CA1142818A - Paintable silicone elastomers - Google Patents
Paintable silicone elastomersInfo
- Publication number
- CA1142818A CA1142818A CA000341042A CA341042A CA1142818A CA 1142818 A CA1142818 A CA 1142818A CA 000341042 A CA000341042 A CA 000341042A CA 341042 A CA341042 A CA 341042A CA 1142818 A CA1142818 A CA 1142818A
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- Prior art keywords
- group
- radicals
- monovalent hydrocarbon
- paint
- hydrocarbon radicals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Supply Devices, Intensifiers, Converters, And Telemotors (AREA)
- Insulating Bodies (AREA)
- Silicon Polymers (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process is provided herein for improving the adhesion of paint to cross-linked organopolysiloxanes. The process includes the first step of applying at least one organosilicon compound selected from the group consisting of a silane having at least one amino group which is bonded to silicon via carbon and at least one monovalent hydrocarbon radical which is bonded to silicon via oxygen and partial hydrolyzates thereof to the cross-linked organopolysiloxane. Then a paint is applied thereto, the paint being selected from the group consisting of lacquers, aqueous dispersions or varnishes based on nitrocellulose, polyvinyl chloride, polyvinyl ace-tate, copolymers of polyvinyl acetate and copolymers of styrene. This process is applicable to several different types or cross-linked organo-polysiloxanes and/or paints. Moreover, readily available organosilicon com-positions may be used. The process finds use on wood substrates, especially on decks of ships, where they are subsequently painted.
A process is provided herein for improving the adhesion of paint to cross-linked organopolysiloxanes. The process includes the first step of applying at least one organosilicon compound selected from the group consisting of a silane having at least one amino group which is bonded to silicon via carbon and at least one monovalent hydrocarbon radical which is bonded to silicon via oxygen and partial hydrolyzates thereof to the cross-linked organopolysiloxane. Then a paint is applied thereto, the paint being selected from the group consisting of lacquers, aqueous dispersions or varnishes based on nitrocellulose, polyvinyl chloride, polyvinyl ace-tate, copolymers of polyvinyl acetate and copolymers of styrene. This process is applicable to several different types or cross-linked organo-polysiloxanes and/or paints. Moreover, readily available organosilicon com-positions may be used. The process finds use on wood substrates, especially on decks of ships, where they are subsequently painted.
Description
T~is invention relates to silicone elastomers, particularly to paintable silicone elastomers and more particularly to a process for pre-paring silicone elastomers having paintable surfaces.
Heretofore, silicone elastomers having a paintable surface have been prepared by adding silane additives to organopolysiloxane compositions prior to crosslinking. Schulz discloses in U.S. Patent N0 3,812,164 issued May 21, 1974 to J.R. Schulz adding an amide silane of the formula O
(CH30)3 Si(C~12)3 S CH2 CH2 CNH2 to an organopolysiloxane composition containing a hydroxyl endblocked poly-dimethylsiloxane,~an ethyl orthosilicate and a metallic salt of a carboxyl-ic acid. The resultant composition vulcanizes at room temperature to form an elastomer whose surface is paintable.
Also Schulz discloses in U.S. Patent No. 3,836,502 issued Sept.
17, 1974 to J.R. Schulz a composition containing (a~ hydroxyl endblocked polydimethylsiloxàne, (b) an alkoxy compound, e.g. ethyl orghosilicate, (c~ a metallic salt and (d) a silane of the formula n (C~30)3 si(C112) S~C>
(CH3) u which is vulcanizable at room temperature to form an elastomer whose sur-face is paintable.
U.S. Patent No. 3,836,503 issued Sept. 17, 1974 to J.R. Schulz discloses the addition of a silane of the formula (CH30)3 Si ch2 CH2 SCH6H5 . ,~
to a room temperature vulcanizable composition to Eorm an elastomer having a paintable surfaca.
-la-~;
z~
Young, discloses applying a silane to an aqueous based paint or caulking shortly after its applicatlon to a substrate. Also, U.S. Patent N0. 4,038, 293 issued July 26, 1977 to Smith et al disclose quinonoid dyes containing organosiloxane units which are used as painting materials.
A room temperature vulcaniæable organopolysiloxane composition con~taining a silane having at least one amino substituent bonded to silicon through Si-C bonding or alkoxyhydrocarbonoxy radical bonded to silicon through silicon-oxygen linkage is disclosed in U.S. Patent N0. 3,678,003 issued July 18, 1972 to W. Kaiser et al. Even though the resultant elasto-mer exhibits improved adhesion to a substrate, the pressure of the silane in the room temperature vulcanizable organopolysiloxane composition does not improve the paintability of the elastomer.
Therefore, an object of this invention is to provide a process for imparting paintable surfaces to silicone elastomers which are obtained from vulcanizable organopolysiloxane compositions.
In accordance with an aspect of this invention, a process is pro-vided for coating a crosslinked organopolysiloxane elastomer with a paint composition which comprises applying at least one silane having at least one amino group bonded to a silicon atom via carbon and at least one mono-valent hydrocarbon radical which is bonded to silicon via oxygen and which may be substituted with an amino or an alkoxy group and/or partial hydroly-zates thereof to a crosslinked organopolysiloxane elastomer; and there-after applying a paint selected from the group consisting of lacquers, aqueous dispersions or varnishes based on nitrocellulose, polyvinyl chlor-ide, polyvinyl acetate, copolymers of pGlyvinyl acetate and copolymers of styrene.
In another embodiment of this in~iention, the silane may be ad-mixed
Heretofore, silicone elastomers having a paintable surface have been prepared by adding silane additives to organopolysiloxane compositions prior to crosslinking. Schulz discloses in U.S. Patent N0 3,812,164 issued May 21, 1974 to J.R. Schulz adding an amide silane of the formula O
(CH30)3 Si(C~12)3 S CH2 CH2 CNH2 to an organopolysiloxane composition containing a hydroxyl endblocked poly-dimethylsiloxane,~an ethyl orthosilicate and a metallic salt of a carboxyl-ic acid. The resultant composition vulcanizes at room temperature to form an elastomer whose surface is paintable.
Also Schulz discloses in U.S. Patent No. 3,836,502 issued Sept.
17, 1974 to J.R. Schulz a composition containing (a~ hydroxyl endblocked polydimethylsiloxàne, (b) an alkoxy compound, e.g. ethyl orghosilicate, (c~ a metallic salt and (d) a silane of the formula n (C~30)3 si(C112) S~C>
(CH3) u which is vulcanizable at room temperature to form an elastomer whose sur-face is paintable.
U.S. Patent No. 3,836,503 issued Sept. 17, 1974 to J.R. Schulz discloses the addition of a silane of the formula (CH30)3 Si ch2 CH2 SCH6H5 . ,~
to a room temperature vulcanizable composition to Eorm an elastomer having a paintable surfaca.
-la-~;
z~
Young, discloses applying a silane to an aqueous based paint or caulking shortly after its applicatlon to a substrate. Also, U.S. Patent N0. 4,038, 293 issued July 26, 1977 to Smith et al disclose quinonoid dyes containing organosiloxane units which are used as painting materials.
A room temperature vulcaniæable organopolysiloxane composition con~taining a silane having at least one amino substituent bonded to silicon through Si-C bonding or alkoxyhydrocarbonoxy radical bonded to silicon through silicon-oxygen linkage is disclosed in U.S. Patent N0. 3,678,003 issued July 18, 1972 to W. Kaiser et al. Even though the resultant elasto-mer exhibits improved adhesion to a substrate, the pressure of the silane in the room temperature vulcanizable organopolysiloxane composition does not improve the paintability of the elastomer.
Therefore, an object of this invention is to provide a process for imparting paintable surfaces to silicone elastomers which are obtained from vulcanizable organopolysiloxane compositions.
In accordance with an aspect of this invention, a process is pro-vided for coating a crosslinked organopolysiloxane elastomer with a paint composition which comprises applying at least one silane having at least one amino group bonded to a silicon atom via carbon and at least one mono-valent hydrocarbon radical which is bonded to silicon via oxygen and which may be substituted with an amino or an alkoxy group and/or partial hydroly-zates thereof to a crosslinked organopolysiloxane elastomer; and there-after applying a paint selected from the group consisting of lacquers, aqueous dispersions or varnishes based on nitrocellulose, polyvinyl chlor-ide, polyvinyl acetate, copolymers of pGlyvinyl acetate and copolymers of styrene.
In another embodiment of this in~iention, the silane may be ad-mixed
- 2 -~28~
with the paint snd the resultant mixture is then applied to the crosslinked organopolysiloxane elastomer.
By a variant thereof, the monovalent hydrocarbon radical is sub-stituted with a group selected from the class consisting of amino groups, alkoxy groups, and mixtures thereof.
By another variant, the silane is represented by the formula [R22N(CH2)mYa(CH2)m~bsi(oR )c 4-b-c where R i6 selected from the group consisting of monovalent hydrocarbon radicals and substituted monovalent hydrocarbon radicals, R2 is selected from the group consisting of hydrogen, monovalent hydrocarbon radicals and substituted monovalent hydrocarbon radicals, R3 is selected from the group consisting of monovalent hydrocarbon radicals, amino substituted monovalent hydrocarbon radicals and alkoxy substituted monovalent hydrocarbon radicals, Y is selected from the group consisting of oxygen and NR , a is 0 or 1, b and c each represent integèrs of 1, 2 or 3, with the proviso that the sum of b + c may not exceed 4, and m is an integer of from 1 to 10.
By other variants, the catalyst selected from the group consisting of a condensation catalyst and a hydrolysis catalyst is applied to the crosslinked organopolysiloxane; or a catalyst selected from the group con-sisting of a condensation catalyst and a hydrolysis catalyst is mixed withthe organosilicon compound.
Compared to Ithe processes described heretofore,for preparing paintable organopolysiloxanes, the process of aspects of this invention has several advantages over the prior art. For example, the process of aspects of this invention is applicable for several different types of crosslin~ed organopolysiloxanes and/or paints. Moreover, readily available organosili-con compositions may be used in the process of aspects of this invention.
Although any crosslinkable organopolysiloxane may be used in the process of aspects of this invention, it is preferred that diorganopoly-silo~ane-based compositions which may be stored under anhydrous conditions but when exposed to atmospheric moisture, crosslink (cure) at room tempera-ture to form elastomers, be employed.
The diorganopolysiloxane-based compositions which may be stored under anhydrous conditions but which crosslink to form elastomers when ex-posed to atmospheric moisture at room temperature, may be prepared from the same constituents and quantities of constituents which have been used heretofore to form silicone elastomers at room temperature. These diorgano-polysiloxane-based compositions are prepared by mixing at least one silicon compound containing at least 3 silicon-bonded hydrolyzable groups with an organopolysiloxane containing terminal condensable groups and other mater-ials, e.g. fillers, e.g., silicon dioxide which is pyrogenically produced in the gaseous phase~ or calcium carbonate, condensation catalysts, e.g. di-butyltin dilaurate, emollients, e.g. dimethylpolysiloxanes which are liquid at room temperature and which are endblocked by trimethylsiloxy groups, and polyoxyalkylene glycols.
Examples of silicon compounds having at least 3 hydrolyzable groups which are bonded to silicon and which may be used in the preparation of the compositions are silanes having the general formula:
a 4-a ' wherein R represents the same or different monovalent hydrocarbon radicals or substituted monovalent hydrocarbon radicals, Z represents the same or different hydrolyzable groups, and a is zero or 1, and partial hydrolysates thereof containing from 2 to 10 silicon atoms per molecule.
Examples of hydrocarbon radicals represented by R are alkyl radi-cals, e.g. thé methyl, ethyl, n-propyl, and isopropyl radicals as well as octadecyl radicals; alkenyl radicals e.g. the vinyl and allyl radicals;
cycloaliphatic hydrocarbon radicals, e.g. the cyclopentyl and cyclohexyl radicals, as well as methylcyclohexyl and cyclohexenyl radicals; aryl radi-cals e.g. the phenyl radical and xenyl radical; aralkyl radicals, e.g.
benzyl, beta-phenylethyl and the beta-phenylpropyl radicals; as well as alkaryl radicals e.g. the tolyl radical.
Exa~ples of substituted hydrocarbon radicals represented by R
are the haloaryl radicals, e.~. chlorophenyl and bromophenyl radicals, as well as cyanoalkyl radicals, e.g. the beta-cyanoethyl radical.
The methyl radical is the preferred R radical since it is readily available.
Examples of hydrolyzable groups represented by Z are acyloxy radicals (-OOCRl), hydrocarbonoxy radicals (-ORl) and substituted hydrocarbonoxy radicals, aminoxy radicals (-ONR2), amino radicals (-NR21), acylamino radicals (-NRlC0Rl), oxime radicals (-ON=CR2) and phosphate radicals [-OP(OR ) ~
In the above formulas R represents the same or dif-ferent, monovalent hydrocarbon radicals or substituted mono-valent hydrocarbon radicals. In some of the formulas described abov~, at least one of the Rl radicals may also represent hydrogen.
Examples of acyloxy radicals are the formyloxy and the acetoxy radicals.
Examples of hydrocarbonoxy radicals are the methoxy, 20ethoxy and the isopropenyloxy radicals.
An example of a substituted hydrocarbonoxy radical - ls the methoxyethyleneoxy radical.
Examples of aminoxy radicals are the dimethylaminoxy and diethylaminoxy radicals.
Examples of amino radicals are the n-butylamino, sec-butylamino and the cyclohexylamino radicals.
An example of an acylamino radical is the benzoyl-amino radical, Examples of oxime radicals are the acetaldoxime, acetonoxime and the 2-butanonoxime radicals.
An example of a phosphate radical is the di-n-butyl-phosphate radical.
~ 5 --B~
Addittonal examples of cross:Linked organopolysiloxanes which may be coated using the process of aspects of this invention are elastomers or resin-like products of the so-called "two-component system". The "two-component system" comprises a dimethylpolysiloxane having an Si-bonded hy-droxyl group in each ot i-~s terminal groups and filler in one package, and a mixture of a polyethylsilicate and a catalyst 9 e.g. dibutyltin dilaurate in a~other package. When the components of these two packages are mixed, they crosslink to form elastomers.
Other examples of crosslinked organopolysiloxanes which may be coated using the process~of aspects of this invention are elastomers or resin-like products which are obtained from the condensation or from the free radical formation of organopolysiloxanes in the presence of, for ex-ample dicumyl peroxide and at elevated temperatures, for example at tempera-tures in excesæ of 100C.
Examples of crosslinked organopolysiloxanes which may be coated using the process of aspects of this invention are elastomers or resln-like products which are obtained by the addition of organopolysiloxanes contain-ing Si-bonded hydrogen atoms, to organopolysiloxanes containing aliphatic multiple bonds in the presence of a catalyst~ e.g. platinum compound which promotes the addition of Si-bonded hydrogen atoms to aliphatic multiple bonds.
Silanes having at least one amino group per molecule which is bonded to carbon via silicon and which contain at least one monovàlent hydro-carbon radical which is bonded to silicon via oxygen, or substituted by an amino or an alkoxy group are the preferred silanes. These compounds may be represented by the general formula: -[R22N(CH2)mYa(cH23m]bsi(oR )c 4-b-c in which R and a are the same as above; R2 represents hydrogen and/or the same or different monovalent hydrocarbon radicals; R3 represents the same or different monovalent hydrocarbon radicals, or radicals substituted by an amino or an alkoxy group; Y is oxygen or NR ; b and c each represent the integers 1, 2 or 3, with the proviso that the sum of b ~ c may not be more than 4;
and m represents the same or different lntegers in the range of from 1 to 10.
Except for the vin~l radical, the examples cited above for the hydrocarbon radicals R are equally applicable to the hydrocarbon radicals represented by R . Additional examples of 'hydrocarbon radicals represented by R2 are the n-butyl, tert-i butyl, 3,5,5-trimethylcyclohexyl and the ~,3,4-triethylcyclo-10 hexyl radicals. It is, however, preferred that at least one R2 be hydrogen.
Other examples of R radicals are alkyl radicals having from 1 to 6 carbon atoms, e.g. the methyl, ethyl and n-butyl radicals as well as the sec,- and tert,-butyl radicals; amino-alkyl radicals, e~g. the beta-aminoethyl radical; alkoxy-alkyl radicals, e.g. the beta-methoxyethyl radi-cal; cycloalkyl radicals, e.g. the cyclohexyl radical, aryl radicals e.g.
the phenyl radical and aralkyl radicals such as the benzyl radical.
Further examples of silanes represented by the above formula are the following:
CH3Si(OCH2CH2NH2)2(CH2)3O(CH2)2 2 (cH3o)3si(cH2)3NH(cH2)2NH2 H2N(cH2)2o(cH2)3si(ocH2cH2NH2)3 H2N(CH2)20(CH2)3Si(oc2H5)3 Additional examples of these silanes are N-beta-aminoethyl-gamma-amlnopropyltriethozysilane, beta-aminoethyltriethoxysilane, N-beta-aminoethyl-delta-amino-butyltriethoxysilane, gamma-aminopropyltriethoxysilane, 2~
aminomethyltrimethoxysilane, N-beta-aminoethyl-gam~a-amino-propyltris-(methoxyethyleneoxy)- silane, and delta-aminobutyl-triethoxysilane.
It is preferred that a silane be used which has for each molecule at least one amino group bonded to silicon via carbon and at least one monovalent hydrocarbon radical which i$
bonded to silicon vla oxygen and which may be substituted by an amino or an alkoxy group, rather than the partial hydrolysates of such a silane.
However, when a partial hydrolysate of a silane is used which has for each molecule at least one amino group bonded to silicon via carbon and at least one monovalent hydro~
carbon radical which may be substituted by an amino or an alkoxy group, then it is preferred that such a partial hydroly-sate contain no more than - 10 silicon atoms per molecule.
It is however poss'ible to use mixtures of various ~silanes having for each molecule at least one amino group which is bonded to silicon via carbon and at least one hydrocarbon radical or substituted hydrocarbon radical which is bonded to silicon via oxygen. , It is preferred that the organosilicon compound having at least one amino group bonded to silicon via carbon be applied to the crosslinked organopolysiloxane prior to the application of paint rather than being mixed with the paint. When the crosslinked organopolysiloxane is coated with the organosilicon compound rather than being mixed with the paint, a smaller amount of organosilicon compound is required in order to improve -the,adhesion o paint to the crosslinked organopolysiloxane.
When the organosilicon compound is applied as a coating, it is preferred that the silane contain for each molecule at least one amino group which is bonded to silicon via carbon and have at least one monovalent hydrocarbon radical bonded to silicon via oxygen and which may be substituted by an amino or an alkoxy group, and/or partial hydrolysates of such silal~es, be diluted with a solvent,.,,Examples of suitable solvents are aliphatic hydrocarbons,e.g. ,~~-alkanes having boiling points in the range of from 120 to!l80C at 1 bar, aromatic hydrocarbons, e.g.
toluene and xylene; ketones, e-g. \ methyl ethyl ketone;
alcohols, e.g. methanol or isopropanol and/or chlorinated hydrocarbons, e.g.
trichloroethylene~ The organosilicon compounds having at least one amino group bonded to silicon via carbon used in accordance with the process of aspects of this invention may be present in an amount of from 1 to 90 per-cent by weight baæed on the total wieght of the organosilicon compound and the solvent.
The organosilicon compound used in accordance with the process of aspects of thls invention to improve the adhesion of paint on crosslinked . ~
organopolysiloxanes, may be applied to the organopolysiloxanes by spraying, brushing, rolling or immersion~ Condensation or hydrolysis catalysts may be applied to the surface of the crosslinked organopolysiloxane which is to be painted prior to the application, r or simultaneously with the application, and/or subsequent to the application of or mixed with the organosilicon compound containing at least one amino group.
Examples of condensation or hydrolysis catalysts which may be em-ployed are metal carboxylic acid salts or organometallic carboxylic acid salts of metals forming the electromotive series from lead to manganese tcf. Handbook of Chemistry and Physics, 31st Edition, Cleveland, Ohio, 1949, page 1465), especially t~ose of tin, e.g. dibutyltin dilaurate, dibutyltin diacetate, mixtures of dibutyltin diacylates, where the acylates are de-rived from carboxylic acids contalning from 9 to 11 carbon atoms per mole-cule and the carboxyl group is bonded to a tertiary carbon atom in at least 90 percent by weight of the acids; dibutyltin dioctoate, distannoxanes, e.g. diacetoxytetrabutyldistannoxane and dioleyoltetramethyldistannoxane.
Other catalysts are iron octoate, lead octoate, lead laurate and cobalt naphthenate; titanium esters, e.g. tetrabutyltitanate; amines,e.g. n-hexyl-amine; and amine salts, e.g. n-hexylamine hydrochloride and n-butylamine acetate.
The paints used in the process of aspects of this invention may - 8 a -consist of lacquers, aqueous dispersions or varnishes, for example those based on alkyd resins, polyurethane or raw materials for polyurethane, nitrocellulose, epoxide, polyester or polyvinyl chloride or copolymers of polyvinyl chloride which are generally dissolved in an organic solvent.
Other materials which may be used are those based on acrylic resin, poly-vinyl acetate or copolymers of polyvinyl acetate and/or styrene, for ex-ample polystyrene acrylate, which are generally used in the form of aque-ous dispersions.
When the organosilicon compound having at least one amino group which is bonded to silicon via carbon which is used in accordance with the process of an aspect of this invention to improve the adhesion of paint on crosslinked organopolysiloxanes, is added to the paint, it is preferred that the amount of organosilicon compound be from 0.1 to lO percent by weight based on the total weight of paint and organosilicon compound.
The silicone elastomers may be used as sealing and caulking com-positiuns on substrates9 e.g. wood su~strates where it is desirable that they be painted~ Also these compositions may be used to seal around win-dow frames and fissures on decks of sh:ips where they are subsequently painted.
In the following examples all parts and percentages are by weight unless otherwise specified.
The organopolysiloxane elastomers used in the follow-ing examples were prepared in the following manner:
Elastomer A
A mixture containing 120 parts of a dimethypolysilox-ane having an Si-bonded hydroxyl group in each of its terminal units and a viscosity of 80,000 mPas at 25C, 80 parts of a dimethyl-trimethylsiloxy terminated dimethylpolysiloxane having a viscosity of 35 mPas at 25C and 8 parts of a polyoxy-alkylene glycol containing ~0 percent by weight of ethylene A' .
_ g _ oxide and 60 percent by weight propylene oxide and having an average molecular weight of 3,400, were mixed with 28 parts of a mixture consisting of 2 moles of methyltris-(butanone-2-oxime)-silane and 1 mole of methyltris-(cyclohexylamino)-silane and then with 2.4 parts of a silane of the formula:
~CH30)3Si(cH2)3NH(cH2)2N 2 , 180 parts of calcium carbonate whose particles are coated with 3 percent of stearic acid are first added to the resultant mixture, then 16 parts of pyrogenically prepared silicon dioxide having a surface area of 150 m2/g, and then 0.4 part of dibutyltin dilaurate are added to the mixture.
, A 5mm thick layer of the composition thus obtained, is placed on a flat base and e~posed to atmospheric moisture.
The resultant composition is crosslinked to form an elastomer and then used 7 days later.
Elastomer ~
~~ ~ 100 parts of a diorganopolysiloxane end-blocked with trimethylsilox~ groups and consisting of 99.93 mol per-cent of dimethylsiloxane units and 0.07 mol percent of vinyl-methylsiloxane units and having a viscosity of ~ ~ 5 ~1o6 mPas at 25C, are mixed first wi-th 7 parts of a dimethylpoly-siloxane navlng an ~i-bonded hydroxyl group in each of its terminal units and a viscosity of 40 mPas at 25C and 40 parts of pyrogenically produced silicon dioxide having a surface area of 200 m /g and then with 1 part of 95 percent dicumyl peroxide. The resultant composition is shaped and heated ~or 15 minutes to 165C and thereafter heated for 4 hours 'at 200C to form an elastomer.
Exampla 1 A portion of the surface of Elastomer A is brushed with a solution containing 50 parts by weight of a silane of the formula:
(cH3o)3si(cH2)3NH(cH2)2 2 ' 60 parts of toluene and 5 parts of tetra-n-butyltitanate. The coating is allowed to dry at room temperature for one hour.
The section of the surface of Elastomer A which was coated with alkyd resin base, [that known by the registered trademark, DUCOLUX, Glanzcolor gray DG 704, manufactured by the Hermann Wiederhold Company; 4010 Hilden], identified as Paint No. l.
Another section of the surface of Elatomer A which was coated with the silane is coated with a commercially available wood varnish based on alkyd resin [Tixoton wood varnish, nut brown, "Meisterpreis" (the terms "TIXOTON" and "MEISTERPREIS" are trade marks of the Spangenberg Company; 4010 Hilden)], iden-tified as Paint No. 2. A third section of the coated Elastomer A is coated with a commercially available two-component poly-urethane lacquer ~Efdedur KRO-423 ~ Efdedur HU 7 in a ratio ~'o~: 9:1. "EFDEDUR" is a trade mark of the Emil Frei Company;
~15 Braunlingen-Doggin-.
- 10 a -gen), identified as Paint.No. 3. A fourth section of Elastomer which was previously coated with the silane is coated with a commercially available white paint consisting of an aqueous dispersion of a copolymer of styrene and vinyl-acetate (available from Wacker-Chemie GmbH; Munich), identified as Paint No. 4. All four paints completely covered the surface and did not migrate from the surface.
Example 2 The process described in Example 1 is repeated, exclept that elastomer B is substituted for elastomer A. The paint spread evenly on the surface of the elastomer without migrating.
Comparison Example (a?
The process described in Example 1 is repeated, except that the paint migrated on the surface of the untreated ,elastomer.
Comparison Example (b?
The process described in Example 2 is repeated, ex-cept that the untreated surface of the elastomer is coated with the paint. The paint migrated on the surface of the elastomer.
~ fter one month, a 2.54 cm square is subdivided on each painted area with the aid of a :razor blade into 100 equal squares having an area of 6.45 mm . A pressure sensitive adhesive tape is placed on the grid thus formed and then slowly removed at a 30 angle. The number of small squares remaining on the elastomer indicates the percentage of paint retained.
Retention factors of at least 95 percent indicate an excellent adhesion, retention factors of no more than 65 percent indicate poor adhesion. The following table shows the average results of various measurements.
~ ~ , " ,- , .,",,.,~ ~"- ,,~ , ,", -,, '~ - :
with the paint snd the resultant mixture is then applied to the crosslinked organopolysiloxane elastomer.
By a variant thereof, the monovalent hydrocarbon radical is sub-stituted with a group selected from the class consisting of amino groups, alkoxy groups, and mixtures thereof.
By another variant, the silane is represented by the formula [R22N(CH2)mYa(CH2)m~bsi(oR )c 4-b-c where R i6 selected from the group consisting of monovalent hydrocarbon radicals and substituted monovalent hydrocarbon radicals, R2 is selected from the group consisting of hydrogen, monovalent hydrocarbon radicals and substituted monovalent hydrocarbon radicals, R3 is selected from the group consisting of monovalent hydrocarbon radicals, amino substituted monovalent hydrocarbon radicals and alkoxy substituted monovalent hydrocarbon radicals, Y is selected from the group consisting of oxygen and NR , a is 0 or 1, b and c each represent integèrs of 1, 2 or 3, with the proviso that the sum of b + c may not exceed 4, and m is an integer of from 1 to 10.
By other variants, the catalyst selected from the group consisting of a condensation catalyst and a hydrolysis catalyst is applied to the crosslinked organopolysiloxane; or a catalyst selected from the group con-sisting of a condensation catalyst and a hydrolysis catalyst is mixed withthe organosilicon compound.
Compared to Ithe processes described heretofore,for preparing paintable organopolysiloxanes, the process of aspects of this invention has several advantages over the prior art. For example, the process of aspects of this invention is applicable for several different types of crosslin~ed organopolysiloxanes and/or paints. Moreover, readily available organosili-con compositions may be used in the process of aspects of this invention.
Although any crosslinkable organopolysiloxane may be used in the process of aspects of this invention, it is preferred that diorganopoly-silo~ane-based compositions which may be stored under anhydrous conditions but when exposed to atmospheric moisture, crosslink (cure) at room tempera-ture to form elastomers, be employed.
The diorganopolysiloxane-based compositions which may be stored under anhydrous conditions but which crosslink to form elastomers when ex-posed to atmospheric moisture at room temperature, may be prepared from the same constituents and quantities of constituents which have been used heretofore to form silicone elastomers at room temperature. These diorgano-polysiloxane-based compositions are prepared by mixing at least one silicon compound containing at least 3 silicon-bonded hydrolyzable groups with an organopolysiloxane containing terminal condensable groups and other mater-ials, e.g. fillers, e.g., silicon dioxide which is pyrogenically produced in the gaseous phase~ or calcium carbonate, condensation catalysts, e.g. di-butyltin dilaurate, emollients, e.g. dimethylpolysiloxanes which are liquid at room temperature and which are endblocked by trimethylsiloxy groups, and polyoxyalkylene glycols.
Examples of silicon compounds having at least 3 hydrolyzable groups which are bonded to silicon and which may be used in the preparation of the compositions are silanes having the general formula:
a 4-a ' wherein R represents the same or different monovalent hydrocarbon radicals or substituted monovalent hydrocarbon radicals, Z represents the same or different hydrolyzable groups, and a is zero or 1, and partial hydrolysates thereof containing from 2 to 10 silicon atoms per molecule.
Examples of hydrocarbon radicals represented by R are alkyl radi-cals, e.g. thé methyl, ethyl, n-propyl, and isopropyl radicals as well as octadecyl radicals; alkenyl radicals e.g. the vinyl and allyl radicals;
cycloaliphatic hydrocarbon radicals, e.g. the cyclopentyl and cyclohexyl radicals, as well as methylcyclohexyl and cyclohexenyl radicals; aryl radi-cals e.g. the phenyl radical and xenyl radical; aralkyl radicals, e.g.
benzyl, beta-phenylethyl and the beta-phenylpropyl radicals; as well as alkaryl radicals e.g. the tolyl radical.
Exa~ples of substituted hydrocarbon radicals represented by R
are the haloaryl radicals, e.~. chlorophenyl and bromophenyl radicals, as well as cyanoalkyl radicals, e.g. the beta-cyanoethyl radical.
The methyl radical is the preferred R radical since it is readily available.
Examples of hydrolyzable groups represented by Z are acyloxy radicals (-OOCRl), hydrocarbonoxy radicals (-ORl) and substituted hydrocarbonoxy radicals, aminoxy radicals (-ONR2), amino radicals (-NR21), acylamino radicals (-NRlC0Rl), oxime radicals (-ON=CR2) and phosphate radicals [-OP(OR ) ~
In the above formulas R represents the same or dif-ferent, monovalent hydrocarbon radicals or substituted mono-valent hydrocarbon radicals. In some of the formulas described abov~, at least one of the Rl radicals may also represent hydrogen.
Examples of acyloxy radicals are the formyloxy and the acetoxy radicals.
Examples of hydrocarbonoxy radicals are the methoxy, 20ethoxy and the isopropenyloxy radicals.
An example of a substituted hydrocarbonoxy radical - ls the methoxyethyleneoxy radical.
Examples of aminoxy radicals are the dimethylaminoxy and diethylaminoxy radicals.
Examples of amino radicals are the n-butylamino, sec-butylamino and the cyclohexylamino radicals.
An example of an acylamino radical is the benzoyl-amino radical, Examples of oxime radicals are the acetaldoxime, acetonoxime and the 2-butanonoxime radicals.
An example of a phosphate radical is the di-n-butyl-phosphate radical.
~ 5 --B~
Addittonal examples of cross:Linked organopolysiloxanes which may be coated using the process of aspects of this invention are elastomers or resin-like products of the so-called "two-component system". The "two-component system" comprises a dimethylpolysiloxane having an Si-bonded hy-droxyl group in each ot i-~s terminal groups and filler in one package, and a mixture of a polyethylsilicate and a catalyst 9 e.g. dibutyltin dilaurate in a~other package. When the components of these two packages are mixed, they crosslink to form elastomers.
Other examples of crosslinked organopolysiloxanes which may be coated using the process~of aspects of this invention are elastomers or resin-like products which are obtained from the condensation or from the free radical formation of organopolysiloxanes in the presence of, for ex-ample dicumyl peroxide and at elevated temperatures, for example at tempera-tures in excesæ of 100C.
Examples of crosslinked organopolysiloxanes which may be coated using the process of aspects of this invention are elastomers or resln-like products which are obtained by the addition of organopolysiloxanes contain-ing Si-bonded hydrogen atoms, to organopolysiloxanes containing aliphatic multiple bonds in the presence of a catalyst~ e.g. platinum compound which promotes the addition of Si-bonded hydrogen atoms to aliphatic multiple bonds.
Silanes having at least one amino group per molecule which is bonded to carbon via silicon and which contain at least one monovàlent hydro-carbon radical which is bonded to silicon via oxygen, or substituted by an amino or an alkoxy group are the preferred silanes. These compounds may be represented by the general formula: -[R22N(CH2)mYa(cH23m]bsi(oR )c 4-b-c in which R and a are the same as above; R2 represents hydrogen and/or the same or different monovalent hydrocarbon radicals; R3 represents the same or different monovalent hydrocarbon radicals, or radicals substituted by an amino or an alkoxy group; Y is oxygen or NR ; b and c each represent the integers 1, 2 or 3, with the proviso that the sum of b ~ c may not be more than 4;
and m represents the same or different lntegers in the range of from 1 to 10.
Except for the vin~l radical, the examples cited above for the hydrocarbon radicals R are equally applicable to the hydrocarbon radicals represented by R . Additional examples of 'hydrocarbon radicals represented by R2 are the n-butyl, tert-i butyl, 3,5,5-trimethylcyclohexyl and the ~,3,4-triethylcyclo-10 hexyl radicals. It is, however, preferred that at least one R2 be hydrogen.
Other examples of R radicals are alkyl radicals having from 1 to 6 carbon atoms, e.g. the methyl, ethyl and n-butyl radicals as well as the sec,- and tert,-butyl radicals; amino-alkyl radicals, e~g. the beta-aminoethyl radical; alkoxy-alkyl radicals, e.g. the beta-methoxyethyl radi-cal; cycloalkyl radicals, e.g. the cyclohexyl radical, aryl radicals e.g.
the phenyl radical and aralkyl radicals such as the benzyl radical.
Further examples of silanes represented by the above formula are the following:
CH3Si(OCH2CH2NH2)2(CH2)3O(CH2)2 2 (cH3o)3si(cH2)3NH(cH2)2NH2 H2N(cH2)2o(cH2)3si(ocH2cH2NH2)3 H2N(CH2)20(CH2)3Si(oc2H5)3 Additional examples of these silanes are N-beta-aminoethyl-gamma-amlnopropyltriethozysilane, beta-aminoethyltriethoxysilane, N-beta-aminoethyl-delta-amino-butyltriethoxysilane, gamma-aminopropyltriethoxysilane, 2~
aminomethyltrimethoxysilane, N-beta-aminoethyl-gam~a-amino-propyltris-(methoxyethyleneoxy)- silane, and delta-aminobutyl-triethoxysilane.
It is preferred that a silane be used which has for each molecule at least one amino group bonded to silicon via carbon and at least one monovalent hydrocarbon radical which i$
bonded to silicon vla oxygen and which may be substituted by an amino or an alkoxy group, rather than the partial hydrolysates of such a silane.
However, when a partial hydrolysate of a silane is used which has for each molecule at least one amino group bonded to silicon via carbon and at least one monovalent hydro~
carbon radical which may be substituted by an amino or an alkoxy group, then it is preferred that such a partial hydroly-sate contain no more than - 10 silicon atoms per molecule.
It is however poss'ible to use mixtures of various ~silanes having for each molecule at least one amino group which is bonded to silicon via carbon and at least one hydrocarbon radical or substituted hydrocarbon radical which is bonded to silicon via oxygen. , It is preferred that the organosilicon compound having at least one amino group bonded to silicon via carbon be applied to the crosslinked organopolysiloxane prior to the application of paint rather than being mixed with the paint. When the crosslinked organopolysiloxane is coated with the organosilicon compound rather than being mixed with the paint, a smaller amount of organosilicon compound is required in order to improve -the,adhesion o paint to the crosslinked organopolysiloxane.
When the organosilicon compound is applied as a coating, it is preferred that the silane contain for each molecule at least one amino group which is bonded to silicon via carbon and have at least one monovalent hydrocarbon radical bonded to silicon via oxygen and which may be substituted by an amino or an alkoxy group, and/or partial hydrolysates of such silal~es, be diluted with a solvent,.,,Examples of suitable solvents are aliphatic hydrocarbons,e.g. ,~~-alkanes having boiling points in the range of from 120 to!l80C at 1 bar, aromatic hydrocarbons, e.g.
toluene and xylene; ketones, e-g. \ methyl ethyl ketone;
alcohols, e.g. methanol or isopropanol and/or chlorinated hydrocarbons, e.g.
trichloroethylene~ The organosilicon compounds having at least one amino group bonded to silicon via carbon used in accordance with the process of aspects of this invention may be present in an amount of from 1 to 90 per-cent by weight baæed on the total wieght of the organosilicon compound and the solvent.
The organosilicon compound used in accordance with the process of aspects of thls invention to improve the adhesion of paint on crosslinked . ~
organopolysiloxanes, may be applied to the organopolysiloxanes by spraying, brushing, rolling or immersion~ Condensation or hydrolysis catalysts may be applied to the surface of the crosslinked organopolysiloxane which is to be painted prior to the application, r or simultaneously with the application, and/or subsequent to the application of or mixed with the organosilicon compound containing at least one amino group.
Examples of condensation or hydrolysis catalysts which may be em-ployed are metal carboxylic acid salts or organometallic carboxylic acid salts of metals forming the electromotive series from lead to manganese tcf. Handbook of Chemistry and Physics, 31st Edition, Cleveland, Ohio, 1949, page 1465), especially t~ose of tin, e.g. dibutyltin dilaurate, dibutyltin diacetate, mixtures of dibutyltin diacylates, where the acylates are de-rived from carboxylic acids contalning from 9 to 11 carbon atoms per mole-cule and the carboxyl group is bonded to a tertiary carbon atom in at least 90 percent by weight of the acids; dibutyltin dioctoate, distannoxanes, e.g. diacetoxytetrabutyldistannoxane and dioleyoltetramethyldistannoxane.
Other catalysts are iron octoate, lead octoate, lead laurate and cobalt naphthenate; titanium esters, e.g. tetrabutyltitanate; amines,e.g. n-hexyl-amine; and amine salts, e.g. n-hexylamine hydrochloride and n-butylamine acetate.
The paints used in the process of aspects of this invention may - 8 a -consist of lacquers, aqueous dispersions or varnishes, for example those based on alkyd resins, polyurethane or raw materials for polyurethane, nitrocellulose, epoxide, polyester or polyvinyl chloride or copolymers of polyvinyl chloride which are generally dissolved in an organic solvent.
Other materials which may be used are those based on acrylic resin, poly-vinyl acetate or copolymers of polyvinyl acetate and/or styrene, for ex-ample polystyrene acrylate, which are generally used in the form of aque-ous dispersions.
When the organosilicon compound having at least one amino group which is bonded to silicon via carbon which is used in accordance with the process of an aspect of this invention to improve the adhesion of paint on crosslinked organopolysiloxanes, is added to the paint, it is preferred that the amount of organosilicon compound be from 0.1 to lO percent by weight based on the total weight of paint and organosilicon compound.
The silicone elastomers may be used as sealing and caulking com-positiuns on substrates9 e.g. wood su~strates where it is desirable that they be painted~ Also these compositions may be used to seal around win-dow frames and fissures on decks of sh:ips where they are subsequently painted.
In the following examples all parts and percentages are by weight unless otherwise specified.
The organopolysiloxane elastomers used in the follow-ing examples were prepared in the following manner:
Elastomer A
A mixture containing 120 parts of a dimethypolysilox-ane having an Si-bonded hydroxyl group in each of its terminal units and a viscosity of 80,000 mPas at 25C, 80 parts of a dimethyl-trimethylsiloxy terminated dimethylpolysiloxane having a viscosity of 35 mPas at 25C and 8 parts of a polyoxy-alkylene glycol containing ~0 percent by weight of ethylene A' .
_ g _ oxide and 60 percent by weight propylene oxide and having an average molecular weight of 3,400, were mixed with 28 parts of a mixture consisting of 2 moles of methyltris-(butanone-2-oxime)-silane and 1 mole of methyltris-(cyclohexylamino)-silane and then with 2.4 parts of a silane of the formula:
~CH30)3Si(cH2)3NH(cH2)2N 2 , 180 parts of calcium carbonate whose particles are coated with 3 percent of stearic acid are first added to the resultant mixture, then 16 parts of pyrogenically prepared silicon dioxide having a surface area of 150 m2/g, and then 0.4 part of dibutyltin dilaurate are added to the mixture.
, A 5mm thick layer of the composition thus obtained, is placed on a flat base and e~posed to atmospheric moisture.
The resultant composition is crosslinked to form an elastomer and then used 7 days later.
Elastomer ~
~~ ~ 100 parts of a diorganopolysiloxane end-blocked with trimethylsilox~ groups and consisting of 99.93 mol per-cent of dimethylsiloxane units and 0.07 mol percent of vinyl-methylsiloxane units and having a viscosity of ~ ~ 5 ~1o6 mPas at 25C, are mixed first wi-th 7 parts of a dimethylpoly-siloxane navlng an ~i-bonded hydroxyl group in each of its terminal units and a viscosity of 40 mPas at 25C and 40 parts of pyrogenically produced silicon dioxide having a surface area of 200 m /g and then with 1 part of 95 percent dicumyl peroxide. The resultant composition is shaped and heated ~or 15 minutes to 165C and thereafter heated for 4 hours 'at 200C to form an elastomer.
Exampla 1 A portion of the surface of Elastomer A is brushed with a solution containing 50 parts by weight of a silane of the formula:
(cH3o)3si(cH2)3NH(cH2)2 2 ' 60 parts of toluene and 5 parts of tetra-n-butyltitanate. The coating is allowed to dry at room temperature for one hour.
The section of the surface of Elastomer A which was coated with alkyd resin base, [that known by the registered trademark, DUCOLUX, Glanzcolor gray DG 704, manufactured by the Hermann Wiederhold Company; 4010 Hilden], identified as Paint No. l.
Another section of the surface of Elatomer A which was coated with the silane is coated with a commercially available wood varnish based on alkyd resin [Tixoton wood varnish, nut brown, "Meisterpreis" (the terms "TIXOTON" and "MEISTERPREIS" are trade marks of the Spangenberg Company; 4010 Hilden)], iden-tified as Paint No. 2. A third section of the coated Elastomer A is coated with a commercially available two-component poly-urethane lacquer ~Efdedur KRO-423 ~ Efdedur HU 7 in a ratio ~'o~: 9:1. "EFDEDUR" is a trade mark of the Emil Frei Company;
~15 Braunlingen-Doggin-.
- 10 a -gen), identified as Paint.No. 3. A fourth section of Elastomer which was previously coated with the silane is coated with a commercially available white paint consisting of an aqueous dispersion of a copolymer of styrene and vinyl-acetate (available from Wacker-Chemie GmbH; Munich), identified as Paint No. 4. All four paints completely covered the surface and did not migrate from the surface.
Example 2 The process described in Example 1 is repeated, exclept that elastomer B is substituted for elastomer A. The paint spread evenly on the surface of the elastomer without migrating.
Comparison Example (a?
The process described in Example 1 is repeated, except that the paint migrated on the surface of the untreated ,elastomer.
Comparison Example (b?
The process described in Example 2 is repeated, ex-cept that the untreated surface of the elastomer is coated with the paint. The paint migrated on the surface of the elastomer.
~ fter one month, a 2.54 cm square is subdivided on each painted area with the aid of a :razor blade into 100 equal squares having an area of 6.45 mm . A pressure sensitive adhesive tape is placed on the grid thus formed and then slowly removed at a 30 angle. The number of small squares remaining on the elastomer indicates the percentage of paint retained.
Retention factors of at least 95 percent indicate an excellent adhesion, retention factors of no more than 65 percent indicate poor adhesion. The following table shows the average results of various measurements.
~ ~ , " ,- , .,",,.,~ ~"- ,,~ , ,", -,, '~ - :
3'L8 TABLE
__ ~xample Percentage o~ paint retained 2 ' . '100 100 100 100 . Comparison . Examples 2 2 O O
(b) 4 O 5 O
. . .
' ' ' .
__ ~xample Percentage o~ paint retained 2 ' . '100 100 100 100 . Comparison . Examples 2 2 O O
(b) 4 O 5 O
. . .
' ' ' .
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for improving the adhesion of paint to a cross-linked organopolysiloxane which comprises: applying at least one organo-silicon compound selected from the group consisting of a silane having at least one amino group which is bonded to silicon via carbon and at least one monovalent hydrocarbon radical which is bonded to silicon via oxygen and partial hydrolyzates thereof to the crosslinked organopolysiloxane;
and thereafter applying a paint selected from the group consisting of lacquers, aqueous dispersions or varnishes based on nitrocellulose, poly-vinyl chloride, polyvinyl acetate, copolymers of polyvinyl acetate and copolymers of styrene.
and thereafter applying a paint selected from the group consisting of lacquers, aqueous dispersions or varnishes based on nitrocellulose, poly-vinyl chloride, polyvinyl acetate, copolymers of polyvinyl acetate and copolymers of styrene.
2. The process of claim 1, wherein the organosilicon compound is admixed with the paint and the mixture is applied to the crosslinked organopolysiloxane.
3. The process of claims 1 or 2, wherein the monovalent hydro-carbon radical is substituted with a group selected from the class consist-ing of amino groups, alkoxy groups, and mixtures thereof.
4. The process of claims 1 and 2, wherein the silane is repre-sented by the formula [R?N(CH2)mYa(CH2)m]bSi(OR3)cR4-b-c , where R is selected from the group consisting of monovalent hydrocarbon radicals and substituted monovalent hydrocarbon radicals, R3 is selected from the group consisting of hydrogen,-monovalent hydrocarbon radicals and substituted monovalent hydrocarbon radicals, R3 is selected from the group consisting of monovalent hydrocarbon radicals, amino substituted monovalent hydrocarbon radicals and alkoxy substituted monovalent hydro-carbon radicals, Y is selected from the group consisting of oxygen and NR2, a is 0 or 1, b and c each represent integers of 1, 2 or 3, with the proviso that the sum of b + c may not exceed 4, and m is an integer of from 1 to 10.
5. The process of claims 1 and 2, wherein a catalyst selected from the group consisting of a condensation catalyst and a hydrolysis cata-lyst is applied to the crosslinked organopolysiloxane.
6. The process of claims 1 and 2, wherein a catalyst selected from the group consisting of a condensation catalyst and a hydrolysis catalyst is mixed with the organosilicon compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2852090.3 | 1978-12-01 | ||
| DE2852090A DE2852090C2 (en) | 1978-12-01 | 1978-12-01 | Process for coating crosslinked organopolysiloxane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1142818A true CA1142818A (en) | 1983-03-15 |
Family
ID=6056100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000341042A Expired CA1142818A (en) | 1978-12-01 | 1979-12-03 | Paintable silicone elastomers |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS5575430A (en) |
| AU (1) | AU5339679A (en) |
| BE (1) | BE880329A (en) |
| CA (1) | CA1142818A (en) |
| CH (1) | CH641191A5 (en) |
| DE (1) | DE2852090C2 (en) |
| ES (1) | ES486473A1 (en) |
| FR (1) | FR2442668A1 (en) |
| GB (1) | GB2039231A (en) |
| IT (1) | IT7950946A0 (en) |
| NL (1) | NL7908083A (en) |
| NO (1) | NO793902L (en) |
| SE (1) | SE438610B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57180674A (en) * | 1981-04-30 | 1982-11-06 | Toray Silicone Co Ltd | Primer composition for heat-curable silicone elastomer |
| JPH066680B2 (en) * | 1985-10-30 | 1994-01-26 | 東レ・ダウコーニング・シリコーン株式会社 | Primer composition |
| US5248334A (en) * | 1988-12-12 | 1993-09-28 | Dow Corning Corporation | Primer composition, coating method and coated silicone substrates |
| US4923946A (en) * | 1988-12-12 | 1990-05-08 | Dow Corning Corporation | Composition and method for priming and coating silicone substrates |
| US4992312A (en) * | 1989-03-13 | 1991-02-12 | Dow Corning Wright Corporation | Methods of forming permeation-resistant, silicone elastomer-containing composite laminates and devices produced thereby |
| US5213617A (en) * | 1991-06-13 | 1993-05-25 | Dow Corning Corporation | Primer for silicone substrates |
| JP6054060B2 (en) * | 2012-05-17 | 2016-12-27 | 株式会社フコク | Rubber member, rubber coating agent, and rubber member manufacturing method |
| DE102018100214A1 (en) * | 2018-01-08 | 2019-07-11 | Jörg Nass | Method for priming silicone surfaces |
-
1978
- 1978-12-01 DE DE2852090A patent/DE2852090C2/en not_active Expired
-
1979
- 1979-11-05 NL NL7908083A patent/NL7908083A/en not_active Application Discontinuation
- 1979-11-29 BE BE0/198344A patent/BE880329A/en not_active IP Right Cessation
- 1979-11-29 IT IT7950946A patent/IT7950946A0/en unknown
- 1979-11-30 CH CH1067079A patent/CH641191A5/en not_active IP Right Cessation
- 1979-11-30 JP JP15451979A patent/JPS5575430A/en active Pending
- 1979-11-30 NO NO793902A patent/NO793902L/en unknown
- 1979-11-30 GB GB7941492A patent/GB2039231A/en not_active Withdrawn
- 1979-11-30 ES ES486473A patent/ES486473A1/en not_active Expired
- 1979-11-30 SE SE7909907A patent/SE438610B/en unknown
- 1979-12-03 CA CA000341042A patent/CA1142818A/en not_active Expired
- 1979-12-03 FR FR7929649A patent/FR2442668A1/en active Granted
- 1979-12-03 AU AU53396/79A patent/AU5339679A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| ES486473A1 (en) | 1980-05-16 |
| IT7950946A0 (en) | 1979-11-29 |
| BE880329A (en) | 1980-05-29 |
| FR2442668B1 (en) | 1984-12-14 |
| FR2442668A1 (en) | 1980-06-27 |
| AU5339679A (en) | 1980-06-05 |
| NL7908083A (en) | 1980-06-03 |
| SE438610B (en) | 1985-04-29 |
| SE7909907L (en) | 1980-06-02 |
| GB2039231A (en) | 1980-08-06 |
| CH641191A5 (en) | 1984-02-15 |
| JPS5575430A (en) | 1980-06-06 |
| NO793902L (en) | 1980-06-03 |
| DE2852090A1 (en) | 1980-06-12 |
| DE2852090C2 (en) | 1984-01-12 |
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