CA1262989A - Acrylic-functional silicone resin compositions - Google Patents
Acrylic-functional silicone resin compositionsInfo
- Publication number
- CA1262989A CA1262989A CA000493897A CA493897A CA1262989A CA 1262989 A CA1262989 A CA 1262989A CA 000493897 A CA000493897 A CA 000493897A CA 493897 A CA493897 A CA 493897A CA 1262989 A CA1262989 A CA 1262989A
- Authority
- CA
- Canada
- Prior art keywords
- units
- silicone resin
- radical
- radicals
- substituted
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- 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
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Silicon Polymers (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
ACRYLIC-FUNCTIONAL SILICONE RESIN COMPOSITIONS
Abstract There is provided a cuble silicone composition, comprising:
(a) from 75 to 100 mole percent chemically combined siloxy units selected from the group consisting of R3SiO0.5 units, RSiO1.5 units and SiO2 units; and (b) from 0 to 25 mole percent R2SiO units, there being present a number of R unlts having he general formula:
Abstract There is provided a cuble silicone composition, comprising:
(a) from 75 to 100 mole percent chemically combined siloxy units selected from the group consisting of R3SiO0.5 units, RSiO1.5 units and SiO2 units; and (b) from 0 to 25 mole percent R2SiO units, there being present a number of R unlts having he general formula:
Description
z~
ACRYLIC~FUNCTIONAL SILICONE RESIN COMPOSITIONS
Background of- the Invention The present invention relates to acrylic-functional silicone compositions. More particularly, the present invention relates to acrylic-Eunctional silicone resins which are curable upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalys-t to compositions useful as conformal coatings or as coatings for optical fibers.
Organopolysiloxanes containing acrylate groups which cure upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst are known in the art. Generally, these compositions are useful only as release coatings because of their cheesy or crumbly nature. 'rO the best of applicant's knowledge, curable acrylate-functional organopolysiloxanes which are useful for makiny conformal coatings or as coatings for optical fibers (i.e. they possess the requisite physical properties~ are unavailable in the art.
Accordingly, there is provided by the present invention solventless, acrylate-functional silicone resins which are curable upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst to a composition useful as a conformal coating or as a coating for optical fibers.
U.S. Patent No. 2,793,223, issued May 21, 1957 to Merker, discloses siloxanes of the formula:
.
~6~
ACRYLIC~FUNCTIONAL SILICONE RESIN COMPOSITIONS
Background of- the Invention The present invention relates to acrylic-functional silicone compositions. More particularly, the present invention relates to acrylic-Eunctional silicone resins which are curable upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalys-t to compositions useful as conformal coatings or as coatings for optical fibers.
Organopolysiloxanes containing acrylate groups which cure upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst are known in the art. Generally, these compositions are useful only as release coatings because of their cheesy or crumbly nature. 'rO the best of applicant's knowledge, curable acrylate-functional organopolysiloxanes which are useful for makiny conformal coatings or as coatings for optical fibers (i.e. they possess the requisite physical properties~ are unavailable in the art.
Accordingly, there is provided by the present invention solventless, acrylate-functional silicone resins which are curable upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst to a composition useful as a conformal coating or as a coating for optical fibers.
U.S. Patent No. 2,793,223, issued May 21, 1957 to Merker, discloses siloxanes of the formula:
.
~6~
- 2 - 60SI 00810 (C~l2 = CR - C - O - CH2) R' SiO3 wherein R is a hydrogen a-tom or methyl, R' is a monovalent hydrocarbon radical, and n has a value from 1 to 2, inclusive. Such acryloxy substituted siloxanes can optionally be copolymerized with siloxanes of the formula:
R''mSiO4 m wherein R'' is a monovalent hydrocarbon radical, an acetoxymethyl radical, or a halogenated monovalent hydrocarbon radical, and m has an average value from 1 to 3, inclusive. Consideration of the teachings of Merker reveals that trifunctional units having acrylate-functional groups bonded thereto as well as tetrafunctional siloxy units are not contemplated.
Merker, U.S. Patent No. 2,922,806, issued January 26, 1960~ expands upon the teaching of the aforementioned U.S. Patent No. 2,793,223, in that there are provided organopolysiloxanes containing polymeric units of the formula:
o 2 CR C ~ ~ (CH2)n R' SiO3 wherein n is an integer from 2 to 4, inclusive, y is an integer from 0 to 1, inclusive, R is a hydrogen atom or a methyl radical, and R' is a monovalent hydrocarbon radical free of aliphatic unsaturation. Again, such acryloxy substi-tuted siloxanes can optionally be copolymerized with siloxanes of the formula:
R''m SiO4 m whereln R'' is a monovalent hydrocarbon radical or a
R''mSiO4 m wherein R'' is a monovalent hydrocarbon radical, an acetoxymethyl radical, or a halogenated monovalent hydrocarbon radical, and m has an average value from 1 to 3, inclusive. Consideration of the teachings of Merker reveals that trifunctional units having acrylate-functional groups bonded thereto as well as tetrafunctional siloxy units are not contemplated.
Merker, U.S. Patent No. 2,922,806, issued January 26, 1960~ expands upon the teaching of the aforementioned U.S. Patent No. 2,793,223, in that there are provided organopolysiloxanes containing polymeric units of the formula:
o 2 CR C ~ ~ (CH2)n R' SiO3 wherein n is an integer from 2 to 4, inclusive, y is an integer from 0 to 1, inclusive, R is a hydrogen atom or a methyl radical, and R' is a monovalent hydrocarbon radical free of aliphatic unsaturation. Again, such acryloxy substi-tuted siloxanes can optionally be copolymerized with siloxanes of the formula:
R''m SiO4 m whereln R'' is a monovalent hydrocarbon radical or a
- 3 - 60SI-00810 halogenated monovalen-t hydrocarbon radical, and m is an in-teger from 0 to 3, inclusive, the average value of m being from 0.8 to 3, inclusive. Analysis of the specification and examples reveals that the presence of tetrafunctional siloxy units is not contemplated and that at least about 33 mole % difunctional siloxy units must be present in the composition.
U.S. Patent No. 3,782,940, issued January 1, 1974 to Ohto et al, discloses oryanopolysiloxanes containing at least one photopolymexizable organic silicon radical represented by the general formula:
,Rl R,2 (R4) HC - C - C - R , 3-a-b Xb 2 wherein Rl is a hydrogen atom or an unsubsti-tuted or halogen-substituted phenyl radical; R2 is a hydrogen atom or a methyl radical; R3 is an unsubstituted or halogen-substituted divalent hydrocarbon radical having from 1 to 10 carbon atoms; R4 is an unsubstituted or a halogen-substituted monovalent hydrocarbon radical having from 1 to 10 carbon atoms, X is a hydroxyl radical or an alkoxy radical having from 1 to 4 carbon atoms, and a and b are each equal to 0, 1 or 2, with the proviso that a ~ b equals 0, 1 or 2. Reference to the specifica-tion and examples makes clear that tetrafunctional siloxy units are not contemplated and that the difunctional siloxy unit concentration must be a-t least about 40 mole percent. U.S. Patent No. 3,865,588, issued February 11, 1975 to Ohto et al discloses substantially the same chemistry as the aforesaid U.S. Patent No. 3,782,940.
U.S. Patent No. 3,878,263, issued April 15, 1975, issued to Martin, discloses organopolysiloxanes of the general formula:
U.S. Patent No. 3,782,940, issued January 1, 1974 to Ohto et al, discloses oryanopolysiloxanes containing at least one photopolymexizable organic silicon radical represented by the general formula:
,Rl R,2 (R4) HC - C - C - R , 3-a-b Xb 2 wherein Rl is a hydrogen atom or an unsubsti-tuted or halogen-substituted phenyl radical; R2 is a hydrogen atom or a methyl radical; R3 is an unsubstituted or halogen-substituted divalent hydrocarbon radical having from 1 to 10 carbon atoms; R4 is an unsubstituted or a halogen-substituted monovalent hydrocarbon radical having from 1 to 10 carbon atoms, X is a hydroxyl radical or an alkoxy radical having from 1 to 4 carbon atoms, and a and b are each equal to 0, 1 or 2, with the proviso that a ~ b equals 0, 1 or 2. Reference to the specifica-tion and examples makes clear that tetrafunctional siloxy units are not contemplated and that the difunctional siloxy unit concentration must be a-t least about 40 mole percent. U.S. Patent No. 3,865,588, issued February 11, 1975 to Ohto et al discloses substantially the same chemistry as the aforesaid U.S. Patent No. 3,782,940.
U.S. Patent No. 3,878,263, issued April 15, 1975, issued to Martin, discloses organopolysiloxanes of the general formula:
4 ~ 60SI-00810 R O ,e ~ ~R' ~
~ CR2 - C ~ C ~ OR'' ~ SiO3 ) ~SiOJ R''' wherein R is selected from hydrogen and monovalent hydro-carbon radicals having from l to 12 carbon atoms, R' is selected from monovalent hydrocarbon radicals, halogenated monovalent hydrocarbon radicals, and cyanoalkyl radicals having from 1 to 18 carbon atoms, R'' is selected from the group consisting of a divalent hydrocarbon radical having from 2 to 18 carbon atoms, and the corresponding divalent hydrocarbon radical containing c - O - C linkages, R''' is a radical selected from the group consisting of R 00, 5 and R SiOo 5/ Z iS a group selected from OR~ R~ or OSiR~3~ in which R'''' is selected ~rom hydrogen and monovalent hydrocarbon radicals, a and b are each numbers from 1 to 20,000, c is a number from 0 to 3 and e is a number from 0 to 2, with the proviso that when c is zero, then a-t least one Z must be OR''''. Martin does not contemplate including tetrafunctional siloxy units in the composition nor, in view of the examples, does he contemplate less than about 60 mole percent difunctional siloxy units.
U.S. Patent No. 3~886~865~ issued June 3r 1975 to Oh-to et al, relates to pho-topolymerizable organopoly-siloxanes of the general formula:
R2 (CH3) a ~ CH3 ~C = C - C ~ R - SiO3_ ) ~6~5 1 ~
wherein Rl is hydrogen, an unsubstituted or halogen-substituted phenyl radical, R2 is a hydrogen atom or a methyl radical, R iS a divalent hydrocarbon radical having from 1 to 3 carbon atoms, R4 iS methyl or tri-fluoropropyl, a is 0 or l, and m and n are positive ~z~
~ CR2 - C ~ C ~ OR'' ~ SiO3 ) ~SiOJ R''' wherein R is selected from hydrogen and monovalent hydro-carbon radicals having from l to 12 carbon atoms, R' is selected from monovalent hydrocarbon radicals, halogenated monovalent hydrocarbon radicals, and cyanoalkyl radicals having from 1 to 18 carbon atoms, R'' is selected from the group consisting of a divalent hydrocarbon radical having from 2 to 18 carbon atoms, and the corresponding divalent hydrocarbon radical containing c - O - C linkages, R''' is a radical selected from the group consisting of R 00, 5 and R SiOo 5/ Z iS a group selected from OR~ R~ or OSiR~3~ in which R'''' is selected ~rom hydrogen and monovalent hydrocarbon radicals, a and b are each numbers from 1 to 20,000, c is a number from 0 to 3 and e is a number from 0 to 2, with the proviso that when c is zero, then a-t least one Z must be OR''''. Martin does not contemplate including tetrafunctional siloxy units in the composition nor, in view of the examples, does he contemplate less than about 60 mole percent difunctional siloxy units.
U.S. Patent No. 3~886~865~ issued June 3r 1975 to Oh-to et al, relates to pho-topolymerizable organopoly-siloxanes of the general formula:
R2 (CH3) a ~ CH3 ~C = C - C ~ R - SiO3_ ) ~6~5 1 ~
wherein Rl is hydrogen, an unsubstituted or halogen-substituted phenyl radical, R2 is a hydrogen atom or a methyl radical, R iS a divalent hydrocarbon radical having from 1 to 3 carbon atoms, R4 iS methyl or tri-fluoropropyl, a is 0 or l, and m and n are positive ~z~
- 5 - 60SI-00810 integers wi-th the proviso -that n exceeds 25, while n/l and n/m are 25 to 20000 and 2.5 to 50, respectively. From -the ra-tios of n/l and n/m it is clear that -the trifunctional siloxy units are not present in a large amount and, further, tetrafunctional siloxy units are not contemplated at all.
U.S. Patent No. 4,201,80~, issued May 6, 1980 to Cully et al, describes photocurable organopolysiloxanes useful as release coatings comprising an organopolysiloxane containing an average of at least one acryloxy and/or methacryloxy group per molecule, a low molecular weight polyacryl crosslinking agent, and, optionally, a photo-sensitizer. The organopolysiloxanes having acryloxy and/or methacryloxy groups have the average formula:
~n SiO4 ) wherein m has an average value greater than about 25, R is, independently, acryloxy, methacryloxy, an unsubstituted monovalent hydrocarbon radical having from l to 20 carbon atoms, or a substitu-ted monovalent hydrocarbon radical wherein the substituents are selected from the group consisting of chloro, fluoro, cyano, amido, ni-tro, ureido, isocyanato, carbalkoxy, hydroxy, acryloxy and methacryloxy, and n has an averaye va]ue from abou-t 1,.8 to 2.2; said organopolysiloxane containing an avera~e of at least one R group which contains an acryloxy or methacryloxy group. Reference to the specification and examples makes clear that the acryloxy-functional polysiloxanes are comprised of substantially all diorganosiloxy units (e.g. free of trifunctional) and tetrafunctional siloxy units).
U.S. Patent No. 4,348,454, issued September 7, 1982 to Eckberg, discloses acrylic functional polysiloxanes which are especially useful for ultraviolet curable silicone release coating applications. As in all release :~2~
U.S. Patent No. 4,201,80~, issued May 6, 1980 to Cully et al, describes photocurable organopolysiloxanes useful as release coatings comprising an organopolysiloxane containing an average of at least one acryloxy and/or methacryloxy group per molecule, a low molecular weight polyacryl crosslinking agent, and, optionally, a photo-sensitizer. The organopolysiloxanes having acryloxy and/or methacryloxy groups have the average formula:
~n SiO4 ) wherein m has an average value greater than about 25, R is, independently, acryloxy, methacryloxy, an unsubstituted monovalent hydrocarbon radical having from l to 20 carbon atoms, or a substitu-ted monovalent hydrocarbon radical wherein the substituents are selected from the group consisting of chloro, fluoro, cyano, amido, ni-tro, ureido, isocyanato, carbalkoxy, hydroxy, acryloxy and methacryloxy, and n has an averaye va]ue from abou-t 1,.8 to 2.2; said organopolysiloxane containing an avera~e of at least one R group which contains an acryloxy or methacryloxy group. Reference to the specification and examples makes clear that the acryloxy-functional polysiloxanes are comprised of substantially all diorganosiloxy units (e.g. free of trifunctional) and tetrafunctional siloxy units).
U.S. Patent No. 4,348,454, issued September 7, 1982 to Eckberg, discloses acrylic functional polysiloxanes which are especially useful for ultraviolet curable silicone release coating applications. As in all release :~2~
- 6 - 60SI-00810 coating applications the polysiloxane consists essentially of diorganosiloxy units and thus is not useful as a conformal coatiny.
Summary of t-he Invention It is an object of the presentinvention to provide novel solventless silicone resin compositions.
It is another obiect of the present invention to provide solventless, acrylate-functional silicone resin compositions which are curable upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst.
Another object of the present invention is to provide silicone resin compositions useful as conformal coatings for electronic components and as coatings for optical fibers.
Still another object of the present invention is to provide methods for making solventless, acrylate-functional silicone resin compositions and methods for making articles having said silicone resin cured thereon.
There is provided in accordance with the teachings of the present invention a silicone resin composition, comprising:
(a) from 75 to 100 mole percent chemically combined siloxy units selected from the group consisting of R3SiOo 5 units, RSiOl 5 units and SiO2 units; and , (b) from 0 to 25 mole percent R2SiO units;
wherein R is a substituted or unsubstituted monovalent oryanic radical, with the proviso that there are present a number of R radicals having the general formula o (R )2 = C - C - O - R2 _ Rl effective for curing said silicone resin composition upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst, wherein Rl is ~ 7 - 60SI-00810 selec-ted, independen-tly, from the yroup consisting of hydrogen ~nd monovalent subs-tituted and unsubstitu-ted hydrocarbon radicals having from 1 to 12 carbon atoms, and R is a divalent substituted or unsubstituted hydro-carbon radical having from 1 to 18 carbon atoms or thecorresponding oxyalkylene radical containing at least one C - O - C linkage, and wherein the total number of siloxy units is four or more, at least one of which has the formula RSiOl 5 or SiO2.
Description o~f the Invention There is provided by the present invention a silicone resin composition, comprising:
(a) from 75 to 100 mole percent chemically combined siloxy units selected from the group consisting of R3SiOo 5 units, RSiOl 5 units and SiO2 units; and (b~ from 0 to 25 mole percent R2SiO units;
wherein R is a substituted or unsubstituted monovalent organic radical, with the proviso that there are present a number of R radicals having the general formula C (R )2 = C - C - o R
Rl effective forcuring said silicone resin composit.ion upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst, wherein R is selected, independently, from the group consisting of hydrogen and monovalent substituted and unsubstituted hydrocarbon radicals having from 1 to 12 carbon atoms, and R is a divalent substituted or unsubstituted hydrocarbon radical having from 1 to 18 carbon atoms or the corresponding oxyalkylene radical containing at least one C - O - C linkage, and wherein the total number of siloxy units is four or more, at least one of which has the formula RSiOl 5 or SiO2.
For purposes of this invention, R can be - 8 - 60SI~00180 any monovalent substituted or unsubs-tituted organic radlcal. Specific examples of unsubstituted radicals are alkyl radicals such as methyl, ethyl, propyl, hexyl, octyl, octadecyl and the likej alkenyl radicals such as vinyl, allyl, hexenyl and the like; cycloaliphatic radicals such as cyclohexvl, cyclohexenyl, cyclopentyl and the like; aromatic radicals such as phenyl, naphthyl and the like; aralkyl radicals such as beta-phenylethyl.
Examples of substituted radicals are any of the foregoing wherein at least one hydrogen atom has been replaced by a substituent selected from the group consisting of halogen, cyano, amido, nitro, ureido, isocyanato, alkoxy, hydroxy and the like. Preferably the R radicals are lower alkyl radicals such as methyl, ethyl, propyl, 3,3,3-trifluoropropyl or an aryl radical such as phenyl. Mostpreferably the R radicals are methyl, phenyl or a mixture thereof.
It is critical to the present invention that there be included among the R radicals a sufficient number of radicals having the formula o (I~ C (R )2 = C - C - O - R
Rl so as to ensure that the resin composition will cure~upon exposure to ultraviolet radiation or upon hea-ting in the presence of a free radical type catalyst. Examples of radicals included within the scope of Rl are hydrogen and substituted or unsubstituted monovalent hydrocarbon radicals having from 1 to 12 carbon atoms. Preferably, Rl is hydrogen, phenyl or a lower alkyl radical such as methyl, ethyl, or propyl. Most preferably Rl is hydrogen, methyl, or phenyl or a mixture thereof. If Rl is a substituted radical it can be substi-tuted by an substituen-t identified hereinabove for R.
R2 can be any divalent substituted or unsubstituted hydrocaxbon radical having from 1 to 18 carbon atoms or the corresponding oxyalkylene radical having at least one C - O - C linkage. Examples of R includes alkylene radicals such as ethylene, propylene, butylene, pentamethylene, hexadecylmethylene and octadecylmethylene;
arylene radicals such as phenylene, biphenylene and the corresponding alkylene and arylene radicals containing an oxygen atom.
The silicone resin composition of the instant invention comprises 75 to 100 mole percent chemically combined siloxy units selected from the group consisting of R3SiOo 5 units (referred to as M units), RSiOl 5 units (.referred to at T units) and SiO2 units (referred to as Q units), and from 0 to 25 mole percent R2SiO units keferred to as D units~. Preferably the silicone resins of the presen-t invention are substantially free of D units and thus consist primarily of M, T, and Q units or mix-tures thereof. Accordingly, the preferred resins are MQ resi.ns, MT resins and MTQ resins.
As indicated hereinabove, it is critical -that be present sufficient radicals defined by Formula I
(referred herein interchangably as acrylic, acrylic~
functional, acrylate/ acrylate-functional and the like) to ensure that the resin will cure upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst. Therefore, the ar-tisan will appreciate that the siloxy units of the resin can have the formulas:
R O R
' l " 2 R - 5iO - , C(R )2 = C - C - O - R SiO -R R
-- 10 - 60SI-OOglO
O R
C(R )2 = C - C - O - R~ ~ SiO -O
C(R ~2 = C - C - O - R
Il R
c (Rl) 2 = f ~ C - O - R
Rl \
C(R )2 = C - C - O - R - SiO -Il o C(Rl)2 = C - C - O ] ~2 Rl R SiO - , C(R )2 = C - C - O - R - SiO -R
and - SiO -wherein R, Rl and R are defined as above.
The total number of acrylate-functional groups present need only be present in a sufficient number to e~fect crosslinking of the resin composition upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst. Thus the number of acrylate-~unctional radicals may be as low as about 0.5 mole percent of the total R groups or it can be as much as 100 percent of the R groups. The artisan will, or course, be able to determine without undue experimentation the number of acrylate-functional radicals necessary to ~ 11 - 60SI-00810 impart sufficient crosslinking for a particular purpose.
Preferably the number of acrylate-functional yroups will be present in an amount ranging from about 0.5 to about ~0 mole percent of the number of R groups.
Al-though it is contemplated that the number of M units to Q units to T units or mix-ture thereof can vary as necessary to obtain desired properties, it has been found that particular ratios impart especially desirable properties to the cured resin. If an MQ resin is employed, the ratio of M units to Q units preferably ranges from about 1:1 to about 3:1; if an MT resin is employed, the ratio of M units to Q units preferably is from about Q.5:1 to ahout 2:1; and if an MTQ resin is employed, the ratio of M units to T units ranges from about 0.5:1 to about 2;1 and the ratio of T units to Q units is from about 0.5:1 to about 3:1.
In addition to the foregoing preferred ratios of the various types of siloxy units, it has been found that when the number of siloxy units per molecule is less than about 500 the resulting silicone resin can be employed free of solvent. Of course such compositions are especially preferable as they eliminate the need for energy-intensive ovens and expensive solvent recovery apparatus. However, resins which require the use of a solvent to aid in their application to substrates such as electronic components ~e.g. conformal coating), optical fibers, and paper (release coating) are also intended to be within the scope of the appended claims.
The most preferred compositions are MQ resins and MTQ resins having less than about 500 siloxy units so that they are solvent free and have a ratio of M units to Q units, and M units to T units to Q units, respectively, as indicated hereinabove.
It is also possible to inc:Lude in the silicone resin of the present invention up to about 25 mole percent diorganosiloxy units (D units) of the formula R2SiO.
- 12 - 60SI-00~10 Preferably, there should not be presen-t more than about 10 mole percent of such diorganosiloxy uni-ts. Those skilled in the art will recognize -tha-t the inclusion of D units will impart flexibility to the cured composition, hence it is important that the number of D units does not exceed about 25 mole percent. The organic radicals bonded to the silicon atom of the D unit can be any of those listed hereinabove. Such diorganosiloxy units can be free of acrylate-functional radicals of Fol-mula I, be a mixture of acrylate-functional radicals and organo radicals, or can all be acrylate functional radicals.
Again, the artisan will be able to determine without undue experimentation what percentage of the R radicals of the diorganosiloxy units should be acrylate-functional for a particular application.
Examples Example 1 15.6 grams of a silicone hydride resin having one weight percent silicon-bonded hydrogen atoms and having the general formula Me ~
/ I \
/ Me - Si - H \
I
Me / O \ Me \ l H - SiO - - SiO -- - Si - H
l l Me \ t / Me \ Me -Si - H
I
Me n where n = 2, 3 and 4 (i.e. a mixture of monomers) and Me is methyl, was added dropwise to a stirred mixture of 20 grams allylmethacrylate, 60 mg. 2,5-di-t-butyl hydro-quinone, 0.16 gram Pt-octanol complex catalyst (3 weight percent P-t) and 150 ml hexane. The reaction mixture was heated at 50 - 55C during the addition of silicone hydride resin and thereafter was rnaintained at 50 - 60~C ~or 9 hours. Hexene was then added and heated to reflux for 4 hours. The reaction mass was then cooled to room temperature and the hexane and hexene allowed to evaporate.
Twenty five grams of an acrylate-functional resin having the above formula but wherein the hydrogen atoms were replaced with acrylate--functional groups was obtained.
Example 2 The methacrylated silicone resin of Example l was mixed with 5 weight percent 2,2-diethoxyacetophenone photoinitiator and coated on a supercalendered kraft (SCK) substrate. The coated SCK subs-trate was UV-cured by passing it under a PPG Model 1202 Processor. All cures were under a nitrogen atmosphere.
Samples 1 through 3 in the following chart illustrate the practice of the present inven-tion to obtain suitable release coatings. Samples A and 5 demonstrate that thicker coatings can be utilized but the lamp power and/or exposure time must be adjusted accordin~ly.
Film Lamp Exposure Sample ~hickness Power Time Result .
1 1 mil 400 watts 0.22 sec. Excellent cure, smear-free hard film glossy appearance 2 l mil 400 watts 0.11 sec. Same as l 3 l mil 400 watts 0.06 sec. Cured wall with slight smear 4 2 mil 400 watts 0.11 sec. Soft cure 2 mil 400 watts 0.04 sec. Cured well with slight smear Examp'l'e 3 Five grams of the methacrylated silicone resin of Example l was mixed with 0.1 gram cumene hydroperoxide.
Duro activator ~source: Loctite Corp.) was applied to one side of a test substrate and to one side of another piece of the test substrate was applied the resin/catalyst mixture. The two pieces were pressed together and allowed to cure at room temperature. The resin was judged to be fully cured when the two pieces of substrate could not be moved by hand as follows:
Substrate Cure Time Glass 30 minutes Stainless Steel 30 minutes This example illustrates the utility of the resins of the instant invention as a bonding material Ex'ampl'e 4 To a mixture of 25 grams (0.114 moles) o (CH3) 2Si Cl (CH2) 3 OCC = CH2 12.3 grams (0.114 moles (CH3~3SiCl, and 16.7 grams (0.111 moles~ CH3 Si C13 there was added dropwise 50 ml of water with stirring at 25 to 40C. P.-fter completion of water addition, the mixture was trans-ferred to a 250 ml separatory funnel. To the mixture there was added 50 ml toluene, thereafter the mixture was washed with water, and finally 5~6 NaElC03 was added until the mixture was neutral.
The organic phase was stripped in a rotary evaporator at 50C/~ mm Hg to yield 33 grams of silicone resin.
Ex'ample 5 The procedure set forth in Example 4 was followed to prepare a silicone resin from the following reactants:
o 25 grams (0.114 moles~ (CH32SiCl(CH2)3OCC = CH2 12.3 grams (O.lla~ moles) (CH3)3SiCl 14.6 grams (0.114 moles) (CH3)2SiC12 16.9 grams (0.114 moles) CH3SiC13 There resulted 64.4 grams of silicone resin.
Example 6 The procedure set forth in Example 4 was followed to prepared a silicone resin from the following reactants:
25 grams (0.114 moles) (CH3)2SiCl(CH2)3OCC = CH2 12.3 grams (0.114 moles) (CH3)3SiCl 16.9 grams (0.114 moles) CH3SiC13 12.9 grams (0.076 moles) SiC14 There resulted 42 grams of silicone resin.
Exampl-e 7 Each of the silicone resins prepared in Examples 4, 5 and 6 were mixed with 3 weight percent 2,2-diethox~acetophenone photoinitiator. Two mil coatings of such mixture were manually applied onto a stainless steel substrate. The thus coated substrate was then exposed to a source of ultraviolet radiation under a nitrogen atmosphere as in Example 2 with the following results:
_ Resin Lamp Exposure ~ s Power _Time Result (watts) 4 400 3 sec Excellen-t cure, hard, glossy fi.nish 400 6 sec Cured to a glossy Finish with slight Flexibility 6 400 6 sec Cured to a hard _ _ _ material
Summary of t-he Invention It is an object of the presentinvention to provide novel solventless silicone resin compositions.
It is another obiect of the present invention to provide solventless, acrylate-functional silicone resin compositions which are curable upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst.
Another object of the present invention is to provide silicone resin compositions useful as conformal coatings for electronic components and as coatings for optical fibers.
Still another object of the present invention is to provide methods for making solventless, acrylate-functional silicone resin compositions and methods for making articles having said silicone resin cured thereon.
There is provided in accordance with the teachings of the present invention a silicone resin composition, comprising:
(a) from 75 to 100 mole percent chemically combined siloxy units selected from the group consisting of R3SiOo 5 units, RSiOl 5 units and SiO2 units; and , (b) from 0 to 25 mole percent R2SiO units;
wherein R is a substituted or unsubstituted monovalent oryanic radical, with the proviso that there are present a number of R radicals having the general formula o (R )2 = C - C - O - R2 _ Rl effective for curing said silicone resin composition upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst, wherein Rl is ~ 7 - 60SI-00810 selec-ted, independen-tly, from the yroup consisting of hydrogen ~nd monovalent subs-tituted and unsubstitu-ted hydrocarbon radicals having from 1 to 12 carbon atoms, and R is a divalent substituted or unsubstituted hydro-carbon radical having from 1 to 18 carbon atoms or thecorresponding oxyalkylene radical containing at least one C - O - C linkage, and wherein the total number of siloxy units is four or more, at least one of which has the formula RSiOl 5 or SiO2.
Description o~f the Invention There is provided by the present invention a silicone resin composition, comprising:
(a) from 75 to 100 mole percent chemically combined siloxy units selected from the group consisting of R3SiOo 5 units, RSiOl 5 units and SiO2 units; and (b~ from 0 to 25 mole percent R2SiO units;
wherein R is a substituted or unsubstituted monovalent organic radical, with the proviso that there are present a number of R radicals having the general formula C (R )2 = C - C - o R
Rl effective forcuring said silicone resin composit.ion upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst, wherein R is selected, independently, from the group consisting of hydrogen and monovalent substituted and unsubstituted hydrocarbon radicals having from 1 to 12 carbon atoms, and R is a divalent substituted or unsubstituted hydrocarbon radical having from 1 to 18 carbon atoms or the corresponding oxyalkylene radical containing at least one C - O - C linkage, and wherein the total number of siloxy units is four or more, at least one of which has the formula RSiOl 5 or SiO2.
For purposes of this invention, R can be - 8 - 60SI~00180 any monovalent substituted or unsubs-tituted organic radlcal. Specific examples of unsubstituted radicals are alkyl radicals such as methyl, ethyl, propyl, hexyl, octyl, octadecyl and the likej alkenyl radicals such as vinyl, allyl, hexenyl and the like; cycloaliphatic radicals such as cyclohexvl, cyclohexenyl, cyclopentyl and the like; aromatic radicals such as phenyl, naphthyl and the like; aralkyl radicals such as beta-phenylethyl.
Examples of substituted radicals are any of the foregoing wherein at least one hydrogen atom has been replaced by a substituent selected from the group consisting of halogen, cyano, amido, nitro, ureido, isocyanato, alkoxy, hydroxy and the like. Preferably the R radicals are lower alkyl radicals such as methyl, ethyl, propyl, 3,3,3-trifluoropropyl or an aryl radical such as phenyl. Mostpreferably the R radicals are methyl, phenyl or a mixture thereof.
It is critical to the present invention that there be included among the R radicals a sufficient number of radicals having the formula o (I~ C (R )2 = C - C - O - R
Rl so as to ensure that the resin composition will cure~upon exposure to ultraviolet radiation or upon hea-ting in the presence of a free radical type catalyst. Examples of radicals included within the scope of Rl are hydrogen and substituted or unsubstituted monovalent hydrocarbon radicals having from 1 to 12 carbon atoms. Preferably, Rl is hydrogen, phenyl or a lower alkyl radical such as methyl, ethyl, or propyl. Most preferably Rl is hydrogen, methyl, or phenyl or a mixture thereof. If Rl is a substituted radical it can be substi-tuted by an substituen-t identified hereinabove for R.
R2 can be any divalent substituted or unsubstituted hydrocaxbon radical having from 1 to 18 carbon atoms or the corresponding oxyalkylene radical having at least one C - O - C linkage. Examples of R includes alkylene radicals such as ethylene, propylene, butylene, pentamethylene, hexadecylmethylene and octadecylmethylene;
arylene radicals such as phenylene, biphenylene and the corresponding alkylene and arylene radicals containing an oxygen atom.
The silicone resin composition of the instant invention comprises 75 to 100 mole percent chemically combined siloxy units selected from the group consisting of R3SiOo 5 units (referred to as M units), RSiOl 5 units (.referred to at T units) and SiO2 units (referred to as Q units), and from 0 to 25 mole percent R2SiO units keferred to as D units~. Preferably the silicone resins of the presen-t invention are substantially free of D units and thus consist primarily of M, T, and Q units or mix-tures thereof. Accordingly, the preferred resins are MQ resi.ns, MT resins and MTQ resins.
As indicated hereinabove, it is critical -that be present sufficient radicals defined by Formula I
(referred herein interchangably as acrylic, acrylic~
functional, acrylate/ acrylate-functional and the like) to ensure that the resin will cure upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst. Therefore, the ar-tisan will appreciate that the siloxy units of the resin can have the formulas:
R O R
' l " 2 R - 5iO - , C(R )2 = C - C - O - R SiO -R R
-- 10 - 60SI-OOglO
O R
C(R )2 = C - C - O - R~ ~ SiO -O
C(R ~2 = C - C - O - R
Il R
c (Rl) 2 = f ~ C - O - R
Rl \
C(R )2 = C - C - O - R - SiO -Il o C(Rl)2 = C - C - O ] ~2 Rl R SiO - , C(R )2 = C - C - O - R - SiO -R
and - SiO -wherein R, Rl and R are defined as above.
The total number of acrylate-functional groups present need only be present in a sufficient number to e~fect crosslinking of the resin composition upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst. Thus the number of acrylate-~unctional radicals may be as low as about 0.5 mole percent of the total R groups or it can be as much as 100 percent of the R groups. The artisan will, or course, be able to determine without undue experimentation the number of acrylate-functional radicals necessary to ~ 11 - 60SI-00810 impart sufficient crosslinking for a particular purpose.
Preferably the number of acrylate-functional yroups will be present in an amount ranging from about 0.5 to about ~0 mole percent of the number of R groups.
Al-though it is contemplated that the number of M units to Q units to T units or mix-ture thereof can vary as necessary to obtain desired properties, it has been found that particular ratios impart especially desirable properties to the cured resin. If an MQ resin is employed, the ratio of M units to Q units preferably ranges from about 1:1 to about 3:1; if an MT resin is employed, the ratio of M units to Q units preferably is from about Q.5:1 to ahout 2:1; and if an MTQ resin is employed, the ratio of M units to T units ranges from about 0.5:1 to about 2;1 and the ratio of T units to Q units is from about 0.5:1 to about 3:1.
In addition to the foregoing preferred ratios of the various types of siloxy units, it has been found that when the number of siloxy units per molecule is less than about 500 the resulting silicone resin can be employed free of solvent. Of course such compositions are especially preferable as they eliminate the need for energy-intensive ovens and expensive solvent recovery apparatus. However, resins which require the use of a solvent to aid in their application to substrates such as electronic components ~e.g. conformal coating), optical fibers, and paper (release coating) are also intended to be within the scope of the appended claims.
The most preferred compositions are MQ resins and MTQ resins having less than about 500 siloxy units so that they are solvent free and have a ratio of M units to Q units, and M units to T units to Q units, respectively, as indicated hereinabove.
It is also possible to inc:Lude in the silicone resin of the present invention up to about 25 mole percent diorganosiloxy units (D units) of the formula R2SiO.
- 12 - 60SI-00~10 Preferably, there should not be presen-t more than about 10 mole percent of such diorganosiloxy uni-ts. Those skilled in the art will recognize -tha-t the inclusion of D units will impart flexibility to the cured composition, hence it is important that the number of D units does not exceed about 25 mole percent. The organic radicals bonded to the silicon atom of the D unit can be any of those listed hereinabove. Such diorganosiloxy units can be free of acrylate-functional radicals of Fol-mula I, be a mixture of acrylate-functional radicals and organo radicals, or can all be acrylate functional radicals.
Again, the artisan will be able to determine without undue experimentation what percentage of the R radicals of the diorganosiloxy units should be acrylate-functional for a particular application.
Examples Example 1 15.6 grams of a silicone hydride resin having one weight percent silicon-bonded hydrogen atoms and having the general formula Me ~
/ I \
/ Me - Si - H \
I
Me / O \ Me \ l H - SiO - - SiO -- - Si - H
l l Me \ t / Me \ Me -Si - H
I
Me n where n = 2, 3 and 4 (i.e. a mixture of monomers) and Me is methyl, was added dropwise to a stirred mixture of 20 grams allylmethacrylate, 60 mg. 2,5-di-t-butyl hydro-quinone, 0.16 gram Pt-octanol complex catalyst (3 weight percent P-t) and 150 ml hexane. The reaction mixture was heated at 50 - 55C during the addition of silicone hydride resin and thereafter was rnaintained at 50 - 60~C ~or 9 hours. Hexene was then added and heated to reflux for 4 hours. The reaction mass was then cooled to room temperature and the hexane and hexene allowed to evaporate.
Twenty five grams of an acrylate-functional resin having the above formula but wherein the hydrogen atoms were replaced with acrylate--functional groups was obtained.
Example 2 The methacrylated silicone resin of Example l was mixed with 5 weight percent 2,2-diethoxyacetophenone photoinitiator and coated on a supercalendered kraft (SCK) substrate. The coated SCK subs-trate was UV-cured by passing it under a PPG Model 1202 Processor. All cures were under a nitrogen atmosphere.
Samples 1 through 3 in the following chart illustrate the practice of the present inven-tion to obtain suitable release coatings. Samples A and 5 demonstrate that thicker coatings can be utilized but the lamp power and/or exposure time must be adjusted accordin~ly.
Film Lamp Exposure Sample ~hickness Power Time Result .
1 1 mil 400 watts 0.22 sec. Excellent cure, smear-free hard film glossy appearance 2 l mil 400 watts 0.11 sec. Same as l 3 l mil 400 watts 0.06 sec. Cured wall with slight smear 4 2 mil 400 watts 0.11 sec. Soft cure 2 mil 400 watts 0.04 sec. Cured well with slight smear Examp'l'e 3 Five grams of the methacrylated silicone resin of Example l was mixed with 0.1 gram cumene hydroperoxide.
Duro activator ~source: Loctite Corp.) was applied to one side of a test substrate and to one side of another piece of the test substrate was applied the resin/catalyst mixture. The two pieces were pressed together and allowed to cure at room temperature. The resin was judged to be fully cured when the two pieces of substrate could not be moved by hand as follows:
Substrate Cure Time Glass 30 minutes Stainless Steel 30 minutes This example illustrates the utility of the resins of the instant invention as a bonding material Ex'ampl'e 4 To a mixture of 25 grams (0.114 moles) o (CH3) 2Si Cl (CH2) 3 OCC = CH2 12.3 grams (0.114 moles (CH3~3SiCl, and 16.7 grams (0.111 moles~ CH3 Si C13 there was added dropwise 50 ml of water with stirring at 25 to 40C. P.-fter completion of water addition, the mixture was trans-ferred to a 250 ml separatory funnel. To the mixture there was added 50 ml toluene, thereafter the mixture was washed with water, and finally 5~6 NaElC03 was added until the mixture was neutral.
The organic phase was stripped in a rotary evaporator at 50C/~ mm Hg to yield 33 grams of silicone resin.
Ex'ample 5 The procedure set forth in Example 4 was followed to prepare a silicone resin from the following reactants:
o 25 grams (0.114 moles~ (CH32SiCl(CH2)3OCC = CH2 12.3 grams (O.lla~ moles) (CH3)3SiCl 14.6 grams (0.114 moles) (CH3)2SiC12 16.9 grams (0.114 moles) CH3SiC13 There resulted 64.4 grams of silicone resin.
Example 6 The procedure set forth in Example 4 was followed to prepared a silicone resin from the following reactants:
25 grams (0.114 moles) (CH3)2SiCl(CH2)3OCC = CH2 12.3 grams (0.114 moles) (CH3)3SiCl 16.9 grams (0.114 moles) CH3SiC13 12.9 grams (0.076 moles) SiC14 There resulted 42 grams of silicone resin.
Exampl-e 7 Each of the silicone resins prepared in Examples 4, 5 and 6 were mixed with 3 weight percent 2,2-diethox~acetophenone photoinitiator. Two mil coatings of such mixture were manually applied onto a stainless steel substrate. The thus coated substrate was then exposed to a source of ultraviolet radiation under a nitrogen atmosphere as in Example 2 with the following results:
_ Resin Lamp Exposure ~ s Power _Time Result (watts) 4 400 3 sec Excellen-t cure, hard, glossy fi.nish 400 6 sec Cured to a glossy Finish with slight Flexibility 6 400 6 sec Cured to a hard _ _ _ material
Claims (17)
1. A curable silicone resin composition, comprising:
(a) from 75 to 100 mole percent chemically combined siloxy units selected from the group consisting of R3SiO0.5 units, RSiO1.5 units and SiO2 units; and (b) from 0 to 25 mole percent R2SiO units;
wherein R is a substituted or unsubstituted monovalent organic radical, with the proviso that there are present a number of R radicals having the general formula effective for curing said silicone resin composition upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst, wherein R1 is selected, independently, from the group consisting of hydrogen and monovalent substituted and unsubstituted hydrocarbon radicals having from 1 to 12 carbon atoms, and R is a divalent substituted or unsubstituted hydro-carbon radical having from 1 to 18 carbon atoms or the corresponding oxyalkylene radical containing at least one C - O - C linkage, and wherein the total number of siloxy units is four or more, at least one of which has the formula RSiO1.5 or SiO2.
(a) from 75 to 100 mole percent chemically combined siloxy units selected from the group consisting of R3SiO0.5 units, RSiO1.5 units and SiO2 units; and (b) from 0 to 25 mole percent R2SiO units;
wherein R is a substituted or unsubstituted monovalent organic radical, with the proviso that there are present a number of R radicals having the general formula effective for curing said silicone resin composition upon exposure to ultraviolet radiation or upon heating in the presence of a free radical type catalyst, wherein R1 is selected, independently, from the group consisting of hydrogen and monovalent substituted and unsubstituted hydrocarbon radicals having from 1 to 12 carbon atoms, and R is a divalent substituted or unsubstituted hydro-carbon radical having from 1 to 18 carbon atoms or the corresponding oxyalkylene radical containing at least one C - O - C linkage, and wherein the total number of siloxy units is four or more, at least one of which has the formula RSiO1.5 or SiO2.
2. The composition of claim 1 wherein R is methyl or phenyl or a mixture thereof.
3. The composition of claim 1 wherein R is hydrogen, methyl or phenyl or a mixture thereof.
4. The composition of claim 1 wherein the silicone resin is substantially-free of R2SiO units.
5. The composition of claim 1 wherein the number of R2SiO units does not exceed about 10 mole percent of the total number of siloxy units.
6. The composition of claim 1 wherein the number of acrylate-functional radicals ranges Erom about 0.5 mo]e percent to 100 mole percent.
7. The composition of claim 1 wherein the number of acrylate-functional radicals ranges from about 0.5 mole percent to about 80 mole percent.
8. A curable silicone resin composition consisting essentially of chemically combined siloxy units of the formula R3SiO0.5 and SiO2, where R is a monovalent substituted or unsubstituted organic radical with the proviso that there are present a number of R radicals having the general formula:
where R1 is selected, independently, from the group consisting of hydrogen and monovalent substituted and unsubstituted hydrocarbon radicals having from 1 to 12 carbon atoms, R2 is a divalent substituted or unsubstituted hydrocarbon radical having from 1 to 18 carbon atoms or the corresponding oxyalkylene radical containing at least one C - O - C linkage, effective for curing said silicone resin composition upon exposure to ultraviolet radiation in the presence of a photoinitiator or upon heating in the presence of a free-radical type catalyst, and wherein the ratio of R3SiO0.5 units to SiO2 units ranges from about 3:1 to about 1:1.
where R1 is selected, independently, from the group consisting of hydrogen and monovalent substituted and unsubstituted hydrocarbon radicals having from 1 to 12 carbon atoms, R2 is a divalent substituted or unsubstituted hydrocarbon radical having from 1 to 18 carbon atoms or the corresponding oxyalkylene radical containing at least one C - O - C linkage, effective for curing said silicone resin composition upon exposure to ultraviolet radiation in the presence of a photoinitiator or upon heating in the presence of a free-radical type catalyst, and wherein the ratio of R3SiO0.5 units to SiO2 units ranges from about 3:1 to about 1:1.
9. A curable silicone resin composition consisting essentially of chemically combined siloxy units of the formula R3SiO0.5 and RSiO1.5, where R is a mono-valent substituted or unsubstituted organic radical with the proviso that there are present a number of R radicals having the general formula where R1 is selected, independently, from the group consisting of hydrogen and monovalent substituted and unsubstituted hydrocarbon radicals having from 1 to 12 carbon atoms, R2 is a divalent substituted or unsubstituted hydrocarbon radical having from 1 to 18 carbon atoms or the corresponding oxyalkylene radical containing at least one C - O - C linkage, effective for curing said silicone resin composition upon exposure to ultraviolet radiation in the presence of a photoinitiator or upon heating in the presence of a free radical type catalyst, and wherein the ratio of R3SiO0.5 units to RSiO1.5 units is from about 2:1 to about 0.5:1.
10. A curable silicone resin composition consisting essentially of chemically combined siloxy units of the formula R3SiO0.5, RSiO1.5 and SiO2, where R is a monovalent substituted or unsubstituted organic radical with the proviso that there are present a number of R
radicals having the general formula where R1 is selected, independently, from the group consisting of hydrogen and monovalent substituted and unsubstituted hydrocarbon radicals having from 1 to 12 carbon atoms, R2 is a divalent substituted or unsubstituted hydrocarbon radical having from 1 to 18 carbon atoms or the corresponding oxyalkylene radical containing at least one C - O - C linkage, effective for curing said silicone resin composition upon exposure to ultraviolet radiation in the presence of a photoinitiator or upon heating in the presence of a free radical type catalyst, and wherein the ratio of R3SiO0.5 units to RSiO1.5 units is from about 2:1 to about 0.5:1.
radicals having the general formula where R1 is selected, independently, from the group consisting of hydrogen and monovalent substituted and unsubstituted hydrocarbon radicals having from 1 to 12 carbon atoms, R2 is a divalent substituted or unsubstituted hydrocarbon radical having from 1 to 18 carbon atoms or the corresponding oxyalkylene radical containing at least one C - O - C linkage, effective for curing said silicone resin composition upon exposure to ultraviolet radiation in the presence of a photoinitiator or upon heating in the presence of a free radical type catalyst, and wherein the ratio of R3SiO0.5 units to RSiO1.5 units is from about 2:1 to about 0.5:1.
11. A method for making a curable silicone resin, comprising reacting sufficient silane monomer to provide (a) from 75 to 100 mole percent chemically combined siloxy units selected from the group consisting of R3SiO0.5 units, RSiO1.5 units and SiO2 units, and (b) from 0 to 25 mole percent R2SiO units;
wherein R is a substituted or unsubstituted monovalent organic radical with the proviso that there are present a number of R radicals having the general formula effective for curing said silicone resin composition upon exposure to ultraviolet radiation in the presence of a photoinitiator or upon heating in the presence of a free radical type catalyst, wherein R1 is selected, independently, from the group consisting of hydrogen and monovalent substituted and unsubstituted hydrocarbon radicals having from 1 to 12 carbon atoms, and R2 is a divalent substituted or unsubstituted hydrocarbon radical having from 1 to 18 carbon atoms or the corresponding oxyalkylene radical containing at least one C - O - C linkage, and wherein the total number of siloxy units is four or more, at least one of which has the formula R SiO1.5 or SiO2.
wherein R is a substituted or unsubstituted monovalent organic radical with the proviso that there are present a number of R radicals having the general formula effective for curing said silicone resin composition upon exposure to ultraviolet radiation in the presence of a photoinitiator or upon heating in the presence of a free radical type catalyst, wherein R1 is selected, independently, from the group consisting of hydrogen and monovalent substituted and unsubstituted hydrocarbon radicals having from 1 to 12 carbon atoms, and R2 is a divalent substituted or unsubstituted hydrocarbon radical having from 1 to 18 carbon atoms or the corresponding oxyalkylene radical containing at least one C - O - C linkage, and wherein the total number of siloxy units is four or more, at least one of which has the formula R SiO1.5 or SiO2.
12. The method of claim 11 wherein the silane monomers are alkoxy-functional.
13. The method of claim 11 wherein the silane monomers are halogen functional.
14. A method for making a coated substrate, comprising:
(A) applying to said substrate a curable silicone resin composition comprising:
(a) from 75 to 100 mole percent chemically combined siloxy units selected from the group consisting of R3SiO0.5 units, RSiO1.5 units and SiO2 units; and (b) from 0 to 25 mole percent R2SiO units wherein R is a substituted or unsubstituted monovalent organic radical, with the proviso that there are present a number of R radicals having the general formula effective for curing said silicone resin composition upon exposure to ultraviolet radiation in the presence of a photoinitiator or upon heating in the presence of a free radical type catalyst, wherein R1 is selected, independently, from the group consisting of hydrogen and monovalent substituted and unsubstituted hydrocarbon radicals having from 1 to 12 carbon atoms, and R2 is a divalent substituted or unsubstituted hydrocarbon radical having from 1 to 18 carbon atoms or the corresponding oxyalkylene radical containing at least one C - O - C linkage, and wherein the total number of siloxy units is four or more, at least one of which has the formula RSiO1.5 or SiO2, and (B) curing said silicone resin composition.
(A) applying to said substrate a curable silicone resin composition comprising:
(a) from 75 to 100 mole percent chemically combined siloxy units selected from the group consisting of R3SiO0.5 units, RSiO1.5 units and SiO2 units; and (b) from 0 to 25 mole percent R2SiO units wherein R is a substituted or unsubstituted monovalent organic radical, with the proviso that there are present a number of R radicals having the general formula effective for curing said silicone resin composition upon exposure to ultraviolet radiation in the presence of a photoinitiator or upon heating in the presence of a free radical type catalyst, wherein R1 is selected, independently, from the group consisting of hydrogen and monovalent substituted and unsubstituted hydrocarbon radicals having from 1 to 12 carbon atoms, and R2 is a divalent substituted or unsubstituted hydrocarbon radical having from 1 to 18 carbon atoms or the corresponding oxyalkylene radical containing at least one C - O - C linkage, and wherein the total number of siloxy units is four or more, at least one of which has the formula RSiO1.5 or SiO2, and (B) curing said silicone resin composition.
15. The method of claim 14 wherein curing is effected by exposing the coated substrate to ultraviolet radiation in the presence of an effective amount of photoinitiator.
16. The method of claim 14 wherein curing is effected by heating the coated substrate in the presence of a free radical type catalyst.
17. The cured substrate of claim 15.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/666,394 US4568566A (en) | 1984-10-30 | 1984-10-30 | Acrylic-functional silicone resin compositions |
| US666,394 | 1984-10-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1262989A true CA1262989A (en) | 1989-11-14 |
Family
ID=24673994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000493897A Expired CA1262989A (en) | 1984-10-30 | 1985-10-25 | Acrylic-functional silicone resin compositions |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4568566A (en) |
| JP (1) | JPS61111330A (en) |
| CA (1) | CA1262989A (en) |
Families Citing this family (86)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0610263B2 (en) * | 1986-02-25 | 1994-02-09 | 関西ペイント株式会社 | Polysiloxane macromonomer |
| EP0266895A3 (en) * | 1986-10-03 | 1990-03-07 | Dow Corning Corporation | Dioxolane, diol and diacrylate silicon compounds and method for their preparation and use |
| JPH0647619B2 (en) * | 1986-11-27 | 1994-06-22 | 東レ・ダウコ−ニング・シリコ−ン株式会社 | Acryloxy group-containing organopolysiloxane, production method thereof and use thereof |
| DE3777808D1 (en) * | 1987-02-06 | 1992-04-30 | Goldschmidt Ag Th | POLYSILOXANES WITH METH ACRYLIC ACID ESTER GROUPS AND THEIR USE AS RADIATION-COATING COATING AGENTS FOR FLAT AREAS. |
| JP2545867B2 (en) * | 1987-07-15 | 1996-10-23 | 日本合成ゴム株式会社 | Photocurable resin composition |
| DE3810140C1 (en) * | 1988-03-25 | 1989-10-05 | Th. Goldschmidt Ag, 4300 Essen, De | |
| DE68926925T2 (en) * | 1988-04-04 | 1997-02-06 | Loctite Corp | MTQ polysiloxane resin, manufacturing process and coating or potting composition |
| DE3820294C1 (en) * | 1988-06-15 | 1989-10-05 | Th. Goldschmidt Ag, 4300 Essen, De | |
| GB8906626D0 (en) * | 1989-03-22 | 1989-05-04 | Dow Corning | Method of making organosiloxane resins |
| GB8906627D0 (en) * | 1989-03-22 | 1989-05-04 | Dow Corning | Siloxane resins and method for making them |
| US5008349A (en) * | 1989-10-26 | 1991-04-16 | Dow Corning Corporation | Silicone primer compositions |
| FR2655993B1 (en) * | 1989-12-19 | 1993-09-17 | Rhone Poulenc Chimie | U.V. CURABLE COMPOSITIONS FOR USE IN PARTICULAR IN THE FIELD OF PAPER NON-STICK AND OPTICAL FIBERS. |
| DE69005283D1 (en) * | 1990-01-09 | 1994-01-27 | Dow Corning | Siloxane composition for hair care. |
| US5024507A (en) * | 1990-05-10 | 1991-06-18 | Polaroid Corporation | Photopolymerizable composition for cladding optical fibers |
| ES2137159T3 (en) | 1990-11-19 | 1999-12-16 | Loctite Corp | COMPOSITION OF PHOTOCURABLE SILICONE AND PREPARATION PROCEDURE. |
| JP2669947B2 (en) * | 1991-01-23 | 1997-10-29 | 信越化学工業株式会社 | Radiation curable organopolysiloxane composition |
| US5391405A (en) * | 1991-01-23 | 1995-02-21 | Shin-Etsu Chemical Co., Ltd. | Method for surface-release coating and coating agent therefor |
| US5240746A (en) * | 1991-02-25 | 1993-08-31 | Delco Electronics Corporation | System for performing related operations on workpieces |
| US5264278A (en) * | 1991-03-20 | 1993-11-23 | Minnesota Mining And Manufacturing Company | Radiation-curable acrylate/silicone pressure-sensitive adhesive coated tapes adherable to paint coated substrates |
| JPH06508862A (en) * | 1991-03-20 | 1994-10-06 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Radiation-curable acrylate/silicone pressure-sensitive adhesive formulations |
| CA2106304A1 (en) * | 1991-03-20 | 1992-09-21 | Mieczyslaw H. Mazurek | Radiation curable vinyl/silicone release coating |
| DE4116013A1 (en) * | 1991-05-16 | 1992-11-19 | Wacker Chemie Gmbh | (METH) ACRYLOXY GROUPS, ORGANOSILICIUM COMPOUNDS, THEIR PRODUCTION AND USE |
| US5308887A (en) * | 1991-05-23 | 1994-05-03 | Minnesota Mining & Manufacturing Company | Pressure-sensitive adhesives |
| US5464659A (en) * | 1991-05-23 | 1995-11-07 | Minnesota Mining And Manufacturing Company | Silicone/acrylate vibration dampers |
| US5334737A (en) * | 1991-05-24 | 1994-08-02 | General Electric Company | Liquid silicone esters |
| US5484822A (en) * | 1991-06-24 | 1996-01-16 | Polaroid Corporation | Process and composition for cladding optic fibers |
| JP2626940B2 (en) * | 1992-01-22 | 1997-07-02 | 昭和高分子株式会社 | Aqueous topcoat agent |
| US5302737A (en) * | 1992-12-23 | 1994-04-12 | Trinity University | Silycarbonylation of 1-alkynes |
| DE4309831A1 (en) * | 1993-03-26 | 1994-09-29 | Goldschmidt Ag Th | Abhesive coating composition with an additive which influences the degree of adhesiveness |
| US5356585A (en) * | 1993-07-01 | 1994-10-18 | Dow Corning Corporation | Process of extruding snythetic thermoplastic resins using organosilicon resinous compositions as extrusion lubricants |
| US5340897A (en) * | 1993-08-04 | 1994-08-23 | Dow Corning Corporation | Moisture curable organosiloxane coating compositions |
| JPH07149905A (en) * | 1993-11-26 | 1995-06-13 | Toray Dow Corning Silicone Co Ltd | Organopolysiloxane and its production |
| WO1995023694A1 (en) * | 1994-03-02 | 1995-09-08 | Avery Dennison Corporation | Radiation curable silicone release compositions and coated substrates |
| US5616629A (en) * | 1994-08-24 | 1997-04-01 | Avery Dennison Corporation | Radiation-curable organopolysiloxane release compositions |
| US5824762A (en) * | 1994-11-28 | 1998-10-20 | Dow Corning Toray Silicone Co., Ltd. | Organopolysiloxane and method for the preparation of the same |
| US5510190A (en) * | 1995-02-27 | 1996-04-23 | Avery Dennison Corporation | Radiation-curable release compositions |
| US5674966A (en) * | 1995-06-05 | 1997-10-07 | General Electric Company | Low molecular weight liquid injection molding resins having a high vinyl content |
| US20100273011A1 (en) * | 1996-12-20 | 2010-10-28 | Bianxiao Zhong | Silicone Composition, Silicone Adhesive, Coated and Laminated Substrates |
| US6285513B1 (en) * | 1999-02-10 | 2001-09-04 | Konica Corporation | Optical element |
| US6548568B1 (en) | 2000-04-11 | 2003-04-15 | Rhodia Inc. | Radiation-curable release compositions, use thereof and release coated substrates |
| US6577802B1 (en) | 2000-07-13 | 2003-06-10 | Corning Incorporated | Application of silane-enhanced adhesion promoters for optical fibers and fiber ribbons |
| US7283715B2 (en) * | 2002-02-06 | 2007-10-16 | Shin-Etsu Chemical Co., Ltd. | Optical waveguide forming material and method |
| DE10359764A1 (en) * | 2003-12-19 | 2005-07-14 | Goldschmidt Ag | Polysiloxanes with (meth) acrylic ester groups bonded via SiOC groups, processes for their preparation and their use as radiation-curable, abhesive coatings |
| KR101275635B1 (en) * | 2004-07-16 | 2013-06-14 | 다우 코닝 코포레이션 | Radiation sensitive silicone resin composition |
| US8092910B2 (en) * | 2005-02-16 | 2012-01-10 | Dow Corning Toray Co., Ltd. | Reinforced silicone resin film and method of preparing same |
| WO2006088645A1 (en) * | 2005-02-16 | 2006-08-24 | Dow Corning Corporation | Reinforced silicone resin film and method of preparing same |
| US20090162596A1 (en) * | 2005-08-02 | 2009-06-25 | World Properties, Inc. | Silicone compositions, methods of manufacture, and articles formed therefrom |
| US20100183814A1 (en) * | 2005-08-02 | 2010-07-22 | Victor Rios | Silicone compositions, methods of manufacture, and articles formed therefrom |
| US20090162651A1 (en) * | 2005-08-02 | 2009-06-25 | World Properties, Inc. | Silicone compositions, methods of manufacture, and articles formed therefrom |
| JP5011294B2 (en) * | 2005-08-02 | 2012-08-29 | ワールド・プロパティーズ・インコーポレイテッド | Silicone composition, manufacturing method, and article formed from silicone composition |
| JP2009503230A (en) * | 2005-08-04 | 2009-01-29 | ダウ・コーニング・コーポレイション | Reinforced silicone resin film and method for producing the same |
| EP2154183A1 (en) * | 2005-10-05 | 2010-02-17 | Dow Corning Corporation | Coated substrates and methods for their preparation |
| ATE517947T1 (en) * | 2005-12-21 | 2011-08-15 | Dow Corning | SILICONE RESIN FILM, PRODUCTION METHOD THEREOF AND NANOMATERIAL-FILLED SILICONE COMPOSITION |
| JP5543111B2 (en) * | 2006-01-19 | 2014-07-09 | ダウ・コーニング・コーポレイション | Self-supporting silicone resin film, preparation method thereof, and nanomaterial-filled silicone composition for self-supporting silicone resin film |
| WO2007097835A2 (en) | 2006-02-20 | 2007-08-30 | Dow Corning Corporation | Silicone resin film, method of preparing same, and nanomaterial-filled silicone composition |
| DE102006008387A1 (en) * | 2006-02-21 | 2007-08-30 | Goldschmidt Gmbh | Process for the preparation of siloxane-containing release coatings |
| DE102006027339A1 (en) * | 2006-06-13 | 2007-12-20 | Goldschmidt Gmbh | Cationic Radiation-curing Controlled Release Coating Materials |
| KR20090074758A (en) * | 2006-10-05 | 2009-07-07 | 다우 코닝 코포레이션 | Silicone resin film and method of preparing same |
| WO2008079179A1 (en) * | 2006-12-20 | 2008-07-03 | Dow Corning Corporation | Glass substrates coated or laminated with cured silicone resin compositions |
| WO2008088407A1 (en) * | 2006-12-20 | 2008-07-24 | Dow Corning Corporation | Glass substrates coated or laminated with multiple layers of cured silicone resin compositions |
| DE102007005508A1 (en) | 2007-02-03 | 2008-08-07 | Evonik Goldschmidt Gmbh | Method for reducing the release value increase in the production of no-label-look labels |
| KR20090107529A (en) * | 2007-02-06 | 2009-10-13 | 다우 코닝 코포레이션 | Silicone resin, silicone composition, coated substrate, and reinforced silicone resin film |
| EP2117836B1 (en) * | 2007-02-22 | 2012-11-07 | Dow Corning Corporation | Reinforced silicone resin films |
| JP2010519381A (en) * | 2007-02-22 | 2010-06-03 | ダウ コーニング コーポレーション | Reinforced silicone resin film and method for preparing the same |
| WO2008103229A1 (en) * | 2007-02-22 | 2008-08-28 | Dow Corning Corporation | Reinforced silicone resin film and method of preparing same |
| WO2008103226A1 (en) * | 2007-02-22 | 2008-08-28 | Dow Corning Corporation | Reinforced silicone resin films |
| EP2142589A2 (en) * | 2007-05-01 | 2010-01-13 | Dow Corning Corporation | Reinforced silicone resin film |
| WO2008134241A1 (en) * | 2007-05-01 | 2008-11-06 | Dow Corining Corporation | Nanomaterial-filled silicone composition and reinforced silicone resin film |
| JP5485896B2 (en) * | 2007-10-12 | 2014-05-07 | ダウ コーニング コーポレーション | Aluminum oxide dispersion and method for preparing the same |
| WO2009048694A1 (en) * | 2007-10-12 | 2009-04-16 | Dow Corning Corporation | Reinforced silicone resin film and nanofiber-filled silicone composition |
| US8450442B2 (en) * | 2008-03-04 | 2013-05-28 | Dow Corning Corporation | Borosiloxane composition, borosiloxane adhesive, coated and laminated substrates |
| WO2009111199A1 (en) * | 2008-03-04 | 2009-09-11 | Dow Corning Corporation | Silicone composition, silicone adhesive, coated and laminated substrates |
| JP5542805B2 (en) * | 2008-05-27 | 2014-07-09 | ダウ・コーニング・コーポレイション | Adhesive tape and laminated glass |
| TW201004795A (en) * | 2008-07-31 | 2010-02-01 | Dow Corning | Laminated glass |
| EP2444450A1 (en) | 2010-10-19 | 2012-04-25 | Hinterwaldner Consulting & Partner (Gbr) | Compounds for producing anti-adhesive coatings |
| JP2014500897A (en) | 2010-11-09 | 2014-01-16 | ダウ コーニング コーポレーション | Hydrosilylation-cured silicone resin plasticized with organophosphate compounds |
| TW201245352A (en) | 2011-03-25 | 2012-11-16 | Dow Corning | Fluoro surface segregated monolayer coating |
| JP2015518071A (en) * | 2012-04-12 | 2015-06-25 | ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ | Silicone-polyester composition |
| CN103012690B (en) * | 2012-12-12 | 2015-02-25 | 广州市高士实业有限公司 | Acrylic resin/organosilicon hybrid composite electronic potting adhesive and preparation method thereof |
| WO2016044547A1 (en) | 2014-09-17 | 2016-03-24 | Dow Corning Corporation | 3d printing method utilizing a photocurable silicone composition |
| USD757882S1 (en) | 2014-12-15 | 2016-05-31 | Arachnigrip LLC | Gun slide grip |
| USD757880S1 (en) | 2014-12-15 | 2016-05-31 | Arachnigrip LLC | Gun slide grip |
| USD757881S1 (en) | 2014-12-15 | 2016-05-31 | Arachnigrip LLC | Gun slide grip |
| US9587905B1 (en) | 2015-01-15 | 2017-03-07 | Arachnigrip LLC | Gun slide grip |
| CN110072919A (en) * | 2016-12-13 | 2019-07-30 | 三菱化学株式会社 | Polysiloxane, constituent polyorganosiloxane composition and its solidfied material and the electrolyte for electrolytic capacitor containing polysiloxane and the electrolytic capacitor using it |
| TW202225289A (en) * | 2020-12-17 | 2022-07-01 | 美商陶氏有機矽公司 | Method of preparing film and composition therefor |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2793223A (en) * | 1954-05-20 | 1957-05-21 | Dow Corning | Acryloxy methyl siloxanes |
| US2922806A (en) * | 1957-02-01 | 1960-01-26 | Dow Corning | Preparation of acryloxyalkyl substituted siloxanes |
| DE2207495A1 (en) * | 1971-02-20 | 1972-08-24 | Dainippon Printing Co Ltd | Planographic printing plates and processes for their manufacture |
| JPS5137617B2 (en) * | 1971-09-17 | 1976-10-16 | ||
| JPS5235718B2 (en) * | 1971-10-22 | 1977-09-10 | ||
| US3878263A (en) * | 1972-07-10 | 1975-04-15 | Stauffer Chemical Co | Acrylate-functional polysiloxane polymers |
| US3884950A (en) * | 1973-12-13 | 1975-05-20 | Toray Silicone Co | Organopolysiloxane composition having improved heat stability |
| JPS525884B2 (en) * | 1973-05-09 | 1977-02-17 | ||
| JPS5950697B2 (en) * | 1976-03-22 | 1984-12-10 | 東レ株式会社 | Coating composition |
| JPS53134085A (en) * | 1977-07-18 | 1978-11-22 | Dainippon Printing Co Ltd | Photopolymerizable composition |
| JPS604848B2 (en) * | 1977-09-19 | 1985-02-07 | 住友化学工業株式会社 | Synthetic resin molded product with modified surface and its manufacturing method |
| US4201808A (en) * | 1978-06-12 | 1980-05-06 | Union Carbide Corporation | Radiation curable silicone release compositions |
| US4216303A (en) * | 1979-01-26 | 1980-08-05 | George F. Tsuetaki | Oxygen-permeable contact lens compositions, methods and articles of manufacture |
| JPS5712057A (en) * | 1980-06-26 | 1982-01-21 | Hitachi Chem Co Ltd | Preparation of silicone compound |
| JPS5813102B2 (en) * | 1980-07-24 | 1983-03-11 | 住友化学工業株式会社 | Abrasion-resistant coating formation method |
| GB2089826B (en) * | 1980-12-18 | 1985-01-03 | Gen Electric | Abrasion resistant ultraviolet light curable hard coating compositions |
| US4348454A (en) * | 1981-03-02 | 1982-09-07 | General Electric Company | Ultraviolet light curable acrylic functional silicone compositions |
| JPS5869217A (en) * | 1981-10-22 | 1983-04-25 | Japan Synthetic Rubber Co Ltd | Photosensitive silicone resin composition |
| US4395496A (en) * | 1981-11-16 | 1983-07-26 | Uco Optics, Inc. | Cured cellulose ester, method of curing same, and use thereof |
-
1984
- 1984-10-30 US US06/666,394 patent/US4568566A/en not_active Expired - Lifetime
-
1985
- 1985-10-25 CA CA000493897A patent/CA1262989A/en not_active Expired
- 1985-10-28 JP JP60239660A patent/JPS61111330A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH058946B2 (en) | 1993-02-03 |
| JPS61111330A (en) | 1986-05-29 |
| US4568566A (en) | 1986-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1262989A (en) | Acrylic-functional silicone resin compositions | |
| CA1241785A (en) | Uv curable silicone block colpolymers | |
| US4558082A (en) | Acrylated polymers | |
| CA1326041C (en) | .alpha.,.beta.-unsaturated carbonyl-functional silicone compositions | |
| US4491508A (en) | Method of preparing curable coating composition from alcohol, colloidal silica, silylacrylate and multiacrylate monomer | |
| US4921880A (en) | Adhesion promoter for UV curable siloxane compositions and compositions containing same | |
| US4455205A (en) | UV Curable polysiloxane from colloidal silica, methacryloyl silane, diacrylate, resorcinol monobenzoate and photoinitiator | |
| CA1080881A (en) | Radiation-curable coating compositions comprising mercaptoalkyl silicone and vinyl monomer | |
| US5188864A (en) | Adhesion promoter for UV curable siloxane compositions and compositions containing same | |
| CA1291149C (en) | Acrylatofunctional organopolysiloxanes | |
| JP2933676B2 (en) | Crosslinking of (meth) acryloxyalkenylene functional prepolymer | |
| KR900001759A (en) | Silicone Composition for Desorption Coding | |
| US4507187A (en) | Siloxane photoinitiators with aryoyl formate groups | |
| EP0576247A2 (en) | Radiation curable hardcoat compositions | |
| CA2034358A1 (en) | Uv-curable silphenylene-containing epoxy functional silicones | |
| US5512605A (en) | One-part UV-curable epoxy silicone compositions | |
| US5064876A (en) | Adhesion promoter method | |
| US4359369A (en) | Photocurable organopolysiloxane compositions | |
| CA1262987A (en) | Curable polysilarylene-polysiloxane copolymers | |
| GB1433461A (en) | Release characteristics of substrates | |
| US4663185A (en) | Novel acrylated polymers | |
| US4783490A (en) | Radiation active silicon compounds having amide limited mercaptan functional groups | |
| JPH05156163A (en) | Ultraviolet-curable silicon resin/organic mercaptan composition | |
| JPH05320511A (en) | Silicone organic conformal coating composition cured by addition of thiol to olefin-functional silicone | |
| US4526955A (en) | Radiation polymerizable compositions containing organopolysiloxanes having a --N--Si-- or --N--O--Si-- linkage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |