TW512162B - Zinc oxide-filled addition-curable silicone rubber compositions - Google Patents

Abstract

A zinc oxide-filled addition-curable silicone rubber composition comprises (A) a diorganopolysiloxane containing at least two alkenyl groups in its molecule, (B) an organohy-drogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in its molecule, (C) a platinum family metal catalyst, and (D) a zinc oxide powder surface treated with a tetraalkoxy silane and/or a partial hydrolysis-condensation product thereof. The composition can further comprise (E) a high thermal-conductive filler. The composition scarcely generates hydrogen gas during storage so as to have an excellent storage stability and provides a cured product excellent in heat resistance, electrical insulating properties, and adhesion to various metals, semiconductors, etc. while keeping good physical properties as a rubber. Further, the composition is easy to deal with and provides a cured product with a high thermal-conductivity and also excellent mechanical properties without lowering adhesion and requiring redispersia compoundven when filled with a high thermal-conductive filler.

Description

512162 Supplementary A7 B7 V. Description of the invention (0 The present invention is related to the practical use of the addition reaction hardened polysiloxane rubber composition and its hardened zinc oxide. (Please read the precautions on the back before filling in this Page) In the prior art, it is known that the silicone rubber composition is filled with zinc oxide to improve the hardening promotion, heat resistance and electrical insulation of the hardened material, etc. In the prior art, the zinc oxide is filled with The millable silicone rubber composition crosslinked and cured after the organic peroxide is carried out by the room temperature curing (RTV) silicone rubber composition which is crosslinked and cured after the polycondensation reaction. It is carried out by cross-linking and curing type silicone rubber composition after additional reaction. The reason is that zinc oxide is added to the addition reaction-hardening type silicone rubber composition as a crosslinking agent and contained in the composition. The organohydrogenpolysiloxane will generate hydrogen gas after reacting with the basic zinc oxide, and the generated composition will foam due to the generation of hydrogen gas, which will cause the internal pressure of the container containing the composition to rise and the container to break. Of Dangerous. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the addition reaction hardening silicone rubber composition is different from the polycondensation reaction hardening RTV silicone rubber composition, which does not need to be hardened for a long time, and it is sealed at high temperature. In the state, the so-called reversion is not caused by the cracking of the polysilicone, which is also a benefit. Therefore, using this advantage, it can be expected to improve its characteristics by filling with zinc oxide. The hardened product of the reinforced hardened silicone rubber composition of the prior art has insufficient adhesion to various metals and semiconductors such as nickel, aluminum, polysiloxane, and copper (especially copper and copper oxide). It is highly anticipated that the adhesion is improved. Therefore, the object of the present invention is to provide a method that generates less hydrogen during storage, has good storage stability, and maintains good rubber properties while applying Chinese national standards for this paper size ( CNS) Α4 specification (210X297 mm) -4- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 512162 A7 __ B7_ V. Description of the invention (2) Heat resistance, electrical Those with good adhesion, hardened materials such as various metals, semiconductors, etc. are those filled with zinc oxide addition reaction hardening type silicone rubber composition. The present invention provides a molecule selected from (A) containing at least two chains in one molecule Alkenyl bisorganopolysiloxane, (B) Organic silicon polysiloxane containing at least two hydrogen atoms in a molecule of silicon, (C) platinum group metal catalyst, trans (D) tetraalkoxy Silane-filled zinc oxide addition reaction hardening type polysiloxane composition containing zinc oxide powder as a surface treatment on at least one compound in a group consisting of partially hydrolyzed polymer of tetrasilane and tetraalkoxysilane, and the composition A hardened product obtained by curing a material. [Forms of Implementing the Invention] The present invention will be described in more detail below. (A) Alkenyl group-containing diorganopolysiloxane The alkenyl group-containing diorganopolysiloxane used in the present invention An alkane-based molecule containing at least two bond groups is 'so'. The general main bond portion is basically composed of one > organic siloxane units. At the same time, both ends of the molecular chain are composed of three organic polysiloxanes. Alkyl-blocked linear ones, which are contained in some molecular structures It may be a branched structure or a ring. However, from the physical properties such as the mechanical strength of the hardened material, a linear two-organic polysiloxane is preferred. The alkene can be bonded based on either the silicon atom at the end of the molecular chain or the silicon atom in the middle of the molecular chain, or it can be bonded to the two. However, from the physical properties of the hardened material, etc. Alkenyl groups of silicon atoms at both ends of the molecular chain are preferred. As a representative example of the two organic polysiloxanes containing this alkenyl group, if the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -5- I—J — * ------ -1 ------ Order——ml (Please read the precautions on the back before filling this page) 512162 A7 B7 V. Description of the invention (3) The following ~ general formula (1) [化 1 R1 X— | iOhSiO. R1 R1

Jnl

-SiO 4—Si—X (1) X R1 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (where 'R1 is a non-substituted or substituted monovalent hydrocarbon group without an aliphatic unsaturated bond alone, X is a chain Alkenyl, n is an integer of 0 or more, and m is an integer of 0 or more.) Examples of two examples of organic polysiloxanes. Examples of the unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond in R 1 in the general formula (1) include methyl, ethyl, and propyl. , Isopropyl, butyl, isobutyl, 3-butyl, pentyl, neogyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl and other alkyl groups; cyclopentyl, cyclo Hexyl, cycloheptyl and other cycloalkyl groups; phenyl, tolyl, xylyl, naphthyl, biphenyl and other aryl groups; benzyl, phenethyl, phenylpropyl, methylbenzyl and other aralkyl groups And at least part of the carbon atoms bonded to this group are hydrogen atoms such as fluorine, chloro, bromine, and other substituted atoms, such as cyano, chloromethyl, 2-bromoethyl, and 3-chloropropyl. , 3 3-trifluoropropyl, chlorophenyl, Mbenzyl, cyanoethyl, 3,3,4,4,5,5,6,6'6-nonfluorohexyl and the like. In this monovalent hydrocarbon group, those having 1 to 12 carbon atoms, especially 1 to 8 are represented by methyl, ethyl, propyl, chloromethyl, bromoethyl, 3,3,3-trifluoropropyl, Non-substituted or substituted alkyl with 1 to 3 carbon atoms such as cyanoethyl, phenyl, chlorophenyl, and fluorophenyl, etc. This paper is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 6 -丨 ϊ ------- ^ — (Please read the notes on the back before filling out this page) Order 512162 A7 B7 ----------------- 5. Description of the invention (4 ) Substituted or substituted phenyl is preferred. (Please read the precautions on the back before filling this page) Alkenyl of X in general formula (1) For example: vinyl, allyl, propenyl, isopropenyl, butanyl, hexenyl, cyclohexene Basically, those having 2 to 8 carbon atoms are preferred, and lower alkenyl groups such as vinyl and allyl are preferred. In the general formula (1), η is an integer of 0 or more, and m is an integer of 0 or more. In addition, η and m are preferably an integer of 10Sn + mS 10,000, more preferably 50 ^ n + mS 2,000, and 〇Sm / (n + m) SO · 2 integer. The two organopolysiloxanes containing this alkenyl group have a viscosity of 10 to 1,000, 000 cs at 25 ° C, especially 100 to 500,000 cst. (B) Organic Hydrogen Siloxanes The Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives, printed the organic hydrogen polysiloxanes used in the composition of the present invention to contain at least two, preferably three or more molecules. Those who cut the gas atom of the atom (that is, S i fluorenyl) may be linear, branched, cyclic, or resinous with a three-membered network structure. For example, the average composition formula (2) of the organic hydrogen polysiloxane is as follows:

Ha R2bS i 〇 (4-ab) / 2 (2) (In the formula, R 2 is an independent non-substituted without aliphatic unsaturated bond. The paper size is applicable to Chinese National Standard (CNS) A4 specification (21〇'〆 297 mm) -7-^ 2162 A 7 B7 V. Description of the invention (5) or substituted monovalent hydrocarbon group, a and b are 0 < a < 2, 0.8Sb S2 and 0 · 8 < a + bS3 Among them, the preferred one is the number of 0. 02 $ a ^ l, 1.5SbS2, and 1.8Sa + bS2.7.) The example of the organopolysiloxane. In the formula, an example of an unsubstituted or substituted monovalent hydrocarbon group which does not contain an aliphatic unsaturated bond in R 2 is the same as the example shown by R 1 in the general formula (1), and represents a carbon number of 1 to 10. In particular, 1 to 7 are preferred, and lower alkyl groups having 1 to 3 carbon atoms such as methyl, phenyl, and 3,3,3-trifluoropropyl are preferred. Examples of the organohydrogenpolysiloxane include: 1,1,3,3-tetramethyldisilaxane, 1,3'5,7-tetramethyltetrasiloxane, 1,3 Siloxane oligomers such as 5,7,8-pentylmethylpentacyclosilane, etc .; dimethyl sand oxygen radicals at both ends of the molecular chain block the methyl hydrogen poly sand oxygen radicals, and tertiary methyl at both ends of the molecular chain Siloxane blocks dimethylsiloxane and methylhydrosiloxane copolymer, silanol groups at both ends of the molecular chain block methylhydropolysiloxanes, silanol groups at both ends of the molecular chain block dimethylsiloxanes Alkane • methylhydrosiloxane copolymer, dimethylhydrosiloxane blocked at the end of the molecular chain, dimethylpolysiloxane, dimethylhydrosiloxane blocked at the end of the molecular chain, methylhydropolysiloxane blocked Dimethyl hydrosiloxane blocked at both ends of the molecular chain dimethyl siloxane • methyl hydrosiloxane copolymer; etc .; R2 (H) S i 〇1 / 2 units and S i〇4 / 2 units Composition, including arbitrary R 3 S i 0 i / 2 units, R 2 (H) Si 〇 2/2 units, R (H) Si 〇 2/2 units, (H) S i 〇 3/2 units, or RS i 〇3 / 2 units of polysiloxane resin (however, in the formula, R and the R 1 Substituted or substituted monovalent hydrocarbon groups are the same.) For other examples, the following formulas are used: The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 8 _ (Please read the precautions on the back before filling in this Page), τ Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 512162 A7 B7 V. Description of the invention (6 [Chemical 2] .ch3 ch3 ch3 CH3 CH3 i 1 1 H—Si—〇—Si—O—Si—H H_si —〇—Si—Η 1 1 ch3 1 ch3 1 CH3, 1 I.?? J * Η_si -〇-Si —H 1 1 ch3 'ch3 H. H CH3 1 1 1 J CH3 CH3, H—Si-1- 〇—Si—O · 1. 1 1—3 | ———— O—Si—〇1 1 1 1 I 9h3 CH—, CsH5 CH3 CHn I CeHg CH3, etc. The examples shown are used in the composition of the present invention The organohydrogenpolysiloxane can be obtained by a known method, and is selected from the following general formula: R 2 S i HC 1 and

R

SHC 1 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where R2 is the same as above.) After co-hydrolysis of at least one chlorosilane or the chlorinated sand The compound is selected from the following general formula: (In the formula, R2 is the same as the above.) At least one chlorosilane is combined with each other and obtained by common hydrolysis. In addition, the organohydrogen polysiloxane can be co-hydrolyzed to obtain a polysiloxane balance. The amount of component (B) is based on the silicon atom in the organohydrogenpolysiloxane of component (B) when the content of component (A) is 1 mol of the alkenyl group in the organic polysiloxane containing alkenyl groups. The hydrogen atom (that is, the Si fluorenyl group) is usually in an amount of 0.5 to 4 moles, preferably in an amount of 1 to 2.5 moles. C) Platinum group metal catalyst

The platinum metal catalyst used in the present invention is a promoting component (A The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -9- 512162 A7 _______B7 V. Description of the invention (7) (Please read the back first (Notes to fill in this page again) The alkenyl group and the hydrogen atom of the silicon atom bound to the component (B) are used as catalysts for the hydrosilylation reaction (addition reaction), and used as the catalyst for the hydrosilylation reaction For example, well-known catalysts. Specific examples include platinum group metal monomers such as platinum (including platinum black), rhodium, and palladium; H2PtCl4 * nH2〇, H2PtCl6 * nH2〇, NaHPtCl6 * nH2〇, ΚΗΡΐ0ΐ6 · ηΗ20, NaePtCle ^ nHeO K2PtCl4 * nH2〇, P t C 1 4 · η Η 2 〇, P t C 1 2. Na2HPtCl4 * nH2〇. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where h is an integer from 0 to 6, The preferred ones are 0 or 6.), such as platinum chloride, chloroplatinic acid, and chloroplatinate; alcohol-denatured chloroplatinic acid (reference book of US Patent No. 3,220,972): chloroplatinic acid and Complexes of olefins (Detailed US Patent No. 3,159,601 Book, as detailed in No. 3,159,662, and referenced in No. 3, 7 7 5, 4 5 2); platinum group metals such as platinum black and palladium are supported on aluminum oxide powder, silicon dioxide Carriers such as carbon and carbon; rhodium-olefin complexes; chlorotris (triphenylphosphine) rhodium (Geoffrey Wilkinson Cuihua agent): chloroplatin, chloroplatinic acid or chloroplatinate and vinylsiloxane In particular, it is an example of a complex with a vinyl-containing cyclic siloxane. The amount of the component (C) can be a so-called catalyst amount. Generally, platinum is converted by the total amount of the component (A) and the component (B). Group metals with a weight of 0. 1 to 500 ppm, especially 0. 5 to 200 ppm (D) are partially hydrolyzed in tetraalkoxysilanes and / or tetraalkoxysilanes. This paper size applies to Chinese national standards (CNS) A4 specification (210X297 mm) 512162 A7 B7 V. Description of the invention (8) Zinc oxide powder after surface treatment on the polymer (Please read the precautions on the back before filling this page) The oxidation used in the present invention Zinc powder is prepared by using tetraalkoxysilane and / or tetraalkoxysilane partially hydrolyzed polycondensate as surface treatment. After the surface treatment, the addition reaction hardening type silicone rubber composition containing zinc oxide is the factor to be considered because of the alkalinity of zinc oxide powder and reducing the dehydrogenation reaction of organic polysiloxane. Therefore, (D) The ingredients in the preservation of the composition of the present invention can prevent foaming, and prevent the container containing the composition from rising in the container from rising in internal pressure. Furthermore, the composition can have properties such as heat resistance and electrical insulation. By. .① Tetraalkoxysilane and / or tetraalkoxysilane partially hydrolyzed polycondensate. The tetraalkoxysilane used in the present invention is as follows:

Si (OR3) 4 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (where R 3 is an independent non-substituted or lower alkoxy-substituted alkyl group). As the unsubstituted or lower alkoxy substituted alkyl group of R 3 in the formula, such as: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 3-butyl, pentyl, Neopentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, etc., and general carbon numbers such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl 1 to 12 are preferred, and 1 to 6 are preferred. The partially hydrolyzed polycondensate of the tetraalkoxysilane has an average composition as shown below. This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) _ _ _ 512162 A7 B7 _ V. Description of the invention (9)

[(R3〇) 3Si〇l / 2] K [(R3〇) 2Si〇2 / 2] L [(R3〇) Si〇3 / 2] M [Si〇4 / 2] N (Please read the Please fill in this page again) (where R3 is the same as above, K'L'M and N are K + L + M + n = 1, 0.002SKS1, O ^ L ^ O. 998, 〇 SMS〇 · 998 and OSN ^ O · 35.) Representative examples, such as the following general formula (3): R 3 0-[S i (OR3) 2 0) j-R 3 (3) (wherein R3 is the same as above, j is 1 or more, generally 2 to 1,000, and preferably an integer of 3 to 500.) The weight average molecular weight of the tetraalkoxysilane and / or its split hydrolyzed polycondensate is preferably from 150 to 100,000. ② Zinc oxide The zinc oxide powder printed and surface-treated by the Employees' Cooperative Cooperative of the Economic and Intellectual Property Bureau can be used by publicly known persons, and the more ideal one is J I S with a high purity. The average particle size of zinc oxide powder is usually from 0.05 to 10 / zm, and it can be appropriately selected according to its application. ③ Surface treatment As the surface treatment method, a known wet treatment method or dry treatment method can be used. As a specific example of the surface treatment method, for example, after dissolving or dispersing the tetraalkoxysilane and / or a part of the hydrolyzed polycondensate of the tetraalkoxysilane with an appropriate solvent, the zinc oxide powder is added to the solution or The paper size in the dispersion is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). 12- '512162 A7 B7 V. Description of the invention (1〇) (Please read the notes on the back before filling this page) Mix After 'heating and drying method. Examples of the solvent include toluene, dimethylbenzene, and the like. For heating and drying conditions, it is recommended to do it at 80 ~ 200 ° C for 0 ~ 5 ~ 10 hours. Also 'other surface treatment methods such as: Partially hydrolyzed polycondensates of zinc oxide powder and tetraalkoxysarane and / or tetraalkoxysilane, plus at least a part of the (A) component (usually 30 weight % Or more, especially 50 to 100% by weight)-after mixing, the method of heating the obtained mixture. The heating conditions are 80 ~ 2 0 0 t: 0.5 ~ 10 hours. This surface treatment method in which zinc oxide powder is mixed with a tetraalkoxysilane and / or a partially hydrolyzed polycondensate of tetraalkoxysilane and at least a part of the component (A) does not require the addition of a solvent and a drying process. It is directly used in the mixing or kneading process of various ingredients when manufacturing the present invention, so it can effectively save energy and shorten engineering time. The used amount of the tetraalkoxysilane and / or the tetraalkoxysilane split hydrolyzed polycondensate can be appropriately adjusted according to the specific surface area and other properties of the zinc oxide powder. Generally, 100 parts by weight of zinc oxide powder It is preferably from 0.1 to 20 parts by weight. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The above surface treatment forms a siloxane film on the surface of the zinc oxide powder to prevent affecting the salinity of the zinc oxide powder. The amount of zinc oxide powder after the surface treatment is generally 5 to 3 0 0 parts by weight when the alkenyl-containing diorganopolysiloxane containing the component (A) is 100 parts by weight, and more preferably 10 to 2 0 0 parts by weight. If the amount is too small, the heat resistance and electrical insulation of the hardened material obtained will be insufficient. On the contrary, when the amount is too large, a zinc-filled zinc oxide addition-reaction-hardened silicone rubber will be obtained. 13- This paper is applicable to China. Standard (CNS) A4 specification (210X297 mm) 512162 A7 B7 V. Description of the invention (11) After the viscosity of the composition increases, the fluidity becomes worse. (Please read the notes on the back before filling this page) Other ingredients In addition to the ingredients (A), (B), (C), (D) of the composition of the present invention, humid silica, Reinforcing inorganic concrete fillers such as humidified titanium dioxide; non-reinforcing inorganic concrete fillers such as calcium silicate, titanium dioxide, second iron oxide, and carbon black; hardening inhibitors (such as acetylene alcohol, etc.), etc. The addition amount of the inorganic filler is usually 0 to 10 parts by weight when the total amount of the ingredients (A) to (D) is 100 parts by weight. Furthermore, for the purpose of improving the adhesiveness of the composition in the composition of the present invention, in addition to the ingredients (A) to (D), an epoxy group-containing polysiloxane compound or ester may be added if necessary. Siloxane compounds (that is, those in which the monovalent radicals bound to the silicon atom are all alkoxy or hydrogen atoms, and the molecule does not contain a silicon-carbon bonded organic siloxane compound). The addition amount of these siloxane compounds is usually one of the components (A) to (D) in a total amount of 100 to 10 parts by weight. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

塡 Zinc oxide addition reaction hardening type silicone rubber composition and its hardened product The composition of the present invention is basically obtained by mixing and kneading the components (A) to (D) and additional components used when necessary . However, before use, it is the same as the general hardening silicone rubber composition. For example, the two components of the components (A), (C), and (D) and the components (A) and (B) are the components (A) to (D). ) Is divided into two liquids, and when used, two liquids are mixed to harden into a two-liquid composition. In addition, -14- obtained from the other surface treatment method mentioned above is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 512162 Α7 Β7 " mini1 丨 || ............ ........................................ ........... 111111 ............................ ........................................ ........................................ ........................................ ................................. V. Explanation of the invention ( 12) (Please read the notes on the back before filling this page) Zinc oxide powder and tetraalkoxysilane and / or tetraalkoxysilane partially hydrolyzed polycondensate and at least part of the (A) component mixed with ( When the mixture is buried under heating), it can also be made into a two-liquid composition with one fluid and other ingredients. In addition, after mixing the components (A) to (D), a small amount of a hardening inhibitor (such as acetylene alcohol, etc.) is further added to mix into a so-called one-liquid composition. The cured product of the present invention is obtained by curing the composition. The hardening conditions may be the same as those of the known addition-reaction hardening type silicone rubber composition, and it may be heated if necessary for sufficient hardening at room temperature.用途 Application of zinc oxide addition reaction hardening type silicone rubber composition The composition of the present invention has good rubber physical properties (hardness, tensile strength, stretchability, etc.) as a hardened material, excellent heat resistance and electrical insulation, and various Metals or semiconductors, especially copper and copper oxides, have good adhesion. It can be effectively used as insulators for electrical appliances, electronic parts, adhesives and protective coating agents for semiconductor devices, and ceramic manufacturing agents. Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Example] Example 1 The general formula (4)

Vi (Me) 2Si (OSiMe2) n〇Si (Me) 2Vi (4) (where Me is methyl, Vi is vinyl, and η are as shown in this formula. -15- This paper size applies to Chinese national standards (CNS ) A4 specification (210X297 mm) 512162 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (^ The organopolysiloxane at 25 ° C has a viscosity of 5,000 c S t. 90% by weight of the linear organopolysiloxane containing a vinyl group shown in ()). In the general formula (4), η is a linear form having a viscosity of 100, 000 cSt at 25 ° C. 10 parts by weight of organopolysiloxane, 100 parts by weight of zinc oxide (average particle size: 0.3 μm) (made by Mitsui Metals Co., Ltd.) with a single purity of j I s, and 2 parts by weight of triethoxysilane After mixing with 3 kinds of rollers, use a planetary mixer to mix the mixture for 3 hours at 160 ° C. To this mixture, add methyl hydrogen polysand oxygen institute [combination Content of hydrogen atom (S i fluorenyl) in sand atom: 0.8 mole / 100 g] 2 parts by weight and octanol modified solution of chloroplatinic acid (platinum content: 2% by weight) 0 · 〇 After 2% by weight After mixing, a curable silicone rubber composition was obtained. The viscosity of the composition (viscosity at 25 ° C, the same applies hereinafter) was measured with a B-type rotational viscometer, and was 2 7 5 P (poise). The composition measures the conductivity of the extracted water, the amount of hydrogen produced, the physical properties of the hardened rubber (hardness, tensile strength, elongation), the electrical characteristics (volume resistivity) of the hardened, the adhesion of the hardened, and the resistance The heat resistance of the compound was observed, and the foaming condition of the hardened product was also observed. The conductivity of the extracted water was 20 parts by weight of the composition, 40 parts by weight of special toluene, and 100 parts by weight of pure water. After shaking for an hour, it was allowed to stand still, so that the water phase was collected. The water conductivity (# S / cm) of the collected water was measured with a conductivity meter. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) ) (Please read the notes on the back before filling this page)

-16- 512162

A7 B7 V. Description of the invention (^ Μ gas generation (please read the precautions on the back before filling in this page) 5 g of this composition is sealed in a head space bottle of 5 0 0 J, and left to stand at room temperature for 4 8 hours The amount of hydrogen generated in the bottle was determined by gas chromatography. The rubber physical properties of the hardened product. The composition was flowed into a mold of 150 mm X 100 mm X 2 mm. After this vacuum defoaming, 1 After heating at 50 ° C for 4 hours, a flaky hardened material was obtained. The obtained hardened material was measured for hardness, tensile strength, and elongation based on JISK 6301. In addition, the hardness was measured using a spring-type hardness tester type A. Electrical characteristics of the hardened material The composition is flowed into a mold of 150 mm X 100 mm X 1 mm. After being degassed in a vacuum, the composition is heated for 4 hours at 150 t to obtain a sheet-like hardened product. The obtained hardened product was measured for volume resistivity based on JIS c 2 1 2 3. The heat resistance of the printed hardened product printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs was the same as that of the user of the rubber physical property measurement. 0 t: Hard after heating for 24 hours And the hardness after heating for 48 hours at the same temperature is measured based on JISK 6 3 01 (used by spring-type hardness tester A). Adhesion of hardened material This paper applies Chinese national standard (CNS) A4 specification (210X297 mm) -17- 512162 A7 B7 V. Description of the invention (15) Composition of nickel in 1 Ommx 1 0 Ommx 1mm, (Please read the precautions on the back before filling this page) Aluminum, polysilicon Oxygen, copper, and acid-corroded copper plates were degassed in a vacuum and heated at 150 ° C for 4 hours to obtain a sheet-like hardened product. A small amount of spoon was used for the obtained hardened product. During this peeling, observe the ratio (area ratio) of the part of the cohesive failure (the cross section of the hardened object being destroyed) and the part of the interface peeling (the broken interface of the hardened object and the substrate), and evaluate the adhesion. 〇: Cohesive failure rate exceeding 80%, with strong adhesion. △: Cohesive failure rate of 20 to 80%, with adhesiveness. X: Cohesive failure rate of 20% or less, almost non-adhesive The foaming state of the hardened material is the same as that used for measuring the physical properties of the rubber. The flaky hardened product was visually observed for the presence or absence of blistering. Example 2 Partially hydrolyzed polycondensate of tetraethoxysilane (S i 0 2 content: 40% by weight printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs) A polysiloxane rubber composition was obtained in the same manner as in Example 1 except that [Kolcode (Company) 's product name ethyl polyoxalate 40 T]] was used in place of 2 parts by weight instead of tetraethoxysilane. The viscosity of this composition was measured with a B-type rotational viscometer to be 2 3 3 P (poise). Various functions were measured for the obtained composition according to the method described in Example 1. -18- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 512162 A7 B7 V. Description of the invention (16) Example 3 Partially hydrolyzed polycondensate with tetramethoxysilane [weight average molecular weight ( M w): 788] A curable polysiloxane rubber composition was obtained in the same manner as in Example 1 except that 2 parts by weight was substituted for tetraethoxysilane. The viscosity of this composition was measured by a B-type rotary viscometer to be 2 4 6 P (poise). Various functions were measured according to the method described in Example 1 for the obtained composition. Example 4 The 2 parts by weight of methyl hydrogen polysand oxygen institute was changed to 1 part by weight, and the methyl hydrogen polysilicon containing the following epoxy group was used. Oxane: (Please read the precautions on the back before filling in this page) | -fCH2) 3〇CH2CH -CH2 -Si—〇Ι CH3 Η I -Si 〇Ι CH3 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in addition to 1 weight A curable polysiloxane rubber composition was obtained in the same manner as in Example 1 except for the other parts. The viscosity of this composition was measured by a B-type rotational viscometer to be 2 6 0 P (poise). According to the obtained composition, various functions were measured according to the method described in Example 1. Comparative Example 1 The following formula is applicable to the Chinese National Standard (CNS) A4 specification (210X297 public director) -19- 512162 A7 __________ B7_ 5. Description of the invention ( 17) (Me) 3Si- [OS (Me) 2] xNH [Si (Me) 2〇] y-Si (Me) 3 (Please read the precautions on the back before filling this page) (where, M. e Except that the average x + y of methyl, X and y is 30.), except for 28 parts by weight of the silyloxysilamine compound instead of tetraethoxysilane. A hardening polymer was obtained in the same manner as in Example 1. Silicone rubber composition. The viscosity of this composition was measured with a B-type rotational viscometer to be 15 5 P (poise) °, and then various functions were measured according to the method described in Example 1 for the obtained composition. Comparative Example 2 3 parts by weight of hexamethyldisilazane A curable silicone rubber composition was obtained in the same manner as in Example 1 except that the tetraethoxyalkylene was replaced. The viscosity of this composition was measured by a B-type rotational viscometer to be 280 P (poise). The obtained composition was measured for various functions according to the method described in Example 1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Comparative Example 3 A curable silicone rubber composition was obtained in the same manner as in Example 1 except that 2 parts by weight of triethoxymethylsilane was used instead of tetraethoxysilane. The viscosity of the mixture was measured using a B-type rotational viscometer to be 2 8 3 P (poise). The obtained composition will be used to determine its various functions according to the method of the example. 0 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 2〇- 512162 A7 ______ B7 V. Description of the invention (18) Comparative Example 4 A curable polysand rubber composition was obtained in the same manner as in Example 4 except that zinc oxide was not used. The viscosity of this composition was measured with a B-type rotational viscometer to be 4 Ο P (poise). Then, the obtained composition was measured for various functions b in place of Example 1. The above results are shown in Tables 1 and 2. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-21-This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 512162 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by a consumer cooperative V. Description of the invention (19) [Table 1] Example 1 Example 2 Example 3 Example 4 Viscosity (P) 275 233 246 260 Extraction water conductivity (// s / cm) 2 2 2 2 Amount of hydrogen produced (// 1 / g) 21 19 20 21 Hardness (JIS-A) 49 47 47 48 Tensile strength (kgf / cm2) 52 45 50 50 Elongation (%) 155 140 145 150 Volume resistivity (Ω cm ) lx 1016 9x ΙΟ15 8x 1015 lx 1016 resistance to 250 ° C / 24hr 57 57 57 56 heat hardness 250 ° C / 72hr 66 65 67 66 hardness foaming presence or absence Μ te JIW M ji adhesion / 4hr later) Ni 〇o 〇o A1 〇〇〇〇〇〇oooo Cu 〇〇oo Cu (after acid corrosion) 〇〇〇〇 (Please read the precautions on the back before filling out this page) This paper size applies to China National standard (CNS) A4 specification (21〇 ×: 297mm) -22- 512162

7 B Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of Invention (20) [Table 2]

Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Viscosity (P) 155 280 283 40 Conductivity of extracted water (// s / cm) 2 3 3 2 Hydrogen generation amount (// 1 / g) 20 100 120 10 Hardness (JIS-A) 35 47 47 19 Tensile strength (kgf / cm2) 20 51 50 5 Elongation (%) 160 170 150 200 Volume resistivity (Ω cm) 5x 1015 7χ ΙΟ15 8χ 1015 7χ ΙΟ14 7Π 1 250 ° C resistant / 24hr 45 57 57 Occurrence of non-measurable hardness and fixed cracking 250t: / 72hr 55 69 69 Identical hardness foaming with or without slight M adhesion (after 150 ° C / 4hr) Ni XXX 〇A1 XXX 〇 Si Δ X Δ 〇 Cu XXXX Cu (after acid rot uranium) XXXX (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -23- 512162 A7 _____B7_ 5. Description of the invention (21) Although the present invention contains zinc oxide, almost no hydrogen is generated during storage, so it can provide a practical type of addition-reaction-hardened polysiloxane rubber with excellent security and qualitative properties. At the same time, the composition not only maintains good rubber properties (hardness, tensile strength, elongation, etc.) after hardening; it also shows excellent heat resistance and electrical insulation, and it is difficult to adhere to various metals, semiconductors, etc., especially in the prior art Copper and copper oxide are both hardened with excellent adhesion. Furthermore, the surface treatment method of zinc oxide in the present invention can save the energy and shorten the engineering time in the manufacturing process of the composition. (Please (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -24- This paper size applies to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

512162 6. Scope of patent application1. A kind of addition reaction hardening type silicone rubber group filled with zinc oxide, which is characterized by containing (please read the precautions on the back before filling this page) (A) 1 molecule Organopolysiloxane containing at least two alkenyl groups, (B) Organopolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule, (c) Platinum group metal catalyst and (D) At least one compound selected from the group consisting of tetraalkoxysilane and tetraalkoxysilane partially hydrolyzed polycondensate as a surface-treated zinc oxide powder, wherein for each mole of the component (A), For the alkenyl group, the SiH group in the (B) component is 0.5 to 5 moles, and for the total amount of the (A) and (B) components, the weight of the platinum group metal of the (C) component is converted to 0. 1 to 1,000 ppm, and (D) component is 5 to 300 parts by weight per 100 parts by weight of component (A). 2 · A kind of hardened product, which is obtained by hardening the addition reaction hardening type silicone rubber composition group of zinc oxide filled with zinc oxide in item 1 of the patent application scope. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 25- This paper size applies to China National Standard (CNS) A4 (210X297 mm)