CA1299802C - Uv activation of addition cure silicone coatings - Google Patents
Uv activation of addition cure silicone coatingsInfo
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- CA1299802C CA1299802C CA000554578A CA554578A CA1299802C CA 1299802 C CA1299802 C CA 1299802C CA 000554578 A CA000554578 A CA 000554578A CA 554578 A CA554578 A CA 554578A CA 1299802 C CA1299802 C CA 1299802C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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Abstract
PATENTS
60S1-1002/JWH:mz/0313p Abstract of the Disclosure There is provided a platinum catalyzed addition curable polyorganosiloxane release coating composition containing a dialkylacetylenedicarboxylte inhibitor for preventing premature gellation at ambient temperatures but which will cure upon ultraviolet light exposure via a hydrosilation reaction to form a coating capable of releasing materials from substrates which would normally adhere thereto.
60S1-1002/JWH:mz/0313p Abstract of the Disclosure There is provided a platinum catalyzed addition curable polyorganosiloxane release coating composition containing a dialkylacetylenedicarboxylte inhibitor for preventing premature gellation at ambient temperatures but which will cure upon ultraviolet light exposure via a hydrosilation reaction to form a coating capable of releasing materials from substrates which would normally adhere thereto.
Description
lZ~9802 W-ACTIVATION OF ADDITION CU~E 8ILIC~NE COATINGS
The present invention relates to the ultraviolet light activated cure of certain silicone coatings. More particularly, the present invention relates to the ultraviolet light activated cure of platinum catalyzed, addition cured silicone coatings which contain dialkyl-acetylenedicarboxylate inhibitors.
Backgroun~ of the invention Silicone compositions which are curable by reaction of =SiH group with silicon-bonded olefinic groups in the presence of a hydrosilation catalyst are well known in B ~ e art; for example, as described in U.S. Patents Nos.
; 3,249,581 and 3,436,366. Because curing begins upon mixing of the aforesaid ingredients, it is the usual practice to provide addition curable compositions in two packages, one of which contains the olefinically unsaturated polysiloxane and the hydrosilation catalyst, and the other the organo-hydrogenpolysiloxane crosslinking agent.
When it is necessary to extend the pot life of addition curable organopolysiloxane compositions or provide one-component addition curable organopoly-siloxane composition, a cure inhibitor can be included therein. Generally, cure inhibitors are compounds which slow curing at ambient temperatures but do not retard curing at elevated temperatures. Such cure inhibitors are heat deactivated cure inhibitors, or are sufficiently volatile to be expelled from coating compositions at elevated temperature.
12~aO2 PATE~TS
60SI-1002/J~H:mz/0313p Particular heat deactivated ture inhibitors are the dialkylacetylenedicarboxylates. These inhibitors are disclosed in U.S. Pat. No. 4,347,346, to the instant inventor, and are described by the formula, ROOCC E CCOOR, where R is a monovalent hydrocarbon radical.
It is an object of the present invention to provide platinum catalyzed, addition tured silicone coa~ing compositions containing dialkylacetylenedicarboxylate inhibitors which are curable with ultraviolet light.
It is a further object of the present invention to provide a method to cure platinum catalyzed, addition curable silicone coating compositions containing dialkylacetylenedicarboxylate inhibitors which contains the step of exposing the coating composition to ultraviolet light.
Summary of the Invention The present invention provides a silicone composition con-taining a dialkylacetylenedicarboxylate inhibitor agent which is effective for retarding a platinum metal catalyzed addition cure hydrosilation reaction at room temperature but which will effectively cure upon exposure to ultraviolet radiation thereby r 20 forming a silicone coating which will tenaciously adhere to a substrate such as paper to which it is applied but will render said substrate substantially nonadherent to materials such as pressure sensitive adhesives which wDuld normally adhere thereto.
~ he release coating composition of the present invention is comprised of:
12~9~2 PATEN~5 60SI-1002/JUR m2/0313p an olefln~rganopoly6ilox-ne having structur~l unite of the formula b ~~-a-b) (I) and b. an organohydrogenpolysiloxane having structural units of the formula a b ~4-a-b~
~herein R i~ an organic radical attached to 6ilicon by a C--Si linkage and is ~elected from the group consisting of nonovalent hydrocDrbon radicals, halogenated ~onova-lent, hydroçarbon radicals, and cyanoalkyl radical~;
generally, ~ contains from 1-30 carbon atoms, straight or branched chained, preferably from 1-12 carbon ators, and st preferably 1-8 carbon atcms; R' is an olefinic hydrocarbon radical attached to silicon by a C--Si link-age and generally contains from 1-20 alip~atic carbons, straight or branch chained, and preferably 1-12 carbon atoms, linked by multiple bonds ~e g , vinyl, allyl, nethallyl, butenyl, pentenyl, ethenyl and the like) has a value of 0 to 3, in~lu~ive, and preferably from 0.5 to about 2, inclusive, b has a value from 0 005 to 2 0, inclusive, and the ~um of a and b is equal to from 0 8 to 3, inclusive, ~herein the release coating com-po~ition is a fluic at room temperature having a visco-sity of, approxi~ately, 25 to 5000 centipoise and preferably 300 to lO00 centipoise at 25C, c. a suf f icient amount of p1atinUm ~etal catalyct, to ca~se the Co-reaction of (a ) and (b ), and lZ9~802 PATENTS
60S~ 02/J~H m2/0313p d an a~4unt oi dial~ylacetylenedicarboxylate effective for Inhibiting ~n eddition cure ~ydro6il~tion reaction between said olefin~rgDnopolytiloxane ~n~ ~aid ~rgano-hydrogenpolysiloxane 5he ~icarboxylcte has the general formula ROOCC c CCOOR where R is s defined bove and is present in nn a unt to inhibit premature gelation of the cataly2ed co-reaction product of (a ) and (b ~ but i6 present in an ~mount insuffisient to prevent curing of said coating composition upon e~posure to u Itraviolet raolatlDn.
DescriPtion ~f the Snvention ~he co~pocition of tbe present lnvention is partlcularly ~ell 6uited for rendering materials nonadherent to other normally adher-ent ~aterials tuch ~s glue ~nd adhesives Additionally, the c~mposition can be applied directly to a substr~te without the need for a solvent, thus ovoiding ~11 of the problems ~ssociated with coating so~vents as described above The composition is an organ~polysilox~ne ~ade up of several constituent ingredients vhich will dhere to nd ther~ally cure on the substrate upon which it is coated, and render the substrate non-adherent ~he olefinorganopolysiloxanes having struc-tural unit~ represented by Por~ula I hereinabove ~re intended t~
broadly cover lov viscosity fluid organopolysiloxane6 suitable for coating vhich preferably, but not necessarily, re Sree of ~ilanic ~ydrogen, ~nd contain olefinic _unsaturation by ~ean~ of double or triple bonds between two ~djacent liphatic carb~n atoms Anonq the radical6 ~hich R iepresents in ~ormula I hereinbove ~re included ~Z~980Z
alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, octyl, dodecyl, and the like; cycloalkyl, such as cyclopentyl, cyclohexyl, cyclopeptyl, and the like;
aryl, such as phenyl, naphthyl, tolyl, xylyl, and the like; aralkyl, such as benzyl, phenylethyl, phenylpropyl, and the like; halogenated derivatives of the aforesaid radicals including chloromethyl, trifluoromethyl, chloropropyl, chlorophenyl, dibromophenyl, tetrachlorophenyl, difluorophenyl, and the like: and cyanoalkyl, such as beta-cyano ethyl, gamma-cyanopropyl, beta-cyanopropyl and the like.
Preferably R is methyl. Moreover, Formula I is intended to include those materials wherein R is a mixture of the aforesaid radicals.
Among the radicals represented by R' in Formula I
hereinabove are included alkenyl, such as vinyl, allyl, methallyl, butenyl, pentenyl, and the like and alkynyl, such as ethynyl, propynyl, butynyl, pentynyl and the like. Preferably R' is vinyl or allyl and most preferably R' is vinyl.
These olefinorganopolysiloxanes encompassed within the scope of Formula I hereinabove are well known in the art, as particularly manifested by U.S. Patent No.
The present invention relates to the ultraviolet light activated cure of certain silicone coatings. More particularly, the present invention relates to the ultraviolet light activated cure of platinum catalyzed, addition cured silicone coatings which contain dialkyl-acetylenedicarboxylate inhibitors.
Backgroun~ of the invention Silicone compositions which are curable by reaction of =SiH group with silicon-bonded olefinic groups in the presence of a hydrosilation catalyst are well known in B ~ e art; for example, as described in U.S. Patents Nos.
; 3,249,581 and 3,436,366. Because curing begins upon mixing of the aforesaid ingredients, it is the usual practice to provide addition curable compositions in two packages, one of which contains the olefinically unsaturated polysiloxane and the hydrosilation catalyst, and the other the organo-hydrogenpolysiloxane crosslinking agent.
When it is necessary to extend the pot life of addition curable organopolysiloxane compositions or provide one-component addition curable organopoly-siloxane composition, a cure inhibitor can be included therein. Generally, cure inhibitors are compounds which slow curing at ambient temperatures but do not retard curing at elevated temperatures. Such cure inhibitors are heat deactivated cure inhibitors, or are sufficiently volatile to be expelled from coating compositions at elevated temperature.
12~aO2 PATE~TS
60SI-1002/J~H:mz/0313p Particular heat deactivated ture inhibitors are the dialkylacetylenedicarboxylates. These inhibitors are disclosed in U.S. Pat. No. 4,347,346, to the instant inventor, and are described by the formula, ROOCC E CCOOR, where R is a monovalent hydrocarbon radical.
It is an object of the present invention to provide platinum catalyzed, addition tured silicone coa~ing compositions containing dialkylacetylenedicarboxylate inhibitors which are curable with ultraviolet light.
It is a further object of the present invention to provide a method to cure platinum catalyzed, addition curable silicone coating compositions containing dialkylacetylenedicarboxylate inhibitors which contains the step of exposing the coating composition to ultraviolet light.
Summary of the Invention The present invention provides a silicone composition con-taining a dialkylacetylenedicarboxylate inhibitor agent which is effective for retarding a platinum metal catalyzed addition cure hydrosilation reaction at room temperature but which will effectively cure upon exposure to ultraviolet radiation thereby r 20 forming a silicone coating which will tenaciously adhere to a substrate such as paper to which it is applied but will render said substrate substantially nonadherent to materials such as pressure sensitive adhesives which wDuld normally adhere thereto.
~ he release coating composition of the present invention is comprised of:
12~9~2 PATEN~5 60SI-1002/JUR m2/0313p an olefln~rganopoly6ilox-ne having structur~l unite of the formula b ~~-a-b) (I) and b. an organohydrogenpolysiloxane having structural units of the formula a b ~4-a-b~
~herein R i~ an organic radical attached to 6ilicon by a C--Si linkage and is ~elected from the group consisting of nonovalent hydrocDrbon radicals, halogenated ~onova-lent, hydroçarbon radicals, and cyanoalkyl radical~;
generally, ~ contains from 1-30 carbon atoms, straight or branched chained, preferably from 1-12 carbon ators, and st preferably 1-8 carbon atcms; R' is an olefinic hydrocarbon radical attached to silicon by a C--Si link-age and generally contains from 1-20 alip~atic carbons, straight or branch chained, and preferably 1-12 carbon atoms, linked by multiple bonds ~e g , vinyl, allyl, nethallyl, butenyl, pentenyl, ethenyl and the like) has a value of 0 to 3, in~lu~ive, and preferably from 0.5 to about 2, inclusive, b has a value from 0 005 to 2 0, inclusive, and the ~um of a and b is equal to from 0 8 to 3, inclusive, ~herein the release coating com-po~ition is a fluic at room temperature having a visco-sity of, approxi~ately, 25 to 5000 centipoise and preferably 300 to lO00 centipoise at 25C, c. a suf f icient amount of p1atinUm ~etal catalyct, to ca~se the Co-reaction of (a ) and (b ), and lZ9~802 PATENTS
60S~ 02/J~H m2/0313p d an a~4unt oi dial~ylacetylenedicarboxylate effective for Inhibiting ~n eddition cure ~ydro6il~tion reaction between said olefin~rgDnopolytiloxane ~n~ ~aid ~rgano-hydrogenpolysiloxane 5he ~icarboxylcte has the general formula ROOCC c CCOOR where R is s defined bove and is present in nn a unt to inhibit premature gelation of the cataly2ed co-reaction product of (a ) and (b ~ but i6 present in an ~mount insuffisient to prevent curing of said coating composition upon e~posure to u Itraviolet raolatlDn.
DescriPtion ~f the Snvention ~he co~pocition of tbe present lnvention is partlcularly ~ell 6uited for rendering materials nonadherent to other normally adher-ent ~aterials tuch ~s glue ~nd adhesives Additionally, the c~mposition can be applied directly to a substr~te without the need for a solvent, thus ovoiding ~11 of the problems ~ssociated with coating so~vents as described above The composition is an organ~polysilox~ne ~ade up of several constituent ingredients vhich will dhere to nd ther~ally cure on the substrate upon which it is coated, and render the substrate non-adherent ~he olefinorganopolysiloxanes having struc-tural unit~ represented by Por~ula I hereinabove ~re intended t~
broadly cover lov viscosity fluid organopolysiloxane6 suitable for coating vhich preferably, but not necessarily, re Sree of ~ilanic ~ydrogen, ~nd contain olefinic _unsaturation by ~ean~ of double or triple bonds between two ~djacent liphatic carb~n atoms Anonq the radical6 ~hich R iepresents in ~ormula I hereinbove ~re included ~Z~980Z
alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, octyl, dodecyl, and the like; cycloalkyl, such as cyclopentyl, cyclohexyl, cyclopeptyl, and the like;
aryl, such as phenyl, naphthyl, tolyl, xylyl, and the like; aralkyl, such as benzyl, phenylethyl, phenylpropyl, and the like; halogenated derivatives of the aforesaid radicals including chloromethyl, trifluoromethyl, chloropropyl, chlorophenyl, dibromophenyl, tetrachlorophenyl, difluorophenyl, and the like: and cyanoalkyl, such as beta-cyano ethyl, gamma-cyanopropyl, beta-cyanopropyl and the like.
Preferably R is methyl. Moreover, Formula I is intended to include those materials wherein R is a mixture of the aforesaid radicals.
Among the radicals represented by R' in Formula I
hereinabove are included alkenyl, such as vinyl, allyl, methallyl, butenyl, pentenyl, and the like and alkynyl, such as ethynyl, propynyl, butynyl, pentynyl and the like. Preferably R' is vinyl or allyl and most preferably R' is vinyl.
These olefinorganopolysiloxanes encompassed within the scope of Formula I hereinabove are well known in the art, as particularly manifested by U.S. Patent No.
3,344,111 to Chalk, and U.S. Patent No. 3,436,366 to Modic. Similarly, their preparation and commercial availability is also well known.
The olefinorganopolysiloxanes encompassed within the scope of the present invention can be characterized as copolymers of (1) siloxane units having the formula:
RCR'dSi4-c-d (IV) whfre R an~ R' are as defined above and c has a value of from 0 to 2, inclusive, and the sum of c and d is e~l to from 0.8 to 3.0, ~%~2 PA~ENl`S
60SI-1002/JWH~ 2l0313p lnclusive, nd (2J organolslloxane unit6 having the ~tructural for~ul~:
~R)nSiO~ (V) -n where R i6 ~5 defined ~ove snd n has value of from O.B to 2.5, lnclusive. mus, Yhere the olefinorganopolyriloxane employed herein i~ a copolymer of units withi the ~cope of For~ula IV with an organopolysiloxane having Dn a~erage formula within the 6cope of Formula v, the copoly~er generally contains from 0.5 to 99.5 mole percent of the units of ~ormula ~V, and fro~ 0.5 to 99.5 ~ole per-cent of units Yithin the scope of Formula V. me prepar~tion of these copolymer~ is also well kno~n in the art. A ~ajor proportion of the co~position is typic~lly n vinyl chainstopped poly~iloxane ha~ing the general formula:
wherein h is a m~novalent hydrocarbon radical free of unsaturation.
Suitable radicals for R include, for example, Dethyl, ethyl, propyl, butyl, and Dther si~ilar unsaturated bydrccarbons, but ordinarily would not include phenyl groups for paper release purposec. R' is a hydrocarbon radical having Dlkenyl unsaturation. Typically, ~' represents vinyl groups but ~ay al60 represent ~llylic or cyclo-~lkenyl unsaturated groups. X snd Y are positive integess 60 th~t the ~inyl chainstopped polysiloxane has up to apProximately 20~ by weight of ~' groups. m e visco~sity of such a polysiloxane ranges from appr~xi~2telY 50 to Dpproximately lOD,000 centipoise at 2~C.
Pre~erably, the vinyl ch~instopped polysiloxane has up to approximatelY 20t by ~eight of vinyl groups represented by R' and the viscosity of this poly~,er ranges fro~, ~pproximately 300 to approximately 550 centipoise at 25~C. The preferred vinyl chainstopped polysiloxane has the general formula:
IH3 / fH3 ~ / CH3 \ fH3 CH2 CH - Si ~ Si ~7 i~s i CH CH2 CH3 CH3/X ~ IlH ~ CH3 wherein X and Y are as described above.
Methylhydrogen fluid is often used by those skilled in the silicone art as a crosslinking agent - for addition-cured silicone systems. Particularly useful as a crosslinking agent for the present invention is a trimethyl chainstopped polymethylhydrogen siloxane fluid having from approximately 10% to approximately 100% SiH groups with the remainder being essentially dimethylsiloxy units and having a viscosity in the range of approximately 25 to approximately l,000 centipoise at 25C.
The organohydrogenpolysiloxanes having structural units represented by Formula II hereinabove are intended to broadly cover fluid organopolysiloxanes which are preferably, but not necessarily, free of olefinic unsaturation, but which contain silanic hydrogen. These organohydrogenpolysiloxanes represented by Formula II hereinabove are also well known in the art as particularly manifested by U.S.
Patent No. 3,344,111 to Chalk, and U.S. Patent 3,436,366.
Among the radicals represented by R in Formula II, hereinabove, similarly to R in Formula I
hereinabove, are included alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, octyl and the like;
..~
.2~?~80Z PAI E N~ 5 60S I -1 002 /J~H ~ /03 1 3p ,8-eycloal~yl, ~uch t cyclopentyl, eyclohexyl, cycloheptyl and the llke; aryl, cuch aE phenyl, naphthyl, tolyl, xylyl, and the li~e, aralkyl, 6uch 6 benzyl, phenylethyl, phenylpropyl, ond the li~e;
halogenatged derivativee of the above radic~lr, including chl~ro-~ethyl, trifluoromethyl, chloropropyl, chlorophenyl, dibro~ophenyl, tetrachlorophenyl, difluorophenyl and the like; and cyanoDlkyl, ~uch a8 beta-cyanoethyl, gamma-cyanopropyl, betD-cyanopropyl ~nd the like. Al~o intended to be included within the ccope of ~ormula II
~re tho6e naterial~ where R is a mixture of the aforesaid radical6.
1~ Preferably the ~ group of ~ormula lI ic methyl.
Haterial~ ~pecifically encompasced within P~rmula II herein-above, include 1,3-dimethyldisiloxane, 1,1,3,3,-tetramethyldi-siloxane, a6 well as higher poly~ers containing up to 100,000 or ~ore 6ilicon atoms per lecule. A160 included within the scope of Formula II hereinabove are cyclic material~, riuch as cyclic polymers of methyl hydrogen 6iloxane having the formula:
(C~3SiH0)x 2~ wherein x i~ a whole number equal to from 3 to 10 or m~re.
Particularly included i6 tetramethylcyclotetrasiloxane.
The organohydrogenpolysiloxanes employed in the practice of the pre~ent invention can ~lco be characterized as copoly~er~
containing at least one unit per molecule having the formula:
RCHdSiO 4 c d ~VI) with t~e remaining ~iloxane units in the organopolysiloxane being with in the 6cope of Formula V hereinabove, where ~, c, d and n are defined ~bove.
12~t302 Within the scope of Formula VI are siloxane units, such as hydrogen siloxane units (H2Sio)l.5l methyl hydrogen siloxane units (HSiCH30), dimethyl hydrogen siloxane units, and dihydrogen siloxane units (H2Sio). In these copolymers, the siloxane units of Formulae V and VI are present in proportions so as to form a hydrogenpolysiloxane within the scope of Formula II hereinabove. In general, these copolymers contain from 0.5 to 99.5 mole percent of the siloxane 10 units of Formula V with from 0.5 to 99.5 mole percent of the siloxane units of Formula VI.
Ordinarily for release coating purposes it is preferred that the organohydrogenpolysiloxane crosslinker be essentially a trimethyl chainstopped methylhydrogenpolysiloxane fluid having a viscosity of, approximately, 10 to 500 centipoise at 25C and a hydrogen content of, approximately, 0.1 to 1.67 weight percent.
The precious metal catalyst component employed in the compositions of the present invention includes all of the well known platinum-metal catalysts which are effective for catalyzing the reaction between silicon-bonded hydrogen groups and silicon-bonded olefinic groups, and which are freely miscible in solvent-free silicone polymers. These materials include, for example, the platinum hydrocarbon complexes shown in U.S. Patent No. 3,159,601 to Ashby and U~S. Patent No. 3,159,662 to Ashby, as well as the platinum alcoholate catalysts described in U.S. Patent 30 No. 3,220,972 to Lamoreaux. Moreover, the platinum chloride-olefin complexes described in U.S. Patent No.
3,516,946 to Modic are also useful herein.
-i2~
PA~ENTS
60SI -1002/J~H:mz/031 3p Small amounts of dialkylacetylenediacraboxylate inhibitor permit exceptionally long catalyzed pot-life without sacrifice of cure performance in a solventless paper release system.
Ordinarily, the effective amount of inhibitor ranges from approximately 0.05X to approximately l.OX by weight, and preferably from 0.1 to 0.25X by weight. Use o~ the inhibitor of the present invention results in adequate pot-life yet the composition rapidly cures to a smear-free and migration-free nonadherent surface when cured with ultraviolet light.
Dialkylacetylenedicarboxylates result from the diesterifi-cation reaction of 2-butynoic dicarboxylic acid with tWD
equivalents of alcohols such as methanol, ethanol, butanol, benzylic alcohol, allyl alcohol or mixtures of such alcohols.
Such reactions can be represented as:
HOOCC ~ CCOOH + 2 ROH -' ROOCC ~ CCOOR ~ 2 H20k or HOOCC - CCOOH + CCOOH + ROH + R'OH ROOCC - CCOOR' ~ 2H20.
Useful diesters prepared in this fashion include dimethyl-acetylenedicarboxylate, diethylacetylenedicarboxylate, dibutyl-acetylenedicarboxylate, methylbutylacetylenedicarboxylate, ~ethylethylacetylenedicarboxylate, etc. Particularly useful for the pract;ce of the present invention are those diesters where R represents methyl or ethyl groups.
Effective levels of dimethylacetylenedicarboxylate are quite soluble in silicone fluids, and it is not significantly volatile, having a boiling point above 200C at atmospheric 2~
~9~31)2 PATE~TS
60SI-1002/~ mz/0313p pressure. Additionally, dimethylacetylenedicarboxylate is readily available commercially. Furthermore, inasmuch as the total inhibitor concentration in the dimethylacetylenedicar-boxylate-inhibited polysiloxane is quite low, the total cost is S significantly reduced. Additionally, the small inhibitory amDunts of dimethylacetyl- enedicarboxylate utilized by the present invention will be substantially wholly included within the crosslinked polymer. Thus free dimethylacetylenedicarboxylate is not extant after the 1~ polymeric composition is cured.
Dimethylacetylenedicarboxylate will also effectively inhibit the platinum catalyzed condensation cure reaction for polysiloxane compositions having silanol functionality as well as inhibit the cure for those compositions exhibiting both silanol and vinyl functionality. A base polymer for such a composition can be, for example, a silanol chain-stopped poly-diorganosiloxane having pendant vinyl groups along the siloxane chain.
The ingredients described above may be mixed in any order and exposed to ultraviolet radiation for cure. Persons skilled in the art are familiar with ultraviolet light cure and are easily able to determine proper spectrum, flux and exposure time to obtain the cure.
A preferred use of the above described composition is as a release coating on a substrate. ~he composition is mixed, applied as a thin film on a substrate, and cured by exposure to PA~EN~S
60SI-lQ02/J~H:~z70313p ultraviolet light. ~he substrate may be non-porous, i.e.
glass, plastic metal foil, etc., but is pre~erably porous, such as, paper and other fibrous materials.
In order that those skilled in the art might be better able to practice the present invent~on, the follow-ng examples are given by way of illustration and not by way of limitatton.
~2~ 3l)2 PATENTS
60SI-1002/J~H:mz703)3p Description of the Preferred Embodiments Example 1 A 500 centipoise vinyl-stoPped linear polydimethylsiloxane fluid was blended with various ~mounts of a Karstedt platinum tatalyst and dimethylacytylenedicarboxylate (DlMAC). ~;thin two minutes of m;xing, an intense orange-yellow color was generated in each of the compositions. ~a~le I shows the compositions which were blended and their contents.
Table 1 DI~AC ~ole Ratio, CompositionPt. conc., ppmconc., ppm Pt/DlMAC
1 25 lOOD 1/55 2 25 250 1/13.7 3 40 200 1.6~11 Example 2 A 400 centipoise vinyl-stopped, dimethyl, methyl-vinyl~
linear silicone polymer with 3.7 wt. X DVi units was blended with various amounts of a Karstedt platinum catalyst and dimethylacetylenedicarboxylate (DIMAC). ~ithin two minutes of mixing, an intense orange-yellow orod was generated in each of the compositions. Table II shows the compositions which were blended dnd their contents.
1 2 ~ 9 ~ 2 PATENTS
60SI-1002/J~H:mz/0313p Table II
Pt. conc., DIMAC conc., Mole Ratio mposition ppm ppm Pt/DIMAC
The olefinorganopolysiloxanes encompassed within the scope of the present invention can be characterized as copolymers of (1) siloxane units having the formula:
RCR'dSi4-c-d (IV) whfre R an~ R' are as defined above and c has a value of from 0 to 2, inclusive, and the sum of c and d is e~l to from 0.8 to 3.0, ~%~2 PA~ENl`S
60SI-1002/JWH~ 2l0313p lnclusive, nd (2J organolslloxane unit6 having the ~tructural for~ul~:
~R)nSiO~ (V) -n where R i6 ~5 defined ~ove snd n has value of from O.B to 2.5, lnclusive. mus, Yhere the olefinorganopolyriloxane employed herein i~ a copolymer of units withi the ~cope of For~ula IV with an organopolysiloxane having Dn a~erage formula within the 6cope of Formula v, the copoly~er generally contains from 0.5 to 99.5 mole percent of the units of ~ormula ~V, and fro~ 0.5 to 99.5 ~ole per-cent of units Yithin the scope of Formula V. me prepar~tion of these copolymer~ is also well kno~n in the art. A ~ajor proportion of the co~position is typic~lly n vinyl chainstopped poly~iloxane ha~ing the general formula:
wherein h is a m~novalent hydrocarbon radical free of unsaturation.
Suitable radicals for R include, for example, Dethyl, ethyl, propyl, butyl, and Dther si~ilar unsaturated bydrccarbons, but ordinarily would not include phenyl groups for paper release purposec. R' is a hydrocarbon radical having Dlkenyl unsaturation. Typically, ~' represents vinyl groups but ~ay al60 represent ~llylic or cyclo-~lkenyl unsaturated groups. X snd Y are positive integess 60 th~t the ~inyl chainstopped polysiloxane has up to apProximately 20~ by weight of ~' groups. m e visco~sity of such a polysiloxane ranges from appr~xi~2telY 50 to Dpproximately lOD,000 centipoise at 2~C.
Pre~erably, the vinyl ch~instopped polysiloxane has up to approximatelY 20t by ~eight of vinyl groups represented by R' and the viscosity of this poly~,er ranges fro~, ~pproximately 300 to approximately 550 centipoise at 25~C. The preferred vinyl chainstopped polysiloxane has the general formula:
IH3 / fH3 ~ / CH3 \ fH3 CH2 CH - Si ~ Si ~7 i~s i CH CH2 CH3 CH3/X ~ IlH ~ CH3 wherein X and Y are as described above.
Methylhydrogen fluid is often used by those skilled in the silicone art as a crosslinking agent - for addition-cured silicone systems. Particularly useful as a crosslinking agent for the present invention is a trimethyl chainstopped polymethylhydrogen siloxane fluid having from approximately 10% to approximately 100% SiH groups with the remainder being essentially dimethylsiloxy units and having a viscosity in the range of approximately 25 to approximately l,000 centipoise at 25C.
The organohydrogenpolysiloxanes having structural units represented by Formula II hereinabove are intended to broadly cover fluid organopolysiloxanes which are preferably, but not necessarily, free of olefinic unsaturation, but which contain silanic hydrogen. These organohydrogenpolysiloxanes represented by Formula II hereinabove are also well known in the art as particularly manifested by U.S.
Patent No. 3,344,111 to Chalk, and U.S. Patent 3,436,366.
Among the radicals represented by R in Formula II, hereinabove, similarly to R in Formula I
hereinabove, are included alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, octyl and the like;
..~
.2~?~80Z PAI E N~ 5 60S I -1 002 /J~H ~ /03 1 3p ,8-eycloal~yl, ~uch t cyclopentyl, eyclohexyl, cycloheptyl and the llke; aryl, cuch aE phenyl, naphthyl, tolyl, xylyl, and the li~e, aralkyl, 6uch 6 benzyl, phenylethyl, phenylpropyl, ond the li~e;
halogenatged derivativee of the above radic~lr, including chl~ro-~ethyl, trifluoromethyl, chloropropyl, chlorophenyl, dibro~ophenyl, tetrachlorophenyl, difluorophenyl and the like; and cyanoDlkyl, ~uch a8 beta-cyanoethyl, gamma-cyanopropyl, betD-cyanopropyl ~nd the like. Al~o intended to be included within the ccope of ~ormula II
~re tho6e naterial~ where R is a mixture of the aforesaid radical6.
1~ Preferably the ~ group of ~ormula lI ic methyl.
Haterial~ ~pecifically encompasced within P~rmula II herein-above, include 1,3-dimethyldisiloxane, 1,1,3,3,-tetramethyldi-siloxane, a6 well as higher poly~ers containing up to 100,000 or ~ore 6ilicon atoms per lecule. A160 included within the scope of Formula II hereinabove are cyclic material~, riuch as cyclic polymers of methyl hydrogen 6iloxane having the formula:
(C~3SiH0)x 2~ wherein x i~ a whole number equal to from 3 to 10 or m~re.
Particularly included i6 tetramethylcyclotetrasiloxane.
The organohydrogenpolysiloxanes employed in the practice of the pre~ent invention can ~lco be characterized as copoly~er~
containing at least one unit per molecule having the formula:
RCHdSiO 4 c d ~VI) with t~e remaining ~iloxane units in the organopolysiloxane being with in the 6cope of Formula V hereinabove, where ~, c, d and n are defined ~bove.
12~t302 Within the scope of Formula VI are siloxane units, such as hydrogen siloxane units (H2Sio)l.5l methyl hydrogen siloxane units (HSiCH30), dimethyl hydrogen siloxane units, and dihydrogen siloxane units (H2Sio). In these copolymers, the siloxane units of Formulae V and VI are present in proportions so as to form a hydrogenpolysiloxane within the scope of Formula II hereinabove. In general, these copolymers contain from 0.5 to 99.5 mole percent of the siloxane 10 units of Formula V with from 0.5 to 99.5 mole percent of the siloxane units of Formula VI.
Ordinarily for release coating purposes it is preferred that the organohydrogenpolysiloxane crosslinker be essentially a trimethyl chainstopped methylhydrogenpolysiloxane fluid having a viscosity of, approximately, 10 to 500 centipoise at 25C and a hydrogen content of, approximately, 0.1 to 1.67 weight percent.
The precious metal catalyst component employed in the compositions of the present invention includes all of the well known platinum-metal catalysts which are effective for catalyzing the reaction between silicon-bonded hydrogen groups and silicon-bonded olefinic groups, and which are freely miscible in solvent-free silicone polymers. These materials include, for example, the platinum hydrocarbon complexes shown in U.S. Patent No. 3,159,601 to Ashby and U~S. Patent No. 3,159,662 to Ashby, as well as the platinum alcoholate catalysts described in U.S. Patent 30 No. 3,220,972 to Lamoreaux. Moreover, the platinum chloride-olefin complexes described in U.S. Patent No.
3,516,946 to Modic are also useful herein.
-i2~
PA~ENTS
60SI -1002/J~H:mz/031 3p Small amounts of dialkylacetylenediacraboxylate inhibitor permit exceptionally long catalyzed pot-life without sacrifice of cure performance in a solventless paper release system.
Ordinarily, the effective amount of inhibitor ranges from approximately 0.05X to approximately l.OX by weight, and preferably from 0.1 to 0.25X by weight. Use o~ the inhibitor of the present invention results in adequate pot-life yet the composition rapidly cures to a smear-free and migration-free nonadherent surface when cured with ultraviolet light.
Dialkylacetylenedicarboxylates result from the diesterifi-cation reaction of 2-butynoic dicarboxylic acid with tWD
equivalents of alcohols such as methanol, ethanol, butanol, benzylic alcohol, allyl alcohol or mixtures of such alcohols.
Such reactions can be represented as:
HOOCC ~ CCOOH + 2 ROH -' ROOCC ~ CCOOR ~ 2 H20k or HOOCC - CCOOH + CCOOH + ROH + R'OH ROOCC - CCOOR' ~ 2H20.
Useful diesters prepared in this fashion include dimethyl-acetylenedicarboxylate, diethylacetylenedicarboxylate, dibutyl-acetylenedicarboxylate, methylbutylacetylenedicarboxylate, ~ethylethylacetylenedicarboxylate, etc. Particularly useful for the pract;ce of the present invention are those diesters where R represents methyl or ethyl groups.
Effective levels of dimethylacetylenedicarboxylate are quite soluble in silicone fluids, and it is not significantly volatile, having a boiling point above 200C at atmospheric 2~
~9~31)2 PATE~TS
60SI-1002/~ mz/0313p pressure. Additionally, dimethylacetylenedicarboxylate is readily available commercially. Furthermore, inasmuch as the total inhibitor concentration in the dimethylacetylenedicar-boxylate-inhibited polysiloxane is quite low, the total cost is S significantly reduced. Additionally, the small inhibitory amDunts of dimethylacetyl- enedicarboxylate utilized by the present invention will be substantially wholly included within the crosslinked polymer. Thus free dimethylacetylenedicarboxylate is not extant after the 1~ polymeric composition is cured.
Dimethylacetylenedicarboxylate will also effectively inhibit the platinum catalyzed condensation cure reaction for polysiloxane compositions having silanol functionality as well as inhibit the cure for those compositions exhibiting both silanol and vinyl functionality. A base polymer for such a composition can be, for example, a silanol chain-stopped poly-diorganosiloxane having pendant vinyl groups along the siloxane chain.
The ingredients described above may be mixed in any order and exposed to ultraviolet radiation for cure. Persons skilled in the art are familiar with ultraviolet light cure and are easily able to determine proper spectrum, flux and exposure time to obtain the cure.
A preferred use of the above described composition is as a release coating on a substrate. ~he composition is mixed, applied as a thin film on a substrate, and cured by exposure to PA~EN~S
60SI-lQ02/J~H:~z70313p ultraviolet light. ~he substrate may be non-porous, i.e.
glass, plastic metal foil, etc., but is pre~erably porous, such as, paper and other fibrous materials.
In order that those skilled in the art might be better able to practice the present invent~on, the follow-ng examples are given by way of illustration and not by way of limitatton.
~2~ 3l)2 PATENTS
60SI-1002/J~H:mz703)3p Description of the Preferred Embodiments Example 1 A 500 centipoise vinyl-stoPped linear polydimethylsiloxane fluid was blended with various ~mounts of a Karstedt platinum tatalyst and dimethylacytylenedicarboxylate (DlMAC). ~;thin two minutes of m;xing, an intense orange-yellow color was generated in each of the compositions. ~a~le I shows the compositions which were blended and their contents.
Table 1 DI~AC ~ole Ratio, CompositionPt. conc., ppmconc., ppm Pt/DlMAC
1 25 lOOD 1/55 2 25 250 1/13.7 3 40 200 1.6~11 Example 2 A 400 centipoise vinyl-stopped, dimethyl, methyl-vinyl~
linear silicone polymer with 3.7 wt. X DVi units was blended with various amounts of a Karstedt platinum catalyst and dimethylacetylenedicarboxylate (DIMAC). ~ithin two minutes of mixing, an intense orange-yellow orod was generated in each of the compositions. Table II shows the compositions which were blended dnd their contents.
1 2 ~ 9 ~ 2 PATENTS
60SI-1002/J~H:mz/0313p Table II
Pt. conc., DIMAC conc., Mole Ratio mposition ppm ppm Pt/DIMAC
5 50 200 2/~1 6 100 300 4/16.5 Example 3 Each of compositions 1-6 were blended with a 350 centipoise linear, trimethyl siloxy-stopped, poly~dimethyl-methylhydrogen)s;loxane with 50 wt X DH units present in a weight ratio of 9 to 1. The resultant bath compositions 1-6 were coated on to aluminum Q panels, polypropylene film, or 40#/ream SCK paper substrates. The - coated substrates were exposed in an oven or in air to ultraviolet light as shown in Table III.
1;~9~2 60SI-1002/JWH:mz/0313p Table III
Coating UV- Oven Thickness Exposure, Conditions Qualitative Comp. Substrate Mil _ J/cm2 min/C Results 1 paper 2 1.5 -- Cured; no smear, no migration, good anchorage 1 aluminum 2 4.5 --1 paper **thin film 1.5 --1 aluminum 2 __ 5/80 "
1~ paper 4 1.5 -- Exposed areas cured shadowed areas wet.
2 paper thin film 1.15 -- Cured; no migration, slight smear 2 paper thin film -- 1.5/80 "
3 paper thin film 0.6 -- Cured; no migration, slight smear 3 paper thin film 0.48 -- Undercured, migrates 3 paper thin film -- 1/80 Cured; slight migration 4 paper thin film 0.6 -- Cured; no migration, slight smear 4 paper thin film 0.48 -- Undercured; sl;ght migration 5 paper thin film 0.96 -- Cured; no migration, slight smear 5 paper thin film 0.64 -- Undercured; migrates 5 polypropylene thin film 1.28 -- Poor cure; migrates, poor anchorage 5 polypropylene 1 2.9 -- Cured; no rigration, but rubs off 6 paper thin film 0.96 -- Cured; no migration, slight smear 6 paper thin film 0.64 -- Undercured; migrates * Shadow set up across coating ~ "thin film" is approximately 5 microns 12~ Z
PA~ENTS
605l-1002/J~H:mz/0313p The above data shows that -DYi- units present in the base polymers appear to slow cure relative to M - functional fluids. High Pt concentrations do not enhance cure so long as inhibitory concentrations of DlMAC are present.
Example 4 This experiment is to verify that ultraviolet light without thermal assist will trigger cure of Pt/DIMAC addition cured systems. A low intensity ultraviolet light source, (UY
Products, Inc. table top lamp, 115 volt, 0.35 amp.) was set up (unfocused) 1 3/4 inches away from an aluminum substrate having a 2 mil coating of bath composition 1. UV flux was determined 1 to be 6 J/cm2 hr. No significant difference could be ~etected between room temperature, 24C, and the measured temperature of the substrate after 15 minutes exposure to the low intensity source. The coating cured to a smear-free well-anchored rubbery surface in about 2.5 hours exposure, i.e.
lS J/cm2 total flux. This observation coupled with the Experiment 3 ~shadow" observation confirms the ultraviolet light nature of this cure mechanism.
Example 5 The pot life of bath compositions 1 and 3-6 was investigated by noting viscosity as a function of time at a given temperature. Table IV shows the timetviscosity relationship at 25C.
~2~9802 60SI -1002/~WH:mz/0313p Table IV
Time, COMPOSITION, viscosity, cps.
hr. 1 3-6 2 686 Gelled in less than 3Q min.
4 760 "
6 842 "
8 1025 "
24 9000 "
Table V shows the time/viscosity relationship at 4C.
Table V
Time, COMPOSITION, viscosity, cps.
hr. 3 4 5 6 2 940 1 ~ 15 860 882
1;~9~2 60SI-1002/JWH:mz/0313p Table III
Coating UV- Oven Thickness Exposure, Conditions Qualitative Comp. Substrate Mil _ J/cm2 min/C Results 1 paper 2 1.5 -- Cured; no smear, no migration, good anchorage 1 aluminum 2 4.5 --1 paper **thin film 1.5 --1 aluminum 2 __ 5/80 "
1~ paper 4 1.5 -- Exposed areas cured shadowed areas wet.
2 paper thin film 1.15 -- Cured; no migration, slight smear 2 paper thin film -- 1.5/80 "
3 paper thin film 0.6 -- Cured; no migration, slight smear 3 paper thin film 0.48 -- Undercured, migrates 3 paper thin film -- 1/80 Cured; slight migration 4 paper thin film 0.6 -- Cured; no migration, slight smear 4 paper thin film 0.48 -- Undercured; sl;ght migration 5 paper thin film 0.96 -- Cured; no migration, slight smear 5 paper thin film 0.64 -- Undercured; migrates 5 polypropylene thin film 1.28 -- Poor cure; migrates, poor anchorage 5 polypropylene 1 2.9 -- Cured; no rigration, but rubs off 6 paper thin film 0.96 -- Cured; no migration, slight smear 6 paper thin film 0.64 -- Undercured; migrates * Shadow set up across coating ~ "thin film" is approximately 5 microns 12~ Z
PA~ENTS
605l-1002/J~H:mz/0313p The above data shows that -DYi- units present in the base polymers appear to slow cure relative to M - functional fluids. High Pt concentrations do not enhance cure so long as inhibitory concentrations of DlMAC are present.
Example 4 This experiment is to verify that ultraviolet light without thermal assist will trigger cure of Pt/DIMAC addition cured systems. A low intensity ultraviolet light source, (UY
Products, Inc. table top lamp, 115 volt, 0.35 amp.) was set up (unfocused) 1 3/4 inches away from an aluminum substrate having a 2 mil coating of bath composition 1. UV flux was determined 1 to be 6 J/cm2 hr. No significant difference could be ~etected between room temperature, 24C, and the measured temperature of the substrate after 15 minutes exposure to the low intensity source. The coating cured to a smear-free well-anchored rubbery surface in about 2.5 hours exposure, i.e.
lS J/cm2 total flux. This observation coupled with the Experiment 3 ~shadow" observation confirms the ultraviolet light nature of this cure mechanism.
Example 5 The pot life of bath compositions 1 and 3-6 was investigated by noting viscosity as a function of time at a given temperature. Table IV shows the timetviscosity relationship at 25C.
~2~9802 60SI -1002/~WH:mz/0313p Table IV
Time, COMPOSITION, viscosity, cps.
hr. 1 3-6 2 686 Gelled in less than 3Q min.
4 760 "
6 842 "
8 1025 "
24 9000 "
Table V shows the time/viscosity relationship at 4C.
Table V
Time, COMPOSITION, viscosity, cps.
hr. 3 4 5 6 2 940 1 ~ 15 860 882
Claims (8)
1. A process for rendering surfaces nonadherent to materials which would normally adhere thereto comprising the steps of:
(A) providing a silicone release coating composition by combining:
(a) an olefinorganopolysiloxane having units of the structural formula:
RaR1bSiO (b) an organohydrogenpolysiloxane having units of the structural formula RaHbSiO wherein R is selected from the group consisting of a monovalent hydrocarbon radical, a halogenated monovalent hydrocarbon radical, a cyanoalkyl radical and mixtures thereof, Rl is an olefinic hydrocarbon radical, wherein a has a value of from 0 to 3, inclusive, b has a value of from 0.005 to 2.0, inclusive, and the sum of a and b is equal to from 0.8 to 3, inclusive;
(c) a sufficient amount of a platinum metal catalyst to cause the co-reaction of (a) and (b);
and (d) a dialkylacetylenedicarboxylate having the general formula:
ROOCC = CCOOR
where R is as defined above and wherein said dialkylacetylenedicarboxylate is present in an amount effective for inhibiting premature gelation but insufficient for preventing cure at elevated temperature; wherein said silicone release coating has a viscosity of, approximately, 25 to 5000 centipoise at 25°C;
(B) coating said silicone release coating on a suitable surface at a thickness of, approximately, 0.005 to 2.0 mils;
(C) curing said silicone release coating with an amount of ultraviolet light effective for overcoming the cure retarding properties of said dialkylacetylene-dicarboxylate wherein the temperature of the coating during cure is maintained within a range which i5 insufficient to effect thermal cure of the coating.
(A) providing a silicone release coating composition by combining:
(a) an olefinorganopolysiloxane having units of the structural formula:
RaR1bSiO (b) an organohydrogenpolysiloxane having units of the structural formula RaHbSiO wherein R is selected from the group consisting of a monovalent hydrocarbon radical, a halogenated monovalent hydrocarbon radical, a cyanoalkyl radical and mixtures thereof, Rl is an olefinic hydrocarbon radical, wherein a has a value of from 0 to 3, inclusive, b has a value of from 0.005 to 2.0, inclusive, and the sum of a and b is equal to from 0.8 to 3, inclusive;
(c) a sufficient amount of a platinum metal catalyst to cause the co-reaction of (a) and (b);
and (d) a dialkylacetylenedicarboxylate having the general formula:
ROOCC = CCOOR
where R is as defined above and wherein said dialkylacetylenedicarboxylate is present in an amount effective for inhibiting premature gelation but insufficient for preventing cure at elevated temperature; wherein said silicone release coating has a viscosity of, approximately, 25 to 5000 centipoise at 25°C;
(B) coating said silicone release coating on a suitable surface at a thickness of, approximately, 0.005 to 2.0 mils;
(C) curing said silicone release coating with an amount of ultraviolet light effective for overcoming the cure retarding properties of said dialkylacetylene-dicarboxylate wherein the temperature of the coating during cure is maintained within a range which i5 insufficient to effect thermal cure of the coating.
2. A process as in claim l wherein said olefinorganopolysiloxane is a dimethylvinyl chainstopped dimethylmethylvinylpolysiloxane copolymer fluid having a viscosity of, approximately, 300 to 1000 centipoise at 25°C and a vinyl content of, approximately, 0.1 to 25 weight percent.
3. A process as in claim 1 wherein said organohydrogenpolysiloxane is a trimethyl chainstopped methylhydrogenpolysiloxane fluid having a viscosity of, approximately, 10 to 500 centipoise at 25°C and a hydrogen content of, approximately 0.1 to 1.67 weight percent.
4. A process as in claim l wherein said platinum metal catalyst is present in an amount sufficient to provide, approximately, 5 to 500 parts platinum metal per million parts of said olefinorganopolysiloxane.
5. A process as in claim 1 wherein said dialkylacetylenedicarboxylate is present in an amount of, approximately, 0.02 to 1.0 weight percent of the silicone coating composition.
6. A process as in claim 1 wherein said dialkylacetylenedicarboxylate is selected from the group consisting of dimethylacetylenedicarboxylate and diethylacetylenedicarboxylate.
7. A process as in claim 3 wherein the group of radicals represented by R also contains hydroxyl radicals.
8. A process as in claim 1 wherein said olefinorganopolysiloxane is a dimethylvinyl chainstopped dimethylmethylvinylpolysiloxane copolymer fluid having a viscosity of, approximately, 1,000 to 100,000 centipoise at 25C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US94541486A | 1986-12-22 | 1986-12-22 | |
| US945,414 | 1986-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1299802C true CA1299802C (en) | 1992-04-28 |
Family
ID=25483057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000554578A Expired - Lifetime CA1299802C (en) | 1986-12-22 | 1987-12-17 | Uv activation of addition cure silicone coatings |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPH0692564B2 (en) |
| KR (1) | KR940011192B1 (en) |
| CA (1) | CA1299802C (en) |
| DE (1) | DE3742000A1 (en) |
| FR (1) | FR2608617B1 (en) |
| GB (1) | GB2198740B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2698509B2 (en) * | 1992-07-02 | 1998-01-19 | 信越化学工業株式会社 | Organopolysiloxane composition for release paper |
| JP2007308581A (en) * | 2006-05-18 | 2007-11-29 | Shin Etsu Chem Co Ltd | Curing method of addition cure silicone rubber composition, and addition cure silicone rubber composition |
| JP2009091403A (en) * | 2007-10-04 | 2009-04-30 | Shin Etsu Chem Co Ltd | Addition-curable type silicone rubber composition and method for curing the same |
| JP2009220384A (en) * | 2008-03-17 | 2009-10-01 | Shin Etsu Chem Co Ltd | Method of forming silicone rubber thin film coating layer and silicone rubber thin film coated article |
| JP5190284B2 (en) * | 2008-03-19 | 2013-04-24 | 日東電工株式会社 | Separator manufacturing method, separator, and adhesive tape with separator |
| JP4877851B2 (en) * | 2009-03-27 | 2012-02-15 | 住友建機株式会社 | Pavement machine controller moving mechanism |
| US20110143148A1 (en) * | 2009-12-13 | 2011-06-16 | General Electric Company | Articles comprising a weather resistant silicone coating |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4064027A (en) * | 1973-09-28 | 1977-12-20 | Dow Corning Corporation | UV curable composition |
| CA1019693A (en) * | 1973-09-28 | 1977-10-25 | George A.L. Gant | Release characteristics of substrates |
| US4347346A (en) * | 1981-04-02 | 1982-08-31 | General Electric Company | Silicone release coatings and inhibitors |
| US4530879A (en) * | 1983-03-04 | 1985-07-23 | Minnesota Mining And Manufacturing Company | Radiation activated addition reaction |
| JPS6013847A (en) * | 1983-07-04 | 1985-01-24 | Shin Etsu Chem Co Ltd | Radiation-curable organopolysiloxane composition |
| FR2554118B1 (en) * | 1983-10-26 | 1986-01-17 | Rhone Poulenc Spec Chim | KETONIC INHIBITOR FOR PLATINUM METAL CATALYST AND ORGANOPOLYSILOXANE COMPOSITIONS CONTAINING THE SAME |
| JPS60177029A (en) * | 1984-02-21 | 1985-09-11 | Toray Silicone Co Ltd | Method for curing organopolysiloxane composition |
| FR2571732B1 (en) * | 1984-10-15 | 1987-01-09 | Rhone Poulenc Spec Chim | ORGANOPOLYSILOXANIC COATING COMPOSITION FOR USE IN PARTICULAR FOR NON-STICK TREATMENT AND METHOD OF APPLICATION |
| EP0184598A1 (en) * | 1984-12-06 | 1986-06-18 | Toray Silicone Company Limited | Ultraviolet and electron-beam curable polyorganosiloxane composition |
| US4670531A (en) * | 1986-01-21 | 1987-06-02 | General Electric Company | Inhibited precious metal catalyzed organopolysiloxane compositions |
-
1987
- 1987-10-27 GB GB8725155A patent/GB2198740B/en not_active Expired - Lifetime
- 1987-12-11 DE DE19873742000 patent/DE3742000A1/en not_active Withdrawn
- 1987-12-17 CA CA000554578A patent/CA1299802C/en not_active Expired - Lifetime
- 1987-12-21 FR FR8717828A patent/FR2608617B1/en not_active Expired - Fee Related
- 1987-12-22 KR KR1019870014660A patent/KR940011192B1/en not_active IP Right Cessation
- 1987-12-22 JP JP62323035A patent/JPH0692564B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0692564B2 (en) | 1994-11-16 |
| GB2198740A (en) | 1988-06-22 |
| KR940011192B1 (en) | 1994-11-26 |
| FR2608617B1 (en) | 1994-01-07 |
| FR2608617A1 (en) | 1988-06-24 |
| GB2198740B (en) | 1991-08-21 |
| GB8725155D0 (en) | 1987-12-02 |
| KR880007671A (en) | 1988-08-29 |
| DE3742000A1 (en) | 1988-06-30 |
| JPS63172776A (en) | 1988-07-16 |
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