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    • 专利摘要:
    The present invention relates to silicone formulations which can be cured rapidly into rigid elastomeric materials through exposure to UV radiation and also optionally through exposure to moisture. Cured products exhibit high resistance to flammability and combustibility.
    公开号:KR20020047050A
    申请号:KR1020017016099
    申请日:2000-09-08
    公开日:2002-06-21
    发明作者:베닝톤레스터디.
    申请人:유진 에프. 밀러；헨켈 록타이트 코오포레이션；
    IPC主号:
    专利说明:

    FLAME-RETARDANT UV AND UV / MOISTURE CURABLE SILICONE COMPOSITIONS
    [2] Brief description of related technology
    [3] Silicone rubber and liquid compositions exist in various forms characterized by their different curing chemistries, viscosities, polymer types and purity. These may be formulated in one-part or two-part systems, and certain silicone compositions may be designed to be curable by two or more mechanisms.
    [4] Among the means used to initiate curing, ie crosslinking of reactive silicones, are moisture-curing mechanisms, heat-curing mechanisms and photo-initiating curing mechanisms. These mechanisms are based on condensation reactions where water hydrolyzes any group on the silicon backbone, or addition reactions that can be initiated by energy forms such as electromagnetic radiation or heat. In some silicone compositions, a combination of these curing mechanisms may be used to achieve the desired result.
    [5] For example, the reactive polyorganosiloxane can be cured by heat in the presence of peroxides. Alternatively, these reactive siloxanes can also be cured by heat in the presence of metal hydrosilylation catalysts such as silicon hydride-containing (-SiH) compounds and organic-platinum catalysts.
    [6] UV curable silicones with methacrylate functional groups are known. For example, US Pat. No. 4,675,346 (Lin), the disclosure of which is expressly incorporated herein by reference, discloses a UV curable silicone comprising at least 50% of a specific type of silicone resin, at least 10% of fumed silica filler, and a photoinitiator. It relates to compositions, and cured compositions thereof.
    [7] Other known UV curable silicone compositions include British Patent No. 1,323,869 [compositions for plate making in printing consisting of organopolysiloxanes containing a (meth) acrylate functional group, a photosensitizer, and a solvent, which cure to a hard film]; U.S. Pat. Reported to be curable upon exposure to UV radiation); And British Patent 2,039,287 (compositions for protective coatings on paper made from the reaction of methacryloxypropyltrimethoxysilane and low molecular weight hydroxyl-terminated polyorganosiloxanes).
    [8] UV / moisture binary curing silicone compositions are also known. See US Pat. Nos. 4,528,081 (Nakos) and 4,699,802 (Nakos), each of which is incorporated herein by reference.
    [9] In some commercial applications of such silicone formulations, flammability and combustibility are of concern, especially when they are a problem for production or end users. As a result, typically only a portion of such silicone formulations have been used in this example.
    [10] In the past, to alleviate this anxiety, thermoset silicone compositions have been used where the molding properties of the composition itself and the electrical properties of the cured product are expected. Such thermosetting silicone compositions have provided resistance to flammability and combustibility through the addition of halogenated materials, fillers, organic-platinum materials, and benzotriazoles.
    [11] However, the use of halogenated materials to obtain their properties is undesirable because they can contaminate toxic and environmental issues, as well as the substrate on which the composition will be located.
    [12] Other methods of providing such heat-curable silicone compositions are also known. For example, European Patent Application Nos. 801 111, 808 874 and 808 875 each relate to liquid silicone rubber known to produce high flame retardant silicone rubber after curing. The composition is a polyorganosiloxane-based and contains a silica filler, aluminum hydroxide, benzotriazole, and platinum-3,5-dimethyl-1-hexyn-3-ol reaction mixture. The composition may further comprise zinc carbonate, polyorganohydrogensiloxane, and hydrosilylation reaction catalyst.
    [13] In addition, the Chemical Abstract citation to a recently issued Chinese patent document mentions flame retardant silicone rubber containing vinyl-siloxane rubber, benzotriazole, chloroplatinic acid, silica filler, and hydroxy silicone oil for dielectric coating of wires. .Chem. Abs. 128: 168854s (1998), cited in Chinese patent document CN 1,144,237. Vinyl-siloxane rubbers can usually be cured by a thermal mechanism.
    [14] However, for some commercial applications, thermoset silicones present disadvantages. These shortcomings include their limited effectiveness on heat-sensitive substrates and / or heat-sensitive electronic circuits. In addition, thermoset silicones generally cure more slowly than silicones that can be cured through other mechanisms such as uv curing. These drawbacks are thought to be a problem for device fabrication, otherwise this slow cure rate will degrade the manufacturing process. Therefore, the applicability of such thermoset silicones across a wide range of end-use applications will be limited.
    [15] Indeed, in these applications where UV curable silicone compositions would be desirable, it was not possible to use them simply because flame retardant materials have been used in thermosetting silicones to impart these properties in the past. That is, these filler materials will generally make the composition less permeable (often opaque) to light (and in the amounts required in EP '111,' 874 and '875 publications). Thus compositions containing such fillers cannot be cured properly by exposure to UV radiation. That is, at most a surface skin is formed, but hardening through the volume will not occur due to filler interference.
    [16] Moreover, in fact, the composition itself will exhibit poor flow characteristics due to the amount of filler used. And, upon curing, the composition may be brittle to reduce the integrity of the bond formed therefrom.
    [17] And, a Chemical Abstract citation to a recently issued Japanese patent document reportedly refers to a uv-curable polysiloxane coating composition having flame retardant capability. These silicone compositions contain a siloxane component, 2-hydroxy-2-methyl-1-phenylpropane and aluminum acetylacetonate. However, these compositions are believed to be unfilled and therefore may not have the strength required for the cured material in sealants or similar coating applications.
    [18] Thus, there is also a need for a UV curable silicone having resistance to flammability and combustibility.
    [19] Despite these demands, it is not until now believed that UV curable filled silicone compositions are made flammable and flame retardant.
    [20] Thus, in spite of state-of-the-art silicone technology for flame and combustion retardance, it would be desirable to be able to cure a flame retardant silicone composition by exposure to UV radiation. It would also be desirable to provide such compositions that have the ability to cure upon exposure to moisture and exhibit a commercially acceptable tack free time upon curing.
    [21] Summary of the Invention
    [22] The present invention relates to silicone formulations that can be quickly cured to a rigid elastomeric material through exposure to UV radiation and, optionally, exposure to moisture. Cured products exhibit high resistance to flammability and combustibility.
    [23] More specifically, the composition of the present invention includes:
    [24] (a) a silicone resin component comprising a reactive polyorganosiloxane having at least one functional group selected from (meth) acrylates, carboxylates, maleates, cinnamates and combinations thereof, and optionally an alkoxy or aryloxy functional group ;
    [25] (b) optionally, an inorganic filler component;
    [26] (c) photoinitiator components; And
    [27] (d) an amount of flame retardant component effective to enhance the resistance of the composition to flammability.
    [28] The flame retardant component can be selected from organometallic or silyl metal materials, alumina, precipitated silica, and combinations thereof.
    [29] The composition of the present invention may further comprise a triazole component and / or a reactive diluent component, examples of which are provided below.
    [30] The invention also provides methods of making the compositions of the invention, methods of using such compositions, and reaction products of such compositions.
    [31] The invention will be more readily understood by reading the following heading "Detailed Description of the Invention".
    [1] The present application relates to UV and UV / moisture binary curable silicone compositions exhibiting high resistance to flammability and combustibility, and silicone (polyorganosiloxane) rubber materials prepared therefrom.
    [32] The composition of the present invention is silicone-based and functionalized with at least one group selected from (meth) acrylates, carboxylates, maleates, cinnamates and combinations thereof. These groups make the silicone material sensitive to UV curing. In addition, in these examples where secondary moisture cure is preferred, the polymerizable component also includes at least one alkoxy or aryloxy functional group.
    [33] The term "(meth) acrylate" as used herein refers to a structure
    [34]
    [35] It is intended to represent a group of wherein R 1 is H or alkyl. Acrylate, methacrylate and acrylate groups are examples of such (meth) acrylate groups.
    [36] The terms "alkoxy group" and "aryloxy group" as used herein are intended to represent structures R 2 -O, wherein R 2 is alkyl or aryl, examples of which include methoxy, ethoxy and phenoxy. Include.
    [37] Representative silicones include those found within the scope of formula (I):
    [38]
    [39] Wherein R 1 , R 2 and R 3 may be the same or different and substituted or unsubstituted aryl, meso such as alkyl such as methyl, ethyl, haloalkyl such as 3,3,3-trifluoropropyl, benzyl or phenyl Organic groups including alkoxy or substituted or unsubstituted aryloxy such as oxy, ethoxy and phenoxy, and others such as vinyl, methacryloxypropyl, mercaptopropyl, hydrogen or benzoin groups; R 4 is H or C 1-5 alkyl; R 5 is alkylene, such as C 1-8 alkylene; And n is at least 80.
    [40] Preferably, R 1 and R 2 are alkyl groups such as methyl: R 3 is methyl; R 4 is methyl; And R 5 is propylene. At least one R 3 in the case of UV / moisture binary curable silicones is preferably methoxy.
    [41] The plurality of repeat units in the silicone of formula (I) should be at least about 80 to achieve the desired gel or elastic properties in the cured material. Although n does not have a theoretical limit, it should not exceed 1500, and if the repeating unit exceeds 1500, polymers are typically produced that can be difficult to process, apply and cure.
    [42] Reactive silicones in Formula 1 may be made from silanol-terminated silicones in Formula 2.
    [43] An optional component of the composition of the present invention is an inorganic filler component. When present, this component adds structural properties to the cured composition, as well as providing flow properties to the uncured composition. This component can often be reinforced silica, such as fumed silica, and can be untreated (hydrophilic) or treated to impart hydrophobicity to them. Virtually all reinforced fumed silica can be used.
    [44] When present, fumed silica should be used at levels up to about 50 weight percent, with a range of about 4 to at least about 10 weight percent being preferred. As long as the exact level of silica can vary depending on the characteristics of the particular silica and the desired properties of the composition and reaction products thereof, those skilled in the art should carefully consider the appropriate level of permeability of the compositions of the present invention so that UV curing occurs.
    [45] Preferred hydrophobic silicas include hexamethylenedisilazane-treated silica such as commercially available from Wacker-Chemie, Adrian, Michigan under the trade name of HDK-2000. Others include those available from Cabot Corporation under the trade name of CAB-O-SIL N70-TS or from Degussa Corporatioon under the trade name of AEROSIL R202. Still other silicas are those available from Degussa under the trade name of AEROSIL R805, and trialkoxyalkyl silane-treated silicas such as trimethoxyoctyl silane-treated silica; And 3-dimethyl dichlorosilane-treated silica available from Degussa under the trade names R972, R974 and R976.
    [46] The photoinitiator component can be any photoinitiator known in the art to cure acrylic functional groups, including benzoin and substituted benzoin (such as alkylester substituted benzoin), Michler's keton, diethoxyacetophenone ("DEAP Dialkoxyacetophenones such as "), benzophenones and substituted benzophenones, acetophenones and substituted acetophenones, and xanthones and substituted xanthones. Preferred photoinitiators are diethoxyacetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, diethoxyxanthone, chloro-thioxanthone, azo-bisisobutyronitrile, N-methyldiethanolamine benzo Phenones, and mixtures thereof. Visible photoinitiators include camphorquinone peroxyester initiators and non-fluorene-carboxylic acid peroxyesters.
    [47] Examples of commercially available photoinitiators include the trade names IGRACURE and DAROCUR under the name Ciba Speciallty Chemicals Corp., Tarrytown, New York, specifically IGRACURE 184 (1-hydroxycyclohexyl phenyl ketone), 907 (2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholino propane-1-one), 369 (2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1-butane On), 500 (combination of 1-hydroxy cyclohexylphenyl ketone and benzophenone), 651 (2,2-dimethoxy-2-phenyl acetophenone), 1700 (bis (2,6-dimethoxybenzoyl-2, Combination of 4-, 4-trimethyl pentyl) phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propane-1-one), and 819 [bis (2,4,6-trimethylbenzoyl) phenyl force Pinoxide] and DAROCUR 1173 (2-hydroxy-2-methyl-1-phenyl-1-propane) and 4265 (2,4,6-trimethylbenzoyldiphenyl-phosphineoxide and 2-hydroxy-2-methyl -1-phenyl-propan-1-one); And visible light [blue] photoinitiator, di-camphorquinone and IRGACURE 784DC (bis (η 5 -2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (1H-pyrrole) -1-yl) phenyl] titanium).
    [48] Particularly preferred photoinitiators include DEAP. In general, the amount of photoinitiator should range from about 0.1% to about 10% by weight, such as from about 2% to about 6% by weight. Photoinitiators can also be polymer bonded. Such photoinitiators are disclosed in US Pat. Nos. 4,477,326 and 4,587,276, each disclosure of which is incorporated herein by reference. Other free radical initiators can be used, such as peroxy initiators.
    [49] In these compositions that also have a moisture curing ability, the moisture curing catalyst should also be included in an amount effective to cure the composition. For example, about 0.1 to about 5 weight percent, such as about 0.25 to about 2.5 weight percent moisture cure catalyst, is preferred. Examples of such catalysts include organic compounds of titanium, tin, zirconium and of course combinations thereof. Tetraisopropoxy citanate and tetrabutoxy titanate are particularly preferred. See also US Pat. No. 4,111,890, the disclosure of which is expressly incorporated herein by reference.
    [50] The flame retardant component should be used in the composition in an amount effective to increase the resistance of the composition to flammability and combustibility.
    [51] Suitable components include complexes of various transition metals with organic ligands or siloxane ligands, assuming that the complex imparts flame retardancy to the composition in which it is used. Suitable transition metals include platinum, ruthenium, rhodium, palladium and the like. Substantially all organic ligands or siloxane lidands assist in retarding the flammability and combustibility of the cured silicone-based resin and, if the resulting complex is compatible with the remaining components in the composition in terms of phase separation, the complex with the transition metal Can be used for formation.
    [52] Commercially available materials suitable for use as flame retardant components include platinum-siloxane complexes commercially available from Bayer Corporation under the trade name BAYSILONE U catalyst Pt / L (CAS 73018-55-0).
    [53] Such organometallic or silyl metal components should be used in amounts ranging from 0.001 to about 1 weight percent, such as from about 0.01 to about 0.2 weight percent, to achieve the desired effect.
    [54] Other components suitable for use as flame retardant components include hydrated alumina, precipitated silica (such as those commercially available from Degussa Corporation under the trade name of AEROSIL), and combinations thereof.
    [55] Such other flame retardant components may be used in amounts up to about 50 weight percent, with about 20 to about 50 weight percent being particularly preferred to achieve the desired effect.
    [56] Another component that may be included in the composition of the present invention is the triazole component. The triazole component assists in the flame and combustion delay properties of the compositions of the present invention. Suitable triazoles include benzotriazoles and other functionalized benzotriazoles that can impart flame retardancy to the compositions in which they are used.
    [57] The triazole component may be included at a level ranging from about 0.0005 to about 1 weight percent, such as about 0.5 weight percent of the present compositions.
    [58] Moreover, another component that may be included in the composition of the present invention is a reactive diluent. In use, reactive diluents are believed to improve the surface stickiness of the silicone (polyorganosiloxane) rubber material prepared therefrom.
    [59] Examples of such reactive diluents include (meth) acrylate-terminated-dimethoxypropyldimethyl siloxane, and other well-known siloxane-based reactive diluents.
    [60] Other reactive diluents include (meth) acrylates as represented by H 2 C═CGCO 2 R 6 , wherein G is hydrogen, halogen or alkyl of 1 to about 4 carbon atoms, and R 6 is 1 to about 16 carbon sources And alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl or aryl groups, all of which may optionally be silane, silicone, oxygen, halogen, carbonyl, hydroxyl, ester, carbon Acids, ureas, urethanes, carbamates, amines, amides, sulfur, sulfonates, sulfones and the like, may be optionally substituted or blocked.
    [61] More specific (meth) acrylates particularly preferred for use as reactive diluents are bisphenol-A di, such as polyethyleneglycol di (meth) acrylate, ethoxylated bisphenol-A di (meth) acrylate ("EBIPA" or "EBIPMA"). (Meth) acrylate, and tetrahydrofuran (meth) acrylate and di (meth) acrylate, citronelyl acrylate and citronelyl methacrylate, hydroxypropyl (meth) acrylate, hexanediol di (meth ) Acrylate ("HDDA" or "HDDMA"), trimethylolpropane tri (meth) acrylate, tetrahydrodicyclopentadienyl (meth) acrylate, ethoxylated trimethylolpropane triacrylate ("ETTA"), Triethyleneglycol diacrylate and triethyleneglycol dimethacrylate ("TRIEGMA"), isobornyl acrylate and isobornyl methacrylate, and Acrylate esters corresponding to formula III:
    [62]
    [63] Wherein R 7 is hydrogen, alkyl of 1 to about 4 carbon atoms, hydroxyalkyl of 1 to about 4 carbon atoms or
    [64]
    [65] And R 8 may be selected from hydrogen, halogen, and alkyl of 1 to about 4 carbon atoms;
    [66] R 9 is hydrogen, hydroxy and
    [67]
    [68] M may be an integer of at least 1, for example 1 to about 8 or more, for example 1 to about 4;
    [69] n is an integer of at least 1, for example 1 to about 20 or more; And
    [70] v is 0 or 1;
    [71] Of course, combinations of these (meth) acrylates may also be used as reactive diluents.
    [72] When present, the reactive diluent may be used in an amount ranging from about 0.01 to about 30, such as from about 0.05 to about 10 weight percent.
    [73] The compositions of the present invention may also include other elements to alter the curing or non-curing properties as needed for special applications. For example, adhesion promoters such as (meth) acryloxypropyltrimethoxysilane, trialkyl- or triallyl-isocyanurate, glycidoxypropyl trimethoxysilane, vinyltrimethoxysilane, etc., are about 5% by weight. It may be included at the following levels. Another optional element is a non- (meth) acrylic silicone diluent or plasticizer at a level of up to 30 weight percent. Non- (meth) acrylic silicones include trimethylsilyl-terminated oils and silicone gums of 100-500 csp viscosity. Non (meth) acrylic silicones may include cocurable groups such as vinyl groups.
    [74] A preferred method of obtaining (meth) acrylated silicon is by reacting a mixture of triethylamine such as polymethyl siloxane and silanol-terminated silicone with dimethylchloro (meth) acryloxypropylsilane and then condensing the resulting aminosilane. To obtain dimethyl (meth) acryloxypropylsilyl-terminated silicone, such as dimethyl (meth) acryloxypropylsilyl-terminated polydimethylsiloxane.
    [75] The silicone oil used in the formulations of the present invention is trimethylsilyl-terminated polydimethylsiloxane having a viscosity of about 100 to 5,000 cps. These oils are used as plasticizers to control the texture and softness of the cured material and as diluents to adjust the final viscosity of the composition. Plastic silicone oils for electronic potting compositions in which gel-like materials are preferred should be present in the range of about 30 to 70 weight percent of the composition. Low amounts of silicone oil produce a composition that results in a soft rubber material. The amount of excess silicone oil of about 70% by weight produces a flowing material even after curing.
    [76] In electronic applications, ion trapping compounds such as crown ethers and cryptates may be useful for reducing ion conductivity, examples of which include 18-crown-6, 12-crown-4, and 15-crown-5. Include. See also US Pat. No. 4,271,425, which describes the use of crown ethers in conventional RTV silicone encapsulants.
    [77] The physical properties of the cured reaction product obtained from a given silicone-based composition will depend on the molecular weight of the reactive silicone of formula (I) as well as the curing method and amount of oil used. In general, high molecular weight reactive silicones should produce softer cured reaction products.
    [78] While photoinitiators are generally used as separate components, it is to be understood that the compositions of the present invention include those present in the backbone of the same organopolysiloxane polymer comprising photocurable groups.
    [79] The present invention also provides a method for preparing the composition, the step of which comprises providing the above components and mixing together.
    [80] Once prepared, the silicone composition of the present invention can be used by applying it to a desired substrate. For example, the compositions of the present invention may be applied to a desired substrate by brush, dip or spray methods, or by pressure-time dispense methods, as is well known in the silicone art. Substrates to which the composition may be applied may include various materials, such as glass, metal or plastic, especially when the composition is used in electronics applications.
    [81] After application is complete, exposure to radiation in the UV region of the electromagnetic spectrum will provide a means for causing curing.
    [82] UV radiation sources useful for curing the composition into cured reaction products include conventional mercury-vapor lamps designed to emit ultraviolet energy in various ultraviolet wavelength bands. For example, useful UV radiation wavelength ranges include 220-400 nm.
    [83] In applications in the electronics, it is not uncommon for high temperatures to be reached, particularly in areas localized in devices to which the composition has been applied and cured. This environment is typically present during operation of crt monitors such as televisions.
    [84] Accordingly, the present invention has been made with particular attention to reducing the flammability or combustibility of the cured reaction products, especially in the environment to be used.
    [85] A standard test for flammability and / or combustibility measurements is known as Underwriters Laboratories UL94, "Flammability Test of Plastics Materials-UL-94" (July 29, 1997), the disclosure of which is hereby expressly incorporated by reference. . In this test, materials are classified as V-0, V-1, or V-2, depending on their flame retardant performance.
    [86] Particularly preferred materials according to the present invention should reach the V-0 classification, although some formulations may be classified at lower levels (such as V-1) depending on the intended end use of the material. A detailed description of the performance of the reaction product cured within the scope of the present invention under these tests and test conditions is provided in the Examples below.
    [87] It will be appreciated that many of the compositions within the scope of the present invention can be formulated to produce a range of typical curable properties of silicone rubber. These materials find a variety of uses, including the coating, sealing and potting of electronic components in assemblies or devices that are often exposed to high temperatures when used in their intended manner. Under these conditions, the products and reaction products of known silicone compositions can ignite or burn to damage electronic components, or assemblies or devices in which they are used, as well as the surrounding environment and possibly end users. The present invention copes with such an environment.
    [88] The following examples are examples of the present invention.
    [89] Example 1
    [90] An acrylate-terminated polydimethylsiloxane having a weight average molecular weight of about 12,000 was prepared using about 100 grams of hydroxyl-terminated polydimethylsiloxane (commercially available from Bayer Chemicals under the tradename MASIL SFR 750) and about 4.1 grams of dimethylchloromethacryl. Oxypropylsilane was prepared by reacting with triethylamine at a temperature of about 70 ° C. to about 100 ° C. for a time period of about 4 to about 6 hours. After this time period, the reaction mixture was filtered to remove triethylamine hydrochloride and transferred to a container for storage.
    [91] The prepared acrylate-terminated polydimethylsiloxane reaction product (92.69 weight percent) was prepared using an inorganic filler component (5.3 weight percent hydrophobic fumed silica, available from Wacker Chemie, Adrian, Michigan under the trade name of HDK-2000), photoinitiator (1.5). Weight percent DEAP, available from First Chemical), organometallic flame retardant component (0.004 weight percent platinum-siloxane complex, BAYSILONE U catalyst Pt / L), and triazole component (0.5 weight percent benzotriazole, Aldrich Chemical Co.) Commercially available).
    [92] Example 2
    [93] The acrylate-terminated polydimethylsiloxane prepared as described above was used in an amount of 50.46 weight percent, and the inorganic filler component (4.22 weight percent hydrophobic fumed silica, purchased from Wacker Chemie, Adrian, Michigan under the trade name of HDK-2000) Available), photoinitiator (0.25 weight percent DEAP, available from First Chemical), flame retardant component (0.64 weight percent platinum-siloxane complex, BAYSILONE U catalyst Pt / L, and 23.93 weight percent hydrated alumina), reactive diluent component ( 20 weight percent of methacrylate-terminated-dimethoxypropyldimethyl silane acid) and an adhesion promoter component [0.5 weight percent of epoxy silane (glycidoxypropyl trimethoxysilane), available from Sivento].
    [94] Example 3
    [95] After curing the compositions prepared in Examples 1 and 2 by exposure to UV radiation for 18 seconds at an intensity of approximately 70 milliwatts per cm 2, a rubbery solid was observed to form.
    [96] These materials were subjected to durometer tests, their hardness was measured, and those having 30 Shore A and 74 Shore 00 values, respectively, were calculated.
    [97] The composition of Example 2 had a UV curing depth of 3.5 mm and its surface stickiness was less than the cured composition of Example 1.
    [98] Example 4
    [99] In this example, a flame retardant UV / moisture cured composition was prepared in an amount of 41.96 weight percent based on dimethoxy methacryloxypropyl-terminated polydimethylsiloxane, and contained an inorganic filler component (5.29 weight percent hydrophobic fumed silica, HDK). -2000, available from Wacker Chemie, Adrian, Michigan), adhesion promoter component [0.5 weight percent epoxy silane (glycidoxypropyl trimethoxysilane), commercially available from Sivento], and flame retardant component (0.4 weight percent) Of platinum-siloxane complex, BAYSILONE U catalyst Pt / L, and 50% by weight of hydrated alumina) were mixed. In addition, a photoinitiator (1.5% by weight of DEAP), and a moisture curing catalyst (0.3% by weight of tetraisopropoxycitanate) were included in the composition.
    [100] Example 5
    [101] The composition of Example 4 was dispensed on a glass slide and cured by exposing it to 100 mW / cm 2 for about 60 seconds on each side of the slide. The UV-cured composition was then cured by exposing it to moisture in the atmosphere for a period of about 3 days.
    [102] Example 6
    [103] In this example, a series of compositions were prepared to evaluate specific physical properties in the uncured and cured states. The composition was used in an amount of 42.26 weight percent based on the pre-mixture of acrylate-terminated polydimethylsiloxanes prepared as described above, incorporating an inorganic filler component (5.29 weight percent hydrophobic fumed silica, HDK-2000). Wacker Chemie, Adrian, available from Michigan), adhesion promoter component [0.5 weight percent epoxy silane (glycidoxyoxy trimethoxysilane), available from Sivento], and flame retardant component (0.4 weight percent platinum-siloxane complex) , BAYSILONE U catalyst Pt / L, and 50 weight percent hydrated alumina) were mixed. To the same pre-mix was added a photoinitiator (0.2 wt% DAROCUR 4265, available from Ciba Specialty Chemicals Corporation), and 0.5-10 wt% reactive diluent component (isobornyl acrylate). More specifically, the compositions of this example were prepared in 6-1 (0.5 weight percent isobornyl acrylate), 6-2 (1 weight percent), 6-3 (5 weight percent), 6-4 (10 weight percent), 6-5 (6 weight percent), 6-6 (7 weight percent) and 6-7 (8 weight percent). Composition 6-0 is a control composition to which no reactive diluent was added. The measured physical properties—hardening depth, viscosity (cone and plate viscometer / spindle cp 52 @ 10 rpm), and finality—are described in the table below.
    [104] Sample No.Cure Depth (mm)Viscosity (cps)Sticky 6-02.020,000pastiness 6-12.0419267.5slightly 6-22.017301.5Some (surface hardening <8 hours) 6-32.111403.2Some (surface hardening <8 hours) 6-42.353342.3Slightly (surface hardening-four hours) 6-52.29830.3Some (surface hardening <8 hours) 6-62.38454.0Slightly (surface hardening-four hours) 6-71.87864.3Slightly (surface hardening-four hours)
    [105] It is desirable that the cure depth is greater than 1 mm to impart a level of protection (for dust, moisture and friction) to larger environments than thin films or capsules. Curing depths greater than 1 mm also ensure that the components sealed by the additionally cured composition do not move. Viscosities below about 20,000 cps are preferred because they improve the dispensability of the composition. Low stickiness is desirable because it suppresses the accumulation of dust and facilitates handling of the components after curing. Thus, the combination of these properties provides improved cure depth, easy dispensability, and quick surface hardening, and is particularly preferred in combination with the V-O grade (see below).
    [106] Example 7
    [107] According to the UL-94 test method, the compositions prepared according to Examples 1, 2, 4 and 6 were dispensed into molds and cured into test pieces of the following sizes as in Example 3: 125 ± 5 mm × 13 ± 5 mm.
    [108] Arrange the five specimens so that the flames can contact the center of the specimen. The flame is held at this position for the specimen for 10 ± 0.5 seconds. The amount of time the flame continues on the specimen after flame removal is referred to as postflame time.
    [109] Once the specimen stops flame, place the flame in the same portion of the specimen for an additional 10 ± 0.5 seconds. After this time period, the flame is removed and the second afterflame time is measured. Then afterglow time was also measured.
    [110] After each flame application, five results were measured for the specimens: (1) the first postflame time; (2) second postflammation time; (3) post-glow time after the second postflammation; (4) whether the specimen burns to the clamp; (5) Whether the test piece drops into flame particles.
    [111] From these results, reference conditions can be measured to determine whether the sample meets the V-O qualification. The reference conditions are described below:
    [112] Standard conditionV-0V-1V-2 Postflammation Time (First or Second) Total Flammability Time for Any Condition Established The sum of the postflame time and the postglow time for each specimen after the application of the flame 2 hour postflame or post glow to the support clamp of any specimen. Cotton indicator lit by flame particles or flame drops≤ 10 seconds ≤ 50 seconds ≤ 30 seconds None≤ 30 seconds ≤ 250 seconds ≤ 60 seconds≤ 30 seconds ≤ 250 seconds ≤ 60 seconds
    [113] The composition from Example 1 performed well according to these standard conditions and demonstrated a V-0 rating. Its values were: <6 seconds, 8 seconds, 0 seconds, none, and none. The composition from Example 2 performed well according to these standard conditions and demonstrated a V-2 rating. The average of five values were: 17 seconds and 37 seconds. The other three measurements were not observed.
    [114] For the composition of Example 4, after dispensing the composition into a film of about 3 mm and initial exposure of each glass surface to 100 mW / cm 2 for 60 seconds, the surface of the composition was not sticky, but the interior was not completely cured. . After moisture cure of the composition for a period of about 24 hours, the curing depth appeared to be good. However, flammability assessment according to UL-94 indicated that the cured composition was slightly burnt. Separate samples of the composition were continued to cure moisture for an additional 48 hours period, where flammability assessment according to UL-94 showed that the cured composition demonstrated a V-0 rating.
    [115] Certain compositions of Example 6 (6-1, 6-2, 6-3 and 6-5) demonstrated a V-0 rating, while the others (6-4, 6-6 and 6-7) were V Proven -1 rating.
    [116] In other commercial applications, the compositions of the present invention can be used in the assembly and manufacture of consumer electronic devices to coat electrical connections.
    [117] It will be apparent to those skilled in the art that there are variations of the invention as described and that such changes are within the spirit and scope of the invention. All such changes will therefore be included within the scope of the claims.
    权利要求:
    Claims (23)
    [1" claim-type="Currently amended] As a flame-retardant silicone composition that can be cured into an elastomer by UV irradiation,
    (a) a reactive polyorganosiloxane having at least one functional group selected from the group consisting of (meth) acrylates, carboxylates, maleates, cinnamates, and combinations thereof, and optionally alkoxy or aryloxy functional groups Reactive silicone resin component;
    (b) optionally, an inorganic filler component;
    (c) photoinitiator components; And
    (d) a flame retardant silicone composition comprising an amount of flame retardant component effective to enhance the resistance of the composition to flammability.
    [2" claim-type="Currently amended] The composition of claim 1 further comprising a triazole component.
    [3" claim-type="Currently amended] The composition of claim 1 further comprising a reactive diluent component.
    [4" claim-type="Currently amended] The composition of claim 1 wherein the reactive silicone resin is in formula (I):
    Formula I

    Wherein R 1 , R 2 and R 3 may be the same or different and may be alkyl, haloalkyl, substituted or unsubstituted aryl, alkoxy, substituted or unsubstituted aryloxy, vinyl, methacryloxypropyl, mercaptopropyl, hydrogen and benzo An organic group selected from the group consisting of phosphorus; R 4 is H or C 1-5 alkyl; R 5 is C 1-8 alkylene; And n is at least 80.
    [5" claim-type="Currently amended] The composition of claim 1 wherein the inorganic filler component is a hydrophobic fumed silica filler.
    [6" claim-type="Currently amended] 6. The composition of claim 5, wherein the fumed silica filler is a member selected from the group consisting of dimethyldichlorosilane-treated silica, hexamethyldisilazane-treated silica, and combinations thereof.
    [7" claim-type="Currently amended] 6. The composition of claim 5, wherein the fumed silica filler is present at a level in the range of about 4 to about 10 weight percent.
    [8" claim-type="Currently amended] The composition of claim 1 wherein the flame retardant component is an organometallic component selected from the group consisting of organic ligand complexes of transition metals, organosiloxane ligand complexes of transition metals, and combinations thereof.
    [9" claim-type="Currently amended] The composition of claim 1 wherein the transition metal is selected from the group consisting of platinum, ruthenium, rhodium, and palladium.
    [10" claim-type="Currently amended] The composition of claim 1, wherein the flame retardant component is a combination of a member selected from the group consisting of hydrated alumina, an organic ligand complex of a transition metal, an organosiloxane ligand complex of a transition metal, and a combination thereof.
    [11" claim-type="Currently amended] The photoinitiator component of claim 1 wherein the photoinitiator component is selected from the group consisting of benzoin and substituted benzoin, mihiraketone, benzophenone and substituted benzophenone, acetophenone and substituted acetophenone, xanthone and substituted xanthone, and combinations thereof A composition characterized by being a selected member.
    [12" claim-type="Currently amended] The photoinitiator component of claim 1 wherein the photoinitiator component is 1-hydroxy cyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino propane-1-one), 2-benzyl- 2-N, N-dimethylamino-1- (4-morpholinophenyl) -1-butanone), benzophenone, 2,2-dimethoxy-2-phenyl acetophenone, bis (2,6-dimethoxy Benzoyl-2,4-, 4-trimethyl pentyl) phosphine oxide, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis (2,4,6-trimethylbenzoyl) phenyl phosphine Oxide, 2-hydroxy-2-methyl-1-phenyl-1-propane, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, visible light [blue] photoinitiator, di-camphorquinone, bis (η 5 -2,4-cyclopentadien-1-yl)-bis [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl] titanium, and combinations thereof The composition characterized in that the.
    [13" claim-type="Currently amended] The composition of claim 1 further comprising a moisture curing catalyst.
    [14" claim-type="Currently amended] The composition of claim 13, wherein the moisture curing catalyst is selected from the group consisting of titanium, tin, zirconium, and combinations thereof.
    [15" claim-type="Currently amended] 3. The composition of claim 2 wherein the triazole component is a member selected from the group consisting of benzotriazole and derivatives thereof.
    [16" claim-type="Currently amended] The composition of claim 3 wherein the reactive diluent is (meth) acrylate-terminated-dimethoxy propyldimethyl siloxane.
    [17" claim-type="Currently amended] 4. The reactive diluent of claim 3 wherein the reactive diluent is in the formula H 2 C = CGCO 2 R 6 , wherein G is hydrogen, halogen or alkyl of 1 to about 4 carbon atoms, and R 6 is alkyl, cyclo of 1 to about 16 carbon atoms It may be selected from alkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl or aryl groups, any of which may be silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea And optionally substituted or blocked with urethanes, carbamates, amines, amides, sulfur, sulfonates, and sulfones.
    [18" claim-type="Currently amended] 4. The reactive diluent of claim 3 wherein the reactive diluent is polyethylene glycol di (meth) acrylate, bisphenol-A di (meth) acrylate, tetrahydrofuran (meth) acrylate and di (meth) acrylate, citronelyl acrylate and Citronelyl methacrylate, hydroxypropyl (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetrahydrodicyclopentadienyl (meth) acrylate, ethoxylated Trimethylolpropane triacrylate, triethylene glycol diacrylate and triethylene glycol dimethacrylate, isobornyl acrylate and isobornyl methacrylate, and a group consisting of acrylate esters corresponding to formula (III) The composition characterized in that the (meth) acrylate selected from:
    Formula III

    Wherein R 7 is hydrogen, alkyl of 1 to about 4 carbon atoms, hydroxyalkyl of 1 to about 4 carbon atoms or

    And R 8 may be selected from hydrogen, halogen, and alkyl of 1 to about 4 carbon atoms;
    R 9 is hydrogen, hydroxy and

    M may be an integer of at least 1, for example 1 to about 8 or more, for example 1 to about 4;
    n is an integer of at least 1, for example 1 to about 20 or more; And
    v is 0 or 1;
    [19" claim-type="Currently amended] The composition of claim 3 wherein the reactive diluent is isobornyl acrylate.
    [20" claim-type="Currently amended] The composition of claim 1, further comprising an adhesion promoter.
    [21" claim-type="Currently amended] The method of claim 20, wherein the adhesion promoter is (meth) acryloxypropyltrimethoxysilane, trialkyl- or triallyl-isocyanurate, glycidoxypropyl trimethoxysilane, vinyltrimethoxysilane and combinations thereof Composition comprising a member selected from the group consisting of.
    [22" claim-type="Currently amended] The reaction product of the composition according to claim 1.
    [23" claim-type="Currently amended] As a method for producing a composition according to claim 1,
    (a) a reactive silicone resin component comprising a reactive polyorganosiloxane having at least one functional group selected from the group consisting of (meth) acrylates, carboxylates, maleates, cinnamates, and combinations thereof: (b) Inorganic filler component: (c) photoinitiator component; And (d) an amount of flame retardant component effective to enhance the resistance of the composition to flammability; And optionally (e) a triazole component; And optionally providing a reactive diluent and mixing together.
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    同族专利:
    公开号 | 公开日
    US6323253B1|2001-11-27|
    CN1370204A|2002-09-18|
    EP1210390A4|2003-04-23|
    MXPA01013205A|2002-06-21|
    CN1146644C|2004-04-21|
    EP1210390A1|2002-06-05|
    JP2003509527A|2003-03-11|
    CA2377109A1|2001-03-15|
    AU7124300A|2001-04-10|
    WO2001018121A1|2001-03-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-09-09|Priority to US09/392,527
    1999-09-09|Priority to US09/392,527
    2000-09-08|Application filed by 유진 에프. 밀러, 헨켈 록타이트 코오포레이션
    2000-09-08|Priority to PCT/US2000/024619
    2002-06-21|Publication of KR20020047050A
    优先权:
    申请号 | 申请日 | 专利标题
    US09/392,527|US6323253B1|1998-06-01|1999-09-09|Flame-retardant UV and UV/moisture curable silicone compositions|
    US09/392,527|1999-09-09|
    PCT/US2000/024619|WO2001018121A1|1999-09-09|2000-09-08|Flame-retardant uv and uv/moisture curable silicone compositions|
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