CA1283421C - Photocurable polymeric compositions containing group via aromatic onium salt - Google Patents
Photocurable polymeric compositions containing group via aromatic onium saltInfo
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- CA1283421C CA1283421C CA000226108A CA226108A CA1283421C CA 1283421 C CA1283421 C CA 1283421C CA 000226108 A CA000226108 A CA 000226108A CA 226108 A CA226108 A CA 226108A CA 1283421 C CA1283421 C CA 1283421C
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Abstract
ABSTRACT OF THE DISCLOSURE
Cationic polymerization of a variety of organic materials such as vinyl monomers, prepolymers, cyclic ethers, cyclic esters, cyclic sulfides and organosilicon cyclics can be achieved by the use of certain radiation sensitive aromatic onium salts of Group VIa elements. In addition, polymerizable compositions are provided which can be used as coating compounds, molding resins, adhesives, etc.
Cationic polymerization of a variety of organic materials such as vinyl monomers, prepolymers, cyclic ethers, cyclic esters, cyclic sulfides and organosilicon cyclics can be achieved by the use of certain radiation sensitive aromatic onium salts of Group VIa elements. In addition, polymerizable compositions are provided which can be used as coating compounds, molding resins, adhesives, etc.
Description
~3~1 RD-71~1 Prio. to the present invention, it was genecally known that a variety of organic materials such as vinyl monomers possessing a high electron density in the double bond, were subject to cationic polymerization~ A small amount of ~ewis Acid c~alyst, such as SnC14, SbF5, AsF5, etc. readily polymerize vinyl monomers such as styrene, butadiene, vinyl alkyl ethers, etc. It is often difficult, however, to generate the Lewis Acid oe~alyst at the appro-priate time for polymerization, or have it properly dispersed throughout the vinyl monomer to achieve uniform results.
; It is also known to cure epoxy resins as "one package"
system, based on the employment of a Lewis Acid cat~yst in the form o~ an amine complex such as boron trifluoride-monoethyl amine. The Lewis Acid is released on heating; cure takes place within 1 to 8 hours and can require a temperature of 160 C and higher. As a result, these one package epoxy compositions cannot be employed to coat heat sensitive devices such as delicate electronic components. ~or can epoxy or other monomers having low boiling points be used due to the resulting losses to evaporation during cure.
As shown by Schlesinger, U S. Patent 3,703,296 issued November 21, 1972 and Watt U.S patent 3,794,576 issued February 26, 1974, certain photosensitiva aromatic diazonium salts can be employed to cure epoxy resins. When photolyzed, these aromatic diazonium salts are capable of releasing, in situ, a Lewis Acid catalyst which can initiate the rapid polymerization of the epoxy resin. However, even though these one package epoxy resin mixtures can provide fast curing compositions, a stabilizer must be used to minîmize cure in the dark during storage of these mixtures. Despite these measures, gellation of the mixture can occur even in the absence of light. In ~834~1 RD-7141 addition, nitrogPn is released during W-cure, which can result in film imperfections. Diazonium salts are generall~
thermally unstable, rendering the use of such materials hazardous because of the possibility of run-away decomposition.
Additional organic materials such as aldehydes, cyclic ethers and cyclic esters also can undergo cationic polymerization from trace amounts of Lewis Acids. Such materials when properly catalyzed can be employed in coatinq applications, as encapsulants, etc. However, optimum results cannot be achieved because it is difficult to achieve dis-persion or generation of the Lewis Acid in a desirable manner. A further description of the principles by which cationic polymerization of the above described organic materials can be achieved with Lewis Acids is described in Principles of Polymer Chemistry, pp 217-222 by P J. Flory, Cornell University Press, Ithica, New York (1953), and Polymer ~eviews by J. Furukawa and T~ Saegusa, Interscience Publishers, New York (1953). Another class of materials which undergoes cationic polymerization in the presence of Lewis Acids is organosilicon cyclics as shown by W. Noll, The ChemistrY and Technoloqy of Silicones, pp 219-226, Academic Press, ~ew York (1968)~
~8~Z'l The present invention is based on the discovery that certain photosensitive aromatic onium salts of Group VIa elements, as illustrated by the formula, ~ ( ~ ) C ~ ~ ~
can be a source of Lewis Acid, such as boron trifluoride, phosphorous pentafluoride, arsenic pentafluoride, etc., when exposed to radiant energy. A variety of radiation polymerizable compositions are provided by incorporating the photosensitive aromatic onium salt into a variety of cationically polymerizable organic materials as defined below. Unlike curable compositions containing the above described diazonium salts, the polymerizable compositions of the present invention, which can be in the form of a solid or liquid, do not require a stabilizer. Even after extended shelf periods under normal ~aylight conditions, the polymerizable compositions of the present invention do not exhibit any significant change in properties. In addition, there is no problem with bubbling as characterized by organic resin compositions containing ~0 diazonium sal~s.
The aromatic onium salts of Group VIa elements utilized in the polymerizable compositions of the present invention can be more particularly defined by the ~ollowing formula, ~ (R~a(R ~b(R ~c X~ ~ Qe ,.~
128~21 where R is a monovalent aromatic organic radical;
Rl is a monovalent organic aliphatic radical select d from alkyl, cycloalkyl and substituted alkyl; R2 is a polyvalent organic radical forming a heterocyclic ring structure or a fused ring structure selected from aliphatic radicals and aromatic radicals; X is a Group VIa element selected from sulfur, selenium and tellurium; M is a metal or a metalloid; Q is a halogen selected from fluorine and chlorine; a is an integer equal to 0 to 3 inclusive, b is an integer equal to 0 to 2 inclusive, c is an integer e~ual to 0 or 1, where the sum of (a + b) + c times the valence of R2 is equal to 3;
f is the valence of M and is an integer equal to 2 to 6 inclusive;
e is greater than f and is an integer having a value up to 7; and d = e - f.
Radicals included by R are, for example, C(6 13~ aromatic hydrocarbon radicals such as phenyl, tolyl, naphthyl, anthryl, and suGh radicals substituted with up to 1 to 4 monovalent radicals such as C(l 8) alkoxy, C(l 8) alkyl, nitro, chloro, hydroxy, etc.;
arylacyl radicals such as benzyl, phenylacyl, etc.;
aromatic heterocyclic radicals such as pyridyl, furfuryl, etc. Rl radicals include C(l 8) alkyl and substituted alkyl such as -C2H4OCH3, -CH2COOC2H5, -CH2COCH3, etc. R2 radicals include such structures as ~2~33~Zl ~' `I ~`J,~ . etc.
Complex anions included by MQe ( )of formula I are, for example, BF4 , PF6 , AsF6 , SbF6 , FeC14 , SnC16 , SbC16 , BiC15 , AlF6 , GaC14 , InF4 , TiF6 ~ ZrF6 , e~c., where M ig a transition metal such as Sb, Fe, Sn, B~, ~1, Ga, In, Tl, - Zr, Sc, V, Cr, Mn, Cs, rare earth elements ~uch as the lanthanides, for example, Ce, Pr, Nd3 etc., actinides, such as Th, Pa, U, Np, etc. and metalloids such as B, P, As, etc.
Group VIa onium salts lncluded by Formula I are, for example, O C~I3 .
~ C CH2 S \ BF4 : C~13 ~C-CH2-5~ Pl/6 02N~C CH2 ~ ~1 AsF6 ~ Sb~6-8 3 4 ~ 1 <~ '' S~ FeC14~
~C -C~ SnC16 ,~
~S Sbc16 '. ~ .
~e+ ~ BiC15 ~ ~ ~ 2 ,5:- ~ BF4 O (~ ' (~C-~C~12S-et~ PF6 3 etc.
There is provided by the present invention, polymeri~ab:le compositions comprising, (A) a monomeric or prepolymeric cationic~lly .
10~ polymerizable organic material selectecl from vinyl organic monomer~, vinyl organic 3LZ ~ ~ 4~L
prepolymers, cyclic organlc ethers, cyclic organic esters, cyclic organic amines, organic silicon cyclics and cyclic organic sulfides, and (B) an effective amount of a radiation sensitive aroma~c onium salt of a Group VIa element capable of e~fec-ting ~he polymeriza~ion of ~A) by release o~ a L~wi~
Acid catalyst when exposed to radiant energy Group VIa onium salts o~ formula I are well ; known and can be made by the procedure shown in J, W, Knapczyk and W E. McEwen, J, Am Chem ~c., 91, 145, (1969); A L Maycock and G. A Berchtold, J, Org, Chem.
35, No. a, 2532 (1970); H, M. Pitt, U. S. Patent 2,807,648, E. Goethals and.P. De Radzetzky, Bul. Soc. Chim Belg , 73, 5~6 (1964); H. M. Leicester and F W Bergstrom, J. Am Chem.
Soc , 51, 3587 (1929), etc Included by the vinyl orgdnic monomers whic.h can be used in the practice of the i.nventi.on to make the , polymerizable-compositions canvertible ~o thermoplastic polymers are, ~or example, styrene, vinyl ace~amide, a-methyl styrene, isobutyl vinylether, n-octyl vinyle~her~ acrolein, l,l-diphenylethylene, ~-pinene; vinyl arenes such as 4-vinyl biphenyl, l-vinyl pyrene, 2-vinyl fluorene, acenaphthyl-ene, 1 and 2-vinyl naphthylene; 9-vinyl carbazole, vinyl pyrrolidone, 3-methyl-1-butene; vinyl cycloalipllatics ~uch as vinylcyc].ohexane, vinylcyclopropane, l-phenylvinylcyclo-lZ834Z1 ~D-71~1 propane; dienes such as isobutylene, isoprene, butadiene, 1,4-pentadiene, etc.
Some of the vinyl organic prepolyme~ which can ~e used to make the polymerizable composition~ o~ the present invention are, or example, CH2=CH-0-(CH2-CH2O)n-CH=CH2, where n i~ a positive integer having a value up to about 1000 or higher: multi-functional vinylethecs, such as 1,2,3-propane trivinyl ether, trimethylolpropane trivinyl ether, prepolymers having the formula, ~C~2~
CH=C~I2 low mole~ular weight polybutadiene having a viscosity of ~rom 200 to 10,000 centipoises at 25 C., etc. Products resulting from the cure of such compositions can be used as potting resins, crosslinked coatings, printing inks, etc.
A further category of the organic materials which can be used to make polymerizable compositions are cyclic ethers which are convertible to thermoplastics. Included by such cyclic ethers are, for example, any monomeric, dLmeric or oligomeric or polymeric epoxy material containing one or aa~plurality of epoxy functional groups. For example, those resins ~hich result from the reaction of bisph2nol-A (4,4'- -isopropylidenediphenol) and epichlorohydrin, or by the reaction of low molecular weight phenol-formaldehyde resins (Novolak resins1 with epichlorohydrin, can be used alone or in combination with an epoxy containing compound as a reactive diluent. Such diluents as phenyl glycidyl ether, 4-vinylcyclo-hexane dioxide, limonene dioxide, 1,2-cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, allyl glycidyl ether, etc., may be added as viRcosity modifying _ ~ _ ~834Z~ RD-7141 agents. In addition, the range of these compounds can be extended to include polymeric materials containing terminal or pendant epoxy groups. Examples o~ these compounds are vinyl copolymers containing glycidyl acrylate or methacrylate as one of the comonomers. Other classes of epoxy containing polymers amenable to cure using the above catalysts are epoxy-siloxane resins, epoxy-polyurethanes and epoxy-polyesters. Such polymers usually have epoxy functional groups at the ends of their chains. Epoxy-siloxane resins and method for making are more particularly shown by E.P.
Plueddemann and G. Fanger, J~ Am. Chem~ Soc. 81 632-5 (1959~.
As described in the literature, epoxy resins can also be modified in a number of standard ways such as reactions with amines, carboxylic acids, thiols, phenols, alcohols, etc. as shown in U.S. patents 2,935,488 issued May 3, 1960;
3,235,620 issued February 15, 1966; 3,369,055 issued February 13, 1968; 3,379,653 issued April 23, 1968; 3,398,211 issued August 20, 1968; 3,403,199 issued September 24, 1968; 3,563,850 issued February 16, 1971; 3,567,797 issued March 2, 1971; 3,677,995 issued July 18, 1972; etc. Further examples of epoxy resins which ~n be used are shown in the Encyclopedia of Polymer Science and Technology, Vol~ 6, 1967, Interscience Publishers, New York, pp 209-271~ me term epoxy resin as hereinafter employed, may signify both curable epoxy polymers, prepolymers and ~onomers or mixtures thereof. Further included by the term cyclic ethers are oxetanes such as 3,3-bischloromethyl-oxetane, alkoxyoxetanes a~ shown by Schroeter U.S. Patent 3,673,216 issued June 27~ 1972, assigned to the same assignee as the present invention; oxolanes such as tetrahydrofuran, oxepanes, oxygen containing spiro compounds, trioxane, dioxolane, etc.
_ g _ ~3 ~D~7141 In addition to cyclic ethers tnere are also included cyclic esters such as ~-lactones, for example, propiolactone, cyclic amines, such as 1,3,3-trimethyl-azetidine and organosilicon cyclics, for example, materials included by the formula, L+ R " 2S iO ~I
where R" can be the same or different monovalent organic radicals such as methyl or ph~'and m is an integer equal to 3 to 8 inclusive. An example of an organosilicon cyclic 0 i9 hexamethyl trisiloxane, octamethyl tetrasiloxane, etc.
The products made in accordance with the present invention are high molecular weight oils and gums.
m e curable compositions of the present invention can be made by blending the polymerizable organic material with an effective amount of the Group VIa onium salt or "onium salt"~ The resulting curable composition which can be in the form of a varnish having a viscosity of from 1 centipoise to 100,000 centipoises at 25 C or a free flowing powder, can be applied to a variety of substrates by conventional means and cured to the tack-free state within 1 second or less to 10 minutes or more~
In particular instances, depending upon the compat-ability of the onium salt with the polymerizable organic material, the onium salt can be dissolved or dispersed in an organic solvent such as nitromethane, methylene chloride, acetonitrile, etc., prior to its incorporation into the organic material. In instances where the polymerizable organic material is a solid e.g. certain of the higher molecular weight bisphenol or novolak based epoxy resin~, incorporation of the onium sal~
~Z3~33~Z~
P.D-7141 may be achieved by dry milling or by melt mixing where the melting point of the resin is suitably low. Experience has shown that the proportion of onium salt to organi~ material can vary widely inasmuch as the salt is substantially inert, unle33 activated. ~ffective results can be achieved for example, if a proportion of rom 0.1% to 15% by weight of onium salt i5 employed, based on the weight of polymerizable compo3ition.
Higher or lower amounts can be used, however, depending upon factors such as the nature of organic material intensity of radiation, polymerization time desired, etc.
It has been found that the onium salts of formula I also can be generated in situ in the presence of the organic material if desired. For example, an onium salt of the formula, 1 2 + -(R )b(R )c X Q~ , where R, Rl, R~, X, a, b and c are as previously defined, and Q a is an anion such as Cl , Br , I , F , HSO4 , and NO3 , etc, can be separately or simultaneously introduced into the organic material with a Lewis Acid of the formula, M'(MQ) where M and Q are as praviously defined and M' is a metal cation such as an alkali metal, for example, ~a, K, etc., alkaline earth, such as Ca, Mg or an organic cationic base such as quaternary ammonium, pyridinium, etc.
m e curable compositions may contain inactive ingre-dients such as inorganic fillers, dyes, pigments, extenders, viscosity control agents, process aids, W-screens, etc. in amounts of up to 100 parts of filler per lO0 parts of epoxy resin. The curable compositions can be applied to such sub-s~rates as metal, rubber, plastic, mol~ed parts or fi~s, paper, wood, glass cloth, concrete, ceramic, etc, ~834Z~ R~7141 Some of the applications in which the curable compositions of the present invention can be used are, for example, protective, decorative and insulating coatings, potting compounds, printing inks, sealants, adhesives, p~oto-resists, wire insulation, textile coatings, laminates, impregnated tapes, printing plates, etc.
Polymerization can be achieved by activating the onium salt to provide the release of the Lewis Acid catalyst.
Activation of the onium salt can be achieved by heating the composition at a temperature in the range of from 150 to 250C. Preferably cure can be achieved by exposi~g the curable composition to radiant energy such as electron beam or ultraviolet light. Electron beam cure can be effected at an accelerator voltage of from about 100 to 1000 KV.
Polymerization composition is preferably achieved by the use of W irradiation having a wavelength of from 1849 R to 4000 A. The lamp systems used to generate such radiation can consist of ultraviolet lamps such as from 1 to 50 dis-charge lamps, for example, xenon, metallic halide, m tallic arc, such as a low, medium or high pressure mercury vapor discharge lamp, etc. having an operating pressure of from a few millimeters to about 10 atmospheres, etc., can be employed. The lamps can include envelopes capable of trans-; mitting light of a wavelength preferably of 2400 A to 4000 A.
me lamp e~velope can consist of quartz, such as Spectrocil or Pyrex, etc. Typical lamps which can be employed for providing ultraviolet radiation are, for example, medium pressure mercury arcs, such as the GE H3T7 arc and the Hanovia 450 W arc lamp~ The cures may be carried out with a combination of various lamps, some or all of which canoperate in an ine~t atmosphere. When using W lamps, the - 1~2 -~3~Z~ R~-7141 irradiation flux in the substrate can be at least 0.01 watts per square inch to effect polymerization of the organic material within 1 to 20 seconds and permit the cure to be carried on continuously as, ~or example, in the curing of a multi~unctional vinyl ether or epoxy resin coated steel strip or paper web to be taken up at a rate of from 100 to 600 feet per minute. m e strip can be cut to a predetermined width for use as printed materiala A combination of heat and light may be used to cure reactive compositions. Such a combination of heat and light may serve to reduce the overall cure time~
In order that those skilled in the art will be better able to practice the invention, the following examples are given by way of illustration and not by way of limita-tion. All parts are by weight.
m~re was added under a nitrogen atmosphere, 0.2 part of triphenyl sulfonium hexafluorophosphate to 39 parts of tetrahydrofuran. The mixture was then exposed to ultra-violet irradiation from a Hanovia lamp. The mixture wasirradiated for lO minutes and the polymerization mixture was allowed to stand for four hoursO There was ob~ained a tough polymer having an intrinsic viscosity of 3.7 dl/g in benzene at 25 C~ The polymer was fabricated into an exceed-ingly tough elastic ~ilm with the use of heat and pressure, ~z ~ RD-7141 Triphenylselenonium chloride was prepared accord-ing to the procedure of H.M. Leicester and F.W. Bergstrom, J. Am. ~hem. Soc~, 51, 3587 (1929) starting with diphenyl selenide. The corresponding fluoroborate, hexafluoro-arsenate and hexafluoroantimonate salts were prepared by adding sodium hexafluoroarsenate, sodium tetrafluoroborate and potassium hexafluoroantimonate, respectively, to an aqueous solution of triphenyl selenonium chloride~ ~he products were white crystalline solids which were dried in vacuoO
Three percent solutions of the above salts in ethylene ~lycol divnyl ether (E) and also in vinylcyclohexene dioxide (V), were respectively cured as 2 mil films on steel panels at a distance of six inches from a GE H3T7 lamp. The following cure times were observed:
Salt Cure Times (~) V
(C6Hs)3Se BF45 sec. 10 sec.
(C6~s)3Se ~SF63 sec. 5 sec.
(C6~s)3Se SbF62 sec. 3 sec.
~Z~33~2~
Rl)-7141 E~AMPLE 3 ~ . , There were added 3 parts o ~odium he~afluoro-- arsenate and 6 parts of a 50% solution of triphenylsulonium chloride to 97 parts diethylene glycol divinyl ether The mixture was stirred for several hours at room ~emperature, allowed to settle and an aliquot of the solution was removed by means of a pipet. The sensitized solution was knife coated onto a 3 in x 6 in steel panel to give a 0 2 mil film and then cured as in Example 2 A hard clear coating was obtained in 3 seconds which could not be remc;ed when rubbed with acetone. The coated steel could be used as a laminate for making transformers.
.
~ - EXAMPLE 4 . .
An aliquot of the solution prepared in Example 3 was~coated onto glass to give a 1 mil fi.lm. A perforated mask was placed over the film and the assembly was irradiated for 5 seconds. After it was washed, the coated substra~e was washed with isopropanol A clear negative image of the mask remained as polymerized film, - 20 Based on the above procedure, the curable compo-sition can be employed as a negative photoresi.st ln partlc-ular applications and for the fabrication of printing plates.
~2~334~
~ . _ Glass cloth was impregnated with a mixture of 97 parts of diethylene glycol divinyl ether and 3 parts of tri-phenylsul~onium hexafluoroantimonate, Two 6 in x 6 in S squares of the impregnated glass cloth were stacked together and irradiated for 30 seconds on each side using the appara~us described in Example 2, The resulting hard and stiff laminate was found to be integrally bonded togethèr, An additional 6 in x 6 in square of impregnated cloth was added to the laminate, It also was curc--l after a 30 second exposure to ultraviolet light, The resulting - laminate composed of three layers of glass cloth could be used for circuit board applications~
. .
There was added 0,2 part o~ triphenylsulfonium hexafluorophosphate to a mlxture composed of 8 parts dimethyl-cyclotrisiloxane and 2 parts of dime~hylcyclotetrasiloxane.
This mixture was then flushed with nitrogen. Polymerization was initiated by exposing the sensitized solution to ultra-violet irradia~ion from a Hanovia 450 wa~t lamp at a distance o~ 3 inches for 10 minutes. The mixture was removed from the irradiation and allowed to stand for one day, A
highly viscous polymer mixture was obtained which was iso-lated by pouring the solution into methanol. There ~as obtained a viscous si]icone oil use~ul for lmparting ~28;~42~
improve(l surf.~ce characteriseics to a variety of substrates, EX~MPLE 7 There was added 0.3 part of triphenylsulonium ~etrafluoroborate to a mixture of 15 parts of trimethylol-propane trivinyl ether and 0,4 part of carbon black, The mixture was agitated for 3 hours on a ball mill and thén used to print onto white paper, Exposure of the printed paper to ultraviolet light at a distance of 3 inches ~rom a GE H3T7 lamp caused the printing to become dry within 1-2 seconds, _ . :
A mixture was prepared composed of 2~/o phenacyltetra-methyl sulfonium fluoroborate, 97.5% ethylene glycol divinyl ether and 0,5% of a surface active agent. This mixture 1,5 was stirred until homogeneous. It was then applied onto ~
3 in x 6 in steel panel using a drawblade having a 0.2 mil - aperture. ~fter exposing the applied mixture to ultra-violet radlation having an intenslty of 200 watts/sq, in.
for a period of l second, a hard film was obtained on the surace of the steel panel. The fllm could not be removed even though the panel was repeatedly dipped into acetone and rubbed with a cloth.
~33~
EXA~IPI.E 9 A (30:70) mixture of 1,2,3-propane ~rivinyl ether and diethylene glycol divinyl ether was sensitlzed with 3 parts of phenacyltetramethylene sulfonium fluoroborate This mixture was coated onto a sheet of Lexan~ pol~carbonate using a draw knife with a 0 2 mil aper ure. The coating was cured for 5 seconds as described in Example 2 There was obtained a polyearbonate sheet having a transparent, scratch-resistant coating which could not be removed by rubbing with I0 acetone.
_XAMPLE 10 A mixture of 0.1 part of triphenylsulfonium fluoroborate and a solution of 13.3 parts of recrystallized N-vinylcarbazole in 39 parts of methylene chloride was lS sealed under a nitrogen atmosphere The mixture was irradiated for 10 minutes at a distance of 3 inches from a 450 watt Hanovia lamp while immersed in an iee bath. The mixture was then allowed to stand. Exothermic poiymerizatio~
took place glving a highly vlscous solution. After 3 hour~, the polymer solution was poured into methanol. Thexe wa8 isolated after filtering, washing and drying, 13 0 parts of polyvinylcarbazole.
. _ A polymerization mixture of 26.6 parts of freshly d~Lstilled styrene, 0 20 part of triphenylsulfonium hexa-~7~834~
fluoroarsenate and 6.5 parts of distilled methylene chloride, sealed under nitrogen, was irradiated for 10-15 minutes under a 450 watt Hanovia medium vapor pressure mercury lamp. Rapid exothermic polymerization took place and the polymerization was allowed to stand in the dark for 5 hours. The viscous reaction mixture was poured into methanol and the solid polymer was filtered and washed. A
white polystyrene having an intrinsic viscosity of 0.16 dl/g in benzene was produced.
A mixture of 11.4 parts of ~-methylstyrene, 0.11 parts of triphenylsulfonium hexafluoroantimonate and 26 parts of methylene chloride was irradiated for 2.5 hours in accordance with the procedure of Example 11.
The resulting highly viscous polymer solution was quenched by adding a small amount of methanol. A product isolated by pouring the solution into a large amount of methanol. After drying, there was obtained, 11.4 parts of polymerized ~-methylstyrene which was useful as a molding resin.
A printing ink was prepared by mixing together 2.5 parts of glycerol trivinyl ether, 3 parts of 3,5-dimethyl-4-hydroxyphenyl dimethylsulfonium fluoroborate and 5 parts of a red fluorescent pigment. These components ~, ~Z~3~1 were used as an ink to print on white paper, The printed paper was exposed for 3 seconds to UV ]ight resulting in a clear, dry, non-smearable printed image, , S A mix~ure of 21,0 parts of N-vinylpyrrolidone and 0.63 part of triphenylsulfonium fluoroborate was irradiated with a Hanovia lamp for 13 minutes, The solution became quite viscous and was allowed to stand in the dark for two days at room temperature, A polymer formed having an in-trinsic viscosity of 0,2~ in water, A mixture of 9.2 parts of recrystallized trioxane~
26 parts of methylene chloride, and 0,06 part of trlphenyl-sulfoniurn fluoroborate was irradiated or 1 hour in the 15-- presence of pyrex filtered W light from a Hanovia lamp, A
white powdery precipitate formed, The solution was then allowed to stand for 8 hours in the dark. The preeipitated polymer was filtered and Iried, There was obtained 7 parts of polyoxymethylene, A solution of diethylene glycol dlvinyl ether containing 2% by weight triphenylsulfonium hexfluoroarsenate was coated onto a 3 in x 6 in steel plate, A perforated mask was placed over the coating and thi~ assembly was -2~
~Z834Z~ R~714i exposed to ultraviolet light using a GE H3T7 medium pres3ure mercury arc lamp at a distance of four inches. After a 5 second exposure, the mask was removed and the plate was washed with i-propanol. A clear, raised negative image of the mask was formed.
EX~MPLE 17 . .
A curable composition was prepared by forming a mixture of 0.2 part of triphenylsulfonium tetra~luoro-horate dissolved in acetonitrile and 5 parts of 4-vinyl--cyclohexene dioxide. A 2 mil film was drawn on a glassplate and exposed to ultraviolet irradiation from a GE
H3T7 lamp at a distance of from 6 inches. The resin had cured to a hard film within 30 seconds. The film was found to be insoluble in dipolar aprotic solvents and it could not be scratched with a fingernail.
A portion of the above curable composition having a viscosity at 25 C of about 6 centipoises was allowed to stand under average daylight conditions for four months in a transparent container. It was found that the viscosity remained substantially the same.
A portion of the curable composition was applied onto a steel strip. T~e treated steel surface was exposed 15 seconds to the ultraviolet radiation of an H3T7 lamp at a distance of 2 inches. A clear, tack-free film was formed which showed no signs of bubble~ or other imperfections.
m e above treated strip was then immersed in lOC
hydroca~bon oil for 48 hours at 120 C to determine its hydrolytic stability in accordance with IFT test ASTM D971-50 Interfacial Tension of Oil Against Water shown on page 322 of the 1970 Annual Book of ASTM Standards, part 17 (November).
The initial reading of the oil was about 39~0 dynes/cm.
~2~3342~
Af-ter the test the oil sh~wed an interfacial tension reading of 38. In order to pass, a reading of at least 30 is required.
ExAMæLE 18 An 80:20 mixture of an epoxy novolaX resin, an epoxy equivalent weight of 173 and 4-vinylcyclohexene dioxide wa~ sensitized with 3% by weight of triphenyl-sulfonium hexafluoroantimonate. ~his solution was used to impregnate glass cloth. Two 6 in x 6 in squares of the clock were then stacked together and cured to form a laminate by irradiating the cloth for l minute on each side using a GE
H3T7 lamp at a distance of six inches. The stiff laminate was integrally bonded and could be used for circuit boards.
There were added three parts phenacyl *etramethylene sulfonium hexafluoroarsenate to a 70:30 mixture of bisphenol-A-diglycidyl ether and 4-vinylcyclohexene dioxide~ The catalyzed mixture of epoxides was then used to impregnate a l inch wide glass fabric tapeO After winding one layer onto a 5" x 2" diameter cylinder, the impregnated tape was cured while rotating the wound cylinder under a GE H3T7 lamp. The total exposure time to W light was 5 minutes. At the end of this time the tape was fully cur~d into the shape of a rigid cylinder. The wound cylinder could then be used as a spool for winding wire to make transformer coil~.
A mixture was prepared consisting of 14.5 g ~0.~5 mole) glycidyl allyl ether, lO mg t-butylcatechol, and three drops of chloroplatinic acid in octyl alcohol~ The reaction mixture was heated to 50 C in a water bath and then 13.0 g of a polydimethyl siloxane resin containing 0.89% by weight Si-H groups was added dropwise by means of a dropping funnel.
Immediate exothermic reaction took place with the tempera-~L283~2~
ture rising to 65C. Reaction proceeded smoothly at this temperature giving a clear fluid resin.
Three parts by weight of triphenylsulfonium fluoroborate dissolved in a small amount of acetonitrile was added to 97 parts of the above silicone epoxy resin. A
2 mil film of the sensitized resin was drawn on a glass plate and then exposed to W light from a ~E H3T7 lamp a~ a distance of six inches. The film was tack-free within 15 to 20 seconds. A small amount of silica was added to the sensitized resin to produce a thixotropic mixture and the resin cured as described previously. A tough, rubbery coating resulted. These UV cured epoxy-siloxanes are useful as sealants and caulks.
There were added 3 parts S-phenyldibenzothio-phenium fluoroborate to 97 parts 4-vinylcyclohexene dioxide. This mixture was spread on a glass plate as a 2 mil film and exposed to irradiation from a GE H3T7 lamp at a distance of six inches. one minuta exposure was required to fully cure the film to a hard, scratch resistant state.
_XAMP~E 2Z
A 3% solution of phenacyl tetramethylene sulfonium hexafluoroarsenate in 40:60 mixture of 4-vinylcyclohexene dioxide and an epoxy novolak having an epoxy equivalent weight of 206 were knife coated onto a steel plate to a Af~
~Z~
P~D--7141 thickness of 3 mil, A mask was placed over the film and the entire assembly irradiated for 1 minute. The mask was removed and the film was washed with i-propanol. The unexposed portions of the film were washed away having a clear sharp negative image of the mask.
___ _ There were added 6 parts of a 50% aqueous solution of triphenylsulfonium chloride and 2.1 parts of NaAsF6 to 97 parts of an 80:20 mixture of blsphenol-A-diglycidyl e~her and 4-vinylcyclohexene dioxide. The reac~ion mixture was agl~a~ed by stlrring for one-half hour and ~hen allowed to settle, An aliquot of the resin was taken and spread onto a glass plate u~ing a draw knife with a 3 ml aperture. A
taclc-free film formed within lS seconds after exposure to an H3T7 lamp at a distance of six inches. The film was hard and clear.
Resistors were potted in ~he above resin by dipping the re~istor into the ~en~itized reYin and then curing it by ro~ating the re~i~tor for 30 second~ beneath the ultraviolet lamp.
An equimolar mixture of diphenyliodonium fluoro-borate and thioxanthene was heated at 200C for 3 hours.
After recrystallization from methylene chlcride-diethyl _ 2*.
~Z~334~
RD--71~1 ether, there was ohtained an 80% yield of produc~ having a m,p, of 168-169~. Based on method o preparation the product was S-pllenylthioxanthene fluoroborate, A hard clear scratch resistant 1 mil coating was obtained, when a 3% solution of the above onium compound in limonene dioxide was kllife coated onto a po`lystyrene sheet and ex-posed to lJV irradiation from a 450 W Hanovia medium pressure mercury arc at a distance of 3 inches.
There were added 2.6 parts phenacyltetramethylene sulfonium bromide to a mixture of 95 parts of 4-vinyLcyclo-hexene dioxide containing 2,2 parts of NaAsF6. The solution was placed in a dark bottle and rolled on a ball mill for 8 hours. After the salts were removed by filtration, the solution was coated onto a 3 in x 6 in steel panel and cured as in Exc~mple 1. A hard coating wa~ ohtained after 15 - seconds expns-lre which coukl not be remo~/ed by rubbing the coating Wit~l acetone.
.
There were dissolved two par~s of ~riphenylsulfon-ium hexafluoroantimonate into a 40:60 mixture of dicyclo-pentadiene dioxide and glycidyl acry]ate ~nl!owillg ~he procedure o example 1, a hard crosslinked 1 r.lil coating wa~
obtained after a 15 second exposure to ultravlolet light.
~834~
There were added four parts of triphenylsulfonium hexafluoroarsenate to 100 parts of a blend of equal parts of 4-vinylcyclohexene dioxide and (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexanecarboxylate. An aliquot of the resulting sensitized resin was spread onto a polycarbonate sheet using a draw-clo1~l blade to give a 0.5 mil ~ilm. The ilm was cured as described in Example 1 for 10 seconds resulting in a clear hard mar reslstant and solvent resistant coating.
- A mixture of 50 parts bisphenol-A-diglycidyl ether and 50 parts (3,4-epoxycyclohexyl)methyl-3,4-epoxycycloh~xane-carboxylate was stirred until homogeneous There was then added 3 parts of triphenylsulfonium hexafluoroantimonate to the solution. It was mixed until the sensitizer had dis-solved. A portion of the above solution ~as coated onto a stecl plate llsing a 0.2 mll drawbar l~he plate was then expo.sed to a GE H3T7 lamp at a distance oE six inches for 5 seconds. A hard cured adherent film ~ormed on the steel.
~20 EXAMPLE 29 A blend of epoxy resins consisting of 50 parts 4-vinylcyclohexene dioxidej 40-parts of a novolak-epoxy resin having an epoxy equivalent weight of 172-178 ~d 10 pclrts r .
~33~
P~D--7141 n-oc~ylglyci-lyl ether were thorough]y mixed tog(-~he-c. A
100 part aliquot was removed to which was added 1 part o triphenylsulfonium hexafluoroarsenate. The resulting mixture was stirred until the onium salt had dissolved T~hen the above mixture was coated onto a 3 in x 6 in steel panel and exposed to a 450 watt medium pressure mercury arc Lamp at a distan.e o 3 inches, a glossy, dry coatLng was obtained in 2 seconds. The coating withstood attack by hot boiling water for four hours, It could not be removed by rubbing with acetone.
, EXI~MPLE 3 0 There was added 10 parts of a solid multifunctional aromatic glycidyl ether having an epoxy equivalent weight of - 210~240 to 40 parts of limonene dioxide. The mixture was combined with 1 part of phenacyltetramct~lene sulfonium hexafluoro~rsenate and stirred at 50C for 0.5 hour to produce a homo~eneous solution. When the mixture was coated onto glass usin~ a 0.5 mil drawbar, and lrradiated for 5 seconds at a dis~ance of 3 inches fro~l a C,E H3T7 mercury arc lamp having an intensity of 200 watts/sq. inch., a hard cured film was produced.
., , .. __ .
There was added 0.2 part of triphenylsulfonium hexafluoroantimonate in 2 parts of 4-vinylcyclohexene dioxide _27-~33,~L'Z RD--7141 to 10 parts of an epoxidized butadiene resin, After rnixing the components thoroughly, the mixture was appLied to a 1/16 inch thick glass plate to a 1 mil thickness, Another plate of glass was placed on top o the first and the assembly was exposed to a GE H3T7 medium pressure mercury arc lamp having an intensity of 200 watts/sq, inch at a distance of three inches, The total exposure time was 30 seconds, ~he glass plates were permanently bonded together, Based on characteristics of the glass laminate, a similar procedure can be used to make a shatterproof windshield for auto-mobiles, .
There were added with stirring 89 parts of alum-inum chloride in small portions to a solution of 122 parts of 2,6-xylenol in 505,12 parts of carbon disulfide main-tained at 10C, To the resulting greenish solution were added 79,5 parts o~ thionyl chloride in a dropwise fashion maintaining the temperature between 10 and 15C. A black precipita~e and solution was obtained which was stirred for an additional 2 hours and then poured-onto 1000 parts of ice containing about 50 parts of concentrated HCl, This mixture was placed on a steam bath to remove CS2 and to decompose the complex, A tan solid was obtained which was iltered, washed with water and dried, .. .. ......... . . _ _ ~z~3342~L
To a solution of 21,5 parts of the above crude product in about 117 parts of hot absolute ethanol were added 11,,4 parts of K~sF6 and 10 parts of water, The reaction mixture was stirred and more water was added to e~ect the precipitation of product. The product was filtered, wa~hed with water and dried, A material was obtained having a m.p. of 245-251C, Based on method of preparation and elemental analysis ~or C24H2703SAsF6, Calc:
% C, 49,3; % H, 4,62; % S, 5,48, Found: % C, 49.4; ~/0 H, 4,59; % S, 5.55, the product was tris-3,r~-(limethyl-4-hydroxy-phenyl sulfonium hexafluoroarsenate, , A three percent 's,olution of the above onium salt was made with'4-~inylcyclohexene dioxide. Cure of the solution was effected by ir,radiating a 2 mil film on glass according to the procedure described in Example 3, A hard mar-resistant co~ting las obtained after 5 seconds of i.rradiation, E~AMPLE -33 'l;hree parts of triphenylsulfonl~ hexafluoro-antimonate were ground to a fine powder, The powder was intimately rnixed with 97 parts Reichhold Epotu~R' 37-834 powder coating resln by tumbling these together for 30 minutes, Tbe powder was then electrostaticall~ sprayed onto 3 ln x 6 in steel panels to form approximately a 2 mil coatlng,usin~ a GE~ model 171 spray gun. Subsequently, the 33~Z~
samples were heated brleEly to 150C to use the powder and then exposed while hot to a GE H3T7 medium pressure mercury arc lamp at a distance of 3 inches. Cured samples r,Jere obtained aEter a lS second irradiation. The cured ilms were adherent and mar resistant, ~,.
Trlphenacyl hexafluoroarsenate was added to a mixture of 67% by weight of a novolak-epoxy resin having an epoxy equivalent weight of 172-178, 33% 4-vinyl,cyclohexene 10 ' dioxidc anc~ 0,5% of ~ sur~ace actlve agenL:. Th~ result-ing mixture contain~d about 1% by weight of the onlum salt.
A coating was applled as a 0.1 mil ~ilm to 3 in x-6 in steel plates and cured or 20 seconds a~ a distance of 4 inches rom a GE H3T7 medlum pressure mercury arc lamp. Some panels were subsequently in~lerse-l for 5 ~ours at room temperature in methylene chlorideA ()t~er panels were immerse~l for 4 h,our~ in acetone. Irl a]l cases, no visible sl~ns of solv(~nt attack of the coatings were obselved. The same were then baked for 1- ho~r at l60C. rests were run separately in boiling 50% KOH solution ~or 30 minutes and in boiling distilLed water for 4 hours. Again, no visible degradation of the coatings was obser~ed, - 30~
~334Z~
Mixtures of triphenylsulfonium hexafluoroarsenate in 4-vinylcyclohexene dioxide having a concentration of 0 to 10% onium salt, were thermally aged at 25gC and 55gC. The viscosities of the mixtures were measured over a two-week period (336 hrs.). The following results were recorded at 25gC:
Viscosity Viscosity at Concentration (%3 Start ~cps) 336 hr (cps) 0 6.0~ 6.06 1 6.26 6.34 3 6.90 6.90 7.65 7.59 9.80 9.71 at 55C:
Viscosity Viscosity at Concentration f~) Start (cps) 336 hr (cps~
0 S.06 6.06 1 Ç.42 6.37 3 6.91 6.93 7.65 7.67 9.75 9.71 Within experimental error, the above results show that there is essentially no viscosity change over the period the sensitizer was tested at a temperature range of 25C to 55C.
~z~33~ R~--7l~l Although the above examples are limited to only a few of the very many polymerizable composition~ and use3 thereof which are included within the scope of the present invention, it should be understood that the present in~ention is intended to cover a much broader cla~s of such composi-tions and uses thereof~ Those sXilled in the art would also know that the polymerizable compositions also cover the use of onium polymers containing Group VIa onium functionality as part of the polymer backbone or in the pendant position.
; It is also known to cure epoxy resins as "one package"
system, based on the employment of a Lewis Acid cat~yst in the form o~ an amine complex such as boron trifluoride-monoethyl amine. The Lewis Acid is released on heating; cure takes place within 1 to 8 hours and can require a temperature of 160 C and higher. As a result, these one package epoxy compositions cannot be employed to coat heat sensitive devices such as delicate electronic components. ~or can epoxy or other monomers having low boiling points be used due to the resulting losses to evaporation during cure.
As shown by Schlesinger, U S. Patent 3,703,296 issued November 21, 1972 and Watt U.S patent 3,794,576 issued February 26, 1974, certain photosensitiva aromatic diazonium salts can be employed to cure epoxy resins. When photolyzed, these aromatic diazonium salts are capable of releasing, in situ, a Lewis Acid catalyst which can initiate the rapid polymerization of the epoxy resin. However, even though these one package epoxy resin mixtures can provide fast curing compositions, a stabilizer must be used to minîmize cure in the dark during storage of these mixtures. Despite these measures, gellation of the mixture can occur even in the absence of light. In ~834~1 RD-7141 addition, nitrogPn is released during W-cure, which can result in film imperfections. Diazonium salts are generall~
thermally unstable, rendering the use of such materials hazardous because of the possibility of run-away decomposition.
Additional organic materials such as aldehydes, cyclic ethers and cyclic esters also can undergo cationic polymerization from trace amounts of Lewis Acids. Such materials when properly catalyzed can be employed in coatinq applications, as encapsulants, etc. However, optimum results cannot be achieved because it is difficult to achieve dis-persion or generation of the Lewis Acid in a desirable manner. A further description of the principles by which cationic polymerization of the above described organic materials can be achieved with Lewis Acids is described in Principles of Polymer Chemistry, pp 217-222 by P J. Flory, Cornell University Press, Ithica, New York (1953), and Polymer ~eviews by J. Furukawa and T~ Saegusa, Interscience Publishers, New York (1953). Another class of materials which undergoes cationic polymerization in the presence of Lewis Acids is organosilicon cyclics as shown by W. Noll, The ChemistrY and Technoloqy of Silicones, pp 219-226, Academic Press, ~ew York (1968)~
~8~Z'l The present invention is based on the discovery that certain photosensitive aromatic onium salts of Group VIa elements, as illustrated by the formula, ~ ( ~ ) C ~ ~ ~
can be a source of Lewis Acid, such as boron trifluoride, phosphorous pentafluoride, arsenic pentafluoride, etc., when exposed to radiant energy. A variety of radiation polymerizable compositions are provided by incorporating the photosensitive aromatic onium salt into a variety of cationically polymerizable organic materials as defined below. Unlike curable compositions containing the above described diazonium salts, the polymerizable compositions of the present invention, which can be in the form of a solid or liquid, do not require a stabilizer. Even after extended shelf periods under normal ~aylight conditions, the polymerizable compositions of the present invention do not exhibit any significant change in properties. In addition, there is no problem with bubbling as characterized by organic resin compositions containing ~0 diazonium sal~s.
The aromatic onium salts of Group VIa elements utilized in the polymerizable compositions of the present invention can be more particularly defined by the ~ollowing formula, ~ (R~a(R ~b(R ~c X~ ~ Qe ,.~
128~21 where R is a monovalent aromatic organic radical;
Rl is a monovalent organic aliphatic radical select d from alkyl, cycloalkyl and substituted alkyl; R2 is a polyvalent organic radical forming a heterocyclic ring structure or a fused ring structure selected from aliphatic radicals and aromatic radicals; X is a Group VIa element selected from sulfur, selenium and tellurium; M is a metal or a metalloid; Q is a halogen selected from fluorine and chlorine; a is an integer equal to 0 to 3 inclusive, b is an integer equal to 0 to 2 inclusive, c is an integer e~ual to 0 or 1, where the sum of (a + b) + c times the valence of R2 is equal to 3;
f is the valence of M and is an integer equal to 2 to 6 inclusive;
e is greater than f and is an integer having a value up to 7; and d = e - f.
Radicals included by R are, for example, C(6 13~ aromatic hydrocarbon radicals such as phenyl, tolyl, naphthyl, anthryl, and suGh radicals substituted with up to 1 to 4 monovalent radicals such as C(l 8) alkoxy, C(l 8) alkyl, nitro, chloro, hydroxy, etc.;
arylacyl radicals such as benzyl, phenylacyl, etc.;
aromatic heterocyclic radicals such as pyridyl, furfuryl, etc. Rl radicals include C(l 8) alkyl and substituted alkyl such as -C2H4OCH3, -CH2COOC2H5, -CH2COCH3, etc. R2 radicals include such structures as ~2~33~Zl ~' `I ~`J,~ . etc.
Complex anions included by MQe ( )of formula I are, for example, BF4 , PF6 , AsF6 , SbF6 , FeC14 , SnC16 , SbC16 , BiC15 , AlF6 , GaC14 , InF4 , TiF6 ~ ZrF6 , e~c., where M ig a transition metal such as Sb, Fe, Sn, B~, ~1, Ga, In, Tl, - Zr, Sc, V, Cr, Mn, Cs, rare earth elements ~uch as the lanthanides, for example, Ce, Pr, Nd3 etc., actinides, such as Th, Pa, U, Np, etc. and metalloids such as B, P, As, etc.
Group VIa onium salts lncluded by Formula I are, for example, O C~I3 .
~ C CH2 S \ BF4 : C~13 ~C-CH2-5~ Pl/6 02N~C CH2 ~ ~1 AsF6 ~ Sb~6-8 3 4 ~ 1 <~ '' S~ FeC14~
~C -C~ SnC16 ,~
~S Sbc16 '. ~ .
~e+ ~ BiC15 ~ ~ ~ 2 ,5:- ~ BF4 O (~ ' (~C-~C~12S-et~ PF6 3 etc.
There is provided by the present invention, polymeri~ab:le compositions comprising, (A) a monomeric or prepolymeric cationic~lly .
10~ polymerizable organic material selectecl from vinyl organic monomer~, vinyl organic 3LZ ~ ~ 4~L
prepolymers, cyclic organlc ethers, cyclic organic esters, cyclic organic amines, organic silicon cyclics and cyclic organic sulfides, and (B) an effective amount of a radiation sensitive aroma~c onium salt of a Group VIa element capable of e~fec-ting ~he polymeriza~ion of ~A) by release o~ a L~wi~
Acid catalyst when exposed to radiant energy Group VIa onium salts o~ formula I are well ; known and can be made by the procedure shown in J, W, Knapczyk and W E. McEwen, J, Am Chem ~c., 91, 145, (1969); A L Maycock and G. A Berchtold, J, Org, Chem.
35, No. a, 2532 (1970); H, M. Pitt, U. S. Patent 2,807,648, E. Goethals and.P. De Radzetzky, Bul. Soc. Chim Belg , 73, 5~6 (1964); H. M. Leicester and F W Bergstrom, J. Am Chem.
Soc , 51, 3587 (1929), etc Included by the vinyl orgdnic monomers whic.h can be used in the practice of the i.nventi.on to make the , polymerizable-compositions canvertible ~o thermoplastic polymers are, ~or example, styrene, vinyl ace~amide, a-methyl styrene, isobutyl vinylether, n-octyl vinyle~her~ acrolein, l,l-diphenylethylene, ~-pinene; vinyl arenes such as 4-vinyl biphenyl, l-vinyl pyrene, 2-vinyl fluorene, acenaphthyl-ene, 1 and 2-vinyl naphthylene; 9-vinyl carbazole, vinyl pyrrolidone, 3-methyl-1-butene; vinyl cycloalipllatics ~uch as vinylcyc].ohexane, vinylcyclopropane, l-phenylvinylcyclo-lZ834Z1 ~D-71~1 propane; dienes such as isobutylene, isoprene, butadiene, 1,4-pentadiene, etc.
Some of the vinyl organic prepolyme~ which can ~e used to make the polymerizable composition~ o~ the present invention are, or example, CH2=CH-0-(CH2-CH2O)n-CH=CH2, where n i~ a positive integer having a value up to about 1000 or higher: multi-functional vinylethecs, such as 1,2,3-propane trivinyl ether, trimethylolpropane trivinyl ether, prepolymers having the formula, ~C~2~
CH=C~I2 low mole~ular weight polybutadiene having a viscosity of ~rom 200 to 10,000 centipoises at 25 C., etc. Products resulting from the cure of such compositions can be used as potting resins, crosslinked coatings, printing inks, etc.
A further category of the organic materials which can be used to make polymerizable compositions are cyclic ethers which are convertible to thermoplastics. Included by such cyclic ethers are, for example, any monomeric, dLmeric or oligomeric or polymeric epoxy material containing one or aa~plurality of epoxy functional groups. For example, those resins ~hich result from the reaction of bisph2nol-A (4,4'- -isopropylidenediphenol) and epichlorohydrin, or by the reaction of low molecular weight phenol-formaldehyde resins (Novolak resins1 with epichlorohydrin, can be used alone or in combination with an epoxy containing compound as a reactive diluent. Such diluents as phenyl glycidyl ether, 4-vinylcyclo-hexane dioxide, limonene dioxide, 1,2-cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, allyl glycidyl ether, etc., may be added as viRcosity modifying _ ~ _ ~834Z~ RD-7141 agents. In addition, the range of these compounds can be extended to include polymeric materials containing terminal or pendant epoxy groups. Examples o~ these compounds are vinyl copolymers containing glycidyl acrylate or methacrylate as one of the comonomers. Other classes of epoxy containing polymers amenable to cure using the above catalysts are epoxy-siloxane resins, epoxy-polyurethanes and epoxy-polyesters. Such polymers usually have epoxy functional groups at the ends of their chains. Epoxy-siloxane resins and method for making are more particularly shown by E.P.
Plueddemann and G. Fanger, J~ Am. Chem~ Soc. 81 632-5 (1959~.
As described in the literature, epoxy resins can also be modified in a number of standard ways such as reactions with amines, carboxylic acids, thiols, phenols, alcohols, etc. as shown in U.S. patents 2,935,488 issued May 3, 1960;
3,235,620 issued February 15, 1966; 3,369,055 issued February 13, 1968; 3,379,653 issued April 23, 1968; 3,398,211 issued August 20, 1968; 3,403,199 issued September 24, 1968; 3,563,850 issued February 16, 1971; 3,567,797 issued March 2, 1971; 3,677,995 issued July 18, 1972; etc. Further examples of epoxy resins which ~n be used are shown in the Encyclopedia of Polymer Science and Technology, Vol~ 6, 1967, Interscience Publishers, New York, pp 209-271~ me term epoxy resin as hereinafter employed, may signify both curable epoxy polymers, prepolymers and ~onomers or mixtures thereof. Further included by the term cyclic ethers are oxetanes such as 3,3-bischloromethyl-oxetane, alkoxyoxetanes a~ shown by Schroeter U.S. Patent 3,673,216 issued June 27~ 1972, assigned to the same assignee as the present invention; oxolanes such as tetrahydrofuran, oxepanes, oxygen containing spiro compounds, trioxane, dioxolane, etc.
_ g _ ~3 ~D~7141 In addition to cyclic ethers tnere are also included cyclic esters such as ~-lactones, for example, propiolactone, cyclic amines, such as 1,3,3-trimethyl-azetidine and organosilicon cyclics, for example, materials included by the formula, L+ R " 2S iO ~I
where R" can be the same or different monovalent organic radicals such as methyl or ph~'and m is an integer equal to 3 to 8 inclusive. An example of an organosilicon cyclic 0 i9 hexamethyl trisiloxane, octamethyl tetrasiloxane, etc.
The products made in accordance with the present invention are high molecular weight oils and gums.
m e curable compositions of the present invention can be made by blending the polymerizable organic material with an effective amount of the Group VIa onium salt or "onium salt"~ The resulting curable composition which can be in the form of a varnish having a viscosity of from 1 centipoise to 100,000 centipoises at 25 C or a free flowing powder, can be applied to a variety of substrates by conventional means and cured to the tack-free state within 1 second or less to 10 minutes or more~
In particular instances, depending upon the compat-ability of the onium salt with the polymerizable organic material, the onium salt can be dissolved or dispersed in an organic solvent such as nitromethane, methylene chloride, acetonitrile, etc., prior to its incorporation into the organic material. In instances where the polymerizable organic material is a solid e.g. certain of the higher molecular weight bisphenol or novolak based epoxy resin~, incorporation of the onium sal~
~Z3~33~Z~
P.D-7141 may be achieved by dry milling or by melt mixing where the melting point of the resin is suitably low. Experience has shown that the proportion of onium salt to organi~ material can vary widely inasmuch as the salt is substantially inert, unle33 activated. ~ffective results can be achieved for example, if a proportion of rom 0.1% to 15% by weight of onium salt i5 employed, based on the weight of polymerizable compo3ition.
Higher or lower amounts can be used, however, depending upon factors such as the nature of organic material intensity of radiation, polymerization time desired, etc.
It has been found that the onium salts of formula I also can be generated in situ in the presence of the organic material if desired. For example, an onium salt of the formula, 1 2 + -(R )b(R )c X Q~ , where R, Rl, R~, X, a, b and c are as previously defined, and Q a is an anion such as Cl , Br , I , F , HSO4 , and NO3 , etc, can be separately or simultaneously introduced into the organic material with a Lewis Acid of the formula, M'(MQ) where M and Q are as praviously defined and M' is a metal cation such as an alkali metal, for example, ~a, K, etc., alkaline earth, such as Ca, Mg or an organic cationic base such as quaternary ammonium, pyridinium, etc.
m e curable compositions may contain inactive ingre-dients such as inorganic fillers, dyes, pigments, extenders, viscosity control agents, process aids, W-screens, etc. in amounts of up to 100 parts of filler per lO0 parts of epoxy resin. The curable compositions can be applied to such sub-s~rates as metal, rubber, plastic, mol~ed parts or fi~s, paper, wood, glass cloth, concrete, ceramic, etc, ~834Z~ R~7141 Some of the applications in which the curable compositions of the present invention can be used are, for example, protective, decorative and insulating coatings, potting compounds, printing inks, sealants, adhesives, p~oto-resists, wire insulation, textile coatings, laminates, impregnated tapes, printing plates, etc.
Polymerization can be achieved by activating the onium salt to provide the release of the Lewis Acid catalyst.
Activation of the onium salt can be achieved by heating the composition at a temperature in the range of from 150 to 250C. Preferably cure can be achieved by exposi~g the curable composition to radiant energy such as electron beam or ultraviolet light. Electron beam cure can be effected at an accelerator voltage of from about 100 to 1000 KV.
Polymerization composition is preferably achieved by the use of W irradiation having a wavelength of from 1849 R to 4000 A. The lamp systems used to generate such radiation can consist of ultraviolet lamps such as from 1 to 50 dis-charge lamps, for example, xenon, metallic halide, m tallic arc, such as a low, medium or high pressure mercury vapor discharge lamp, etc. having an operating pressure of from a few millimeters to about 10 atmospheres, etc., can be employed. The lamps can include envelopes capable of trans-; mitting light of a wavelength preferably of 2400 A to 4000 A.
me lamp e~velope can consist of quartz, such as Spectrocil or Pyrex, etc. Typical lamps which can be employed for providing ultraviolet radiation are, for example, medium pressure mercury arcs, such as the GE H3T7 arc and the Hanovia 450 W arc lamp~ The cures may be carried out with a combination of various lamps, some or all of which canoperate in an ine~t atmosphere. When using W lamps, the - 1~2 -~3~Z~ R~-7141 irradiation flux in the substrate can be at least 0.01 watts per square inch to effect polymerization of the organic material within 1 to 20 seconds and permit the cure to be carried on continuously as, ~or example, in the curing of a multi~unctional vinyl ether or epoxy resin coated steel strip or paper web to be taken up at a rate of from 100 to 600 feet per minute. m e strip can be cut to a predetermined width for use as printed materiala A combination of heat and light may be used to cure reactive compositions. Such a combination of heat and light may serve to reduce the overall cure time~
In order that those skilled in the art will be better able to practice the invention, the following examples are given by way of illustration and not by way of limita-tion. All parts are by weight.
m~re was added under a nitrogen atmosphere, 0.2 part of triphenyl sulfonium hexafluorophosphate to 39 parts of tetrahydrofuran. The mixture was then exposed to ultra-violet irradiation from a Hanovia lamp. The mixture wasirradiated for lO minutes and the polymerization mixture was allowed to stand for four hoursO There was ob~ained a tough polymer having an intrinsic viscosity of 3.7 dl/g in benzene at 25 C~ The polymer was fabricated into an exceed-ingly tough elastic ~ilm with the use of heat and pressure, ~z ~ RD-7141 Triphenylselenonium chloride was prepared accord-ing to the procedure of H.M. Leicester and F.W. Bergstrom, J. Am. ~hem. Soc~, 51, 3587 (1929) starting with diphenyl selenide. The corresponding fluoroborate, hexafluoro-arsenate and hexafluoroantimonate salts were prepared by adding sodium hexafluoroarsenate, sodium tetrafluoroborate and potassium hexafluoroantimonate, respectively, to an aqueous solution of triphenyl selenonium chloride~ ~he products were white crystalline solids which were dried in vacuoO
Three percent solutions of the above salts in ethylene ~lycol divnyl ether (E) and also in vinylcyclohexene dioxide (V), were respectively cured as 2 mil films on steel panels at a distance of six inches from a GE H3T7 lamp. The following cure times were observed:
Salt Cure Times (~) V
(C6Hs)3Se BF45 sec. 10 sec.
(C6~s)3Se ~SF63 sec. 5 sec.
(C6~s)3Se SbF62 sec. 3 sec.
~Z~33~2~
Rl)-7141 E~AMPLE 3 ~ . , There were added 3 parts o ~odium he~afluoro-- arsenate and 6 parts of a 50% solution of triphenylsulonium chloride to 97 parts diethylene glycol divinyl ether The mixture was stirred for several hours at room ~emperature, allowed to settle and an aliquot of the solution was removed by means of a pipet. The sensitized solution was knife coated onto a 3 in x 6 in steel panel to give a 0 2 mil film and then cured as in Example 2 A hard clear coating was obtained in 3 seconds which could not be remc;ed when rubbed with acetone. The coated steel could be used as a laminate for making transformers.
.
~ - EXAMPLE 4 . .
An aliquot of the solution prepared in Example 3 was~coated onto glass to give a 1 mil fi.lm. A perforated mask was placed over the film and the assembly was irradiated for 5 seconds. After it was washed, the coated substra~e was washed with isopropanol A clear negative image of the mask remained as polymerized film, - 20 Based on the above procedure, the curable compo-sition can be employed as a negative photoresi.st ln partlc-ular applications and for the fabrication of printing plates.
~2~334~
~ . _ Glass cloth was impregnated with a mixture of 97 parts of diethylene glycol divinyl ether and 3 parts of tri-phenylsul~onium hexafluoroantimonate, Two 6 in x 6 in S squares of the impregnated glass cloth were stacked together and irradiated for 30 seconds on each side using the appara~us described in Example 2, The resulting hard and stiff laminate was found to be integrally bonded togethèr, An additional 6 in x 6 in square of impregnated cloth was added to the laminate, It also was curc--l after a 30 second exposure to ultraviolet light, The resulting - laminate composed of three layers of glass cloth could be used for circuit board applications~
. .
There was added 0,2 part o~ triphenylsulfonium hexafluorophosphate to a mlxture composed of 8 parts dimethyl-cyclotrisiloxane and 2 parts of dime~hylcyclotetrasiloxane.
This mixture was then flushed with nitrogen. Polymerization was initiated by exposing the sensitized solution to ultra-violet irradia~ion from a Hanovia 450 wa~t lamp at a distance o~ 3 inches for 10 minutes. The mixture was removed from the irradiation and allowed to stand for one day, A
highly viscous polymer mixture was obtained which was iso-lated by pouring the solution into methanol. There ~as obtained a viscous si]icone oil use~ul for lmparting ~28;~42~
improve(l surf.~ce characteriseics to a variety of substrates, EX~MPLE 7 There was added 0.3 part of triphenylsulonium ~etrafluoroborate to a mixture of 15 parts of trimethylol-propane trivinyl ether and 0,4 part of carbon black, The mixture was agitated for 3 hours on a ball mill and thén used to print onto white paper, Exposure of the printed paper to ultraviolet light at a distance of 3 inches ~rom a GE H3T7 lamp caused the printing to become dry within 1-2 seconds, _ . :
A mixture was prepared composed of 2~/o phenacyltetra-methyl sulfonium fluoroborate, 97.5% ethylene glycol divinyl ether and 0,5% of a surface active agent. This mixture 1,5 was stirred until homogeneous. It was then applied onto ~
3 in x 6 in steel panel using a drawblade having a 0.2 mil - aperture. ~fter exposing the applied mixture to ultra-violet radlation having an intenslty of 200 watts/sq, in.
for a period of l second, a hard film was obtained on the surace of the steel panel. The fllm could not be removed even though the panel was repeatedly dipped into acetone and rubbed with a cloth.
~33~
EXA~IPI.E 9 A (30:70) mixture of 1,2,3-propane ~rivinyl ether and diethylene glycol divinyl ether was sensitlzed with 3 parts of phenacyltetramethylene sulfonium fluoroborate This mixture was coated onto a sheet of Lexan~ pol~carbonate using a draw knife with a 0 2 mil aper ure. The coating was cured for 5 seconds as described in Example 2 There was obtained a polyearbonate sheet having a transparent, scratch-resistant coating which could not be removed by rubbing with I0 acetone.
_XAMPLE 10 A mixture of 0.1 part of triphenylsulfonium fluoroborate and a solution of 13.3 parts of recrystallized N-vinylcarbazole in 39 parts of methylene chloride was lS sealed under a nitrogen atmosphere The mixture was irradiated for 10 minutes at a distance of 3 inches from a 450 watt Hanovia lamp while immersed in an iee bath. The mixture was then allowed to stand. Exothermic poiymerizatio~
took place glving a highly vlscous solution. After 3 hour~, the polymer solution was poured into methanol. Thexe wa8 isolated after filtering, washing and drying, 13 0 parts of polyvinylcarbazole.
. _ A polymerization mixture of 26.6 parts of freshly d~Lstilled styrene, 0 20 part of triphenylsulfonium hexa-~7~834~
fluoroarsenate and 6.5 parts of distilled methylene chloride, sealed under nitrogen, was irradiated for 10-15 minutes under a 450 watt Hanovia medium vapor pressure mercury lamp. Rapid exothermic polymerization took place and the polymerization was allowed to stand in the dark for 5 hours. The viscous reaction mixture was poured into methanol and the solid polymer was filtered and washed. A
white polystyrene having an intrinsic viscosity of 0.16 dl/g in benzene was produced.
A mixture of 11.4 parts of ~-methylstyrene, 0.11 parts of triphenylsulfonium hexafluoroantimonate and 26 parts of methylene chloride was irradiated for 2.5 hours in accordance with the procedure of Example 11.
The resulting highly viscous polymer solution was quenched by adding a small amount of methanol. A product isolated by pouring the solution into a large amount of methanol. After drying, there was obtained, 11.4 parts of polymerized ~-methylstyrene which was useful as a molding resin.
A printing ink was prepared by mixing together 2.5 parts of glycerol trivinyl ether, 3 parts of 3,5-dimethyl-4-hydroxyphenyl dimethylsulfonium fluoroborate and 5 parts of a red fluorescent pigment. These components ~, ~Z~3~1 were used as an ink to print on white paper, The printed paper was exposed for 3 seconds to UV ]ight resulting in a clear, dry, non-smearable printed image, , S A mix~ure of 21,0 parts of N-vinylpyrrolidone and 0.63 part of triphenylsulfonium fluoroborate was irradiated with a Hanovia lamp for 13 minutes, The solution became quite viscous and was allowed to stand in the dark for two days at room temperature, A polymer formed having an in-trinsic viscosity of 0,2~ in water, A mixture of 9.2 parts of recrystallized trioxane~
26 parts of methylene chloride, and 0,06 part of trlphenyl-sulfoniurn fluoroborate was irradiated or 1 hour in the 15-- presence of pyrex filtered W light from a Hanovia lamp, A
white powdery precipitate formed, The solution was then allowed to stand for 8 hours in the dark. The preeipitated polymer was filtered and Iried, There was obtained 7 parts of polyoxymethylene, A solution of diethylene glycol dlvinyl ether containing 2% by weight triphenylsulfonium hexfluoroarsenate was coated onto a 3 in x 6 in steel plate, A perforated mask was placed over the coating and thi~ assembly was -2~
~Z834Z~ R~714i exposed to ultraviolet light using a GE H3T7 medium pres3ure mercury arc lamp at a distance of four inches. After a 5 second exposure, the mask was removed and the plate was washed with i-propanol. A clear, raised negative image of the mask was formed.
EX~MPLE 17 . .
A curable composition was prepared by forming a mixture of 0.2 part of triphenylsulfonium tetra~luoro-horate dissolved in acetonitrile and 5 parts of 4-vinyl--cyclohexene dioxide. A 2 mil film was drawn on a glassplate and exposed to ultraviolet irradiation from a GE
H3T7 lamp at a distance of from 6 inches. The resin had cured to a hard film within 30 seconds. The film was found to be insoluble in dipolar aprotic solvents and it could not be scratched with a fingernail.
A portion of the above curable composition having a viscosity at 25 C of about 6 centipoises was allowed to stand under average daylight conditions for four months in a transparent container. It was found that the viscosity remained substantially the same.
A portion of the curable composition was applied onto a steel strip. T~e treated steel surface was exposed 15 seconds to the ultraviolet radiation of an H3T7 lamp at a distance of 2 inches. A clear, tack-free film was formed which showed no signs of bubble~ or other imperfections.
m e above treated strip was then immersed in lOC
hydroca~bon oil for 48 hours at 120 C to determine its hydrolytic stability in accordance with IFT test ASTM D971-50 Interfacial Tension of Oil Against Water shown on page 322 of the 1970 Annual Book of ASTM Standards, part 17 (November).
The initial reading of the oil was about 39~0 dynes/cm.
~2~3342~
Af-ter the test the oil sh~wed an interfacial tension reading of 38. In order to pass, a reading of at least 30 is required.
ExAMæLE 18 An 80:20 mixture of an epoxy novolaX resin, an epoxy equivalent weight of 173 and 4-vinylcyclohexene dioxide wa~ sensitized with 3% by weight of triphenyl-sulfonium hexafluoroantimonate. ~his solution was used to impregnate glass cloth. Two 6 in x 6 in squares of the clock were then stacked together and cured to form a laminate by irradiating the cloth for l minute on each side using a GE
H3T7 lamp at a distance of six inches. The stiff laminate was integrally bonded and could be used for circuit boards.
There were added three parts phenacyl *etramethylene sulfonium hexafluoroarsenate to a 70:30 mixture of bisphenol-A-diglycidyl ether and 4-vinylcyclohexene dioxide~ The catalyzed mixture of epoxides was then used to impregnate a l inch wide glass fabric tapeO After winding one layer onto a 5" x 2" diameter cylinder, the impregnated tape was cured while rotating the wound cylinder under a GE H3T7 lamp. The total exposure time to W light was 5 minutes. At the end of this time the tape was fully cur~d into the shape of a rigid cylinder. The wound cylinder could then be used as a spool for winding wire to make transformer coil~.
A mixture was prepared consisting of 14.5 g ~0.~5 mole) glycidyl allyl ether, lO mg t-butylcatechol, and three drops of chloroplatinic acid in octyl alcohol~ The reaction mixture was heated to 50 C in a water bath and then 13.0 g of a polydimethyl siloxane resin containing 0.89% by weight Si-H groups was added dropwise by means of a dropping funnel.
Immediate exothermic reaction took place with the tempera-~L283~2~
ture rising to 65C. Reaction proceeded smoothly at this temperature giving a clear fluid resin.
Three parts by weight of triphenylsulfonium fluoroborate dissolved in a small amount of acetonitrile was added to 97 parts of the above silicone epoxy resin. A
2 mil film of the sensitized resin was drawn on a glass plate and then exposed to W light from a ~E H3T7 lamp a~ a distance of six inches. The film was tack-free within 15 to 20 seconds. A small amount of silica was added to the sensitized resin to produce a thixotropic mixture and the resin cured as described previously. A tough, rubbery coating resulted. These UV cured epoxy-siloxanes are useful as sealants and caulks.
There were added 3 parts S-phenyldibenzothio-phenium fluoroborate to 97 parts 4-vinylcyclohexene dioxide. This mixture was spread on a glass plate as a 2 mil film and exposed to irradiation from a GE H3T7 lamp at a distance of six inches. one minuta exposure was required to fully cure the film to a hard, scratch resistant state.
_XAMP~E 2Z
A 3% solution of phenacyl tetramethylene sulfonium hexafluoroarsenate in 40:60 mixture of 4-vinylcyclohexene dioxide and an epoxy novolak having an epoxy equivalent weight of 206 were knife coated onto a steel plate to a Af~
~Z~
P~D--7141 thickness of 3 mil, A mask was placed over the film and the entire assembly irradiated for 1 minute. The mask was removed and the film was washed with i-propanol. The unexposed portions of the film were washed away having a clear sharp negative image of the mask.
___ _ There were added 6 parts of a 50% aqueous solution of triphenylsulfonium chloride and 2.1 parts of NaAsF6 to 97 parts of an 80:20 mixture of blsphenol-A-diglycidyl e~her and 4-vinylcyclohexene dioxide. The reac~ion mixture was agl~a~ed by stlrring for one-half hour and ~hen allowed to settle, An aliquot of the resin was taken and spread onto a glass plate u~ing a draw knife with a 3 ml aperture. A
taclc-free film formed within lS seconds after exposure to an H3T7 lamp at a distance of six inches. The film was hard and clear.
Resistors were potted in ~he above resin by dipping the re~istor into the ~en~itized reYin and then curing it by ro~ating the re~i~tor for 30 second~ beneath the ultraviolet lamp.
An equimolar mixture of diphenyliodonium fluoro-borate and thioxanthene was heated at 200C for 3 hours.
After recrystallization from methylene chlcride-diethyl _ 2*.
~Z~334~
RD--71~1 ether, there was ohtained an 80% yield of produc~ having a m,p, of 168-169~. Based on method o preparation the product was S-pllenylthioxanthene fluoroborate, A hard clear scratch resistant 1 mil coating was obtained, when a 3% solution of the above onium compound in limonene dioxide was kllife coated onto a po`lystyrene sheet and ex-posed to lJV irradiation from a 450 W Hanovia medium pressure mercury arc at a distance of 3 inches.
There were added 2.6 parts phenacyltetramethylene sulfonium bromide to a mixture of 95 parts of 4-vinyLcyclo-hexene dioxide containing 2,2 parts of NaAsF6. The solution was placed in a dark bottle and rolled on a ball mill for 8 hours. After the salts were removed by filtration, the solution was coated onto a 3 in x 6 in steel panel and cured as in Exc~mple 1. A hard coating wa~ ohtained after 15 - seconds expns-lre which coukl not be remo~/ed by rubbing the coating Wit~l acetone.
.
There were dissolved two par~s of ~riphenylsulfon-ium hexafluoroantimonate into a 40:60 mixture of dicyclo-pentadiene dioxide and glycidyl acry]ate ~nl!owillg ~he procedure o example 1, a hard crosslinked 1 r.lil coating wa~
obtained after a 15 second exposure to ultravlolet light.
~834~
There were added four parts of triphenylsulfonium hexafluoroarsenate to 100 parts of a blend of equal parts of 4-vinylcyclohexene dioxide and (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexanecarboxylate. An aliquot of the resulting sensitized resin was spread onto a polycarbonate sheet using a draw-clo1~l blade to give a 0.5 mil ~ilm. The ilm was cured as described in Example 1 for 10 seconds resulting in a clear hard mar reslstant and solvent resistant coating.
- A mixture of 50 parts bisphenol-A-diglycidyl ether and 50 parts (3,4-epoxycyclohexyl)methyl-3,4-epoxycycloh~xane-carboxylate was stirred until homogeneous There was then added 3 parts of triphenylsulfonium hexafluoroantimonate to the solution. It was mixed until the sensitizer had dis-solved. A portion of the above solution ~as coated onto a stecl plate llsing a 0.2 mll drawbar l~he plate was then expo.sed to a GE H3T7 lamp at a distance oE six inches for 5 seconds. A hard cured adherent film ~ormed on the steel.
~20 EXAMPLE 29 A blend of epoxy resins consisting of 50 parts 4-vinylcyclohexene dioxidej 40-parts of a novolak-epoxy resin having an epoxy equivalent weight of 172-178 ~d 10 pclrts r .
~33~
P~D--7141 n-oc~ylglyci-lyl ether were thorough]y mixed tog(-~he-c. A
100 part aliquot was removed to which was added 1 part o triphenylsulfonium hexafluoroarsenate. The resulting mixture was stirred until the onium salt had dissolved T~hen the above mixture was coated onto a 3 in x 6 in steel panel and exposed to a 450 watt medium pressure mercury arc Lamp at a distan.e o 3 inches, a glossy, dry coatLng was obtained in 2 seconds. The coating withstood attack by hot boiling water for four hours, It could not be removed by rubbing with acetone.
, EXI~MPLE 3 0 There was added 10 parts of a solid multifunctional aromatic glycidyl ether having an epoxy equivalent weight of - 210~240 to 40 parts of limonene dioxide. The mixture was combined with 1 part of phenacyltetramct~lene sulfonium hexafluoro~rsenate and stirred at 50C for 0.5 hour to produce a homo~eneous solution. When the mixture was coated onto glass usin~ a 0.5 mil drawbar, and lrradiated for 5 seconds at a dis~ance of 3 inches fro~l a C,E H3T7 mercury arc lamp having an intensity of 200 watts/sq. inch., a hard cured film was produced.
., , .. __ .
There was added 0.2 part of triphenylsulfonium hexafluoroantimonate in 2 parts of 4-vinylcyclohexene dioxide _27-~33,~L'Z RD--7141 to 10 parts of an epoxidized butadiene resin, After rnixing the components thoroughly, the mixture was appLied to a 1/16 inch thick glass plate to a 1 mil thickness, Another plate of glass was placed on top o the first and the assembly was exposed to a GE H3T7 medium pressure mercury arc lamp having an intensity of 200 watts/sq, inch at a distance of three inches, The total exposure time was 30 seconds, ~he glass plates were permanently bonded together, Based on characteristics of the glass laminate, a similar procedure can be used to make a shatterproof windshield for auto-mobiles, .
There were added with stirring 89 parts of alum-inum chloride in small portions to a solution of 122 parts of 2,6-xylenol in 505,12 parts of carbon disulfide main-tained at 10C, To the resulting greenish solution were added 79,5 parts o~ thionyl chloride in a dropwise fashion maintaining the temperature between 10 and 15C. A black precipita~e and solution was obtained which was stirred for an additional 2 hours and then poured-onto 1000 parts of ice containing about 50 parts of concentrated HCl, This mixture was placed on a steam bath to remove CS2 and to decompose the complex, A tan solid was obtained which was iltered, washed with water and dried, .. .. ......... . . _ _ ~z~3342~L
To a solution of 21,5 parts of the above crude product in about 117 parts of hot absolute ethanol were added 11,,4 parts of K~sF6 and 10 parts of water, The reaction mixture was stirred and more water was added to e~ect the precipitation of product. The product was filtered, wa~hed with water and dried, A material was obtained having a m.p. of 245-251C, Based on method of preparation and elemental analysis ~or C24H2703SAsF6, Calc:
% C, 49,3; % H, 4,62; % S, 5,48, Found: % C, 49.4; ~/0 H, 4,59; % S, 5.55, the product was tris-3,r~-(limethyl-4-hydroxy-phenyl sulfonium hexafluoroarsenate, , A three percent 's,olution of the above onium salt was made with'4-~inylcyclohexene dioxide. Cure of the solution was effected by ir,radiating a 2 mil film on glass according to the procedure described in Example 3, A hard mar-resistant co~ting las obtained after 5 seconds of i.rradiation, E~AMPLE -33 'l;hree parts of triphenylsulfonl~ hexafluoro-antimonate were ground to a fine powder, The powder was intimately rnixed with 97 parts Reichhold Epotu~R' 37-834 powder coating resln by tumbling these together for 30 minutes, Tbe powder was then electrostaticall~ sprayed onto 3 ln x 6 in steel panels to form approximately a 2 mil coatlng,usin~ a GE~ model 171 spray gun. Subsequently, the 33~Z~
samples were heated brleEly to 150C to use the powder and then exposed while hot to a GE H3T7 medium pressure mercury arc lamp at a distance of 3 inches. Cured samples r,Jere obtained aEter a lS second irradiation. The cured ilms were adherent and mar resistant, ~,.
Trlphenacyl hexafluoroarsenate was added to a mixture of 67% by weight of a novolak-epoxy resin having an epoxy equivalent weight of 172-178, 33% 4-vinyl,cyclohexene 10 ' dioxidc anc~ 0,5% of ~ sur~ace actlve agenL:. Th~ result-ing mixture contain~d about 1% by weight of the onlum salt.
A coating was applled as a 0.1 mil ~ilm to 3 in x-6 in steel plates and cured or 20 seconds a~ a distance of 4 inches rom a GE H3T7 medlum pressure mercury arc lamp. Some panels were subsequently in~lerse-l for 5 ~ours at room temperature in methylene chlorideA ()t~er panels were immerse~l for 4 h,our~ in acetone. Irl a]l cases, no visible sl~ns of solv(~nt attack of the coatings were obselved. The same were then baked for 1- ho~r at l60C. rests were run separately in boiling 50% KOH solution ~or 30 minutes and in boiling distilLed water for 4 hours. Again, no visible degradation of the coatings was obser~ed, - 30~
~334Z~
Mixtures of triphenylsulfonium hexafluoroarsenate in 4-vinylcyclohexene dioxide having a concentration of 0 to 10% onium salt, were thermally aged at 25gC and 55gC. The viscosities of the mixtures were measured over a two-week period (336 hrs.). The following results were recorded at 25gC:
Viscosity Viscosity at Concentration (%3 Start ~cps) 336 hr (cps) 0 6.0~ 6.06 1 6.26 6.34 3 6.90 6.90 7.65 7.59 9.80 9.71 at 55C:
Viscosity Viscosity at Concentration f~) Start (cps) 336 hr (cps~
0 S.06 6.06 1 Ç.42 6.37 3 6.91 6.93 7.65 7.67 9.75 9.71 Within experimental error, the above results show that there is essentially no viscosity change over the period the sensitizer was tested at a temperature range of 25C to 55C.
~z~33~ R~--7l~l Although the above examples are limited to only a few of the very many polymerizable composition~ and use3 thereof which are included within the scope of the present invention, it should be understood that the present in~ention is intended to cover a much broader cla~s of such composi-tions and uses thereof~ Those sXilled in the art would also know that the polymerizable compositions also cover the use of onium polymers containing Group VIa onium functionality as part of the polymer backbone or in the pendant position.
Claims (89)
1. A photocurable composition consisting essentially of:
(A) a monomeric or prepolymeric cationically polymerizable organic material selected from vinyl organic monomers, vinyl organic prepolymers, cyclic organic ethers, cyclic organic esters, cyclic organic sulfides, cyclic amines and organosilicon cyclics, and (B) from about 0.1% to 15% by weight, based on the weight of (A) plus (B), of a photodecomposable aromatic onium salt of a Group VIa element capable of effecting the cationic polymerization of (A) when exposed to radiant energy, where said photodecomposable aromatic onium salt of a Group VIa element has the formula:
[ (R)a(R1)b(R2)cX)? [MQe]-(e-f) where R is a monovalent aromatic organic radical; R1 is a monovalent organic aliphatic radical selected from alkyl, cycloalkyl and substituted alkyl; R2 is a polyvalent organic radical forming a heterocyclic ring structure or a fused ring structure selected from aliphatic radicals and aromatic radicals;
X is a Group VIa element selected from sulfur, selenium and tellurium; M is a metal or a metalloid; Q is a halogen selected from fluorine and chlorine, a is an integer equal to 0 to 3 inclusive, b is an integer equal to 0 to 2 inclusive, c is an integer equal to 0 or 1, where the sum of (a + b) + c times the valence of R2 is equal to 3;
f is the valence of M and is an integer equal to
(A) a monomeric or prepolymeric cationically polymerizable organic material selected from vinyl organic monomers, vinyl organic prepolymers, cyclic organic ethers, cyclic organic esters, cyclic organic sulfides, cyclic amines and organosilicon cyclics, and (B) from about 0.1% to 15% by weight, based on the weight of (A) plus (B), of a photodecomposable aromatic onium salt of a Group VIa element capable of effecting the cationic polymerization of (A) when exposed to radiant energy, where said photodecomposable aromatic onium salt of a Group VIa element has the formula:
[ (R)a(R1)b(R2)cX)? [MQe]-(e-f) where R is a monovalent aromatic organic radical; R1 is a monovalent organic aliphatic radical selected from alkyl, cycloalkyl and substituted alkyl; R2 is a polyvalent organic radical forming a heterocyclic ring structure or a fused ring structure selected from aliphatic radicals and aromatic radicals;
X is a Group VIa element selected from sulfur, selenium and tellurium; M is a metal or a metalloid; Q is a halogen selected from fluorine and chlorine, a is an integer equal to 0 to 3 inclusive, b is an integer equal to 0 to 2 inclusive, c is an integer equal to 0 or 1, where the sum of (a + b) + c times the valence of R2 is equal to 3;
f is the valence of M and is an integer equal to
2 to 6 inclusive;
e is greater than f and is an integer having a value up to 7; and d = e - f.
2. The composition of claim 1, wherein the organic material is a vinyl organic monomer.
e is greater than f and is an integer having a value up to 7; and d = e - f.
2. The composition of claim 1, wherein the organic material is a vinyl organic monomer.
3. The composition of claim 1, wherein the organic material is a vinyl organic prepolymer.
4. The composition of claim 1, wherein the organic material is a cyclic organic ether.
5. The composition of claim 4, wherein said cyclic ether is an epoxy resin.
6. The composition of claim 3, wherein the vinyl organic prepolymer is a polyvinyl ether.
7. The composition of claim 1, wherein the organic material is a cyclic organosilicon compound.
8. The composition of claim 1, wherein the organic material is a cyclic organic ester.
9. The composition of claim 1,2 or 5, wherein the aromatic onium salt is selected from sulfur, selenium and tellurium salts.
10. The composition of claim 5, wherein the aromatic onium salt is a dialkyl phenacyl sulfonium salt.
11. The composition of claim 1, 2 or 5, wherein the aromatic onium salt is prepared in situ.
12. The composition of claim 5 or 10, wherein the epoxy resin is a reaction product of 4,4'isopropylidene diphenol and epichlorohydrin.
13. A curable composition consisting essentially of:
(A) an organic material which is polymerizable to a state of higher molecular weight under the influence of a cationic catalyst, and (B) an effective amount of a photodecomposable aromatic onium salt of a Group VIa element capable of effecting the cationic polymerization of (A) when exposed to radiant energy, where said photodecomposable aromatic onium salt of a Group VIa element has the formula:
[ (R)a(R1)b(R2)cX]?[MQe]-(e-f) where R is a monovalent aromatic organic radical, R1 is a monovalent organic aliphatic radical selected from alkyl, cycloalkyl and substituted alkyl; R2 is a polyvalent organic radical forming a heterocyclic ring structure or a fused ring structure selected from aliphatic radicals and aromatic radicals; X is a Group VIa element selected from sulfur, selenium and tellurium; M is a metal or a metalloid;
Q is a halogen selected from fluorine and chlorine; a is an integer equal to 0 to 3 inclusive, b is an integer equal to 0 to 2 inclusive, c is an integer equal to 0 or 1, where the sum of (a + b) + c times the valence of R2 is equal to 3, f is the valence of M and is an integer equal to 2 to 6 inclusive;
e is greater than f and is an integer having a value up to 7; and d = e - f.
(A) an organic material which is polymerizable to a state of higher molecular weight under the influence of a cationic catalyst, and (B) an effective amount of a photodecomposable aromatic onium salt of a Group VIa element capable of effecting the cationic polymerization of (A) when exposed to radiant energy, where said photodecomposable aromatic onium salt of a Group VIa element has the formula:
[ (R)a(R1)b(R2)cX]?[MQe]-(e-f) where R is a monovalent aromatic organic radical, R1 is a monovalent organic aliphatic radical selected from alkyl, cycloalkyl and substituted alkyl; R2 is a polyvalent organic radical forming a heterocyclic ring structure or a fused ring structure selected from aliphatic radicals and aromatic radicals; X is a Group VIa element selected from sulfur, selenium and tellurium; M is a metal or a metalloid;
Q is a halogen selected from fluorine and chlorine; a is an integer equal to 0 to 3 inclusive, b is an integer equal to 0 to 2 inclusive, c is an integer equal to 0 or 1, where the sum of (a + b) + c times the valence of R2 is equal to 3, f is the valence of M and is an integer equal to 2 to 6 inclusive;
e is greater than f and is an integer having a value up to 7; and d = e - f.
14. The composition of claim 13, wherein X is sulfur.
15. The composition of claim 14, wherein c is zero.
16. The composition of claim 13, 14 or 15, wherein said organic material is vinyl group containing.
17. The composition of claim 13, 14 or 15, wherein said organic material is cyclic ether group containing.
18. The composition of claim 13, 14 or 15, wherein said organic material is cyclic ester group containing.
19. The composition of claim 13, 14 or 15, wherein said organic material is cyclic thioether group containing.
20. The composition of claim 13, 14 or 15, wherein said organic material is cyclic amine group containing.
21. The composition of claim 13, 14 or 15, wherein said organic material is cyclic siloxane group containing.
22. The composition of claim 13, 14 or 15, wherein said organic material is selected from epoxide, oxetane and oxepane group containing materials.
23. The composition of claim 13, 14 or 15, wherein said organic material is epoxide group containing.
24. The composition 13, 14 or 15, wherein said organic material is an epoxy resin.
25. The composition of claim 13, 14 or 15, wherein said organic material comprises an epoxy group containing material and a modifier therefor.
26. The composition of claim 13, 14 or 15, wherein said organic material comprises an epoxy resin and an alcohol group containing material as a modifier therefor.
27. The composition of claim 13, 14 or 15, wherein the R radicals are independently selected from aromatic carbocyclic radicals.
28. The composition of claim 13, 14 or 15, wherein the R radicals are independently selected from substituted aromatic carbocyclic radicals and non substituted aromatic carbocyclic radicals.
29. The composition of claim 13, 14 or 15, wherein the R radicals are independently selected from phenyl radicals and phenacyl radicals.
30. The composition of claim 13, 14, or 15, wherein at least one of said R radicals is substituted by a substituent selected from C1-0 alkyl, C1-8 alkoxy, nitro and chloro groups.
31. The composition of claim 13, 14 or 15, wherein at least one of said R radicals is substituted by a substituent selected from methyl, methoxy, nitro and chloro.
32. The composition of claim 13, 14 or 15, wherein M is a transition group metal.
33. The composition of claim 13, 14 or 15, wherein M is a metalloid.
34. The composition of claim 13, 14 or 15, wherein M is selected from B, P, As, Sb and Bi.
35. The composition of claim 13, 14 or 15, wherein MQe is selected from BF4, PF6, SbF6 and AsF6.
36. A photopolymerizable composition comprising at least one acid-polymerizable or acid-curable material other than a polycarboxylic acid anhydride as photosensitizer at least one salt of formula wherein A is sulphur, or selenium n is 1 or 2, R1, R2 and R3, which are the same or different, each is an alkyl, cycloalkyl, aryl, alkaryl or aralkyl group or substituted derivative thereof, wherein said alkyl or substituted alkyl group contains from 1 to 20 carbon atoms, and Xn- is an anion derived from an acid which polymerizes or cures the acid-polymerizable or acid-curable material.
37. A photopolymerizable composition as claimed in claim 36, wherein in the photosensitizer the element A is sulphur.
38. A photopolymerizable composition as claimed in claim 36, wherein the amount of the photosensitizer is from 0.01% to 10% by weight based on the weight of the acid-polymerizable or acid-curable material.
39. A photopolymerizable composition as claimed in claim 38, wherein the amount of the photosensitizer is from 0.05% to 5% by weight based on the weight of the acid-polymerizable or acid-curable material.
40. A photopolymerizable composition as claimed in claim 39, wherein the amount of the photosensitizer is from 3% to 5% by weight based on the weight of the acid-polymerizable or acid-curable material.
41. A photopolymerizable composition as claimed in claim 36, wherein the anion Xn- is a halogen-containing complex ion selected from C104- and metal halogenides.
42. A photo polymerizable composition as claimed in claim 41, wherein the anion Xn- is a polyhalide of boron, antimony, tin, silicon, phosphorus, arsenic, bismuth or iron.
43. A photopolymerizable composition as claimed in claim 42, wherein the anion Xn- is the tetrafluoroborate ion.
44. A photopolymerizable composition as claimed in claim 36, wherein the photosensitizer is soluble in the acid-polymerizable or acid-curable material.
45. A photopolymerizable composition as claimed in claim 36, wherein in the photosensitizer at least one of the groups R is an aryl group or substituted aryl group.
46. A photopolymerizable composition as claimed in claim 45, wherein in the photosensitizer each of the group R
is an aryl group or substituted aryl group.
is an aryl group or substituted aryl group.
47. A photopolymerizable composition as claimed in claim 45, wherein two of the groups R are aryl groups or substituted aryl groups, the other group R being an alkyl group.
48. A photopolymerizable composition as claimed in claim 45, 46 or 47, wherein the photosensitizer contains at least one phenyl group.
49. A photopolymerizable composition as claimed in claim 36, wherein the acid-curable material comprises an epoxy resin.
50. A photopolymerizable composition as claimed in claim 36, wherein the acid-polymerizable material is an acid-polymerizable monomer.
51. A polymeric composition derived from a photopolymerizable composition as claimed in claim 36 by subjecting the photopolymerizable composition to radiation of wavelength such as to activate the photosenitizer and polymerize or cure the composition.
52. A polymeric composition as claimed in claim 51, which in the form of a surface coating on a substrate.
53. A process for the preparation of a polymeric composition as claimed in claim 36 to radiation of wavelength such as to activate the photosensitizer and polymerize or cure the composition.
54. A process as claimed in claim 53, wherein the radiation comprises ultra-violet radiation.
55. A process as claimed in claim 53 or 54, wherein the wavelength of the radiation is in the range from 200 microns to 600 microns.
56. A photopolymerizable composition comprising:
(a) an organic material which is cationically polymerizable; and (b) about 0.1 to 30 parts by weight, per 100 parts by weight of said organic material, of an aromatic sulfonium complex salt photoinitiator of the formula wherein R1, R2 and R3 are selected from the group consisting of aromatic carbocyclic and aromatic heterocyclic groups having 4 to 20 carbon atoms and alkyl radicals having 1 to 20 carbon atoms; wherein at least one of R1, R2 and R3 is aromatic; wherein Z is selected from the group consisting of oxygen; sulfur; ?=O, ?=O, O=?=O; R-? where R is aryl or acyl;
a carbon-to-carbon bond; or R4-?-R5 where R4 and R5 are selected from the group consisting of hydrogen, an alkyl radical having 1 to 4 carbon atoms, and an alkenyl radical having 2 to 4 carbon atoms; and n is zero or 1 such that when n is zero there is no bond between R1 and R2; and X- is a halogen-containing complex anion selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.
(a) an organic material which is cationically polymerizable; and (b) about 0.1 to 30 parts by weight, per 100 parts by weight of said organic material, of an aromatic sulfonium complex salt photoinitiator of the formula wherein R1, R2 and R3 are selected from the group consisting of aromatic carbocyclic and aromatic heterocyclic groups having 4 to 20 carbon atoms and alkyl radicals having 1 to 20 carbon atoms; wherein at least one of R1, R2 and R3 is aromatic; wherein Z is selected from the group consisting of oxygen; sulfur; ?=O, ?=O, O=?=O; R-? where R is aryl or acyl;
a carbon-to-carbon bond; or R4-?-R5 where R4 and R5 are selected from the group consisting of hydrogen, an alkyl radical having 1 to 4 carbon atoms, and an alkenyl radical having 2 to 4 carbon atoms; and n is zero or 1 such that when n is zero there is no bond between R1 and R2; and X- is a halogen-containing complex anion selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.
57. A photopolymerizable composition in accordance with claim 56, wherein said organic material is an epoxide having functionality of at least 1.
58. A photopolymerizable composition in accordance with claim 57, wherein said organic material is selected from the group consisting of epichlorohydrins, alkylene oxides, cycloaliphatic epoxides, glycidyl esters, glycidyl ethers, epoxy novolaka, and copolymers of acrylic acid esters of glycidol and copolymerizable vinyl compounds.
59. A photopolymerizable composition in accordance with claim 56, wherein said R1, R2 and R3 are each selected from the group consisting of substituted and unsubstituted phenyl, naphthyl and thienyl groups.
60. A photopolymerizable composition in accordance with claim 59, wherein said R1, R2 and R3 are selected from the group consisting of phenyl and substituted phenyl groups.
61. A photopolymerizable composition in accordance with claim 56, wherein n is zero; R1 is alkyl; and R2 and R3 are selected from the group consisting of substituted and unsubstituted phenyl, naphthyl and thienyl groups.
62. A photopolymerizable composition in accordance with claim 59, wherein n is 1 and z is a carbon-to-carbon bond.
63. A photopolymerizable composition in accordance with claim 60, wherein n is zero.
64. A photopolymerizable composition in accordance with claim 56, wherein said halogen-containing complex anion is selected from the group consisting of tetrafluoroborate, hexafluorophosphate, and hexafluoroantimonate.
65. A photopolymerizable composition in accordance with claim 56, wherein said photoinitiator is present in an amount of about 1 to 7 parts by weight per 100 parts by weight of said organic compound.
66. A photopolymerizable composition in accordance with claim 56, wherein said organic material contains a vinyl ether group.
67. A photopolymerizable composition in accordance with claim 56, wherein said organic material contains an oxetane group.
68. A photopolymerizable composition in accordance with claim 56, wherein said organic material is a lactone.
69. A process for obtaining a cured coating comprising:
(a) applying a thin layer of the composition of claim 56 to a substrate, and (b) exposing said layer to actinic radiation or electron beam irradiation.
(a) applying a thin layer of the composition of claim 56 to a substrate, and (b) exposing said layer to actinic radiation or electron beam irradiation.
70. A substrate bearing a thin layer of the composition of claim 56 which has been cured in situ.
71. A process for bonding a radiation-transparent substrate to a second substrate comprising:
(a) disposing a layer of the composition of claim 56 between said substrates and in contact therewith; and (b) exposing said layer to actinic radiation or electron beam irradiation through said radiation-transparent substrate in an amount and for a time sufficient to render said layer insoluble.
(a) disposing a layer of the composition of claim 56 between said substrates and in contact therewith; and (b) exposing said layer to actinic radiation or electron beam irradiation through said radiation-transparent substrate in an amount and for a time sufficient to render said layer insoluble.
72. A photopolymerizable composition in accordance with claim 56, further containing up to 50% by volume of a filler.
73. An aromatic sulfonium complex salt of the formula X-wherein R1, R2 and R3 are selected from the group consisting of aromatic carbocyclic and aromatic heterocyclic groups having 4 to 20 carbon atoms and alkyl radicals having 1 to 20 carbon atoms, wherein at least one of R1, R2 and R3 is aromatic; wherein Z is selected from the group consisting of oxygen; sulfur; ?=O; ?=O; O=?=O; R? where R is aryl or acyl; a carbon-to-carbon bond; or R4-?-R5 where R4 and R5 are selected from the group consisting of hydrogen, an alkyl radical having 1 to 4 carbon atoms, and an alkenyl radical having 2 to 4 carbon atoms; and n is zero or 1 such that when n is zero there is no bond between R1 and R2; and wherein X-is a halogen-containing complex anion selected from the group consisting of hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.
74. An aromatic sulfonium complex salt in accordance with claim 73, wherein X- is hexafluorophosphate.
75. An aromatic sulfonium complex salt in accordance with claim 73, wherein X- is hexafluoroantimonate.
76. An aromatic sulfonium complex salt in accordance with claim 73, wherein X- is hexafluoroarsenate.
77. A photopolymerizable composition comprising at least one acid-polymerizable or acid-curable material other than a polycarboxylic acid anhydride and as photosensitizer at least one salt of the formula wherein A is sulphur or selenium; X is a metal or metalloid halogenide with the halogen selected from fluorine and chlorine;
n is 1 or 2; R1, R2 and R3, which are the same or different, are alkyl, cycloalkyl, aryl, alkaryl, aralkyl or heterocyclic groups or substituted derivatives thereof, provided that at least one of the R1, R2 and R3 groups is an aryl, alkaryl or aralkyl group, or two of the groups R1, R2 and R3 together are an alkylene group and with the element A form a heterocyclic structure, the other group being an aryl or substituted aryl group.
n is 1 or 2; R1, R2 and R3, which are the same or different, are alkyl, cycloalkyl, aryl, alkaryl, aralkyl or heterocyclic groups or substituted derivatives thereof, provided that at least one of the R1, R2 and R3 groups is an aryl, alkaryl or aralkyl group, or two of the groups R1, R2 and R3 together are an alkylene group and with the element A form a heterocyclic structure, the other group being an aryl or substituted aryl group.
78. A curable composition consisting essentially of:
(A) an organic material which is polymerizable to a stats of higher molecular weight under the influence of a cationic catalyst, and (B) an effective amount of a photodecomposable aromatic sulfonium salt capable of effecting the cationic polymerization of (A) when exposed to radiant energy, where said photodecomposable aromatic sulfonium salt has the formula:
{ (R)a(R1)b(R2)CS }+X-where R is a monovalent aromatic organic radical, R- is an alkyl or substituted alkyl radical; R2 is a polyvalent organic radical forming a heterocyclic ring structure or a fused ring structure selected from aliphatic radicals and aromatic radicals; X- is BF4-, PF6-, AsF6- or SbF6-; a is an integer equal to 0 to 3 inclusive, b is an integer equal to 0 to 2 inclusive, c is an integer equal to 0 or 1, where the sum of (a + b) + c times the valence or R2 is equal to 3.
(A) an organic material which is polymerizable to a stats of higher molecular weight under the influence of a cationic catalyst, and (B) an effective amount of a photodecomposable aromatic sulfonium salt capable of effecting the cationic polymerization of (A) when exposed to radiant energy, where said photodecomposable aromatic sulfonium salt has the formula:
{ (R)a(R1)b(R2)CS }+X-where R is a monovalent aromatic organic radical, R- is an alkyl or substituted alkyl radical; R2 is a polyvalent organic radical forming a heterocyclic ring structure or a fused ring structure selected from aliphatic radicals and aromatic radicals; X- is BF4-, PF6-, AsF6- or SbF6-; a is an integer equal to 0 to 3 inclusive, b is an integer equal to 0 to 2 inclusive, c is an integer equal to 0 or 1, where the sum of (a + b) + c times the valence or R2 is equal to 3.
79. A photopolymerizable composition comprising at least one acid-polymerizable or acid-curable material other than a polycarboxylic acid anhydride and as photo-sensitizer at least one salt of the formula wherein X- is BF4-, PF6-, AsF6- or CbF6- and R1, R2 and R3, where are the same or different, are alkyl, cycloalkyl, aryl, alkaryl, aralkyl or heterocyclic groups or substituted derivatives thereof, provided that at least one of the R1, R2 and R3 groups is an aryl, alkaryl or aralkyl group, or two of the groups R1, R2 and R3 together are an alkylene group and witn the element A form a heterocyclic structure, the other group being an aryl or substituted aryl group.
80. An aromatic sulfonium complex salt [ (R)a (R1)b (R2)c S ]+X-where R is a monovalent aromatic organic radical; R1 is an alkyl or substituted alkyl radical; R2 is a polyvalent organic radical forming a heterocyclic ring structure or a fused ring structure selected from aliphatic radicals and aromatic radicals; X- is PF6-, AsF6- or SbF6-; a is an integer equal to 0 to 3 inclusive; b is an integer equal to 0 to 2 inclusive, c is an integer equal to 0 or 1, where the sum of (a + b) + c times the valence of R2 is equal to 3.
81. A photopolymerizable composition in accordance with claim 57, wherein said organic material comprises glycidal ether of the formula where R' is alkyl or aryl and n is an integer of 1 to 5.
82. A method for effecting the cationic polymerization of epoxy resin which comprises, (1) forming a mixture consisting essentially of the epoxy resin and from 0.1 to 15% by weight of a radiation sensitive aromatic onium salt of a Group VIa element having the formula, [ (R)a (R1)b (R2)c X ]+ [MQe]-(e-f), where R is a monovalent aromatic organic radical, R1 is a monovalent organic aliphatic radical selected from alkyl, cycloalkyl and substituted alkyl, R2 is a polyvalent organic radical forming a heterocyclic ox fused ring structure selected from aliphatic radicals and aromatic radicals, X is a Group VIa element selected from sulfur, selenium and tellurium, M is a metal or metalloic, Q is a halogen radical, a is a whole number equal to 0 to 3 inclusive, b is a whole number equal to 0 to 2 inclusive, c is a whole number equal to 0 or 1, where the sum of a + b + c is a value equal to 3 or the valence of X, d=e-f, f=valence of M and is an integer equal to from 2 to 7 inclusive, e is > f and is an integer having a value up to 8, (2) exposing said mixture to radiant energy to effect the cure of the epoxy resin.
83. A method in accordance with claim 82, using ultraviolet light to effect the cure.
84. A method in accordance with claim 82, using electron beam to effect the cure.
85. A method in accordance with claim 82, where the mixture is applied to a substrate prior to cure.
86. A method in accordance with claim 82, wherein the cured epoxy resin is subsequently heat treated.
87. A method in accordance with claim 85, where the mixture is applied to the substrate by the use of an organic solvent.
88. A method in accordance with claim 85, where a smask is employed to generate a photo image.
89. The photopolymerizable composition as claimed in claim 36 wherein the acid-curable material is selected from a phenol/formaldehyde, a urea/formaldehyde or a melamine/formal-dehyde condensate.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US46637474A | 1974-05-02 | 1974-05-02 | |
| US46637374A | 1974-05-02 | 1974-05-02 | |
| US466,374 | 1974-05-02 | ||
| US466,373 | 1974-05-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1283421C true CA1283421C (en) | 1991-04-23 |
Family
ID=27041630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000226108A Expired - Fee Related CA1283421C (en) | 1974-05-02 | 1975-05-02 | Photocurable polymeric compositions containing group via aromatic onium salt |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1283421C (en) |
-
1975
- 1975-05-02 CA CA000226108A patent/CA1283421C/en not_active Expired - Fee Related
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