 H29) SiO2/2 siloxane units expressed 48.0 mol % formula (CH3)3 SiO1/2 siloxane units expressed by the 4.0 mol % a liquid organopolysiloxane instead of liquid organopolysiloxane (I) other than, other embodiment 2 similarly modulation smectically polysiloxane composition.
[51][Comparative example 7]
[52]Inputs to the planetary mixer viscosity of the 350 MPa s, the end of the molecular chain with trimethyl silyl oxygen radical sealed end linear dimethyl polysiloxane of 95 parts by weight, an average particle size of 5.0 the quartz powder crushing m 600 parts by weight, and as the aforesaid powder of surface-treating agent decyl trimethoxysilane 5 parts by weight, after the stirring, the stirring at room temperature under reduced pressure for 30 minutes, modulation smectically polysiloxane composition.
[53][Comparative example 8]
[54]In the embodiment 3 in, in addition to the viscosity for the 950 MPa s, by formula : (CH3) {CH2 CH (CH3) C6 H5} SiO2/2 siloxane units expressed by 20.0 mol %, type (CH3) (C14 H29) SiO2/2 siloxane units expressed by the 4.0 mol % formula : (CH3)3 SiO1/2 siloxane units expressed 76.0 mol % a liquid organopolysiloxane instead of liquid organopolysiloxane (I) other than, the embodiment of other and 3 similarly to, but not able to obtain polysiloxane composition smectically.
[55][Comparative example 9]
[56]In the implementation of the example 4 in, in addition to the viscosity for the 95OmPa s, by formula : (CH3) {CH2 CH (CH3) C6 H5} SiO2/2 siloxane units expressed by 20.0 mol %, type (CH3) (C14 H29) SiO2/2 siloxane units expressed by the 4.0 mol %, of the formula : (CH3)3 SiO1/2 siloxane units expressed 76.0 mol % a liquid organopolysiloxane instead of liquid organopolysiloxane (I) other than, the embodiment of other and 4 similarly modulation smectically polysiloxane composition.
[57][Comparative example 10]
[58]In the embodiment 5 in, in addition to the viscosity for the 950 MPa s, by formula : (CH3) {CH2 CH (CH3) C6 H5} SiO2/2 siloxane units expressed by 20.0 mol %, type : (CH3) (C14 H29) SiO2/2 siloxane units expressed by the 4.0 mol % formula (CH3)3 SiO1/2 siloxane units expressed 76.0 mol % a liquid organopolysiloxane instead of liquid organopolysiloxane (I) other than, the embodiment of other and 5 similarly modulation smectically polysiloxane composition.
[59][Comparative example 11]
[60]In the implementation of the example 6 in, in addition to the viscosity for the 950 MPa s, by formula : (CH3) {CH2 CH (CH3) C6 H5} SiO2/2 siloxane units expressed by 20.0 mol %, type (CH3) (C14 H29) SiO2/2 siloxane units expressed by the 4.0 mol % formula : (CH3)3 SiO1/2 siloxane units expressed 76.0 mol % a liquid organopolysiloxane instead of liquid organopolysiloxane (I) other than, the embodiment of other and 6 similarly modulation smectically polysiloxane composition.
[63]Furthermore, table, after the heat resistance test, the consistency of the "-" value in said as the polysiloxane composition smectically is solidified in the heat resistance test, the consistency can not measure.
[64]The possibility of industrial utilization
[65]Polysiloxane composition smectically of the present invention, characterized in that containing thickening agent can be a large amount, and has good heat resistance.
