Addition curable silicone rubber compositions, their preparation and use

Abstract: An addition reaction curing type silicone rubber composition comprising (A) an alkenyl-containing diorganopolysiloxane, (B) an alkaline earth metal carbonate powder surface treated with a diorganopolysiloxane, (C) an organohydrogenpolysiloxane, and (D) a platinum group metal catalyst has improved storage stability in that it gives off little or no hydrogen gas during storage. The composition has improved adhesion and a good ability to protect electric or electronic parts from corrosion and finds typical use in the sealing of electric or electronic parts.

Description: This invention relates to a silicone rubber composition of the addition reaction curing type loaded with alkaline earth metal carbonate powder and a method for preparing the same. BACKGROUND In the prior art, alkaline earth metal carbonate powder is used in combination with rubbers for the purposes of improving the heat resistance and electrical insulation of silicone rubber and the acid resistance of cured rubber. Most often, the alkaline earth metal carbonate powder is used in millable silicone rubber compositions relying on organic peroxide crosslinking and RTV silicone rubber compositions relying on condensation crosslinking. However, it is not used in silicone rubber compositions relying on addition reaction crosslinking. The reason is that customary alkaline earth metal carbonate powder used as a filler is alkaline and can react with an organohydrogenpolysiloxane contained as the crosslinking agent in silicone rubber compositions of the addition reaction curing type, giving off hydrogen gas. The evolution of hydrogen gas causes the composition to foam during shelf storage or boosts the internal pressure of a container having the composition received therein, with the danger of eventual rupture of the container. In the prior art, US 6043309 describes addition-curable silicone rubber compositions, intended for electrical insulation, in which powdered aluminium hydroxide is combined with powdered metal carbonate or metal hydrogen carbonate to improve high-voltage insulation. Carbonates used include barium, calcium and magnesium carbonates. Storage issues are not discussed. EP 1106654, filed before but published after the present priority date, describes the incorporation of calcium carbonate powder into silicone rubbers - both peroxide-cured and addition-cured - for making keypads. Examples used 'heavy calcium carbonate' i.e. calcium hydrogen carbonate. Addition reaction curing type silicone rubber compositions have many advantages over the condensation type RTV silicone rubber compositions. The former do not require such a long time for curing as the latter. The latter suffer from a reversion in that a polysiloxane contained therein undergoes cleavage at elevated temperature under sealed conditions, whereas the former does not give rise to the reversion. Therefore, an addition reaction curing type silicone rubber composition loaded with alkaline earth metal carbonate powder would be highly desirable. One particular preferred desire is for an addition reaction curing type silicone rubber composition loaded with alkaline earth metal carbonate powder and adapted to improve its adhesion, e.g. for use as an adhesive, and which composition remains stable during storage. Therefore, an object of the invention is to provide an addition reaction curing type silicone rubber composition loaded with alkaline earth metal carbonate powder, which composition has good storage stability e.g. gives off a minimized amount of hydrogen gas during storage. Another object is to provide a method for preparing the same composition. It has been found that an addition reaction curing type silicone rubber composition having improved storage stability is obtainable using an alkaline earth metal carbonate which has been surface treated substantially with a diorganopolysiloxane. When the resulting silicone rubber composition is used in conjunction with electric and electronic parts for the purpose of providing a seal around the parts, the rubber is also effective for preventing the parts from corrosion by air-borne corrosive gases. This offers a useful means for overcoming the corrosion problem of electric and electronic parts with automotive emissions such as NOx and SOx. The invention is predicated on this finding. In a first aspect as set out in claim 1, the invention provides a silicone rubber composition of addition reaction curing type, comprising (A) diorganopolysiloxane containing at least two alkenyl groups per molecule; (B) alkaline earth metal carbonate powder surface pre-treated with diorganopolysiloxane; (C) organohydrogenpolysiloxane containing at least two silicon atom-attached hydrogen atoms per molecule; (D) platinum group catalyst, and (E) adhesive agent having one or more functional groups selected from epoxy, alkoxysilyl, carbonyl and phenyl groups. In a second aspect as set out in claims 13 and 14, the invention provides the method of preparation of a silicone rubber composition as set out in the first aspect, preferably comprising the steps of: mixing a portion or all of the diorganopolysiloxane (A) containing at least two alkenyl groups per molecule with the alkaline earth metal carbonate powder to surface-treat the alkaline earth metal carbonate powder, with heating; mixing the resulting mixture of the treated powder with the remainder of the diorganopolysiloxane (A), if only a portion thereof was used in the first mixing step, and mixing the mixture with the organohydrogenpolysiloxane (C) and the platinum group catalyst (D). A third aspect as set out in claim 16 is the use, for making seals for vehicle-mounted electric equipment, of a silicone rubber composition of the addiction-curing type comprising (A) diorganopolysiloxane containing at least two alkenyl groups per molecule, (B) alkaline earth-metal carbonate powder surface treated with diorganopolysiloxane, (C) organohydrogenpolysiloxane containing at least two silicon atom-attached hydrogen atoms per molecule, and (D) platinum group catalyst. FURTHER EXPLANATIONS; OPTIONS AND PREFERENCES (A) Alkenyl-containing diorganopolysiloxane The alkenyl-containing diorganopolysiloxane used as a base polymer in the inventive composition is a diorganopolysiloxane containing at least two alkenyl groups in a molecule. It may be chosen freely in line with conventional practice. Preferably it has the average compositional formula (1) : R a SiO (4-a) wherein R, which may be the same or different, is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and "a" is a positive number of 1.5 to 2.8, preferably 1.8 to 2.5, and more preferably 1.95 to 2.05. Examples of the substituted or unsubstituted monovalent hydrocarbon groups attached to silicon atoms, represented by R, include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and dodecyl; cycloalkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl; aryl groups such as phenyl, tolyl, xylyl, naphthyl and biphenyl; aralkyl groups such as benzyl, phenylethyl, phenylpropyl and methylbenzyl; alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl and cyclohexenyl; and substituted ones of the foregoing groups in which some or all of the hydrogen atoms are replaced by halogen atoms (e.g., fluoro, bromo and chloro), cyano groups or the like, such as chloromethyl, 2-bromoethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, chlorophenyl, fluorophenyl, cyanoethyl and 3,3,4,4,5,5,6,6,6-nonafluorohexyl. Of these, preferred are substituted or unsubstituted alkyl groups of 1 to 3 carbon atoms such as methyl, ethyl, propyl, chloromethyl, bromoethyl, 3,3,3-trifluoropropyl, and cyanoethyl, and substituted or unsubstituted phenyl groups such as phenyl, chlorophenyl and fluorophenyl. Of the alkenyl groups, lower alkenyl groups such as vinyl and allyl are preferred. This is all established practice. At least two of the R groups must be alkenyl groups, preferably of 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms. It is noted that the content of alkenyl groups is preferably 0.001 to 20 mol%, especially 0.01 to 10 mol% based on the entire organic groups attached to silicon atoms (that is, the substituted or unsubstituted monovalent hydrocarbon groups included as R in average compositional formula (1)). The alkenyl groups may be attached to silicon atoms at ends of the molecular chain and/or silicon atoms midway the molecular chain. When the cure rate of the composition and the physical properties of cured products are taken into account, the organopolysiloxane should preferably have at least some alkenyls attached to the silicon atoms at molecular chain ends. With respect to the structure, the organopolysiloxane is generally a linear diorganopolysiloxane whose backbone is comprised of recurring diorganosiloxane units and which is blocked with a triorganosiloxy group at either end of the molecular chain. However, it may have a partially branched or cyclic structure. A linear diorganopolysiloxane is preferred from the standpoint of the mechanical strength and other physical properties of cured products. The alkenyl-containing diorganopolysiloxane preferably has a viscosity of about 10 to 1,000,000 centistokes (cSt) at 25°C, and more preferably about 100 to 500,000 cSt at 25°C. One preferred, non-limiting, class of alkenyl-containing diorganopolysiloxanes includes those of the following general formula. Herein, R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group free of aliphatic unsaturation, examples of which are the same as exemplified above for R except the alkenyl groups. X is an alkenyl group, examples of which are the same as exemplified above. Letter n is 0 or an integer of at least 1, m is 0 or an integer of at least 1, preferably satisfying 10 ≤ n+m ≤ 10,000, more preferably 50 ≤ n+m ≤ 2,000 and 0 ≤ m/(n+m) ≤ 0.2. (B) Alkaline earth metal carbonate powder The alkaline earth metal carbonate powder used herein is originally a basic one such as calcium carbonate and magnesium carbonate. The alkaline earth metal carbonate powder should have been surface treated substantially with a diorganopolysiloxane. The alkaline earth metal carbonate powder is typically selected from calcium carbonate and magnesium carbonate. Of these, calcium carbonate is readily available and suitable on commercial use. The calcium carbonate powder used herein may be selected from well-known species such as heavy, precipitated and colloidal ones. Since those calcium carbonate powders which have been surface treated with resin acids alone or in admixture can alter the organohydrogenpolysiloxane (C), originally untreated calcium carbonate powders are preferred. The alkaline earth metal carbonate powder including secondary agglomerates preferably has an average particle size of 0.05 to 50 µm, more preferably 0.5 to 30 µm when the flow and reinforcement of silicone rubber compositions loaded therewith are taken into consideration. The average particle size as used herein may be determined, for example, as a weight-average value (median size) by laser light diffraction. The diorganopolysiloxane used for the surface treatment of alkaline earth metal carbonate powder may be substantially a linear organopolysiloxane having diorganosiloxane units as a main chain and blocked with silanol groups (i.e., hydroxy groups bonded to silicon atoms) or triorganosiloxy groups such as trimethylsiloxy groups and vinyldimethylsiloxy groups at both ends of the molecular chain, and may be selected from nonfunctional diorganopolysiloxanes (not containing a reactive functional group such as alkenyl in a molecule) such as dimethylpolysiloxane and methylphenylpolysiloxane, and diorganopolysiloxanes containing alkenyl groups in a molecule. The diorganopolysiloxane having a viscosity of about 10 to 1,000,000 cSt, especially about 100 to 500,000 cSt at 25°C is preferably used. Preferably it is an alkenyl-containing diorganopolysiloxane selected from the above options for (A), and most preferably is the same as the specific (A) used. In this embodiment, the alkaline earth metal carbonate powder may be pre-surface treated with a portion of component (A) and the resulting mixture is admixed with the remainder of component (A) and other components. Alternatively, the alkaline earth metal carbonate powder is mixed with the entirety of component (A) to effect surface treatment with component (A). Typical surface treating means is by heating a mixture of the diorgano(e.g. methyl)polysiloxane and the metal carbonate powder at an elevated temperature. Suitable elevated temperature is about 50°C or higher, preferably about 80 to 200°C. Heat treatment may be effected under atmospheric pressure (1 atm.) although a vacuum may be used to promote the heat treatment. The vacuum is not critical as long as it is lower than 760 mmHg. Often heat treatment is effected under a vacuum of about 1 to 250 mmHg, preferably about 5 to 100 mmHg. The treating time is preferably about 10 to 600 minutes, and especially about 30 to 180 minutes. It appears that the treatment with diorganopolysiloxane causes the alkaline earth metal carbonate powder to release moisture that it has borne, with the result that the carbonate powder can be blended in an addition reaction curing type silicone rubber composition without the risk of altering the organohydrogenpolysiloxane (C). The resulting addition reaction curing type silicone rubber composition can be substantially or fully stable. An appropriate amount of the alkaline earth metal carbonate powder (B) blended is usually 1 to 100 parts, especially about 3 to 50 parts by weight per 100 parts by weight of component (A) (inclusive of the portion of component (A) used for the surface treatment of component (B)). Too less an amount of component (B) may result in a composition which is inferior in adhesion and barrier seal against corrosive gases. Too much an amount of component (B) may result in a failure to provide cured silicone rubber having stable rubber elasticity. (C) Organohydrogenpolysiloxane The organohydrogenpolysiloxane used herein serves as a crosslinking agent and may be selected from linear, branched and cyclic ones and three-dimensional network resinous ones as long as it contains at least two, preferably at least three silicon atom-bound hydrogen atoms (i.e., SiH groups). Typical organohydrogenpolysiloxanes have the following average compositional formula (2). H b R 2 c SiO (4-b-c)/2 Herein, R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group free of aliphatic unsaturation, b and c are numbers in the range of 0 < b < 2.0, 0.8 ≤ c ≤ 2 and 0.8 < b+c ≤ 3, and preferably 0.01 ≤ b ≤ 1, 1.5 ≤ c ≤ 2 and 1.8 ≤ b+c ≤ 2.7. Examples of the substituted or unsubstituted monovalent hydrocarbon group free of aliphatic unsaturation, represented by R 2 , are the same as exemplified for R in average compositional formula (1). Typical hydrocarbon groups are those having 1 to 10 carbon atoms, especially 1 to 7 carbon atoms, preferably lower alkyl groups of 1 to 3 carbon atoms such as methyl, phenyl and 3,3,3-trifluoropropyl. Exemplary organohydrogenpolysiloxanes include siloxane oligomers such as 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyltetracyclosiloxane and 1,3,5,7,8-pentamethylpentacyclosiloxane; both end trimethylsiloxy-blocked methylhydrogenpolysiloxane, both end trimethylsiloxy-blocked dimethylsiloxane-methylhydrogensiloxane copolymers, both end silanol-blocked methylhydrogenpolysiloxane, both end silanol-blocked dimethylsiloxane-methylhydrogensiloxane copolymers, both end dimethylhydrogensiloxy-blocked dimethylpolysiloxane, both end dimethylhydrogensiloxy-blocked methylhydrogenpolysiloxane, both end dimethylhydrogensiloxy-blocked dimethylsiloxane-methylhydrogensiloxane copolymers, both end trimethylsiloxy-blocked dimethylsiloxane-diphenylsiloxane-methylhydrogensiloxane copolymers, and both end dimethylhydrogensiloxy-blocked dimethylsiloxane-diphenylsiloxane-methylhydrogensiloxane copolymers, as well as silicone resins comprising R 2 2 (H)SiO 1/2 units and SiO 4/2 units which optionally contain R 2 3 SiO 1/2 units, R 2 2 SiO 2/2 units, R 2 (H)SiO 2/2 units, (H)SiO 3/2 units or R 2 SiO 3/2 units wherein R 2 is a substituted or unsubstituted monovalent hydrocarbon group as defined above. Also included are organohydrogenpolysiloxanes of the following formulae. Herein L is an integer of 1 to 200, M is an integer of 0 to 300, L+M is an integer of 1 to 300, P is an integer of 1 to 200, Q is an integer of 2 to 300, and P+Q is an integer of 2 to 300. It is noted that the organohydrogenpolysiloxane may have a degree of polymerization (number of silicon atoms per molecule) in the range of about 2 to about 300, desirably about 4 to about 200, and a viscosity of about 0.1 to 1,000 cSt at 25°C, desirably about 0.5 to 500 cSt at 25°C. The organohydrogenpolysiloxane used herein may be prepared by well-known methods, for example, by subjecting to (co)hydrolysis at least one chlorosilane selected from the following formulae: R 2 SiHCl 2 and R 2 2 SiHCl wherein R 2 is as defined above, or by subjecting to cohydrolysis a combination of the chlorosilane with at least one chlorosilane selected from the following formulae: R 2 3 SiCl and R 2 2 SiCl 2 wherein R 2 is as defined above. If desired, the polysiloxanes resulting from such cohydrolysis is further subjected to equilibration reaction, resulting in an organohydrogenpolysiloxane which is also useful. The organohydrogenpolysiloxane (C) is preferably used in such amounts that 0.5 to 4 mol, especially 1 to 2.5 mol of silicon atom-bound hydrogen atoms (i.e., SiH groups) in the organohydrogenpolysiloxane (C) are available per mol of alkenyl groups in the alkenyl-containing diorganopolysiloxane (A). All of the above may be in accordance with conventional practice as regards organohydrogenpolysiloxanes. (D) Platinum group metal catalyst The platinum group metal catalyst used herein is a catalyst for promoting addition reaction between silicon atom-bound alkenyl groups in component (A) and silicon atom-bound hydrogen atoms in component (B). Well-known catalysts used in hydrosilylation reaction are useful. Exemplary catalysts are platinum, palladium and rhodium base catalysts including elemental platinum group metals such as platinum (inclusive of platinum black), rhodium and palladium; platinum chloride, chloroplatinic acid and chloroplatinates such as H 2 PtCl 4 ·nH 2 O, H 2 PtCl 6 ·nH 2 O, NaHPtCl 6 ·nH 2 O, KHPtCl 6 ·nH 2 O, Na 2 PtCl 6 ·nH 2 O, K 2 PtCl 4 ·nH 2 O, PtCl 4 ·nH 2 O, PtCl 2 and Na 2 HPtCl 4 ·nH 2 O wherein n is an integer of 0 to 6, preferably 0 or 6; alcohol-modified chloroplatinic acid (see USP 3,220,972); complexes of chloroplatinic acid with olefins (see USP 3,159,601, 3,159,662 and 3,775,452); platinum group metals such as platinum black and palladium on carriers such as alumina, silica and carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (Wilkinson catalyst); and complexes of platinum chloride, chloroplatinic acid or chloroplatinates with vinyl-containing siloxanes, especially vinyl-containing cyclic siloxanes. The catalyst (D) is used in a catalytic amount, typically about 0.1 to 1,000 parts, preferably about 0.2 to 500 parts, and more preferably about 0.5 to 200 parts by weight of platinum group metal per million parts by weight of components (A) and (C) combined. (E) Adhesive agent An adhesive agent or adhesiveness-imparting component (E) is blended in the composition in the first aspect. In this aspect the adhesive agent (E) is selected from organic compounds or organosilicon compounds containing in a molecule at least one group selected from among Si-H (i.e., silicon atom-bound hydrogen atom), alkenyl, acrylic, methacrylic, epoxy, alkoxysilyl, ester, carboxy anhydride, amino and amide groups, or a mixture thereof. The preferred adhesive agents are organosilicon compounds, typically linear or cyclic organosiloxane oligomers and organoalkoxysilanes of about 1 to 30 silicon atoms, preferably about 2 to 20 silicon atoms, and more preferably about 4 to 10 silicon atoms, having in a molecule at least one, often 1 to 10, especially 2 to 6, Si-H groups (i.e., silicon atom-bound hydrogen atoms) and/or alkenyl groups as well as one or more groups selected from among epoxy groups (e.g. glycidoxy), alkoxysilyl groups (e.g., trimethoxysilyl, triethoxysilyl and methyldimethoxysilyl), acrylic, methacrylic, ester, carboxy anhydride, amino, and amide groups. More illustratively, suitable compounds containing epoxy, alkoxysilyl, ester, alkenyl, amino, carboxy anhydride, acrylic, and methacrylic groups include non-silicon organic compounds having alkenyl and epoxy groups such as allyl glycidyl ether; and organoalkoxysilanes, for example, epoxy functional group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; alkenyl group-containing alkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane and vinyltri(methoxyethoxy)silane; amino group-containing alkoxysilanes such as γ-aminopropyl-trimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane; and acrylic or methacrylic group-containing alkoxysilanes such as γ-methacryloxypropyltrimethoxysilane and γ-acryloxypropyl-trimethoxysilane. Other useful compounds are organosiloxane oligomers carrying such functional group(s) e.g. as shown below: The foregoing silicon compounds containing epoxy, alkoxy and carboxy anhydride groups can promote effective bonding with metals and organic resins. As compounds which promote effective bonding with thermoplastic resins or compositions comprising the same, but not easily with metals, use may be made of organosilicon compounds including linear, branched or cyclic organosiloxane oligomers of about 1 to 30 silicon atoms, preferably about 2 to 20 silicon atoms, and especially about 4 to 12 silicon atoms, containing at least one, preferably about 1 to 20, and more preferably about 3 to 10, Si-H groups in a molecule and having a mono- to trivalent phenyl or phenylene skeleton not directly bound to a silicon atom. These compounds are exemplified below. Among others, those compounds having two or more phenyl or phenylene skeletons are especially preferred. In the formulae, n is 2 to 30, and R 1 is as previously defined. As the adhesive agent compounds having amino and amide groups, art-recognized compounds are useful. Other useful compounds are exemplified below. X-C 3 H 6 -NH-Ph-NH-C 3 H 6 -X X-C 3 H 6 -NH-Ph-Ph-NH-C 3 H 6 -X X-C 3 H 6 -NH-Ph-CH 2 -Ph-NH-C 3 H 6 -X X-C 2 H 4 -CO-NH-Ph-NH-CO-C 2 H 4 -X X-C 2 H 4 -CO-NH-Ph-CH 2 -Ph-NH-CO-C 2 H 4 -X X-C 3 H 6 -CO-NH-Ph-CH 2 -Ph-NH-CO-C 3 H 6 -X X-C 2 H 4 -CO-NH-Ph-O-Ph-NH-CO-C 2 H 4 -X X-C 3 H 6 -NH-CO-Ph-CO-NH-C 3 H 6 -X X-C 3 H 6 -NH-CO-Ph-CO-Ph-CO-NH-C 3 H 6 -X X-C 3 H 6 -O-CO-NH-Ph-NH-CO-O-C 3 H 6 -X X-C 3 H 6 -O-CO-NH-CH 2 -Ph-CH 2 -NH-CO-O-C 3 H 6 -X X-C 3 H 6 -O-CO-NH-Ph-CH 2 -Ph-NH-CO-O-C 3 H 6 -X X-C 3 H 6 -NH-CO-NH-Ph-NH-CO-NH-C 3 H 6 -X X-C 3 H 6 -NH-CO-NH-Ph-CH 2 -Ph-NH-CO-NH-C 3 H 6 -X Note that X is 1,3,5,7-tetramethyl-3,5,7-trihydrocyclo-tetrasiloxane, and Ph is phenyl or phenylene. An appropriate amount of the adhesive agent (E) used is usually up to 10 parts by weight (i.e., 0 to 10 parts by weight), preferably 0.1 to 10 parts, more preferably 0.5 to 5 parts by weight per 100 parts by weight of component (A). Other components In addition to the above-described components, there may be added reinforcing inorganic fillers such as fumed silica, precipitated silica, and fumed titanium dioxide; reinforcing silicone resins; and non-reinforcing inorganic fillers such as calcium silicate, titanium dioxide, ferric oxide, and carbon black. These inorganic fillers are generally used in amounts of 0 to 200 parts by weight, preferably 0.1 to 100 parts by weight per 100 parts by weight of all the components excluding the inorganic fillers. The silicone rubber composition may be prepared for example by mixing a portion of component (A) with component (B) and heating the mixture for surface treating component (B) with component (A), adding the remainder of component (A) and an optional inorganic filler to the mixture, and milling the mixture to form a silicone rubber base compound. Alternatively, a silicone rubber base compound is obtained by adding the entirety of component (A), component (B) and an optional inorganic filler, mixing them, and heat treating the mixture for surface treating component (B) with component (A). Then components (C) and (D) and optional component (E) are added to the silicone rubber base compound, followed by milling, resulting in a one part type silicone rubber composition. Alternatively, the silicone rubber composition may be prepared as two part type consisting of the silicone rubber base compound and a blend obtained by separately milling components (C) and (D) and optional component (E), the two parts being admixed on use. Preferably the silicone rubber composition of the invention is liquid and has a viscosity of about 1 to 1,000 Pa·sec (about 1,000 to 1,000,000 centipoise) at 25°C, and especially about 5 to 300 Pa·sec at 25°C. The silicone rubber composition obtained by the above method exhibits a smooth flow. Curing conditions may be the same as used in prior art addition reaction curing type silicone rubber compositions. The inventive composition satisfactorily cures even at room temperature, for example. If desired, the composition is heated at about 40 to 200°C, and especially about 60 to 180°C. The inventive silicone rubber composition cures into a product or silicone rubber having good heat resistance and electrical insulation. We have also found that when addition reaction curing type silicone rubber compositions of this kind were used for providing a seal around an electric or electronic part, the cured composition is effective for protecting the electric or electronic part from corrosion by air-borne corrosive gases. Then the composition is quite effective as a means for reducing the corrosion problem with NOx and SOx of electric and electronic parts in vehicle-mounted electrical equipment (including air flow sensors, pressure sensors, slot control modules, crank angle sensors, knocking sensors, temperature sensors, oxygen sensors, NOx sensors, acceleration sensors, engine control circuits, and discharge lamp control circuits). EXAMPLE Examples of the invention are given below by way of illustration and not by way of limitation. Examples & Comparative Examples Silicone rubber compositions as shown in Tables 1 and 2 were prepared using the following ingredients. (a) Diorganopolysiloxane Vinyl group-containing linear dimethylpolysiloxane of the formula: wherein n is such a number that the diorganopolysiloxane has a viscosity of 10,000 cSt at 25°C. (b) Powder (b-1) untreated calcium carbonate (Whiten SSB by Shiraishi Industry Co., Ltd., average particle size about 1.5 µm) (b-2) resin acid-treated calcium carbonate (MT-100 by Maruo Calcium Co., Ltd., average particle size about 2 µm) (b-3) untreated magnesium carbonate (c) Platinum-divinyltetramethyldisiloxane complex/toluene solution (platinum element content 0.5 wt%) (d) Organohydrogenpolysiloxane (e) Curing regulator (50% toluene solution of ethynyl cyclohexanol) (f) Adhesive agent (g) Fumed silica (Degussa R8200) The above ingredients were milled in a 3-liter Sinagawa universal mixer which could be heated in vacuum. First, ingredients (a), (b) and (g) were mixed and heat treated for 2 hours under the conditions shown in Table 1. After cooling, ingredients (c), (d), (e) and (f) were added to the mixture, which was further mixed (Examples 1-7). Compositions of Comparative Examples were prepared as in Examples except that ingredients (a), (b) and (g) were mixed without heating, that is, at 30°C in Comparative Examples 1-4; and ingredient (b) was omitted from the mixing/heating step in Comparative Examples 5. For the evaluation of storage stability, the composition was placed in a 500-ml metal container, which was sealed and held for 24 hours at 40°C. Then an internal pressure within the container was inspected. For the evaluation of cure and adhesion, the composition was cured to a metal or resin at 120°C for one hour. The appearance of a cross section of the cured product was observed, and the adhesion of the cured product to the metal or resin was examined. The rating was "Bond" when a firm bond was ascertained and "Strip" when the cured product was stripped from the metal or resin. The metal was aluminum and the resins were polybutylene terephthalate (PBT) and polyphenylene sulfide (PPS). The results are shown in Tables 1 and 2. Ingredients (pbw) Example 1 2 3 4 5 6 7 a 500 500 500 500 500 500 500 b-1 200 200 200 200 200 b-2 200 b-3 200 g 5 5 5 5 5 5 Treatment Temperature (°C) 80 100 150 100 100 150 100 Pressure (mmHg) 760 760 760 200 760 200 200 c 0.1 0.1 0.1 0.1 0.1 0.1 0.1 e 0.3 0.3 0.3 0.3 0.3 0.3 0.3 d 2 2 2 2 2 2 2 f 3 3 3 3 3 3 3 Viscosity (Pa·sec) 82 76 76 79 55 96 72 Hardness (Durometer A) 29 34 35 34 28 33 36 Storage stability (gas evolution) No No No No No Some No Cured appearance (foam) No No No No No Some No Adhesive Aluminum Bond Bond Bond Bond Bond Bond Bond PBT Bond Bond Bond Bond Bond Bond Bond PPS Bond Bond Bond Bond Bond Strip Bond Ingredients (pbw) Comparative Example 1 2 3 4 5 a 500 500 500 500 500 b-1 200 200 b-2 b-3 g 5 5 5 Treatment Temperature (°C) 30 30 30 30 100 Pressure (mmHg) 760 760 760 760 760 c 0.1 0.1 0.1 0.1 0.1 e 0.3 0.3 0.3 0.3 0.3 d 2 2 2 2 2 f 3 3 3 3 3 Viscosity (Pa·sec) 62 83 42 59 60 Hardness (Durometer A) 35 26 29 18 35 Storage stability (gas evolution) No Found No Found No Cured appearance (foam) No Found No Found No Adhesive Aluminum Bond Bond Bond Bond Bond PBT Bond Bond Bond Bond Bond PPS Strip Bond Strip Bond Strip As seen from Tables 1 and 2, the compositions (Examples 1-5) within the scope of the invention were improved in adhesion to metal and resin, storage stability and cured appearance, due to the addition of calcium carbonate. The composition of Example 6 exhibits satisfactory adhesion, but somewhat unfavorable in storage stability and cured appearance, indicating that resin acid-treated calcium carbonate is less preferable. Examples 1-5 and 7 using initially untreated calcium carbonate or magnesium carbonate exhibit satisfactory rubber characteristics, attaining the intended purposes. Additionally, the compositions of Example 3 and Comparative Example 5 were examined for an ability as a sealant to protect electric or electronic parts from corrosive gases. Examination was made by two test procedures under the conditions described below. Test procedures: (1) The composition was directly applied onto a B type comb-shaped electrode, and heat cured at 120°C for one hour. (2) An electrode was placed in a case consisting of a glass casing and a glass lid. The composition was applied as a bonding seal between the casing and the lid and heat cured at 120°C for one hour. Test atmosphere: a mixture of air with 30 ppm of NO 2 gas and 30 ppm of SO 2 gas Test temperature: 23°C Time: 500 hours Electrode: JIS B type comb-shaped electrodes of copper and aluminum Applied voltage: DC 12 volts The degree of corrosion was examined by scraping off the sealant to expose the electrode surface at the end of the test and observing whether or not the appearance of the electrode surface changed. The results are shown in Table 3. Composition Example 3 Comparative Example 5 Electrode Copper Aluminum Copper Aluminum Sealing procedure (1) (2) (1) (2) (1) (2) (1) (2) Evaluation 0hr OK OK OK OK OK OK OK OK 100hr OK OK OK OK OK OK Corroded OK 200hr OK OK OK OK OK OK Corroded Corroded 300hr OK OK OK OK Corroded OK Corroded Corroded 400hr OK OK OK OK Corroded Corroded Corroded Corroded 500hr OK OK OK OK Corroded Corroded Corroded Corroded There have been described addition reaction curing type silicone rubber compositions loaded with alkaline earth metal carbonate powder, which compositions have good storage stability. They gave off a minimized amount of hydrogen gas during storage. Embodiments showed improved adhesion and a good ability to protect electric or electronic parts from corrosion and finds use in a variety of applications, typically in the sealing of electric or electronic parts. Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described in the Examples.

Claims: A silicone rubber composition of addition reaction curing type, comprising (A) diorganopolysiloxane containing at least two alkenyl groups per molecule; (B) alkaline earth metal carbonate powder surface pre-treated with diorganopolysiloxane; (C) organohydrogenpolysiloxane containing at least two silicon atom-attached hydrogen atoms per molecule; (D) platinum group catalyst, and (E) adhesive agent having one or more functional groups selected from epoxy, alkoxysilyl, carbonyl and phenyl groups. A silicone rubber composition according to claim 1 in which the adhesive agent imparts self-adhesion of the composition to metals and/or to organic resins. A silicone rubber composition according to claim 1 in which the adhesive agent is selected from linear and cyclic organosiloxane oligomers and organoalkoxysilanes of from 1 to 30 silicon atoms having per molecule at least one silicon atom-bound hydrogen atom and/or alkenyl group as well as one or more groups selected from epoxy groups, alkoxysilyl groups, acrylic, methacrylic, ester, carboxy anhydride, amino and amide groups. A silicone rubber composition according to claim 2 in which the adhesive agent is selected from: non-silicon containing organic compounds having both alkenyl and epoxy groups; organoalkoxysilanes; alkenyl group-containing alkoxysilanes; amino group-containing alkoxysilanes; and (meth)acrylic group-containing alkoxysilanes. A silicone rubber composition according to claim 1 in which the adhesive agent is selected from linear, branched and cyclic organosiloxane oligomers of from 2 to 20 silicon atoms, containing at least one Si-H group per molecule and having a mono-, di- or trivalent phenyl or phenylene skeleton not directly bound to silicon atom. A silicone rubber composition according to claim 1 in which the adhesive agent is selected from the following compounds: X-C 3 H 6 -NH-Ph-NH-C 3 H 6 -X X-C 3 H 6 -NH-Ph-Ph-NH-C 3 H 6 -X X-C 3 H 6 -NH-Ph-CH 2 -Ph-NH-C 3 H 6 -X X-C 2 H 4 -CO-NH-Ph-NH-CO-C 2 H 4 -X X-C 2 H 4 -CO-NH-Ph-CH 2 -Ph-NH-CO-C 2 H 4 -X X-C 3 H 6 -CO-NH-Ph-CH 2 -Ph-NH-CO-C 3 H 6 -X X-C 2 H 4 -CO-NH-Ph-O-Ph-NH-CO-C 2 H 4 -X X-C 3 H 6 -NH-CO-Ph-CO-NH-C 3 H 6 -X X-C 3 H 6 -NH-CO-Ph-CO-Ph-CO-NH-C 3 H 6 -X X-C 3 H 6 -O-CO-NH-Ph-NH-CO-O-C 3 H 6 -X X-C 3 H 6 -O-CO-NH-CH 2 -Ph-CH 2 -NH-CO-O-C 3 H 6 -X X-C 3 H 6 -O-CO-NH-Ph-CH 2 -Ph-NH-CO-O-C 3 H 6 -X X-C 3 H 6 -NH-CO-NH-Ph-NH-CO-NH-C 3 H 6 -X X-C 3 H 6 -NH-CO-NH-Ph-CH 2 -Ph-NH-CO-NH-C 3 H 6 -X in which X is 1,3,5,7-tetramethyl-3,5,7-trihydrocyclo-tetrasiloxane, and Ph is phenyl or phenylene. A silicone rubber composition according to any one of the preceding claims in which the adhesive agent (E) is used at from 0.1 to 10 parts by weight per 100 parts by weight of component (A). A silicone rubber composition of any one of the preceding claims wherein the alkaline earth metal carbonate powder is a calcium carbonate powder. A silicone rubber composition of claim 8 wherein the calcium carbonate powder has an average particle size of from 0.05 to 50 µm. A silicone rubber composition of any one of the preceding claims wherein the surface pre-treated alkaline earth metal carbonate powder (B) is one obtainable by heating a mixture of a starting alkaline earth metal carbonate powder with diorganopolysiloxane. A silicone rubber composition of claim 10 wherein said starting powder was calcium carbonate powder without treated particle surfaces. A silicone rubber composition according to any one of the preceding claims which is of one-part type. A method comprising the preparation of a composition according to any one of claims 1 to 12. A method according to claim 13 comprising the steps of: mixing a portion or all of the diorganopolysiloxane (A) containing at least two alkenyl groups per molecule, with the alkaline earth metal carbonate powder to surface-treat the alkaline earth metal carbonate powder, with heating; mixing the resulting mixture of the treated powder with the remainder of the diorganopolysiloxane (A), if only a portion thereof was used in the first mixing step, and mixing the mixture with the organohydrogenpolysiloxane (C) and the platinum group catalyst (D). A method according to claim 14 in which the heat treatment of the metal carbonate powder with the diorganopolysiloxane (A) is for from 10 to 600 minutes at a temperature of from 80 to 200°C. The use, for making seals for vehicle-mounted electric equipment, of a silicone rubber composition of the addition-curing type comprising (A) diorganopolysiloxane containing at least two alkenyl groups per molecule, (B) alkaline earth metal carbonate powder surface treated with diorganopolysiloxane, (C) organohydrogenpolysiloxane containing at least two silicon atom-attached hydrogen atoms per molecule, and (D) platinum group catalyst. Use according to claim 16 which is making a seal for the electric or electronic parts of any of a vehicle air flow sensor, pressure sensor, slot control module, crank angle sensor, knocking sensor, temperature sensor, oxygen sensor, NOx sensor, acceleration sensor, engine control circuit and a discharge lamp control circuit. Use according to claim 16 or 17 in which the silicone rubber composition comprises an adhesive agent. Use according to claim 18 in which the adhesive agent has one or more functional groups selected from epoxy, alkoxysilyl, carbonyl and phenyl groups. Use according to claim 18 in which the adhesive agent accords with any one of claims 2 to 7 above. Use according to any one of claims 16 to 20 in which the alkaline earth metal carbonate powder is a calcium carbonate powder. Use according to claim 21 in which the calcium carbonate powder has an average particle size of from 0.05 to 50 µm. Use according to any one of claims 16 to 22 in which the surface treated alkaline earth metal carbonate powder (B) is one obtainable by heating a mixture of a starting alkaline earth metal carbonate powder with diorganopolysiloxane. Use according to claim 23 wherein said starting powder was a calcium carbonate powder without treated particle surfaces. Use according to any one of claims 16 to 24 in which the composition is of one-part type.

Inventors: AKETA TAKASHIMI, HARA HIROYASU, INOUE YOSHIFUMI, SUGAHARA HIDEKI, AKETA, TAKASHIMI, HARA, HIROYASU, INOUE, YOSHIFUMI, SUGAHARA, HIDEKI, Aketa, Takashimi, c/o Silicone-El. Mat. Res. Ctr., Hara, Hiroyasu, c/o Silicone-El. Mat. Res.Ctr., Inoue, Yoshifumi, c/o Silicone-El. Mat. Res. Ctr., Sugahara, Hideki, c/o Silicone-El. Mat. Res. Ctr.
Applicants: SHINETSU CHEMICAL CO, SHIN-ETSU CHEMICAL CO., LTD.
Application year: 2001
Main classification: C08L83
IPC codes: C09K3, C08K9, C08L83, F16J15, C08K5