Patent GB-670244-A (GB)
Title: Improvements in or relating to laminated articles and methods of making the same
IPC: B32B27/00
Filed: 1948-07-02
Abstract: Laminated articles are made from cellulosic materials, such as cellulosic fabrics and paper or mixtures of such fabrics and paper, by treating lamin  thereof with a colloidal solution of silica, drying the treated lamin  and bonding them together with a contact pressure type resin.  The colloidal solution of silica may be prepared as in Specifications 649,896, 649,897, or 654,850, [all in Group III].  The contact pressure type resin is preferably a liquid resin comprising a mixture of a polyester condensation product and a vinyl compound; alkyd resins or allyl resins may also be used.  The polyester condensation products are made by reacting, with stirring and in an inert atmosphere, e.g. of carbon dioxide or nitrogen, an unsaturated aliphatic polybasic acid or its anhydride such as an a ,b -unsaturated organic acid, with or without the addition of an aromatic dicarboxylic acid or its anhydride, with a polyhydric alcohol, the reaction being carried out under an air condenser permitting escape of evolved water. The unsaturated aliphatic polybasic acid of anhydride may be a dicarboxylic aliphatic acid having ethylenic unsaturation and not more than 8 carbon atoms in the molecule, or the anhydride thereof, e.g. maleic acid, fumaric acid, citraconic acid, mesaconic acid, methyl ethyl maleic acid, or diethyl maleic acid or an acid or anhydride of the general formula <FORM:0670244/IV (a)/1> (where R and R1 are hydrogen, halogen or alkyl groups, and R2 and R3 are hydroxyl or together stand for oxygen). As the aromatic dicarboxylic acid or anhydride there may be used, for example, phthalic acid, or its anhydride or terephthalic acid. As glycols, ethylene glycol, diethylene glycol, propylene glycols such as 1,2- and 1,3-propanediol, butylene glycols such as 1,2-, 1,3- and 1,4-butanediol and triethylene glycols are mentioned. Long-chain aliphatic acids, or the corresponding glycerides may be added to the reaction mixture, wholly or partially replacing the aromatic dicarboxylic acids; examples quoted are: saturated acids which may have straight, branched or substituted chains, e.g. decanoic and pentadecanoic acids, nonochloroctadecanoic acid, 12-hydroxyoctadecanoic acid, unsaturated acids such as 7 - hexadecenoic acid, 10 - undecenoic acid, 9,12 - octadecadienoic acid, 9,12,15 - octadecatrienoic acid and substituted olefinic acids, such as 16-hydroxy-7-hexadecenoic acid, 2-chloro-9-octadecenoic acid, and acids derived by dehydrogenation of castor oil acids, followed by chlorination.  Styrene or other vinyl compound may be added to the polyester condensation product, a preferred group of such compounds being alpha-substituted ethylene compounds of the general formula <FORM:0670244/IV (a)/2> where R1 is a negative group such as aryl, vinyl, ethyl, carboxyl, halogen, halovinyl, acyloxy or carbalkoxy and R2 is hydrogen or alkyl.  Copolymerization between the polyester and the vinyl compound may be effected by heating in presence of a catalyst, e.g. benzoyl peroxide.  In examples, a cotton duck fabric is treated with a colloidal silica solution prepared as described above, dried, and impregnated with a liquid resin made by reacting maleic anhydride and phthalic anhydride with ethylene glycol, and reacting the resultant polymer with styrene using benzoyl peroxide as catalyst. Alternate plies are then laid with their warps at right angles, the whole is wrapped in regenerated cellulose film, placed between polished metal plates in a press and cured.