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EP2576140A1 - Adhesive composition containing a water-soluble or water-dispersible unsaturated polyester and an ethylene-unsaturated monomer, and uses thereof - Google Patents

Adhesive composition containing a water-soluble or water-dispersible unsaturated polyester and an ethylene-unsaturated monomer, and uses thereof

Info

Publication number
EP2576140A1
EP2576140A1 EP11726913.4A EP11726913A EP2576140A1 EP 2576140 A1 EP2576140 A1 EP 2576140A1 EP 11726913 A EP11726913 A EP 11726913A EP 2576140 A1 EP2576140 A1 EP 2576140A1
Authority
EP
European Patent Office
Prior art keywords
acid
composition according
unsaturated
water
polyester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11726913.4A
Other languages
German (de)
French (fr)
Inventor
Lidia Jasinska
Cornelis Eme Koning
Alix Arnaud
Clément HOUGA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Recherche SA
Original Assignee
Saint Gobain Recherche SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saint Gobain Recherche SA filed Critical Saint Gobain Recherche SA
Publication of EP2576140A1 publication Critical patent/EP2576140A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D11/00—Constructional features of flexible abrasive materials; Special features in the manufacture of such materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
    • B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6858—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/126—Copolymers block

Definitions

  • the invention relates to the field of binders intended to bind together elements made of natural or synthetic material, in particular minerals, such as abrasive particles, glass or rock fibers, and glass threads.
  • the invention more particularly relates to an adhesive composition which contains at least one unsaturated polyester water-soluble or dispersible in water and at least one ethylenically unsaturated monomer.
  • thermosetting resins based on formaldehyde in particular urea-formaldehyde, melamine-formaldehyde and phenol-formaldehyde resins. These resins have good crosslinking ability, are water soluble, have good affinity for minerals and are relatively inexpensive.
  • the object of the present invention is to provide an adhesive composition containing no formaldehyde, capable of bonding together elements consisting of natural or synthetic materials, in particular mineral materials, in particular abrasive particles, glass or rock fibers and yarns. of glass.
  • the adhesive composition according to the present invention is an aqueous composition which contains at least one water-soluble or water-dispersible unsaturated polyester and at least one ethylenically unsaturated monomer, said unsaturated polyester being obtained by co-polymerization (A) of at least one monomeric or oligomeric polyol, (B) at least one unsaturated polycarboxylic acid or an unsaturated acid anhydride and (C) at least one polymer water-soluble composition containing at least two hydroxyl, amine and / or epoxy reactive functional groups.
  • aqueous composition is meant a composition which contains at least 20% by weight of water, preferably at most 70% and more preferably 40 to 60%.
  • part of the water may be substituted with an organic solvent, for example tetrahydrofuran (THF) or methyl tetrahydro rofuran. born .
  • THF tetrahydrofuran
  • methyl tetrahydro rofuran born .
  • the proportion of water replaced by the solvent is at most equal to 50% by weight, preferably at most 30% and advantageously at most 20%.
  • the polyol (A) according to the present invention comprises at least two hydroxyl functional groups capable of reacting with the carboxylic functions carried by the abovementioned unsaturated polycarboxylic acid or obtained by the hydrolysis of the unsaturated acid anhydride.
  • the polyol comprises at most 35 hydroxyl functions, and advantageously at most 15.
  • the polyol is a monomeric or oligomeric polyol, that is to say comprising at most 10 monomer residues polyols, preferably at most 4.
  • the polyol (A) is chosen from polyols originating from a renewable source, in particular obtained from plants, such as saccharides, or generated by fermentation of plant materials, such as 1,3-propanediol and 1,4-butanediol.
  • saccharides As an example of saccharides, mention may be made of monosaccharides, preferably containing 3 to 8 carbon atoms, in particular hexoses such as glucose, mannose, galactose, derivatives of these hexoses in the form of alcohols. alicyclics and derivatives of these alicyclic alcohols, such as isosorbide, and oligosaccharides such as maltose, cellobiose, lactose, sucrose, trehalose, raffinose, stachyose and dextrins.
  • the preferred saccharide is isosorbide.
  • the unsaturated polycarboxylic acid (B) comprises at least two carboxylic functions, preferably at most four, and advantageously at most three carboxylic functions, and at least one ethylenic unsaturation.
  • unsaturated polycarboxylic acid By way of examples of unsaturated polycarboxylic acid (B), mention may be made of linear or branched aliphatic acids, such as fumaric acid, itaconic acid, maleic acid, traumatic acid, and acid. metaconic acid, citraconic acid and aconitic acid, cyclic acids such as 2,5-furan dicarboxylic acid (dehydromucic acid) and aromatic acids such as phthalic acid, tetrahydrophthalic acid, isophthalic acid, terephthalic acid, trimesic acid or pyromellitic acid.
  • linear or branched aliphatic acids such as fumaric acid, itaconic acid, maleic acid, traumatic acid, and acid. metaconic acid, citraconic acid and aconitic acid, cyclic acids such as 2,5-furan dicarboxylic acid (dehydromucic acid) and aromatic acids such as phthalic acid, tetrahydrophthalic acid
  • the unsaturated polycarboxylic acid (B) can also be obtained from the corresponding unsaturated acid anhydride which, by hydrolysis, generates the carboxylic functions.
  • the unsaturated acid anhydride is, for example, maleic anhydride.
  • the unsaturated polycarboxylic acid (B) and the unsaturated acid anhydride are monomeric.
  • the polymer (C) is water-soluble and thus makes it possible to introduce hydrophilic segments in the co-polyester, which gives it a better solubility in polar solvents such as water.
  • the polymer (C) contains at least two hydroxyl, amine and / or epoxy functional groups.
  • the polymer (C) is chosen from the group consisting of poly (oxyalkylenes), for example polyethylene glycols and polyethylenepropylene glycols which may carry one or more additional amino functions, polyvinylpyrrolidones, polyethyleneimines and polyoxazolines.
  • the polymer (C) comprises at least 4 monomer units.
  • the polymer (C) is a polyol, it is necessarily different from the polyol (A).
  • the polyethylene glycol has a molar mass of less than or equal to 600 g / mol and advantageously greater than or equal to 200 g / mol.
  • the ratio of the number of hydroxyl, amine and epoxy functional equivalents to the number of carboxylic functional equivalents ranges from 1.01 / 1 to 2/1, preferably from 1.05 / 1 to 1.5 / 1 and better still 1, 10/1 to 1, 2/1.
  • the percentage of the number of monomer units of the polymer (C) to the total number of monomer units of the polyol (A) and the polymer (C) ranges from 70 to 95% and preferably 70 to 85%.
  • the co-polymerization reaction of the monomeric or oligomeric polyol (A), the unsaturated polycarboxylic acid or the unsaturated acid anhydride (B) and the water-soluble polymer (C) is preferably carried out in the presence of a catalyst.
  • a catalyst for example titanium n-butoxide (IV).
  • Said agent is generally added in an amount representing 0.005 to 4 mol% of the compound (B) and preferably 0.01 to 1%.
  • an antioxidant may be introduced into the polymerization medium, for example 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, an amount at most equal to 1% of the total weight of the unsaturated polycarboxylic acid and the unsaturated acid anhydride (B).
  • the co-polymerization is generally carried out at a temperature ranging from 140 to 230 ° C, preferably 150 to 220 ° C, and preferably 160 to 210 ° C.
  • the co-polymerization can be carried out in several steps, in particular according to the following thermal cycle: 160 ° C. for 1 to 15 hours, 210 ° C. for 2 to 10 hours at atmospheric pressure and 210 ° C. for 1 to 5 hours under a reduced pressure, of the order of 3 to 5 mbar.
  • the preferred heat cycle is 160 ° C for 1 to 10 hours, 210 ° C for 2 to 2 hours at atmospheric pressure and 210 ° C for 1 to 4 hours under reduced pressure.
  • the unsaturated co-polyester according to the invention is solid at ambient temperature (of the order of 20 ° C.) and can be easily solubilized or dispersed in water.
  • the co-polyester is also soluble in organic solvents, especially in chlororforme.
  • the preferred unsaturated co-polyester is a polymer obtained by co-polymerization of isosorbide, maleic anhydride and polyethylene glycol.
  • the adhesive composition according to the invention comprises at least one ethylenically unsaturated monomer used as crosslinking agent of the co-polyester.
  • the ethylenically unsaturated monomer used as the co-polyester crosslinking agent is generally selected from the group consisting of by (meth) acrylic acids and (meth) acrylates, in particular 2-hydroxyethyl methacrylate, methacrylamide, N-vinylpyrrolidone and unsaturated carboxylic acids, especially the unsaturated polycarboxylic acids mentioned above, in particular itaconic acid and citraconic acid, or their anhydrides, in particular maleic anhydride.
  • the ethylenically unsaturated monomer is preferably soluble in water.
  • the ethylenically unsaturated monomer is added to the aqueous adhesive composition in such proportions that the weight ratio of unsaturated monomer to co-polyester ranges from 1/10 to 1/1, preferably 1/3 to 1/1.
  • a free radical initiator may be introduced into the aqueous adhesive composition to initiate crosslinking.
  • peroxides especially 2-butanone peroxide, persulfates and azobisisobutyronitrile (AIBN).
  • AIBN azobisisobutyronitrile
  • the amount of said initiator generally represents 0.5 to 2% of the total weight of the unsaturated co-polyester and the ethylenically unsaturated monomer.
  • the crosslinking of the aqueous adhesive composition is carried out at a temperature ranging from 50 to 180 ° C, preferably 60 to 150 ° C, for a period which may vary from 5 minutes to 6 hours, preferably 15 minutes to 2 hours.
  • the crosslinked co-polyester is an amorphous polymer which, therefore, does not have a melting point.
  • the cross-linked co-polyester has sufficient thermal stability for the intended applications.
  • the aqueous adhesive composition according to the present invention can be used to bind any type of elements composed of natural or synthetic material, in particular mineral elements such as abrasive particles, glass or rock fibers and glass fibers, especially with a view to making sails and fabrics.
  • the aqueous adhesive composition according to the invention is particularly intended to be used for producing coated abrasive articles, in particular abrasives whose medium consists of paper or fabrics made from cotton, polyester or a blend of cotton and polyester. These abrasive articles constitute another object of the invention.
  • the molar mass (in g / mol) is determined by gel permeation chromatography using a modified silica column (PFG® marketed by PSS), 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as eluent and standards of polymethylmethacrylates of a given molar mass;
  • PFG® modified silica column
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • the polydispersity index is the ratio of the molar mass in mass (M m ) to the molar mass in number (M n );
  • the number of iodine (in gl 2/100 g of co-polyester) is measured by titration in N-methyl-pyrrolidone. It is representative of the level of unsaturation in the co-polyester;
  • the thermal stability of the crosslinked product is evaluated by measuring the temperature corresponding to a mass loss of 10%
  • Tg The glass transition temperature (Tg) is measured by DSC ("Differential Scanning Calorimetry) at a rate of 10 ° C / min under nitrogen.
  • the flask is heated to 160 ° C until a uniform reaction mixture is obtained. 3.3 mg of titanium n-butoxide (IV) are then added to 1.5 g of toluene.
  • the reaction mixture is placed under an argon atmosphere and heated at 210 ° C. for 3 hours. The reaction is continued for a further 3 hours at 210 ° C. under reduced pressure (3-5 mbar).
  • reaction mixture After cooling to room temperature, the reaction mixture is dissolved in chloroform and precipitated in methanol at about 10 ° C. The mixture is then filtered, washed several times and dried under vacuum at 85-90 ° C.
  • the co-polyester has a molar mass in number (Mn) equal to 4400 g / mol, a polydispersity index equal to 4.5, an iodine number equal to 50 g / 100 g and a glass transition temperature Tg equal to -17 ° C.
  • the weight ratio of the co-polyester to the ethylenically unsaturated monomer is 2/1.
  • the mixture is heated to 50 ° C and 0.2 g of 2-butanone peroxide is added. After complete homogenization of the mixture, the heating is stopped.
  • the mixture is deposited on a flat substrate (glass or aluminum) and crosslinked for 15 minutes at 85 ° C. and then 12 hours at 115 ° C.
  • the co-polyester obtained in step a) has a number-average molecular weight (Mn) equal to 3200 g / mole, a polydispersity index equal to 2.1, and an iodine number equal to 66 g / 100 g. and a glass transition Tg of -20 ° C.
  • Adhesive compositions 1-1-3 and 2.1 are used to make adhesive papers.
  • the adhesive compositions have a life of at least 24 hours (stable viscosity during this period).
  • a first layer of the adhesive composition (thickness: 150 ⁇ ) is applied and abrasive grains are then distributed homogeneously over said layer. The whole is heated at 85 ° C for 15 minutes. Good adhesion of the adhesive layer to the paper and good anchoring of the abrasive grains are observed (these do not come off when subjected to the test of passing the hand on the grain surface).
  • a second layer of the adhesive composition is applied to cover the abrasive grains and treated at 60 ° C for 50 minutes.
  • the abrasive paper obtained with each of the adhesive compositions tested is devoid of tackiness.
  • the abrasive paper obtained then undergoes an additional heat treatment (post-baking) at 120 ° C. for 2 hours.
  • the second layer of adhesive adheres well to the first layer, covers the abrasive grains satisfactorily and maintains them effectively.
  • the manual peel test of the abrasive paper shows a cohesive break in the paper with all the adhesive compositions tested, which indicates a very good adhesion of the adhesive composition to the support.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention relates to an adhesive composition which contains at least one water-soluble or water-dispersible unsaturated polyester and at least one ethylene-unsaturated monomer. Specifically, said unsaturated polyester is obtained by co-polymerisation of (A) at least one monomeric or oligomeric polyol, (B) at least one unsaturated polycarboxylic acid or one unsaturated acid anhydride and (C) at least one water-soluble polymer containing at least two hydroxyl, amine and/or epoxy reactive functions. The invention also relates to the use of said composition for bonding elements of natural or synthetic materials, in particular abrasive particles, glass or rock fibre and spun glass.

Description

COMPOSITION ADHESIVE RENFERMANT UN POLYESTER INSATURE HYDROSOLUBLE OU DISPERSABLE DANS L'EAU ET UN MONOMERE  ADHESIVE COMPOSITION COMPRISING AN UNSATURATED WATER-DISSOLVABLE WATER DISPERSIBLE POLYESTER AND A MONOMER
ETHYLENIQUEMENT INSATURE, ET UTILISATIONS  ETHYLENICALLY UNSATURATED AND USES
L'invention se rapporte au domaine des liants destinés à lier ensemble des éléments en matière naturelle ou synthétique, notamment minéraux, tels que des particules abrasives, des fibres de verre ou de roche, et des fils de verre. The invention relates to the field of binders intended to bind together elements made of natural or synthetic material, in particular minerals, such as abrasive particles, glass or rock fibers, and glass threads.
L'invention concerne plus particulièrement une composition adhésive qui renferme au moins un polyester insaturé hydrosoluble ou dispersable dans l'eau et au moins un monomère éthyléniquement insaturé.  The invention more particularly relates to an adhesive composition which contains at least one unsaturated polyester water-soluble or dispersible in water and at least one ethylenically unsaturated monomer.
Il est connu d'utiliser pour la fabrication de produits minéraux incorporant des particules, des fibres ou des fils minéraux des résines thermodurcissables à base de formaldéhyde, notamment des résines urée- formaldéhyde, mélamine-formaldéhyde et phénol-formaldéhyde. Ces résines présentent une bonne aptitude à réticuler, sont solubles dans l'eau, possèdent une bonne affinité pour les minéraux et sont relativement peu coûteuses.  It is known to use, for the manufacture of mineral products incorporating particles, fibers or mineral threads, thermosetting resins based on formaldehyde, in particular urea-formaldehyde, melamine-formaldehyde and phenol-formaldehyde resins. These resins have good crosslinking ability, are water soluble, have good affinity for minerals and are relatively inexpensive.
Il subsiste cependant dans ces résines une proportion variable de formaldéhyde libre qui peut persister dans le produit final. Or, on sait que le formaldéhyde peut s'avérer préjudiciable pour les opérateurs sur lignes industrielles, les consommateurs finaux et l'environnement.  There remains, however, in these resins a variable proportion of free formaldehyde which may persist in the final product. However, it is known that formaldehyde can be detrimental for operators on industrial lines, end consumers and the environment.
La réglementation en matière d'émissions de formaldéhyde devenant de plus en plus contraignante oblige les fabricants de produits minéraux à rechercher des solutions alternatives aux résines précitées.  The formaldehyde emission regulations are becoming more and more restrictive, forcing mineral product manufacturers to seek alternative solutions to the abovementioned resins.
La présente invention a pour but de proposer une composition adhésive ne contenant pas de formaldéhyde, apte à lier entre eux des éléments constitués de matières naturelles ou synthétiques, notamment minérales, en particulier des particules abrasives, des fibres de verre ou de roche et des fils de verre.  The object of the present invention is to provide an adhesive composition containing no formaldehyde, capable of bonding together elements consisting of natural or synthetic materials, in particular mineral materials, in particular abrasive particles, glass or rock fibers and yarns. of glass.
La composition adhésive conforme à la présente invention est une composition aqueuse qui contient au moins un polyester insaturé hydrosoluble ou dispersable dans l'eau et au moins un monomère éthyléniquement insaturé, ledit polyester insaturé étant obtenu par co-polymérisation (A) d'au moins un polyol monomérique ou oligomérique, (B) d'au moins un acide polycarboxylique insaturé ou un anhydride d'acide insaturé et (C) d'au moins un polymère hydrosoluble renfermant au moins deux fonctions réactives hydroxyle, aminé et/ou epoxy. The adhesive composition according to the present invention is an aqueous composition which contains at least one water-soluble or water-dispersible unsaturated polyester and at least one ethylenically unsaturated monomer, said unsaturated polyester being obtained by co-polymerization (A) of at least one monomeric or oligomeric polyol, (B) at least one unsaturated polycarboxylic acid or an unsaturated acid anhydride and (C) at least one polymer water-soluble composition containing at least two hydroxyl, amine and / or epoxy reactive functional groups.
Par « composition aqueuse » on entend une composition qui renferme au moins 20 % en poids d'eau, de préférence au plus 70 % et mieux encore de 40 à 60 %.  By "aqueous composition" is meant a composition which contains at least 20% by weight of water, preferably at most 70% and more preferably 40 to 60%.
Dans le but d'améliorer la dispersion du polyester insaturé et/ou du monomère éthyléniquement insaturé, on peut substituer une partie de l'eau par un solvant organique, par exemple le tétrahydrofurane (THF) ou le m éthy I tétra hyd rof u ra n e .  In order to improve the dispersion of the unsaturated polyester and / or the ethylenically unsaturated monomer, part of the water may be substituted with an organic solvent, for example tetrahydrofuran (THF) or methyl tetrahydro rofuran. born .
La proportion d'eau remplacée par le solvant est au plus égale à 50 % en poids, de préférence au plus 30 % et avantageusement au plus 20 %.  The proportion of water replaced by the solvent is at most equal to 50% by weight, preferably at most 30% and advantageously at most 20%.
Le polyol (A) conforme à la présente invention comprend au moins deux fonctions hydroxyles aptes à réagir avec les fonctions carboxyliques portées par l'acide polycarboxylique insaturé précité ou obtenues par l'hydrolyse de l'anhydride d'acide insaturé. De préférence, le polyol comprend au plus 35 fonctions hydroxyles, et avantageusement au plus 15.  The polyol (A) according to the present invention comprises at least two hydroxyl functional groups capable of reacting with the carboxylic functions carried by the abovementioned unsaturated polycarboxylic acid or obtained by the hydrolysis of the unsaturated acid anhydride. Preferably, the polyol comprises at most 35 hydroxyl functions, and advantageously at most 15.
Le polyol est un polyol monomérique ou oligomérique, c'est-à-dire comprenant au plus 10 résidus de monomères polyols, de préférence au plus 4.  The polyol is a monomeric or oligomeric polyol, that is to say comprising at most 10 monomer residues polyols, preferably at most 4.
De préférence, le polyol (A) est choisi parmi les polyols provenant d'une source renouvelable, notamment obtenus à partir de végétaux, tels que les saccharides, ou générés par fermentation de matières végétales, tels que le 1 ,3-propanediol et le 1 ,4-butanediol.  Preferably, the polyol (A) is chosen from polyols originating from a renewable source, in particular obtained from plants, such as saccharides, or generated by fermentation of plant materials, such as 1,3-propanediol and 1,4-butanediol.
A titre d'exemple de saccharides, on peut citer les monosaccharides, de préférence renfermant 3 à 8 atomes de carbone, en particulier les hexoses tels que le glucose, le mannose, le galactose, les dérivés de ces hexoses sous la forme d'alcools alicycliques et les dérivés de ces alcools alicycliques, tels que l'isosorbide, et les oligosaccharides tels que le maltose, le cellobiose, le lactose, le sucrose, le tréhalose, le raffinose, le stachyose et les dextrines. Le saccharide préféré est l'isosorbide. L'acide polycarboxylique insaturé (B) comprend au moins deux fonctions carboxyliques, de préférence au plus quatre, et avantageusement au plus trois fonctions carboxyliques, et au moins une insaturation éthylénique. As an example of saccharides, mention may be made of monosaccharides, preferably containing 3 to 8 carbon atoms, in particular hexoses such as glucose, mannose, galactose, derivatives of these hexoses in the form of alcohols. alicyclics and derivatives of these alicyclic alcohols, such as isosorbide, and oligosaccharides such as maltose, cellobiose, lactose, sucrose, trehalose, raffinose, stachyose and dextrins. The preferred saccharide is isosorbide. The unsaturated polycarboxylic acid (B) comprises at least two carboxylic functions, preferably at most four, and advantageously at most three carboxylic functions, and at least one ethylenic unsaturation.
A titre d'exemples d'acide polycarboxylique insaturé (B), on peut citer les acides aliphatiques, linéaires ou ramifiés, tels que l'acide fumarique, l'acide itaconique, l'acide maléique, l'acide traumatique, l'acide mésaconique, l'acide citraconique et l'acide aconitique, les acides cycliques tels que l'acide 2,5- furane dicarboxylique (acide déhydromucique) et les acides aromatiques tels que phtalique, l'acide tétrahydrophtalique, l'acide isophtalique, l'acide téréphtalique, l'acide trimésique ou l'acide pyromellitique.  By way of examples of unsaturated polycarboxylic acid (B), mention may be made of linear or branched aliphatic acids, such as fumaric acid, itaconic acid, maleic acid, traumatic acid, and acid. metaconic acid, citraconic acid and aconitic acid, cyclic acids such as 2,5-furan dicarboxylic acid (dehydromucic acid) and aromatic acids such as phthalic acid, tetrahydrophthalic acid, isophthalic acid, terephthalic acid, trimesic acid or pyromellitic acid.
L'acide polycarboxylique insaturé (B) peut également être obtenu à partir de l'anhydride d'acide insaturé correspondant qui, par hydrolyse, génère les fonctions carboxyliques. L'anhydride d'acide insaturé est par exemple l'anhydride maléique.  The unsaturated polycarboxylic acid (B) can also be obtained from the corresponding unsaturated acid anhydride which, by hydrolysis, generates the carboxylic functions. The unsaturated acid anhydride is, for example, maleic anhydride.
De préférence, l'acide polycarboxylique insaturé (B) et l'anhydride d'acide insaturé sont monomériques.  Preferably, the unsaturated polycarboxylic acid (B) and the unsaturated acid anhydride are monomeric.
Le polymère (C) est hydrosoluble et permet donc d'introduire des segments hydrophiles dans le co-polyester, ce qui lui confère une meilleure solubilité dans les solvants polaires tels que l'eau.  The polymer (C) is water-soluble and thus makes it possible to introduce hydrophilic segments in the co-polyester, which gives it a better solubility in polar solvents such as water.
Comme indiqué précédemment, le polymère (C) contient au moins deux fonctions hydroxyle, aminé et/ou epoxy.  As indicated above, the polymer (C) contains at least two hydroxyl, amine and / or epoxy functional groups.
Le polymère (C) est choisi dans le groupe constitué par les poly(oxyalkylènes), par exemple les polyéthylène glycols et les polyéthylène- propylène glycols pouvant porter une ou plusieurs fonctions aminés supplémentaires, les polyvinylpyrrolidones, les polyéthylèneimines et les polyoxazolines. Le polymère (C) comprend au moins 4 unités monomères.  The polymer (C) is chosen from the group consisting of poly (oxyalkylenes), for example polyethylene glycols and polyethylenepropylene glycols which may carry one or more additional amino functions, polyvinylpyrrolidones, polyethyleneimines and polyoxazolines. The polymer (C) comprises at least 4 monomer units.
Lorsque le polymère (C) est un polyol, celui-ci est nécessairement différent du polyol (A).  When the polymer (C) is a polyol, it is necessarily different from the polyol (A).
De préférence, le polyéthylène glycol a une masse molaire inférieure ou égale à 600 g/mole et avantageusement supérieure ou égale à 200 g/mole.  Preferably, the polyethylene glycol has a molar mass of less than or equal to 600 g / mol and advantageously greater than or equal to 200 g / mol.
Le rapport du nombre d'équivalent de fonctions hydroxyle, aminé et epoxy) au nombre d'équivalent de fonctions carboxyliques varie de 1 ,01/1 à 2/1 , de préférence 1 ,05/1 à 1 ,5/1 et mieux encore 1 ,10/1 à 1 ,2/1 . De préférence, le pourcentage du nombre d'unités monomères du polymère (C) au nombre total d'unités monomères du polyol (A) et du polymère (C) varie de 70 à 95 % et de préférence 70 à 85 %. The ratio of the number of hydroxyl, amine and epoxy functional equivalents to the number of carboxylic functional equivalents ranges from 1.01 / 1 to 2/1, preferably from 1.05 / 1 to 1.5 / 1 and better still 1, 10/1 to 1, 2/1. Preferably, the percentage of the number of monomer units of the polymer (C) to the total number of monomer units of the polyol (A) and the polymer (C) ranges from 70 to 95% and preferably 70 to 85%.
La réaction de co-polymérisation du polyol monomérique ou oligomérique (A), de l'acide polycarboxylique insaturé ou de l'anhydride d'acide insaturé (B) et du polymère hydrosoluble (C) est effectuée de préférence en présence d'un catalyseur, par exemple le n-butoxyde de titane (IV). Ledit agent est généralement ajouté en une quantité représentant 0,005 à 4 % en mole du composé (B) et de préférence 0,01 à 1 %.  The co-polymerization reaction of the monomeric or oligomeric polyol (A), the unsaturated polycarboxylic acid or the unsaturated acid anhydride (B) and the water-soluble polymer (C) is preferably carried out in the presence of a catalyst. for example titanium n-butoxide (IV). Said agent is generally added in an amount representing 0.005 to 4 mol% of the compound (B) and preferably 0.01 to 1%.
Eventuellement, un agent antioxydant peut être introduit dans le milieu de polymérisation, par exemple le 1 ,3,5-triméthyl-2,4,6-tris(3,5-di-ter-butyl-4- hydroxybenzyl)benzène, en une quantité au plus égale à 1 % du poids total de l'acide polycarboxylique insaturé et de l'anhydride d'acide insaturé (B).  Optionally, an antioxidant may be introduced into the polymerization medium, for example 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, an amount at most equal to 1% of the total weight of the unsaturated polycarboxylic acid and the unsaturated acid anhydride (B).
La co-polymérisation est généralement effectuée à une température qui varie de 140 à 230°C, de préférence 150 à 220°C, et avantageusement 160 à 210°C. A titre d'exemple, la co-polymérisation peut être effectuée en plusieurs étapes, notamment selon le cycle thermique suivant : 160°C pendant 1 à 15 heures, 210°C pendant 2 à 10 heures à la pression atmosphérique et 210°C pendant 1 à 5 heures sous une pression réduite, de l'ordre de 3 à 5 mbar. Le cycle thermique préféré est 160°C pendant 1 à 10 heures, 210°C pendant 2 à heures à la pression atmosphérique et 210°C pendant 1 à 4 heures sous une pression réduite.  The co-polymerization is generally carried out at a temperature ranging from 140 to 230 ° C, preferably 150 to 220 ° C, and preferably 160 to 210 ° C. By way of example, the co-polymerization can be carried out in several steps, in particular according to the following thermal cycle: 160 ° C. for 1 to 15 hours, 210 ° C. for 2 to 10 hours at atmospheric pressure and 210 ° C. for 1 to 5 hours under a reduced pressure, of the order of 3 to 5 mbar. The preferred heat cycle is 160 ° C for 1 to 10 hours, 210 ° C for 2 to 2 hours at atmospheric pressure and 210 ° C for 1 to 4 hours under reduced pressure.
Le co-polyester insaturé conforme à l'invention est solide à la température ambiante (de l'ordre de 20°C) et peut être facilement solubilisé ou dispersé dans l'eau. Le co-polyester est également soluble dans les solvants organiques, notamment dans le chlororforme.  The unsaturated co-polyester according to the invention is solid at ambient temperature (of the order of 20 ° C.) and can be easily solubilized or dispersed in water. The co-polyester is also soluble in organic solvents, especially in chlororforme.
Le co-polyester insaturé préféré est un polymère obtenu par co- polymérisation d'isosorbide, d'anhydride maléique et de polyéthylène glycol .  The preferred unsaturated co-polyester is a polymer obtained by co-polymerization of isosorbide, maleic anhydride and polyethylene glycol.
Comme déjà mentionné, la composition adhésive conforme à l'invention comprend au moins un monomère éthyléniquement insaturé utilisé en tant qu'agent de réticulation du co-polyester.  As already mentioned, the adhesive composition according to the invention comprises at least one ethylenically unsaturated monomer used as crosslinking agent of the co-polyester.
Le monomère éthyléniquement insaturé utilisé en tant qu'agent de réticulation du co-polyester est généralement choisi parmi le groupe constitué par les acides (méth)acryliques et les (méth)acrylates, en particulier le 2- hydroxyéthyl méthacrylate, le méthacrylamide, la N-vinylpyrrolidone et les acides carboxyliques insaturés, notamment les polyacides carboxyliques insaturés mentionnés précédemment, en particulier l'acide itaconique et l'acide citraconique, ou leurs anhydrides, en particulier l'anhydride maléique. The ethylenically unsaturated monomer used as the co-polyester crosslinking agent is generally selected from the group consisting of by (meth) acrylic acids and (meth) acrylates, in particular 2-hydroxyethyl methacrylate, methacrylamide, N-vinylpyrrolidone and unsaturated carboxylic acids, especially the unsaturated polycarboxylic acids mentioned above, in particular itaconic acid and citraconic acid, or their anhydrides, in particular maleic anhydride.
Le monomère éthyléniquement insaturé est de préférence soluble dans l'eau.  The ethylenically unsaturated monomer is preferably soluble in water.
Le monomère éthyléniquement insaturé est ajouté à la composition aqueuse adhésive dans des proportions telles que le rapport pondéral du monomère insaturé au co-polyester varie de 1 /10 à 1 /1 , de préférence 1 /3 à 1 /1 .  The ethylenically unsaturated monomer is added to the aqueous adhesive composition in such proportions that the weight ratio of unsaturated monomer to co-polyester ranges from 1/10 to 1/1, preferably 1/3 to 1/1.
Un initiateur de radicaux libres peut être introduit dans la composition aqueuse adhésive afin d'amorcer la réticulation. A titre d'exemple, on peut citer les peroxydes, notamment le peroxyde de 2-butanone, les persulfates et l'azobisisobutyronitrile (AIBN). La quantité dudit initiateur représente généralement 0,5 à 2 % du poids total du co-polyester insaturé et du monomère éthyléniquement insaturé.  A free radical initiator may be introduced into the aqueous adhesive composition to initiate crosslinking. By way of example, mention may be made of peroxides, especially 2-butanone peroxide, persulfates and azobisisobutyronitrile (AIBN). The amount of said initiator generally represents 0.5 to 2% of the total weight of the unsaturated co-polyester and the ethylenically unsaturated monomer.
La réticulation de la composition aqueuse adhésive est effectuée à une température qui varie de 50 à 180°C, de préférence 60 à 150°C, pendant une durée qui peut varier de 5 minutes à 6 heures, de préférence 15 minutes à 2 heures.  The crosslinking of the aqueous adhesive composition is carried out at a temperature ranging from 50 to 180 ° C, preferably 60 to 150 ° C, for a period which may vary from 5 minutes to 6 hours, preferably 15 minutes to 2 hours.
Le co-polyester réticulé est un polymère amorphe qui, par conséquent, ne présente pas de point de fusion.  The crosslinked co-polyester is an amorphous polymer which, therefore, does not have a melting point.
Ledit co-polyester réticulé présente une stabilité thermique suffisante pour les applications visées.  The cross-linked co-polyester has sufficient thermal stability for the intended applications.
La composition adhésive aqueuse conforme à la présente invention peut être utilisée pour lier tout type d'éléments composés de matière naturelle ou synthétique, en particulier des éléments minéraux tels que des particules abrasives, des fibres de verre ou de roche et des fils de verre, notamment en vue de réaliser des voiles et des tissus.  The aqueous adhesive composition according to the present invention can be used to bind any type of elements composed of natural or synthetic material, in particular mineral elements such as abrasive particles, glass or rock fibers and glass fibers, especially with a view to making sails and fabrics.
La composition adhésive aqueuse selon l'invention est tout particulièrement destinée à être utilisée pour fabriquer des articles abrasifs appliqués (« coated abrasives » en anglais), notamment des abrasifs dont le support est constitué d'un papier ou d'un tissus à base de coton, de polyester ou d'un mélange de coton et de polyester. Ces articles abrasifs constituent un autre objet de l'invention. The aqueous adhesive composition according to the invention is particularly intended to be used for producing coated abrasive articles, in particular abrasives whose medium consists of paper or fabrics made from cotton, polyester or a blend of cotton and polyester. These abrasive articles constitute another object of the invention.
Les exemples qui suivent permettent d'illustrer l'invention sans toutefois la limiter.  The following examples illustrate the invention without limiting it.
Dans ces exemples :  In these examples:
- la masse molaire (en g/mole) est déterminée par chromatographie par perméation de gel utilisant une colonne de silice modifiée (PFG® commercialisée par PSS), du 1 ,1 ,1 ,3,3,3-hexafluoro-2-propanol (HFIP) en tant qu'éluant et des étalons de polyméthacrylates de méthyle de masse molaire donnée;  the molar mass (in g / mol) is determined by gel permeation chromatography using a modified silica column (PFG® marketed by PSS), 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as eluent and standards of polymethylmethacrylates of a given molar mass;
- l'indice de polydispersité est le rapport de la masse molaire en masse (Mm) à la masse molaire en nombre (Mn); the polydispersity index is the ratio of the molar mass in mass (M m ) to the molar mass in number (M n );
- le nombre d'iode (en g l2/100 g de co-polyester) est mesuré par titration dans la N-méthyl-pyrrolidone. Il est représentatif du taux d'insaturation dans le co-polyester; - the number of iodine (in gl 2/100 g of co-polyester) is measured by titration in N-methyl-pyrrolidone. It is representative of the level of unsaturation in the co-polyester;
- la stabilité thermique du produit réticulé est évaluée en mesurant la température correspondant à une perte de masse de 10 %;  the thermal stability of the crosslinked product is evaluated by measuring the temperature corresponding to a mass loss of 10%;
- la fraction soluble du produit réticulé (en %) dans le chloroforme et l'eau est mesurée par pesée;  the soluble fraction of the crosslinked product (in%) in chloroform and water is measured by weighing;
- la température de transition vitreuse (Tg) est mesurée par DSC (« Differential Scanning Calorimetry), à la vitesse de 10°C/min sous azote.  - The glass transition temperature (Tg) is measured by DSC ("Differential Scanning Calorimetry) at a rate of 10 ° C / min under nitrogen.
EXEMPLE 1  EXAMPLE 1
a) synthèse du co-polyester isosorbide-anhydride maléique- polyéthylène glycol  a) Synthesis of Isosorbide Co-Polyester-Maleic Anhydride-Polyethylene Glycol
Dans un ballon équipé d'une colonne Vigreux et d'un condenseur Dean-Stark, on introduit 5,85 g (0,04 mole) d'isosorbide, 4,13 g (0,042 mole) d'anhydride maléique, 5,05 g (0,0084 mole) de polyéthylène glycol (Mn = 600 g/mole) et 0,04 g (5,16 x 10"5 mole) de 1 ,3,5-triméthyl -2 ,4,6-tris(3,5-d i-ter-butyl - 4-hydroxy-benzyl)benzène. In a flask equipped with a Vigreux column and a Dean-Stark condenser, 5.85 g (0.04 mole) of isosorbide, 4.13 g (0.042 mole) of maleic anhydride, 5.05 g are added. g (0.0084 mol) of polyethylene glycol (Mn = 600 g / mol) and 0.04 g (5.16 × 10 -5 mol) of 1,3,5-trimethyl -2,4,6-tris ( 3,5-di-tert-butyl-4-hydroxy-benzyl) benzene.
Le ballon est chauffé à 160°C jusqu'à l'obtention d'un mélange réactionnel uniforme. On ajoute ensuite 3,3 mg de n-butoxyde de titane (IV) dans 1 ,5 g de toluène. On place le mélange réactionnel sous atmosphère d'argon et on chauffe à 210°C pendant 3 heures. La réaction est poursuivie pendant 3 heures supplémentaires à 210°C sous pression réduite (3-5 mbar). The flask is heated to 160 ° C until a uniform reaction mixture is obtained. 3.3 mg of titanium n-butoxide (IV) are then added to 1.5 g of toluene. The reaction mixture is placed under an argon atmosphere and heated at 210 ° C. for 3 hours. The reaction is continued for a further 3 hours at 210 ° C. under reduced pressure (3-5 mbar).
Après refroidissement à la température ambiante, le mélange réactionnel est dissous dans du chloroforme et précipité dans du méthanol à environ 10°C. Le mélange est ensuite filtré, lavé plusieurs fois et séché sous vide à 85-90°C.  After cooling to room temperature, the reaction mixture is dissolved in chloroform and precipitated in methanol at about 10 ° C. The mixture is then filtered, washed several times and dried under vacuum at 85-90 ° C.
Le co-polyester présente une masse molaire en nombre (Mn) égale à 4400 g/mole, un indice de polydispersité égal à 4,5, un nombre d'iode égal à 50 g /l OO g et une température de transition vitreuse Tg égale à -17°C.  The co-polyester has a molar mass in number (Mn) equal to 4400 g / mol, a polydispersity index equal to 4.5, an iodine number equal to 50 g / 100 g and a glass transition temperature Tg equal to -17 ° C.
Le rendement de la réaction est égal à 87 %.  The yield of the reaction is 87%.
b) réticulation du co-polyester  b) cross-linking of the co-polyester
Dans un ballon tricol, on introduit 18,3 g d'eau, 10 g du co-polyester obtenu à l'étape a) et 5 g de 2-hydroxyéthyl-méthacrylate (HEMA), de N- vinylpyrrolidone (NPV) ou méthacrylamide (Mam).  3 g of the co-polyester obtained in step a) and 5 g of 2-hydroxyethyl methacrylate (HEMA), (Mam).
Le rapport pondéral du co-polyester au monomère éthyléniquement insaturé est égal à 2/1 .  The weight ratio of the co-polyester to the ethylenically unsaturated monomer is 2/1.
On chauffe le mélange à 50°C et on ajoute 0,2 g de peroxyde de 2- butanone. Après homogénéisation complète du mélange, on arrête le chauffage.  The mixture is heated to 50 ° C and 0.2 g of 2-butanone peroxide is added. After complete homogenization of the mixture, the heating is stopped.
Le mélange est déposé sur un substrat plan (en verre ou en aluminium) et réticulé pendant 15 minutes à 85°C puis 12 heures à 1 15°C.  The mixture is deposited on a flat substrate (glass or aluminum) and crosslinked for 15 minutes at 85 ° C. and then 12 hours at 115 ° C.
Les caractéristiques du produit réticulé sont données dans le tableau 1 .  The characteristics of the crosslinked product are given in Table 1.
EXEMPLE 2  EXAMPLE 2
On procède dans les conditions de l'exemple 1 en présence des composés suivants : 3,37 g (0,023 mole) d'isosorbide, 4,13 g (0,042 mole) d'anhydride maléique, 5,04 g (0,025 mole) de polyéthylène glycol (Mn = 200 g/mole), 0,04 g (5,16 x 10"5 mole) de 1 ,3,5-triméthyl-2,4,6-tris(3,5-di-ter-butyl-4- hydroxy-benzyl)benzène et 2,75 mg de n-butoxyde de titane (IV) dans 1 ,2 g de toluène. Le co-polyester obtenu à l'étape a) présente une masse molaire en nombre (Mn) égale à 3200 g/mole, un indice de polydispersité égal à 2,1 , un nombre d'iode égal à 66 g /l OO g et une transition vitreuse Tg égale à -20°C. The procedure described in Example 1 is followed in the presence of the following compounds: 3.37 g (0.023 mol) of isosorbide, 4.13 g (0.042 mol) of maleic anhydride, 5.04 g (0.025 mol) of polyethylene glycol (Mn = 200 g / mole), 0.04 g (5.16 x 10 -5 mole) of 1,3,5-trimethyl-2,4,6-tris (3,5-di-ter- butyl-4-hydroxy-benzyl) benzene and 2.75 mg of titanium n-butoxide (IV) in 1.2 g of toluene. The co-polyester obtained in step a) has a number-average molecular weight (Mn) equal to 3200 g / mole, a polydispersity index equal to 2.1, and an iodine number equal to 66 g / 100 g. and a glass transition Tg of -20 ° C.
Les caractéristiques du produit réticulé sont données dans le tableau 1 .  The characteristics of the crosslinked product are given in Table 1.
Tableau 1 Table 1
EXEMPLE 3 EXAMPLE 3
Les compositions adhésives 1 .1 à 1 .3 et 2.1 sont utilisées pour fabriquer des papiers adhésifs.  Adhesive compositions 1-1-3 and 2.1 are used to make adhesive papers.
Les compositions adhésives ont une durée de vie d'au moins 24 heures (viscosité stable durant cette période).  The adhesive compositions have a life of at least 24 hours (stable viscosity during this period).
On applique une première couche de la composition adhésive (épaisseur : 150 μιτι) et on répartit ensuite des grains abrasifs de manière homogène sur ladite couche. L'ensemble est chauffé à 85°C pendant 15 minutes. On observe une bonne adhésion de la couche d'adhésif sur le papier et un bon ancrage des grains abrasifs (ceux-ci ne se détachent pas lorsqu'ils sont soumis au test consistant à passer la main à la surface des grains).  A first layer of the adhesive composition (thickness: 150 μιτι) is applied and abrasive grains are then distributed homogeneously over said layer. The whole is heated at 85 ° C for 15 minutes. Good adhesion of the adhesive layer to the paper and good anchoring of the abrasive grains are observed (these do not come off when subjected to the test of passing the hand on the grain surface).
On applique une deuxième couche de la composition adhésive afin de recouvrir les grains abrasifs et on traite l'ensemble à 60°C pendant 50 minutes. Le papier abrasif obtenu avec chacune des compositions adhésives testées est dénué de pégosité. Le papier abrasif obtenu subit ensuite un traitement thermique supplémentaire (post-cuisson) à 120°C pendant 2 heures. A second layer of the adhesive composition is applied to cover the abrasive grains and treated at 60 ° C for 50 minutes. The abrasive paper obtained with each of the adhesive compositions tested is devoid of tackiness. The abrasive paper obtained then undergoes an additional heat treatment (post-baking) at 120 ° C. for 2 hours.
On constate que la deuxième couche d'adhésif adhère correctement à la première couche, recouvre les grains abrasifs de manière satisfaisante et les maintient efficacement.  It is found that the second layer of adhesive adheres well to the first layer, covers the abrasive grains satisfactorily and maintains them effectively.
De plus, le test de pelage manuel du papier abrasif montre une rupture cohésive dans le papier avec toutes les compositions adhésives testées, ce qui dénote une très bonne adhésion de la composition adhésive au support.  In addition, the manual peel test of the abrasive paper shows a cohesive break in the paper with all the adhesive compositions tested, which indicates a very good adhesion of the adhesive composition to the support.

Claims

REVENDICATIONS
1. Composition adhésive aqueuse, notamment destinée à lier des éléments composés de matière naturelle ou synthétiques, caractérisée en ce qu'elle contient au moins un polyester insaturé hydrosoluble ou dispersable dans l'eau et au moins un monomère éthyléniquement insaturé, ledit polyester insaturé étant obtenu par co-polymérisation (A) d'au moins un polyol monomérique ou oligomérique, (B) d'au moins un acide polycarboxylique insaturé ou un anhydride d'acide insaturé et (C) d'au moins un polymère hydrosoluble renfermant au moins deux fonctions réactives hydroxyle, aminé et/ou epoxy.  An aqueous adhesive composition, in particular intended to bind elements composed of natural or synthetic materials, characterized in that it contains at least one water-soluble or water-dispersible unsaturated polyester and at least one ethylenically unsaturated monomer, said unsaturated polyester being obtained by co-polymerization (A) of at least one monomeric or oligomeric polyol, (B) at least one unsaturated polycarboxylic acid or unsaturated acid anhydride and (C) at least one water-soluble polymer containing at least one two hydroxyl, amine and / or epoxy reactive functions.
2. Composition selon la revendication 1 , caractérisée en ce qu'elle renferme au moins 20 % en poids d'eau, de préférence au plus 70 % et mieux encore de 40 à 60 %.  2. Composition according to claim 1, characterized in that it contains at least 20% by weight of water, preferably at most 70% and more preferably 40 to 60%.
3. Composition selon la revendication 1 ou 2, caractérisée en ce que le polyol comprend au plus 35 fonctions hydroxyles, de préférence au plus 15.  3. Composition according to claim 1 or 2, characterized in that the polyol comprises at most 35 hydroxyl functions, preferably at most 15.
4. Composition selon l'une des revendications 1 à 3, caractérisée en ce que le polyol oligomérique comprend au plus 10 résidus de monomères polyols et de préférence au plus 4.  4. Composition according to one of claims 1 to 3, characterized in that the oligomeric polyol comprises at most 10 monomer residues polyols and preferably at most 4.
5. Composition selon l'une des revendications 1 à 4, caractérisée en ce que le polyol est choisi parmi les saccharides, le 1 ,3-propanediol et le 1 ,4- butanediol.  5. Composition according to one of claims 1 to 4, characterized in that the polyol is chosen from saccharides, 1,3-propanediol and 1,4-butanediol.
6. Composition selon la revendication 5, caractérisée en ce que le saccharide est un monosaccharide, de préférence renfermant 3 à 8 atomes de carbone, en particulier un hexose ou un oligosaccharide.  6. Composition according to claim 5, characterized in that the saccharide is a monosaccharide, preferably containing 3 to 8 carbon atoms, in particular a hexose or an oligosaccharide.
7. Composition selon la revendication 6, caractérisée en ce que le monosaccharide est le glucose, le mannose, le galactose, un dérivé de ces hexoses sous la forme d'alcool alicyclique ou un dérivé déshydraté de cet alcool alicyclique tels que l'isosorbide, et l'oligosaccharide est le maltose, le cellobiose, le lactose, le sucrose, le tréhalose, le raffinose, le stachyose ou une dextrine.  7. Composition according to claim 6, characterized in that the monosaccharide is glucose, mannose, galactose, a derivative of these hexoses in the form of alicyclic alcohol or a dehydrated derivative of this alicyclic alcohol such as isosorbide, and the oligosaccharide is maltose, cellobiose, lactose, sucrose, trehalose, raffinose, stachyose or dextrin.
8. Composition selon l'une des revendications 1 à 7, caractérisée en ce que l'acide polycarboxylique insaturé comprend au moins deux fonctions carboxyliques, de préférence au plus quatre, et avantageusement au plus trois fonctions carboxyliques, et au moins une insaturation éthylénique. 8. Composition according to one of claims 1 to 7, characterized in that the unsaturated polycarboxylic acid comprises at least two functions carboxylic acids, preferably at most four, and advantageously at most three carboxylic functions, and at least one ethylenic unsaturation.
9. Composition selon la revendication 8, caractérisée en ce que l'acide polycarboxylique insaturé est un acide aliphatique, linéaire ou ramifié, tel que l'acide fumarique, l'acide itaconique, l'acide maléique, l'acide traumatique, l'acide mésaconique, l'acide citraconique et l'acide aconitique, un acide cyclique tel que l'acide 2,5-furane dicarboxylique (acide déhydromucique) ou un acide aromatique tels que phtalique, l'acide tétrahydrophtalique, l'acide isophtalique, l'acide téréphtalique, l'acide trimésique ou l'acide pyromellitique.  9. A composition according to claim 8, characterized in that the unsaturated polycarboxylic acid is a linear or branched aliphatic acid, such as fumaric acid, itaconic acid, maleic acid, traumatic acid, mesaconic acid, citraconic acid and aconitic acid, a cyclic acid such as 2,5-furan dicarboxylic acid (dehydroucic acid) or an aromatic acid such as phthalic acid, tetrahydrophthalic acid, isophthalic acid, terephthalic acid, trimesic acid or pyromellitic acid.
10. Composition selon l'une des revendications 1 à 9, caractérisée en ce que l'acide polycarboxylique insaturé et l'anhydride d'acide insaturé sont monomériques.  10. Composition according to one of claims 1 to 9, characterized in that the unsaturated polycarboxylic acid and the unsaturated acid anhydride are monomeric.
11. Composition selon l'une des revendications 1 à 10, caractérisée en ce que le polymère hydrosoluble (C) est choisi dans le groupe constitué par les poly(oxyalkylènes), les polyvinylpyrrolidones, les polyéthylèneimines et les polyoxazolines.  11. Composition according to one of claims 1 to 10, characterized in that the water-soluble polymer (C) is selected from the group consisting of poly (oxyalkylenes), polyvinylpyrrolidones, polyethyleneimines and polyoxazolines.
12. Composition selon la revendication 1 1 , caractérisée en ce que le polymère hydrosoluble (C) est un polyéthylène glycol ayant une masse molaire inférieure ou égale à 600 g/mole et de préférence supérieure ou égale à 200 g/mole.  12. Composition according to claim 1 1, characterized in that the water-soluble polymer (C) is a polyethylene glycol having a molar mass less than or equal to 600 g / mol and preferably greater than or equal to 200 g / mol.
13. Composition selon la revendication 1 1 , caractérisée en ce que le polymère (C) comprend au moins 4 unités monomères.  13. Composition according to claim 1 1, characterized in that the polymer (C) comprises at least 4 monomer units.
14. Composition selon l'une des revendications 1 à 13, caractérisée en ce que le polyester insaturé présente un rapport du nombre d'équivalent de fonctions hydroxyle, amine et epoxy) au nombre d'équivalent de fonctions carboxyliques qui varie de 1 ,01/1 à 2/1 , de préférence 1 ,05/1 à 1 ,5/1 et mieux encore 1 ,10/1 à 1 ,2/1 .  14. Composition according to one of claims 1 to 13, characterized in that the unsaturated polyester has a ratio of the number of equivalent hydroxyl functions, amine and epoxy) to the number of equivalent carboxylic functions which varies from 1, 01 / 1 to 2/1, preferably 1, 05/1 to 1, 5/1 and more preferably 1, 10/1 to 1, 2/1.
15. Composition selon l'une des revendications 1 à 14, caractérisée en ce que le pourcentage du nombre d'unités monomères du polymère (C) au nombre total d'unités monomères du polyol (A) et du polymère (C) varie de 70 à 95 % et de préférence 70 à 85 %. 15. Composition according to one of claims 1 to 14, characterized in that the percentage of the number of monomer units of the polymer (C) to the total number of monomer units of the polyol (A) and the polymer (C) varies from 70 to 95% and preferably 70 to 85%.
16. Composition selon l'une des revendications 1 à 15, caractérisée en ce que le polyester insaturé est un co-polyester d'isosorbide, d'anhydride maléique et de polyéthylène glycol. 16. Composition according to one of claims 1 to 15, characterized in that the unsaturated polyester is a co-polyester of isosorbide, maleic anhydride and polyethylene glycol.
17. Composition selon l'une des revendications 1 à 16, caractérisée en ce que le monomère éthyléniquement insaturé est choisi parmi le groupe constitué par les acides (méth)acryliques et les (méth)acrylates, le méthacrylamide, la N-vinylpyrrolidone et les acides carboxyliques insaturés.  17. Composition according to one of claims 1 to 16, characterized in that the ethylenically unsaturated monomer is chosen from the group consisting of (meth) acrylic acids and (meth) acrylates, methacrylamide, N-vinylpyrrolidone and the unsaturated carboxylic acids.
18. Composition selon la revendication 17, caractérisée en ce que le monomère éthyléniquement insaturé est le 2-hydroxyéthyl méthacrylate, l'acide itaconique, l'acide citraconique, l'anhydride maléique.  18. A composition according to claim 17, characterized in that the ethylenically unsaturated monomer is 2-hydroxyethyl methacrylate, itaconic acid, citraconic acid, maleic anhydride.
19. Composition selon l'une des revendications 1 à 18, caractérisée en ce que le monomère éthyléniquement insaturé est soluble dans l'eau.  19. Composition according to one of claims 1 to 18, characterized in that the ethylenically unsaturated monomer is soluble in water.
20. Composition selon l'une des revendications 1 à 19, caractérisée en ce que le rapport pondéral du monomère éthyléniquement insaturé au co- polyester varie de 1/10 à 1/1 et de préférence 1/3 à 1/1 .  20. Composition according to one of claims 1 to 19, characterized in that the weight ratio of the ethylenically unsaturated monomer to co-polyester ranges from 1/10 to 1/1 and preferably 1/3 to 1/1.
21. Composition selon l'une des revendications 1 à 20, caractérisée en ce qu'elle contient en outre un initiateur de radicaux libres choisi parmi les peroxydes, notamment le peroxyde de 2-butanone, les persulfates et l'azobisisobutyronitrile (AIBN).  21. Composition according to one of claims 1 to 20, characterized in that it further contains a free radical initiator selected from peroxides, including 2-butanone peroxide, persulfates and azobisisobutyronitrile (AIBN).
22. Composition selon la revendication 21 , caractérisée en ce que la quantité d'initiateur de radicaux libres représente 0,5 à 2 % du poids total du co- polyester insaturé et du monomère éthyléniquement insaturé.  22. Composition according to claim 21, characterized in that the amount of free radical initiator represents 0.5 to 2% of the total weight of the unsaturated co-polyester and the ethylenically unsaturated monomer.
23. Article abrasif appliqué contenant des particules abrasives liées par une composition adhésive selon l'une des revendications 1 à 22.  23. Applied abrasive article containing abrasive particles bonded by an adhesive composition according to one of claims 1 to 22.
24. Article selon la revendication 23, caractérisé en ce qu'il s'agit d'un abrasif dont le support est constitué d'un papier ou d'un tissu à base de coton, de polyester ou d'un mélange de coton et de polyester.  24. Article according to claim 23, characterized in that it is an abrasive whose support is made of a paper or a fabric based on cotton, polyester or a mixture of cotton and of polyester.
EP11726913.4A 2010-05-28 2011-05-27 Adhesive composition containing a water-soluble or water-dispersible unsaturated polyester and an ethylene-unsaturated monomer, and uses thereof Withdrawn EP2576140A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1054156A FR2960546B1 (en) 2010-05-28 2010-05-28 ADHESIVE COMPOSITION COMPRISING WATER - DISSOLVABLE WATER DISSOLVABLE UNSATURATED POLYESTER AND ETHYLENICALLY UNSATURATED MONOMER, AND USES THEREOF.
PCT/FR2011/051213 WO2011148111A1 (en) 2010-05-28 2011-05-27 Adhesive composition containing a water-soluble or water-dispersible unsaturated polyester and an ethylene-unsaturated monomer, and uses thereof

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EP2753354A4 (en) 2011-09-09 2015-04-15 Nanobio Corp SUBUNIT VACCINE AGAINST NANOEMULSION SYNCYTIAL RESPIRATORY VIRUS (RSV)
WO2022194945A1 (en) * 2021-03-17 2022-09-22 Akzo Nobel Coatings International B.V. Alkyd resin, coating composition, and substrate coated with such coating compositon

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JPS5118977B1 (en) * 1971-01-28 1976-06-14
JPS5218956B2 (en) * 1973-02-20 1977-05-25
JPS52108488A (en) * 1976-03-08 1977-09-10 Kao Corp Preparation of liquid resin dispersions
GB2014170B (en) * 1978-02-13 1982-11-24 Asahi Chemical Ind Hot melt adhesive and method of bonding adherends
JPH0747267B2 (en) * 1986-06-26 1995-05-24 東亜製砥工業株式会社 Method of manufacturing foamed abrasive body
FI990195L (en) * 1998-09-29 2000-03-30 Neste Oyj Unsaturated polyester resin and its use

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FR2960546A1 (en) 2011-12-02
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