FR2676473A1 - COMPOSITION FOR COATING TISSUE, AND MATERIAL FOR SAILING PARAPLAN. - Google Patents

Abstract

Coating composition for a fabric obtained by dispersing, in an organic solvent, 100 parts by weight of an organopolysiloxane composition comprising: a) 50 to 90 parts by weight of a diorganopolysiloxane terminated at both ends with hydroxyl groups, represented by the general formula (1): (CF DRAWING IN BOPI) wherein R is a substituted or unsubstituted monofunctional hydrocarbon group having 1 to 20 carbon atoms, and m is a degree of polymerization between 20 and 10,000, b ) a crosslinking agent in an amount of 1 to 30 parts by weight relative to the diorganopolysiloxane terminated by hydroxyl groups, and c) 1 to 50 parts by weight of an inorganic filler. The canopy material uses a fabric made of nylon and / or polyester fibers as a fabric and has on its surface a coating of the above coating composition which gives it excellent properties including water repellency, waterproofing. and elasticity.

Description

J 1 t

4 2676473

  The invention relates to a coating composition which, when applied to a fabric, renders it water-repellent, impermeable, impervious and elastic, and particularly relates to a coating composition. used for paraglider sail materials.

  The practice of the paraglider is a sport still in its infancy.

  However, anyone can benefit without special training, and as it is also very fashionable while being simple and safe, it has become in a short time an aerial sport

having a large number of followers.

  The required characteristics of a paraglider wing material are, first of all, from the safety point of view, that the seam strength and the tear resistance are sufficiently high and do not deteriorate with time; second, that it has good flight performance, a good surface smoothness so that it can be easily transported, and be light; third, that it has sufficient water-repellent properties and low water absorption, so that its weight does not increase, even when wet by rain; and, fourthly, that it has a long life, with a high weather resistance and a color fastness that increases its value as a fashion object.

  Since it has already been used for parachute

  nylon fabric is often used as a paraplaner fabric (Japanese Patent Application Laid-Open Without Exam TOKKAI SHO 54-49799), the nylon fabric being usually coated with a waterproofing polyurethane resin for

  improve its weather resistance.

  However, nylon-based materials are extremely sensitive to UV light, and therefore lose their water repellency and elasticity after about a year of use. Paraplaners using polyester materials instead of nylon have resistance to UV light almost double that of nylon-based materials, but, as in the case of nylon, their initial properties decline

in time.

  Recently, a fabric obtained by pretreating polyester fibers with a polysiloxane resin terminated at both ends by hydroxyl groups, and coating them with a polyurethane resin or a polysiloxane-modified polyurethane resin, has been particularly widely used. because it exhibits high tear strength over long periods of time, does not readily absorb water and is light

  (Japanese patent application published without examination TOKKAI HEI 2-

  41475) This material has both high strength and lightness, which are the main requirements of a paraplaner fabric. However, if a polyurethane resin or a polysiloxane-modified polyurethane resin was deposited on a fabric as described above, the urethane bond having a low resistance to UV light, its water-repellent and waterproofing properties, its seal and its elasticity declined.

  inevitably for long periods of use.

  There are in the art coating agents based on organosilazanesiloxane polymers which could obviously

  overcome the above-mentioned drawbacks However, as the

  While large paragliders are not easy, it was desirable to obtain a paraglider wing material that retained its water repellency and impermeability, sealability and initial elasticity over long periods of time.

  without resorting to the employment of maintenance agents.

  In-depth studies led to the discovery that

  The above requirements could be met by a

  crosslinked organopolysiloxane having a mixing formula

  determined, which led to the present invention.

  A first object of the invention is therefore to provide an agent of

  coating which can impart to a fabric hydrofluoric properties

  ges, impermeability properties, tightness and elasticity. A second object of the invention is to provide a paraglider wing material that retains its water-repellent properties, impermeability properties, tightness and elasticity.

over long periods.

  These objects are achieved according to the invention by a coating composition of a fabric obtained by dispersing in a solvent

  100 parts by weight of an organopolysaccharide composition.

  siloxane composition comprising a) 50 to 90 parts by weight of a hydroxyl terminated diorganopolysiloxane represented by the general formula (1)

1100 H

  Wherein R is a substituted or unsubstituted monofunctional hydrocarbon group having 1 to 20 carbon atoms, and m is a degree of polymerization of from 20 to 10,000, b) 1 to 30 parts by weight of a crosslinking for the aforementioned hydroxyl terminated diorganopolysiloxane, and

  c) 1 to 50 parts by weight of an inorganic filler.

  The coating composition according to the invention can easily impart to a fabric water-repellent properties, impermeability properties, sealing, smoothness and elasticity by a simple procedure, including deposition on the fabric and drying at ordinary temperature for a period of time. a duration of several hours to several days, and its properties are preserved over a long period. In addition, the fabric coated with the composition is light because the amount of coating composition required to impart these properties is low, so that the present composition provides much higher characteristics than

  known materials for paraglider sails.

  In the first component of the composition, namely the diorganopolysiloxane terminated at both ends by hydroxyl groups, the substituent group R is a substituted or unsubstituted monofunctional hydrocarbon group having 1 to 20 carbon atoms. Specific examples are alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, tetradecyl and hexadecyl; of the

  aryl groups such as phenyl and tolyl, cycloalkyl groups,

  such as cyclopentyl and cyclohexyl, and monofunctional hydrocarbon groups in which all or part of the hydrogen atoms bonded to the carbon atoms are replaced by

  fluorine, chlorine or cyano groups such as chloromethyl

  chloroethyl, chloropropyl, chlorophenyl, 3,3,3-trifluoro-

  propyl, cyanomethyl and cyanoethyl.

  In the present invention, it is particularly advantageous that the proportion of the methyl groups with respect to the totality of the R groups is not less than 50 mol%. The degree of polymerization m is preferably between 20 and 10,000, and more advantageously between 100 and 5000 If m is less than, the crosslinked film obtained is too hard and its elasticity deteriorates This leads to the appearance of cracks and crevices which degrade its water-repellent properties and its tightness If m is greater than -10 000, on the other hand, its spreading and extensibility properties deteriorate, which

alters the uniformity of the film.

  Examples of the crosslinking agent, which is the second component of the composition, include the acetic derivatives of the

  such as triacetoxymethylsilane and triacetoxyvinyl

  silane, oximated derivatives of silane such as tris (ethyl

  thylketoximo) methylsilane and tris (ethylmethylketoximo) vinyl

  silane, alcoholic derivatives of silane such as

  thoxymethylsilane and trimethoxyvinylsilane, and other silane derivatives by amides or acetone, known in the art In the invention, among the above compounds,

  odorless oxime-type crosslinking agents are particularly

favorite.

  The inorganic filler which is the third component of the invention may be silica, diatomite, quartz powder, calcium carbonate, titanium oxide, perlite or various types of clay. This component confers additional resistance to the organopolysiloxane film obtained, and it is advantageous for silica, and silica in the form of fumed silica, to constitute at least 50% of the

inorganic filler.

  In the invention, on 100 parts by weight of the organopolysiloxane composition comprising the first, second and third components, the proportion of dosage of the first component is preferably from 50 to 90 parts by weight and more preferably from 60 to 80 parts by weight. By weight If the proportion is less than parts by weight, the extensibility of the composition declines, the uniformity of the film is affected and its flexibility declines, its water repellency and elasticity deteriorate If the proportion is greater than 90 parts by weight, the

  tensile strength of the resulting film deteriorates.

  On 100 parts by weight of the organopolysiloxane composition according to the invention, the proportion of dosage of the second component

  is preferably 1 to 30 parts by weight and more preferably

  If the proportion is less than 1 part by weight, the curing properties of the film are insufficient, so that the water-repellent properties and the sealing deteriorate. A proportion of greater than 30 parts by weight, preferably less than 1 part by weight. On the other hand, is more than the

  necessary, which implies a loss of money.

  On 100 parts by weight of the organopolysiloxane composition of the invention, the dosage proportion of the third component is from 1 to 50 parts by weight and preferably from 50 to 30 parts by weight. If the proportion is less than 1 part by weight, sufficient additional strength is not obtained, whereas if it is greater than 50 parts in

  weight, flexibility is deteriorating, which affects the elasticity.

  In the present invention, in addition to the aforementioned first, second and third components, a wetting agent may also be added. Examples of such a wetting agent are hydroxysilanes, hydroxysiloxanes, alkoxysilanes, silazanes, organic acid esters, and the like. and polyhydric alcohols. In the present invention, the crosslinked organopolysiloxane composition comprising the first, second and third components and a wetting agent, if necessary, are dispersed in an organic solvent to provide the fabric coating composition of the invention. boiling point of the organic solvent used is preferably between 40 and 250 ° C.

  atmospheric pressure, and the concentration of organopoly-

  siloxane is preferably between 0.1 and 20% by weight.

  The organic solvent is typically a chlorinated solvent such as dichloroethane, trichloroethane or methylene chloride; an aromatic hydrocarbon such as toluene or xylene; an aliphatic or alicyclic hydrocarbon such as petroleum ether, kerosene, nhexane, n-heptane, cyclohexane or isoparaffin; or a volatile organopolysiloxane such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,

  hexamethyldisiloxane, octamethyltrisiloxane or

  thyltétrasiloxane. The coating composition according to the invention is applied to the surface of a paraplaner fabric such as nylon or

  polyester by brush, roller, spray coating

  or the impregnation, and the solvent is allowed to evaporate at room temperature or evaporated at a slightly higher temperature. The coating composition undergoes a firing reaction in one hour, even at room temperature, and the stickiness the surface disappears It is however preferable to leave it at room temperature for a period of 1 to 3 days to allow complete cooking. In the present invention, a cooking catalyst can also be added to the composition to promote cooking. This catalyst can be chosen, for example, from zinc octate, iron octate, organic acid salts of cobalt,

  tin and the like, titanates such as tetrabutyltitanium;

  nate, tetrapropyltitanate and the like, or the compounds

organic amines.

  A coating of a fabric by the coating composition in a single application is normally sufficient, but an effect

  improved can be obtained by two to three applications.

  To give the above properties to a fabric and get a

  paraplaner wing material, the organopoly composition

  crosslinked lysiloxane according to the invention must be applied to the object to be treated, so that the amount of polymers per unit area is between 1.0 and 10.0 g / m 2. When this amount is less than 1, 0 g / m 2, sufficient properties can not be conferred on the fabric When on the other hand the amount is greater than 10.0 g / m 2, it does not get

  This is not only an anti-

  economic, but also increases the weight of the sail material,

which is not desirable.

  The coating composition according to the invention is effective for

  avoid deterioration of the water-repellent and waterproof properties

  It can also be used for similar purposes in the treatment of fabrics for folding canoes using UV-stabilized paraglider wing materials, or to restore these properties. hulls of boats, free wings, acrobatic kites, sails of

  sailboards and sails of yachts.

EXAMPLES

  The invention will be described in more detail with reference to specific examples, but it should be understood that these examples

  in no way limit the invention.

  Examples 1 to 4 and Comparative Example 1: 500 g of a terminally endblocked dimethylpolysiloxane, denoted by A (650 centistokes, average degree of polymerization m = 190) and 450 g of a hydroxyl endblocked dimethylpolysiloxane, designated B, (in a rubbery state, average degree of polymerization m = 190) as the first component, and 250 g of silica fume designated as A (average particle size 16 mg, surface area 200 m 2 / g) as the third component. 60 g of hexamethyldisilazane are added with stirring, the temperature is raised to 140-150 ° C., and the mixture is stirred at this temperature for 1 hour. reduces the pressure in the reactor to mm Hg, the mixture is stirred for 30 minutes and the

volatile components.

  of the reaction product obtained are introduced into 1126 g

  toluene and dispersed by stirring, then 15.5 g of tris (e.g.

  thylmethylketoximo) vinylsilane are added as the second component and homogeneously dissolved to give a fabric coating agent A. The fabric coating agent A thus obtained contains 67 parts by weight of the first component, 13 parts by weight of the weight of the second component and 20 parts by weight of the third component per 100 parts by weight of the crosslinked organopolysiloxane composition. As shown in Table 1, fabric coating agent A is dipped in various amounts onto a polyester paraplaner fabric, and left at room temperature

  for 24 hours Air leakage, volatility and sensitivity

  deterioration are then measured by the methods

  described below Air leakage is a measure of airtightness

  you. (Air leakage) The air leakage is measured according to JIS L-1079 using a Flagyl type tester (Toyoseiki Co, Ltd, Apparatus

air leak test for fabric).

  (Water-repellent properties) The water-repellent properties are measured according to JIS L-1079 by the spray method using a test apparatus of

water-repellent properties.

  (Resistance to deterioration) A fabric whose initial air leakage has been measured is flexed in the hands for 30 seconds, and its air leak is

new measured.

Table i

Ex 3 Ex 4

Ex comparison

  ratlf i Quantity 10.0 7.7 6.4 4.0 0.8 coated (g / m 2) Air leakage * lower lower 0.6 3.2 12.3

at 0.3 to 0.3

  Properties 90 90 90 90 20 water-repellent Lower sensitivity lower 0.6 3, 2 i 12.6 in the summer to 0.3 to 0.3 rioration *: cm 2 / cm 2 S (0.3 is the lower limit of measurement EXAMPLE 2 Comparative Example 2 The method is similar to that of Example 1, except that 950 g of a chain terminated dimethylpolysiloxane terminated at both ends with hydroxyl groups, designated C, (35 centistokes, average degree of polymerization m = 16) in place of the hydroxyl terminated dimethylpolysiloxanes A and B which constituted the first component of Example 1. A fabric coating agent B was obtained. obtained fabric coating B is deposited by soaking on a polyester paraplaner fabric in an amount of

  9.9 g / m 2, and left at room temperature for 24 hours.

  Its properties are measured by the same methods used in Example 1. The air leak is 7.3 cm 2 / cm 2 s, the water-repellent properties are 90 and the sensitivity to deterioration is 10.4 cm 2 / cm 2 s Air leakage and sensitivity to deterioration are worse than in all

previous examples.

Example 5

  The aforementioned properties of the fabric coated with the coating agent

  The surface area obtained in Example 2 is measured after irradiation of the fabric with UV light for 1000 hours using an "Atlas UV Con" (TOYO KIKAI SEISAKUJO). The water-repellent properties are reduced to 80, but no changes whatever. either is observed with respect to the air leak

  and sensitivity to deterioration.

  Comparative Example 3: The same tests as in Example 5 are carried out on a paraplaner fabric surface-coated with a commercial urethane resin. It is found that the air leakage and the deterioration sensitivity are much poorer.

  Water repellents of this commercial fabric are also inappropriate.

  The results of Example 5 and Comparative Example 3 are

summarized in Table 2.

Table 2

  Ex 5 Ex Comparative 3 Type of Resin Silicone Resin Urethane Resin Initial Air Leakage Less than 0.3 0.4 (cm 2 / cm 2 s) Initial 90 O Water Resistant Properties Initial Initial Damage Sensitivity <0, 3 Air leak after less than 0.3 8, 3

1000 hours of exposure

  UV resistance (cm 2 / cm 2 s) Water-repellent properties 80 O after 1000 hours of UV exposure Summer sensitivity less than 0.3 i 5.2 rioration after

1000 hours of exposure

  The above clearly shows that a fabric coated with the coating composition according to the invention has a seal, water repellency and elasticity far superior to those of the fabrics. for known paraplaners, and also has excellent resistance to irradiation with UV light over long periods.

Claims (16)

claims   1. A coating composition of a fabric obtained by dispersing,   in an organic solvent, 100 parts by weight of a   organopolysiloxane composition comprising: a) 50 to 90 parts by weight of a hydroxyl terminated diorganopolysiloxane represented by the general formula (1): wherein R is monofunctional substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and m is a degree of polymerization of from 20 to 10,000, b) 1 to 30 parts by weight of a crosslinking agent for said group terminated diorganopolysiloxane hydroxyl, and   c) 1 to 50 parts by weight of an inorganic filler.   2. Composition according to claim 1, characterized in that the proportion of methyl groups relative to the totality of the R groups in the general formula (1) of said component a) is not not less than 50 mol%.   3. Composition according to one of claims 1 and 2, characterized   in that the degree of polymerization m is between and 5000.   4. Composition according to one of the preceding claims,   characterized in that said component b) is an agent of oxime type crosslinking.   5. Composition according to one of the preceding claims,   characterized in that the inorganic filler of said component c)   comprises at least 50% by weight of silica.   6 Composition according to claim 5, characterized in that   said silica is silica fume.   7. Composition according to one of the preceding claims,   characterized in that said component a) is dosed in one   amount of between 60 and 80 parts by weight.   8. Composition according to one of the preceding claims,   characterized in that the proportion of component b) is   between 5 and 20 parts by weight.   9. Composition according to one of the preceding claims,   characterized in that said component c) is dosed in one   amount of between 5 and 30 parts by weight.   Composition according to one of the preceding claims,   characterized in that said organic solvent has a point   between 40 and 250 ° C at atmospheric pressure   and is selected from chlorinated solvents, aromatic hydrocarbons, aliphatic hydrocarbons, hydrocarbons   alicyclic and volatile organopolysiloxanes.   11. Composition according to one of the preceding claims,   characterized in that the concentrations of said components a), b) and c) in an organic solvent are between 0.1 and 20% by weight in total.   12. Composition according to one of the preceding claims,   characterized in that it further contains a wetting agent.   Composition according to Claim 12, characterized in that the said wetting agent comprises at least one chosen compound   hydroxysilanes, hydroxysiloxanes, alkoxysilanes,   silazanes, organic acid esters and polyhydric alcohols.   14. Apparatus for paragliding wing using a fabric formed of nylon and / or polyester fibers, characterized in that the organopolysiloxane composition according to one of the   preceding claims is applied to the surface of said   cloth then dried to adhere to it, at a rate of 1.0 to , 0 g / m 2.   15. Fabric coating composition according to one of   Claims 1 to 13, characterized in that said fabric is   intended for paragliders, folding canoes using boat hull fabrics, free wings, acrobatic kites, windsurf sails and yachts sails. 16. Fabric coating composition according to any one of   Claims 1 to 13, characterized in that said fabric is a   paraplaner wing material.