WO2001005846A1 - Compositions de silicone renforcees par de la resine durcissables aux u.v., a l'humidite et a la fois aux u.v. et a l'humidite - Google Patents

Compositions de silicone renforcees par de la resine durcissables aux u.v., a l'humidite et a la fois aux u.v. et a l'humidite Download PDF

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WO2001005846A1
WO2001005846A1 PCT/US2000/016312 US0016312W WO0105846A1 WO 2001005846 A1 WO2001005846 A1 WO 2001005846A1 US 0016312 W US0016312 W US 0016312W WO 0105846 A1 WO0105846 A1 WO 0105846A1
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composition
moisture
group
silicone
resin
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PCT/US2000/016312
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Hsien-Kun Chu
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Loctite Corporation
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Priority to AU60489/00A priority Critical patent/AU6048900A/en
Priority to US10/031,361 priority patent/US6828355B1/en
Publication of WO2001005846A1 publication Critical patent/WO2001005846A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature

Definitions

  • This invention relates to resin-reinforced silicone compositions curable upon exposure to radiation in the electromagnetic spectrum, which compositions when cured demonstrate improved elastomeric properties, such as tensile strength, modulus and elongation.
  • the inventive resin- reinforced silicone compositions may alternatively be rendered curable by exposure to moisture.
  • the inventive composition may be rendered curable by exposure to radiation in the electromagnetic spectrum, and exposure to moisture.
  • the inventive silicone compositions are particularly well suited for use in electronic conformal coating and potting applications, as well as in automotive gasketing applications, pressure sensitive adhesive applications and the like.
  • Silicone elastomers have been used for potting and encapsulating electrical devices, such as integrated circuits, because of their excellent thermal stability, low temperature flexibility and high dielectric strength. They typically provide shock, vibrational and thermal stress protection on fragile electronic components. [See U.S. Patent Nos . 3,933,712; 4,072,635; 4,087,585; 4,271,425; 4,374,967; and D. Dickson, Jr., Proc . Electric/Electronic Intel. Conf., 12, 92 (1975). See also U.S. Patent No. 4,374,967.]
  • Certain silicones containing (meth) acrylate functional groups may be cured by ultraviolet light ("UV light"). See U.S. Patent Nos. 4,201,808 and 4,348,454, and U.K. Patent Application GB 2039287A, which, though not producing elastomeric materials, describe UV light curing compositions of silicones containing (meth) acrylates for paper release coatings.
  • UV light ultraviolet light
  • Room temperature vulcanization also called moisture curable silicone compositions are well known, such as those sold under the ULTRA tradename .
  • Loctite Corporation has for a number of years sold under the "NUVASIL” tradename a variety of UV and UV/moisture curable silicone compositions -- that is, silicone compositions curable upon exposure to UV light or UV light, followed by exposure to moisture. These compositions generally provide a reactive polyorganosiloxane component, and a photoinitiator component. Where moisture cure capabilities are also desirable, a moisture cure catalyst is also included.
  • a non-reactive silicone fluid such as a polydimethyl siloxane, for instance one terminated with alkyl silyl groups (e.g.
  • Silicone elastomers are inherently very weak materials due to weak intermolecular van der Waals forces between the siloxane chains.
  • improved strength has been imparted to certain of these compositions by including a fumed silica as a reinforcing filler. See U.S. Patent No. 4,675,346 (Nakos), the disclosure of which is expressly hereby incorporated herein by reference.
  • One drawback to this approach in some instances is that dispensability may become difficult, as oftentimes even a small amount of fumed silica tends to increase viscosity.
  • Such reinforcing filler tends to confer a translucent or "milky" appearance to the silicone compositions.
  • Such an appearance can be disadvantageous in many applications, particularly where cure is to occur through exposure to radiation in the electromagnetic spectrum and/or where clarity of the cured elastomer is a desirable property. Radiation cure may become impeded when the composition has a translucent appearance because the radiation pathway through the composition may become blocked.
  • Loctite Corporation made an advance in the field of anaerobically-curable silicone compositions by providing compositions including (a) a silicone fluid formed as the reaction product of a first silane having at least one hydrolyzable functional group, and a second silane having a (meth) acrylic functional group and at least one hydrolyzable functional group, (b) a (meth) acrylate monomer; and (c) polymerization initiator.
  • a silicone fluid formed as the reaction product of a first silane having at least one hydrolyzable functional group and a second silane having a (meth) acrylic functional group and at least one hydrolyzable functional group
  • a (meth) acrylate monomer a (meth) acrylate monomer
  • polymerization initiator See U.S. patent No. 5,605,999 (Chu) and 5,635,546 (Rich), the disclosures of each of which are hereby expressly incorporated herein by reference.
  • Silicone products of the type noted above (sometimes referred to as "MQ" resins) have been used to impart reinforcement properties to cured elastomers of heat-curable silicone compositions without increasing the viscosity of the composition, and while maintaining the clarity of the composition.
  • MQ resins generally are copolymers of siloxanes formed from reactive trialkylsilyl (“M”) and tetra functional silicate (“Q") structures that can be prepared by either cohydrolyzing silanes containing M and Q units or by silylating inorganic silicates with a trialkylsilyl containing silanes .
  • M reactive trialkylsilyl
  • Q tetra functional silicate
  • Vinyl- or hydride-containing silanes have been added during preparation to yield MQ resins suitable for use in heat-cure silicone compositions.
  • the vinyl groups on the MQ resin and the silicone fluid polymerize in a crosslinked network with the MQ resin incorporated in the network for reinforcement .
  • MQ resins have been used to impart reinforcement properties to room temperature vulcanization ("RTV") silicone compositions, as well. See U.S. Patent No. 5,340,887 and European Patent Document EP 767 216. Here, the use of a resin-polymer system is described where both resin and polymer contain hydroxl groups and may be crosslinked with the addition of an oxime crosslinker.
  • RTV room temperature vulcanization
  • One drawback to the use of MQ resins to reinforce reaction products of silicone-based compositions is their compatibility with the remaining components of the composition -- that is, phase separation is oftentimes seen to occur. This results in a compromised shelf life stabiliity for certain one-part silicone-based compositions.
  • the present invention meets the desires discussed above by providing resin-reinforced silicone compositions capable of curing upon exposure to radiation in the electromagnetic spectrum, such as UV light, and exposure to moisture, such as is found under atmospheric conditions, and a combination thereof:
  • compositions include:
  • a polyorganosiloxane having photocurable groups, such as (meth) acrylate or glycidoxyl functionality, like methacryloxypropyl, vinyl ether groups and the like and/or moisture curable groups, such as alkoxy or aryloxy groups, like methoxy, acetoxy groups, oximino groups, enoloxy groups, imido groups, amino groups, and the like.
  • photocurable groups such as (meth) acrylate or glycidoxyl functionality, like methacryloxypropyl, vinyl ether groups and the like
  • moisture curable groups such as alkoxy or aryloxy groups, like methoxy, acetoxy groups, oximino groups, enoloxy groups, imido groups, amino groups, and the like.
  • a silicone resin selected from (i) those formed from at least one silane within the formula R ⁇ R ⁇ Si (X) -( m+P ) I, where R 1 is a (meth) acrylate functional group or a hydrolyzable group, and R 2 may be the same or different and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C 1 - 12 alkyl, C 6 - ⁇ 2 aryl, C -i8 alkylaryl, or a hydrolyzable group, X is a hydrolyzable group, m is an integer from 1 to 3, and m+p is an integer from 1 to 3; (ii) those formed from at least one silane within the formula R 3 q Si(X) 4 - q II, where R 3 may be the same as or different from R 2 above and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C 1 - 12 alkyl, C6- 12 aryl, and C7
  • compositions include:
  • a polyorganosiloxane having photocurable groups, such as (meth) acrylate functionality, like methacryloxypropyl, and/or moisture curable groups, such as alkoxy or aryloxy groups, like methoxy;
  • R 1 is a (meth) acrylate functional group or a hydrolyzable group
  • R 2 may be the same or different and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C 1 - 12 alkyl, C6- 12 aryl, C 7 - ⁇ 8 arylalkyl, C7- 18 alkylaryl, or a hydrolyzable group
  • X is a hydrolyzable group
  • m is an integer from 1 to 3
  • m+p is an integer from 1 to 3
  • R may be the same or different and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C ⁇ _ 12 alkyl, C 6 -i2 aryl, C 7 - ⁇ 8 arylalkyl, C 7 _ ⁇ 8 alkylaryl, haloalkyl, and haloaryl
  • X is a hydrolyzable functionality
  • n is an integer of from 0 to 3;
  • the invention further provides a process for preparing reaction products from the compositions of the present invention, the steps of which include applying the composition to a desired substrate surface, particularly one having shadow areas not readily accessible to light, and irradiating the coated substrate surface to conditions which are appropriate to effect cure thereof — e.g., exposure to radiation in electromagnetic spectrum.
  • the composition may then be exposed to moisture to further cure the composition.
  • the invention of course provides the reaction products so-formed by the above-described process, which reaction products demonstrate improved physical properties, such as tensile strength, modulus and elongation.
  • reaction products demonstrate improved physical properties, such as tensile strength, modulus and elongation.
  • compositions include:
  • a polyorganosiloxane having photocurable groups, such as (meth) acrylate functionality, like methacryloxypropyl, and/or moisture curable groups, such as alkoxy or aryloxy groups, like methoxy;
  • photocurable groups such as (meth) acrylate functionality, like methacryloxypropyl, and/or moisture curable groups, such as alkoxy or aryloxy groups, like methoxy;
  • a silicone resin selected from
  • R 1 is a (meth) acrylate functional group or a hydrolyzable group
  • R 2 may be the same or different and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C 1 - 12 alkyl, C 6 - 1 2 aryl, C7-18 alkylaryl, or a hydrolyzable group
  • X is a hydrolyzable group
  • m is an integer from 1 to 3
  • m+p is an integer from 1 to 3;
  • R 3 may be the same as or different from R 2 above and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C ⁇ _i 2 alkyl, C 6 - 12 aryl, C 7 - 18 alkylaryl, and q is an integer from 1 to 3, reacted with at least another silane within the formula of R r R 5 s Si (X) 4 - (r+s) III, where R 4 and R 5 may be the same or different and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C ⁇ _ ⁇ alkyl, C 6 -i2 aryl, C7-18 alkylaryl, r is an integer from 1 to 3, and r+s is an integer from 1 to 3, provided the silicone resin form contains at least some hydrolyzable group, X; and combinations thereof; and
  • compositions include:
  • a polyorganosiloxane having photocurable groups, such as (meth) acrylate functionality, like methacryloxypropyl, and/or moisture curable groups, such as alkoxy or aryloxy groups, like methoxy;
  • R 1 is a (meth) acrylate functional group or a hydrolyzable group
  • R 2 may be the same or different and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C ⁇ _i 2 alkyl, C 6 - 12 aryl, C 7 - ⁇ 8 arylalkyl, C 7 - ⁇ 8 alkylaryl, or a hydrolyzable group
  • X is a hydrolyzable group
  • m is an integer from 1 to 3
  • m+p is an integer from 1 to 3
  • R may be the same or different and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C ⁇ _ ⁇ 2 alkyl, C 6 -i2 aryl, C 7 _i8 arylalkyl, C- ⁇ a alkylaryl, haloalkyl, and haloaryl
  • X is a hydrolyzable functionality
  • n is an integer of from 0 to 3;
  • inventive compositions may be used as adhesives, coatings, sealants, as well as molding compounds, in applications ranging for instance from preapplied gasketing applications, to virtually any existing RTV silicone application that can accommodate a UV light cure step.
  • the inventive compositions are capable of being rapidly cured by exposure to UV light, and if desired exposure to atmospheric moisture. Cure typically occurs through exposure to light with a UV intensity of 70,000 mW/cm 2 .
  • the cured compositions are tough elastomeric materials that display typical silicone elastomer properties including wide usable temperature range, and good water resistance.
  • the polyorganosiloxane should have an average linear molecular size of at least about 50 siloxane units, with (meth) acrylate, (meth) acryloxyalkyldialkoxysilyl and/or (meth) acryloxyalkyldiaryloxysilyl groups on the polyorganosiloxane, such as at the terminal ends.
  • the (meth) acryloxyalkyldialkoxysilyl group should be a (meth) acryloxypropyldimethoxysilyl group.
  • the polyorganosiloxane may be selected from compounds within formula V below: where R 6 , R 7 , R 8 and R 9 may be the same or different and are alkyl, alkenyl, aryl, (meth)acryl, and the like, provided that at least one of R 6 , R 7 , R 8 and R 9 is (meth)acryl, having up to 10 carbon atoms (C ⁇ - ⁇ o) , or substituted versions thereof, such as halo- or cyano-substituted; R 10 is alkyl having up to 10 carbon atoms (C ⁇ - ⁇ o) ; n is an integer between about 100 and 1,200; a is 1 or 2; b is 0, 1 or 2; and a+b is 1, 2 or 3.
  • R 6 , R 7 , R 8 and R 9 may be the same or different and are alkyl, alkenyl, aryl, (meth)acryl, and the like, provided that at least one of R 6 , R 7 , R 8 and R
  • R 6 and R 7 are methyl, R 8 is (meth) acrylate; R 9 and R 10 is alkyl, such as methyl, and n is an integer between about 100 and 1,200, inclusive.
  • MA is (meth) acrylate and c is 0, 1 or 2.
  • the silicone resins are a family of silicone-based materials with a structure represented generally by (R 3 SiO ⁇ 2 ) Struktur (R 2 Si0 2 /2) x (RSi0 3 / 2 ) y (Si0 4 2 ) z , where a portion of the total R content includes (meth) acrylate functionality.
  • the total (meth) acrylate containing silicon functionality on the silicone resin may be up to about 15 mole% of the silicone resin, such as in the range of about 1 mole% to about 10 mole%, for instance about 4 mole% to about 8 mole%.
  • Silicone resins may be formed from at least one silane within the formula R 1 m R 2 p Si (X) 4 -( m+ p) I , where R 1 is a (meth) acrylate functional group or a hydrolyzable group, and R ⁇ may be the same or different and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C ⁇ _i 2 alkyl, C ⁇ -i2 aryl, C 7 - ⁇ 8 arylalkyl, C 7 _i 8 alkylaryl, or a hydrolyzable group, X is a hydrolyzable functionality, m is an integer of from 1 to 3 and m+p is an integer from 1 to 3, or as reaction products of that at least one silane and at least one second silane within the formula R n Si(X) 4 - n I_I, where R may be the same or different and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C1- 12 alkyl
  • the silicone resins may be formed through hydrolysis and condensation reactions.
  • silicone resins may also be prepared by (1) acidifying water-soluble sodium silicate, and thereafter capping the resulting sol with a trialkylsilyl group as well as with (meth) acrylate-containing silane or (2) co-hydrolyzing and/or co-condensing silanes containing trialkylsilane groups, vinyl silane groups and tetraalkoxysilane .
  • silicone resins generally, see R.H. Blaney et al., "Silsesquioxanes", Chem. Rev., 95, 1409-30 (1995).
  • a first silane should be used in an amount within the range of from about 1 to about 10 mole%, such as from about 4 to about 8 mole% of the combination of the first and second silanes .
  • the other silane (s) should be used in an amount with the range of from about 90 to about 99 mole%, such as from about 92 to about 96 mole% of the combination of the first and the other silanes.
  • the hydrolyzable functionality in the silanes may be any functionality which, when attached to a silicon atom through a Si-O, Si-halo, Si-N or Si-S bond, is readily hydrolyzable in the presence of water.
  • examples of such functionality include, but are not limited to, halogen (meth) acryloxy, alkoxy, aryloxy, isocyanato, amino, acetoxy, oximinoxy, aminoxy, amidato and alkenyloxy.
  • R may be chosen from C1- 1 2 alkyl, C 6 -12 aryl, alkenyl,
  • examples of the first silane include, but are not limited to, (meth) acryloxypropyl trimethoxysilane, (meth) acryloxypropyl trichlorosilane, (meth) acryloxypropyl dimethylchloro silane, (meth) acryloxymethyl dichlorosilane and (meth) acryloxymethyldimethyl acryloxysilane .
  • R 1 on the other silane is chosen from C 1 - 12 alkyl, C 6 -12 aryl
  • the other silane itself may be dimethylchlorosilane, phenyltrichlorosilane, tetrachlorosilane, trimethylchlorosilane, trimethylmethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane and tetraethoxysilane .
  • first silane may be used as the first silane component; likewise appropriate combinations of the other silane (s) may be used as the other silane component.
  • the photoinitiator may include any one of those known in the art to initiate the curing of (meth) acrylate functional groups. These photoinitiators include benzoin and substituted benzoins, benzophenone, Michler's ketone, dialkoxyacetophenones, such as diethoxyacetophenone, and the like. Generally, the amount of photoinitiator chosen should be within the range of from 0.1 to about 5% by weight. In those compositions in which moisture cure capabilities are also present, a moisture cure catalyst should also be included in an amount effective to cure the composition. For example, from about 0.1 to about 5% by weight, such as about 0.25 to about 2.5% by weight, of the moisture cure catalyst is desirable. Examples of such catalysts include organic titanium, tin, and zirconium complexes and of course combinations thereof.
  • Tetraisopropoxytitanium and tetrabutoxytitanium are particularly desirable. See also U.S. Patent No. 4,111,890, the disclosure of which is expressly incorporated herein by reference.
  • compositions may also include a diluent component reactive at elevated temperature conditions .
  • Reactive diluents include those materials which are particularly (1) unreactive at ambient temperature conditions and (2) reactive at elevated temperature conditions.
  • such diluents should be capable of not only reacting with other components of the inventive adhesive compositions, but also with reactive moities on itself. This feature allows the diluent to self-polymerize as well as polymerize with reactive moities on the other components of the composition. As such, the reactive diluent becomes incorporated into the polymeric matrix which forms at ambient temperature and which further forms at increased temperatures. The incorporation of the reactive diluent provides at least in part for the high temperature performance demonstrated by the cured composition.
  • reactive diluents include alkenyl- or alkynyl-terminated silicone fluids, an example of which is vinyl-terminated polydimethylsiloxane .
  • Other examples of reactive diluents based on silicone fluids include alkenyl- or alkynyl-terminated silicone resins.
  • the reactive diluent When used, the reactive diluent should be employed in an amount within the range of about 1 to about 50% by weight, based on the total weight of the composition.
  • compositions of the invention may also include other constituents to modify the physical properties of the composition or reaction products thereof, as desired depending on the specific application for which a composition within the scope of this invention is destined for use.
  • adhesion promoters such as (meth) acryloxypropyltrimethoxysilane, trialkylisocyanurate, and the like, may be included in an amount of up to about 5% by weight.
  • Conventional silicone fillers such as fumed and precipitated silica [see e.g. U.S. Patent No. 4,675,346 (Nakos) ] , iron oxide, barium zirconate and calcium carbonate, may also be included in the inventive compositions.
  • non- (meth) acrylate functionalized silicone diluents including silicone fluids having viscosities of between about 100 and 1,500 cps, which may or may not be terminated with hydrogen, alkyl, alkenyl, alkoxy or hydroxyl functionality, such as trimethylsilyl groups
  • plasticizers each of which may be present in an amount of up to about 30% by weight.
  • the plasticizers may be chosen from a wide variety of plasticizers depending on the desired properties of the composition and/or reaction product thereof. See e.g., U.S. Patent No. 3,794,610 (Bachmann) , the disclosure of which is hereby expressly incorporated herein by reference.
  • the compositions of the present invention may be prepared using conventional methods that are well known to those persons of skill in the art. For instance, the components of the inventive compositions may be mixed together in any convenient order consistent with the roles and functions the components are to perform in the compositions. Conventional mixing techniques using known apparatus may be employed.
  • the invention also provides a process for preparing reaction products from the compositions of the present invention, the steps of which include applying the composition to a desired substrate surface and exposing the coated substrate surface to conditions which are appropriate to effect cure thereof — e.g., exposure to radiation in the electromagnetic spectrum.
  • the invention of course provides reaction products so-formed by the above-described process, which reaction products demonstrate improved physical properties, such as tensile strength, modulus and elongation.
  • reaction products demonstrate improved physical properties, such as tensile strength, modulus and elongation.
  • (meth) acrylate-functional trimethylsilylated silicate [ (meth) acrylate-functional MQ] may be prepared by the co-hydrolysis, co-condensation of trimethylchlorosilane, methacryloxypropyltrimethoxysilane and tetraethoxysilane. As described here, for a MQ resin with an M/Q ratio of about 0.9 and a (meth) acrylate content of about 8 mole% may be prepared. Of course, variations of the M/Q ratio and (meth) acrylate content may be achieved through routine variations in the amount of starting material.
  • the mixture was further heated at reflux for an additional period of time of about three hours, after which the mixture was allowed to cool to room temperature and phase separated in a separatory funnel.
  • the lower layer of the reaction mixture in toluene was collected and returned to the three-neck round bottom flask.
  • Hexamethyldisilazane (66.0 g) was added to the stirring reaction mixture in toluene through the addition funnel. The mixture was heated at reflux with stirring for a period of time of about three hours, after which the mixture was allowed to cool to room temperature and then filtered. The filtrate was then distilled to remove the toluene-water azeotrope to yield a solution of the MQ resin, whose solids content was determined to be about 50-60%.
  • MQ may also be prepared by the reaction of trimethylchlorosilane, methacryloxypropyltrimethoxysilane and sodium silicate.
  • a MQ resin with an M/Q ratio of about 0.6 and a (meth) acrylate content of about 4 mole% may be prepared.
  • variations of the M/Q ratio and (meth) acrylate content may be achieved through routine variations in the amount of starting material.
  • a 16.5% hydrochloric acid solution was prepared by mixing 51.03 g of concentrated hydrochloric acid (37%) and 63.41 g of de-ionized water. The acid was then charged into a one-liter three-neck round bottom flask equipped with condenser, mechanical stirrer and addition funnel.
  • the mixture was heated to reflux for a period of time of about 3 hours, after which time toluene (150 g) was added.
  • the mixture was allowed to cool to room temperature and phase separated in a separatory funnel.
  • About 190 g of the top layer was collected and placed in a 500 ml, three-neck round bottom flask equipped with a reflux condenser, a mechanical stirrer and an additional funnel.
  • Hexamethyldisilazane (38 g) was added to the stirring reaction mixture to the solution through the addition funnel.
  • the mixture was heated at reflux for a period of time of about 3 hours and was then allowed to cool to room temperature.
  • the mixture was then filtered, and the solids content determined to be 28%.
  • UV Curable Silicones For instance, to prepare the silicone designated as "A" in Table 1, three hundred (300) grams (96% by weight of the reactants) of the silanol terminated polydimethylsiloxane fluid (having a viscosity of 750 cps and a molecular weight of 12,000) was placed in a one-liter three-neck round bottom flask and mixed with 12.6 g (4% by weight of the reactants) of acryloxymethyldimethylacryloxysilane at room temperature. The mixture was heated under vacuum to remove the acrylic acid byproduct formed.
  • the solids content of the resin in a toluene solution was first determined as follows. An aluminum dish filled with one gram of the silicone resin/toluene solution was heated at a temperature within the range of about 100 to about 150C. Such heating causes the toluene to evaporate leaving a solid at a constant weight. For a 50% filled composition, the weight of the solution containing 25 g of the resin was then mixed with 25 g of a UV curable silicone fluid (for instance, an acryloxymethyl-terminated polydimethylsiloxane, as described in U.S. Patent No.
  • a UV curable silicone fluid for instance, an acryloxymethyl-terminated polydimethylsiloxane, as described in U.S. Patent No.
  • a UV/moisture dual cure silicone fluid for instance, a methacryloxypropyldimethoxysilyl-terminated polydimethylsiloxane, as described in U.S. Patent No. 5,663,269) .
  • a UV/moisture dual cure silicone fluid for instance, a methacryloxypropyldimethoxysilyl-terminated polydimethylsiloxane, as described in U.S. Patent No. 5,663,269
  • different levels of filling may also be achieved by varying the amount of resin and polydimethylsiloxane chosen.
  • the mixed polymer-resin solution was subjected to rotary vacuum stripping to remove the toluene solvent for a time sufficient to reach a weight of about 50 g.
  • diethoxyacetophenone ("DEAP", as a photoinitiator) in an amount of 1.5% by weight.
  • a moisture cure catalyst such as tetraisopropyltitanium in an amount of 0.
  • UV and UV/moisture silicone compositions certain of which being filled with silicone resins for comparative purposes, are given below in Table 1.
  • Silicone A is a linear acrylate-terminated polydimethylsiloxane prepared by condensation of a hydroxyl- terminated polydimethylsiloxane having a weight average molecular weight of 12,000 with acryloxymethyldimethylacryloxysilane .
  • This silicone is used as Sample No. 1.
  • Silicone B is an acrylate-terminated polydimethylsiloxane silicone prepared as above, though from a hydroxyl-terminated polydimethylsiloxane having a weight average molecular weight of 28,000. This silicone is used as Sample No. 2.
  • Silicone C is a methacryloxypropyldimethoxy- terminated polydimethylsiloxane having a weight average molecular weight of 20,000. This silicone is used as Sample No. 3.
  • Sample Nos. 4 and 5 were prepared by mixing silicone A and B with a non-functional MQ resin.
  • Sample Nos. 6 and 7 were prepared by mixing silicone A and B with a trimethyl- terminated polydimethylsiloxane (having a viscosity of 100 cps) .
  • the samples as described in Table 1 were cured into 75 mil films by exposure for one minute on each side to UV light emitted from a medium pressure mercury lamp with an intensity of 70 mW/c ⁇ i2 (at 365 nm) . Where moisture cure was also desirable, the cured films were allowed to stand at ambient conditions for additional time (such as at least about three to about seven days) before physical properties of cured films were determined.
  • silicone resins were prepared for evaluation with various levels of M, T and Q, with the "T" unit representing methacryloxyalkyltrifunctional silyl. These resins may be designated as: M 4 T MA 3 Q55 (1), M 4 o.8T MA 5 .8Q53. (2), sT MA 5 Q 5 o (3) and M T MA 8 Q 48 (4), where the numerical subscript represents the mole% of M, T and Q starting material used during resin preparation, as described in Section 1 above. These resins were mixed together with Silicone B to prepare the compositions to be evaluated.
  • Resins 1 and 2 had a M/Q ratio of 0.764; Resin 3 had a M/Q ratio of 0.9; and Resin 4 had a M/Q ratio of 0.917.
  • Resin 2 had a (meth) acrylate content of twice that of Resin 1
  • Resin 4 had a (meth) acrylate content 1.6 times that of Resin 3.
  • These resins were each mixed with Silicone B in ratios ranging from 1:2 to 2:1, as described in Section 3 above.
  • the M/Q ratios, (meth) acrylate content and resin/siloxane ratios are given in Table 3a below.
  • the resin-reinforced compositions were cured by the method described in Section 4 above.
  • the physical properties of the cured silicone elastomers are given below in Table 3b.
  • UV cure with photoinitiator added but no moisture curing catalyst present
  • UV/moisture dual cure conditions both photoinitiator and moisture curing catalyst present; UV cure followed by at least 2 days additional moisture cure
  • M/Q ratio gives a relative measure of the molecular weight of the resin.
  • a resin with a low M/Q ratio tends to be of higher molecular weight (and therefore more viscous), and a resin with high M/Q ratios tend to be of low molecular weight (and therefore less viscous) .
  • Resins with high M/Q ratios tend to be more compatible with UV silicones and possess lower viscosities .
  • the number of polymerizable groups on the resin itself is determined by its total methacrylate content as well as its M/Q ratio.
  • the resin having a lower M/Q ratio will have a higher number of methacrylate per resin molecule due to the total methacrylate groups being evenly distributed to fewer molecules. This is due to higher molecular weight associated with a lower M/Q ratio.
  • resins having low M/Q ratios but high methacrylate contents may offer better reinforcement.
  • a moisture curable resin reinforced silicone formulation was prepared by mixing 352 g of a MQOH-1 resin (50% solid in xylene with 1% silanol, available from PCR, Gainesville, Florida) with 250 g of a silanol-terminated polydimethylsiloxane with a molecular weight of 12,000. To this mixture was further added 50.74 g of vinyltrimethoxysilane . One ml of a 1.6M n-butyllithium was then added and the mixture was heated to distill away the methanol that was formed from capping of the vinyltrimethoxysilane to the silanol.
  • a typical unfilled room temperature vulcanizing formulation would exhibit physical properties with less than 100 psi tensile and less than 100% elongation under these conditions, much like the physical properties shown by unfilled Sample Nos. 1-3.
  • a resin with moisture cure capability was prepared by reacting 500 g of MQOH-1 (commercially available from PCR; 50% solids in xylene) with 60 g of vinyltrimethoxysilane using 1 ml of a 1.6M n-butyllithium. The mixture was distilled at a temperature of about 60 °C to remove approximately 60 g of methanol. The solids content of the resulting resin was determined by heating 1.00 g thereof in an aluminum dish on a hot plate until constant weight was reached. It was found to be 60%.
  • the catalyzed mixture was exposed to UV radiation to form cured silicone elastomers.
  • the physical properties of the initially UV cured elastomer (Sample No. 36) as well as elastomers cured by exposure to UV radiation, followed by exposure to atmospheric moisture for 3 days (Sample No. 37), 7 days (Sample No. 38) and 10 days (Sample No. 39) were determined and are shown below in Table 7.
  • UV/Moisture Curable Resin Reinforced UV/Moisture Curable Silicones A UV/moisture curable resin was prepared by reacting
  • a UV curable silicone may be formulated with a
  • UV/moisture curable resin to yield an elastomer cured by both UV and moisture, having beneficial properties.

Abstract

Cette invention concerne des compositions de silicone renforcées par de la résine durcissables lors d'une exposition à un rayonnement se situant dans le spectre électromagnétique, lesquelles compositions, une fois durcies, présentent des propriétés élastomères améliorées telles que la résistance à la traction, le module d'élasticité en traction et l'allongement. Les compositions de silicone renforcées par résine de l'invention peuvent aussi être rendues durcissables par exposition à l'humidité. De plus, la composition de l'invention peut être rendue durcissable par exposition à un rayonnement se situant dans le spectre électromagnétique, et exposition à l'humidité. Les compositions de silicone de l'invention sont particulièrement bien adaptées à une utilisation dans des applications de revêtement et d'enrobage électroniques conformes, de même que dans des applications de joint pour automobile, des applications d'adhésif autocollant et analogues.
PCT/US2000/016312 1999-07-19 2000-07-07 Compositions de silicone renforcees par de la resine durcissables aux u.v., a l'humidite et a la fois aux u.v. et a l'humidite WO2001005846A1 (fr)

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US6803412B2 (en) 2003-03-13 2004-10-12 H.B. Fuller Licensing & Financing Inc. Moisture curable hot melt sealants for glass constructions
EP1728839A2 (fr) 2005-05-31 2006-12-06 Chemque, Incorporated Composition de revêtement durcissable par rayonnement actinique
US7189781B2 (en) 2003-03-13 2007-03-13 H.B. Fuller Licensing & Finance Inc. Moisture curable, radiation curable sealant composition
US7368171B2 (en) 2004-09-03 2008-05-06 H.B. Fuller Licensing & Financing, Inc. Laminating adhesive, laminate including the same, and method of making a laminate
WO2018225430A1 (fr) * 2017-06-06 2018-12-13 信越化学工業株式会社 Composition adhésive de silicone sensible à la pression, durcissable aux ultraviolets, et objet durci obtenu à partir de cette dernière
CN110799615A (zh) * 2017-07-05 2020-02-14 信越化学工业株式会社 紫外线固化型有机硅压敏粘合剂组合物和有机硅压敏粘合膜
CN110997816A (zh) * 2017-07-31 2020-04-10 美国陶氏有机硅公司 双重可固化有机硅组合物
EP3689995A4 (fr) * 2017-09-29 2021-04-28 Shin-Etsu Chemical Co., Ltd. Composition adhésive à base de silicone durcissable par uv et produit durci de celle-ci

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US6803412B2 (en) 2003-03-13 2004-10-12 H.B. Fuller Licensing & Financing Inc. Moisture curable hot melt sealants for glass constructions
US7189781B2 (en) 2003-03-13 2007-03-13 H.B. Fuller Licensing & Finance Inc. Moisture curable, radiation curable sealant composition
US7368171B2 (en) 2004-09-03 2008-05-06 H.B. Fuller Licensing & Financing, Inc. Laminating adhesive, laminate including the same, and method of making a laminate
US7754334B2 (en) 2004-09-03 2010-07-13 H.B. Fuller Company Laminating adhesive, laminate including the same, and method of making a laminate
EP1728839A2 (fr) 2005-05-31 2006-12-06 Chemque, Incorporated Composition de revêtement durcissable par rayonnement actinique
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CN110709488A (zh) * 2017-06-06 2020-01-17 信越化学工业株式会社 紫外线固化型有机硅压敏粘合剂组合物及其固化物
WO2018225430A1 (fr) * 2017-06-06 2018-12-13 信越化学工業株式会社 Composition adhésive de silicone sensible à la pression, durcissable aux ultraviolets, et objet durci obtenu à partir de cette dernière
US11124680B2 (en) 2017-06-06 2021-09-21 Shin-Etsu Chemical Co., Ltd. Ultraviolet-curable pressure-sensitive silicone adhesive composition and cured object obtained therefrom
CN110709488B (zh) * 2017-06-06 2022-01-14 信越化学工业株式会社 紫外线固化型有机硅压敏粘合剂组合物及其固化物
CN110799615A (zh) * 2017-07-05 2020-02-14 信越化学工业株式会社 紫外线固化型有机硅压敏粘合剂组合物和有机硅压敏粘合膜
EP3650514A1 (fr) * 2017-07-05 2020-05-13 Shin-Etsu Chemical Co., Ltd. Composition adhésive en silicone durcissable sous l'effet des ultraviolets et film adhésif en silicone
EP3650514A4 (fr) * 2017-07-05 2021-03-31 Shin-Etsu Chemical Co., Ltd. Composition adhésive en silicone durcissable sous l'effet des ultraviolets et film adhésif en silicone
CN110799615B (zh) * 2017-07-05 2022-05-24 信越化学工业株式会社 紫外线固化型有机硅压敏粘合剂组合物和有机硅压敏粘合膜
CN110997816A (zh) * 2017-07-31 2020-04-10 美国陶氏有机硅公司 双重可固化有机硅组合物
CN110997816B (zh) * 2017-07-31 2022-08-23 美国陶氏有机硅公司 双重可固化有机硅组合物
TWI791572B (zh) * 2017-07-31 2023-02-11 美商陶氏有機矽公司 可雙重固化聚矽氧組成物
EP3689995A4 (fr) * 2017-09-29 2021-04-28 Shin-Etsu Chemical Co., Ltd. Composition adhésive à base de silicone durcissable par uv et produit durci de celle-ci

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