WO1993008235A1 - Unsaturated polyester compositions for laminates and method for using same - Google Patents

Unsaturated polyester compositions for laminates and method for using same Download PDF

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Publication number
WO1993008235A1
WO1993008235A1 PCT/FR1992/000941 FR9200941W WO9308235A1 WO 1993008235 A1 WO1993008235 A1 WO 1993008235A1 FR 9200941 W FR9200941 W FR 9200941W WO 9308235 A1 WO9308235 A1 WO 9308235A1
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Prior art keywords
composition according
unsaturated polyester
monomer
weight
composition
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PCT/FR1992/000941
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French (fr)
Inventor
François Juhasz
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Cray Valley S.A.
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Publication of WO1993008235A1 publication Critical patent/WO1993008235A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters

Definitions

  • the present invention relates to unsaturated polyester compositions which can be used for the production of laminates.
  • unsaturated polyester resins are well known for the production of multilayer laminates, in particular in the field of shipbuilding where they are sought after for the aesthetic appearance, for good resistance to hydrolysis and for the ease of implementation by various methods.
  • One of the environmental protection problems posed by such resins consists in the emission of styrene, the aim of which is to reduce the rate to as low a level as possible.
  • the emission of styrene in the use of unsaturated polyester resins for shipbuilding is generally significant since the surface area worked in the open air is very large.
  • a solution recommended for lowering the evaporation rate of styrene consists in adding paraffin wax, generally at a rate of 0.05 to 0.5% by weight, and / or surfactants in the unsaturated polyester resin, in order to form a "film" on the surface thereof.
  • this solution does not entirely solve the problem because other parameters, such as the nature of the catalytic system, the degree of unsaturation of the resin and especially the exothermic peak of the resin, very strongly influence the phenomenon of emission of styrene.
  • an n waxy material capable of forming a film for example paraffin
  • an adhesion promoter e.g. polyacrylate
  • a nonionic surfactant e.g., a nonionic surfactant or a copolymer of a hemi-ester of maleic acid and a polyethylene glycol with a monoalkenylaromatic monomer.
  • adhesion promoters which can be used according to this document are stearyl and lauryl methacrylates and alkyl esters of acrylic acid and their (co) polymers.
  • the envisaged adhesion promoters suffer from the drawback of being only partially soluble in resins containing styrene, which justifies the need for the stabilizer (e).
  • the present invention has the advantage of responding to this need by means of an additive simultaneously playing the roles of anti-shrinkage and adhesion promoter without making necessary the use of a stabilizer such as those of patent EP-A-369 683.
  • the present invention proposes to solve these problems by means of a composition of unsaturated polyester, of monomer copolymerizable with the unsaturated polyester and of paraffin, characterized in that it also comprises at least 1.5% by weight, by based on the combined weight of the polyester and the monomer, of at least one alkyl methacrylate polymer in which the alkyl group has from 1 to 6 carbon atoms, said polymer being soluble in the monomer and miscible with the unsaturated polyester.
  • alkyl methacrylate polymer within the meaning of the present invention means firstly the homopolymers of such methacrylates, in particular preferably polymethyl methacrylate.
  • the copolymers of these methacrylates which may contain up to approximately 20% by weight of ethylenically unsaturated comonomers copolymerizable with alkyl methacrylates, such as for example alkyl and hydroxyalkyl acrylates of which the alkyl group has from 1 to 8 carbon atoms, N-substituted maleimides, etc.
  • alkyl methacrylates such as for example alkyl and hydroxyalkyl acrylates of which the alkyl group has from 1 to 8 carbon atoms, N-substituted maleimides, etc.
  • the compositions according to the invention can comprise up to approximately 10% by weight of alkyl methacrylate polymer, the latter preferably having a very high molecular weight, for example between 10 5 and 10 6 approximately.
  • the alkyl methacrylate polymer present in the compositions according to the invention may be in the form of a solution of this polymer in the monomer, this presentation promoting the homogeneity of the
  • compositions according to the invention usually comprise in particular when they are intended for producing multilayer laminates for shipbuilding, from 0.05% to about 0.5% by weight, relative to the combined weight of the polyester and the monomer, paraffin such as for example an aliphatic wax. They also comprise an unsaturated polyester resin and at least one monomer copolymerizable in usual proportions, that is to say at a rate of approximately 10 to 50 parts by weight of monomer per 100 parts of the combined weight of the polyester and of the monomer.
  • the unsaturated polyester resins present in the compositions according to the invention are the polycondensation products of polycarboxylic acids or anhydrides ⁇ , ⁇ - ethylenically unsaturated, optionally mixed with saturated polycarboxylic acids or anhydrides, and polyhydric alcohols or alkylene oxides
  • the molecular weight of the unsaturated polyester resin is not critical and can vary over a wide range, generally between 250 and 5000 approximately and more particularly between 350 and 2500.
  • Unsaturated polycarboxylic acids or anhydrides which can be used include in particular maleic, fumaric, chloromaleic, citraconic, metaconic, itaconic, tetraconic or similar acids or, where the corresponding anhydrides exist.
  • Saturated polycarboxylic acids or anhydrides which can be used to partially replace, for example up to around 95 mol%, and preferably up to around 45 mol%, unsaturated acids or anhydrides, in particular include orthophtaiic, isophthalic, terephthalic acids , succinic, methylsuccinic, adipic, sebacic, tetrabromo-phthalic, tetrachlorophthalic, glutaric, pimelic or the like or, when the corresponding anhydrides exist.
  • saturated aliphatic diols are generally preferred such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethyiene glycol, tetraethylene glycol, 1,3-butanediol , 1,4-butanediol, tripropyieneglycoL pentanediol hexanediol and neopentylglycoL Bisphenol A and its alkoxylated derivatives, as well as other aromatic polyols can also be used.
  • Ethylene and propylene oxides can also be used.
  • the unsaturated polyester resin is prepared from maleic anhydride, it is advantageous to carry out their preparation in the presence of morpholine in order to increase the rate of isomerization of the maleate functions into fumarate functions.
  • the amount of morpholine used in this case can reach up to 1% by weight, and is preferably between 0.1% and 0.5% by weight of the polyester.
  • compositions of the present invention it is also preferable to incorporate at least one agent capable of forming radicals.
  • agents there may be mentioned inter alia organic peroxides, peroxydicarbonates and peroxyesters such as benzoyl peroxide, tertiary butyl hydroperoxide, tertiary butyl peroxide, dicumyl peroxide, 2,2 bis (ter-butylperoxy) butane, paracetal, 1,1-bis (t-butylperoxy) 3,3,5-trimethyicyclohexane.
  • compositions according to the invention can also comprise additives, such as quaternary ammonium compounds or oxyethylated tertiary amines which facilitate the wetting of glass fibers, inhibitors and accelerators.
  • additives such as quaternary ammonium compounds or oxyethylated tertiary amines which facilitate the wetting of glass fibers, inhibitors and accelerators.
  • styrene As monomer copolymerizable with the unsaturated polyester in order to generate a crosslinked structure, mention may be made of styrene, vinyltoluene, tert-butylstyrene, ralphamethylstyrene, chlorostyrene, dichloro-stryrene, lower alkyl esters (C 1 to C 8 ) acrylic acid and methacrylic acid, cyclic acrylates and methacrylates, such as those of cyciohexyl and benzyl, bi-cyclic methacrylates and acrylates such as those of isobornyl, diallyl phthalate, diallyl maleate, diallyl fumarate, triallyl cyanurate, acetate, crotonate and vinyl propionate, divinylether, conjugated dienes such as 1,3-butadiene, isoprene.
  • styrene vinyltoluene
  • 1,4-pentadiene 1,4-hexadiene, 1,5-hexadiene, 1-9-decadiene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 2-alkyl-2,5-norbornadienes, 5-ethylidene-2-norbornene, 5- (2-pro ⁇ enyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 1,5-cyclooctadiene. the bicyclo [2.2,2] octa-2.5-diene.
  • cyclopentadiene 4,7,8,9-tetrahydroindene and isopropylidene tetra-hydroindene
  • unsaturated nitriles such as racrylonitrile and methacrylonitrile as well as (meth) polyol acrylates such as diacrylates and dimethacrylates of ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexane-diol, neopentyl-glycol, 1,4-cyclo-hexane-diol, 1,4 - cyclo-hexane -dimethanol, 2,2,4-trimé-thyl-1,3-pentanediol, 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, diethylene glycol dipropylene glycol, tri
  • compositions according to the invention have numerous advantages such as a low monomer emission rate, a low exothermic peak and the absence of delamination phenomenon while retaining the traditional properties of polyester resins such as good resistance to l 'hydrolysis.
  • the delamination phenomenon is reduced to such an extent that it is possible, after having left a laminate produced from such a composition at room temperature for one month, to resume the stratification by the addition of additional layers without making undergo no treatment prior to the laminate.
  • compositions according to the invention can also comprise:
  • - glass fibers preferably having a length at least equal to approximately 25 mm, generally present in an amount of approximately 20 to 50 parts by weight per 100 parts by weight of the mixture of polyester, monomer and polymer of methacrylate alkyl,
  • At least one flame retardant such as an alumina hydrate, and / or
  • At least one thixotropic agent such as colloidal silica or pyrolysis clay in an amount of approximately 0.5 to 1.5 by weight per 100 parts of composition.
  • a second object of the present invention therefore relates to a multilayer laminate characterized in that it comprises at least one layer produced from a composition as described above.
  • the layer produced from a composition according to the The invention may have a thickness of between 3 and 15 mm approximately.
  • the multilayer laminates according to the invention have a low emission rate of monomer and good hydrolysis resistance which make them perfectly suitable for use not only for shipbuilding (manufacture of large boat parts) but also for the manufacture of parts such as tanks and pipes and also for automobile industry.
  • a third object of the present invention consists of a process for using the compositions described above for the production of laminated parts, by the so-called “contact process” or else by the so-called “simultaneous projection” process.
  • the contact process consists in forming a part by manual impregnation of superimposed layers of mat or glass fibers with the composition according to the invention using a brush or a roller.
  • the other method consists in the simultaneous projection of the composition of unsaturated polyester, of monomer, of paraffin and of polymethylmethacrylate on the one hand of the agent forming radicals and of glass fibers cut on the other hand in a mold or in a mandrel using a spray gun equipped with a glass cutter.
  • the glass-based reinforcing material is generally used in this process at a rate of about 20 to 40 parts by weight per 100 parts of resin composition, although proportions outside these limits may also be necessary in specific applications.
  • the implementation process according to the invention is particularly easy because of the generally low viscosity of the compositions according to the invention, which promotes wetting of the reinforcing material and allows a high impregnation speed.
  • compositions according to the invention can also contain at least one thixotropic agent such as colloidal silica or pyrolyzed clay in an amount of approximately 0.5 to 1.5 by weight per 100 parts of composition.
  • thixotropic agent such as colloidal silica or pyrolyzed clay
  • An unsaturated polyester resin is first prepared from 10.6 moles of propylene glycol 1.2, 3.5 moles of maleic anhydride and 6.5 moles of phthalic anhydride.
  • a composition is then prepared comprising 57 parts by weight of the polyester resin obtained above, 38 parts by weight of styrene, 0.15 parts by weight of paraffin and 4.85 parts by weight of a solution of polymethyl methacrylate to 40% in styrene, the properties measured on this composition are as follows:

Abstract

A composition consisting of an unsaturated polyester, a monomer which is copolymerizable with said unsaturated polyester, and paraffin, and further including 1.5 wt %, based on the weight of the polyester/styrene conjugate, of at least one alkyl methacrylate polymer in which the alkyl group has 1-6 carbon atoms. The composition is used to produce multilayered laminates.

Description

COMPOSITIONS DE POLYESTERS INSATURES POUR STRATIFIES ET LEUR PROCEDE DE MISE EN OEUVRE.  UNSATURATED POLYESTER COMPOSITIONS FOR LAMINATES AND THEIR PROCESS.
La présente invention se rapporte à des compositions de polyesters insaturés pouvant être mis en oeuvre pour la réalisation de stratifiés.  The present invention relates to unsaturated polyester compositions which can be used for the production of laminates.
L'utilisation de résines polyesters insaturés est bien connue pour la réalisation de stratifiés multicouch.es, notamment dans le domaine de la construction navale où ils sont recherchés pour l'aspect esthétique, pour la bonne tenue à l'hydrolyse et pour la facilité de mise en oeuvre par divers procédés. L'un des problèmes de protection de l'environnement posés par de telles résines consiste en l'émission de styrène, dont on cherche à abaisserle taux à un niveau aussi faible que possible. En effet, l'émission de styrène dans l'utilisation des résines polyesters insaturés pour la construction navale est généralement importante étant donné que la surface travaillée à l'air libre est très grande. Une solution préconisée pour abaisser le taux d'évaporation du styrène consiste à ajouter de la cire de paraffine, généralement à raison de 0,05 à 0,5 % en poids, et/ou des agents tensio- actifs dans la résine polyester insaturé, afin de former un "film" en surface de celle-ci. Toutefois, cette solution ne résoud pas entièrement le problème car d'autres paramètres, tels que la nature du système catalytique, le degré d'insaturation de la résine et surtout le pic exothermique de la résine, influencent très fortement le phénomène d'émission de styrène.  The use of unsaturated polyester resins is well known for the production of multilayer laminates, in particular in the field of shipbuilding where they are sought after for the aesthetic appearance, for good resistance to hydrolysis and for the ease of implementation by various methods. One of the environmental protection problems posed by such resins consists in the emission of styrene, the aim of which is to reduce the rate to as low a level as possible. In fact, the emission of styrene in the use of unsaturated polyester resins for shipbuilding is generally significant since the surface area worked in the open air is very large. A solution recommended for lowering the evaporation rate of styrene consists in adding paraffin wax, generally at a rate of 0.05 to 0.5% by weight, and / or surfactants in the unsaturated polyester resin, in order to form a "film" on the surface thereof. However, this solution does not entirely solve the problem because other parameters, such as the nature of the catalytic system, the degree of unsaturation of the resin and especially the exothermic peak of the resin, very strongly influence the phenomenon of emission of styrene.
D'autre part l'ajout de paraffine dans une résine polyester insaturé présente l'inconvénient de provoquer un phénomène de délaminage lorsque la composition de polyester et de paraffine est utilisée pour la réalisation de stratifiés multicouches. Ce phénomène exige de procéder à un traitement préalable (par exemple ponçage) du stratifié avant de procéder à l'application de la couche ultérieure. Ce traitement supplémentaire est très coûteux en temps de main d'oeuvre et élève le prix de revient des stratifiés multicouches ainsi fabriqués, sans totalement écarter le risque d'un déiaminage ultérieur de la pièce stratifiée. Ce phénomène de délaminage est d'ailleurs exposé dans le brevet EP-A-369 683 qui décrit une composiiton comprenant :  On the other hand, the addition of paraffin in an unsaturated polyester resin has the disadvantage of causing a delamination phenomenon when the polyester and paraffin composition is used for the production of multilayer laminates. This phenomenon requires a prior treatment (for example sanding) of the laminate before proceeding with the application of the subsequent layer. This additional treatment is very costly in terms of labor time and raises the cost price of the multilayer laminates thus produced, without totally eliminating the risk of subsequent de-diamination of the laminated part. This delamination phenomenon is moreover exposed in patent EP-A-369 683 which describes a composition comprising:
(a) une résine polyester insaturée,  (a) an unsaturated polyester resin,
(b) un monomère polymérisable,  (b) a polymerizable monomer,
(c) un n matériau cireux capable de former un film (par exemple de la paraffine), (d) un promoteur d'adhésion (par ex. polyacrylate), et (c) an n waxy material capable of forming a film (for example paraffin), (d) an adhesion promoter (e.g. polyacrylate), and
(ei à titre de stabilisant un surfactant non-ionique ou bien un copolymère d'un hémi-ester de l'acide maléique et d'un polyéthylène glycol avec un monomère monoalcénylaromatique.  (ei as stabilizer a nonionic surfactant or a copolymer of a hemi-ester of maleic acid and a polyethylene glycol with a monoalkenylaromatic monomer.
Parmi les promoteurs d'adhésion utilisables selon ce document figurent des méthacrylates de stéaryle et de lauryle et des esters d'alkyle de l'acide acrylique et leurs (co)polymères. Toutefois les promoteurs d'adhésion envisagés souffrent de l'inconvénient d'être seulement partiellement solubles dans des résines contenant du styrène, ce qui justifie la nécessité du stabilisant (e).  Among the adhesion promoters which can be used according to this document are stearyl and lauryl methacrylates and alkyl esters of acrylic acid and their (co) polymers. However, the envisaged adhesion promoters suffer from the drawback of being only partially soluble in resins containing styrene, which justifies the need for the stabilizer (e).
Il existe donc un besoin pressant pour la mise au point de compositions de polyester insaturé pour pièces stratifiées offrant simultanément un faible taux d'émission de styrène, une absence de déiaminage et un faible pic exothermique.  There is therefore a pressing need for the development of unsaturated polyester compositions for laminated parts simultaneously offering a low emission rate of styrene, an absence of de-diamination and a low exothermic peak.
Par ailleurs il est connu d'introduire dans une résine polyester msaturé un (co)polymère (mêth)acrylique thermoplastique afin de limiter le phénomène de retrait volumétrique, lors du moulage, qui se produit au fur et à mesure que la résine polyester polymérise. Ce retrait volumétrique est à l'origine, pour les pièces moulées, d'une surface finie rugueuse qui permet de reconnaître les fibres de verre qui apparaissent généralement en saillie sur la surface du produit fini et laissent même deviner des ondulations.  Furthermore, it is known to introduce a (co) polymer (meth) acrylic thermoplastic into a msaturated polyester resin in order to limit the phenomenon of volumetric shrinkage, during molding, which occurs as the polyester resin polymerizes. This volumetric shrinkage is at the origin, for molded parts, of a rough finished surface which makes it possible to recognize the glass fibers which generally appear protruding on the surface of the finished product and even suggest ripples.
Une telle technique est décrite notamment par le brevet US-A-3 701 748. Le document JP-A-71/85 739 décrit aussi une composition comprenant de 20 à 70 parties de polyester insaturé, de 25 à 75 parties de styrène et de 1 à 25 parties de copolymère acrylate de méthyie/acrylate d'hydroxypropyle en tant qu'agent anti-retrait Toutefois il est connu qu'un tel copolymère acrylate de méthyie/acrylate d'hydroxypropyle n'est pas miscible avec le polyester insaturé, et qu'un copolymère méthacrylate de méthyle (87)/acrylate d'éthyle (13) tel que celui des exemples 1 à 3 du brevet US-A-3 701 748 conduit à des mélanges non compatibles, c'est-à-dire présentant une séparation de phases, avec le polyester et le styrène.  Such a technique is described in particular by US Pat. No. 3,701,748. Document JP-A-71 / 85,739 also describes a composition comprising from 20 to 70 parts of unsaturated polyester, from 25 to 75 parts of styrene and of 1 to 25 parts of methyl acrylate / hydroxypropyl acrylate copolymer as anti-shrinkage agent However, it is known that such methyl acrylate / hydroxypropyl acrylate copolymer is not miscible with the unsaturated polyester, and that a methyl methacrylate (87) / ethyl acrylate (13) copolymer such as that of Examples 1 to 3 of US Pat. No. 3,701,748 leads to mixtures which are incompatible, that is to say having phase separation, with polyester and styrene.
Il existe donc également un besoin pour la mise au point de compositions de polyester insaturé offrant simultanément un faible taux d'émission de styrène, une absence de délaminage et un faible retrait volumétrique. La présente invention possède l'avantage de répondre à ce besoin au moyen d'un additif jouant simultanément les rôles d'anti-retrait et de promoteur d'adhésion sans rendre nécessaire l'emploi d'un stabilisant tel que ceux du brevet EP-A-369 683. There is therefore also a need for the development of unsaturated polyester compositions which simultaneously offer a low rate of styrene emission, an absence of delamination and a low volumetric shrinkage. The present invention has the advantage of responding to this need by means of an additive simultaneously playing the roles of anti-shrinkage and adhesion promoter without making necessary the use of a stabilizer such as those of patent EP-A-369 683.
La présente invention se propose de résoudre ces problèmes au moyen d'une composition de polyester insaturé, de monomère copolymérisable avec le polyester insaturé et de paraffine, caractérisée en ce qu'elle comprend en outre au moins 1,5 % environ en poids, par rapport au poids conjugué du polyester et du monomère, d'au moins un polymère de méthacrylate d'alkyle dont le groupe alkyle possède de 1 à 6 atomes de carbone, iedit polymère étant soluble dans le monomère et miscible avec le polyester insaturé. Par polymère de méthacrylate d'alkyle au sens de la présente invention on entend d'une part les homopolymères de tels méthacrylates, notamment de manière préférée le polyméthacrylate de méthyle. et d'autre part les copolymères de ces méthacrylates pouvant contenir jusqu'à 20 % environ en poids de comonomères insaturés éthyléniquement copolymérisables avec les méthacrylates d'alkyle, tels que par exemple les acrylates d'alkyle et d'hydroxyalkyle dont le groupe alkyle possède de 1 à 8 atomes de carbone, les maléimides N-substituées, etc. Les compositions selon l'invention peuvent comprendre jusqu'à 10 % environ en poids de polymère de méthacrylate d'alkyle, celui-ci ayant de préférence un poids moléculaire très élevé, par exemple compris entre 105 et 106 environ. Le polymère de méthacrylate d'alkyle présent dans les compositions selon l'invention peut se présenter sous forme d'une solution de ce polymère dans le monomère, cette présentation favorisant l'homogénéité de la composition ainsi que son mode de préparation. The present invention proposes to solve these problems by means of a composition of unsaturated polyester, of monomer copolymerizable with the unsaturated polyester and of paraffin, characterized in that it also comprises at least 1.5% by weight, by based on the combined weight of the polyester and the monomer, of at least one alkyl methacrylate polymer in which the alkyl group has from 1 to 6 carbon atoms, said polymer being soluble in the monomer and miscible with the unsaturated polyester. The term “alkyl methacrylate polymer” within the meaning of the present invention means firstly the homopolymers of such methacrylates, in particular preferably polymethyl methacrylate. and on the other hand, the copolymers of these methacrylates which may contain up to approximately 20% by weight of ethylenically unsaturated comonomers copolymerizable with alkyl methacrylates, such as for example alkyl and hydroxyalkyl acrylates of which the alkyl group has from 1 to 8 carbon atoms, N-substituted maleimides, etc. The compositions according to the invention can comprise up to approximately 10% by weight of alkyl methacrylate polymer, the latter preferably having a very high molecular weight, for example between 10 5 and 10 6 approximately. The alkyl methacrylate polymer present in the compositions according to the invention may be in the form of a solution of this polymer in the monomer, this presentation promoting the homogeneity of the composition as well as its method of preparation.
Les compositions selon l'invention comprennent habituellement notamment lorsqu'elles sont destinées à la réalisation de stratifiés multicouches pour la construction navale, de 0,05 % à 0,5 % environ en poids, par rapport au poids conjugué du polyester et du monomère, de paraffine telle que par exemple une cire aliphatique. Elles comprennent en outre une résine polyester insaturé et au moins un monomère copolymérisable en proportions usuelles, c'est-à-dire à raison de 10 à 50 parties en poids environ de monomère pour 100 parties du poids conjugué du polyester et du monomère. Les résines polyester insaturé présentes dans les compositions selon l'invention sont les produits de polycondensation d'acides ou anhydrides polycarboxyliques α, β- éthyiéniquement insaturés, le cas échéant en mélange avec des acides ou anhydrides polycarboxyliques saturés, et d'alcools polyhydriques ou d'oxydes d'alkylène The compositions according to the invention usually comprise in particular when they are intended for producing multilayer laminates for shipbuilding, from 0.05% to about 0.5% by weight, relative to the combined weight of the polyester and the monomer, paraffin such as for example an aliphatic wax. They also comprise an unsaturated polyester resin and at least one monomer copolymerizable in usual proportions, that is to say at a rate of approximately 10 to 50 parts by weight of monomer per 100 parts of the combined weight of the polyester and of the monomer. The unsaturated polyester resins present in the compositions according to the invention are the polycondensation products of polycarboxylic acids or anhydrides α, β- ethylenically unsaturated, optionally mixed with saturated polycarboxylic acids or anhydrides, and polyhydric alcohols or alkylene oxides
La masse moléculaire de la résine polyester insaturée n'est pas critique et peut varier dans une gamme importante, généralement comprise entre 250 et 5000 environ et plus particulièrement entre 350 et 2500.  The molecular weight of the unsaturated polyester resin is not critical and can vary over a wide range, generally between 250 and 5000 approximately and more particularly between 350 and 2500.
Des acides ou anhydrides polycarboxyliques insaturés utilisables comprennent notamment les acides maléique, fumarique, chloromaléique, citraconique, métaconique, itaconique, tétraconique ou similaires ou, lorsqu'ils existent les anhydrides correspondants. Des acides ou anhydrides polycarboxyliques saturés utilisables pour remplacer partiellement par exemple jusqu'à 95 % en moles environ, et de préférence jusqu'à 45 % en moles environ, les acides ou anhydrides insaturés, comprennent notamment les acides orthophtaiique, isophtalique, téré-phtalique, succinique, méthylsuccinique, adipique, sébacique, tétrabromo-phtalique, tétrachlorophtalique, glutarique, pimêlique ou similaires ou, lorsqu'ils existent les anhydrides correspondants.  Unsaturated polycarboxylic acids or anhydrides which can be used include in particular maleic, fumaric, chloromaleic, citraconic, metaconic, itaconic, tetraconic or similar acids or, where the corresponding anhydrides exist. Saturated polycarboxylic acids or anhydrides which can be used to partially replace, for example up to around 95 mol%, and preferably up to around 45 mol%, unsaturated acids or anhydrides, in particular include orthophtaiic, isophthalic, terephthalic acids , succinic, methylsuccinic, adipic, sebacic, tetrabromo-phthalic, tetrachlorophthalic, glutaric, pimelic or the like or, when the corresponding anhydrides exist.
Parmi les alcools polyhydriques utilisables, on préfère généralement les diols aliphatiques saturés tels que l'éthylène glycol, le propylène glycol, le butylène glycol, le diéthylène glycol, le dipropylène glycol, le triéthyiène glycol, le tétraéthylène glycol, le 1,3-butanédiol, le 1,4-butanédiol, le tripropyièneglycoL le pentanédioL l'hexanédiol et le néopentylglycoL Le bisphénol A et ses dérivés alcoxylés, ainsi que d'autres polyols aromatiques peuvent également être utilisés. Les oxydes d'éthylène et de propylène sont également utilisables.  Among the polyhydric alcohols that can be used, saturated aliphatic diols are generally preferred such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethyiene glycol, tetraethylene glycol, 1,3-butanediol , 1,4-butanediol, tripropyieneglycoL pentanediol hexanediol and neopentylglycoL Bisphenol A and its alkoxylated derivatives, as well as other aromatic polyols can also be used. Ethylene and propylene oxides can also be used.
Lorsque la résine polyester insaturée est préparée à partir d'anhydride maléique, il est avantageux d'effectuer leur préparation en présence de morpholine afin d'augmenter le taux d'isomérisation des fonctions maléates en fonctions fumarates. La quantité de morpholine utilisée dans ce cas peur atteindre jusqu'à I % en poids, et est de préférence comprise entre 0,1 % et 0,5 % en poids du polyester.  When the unsaturated polyester resin is prepared from maleic anhydride, it is advantageous to carry out their preparation in the presence of morpholine in order to increase the rate of isomerization of the maleate functions into fumarate functions. The amount of morpholine used in this case can reach up to 1% by weight, and is preferably between 0.1% and 0.5% by weight of the polyester.
Dans les compositions de la présente invention, on incorpore également de préférence au moins un agent capable de former des radicaux. Comme agents appropriés, on peut citer entre autres des peroxydes organiques, peroxydicarbonates et peroxyesters tels que le peroxyde de benzoyle, l'hydroperoxyde de butyle tertiaire, le peroxyde de butyle tertiaire, le peroxyde de dicumyle, le 2,2 bis (ter-butylperoxy) butane, le paracétal, le 1,1-bis (t-butylperoxy) 3,3,5-triméthyicyclohexane. le perbenzoate de butyle tertiaire, le peroxyoctoate de butyle tertiaire, le ter-butyl peroxy isopropylcarbonate, le perisononanoate de butyle tertiaire, le permaléinate de butyle tertiaire, le péracétal cyclique, le 2,5-diméthyl-2,5-bis (2- éthylhexolperoxy) hexane. le peroxyde de méthyléthylcétone, le peroxyoctoate de tertioamyle, le 2,5-diρéroxyoctoate, ou encore le peroxyde de 2,4-ρentanédione. In the compositions of the present invention, it is also preferable to incorporate at least one agent capable of forming radicals. As suitable agents, there may be mentioned inter alia organic peroxides, peroxydicarbonates and peroxyesters such as benzoyl peroxide, tertiary butyl hydroperoxide, tertiary butyl peroxide, dicumyl peroxide, 2,2 bis (ter-butylperoxy) butane, paracetal, 1,1-bis (t-butylperoxy) 3,3,5-trimethyicyclohexane. tertiary butyl perbenzoate, tertiary butyl peroxyoctoate, tert-butyl peroxy isopropylcarbonate, tertiary butyl perisononanoate, tertiary butyl permaleinate, cyclic peracetal, 2,5-dimethyl-2,5-bis (2- ethylhexolperoxy) hexane. methyl ethyl ketone peroxide, tertioamyl peroxyoctoate, 2,5-diρéroxyoctoate, or 2,4-ρentanédione peroxide.
Les compositions selon l'invention peuvent également comprendre des additifs, tels que des composés ammoniums quaternaires ou des aminés tertiaires oxyéthylées qui facilitent le mouillage des fibres de verre, des inhibiteurs et des accélérateurs.  The compositions according to the invention can also comprise additives, such as quaternary ammonium compounds or oxyethylated tertiary amines which facilitate the wetting of glass fibers, inhibitors and accelerators.
Comme monomère copolymérisable avec le polyester insaturé afin de générer une structure réticulée, on peut citer le styrène, le vinyltoluène, le tertio-butyl-styrène, ralphaméthylstyrène, le chlorostyrène, le dichloro- stryrène, les esters d'alkyle inférieur (C 1 à C8) d'acide acrylique et d'acide méthacrylique, les acrylates et méthacrylates cycliques, comme ceux de cyciohexyle et de benzyle, les méthacrylates et acrylates bi-cycliques comme ceux d'isobornyle, Je phtalate de diallyle, le maléate de diallyle, le fumarate de diallyle, le cyanurate de triallyle, l'acétate, le crotonate et le propionate de vinyle, le divinylether, les diènes conjugués tels que le butadiène-1,3, l'isoprέne. le 1.3-pentadiène. le 1,4-pentadiène. le 1,4-hexadiène, le 1,5-hexadiène, le 1-9-décadiène, le 5-méthylène-2-norbornène, le 5-vinyl-2-norbornène, les 2-alkyl-2,5-norbornadiènes, le 5-éthylidène-2-norbornène, le 5-(2-proρenyl)-2-norbornène, le 5-(5-hexenyl)-2-norbornène, le 1,5 -cyclooctadiène. le bicyclo [2.2,2] octa-2.5-diène. le cyclopentadiène, le 4,7,8,9-têtrahydroindène et l'isopropylidène tétra-hydroindène, et les nitriles insaturés tels que racrylonitrile et le méthacrylonitrile ainsi que les (méth)acrylates de polyol comme les diacrylates et diméthacrylates de i'éthylèneglycol, du propylèneglycol, du 1,3-butanédiol, du 1,4-butanédiol, du 1,6-hexane-diol, du néopentyl-glycol, du 1,4-cyclo-hexane-diol, du 1,4 - cyclo-hexane-diméthanol, du 2,2,4-trimé-thyl-1,3-pentanédiol, du 2-éthyl-2-méthyl-1,3-propanédiol, du 2,2-diéthyl-1,3-propanédiol, du diéthylèneglycol du dipropylèneglycol, du triéthyiène-glycol, du tripropyièneglycol, du tétraéthylèneglycol, du tétrapropylène-glycol, du triméthyloléthane, du triméthylopropane, du glycérol, du penta-érythritol, les triacrylates et triméthacrylates du triméthyloléthane, du triméthylolpropane, du glycérol, du pentaerythritoL les tétraacrylates et tétraméthacrylates du pentaerythritol, les di(meth)acryiates à hexa(meth)-acryiates du dipentaerythritol, les poly(meth)acrylates de polyols mono- ou polyéthoxylés ou mono- ou polyproxylés tels que le triacryiate et le triméthacrylate du triméthyol-propane triéthoxylé, du triméthylolpropane tripropoxylé , le triacryiate et le triméthacrylate du glycérol tripropoxylé, le triacryiate, le triméthacrylate, le tétraacrylate et le tétraméthacrylate du pentaérythritol tétraéthoxylé, et leurs mélanges en toutes proportions. As monomer copolymerizable with the unsaturated polyester in order to generate a crosslinked structure, mention may be made of styrene, vinyltoluene, tert-butylstyrene, ralphamethylstyrene, chlorostyrene, dichloro-stryrene, lower alkyl esters (C 1 to C 8 ) acrylic acid and methacrylic acid, cyclic acrylates and methacrylates, such as those of cyciohexyl and benzyl, bi-cyclic methacrylates and acrylates such as those of isobornyl, diallyl phthalate, diallyl maleate, diallyl fumarate, triallyl cyanurate, acetate, crotonate and vinyl propionate, divinylether, conjugated dienes such as 1,3-butadiene, isoprene. 1.3-pentadiene. 1,4-pentadiene. 1,4-hexadiene, 1,5-hexadiene, 1-9-decadiene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 2-alkyl-2,5-norbornadienes, 5-ethylidene-2-norbornene, 5- (2-proρenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 1,5-cyclooctadiene. the bicyclo [2.2,2] octa-2.5-diene. cyclopentadiene, 4,7,8,9-tetrahydroindene and isopropylidene tetra-hydroindene, and unsaturated nitriles such as racrylonitrile and methacrylonitrile as well as (meth) polyol acrylates such as diacrylates and dimethacrylates of ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexane-diol, neopentyl-glycol, 1,4-cyclo-hexane-diol, 1,4 - cyclo-hexane -dimethanol, 2,2,4-trimé-thyl-1,3-pentanediol, 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, diethylene glycol dipropylene glycol, triethyleneglycol, tripropyiene glycol, tetraethylene glycol, tetrapropylene glycol, trimethylolethane, trimethylopropane, glycerol, pentaerythritol, triacrylates and trimethylolethane trimethacrylates, trimethylolpropane, glycerol, pentaerythritoL pentaerythritol tetraacrylates and tetramethacrylates, hex (meth) acryiates di (meth) acrylates, dipentaerythritol acrylates or poly (meth) polyol monoxides or polyproxylates such as the triacryiate and the trimethacrylate of trimethyol-propane triethoxylated, of trimethylolpropane tripropoxylated, the triacryiate and the trimethacrylate of glycerol tripropoxylated, the triacryiate, the trimethacrylate, the tetraacrylate and the tetraacryl tetrametra tetrametra tetrametra tetrametra tetrametra tetra
Les compositions selon l'invention présentent de nombreux avantages tels qu'un faible taux d'émission de monomère, un faible pic exothermique et l'absence de phénomène de dêlaminage tout en conservant les propriétés traditionnelles des résines polyesters telie que la bonne tenue à l'hydrolyse. Le phénomène de délaminage est réduit à un point tel qu'il est possible, après avoir laissé un stratifié réalisé à partir d'une telle composition à la température ambiante pendant un mois, de reprendre la stratificatiαn par l'addition de couches supplémentaires sans faire subir aucun traitement préalable au stratifié.  The compositions according to the invention have numerous advantages such as a low monomer emission rate, a low exothermic peak and the absence of delamination phenomenon while retaining the traditional properties of polyester resins such as good resistance to l 'hydrolysis. The delamination phenomenon is reduced to such an extent that it is possible, after having left a laminate produced from such a composition at room temperature for one month, to resume the stratification by the addition of additional layers without making undergo no treatment prior to the laminate.
En fonction de la plupart des applications dans lesquelles elles sont susceptibles d'être utilisées, les compositions selon l'invention peuvent en outre comprendre :  Depending on most of the applications in which they are capable of being used, the compositions according to the invention can also comprise:
- des fibres de verre, ayant de préférence une longueur au moins égale à 25 mm environ, généralement présentes à raison de 20 à 50 parties environ en poids pour 100 parties en poids du mélange de polyester, de monomère et de polymère de méthacrylate d'alkyle,  - glass fibers, preferably having a length at least equal to approximately 25 mm, generally present in an amount of approximately 20 to 50 parts by weight per 100 parts by weight of the mixture of polyester, monomer and polymer of methacrylate alkyl,
- au moins un retardateur de flamme tel qu'un hydrate d'alumine, et/ou  - at least one flame retardant such as an alumina hydrate, and / or
- au moins un pigment organique ou minéral, et/ ou  - at least one organic or inorganic pigment, and / or
- au moins un agent thixotropique tel que la silice colloïdale ou l'argile pyrolyse à raison de 0,5 à 1,5 en poids environ pour 100 parties de composition.  at least one thixotropic agent such as colloidal silica or pyrolysis clay in an amount of approximately 0.5 to 1.5 by weight per 100 parts of composition.
Un second objet de la présente invention concerne donc un stratifié multicouche caractérisé en ce qu'il comprend au moins une couche réalisée à partir d'une composition telle que décrite précédemment Dans un tel stratifié, la couche réalisée à partir d'une composition selon l'invention peut avoir une épaisseur comprise entre 3 et 15 mm environ. Les stratifiés multicouches selon l'invention possèdent un faible taux d'émission de monomère et une bonne tenue à l'hydrolyse qui les rendent parfaitement adaptés à une utilisation non seulement pour la construction navale (fabrication de pièces de bateaux de grande dimension) mais aussi pour la fabrication de pièces telles que cuves et tuyaux et encore pour l'industrie automobile. A second object of the present invention therefore relates to a multilayer laminate characterized in that it comprises at least one layer produced from a composition as described above. In such a laminate, the layer produced from a composition according to the The invention may have a thickness of between 3 and 15 mm approximately. The multilayer laminates according to the invention have a low emission rate of monomer and good hydrolysis resistance which make them perfectly suitable for use not only for shipbuilding (manufacture of large boat parts) but also for the manufacture of parts such as tanks and pipes and also for automobile industry.
Un troisième objet de la présente invention consiste en un procédé de mise en oeuvre des compositions décrites précédemment pour la réalisation de pièces stratifiées, par la méthode dite "procédé de contact" ou bien par le procédé dit de "projection simultanée". Le procédé de contact consiste à former une pièce par imprégnation manuelle de couches superposées de mat ou de fibres de verre avec la composition selon l'invention à l'aide d'un pinceau ou d'un rouleau. L'autre procédé consiste en la projection simultanée de la composition de polyester insaturé, de monomère, de paraffine et de polyméthacrylate d'alkyle d'une part de l'agent formant des radicaux et de fibres de verre coupées d'autre part dans un moule ou dans un mandrin à l'aide d'un pistolet de projection équipé d'un coupeur de verre. La matière de renforcement à base de verre, est généralement utilisée dans ce procédé à raison de 20 à 40 parties en poids environ pour 100 parties de composition de résine, bien que des proportions sortant de ces limites puissent aussi être nécessaires dans des applications spécifiques. Le procédé de mise en oeuvre selon l'invention est particuiièrement aisé en raison de la viscosité généralement faible des compositions selon l'invention, qui favorise le mouillage de la matière de renforcement et permet une grande vitesse d'imprégnation.  A third object of the present invention consists of a process for using the compositions described above for the production of laminated parts, by the so-called "contact process" or else by the so-called "simultaneous projection" process. The contact process consists in forming a part by manual impregnation of superimposed layers of mat or glass fibers with the composition according to the invention using a brush or a roller. The other method consists in the simultaneous projection of the composition of unsaturated polyester, of monomer, of paraffin and of polymethylmethacrylate on the one hand of the agent forming radicals and of glass fibers cut on the other hand in a mold or in a mandrel using a spray gun equipped with a glass cutter. The glass-based reinforcing material is generally used in this process at a rate of about 20 to 40 parts by weight per 100 parts of resin composition, although proportions outside these limits may also be necessary in specific applications. The implementation process according to the invention is particularly easy because of the generally low viscosity of the compositions according to the invention, which promotes wetting of the reinforcing material and allows a high impregnation speed.
Enfin les compositions selon l'invention peuvent en outre contenir au moins un agent thixotropique tel que la silice colloïdale ou l'argile pyrolysée à raison de 0,5 à 1,5 en poids environ pour 100 parties de composition.  Finally, the compositions according to the invention can also contain at least one thixotropic agent such as colloidal silica or pyrolyzed clay in an amount of approximately 0.5 to 1.5 by weight per 100 parts of composition.
L' exemple suivant est fourni à titre illustratif et non limitatif de la présente inventioa  The following example is provided by way of illustration and without limitation of the present invention.
EXEMPLE EXAMPLE
On prépare d'abord une résine polyester insaturé à partir de 10,6 moles de propylène glycol 1,2, 3,5 moles d'anhydride maléique et 6,5 moles d'anhydride phtalique. On prépare ensuite une composition comprenant 57 parties en poids de la résine polyester obtenue ci-dessus, 38 parties en poids de styrène, 0,15 partie en poids de paraffine et 4,85 parties en poids d'une solution de polyméthacrylate de méthyle à 40 % dans le styrène, les propriétés mesurées sur cette composition sont les suivantes : An unsaturated polyester resin is first prepared from 10.6 moles of propylene glycol 1.2, 3.5 moles of maleic anhydride and 6.5 moles of phthalic anhydride. A composition is then prepared comprising 57 parts by weight of the polyester resin obtained above, 38 parts by weight of styrene, 0.15 parts by weight of paraffin and 4.85 parts by weight of a solution of polymethyl methacrylate to 40% in styrene, the properties measured on this composition are as follows:
. température de déformation à la chaleur (norme NF T 5100E) : 61°C . résistance à la flexion (norme NF T 51001) : 75 MPa  . heat deformation temperature (standard NF T 5100E): 61 ° C. flexural strength (standard NF T 51001): 75 MPa
. résistance à la traction (norme NF T 51034) : 40 MPa  . tensile strength (standard NF T 51034): 40 MPa
. résistance au choc (norme NFT 51035) : 6,5 KJ/m2 . impact resistance (standard NFT 51035): 6.5 KJ / m 2
Mise en oeuvre par projection simultanée avec des fibres de verre, cette composition ne présente aucun phénomène de délaminage après Implementation by simultaneous projection with glass fibers, this composition exhibits no delamination phenomenon after
30 jours et permet d'opérer une nouvelle stratification, à l'issue de ce délai, sans procéder à un traitement préalable de surface. 30 days and allows for a new stratification, at the end of this period, without carrying out a prior surface treatment.

Claims

REVENDICATIONS
1. Composition de polyester insaturé, de monomère copolymérisable avec le polyester insaturé et de paraffine, caractérisée en ce qu'elle comprend en outre au moins 1,5 % en poids, par rapport au poids conjugué du polyester et du monomère, d'au moins un polymère de méthacrylate d'alkyle dont le groupe alkyle possède de 1 à 6 atomes de carbone, ledit polymère étant soluble dans le monomère et miscible avec le polyester insaturé. 1. Composition of unsaturated polyester, of monomer copolymerizable with the unsaturated polyester and of paraffin, characterized in that it additionally comprises at least 1.5% by weight, relative to the combined weight of the polyester and of the monomer, of at least at least one polymer of alkyl methacrylate in which the alkyl group has from 1 to 6 carbon atoms, said polymer being soluble in the monomer and miscible with the unsaturated polyester.
2 Composition selon la revendication 1, caractérisée en ce que le polymère de méthacrylate d'alkyle est le polyméthacrylate de méthyle.  2 Composition according to Claim 1, characterized in that the polymer of alkyl methacrylate is polymethyl methacrylate.
3. Composition selon l'une des revendications 1 et 2, caractérisée en ce qu'elle comprend de 0,05 % à 0,5 % en poids, par rapport au poids conjugué du polyester et du monomère, de paraffine. 3. Composition according to one of claims 1 and 2, characterized in that it comprises from 0.05% to 0.5% by weight, relative to the combined weight of the polyester and the monomer, of paraffin.
4, Composition selon l'une des revendications 1 à 3, caractérisée en ce que le poids moléculaire du polymère de méthacrylate d'alkyle est compris entre 105 et 106. 4, Composition according to one of claims 1 to 3, characterized in that the molecular weight of the polymer of alkyl methacrylate is between 10 5 and 10 6 .
5. Composition selon l'une des revendications 1 à 4, caractérisée en ce qu'elle comprend en outre au moins un agent capable de former des radicaux. 5. Composition according to one of claims 1 to 4, characterized in that it further comprises at least one agent capable of forming radicals.
6. Composition selon l'une des revendications 1 à 5, caractérisée en ce qu'elle comprend en outre des fibres de verre.  6. Composition according to one of claims 1 to 5, characterized in that it further comprises glass fibers.
7, Composition selon l'une des revendications 1 à 6, caractérisée en ce qu'elle comprend en outre au moins un agent thixotropique. 7, Composition according to one of claims 1 to 6, characterized in that it further comprises at least one thixotropic agent.
8. Composition selon l'une des revendications 1 à 7, caractérisée en ce qu'elle comprend en outre au moins un pigment organique ou minéral. 8. Composition according to one of claims 1 to 7, characterized in that it further comprises at least one organic or inorganic pigment.
9. Composition selon l'une des revendications 1 à 8, caractérisée en ce qu'elle comprend en outre au moins un retardateur de flamme. 9. Composition according to one of claims 1 to 8, characterized in that it further comprises at least one flame retardant.
10 Stratifié multicouche, caractérisé en ce qu'il comprend au moins une couche réalisée à partir d'une composition selon l'une des revendications 1 à 9. 10 Multilayer laminate, characterized in that it comprises at least one layer produced from a composition according to one of claims 1 to 9.
11. Stratifié multicouche selon la revendication 10, caractérisé en ce que ladite couche comprend en outre une matière de renforcement à base de verre. 11. Multilayer laminate according to claim 10, characterized in that said layer further comprises a glass-based reinforcing material.
12. Procédé de mise en oeuvre d'une composition selon l'une des revendications 1 à 9, caractérisé en ce que ladite composition est utilisée pour la réalisation de pièces stratifiées par la méthode dite "procédé de contacf ou bien par projection simultanée avec une matière de renforcement à base de verre. 12. Method of using a composition according to one of claims 1 to 9, characterized in that said composition is used for the production of laminated parts by the so-called "contact process" or by simultaneous projection with a glass-based reinforcement material.
PCT/FR1992/000941 1991-10-14 1992-10-09 Unsaturated polyester compositions for laminates and method for using same WO1993008235A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR91/12607 1991-10-14
FR9112607A FR2682393B1 (en) 1991-10-14 1991-10-14 UNSATURATED POLYESTER COMPOSITIONS FOR LAMINATES AND THEIR IMPLEMENTATION METHOD.

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AU (1) AU2909292A (en)
FR (1) FR2682393B1 (en)
SI (1) SI9200257A (en)
WO (1) WO1993008235A1 (en)
ZA (1) ZA927799B (en)

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US6802759B1 (en) 1999-12-31 2004-10-12 Voith Paper Holding Gmbh Grinder

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US3701748A (en) * 1966-07-20 1972-10-31 Rohm & Haas Unsaturated polyester resinous compositions
GB2011918A (en) * 1978-01-05 1979-07-18 Syntes Ab Unsaturated curable polyester composition
EP0369683A2 (en) * 1988-11-10 1990-05-23 The Dow Chemical Company Stable low styrene emission vinyl ester and unsaturated polyester resin compositions

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JPS4849884A (en) * 1971-10-27 1973-07-13
JPH03142238A (en) * 1989-10-30 1991-06-18 Kanegafuchi Chem Ind Co Ltd Metallic-foil clad laminated board for electricity

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US3701748A (en) * 1966-07-20 1972-10-31 Rohm & Haas Unsaturated polyester resinous compositions
GB2011918A (en) * 1978-01-05 1979-07-18 Syntes Ab Unsaturated curable polyester composition
EP0369683A2 (en) * 1988-11-10 1990-05-23 The Dow Chemical Company Stable low styrene emission vinyl ester and unsaturated polyester resin compositions

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6802759B1 (en) 1999-12-31 2004-10-12 Voith Paper Holding Gmbh Grinder

Also Published As

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FR2682393A1 (en) 1993-04-16
ZA927799B (en) 1993-04-21
FR2682393B1 (en) 1994-07-08
SI9200257A (en) 1993-06-30
AU2909292A (en) 1993-05-21

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