GB2066833A

GB2066833A - Self-bonding Addition Cured Silicone Systems

Info

Publication number: GB2066833A
Application number: GB8040129A
Authority: GB
Original assignee: General Electric Co
Current assignee: General Electric Co
Priority date: 1980-01-04
Filing date: 1980-12-15
Publication date: 1981-07-15
Also published as: IT8026845A0; GB2066833B; DE3049550A1; BE886952A; IT1134840B; NL8100008A; AU6569680A; AU539546B2; FR2474519A1; JPS5699253A; JPS6334901B2

Abstract

A self-bonding addition curing silicone system comprising a vinyl containing base polymer, a platinum catalyst, a hydride resin as a cross- linking agent and as the self-bonding additive an acryloxy silane or siloxane compound. Preferably the acryloxy compound is gamma methacryloxypropyltrimethoxysilane. In the preferred process for preparing the composition, the acryloxy compound is first mixed with the hydride silicone resin before the rest of the ingredients are added or mixed into the composition.

Description

SelCBonding Addition Cueed Silicone Sisterns The present invention relates to an SiH Olefin platinum catalyzed addition silicone composition and more particularly the present invention relates to self-bonding SiH Olefin platinum catalyzed compositions.

Si Olefin platinum catalyzed compositions are well known. Such compositions are also referred to as addition curing systems or compositions. Such compositions generally comprise a base vinyl containing polysiloxane copolymer, a hydride cross-linking agent which can be either a hydride resin composed of monofunctional units and tetrafunctional units or a hydride resin composed of monofunctional units and tetrafunctional units and difunctional units of a hydride containing linear polysiloxane fluid. The addition of the hydrogen in the hydride cross-linking agent to the vinyl of the polysiloxane so as to cure the system is carried out under the influence of a platinum catalyst.Many platinum catalysts have been developed for such a purpose particularly platinum complexes of aldehydes and alcohols or a platinum complex catalyst formed by reacting chloroplatinic acid with a vinyl containing polysiloxane.

There is also disclosed by the prior art that there may also be incorporated in such compositions resins containing vinyl substitution such as disclosed in the patent of Frank J. Modic, U.S.P. 3,436,366.

It is disclosed in the foregoing patent that may be incorporated in such SiH I Olefin platinum catalyzed compositions or addition systems, fillers, such as fumed silica or precipitated silica or extending fillers.

Such compositions are prepared by placing the vinyl polysiloxane filler in one package and by mixing the hydride cross-linking agent by itself with or without filler and having the platinum catalyst with the vinyl siloxane which is present in a separate package. The composition is packaged or prepared into two components or two packages. When it is desired to cure the composition, the vinyl siloxane and the platinum catalyst is brought together with the hydride and can be cured at room temperature to a silicone elastomer.

It has been found that inhibitor compounds may be incorporated in such compositions so that they they remain uncured at room temperature or can be cured in a relatively rapid pace at elevated temperatures such as temperatures above 1 00 and 1 50 C. Examples of such inhibitors are for instance, triallylisocyanurate and hydroperoxy compounds as disclosed in the patent of William J.

Bobear, U.S.P. 4,061,609. The disclosure of the above patents are incorporated in the present case by reference. The inhibitor compounds of the Bobear patent allows the composition to be packaged in a single package which without the curing of the composition for a period of 6 months to a year or more, and then by heating the composition at elevated temperatures, the composition cures to a silicone elastomer. It should be noted that in the Bobear patent the hydroperoxide compounds are disclosed solely as inhibitor compounds. The compositions which cure to a silicone elastomer result in good potting and encapsulation compositions, for the dielectric properties of the addition cure silicone are aptly suited for these uses.However, the lack of adhesion of such compositions which are normally not adhesive results at times in the causing of the delamination of the encapsulated electronic components. This results in subjecting the electrical components to moisture, vibration, and damage.

There may result in such heavy damage or destruction that electrical discharges can occur across coating voids resulting from the delamination of the encapsulant. The lack of adhesiveness of such addition cure silicone composition make them admirably suited as molding compounds but is decidedly a disadvantage when such compositions are to utilized to encapsulate or pot electrical components. It should be noted that such addition pure silicone systems or silicone elastomers have outstanding properties such as optical clarity, tensile strength, elongation and tear properties, resistance to reversions, and high temperature.

The lack of adhesion of such addition cure silicone compositions is a decided disadvantage when such composition are, for instance, to be applied for gasketing applications, glass cloth impregnation and silk screening applications. Primers may be utilized to improve the adhesion or result in the desirable adhesion of the silicone cured elastomer to a substrate, however such primers represent an additional step in the application of the system increasing the cost of the application of addition cure systems. Also such primers are hard to apply to complex shapes and in complex printing systems such as the silk screening printing system. An example of a primer for condensation RTV compositions is to be found in Smith U.S.P. 4,177,301.

Recently in condensation curing RTV and in heat curable vulcanizable silicone rubber composition there has been developed self-bonding additives. For example, see the patent application of Smith, DeZuba and Mitchell, 60 S1-225, Serial No. 16,254, which is incorporated into the present case by reference, disclosing the use of silyl maleates and fumerates and succinates to produce self-bonding condensation cured one-component room temperature vulcanizable silicone rubber compositions.

However, such self-bonding additives are useless in an addition cure system. One example of an attempt to produce a viable self-bonding addition cure system is to be found in the patent of Ballard, lJ.S.P, 3,527,655. However, it did not produce enough self-bonding or adhesive properties in the composition. Another more successful attempt is to be found in the disclosure of DuJack and Hardman, Docket 60 Sl-275, filed 3/12/79, Serial No.20,104, entitled "Self-Bonding Silicone Rubber Compositions" which is hereby incorporated in the present case. This case has two divisional applications pending from it. The Ballard patent discloses a vinyl alkoxy silane that is a self-bonding addition system with such an additive which did not function satisfactorily in all cases.A more suitable self-bonding addition system was produced in the Hardman and DuJack application by utilizing a partial hydrolyzate of a vinyl triethoxy silane. However, such a system was not satisfactory as would be desired in that the self-bonding properties or adhesion was not as good as would be desired, but nevertheless, was superior to that of the Ballard system.

Accordingly, there has been made a constant effort and a constant attempt to produce a selfbonding addition cure system and specifically for the production of a self-bonding addition cure RTV that could be utilized to produce gaskets on metal substrates and on plastic substrates and which could be utilized in various printing techniques. It should be noted that the silk screen printing methods are utilized to produce gaskets from various materials on various types of metal and plastic substrates. The purpose of the silk screening method is to print out a complex configuration. Machinery can be utilized to print a relatively simple configuration, but silk screening printing methods are utilized to produce gaskets of a complex configuration.As previously stated, the silk screening printing method comprises wherein a silk screen of a certain thickness is taken and everything but the shape of the gasket is varnished. Then the composition that is desired to be printed is applied over the figure that is to be printed. Wiper blades force the composition through the silk screen in the exact thickness of the silk screen so that it comes through the silk screen and fall on the substrate in the exact figuration which it is desired that the composition be printed. This method results in the printing of complex configurations and shapes on various types of substrates. In order for the method to work, the composition has to have adhesion or self-bonding to the substrate.Accordingly, prior to the present invention, addition cure compositions could not be utilized in the silk screening method to produce a complex gasket on substrate such as a metallic, plastic and ceramic substrate.

In accordance with the above, there is provided by the present invention a self-bonding addition curing silicone composition comprising self-bonding addition curing silicone composition comprising (A) 100 parts by weight of a base vinyl containing diorganopolysiloxane of a viscosity varying from 100 to 500,000 centipoise at 250C where the vinyl content varies from 0.04 to 1.5 percent by weight, the organo group is a monovalent hydrocarbon radical; (B) from 1 to 500 ppm of platinum catalyst; (C) from .1 to 25 parts by weight of a hydride resin selected from the class consisting of resins having HR2SiOo 5 units and SiO2 units where the ratio of H+R to Si varies from 1.0 to 2.7 and resins having HR2Si005 units, SiO2 units and R2 SiO units where the ratio of H+R+R' to Si varies from 1.2 to 2.7 where R is a monovalent hydrocarbon radical and R7 is selected from hydrogen and a monovalent hydrocarbon radical and (D) from 0.5 to 8 parts by weight of a self-bonding additive selected from the claim consisting of silanes of the formula,

where R2, R4, R5 are monovalent hydrocarbon radicals, R3 is a divalent hydrocarbon radical and a is a whole number 0 to 2, and siloxanes of the formula,

where R2, R3 as defined where, R" is a monovalent hydrocarbon radical, a' varies from 0.005 to 2.0, b varies from 1.0 to 2.5 and the sum of a+b varies from 1.005 to 3.0. To increase the self-bonding properties of the composition, there may be added at least 400 parts per million of self-bonding promoter containing at least one hydroperoxy radical and from 2 to 25 parts by weight based on 100 parts of the base polymer of a fumed silica filler treated with silazanes. It should be noted that in the process for forming such compositions the hydride resin must be mixed with the acryloxy compound first before the other compounds are mixed into the hydride resin or the acryloxy compounds.The preferred acryloxy compound is e-methacryloxypropyltrirnethoxysilane. Other details of the respective present invention will be given below.

The base vinyl containing diorganopolysiloxane polymer may be any vinyl containing diorganopolysiloxane polymer that is utilized in SiH Olefin platinum catalyzed compositions. The vinyl may be vinyl in the chain or the vinyl may be on the siloxy terminal units or it may be both in the and on the siloxy terminal units. Preferably the base vinyl containing diorganopolysiloxane polymer has a viscosity varying from 100 to 500,0duo centipoise at 250C and more preferably a viscosity varying from 100 to 200,000 centipoise at 250C where the vinyl content generally varies from 0.04 to 1.5 percent by weight and more preferably varies from 0.04 to 1.0 percent by weight.The organo groups other than vinyl of such a polymer may be any monovalent hydrocarbon radical such as alkyl radical of 1 to 8 carbon atoms such as methyl ethyl, etc; alkenyl radicals such as vinyl, allyl, etc; mononuclear aryl radicals such as phenyl, menthyiphenyl, etc.; cyclo alkyl radicals such as cyclohexyl, cyclo heptyl, etc.; and fluoroalkyl radicals such as 3,3,3-trifluoropropyl. Preferably the organo groups are selected from vinyl phenyl and methyl and most preferably being selected from vinyl and methyl, generally such a polymer may have the formula,

where Vi is vinyl and R10 is a monovalent hydrocarbon radical. The radical R'O may be any of the radicals noted for the organo groups in the definition of the diorganopolysiloxane vinyl containing polymer.However, preferably, the vinyl containing vinyl polysiloxane polymer has the Formula (3) above such that vinyl unit only on the terminal position of the chain and R10 is a monovalent hydrocarbon radical other than a aliphatically unsaturated hydrocarbon radical. Most preferably R10 is selected from the class consisting of methyl phenyl and fluoro alkyl radicals and x and y in the formula vary such that the viscosity of the polymer varies from 100 to 500,000 centipoise at 250C and more preferably varies from 100 to 200,000 centipoise at 250C.

Another basic ingredient in the composition is from 0.1 to 25 parts by weight of a hydride resin defined above. Preferably the hydride resin contains a hydride content broadly at .05 to 5 percent weight and more preferably .1 to 1 percent by weight. It should be noted that the hydride resin must be present in the SiH olefin platinum catalyzed composition of the instant case for solubility purposes.

Accordingly, per 100 parts of the base vinyl containing diorganopolysiloxane polymer, there must be present from .1 to 25 parts by weight of a hydride resin as defined above. As pointed out previously, R is selected from monovalent hydrocarbon radicals and R' is selected from hydrogen and monovalent hydrocarbon radicals. The monovalent hydrocarbon radicals can be any radical other then the aliphatically unsaturated hydrocarbon radicals. Accordingly R and R' insofar are monovalent hydrocarbon radical that can be selected from alkyl radicals of 1 to 8 carbon atoms, cyclo alkyl radicals, and mononuclear aryl radicals and fluoro alkyl radicals, all up to 8 carbon atoms. Most preferablv R is selected from methyl, phenyl, and 3,3,3-trifluoropropyl and most preferably R' is selected from hydrogen, methyl, phenyl, and 3,3,3fluoropropyl.It should be noted that the hydride resin might have some vinyl unsaturation but if it does have such vinyl unsaturation it is important the platinum catalyst not be mixed with it, otherwise the resin will cross-link with itself.

The hydride resin is produced by methods well known in the art. Such methods generally comprises the hydrolysis of the appropriate hydride chlorosilanes, preferably in a water hydrocarbon solvent mixture with the extraction and purification of the resin product. The other necessary ingredient in the composition is from 1 to 500 parts per million of platinum catalyst and more preferably from 1 to 200 parts per million of platinum catalyst. It should be noted that the platinum catalyst may be present as solid platinum deposited on charcoal or on gamma alumina or it may be solubilized platinum complex. Most preferably it is a solubilized platinum complex.

Generally, there must utilized at least 0.1 parts per million of a platinum catalyst in terms of parts of platinum metal. This platinum catalyst may be in any form. It may be a solid platinum metal deposited on a solid carrier or it may be a solubilized platinum complex. Any type of platinum catalyst will work in the instant invention. More preferably, the platinum complex is a solubilized platinum complex. Many types of platinum compounds for this SiH-olefin addition reaction are known and such platinum catalyst may be used for the reaction of the present case. The preferred platinum catalyst especially when optical clarity is required are those platinum compound catalyst which are soluble in the present reaction mixture.The platinum compound can be selected from those having the formula (PtCl2 Olefin)2 and H(PtCl2 Olefin) as described in U.S. Pat. No. 3,1 59,601, Ashby. The olefin shown in the previous two formulas can be almost any type of olefin but is preferably an alkenylene having from 2 to 8 carbon atoms, a cycloalkenylene having from 5 to 7 carbon atoms or styrene. Specific olefins utilizable in the above formulas are ethylene, propylene, the various isomers of butylene, octylene, cyclopentene, cyclohexene, cycloheptene, etc.

A further platinum containing material usable in the composition of the present invention is the platinum chloride cyclopropane complex (PtCl2C3H6)2 described in U.S. Pat. No. 3,159,662, Ashby.

Still, further, the platinum containing material can be a complex formed from chloroplatinic acid with up to 2 moles per gram of platinum of a member selected from the class consisting of alcohols, ethers, aldehydes and mixtures of the above as described in U.S. Pat. No.3,220,972, Lamoreaux.

All the patents and patent applications mentioned in this present specification are incorporated into the present application by reference.

The preferred platinum compound to be used not only as a platinum catalyst but also as a flame retardant additive is that disclosed in Karstedt U.S. patent 3,81 5,730. Generally speaking, this type of platinum complex is formed by reacting chloroplatinic acid containing 4 moles of water of hydration with tetravinylcyclotetrasiloxane in the presence of sodium bicarbonate in an ethanol solution.

It should be noted that the preparation of such hydride resins and also the solubilized platinum catalyst are well known to a worker skilled in the art. Preparation of a base vinyl containing polymer is also well known to a worker skilied in the art and generally comprises taking cyclotetrasiloxanes of the appropriate organo substitution or of the desired organo substitution, and equilibrating them at elevated temperatures in the presence of an alkali metal hydroxide with the appropriate amount of chain stoppers. The chain stoppers are preferably low molecular weight vinyl terminated diorganopolysiloxane polymers; for instance, divinyltetramethyldisiloxane.From the resulting equilibration there results the desired polymer and when the equilibration is complete that is when about 85 percent of cyclotetrasiloxane have been converted to linear polymer, the reaction temperature is lowered, the alkali metal hydroxide catalyst is neutralized preferably with acidic agent such as a chiorosilane or a silyl phosphate or a phospheric acid and the excess cyclics that are unreacted are vented off to give the desired polymer. When it is desired to produce a low molecular weight diorganopolysiloxane polymer in the viscosity range of 50 to 10,000 centipoise at 25 C, then there may be utilized an acidic catalyst in such equilibration reaction such as toluene sulfonic acid or acid treated clay such as Filtrol, manufactured and sold by the Filtrol Corporation of Los Angeles, California.Another necessary ingredient in the composition is generally from .5 to 8 parts by weight and more preferably from 1 to 5 parts by weight of the acryloxy silane. In formula 1 above, R2, R4 and R5 are monovalent hydrocarbon radicals. Such monovalent hydrocarbon radicals can be any of the monovalent hydrocarbon radicals defined previously for the vinyl containing base polymer.Accordingly, such monovalent hydrocarbon radicals can be alkyl radicals of 1 to 8 carbon atoms, mononuclear aryl radicaic such as phenyl, alkenyl radicals such as vinyl, cyclo alkyl radicals such as cyclo hexyl, fluoro alkyl radicals such as 3,3,3-trifluoropropyl. Most preferably R2, R4, R5 are selected from alkyl radicals of 1 to 8 carbon atoms such as methyl, and R3 is a divalent hydrocarbon radical and is preferably selected from alkylene and arylene radicals of up to 8 carbon atoms. Preferably R3 has at least 3 carbon atoms.

It has been found that the compound is not hydrolytically stable if it has less than 3 carbon atoms.

More preferably, R3 is propyl since the propyl group is hydrolytically stable and is most readily available for producing the compounds of formula (1), A can be as a is a whole number that varies from 0 to 2 and is most preferably 0. Preferably the compound of formula 1 is formed by the following reaction.

where R13 is an aliphatically unsaturated monovalent hydrocarbon radical of at least 3 carbon atoms, generally of 3 to 8 carbons where R2, R4 and R5 are as previously defined. The above reaction is carried out in the presence of a platinum catalyst and is well known in the silicone chemical art. The hydrogen group adds on to the olefinically unsaturated group R13 in the presence of the platinum catalyst to form the compound of Formula (1), the acryloxyintermediateforformingthe compound of Formula (1) is readily available in the industry and is sold by chemical companies such as Union Carbide Corporation and Dynamit Nobel Chemicals Co.

In place of the acryloxy silane self-bonding additive that may be utilized at the same concentrations and the acryloxy polysiloxane self-bonding additive of Formula (2). Such aclyloxy polysiloxane compounds are formed from the following reaction:

Again, this is a well-known reaction in silicone chemistry which is cured out presence of platinum catalyst and can be any of the platinum catalyst identified previously for the compositions of the present invention. In the above formulas of the hydride polysiloxane a varies from 0.05 to 2.0, b varies from 1.0 to 2.5 and the sum of a plus b varies from 1.005 to 3.0.

In the Formula (1) and as well as in the hydride formula polysiloxane above, R" is a monovalent hydrocarbon radical that can be any of the monovalent hydrocarbon radicals identified previously for the base vinyl containing polymer. Accordingly, R" can be the alkyl radical of 1 to 8 carbon atoms, a mononuclear aryl radical, an alkenyl radical, a cycloalkyl radical or a fluoroalkyl radical. Most preferably R11 is selected from methyl vinyl and phenyl and 3,3,3-trifluoropropyl. The acryloxy olefinic unsaturated compounds which are utilized in this reaction to produce the acryloxy polysiloxanes and the acryloxy silanes can be obtained from the above manufacturers of chemical compounds as identified previously.

In preparing the composition, the acryloxy silane or siloxane is first mixed with a hydride resin and has to be mixed with resin first, irrespective of whether additional ingredients are then added as will be described below. The platinum catalyst is mixed with a vinyl containing polysiloxane base polymer.

When it is desired to cure the composition, the two components are mixed and applied to whatever substrate it is desired to adhere thereto and the composition will at room temperature cure to a silicone elastomer or cure at elevated temperatures to silicone elastomers, that is above 8COC and 1 500C. The cure at above 1 000C is extremely rapid, in a matter of minutes or even seconds.

However, to improve the self-bonding properties of the compositions, there may be added to the composition, at least 400 parts per million of a self-bonding promoter having at least one hydroperoxy radical. Accordingly, generally there may be utilized 400 to 10,000 parts per million of a hydroperoxy compound as a self-bonding promoter, or preferably from 400 to 2,000 parts per million of a selfbonding promoter, which compound contains a hydroperoxy radical. Most preferably the self-bonding promoter is methyl ethyl ketone hydroperoxide.Other hydroperoxide self-bonding promoters that may be utilized are 1,1 ,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-dihydroperoxy hexane, cumene hydroperoxide, tetrabutyl hydroperoxide, 1 -hydroxycyclohexyl hydroperoxide, 1,1,3,3tetramethylbutylhydroperoxide, 2,5 dimethyl-2,5, dihydroperoxy hexane, decalin hydroperoxide, 1,1 ,2,2-tetramethylpropyl, p-methane hydroperoxide and pinane hydroperoxide. These compounds are manufactured and sold by Pennwalt Corp., Hercules, Inc., and Lucidol Chemical Company.

It should be noted that these compounds are taken out of U.S.P. 4,061,609, which is incorporated into the present case by reference. It should be noted these hydroperoxy compounds are disclosed in the foregoing '609 patent and as inhibitors, and as very effective inhibitors in SiH olefin platinum catalyzed compositions. They are not disclosed in the patent as self-bonding promoters. It is only in the present application that they are disclosed as self-bonding promoters.

It also should be noted that the most effective acryloxy silane self-bonding additive that is desirably utilized in the present invention, is a-methacryloxy propyl trimethoxy silane. To further increase the self-bonding properties of the composition there may be also incorporated per 100 parts of the base polymer from 2 to 25 parts by weight of a fumed silica which is treated with silazanes. This is another self-bonding promoter which by the use of siloxane treated fumed silica the self bonding properties of the composition are improved over compositions not having such silazane treated fumed silica. The fumed silica may also be treated with cyclotetrasiloxanes in addition to the silazanes.

However, this is not necessary. An example of such treatment of such fillers is for instance to be found in the Beers U.S.P. 3,837,878. Preferably, there is utilized only from 2 to 1 5 parts by weight of fumed silica treated with silazanes. However, it is not desired to utilize more than 25 parts of fumed silica in any case because the viscosity of the composition becomes to high for the composition to be used in silk screen printing applications. However, the composition with a high viscosity may be utilized in other applications such as encapsulation and potting of electrical components. The treatment of fumed silica with cyclotetra siloxane and silazanes is well known in the art.

In addition to such treatment and utilization of fumed silica there may be utilized an extending filler. Generally there may be utilized anywhere from 5 to 100 parts of an extending filler and more preferably from 5 to 50 parts of an extending filler based on 100 parts by weight of the base vinyl containing polymer where the extending filler is selected from a class consisting of titaninum oxide, lithopone, zinc oxide, zirconium silicate, silica aerogel, iron oxide, diatomaceous earth, calcium carbonate, glass fibers, magnesium oxide, chromic oxide, zirconium oxide, magnesium oxide, alpha quartz, calcined clay, carbon graphite, cork, cotton and synthetic fibers. These fillers are disclosed in the Patent Application of William Bobear, l U.S.P. 4,061,609 which is incorporated by reference in the present case.A patent on the use of the silazanes to treat fumed silica is U.S.P. 3,635,743.

Accordingly, with these additional ingredients of the hydroperoxy compound, along with a silazane treated fumed silica there is disclosed a very desirable and advantageous self-bonding SiH olefin platinum catalyzed composition. Accordingly, with the hydroperoxy self-bonding promoter and the silazane treated fumed silica which can be added with advantages to the acryloxy silane or siloxane composition, there is obtained a very advantageous self-bonding addition cure system. It may be utilized in silk screening applications as it has the desired adhesion to various types of substrates.

The substrates to which good adhesion is obtained from by the above composition with the foregoing self-bonding promoters are copper, aluminum, polyvinylchloride, glass, polyethylene terephthalate, epoxy fiberglass, phenolic-linen, Lexan, tradename for polycarbonates, styrene, nylon, polyphenylene oxides. It should be noted that most preferably the extending filler is alpha quartz, since alpha quartz increases the tensile strength of the composition without increasing to too great an extent the viscosity of the uncured compositions. It should be noted that any of the extending fillers may be utilized with advantage to increase the tensile strength of the composition without necessarily increasing the viscosity of the uncured composition by a great extent.In the present case, there may also be incorporated additional hydride for curing purposes, to increase the rate of cure when it is desired, that is by the heating of the composition by elevated temperatures. There may be present from 1 to 50 parts by weight of a resin hydride polysiloxane of the formula,

where Re is selected from the class consisting of a monovalent hydrocarbon radical and a mixture of hydrogen and a monovalent hydrocarbon radical s is 0 or a positive number and t is a 0 or a positive number such that the polymer was a viscosity varying from 10 to 1,000 centipoise at 250C or more preferably has a viscosity varying from 10 to 100 centipoise at 250C.The R6 radical is preferably selected from alkyl radicals of 1 to 8 carbon atoms, cycloalkyl radicals, mononuclear aryl radicals, fluoroalkyl radicals, and other monovalent hydrocarbon radicals. It should be noted that Re can be alkenyl radicals such as vinyl as long as the platinum catalyst is not packaged with it in the formation of the 2 component composition system. The radical R6 is preferably selected from methyl, phenyl, and 3,3,3-trifluoropropyl radicals. Normally the hydride polysiloxane generally has a hydride content varying anywhere from 0.15 to 2.0 percent by weight and more preferably has a hydride content varying from 0.25 to 1.7 percent by weight. Preferably there is utilized as an additional hydride polysiloxane 1 to 20 parts by weight of the hydride polysiloxane based on 100 parts of the base vinyl containing polymer of formula 3.

It should be noted that there must be present in the composition of the instant cast in order for it to be soluble, the hydride resin. Such a hydride resin should be present in the composition and must be first mixed with the acryloxy silane to be soluble. As an additional hydride additive or in place of the hydride resin in order to increase the cure rate of the system, there may be present a linear hydride polysiloxane of the formula shown above. The hydride of polysiloxane of the formula shown above is a well known chemical in the art and may be obtained by the hydrolysis of the appropriate chiorosilanes to produce the desired hydride polysiloxane.Preferably, there should be a hydride resin in the composition and such hydride resin must be first mixed with the acryloxy silane and acryloxy polysiloxane initially in order for the composition to have the desired solubility properties of the instant case. After the hydride resin has been mixed with the acryloxy silane and polysiloxane, there may be added to it, the linear hydride polysiloxane polymer disclosed above. There may also be added to the composition reinforcing resins.Such resins take the place of silica fillers and increase the tensile strength of the cured composition as well as the tear strength of the cured composition without unduly increasing the uncured viscosity of the composition so that there may be incorporated into the composition per 100 parts of the base polymer from 1 to 70 parts by weight of a resin composed of R37 SiOO 5 Si 02 where R7 is a radical selected from the class consisting of vinyl radicals, alkyl radicals and aryl radicals and fluoroalkyl radicals of 1 to 8 carbon atoms with a ratio of monofunctional units to tetrafunctional units and is from 0.5 to 1:1 and where from about 2.5 to 10 mole percent of the silicone atoms contain silica bonded vinyl groups.

In place of such a resin there may be incorporated in the composition of a resin composed of monofunctional units, tetrafunctional units, difunctional units. Accordingly, per 100 parts of a base vinyl containing polymer, there may be incorporated in the composition from 1 to 70 parts by weight of a resin comprising R3 SiO0,5, R7 SiO units and SiO2 units where R7 is a radical selected from the class consisting of vinyl radicals, alkyl radicals, aryl radicals and fluoro alkyl radicals where the ratio of monofunctional units to the tetrafunctional units is from .5 to 1 and 1::1 and the difunctional units are present in an amount equal to about 1 to 10 mole percent based on the total number of moles of siloxane units in the copolymer and wherein from about 2.5 to 10 mole percent of the silicone atoms containing silicone bonded vinyl groups. Such resins are known for such olefin platinum catalyst compositions as disclosed in Modic U.S.P. 3,426,266.

The composition may also contain other additives and ingredients such as heat aging additives, additional flame retardant additives and swell resistant additives, if the composition is not fluorosilicone, etc. It should be noted that the hydroperoxy compound in the composition will act as an inhibitor. However, if used in the present invention it is being utilized first of all as a self bonding additive and then as an inhibitor. Accordingly, per 100 parts of the total composition there may be utilized from 100 to 10,000 parts per million of an additional inhibitor compound in the composition such as trialkenylisocyanurate. Suitable inhibitor compounds may be utilized as long as they do not conflict with the self-bonding properties or self-bonding activity in the system of the acryloxy silane and siloxane.

It has been found that trialkyenylisocyanurate does not interfere with the self bonding properties of acryloxy silane and acryloxy polysiloxane. The inhibited composition has a desirable work life at room temperature but when heated at elevated temperatures would cure in the matter of minutes or seconds to a silicone elastomer. With an inhibitor such as trialkenylisocyanurate in the composition, the composition may have hours or even days of shelf life without curing at room temperature. The hydroperoxy compound may be utilized also as an inhibitor but should be preferably utilized in the concentrations disclosed used above it if it is to act as a self-bonding promoter in the instant composition and secondly as an inhibitor.If it is utilized at more than the concentrations indicated above, then the self-bonding promoter properties of the hydroperoxide are not changed but the composition is considerably more inhibited.

To prepare the cured composition the vinyl polymer optionally, the vinyl resin, the filler are all mixed together along with the platinum catalyst to form one component. Then the hydride resin is mixed with the acryloxy silane or acryloxy polysiloxane, and then there is added to them preferably a linear hydride polysiloxane. A hydroperoxy self-bonding promoter additive and optionally the filler is added to the vinyl polymer. Accordingly, when it is desired to cure the composition the two components are mixed together to form a uniform mixture preferably in a 10 to 1 mixing weight ratio, then the composition is applied to whatever form itls desired.In one embodiment the composition can be applied to a silk screen and then pressed through the silk screen by the wiper bars into the substrate below which may be of ceramic, plastic or glass and the composition is then heated at elevated temperatures to cure the composition to the desired shape so as to form for instance a gasket on a metal, plastic or ceramic substrate by the silk screen printing method. It should be noted that the silk screen is varnished in all the areas except the areas it is desired that the composition pass through it to form the desired shape for the printed matter that is going to be placed on the substrate.

All parts in the examples below are by weight. The examples below are given for the purpose of illustrating the present invention and they are not given for the purpose of setting limits and boundaries of the present invention. In the examples below there was utilized a composition A. Such composition may comprise of 1 00 parts of vinyl terminated dimethylpolysiloxane polymer having 0.14 percent vinyl and a viscosity of 3800 centipoise at 250C.With this polymer there is mixed 33 parts of a resin composed of trimethylsiloxane units of SiO2 and methyl vinyl SiO units with a ratio of mono unit to the tetra and the difunctional units in an amount sufficient to provide 0.8 trimethylsiloxane units per SiO2 unit and with the methylvinylsiloxane units being present in an amount such that 7.0 mole percent of the methylvinylsiloxane atoms are present as methylvinylsiloxane units and the remaining silicone atoms are present as a portion of a dimethyl siloxane unit or an SiO2 unit.In the examples there was utilized a linear hydride composed of hydride dimethylsiloxy terminal units and methyl hydrogen siloxane units in the internal portion of the polymer chain where the viscosity of the polymer was 10 centipoise at 250C and the hydride concentration of the polymer was 1.7 percent by weight.

Example 1 Composition A above was taken and there was mixed into 100 parts of Composition A, 10 parts of Composition B by mixing 28 parts of gamma methacryloxypropyltrimethoxysilane with 64 parts of a resin composed of hydrogen dimethylsiloxy units and SiO2 units, containing an average of two of the dimethyl hydrogen units per SiO2 unit and 7 parts of the linear hydride disclosed above. This was the weight ratio of one component to the other in component B. From the cured composition ASTM sheets were made and cured at 100 C for 1 hour in a heated press. The adhesion was measured via a lap joint adhesion using Alclad aluminum panels and 1 square inch, 25 mil thick bond. The samples were pulled at .5 inches per minute. The test on the physical properties yield the following result.Durometer, Shore: 41; Tensile psi: 575, Elongation %: 110; Tear Ibjin.: 15; lap shear psi: 500, % Cohesion: 100%.

Example 2 To 100 parts of Composition A there was added 10 parts of component B comprising 50 parts of the resin hydride in Example 1 and 50 parts of a vinyl terminated dimethylpolysiloxane polymer having 0.14 percent vinyl and a viscosity of 3800 centipoise at 250C.

The resulting cured sheets had the following properties: Shore A durometer, 35; tensile psi: 750; Elongation %: 120; Tear Ibs/in.,: 10; Lap Shear psi: less than 1; Percent Cohesion: 0.

Example 3 The composition of Example 1 was used as a potting compound for 1 "x4" strips of a substrate shown in Table I. The silicone was cured at 800C for 1 hour. The silicone was examined for adhesion to the substrates by scrapping and pulling the silicone off with a razor blade. Composition A was cured with Composition B of Example 2 at a 10 to 1 ratio and used to pot the substrates for the sake of comparison. Characteristic of dimethylvinyl chain-stopped organopolysiloxanes, the cured silicone elastomer delaminated and readily released free of the substrates.

Example 4 Then to Composition A above there was added 610 parts per million of methylethylketone hydroperoxide. With the hydroperoxide the shelf life exceeded 6 months for the catalyzed composition.

Pot life exceeding 6 months are obtained when the hydroperoxide is added to the mixture of Example I.

Further, the number of plastics to which the composition adheres to is increased as shown in Table 1 below. With the addition of the hydroperoxide the catalyst composition must be subjected to a post bake of 1 250C for 10 minutes to complete the cure. In all other respects the composition was processed the same as in the Example 1. The results are set forth in Table I below.

TABLE I Cohesive Adhesion Substrate Example 3 Example 4 Polyvinyl chloride Good Good Copper Good Good Glass Good Good Polyethylene terephthalate Good Good Epoxy-fiberglass Good Good Phenolic-linen Good Good Lexan None Good Styrene None Good Nylon None Good Noryl None Good Polyvinyl acetate None None Acrylic None None Example 5 Prepared a Composition C which had the same composition as Composition A but the proportion of a vinyl polymer to a vinyl resin was 60% by weight of polymer per 40% by weight of resin while the composition is 75% by weight of polymer to 25% by weight of vinyl resin in Composition A. The composition C was cured with the component B of Example 1 at room temperature. The silicone gelled within 24 hours and cured to a transparent compound with a shore Hardness of 35.In comparison when the gamma methyl acryloxy propyl trimethoxy silane was added directly to composition A a percipitate immediately developed. The percipitate remained even after the addition of the linear silicone hydride. This mixture cured either at room temperature or up to 1 500C resulted in an opaque compound exhibiting intermittant cohesive bonding with less than 25% to aluminum panels.

The acryloxy silane of Example 1 was added to dimethylvinyl chain-stopped organopolysiloxane having a viscosity of 80,00Q centipoise at 250C and a dimethylvinyl terminated polysiloxane polymer having a viscosity of 3800 centipoise at 250C. A percipitate formed and after 24 hours yellow liquid was collected with was identified as the acryloxysilane of Example 1. These results were duplicated using the linear hydride polysiloxane as well. The acryloxysilane was soluble and stable for more than a year only when first mixed with the methyl hydride resin. The resin hydride may be made by reacting ethylsilicate with dimethylhydrogen chlorosilane in water. When the acryloxy of Example 1 is first mixed with the resin hydride, shelf stable solutions using other linear hydrogen polysiloxanes and a clear organo polysiloxane compounds can be made.

Examples 6 to 15 In these examples, solutions of curing agents containing the acryloxysilane of Example 1 and silicon hydrides were made and cured and used to cure composition A, a resin reinforced vinyl chainstopped polymer. The solutions were made by first mixing together the acryloi:ysilanes of Example 1 and the hydride resin and then adding the remaining component. Ten parts of curing agent were added to 100 parts of polymer. Adhesion was tested to aluminum by curing 30 grams ol the mixed compound on an aluminum weighing dish. The samples were cured for 1 hour. Wnen methylethylketone hydroperoxide was added to composition A, a cure temperature of 1 250C was used.The adhesion was determined by the cutting of 1/2" strips of the cured compound out of the aluminum dishes and peeling the aluminum strip off using an Instron, Model TM. The strip was pulled at 900 at a rate of 12" per minute. The values are reported in pounds/inch and the strips were examined for cohesive faire re as set forth in Table II below.

TABLE II Example 6 7 8 9 10 11 12 13 14 15 B Component Hydride Resin of Example 1 64.2 74.8 47 83.6 79.1 74 83.7 81.9 61.7 35.5 Acryloxy Silane of Example 1 28.3 16.4 44.2 16.4 16.5 16.4 16.3 18 13.6 7.8 Linear Hydride 1 7.5 8.8 8.8 4.4 24.7 56.7 Linear Hydride 2 8.6 Methyl ethyl ketone hydroperoxide (added to 'A' parts) ppm 606 606 606 Properties Cure Temp. OC for1hr. 100 80 100 100 100 100 125 125 125 100 % Cohesive 100 100 100 100 100 100 100 100 100 100 Bond Strength Ibs./in. 3 2.5 3.2 2.8 2.7 2.9 2.6 2.6 2.6 2.5 Shore A 32 32 30 33 32 31 33 31 29 Room Temp.

Gel Time, hrs. 24 5 24 24 24 24 720 720 720 5 % Memos in Part B 28.3 16.4 44.2 16.4 16.5 16.4 16.3 18 13.6 7.8 % Memos in cured RTV 2.6 1.5 4.0 1.5 1.5 1.5 1.5 1.6 1.2 0.7 1. Linear hydride of Example 1.

2. Linear hydride comprising a polysiloxane having hydrogen dimethyl terminal units and methyl hydrogen on chain with a viscosity of 55 centipoise at 250C and weight percent hydrogen of 1.0%.

Example 16 The composition of Example 6 was mixed and weighed into an aluminum dish. The compound was cured at 1 000C for one hour and percent solids as weight was determined. The loss was found to be .4 percent by weight. The cured sample was heated further at 1 500C for 720 hours without experiencing any further weight loss. A sample of composition A and composition B of Example 2 was tested under the same condition and had a weight loss of .2 percent by weight.

Example 17 Solutions of the hydride resin containing 10, 20 and 50 percent weight of methyl methacrylate were made and were used to cure composition A using a ratio of 100 parts of composition A to one part of the cuing agent. The cure was carried out at either 800 or 1 OODC. The samples did not evidence any adhesion to aluminum and developed a cloudy 2 phase system. No adhesion was obtained with addition to the system of methyl ethyl ketone hydroperoxide. Substitution with triallylisocyranuate resulted in no cure or adhesion.

Claims

1. A self-bonding additive curing silicone composition comprising (A) 100 parts by weight of a base vinyl containing diorganopolysiloxane of a viscosity varying from 100 to 500,000 centipoise at 250C where the vinyl content varies from 0.04 to 1.5 percent by weight, the organo group is a monovalent hydrocarbon radicals; (B) from 0.1 to 500 ppm of platinum catalyst; (C) from .1 to 25 parts by weight of a hydride resin selected from the class consisting of resins having HR2SiO0,5 units and SiO2 units where the ratio of H+R to Si caries from 1.0 to 2.7 and resins having HR2SiOo 5 units, SiO2 units and R2 SiO units where the ratio of H+R+R to Si varies from 1.2 to 2.7 where R is a monovalent hydrocarbon radical and R7 is selected from hydrogen and a monovalent hydrocarbon radical and (D) from 0.5 to 8 parts by weight of a self-bonding additive selected from the class consisting of silanes of the formula,

where R2, R4, R5 are monovalent hydrocarbon radicals, R3 is a diva lent hydrocarbon radical and a is a whole number 0 to 2 and siloxanes of the formula,

where R2, R3 as defined where, R11 is a monovalent hydrocarbon radical, a' varies from 0.005 to 2.0, b varies from 1.0 to 2.5 and the sum of a1+b varies from 1.005 to 3.0.

2. The composition of Claim 1 wherein there is further present at least 400 parts per million of self-bonding promoter having at least one hydroperoxy radical.

3. The composition of Claim 2 further comprising from 2 to 25 parts by weight of a fumed silica treated with silazanes.

4. The composition of Claim 1 where R2, R5 are methyl, a is 0 and R3 is a divalent hydrocarbon radical of 3 to 8 carbon atoms.

5. The composition of Claim 4 wherein the self-bonding additive is ymethacryloxypropyltrimethoxysilane.

6. The composition of Claim 5 wherein the self-bonding promoter is present at a concentration of 400 to 2000 parts per million.

7. The composition of Claim 6 wherein the self-bonding promoter is methyl ethyl ketone hydroperoxide.

8. The composition of Claim 7 wherein there is further present from 5 to 100 parts of an extending filler.

9. The composition of Claim 8 wherein said extending filler is alpha quartz.

10. The composition of Claim 1 wherein there is further present from 1 to 50 parts of hydride polysiloxane of the formula,

where R6 is selected from the class consisting of a monovalent hydrocarbon radical and a mixture of hydrogen and a monovalent hydrocarbon radical s is O or a positive number and t is a 0 or a positive number such that the polymer was a viscosity varying from 10 to 1,000 centipoise at 25oC.

11. The composition of Claim 1 wherein there is further present from 1 to 70 parts by weight of a resin comprising (R7,3 Silo 5 units and SiO2 units where R7 is a radical selected from the class consisting of vinyl radicals, alkyl radicals, aryl radicals, and fluoroalkyl radical where the ratio of monofunctional units to tetrafunctional units is from 0.5:1 to 1:1 and where from about 2.5 to 10 mole percent of the silicone atoms contain silicone bonded vinyl groups.

12. The composition of Claim 1 wherein there is further present from 1 to 70 parts by weight of a resin comprising (R7)3 Silo 5 units, R7SiO units and SiO2 units, where R7 is a radical selected from the class consisting of vinyl radicals, alkyl radicals, aryl radicals and fluoroalkyl radicals where the ratio of mono-functional units to tetra functional units is from about 0.5:1 to 1:1 and the difunctional units are present in an amount to equal to from about 1 to 10 mole percent based on the total number of moles of siloxane units in the copolymer and where from about 2.5 to 10 mole percent of the silicone atoms contain silicone bonded vinyl groups.

13. The composition of Claim 1 where the base vinyl containing diorganopolysiloxane polymer has the formula,

where Vi is vinyl, R10 is selected from the class consisting of methyl, phenyl and fluoroalkyl and x, z vary such that the viscosity of the polymer varies from 100 to 500,000 centipoise at 250C.

14. The composition of Claim 1 where the platinum catalyst is platinum complexed with a compound selected from the class consisting of an alkenyl and aryl alcohols.

1 5. The composition of Claim 1 wherein the platinum catalyst is platinum complexed with a vinyl containing dimethylpolysiloxane.

1 6. The composition of Claim 1 further comprising from 100 to 10,000 parts per million of an inhibitor compound.

1 7. The composition of Claim 1 6 wherein the inhibitor compound is triallylisocyanurate.

18. A process for forming a self-bonding addition cured silicone composition comprising (1) mixing from .1 to 25 parts by weight of a hydride resin selected from the class consisting of resin having HR2SiO05 units and SiO2 units where the ratio of H+R to Si varies from 1.0 to 2.7 and resins having HR2SiO05 units, and SiO2 units and R2 SiO units where the ratio of H+R+R' to Si varies from 1.2 to 2.7 where R is a monovalent hydrocarbon radical and R' is selected from hydrogen and monovalant hydrocarbon radical with .5 to 8 parts by weight of a self-bonding additive of the formula,

where R2, R4, R5 are monovalent hydrocarbon radicals, R3 is a diva lent hydrocarbon radical and a is a whole number 0 to 2, and siloxanes of the formula,

where R2, R3 as defined where, R" is a monovalent hydrocarbon radical, a' varies from 0.005 to 2.0, b varies from 1.0 to 2.5 and the sum of a a'+b varies from 1.005 to 3.0, (2) after such mixture is complete, adding to such mixture 100 parts by weight of a base vinyl containing diorganopolysiloxane polymer having a viscosity varying from 100 to 500,000 centipoise at 250C where the vinyl content varies from 0.004 percent to 1.5 percent by weight and the organic group is a monovalent hydrocarbon radical and from to 0.1 to 500 parts per million of a platinum catalyst and (3) curing the composition so as to produce a silicone elastomer that is self-bonding to substrates.

19. The composition of Claim 1 8 where there is further present at least 400 parts per million of a self-bonding promoter having at least one hydroperoxy radical.

20. The composition of Claim 1 9 further comprises from 2 to 25 parts by weight of fumed silica treated with silazanes.

21. The process of Claim 20 wherein R2 or R5 are methyl, a is 0 and R3 is a divalent hydrocarbon radical having from 3 to 8 carbon radicals.

22. The process of Claim 21 wherein the self-bonding additive is a gamma metha acryloxypropryltrimethoxysilane.

23. The process of Claim 22 wherein the self-bonding promoter is present in the concentration of 400 to 2000 parts per million.

24. The process of Claim 23 wherein the self-bonding promoter is methyl ethyl ketone hydroperoxide.

25. The process of claim 24 where there is further present 5 to 100 parts by weight of an extending filler.

26. The process of Claim 25 where the extending filler is alpha quartz.

27. The process of Claim 1 8 where there is further present from 1 to 50 parts of hydride polysiloxane of the formula,

where R6 is selected from the class consisting of a monovalent hydrocarbon radical and a mixture of hydrogen and a monovalent hydrocarbon radical s is 0 or a positive number and t is a O or a positive number such that the polymer has a viscosity varying from 10 to 1 ,000 centipoise at 250C.

28. The process of Claim 1 8 wherein there is further present from 1 to 70 parts by weight of a resin comprising R3 SiO0 5 units and SiO2 units where R7 is a radical selected from the class consisting of vinyl radicals, alkyl radicals, aryl radicals, and fluoroalkyl radicals where the ratio of monofunctional units to tetrafunctional units is from 0.5:1 to 1:1 and where from about 2.5 to 10 mole percent of the silicone atoms contain silicone bonded vinyl groups.

29. The process of Claim 1 8 where there is further present from 1 to 70 parts by weight of a resin comprising R3 SiO,, units, R7SiO units and SiO2 units, where R7 is a radical selected from the class consisting of vinyl radicals, alkyl radicals, aryl radicals and fluoroalkyl radicals where the ratio of monofunctional units to tetrafunctional units is from 0.5:1 to 1:1 and the difunctional units are present in an amount to equal to from about 1 to 10 mole percent based on the total number of moles of siloxane units in the copolymer and where from about 2.5 to 1 0 mole percent of the silicone atoms contain silicone bonded vinyl groups.

30. The process of Claim 1 8 where the base vinyl containing diorganopolysiloxane polymer has the formula,

when3 Vi is vinyl, R'O is selected from the class consisting of methyl, phenyl and fluoroalkyl and x, z, vary such that the viscosity of the polymer varies from 100 to 500,000 centipoise at 250C.

31. The process of Claim 18 where the platinum catalyst is platinum complexed with a compound selected from the class consisting of aldehydes and alcohols.

32. The process of Claim 1 8 wherein the platinum catalyst is platinum complexed with vinyl containing dimethyl polysiloxane.

33. The process of Claim 18 further comprises from 100 to 10,000 parts per million of an inhibitor compound.

34. The process of Claim 18 wherein the inhibitor is triallylisocyanurate.

35. The process for forming a laminate of an addition cured silicone elastomer on a plastic or metal substrate and the substrate is selected from metal, ceramic, and plastic substrates comprising (1) mixing from .1 to 25 parts by weight of a hydride resin selected from the class consisting of resins having HR2SiO05 units and SiO2 units where the ratio of H+R to Si varies from 1.0 to 2.7 and resins having HR2SiOG 5 units, SiO2 units and R2 SiO units where the ratio of H+R+R1 to Si varies from 1.2 to 2.7 where R is a monovalent hydrocarbon radical and R1 is selected from the class consisting of hydrogen and a monovalent hydrocarbon radical with (B) from 0.5 to 8 parts by weight of a selfbonding additive of the formula,

where R2, R4, RC are monovalent hydrocarbon radicals, R3 is a divalent hydrocarbon radical and a is a whole number 1 to 2, and siloxanes of the formula,

where R2, R3 as defined where, R" is a monovalent hydrocarbon radical, a1 varies from 0.605 to 2.0, b varies from 1.0 to 2.5 and the sum of a'+b varies from .005 to 3.0, and (2) taking such a mixture adding to it 100 parts by weight of a base vinyl containinrj diorganopolysiloxane polymer of a viscosity varying from 100 to 500,000 centipoise at 2gOC where the vinyl content varies from 0.04 to 1.5 percent by weight and the organo group Is a monovalent hydrocarbon radical and from 0.1 to 500 parts per million of a platinum catalyst and (3) applying the composition to a substrate selected from metal, ceramic, and plastic substrates and (4) allowing the composition to cure.

36. The process of Claim 35 where there is further present at least 400 parts per million of a selfbonding promoter having at least hydroperoxy radical in step (2).

37. The process of Claim 36 further comprising where in Step (2) there is additionally present from 2 to 25 parts by weight of fumed silica treated with silazanes.

38. A laminate that is formed with substrates selected from metal, ceramic, and plastic substrates with an addition cured self-bonding silicone elastomer comprising a substrate selected from the class comprising of plastic, ceramic and metal substrates and adhered to the substrate without the use of a primer or self-bonding addition cured silicone composition comprising (A) 100 parts by weight of a vinyl containing diorganopolysiloxane polymer of 100 to 500,000 centipoise at 250C where the vinyl content varies from 0.04 to 1.5 percent by weight, the organo group is a monovalent hydrocarbon radical: (B) from 0.1 to 500 ppm of platinum catalyst; (C) from .1 to 25 parts by weight of a hydride resin selected from the class consisting of resins having HR2SiO0.e units and SiO2 units where the ratio H+R to Si varies from 1.Q to 2.7 and resins having HR2SiO05 units, SiO2 units and R2 SiO units where the ratio of H+R+R to Si: varies from 1.2 to 2.7 where r is a monovalent hydrocarbon radical and R is selected from hydrogen and a monovalent hydrocarbon radical and (D) from 0.5 to 8 parts by weight of a self-bonding additive selected from the class consisting of silanes of the formula,

where R2, R3 as defined where, R11 is a monovalent hydrocarbon radical, a1 varies from 0.005 to 2.0 b varies from 1.0 to 2.5 and the sum of a1+b varies from 1.005 to 3.0.

39. The laminate of Claim 38 where there is further present in said addition cured silicone composition at 400 parts per million of a self-bonding promoter having at least one hydroperoxy radical.

40. The laminate of Claim 39 further comprising wherein in said silicone composition there is further present from 2 to 25 parts by weight of a fumed silica filler treated with silazanes.

41. A silicone elastomer gasket which is self-bonding to a substrate selected from metal, ceramic, and plastic substrates which is applied by the silk screening printed method comprising (1) a substrate selected from metal ceramic and plastic substrates; (2) or an addition curing silicone composition which is applied with a silk screen which cures to form a silicone elastomeric gasket comprising (A) 100 parts by weight of a vinyl containing diorganopolysiloxane polymer of a viscosity varying from 100 to 500,000 centipoise at 250C where the vinyl content varies from 0.04 to 1.5 percent by weight, the organo group is a monovalent hydrocarbon radical; (B) from 0.1 to 500 ppm of platinum catalyst; (C) from .1 to 25 parts by weight of a hydride resin selected from the class consisting of resins having HR2SiO05 units and SiO2 units where the ratio of H+R to Si varies from 1.0 to 2.7 and resins having HR2 Sino 5 units, SiO2 units where the ratio of H+R+R to Si varies from 1.2 to 2.7 where R is a monovalent hydrocarbon radical and R1 is selected from hydrogen and a monovalent hydrocarbon radical and (D) from 0.5 to 8 parts by weight of a self-bonding additive selected from the class consisting of silanes of the formula,

where R2, R3 as defined where R" is a monovalent hydrocarbon radical, a' varies from 0.005 to 2.0, b varies from 1.0 to 2.5 and the sum of a'+b varies from 1.005 to 3.0.

42. The silicone gasket applied to metal substrate by a silk screen printing equipment as set forth in Claim 41 where there is further present in said silicone addition curing uncured system at least 400 parts per million of a self-bonding promoter having at least 1 hydroperoxy radical.

43. The silicone gasket produced by silk screening equipment as set forth in Claim 42 wherein in the silicone uncured composition there is further present from 2 to 25 parts by weight of a fumed silica filler treated with silazanes.

44. A method of printing a silicone elastomeric composition with a silk screening printing method on a substrate comprising (1) applying to a substrate selected from the class consisting of metal, ceramic and plastic substrates utilizing the silk screening method a self-bonding addition cured silicone composition formed by (a) mixing from .1 to 25 parts by weight of a hydride resin selected from the class consisting of resins having HR2SiOo 5 and SiO2 units where the ratio of H+S to Si varies from 1.0 to 2.7 and resins having HR2SiOo 5 units, SiO2 units and R2 SiO units where the ratio of H+R+R1 to Si varies from 1.2 to 2.7 where R is a monovalent hydrocarbon radical and R' is selected from hydrogen and a monovalent hydrocarbon radical with from .5 to 8 parts by weight of a self-bonding additive of the formula,

where R2, R3 as defined where, R11 is a monovalent hydrocarbon radical, a' varies from 0.005 to 2.0, b varies from 1.0 to 2.5 and the sum of a1+b varies from 1.005 to 3.0 (b) adding to such mixture 100 parts by weight of a vinyl containing diorganopolysiloxane polymer having a viscosity varying from 100 to 500,000 centipoise at 250C where the vinyl content varies from 0.04 to 1.5 percent by weight and the organic group is a monovalent hydrocarbon radical and from 0.1 to 500 parts per million of platinum catalyst; and (2) allowing the composition to cure to a silicone elastomer.

45. The method of Claim 44 wherein the silicone composition is cured at room temperature.

46. The method of Claim 44 wherein the silicone composition is cured at elevated temperatures.

47. The method of Claim 44 wherein the substrate is selected from the class consisting of copper, aluminum polyvinyl chloride, glass polyethylene, terephthalate, epoxy-fiberglass, phenolic-line, polycarbonates, styrene, nylon, polyphenylene oxides.

48. The method of Claim 44 wherein in step (1) there is further added at least 400 parts per million of a self-bonding promoter having at least one hydroperoxy radical.

49. The method of Claim 48 wherein in step (1) there is further added from 2 to 25 parts by weight of a fumed silica filler treated with silazanes.

50. A self-bonding additive curing silicone composition substantially as hereinbefore described with reference to any one of Examples 1 to 16 of the foregoing Examples.

51. A process for forming a self-bonding addition cured silicone composition substantially as hereinbefore described with reference to any one of Examples 1 to 1 6 of the foregoing Examples.