JPS6334901B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to SiH olefin platinum catalyzed addition silicone compositions, and in particular the present invention relates to self-bonding SiH olefin platinum catalyzed addition silicone compositions.
The present invention relates to an olefin platinum contact (catalyzed) composition. Si olefin platinum contact compositions are well known. Such compositions are also referred to as addition-curable compositions. Such compositions generally contain a base vinyl-containing polysiloxane polymer, a hydride crosslinker, and such hydride crosslinker comprises a hydrogenated resin or monofunctional resin consisting of mono- and tetra- and di-functional units. It can be either a hydrogenated resin consisting of units and tetrafunctional units, or a hydrogen-containing linear polysiloxane fluid. The addition of hydrogen in the hydride crosslinker to the vinyl of the polysiloxane to cure the composition takes place under the influence of a platinum catalyst. A number of platinum catalysts have been developed for such purposes, particularly those formed by reacting platinum complexes of aldehydes and alcohols or chloroplatinic acid with vinyl-containing polysiloxanes. The prior art also discloses the incorporation of resins containing vinyl substituents into such compositions, as described in US Pat. No. 3,436,366. The above-mentioned patent describes that such SiH olefin platinum contact compositions or additive compositions can be incorporated with fillers such as fumed silica or precipitated silica or extending fillers. Such compositions are made by containing the vinyl polysiloxane and filler in one package and the platinum catalyst in another package, mixed with a hydride crosslinker with or without filler. The composition is made up of two components or packaged in two packages. When the composition is to be cured, the vinyl siloxane and platinum catalyst can be combined with a hydride and cured to a silicone elastomer at room temperature. It has been found that inhibitor compounds can be incorporated into such compositions so that they can remain uncured at room temperature or can be cured relatively rapidly at elevated temperatures, such as temperatures of 100-150°C. Examples of such inhibitors include, for example, triallylisocyanurate and hydroperoxy compounds such as those described in Bobea, US Pat. No. 4,061,609. The disclosures of the above patents are hereby incorporated by reference. The patented inhibitor compound allows the composition to be packaged in one package for six months to more than one year without causing hardening of the composition, and by heating the composition at elevated temperatures, silicone Can be cured into an elastomer. It should be noted that only hydroperoxy compounds are mentioned as inhibitor compounds in the Bovea patent. Compositions that cure to silicone elastomers yield good potting and enveloping compositions and are suitable for these applications due to the dielectric properties of addition cured silicones. However, the lack of adhesion of such compositions, which are not normally adhesives, can sometimes result in detachment of the encapsulated electronic components.
This occurs when electrical components are exposed to moisture, vibration and damage. Damage or destruction may occur such as electrical discharge across the coating gap resulting from peeling of the coating material. Although the lack of adhesion of such addition cure silicone compositions makes them well suited as molding materials, it is a critical drawback for the use of such compositions in encapsulating or potting electrical components. It should be noted that such addition cure silicone compositions or silicone elastomers have remarkable properties such as optical clarity, tensile strength, elongation and tear properties, resistance to reversion and high temperatures. The lack of adhesion of such addition-cure silicone compositions is a critical drawback when such compositions are used, for example, in gasket applications, glass fabric impregnation, and silk screening. To improve adhesion,
Alternatively, a primer can be used to create the desired adhesion of the silicone cured elastomer to the substrate. However, such primers require additional steps in their application, increasing the cost of addition cure composition applications. Furthermore, such primers are difficult to apply to complex shapes and with complex printing techniques such as silk screen printing. Examples of primers for condensed RTV compositions include Smith U.S. Pat.
4177301. Self-bonding additives have recently been developed in condensation curable RTV and thermosetting silicone rubber compositions. For example, U.S. Patent Application No. 16254 to Smith et al.
No. 1, which is hereby incorporated by reference. It describes the use of silyl maleate and fumarate and succinate to make one-component room temperature curable silicone rubber compositions that undergo self-bond condensation curing. However, such self-binding additives are not useful in addition cure compositions. An example of a scheme for making self-bonding addition cure compositions is found in Ballard, US Pat. No. 3,527,655. However, it does not provide sufficient self-bonding or adhesive properties to the composition. Another more successful scheme is found in Duziak et al., US Patent Application No. 20104, which is incorporated herein by reference. In this case, two divisional applications have been filed from this patent application. The Ballard patent describes vinylalkoxysilanes that are self-bonding addition systems, and such additives did not perform satisfactorily in all cases.
A further preferred self-bonding addition system was made in the Duziak et al. patent application utilizing partial hydrolysis of vinyltriethoxysilane. However, the self-bonding or adhesive properties of such materials were not as good as desired and did not provide as much satisfaction as desired, although they were better than that of Ballard's material. Continuing efforts and efforts are therefore being made to produce self-bonding addition-curing compositions, particularly self-bonding addition-curing RTV compositions that can be used in a variety of printing techniques and for making gaskets on metal or plastic substrates. It has been done. It should be noted that silk screen printing processes are utilized to make gaskets from a variety of materials on a variety of metal and plastic substrates. The purpose of silkscreening is to create complex shapes. Machines are available to print relatively simple shapes, but silk screen printing is used to make gaskets with complex shapes. As mentioned above, in the silk screen printing method, a silk screen of a certain thickness is taken and everything except the gasket shape is finished with varnish. The composition desired to be printed is then applied onto the graphic to be printed. The wiper blade forces the composition into the silkscreen at the exact thickness of the silkscreen, thus causing it to enter the silkscreen and fall onto the substrate in the exact shape desired to print the composition. This method results in the printing of complex geometries and shapes on a variety of substrates. In order to carry out this method, the composition must have adhesive or self-bonding properties to the substrate. Therefore, prior to the present invention, it was difficult to make complex gaskets on substrates such as metal, plastic, and ceramic substrates.
Addition-curing compositions were not available for silk-screening. From the foregoing, it can be seen that according to the present invention there is provided a self-bonding addition-curable silicone composition, which composition according to the present invention (A) has a viscosity varying from 100 to 500,000 centipoise at 25°C; Rate is
100 parts by weight of a base vinyl-containing diorganopolysiloxane varying from 0.04 to 1.5% by weight and in which the organic groups are monovalent hydrocarbon groups, (B) 0.1 to 500 ppm of platinum catalyst, (C)
HR ₂ SiO _0.5 unit and SiO ₂ unit, H+R pair
Resin with Si ratio varying from 1.0 to 2.7, and
A resin having _0.5 units of HR ₂ SiO, ₂ units of SiO and 2 units of R ¹ ₂ SOiO, and a ratio of H+R+R ¹ to Si of 1.2 to 2.7 (in the above formula, R is a monovalent hydrocarbon group, and R ¹ is hydrogen and 0.1 to 25 parts by weight of a hydrogenated resin selected from the group consisting of
(D) General formula (In the formula, R ² , R ⁴ , R ⁵ are monovalent hydrocarbon groups, R ³
is a divalent hydrocarbon group, a is an integer of 0 to 2), and a silane of the general formula (In the formula, R ² and R ³ are as described above, R ¹¹ is a monovalent hydrocarbon group, a′ varies from 0.005 to 2.0,
b varies from 1.0 to 2.5, and the sum of a'+b is 1.005 to 3.0
0.5 to 8 parts by weight of a self-bonding additive selected from the group consisting of siloxanes (varying in weight).
treatment with at least 400 ppm of a self-binding promoter containing at least one hydroperoxy group and 2 to 25 parts by weight of silazane based on 100 parts by weight of the base polymer to increase the self-binding properties of the composition; A fumed silica filler may also be added. It should be noted that in forming such compositions, the hydrogenated resin must first be mixed with the acryloxy compound before mixing the other ingredients into the hydrogenated resin or acryloxy compound. A preferred acryloxy compound is γ-methacryloxypropyltrimethoxysilane. Other details of each invention are provided below. The base vinyl-containing diorganopolysiloxane polymer can be any vinyl-containing diorganopolysiloxane polymer utilized in SiH olefin platinum contact compositions. The vinyl may be the vinyl in the chain, or the vinyl may be on the siloxy terminal unit, or it may be both on the siloxy terminal unit and in the chain.
Preferably the base vinyl-containing diorganopolysiloxane polymer has a viscosity varying from 100 to 500,000 centipoise at 25°C, more preferably from 100 to 500,000 centipoise at 25°C.
It has a viscosity that varies by 200,000 centipoise, and the vinyl content generally varies from 0.04 to 1.5% by weight, more preferably from 0.04 to 1.0% by weight. Organic groups other than vinyl groups in such polymers include, for example, alkyl groups having 1 to 8 carbon atoms such as methyl group and ethyl group; alkenyl groups such as vinyl group and allyl group; monomer groups such as phenyl group and methylphenyl group. It can be any monovalent hydrocarbon group such as a nuclear aryl group; a cycloalkyl group such as a cyclohexyl group, a cycloheptyl group, etc.; and a fluoroalkyl group such as a 3,3,3-trifluoropropyl group.
Preferably the organic groups are selected from vinyl, phenyl and methyl groups, most preferably from vinyl and methyl groups; generally such polymers have the general formula (wherein Vi is a vinyl group and R ¹⁰ is a monovalent hydrocarbon group). The radical R ¹⁰ can be any of the radicals indicated for organic radicals in the definition of diorganopolysiloxane vinyl-containing polymers. Preferably, however, vinyl-containing organopolysiloxane polymers are of the general formula above, in which the vinyl units are only in terminal positions of the chain, and R ¹⁰ is a monovalent hydrocarbon group other than an aliphatically unsaturated hydrocarbon group.
(3). Most preferably R ¹⁰ is selected from the group consisting of methyl, phenyl and fluoroalkyl groups, where x and y are such that the viscosity of the polymer is 25
It changes by 100 to 500,000 centipoise at ℃, more preferably from 100 to 200,000 centipoise at 25℃. The other basic ingredient in the composition is 0.1 to 25 parts by weight of the hydrogenated resin described above. Hydrogenated resin is widely used
It is preferred to have a hydride content of 0.05 to 5% by weight, preferably 0.1 to 1% by weight. It should be noted that the hydrogenated resin must be present in the SiH olefin platinum contact composition for the present invention due to solubility considerations. Therefore, for every 100 parts by weight of the base vinyl-containing diorganopolysiloxane polymer, from 0.1 to 25 parts by weight of the hydrogenated resin as described above must be present. As previously stated, R is selected from monovalent hydrocarbon groups and R ¹ is selected from hydrogen and monovalent hydrocarbon groups. The monovalent hydrocarbon group can be any group other than an aliphatic unsaturated hydrocarbon group. Therefore, as far as R and R ¹ are concerned, they are monovalent hydrocarbon groups which can be selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups and mononuclear aryl groups and fluoroalkyl groups (all having 8 or less carbon atoms). Most preferably R is a methyl group,
selected from phenyl group and 3,3,3-trifluoropropyl group, most preferably R ¹ is hydrogen,
Selected from methyl, phenyl and 3,3,3-trifluoropropyl. The hydrogenated polymer may contain some vinyl unsaturation, but if it contains such vinyl unsaturation,
It is important that the platinum catalyst is not mixed with it,
Otherwise the resin will crosslink itself. Hydrogenated polymers are made by well known methods.
Such processes generally consist of hydrolyzing a suitable hydrogenated chlorosilane, preferably in a water-hydrocarbon solvent mixture (which extracts and purifies the resin product). Other ingredients needed in the composition are 0.1-500ppm
of platinum catalyst, more preferably 1 to 200 ppm of platinum catalyst. The platinum catalyst may be present as solid platinum deposited on activated carbon or gamma alumina, or it may be a solubilized platinum complex. Most preferred are solubilized platinum complexes. Generally at least 0.1 ppm of platinum catalyst, expressed as parts of platinum metal, should be utilized. It can be solid platinum metal deposited on a solid carrier, or it can be a solubilized platinum complex. Any type of platinum catalyst is useful in this invention. Preferably the platinum complex is a solubilized platinum complex. Many types of platinum compounds are known for this SiH olefin addition reaction, and such platinum catalysts can be used in the reaction in the present case. Preferred platinum catalysts, especially when optical clarity is required, are platinum compound catalysts that are soluble in the reaction mixture of the invention. The platinum compounds can be selected from those having the formulas (PtCl ₂ -olefin) ₂ and H (PtCl ₂ -olefin) as described in U.S. Pat. No. 3,159,601 to Ashyubay. The olefin shown in both formulas above can be almost any olefin, including alkylene having 2 to 8 carbon atoms, 5 to 8 carbon atoms,
Cycloalkylene or styrene having 7 is preferred. Specific olefins that may be utilized in the above formula include ethylene, propylene, isomeric forms of butylene, octylene, cyclopentene, cyclohexene, cycloheptene, and the like. Yet another platinum-containing material is formed from chloroplatinic acid with up to 2 moles of one selected from alcohols, ethers, aldehydes and mixtures thereof per gram of platinum, as described in U.S. Pat. No. 3,220,972 to Lamoreau. It can be a complex. All patents and patent applications mentioned herein are hereby incorporated by reference. Preferred platinum compounds that can be used not only as platinum catalysts but also as flame retardant additives are described in Karstedt, US Pat. No. 3,815,730. Generally speaking, platinum complexes of this type are formed by reacting tetravinylcyclotetrasiloxane with chloroplatinic acid containing 4 moles of water of hydration in an alcoholic solution in the presence of sodium bicarbonate. It should be noted that the production of such hydrogenated resins and solubilized platinum catalysts is well known. The production of base vinyl-containing polymers is also well known and generally involves taking cyclotetrasiloxanes with suitable or desired organic substituents and placing them together with an appropriate amount of chain terminator in the presence of an alkali metal hydroxide. The process consists of equilibration at high temperature. Preferably, the chain terminator is a low molecular weight vinyl-terminated diorganopolysiloxane, such as divinyltetramethyldisiloxane. The equilibrium formed yields the desired polymer. When the equilibrium is complete, i.e. approximately 85% of the cyclotetrasiloxane has been converted to linear polymer, the reaction temperature is lowered and the alkali metal hydroxide catalyst is replaced with the chlorosilane. Alternatively, the desired polymer is obtained by neutralizing with an acidic compound such as silyl phosphate or phosphoric acid and removing unreacted excess cyclic compound. When it is desired to make low molecular weight diorganopolysiloxane polymers with viscosities ranging from 50 to 10,000 centipoise at 25°C, acidic catalysts such as toluenesulfonic acid or those commercially available from Filtrol Corporation, Los Angeles, USA, are used in such equilibrium reactions. Acid-treated clays such as Filtrol can be used. Other ingredients required in the composition generally range from 0.5 to 8 parts by weight, preferably 1
~5 parts by weight of acryloxysilane. In the above general formula (1), R ² , R ⁴ and R ⁵ are monovalent hydrocarbon groups. Such monovalent hydrocarbon groups can be any of the monovalent hydrocarbon groups described above for vinyl-containing base polymers. Therefore, such monovalent hydrocarbon groups include alkyl groups having 1 to 8 carbon atoms, mononuclear aryl groups such as phenyl, alkenyl groups such as vinyl, cycloalkyl groups such as cyclohexyl, 3,3,3-tri- It can be a fluoroalkyl group such as a fluoropropyl group.
Most preferably R ² , R ⁴ , R ⁵ are selected from alkyl groups having 1 to 8 carbon atoms such as methyl, and R ³ is a divalent hydrocarbon group, preferably an alkylene group having up to 8 carbon atoms and Select from arylene groups. Preferably R ³ has at least 3 carbon atoms. It has been found that a compound is not hydrolytically stable when it has fewer than 3 carbon atoms. Most preferably R ³ is a propyl group, since propyl is hydrolytically stable and most readily available for making compounds of general formula (1), and a is 0 to 2. is an integer, most preferably zero. Preferred compounds of general formula (1) are formed by the following reaction. (wherein R ¹³ is an aliphatic unsaturated monovalent hydrocarbon group having at least 3 carbon atoms, generally 3 to 8 carbon atoms, and R ² , R ⁴ and R ⁵ are as described above. ). The above reaction is carried out in the presence of a platinum catalyst and is a reaction well known to those skilled in the art. Hydrogen groups are formed into olefinic unsaturated groups in the presence of a platinum catalyst.
is added to R ¹³ to form a compound of general formula (1). Acryloxy intermediates for forming compounds of general formula (1) are readily available and commercially available, for example, from chemical companies such as Union Carbide Corporation and Dynamite Novel Chemicals Company. Instead of the acryloxysilane self-binding additive, an acryloxypolysiloxane self-binding additive of general formula (2) may also be utilized at the same concentration. Such acryloxypolysiloxane compounds are formed from the following reaction. This is also a well-known reaction in silicone chemistry and can be carried out in the presence of a platinum catalyst, and any of the platinum catalysts described above for the compositions of the invention can be used. In the above formula of hydrogenated polysiloxane,
a' varies from 0.005 to 2.0, b varies from 1.0 to 2.5,
The sum of a'+b varies from 1.005 to 3.0. In general formula (1) and the above hydrogenated polysiloxane formula, R ¹¹ can be any monovalent hydrocarbon described above for vinyl-containing polymers. Therefore, R ¹¹ can be an alkyl group having 1 to 8 carbon atoms, a mononuclear aryl group, an alkyl group, a cycloalkyl group or a fluoroalkyl group. Most preferably R ¹¹ is selected from methyl, vinyl, phenyl and 3,3,3-trifluoropropyl. The acryloxyolefinic unsaturated compounds utilized in this reaction to form the acryloxypolysiloxane and acryloxysilane are available from the chemical manufacturers listed above. In preparing the composition, the acryloxysilane or siloxane must first be mixed with the hydrogenated resin, and whether or not additional ingredients such as those described above are added. The platinum catalyst is mixed with the base vinyl-containing polysiloxane polymer. When it is desired to cure the composition, the two components are mixed and applied to the substrate to which it is desired to adhere, and the composition is cured at room temperature to form a silicone elastomer, or cured at elevated temperatures, i.e. above 80°C and 150°C. It becomes a silicone elastomer. Curing at temperatures above 100°C is extremely rapid, curing in minutes or even seconds. However, to improve the self-binding properties of the composition, at least 400 ppm of at least one
A self-bonding promoter having 2 hydroperoxy groups may also be added. Therefore, it is common to use hydroperoxy compounds as self-binding promoters.
10000 ppm of self-bonding promoter preferably containing hydroperoxy groups, preferably 400 to 400 ppm
Use 2000ppm. The most preferred self-binding promoter is methyl ethyl ketone hydroperoxide. Other hydroperoxide self-association promoters that may be utilized include 1,1,3,3-tetramethylbutylhydroperoxide, 2,5-dimethyl-2,5-dihydroperoxyhexane, cumene hydroperoxide, Tetrabutyl hydroperoxide, 1-hydroxycyclohexyl hydroperoxide, decalin hydroperoxide, 1,1,2,2-tetramethylpropyl-
There are p-methane hydroperoxide and pinane hydroperoxide. These compounds are manufactured by Pennwalt Corporation, Hercules
It is marketed by Incorporated and Lucidor Chemical Company. These compounds can be taken from US Pat. No. 4,061,609. It should be noted that these hydroperoxy compounds are described in the above patent specifications and are described as inhibitors, particularly as highly effective inhibitors in SiH olefin platinum contact compositions. They are not mentioned in the above patent specifications as self-binding promoters. It is only in the present specification that they are announced as self-association promoters. It should be noted that the most effective acryloxysilane self-bonding additive desirable to utilize in this invention is gamma-methacryloxypropyltrimethoxysilane. To further increase the self-bonding properties of the composition, 2 to 25 parts by weight of silazane-treated fumed silica per 100 parts by weight of base polymer may also be incorporated. This is another self-bonding promoter, and the use of siloxane-treated fumed silica improves the self-bonding properties of the composition over compositions that do not contain such siloxane-treated fumed silica. Fumed silica can also be treated with cyclotetrasiloxane in addition to silazane. However, this is not necessary. An example of such treatment of such fillers can be found in Beers US Pat. No. 3,837,878. Preferably, only 2 to 15 parts by weight of silazane-treated fumed silica is utilized. However, it is undesirable in any case to use more than 25 parts of fumed silica, since the viscosity of the composition becomes too high for use in silk screen printing. However, compositions with high viscosities can be used for other applications such as packaging and potting of electrical appliances. Treatment of fumed silica with cyclotetrasiloxane and silazane is well known. In addition to such fumed silica treatments and uses, extender fillers can be used. Typically 5 parts by weight of extender filler per 100 parts by weight of base vinyl-containing polymer.
Such extender fillers, which may be utilized up to 100 parts by weight, more preferably 5 to 50 parts by weight, include titanium oxide, lithopone, zinc oxide, zirconium silicate, silica aerogel, iron oxide, diatomaceous earth, calcium carbonate, glass fiber, magnesium oxide. , chromic oxide, zirconium oxide, alpha quartz, calcined clay, carbon, graphite, coke, cotton and synthetic fibers. These fillers are described in Bobair, US Pat. No. 4,061,609. Patents on the use of silazane to treat fumed silica include US Pat. No. 3,635,743. The use of an additional component of a hydroperoxy compound in conjunction with silazane-treated fumed silica provides highly desirable and advantageous self-bonding SiH olefin platinum contact compositions. The use of hydroperxy self-bonding promoters and silazane-treated fumed silicas that can add benefits to acryloxysilane or siloxane compositions provides highly advantageous self-bonding addition cure compositions. It has desirable adhesion to a variety of substrates and can be used for silk screening. Substrates to which good adhesion can be obtained with the above composition using the above self-bonding promoter include copper, aluminum, polyvinyl chloride, glass, polyethylene terephthalate, epoxy fiberglass, phenolic linen, polycarbonate, styrene,
There are nylon and polyphenylene oxide. It should be noted that the most preferred extending filler is alpha quartz. This is because alpha quartz increases the tensile strength of the uncured composition without increasing the viscosity of the composition too much. Optional extending fillers may be utilized without necessarily increasing the viscosity of the uncured composition to an excessive degree.
It should be noted that it has the advantage of increasing the tensile strength of the composition. In the case of the present invention, additional hydrides for curing purposes can also be incorporated if desired, ie to increase the curing rate by heating the composition at elevated temperatures. It is preferable to include 1 to 50 parts by weight of a resin hydrogenated polysiloxane represented by the following general formula (4). where R ⁶ is selected from the group consisting of monovalent hydrocarbon groups and mixtures of hydrogen and monovalent hydrocarbon groups, and s and t are such that the polymer has a viscosity of 10 to 1000 centipoise and more preferably 10 to 100 centipoise at 25°C. It is 0 or a positive number such that . Preferably, the R ⁶ group is selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups, mononuclear aryl groups, fluoroalkyl groups and other monovalent hydrocarbon groups. R ⁶ can be an alkenyl group such as vinyl unless packaged with a platinum catalyst to form the two-component composition. Preferably, the radical R ⁶ is selected from methyl, phenyl and 3,3,3-trifluoropropyl. Usually the hydrogenated polysiloxane has a hydrogen content of 0.15 to 2.0% by weight, more preferably 0.25 to 1.7% by weight. As the additional hydrogenated polysiloxane, hydrogenated polysiloxane 1 to 100 parts by weight of the base vinyl-containing polymer of general formula (3) is used.
Preferably, 20 parts by weight are utilized. It should be noted that in the composition of the invention the hydrogenated resin must be present in order to make it soluble. Such hydrogenated resins should be present in the composition and must first be mixed with the acryloxysilane so that they are soluble. A linear hydrogenated polysiloxane of the above-described formula may be present in place of the hydrogenated resin or as an additional hydrogenation agent to increase the curing rate of the composition. Hydrogenates of polysiloxanes of the above-mentioned formula are well known to those skilled in the art and can be obtained by hydrolysis of appropriate chlorosilanes to produce the desired hydrogenated polysiloxanes. Preferably there should be a hydrogenated resin in the composition; such hydrogenated resin must first be mixed with the acryloxysilane and acryloxypolysiloxane in order to obtain a composition with the desired solubility in the case of the present invention. . After the hydrogenated resin is mixed with the acryloxysilane and polysiloxane, the linear hydrogenated polysiloxane polymer described above may be added thereto. A reinforcing resin may also be added to the composition. Such resins replace silica fillers and increase the tear strength as well as the tensile strength of the cured composition without unduly increasing the uncured viscosity of the composition. Accordingly, 1 to 70 parts by weight of the following resins can be incorporated into the composition per 100 parts by weight of the base polymer. This resin consists of R ⁷ ₃ SiO _0.5 units and SiO ₂ units, where R ⁷ is a group selected from the group consisting of vinyl, alkyl, aryl and fluoroalkyl groups, and a monofunctional unit The ratio of functional units is between 0.5:1 and 1:1, with approximately
2.5-10 mol% contains silicon-bonded vinyl groups. Instead of such resins, resins consisting of mono-, tetra- and di-functional units can be incorporated into the composition. For 100 parts by weight of base vinyl-containing polymer, _0.5 units of R ⁷ ₃ SiO, 0.5 units of R ⁷ SiO and
1 to 70 parts by weight of resin consisting of SiO ₂ units can be incorporated, where R ⁷ is a group selected from the group consisting of vinyl, alkyl, aryl and fluoroalkyl groups, monofunctional units versus tetrafunctional The ratio of units is from 0.5:1 to 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 the silicon atoms about 2.5 to 10 mole percent of the silicon-bonded vinyl groups. Such resins are described in Moditzk's U.S. Patent No.
Olemine platinum catalyst compositions such as those described in US Pat. No. 3,426,266 are known. When the composition is not a fluorosilane or the like, the composition may also contain other additives and components such as heat aging inhibitors, additional flame retardant additives, and anti-swelling additives. It should be noted that the hydroperoxy compounds in the composition also act as inhibitors. However, when it is used in the present invention, it is utilized primarily as a self-binding additive and secondly as an inhibitor. Thus, for every 100 parts by weight of the total composition, 100 to 10,000 ppm of additional inhibitor compound such as trialkenyl isocyanurate may be utilized in the composition. Suitable inhibitor compounds may be utilized in acryloxysilane and siloxane compositions so long as they do not counteract self-bonding properties or self-bonding activity. It has been found that trialkenyl isocyanurates do not interfere with the self-bonding properties of acryloxysilanes and acryloxypolysiloxanes. The inhibited composition has a desirable pot life at room temperature, but cures to a silicone elastomer in minutes or seconds when heated to elevated temperatures. When inhibitors such as trialkenyl isocyanurates are used in the composition,
The composition can have a shelf life of hours or days at room temperature without curing. Although the hydroperoxy compound can also be used as an inhibitor, when it is to act as a self-association promoter and secondly as an inhibitor in the composition of the invention, it may be used at the concentrations mentioned above. It is preferable that it should be used. When utilized above the above-mentioned concentrations, the composition is significantly inhibited from curing without changing the self-bonding promoting properties of the hydroperoxide. To make the cured composition, the vinyl polymer, optionally the vinyl resin, and filler, along with the platinum catalyst, are all mixed together to form one component. Preferably, the hydrogenated resin is then mixed with the acryloxysilane or acryloxypolysiloxane and then the linear hydrogenated polysiloxane is added thereto.
Hydroperoxy self-bonding promoter additives and optional fillers are added to the vinyl polymer. Therefore, when the composition is to be cured, the two components are mixed together to form a homogeneous mixture, preferably in a mixing weight ratio of 10 to 1, and the composition is then heated to the point where it is desired to form it. Give. In one embodiment, the composition is applied to a silk screen and then extruded by a wiper bar through the silk screen onto the underlying substrate (which can be ceramic, plastic or glass), and then The composition is heated to an elevated temperature to cure the composition into the desired form, such as by silk screen printing, to form a gasket on a metal, plastic or ceramic substrate. It should be noted that the silk screen is varnished in all but the areas through which the composition is desired to pass, in order to form the desired shape of the print to be placed on the substrate. In the examples shown below, all parts are parts by weight. The examples are intended to illustrate the invention and are not intended to limit the invention. Composition A was utilized in each example. Such compositions are heated at 25°C.
Contains 100 parts of a vinyl-terminated dimethylpolysiloxane polymer with a viscosity of 3800 centipoise and 0.14% vinyl. This polymer contains trimethylsiloxane units, SiO ₂ units and methylvinyl SiO ₂
The resin is mixed with 33 parts of resin consisting of _methyl The vinylsiloxane units were present in an amount such that 7.0 mol% of the silicon atoms of the methylvinylsiloxane were present as methylvinylsiloxane units, and the remaining silicon atoms were present as part of the trimethylsiloxane units or _SiO2 units. In the examples, a linear hydrogenated polymer consisting of hydrogenated dimethylsiloxy terminal units and methylhydrogensiloxane units within the polymer chain was utilized, the viscosity of this polymer was 10 centipoise at 25°C, and the The hydride concentration was 1.7% by weight. Example 1 Composition A was taken, and 10 parts of composition B was mixed into 100 parts of composition A. Composition B contains 28 parts of γ-methacryloxypropyltrimethoxysilane and 1 part of SiO ₂
It was prepared by mixing 64 parts of a resin consisting of hydrogen dimethylsiloxy units and SiO ₂ units containing an average of 2 dimethyl hydrogen units per unit and 7 parts of the linear hydride described above. This was the weight ratio of one component to the other in component B. from the curing composition
Make an ASTM sheet and heat it at 100℃ in a heated press.
Allowed to cure for hours. Adhesion was measured by lap splice bonding using a 1 square inch, 25 mil thick adhesive layer and Alclad aluminum panels. The sample is
It was pulled at 0.5 in./min. Tests on physical properties showed the following results. Durometer, Shore A hardness 41; tensile strength
575psi; elongation rate 110%; tear strength 15lb/in.;
Lap shear strength 500psi; 100% adhesion. Example 2 To 100 parts of Composition A are added 10 parts of Composition B consisting of 50 parts of a vinyl-terminated dimethylpolysiloxane polymer having a viscosity of 3800 centipoise at 25°C and 0.14% vinyl and 50 parts of the resin hydride of Example 1. Ta. The cured sheet formed had the following properties. Durometer, Shore A hardness 35; tensile strength
750psi; elongation rate 120%, tear strength 10lbs/in.;
Lap shear strength less than 1psi; adhesion 0%. Example 3 The composition of Example 1 was used as a potting compound for the 1 in. x 4 in. substrate pieces shown in the table. The silicone was cured at 80°C for 1 hour. The silicone is scratched with a razor blade for adhesion to the substrate.
Tested by peeling off the silicone. Composition A was cured with the composition of Example 2 in a 10 to 1 ratio and used to pottate substrates for comparison.
The properties of the dimethylvinyl chain-terminated organopolysiloxane were such that the cured silicone elastomer delaminated and was easily released from the substrate. Example 4 Next, 610 ppm of methyl ethyl ketone hydroperoxide was added to the above composition A. With the hydroperoxide, the contact composition had a shelf life of over 6 months. When hydroperoxide was added to the mixture of Example 1, a pot life of over 6 months was obtained. Additionally, the number of plastics to which the composition adhered increased as shown in the table below. With hydroperoxide, the catalyst composition had to be post-baked at 125° C. for 10 minutes to complete curing. In all other respects,
The composition was processed as in Example 1. The results are shown in the table below.

[Table] Example 5 Composition C was made having the same composition as Composition A, but with the ratio of vinyl polymer to vinyl resin being 40% by weight of resin and 60% by weight of polymer. On the other hand, in composition A, the composition was 25% by weight of vinyl resin and 75% by weight of polymer. Composition C was cured with Composition B of Example 1 at room temperature. Silicone is 24
It gelled within hours and hardened to a transparent compound with a Shore hardness of 35. For comparison, when gamma-methylacryloxypropyltrimethoxysilane was added directly to Composition A, a precipitate immediately began to form. The precipitate remained even after adding the linear silicone hydride. The mixture was cured at room temperature and below 150°C to form an opaque compound that exhibited less than 25% discontinuous cohesive bonding to the aluminum panel. The acryloxysilane of Example 1 was heated at 25°C.
Dimethylvinyl-terminated organopolysiloxane with a viscosity of 80000 centipoise and at 25 °C
A dimethylvinyl-terminated polysiloxane polymer having a viscosity of 3800 centipoise was added. A precipitate formed and after 24 hours a yellow liquid was collected which was identified as the acryloxysilane of Example 1. These results were exactly the same as when using linear hydrogenated polysiloxane. Acryloxysilane was soluble and stable for over a year only when first mixed with the methyl hydrogenated resin. Resin hydrides can be made by reacting ethyl silicate with dimethylhydrogenchlorosilane in water. When the acryloxy of Example 1 is first mixed with a resin hydride, storage stable solutions and transparent organopolysiloxane compounds can be made with other linear hydrogen polysiloxanes. Examples 6-15 In these examples, a curing agent solution containing the acryloxysilane and silicon hydride of Example 1 was made, cured, and used to prepare Composition A,
The resin-reinforced vinyl-terminated polymer was cured. The acryloxysilane and hydride resin of Example 1 were first mixed to form a solution, and then the remaining ingredients were added. 10 parts of curing agent were added to 100 parts of polymer. Adhesion to aluminum was tested by curing 30 g of the mixed compound on an aluminum weighing pan. The samples were cured for 1 hour. When adding methyl ethyl ketone hydroperoxide to Composition A, a curing temperature of 125°C was used. Adhesion was measured by cutting a 0.5 inch piece of the cured compound from an aluminum pan and using an Instron Model M to peel off the aluminum piece. The strips were peeled at 90° at a speed of 12 in./min. Values are given in lbs/in. and each piece was tested for adhesive failure as shown in the table below.

Table: Example 16 The composition of Example 6 was mixed and weighed into an aluminum pan. The compounds were cured at 100° C. for 1 hour and the percent solids was determined by weight. The loss is 0.4
% by weight. 150 cured samples
Further heating at ℃ for 720 hours resulted in no further weight loss. Samples of Composition B and Composition A of Example 2 were tested under the same conditions and had a weight loss of 0.2% by weight. Example 17 Solutions of hydride resins containing 10, 20 and 50% by weight of methyl methacrylate were made and hardener 1
Composition A using a ratio of 100 parts to 100 parts of Composition A
used for curing. Curing at 80℃ or
It was carried out at 100℃. The sample showed no adhesion to the aluminum and appeared as a hazy two-phase system. No adhesion was obtained with the addition of methyl ethyl ketone hydroperoxide to the system. Substitution with triallyl isocyanurate resulted in no curing or adhesion.

Claims (1)

[Scope of Claims] 1 (A) The vinyl content is 0.04 to 1.5% by weight,
The organic group is a monovalent hydrocarbon group, and at 25℃
100 parts by weight of a base vinyl-containing diorganopolysiloxane with a viscosity of 500,000 centipoise, (B) a platinum catalyst
0.1 to 500 ppm, (C) HR ₂ SiO _0.5 units with a H+R to Si ratio varying from 1.0 to 2.7 and resins with SiO ₂ units and HR ₂ SiO _0.5 units with a H+R+R ¹ to Si ratio varying from 1.2 to 2.7. , a hydrogenated resin selected from the group consisting of resins having SiO ₂ units and R ¹ ₂ SiO units (in each of the above formulas, R is a monovalent hydrocarbon group, and R ¹ is selected from hydrogen and a monovalent hydrocarbon group) )0.1~25
Parts by weight, and (D) general formula (In the formula, R ² , R ⁴ , R ⁵ are monovalent hydrocarbon groups, R ³
is a divalent hydrocarbon group, a is an integer of 0 to 2), and a silane of the general formula (In the formula, R ² and R ³ are as described above, R ¹¹ is a monovalent hydrocarbon, a′ varies from 0.005 to 2.0, and b
A self-bonding addition-curing silicone composition containing from 0.5 to 8 parts by weight of a self-bonding additive selected from the group consisting of siloxanes with a'+b varying from 1.0 to 2.5 and a'+b varying from 1.005 to 3.0. 2. The composition of claim 1 further comprising at least 400 ppm of a self-binding promoter having at least one hydroperoxy group. 3 Humid silica 2 further treated with silazane
2. The composition of claim 2 containing .about.25 parts by weight. 4 R ² and R ⁵ are methyl groups, a is 0,
3. The composition according to claim 2, wherein ^R3 is a divalent hydrocarbon group having 3 to 8 carbon atoms. 5. Claim 4, wherein the self-binding additive is γ-methacroxypropyltrimethoxysilane.
Compositions as described in Section. 6. A composition according to claim 5, wherein the self-binding promoter is present in a concentration of 400 to 2000 ppm. 7. The composition of claim 6, wherein the self-binding promoter is methyl ethyl ketone hydroperoxide. 8. The composition according to claim 7, further comprising 5 to 100 parts by weight of an extender filler. 9. The composition of claim 8, wherein said extending filler is alpha quartz. 10 General formula (where R ⁶ is selected from the group consisting of monovalent hydrocarbon groups and mixtures of hydrogen and monovalent hydrocarbon groups, and t is 0 or 0 such that the polymer has a viscosity varying from 10 to 1000 centipoise at 25°C. Select a positive number, s is 0
2. The composition of claim 1, further comprising 1 to 50 parts by weight of a hydrogenated polysiloxane (or selected from a positive number). 11 (R ⁷ ) ₃ SiO _0.5 unit and SiO ₂ unit (R ⁷ in the formula
is a group selected from the group consisting of vinyl group, alkyl group, aryl group and fluoroalkyl group), the ratio of monofunctional units to tetrafunctional units is 0.5:1 to 1:1, and silicon atoms Approximately 2.5 ~
Resin 1 containing 10 mol% silicon-bonded vinyl groups
2. A composition according to claim 1 further comprising ~70 parts by weight. 12 (R ⁷ ) ₃ SiO _0.5 unit, R ⁷ SiO unit and SiO ₂
(wherein R ⁷ is a group selected from the group consisting of vinyl, alkyl, aryl and fluoroalkyl groups) in a ratio of monofunctional units to tetrafunctional units of about 0.5:1 to 1. :1, 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 about 2.5 to 10 mole percent of the silicon atoms are silicon-bonded. The composition according to claim 1, further comprising 1 to 70 parts by weight of a resin containing vinyl groups. 13 The base vinyl-containing diorganopolysiloxane polymer has the general formula (In the formula, Vi is a vinyl group, ^R10 is selected from the group consisting of a methyl group, a phenyl group, and a fluoroalkyl group, and x and y are such that the viscosity of the polymer is 100 to 100 at 25°C.
(varies to vary by 500000 centipoise)
The composition according to claim 1, having the following. 14. The composition of claim 1, wherein the platinum catalyst is platinum complexed with a compound selected from the group consisting of alkenyl alcohols and aryl alcohols. 15. The composition of claim 1, wherein the platinum catalyst is platinum complexed with vinyl-containing dimethylpolysiloxane. 16. The composition according to claim 1, further comprising 100 to 10,000 ppm of an inhibitor compound. 17. The composition of claim 16, wherein the inhibitor compound is triallylisocyanurate. 18 (1) Resins having _0.5 HR ₂ SiO units and SiO ₂ units, with a ratio of H+R to Si varying from 1.0 to 2.7;
and HR ₂ SiO _0.5 units and SiO ₂ units and R ¹ ₂
It has SiO units and the ratio of H+R+R ¹ to Si is 1.2~
2.7 Hydrogenated resins selected from the group consisting of ^:
0.1 to 25 parts by weight, general formula (In the formula, R ² , R ⁴ and R ⁵ are monovalent hydrocarbon groups,
R ³ is a divalent hydrocarbon group, a is an integer from 0 to 2) and the general formula (In the formula, R ² and R ³ are as described above,
R ¹¹ is a monovalent hydrocarbon group, 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). (2) After such mixing is complete, 25 parts by weight of a self-binding additive is added to the mixture.
It has a viscosity of 100-500000 centipoise at °C
Adding 100 parts by weight of a base vinyl-containing diorganopolysiloxane polymer having a vinyl content of 0.04 to 1.5% by weight and in which the organic groups are monovalent hydrocarbon groups and 0.1 to 500 ppm of a platinum catalyst; A method of making a self-bonding addition-cure silicone composition comprising curing the composition to form a silicone elastomer that is self-bonding. 19. The method of claim 18, further comprising at least 400 ppm of a self-bonding promoter having at least one hydroperoxy group. 20 Claim 19 further comprising 2 to 25 parts by weight of fumed silica treated with silazane
The method described in section. 21. The method according to claim 20, wherein ^R2 and ^R5 are methyl groups, a is 0, and ^R3 is a divalent hydrocarbon group having 3 to 8 carbon atoms. 22. The method of claim 21, wherein the self-binding additive is γ-methacryloxypropyltrimethoxysilane. 23. The method of claim 22, wherein the self-binding promoter is present in a concentration of 400 to 2000 ppm. 24 Claim 23, wherein the self-binding promoter is methyl ethyl ketone hydroperoxide
The method described in section. 25. The method of claim 24, wherein 5 to 100 parts by weight of extender filler are further present. 26. The method of claim 25, wherein the extender filler is alpha quartz. 27 General formula (where R ⁶ is selected from the group consisting of monovalent hydrocarbon groups and mixtures of hydrogen and monovalent hydrocarbon groups, and t is 0 or a positive number such that the polymer varies from 10 to 1000 centipoise at 25 °C and s is 0 or a positive number) hydrogenated polysiloxane 1~
Claim 18 further comprising 50 parts by weight
The method described in section. 28 R ⁷ ₃ SiO _0.5 unit and SiO ₂ unit (wherein R ⁷ is a group selected from the group consisting of vinyl group, alkyl group, aryl group and fluoroalkyl group), monofunctional unit versus tetrafunctional unit. The ratio of units is
0.5:1 to 1:1, about 2.5 to 10 silicon atoms
Resin containing silicon-bonded vinyl groups in mol% 1~
Claim 18 further comprising 70 parts by weight
The method described in section. 29 Consists of R ⁷ ₃ SiO _0.5 unit, R ⁷ SiO unit and SiO ₂ unit (wherein R ⁷ is a group selected from the group consisting of vinyl group, alkyl group, aryl group and fluoroalkyl group), and is monofunctional. The ratio of units to tetrafunctional units is from 0.5:1 to 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. 19. The method of claim 18, further comprising 1 to 70 parts by weight of a resin in which about 2.5 to 10 mole percent of the silicon atoms contain silicon-bonded vinyl groups. 30 The base vinyl-containing diorganopolysiloxane polymer has the general formula (In the formula, Vi is a vinyl group, ^R10 is selected from the group consisting of a methyl group, a phenyl group, and a fluoroalkyl group, and x and y are such that the viscosity of the polymer is 100 to 100 at 25°C.
19. The method of claim 18, wherein the oscillation rate varies by 500,000 centipoise. 31. The method of claim 18, wherein the platinum catalyst is platinum complexed with a compound selected from the group consisting of aldehydes and alcohols. 32 Claim 18, wherein the platinum catalyst is platinum complexed with vinyl-containing dimethylpolysiloxane
The method described in section. 33. The method of claim 18, further comprising 100 to 10,000 ppm of an inhibitor compound. 34. The method of claim 18, wherein the inhibitor compound is triallylisocyanurate. 35 (1) (A) Resins having _0.5 units of HR ₂ SiO and 0.5 units of SiO ₂ with a ratio of H+R to Si varying from 1.0 to 2.7 and _0.5 units of HR ₂ SiO, 0.5 units of SiO ₂ and R ¹ SiO
from a resin having H + R + R ¹ to Si ratio varying from 1.7 to 2.7 (wherein R is a monovalent hydrocarbon radical and R ¹ is selected from the group consisting of hydrogen and monovalent hydrocarbon radicals) 0.1 to 25 parts by weight of a hydrogenated resin selected from the group consisting of (B) general formula (In the formula, R ² , R ⁴ and R ⁵ are monovalent hydrocarbon groups,
R ³ is a divalent hydrocarbon group, a is an integer from 0 to 2) and the general formula (In the formula, R ² and R ³ are as described above, R ¹¹ is a monovalent hydrocarbon group, a' varies from 0.005 to 2.0, b varies from 1.0 to 2.5, and the sum of a' + b teeth
0.5 to 8 parts by weight of a self-bonding additive selected from the group consisting of siloxanes (varying from 1.005 to 3.0);
100 parts by weight of a base vinyl-containing diorganopolysiloxane polymer with a viscosity of 500,000 centipoise, vinyl content varying from 0.04 to 1.5% by weight, where the organic group is a monovalent hydrocarbon group and a platinum catalyst of 0.1 to 500 ppm. in addition, (3) applying the composition to a substrate selected from metal, ceramic, and plastic substrates, and (4) curing the composition on and to a substrate selected from metal, ceramic, and plastic substrates; A method for producing a laminate made of addition-cured silicone elastomer. 36 In step (2), at least the self-binding polymer having at least one hydroperoxy group is
36. The method according to claim 35, wherein 400 ppm is further present. 37. The method of claim 36, wherein in step (2) 2 to 25 parts by weight of fumed silica treated with silazane is further present. 38 By silk-screening, _a substrate selected from the group consisting of metal, _ceramic and _plastic substrates is coated with: changing resin,
and a resin having _0.5 units of HR ₂ SiO, 0.5 units of SiO ₂ and R ¹ SiO units, with a ratio of H+R+R ¹ to Si varying from 1.2 to 2.7 (where R is a monovalent hydrocarbon group and R ¹
0.1 to 25 parts by weight of a hydrogenated resin selected from the group consisting of (In the formula, R ² , R ⁴ , R ⁵ are monovalent hydrocarbon groups, R ³
is a divalent hydrocarbon group, a is an integer of 0 to 2) and the general formula (In the formula, R ² and R ³ are as described above, R ¹¹ is a monovalent hydrocarbon group, a′ varies from 0.005 to 2.0,
b varies from 1.0 to 2.5, and the sum of a'+b is 1.005 to 3.0
(b) mixed with 0.5 to 8 parts by weight of a self-binding additive selected from the group consisting of siloxanes (varying in
100% by weight of vinyl-containing diorganopolysiloxane polymers having a viscosity of 100 to 500,000 centipoise at 25°C, a vinyl content varying from 0.04 to 1.5% by weight, and in which the organic groups are monovalent hydrocarbon groups, are added to such a mixture. and (2) curing the composition to form a silicone elastomer. A method of printing a silicone elastomer composition by a printing method. 39. The method of claim 38, wherein the silicone composition is cured at room temperature. 40. The method of claim 38, wherein the silicone composition is cured at high temperature. 41 The substrate is copper, aluminum, polyvinyl chloride, glass, polyethylene terephthalate,
39. The method of claim 38, wherein the material is selected from the group consisting of epoxy-fiberglass, phenolic line, polycarbonate, styrene, nylon, polyphenylene oxide. 42 At least a self-bonding promoter having at least one hydroperoxy group in step (1)
39. The method of claim 38, further comprising 400 ppm. 43. The method according to claim 42, wherein in step (1), 2 to 25 parts by weight of a fumed silica filler treated with silazane is further added.