NL8100008A - SELF-ADHESIVE, ADDITION-CURING SILOXAN-CONTAINING SYSTEMS. - Google Patents

Description

. . vTs * 't - * S 2348-lliO' * v * P & c

Self-adhesive addition-hardening siloxane-containing systems,

The invention relates to a SiH (siloxanhydride), olefin (vinylsiloxane) and platinum-containing catalyst, addition-hardening slloxan material; more particularly, the invention relates to self-adhesive materials containing SiH olefin and platinum as catalyst.

SiH, olefin and platinum catalyst-containing materials are known.

These materials are also referred to as addition-curing systems or compositions. These compositions generally contain a vinyl-containing polysiloxane, a hydride cross-linking agent, which cross-linking agent comprises a monofunctional and tetrafunctional units hydride resin or a monofunctional units, tetrafunctional units and difunctional units hydride resin or a flowable hydride-containing linear silicone.

The addition of the hydrogen of the cross-linking hydride to the vinyl of the silicone, whereby the system is carded, takes place under the influence of. a platinum-containing catalyst. Many platinum-containing catalysts have been developed for this purpose, in particular platinum complexes of aldehydes and alcohols and a platinum complex formed by reacting chloroplatinic acid with a vinyl-containing silicone.

It is stated in the literature that these compositions may also incorporate resins containing vinyl groups as substituents, as described in U.S. Pat. No. 3,436,366. In this US patent it is also stated that fillers, such as silica obtained from the gas phase or precipitated silica or adjuvant fillers, can be incorporated in these SiH, olefin and platinum as catalyst-containing compositions or addition systems. These materials are prepared by including the vinyl polysiloxane in a package. as a cross-linking agent, hydride, whether or not mixed with filler, and mixing the platinum-containing catalyst with the vinylsiloxane contained in a separate package. The composition is packaged in two components or packages. When it is desired to cure the composition, the vinyl siloxane and the platinum-containing catalyst are combined with the hydride and curing can take place at room temperature to form an elastomeric siloxane.

It has been found that inhibitors can be included in these compositions so that these materials remain uncured at room temperature or can be cured relatively quickly at elevated temperatures, for example 100 ° -50 ° C. Examples of these inhibitors are triallyl isocyanurate and hydroperoxy compounds as described in U.S. Patent 840,000,8 *. · '................................................ .......'....... -2- script 4.061.609. By recording the. inhibitors listed in the latter U.S. Patent. it is made possible to allow the composition to be packaged in one package, during a period of. 6 months, up to. no curing takes place for a year or more; by subsequently heating the composition at elevated temperatures, the composition cures to an elastomeric siloxane. It is noted that it. U.S. Patent 4,061,609 discloses the hydroperoxide compounds only as inhibitors. The elastomer siloxane compositions provide good casting and encapsulation materials since the dielectric properties of the addition cured siloxanes are well suited for these applications. The lack of attachment of. these materials, which normally do not. however, sometimes leads. to delamination. of the encapsulated electronic components. As a result, the electronic components are exposed to moisture, vibrations and damage. Such serious damage can occur. that electric. discharges can occur over coating voids resulting from delamination of the encapsulant. The lack of attachment of. these addition-cured, siloxane-containing materials make these compositions excellent as molding materials, but this lack of adhesion is clearly a disadvantage when these materials are used for encapsulating or pouring electronic components. It should be noted that these addition-cured silicone elastomers have excellent properties, such as optical clarity, tensile strength, good elongation and tear properties. and resistance to current reversal and high temperatures.

The lack of adhesion of these materials by addition curing, siloxane containing materials is one. clear disadvantage when these materials are used, for example, for gaskets, impregnation of glass cloth and in screen printing. One can apply base coats: for it. improving the adhesion or to obtain the desired adhesion of the. cured silicone elastomer more to a substrate, however, the use of these primers involves an additional step in the application of the system, thereby increasing the cost of using addition-hardening systems. These are also primer materials. difficult to apply to complex shapes and complex printing systems such as the screen printing system. A. Example Of a primer material for -RTV materials [at room temperature vulcanizable materials]: which cure by condensation is disclosed in U.S. Patent 4,177,301.

Recently, self-adhesive additives have been developed for condensation-hardening KEV materials and heat-curable silicone rubber 40-containing materials. Thus, US patent applications 16,254 81 00 00 8 describe; 1, ♦ the use of silyl maleates and famerates ai succinates. for preparing self-adhesive, condensation-cured, one-pack, vulcanizable, siloxane-containing materials at room temperature.

However, these self-adhesive additives are unsuitable in an addition curing system. example of an attempt to prepare a suitable self-adhesive, addition-curing system is described in U.S. Pat. No. 3,527,655 ► However, this system does not exhibit sufficient adhesion. Another more successful attempt is described in the U.S. patent application. 20,104.. U.S. Patent 3,527,655 10 describes. a vinyl alkoxy silane to provide a self-adhesive addition system that does not function satisfactorily in all cases.

United States Patent Application 20,104 discloses a more suitable self-adhesive addition system using a partial hydrolyzate of a vinyl triethoxy silane. A. however, such a system is not as satisfactory as. would be desirable there. the adhesion properties are not as good as would be desired, but. nevertheless, this system is superior to the system of U.S. Patent 3,527,655.

Therefore, efforts have been made continuously to prepare a self-adhesive, addition-hardening system, in particular a self-adhesive, addition-hardening RTV material which can be used to produce gaskets per metal substrates. and on plastic substrates and in various printing methods. It is noted that the screen printing methods are used to obtain gaskets of different materials on different types of substrates. made of metal and plastic.

25 The purpose of the screen printing method is to print a complex configuration. One can print a relatively simple configuration with machines, but screen printing methods are used to obtain packings of a complex configuration. The screen printing method uses a screen of a certain thickness. and provides the entire surface with a coating layer 30 except the shape of the gasket. Then the material to be printed is applied over the figure to be printed. The material is pressed through the sieve by means of knives and, after passing the sieve, falls on the substrate in exactly the desired configuration for the material to be printed. This method leads to the printing of complex. configurations and shapes on different types of substrates. For this method to work, the material must adhere to the substrate. Therefore, hitherto addition-curable materials have not been able to be used in screen printing to obtain a complex packing on substrates such as metal, plastic and ceramic materials.

The invention provides a self-adhering, addition-hardening, 810000 siloxane-containing material containing (A) 100 parts by weight. of a vinyl-containing diorganopolysiloxane with. a. viscosity of 100-500,000 centipoise at 25 ° C, of which silicone. the vinyl content is 0.04-1.5% by weight and the organic groups are monovalent hydrocarbon groups; (B) 0.1-500 ppm platinum as a catalyst; (C) 0.1-25 parts by weight. of a hydride resin selected from resins with HR 4 SiO units and SiO units, U / O a in which the ratio between H + R. and -: - Sl ranges from 1.0: 1 to 2.7: 1, and resins with HRoSiOft c units, SiO4 units and R_ SiO units, in which the ratio between H + R + R1 and. Si ranges from 1.2: 1. up to 2.7: 1, wherein R represents a monovalent hydrocarbon group and R represents a hydrogen atom or a monovalent hydrocarbon group; and. (D) 0.5-8 parts by weight of a self-adhesive additive, a silane according to formula (1) of the formula sheet, in which each of the symbols R, R and R represents a monovalent hydrocarbon group, R 1 represents a divalent hydrocarbon group and a represents an integer of value 0-2. or ·. a siloxane of the formula (2) of the formula sheet wherein R and R have the meanings given above, R "represents a monovalent hydrocarbon group, a is a number ranging from 0.005 to 2.0 and b is a. number is from 1.0 to 2.5, with a + b ranging from 1.005 to 3.0 To improve the self-adhesive properties of the material, at least 400 ppm of an agent can be used for promoting adhesion, containing at least one hydroperoxy group, and adding 2-25 parts by weight of the gaseous and silazan-treated silica as a filler per 100 parts by weight of the base polymer. in the preparation of these materials the hydride resin must first be mixed with the acryloxy compound before the other compounds are mixed with the hydride resin or the acryloxy compound The preferred acryloxy compound is -methacryloxy-propyltrimethoxysilane. The invention is set forth below.

30 Preferred Embodiments

The vinyl-containing diorganopolysiloxane base polymer can be any vinyl-containing diorganopolysiloxane used in SiH, alkeh and platinum catalyst-containing compositions. The vinyl can be present on the chain and / or on. the terminal siloxy units. Preferably, the vinyl containing diorganopolysiloxane has a viscosity of 100-500,000 centipoise at 25 ° C and even more preferably of 100-200,000 centipoise at 25 ° C; the vinyl content generally ranges from 0.04 to 1.5 wt% and is preferably 0.04-1.0 wt%. The organic groups of this polymer that are not vinyl groups can be any monovalent carbon-40 hydrogen group, for example, alkyl group member with 1-8 carbon atoms, such as 8100008. * ί .......... '..... - 5 -........'........' ........... ..........................

methyl, ethyl, etc .; alkenyl group such as vinyl, allyl, etc .; single-core aryl. groups such as phenyl, methylphenyl, etc .; cycloalkyl groups such as cyclohexyl, cycloheptyl, etc .; and fluoroalkyl groups such as 3,3,3-trifluoropropyl. Preferably, the organic groups are selected from vinyl, phenyl and methyl and most preferably from vinyl and methyl. In general, such a polymer may have the formula (3) of the formula sheet, in which formula V represents a vinyl group and R 1 represents a venerable hydrocarbon group. The group R ** "* can be any of the groups mentioned above for the organic groups of the vinyl-containing diorganopolysiloxane. Preferably, the vinyl-containing polysiloxane is a polymer of the formula (3) in which the vinyl groups are only end-chained and R ^ is a monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon group Most preferably R * is selected from methyl, phenyl and fluoroalkyl and x and y have formula (3) such that the viscosity of the polymer ranges from 100 to 500,000 centipoise at 25 ° C and even more preferably is 100-200,000 centipoise at 25 ° C.

Another basic component of the present materials is constituted by a hyde resin defined above in an amount of 0.01-25 parts by weight. Preferably, the hydride resin contains a hydride content of broadly 0.05-5% by weight and even more preferably 0.1-1% by weight. It is noted that the hydride resin in the present SiH, olefin and platinum must be present as a catalyst-containing material for solubility reasons. Per 100 parts by weight. of the vinyl containing diorganopoly-siloxane base polymer should be 0.1-25 parts by weight. of a hydride resin defined above. As mentioned earlier, R is a monovalent hydrocarbon group and R * is a hydrogen atom or a monovalent hydrocarbon group. The monovalent hydrocarbon group can be any group other than an aliphatic one. unsaturated hydrocarbon group are, for example, an alkyl group with 1-8 carbon atoms, a cycloalkyl group, a single-core aryl group or - a fluoroalkyl group with up to 8 carbon atoms. Most preferably R is a methyl group, a phenyl group or a 3,3,3-trifluoropropyl group and most preferably R 'is a hydrogen atom, a methyl group, a phenyl group or a 3,3,3-trifluoropropyl group. It is noted that the hydride resin may contain some vinyl unsaturation, but if this vinyl unsaturation is present it is important that the platinum containing catalyst is not mixed with the hydride resin, otherwise the resin cross-links with itself.

The hydride resin can be prepared by known methods. Generally, according to these methods, hydrolysis of the appropriate hydride takes place. Chlorosilanes, preferably in a mixture of water and a hydrocarbon; the resin obtained as a product is extracted and purified.

The other necessary ingredient in the composition is 0.1-500 ppm platinum as a catalyst; preferably 1-200 µm platinum is used. The catalyst serving as platinum can be present as solid platinum deposited on charcoal or on alumina or as soluble platinum complex. Most preferably, a soluble platinum complex is used.

In general one should. use at least 0.1 ppm platinum-containing catalyst (expressed in ppm platinum metal). This platinum-containing catalyst can be used in any suitable form, for example solid platinum metal supported on a solid support, or a soluble platinum complex. Any type of platinum-containing catalyst is suitable according to the invention. A soluble platinum complex is preferably used.

Many types of platinum compounds are known for this SiH-olefin addition reaction which can be used for the present reaction. Particularly when optical clarity is required, the platinum-containing catalysts are preferably platinum compounds which are soluble in the present reaction mixture, e.g. 3,159,601. The olefin in the previous two formulas can be almost any type of olefin. but is preferably an olefin. with 2-8 carbon atoms, a cycloolefin with 5-7. carbon atoms or styrene. Specific examples of suitable olefins are ethylene, propylene. the. isomers of. butene, »... octene, cyclopentene, eyclohexene, eycloheptene, etc.

Another platinum-containing material which can be used in the compositions of the invention. The platinum chloride cyclopropane complex (PtCl ^ C ^ Hg) ^ is described in U.S. Pat. No. 3,159,662.

Still other platinum-containing materials are complexes formed from chloroplatinic acid and up to 2 moles of an alcohol, ether, aldehyde or a mixture of these materials per gram of platinum. described in U.S. Patent 3,220,972.

The preferred platinum compound, which. used not only as a catalyst but also as a flame retardant additive, the compound disclosed in U.S. Pat. No. 3,815,730.

Generally, this type of platinum complex is formed by conversion of chloroplatinic acid, which is 4 moles. hydrate water containing tetravinylcyclotetrasiloxane in the presence of sodium bicarbonate in ethanol as a solvent.

It is noted that the preparation of the hydride resins and also the preparation of the soluble platinum-containing catalyst are known. The be-8 1 0 0 00 8 β i * "....... -7 - ..... '.............: .......

preparation of the vinyl-containing base polymer is also known; according to this preparation, cyclotetrasiloxanes. balanced with the appropriate or desired organic substituents at elevated temperatures in the presence of an alkali metal hydroxide using an appropriate amount of chain stopper. Preferably, the chain stoppers are low molecular weight terminal vinyl containing diorganopolysiloxanes, for example, divinyltetramethyldisiloxane. This gives the desired polymer and when the equilibrium adjustment is complete, ie when about 85% cyclotetrasiloxane has been converted to linear polymer, the reaction temperature is lowered, the alkali metal hydroxide serving as catalyst is neutralized, preferably with an acidic material such as chlorosilane or a silyl phosphate or a -phosphoric acid, and the unreacted excess cyclic compounds are vented as gas, to obtain the desired polymer, when it is desired a low molecular weight diorganopolysiloxane having a viscosity of 50-10,000 centipoise at 25 ° C In this parallel reaction, one may use an acidic catalyst such as toluene sulfonic acid or with. acid-treated clay, such as "Filtrol1 * (a product of Filtrol Corporation of Los Angeles). Another necessary ingredient in the composition is the acryloxysilane in an amount of 0.5-8 parts by weight.

20 and preferably in an amount of 1-5 parts by weight. In formula (1), 2 4 5 R, R and R are monovalent hydrocarbon groups. These monovalent hydrocarbon groups can be any of the monovalent hydrocarbon groups defined above for the vinyl-containing base polymer, for example alkyl groups of 1-8. carbon atoms ,. mononuclear aryl groups such as phenyl, alkenyl groups such as vinyl, cycloalkyl groups such as cyelohexyl, and fluoroalkyl groups such as 3,3,3-trifluoropropyl. Most preferably, R 4, R 5 and R are selected from alkyl groups containing 1 to 8 carbon atoms. such as methyl.

3 R is a divalent hydrocarbon group which is preferably selected from alkylene groups and. arylene groups with up to 8 carbon atoms. Preferably R has at least .3 carbon atoms. It has been found that the compound is not resistant to hydrolysis when it contains less than 3 carbon atoms.

3

Most preferably R is a propyl group, since the propyl group is hydrolysis resistant and readily available for preparing the compounds of formula (1); a is an integer ranging from 35 o to 2 and most preferably 0. Preferably, the compound of formula (1) is obtained by reaction (A) of the formula sheet, wherein R * 1 is an aliphatic unsaturated monovalent. hydrocarbon group having at least 3 carbon atoms and generally 3-8 carbon atoms and 2 4 5 R, R and R having the meanings given above. This reaction is carried out in the presence of a platinum-containing catalyst and is in 8100008% -8. - the silicone chemistry is a known reaction. The hydrogen is added to the ethylenically unsaturated 13 group R in the presence of the platinum-containing catalyst to form the compound of formula (1). The acryloxy compound used as starting material for preparing the compound of formula (1). is readily available and is manufactured, inter alia, by Union Carbide Corporation. and Dynamit Nobel Chemicals Co. placed on the market.

Instead of the aforementioned adryloxysilane used as a self-adhesive additive, a self-adhesive acryloxy-siloxane according to formula (2) can be used in the same concentrations. These acryloxy siloxanes are prepared according to the reaction B of the formula sheet, which reaction is also. a known reaction in the silicone chemistry is and is carried out in the presence of a platinum-containing catalyst which may be any platinum-containing catalyst mentioned above for the compositions of the invention. In the siloxane hydride, a * 0.05-2.0 , b 1.0-2.5 and the sum of a..and „b 1.005-3.0.

11

In the siloxane hydride of reaction B. R is a monovalent hydrocarbon group which is any of the monovalent. cabbage waters can be cool groups that are 11

above for the vinyl containing base polymer. Therefore, R

20 are an alkyl group of 1-8 carbon atoms, a mononuclear aryl group, an alkenyl group, a cyloalkyl group or a fluoroalkyl group. Most preferably R is selected from methyl, vinyl, phenyl and 3,3,3-trifluoropropyl. The ethylenically unsaturated acryloxy compounds used in these reactions. used to prepare the acryloxy siloxanes and the acryloxy silanes. Union Carbide Corporation and Dynamit. Nobel Chemicals marketed.

In preparing the composition, the acryloxysilane or siloxane is first mixed with a hydride resin and must. mixed with resin first, regardless of whether. further ingredients are then added, as set forth below. The platinum-containing catalyst is mixed with a vinyl-containing base silicone. When it is desired to cure the composition, the two components are mixed and applied to the substrate to which the composition is to adhere; the composition hardens at room temperature or at elevated temperatures, i.e., between 80 ° C and 150 ° C, to an elastomer - siloxane. Curing above 100 ° C is extremely fast, namely in a few minutes or even seconds.

To improve the self-adhesive properties of the compositions, at least 400 ppm of an adhesion promoter containing at least one hydroperoxy group can be added to the composition. > * add. In general, 400-10,000 ppm and preferably 400-2,000 ppm of a hydroperoxy compound can be added as an adhesion promoter. Most preferably, this adhesion promoter is methyl ethyl ketone hydroperoxide. Other hydroperoxides which can be used as adhesion promoters are 1.1.3.3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-dihydroperoxyhexane, cumene hydroperoxide, tetrabutyl hydroperoxide, 1-hydroxycyclohexylhydroperoxide, 1.1.3.3-tetramethylbutylhydroperoxide. 2,5-dimethyl-2,5-dihydroperoxyhexane, decaline hydroperoxide, 1,1,2,2-tetramethylpropyl, p-methane hydroperoxide and pinane hydroperoxide. These compounds are marketed by Pennwalt Corp., Hercules Ine., And Lucidol Chemical Company.

These compounds are described in U.S. Pat. No. 4,061,609. It is noted that. these hydroperoxy compounds are disclosed in U.S. Pat. No. 4,061,609 as inhibitors, namely highly effective inhibitors in SiH, olefin. and platinum catalyst-containing compositions. They are not disclosed in this U.S. patent as adhesion promoters, unlike the present application.

It should be noted that the acryloxysilane which is most effective as a self-adhesive additive 20 and is preferably used according to the invention is Y-methacryloxypropyltrimethoxysilane. For further improvement of the self-adhesive properties of the composition, 2-25 parts by weight can be added. gaseous and silazan treated silica per 100 parts by weight. of the base polymer into the composition. This is another adhesion promoter, which improves the self-adhesive properties of the composition over compositions that do not include such silica-treated gas phase silica. The silica obtained from the gas phase may, in addition to being treated with silazanes, also be treated with cyclotetrasiloxanes. However, this is not necessary. An example of such treatment of these fillers is disclosed, for example, in U.S. Pat. No. 3,837,878. Preferably only 2-15 parts by weight are used. gas-phase-treated silica from silazanes. However, it is not desired to exceed 25 parts by weight. use of the gaseous silica because the viscosity of the composition then becomes too great to be used in sieving applications. However, the high viscosity compositions can be used for other applications such as encapsulation and casting of electrical components. The treatment of gas phase silica with eyelotetrasilaxane and silazanes is known.

81 0000 8

♦ Q

- -

In addition to silica obtained from the gaseous phase, an adjuvant filler can be used. In general, 5-100 parts by weight can be used. and preferably 5-50 parts by weight. of an adjuvant filler at 100 parts by weight. of the vinyl-containing base polymer. The adjuvant filler may be selected from titanium oxide, lithopone, zinc oxide, zirconium silicate, silica airgel, iron oxide, diatomaceous earth, calcium carbonate, glass fibers, magnesium oxide, chromium oxide, zirconium oxide, magnesium oxide. α quartz, calcined clay, graphite, cork, cotton and synthetic fibers. These fillers are disclosed in U.S. Pat. No. 4,061,609. U.S. Pat. No. 3,635,743 describes the use of. silazanes for treating gas-phase silica.

When these further ingredients, hl. the hydroperoxy compound and a silazan treated gaseous oxide obtained in the present composition is incorporated, a highly desirable and advantageous self-adhering SiH, olefin, platinum as catalyst and acryloxysilane or siloxane containing an addition-curable composition. This composition can be used in screen printing as it exhibits the desired adhesion to different types of substrates.

The substrates to which good adhesion is obtained with the present compositions with the above adhesion promoters are twill, aluminum, polyvinyl chloride, glass, polyethylene terephthalate, epoxy resin treated fiber glass, phenolic resin containing substrates, "Lexan "(trade name for polycarbonates), styrene, nylon and polyphenylene oxides. It should be noted that the adjuvant filler, most preferably is 25 α quartz, since α quartz increases the tensile strength of the composition without the viscosity of the uncured materials To increase it too much It is advantageous to use any adjuvant filler to increase the tensile strength of the composition without necessarily increasing the viscosity of the uncured composition.

30 in it. In the present case, it is also possible to incorporate a further amount of hydride for curing, i.e., to increase the curing speed when desired, i.e., by heating the composition at elevated temperatures. 1-50 parts by weight of a silicone hydride according to formula (4) can be present, in which formula the groups R are monovalent hydrocarbon groups. or .hydrogen atoms and monovalent hydrocarbon groups and s and t represent 0 or a positive number, a. and other such that the polymer has a viscosity of 10-1,000 centipoise or higher at 25 ° C; preferably the viscosity is 10-100 centipoise at 25 ° C. The group R 6 is preferably an alkyl group with 1-8 carbon atoms, a cycloalkyl-40 group, a mononuclear aryl group, a fluoroalkyl group or another monovalent hydrocarbon group. It should be noted that R may be an alkenyl group, such as a vinyl group, but the platinum-containing catalyst is not packaged together with this resin in the two-pack system.

6

The group R is preferably methyl, phenyl or 3,3,3-trifluoropropyl. Normally, the silicone anhydride generally has a hydride content of 0.15-2.0 wt%, and preferably 0.25-1.7 wt%. Preferably, 1 to 20 parts by weight are used as additional silicone anhydride. from. the silicone anhydride per 100 parts by weight. of the vinyl-containing base polymer of formula (3).

The hydride resin should be present in the present composition. 10 to obtain a solution. This hydride resin must first be mixed with the acryloxysilane to obtain a solution. As a further hydride or in place of the hydride resin, a linear silicone hydride of the above formula may be present to increase the cure speed of the system. The silicone hydride of the above formula is a known material and can be obtained by hydrolysis of the appropriate chlorosilanes to form the desired silicone hydride. Preferably, such a hydride resin is in the composition, which must first be mixed with the acryloxysilane. or acryloxy-siloxane so that the composition has the desired solubility properties. After the. hydride resin is mixed with. the acryloxysilane and polysiloxane ,. to this may become the aforementioned linear silicone anhydride. added. Reinforcing resins can also be used. the composition are included. These resins can be used in place of silicon oxide as a filler, and increase the. tensile strength as well as the tear strength of the cured composition without significantly increasing the viscosity of the uncured composition, so that 1-70 parts by weight can be included in the composition. of a resin consisting of R 1 SiO 4 units and SiO 2 units, wherein R 1 represents a group selected from vinyl, alkyl and aryl groups, and fluoroalkyl groups having 1 to 8 carbon atoms, the ratio being between monofunctional units and tetrafunctional units is 0.5: 1-1: 1 and about 2.5-10 mole% of the silicon atoms bonded to silicon contain vinyl groups, per .100 parts by weight base polymer.

Instead of. this resin can be included in the composition as a resin consisting of monofunctional units, tetrafunctional units and di-functional units. Thus, in the composition, per 100 parts by weight. of 1-7 parts by weight of a vinyl-containing base polymer. of a resin containing 7 7 "7 R ^ SiOg ^ units, R SiO units and. Contains SiO 2 units where R represents a group selected from vinyl, alkyl groups, aryl groups, and fluoroalkyl groups, the ratio between monofunctional units 40 and tetrafunctional units being 0.5: 1 - 1: 1 and the difunctional 8100008 ... ...- 12 -...............

units are present in an amount equal to about 1-10 mole% based on the total moles of siloxane units in the copolymer and contain about 2.5-10 mole% of the silicon atoms vinyl bonded to silicon groups. These resins are known for these olefin and platinum catalyst-containing compositions (see U.S. Pat. No. 3,426,266)

The composition may also contain other additives and ingredients such as additives for influencing thermal aging, flame retardants and additives for imparting swelling resistance if the composition does not contain fluorosiloxane, etc.

10 It is noted that. the hydroperoxy compound in the composition acts as an inhibitor. According to the invention, however, this compound is used primarily as a self-adhesive additive and only secondly as an inhibitor. The composition can contain 100-10,000 ppm of a further inhibitor. For example, a. trialkenyl isocyanurate, per 100 parts by weight. of the 15 total composition. Suitable inhibitors can be used provided they do not detract from the self-adhesive properties in the acryloxy-silane and siloxane-containing system.

It has been found that trialkenyl isocyanurates do not detract from the self-adhesive properties of acryloxysilane and acryloxy-siloxane. The inhibitor-containing composition has a desired processing life at room temperature, but when heated to elevated temperatures, the composition hardens to an elastomer-siloxane in minutes or seconds. When an inhibitor, such as a trialkenyl isocyanurate, is used in the composition , can. the life of the. 25 hours or even days on storage without curing at room temperature. The hydroperoxy compound can also be used as an inhibitor, but is preferably used in the. The above concentrations are used if this compound is primarily used as a adhesion promoter. second place if. inhibitor- must act. If this compound is used. at higher concentrations than stated above, the properties of the hydroperoxide as an agent for the. enhancement of adhesion, not changed, but a considerably stronger "inhibition" of the composition occurs.

To prepare the cured composition, the vinyl-containing polymer and filler are mixed together with the platinum-containing catalyst to form a component or package. The hydride resin is then mixed with the acryloxysilane or. the acryloxy-siloxane, and preferably this mixing becomes a. linear, silicone anhydride. added. A hydroperoxy compound can be added to the vinyl-containing polymer as an additive for promoting adhesion and. a filler may be added, if desired. # 4 0 0 0 0 8 ....... · - - -------- - 13 - --------

When it is desired to cure the composition, the two components or packages are mixed together, preferably in a weight ratio of 10: 1, to form a uniform mixture; the composition is then used for the desired application. According to an embodiment, the composition can be applied to a screen cloth and then pressed through the screen cloth by means of the iron bars on the substrate below, which can be a ceramic material, a plastic or glass; then the composition is heated to cure the composition into the desired shape to obtain, for example, a packing on a substrate of metal, plastic or ceramic material by this screen printing method. It should be noted that the screen cloth is coated in all areas except the areas through which the composition is pressed to obtain the desired shape for the printed material to be applied to the substrate.

All parts given in the non-limiting examples below are parts by weight. In these examples, a composition A was used containing 100 parts by weight. dimethylpolysiloxane. containing terminal vinyl groups and 0.14% vinyl and a viscosity of 3800 centipoise at 25 ° C. 33 parts by weight were mixed with this polymer. of a resin of trimethylsiloxane units, SiO 2 units and methyl vinyl SiO units, the ratio between the monofunctional units and the tetra and difunctional units being sufficient to provide 0.8. trimethyl 1 siloxane unit per SiO 2 unit and the methyl vinyl siloxane units were present in an amount such that 7.00% of the methyl vinyl siloxane atoms were present as methyl vinyl siloxane units and. the remaining silicon atoms as part of a trimethylsiloxane unit or a SiO2 unit. In the examples, a linear hydride of terminal dimethylsiloxy-hydride units and methyl-hydrosiloxane units was used in the inner part of the polymer chain, the polymer having a viscosity of 10 centipoise at 25 ° C and a hydride content of 1. 7 wt%.

EXAMPLE I

With 100 parts by weight. of composition A was mixed 10 parts by weight. of composition B; composition B was prepared by 28 parts by weight. Mix Y-methacry-35 loxypropyltrimethoxysilane with 64 parts by weight. of a resin of hydro-dimethylsiloxy units and SiCl 2 units, said resin containing on average two hydro-dimethylsiloxy units per SiCl 2 unit and 7 parts by weight. of the above-mentioned linear hydride. ASTtt sheets were prepared from the cured composition, which sheets were cured for 1 hour at 100 ° C in a heated press 40. The adhesion was determined, with an overlap connection below 81.00008. ........ '................................. - 14 - ".... .......... '............

use of Alclad aluminum panels and a bonding of 6.45 cm2 and a thickness of .635 micron. The samples were subjected to a drawing speed of about 1.3 cm / min. The examination of the physical properties gave the following results: Durometer, shore hardness: 41: Tensile strength: 3965 kPa; 5 percent, 110%; tear strength: 26.3 N / cm; shear strength of the overlap connection: 3447 kPa; cohesion: 100%.

EXAMPLE II

To 100 parts by weight. 10 parts by weight of composition A were added. of component B, consisting of 50 parts by weight. of the hydride resin of Example 10 and 50 parts by weight. of a terminal vinyl containing dimethylpoysiloxane with 0.14% vinyl and a viscosity of 3800 centipoise at 25 ° C.

The cured sheets obtained had the following properties:

Shore A hardness (durometer): 35; tensile strength: 5170 kPa; elongation: 120%; tear strength 17.5 N / cm; shear strength of the overlap connection: 15 less than approx. 6.9 kPa; cohesion: 0%.

EXAMPLE III

The composition of Example 1 was used as the insert material for strips of a substrate listed in Table A, measuring 2.54 cm by 10.2 cm. The siloxane material was cured at 80 ° C for one hour.

The siloxane material was examined for adhesion to the substrates by scraping it off with a razor and pulling it off. Composition A. cured with composition B of example II in a ratio of 10: 1 and used for the casting of the substrates for comparison purposes. The cured elastomeric siloxane delaminated and was easily released from the substrates * which is typical for organopolysiolanes with dimethylvinyl end groups.

EXAMPLE IV

The above composition A was added. 610 ppm of methyl ethyl ketone hydroperoxide. Due to the opinion of the hydroperoxide, the storage life for the catalyst-containing composition was more than 6 months. Adding the hydroperoxide to the mixture of Example 1 gives a storage life of more than 6 months. Furthermore, the number of plastics to which the composition adheres increases, as shown in Table A below. By adding the hydro-peroxide, the catalyst-containing composition must be subjected to a post-heating at 125 ° C for 10 minutes in order to curing to complete. In all other respects, the composition was used up. processed in the same manner as in Example I. The results are shown in Table A below.

81 00 00 8

- 15 TABLE A

- Cohesive bonding

Substrate Example III Example IV

Polyvinyl chloride good good 5 Copper good good

Glass good good

Polyethylene terephthalate good good

Epoxy fiber glass good .. good

Phenolic resin containing substrate good well

Lexan. no good

Styrene no good

Nylon no good

Noryl no good

Polyvinyl acetate. no none

Acrylic resin none none

EXAMPLE V

A composition C with the same composition as material A was prepared, except that the amount of vinyl containing dimethylpolysiloxane was 60% by weight and the amount of trimethylsiloxane units 20 and methylvinyl-SiO units containing resin was 40% by weight, while in composition These amounts were 75% by weight and 25% by weight, respectively. Composition C was cured with composition B of Example I at room temperature. The siloxane gelled within 24 hours and cured to a transparent material with a Shore hardness of 35. Upon the direct addition of 25% of the o-methyl acryloxypropyltrimethoxysilane to composition A, a precipitate immediately developed. Even after addition of the linear siloxane hydride This Precipitation Present This mixture cured at room temperature and at temperatures up to 150 ° C to obtain an opaque material that exhibited a discontinuous cohesive adhesion of less than 25% to aluminum panels.

The acryloxysilane of Example X was added to terminal dimethylvinyl containing organopolysiloxane having a viscosity of 80 centipoise at 25 ° C and a terminal dimethylvinyl-containing silicone having a viscosity of 3800 centipoise at 25 ° C. A precipitate formed and after 24 hours a yellow liquid was collected which was identified as. the acryloxysilane of Example 1. The same results were obtained when the linear polysiloxane hydride was also used. Only when the acryloxysilane is first mixed with the methyl hydride resin, the acryloxysilane was soluble and stable for more than a year. The hybrid 81 00 00 8% - 16 - can be prepared by reacting ethyl silicate with dimethylhydrochlorosilea in water. When the acryloxy compound of Example I is first mixed with the hydride, stable solutions can be stored using other linear hydro * polysiloxanes and. clear organopolysiloxanes are prepared.

EXAMPLE .VII-XV

In these examples, curing agent solutions containing the acryloxysilane of Example 1 and silicone anhydrides were prepared and cured and used to cure Composition A, one with resin. armed. 10 terminal vinyl containing polymer. The solutions were prepared by first mixing the acryloxysilane of Example I and the hydride resin and then adding the other component. Per 100 parts by weight. polymer were 10 parts by weight. curing agent.added. The adhesion to aluminum was tested by. Harden 30 grams of the mixture on an aluminum scale. The samples were monitored. Hardened for 1 hour. On addition of methyl ethyl ketone hydroperoxide to composition A, a cure temperature of 125 ° C was used. The adhesion was determined by strips of about 1.3 cm. the hardened material from the aluminum seals. and peel off the aluminum strip using an Instron-20 device, model TM. . The strip was peeled at an angle of 90 ° at a rate of about 30.5 cm per minute. The values are given in Newton / cm and the strips were examined for cohesive adhesion (see Table B below).

TABLE B

Example 25: vi, vii .. vin .IX. X. xi XII xiii xiv: xv

Component B

Hydiide resin 64.2 74.8 47 83.6 79.1 74 83.7 81.9 61.7 35.5

of example I.

Acryloxysilane of Example I 28.3.16.4 44.2 16.4 16.5 16.4 16.3 18 13.6 7.8 30.

Linear hydride 1 7.5 8.8 8.8 4.4 24.7 56.7

Linear hydride 2 8.6

Methyl ethyl ketone- 606 606 606 hydroperoxide (added to "A"), ppm 35 Properties

Curing temp. (° C) for 1 hour 100 80 100 100 100 100 125 125 125 100% Cohesive Adhesion 100 100 100 100. 100 100 100 100 100 100

Bond strength N / cm 5.3 4.4 5.6 4.9 4.7 5.1 4.6 4.6 4.6 4.6 2.5

Shore A hardness 32 32 30 33 32 31 33 31 29 81 0000 8. J = · ......... - ------------ - 17 -...... ......... ....... .............

Gel time at room temp., Hours 24 5 24 24 24 24 720 720 720 5 3)% MEMOS in part B 28.3 16.4 44., 2 16.4 16.5 16.4 16/3 18 13.6 7 .8 5% MEMOS3 * in hardened KEV material 2.6 1.5 4.0 1.5 1.5 1.5 1.5 1.6 1.2 0.7 3)

Methacryloxypropyltrimethoxysilane.

example XVI

The composition of Example VI was weighed on an aluminum tray. The material was cured at 100 ° C for 1 hour and the weight percentage of solid was determined. The loss was found to be 0.4% by weight. The cured sample was further heated at 150 ° C for 720 hours without any further weight loss. A sample of Composition A and Composition B- of Example II was tested under the same conditions and showed a weight loss of 0.2% by weight.

EXAMPLE XVII

Hydride resin solutions containing 10, 20 and 50 wt% methyl metacrylate were prepared and used to cure composition A using a weight ratio of composition A to the curing agent of 100: 1. Curing was performed at 80 ° C and 100 eC, respectively. The samples showed no adhesion to aluminum and developed a cloudy two-phase system. Adhesion was not obtained upon addition of methyl ethyl ketone hydroperoxide to the system.

Replacement with triallyl isocyanurate did not cure or bond.

81 0000 8

Claims (46)

Self-adhesive addition-curing siloxane-containing material, characterized by (A) 100 parts. of a vinyl-containing diorganopolysiloxane with a viscosity of 100-500,000 centipoise at 25 ° C and a vinyl content of 0.04-1.5% by weight, in which the organic groups are monovalent hydrocarbon groups, * 6B) 0.1 -500 ppm platinum as a catalyst; *. CC) 0.1-25 parts by weight. of a hydride resin selected from resins with EB ^ SiOg ^ units and Si © 2 units, in which the ratio between H + R and Si ranges from 1.0sl to 2.7: 1, and resins with HR'SiOn - units, SiO units and R 1 SiO units, 10 in which the ratio between H + R + RA and Si ranges from 1.2: 1 to 2.7: 1, where R is a monovalent hydrocarbon group and R1 is a hydrogen atom or a monovalent represents a hydrocarbon group; and (D) 0.5-8 parts by weight. of a self-adhesive additive, namely a silane of formula (1) of the formula sheet, wherein each of the symbols R, R and R represents a monovalent hydrocarbon group, R is a divalent hydrocarbon group and a an integer with a value of 0-2, or a siloxane according to formula 2 (2) of the formula sheet, wherein R and R have the meanings given above, R "represents a monovalent hydrocarbon group, a * ranges from 0.005 to 2 , 0, b ranges from 1.0 to 2.5 and a * + b from 20 ranges from 1.005 to 3.0. 2. Material according to claim 1, characterized in that further at least 400 ppm of an adhesion promoter is present, which agent contains at least one hydroperoxy group. - Material according to claim 2, characterized in that the adhesion promoter 25 is present in a concentration of 400-2000 ppm. The material of claim 2 or. 3, characterized in that the adhesion promoter is methyl ethyl ketone hydroperoxide. 5. Material according to claims 1-4, characterized in that also a silazan-treated silica obtained from the gas phase in an amount of 2-255 parts by weight. is present. 2 5 6. Material according to claims. 1-5, characterized in that R and R 3 are methyl groups, a has the value 0 and R is a divalent hydrocarbon group with. Represents 3-8 carbon atoms. The material according to claim 6, characterized in that the self-adhesive additive is 1f-methacryloxypropyltrimethoxysilane. Material according to claims 1-7, characterized in that further an adjuvant filler in one. amount of 5-100 parts by weight. is present. 9. Material according to claim 8, characterized in that the adjuvant filler is α-quartz. ..... 81 00 00 8 - 19 - 10 *. Material according to claims 1-9, characterized in that a polysiloxane hydride according to formula (4) is furthermore in an amount of 1-50 6 parts by weight. is present, in which formula the groups R represent monovalent hydrocarbon groups or hydrogen atoms and monovalent hydrocarbon groups 5 and s and t represent 0 or a positive number, all such that the polymer has a viscosity of 10-1,000 centipoise at 25 ° C . Material according to claims 1-10, characterized by 1-70 parts by weight. 7 of a resin containing (R) ^ SiOQ ^ units and SiO ^ units, wherein R10 is a vinyl group, alkyl group, aryl group or fluoroalkyl group and the ratio between monofunctional units and tetrafunctional units 0.5: 1-1 : 1 and contain about 2.5-10 mol% of the silicon atoms vinyl bonded to silicon groups. Material according to claims 1-10, characterized by 1-70 parts by weight. 7 7 15 of a resin containing (R SiOg ^ units, R SiO units and SiO2 units, where h7 represents a vinyl group, alkyl group, aryl group or fluoroalkyl group, the ratio between monofunctional units and tetrafunctional units 0.5: 1 -1: 1 and the difunctional units are present in an amount of about 1-10 mol%, based on the total number of moles of 20 siloxane units in the copolymer, and about 2.5-10 mol% of the silicon atoms and silicon-bonded vinyl groups. 13. Material according to claims 1-12, characterized in that the vinyl-containing diorganopolysiloxane (A) has the formula (3) of the formula sheet, in which the symbol Vi represents vinyl, each of the symbols R * ^ a methyl group, phenyl group or represents the fluoroalkyl group and x and z have such values that the viscosity of the polymer is 100-500,000 centipoise at 25 ° C. 14. Material according to claims 1-13, characterized in that the platinum-containing catalyst is a complex of platinum and an olefin or an aryl alcohol. Material according to claims 1 to 13, characterized in that the platinum-containing catalyst is a complex of platinum and a vinyl-containing dimethylpolysiloxane. 16. Material according to claims 1-15, characterized in that: 100-10,000 ppm of an inhibitor. The material according to claim 16, characterized in that the inhibitor is triallyl isocyanurate. t 18. Process for the preparation of a. self-adhesive addition-hardened siloxane-containing material, characterized in that (1) 0.1-25 parts by weight. 40 of a hydride resin, namely a resin with HR 2 SiO 2 units and SiO 2 units, 8 1 0 0 00 8 Λ '. · - .................. Γ ”.........." ...............> 20 -........ ~ ........ ....... '' 'in which the ratio between H + R and Si ranges from 1.0si to 2.7: 1, or a resin with HR2SiOQ ^ units, SiO2 units and R ^ SiO units, wherein the ratio between H + R + R 'and Si ranges from 1.2: 1 to 2.7: 1, where R is a monovalent hydrocarbon group and R 'represents a hydrogen atom or a monovalent hydrocarbon group, mixes with 0.5-8 parts by weight of a self-adhering additive according to formula (1) of the formula sheet 2 4 5 wherein, each of the symbols R, R and R represents a monovalent hydrocarbon group 3, R is a divalent hydrocarbon group and a represents an integer with a value of 0-2, or a siloxane of formula (2) of 2 3, 10 the formula sheet, wherein R and R are those given above have meanings, R "represents a monovalent hydrocarbon group, a ranges from 0.005 to 2.0, b ranges from 1.0 to 2.5, and a + b ranges from 1.005 to 3.0; (2). After completing the mixing, add 100 parts by weight to the resulting mixture. of a vinyl containing diorganopolysiloxane having a viscosity of 100-500,000 centipoise at 25 ° C and a vinyl content of 0.004-1.5 wt%, in which the organic groups are monovalent hydrocarbon groups, and 0.1-500 ppm platinum as a catalyst; and (3) the composition cures to obtain an elastomer & Loxan which is self-adhesive to substrates. Method according to claim 18, characterized in that at least 400 ppm of an at least one hydroperoxy group-containing agent is used for promoting the adhesion. 20. Process according to claim 19, characterized in that the adhesion promoter is used in a concentration of 400-2000 ppm. 21. A method according to claim 19 or 20, characterized in that methyl adhesives such as methyl ethyl ketone hydroperoxide are used as adhesion promoters. Method according to claims 18 = 21, with. the feature that one also 2- 30 2-25 parts by weight. gas phase silica-treated silica. 2 23. Process according to claims 18-22, characterized in that R and / or R 3 are (is) methyl, a has the. Value of 0 and R is a divalent hydrocarbon group with 3-8 carbon atoms. The method of claim 23. with the characteristic that. 1-methacryloxypropyltrimethoxysilane is used as the self-adhesive additive. 25. Process according to claims 18-24, characterized in that also 5-100 parts by weight. of an adjuvant filler. 26. Process according to claim 25, characterized in that cc quartz is used as the adjunct filler. 81 00 00 8 »* - 21 - 27. Process according to claims 18-26, characterized in that also 11-50 parts by weight. of a polysiloxane hydride according to formula (4), in which formula the groups R represent honorable hydrocarbon groups or hydrogen atoms and honorable hydrocarbon groups and s and t represent 0 or a 5 positive number, such that the polymer has a viscosity of 10 -1000 centipoise at 25 ° C. 28. Process according to claims 18-27, characterized in that 7-170 parts by weight are also included. of a resin of R 2 SiO 2 units and SiO 2 units in which R 1 represents a vinyl group, alkyl group, aryl group or fluoroalkyl group, the ratio between monofunctional units and tetrafunctional units 0.5: 1-1: 1 and contain about 2.5-10 mol% of the silicon atoms of silicon-bonded vinyl groups. 29. Process according to claims 18-27, characterized in that 7-7-27 parts by weight are also used. of a resin of R ^ SxOq ^ units, R. SiO units and SiC ^ -15 units, wherein R ^ represents a vinyl group, alkyl group, aryl group or fluoroalkyl group, the ratio between monofunctional units and tetrafunctional units 0.5: 1 -1 rl and the difunctional units are present in an amount of about 1-10 mol%, based on the total number of mol. siloxane units in the copolymer and about 2.5-10 mole% of the silicon atoms contain silicon-bonded vinyl groups. A method according to claims 18-29, characterized in that the vinyl (containing diorganopolysiloxane has the formula (3) of the formula sheet, in which formula the symbol Vi represents a vinyl group, each of the symbols R * 1 represents a methyl group, vinyl group. or fluoroalkyl group and x and z have values such that the viscosity of the polymer is 100-500,000 centipoise at 25 ° C. 31. Process according to claims 18-30, characterized in that as platinum-containing catalyst a complex of platinum and an aldehyde or an alcohol is used. 32. A method according to claims 18-30. characterized in that the platinum-containing catalyst used is a complex of platinum and a vinyl-containing dimethylpolysiloxane. 33. Process according to claims 18-32, characterized in that 100-10,000 ppra of an inhibitor is also used. 34. A method according to claim 33, characterized in that. used as inhi bitor triallyl isocyanurate. 35. A method of manufacturing a laminate of an addition-cured elastomeric siloxane on a substrate of metal, ceramic or plastic, characterized in that (1) 0.1-25 parts by weight. of a 81 0000 8 ·> · »o hydride resin, a resin with HR-SiOrt units, and SiO 2 units, in which the ratio between H + R and Si ranges from 1.0: 1 up to 2.7: 1, or a resin with HR-SiCL. units, SiO units and R 2 SiO units, wherein the 6 Uf O j 6 ratio between H + R + R1 and Si ranges from 1.2: 1 to 2.7: 1, where R _ 1 5 is a monovalent hydrocarbon group and R is a hydrogen atom or a monovalent hydrocarbon group represents 0.5-8 parts by weight with (B). of a self-adhesive additive according to formula (1) of the formula sheet, wherein 2 4 5 3 R, R and R represent monovalent hydrocarbon groups, R represents a divalent hydrocarbon group and a an integer with a value of 1 ... or 2 is whether a siloxane of formula (2) of the formula sheet, wherein R and R have the meanings given above, R "represents a monovalent hydrocarbon group, a ranges from 0.005 to 2.0, b ranges from 1 , 0 to 2.5 and a + b range from 1.005 to 3.0, and (2) add to the resulting mixture 100 parts by weight of a vinyl containing diorganopolysiloxane having a viscosity of 100-500,000 centipoise at 25 ° C. wherein the vinyl content is 0.04-1.5 wt% and the organic groups are monovalent hydrocarbon groups, and 0.1-500 ppm platinum as the catalyst, and (3) applies the composition to a substrate of metal, ceramic material or plastic, and (4) allowing the composition to cure. A method according to claim 35, characterized in that in step (2) at least 400 ppm of. a means of promoting adhesion, which. agent contains at least 1. hydroperoxy group. A method according to claim 35 or 36, characterized in that 2-25 parts by weight are also added in step (2). gaseous phase silazan treated silica applied. . 38. Laminate, containing one. metal, a ceramic material or a plastic as a substrate and an addition-cured, self-adhesive elastomeric silicone which is adhered to the substrate without primer, characterized by (A) 100 parts by weight. .from. a vinyl containing diorganopolysiloxane with a viscosity of 100-500,000 centipoise at 25 ° C, wherein the vinyl content is 0.04-1.5 wt. % and the organic groups are monovalent hydrocarbon groups; (B). 0.1-500 ppm platinum as a catalyst; (C) 0.1-25 parts by weight. of a hydride resin, namely a resin with HR ^ SiOq ^ units and SiOj units, wherein the ratio between H + R and Si ranges from 1.0: 1 to 2.7: 1, or a resin with HR ^ xOq ^ units, SiC ^ units and R2 SiO units, in which the ratio between H + R + R and Si ranges from 1.2: 1 to 2.7: 1, where R is a monovalent hydrocarbon group and R * represents a hydrogen atom or a monovalent hydrocarbon group; and (D) 0.5-8 parts by weight. of a ...... self-adhesive additive, namely a silane according to formula (1) of the formula sheet, wherein R 1, R 2 and R 1 are monovalent. hydrocarbon groups proposal - --- 81 0000 8 3 - 23 - leri / R a. bivalent hydrocarbon group and a is an integer with a value of 0-2, or a siloxane according to formula (2) of the formula 2-3 mule sheet, wherein R and R have the meanings given above, R "is a monovalent hydrocarbon group represents, a * is 0.005-2.0, b 5 is 1.0-2.5 and a * + b is 1.005-3.0. 39. Laminate according to claim 38, characterized in that the addition-cured siloxane material contains an at least one hydroperoxy group containing agent for promoting adhesion in an amount of at least 400 ppm. Laminate according to claim 38 or 39, characterized in that in the siloxane material a silazan-treated silica obtained from the gas phase as filler in an amount of 2-25 parts by weight. is present. 41. Self-adhesive packing of elastomeric siloxane, which has been applied by screen printing method to a substrate of metal, ceramic material or plastic, characterized by C1) a substrate of metal ceramic material or plastic; (2) An addition-cured, siloxane-containing material which has been screen-printed and cured to a gasket of elastomeric slloxan containing (A) 100 parts by weight. a vinyl-containing diorganopolysiloxane having a viscosity of 100-500,000 centipoise at 25 ° C, wherein the vinyl content is 0.04-1.5% by weight and the organic groups are monovalent hydrocarbon groups; (B) 0.1-500 ppm platinum as a catalyst; (C) 0.1-25 parts by weight. of a hydride resin, namely a resin with HR 2 SiO 2 units and SiO 2 units in which the ratio between H + R and Si is 1.0: 1 - 2.7: 1 or a resin with HR 2 SiO2 units, SiO2 units ^ 2 UfO ^ 2 25 and R 'Si units, wherein the ratio between H + R + R and Si is 1.2: 1 - 2.7: 1 z 1, wherein R represents a monovalent hydrocarbon group and R represents a hydrogen atom or a monovalent hydrocarbon group; and (D) 0.5-8 parts by weight. of a self-adhering additive, namely a silane of formula (1) 2 4 5 of the formula sheet, wherein R, R and R are monovalent hydrocarbon radicals, R is a divalent hydrocarbon radical and a is an integer with a value of 0-2, or a siloxane of formula (2) of the formula sheet, wherein R and R have the meanings given above, R "represents a monovalent hydrocarbon group, a * 0.005-2.0, b 1.0- 2.5 and a + b is 1.005-3.0. Packing according to claim 41, characterized in that the uncured siloxane-containing system further comprises an at least one hydroperoxy group-containing adhesion promoter in an amount of at least 400 ppm. 43. A gasket according to claim 41 or 42, characterized in that in the 40 unhardened siloxane-containing composition, also obtained from the gas phase, silazan-treated silicon oxide as filler in an amount of - 8100008 *. ·. 'ï ^ ·' · * - - -: ........ *: ~~ 24 - ................... "" "" 7. .... "· 2-25 parts by weight is present. 44. A method of applying an elastomer, siloxane. mounting material by screen-printing on a substrate, characterized in that (1) on a substrate of metal, ceramic or plastic material: a self-adhering, addition-hardening, siloxane-containing composition is applied by screen-printing, which obtained by (a) is 0.1-25 parts by weight. of a hydride resin, namely a resin with HR ^ SxOq ^ units and SiO units, in which the ratio between H + R and Si 1.0: 1 - 2.7: 1 1. bed, or a resin with HR SiOrt units, SiO units and R-SiO units - UfD. 2, 10, wherein the ratio between H + R + R 1 and Si is 1.2: 1 - 2.7: 1, where R represents a monovalent hydrocarbon group and R hydrogen represents a monovalent hydrocarbon group, to be mixed with 0 , 5-8 parts by weight. of a self-adhering additive of formula (1) - of the formula sheet, wherein 2 4, 5 3 R, R and R are monovalent hydrocarbon groups, R represents a divalent hydrocarbon group and a is an integer with a value of 2 0-2, or a siloxane of the formula (2) of the formula sheet, wherein R 3 and. R. have the meanings given above, R "represents a monovalent hydrocarbon group, a is 0.005-2.0, b is 1.0-2.5, and ta + b is 1.005-3.0; obtained mixture 100 parts by weight of a vinyl-containing diorganopolysiloxane with a viscosity of 100-500,000 centipoise at 25 ° C, wherein the vinyl content is 0.04-1.5% by weight and the organic groups are monovalent hydrocarbon groups, and adding 0.1-500 ppm platinum as a catalyst, and (2) allowing the composition to cure to an elastomeric siloxane. 45. Process according to claim 44, characterized in that the siloxane-containing material is allowed to cure at room temperature. Γ 46. Process: according to claim 44, characterized in that the siloxane-containing material is allowed to cure at elevated temperature. 47. Process according to claims 44-46, characterized in that as ... 30 substrate copper, aluminum, polyvinyl chloride, glass, polyethylene terephthalate, epoxy resin-treated fiber glass, phenolic resin-containing substrate, poly-. carbonate, styrene, polyamide. (nylon), or polyphenylene oxide. 48. Process according to claims 44-47, characterized in that in step (1) further at least 400 ppm of one. uses at least one hydroperoxy group-containing adhesion promoter. 49. Process according to claims 44-48, characterized in that 2-25 parts by weight are further added in step (1). from the gaseous phase, using silazan-treated silicon oxide as a filler. 8TOOOO 8 - * S 2348-1110. - General Electric Company R, O R * (1). L2-3 la 5 CH. “C - C - O - R- Si CO R L. 2.!. j-a R2 | ï (2) CH - c - C - O - R3 R "SiO. 1 · b 4-ao. 2. y ——- x β Η * ·. R10 r" _ R10 II. III I. Vi.Si O --SiO ---- Si 0 - Vi (3 'Ua ha lio RRR * = ly R6 / 1 B6 1 wr —— li — o—- L .--- L — L — ai * T * ij · . {stand R2 O REACTION A - 8 .. - | s 132 = C- c —— o a13 + - "Λ -: s <Γ s H-si · Coa 1. yes? 2 O. 1 * REACTION B. ^ CCO t> 13 + - HR1? SiO Λ 8 1 0 0 0 0 8 - 'V ~ b-