UV-Curable epoxy silicones.

Background of the Invention

0001This invention relates to epoxy-functional organopolysiloxanes. More particularly, this invention relates to blends of epoxy-functional organopolysiloxanes and their use as conformal coatings, optical fiber coatings, and electrical encapsulation.

0002Silicone compositions have become widely accepted as protective coatings for electronic components mounted on circuit boards. The moisture resistance, thermal stability and resistivity of silicones make them ideal for this purpose. The cure chemistry of radiation curable silicones is most often free-radical in nature, requiring a high flux of radicals generated by UV light radiation of photoinitiators.

0003A drawback to free-radical crosslinking processes is that such processes are subject to inhibition by atmospheric oxygen. The "oxygen effect" is particularly troublesome in oxygen-permeable silicone systems. Prompt cure response, therefore, is dependent on either efficient nitrogen blanketing to forestall oxygen cure inhibition or the use of amine-benzophenone-type synergist catalyst systems to overcome the oxygen effect.

0004Production ultraviolet facilities are not easily nor economically inerted, particularly if wide web converting or high speed processing is practiced. Furthermore, amine-benzophenone-type synergist catalyst systems, which are useful for overcoming oxygen inhibition in organic acrylate UV cure resins, are usually incompatible with dimethyl silicone polymers. Fast non-inerted UV cure is achievable by combining mercapto- and acrylated-silicones with certain photosensitizers, but such systems are meta-stable and subject to shelf-life and pot-life limitations.

0005Currently, UV-curable silicone coatings useful for conformal coatings, optical fiber coatings, and electrical encapsulation contain silicon-bonded mercapto-olefin or acrylate radicals. Reference is made, for example, to U.S. Patent Nos. 4,558,082; 4,585,669; 4,587,137; 4,496,210; and 4,780,486.

0006However, the use of mercapto-olefins or acrylates has several drawbacks. For example, acrylates are toxic and both acrylate monomers and mercaptans give off highly offensive odors which can persist in the cured products, and because of precautionary/safety measures entailed by their use, they are not readily adapted to industrial applications.

0007It is desirable therefore to provide conformal coatings and coatings for optical fibers and electrical encapsulation which are made from UV-curable silicone compositions which do not contain mercapto-olefin or acrylate functionality and which do not cure in a free-radical based crosslinking process.

0008Cationic (non-radical) UV cure processes are not affected by oxygen and are therefore well suited for high speed silicone coating and curing processes. Cationic UV cure of silicones has been found to be most practical with epoxy-functional silicones.

0009It would be desirable, therefore, to provide conformal coatings and coatings for optical fibers and electrical encapsulation which are made from UV-curable epoxy-functional silicone compositions.

0010Epoxysilicone compositions containing epoxy-functionalized silicone polymers and silicone miscible iodonium photocatalysts are presently used as release coatings.

0011High speed solventless silicone release processing requirements dictate that UV-curable epoxysilicone release compositions be limited to unfilled, low molecular weight, highly organofunctionalized polymers whose cured films are therefore brittle, easily abraded, weak substances unsuited for other coating applications.

0012Conformal coatings are desired to be tough and have high tensile strength and high percents of elongation.

0013Accordingly, it was desirable to provide UV-curable epoxy-functional silicone coatings with improved film properties for use as conformal coatings and coatings for optical fibers and electrical encapsulation.

0014It was further desirable to provide epoxy-functional silicone coatings with improved film properties without using fillers. Fillers tend to block UV light which consequently slows down cure dramatically. Furthermore, it is difficult to incorporate fillers into low viscosity matrices such as epoxy-functional silicone polymers.

Summary of the Invention

0015Accordingly, it is an object of the present invention to provide UV-curable epoxy-functional silicone coatings which combine non-oxygen inhibited fast UV cure with improved film properties for use as conformal coatings and coatings for optical fibers and electrical encapsulation.

0016It is further object of the present invention to provide UV-curable epoxy-functional silicone coatings with improved film properties without using fillers.

0017These objects are achieved in the present invention.

0018The present invention provides an ultraviolet radiation-curable composition, comprising: <ul id="ul0001" list-style="none"><li>(A) a blend of epoxy-functional dialkylpolysiloxanes comprising by weight: <ul id="ul0002" list-style="none"><li>(a) about 5 to about 25 weight % of an epoxy-functional dialkylpolysiloxane having the general formula <chemistry id="chem0001" num="0001"><img file="EP0449027A2_D0001.tif" /></chemistry> wherein x is a value in the range of about 200 to about 550;</li><li>(b) about 10 to about 30 weight % of an epoxy-functional dialkylpolysiloxane having the general formula: <chemistry id="chem0002" num="0002"><img file="EP0449027A2_D0002.tif" /></chemistry> or an epoxy-functional dialkylpolysiloxane having the general formula: <chemistry id="chem0003" num="0003"><img file="EP0449027A2_D0003.tif" /></chemistry> or a mixture of the foregoing, wherein y is a value in the range of about 3 to about 5, and y¹ is a value in the range of about 20 to about 100; and</li><li>(c) about 45 to about 85 weight % of an epoxy-functional dialkylpolysiloxane having the general formula <chemistry id="chem0004" num="0004"><img file="EP0449027A2_D0004.tif" /></chemistry> wherein z is a value in the range of 75 to about 150; wherein E represents an epoxy-functional organic radical having from 2 to 20 carbon atoms and R is individually a lower alkyl radical having 1 to 8 carbon atoms, and</li></ul></li><li>(B) a catalytic amount of an onium salt photoinitiator or a combination of onium salt photoinitiators.</li></ul>

0019The composition provided by this invention has a tensile strength of at least about 40 pounds per square inch (psi) and an elongation of about 60%.

0020In other embodiments, the present invention provides a method for preparing the composition described above as well as articles coated with the composition.

Detailed Description of the Invention

0021For purposes of simplicity, the epoxy-functional silicones of parts (a), (b), and (c) in component A of the composition of this invention, will be referred to hereinafter as polymer (a), polymer (b), and polymer (c), respectively.

0022In general, conformal coatings should have a tensile strength of at least about 40 pounds per square inch (psi) and elongation of at least about 60%.

0023It was found that tensile strength and hardness generally increased as increased amounts of polymer (b) and decreased amounts of polymer (a) were used. On the other hand, % elongation was found to generally increase as increased amounts of polymer (a) and decreased amounts of polymer (b) were used. It was desirable to obtain a blend which would provide the optimal balance of tensile strength and elongation values.

0024It was found that a blend containing about 5 to about 25 weight % of polymer (a) about 10 to about 30 weight % of polymer (b), and about 45 to about 85 weight % of polymer (c), provided the tensile strength and elongation values mentioned above. In the preferred embodiment of this invention, component (A) contains about 5 to about 25 weight % of polymer a, about 15 to about 25 weight % of polymer (b),and about 55 to about 80 weight % of polymer (c), which provides a tensile strength in the range of about 55 to about 90 psi and an elongation of about 80 to about 125 %. In the preferred embodiment of this invention, component (A) contains about 10 to about 20 weight % of polymer (a), about 15 to about 20 weight % of polymer (b), and about 60 to about 80 weight % of polymer (c), which will provide a tensile strength of about 55 to about 75 psi and an elongation of about 100 to about 125 weight %.

0025In formulas (I) - (IV), R is a lower alkyl radical having 1 to about 8 carbon atoms, preferably methyl. E is an epoxy-functional organic radical having from 2 to 20 carbon atoms. Preferably, E is derived from 4-vinylcyclohexeneoxide and has the formula: <chemistry id="chem0005" num="0005"><img file="EP0449027A2_D0005.tif" /></chemistry>

0026In formula (I), x is about 200 to about 550, preferably about 250 to about 510, and most preferably about 350 to about 510. In formula (II), y is about 3 to about 5, preferably about 3 to about 4, and most preferably about 3; and y¹ is about 20 to about 100, preferably about 20 to about 50, and most preferably about 20 to about 30.

0027Polymers (a) and (c) are prepared in a two-step process wherein (1) an ethylenically unsaturated epoxy monomer is reacted in the presence of a platinum catalyst with a sym-tetraalkyldisiloxane to form a sym-1,3-epoxy-tetraalkyldisiloxane which is then (2) reacted with an octaalkylcyclotetrasiloxane in the presence of a tetraalkylammonium hydroxide to form a linear epoxy-stopped dialkylsiloxane having the general formulas (I) and (IV) above.

0028The desired number of repeating dialkyl siloxane units, i.e., x, in polymers (a) and (c) is obtained by using the proper molar ratio (n) of octaalkylcyclotetrasiloxane to epoxy-functional siloxane produced in step (1) of the process described above. In general, 1 mole of octaalkylcyclotetrasiloxane is required for every 4 units of dialkyl siloxane, i.e., x = 4. Thus, for example, in the preparation of polymer (a) having an x value of 400, 100 moles of octaalkylcyclotetrasiloxane are used per mole of the epoxy-functional siloxane produced in step (1). If x = 100 is desired, 25 moles of octaalkylcyclotetrasiloxane are used per mole of the epoxy-functional siloxane produced in step (1).

0029Polymer (c) is also prepared in a two-step process. In step (1), a trialkylchainstoppedpolydialkyl-alkyl hydrogen siloxane copolymer is reacted with a dialkylvinylchain-stopped linear polydialkylsiloxane in the presence of a platinum catalyst. In step (2), an ethylenically unsaturated epoxy monomer is reacted with the mixture prepared in step (1) to form polymer (c).

0030Suitable epoxy compounds for use in the processes described above include olefinic epoxy monomers such as limoneneoxide, 4-vinylcyclohexeneoxide, allylglycidylether, 7-epoxy-1-octene, vinylcyclohexenedioxide, bis(2,3-epoxycyclopentyl)ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, cresylglycidyl ether, butanedioldiglycidyl ether and the like. Because their cationic cure response is much faster than that of their glycidyl ether analogs, cycloaliphatic epoxides are preferred for use in the present invention. The preferred cycloaliphatic epoxide is 4-vinylcyclohexeneoxide.

0031The catalyst used in step (1) of the process above is a platinum metal catalyst effective for adding hydrogen to the double bond of the vinyl group. Ordinarily, approximately 5 parts platinum metal per million parts of siloxane will be effective to promote this hydrosilation reaction. Examples are those exemplified in U.S. patent Nos. 3,220,972; 3,814,730; 3,775,452; and 3,715,334, each of which is herein incorporated by reference. Particularly useful are those platinum catalysts derived from chloroplatinic acid which has been treated with tetramethyldivinyldisiloxane, as described in U.S. Patent No. 3,814,730 to Karstedt (hereinafter referred to as the "Karstedt catalyst."), which is incorporated by reference.

0032The amount of catalyst present in the composition of this invention is not critical, so long as proper polymerization is effected. As with any catalyst, it is preferable to use the smallest effective amount possible; for the purposes herein, catalyst levels of from about 0.014%-0.04% by weight have been found suitable.

0033Component B of the composition of this invention is an onium salt photoinitiator. Suitable photoinitiators are the onium salts having the formulae: <maths id="math0001" num=""><math display="inline"><mrow><msub><mrow><mtext>R₂I⁺MX</mtext></mrow><mrow><mtext>n</mtext></mrow></msub></mrow></math><img file="EP0449027A2_D0006.tif" /></maths><maths id="math0002" num=""><math display="inline"><mrow><msub><mrow><mtext>R₃S⁺MX</mtext></mrow><mrow><mtext>n</mtext></mrow></msub><mtext>-</mtext></mrow></math><img file="EP0449027A2_D0007.tif" /></maths><maths id="math0003" num=""><math display="inline"><mrow><msub><mrow><mtext>R₃Se⁺MX</mtext></mrow><mrow><mtext>n</mtext></mrow></msub><mtext>-</mtext></mrow></math><img file="EP0449027A2_D0008.tif" /></maths><maths id="math0004" num=""><math display="inline"><mrow><msub><mrow><mtext>R₄P⁺MX</mtext></mrow><mrow><mtext>n</mtext></mrow></msub><mtext>-</mtext></mrow></math><img file="EP0449027A2_D0009.tif" /></maths><maths id="math0005" num=""><math display="inline"><mrow><msub><mrow><mtext>R₄N⁺MX</mtext></mrow><mrow><mtext>n</mtext></mrow></msub><mtext>-</mtext></mrow></math><img file="EP0449027A2_D0010.tif" /></maths> where radicals represented by R can be the same or different organic radicals from 1 to 30 carbon atoms, including aromatic carbocyclic radicals of from 6 to 20 carbon atoms which can be substituted with from 1 to 4 monovalent radicals selected from C_(1-8) alkoxy, C_(1-8) alkyl, nitro, chloro, bromo, cyano, carboxy, mercapto, and the like, and also including aromatic heterocyclic radicals including, e.g., pyridyl, thiophenyl, pyranyl, and the like; and MX_n- is a non-basic, non-nucleophilic anion, such as BF₄-, PF₆-, AsF₆-, SbF₆-, SbCl₆-, HSO₄-, ClO₄-, and the like.

0034The preferred onium salts for use herein are the diaryliodonium salts and the bis-diaryl iodonium salts. Examples of suitable diaryliodonium salts are disclosed, for example, in U.S. patent No. 4,882,201, which is incorporated herein by reference. The most preferred of these salts is that having the formula <chemistry id="chem0006" num="0006"><img file="EP0449027A2_D0011.tif" /></chemistry>

0035Examples of suitable bis-diaryl iodonium salts include, for example, bis(dodecyl phenyl)iodonium hexafluoroarsenate, and bis(dodecyl phenyl) iodonium hexafluoroantimonate, are preferred. Most preferred of the bis-diaryl iodonium salts is bis(dodecyl phenyl) iodonium hexafluoroantimonate.

0036The amount of catalyst present in the composition of this invention is not critical, so long as proper polymerization is effected. As with any catalyst, it is preferable to use the smallest effective amount possible; for the purposes herein, catalyst levels of from about 0.5%-3% by weight have been found suitable.

0037The curable compositions are prepared merely by combining the various ingredients. The articles of the present invention are prepared by applying such composition to a substrate such as a circuit board if the composition is to be used as a conformal coating, thereafter exposing the coated substrate to ultraviolet radiation sufficient to set the composition, and finally allowing curing to be completed by exposing the article to either room temperature or elevated temperature.

0038In order that those skilled in the art might be better able to practice the present invention, the following examples are given by way of illustration and not by way of limitation.

Experimental

0039In the examples below, a shorthand system commonly used in the silicone industry will be used to abbreviate silicone structures. Chainstop siloxy units are designated "M", while siloxane units comprising linear polysiloxanes are referred to as "D". Superscripts refer to organic groups other than methyl while subscripts refer to linear polysiloxane chains. Examples of these designations include the following:         M = (CH₃)₃-SiO_1/2<chemistry id="chem0007" num="0007"><img file="EP0449027A2_D0012.tif" /></chemistry>         M^H = (CH₃)₂HSiO_1/2-         D = -(CH₃)₂SiO-

Examples 1-9

0040A series of epoxy-stopped dimethylsilicones were prepared having the formula <chemistry id="chem0008" num="0008"><img file="EP0449027A2_D0013.tif" /></chemistry> wherein the value of "x" varied in each example.

Example 1

X = 0

00416.05 moles of 4-vinylcyclohexeneoxide (VCHO, UCC) were dissolved in 1.5 kg hexane in a 5 liter flask. Sufficient Karstedt platinum catalyst was added to furnish 5 ppm Pt to the total reaction mixture. 3.0 moles of sym-tetramethyldisiloxane were then added dropwise, initiating an exothermic reaction which raised the temperature of the agitating mixture to 72° reflux. Following the addition, infrared spectra of the reaction mixture confirmed that no SiH remined. 1145g (3 moles) of the sym-1,3-epoxy-tetramethyldisiloxane product were isolated as a mobile fluid, N<maths id="math0006" num=""><math display="inline"><mrow><mfrac linethickness="0"><mrow><mtext>25</mtext></mrow><mrow><mtext>D </mtext></mrow></mfrac></mrow></math><img file="EP0449027A2_D0014.tif" /></maths> - 1.4726 vs. literature value of 1.4731.

Example 2

X = 2

0042382g (1 mole) of the sym-1,3-epoxy-tetramethyldisiloxane product formed in Example 1 above and 148g (0.5 moles) of octamethylcyclotetrasiloxane and 0.7g tetramethylammonium hydroxide (as a 20% solution in methanol) were agitated at 80°C for 5 hours under nitrogen until equilibration was complete by GC analysis. The reaction was heated to 160°C with a vigorous nitrogen sparge to decompose the catalyst and remove cyclic siloxane light ends. Devolatilization was considered complete when GC analysis revealed 0.25 weight% non-epoxy-functionalized silicones present.

Example 3

X = 4

0043The procedure of Example 2 was followed except that 296g (1 mole) of octamethylcyclotetrasiloxane were used.

Example 4

X = 8

0044The procedure of Example 2 was followed except that 592g (2 moles) of octamethylcyclotetrasiloxane were used.

Example 5

X = 14

0045The procedure of Example 2 was followed except that 1036g (3.5 moles) of octamethylcyclotetrasiloxane were used.

Example 6

X = 18

0046The procedure of Example 2 was followed except that 1332g (4.5 moles) of octamethylcyclotetrasiloxane were used.

Example 7

X = 50

0047The procedure of Example 2 was followed except that 3700g (12.5 moles) of octamethylcyclotetrasiloxane were used.

Example 8

X = 100

0048The procedure of Example 2 was followed except that 7400g (25 moles) of octamethylcyclotetrasiloxane were used.

Example 9

X = 400

0049The procedure of Example 2 was followed except that 29,600g (100 moles) of octamethylcyclotetrasiloxane were used.

0050The important physical properties of the silicones formed in Examples 1-9 are shown in Table 1 below. <tables id="tabl0001" num="0001"><img file="EP0449027A2_D0015.tif" /></tables>

0051Two sets of experiments were conducted with the M^ED_XM^E compositions prepared in Examples 1-9.

UV Cure Efficiency

0052UV Cure efficiency was assessed by blending 0.5 wt. % photocatalyst I and II with the sample, manually coating 2 mil thick films onto polyethylene kraft paper (PEK) substrate, then determining minimum UV flux required to convert the film to a smear-, migration-, tack-free 2 mil thick coating either in the RPC UV Processor or with the Portacure device. UV flux was measured with an International Light Photometer equipped with an A309 Lightbur accessory. The 2 mil cure results are noted in Table 2. <tables id="tabl0002" num="0002"><img file="EP0449027A2_D0016.tif" /></tables>

0053Low molecular weight members of the series display very fast UV cure response, but as epoxy content decreases due to diminished reactivity and reduced solubility of polar iodonium catalysts in nonpolar silicone media. These results conform to expectations and are similar to UV cure speed results for acrylate analogs.

UV-Cured Film Properties

0054Physical property profiles of cured M^ED_XM^E films were then determined on thicker sections of the materials. 1.0 wt. % photocatalyst I was mixed with M^ED_XM samples until uniform solutions or suspensions were obtained. 12.5 to 15.0 grams of catalyzed epoxysilicones were weighed into shallow 12 cm diameter circular weighing pans, then allowed to sit undisturbed while air bubbles dissipated and the fluid leveled. Assuming 1.0 g/cc density, slabs were cured which were 40 to 50 mils thick. Less than 5 J/cm² total UV flux was required for through-cure of the samples, which were extricated from their molds, then briefly exposed on their undersides to eliminate any uncured spots. Tensile bars were cut per ASTM D412-83 and peak tensile strength and peak elongation measured on a Monsanto T-10 tensionmeter (1 inch gauge, 20 ipm pull). Imperfections and uneven thickness of the UV-cured sheets prevented their conforming to ASTM sample specifications, so these results do not meet ASTM standards. In addition, the low molecular weight members of the M^ED_XM^E series cured to such brittle slabs that tensile determinations are presumed to be invalid. <tables id="tabl0003" num="0003"><img file="EP0449027A2_D0017.tif" /></tables>

0055It was found that high tensile and elongation properties were not achieved with individual M^ED_XM^E polymers. Improvements in properties obtained by decreasing crosslink density are offset by loss of cure speed and catalyst compatibility which accompany molecular weight build.

0056Improved tensile and elongation properties were achieved by blending the more reactive, low molecular weight epoxy-stopped dimethylsiloxanes with their higher molecular homologs, as illustrated in Examples 19-54 below

Examples 19-25

Example 19

0057Epoxy-functional silicone polymers designated MD<maths id="math0007" num=""><math display="inline"><mrow><mfrac linethickness="0"><mrow><mtext>E</mtext></mrow><mrow><mtext>3</mtext></mrow></mfrac></mrow></math><img file="EP0449027A2_D0018.tif" /></maths>D₂₀M were prepared as follows: 720 grams of trimethyl chain stopped polydimethyl-methyl-hydrogen siloxane copolymer with a viscosity of 25 centipoise and 120 grams of dimethylvinyl chainstopped linear polydimethyl siloxane with a viscosity of 300 centipoise were mixed with 1.0 grams of platinum catalyst in a 2 liter flask. The mixture had a viscosity = 25 cstk. The temperature of this mixture was raised to 50°C and held for 2 hours, raising the viscosity to 60 cstk. Then 160 grams of 4-vinylcyclohexene oxide (VCHO) were added slowly to the above mixture while maintaining reaction temperature in the 50°C to 70°C range. Minimum addition time is two hours. After adding all the VCHO, the batch temperature was brought to 60°C. An analysis was then made for ppm hydrogen. When ppm is less than 40, it is necessary to strip batch at 160 ± 5°C under vacuum to remove volatiles.

Examples 20 - 26

0058Various blends of two of the silicone polymers prepared in Examples 8, 9, and 19 above were prepared as indicated in Table 4 below. The properties of these blends are also presented in Table 4. <tables id="tabl0004" num="0004"><img file="EP0449027A2_D0019.tif" /></tables>

Examples 27-52

0059Ternary blends of the polymers prepared in Examples 8, 9, and 19 were prepared in Examples 27-52, as indicated in Table 5 below. The properties of these blends are summarized in Table 5. <tables id="tabl0005" num="0005"><img file="EP0449027A2_D0020.tif" /></tables>

0060Incorporating higher levels of M^ED₁₀₀M^E and M^ED₄₀₀M^E into the blends yielded materials with higher elongation properties. Tensile properties also increased as the weight percent M^ED₁₀₀M^E in the blends increased. However, increasing the weight percent M^ED₄₀₀M^E in the blends caused tensile properties to decrease.