JPH0129511B2 - - Google Patents

Description

[Detailed description of the invention]

Reference is made to co-pending U.S. Patent Application No. 656,106 to Richard P. Eckberg, filed on the same date as this application and assigned to the assignee of the present invention. BACKGROUND OF THE INVENTION The present invention relates generally to compositions that can be cured by two different mechanisms, and more particularly to compositions that can be cured by both a free radical photoinitiated crosslinking reaction and a platinum catalyzed thermal hydrosilation reaction. It depends. Silicone compositions are becoming widely accepted as protective coatings for electronic components mounted on circuit boards. Silicones are ideal for this purpose because of their moisture resistance, thermal stability and resistance. Silicone-compatible coatings that have already been developed are thermosetting and provided in the form of solutions in organic solvents. However, safety and environmental concerns as well as high energy costs have led to the development of alternative technologies such as silicone compatible coatings that can be cured by ultraviolet radiation. Both heat-curable and UV-curable silicone compatible coatings have some drawbacks. The use of thermoset coatings risks damaging many fragile and heat sensitive electronic components. Therefore, the heat curing cycle becomes extremely long, and as a result, the productivity of the coated circuit board decreases. Radiation-curable silicone compatible coatings, on the other hand, allow faster processing speeds and avoid damage to electronic components, but the compatible coatings often do not fully cure due to the so-called "shadow effect." Simply put, this shadow effect occurs because elements mounted on a circuit board protrude from the surface of the board and create shadows, thus preventing effective curing.
Although one skilled in the art can largely overcome this shadow effect by using mirrors, there may be cracks and the like where ultraviolet light cannot easily penetrate and therefore the UV-curable composition cannot cure. In view of the above, it is highly desirable for those skilled in the art to obtain compositions that are both UV curable and thermally curable (either at room temperature or at elevated temperatures) in order to overcome the aforementioned drawbacks. Probably. It would also be desirable if such compositions could be utilized in other applications, such as as silicone release coatings. Platinum-catalyzed addition-curable silicone compositions are well known in the art. For example, Grenoble, U.S. Pat. By coating a flexible sheet material with a coating composition made from a platinum catalyst effective to Disclosed. Other variations of such techniques are Eckberg U.S. Pat.
Disclosed in the issue. Both of these patents are assigned to the assignee of the present invention and are incorporated by reference into this disclosure. U.S. Pat. No. 3,865,588 to Ohto et al. discloses photopolymerizable compositions containing at least one organopolysiloxane having unsaturated groups of the formula: Here, R ¹ is a hydrogen atom, a phenyl group, or a phenyl group substituted with a halogen, and R ² is a hydrogen atom or a methyl group. Examples of such radicals are acryloxy, methacryloxy, cinnamoyloxy or halogenated cinnamoyloxy. U.S. Patent No. 3726710 to Berger et al.
No. 1, No. 1, No. 1, No. 1, No. 1, No. 2003, No. 1, No. 1, No. 1, No. 1, No. 1, No. 2003, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, 2003, 2, 3, 3, 4, 6, 6, 6, 6, 9, 7, 8, 9, 9, 9, 9, 10, 10, and 11, 11, 10, 10, 10, 10, 10, 1s, and 1s 1s to disclose compositions consisting of polyorganosiloxanes containing vinyl groups and sensitizers, which can be cured by exposure to high-intensity ultraviolet light. Hatanaka et al. U.S. Patent No.
A silicone elastomer composition suitable for ultraviolet curing disclosed in No. 4451634 includes (A) 100 parts by weight of a polyorganosiloxane of the following general formula: (CH ₃ ) ₂ R ¹ SiO—(R ² ₂ SiO—) _o SiR ¹ (CH ₃ ) ₂ (wherein R ¹ represents hydrogen or a monovalent group selected from methyl, vinyl and hydroxy; R ² represents hydrogen or a substituted or unsubstituted monovalent hydrocarbon group; , for the total number of groups R ¹ and R ²
0.02 to 49.95% are vinyl groups, 0.05 to 49.98% to the total number of groups R ¹ and R ² are hydrogen, n is 10
~10000), (B) 0.5 to 10 parts by weight of a polyorganosiloxane having the following formula: (where R ³ is a substituted or unsubstituted monovalent hydrocarbon group other than vinyl, and a is on average 0.01
a1, b represents the average number of 0b3, a+b is a number from 1 to 3), and (C) 0.1 to 10 parts by weight of a peroxyester of the following formula: (wherein R ⁴ is a substituted or unsubstituted monovalent aliphatic group and R ⁵ is a substituted or unsubstituted monovalent aromatic group). The ultraviolet curable composition disclosed in Eckberg et al., U.S. Pat. 'SiO (However, R is hydrogen or C _1-8 alkyl group, R' is hydrogen, C _1-8
an alkyl group or a monovalent mercaptoalkoxyalkyl functional organic group of 2 to 20 carbon atoms)
Diorganopolysiloxane consisting of units of (B) formula (CH ₂ = CH) R _o SiO _(3-o) /2 (wherein R is hydrogen or a C _1-8 alkyl group, and n is 0 to 2 vinyl-functional siloxane units with a value of 0.5 to 100
(C) a catalytic amount of a photoinitiator. However, to the best of the applicant's knowledge, it cures both by free radical-catalyzed UV hydrosilation reactions and by platinum-catalyzed hydrosilation reactions, thus eliminating the drawbacks of compositions that cure by only one of the aforementioned mechanisms. Silicone compositions to avoid are nowhere disclosed or suggested. SUMMARY OF THE INVENTION One object of the present invention is to provide a composition that is curable by both a free radical photoinitiated crosslinking reaction and a noble metal catalyzed hydrosilation reaction. Another object of the present invention is to provide an article having the above composition cured on a circuit board or the like. Another object of the invention is to provide a method for making the compositions and articles described above. The curable composition provided according to a preferred embodiment of the present invention consists of the following (A) to (F). (A) A polysiloxane having the following general formula: where each R is independently selected and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ¹ is hydrogen, a hydroxyl group, or a hydrogen group having 1 to 20 carbon atoms. is a substituted or unsubstituted, saturated or unsaturated hydrocarbon or hydrocarbon oxy group, A is an acrylate group having the following general formula, (However, R ² and R ³ are each independently hydrogen or a substituted or unsubstituted hydrocarbon group, and R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms), x is an acrylate Contains siloxy units approximately 0.1
~50 mole percent, y is a number such that from approximately 0 to about 50 mole percent hydrogen-containing siloxy units are present, and x + y + z is such that the viscosity of the polysiloxane is 25
The number is about 25 centipoise to about 2,500,000 centipoise in degrees Celsius. (B) Free radical type photoinitiator. (C) Hydrosilation catalysts of or containing precious metals. (D) Organohydrogenpolysiloxane when y equals 0. (E) Optionally an olefin-containing polysiloxane. (F) Optionally, a hydrosilation inhibitor. Most preferably, the polysiloxane of formula () contains up to about 20 mole percent alkenyl-containing siloxy units. This is because the addition of SiH to the acrylate group of formula () catalyzed by a noble metal results in the addition of SiH to an alkenyl group (such as vinyl or allyl).
This is because it is very slow compared to addition. Therefore, rapid thermal curing is ensured by incorporating alkenyl groups into the system, either as part of the polysiloxane of formula () or as a separate component (E). Therefore, those skilled in the art will appreciate that the siloxane of formula () preferably has the structure of the following general formula. where R, ^{R 1} , A, It is a number that exists up to %. Of course, those skilled in the art will appreciate that there are many variations available to provide silicon-bonded acrylate, hydrogen and alkenyl groups. DESCRIPTION OF THE INVENTION Broadly speaking, the present invention provides that both a radical-type photoinitiator or photocatalyst and a noble metal or noble metal-containing hydrosilation catalyst are combined with a silicon-bonded hydrogen atom and a silicon-bonded acrylate group of the general formula: including adding it to a curable composition comprising: Here, R ² and R ³ are each independently hydrogen or a substituted or unsubstituted hydrocarbon group (preferably methyl), and R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms. be. The silicon-bonded hydrogen atoms and silicon-bonded acrylate groups can be on the same or different polysiloxane chains. What is essential for the present invention is that the presence of a photocatalyst causes silicon-bonded hydrogen atoms and silicon-bonded acrylate groups to crosslink when exposed to ultraviolet light, and that the presence of a noble metal catalyst or noble metal-containing catalyst causes crosslinking between silicon-bonded hydrogen atoms and silicon-bonded acrylate groups. In other words, a silicon-bonded hydrogen atom and a silicon-bonded acrylate group or a silicon-bonded alkenyl group form a crosslink at room temperature or high temperature. In one preferred embodiment of the present invention, a curable composition consisting of the following (A) to (F) is obtained. (A) A polysiloxane having the following general formula: Here, each R is independently selected,
A substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ¹ is hydrogen, a hydroxy group, or a substituted or unsubstituted hydrocarbon or hydrocarbon oxy group having 1 to 20 carbon atoms. and A is an acrylate group having the following general formula: (However, R ² and R ³ are each independently hydrogen or a substituted or unsubstituted hydrocarbon group, and R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms), x is Acrylate containing siloxy unit is approximately 0.1
~50 mole percent, and y is approximately 0 to approximately 50 hydrogen-containing siloxy units.
x+y+z is the number such that the polysiloxane has a viscosity of 25
The number is about 25 centipoise to about 2,500,000 centipoise in degrees Celsius. (B) Free radical type photoinitiator. (C) Noble metal or noble metal-containing hydrosilation catalyst. (D) Optionally, an organohydrogen polysiloxane. (E) Optionally, olefin-containing polysiloxanes. (F) Optionally, hydrosilation inhibitors. In even more preferred embodiments, the curable compositions of the present invention contain up to about 20 mole percent alkenyl-containing siloxy units. Such alkenyl-containing siloxy units (vinyl is preferred) are included because noble metal-catalyzed SiH addition to acrylate groups of formula () is slow compared to SiH addition to alkenyl groups such as vinyl or allyl. is preferable. Thus, the inclusion of alkenyl groups ensures faster thermal curing of the composition. Therefore, those skilled in the art will appreciate that the siloxane of formula () preferably has the structure: where R, ^{R 1} , A, It is a number that will exist up to %. Of course, it is within the contemplation of this invention to include such alkenyl groups in other polysiloxanes. Note that for the purposes of this invention the term "hydrogen-containing siloxy unit" means that the hydrogen is bonded directly to the silicon. The polysiloxane (A) of the present invention is represented by the above formula (). In the formula (), the group R has 1 to 1 carbon atom
Any of the 20 substituted or unsubstituted hydrocarbon groups, for example alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl and decyl, alkenyl groups such as vinyl and allyl, cyclohexyl and Cycloalkyl groups such as cycloheptyl, aryl groups such as phenyl, aralkyl groups such as β-phenylethyl, as well as halogens such as fluorine, chlorine or bromine, in which some or all of the hydrogen atoms of these groups are Any group substituted with an atom, a cyanoethyl group, or a 3,3,3-trifluoropropyl group. From the standpoint of availability and ease of synthesis, it is preferred that almost all R groups be methyl or methyl and phenyl. In another preferred embodiment, substantially all R groups are selected from the group consisting of methyl, vinyl and phenyl. The group R ¹ may be any of the R groups mentioned above, and may also be a hydrogen atom, a hydroxy group or a hydrocarbonoxy group having 1 to 20 carbon atoms, such as methoxy, ethoxy or propoxy. Group A has the general formula: where R ² and R ³ are each independently selected from the group consisting of hydrogen and substituted or unsubstituted hydrocarbon groups, and R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms. . Examples of organic functional groups represented by A include acryloxy, methacryloxy, cinnamoyl and crotonate, as well as any other organic group that crosslinks in the presence of photo- or heat-generated free radicals and contains a C═C structure. Included. R ⁴ is preferably a divalent group having 2 to 5 carbon atoms, most preferably 3 carbon atoms. R ² and R ³ are each independently hydrogen or C1
-3 hydrocarbon group is preferred. It is not necessary for the polysiloxane (A) to contain a silicon-bonded hydrogen atom and a silicon-bonded acrylate group in the same molecule. However, when y in formula () is zero, it is necessary to provide the silicon-bonded hydrogen atom in the form of a separate organohydrogen polysiloxane, as explained in more detail below. The number of acrylate-containing siloxy units is usually from about 0.1 to about 50 mole percent, based on the total number of siloxy units in polysiloxane (A). The number of hydrogen-containing siloxy units must be sufficient to react with substantially all of the acrylate-containing siloxy units and/or substantially all of the alkenyl groups attached to the siloxane. Generally, the hydrogen-containing siloxy units are about 0.1 to 50 mole percent based on the total number of siloxy units in polysiloxane (A). One skilled in the art will be able to adjust the number of hydrogen-containing siloxy units and acrylate or alkenyl-containing siloxy units to obtain a cured composition with predetermined properties. It will be understood by those skilled in the art that the value of x in formula () may be zero, provided that in that case R ¹ is an acrylate group of formula (). It is also possible to use mixtures of polymers, for example those having hydrogen only on the polymer chain and acrylate groups at the end. Similarly, mixtures can be used in which hydrogen is present only at the ends and acrylate groups are present only on the polymer chain. Other variations will be apparent to those skilled in the art. As already mentioned, the value of y in formula () can be zero, but the silicon-bonded hydrogen atoms must be obtained from other sources. Preferred compositions when y=0 have w greater than zero such that the polymer of formula () contains acrylate and alkenyl functionality. However, it is to be understood that the practice of the present invention requires only the provision of a silicon-bonded hydrogen atom and a silicon-bonded acrylate group along with a free-radical photoinitiator and a noble metal or noble metal-containing hydrosilation catalyst. . If the number of silicon-bonded hydrogen atoms or acrylate groups is smaller than the above ranges, the adhesive ability of the cured composition will be reduced. If the number of each of these substituents is larger than the above-mentioned ranges, the heat resistance will be reduced or the curing rate will be inadequate. If the number of silicon-bonded hydrogen atoms and silicon-bonded acrylate groups is within the above-mentioned range, no bubbles will occur due to the formation of hydrogen gas when exposed to ultraviolet light, and the composition will be easily exposed to UV irradiation. After exposure, the coated article can be sufficiently hardened and placed anywhere to heat cure the coated article. Heat curing for the purposes of the application of the present invention involves raising the composition to a high temperature, or simply The number of diorganosiloxy groups present in the polysiloxane (A) is not critical and may range from 0 to about 99.8.
Any value of mol% may be used. Generally, the viscosity of polysiloxane (A) is about 25 centipoise to about 25 centipoise at 25°C.
There should be enough diorganosiloxy units to give 2.5 million centipoise. It is particularly preferred if some of the R groups of polysiloxane (A) are alkenyl groups such as vinyl. It has been found that optimal results are obtained when the number of vinyl-containing siloxy units is from about 1 to about 10 mole percent, based on the number of siloxy units in polysiloxane (A). In addition to the bifunctional units exemplified in formula (),
It will be understood by those skilled in the art that trifunctional siloxy units of RSiO _1.5 (R as previously defined) and/or tetrafunctional siloxy units of formula SiO ₂ may be present. The number of such units used, if any, will depend on the particular application contemplated and will be readily determined by one skilled in the art without experimentation. In one preferred embodiment of the invention, about 2 to about 20 mole percent acrylate-containing siloxy units, about 2 to about 20 mole percent hydrogen-containing siloxy units, and about 2 to about 10 mole percent vinyl-containing siloxy units are present. , the viscosity of the polysiloxane (A) is from about 100 centipoise to about 5000 centipoise at 25°C. Free radial photoinitiators or photocatalysts are well known in the industry. The photoinitiator (B) of the present invention is any known silicone-compatible compound that is effective for inducing crosslinking between silicon-bonded hydrogen atoms and unsaturated groups such as silicon-bonded acrylates and vinyl. A free radical type photoinitiator may be used. A particularly preferred photoinitiator for inducing cross-linking of unsaturated groups with SiH groups is U.S. Patent Application No. 527,299 to Eckberg et al., filed August 26, 1983 and assigned to the assignee of the present invention. Disclosed in the issue. The teachings of this patent application regarding the aforementioned photoinitiators are incorporated into this application by reference. In summary, Eckberg et al. have shown that the combination of certain perbenzoate esters with the general formula () with photosensitizers such as benzophenone
discloses photocatalyzing the addition reaction between SiH groups and unsaturated groups bonded to siloxy units: Here, R ⁵ is a monovalent alkyl or aryl group, and Z is hydrogen, alkyl, halogen, nitro, amino or amido. The nature of the substituent Z influences the stability of the peroxy bond. That is, electron-deficient substituents stabilize the peroxy bond, and electron-rich substituents increase the reactivity of the peroxy bond. These perbenzoic acid esters are
Reacting benzoyl halides with hydroperoxides (Blomquist and Berstein, J.Amer.Chem.
Soc.), vol. 73, p. 5546 (1951))
It can be synthesized by known methods such as. Preferred perbenzoate esters include t-butyl perbenzoate and its para-substituted derivatives, i.e. t-
Included are butyl per-p-nitrobenzoate, t-butyl per-p-methoxybenzoate, t-butyl per-p-methylbenzoate and t-butyl per-p-chlorobenzoate. The amount of photoinitiator used is not critical as long as proper crosslinking is achieved. Any amount greater than or equal to the smallest possible effective amount of any catalyst, ie, 1 part by weight per 100 parts by weight of polysiloxane (A), may be used. Generally, the amount of photoinitiator is preferably from 1 to about 10 parts by weight per 100 parts by weight of polysiloxane (A). Preferably, the photoinitiator concentration is from about 1 to about 5 parts by weight per 100 parts by weight of polysiloxane (A). Other photoinitiators are U.S. Pat. No. 3,759,807;
No. 3968305, No. 3966573, No. 4113592, No.
No. 4,131,529, No. 4,310,600 and No. 4,348,462, and one skilled in the art can easily determine whether it is appropriate for use in a particular situation. Diethoxyacetophenone is one example of a silicone soluble photoinitiator that is particularly useful for photocatalytic crosslinking of acryloxy-containing silicones. The teachings regarding photoinitiators of all of the above patents are incorporated herein by reference. Component (C) can be any noble metal or noble metal-containing catalyst effective to initiate a thermal hydrosilation curing reaction. In particular, all well-known platinum and rhodium catalysts useful for catalyzing addition reactions between silicon-bonded hydrogen atoms and silicon-bonded olefinic groups are included. Platinum or platinum-containing complexes are the most preferred noble metal catalysts, such as platinum metal supported on charcoal, the platinum-hydrocarbon complexes described in Ashby U.S. Pat. Nos. 3,159,601 and 3,159,662; Platinum-alcoholate catalysts as described in U.S. Pat. No. 3,220,970 to Lamoreaux, platinum complexes as described in U.S. Pat. No. 3,814,730 to Karstedt, and platinum chloride as described in U.S. Pat. No. 3,516,946 to Modic. -There is an olefin complex. All of the above US patents relating to platinum or platinum-containing catalysts are incorporated herein by reference. The most preferred catalyst for facilitating the thermal hydrosilation reaction is the Ashby catalyst described in US Pat. Nos. 3,159,601 and 3,159,662. Other platinum metal or platinum-containing catalysts that can be used in the present invention are well known to those skilled in the art. Hydrosilation catalysts other than those based on platinum can also be used to effect thermal curing. For example, complexes of metals such as rhodium, ruthenium, palladium, osmium and iridium can be utilized. Of the non-platinum based catalysts, those based on rhodium are most preferred. Preferred rhodium catalyst preparations and types are described in Eckberg, US Pat. No. 4,347,346, also incorporated herein by reference. As with the photoinitiator (B), the amount of noble metal or noble metal-containing catalyst (C) is not critical as long as proper crosslinking is achieved. Typically, the amount of noble metal or noble metal-containing catalyst is from about 10 to about 500 ppm as metal atoms based on polysiloxane (A). It may be desirable to use higher amounts of catalyst (C) when organohydrogen polysiloxanes (D) and vinyl-containing polysiloxanes (E) are optionally included. Of course, appropriate amounts of catalysts (B) and (C) can be determined by those skilled in the art without undue experimentation. It will also be understood by those skilled in the art that it is within the scope of the invention to use mixtures of various photocatalysts and noble metal or noble metal-containing catalysts. The organohydrogensiloxane (D) can be any of the fluids, resins, or mixtures thereof utilized by those skilled in the art as crosslinking agents in addition-curable silicone systems. Organohydrogenpolysiloxanes particularly useful in the practice of this invention have about 10% to 100% SiH groups with the remaining groups being dimethylsiloxy units and have about 10% SiH groups at 25°C.
A trimethyl-terminated polymethylhydrogen siloxane fluid having a viscosity in the range of ~1000 centipoise. However, any organohydrogenpolysiloxane having the following general formula is within the scope of this invention. Such organohydrogenpolysiloxanes are well known in the art, as described, for example, in US Pat. No. 3,344,111 and US Pat. No. 3,436,366, both of which are incorporated by reference. Groups included in R in formula () include alkyl such as methyl, ethyl and propyl, cycloalkyl such as cyclopentyl, cyclohexyl and cycloheptyl, aryl such as phenyl, naphthyl, tolyl and xylyl, phenylethyl and phenylethyl. aralkyl, such as enylpropyl, and substituted groups of the foregoing, such as halogen-substituted and cyanoalkyl-substituted versions. Other organohydrogenpolysiloxane fluids are well known in the industry and include Grenoble and Eckberg, U.S. Pat. No. 4,448,815;
No. (also incorporated herein by reference)
It is described in more detail. Organohydrogenpolysiloxane resins can be utilized in place of or in conjunction with organohydrogenpolysiloxane fluids. Such organohydrogenpolysiloxane resins are well known in the art, as described, for example, in Jeram, US Pat. No. 4,041,010, which is incorporated herein by reference. In summary, organohydrogen polysiloxane resins are

[Formula] units and SiO ₂ units (wherein the ratio of R+H units to SiO ₂ units ranges from 1.0 to 2.7, and R is as defined above), or

[Formula] Unit, R ₂ SiO unit and SiO ₂ unit (However, R + H unit pair
The ratio of SiO ₂ units ranges from 1.2 to 2.0 and R is as defined above). When organohydrogenpolysiloxanes are used, they can be used in any amount so as to obtain specific properties in the cured product. Generally, a range of from about 1.0 parts to about 10 parts by weight per 100 parts by weight of polysiloxane (A) should be used. One preferred embodiment uses a mixture of organohydrogenpolysiloxane fluid and organohydrogenpolysiloxane resin. Although no particular ratio of fluid to resin is required, it has been found that from about 0.1 parts to about 10 parts fluid per part resin, by weight, provides a composition suitable for use as a coating composition. Another optional component for the practice of this invention is an olefin-containing polydiorganosiloxane (E). Like the organohydrogenpolysiloxane (D), the olefin-containing polydiorganosiloxane (E) can be either a fluid or a resin, although mixtures thereof are preferred.
Most preferably component (E) is a vinyl-containing polydiorganosiloxane. A typical vinyl-containing polydiorganosiloxane fluid has the following formula: Here, R is as defined previously and R ⁵
is a group having alkenyl unsaturation, preferably vinyl, and a and b are positive integers such that the vinyl-terminated polysiloxane will have up to about 20% by weight R ⁵ groups. The viscosities of such polysiloxanes range from about 50 to about 100,000 centiboads at 25°C. These polysiloxane fluids are also described in Grenoble and Eckberg, US Pat. No. 4,448,813. Vinyl-containing silicone resins are also known in the art, as described, for example, in Jeram, US Pat. No. 4,041,010. Generally these resins have _0.5 units of ViR ₂ SiO and _{0.5 units of SiO 2} (but the ratio of hydrocarbon-substituted substrate Si is between 0.8 and 2.7) and _0.5 units of ViR ₂ SiO, R ₂ SiO units and SiO ₂ units. resin (however, the ratio of hydrocarbon substituents to Si is
0.8 to 2.4). More specific details regarding these resins and their manufacture can be found in the Jeram patent no.
Please refer to No. 4041010. Vinyl-containing polysiloxanes can be used in any amount in the present invention. As those skilled in the art will appreciate, placing the noble metal or precious metal-containing catalyst (C) in the same package as the polysiloxane (A)
If the polysiloxane (A) contained silicon-bonded hydrogen atoms, the product would gel or harden before reaching the consumer. Therefore, olefin-containing polysiloxanes are available on the market.
(E) mainly serves as a support for the noble metal catalyst (C). Thus, in one embodiment of the invention, the curable composition is provided in two or more packages. One package contains the alkenyl-containing polysiloxane, noble metal catalyst, and optional inhibitor, and another package contains the remaining ingredients. Such two package systems are well known in the industry. Particularly preferred multicomponent packaging systems are Grenoble and Eckberg.
No. 4,448,815. It is also contemplated that hydrosilation inhibitors (F) can be included in the compositions to extend the pot life of the compositions of the invention. One example of a suitable inhibitor is Eckberg, U.S. Pat.
No. 4,256,870, which teaches the use of organic esters of maleic acid to selectively inhibit thermal addition cure reactions. Eckberg U.S. Patent No.
No. 4,262,107 discloses olefinic carboxylic acid esters of aliphatic alcohols such as certain acetylenic compounds, vinyl acetate, alkenyl isocyanurates and mixtures thereof as other suitable inhibitor compounds. Eckberg U.S. Pat. It has been disclosed that blends of dicarboxylic esters with olefinic carboxylic esters of aliphatic alcohols are particularly effective as inhibitors. The Eckberg patents and patent applications cited above are each incorporated herein by reference. In another aspect of the present invention, methods of making the curable compositions of the present invention and articles having the cured compositions on their surfaces are provided. To prepare the curable composition of the present invention, simply
Concentrating the various ingredients or mixing packages containing the various ingredients. To make articles of the invention, the compositions of the invention may be applied to substrates such as circuit boards if the composition is intended to be used as a conformable coating, or to Mylar if it is to be used as a releasable coating. )
The composition is applied to a flexible sheet material, such as paper or paper, followed by exposing the coated substrate to sufficient ultraviolet light to harden the composition, and finally curing the article at room or elevated temperature. Of course, the higher the temperature, the faster complete curing will occur. The following examples are provided by way of illustration and not limitation to enable those skilled in the art to better practice the invention. All parts are by weight unless otherwise specified. Example 1 Dimethyldichlorosilane 155 in flask 1
g (1.2 mol) and 42 g (0.3 mol) of methylvinyldichlorosilane were added. These monomers were then hydrolyzed with 24 g (1.33 mol) of water dispersed in 33 g of acetone at 18-24 DEG C. for 75 minutes. The reaction mixture was maintained at 20°C for 40 min, then at 40°C for 40 min, and then stripped for 15 min at 105°C under 33 mm vacuum to produce a Cl-terminated linear copolymer.
107g was obtained. This linear chloro-terminated species was then treated with 114 g (0.47 mole) of methylmethacryloxypropyldichlorosilane, 53 g (0.36 mole) of methyltrichlorosilane, and 54 g of a linear dimethylpolysiloxane fluid terminated with 700 centiboad silanol. and hydrolyzed with 130 g of water in a 1:1 toluene:acetone reaction medium at 54-68°C. Thus 264 g of a clear 392 centipoise fluid (designated polysiloxane (A ¹ ))
was gotten. Analysis of the terminal groups revealed that the hydroxy functional group was 2.0% as OH. This fluid 150
g (approximately 0.18 moles of OH) is then mixed with 38.3 g (0.35 moles) of trimethylchlorosilane in excess water.
Hydrolyzed at ℃. Solvent and by-products (Me ₃ SiO _0.5 ) ₂
was removed under reduced pressure to obtain the final product (designated polysiloxane (A ² )). It has a viscosity of about 175 centipoise at 25°C and a hydroxy content of about
It was 0.12%. These polysiloxanes (e.g. A ¹ and A ² )
The UV curing ability of the material was evaluated. Its comparative properties are shown in Table 1.

[Table] Next, we investigated the thermal curing of the following blends. a Polysiloxane (A ² ) 100 parts + MD _X ^H M4 parts +
Pt-containing catalyst 100ppm (as Pt). b Polysiloxane (A ² ) 90 parts + MD _X ^H M 10 parts +
Pt-containing catalyst 100ppm (as Pt). c Polysiloxane (A ² ) 90 parts + MD _X ^H M 10 parts +
Pt-containing catalyst 50ppm (as Pt). The results of this thermosetting study are shown in the table.

[Table] Defined above.
Addition of 4% DEAP to blend (c) enabled UV curing comparable to polysiloxane (A ² ) despite the presence of 10% methylhydrogen polysiloxane crosslinker. Blend (c) was then applied in a 5 mil thick layer to a stainless steel Q panel and passed through a UV processor in a 400 watts per square inch lamp under a nitrogen atmosphere at 50 feet/minute. The shaded areas were observed to harden to a non-stick surface after standing in the dark at 25°C for 20 hours. The exposed area was sufficiently UV cured immediately after exposure. This example shows the most preferred embodiment of the invention. A preferred package for such a dual-cure composition comprises, in package A, a UV-curable polymer, a photoinitiator, and a noble metal or precious metal-containing catalyst;
Package B would contain an organohydrogenpolysiloxane crosslinker. A small amount of an inhibitor such as butyl allyl maleate or vinyl acetate may be included in package A. Example 2 In this example, 25 g of methylhydrogen polysiloxane fluid at 20 cps, 30 g of sym-tetramethyltetravinylcyclotetrasiloxane, and 445 g of octamethylcyclotetrasiloxane were heated with nitrogen using 5 g of Filtrol 20 acidic clay catalyst. Equilibration for 18.5 hours at 83°C yielded a 2000 centipoise fluid with the following general formula: _MD ^{_ _} _{_ _} ^{_ _} To the equilibrium mixture was added 100 g of a methacrylate-functional silane having the following formula along with 0.05 g of di-t-butylhydroquinone. The mixture was stirred at 83° C. for 1 hour and then filtered to remove the heterogeneous catalyst. The resulting fluid was a 70 centipoise fluid containing 3.22% by weight of hydrolyzable chloride as a chain terminator. Then fluid 100 stopped with this 70cps chloro
g was placed in a 500 ml flask with 50 g of toluene (Cl 0.0882 mol). While stirring this solution at 30° C., 1.56 g (0.0867 mol) of water dissolved in 20 g of acetone was slowly added over 10 minutes. The temperature was kept at 30-35°C for 30 minutes after the addition of water. then water
25 g was added to eliminate any remaining hydrolyzable chloride. Transfer the resulting mixture to a separatory funnel;
The aqueous layer was discarded and the organic layer was washed with 100 ml of 5% aqueous sodium bicarbonate solution. Stripping at 120°C and 15 mm vacuum yields a 700 centipoise fluid (designated polysiloxane (A ³ )) with the formula: 85
g was obtained. Here, the molecular weight is about 11000, and b is approximately c
, and c is approximately equal to 1/8a. A coating bath consisting of 10 parts of polymer, 2.5 parts of benzophenone and 4 parts of diethoxyacetophenone was prepared and the UV curing properties were determined. Cure testing was conducted on a PPG Model 1202QC processor with a focal total UV power of 400 watts per square inch. The results are shown in the table.

[Table] The hardened coating is Scotch.
The observation that the compositions of the present invention did not migrate to #610 cellophane tape suggested that the compositions of the present invention functioned as release coatings. Therefore, a coating bath was prepared as follows. That is, 10 g of the above polysiloxane (A ³ ), benzophenone
and 0.4 g of diethoxyacetophenone dispersed in 50 g of acetone and 5 g of hexane.
Add this mixture using a #8 wire-wound rod.
After coating the SCK, it was cured by exposure to 400 watts per square inch of UV radiation at a line speed of 100 feet per minute (fpm) under nitrogen. aggressive
After applying a 7 mil coat of SBR adhesive (Fasson SS-1) and curing on the silicone layer,
Top coated with another SCK layer. A 2 inch wide tape was made and the silicone layer was peeled from the adhesive layer at a 180° angle with a pull speed of 400 feet/minute. A force of 70 to 80 g was required to separate the laminate, indicating good peelability. Next, the thermosetting ability of polysiloxane (A ³ ) was tested. 9 g of polysiloxane (A ³ ) was combined with 1 g of 400 centipoise vinyl-terminated dimethylpolysiloxane and 300 ppm of platinum-containing hydrosilation catalyst (as platinum metal).
A clear fluid containing 30 ppm catalyst as Pt metal was obtained. The curing properties were evaluated at 150°C on an SCK substrate. The results are shown in the table.

[Table] Defined) It became a sex film.
The above illustrates that polysiloxane (A ³ ) can be combined with both UV and heat curing to overcome the "shadow effect" seen in prior art compositions that utilize only UV curing. . Additionally, in this example, the releasable coating was completely cured by heat curing.
It has also been shown that UV curing speed can be increased. Example 3 In this example, 850g of dimethyldichlorosilane
(6.6 mol), 92 g (0.8 mol) of methylhydrogen dichlorosilane
mole) and 86 g of methylvinyldichlorosilane
(0.6 mol) in 130 g of water dispersed in 180 g of acetone.
g (7.22 mol) of dispersion was added to the aqueous phase slowly over 150 minutes. The temperature was maintained at 16-26°C during this addition. Stripping the hydrolyzate at 100°C and 40 mm vacuum yields 6.04% by weight D ^H units and 0.4% by weight hydrolysable chloride (as HCl).
504 g of 120 centipoise fluid was produced.
Add 200g of this chloride-stopped fluid to acetone.
200 g of methylmethacryoxypropyldichlorosilane and 400 ml of toluene in a blend of
Combined with 200 g of dimethylpolysiloxane fluid terminated with 700 cps of silanol. Next, add this mixture to
The treatment was carried out by adding 300 ml of water dropwise over 75 minutes at 45-60°C. After hydrolysis, the product mixture was transferred to a separatory funnel, the aqueous layer was discarded, and the organic phase was dissolved in 5% _NaHCO3 solution at 300 mL.
Washed with ml. Stripping of the solvent and light products from the organic phase at 100° C. and 25 mm vacuum yielded 454 g of polysiloxane (A ⁴ ). 9.1 g of benzophenone and 18.2 g of diethoxyacetophenone were added to this polysiloxane (A ⁴ ). The final product is
It was a 160 centipoise fluid with 3.0% by weight D ^H units. It is convenient to prepare the Cl-D ^H -D ^Vi -D-Cl precursor fluid in situ and then simultaneously hydrolyze it with the acrylic functional silane in the same pot. This eliminates the need to isolate the hydrolytically unstable chloride terminated polydimethyl-methylhydrogen-methyl-vinylsiloxane intermediate. Polysiloxane (A ⁵ ) was prepared using in situ preparation of a chloride-terminated precursor as follows. i.e. dimethyldichlorosilane
136g (1.054mol), methylhydrogendichlorosilane
35 g (0.304 mol) and 21 g (0.149 mol) of methylvinyldichlorosilane were hydrolyzed by adding 23.3 g (1.29 mol) of water dispersed in 32.3 g of acetone at 18-25 DEG C. over 1 hour. Stripping this yielded 90 g of fluid containing 0.15% hydrolyzable chloride. This chloride-terminated polymer is then treated with toluene.
150 ml and acetone, 90 g of methylmethacryloxypropyldichlorosilane, 45 g of silanol-terminated dimethylpolysiloxane with a viscosity of approximately 700 cps, and 45 g of methyltrichlorosilane.
It was treated with g. This silane solution was then mixed with 125% water.
ml was added over 45 minutes at 45-58°C for hydrolysis.
The resulting polysiloxane (A ⁵ ) had a viscosity of approximately 470 cps and contained 4.05% D ^H units (yield 217
g). Adding benzophenone to polysiloxane (A ⁵ )
4.9g and 8.6g of diethoxyacetophenone were added. The third polymer (designated polysiloxane (A ⁶ )) allowed the reactants to yield 209 g of 130 cps of product with 5.8% D ^H units (Cl−DD ^H D ^Vi −
Cl fluid 85g, methyl methacryl dichlorosilane 85
The same procedure as for polysiloxane (A ⁶ ) was carried out except that 470 cps of silanol-terminated polydimethylsiloxane and 21 g of methyltrichlorosilane) were used. 2% by weight of benzophenone and 4% by weight of diethoxyacetophenone were added to polysiloxane (A ⁶ ). All three compositions based on polysiloxanes (A ⁴ ), (A ⁵ ) and (A ⁶ ) were completed part products for UV curing. The UV curing properties were qualitatively evaluated in the same manner as in Example 2. The results are shown in Table V.

【table】

【table】
arrive.
〃 〃 Air 10fpm
Hardening. It's a little dirty.
A catalyst mixture was then prepared as follows. i.e. dimethyl fluid stopped with dimethyl vinyl 95
400 cps of 5 parts of soft (MW~300000) dimethyl vinyl end-terminated dimethyl silicone gum
490 g of the blend was combined with enough platinum-containing catalyst to provide 300 ppm Pt metal. 11.8 g (2% by weight) of benzophenone was added to this mixture. This fluid consists of methacrylated polysiloxane (A ⁴ ),
It was proven that it is compatible with (A ⁵ ) and (A ⁶ ) and forms a transparent mixture. One part of this catalyst blend was blended with 9 parts each of polysiloxanes (A ⁴ ), (A ⁵ ), and (A ⁶ ) to verify thermal curing. Pt in each blend
There was 30ppm of catalyst as metal. Each experimental composition was applied to an SCK substrate at a thickness of 2 mils and placed in a forced air oven maintained at 150°C. The heat curing results are shown in the table.

TABLE Next, a "shadow effect" experiment was performed using a 9:1 blend of polysiloxane (A ⁵ ) and the catalyst mixture described above. After the 4 mil thick coating was applied to the stainless steel panel, a 1 inch L-shaped metal strip was placed across the coated panel in a 1 inch wide strip to effectively block UV radiation from hitting the composition. Blocked. The coating was exposed to 400 watts of focused UV radiation in a nitrogen atmosphere.
100 ft/min line speed exposure cures to a clean, glossy surface. The unexposed area was still damp after being removed from the UV processor, but it hardened to a non-viscous surface after 16 hours at 25°C in the dark. EXAMPLE 4 These dually curable acrylated (methacrylated) silicone polymers were subjected to high-acid reverse hydrolysis (high-acid reverse hydrolysis) as exemplified in some of the previous examples.
It can be produced in many other ways besides acid reverse hydrolyses. A dual cure composition designated A ⁷ was synthesized as follows. Methylmethacryloxypropyldichlorosilane 48g (0.2mol) + methylvinyldichlorosilane 7g (0.05mol) + dimethyldichlorosilane 208g
(1.75 mol) was dispersed in 300 c.c. of toluene, and then this silane solution was dissolved in 1000 g of water at a temperature of 25-40°C.
I added it slowly over time. The organic phase thus obtained by low-acid hydrolysis was stripped at 28 mm at 150°C to obtain a polysiloxane terminated with a low molecular weight silanol expressed as HO {DD ^Vi D ^MA }OH.
I got 95g. The silanol content was approximately 5% by weight as OH. Next, this hydrolysis product was dispersed in 300 g of toluene, heated under reflux (113°C), and 0.8 g of stannous octoate was added. After 10 minutes at 113℃
Approximately 0.6 ml of H ₂ O was produced, which was trapped and removed in a Claisen apparatus. The reaction mixture was cooled to 70 °C, 20 g (0.17 mol) of dimethylvinylchlorosilane was added, and then heated with H ₂ O50 at 70 °C.
Add cc dropwise to add silanol chain terminator to V ^Vi
Converted to chain terminator. The product was dissolved in 5% _NaHCO3
It was washed with an aqueous solution and isolated by stripping at 90°C and 15 mm vacuum. Finally M ^Vi {DD ^Vi D ^MA }
M ^Vi 98g Diethoxyacetophenone Photoinitiator 3.9
g and enough soluble platinum catalyst to give ~25 ppm Pt. The fully blended product was a clear 57 cps fluid. (Those skilled in the art will appreciate that the viscosity of this product can be controlled by monitoring the amount of water condensed during the tin octoate thickening step.) 2 mils of product A ⁷ coating in nitrogen
It is cured by exposure to focused UV light at a power of 400 watts/in2 at a line speed of 100 ft/min.
A clean, glossy surface was formed on the SCK substrate. After blending 100 parts of ^A7 with 4 parts of polymethylhydrogen fluid stopped with 25 cps of trimethylsiloxy and applying it to SCK paper at a thickness of 2 mils,
After 30 minutes of residence at 10°C, it cured to a clean, migration-free coating. This 100:
UV-curing ability of 4 blends is not blended
It could not be distinguished from the ^A7 product. The blended mixture was a clear fluid that solidified into a soft gel in 2 hours at 25°C. This Example ^A7 demonstrated that the invention is not limited to process mode and that the compositions illustrated in these examples fall within the scope of this application no matter how they are made.

Claims (1)

[Scope of Claims] 1. A curable composition containing a polymer having a silicon-bonded hydrogen atom and a polymer having a silicon-bonded acrylate group, the composition comprising at least one free radical type photoinitiator. and at least one noble metal or noble metal-containing hydrosilation catalyst for crosslinking the silicon-bonded hydrogen atom and the silicon-bonded acrylate group, and the photoinitiator comprises a silicon-bonded hydrogen atom and at least one noble metal-containing hydrosilation catalyst for crosslinking the silicon-bonded hydrogen atom and the silicon-bonded acrylate group. 1. A curable composition characterized in that the amount is 1 part by weight or more per 100 parts by weight of a polymer having a silicon-bonded acrylate group and a polymer having a silicon-bonded acrylate group. 2 (A) General formula: [wherein each R is an independently selected substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ¹ is hydrogen, a hydroxyl group, or a hydrogen group having 1 to 20 carbon atoms] is a substituted or unsubstituted hydrocarbon or hydrocarbonoxy group having the general formula: (wherein R ² and R ³ are each independently hydrogen or a substituted or unsubstituted monovalent hydrocarbon group, and R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms) is an acrylate group, x
has an acrylate containing siloxy unit of about 0.1 to about 50
y is a number such that 0 to about 50 mol % of hydrogen-containing siloxy units are present (provided that if y is 0, an organohydrogen polysiloxane is present), and x +
y+z is the viscosity of this polysiloxane at 25℃, approximately 25
centipoise to about 2,500,000 centipoise]; (B) 1 part by weight or more of a free radical type photoinitiator per 100 parts by weight of the polysiloxane; and (C) a noble metal or noble metal-containing hydrosilane. A curable composition comprising a silica catalyst. 3. The composition according to claim 2, wherein y is 0 and further contains an organohydrogen polysiloxane. 4. Composition according to claim 2, characterized in that almost all R groups are selected from the group consisting of methyl, vinyl and phenyl groups. 5 R ² and R ³ are each independently hydrogen and C1−
3 selected from the group consisting of monovalent hydrocarbon radicals, R ⁴
3. The composition according to claim 2, wherein is a C1-3 divalent hydrocarbon group. 6. The composition of claim 2, wherein up to about 20 mole percent of the R groups of the formula units are vinyl groups. 7 x is about 2 acrylate-containing siloxy units
~20 mole percent of the hydrogen-containing siloxy units are present, y is a number such that about 2 to about 20 mole percent of the hydrogen-containing siloxy units are present, and x+y+z is the polysiloxane.
3. The composition of claim 2, wherein the viscosity of (A) is from about 200 centipoise to about 5000 centipoise at 25<0>C. 8 The free radical type photoinitiator has the general formula: (wherein R ⁵ is a monovalent alkyl or aryl group, and Z is hydrogen, alkyl, halogen, nitro, amino or amido) The composition described in Section. 9 Free radical type photoinitiators are selected from t-butyl perbenzoate, t-butyl per-p-nitrobenzoate, t-butyl per-p-methoxybenzoate, t-butyl per-p-methylbenzoate and t-butyl per-p-chlorobenzoate. 9. A composition according to claim 8, characterized in that it is selected from the group consisting of: 10. The composition according to claim 9, wherein the free radical photoinitiator is t-butyl perbenzoate. 11. The free radical type photoinitiator further comprises a sensitizer which is an aromatic compound having at least one benzene ring at α-position with respect to a carbonyl group. Composition. 12. The composition according to claim 11, wherein the sensitizer is benzophenone. 13. Composition according to claim 1 or 2, characterized in that the noble metal or noble metal-containing hydrosilation catalyst is selected from the group consisting of platinum metal, platinum complexes, rhodium metal and rhodium complexes. 14 The free radical type photoinitiator is present in an amount of about 1 to about 10 parts by weight per 100 parts by weight of polysiloxane (A), and the noble metal or precious metal-containing catalyst is present in an amount of about 10 ppm to about
Composition according to claim 1 or 2, characterized in that it is present in an amount of 500 ppm. 15. The composition according to claim 2, further comprising an organohydrogen polysiloxane. 16. The composition of claim 2, further comprising a vinyl-containing polysiloxane. 17. The composition of claim 2, further comprising an organohydrogen polysiloxane and a vinyl-containing polysiloxane. 18. The composition according to any one of claims 2 to 17, further comprising an inhibitor. 19 (A) General formula: [wherein the R groups are almost all selected from the group consisting of methyl, vinyl and phenyl groups, R ¹
selected from the group consisting of a hydrogen atom, a hydroxyl group, a methyl group and a methoxy group, and A is of the general formula: (wherein R ² and R ³ are each independently selected from the group consisting of hydrogen and C _1-3 hydrocarbon groups, and R ⁴
is an acrylate group having C _1-3 divalent hydrocarbon group), R ⁵ is an olefinic unsaturated hydrocarbon group,
w is a number such that up to 20 mole percent of siloxy units having olefinically unsaturated hydrocarbon groups are present;
20 mole percent, y is a number such that the hydrogen-containing siloxy units are from 0 to about 20 mole percent, and w+x+y+z is the viscosity of the polysiloxane.
(B) 0.1 to 10 parts by weight of t-butyl perbenzoate per 100 parts by weight of polysiloxane (A); -butyl per-p-nitrobenzoate, t-butyl per-p-methoxybenzoate, t-butyl per-p-methylbenzoate, t-butyl per-p-chlorobenzoate, benzophenone, t-butylanthraquinone and diethoxyacetophenone a free radical type photoinitiator selected from (C) as platinum metal for polysiloxane (A);
A curable composition consisting of 10 ppm to 500 ppm of a platinum metal or platinum-containing hydrosilation catalyst, (D) an optional organohydrogen polysiloxane, (E) an optional vinyl-containing polydiorganosiloxane, and (F) an inhibitor. thing. 20 A method for producing a curable composition comprising a polymer having a silicon-bonded hydrogen atom and a polymer having a silicon-bonded acrylate group, wherein at least one free radical type photoinitiator and the silicon at least one noble metal or noble metal-containing hydrosilation catalyst for crosslinking bonded hydrogen atoms and said silicon-bonded acrylate groups, said photoinitiator being a polymer having silicon-bonded hydrogen atoms; and 1 part by weight or more per 100 parts by weight of the polymer having silicon-bonded acrylate groups. 21 The free radical type photoinitiator has the general formula: (wherein R ⁵ is a monovalent alkyl or aryl group, and Z is hydrogen, alkyl, halogen, nitro, amino or amido) Method. 22 The free radical type photoinitiator is selected from t-butyl perbenzoate, t-butyl per-p-nitrobenzoate, t-butyl per-p-methoxybenzoate, t-butyl per-p-methylbenzoate and t-butyl per-p-chlorobenzoate. 22. A method according to claim 21, characterized in that the method is selected from the group consisting of: 23. The method according to claim 22, characterized in that the free radical type photoinitiator is t-butyl perbenzoate. 24. The free radical type photoinitiator further comprises a sensitizer which is an aromatic compound having at least one benzene ring at the α-position relative to the carbonyl group. Method. 25. The method according to claim 24, wherein the sensitizer is benzophenone. 26. Process according to claim 20, characterized in that the noble metal or noble metal-containing hydrosilation catalyst is selected from the group consisting of platinum metal, platinum complexes, rhodium metal and rhodium complexes. 27 The free radical type photoinitiator is present in an amount of from about 1 to about 10 parts by weight per 100 parts by weight of polysiloxane (A), and the noble metal or precious metal-containing catalyst is present in an amount of from about 10 ppm to about 10 parts by weight as noble metal based on polysiloxane (A).
21. A method according to claim 20, characterized in that it is present in an amount of 500 ppm. 28 (a) 100 parts by weight of component A, and (b) 1 to 100 parts by weight of component B, where component A is (i) one or more polysiloxanes having silicon-bonded acrylate groups, and (ii) 100 parts by weight of polysiloxane. 1 part by weight or more of a free radical type photoinitiator, and (iii) a mixture of a noble metal or a hydrosilation catalyst containing a noble metal, wherein component B consists of an organohydrogen polysiloxane, and component A and component B are contained separately from each other. Manufactured products. 29 (a) 100 parts by weight of component A and (b) 1 to 100 parts by weight of component B, wherein component A comprises (i) one or more polysiloxanes having silicon-bonded acrylate groups and silicon-bonded hydrogen atoms, and (ii) ) Polysiloxane 100
Component B consists of a noble metal or noble metal-containing hydrosilation catalyst dispersed in a vinyl-containing polysiloxane, and component A and component B are separated from each other. Manufactured products containing it. 30. Claim 29, characterized in that component A is a mixture of a polysiloxane having silicon-bonded acrylate groups, a polysiloxane having silicon-bonded hydrogen atoms, and a free radical type photoinitiator. goods. 31 I (A) General formula: [wherein each R is an independently selected substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ¹ is hydrogen, a hydroxyl group, or a hydrogen group having 1 to 20 carbon atoms] is a substituted or unsubstituted hydrocarbon or hydrocarbonoxy group having the general formula: (wherein R ² and R ³ are each independently hydrogen or a substituted or unsubstituted monovalent hydrocarbon group,
R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms), and x is an acrylate group containing from about 0.1 to 10 acrylate-containing siloxy units.
y is a number such that about 50 mole % of the hydrogen-containing siloxy units are present (however, if y is 0, an organohydrogen polysiloxane is present), and x + y + z is The viscosity of this polysiloxane is 25℃
from about 25 centipoise to about 2,500,000 centipoise]; (B) 1 part by weight or more of a free radical type photoinitiator per 100 parts by weight of polysiloxane; and (C) a noble metal or noble metal-containing. mixing to form a curable composition comprising a hydrosilation catalyst, applying a coating of the curable composition to a substrate, exposing the coated substrate to a UV source to cure the coating on the substrate, and then A method of manufacturing a coated article comprising thermally curing said coating. 32. The method according to claim 31, wherein the substrate is paper. 33. The method according to claim 31, wherein the substrate is a circuit board. 34. The method according to claim 31, characterized in that thermosetting is carried out at room temperature. 35. The method according to claim 31, characterized in that thermosetting is carried out at a high temperature. 36 A catalyst composition comprising a mixture of a free radical photoinitiator and a noble metal or noble metal-containing hydrosilation catalyst. 37 The free radical type photoinitiator has the general formula: (wherein R ⁵ is a monovalent alkyl or aryl group and Z is hydrogen, alkyl, halogen, nitro, amino or amido) Composition. 38. The free radical type photoinitiator further comprises a sensitizer which is an aromatic compound having at least one benzene ring at the α-position with respect to the carbonyl group. Composition. 39. Claim 36 or 3, characterized in that the noble metal or noble metal-containing hydrosilation catalyst is selected from the group consisting of platinum metal, platinum complexes, rhodium metal and rhodium complexes.
Composition according to item 7. 40. A composition according to claim 36, characterized in that the composition is provided as two components.