Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
  • D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/59—Polyamides; Polyimides
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
  • D06M2101/16—Synthetic fibres, other than mineral fibres
  • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M2101/34—Polyamides
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
  • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides

Definitions

• the general field of the invention is that of the coating of silicone compositions which can be cold vulcanized (but whose vulcanization is generally accelerated by heat), in particular those of the two-component type (EVF II), crosslinking by hydrosilylation or polyaddition. to produce an elastomeric coating.
• silicone compositions which can be cold vulcanized (but whose vulcanization is generally accelerated by heat), in particular those of the two-component type (EVF II), crosslinking by hydrosilylation or polyaddition.
• EVF II two-component type
• crosslinking by hydrosilylation or polyaddition to produce an elastomeric coating.
• These coatings are suitable, for example for the protection or mechanical reinforcement of different substrates, in particular textile material such as fibrous, woven, knitted or non-woven supports.
• Silicone elastomer coatings on textile substrates provide some of the intrinsic characteristics of silicones to the resulting composites. According to the applications one seeks for example: a thermal protection associated with a mechanical reinforcement in the case of tissues for airbag without weighing down the resulting part, a mechanical function coupled with an anti-fouling character for the complexes intended for the textile architecture, and or - a character of pronounced mechanical strength for the conveyor belts.
• Silicones do not always have all the characteristics in question and it is often a question of settling compromises. Thus, in the case of textile architecture, silicones do not make it possible to satisfy the anti-fouling nature and they must be covered by a hard varnish; this varnish deposited on a soft substrate tends to fragment during mechanical stresses and it does not reveal its full potential.
• one of the essential objectives of the present invention is to provide a method for preparing a woven, knitted, or nonwoven fibrous support coated on one or both sides with at least one reinforced elastomeric silicone layer.
• the Applicant has found, quite fortuitously and surprisingly: a) that the mechanical properties of the silicone crosslinkings can be optimized on a woven, knitted or non-woven fibrous support, in particular to increase their stiffness without penalizing their elongation capacity by adding short microfibers in their formulation, b) this operation is not at the expense of the density of the resulting elastomer, and c) that such compositions are thin-film-enducible on the targeted textile media.
• a crosslinkable silicone coating composition characterized in that it comprises, per 100 parts by weight of organopolysiloxane: from 0.5 to 15 parts by weight, preferably from 0.5 to 10 parts by weight and even more preferably from 2 to 6 parts by weight, of a reinforcement consisting of polyester, polyolefin or polyamide microfibers which have:
• said polyamide is chosen from the group consisting of: polyamide 6, polyamide 6.6, polyamide 4, polyamide 11, polyamide 12, polyamides 4-6, 6-10, 6-12, 6-36, 12-12, their copolymers and mixtures, b) the application of at least 20 g / m 2, preferably at least 40 g / m 2 and still more preferably at least 100 g / m 2, on one or both sides of a woven, knitted, or nonwoven fibrous support of the silicone coating composition (A) prepared in step a), and c) the crosslinking, in particular by heating or by electromagnetic radiation, of the deposit formed in step b) to form at least one reinforced elastomeric silicone layer.
• polyester or polyolefin microfibers mention may be made of:
• PET polyethylene terephthalate
• PE polyethylene
• the invention relates to a process for preparing a woven, knitted or non-woven fibrous support coated on one or both sides with at least one reinforced elastomeric silicone layer comprising the following steps: a) the preparation of a composition silicone coating (A) crosslinkable characterized in that it comprises per 100 parts by weight of organopolysiloxane: from 0.5 to 15 parts by weight, preferably from 0.5 to 10 parts by weight and even more preferably from
• said polyamide is chosen from the group consisting of: polyamide 6, polyamide 6.6, polyamide 4, polyamide 11, polyamide 12, polyamides 4-6, 6-10, 6-12, 6-36, 12-12, their copolymers and mixtures, b) the application of at least 20 g / m 2, preferably at least 40 g / m 2 and still more preferably at least 100 g / m 2, on one or both sides of a woven, knitted, or nonwoven fibrous support of the silicone coating composition (A) prepared in step a), and c) the crosslinking, in particular by heating or by electromagnetic radiation, of the deposit formed in step b) to form at least one reinforced elastomeric silicone layer.
• microfibers of polyamides according to the invention are obtained by cutting son, filaments or cables using a cutting technique known to those skilled in the art, for example using a guillotine or a knife wheel.
• cables is meant a large set of continuous filaments made without torsion, assembled in a form similar to a loose rope and held together.
• a cable is generally obtained by melt spinning filaments, gathering and stretching these filaments.
• microfibres according to the invention are manufactured according to the standard methods known to those skilled in the art and for example by extrusion of the polyamide material melted through a die and then optionally stretching the son, ribbons, cables or plies, then cutting these microfiber products.
• any step, conventional in the field of the manufacture of textile microfibers, intended for example to dimensionally stabilize the fibers (heat setting) or to give them volume through a compression box (crimping), can be applied .
• Any other microfiber manufacturing process is also suitable.
• microfibers used in the present invention may have sections of any shape, whether round, serrated or fluted, or in the form of beans, but also multi-lobed, in particular trilobed or pentalobed, X-shaped, ribbon, hollow, square, triangular, elliptical and others.
• microfiber section is however not an essential feature of the invention. All forms of fiber section resulting from the process of manufacturing said microfibers are acceptable. Similarly, the microfibers used in the present invention may be of diameter and / or constant section or have variations.
• the polyamide microfibers used are characterized:
• polyamide which is chosen from the group consisting of: polyamide 6, polyamide 6.6, polyamide 4, polyamide 11, polyamide 12, polyamides 4-6, 6-10, 6-12, 6 36, 12-12, their copolymers and mixtures.
• the polyamide microfibers come from the section of cables formed from a plurality of continuous filaments of polyamide 6 or polyamide 6.6. All cut fibers thus obtained are called “Flock” because they are commonly used in flocking processes to achieve, for example, coatings for applications in the automobile or building.
• the polyamide microfibers have the following characteristics: a uniform and calibrated length of between 0.1 and 10 mm, preferably between 0.1 and 6 mm and even more preferentially between 0.3 and 5 mm, and
• a titre between 0.1 and 15 dtex, preferably between 0.1 and 10 dtex and even more preferably between 0.5 and 2.5 dtex.
• the polyamide microfibers are in the form of flocks before incorporation into said composition.
• the raw polyamide microfiber may be treated, before being mixed with the slurry containing the hydraulic binder, with one or more of the additives known in the field of the manufacture of textile fibers or microfibers according to various known methods.
• This treatment can be carried out at different stages of the manufacture of the microfiber. These include, among other things, all the steps in which sizing is conventionally added. It is thus possible to apply the additive at the bottom of the spinning machine before winding. It is also possible, in the case of "fiber" processes, to apply the additive before, during or after the drawing, crimping or drying steps, for example.
• additives include delustrants, mattifying agents, for example particles of titanium dioxide and / or zinc sulphide, colored pigments, stabilizers, modifiers of properties such as antistaticity, hydrophylia , anti-stain or anti-fouling effect and fireproofing.
• Silicone coating is defined as the action of coating a support with a crosslinkable liquid silicone composition and then cross-linking the coated film on the support to produce a coating.
• curable polyorganosiloxane compositions contemplated in the context of the present invention, presented in one or several packages (mono- or multicomponents), contain, in addition to the microfibres according to the invention, a main constituent formed of one or more constituent (s) polyorganosiloxane (s), a suitable catalyst and optionally one or more compound (s) such as, for example, reinforcing fillers, crosslinking agents, anti-structuring agents, adhesion promoters, catalyst inhibiting agents and various and varied additives,
• the invention is particularly applicable to a silicone coating composition (A) which comprises:
• the silicone coating compositions (A) are polyorganosiloxane compositions, two-component or one-component, crosslinking at room temperature or with heat by polyaddition reactions, essentially by reaction of hydrogenosilyl groups with alkenylsilyl groups, in the presence of A metal catalyst, generally based on platinum, is described, for example, in US Pat. Nos. 3,220,972, 3,284,406, 3,436,366, 3,697,473 and 4,340,709.
• a silicone coating composition (A ) very particularly preferred is described in the patent application FR-2861753.
• an inhibitor (f) of the platinum catalyst may be added to the polyorganosiloxane crosslinking composition by polyaddition reactions.
• the inhibitor when one is used, is engaged at the rate of 0.005 to 5 parts by weight, preferably 0.01 to 3 parts by weight, per 100 parts of the gum (a ').
• R 2 is H or a linear or branched alkyl radical, or a phenyl radical
• the radicals R 1 , R 2 and the carbon atom at a of the triple bond may optionally form a ring;
• the total number of carbon atoms contained in R 1 and R 2 being at least 5, preferably 9 to 20.
• Said alcohols are preferably chosen from those having a boiling point greater than 250 ° C. Examples that may be mentioned include: ethynyl-1-cyclohexanol 1;
• Examples of two-component or one-component organopolysiloxane compositions which crosslink at room temperature by moisture-containing polycondensation reactions, in the generally presence of a metal catalyst, for example a tin or titanium compound, are described by US Pat. example for the single-component compositions in US-A-3,065,194, 3,542,901, 3,779,986, 4,417,042, and in FR-A-2,638,752, and for the two-component compositions in the US Pat. A-3,678,002, 3,888,815, 3,993,729 and 4,064,096.
• the polycondensation composition may also comprise a silane bearing two hydrolysable groups and serving as extending silane. These difunctional silanes are well known to those skilled in the art.
• the last subject of the invention relates to a woven, knitted or non-woven fibrous support, coated on one or both faces, obtainable by the process according to the invention and as described above.
• the support sample is a glass fabric (indifferent nature) with a surface weight of approximately 250 g / m 2 .
• the coating of the support is carried out with a laboratory squeegee allowing a deposit of the order of 200 .mu.m; its crosslinking on the support is carried out for 2 minutes in a ventilated oven maintained at 160 ° C.
• Fibrous reinforcement This is polyamide 6-6 microfibers initially in the form of flocks (microfibres of 0.9 dtex title with a calibrated length cut to 0.4 mm, washing desensitization and simple drying). These suitably dried fibers are incorporated into the composition. elastomer using a centrifugal type laboratory stirrer.
• a varnish is applied to the silicone support by means of a Mayer bar suitable for a deposit of the order of 5 g / m 2 ; the crosslinking is carried out by living in a ventilated oven at 180 0 C for 2 minutes.
• composition of the varnish is described in the patent application FR-2849445.
• a glass fabric pre-impregnated on one face is coated and varnished.
• the crosslinking of the coating is done in 2 minutes at 160 ° C.
• the crosslinking of the varnish is made in 1 minute at 120 0 C

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Woven Fabrics (AREA)

Applications Claiming Priority (2)

Publications (1)

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Family Applications (1)

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Family Cites Families (5)

• 2006
  • 2006-12-22 FR FR0611272A patent/FR2910499A1/fr active Pending
• 2007
  • 2007-12-20 WO PCT/EP2007/064286 patent/WO2008080867A1/fr active Application Filing
  • 2007-12-20 EP EP07857907A patent/EP2122046A1/fr not_active Withdrawn
  • 2007-12-20 KR KR1020097012885A patent/KR20090083938A/ko not_active Application Discontinuation

Non-Patent Citations (1)

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