EP2190927A2 - Compositions de silicone autoadhésives réticulant par addition - Google Patents

Compositions de silicone autoadhésives réticulant par addition

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Publication number
EP2190927A2
EP2190927A2 EP08803922A EP08803922A EP2190927A2 EP 2190927 A2 EP2190927 A2 EP 2190927A2 EP 08803922 A EP08803922 A EP 08803922A EP 08803922 A EP08803922 A EP 08803922A EP 2190927 A2 EP2190927 A2 EP 2190927A2
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EP
European Patent Office
Prior art keywords
addition
group
carbon atoms
monovalent
general formula
Prior art date
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Application number
EP08803922A
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German (de)
English (en)
Inventor
Thomas Frese
Armin Fehn
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Wacker Chemie AG
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Wacker Chemie AG
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Publication of EP2190927A2 publication Critical patent/EP2190927A2/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
    • 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
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • 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
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • 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
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl 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
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-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
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond

Definitions

  • the present invention relates to self-adhesive addition-crosslinking silicone compositions and to a process for their preparation.
  • the invention includes silicone elastomers and composites as well as a process for making the composite materials prepared from the pressure-sensitive addition-curing silicone compositions of the present invention.
  • silicone rubbers which are brought into contact with common substrate materials such as organic plastics, metals or glasses and then vulcanized, have a low adhesive strength, so that the silicone elastomer obtained therefrom usually with relatively low tensile forces of the respective substrate material can be delaminated again.
  • An exemplary method is the pretreatment of the surface of the substrate materials with UV irradiation, flame treatment, corona or plasma treatment.
  • the surface or near-surface layer of the substrate material is activated, ie functional, predominantly polar groups are created which achieve the state enable a connection and in this way to realize a durably stable hard Soft composite of silicone elastomer and substrate material contribute.
  • EP0143994 describes the provision of an organohydrogenpolysiloxane-containing organic plastic which, after vulcanization with an addition-crosslinking silicone composition, also enables the production of a permanently strong composite material.
  • EP0875536 describes a self-adhesive
  • a particularly preferred mixture of the additive of the glycidoxypropyltrimethoxysilane (glymo ®) is described, with which in particular can be achieved relatively high adhesive strength in composite materials with some organic plastics.
  • crosslinkers having 30 SiH groups per molecule described in EP0875536 in the examples have the disadvantage that such highly functional crosslinkers lead to a considerable reduction in storage stability due to an increase in viscosity (strain) and, ultimately, the processing quality of the silicone compositions is also adversely affected.
  • a major disadvantage of the use of epoxy-functional alkoxysilanes / siloxanes is the elimination of the alcohol group (s), the use of reactive and polar groups and in the case of the functional alkoxysilanes the problem of "efflorescence" and "exudation".
  • EP1106662 describes self-adherent addition-crosslinking silicone compositions containing an organosilicon compound containing both an epoxy and a hydrolyzable group and an organohydrogenpolysiloxane having at least one aromatic C ⁇ ring and a very good adhesion to numerous organic plastics and various metals leads.
  • the organohydrogenpolysiloxane acts both as adhesion promoter and as crosslinker.
  • compositions have the disadvantage that the specified additives on the one hand due to their relatively high reactivity cause accelerated SiH degradation and also the crosslinking rate is lowered (inhibition effect).
  • EP1510553 discloses self-adhesive addition-crosslinking silicone rubber compositions comprising (A) an organohydrogenpolysiloxane, (C) an adhesion-promoting compound of the general formula (R 12 ) 5 Ph-X r -Ph (R 12 ) 5 and as additional adhesion promoter (D) at least one terminal SiH Group carrying organopolysiloxane contains.
  • these compositions have the disadvantage that Si-H-terminated polymers, which are also frequently used for chain extension, have a negative influence on the processing quality in the injection molding process, which manifests itself in a narrower processing window.
  • EP 0601883 describes self-adhesive addition-curing silicone rubber compositions containing a silane or silane coupling agent
  • Siloxane group as a coupling agent containing at least one aromatic group and at least one SiH function.
  • the described self-adhesive addition-crosslinking silicone rubber compositions are characterized by a good adhesion to the specified organic plastics and low adhesion to metals.
  • the storage-stable preparation of the adhesion promoters listed in the examples, however, is generally very complicated and therefore expensive to look at, which ultimately results in a reduced efficiency.
  • EP0686671A2 describes a pressure-sensitive addition-curing silicone composition which does not use special adhesion promoters, since the adhesion-promoting component is either an organohydrogenpolysiloxane having on average per molecule at least two SiH groups and its monovalent Si-bonded radicals to at least 12 mol .-% of hydrocarbon radicals with a aromatic ring, or is such a compound, the average per
  • Molecule has at least one SiH group and which contains a group consisting of two aromatic rings, wherein the two aromatic rings by -R 13 R 14 Si, -R 13 R 14 SiO-, - OR 13 R 14 SiO- or -R 13 R 14 SiOR 13 R 14 Si are separated from each other and the radicals R 13 and R 14 represent monovalent hydrocarbon radicals.
  • the adhesion-promoting constituent may therefore at the same time be the crosslinker of the silicone elastomer composition. With this composition, a good adhesion to organic plastics, in particular acrylonitrile-butadiene-styrene copolymer (ABS) is achieved, but at the same time shows easy mold release from metals.
  • ABS acrylonitrile-butadiene-styrene copolymer
  • SiH-containing crosslinker which is completely compatible with the silicone composition must be used, but this has other disadvantages, for example increased values of the compression set and increased exudation tendency of the adhesion-promoting constituent.
  • Ingredient greater than 12 mole percent also causes a high intrinsic viscosity of the silicone elastomer composition which is undesirable in numerous applications, for example, injection molding of liquid silicone rubber.
  • the specified adhesion promoter is a compound which contains at least one aliphatically unsaturated group and at least two phenylene groups.
  • EP1106662B1 describes self-adhesive addition-curing silicone compositions which allow good adhesion by combining a specific Si-H crosslinker (B) and an organosilicon compound (C) comprising epoxide groups and hydrolyzable groups. These Although patent specification offers a solution with regard to the crosslinker, it still has disadvantages with respect to the adhesion-promoting additive (C).
  • High performance thermoplastics constitute a blend partner, easy mold release from particular metallic vulcanization forms immediately after vulcanization, sufficient resistance to hydrolysis of the adhesive bond at high temperatures and a high level of performance characteristics (transparency, non-corrosivity, mechanical property profile).
  • An object of the invention are addition-crosslinking silicone compositions containing
  • R 1 is hydroxyl or a monovalent, optionally halogen-substituted, optionally 0, N, S or P atoms-containing hydrocarbon radical having 1 to 20 carbon atoms, which is free of aliphatically unsaturated groups,
  • R 2 is a monovalent, aliphatically unsaturated, optionally halogen-substituted, optionally 0, N, S, or P atoms containing hydrocarbon radical having 2 to 10 carbon atoms, b values of 0.0001 to 2, with the proviso that 1.5 ⁇ (a + b) ⁇ 3.0, and that per molecule on average at least two aliphatically unsaturated Residues R 2 are contained and that the determined at 25 ° C viscosity of the diorganopolysiloxanes (A) 1 to 40,000,000 mPa * s,
  • R 3 is a monovalent aliphatic saturated
  • Hydrocarbon radical having 1 to 20 carbon atoms R 4 (a) a monovalent, unsubstituted or halogen-substituted hydrocarbon radical having 6 to 15 carbon atoms, which contains at least one aromatic C ⁇ ⁇ ring, or
  • R 5 is a divalent Si-bonded bivalent, unsubstituted or halogen-substituted hydrocarbon radical having 6 to 20 carbon atoms in which individual carbon atoms may be replaced by 0, N, S or P atoms, c and f are positive numbers, and d and e are zero or a positive number, with the proviso that the sum (c + d + 2e + f) is ⁇ 3, the
  • Organohydrogenpolysiloxane (B) per molecule contains an average of at least 3 SiH groups, and that determined at 25 ° C viscosity of the
  • Organohydrogenpolysiloxane (B) is 5 mPa * s to 5,000 mPa * s, and that the organohydrogenpolysiloxane (B) is not a cyclic organohydrogenpolysiloxane of the general formula (SiHR 7 O) 5 (SiR 8 R 9 O) h .
  • R 7 is hydrogen or the same as R 8 , and R 8 and R 9 are independently (a) a monovalent aliphatic saturated
  • Hydrocarbon radical having 1 to 20 carbon atoms Hydrocarbon radical having 1 to 20 carbon atoms
  • (C) a monovalent cycloaliphatic optionally halogen-substituted hydrocarbon radical having 3 to 20 carbon atoms, or
  • g is a number greater than or equal to 1
  • h is zero or a positive number, preferably 0, 1, 2 and particularly preferably 0, with the proviso that the sum of g and h is a number greater than or equal to 4,
  • R 12 is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl, alkenyl, alkoxy, alkenyloxy or aryl group or a monovalent organic group which has an alkenyl, alkoxy, glycidyl, carbonyl, carbonyloxy, Silyloxy or alkoxysilyl group, wherein at least one of R 12 is an alkenyl group (s) or alkenyl group-containing monovalent organic group,
  • X is selected from the following groups:
  • R 13 represents a hydrogen atom, a halogen atom or a substituted or unsubstituted alkyl, aryl, alkenyl or alkynyl group and s is a positive number of at least 2, preferably 2 to 4, and r is 0 or 1,
  • the components (A), (B), (C) and (D) contain a compound or a mixture of various compounds.
  • radicals R 1 are alkyl radicals, such as methyl, ethyl, propyl, isopropyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert.
  • the radicals R 2 are accessible to a hydrosilylation reaction.
  • alkenyl and alkynyl radicals such as vinyl, allyl, isopropenyl, 3-butenyl, 2,4-pentadienyl, butadienyl, 5-hexenyl, undecenyl, ethynyl, propynyl and hexynyl; Cycloalkenyl radicals, such as cyclopentenyl, cyclohexenyl, 3-cyclohexenylethyl, 5-bicycloheptenyl, norbornenyl, 4-cyclooctenyl or cyclooctadienyl radical; Alkenylaryl radicals, such as styryl or styrylethyl radical, and halogenated and heteroatom-containing derivatives of the above radicals, such as 2-bromovinyl, 3-bromo-1-propynyl, 1-chloro-2-
  • the viscosity determined at 25 ° C. is preferably between 1 and 40,000,000 mPa * s.
  • different viscosity ranges are preferred for the diorganopolysiloxanes (A).
  • RTV-2 Room Temperature Vulcanizing
  • R 3 examples are alkyl radicals, such as methyl, ethyl, propyl, isopropyl, tert. Butyl, n-octyl, 2-ethylhexyl and octadecyl, and cycloalkyl, such as cyclopentyl, cyclohexyl, norbornyl or Bornylrest.
  • Preferred radicals R 3 are hydrocarbon radicals having 1 to 10 carbon atoms. Particularly preferred radical R 3 is the methyl radical.
  • R 4 are the phenyl, tolyl, xylyl, biphenylyl, anthryl, indenyl, phenanthryl, naphthyl, benzyl, phenylethyl or phenylpropyl radical, and also halogenated and organically functionalized derivatives of the above radicals, such as o-, m-, p-chlorophenyl-,
  • Pentafluorophenyl bromotolyl, trifluorotolyl, phenoxy, benzyloxy, benzyloxyethyl, benzoyl, benzoyloxy, p-tert-butylphenoxypropyl, 4-nitrophenyl, quinolinyl or pentafluorobenzoyloxy.
  • Carbon atoms are radicals such as 3-chloropropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl, 2-fluoroethyl, 1,1-
  • Preferred radicals R 4 are the phenyl radical and the 3, 3, 3-trifluoropropyl radical. Particularly preferred radical R 4 is the phenyl radical.
  • Preferred radicals R 5 correspond to the general formula (Z)
  • R 6 may be the same or different and a bivalent, unsubstituted or halogen-substituted
  • Hydrocarbon radical having 1 to 10 carbon atoms which may be replaced by free of aliphatic unsaturated groups and in the individual carbon atoms by 0, N, S, or P atoms, such as -CH 2 -, -CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -, -CF 2 -, -CH 2 -CF 2 -, -CH 2 -CH (CH 3 ) -, -C (CH 3 ) 2 -, -CH 2 -
  • M is a bivalent radical such as -Ph-, - Ph-O-Ph, Ph-S-Ph, Ph-SO 2 Ph, Ph-C (CH 3 ) 2 Ph, Ph-C (CF 3 ) 2 Ph, -Ph-C (O) -Ph-, cyclohexylene or norbornylene, wherein Ph denotes a phenylene group.
  • Particularly preferred radical R 5 is the phenylene radical and the norbornylene radical.
  • organohydrogenpolysiloxanes (B) of the general formula (II) are linear and branched
  • Organohydrogenpolysiloxanes these preferably from units of the formulas (CH 3 ) 3 Si0i / 2 , H (CH 3 ) 2 Si0i / 2 , H (CH 3 ) SiO 2/2 , (CH 3 ) (C 6 H 5 ) SiO 272 , (C 6 Hs) 2 SiO 272 , (C 6 H 5 ) SiO 372 , (CH 3 ) 2 Si0 2/2 or Oi 72 (CH 3 ) 2 Si-C 6 H 4 - (CH 3 ) 2 Si0i 72 , or consist of mixtures thereof.
  • Organohydrogenpolysiloxanes (B) of the general formula (II) are linear and branched organohydrogenpolysiloxanes more preferably selected from units of formulas (CH3) 3 Si0i / 2, H (CH 3) SiO 2/2, and (CH 3) 2 SiO 2/2, or consist of mixtures of different such organohydrogenpolysiloxanes.
  • the organohydrogenpolysiloxane (B) of the general formula (II) preferably contains on average 5 to 40 SiH groups per molecule. On average, 10 to 25 SiH groups per molecule are particularly preferred.
  • Organohydrogenpolysiloxane (B) of the general formula (II) free of aromatic groups
  • the viscosity of the component (B) measured at 25 ° C is preferably 2 to 1,000 mPa * s.
  • Component (B) have a low content, typically less than 100 ppm by weight, Si-bonded OH groups.
  • organohydrogenpolysiloxanes (B) are, for example
  • Copolymers containing H (CH3) SiO2 / 2 and (CH 3) 2 Si0 2/2 units comprising H (CH 3) 2 Si0i / 2 end groups copolymers containing (Ph) 2 Si0 2/2 and H (CH 3 ) SiO 2/2 units having (CH 3 ) 3 Si0i / 2 end groups,
  • Copolymers comprising (Ph) SiO 3/2 , (CH 3 ) 2 SiO 2/2 and H (CH 3 ) Si 2/2 units having (CH 3 ) 3 Si0i / 2 end groups, Copolymers containing (Ph) (CH 3 ) SiO 2/2 , (CH 3 ) 2 Si0 2/2 and H (CH 3 ) Si 2/2 units having (CH 3 ) 3 Si0i / 2 end groups, copolymers containing (Ph) (CH 3 ) SiO 2/2 , (CH 3 ) 2 Si0 2/2 and H (CH 3 ) Si 2/2 units comprising H (CH 3 ) 2 Si0i / 2 end groups, copolymers containing (Ph) (CH 3 ) SiO 2/2 and H (CH 3 ) Si 2/2 units having (CH 3 ) 3 Si0i / 2 end groups,
  • Copolymers containing -Si (CH 3 ) 2 -C 6 H 4 -Si (CH 3 ) 2 O 2/2 and (CH 3 ) HSiO 2/2 units containing -Si (CH 3 ) 2 -C 6 H 4 -Si (CH 3 ) 2 O 2/2 and (CH 3 ) HSiO 2/2 units.
  • organohydrogenpolysiloxanes (B) are, for example, copolymers comprising H (CH 3 ) SiO 2/2 and (CH 3 ) 2 SiO 2/2 units having (CH 3 ) 3 Si0i / 2 end groups, and
  • Copolymers containing H (CH 3 ) SiO 2/2 and (CH 3 ) 2 Si0 2/2 units containing H (CH 3 ) 2 Si0i / 2 end groups containing H (CH 3 ) Si0i / 2 end groups.
  • organohydrogenpolysiloxanes (B) are particularly preferred which consist of -Si (CH 3 ) HO- and -Si (CH 3 ) 2 -O- units with a molar ratio of 3: 1 having (CH 3 ) 3 Si-O end groups , or -Si (CH 3 ) HO- and -Si (CH 3 ) 2 -O-units having a molar ratio of 1: 1 having (CH 3 ) 3 Si-O end groups, or -Si (CH 3 ) HO and -Si (CH 3 ) 2 -O units with a molar ratio of 1: 2 having (CH 3 ) 3 Si-O end groups.
  • the ratio of SiH from component (B) to the total number of Si-vinyl-bonded groups in the pressure-sensitive addition-crosslinking silicone composition is preferably between 0.5 and 5, and particularly preferably between 0.6 and 1.8.
  • radicals R 7 , R 8 and R 9 of the cyclic organohydrogenpolysiloxane (C) of the general formula (III), are Si-bonded hydrogen and alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert. Pentyl, n-octyl, 2-ethylhexyl, 2, 2, 4-trimethylpentyl and n-nonyl radicals.
  • Aryl radicals such as phenyl, ethylphenyl, tolyl, xylyl, mesityl or naphthyl radical;
  • Aralkyl radicals such as benzyl, phenylethyl or phenylpropyl radical; cyclic alkyl radicals having three to 12 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl radicals; and halogen-substituted or heteroatom-containing derivatives of the above radicals, such as 3-chloropropyl, 3-bromopropyl, (p-chloromethyl) phenyl, (p-chloromethyl) phenethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, 3, 3, 3-trifluoropropyl, acetyl, acetoxymethyl, acetoxyethyl
  • radicals R 7 , R 8 and R 9 are Si-bonded hydrogen, methyl, ethyl, propyl, butyl, octyl, cyclohexyl, phenyl and 3, 3, 3-trifluoropropyl.
  • Particularly preferred radicals R 7, R 8 and R 9 are Si-bound hydrogen, methyl and phenyl radical, where thereof still Si- bonded hydrogen and the methyl group are the most preferred radicals.
  • the cyclic organohydrogenpolysiloxanes (C) are preferably copolymers containing H (CH3) SiO2 / 2 and (CH 3) 2 Si0 2/2 units, and homopolymers containing only H (CH 3) SiO 2/2 ⁇ units, as well as mixtures thereof, the homo-oligomers being more preferred.
  • cyclic organohydrogenpolysiloxanes (C) are homopolymers such as pentamethylcyclopentasiloxane (SiMe (H) O) 5 ; D 5 H or hexamethylcyclohexasiloxane (SiMe (H) O) ⁇ ! D ⁇ H , or Heptamethylcycloheptasiloxane (SiMe (H) O) 7 ; D 7 H , or octamethylcyclooctasiloxane (SiMe (H) 0) s; Ds H , mean, or mixtures of the homopolymers.
  • cyclic organohydrogenpolysiloxanes (C) preferably contain comparatively small amounts of homopolymers such as trimethylcyclotrisiloxane (SiMe (H) O) 3 ; D 3 H and
  • cyclic organohydrogenpolysiloxane (C) is a compound of the general formula (III), with the proviso that the sum of g and h is a number greater than or equal to 5.
  • the cyclic organohydrogenpolysiloxane (C) of the general formula (III) is free of aromatic groups.
  • the coupling agent (D) of the general formula (IV) is a compound with at least one aliphatic unsaturated
  • the coupling agent (D) in combination with the organohydrogenpolysiloxane (B) and cyclic organopolysiloxane (C), increases the adhesion of the composition further containing the component (A) so that the composition has sufficient
  • the adhesion promoter (D) preferably contains aliphatic, unsaturated groups, such as alkenyl groups, and p-phenylene groups.
  • the adhesion promoter (D) preferably has the general formula (IV).
  • R 12 each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl, alkenyl, alkoxy, alkenyloxy or aryl group or a monovalent organic group containing an alkenyl, alkoxy , Glycidyl, carbonyl, carbonyloxy, silyloxy or alkoxysilyl group.
  • at least one, preferably 1 to 4, radicals R 12 denotes an alkenyl group or an alkenyl group-containing, monovalent, organic group.
  • R 13 are each independently of one another a hydrogen atom, a halogen atom or a substituted or unsubstituted alkyl radical;
  • Aryl, alkenyl or alkynyl group, and s is a positive number of at least 2, preferably 2 to 4.
  • the index r is preferably 0 or 1.
  • the alkyl and alkoxy groups should preferably have 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, most preferably 1 to 6 carbon atoms.
  • the aryl group should preferably have 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms.
  • the alkenyl, alkynyl and alkenyloxy groups should preferably have 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms.
  • the monovalent organic group should preferably have 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms.
  • alkyl, alkenyl and aryl groups are, for alkyl groups, the methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, cyclohexyl and octyl group, for alkenyl groups the vinyl, allyl Propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl; for aryl groups, phenyl, tolyl, xylyl, aralkyl, such as benzyl and phenylethyl.
  • alkynyl group include the acetylene group.
  • alkoxy and alkenyloxy groups are methoxy, ethoxy, propoxy-isopropoxy, butoxy, tert-butoxy, methoxyethoxy, ethoxyethoxy, vinyloxy, allyloxy, propenoxy, isopropenoxy and butenoxy.
  • Preferred embodiments of the monovalent organic group containing an alkenyl, alkoxy, glycidyl, carbonyl, carbonyloxy, silyloxy or alkoxysilyl group are, for example, the following groups:
  • R ' represents a hydrogen atom or a methyl group
  • R " is a monovalent hydrocarbon group having 1 to 6 carbon atoms, such as an alkyl group, a
  • Alkenyl group and an aryl group x is 1, 2 or 3 and y is an integer from 0 to 6,
  • z is an integer of 1 to 6
  • R 14 in the general formula (V) each independently represents hydrogen atom, hydroxyl group, halogen atom, alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms, or alkenyl group having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms.
  • R 15 is also each independently of one another for an alkenyl group having 2 to 12, preferably 2 to 10,
  • R 16 is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
  • the letter t is 0 or 1.
  • R 17 is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • At least one of R 15 should preferably have a
  • Alkenyl group or a monovalent organic group containing an alkenyl group is Alkenyl group or a monovalent organic group containing an alkenyl group.
  • alkyl, alkenyl and alkenyl group-containing monovalent organic group are the same as given for R 12 .
  • Preferred embodiments of the alkylene group include, for example, the methylene, ethylene, trimethylene, tetramethylene, hexamethylene and methylethylene groups.
  • adhesion promoter (D) of the general formula (V) are:
  • X 1 is -O-, -CH 2 , - (CH 3 -) C (-CH 3 ) - or -O- (CH 3 -) Si (-CH 3 ) -O-, and R 18 are each independently a hydrogen atom, a vinyl group or an allyl group.
  • adhesion promoter (D) it is essential that this is used in combination with the organohydrogenpolysiloxane (B) and cyclic organopolysiloxane (C). Only then is surprisingly observed a very good adhesion to particular bisphenol A-containing thermoplastics.
  • the hydrosilylation catalyst (E) serves as a catalyst for the addition reaction between the aliphatically unsaturated hydrocarbon radicals R 2 of the diorganopolysiloxanes (A) and the unsaturated groups of the adhesion promoter (D) with the Si-bonded hydrogen atoms of the organohydrogenpolysiloxanes (B) and the cyclic organohydrogensiloxanes (C).
  • Numerous suitable hydrosilylation catalysts are described in the literature.
  • hydrosilylation catalyst (E) metals and their compounds such as platinum, rhodium, palladium, ruthenium and iridium, preferably platinum and rhodium, can be used.
  • the metals may be fixed on finely divided support materials such as activated carbon, metal oxides such as alumina or silica.
  • platinum and platinum compounds are used. Particularly preferred are those platinum compounds which are soluble in polyorganosiloxanes. As soluble
  • Platinum compounds can be used, for example, the platinum-olefin complexes of the formulas (PtCl 2 .Olfin) 2 and H (PtCl 3 .olefin), preferably alkenes having 2 to 8 carbon atoms, such as ethylene, propylene, isomers of butene and octene, or Cycloalkanes having 5 to 7 carbon atoms, such as cyclopentene, cyclohexene and cyclohepten be used.
  • the platinum-olefin complexes of the formulas (PtCl 2 .Olfin) 2 and H (PtCl 3 .olefin) preferably alkenes having 2 to 8 carbon atoms, such as ethylene, propylene, isomers of butene and octene, or Cycloalkanes having 5 to 7 carbon atoms, such as cyclopentene, cyclohexene and cyclohepten be used
  • Platinum-cyclopropane complex of the formula (PtCl 2 CsHe) 2 , the Reaction products of hexachloroplatinic acid with alcohols, ethers and aldehydes or mixtures thereof or the reaction product of hexachloroplatinic acid with
  • Methylvinylcyclotetrasiloxane in the presence of sodium bicarbonate in ethanolic solution platinum catalysts with
  • Phosphorus, sulfur and amine ligands can be used, eg (Ph 3 P) 2 PtCl 2 .
  • Particular preference is given to complexes of platinum with vinylsiloxanes, such as sym-divinyltetramethyldisiloxane.
  • the amount of hydrosilylation catalyst (E) used depends on the desired crosslinking rate and on economic aspects. Usually weight per one hundredth parts by diorganopolysiloxanes (A) 1 x 10 -5 to 5 ⁇ 10 -2 parts by weight, preferably 1 ⁇ 10 4 to 1 x 10 -2 and more preferably 5 ⁇ 10 4 to 5 x 10 ⁇ 3 parts by weight of platinum catalysts, calculated as platinum metal used.
  • the self-adhesive addition-crosslinking silicone compositions may optionally contain other ingredients, such as fillers (F), inhibitors (G) and other additives (H), such as stabilizers, pigments and catalysts.
  • other ingredients such as fillers (F), inhibitors (G) and other additives (H), such as stabilizers, pigments and catalysts.
  • active reinforcing fillers (F) are used in particular precipitated and fumed silicas, and mixtures thereof.
  • the specific surface area of these active reinforcing fillers should be at least 50 m 2 / g or preferably in the range from 100 to 400 m 2 / g as determined by the BET method.
  • active reinforcing fillers are well known materials in the silicone rubber art.
  • the silicic acid fillers mentioned can have a hydrophilic character or be hydrophobized by known processes. When incorporating hydrophilic fillers, it is necessary to add a hydrophobing agent.
  • the content of the crosslinkable composition of active reinforcing filler (F) according to the invention is in the range from 0 to 70% by weight, preferably from 0 to 50% by weight.
  • inhibitors (G) may be present as a further additive, which serve for the targeted adjustment of the processing time, light-off temperature and crosslinking rate of the compositions according to the invention. These inhibitors (G) are also well known in the field of addition-crosslinking compositions.
  • acetylenic alcohols such as 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol and 3, 5-dimethyl-1-hexyn-3-o1, 3-methyl-1-dodecin 3-ol
  • polymethylvinylcyclosiloxanes such as 1,3,5,7 Tetravinyltetramethyltetracyclosiloxan
  • alkyl maleates such as diallyl maleates, dimethyl maleate and diethyl maleate
  • alkyl fumarates such as diallyl fumarate and diethyl fumarate
  • organic hydroperoxides such as cumene hydroper
  • the effect of these inhibitors (H) depends on their chemical structure, so it must be determined individually.
  • the content of inhibitors in the silicone compositions according to the invention is preferably 0 to 50,000 ppm, particularly preferably 20 to 2,000 ppm, in particular 100 to 1,000 ppm.
  • the silicone composition according to the invention may optionally contain as component further additives (H) in an amount of preferably up to 70% by weight, preferably 0.0001 to 40% by weight.
  • additives may be, for example, inactive fillers, quartz, talc, resinous polyorganosiloxanes, dispersants, solvents, further adhesion promoters, pigments, dyes, plasticizers, organic polymers,
  • Heat stabilizers and so on include additives such as activated carbon, quartz powder, diatomaceous earth, clays, chalk, lithopones, carbon blacks, graphite, metal oxides, metal carbonates, sulfates, metal salts of carboxylic acids, metal dusts, fibers such as glass fibers, plastic fibers, plastic powder, dyes, pigments, etc ..
  • constituents (K) which are used in conventional pressure-sensitive addition-crosslinking silicone rubber compositions may be added.
  • these are preferably organopolysiloxane compounds.
  • Even more preferred are cyclic or linear organopolysiloxane compounds having at least one SiH group and at least one alkoxysilyl and / or glycidyl group per molecule.
  • composition according to the invention usually contains 100 parts by weight of diorganopolysiloxanes (A) of the general formula
  • Hydrosilylation catalyst (E) and optionally 0 to 100 parts by weight of at least one reinforcing filler
  • At least one inhibitor in particular 0.01 to 0.2 parts by weight, and 0 to 60 parts by weight of further additives (H) and / or (K).
  • the ratio of the total amount of Si-H groups to the total amount of Si-vinyl groups may vary in the range of 0.5 to 15, with 1.0 to 7 being preferred and 1.2 to 4.5 being particularly preferred.
  • addition-crosslinking silicone compositions characterized in that the composition consists of two components (i) and (ii), component (i) comprising components (A) and (E) and also optionally (D), and component (ii) contains components (A), (B) and (C) and optionally (D), where (D) may be present in both parts simultaneously but contain at least one of the parts but more preferably in part (ii).
  • component (F) the components (F),
  • (G), (H) and (K) may optionally be present in both components (i) and (ii), the presence of the component (F) in both components as well as the presence of the component (G) in both or at least in one of components (i) and (ii) is preferred.
  • the compounding of the self-adhesive addition-crosslinking silicone compositions is carried out by mixing the abovementioned components (i) and (ii) in any order.
  • the crosslinking of the self-adhesive addition-crosslinking silicone compositions is effected by heating, usually at 40 to 250 0 C, preferably at least 50 0 C, particularly preferably at least 80 0 C, preferably at most 200 0 C, in particular at most 180 0 C.
  • the invention also provides addition-crosslinked silicone elastomers which are prepared from the silicone compositions according to the invention.
  • Another object of the invention is a process for the preparation of addition-crosslinking silicone compositions according to at least one of claims 1 to 5, characterized in that the components (A), (B), (C), (D) and (E) are mixed together.
  • the cyclic organohydrogenpolysiloxane (C) is a compound of the general formula (III), provided that the sum of g and h is a number greater than or equal to 5.
  • the cyclic organohydrogenpolysiloxane (C) of the general formula (III) is free of aromatic groups.
  • the organohydrogenpolysiloxane (B) contains an average of 5 to 40 SiH groups.
  • the adhesion promoter (D) of the general formula (V) of the general formula (V)
  • X 1 -O-, -CH 2 , - (CH 3 -) C (-CH 3 ) - or -O- (CH 3 -) Si (-CH 3 ) -O-, and R 18 are each independently a hydrogen atom, a vinyl group or an allyl group.
  • the addition-crosslinking silicone compositions additionally contain at least one reinforcing filler (F), at least one inhibitor (G), and optionally further additives (H) and / or (K).
  • the mixing takes place preferably via discontinuous and / or continuous mixing units, such as kneaders, dissolvers or planetary mixers.
  • the subject of the invention is also a composite material in which at least a part of the composite material consists of an addition-crosslinking silicone elastomer, which consists of the addition-crosslinking according to the invention
  • Silicone compositions is produced, which is firmly connected to at least one substrate material.
  • the invention also relates to a process for the production of composite materials, in which the addition-crosslinking silicone composition of the invention is applied to the substrate and then crosslinked by heating to 40 to 250 0 C to form a composite material.
  • the addition-crosslinking silicone compositions can be bonded to the substrates by applying the addition-crosslinking silicone composition to at least one substrate and then crosslinking it by heating to form a composite material.
  • the self-adhesive addition-crosslinking silicone compositions according to the invention can be advantageously used in particular wherever good adhesion between the addition-crosslinked silicone elastomer and at least one substrate, preferably consisting of organic plastics and here in particular on technical and high-performance thermoplastics such as bisphenol A units containing thermoplastics (for example, polycarbonates and polyetherimides) as well as polyamides and polyesters, metals or Glasses, is desired.
  • the substrate may be present as a molded part, film or coating.
  • the self-adhesive addition-crosslinking silicone compositions are suitable for the production of
  • composite material by coating, bonding, potting and for the production of molded articles.
  • the self-adhesive addition-crosslinking silicone compositions are also suitable for potting and for bonding electrical and electronic components as well as for producing composite molded parts.
  • composite molded parts are understood as meaning a uniform molded article made of a composite material which is composed of a silicone elastomer part produced from the silicone compositions according to the invention and at least one substrate in such a way that the parts have a solid, durable
  • connection exists.
  • the production of such a composite molding takes place by an organic plastic is processed into a molded article and then the silicone composition according to the invention are brought into connection with this molding and crosslinked, which can be done for example by injection molding, by extrusion or in the so-called Pressvulkanisationsvon.
  • Composite materials and in particular composite moldings can be used in a wide variety of applications, for example in the electronics, household appliances, consumer goods, construction and
  • the advantageous properties of the silicone composition is that the self-adhesion is achieved by a component which is in any case present in addition-crosslinking silicone compositions, namely the SiH-containing crosslinker (B), in combination with the cyclic organohydrogenpolysiloxane (C) and the adhesion promoter (D) Proportion of the bonding agent (D) should be kept low so that no negative influence on the crosslinking characteristic, a reduction in storage stability or a significant reduction in the transparency of the crosslinked silicone elastomer and no unwanted "efflorescence" due to the interfacial activity of this compound.
  • a component which is in any case present in addition-crosslinking silicone compositions namely the SiH-containing crosslinker (B), in combination with the cyclic organohydrogenpolysiloxane (C) and the adhesion promoter (D)
  • Proportion of the bonding agent (D) should be kept low so that no negative influence on the crosslinking characteristic, a reduction in storage stability or
  • thermoplastics • a high adhesive strength on organic plastics, in particular on technical and high-performance thermoplastics such as bisphenol A units containing thermoplastics
  • polycarbonates and polyetherimides and polyamides and polyesters can be achieved • a slight mold release from particular metallic vulcanization is given when the
  • PC-I polycarbonate
  • PC-2 Lexan® 14 IR (GE Plastics)
  • PC-3 polycarbonate
  • PC-4 Xantar UR 19 (DSM)
  • PC-5 Caliber 301-22 (LG-Dow Polycarbonate)
  • PC -SECTION Polycarbonate-acrylonitrile-butadiene-styrene blend
  • Bayblend® DP T50 (Bayer MaterialScience AG) i) Polycarbonate-Polyethylene Terephthalate (PC-PET): Makroblend® DP 2-7655 (Bayer MaterialScience AG) j) High Temperature Polycarbonate (HT-PC): APEC® 1895 (Bayer MaterialScience AG)
  • PC-PET Polycarbonate-Polyethylene Terephthalate
  • HT-PC High Temperature Polycarbonate
  • VA steel (industrial grade) (industrial grade)
  • Substrate materials for the Pressvulkanisationsvon respectively the thermoplastic granules for the injection molding process according to the manufacturer's instructions dried in a suitable manner.
  • Silicone elastomers does not distort the results, while a textile tape was inserted into the silicone composition.
  • the vulcanization was carried out over a period of 3 minutes at a temperature of 120 0 C and a pressure of 30 tons for the substrate materials PC-I, PC-2 and PC-ABS, in which a complete crosslinking of the liquid silicone composition was carried out.
  • the substrate material VA vulcanization was carried out at 180 0 C over a period of 10 minutes and for the HT-PC, the vulcanization was carried out at 180 0 C over a period of 3 minutes. Then all were
  • Peel test piece cooled to room temperature.
  • the peel test body produced in this way consisting of substrate and 2.5 mm thick liquid silicone elastomer layer with inserted textile tape, was initially stored for at least 16 hours at room temperature after removal from the mold. Thereafter, the peel test specimen was clamped in a tensile tester and the maximum release force necessary to remove the adhered silicone elastomer strip was determined. Tensile stress results in either a cohesive crack within the silicone elastomer or an adhesive release between silicone elastomer and substrate.
  • thermoplastic body which was conveyed via a rotating turntable to the second injection molding.
  • the addition-crosslinking silicone composition according to the invention was sprayed onto the finished thermoplastic base body and vulcanized onto the substrate.
  • the injection pressure for self-adhesive addition-crosslinking silicone compositions is usually in the range from 200 to 2000 bar, but may in exceptional cases exceed or exceed these values.
  • the injection temperature for self-adhesive addition-crosslinking silicone compositions is usually in the range 15 to 50 ° C, and these temperatures may also be below or exceeded in individual cases.
  • FIGS. 1 a and 1 b The peel test specimens produced in the 2-component injection molding method and used for assessing the adhesive strength of the silicone elastomers according to the invention on the substrates are shown schematically in FIGS. 1 a and 1 b.
  • FIG. 1a is a cross-sectional view of a peel test body produced in the injection molding process, wherein (a) the addition-crosslinked silicone elastomer and (b) the thermoplastic base body.
  • Fig. Ib. is a plan view of a peel test body produced in the injection molding process, again (a) the addition-crosslinked silicone elastomer and (b) means the thermoplastic body.
  • the peel test specimens prepared by the 2-component injection molding method were also stored at room temperature for at least 16 hours.
  • the adhesion test and the crack pattern evaluation were carried out in the same manner as with the peel test pieces from the press vulcanization.
  • the adhesion of the composites consisting of silicone elastomer and thermoplastic base body was quantified on the basis of the adhesion test according to DIN ISO 813.
  • the so-called 90 ° peeling process was carried out so that substrate and silicone elastomer strips have an angle of 90 ° to one another and the withdrawal speed is preferably 50 mm / min.
  • the determined release force (TK) was given by the quotient of the maximum force N and the width of the specimen in N / mm.
  • compositions of the examples the following basic material, the specified cyclic organohydrogenpolysiloxanes and the adhesion promoters HF 1 and HF 2 were used as constituents.
  • DAEBPA diallyl ether bisphenol A
  • Preparation of the A component 345.8 g of base were mixed with 3.5 g of a dimethylvinylsiloxyendgestopperten polydimethylsiloxane with methylvinylsiloxy having a vinyl content of 2.5 mmol / g and a viscosity of 350 mm 2 / s and 0.7 g of a catalyst solution with a Pt content of 1% by weight containing a platinum-divinyltetramethyldisiloxane complex in silicone polymer.
  • component A and component B were carried out analogously to Example 1, with the difference that in component B instead of 1 g Pentamethylcyclopentasiloxan the same amount of a mixture of pentamethylcyclopentasiloxane and hexamethylcyclohexasiloxane in the ratio 1: 1 was used.
  • component A and component B were carried out analogously to Example 1, with the difference that in component B instead of 1 g of pentamethylcyclopentasiloxane, 1 g of tetramethylcyclotetrasiloxane was used.
  • Component A was prepared analogously to Example 1.
  • the starting material 90 g of the starting material were mixed with 0.1 g of 1-ethynyl-1-cyclohexanol and 5.5 g of a vinyldimethylsiloxy-terminated polydimethylsiloxane having a viscosity of 20,000 mPa * s ( 25 ° C), 1.8 g of a copolymer of dimethylsiloxy and methylhydrogensiloxy units in the molar ratio 1: 1 with trimethylsiloxy end groups and a viscosity of 65 mPa * s and a Si-H content of 0.75%, 1 g a mixture of pentamethylcyclopentasiloxane and hexamethylcyclohexasiloxane in the ratio 3: 2, and 1.2 g of HF 1, mixed.
  • component A was carried out analogously to Example 1.
  • B component 90 g of base material with 0.1 g of 1-ethynyl-1-cyclohexanol, 2.5 g of a vinyldimethylsiloxy-terminated polydimethylsiloxane having a viscosity of 20,000 mPa * s (25 ° C), 5.3 g of a copolymer of
  • Example 6 noninventive comparative example
  • component A was carried out analogously to Example 1
  • B component 90 g base with 0.1 g of 1-ethynyl-1-cyclohexanol, 3 g of a vinyldimethylsiloxy-terminated polydimethylsiloxane having a viscosity of 20,000 mPa * s (25 ° C), 5.5 g of a copolymer of methylhydrogensiloxy and dimethylsiloxy units in the molar ratio 1: 2 and trimethylsiloxy end groups and a viscosity of 100 mPa * s and a Si-H content of 0.5%, 1.5 g HF 1 mixed.
  • component A was carried out analogously to Example 1.
  • B component 90 g base with 0.1 g of 1-ethynyl-1-cyclohexanol, 6 g of a vinyldimethylsiloxy-terminated polydimethylsiloxane having a viscosity of 20,000 mPa * s (25 ° C), 2.7 g of a copolymer of methylhydrogensiloxy and dimethylsiloxy units in the molar ratio 1: 2 and trimethylsiloxy end groups and a viscosity of 100 mPa * s and a Si-H content of 0.5%, and 1 g a mixture of pentamethylcyclopentasiloxane and hexamethylcyclohexasiloxane in the ratio 1: 1 mixed.
  • Component A was prepared analogously to Example 1.
  • the starting material 90 g of the starting material were mixed with 0.1 g of 1-ethynyl-1-cyclohexanol, 5.2 g of a vinyldimethylsiloxy-terminated polydimethylsiloxane having a viscosity of 20,000 mPa * s ( 25 ° C), 2.6 g of a copolymer of Methylhydrogensiloxy- and dimethylsiloxy units in Molar ratio 1: 2 and trimethylsiloxy end groups and a viscosity of 100 mPa * s and a Si-H content of 0.5%, and 0.8 g of a Organohydrogenpolysiloxans with an average content of 30 methylhydrogensiloxy units with trimethylsiloxy end groups and a Si-H content of 1.5%, 1.1 g HF 1 mixed.
  • component A was carried out analogously to Example 1.
  • B component 90 g base with 0.1 g of 1-ethynyl-1-cyclohexanol, 5 g of a vinyldimethylsiloxy-terminated polydimethylsiloxane having a viscosity of 20,000 mPa * s (25 ° C), 2.4 g of a copolymer of methylhydrogensiloxy and dimethylsiloxy units in
  • Silicone compositions from Examples 1-5 are given in Table 1:
  • Tackiness on steel is an essential prerequisite for a reliable demolding process in the production of hard-soft composite components in the quasi-continuous 2-component injection molding process, whereby a high process reliability is given.
  • Polyetherimide such as on Ultem® 1000 from GE
  • Plastics which is sufficient at least for applications where a loss of security is required, is sufficient.
  • polyetherimides are also critical as thermoplastic composite partners in the application of self-adhesive addition-crosslinking
  • Organohydrogenpolysiloxane used with an average content of 30 methylhydrogensiloxy units with trimethylsiloxy end groups and a Si-H content of 1.5%, so no adhesion to the corresponding substrates can be achieved (Comparative Example 7).
  • HFl can be arbitrarily replaced by another adhesion promoter, wherein the As used herein, HF2 is a prior art known coupling agent commonly used in pressure-sensitive addition-curing silicone compositions.
  • Silicone compositions from Example 2 are given in Table 3:
  • the addition-crosslinking silicone composition of the invention is basically also suitable for applications under relatively extreme conditions, as required, for example, in the household goods sector.
  • the silicone composition according to the invention from Example 2 has only a very slight increase in viscosity after storage.
  • the silicone composition of Example 9 shows a marked increase in viscosity on storage, which has a negative effect on the processing properties.
  • the values of the mechanical vulcanizate properties of the addition-crosslinking silicone elastomer according to the invention according to Example 2 given in Table 6 demonstrate the very balanced mechanical property profile. In addition, it can be clearly seen from the result that none of the adhesion-promoting constituents according to the invention has a has negative influence on the mechanical properties.
  • the vulcanizates obtained are also distinguished by a balanced vulcanization characteristic and a high degree of optical transparency.

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Abstract

La présente invention concerne des compositions de silicone autoadhésives réticulant par addition, leur procédé de production ainsi que les élastomères de silicone et matériaux composites fabriqués à partir desdites compositions. L'adhérence étonnamment bonne de la composition de silicone sur des thermoplastiques contenant en particulier du bisphénol A est obtenue grâce à la coopération synergique des composants promoteurs d'adhésion suivants : un organohydrogénopolysiloxane (B), un organohydrogénopolysiloxane cyclique (C) de formule générale (III) (SiHR7O)g (SiR8R9O)h et un promoteur d'adhésion (D). Le promoteur d'adhésion (D) correspond à la formule générale (IV), dans laquelle R12 représente un atome d'hydrogène, un groupe hydroxyle, un atome d'halogène, un groupe alkyle, alcényle, alcoxy, alcényloxy ou aryle ou bien un groupe organique monovalent, qui contient un groupe alcényle, alcoxy, glycidyle, carbonyle, carbonyloxy, silyloxy ou alcoxysilyle, au moins un des radicaux R12 représentant un groupe alcényle ou un groupe organique monovalent contenant un groupe alcényle, et X est sélectionné parmi les groupes suivants : -(R13-)C(-R13)-, -(0=)S(=0)-, -(0=)S-, -C(=0)-, -O-(CH3-)Si(- CH3) -0-, -(CH2)s- et -0-, R13 désignant un atome d'hydrogène, un atome d'halogène ou un groupe alkyle, aryle, alcényle ou alcinyle substitué ou non substitué, s représentant un nombre positif (au moins 2) et r signifiant 0 ou 1.
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CN101802100A (zh) 2010-08-11
KR20100072272A (ko) 2010-06-30
WO2009037156A3 (fr) 2009-05-07
US20100210794A1 (en) 2010-08-19
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