WO1993011200A1 - Systems for cross-linkable hot-melt adhesives, their preparation method and an assembly method using same - Google Patents
Systems for cross-linkable hot-melt adhesives, their preparation method and an assembly method using same Download PDFInfo
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- WO1993011200A1 WO1993011200A1 PCT/FR1992/001001 FR9201001W WO9311200A1 WO 1993011200 A1 WO1993011200 A1 WO 1993011200A1 FR 9201001 W FR9201001 W FR 9201001W WO 9311200 A1 WO9311200 A1 WO 9311200A1
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title description 4
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- 150000001875 compounds Chemical class 0.000 claims abstract description 18
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000000470 constituent Substances 0.000 claims description 30
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- 238000004132 cross linking Methods 0.000 claims description 7
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- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- WSDQIHATCCOMLH-UHFFFAOYSA-N phenyl n-(3,5-dichlorophenyl)carbamate Chemical compound ClC1=CC(Cl)=CC(NC(=O)OC=2C=CC=CC=2)=C1 WSDQIHATCCOMLH-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229930006696 sabinene Natural products 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical class OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
- C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09J131/04—Homopolymers or copolymers of vinyl acetate
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
Definitions
- the present invention relates to systems for hot-melt adhesives which have the particularity to lead, after application to the surfaces to be assembled, to a crosslinked product which is substantially irreversible making it infusible or difficult to fuse. It also relates to the preparation of these systems, thus that an assembly process using them.
- the systems for crosslinkable hot-melt adhesives in accordance with the present invention have the double advantage of being able to be implemented very easily in industrial installations, in particular automated installations (robots), such as those of the automobile industry. , and can be applied to many types of objects made from very diverse materials, such as wood, metals, woven or non-woven textiles, glass, porcelain, ceramics, cardboard, paper, stone, concrete and plastics.
- Patent application EP-A-252,795 discloses a system for hot-melt adhesive comprising: (A) a first composition not containing anhydride groups and comprising: a) at least one polymer chosen from thermoelastic polymers and rubbers synthesis; b) at least one compound containing at least one group capable of reacting with anhydrous groups; c) at least one tackifying resin; d) the.
- At least one plasticizer if necessary, at least one plasticizer; (B) a second composition comprising: a) at least one polymer chosen from thermoelastic polymers and synthetic rubbers; b) at least one compound containing at least one anhydride group; c) at least one tackifying resin; and d) where appropriate, at least one plasticizer; and
- a second problem to be solved by the present invention therefore consists in providing a hot-melt adhesive having a breaking stress at least equal to 4 MPa so as to allow the assembly of polyester on polyester or aluminum.
- the adhesive systems according to the present invention are in particular two-component systems (hereinafter called A and B), one containing in particular epoxy groups and the other including in particular groups susceptible Wheat to react with the latter, once the oxirane cycles are open.
- a and B two-component systems
- These components can, each in turn, be melted and kept in fusion for relatively long times compatible with the requirements of an implementation on an industrial scale, cooled and remelted without causing crosslinking.
- these two components are brought into contact in the molten state (intimate mixing or superposition of a layer of one on a layer of the other), and the expected crosslinking then occurs under the effect of a rise in temperature.
- A a first composition not containing epoxy groups and comprising: a) at least one polymer chosen from thermoelastic polymers and synthetic rubbers; b) at least one compound containing at least one group capable of reacting with epoxy groups; c) at least one tackifying resin; and d) where appropriate, at least one plasticizer or a wax;
- (B) a second composition comprising: a) where appropriate at least one polymer chosen from thermoelastic polymers and synthetic rubbers; b) at least one compound containing at least one epoxy group; c) at least one tackifying resin; and d) where appropriate, at least one plasticizer or a wax; and (C) if necessary at least one activator of the reaction between the reactive groups of the constituent (Ab) and the epoxy functions of the constituent (Bb).
- the molar ratio of the reactive groups of the constituent (Ab) to the epoxy groups constituent (Bb) is at least equal to 1.
- the latter preferably comprises: from 10 to 60 parts by weight of the constituent (Aa);
- composition (B) comprises in particular: from 0 to 40 parts by weight of the constituent (Ba); from 20 to 60 parts by weight of the constituent (Bb); from 10 to 60 parts by weight of the constituent (Bc); and - from 0 to 40 parts by weight of the constituent (Bd).
- thermoelastic polymers falling within the definition of the constituents (Aa) and (Ba) are preferably chosen from the group of copolymers of ethylene and vinyl acetate or of high-strength alkyl acrylate (approximately 20 to 50% by weight) in acetate or acrylate and of high molecular weight (approximately 5,000 to 30,000).
- Synthetic rubbers falling under the definition of constituents (Aa) and. (Ba) are preferably chosen from copolymers with linear or star blocks, styrene / butadiene, or styrene / isoprene.
- the compound (Ab) contains at least one amino group.
- a compound (Ab) there may be mentioned a polyamide with free amino functions.
- Polyamides which can be used are in particular polyamides obtained from (a) 35 to 49.5% by mole of acid dimeric fat, (b) 0.5 to 15 mol% of monomeric fatty acid with a chain length of 12 to 22 carbon atoms, (c) 2 to 35 mol% of polyetheramine of general formula: H 2 N - R-_ - 0 - (RO) ⁇ - R 2 - NH 2 in which x represents a number between 8 and 80, in particular, between 8 and 40; R and R 2 represent identical or different, aliphatic and / or cycloaliphatic hydrocarbon residues; and R represents an optionally branched aliphatic hydro ⁇ carbon residue having 1 to 6 carbon atoms, and (d) 15 to 48 mol% of aliphatic diamine containing 2 to 40 carbon atoms in the carbon skeleton, the dimer fatty acids possibly be replaced up to 2/3 by aliphatic dicarboxylic acids having 4 to 12 carbon atoms; and polyamides obtained from
- the compound (Bb) is in particular a polymer containing epoxy groups, and in particular glycidyl groups.
- epoxidized resins having a functionality, defined as the number of epoxy functions per molecule, at least equal to 2, such as the diglycidyl ether of bisphenol A, butadiene diepoxide, 3,4 3,4-epoxycyclohexylmethyl-epoxycyclohexane carboxylate, vinylcyclohexene dioxide, 4,4'-di (1,2-epoxyethyl) iphenyl ether, 4,4'- (1,2-epoxyethyl) -biphenyl, 2,2-bis (3,4-epoxycyclohexyl) - propane, diglycidyl ether of resorcinol, diglycidyl ether of phloroglucinol, bis (2,3-epoxycyclopentyl)
- R 3 is a group of formula -CH -0 — R -0-CH - in which R ⁇ is a divalent group chosen from alkylene groups having from 2 to 12 carbon atoms and those comprising at least one aliphatic ring or aromatic substituted or not.
- triepoxidized or tetraepoxidized resins such as, for example, the triglycidic ether of p-aminophenol, the polyaryl glycidyl ethers, the 1,3,5-tri (1,2-epoxy) enzyme, the 2,2 ',, 4'-tetra-glycidoxybenzophenone, tetraglycidoxytetraphenylethane, 1 * polyglycidyl ether of the novolak phenolformaldehyde resin, triglycidyl ether of glycerol, triglycidyl ether of trimethylolpropane and tetraglycidyl- 4,4'-diaminodipen.
- the triglycidic ether of p-aminophenol the polyaryl glycidyl ethers
- the 1,3,5-tri (1,2-epoxy) enzyme the 2,2 ',, 4'-tetra-glycidoxy
- This polymer (Bb) can also contain, in addition to epoxy groups such as units derived from a monomer glycidyl, units derived from at least one alkene and, where appropriate, units derived from at least one comonomer, chosen in particular from C 1 -C 12 alkyl acrylates and methacrylates.
- Such copolymers can be obtained either by direct copolymerization of the monomers in accordance with patents FR-A-1,569,004 and FR-A-2,130,279, or by grafting the glycidyl monomer onto an alkene homopolymer or an ethylene copolymer / (meth) acrylate as described in particular by GALUCCI et al. in J. Appl.
- such a polymer (Bb) contains from 5 to 20% approximately by weight of glycidyl monomer.
- glycidyl monomers mention may be made of glycidyl acrylate and methacrylate, as well as those of the general formula:
- - X is chosen from oxygen and sulfur atoms, the NH radical, the NR 7 radicals in which R 7 is an alkyl group having from 1 to 12 carbon atoms, and the oxyalkylene radicals 0- (CH 2 ) n in which n is an integer ranging from 3 to 16 approximately, R 5 is chosen from the hydrogen atom and the alkyl radicals having from 1 to 5 carbon atoms, and R 6 denotes a hydrocarbon chain comprising from 2 to 20 carbon atoms chosen from linear or branched alkyl, cycloalkyl or heteroxyclo- alkyl mono- or polycyclic and alkylaryl alkyl chains, said hydrocarbon chain comprising an oxirane group in the chain, or at the end of the chain in the case of an alkyl or alkylaryl chain , or an oxirane group exo- or endocyclic in the case of a mono- or polycyclic cycloalkyl or heterocycloalkyl chain.
- alkenylaro atic units which can enter into the constitution of these resins, mention may in particular be made of units derived from styrene, alphamethylstyrene, indene, vinyl toluene, methylindenes, betamethylstyrene and paratertiobutylstyrene.
- terpene units which can enter into the constitution of these resins, mention may in particular be made of units derived from unsaturated cyclic terpenes, preferably monounsaturated, in particular monocyclic, such as 1-p-menthene and tetramethylcyclohexene, and bicyclic monoinsatural such as pinenes, keels, limonene, 4 (10) -thujene, 5-isopropylbicyclo [3.1.0] hex-2-ene, 4-methylenepinane, 2-bornene, 2,2,7-trimen- thyl-2-norbornene and camphene as well as certain bi-unsaturated monocyclic terpenes such as menthadienes.
- resins which can be used in the context of the present invention are described in documents EP-A-011 393, EP-A-132 291, EP-A-233 074 and FR-A-2 659 972.
- the plasticizers (Ad) and (Bd) are chosen in particular on the one hand, from semi-aliphatic oils, polyisobutylenes of very low molecular weight, and aromatic, naphthenic or paraffinic petroleum oils, alkylbenzenes, and, d on the other hand, esters derived from acids saturated organics such as phthalates, adipates, sebacates and alkyl azelates.
- Examples of the latter include diethyl, dibutyl, dicyclohexyl, diethylhexyl, dioctyl, didecyl, butylethylhexyl phthalates, dibutyl, dioctyl, diisooctyl adipates, dibutyl sebacates , dioctyl, diisooctyl, dioctyl and diisooctyl azelates.
- plasticizers (Ad) and (Bd) of ethylene-vinyl acetate copolymers of very low molecular weight (of the order of 1000-1500), an example of such a copolymer being that containing 28% by weight of vinyl acetate.
- the waxes (Ad) and (Bd) are chosen in particular from low molecular weight polyethylene waxes (generally less than 5,000) and paraffins.
- the activator (C) is chosen in particular from tertiary amines, such as dimethylparatoluidine, dimethyllaurylamine, N-bu ' tylmorpholine, N, N-dimethyl-cyclohexylamine, benzyldi ethylamine, pyridine, dimethylamino-4-pyridine , methyl-1-imidazole, tetramethylethylenediamine, tetramethylguanidine, tetramethylhydrazine, N, N-dimethylpiperazine, N, N, N'N'-tetramethyl-1,6-hexanediamine; phosphines, such as triphenylphosphine; aryl- or alkylphosphonium halides, such as ethyltriphenylphosphonium iodide; and tertiary amides of fatty acids, such as tertiary amides of soy fatty acids.
- compositions (A) and (B) may contain up to 10 parts by weight, per 100 parts by weight of the said composition, of at least one adjuvant such as a wax or paraffin, like polyethylene wax.
- At least one of the compositions (A) and (B) may contain up to 5 parts by weight, per 100 parts by weight of the said composition, of at least one mineral filler, chosen in particular from silica, alumina, mineral silicates, aluminates and silicoaluminates and talc.
- at least one mineral filler chosen in particular from silica, alumina, mineral silicates, aluminates and silicoaluminates and talc.
- At least one of the compositions (A) and (B) may contain up to 1 part by weight, per 100 parts by weight of the said composition, of at least one antioxidant chosen in particular from 2,6-ditertiobutyl - paracresol, bishydroxyanisol, 2,2'-thiodiethyl-bis-3- (3,5-ditertiobutyl-4-hydroxyphenyl) propionate, tetrakis- (methylene 3- (3 ', 5'-ditertiobutyl-4) - hydroxyphenyl) ropionate) ethane, 2,4-bis-N-octylthio-6- (4-hydroxy 3,5-ditertiobutylanilino) 1,3,5-triazine, ditertiobutyl-3,5 hydroxy-4 phenyl- 3 propionate and octadecyl-3,5-ditertio-butyl-4-hydroxyhydrocinnamate.
- at least one antioxidant chosen in particular
- the present invention also relates to systems as defined above in which, when it is present, the activator (C) is at least partially incorporated in the composition (A) and / or in the composition ( B).
- the activator (C) can advantageously be completely incorporated in the composition (A) and / or in the composition (B), so as to form a two-component system as in the case where it is absent.
- the aforementioned two-component system further comprises a film of thermoplastic material chemically inert with respect to each of the two components and carrying on each of its faces a layer of one of said components.
- the inert film will consist, for example, of polyethylene or polypropylene or also of an ethylene / alkyl acrylate or ethylene / vinyl acetate copolymer.
- the present invention also relates to a process for the preparation of a two-component system as defined above. This process is characterized by the fact that the constituents of composition (A) and those of composition (B) are mixed separately at a temperature sufficient to obtain homogeneous liquids, and that each of the two liquid mixtures is cooled. while incorporating the case optionally the activator (C) to at least one of said compositions (A) and (B).
- each composition (A) and (B) Preferably, mixing the constituents of each composition (A) and (B) at a temperature which is higher by at least 10 ° C above the softening point of said composition, for example between 120 ° C and 170 C.
- the ⁇ temperature at which one incorporates if necessary 1 * activa ⁇ tor (C) is in particular between 120 ° C and 170 ° C.
- the process indicated below comprises, after having prepared its two components, the step consisting in applying one of them to one face of said film and the other on the other side.
- the application of a component to one face of the film can be carried out by coextrusion, or by coating, for example with a roller or by means of a flat die.
- a mixture (A) comprising:
- a mixture (B) comprising:
- a first composition (A) is prepared comprising: - 5.5 parts by weight of VERSAMIDE 140,
- This composition (A) has a viscosity at 175 ° C of 3900 centipoise.
- the following properties are determined for the two-component system obtained by equiponderal mixing of the composition (A) described above and of the composition (B) of Example 1 - softening temperature (according to NFT 76106): 113 ° C after 4 days. breaking stress (according to NFT 76 107): 1.4 MPa peeling force (according to NFT 76 112): 4.4 N.
- a first composition (A) comprising:
- composition (A) has a viscosity at 175 ⁇ C of 30,800 centipoise.
- composition (B) is prepared comprising:
- n 2 or 3
- This composition (B) has a viscosity at 175 ° C of 1250 centipoise.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A system for a cross-linkable hot-melt adhesive, comprising (A) a first composition which contains no epoxy groups and comprises: (a) at least one polymer chosen from thermoelastic polymers and synthetic rubbers; (b) at least one compound containing at least one grouping which may react with epoxy groups; (c) at least one tackifying resin; and (d) if required, at least one plasticizer or a wax; and (B) a second composition which comprises: (a) if required, at least one polymer chosen from thermoelastic polymers and synthetic rubbers; (b) at least one compound containing at least one epoxy group; (c) at least one tackifying resin; (d) if required, at least one plasticizer or a wax; and (e) if required, at least one activator of the reaction between the reactive groupings of component (Ab) and the epoxy functions of component (Bb). The system may be used to assemble two objects.
Description
SYSTEMES POUR ADHESIFS THERMOFUSIBLES RETICULABLES, LEUR PREPARATION ET PROCEDE D'ASSEMBLAGE LES UTILISANT SYSTEMS FOR CROSS-LINKABLE HEAT MELT ADHESIVES, THEIR PREPARATION AND ASSEMBLY METHOD USING THE SAME
La présente invention concerne des systèmes pour adhésifs thermofusibles qui ont la particularité de conduire, après application sur les surface à assembler, à un produit réticulé de manière sensiblement irréversible le rendant infusible ou difficilement fusible.- Elle concerne également la préparation de ces systèmes, ainsi qu'un procédé d'assem¬ blage les utilisant. Les systèmes pour adhésifs thermofusibles réticula- bles conformes à la présente invention possèdent le double avantage de pouvoir être mis en oeuvre de façon très aisée dans des installations industrielles, notamment des installa¬ tions automatisées (robots) , telles que celles de l'industrie automobile, et de pouvoir être appliqués à de nombreux types d'objets réalisés à partir de matériaux très divers, tels que le bois, les métaux, les textiles tissés ou non-tissés, le verre, la porcelaine, les céramiques, le carton, le papier, la pierre, le béton et les matières plastiques. Ils présen- tent notamment un excellent pouvoir d'adhésion vis-à-vis des substrats fermés non poreux, tels que l polystyrène, le polyéthylène non traité, le poly(chlorure de vinyle) non traité, les caoutchoucs acrylonitrile-butadiène-styrène, le poly(méthacrylate de méthyle) , le verre, et l'aluminium. On connaît par la demande de brevet EP-A-252 795 un système pour adhésif thermofusible comportant : (A) une première composition ne renfermant pas de groupes anhydride et comportant : a) au moins un polymère choisi parmi les polymères thermoélastiques et les caoutchoucs de synthèse ; b) au moins un composé renfermant au moins un groupe¬ ment susceptible de réagir avec des groupes anhy¬ dride ; c) au moins une résine tackifiante ; d) le. cas échéant, au moins un plastifiant ;
(B) une seconde composition comportant : a) au moins un polymère choisi parmi les polymères thermoélastiques et les caoutchoucs de synthèse ; b) au moins un composé renfermant au moins un groupe anhydride ; c) au moins une résine tackifiante ; et d) le cas échéant, au moins un plastifiant ; etThe present invention relates to systems for hot-melt adhesives which have the particularity to lead, after application to the surfaces to be assembled, to a crosslinked product which is substantially irreversible making it infusible or difficult to fuse. It also relates to the preparation of these systems, thus that an assembly process using them. The systems for crosslinkable hot-melt adhesives in accordance with the present invention have the double advantage of being able to be implemented very easily in industrial installations, in particular automated installations (robots), such as those of the automobile industry. , and can be applied to many types of objects made from very diverse materials, such as wood, metals, woven or non-woven textiles, glass, porcelain, ceramics, cardboard, paper, stone, concrete and plastics. In particular, they exhibit excellent adhesion power with respect to closed non-porous substrates, such as polystyrene, untreated polyethylene, untreated polyvinyl chloride, acrylonitrile-butadiene-styrene rubbers, poly (methyl methacrylate), glass, and aluminum. Patent application EP-A-252,795 discloses a system for hot-melt adhesive comprising: (A) a first composition not containing anhydride groups and comprising: a) at least one polymer chosen from thermoelastic polymers and rubbers synthesis; b) at least one compound containing at least one group capable of reacting with anhydrous groups; c) at least one tackifying resin; d) the. if necessary, at least one plasticizer; (B) a second composition comprising: a) at least one polymer chosen from thermoelastic polymers and synthetic rubbers; b) at least one compound containing at least one anhydride group; c) at least one tackifying resin; and d) where appropriate, at least one plasticizer; and
(C) au moins un activateur de la réaction entre les groupe¬ ments réactifs du constituant (Ab) et les fonctions anhydride du constituant (Bb) .(C) at least one activator of the reaction between the reactive groups of the constituent (Ab) and the anhydride functions of the constituent (Bb).
Ce système trouve une application particulièrement avantageuse dans le domaine du brochage des livres. Toute¬ fois dans cette application on recherche en permanence, tout en conservant un adhésif thermofusiblê de température de ramollissement au moins égale à 120 °C et de température de fragilisation à froid au plus égale à -10°C, à améliorer la force d'arrachage pour les diverses qualités de papier. Dans ce domaine donc, le problème à résoudre par la présente invention consiste, toutes autres propriétés étant égales par ailleurs, à procurer un adhésif thermofusible possédant une force d'arrachage supérieure à celle de l'adhésif du document EP-A-252 795.This system finds a particularly advantageous application in the field of book binding. However, in this application, we constantly seek, while retaining a hot-melt adhesive with a softening temperature at least equal to 120 ° C. and a cold embrittlement temperature at most equal to -10 ° C., to improve the strength of grubbing up for the various qualities of paper. In this field, therefore, the problem to be solved by the present invention consists, all other properties being equal, of providing a hot-melt adhesive having a peeling force greater than that of the adhesive of document EP-A-252,795.
Dans d'autres applications telles que celle du collage de polyester sur polyester ou bien de polyester sur aluminium dans le secteur de l'industrie automobile, le système adhésif décrit par le document EP-A-252 795 est difficilement utilisable car il possède une contrainte à la rupture généralement inférieure aux exigences requises par les constructeurs automobiles. Un second problème à résoudre par la présente invention consiste donc à procurer un adhésif thermofusible possédant une contrainte à la rupture au moins égale à 4 MPa de manière à permettre l'assemblage de poly¬ ester sur polyester ou bien aluminium.In other applications such as that of bonding polyester to polyester or else polyester to aluminum in the automotive industry, the adhesive system described in document EP-A-252,795 is difficult to use because it has a constraint. at break generally less than the requirements required by car manufacturers. A second problem to be solved by the present invention therefore consists in providing a hot-melt adhesive having a breaking stress at least equal to 4 MPa so as to allow the assembly of polyester on polyester or aluminum.
Les systèmes pour adhésifs selon la présente invention sont notamment des systèmes à deux composants, (ci- après appelés A et B) , l'un renfermant notamment des groupes époxy et l'autre renfermant notamment des groupes suscepti-
blés de réagir avec ces derniers, une fois les cycles oxirannes ouverts. Ces composants peuvent, chacun de leur côté, être fondus et tenus en fusion pendant des temps relativement longs compatibles avec les exigences d'une mise en oeuvre à l'échelle industrielle, refroidis et refondus sans provoquer de réticulation. Au moment de l'emploi, ces deux composants sont mis en contact à 1 'état fondu (mélange intime ou superposition d'une couche de l'un sur une couche de l'autre), et la réticulation attendue se produit alors sous l'effet d'une élévation de la température.The adhesive systems according to the present invention are in particular two-component systems (hereinafter called A and B), one containing in particular epoxy groups and the other including in particular groups susceptible Wheat to react with the latter, once the oxirane cycles are open. These components can, each in turn, be melted and kept in fusion for relatively long times compatible with the requirements of an implementation on an industrial scale, cooled and remelted without causing crosslinking. At the time of use, these two components are brought into contact in the molten state (intimate mixing or superposition of a layer of one on a layer of the other), and the expected crosslinking then occurs under the effect of a rise in temperature.
Ce mécanisme de la réticulation entre les groupes époxy ouverts et les autres groupes réactifs est connu en tant que tel, mais il n'avait jamais été appliqué de cette manière aux collages industriels. Les systèmes selon l'invention n'ont pas besoin d'apport d'agents extérieurs pour réticuler, les composants A et B renfermant tous les ingrédients nécessaires à la réticulation..This mechanism of crosslinking between open epoxy groups and other reactive groups is known as such, but it has never been applied in this way to industrial bonding. The systems according to the invention do not require the addition of external agents to crosslink, components A and B containing all the ingredients necessary for crosslinking.
La présente invention a donc d'abord pour objet un système pour adhésif thermofusible reticulable caractérisé par le fait qu'il comporte :The present invention therefore firstly relates to a system for crosslinkable hot-melt adhesive, characterized in that it comprises:
(A) une première composition ne renfermant pas de groupes époxy et comportant : a) au moins un polymère choisi parmi les polymères thermoélastiques et les caoutchoucs de synthèse ; b) au moins un composé renfermant au moins un groupe¬ ment susceptible de réagir avec des groupes époxy; c) au moins une résine tackifiante ; et d) le cas échéant, au moins un plastifiant ou une cire ;(A) a first composition not containing epoxy groups and comprising: a) at least one polymer chosen from thermoelastic polymers and synthetic rubbers; b) at least one compound containing at least one group capable of reacting with epoxy groups; c) at least one tackifying resin; and d) where appropriate, at least one plasticizer or a wax;
(B) une seconde composition comportant : a) le cas échéant au moins un polymère choisi parmi les polymères thermoélastiques et les caoutchoucs de synthèse ; b) au moins un composé renfermant au moins un groupe époxy ; c) au moins une résine tackifiante ; et
d) le cas échéant, au moins un plastifiant ou une cire ; et (C) le cas échéant au moins un activateur de la réaction entre les groupements réactifs du constituant (Ab) et les fonctions époxy du constituant (Bb) .(B) a second composition comprising: a) where appropriate at least one polymer chosen from thermoelastic polymers and synthetic rubbers; b) at least one compound containing at least one epoxy group; c) at least one tackifying resin; and d) where appropriate, at least one plasticizer or a wax; and (C) if necessary at least one activator of the reaction between the reactive groups of the constituent (Ab) and the epoxy functions of the constituent (Bb).
De préférence, le rapport molaire des groupements réactifs du constituant (Ab) aux groupes époxy constituant (Bb) est au moins égal à 1.Preferably, the molar ratio of the reactive groups of the constituent (Ab) to the epoxy groups constituent (Bb) is at least equal to 1.
En outre, pour 100 parties en poids de la composi- tion (A) , celle-ci comprend de préférence : de 10 à 60 parties en poids du constituant (Aa) ;In addition, per 100 parts by weight of the composition (A), the latter preferably comprises: from 10 to 60 parts by weight of the constituent (Aa);
- de 3 à 15 parties en poids du constituant (Ab) ;- from 3 to 15 parts by weight of the constituent (Ab);
- de 10 à 60 parties en poids du constituant (Ac) ; et de 0 à 40 parties en poids du constituant (Ad) . De même, pour 100 parties en poids de la composi¬ tion (B) , celle-ci comprend notamment : de 0 à 40 parties en poids du constituant (Ba) ; de 20 à 60 parties en poids du constituant (Bb) ; de 10 à 60 parties en poids du constituant (Bc) ; et - de 0 à 40 parties en poids du constituant (Bd) .- from 10 to 60 parts by weight of the constituent (Ac); and from 0 to 40 parts by weight of the constituent (Ad). Likewise, for 100 parts by weight of the composition (B), it comprises in particular: from 0 to 40 parts by weight of the constituent (Ba); from 20 to 60 parts by weight of the constituent (Bb); from 10 to 60 parts by weight of the constituent (Bc); and - from 0 to 40 parts by weight of the constituent (Bd).
Les polymères thermoélastiques entrant dans la définition des constituants (Aa) et (Ba) sont choisis, de préférence, dans le groupe des copolymères d'éthylène et d'acétate de vinyle ou d'acrylate d'alkyle à forte teneur (environ 20 à 50% en poids) en acétate ou acrylate et de haut poids moléculaire (environ 5 000 à 30 000).The thermoelastic polymers falling within the definition of the constituents (Aa) and (Ba) are preferably chosen from the group of copolymers of ethylene and vinyl acetate or of high-strength alkyl acrylate (approximately 20 to 50% by weight) in acetate or acrylate and of high molecular weight (approximately 5,000 to 30,000).
Les caoutchoucs de synthèse entrant dans la définition des constituants (Aa) et. (Ba) sont choisis, de préférence, parmi les copolymères à blocs linéaires ou en étoile, styrène/butadiène, ou styrène/isoprène.Synthetic rubbers falling under the definition of constituents (Aa) and. (Ba) are preferably chosen from copolymers with linear or star blocks, styrene / butadiene, or styrene / isoprene.
Conformément à un mode de réalisation du système pour adhésif thermofusible selon l'invention, le composé (Ab) renferme au moins un groupement aminé. A titre d'exemple d'un tel composé (Ab) , on peut mentionner un polyamide à fonctions aminé libres.According to one embodiment of the system for hot-melt adhesive according to the invention, the compound (Ab) contains at least one amino group. As an example of such a compound (Ab), there may be mentioned a polyamide with free amino functions.
Des polyamides utilisables sont notamment des polyamides obtenus à partir de (a) 35 à 49,5% en mole d'acide
gras dimère, (b) 0,5 à 15% en mole d'acide gras monomère d'une longueur de chaîne de 12 à 22 atomes de carbone, (c) 2 à 35% en mole de polyétheramine de formule générale : H2N - R-_ - 0 - (RO)χ - R2 - NH2 dans laquelle x représente un nombre compris entre 8 et 80, en particulier, entre 8 et 40 ; R et R2 représentent des restes hydrocarbonés, identiques ou différents, aliphatiques et/ou cycloaliphatiques ; et R représente un reste hydro¬ carboné aliphatique éventuellement ramifié, possédant 1 à 6 atomes de carbone, et (d) 15 à 48% en mole de diamine aliphatique renfermant 2 à 40 atomes de carbone dans le squelette carboné, les acides gras dimères pouvant être remplacés jusqu'aux 2/3 par des acides dicarboxyliques aliphatiques possédant 4 à 12 atomes de carbone ; et des polyamides obtenus à partir de (a) 20 à 49,5% en mole d'acides gras dimères, (b) 0,5 à 15% en mole d'acides gras monomères d'une longueur de chaîne de 12 à 22 atomes de carbone ; et (c) jusqu'à 20 à 55% en mole d'une aminé portant au moins deux groupes amino primaires et possédant 2. à 40 atomes de carbone dans le squelette carboné, les acides gras dimères pouvant être remplacés jusqu'aux 2/3 par des acides dicarboxyliques aliphatiques possédant 4 à 12 atomes de carbone. Ces polyamides présentent avantageusement des groupes terminaux acides, leur indice d'acide allant de 1 à 50, de préférence, de 2 à 30, en particulier de 4 à 12 ; ils peuvent aussi porter des groupes terminaux amino, leur indice d'aminé allant de 2 à 15, en particulier de 4 à 10.Polyamides which can be used are in particular polyamides obtained from (a) 35 to 49.5% by mole of acid dimeric fat, (b) 0.5 to 15 mol% of monomeric fatty acid with a chain length of 12 to 22 carbon atoms, (c) 2 to 35 mol% of polyetheramine of general formula: H 2 N - R-_ - 0 - (RO) χ - R 2 - NH 2 in which x represents a number between 8 and 80, in particular, between 8 and 40; R and R 2 represent identical or different, aliphatic and / or cycloaliphatic hydrocarbon residues; and R represents an optionally branched aliphatic hydro¬ carbon residue having 1 to 6 carbon atoms, and (d) 15 to 48 mol% of aliphatic diamine containing 2 to 40 carbon atoms in the carbon skeleton, the dimer fatty acids possibly be replaced up to 2/3 by aliphatic dicarboxylic acids having 4 to 12 carbon atoms; and polyamides obtained from (a) 20 to 49.5% by mole of dimeric fatty acids, (b) 0.5 to 15% by mole of monomeric fatty acids with a chain length of 12 to 22 carbon atoms; and (c) up to 20 to 55 mol% of an amine carrying at least two primary amino groups and having 2 to 40 carbon atoms in the carbon skeleton, the dimer fatty acids being able to be replaced up to 2 / 3 by aliphatic dicarboxylic acids having 4 to 12 carbon atoms. These polyamides advantageously have acid terminal groups, their acid number ranging from 1 to 50, preferably from 2 to 30, in particular from 4 to 12; they can also carry amino terminal groups, their amine index ranging from 2 to 15, in particular from 4 to 10.
A titre de second exemple de composé (Ab) , on peut également citer des aminoalkylimidazolidones de formule :As a second example of compound (Ab), mention may also be made of aminoalkylimidazolidones of formula:
H2N-(CH2)n-N - CH2 H 2 N- (CH 2 ) n -N - CH 2
C CH2 C CH 2
// \ /// \ /
0 N H0 N H
dans laquelle n est un nombre entier de 1 à 20.
Le composé (Bb) est notamment un polymère renfer¬ mant des groupes époxy, et en particulier des groupes glycidyles. A titre d'exemple on peut citer des résines époxydées présentant une fonctionnalité, définie comme le nombre de fonctions époxydes par molécule, au moins égale à 2, telles que 1'éther diglycidylique du bisphénol A, le diépoxyde de butadiène, le 3,4-époxycyclohexane-carboxylate de 3,4-époxycyclohexylméthyle, le dioxyde de vinylcyclo- hexèn , le 4,4'-di(l,2-époxyéthyl) iphényléther, le 4,4'- (1,2-époxyéthyl)-biphényle, le 2,2-bis(3,4-époxycyclohexyl)- propane, l'éther diglycidylique du résorcinol, l'éther diglycidylique du phloroglucinol, le bis(2,3-époxycyclo- pentyl)éther, le 2-(3,4-époxy)cyclohexane-5,5-spiro(3,4- époxy)cyclohexane-m-dioxane, l'adipate de bis-(3,4-époxy-6- méthyl-cyclohexyle) , le N,N-m-(phénylènebis-4,5-époxy-l,2- cyclohexane-dicarboxamide) , un composé diépoxy contenant un cycle hydantoîne, etc. De telles résines peuvent généra¬ lement être représentées par" la formule :where n is an integer from 1 to 20. The compound (Bb) is in particular a polymer containing epoxy groups, and in particular glycidyl groups. By way of example, there may be mentioned epoxidized resins having a functionality, defined as the number of epoxy functions per molecule, at least equal to 2, such as the diglycidyl ether of bisphenol A, butadiene diepoxide, 3,4 3,4-epoxycyclohexylmethyl-epoxycyclohexane carboxylate, vinylcyclohexene dioxide, 4,4'-di (1,2-epoxyethyl) iphenyl ether, 4,4'- (1,2-epoxyethyl) -biphenyl, 2,2-bis (3,4-epoxycyclohexyl) - propane, diglycidyl ether of resorcinol, diglycidyl ether of phloroglucinol, bis (2,3-epoxycyclopentyl) ether, 2- (3,4 -epoxy) cyclohexane-5,5-spiro (3,4- epoxy) cyclohexane-m-dioxane, bis- (3,4-epoxy-6-methyl-cyclohexyl) adipate, N, Nm- (phenylenebis -4,5-epoxy-1,2-cyclohexane-dicarboxamide), a diepoxy compound containing a hydantoin ring, etc. Such resins can generally be represented by " the formula:
H2C C R3 C CH2 \ / \ /H 2 CCR 3 C CH 2 \ / \ /
0 00 0
dans laquelle R3 est un groupement de formule -CH -0—R -0-CH - dans laquelle R^ est un groupement divalent choisi parmi les groupements alkylène ayant de 2 à 12 atomes de carbone et ceux comprenant au moins un cycle aliphatique ou aromatique substitué ou non. On peut aussi utiliser des résines triépoxydées ou tétraépoxydées comme, par exemple, l'éther triglycidique du p-aminophénol, les éthers polyarylglycidi- ques, le 1,3,5-tri(1,2-époxy) enzène, la 2,2' , ,4'-tétra- glycidoxybenzophenone, le tétraglycidoxytétraphényléthane, 1*éther polyglycidylique de la résine phénolformaldéhyde de type novolaque, l'éther triglycidylique du glycérol, l'éther triglycidylique du triméthylolpropane et le tétraglycidyl- 4,4'-diaminodiphénylméthane. Ce polymère (Bb) peut également renfermer, outre des groupes époxy tels que des motifs dérivés d'un monomère
glycidylique, des motifs dérivés d'au moins un alcène et, le cas échéant, des motifs dérivés d'au moins un comonomère, choisi notamment parmi les acrylates et méthacrylates d'alkyle en C1-C12. De tels copolymères peuvent être obtenus, soit par copolymérisation directe des monomères conformément aux brevets FR-A-1 569 004 et FR-A-2 130 279, soit par greffage du monomère glycidylique sur un homo- polymère d'alcène ou un copolymere éthylène/(méth)acrylate d'alkyle tel que décrit notamment par GALUCCI et al. dans J. Appl. Polym. Sci. 27(2), pages 425 à 437 (1982). Dans le cadre de la présente invention, il est préférable qu'un tel polymère (Bb) contienne de 5 à 20% environ en poids de monomère glycidylique. Comme exemples de monomères glycidy- liques on peut citer l'acrylate et le méthacrylate de glycidyle, ainsi que ceux de la formule générale :in which R 3 is a group of formula -CH -0 — R -0-CH - in which R ^ is a divalent group chosen from alkylene groups having from 2 to 12 carbon atoms and those comprising at least one aliphatic ring or aromatic substituted or not. It is also possible to use triepoxidized or tetraepoxidized resins such as, for example, the triglycidic ether of p-aminophenol, the polyaryl glycidyl ethers, the 1,3,5-tri (1,2-epoxy) enzyme, the 2,2 ',, 4'-tetra-glycidoxybenzophenone, tetraglycidoxytetraphenylethane, 1 * polyglycidyl ether of the novolak phenolformaldehyde resin, triglycidyl ether of glycerol, triglycidyl ether of trimethylolpropane and tetraglycidyl- 4,4'-diaminodipen. This polymer (Bb) can also contain, in addition to epoxy groups such as units derived from a monomer glycidyl, units derived from at least one alkene and, where appropriate, units derived from at least one comonomer, chosen in particular from C 1 -C 12 alkyl acrylates and methacrylates. Such copolymers can be obtained either by direct copolymerization of the monomers in accordance with patents FR-A-1,569,004 and FR-A-2,130,279, or by grafting the glycidyl monomer onto an alkene homopolymer or an ethylene copolymer / (meth) acrylate as described in particular by GALUCCI et al. in J. Appl. Polym. Sci. 27 (2), pp. 425-437 (1982). In the context of the present invention, it is preferable that such a polymer (Bb) contains from 5 to 20% approximately by weight of glycidyl monomer. As examples of glycidyl monomers, mention may be made of glycidyl acrylate and methacrylate, as well as those of the general formula:
R-R-
\\
C - C - X - Rc /C - C - X - R c /
H2CH 2 C
dans laquelle :in which :
- X est choisi parmi les atomes d'oxygène et de soufre, le radical NH, les radicaux NR7 dans lesquels R7 est un groupe alkyle ayant de 1 à 12 atomes de carbone, et les radicaux oxyalkylènes 0-(CH2)n dans lesquels n est un nombre entier allant de 3 à 16 environ, R5 est choisi parmi l'atome d'hydrogène et les radicaux alkyles ayant de 1 à 5 atomes de carbone, et R6 désigne une chaîne hydrocarbonée comprenant de 2 à 20 atomes de carbone choisie parmi les chaînes alkyles linéaires ou ramifiées, cycloalkyles ou hétéroxyclo- alkyles mono- ou polycycliques et alkylaryles, ladite chaîne hydrocarbonée comprenant un groupe oxiranne dans la chaîne, ou en bout de chaîne dans le cas d'une chaîne alkyle ou alkylaryle, ou un groupe oxiranne exo- ou
endocyclique dans le cas d'une chaîne cycloalkyle ou hétérocycloalkyle mono- ou polycyclique.- X is chosen from oxygen and sulfur atoms, the NH radical, the NR 7 radicals in which R 7 is an alkyl group having from 1 to 12 carbon atoms, and the oxyalkylene radicals 0- (CH 2 ) n in which n is an integer ranging from 3 to 16 approximately, R 5 is chosen from the hydrogen atom and the alkyl radicals having from 1 to 5 carbon atoms, and R 6 denotes a hydrocarbon chain comprising from 2 to 20 carbon atoms chosen from linear or branched alkyl, cycloalkyl or heteroxyclo- alkyl mono- or polycyclic and alkylaryl alkyl chains, said hydrocarbon chain comprising an oxirane group in the chain, or at the end of the chain in the case of an alkyl or alkylaryl chain , or an oxirane group exo- or endocyclic in the case of a mono- or polycyclic cycloalkyl or heterocycloalkyl chain.
Les résines tackifiantes (Ac) et (Bc) sont choisies notamment parmi les polyterpènes, le cas échéant fonction- nalisés par des novolaques, les colophanes et esters de colophane et leurs dérivés hydrogénés, ainsi que les résines de pétrole. Les résines de pétrole utilisables dans les systèmes selon 1'invention sont des résines préparées à partir de fractions d'hydrocarbures provenant du craquage à la vapeur de naphtas, tels que des coupes aromatiques contenant au moins un monomère alcénylaromatique, des coupes aliphatiques contenant un monomère contenant de 5 à 6 atomes de carbone, tel que le cyclopentadiène et ses dérivés et le cyclohexadiène, ou encore des coupes terpéniques telles que des essences de térébenthine. Comme exemples de motifs alcénylaro atiques pouvant entrer dans la constitution de ces résines, on peut citer notamment les motifs dérivés du styrène, de l'alphaméthylstyrène, de l'indène, du vinyl- toluène, des méthylindènes, du bêtaméthylstyrène et du paratertiobutylstyrène. Comme exemples de motifs terpéniques pouvant entrer dans la constitution de ces résines, on peut citer notamment les motifs dérivés de terpènes cycliques insaturés, de préférence monoinsatures, notamment monocycli¬ ques tels que le 1-p-menthène et le tétraméthylcyclohexène et bicycliques monoinsatures tels que les pinènes, carènes, le limonène, le 4(10)-thujène, le 5-isopropylbicyclo[3.1.0]hex- 2-ène, le 4-méthylènepinane, le 2-bornène, le 2,2,7-trimé- thyl-2-norbornène et le camphène ainsi que certains terpènes monocycliques bi-insaturés tels que les menthadiènes. Des exemples de résines utilisables dans le cadre de la présente invention sont décrits dans les documents EP-A-011 393, EP-A-132 291, EP-A-233 074 et FR-A-2 659 972.The tackifying resins (Ac) and (Bc) are chosen in particular from polyterpenes, optionally functionalized with novolaks, rosins and rosin esters and their hydrogenated derivatives, as well as petroleum resins. The petroleum resins which can be used in the systems according to the invention are resins prepared from hydrocarbon fractions originating from the steam cracking of naphthas, such as aromatic cuts containing at least one alkenylaromatic monomer, aliphatic cuts containing a monomer containing 5 to 6 carbon atoms, such as cyclopentadiene and its derivatives and cyclohexadiene, or even terpene cuts such as turpentine. As examples of alkenylaro atic units which can enter into the constitution of these resins, mention may in particular be made of units derived from styrene, alphamethylstyrene, indene, vinyl toluene, methylindenes, betamethylstyrene and paratertiobutylstyrene. As examples of terpene units which can enter into the constitution of these resins, mention may in particular be made of units derived from unsaturated cyclic terpenes, preferably monounsaturated, in particular monocyclic, such as 1-p-menthene and tetramethylcyclohexene, and bicyclic monoinsatural such as pinenes, keels, limonene, 4 (10) -thujene, 5-isopropylbicyclo [3.1.0] hex-2-ene, 4-methylenepinane, 2-bornene, 2,2,7-trimen- thyl-2-norbornene and camphene as well as certain bi-unsaturated monocyclic terpenes such as menthadienes. Examples of resins which can be used in the context of the present invention are described in documents EP-A-011 393, EP-A-132 291, EP-A-233 074 and FR-A-2 659 972.
Les plastifiants (Ad) et (Bd) sont choisis notam¬ ment d'une part, parmi les huiles semi-aliphatiques, les polyisobutylènes de très bas poids moléculaire, et les huiles pétrolières aromatiques, naphténiques ou paraffiniques, les alkylbenzènes, et, d'autre part, les esters dérivés d'acides
organiques saturés tels que les phtalates, adipates, séba- cates et azélates d'alkyle. A titre d'exemples de ces derniers, on peut citer les phtalates de diéthyle, de dibutyle, de dicyclohexyle, de diéthylhexyle, de dioctyle, de didécyle, de butyléthylhexyle, les adipates de dibutyle, de dioctyle, de diisooctyle, les sébacates de dibutyle, de dioctyle, de diisooctyle, les azélates de dioctyle et de diisooctyle. On peut également mentionner, comme plas¬ tifiants (Ad) et (Bd) , les copolymères éthylène-acétate de vinyle de très bas poids moléculaire (de l'ordre de 1000- 1500) , un exemple de tel copolymere étant celui renfermant 28% en poids d'acétate de vinyle.The plasticizers (Ad) and (Bd) are chosen in particular on the one hand, from semi-aliphatic oils, polyisobutylenes of very low molecular weight, and aromatic, naphthenic or paraffinic petroleum oils, alkylbenzenes, and, d on the other hand, esters derived from acids saturated organics such as phthalates, adipates, sebacates and alkyl azelates. Examples of the latter include diethyl, dibutyl, dicyclohexyl, diethylhexyl, dioctyl, didecyl, butylethylhexyl phthalates, dibutyl, dioctyl, diisooctyl adipates, dibutyl sebacates , dioctyl, diisooctyl, dioctyl and diisooctyl azelates. Mention may also be made, as plasticizers (Ad) and (Bd), of ethylene-vinyl acetate copolymers of very low molecular weight (of the order of 1000-1500), an example of such a copolymer being that containing 28% by weight of vinyl acetate.
Les cires (Ad) et (Bd) sont choisies notamment parmi les cires de polyéthylène de bas poids moléculaire (généralement inférieur à 5 000) et les paraffines.The waxes (Ad) and (Bd) are chosen in particular from low molecular weight polyethylene waxes (generally less than 5,000) and paraffins.
L'activateur (C) est choisi notamment parmi les aminés tertiaires, comme la diméthylparatoluidine, la diméthyllaurylamine, la N-bu'tylmorpholine, la N,N-diméthyl- cyclohexylamine, la benzyldi éthylamine, la pyridine, la diméthylamino-4-pyridine, le méthyl-1-imidazole, la tétra- méthyléthylènediamine, la tétraméthylguanidine, la tétra- éthylhydrazine, la N,N-diméthylpipérazine, la N,N,N'N'- tétraméthyl-l,6-hexanediamine ; les phosphines, comme la triphénylphosphine ; les halogénures d'aryl- ou alkyl- phosphonium, comme l'iodure d'ethyltriphénylphosphonium ; et les amides tertiaires d'acides gras, comme les amides tertiaires d'acides gras de soja.The activator (C) is chosen in particular from tertiary amines, such as dimethylparatoluidine, dimethyllaurylamine, N-bu ' tylmorpholine, N, N-dimethyl-cyclohexylamine, benzyldi ethylamine, pyridine, dimethylamino-4-pyridine , methyl-1-imidazole, tetramethylethylenediamine, tetramethylguanidine, tetramethylhydrazine, N, N-dimethylpiperazine, N, N, N'N'-tetramethyl-1,6-hexanediamine; phosphines, such as triphenylphosphine; aryl- or alkylphosphonium halides, such as ethyltriphenylphosphonium iodide; and tertiary amides of fatty acids, such as tertiary amides of soy fatty acids.
Par ailleurs, au moins l'une des compositions (A) et (B) peut renfermer jusqu'à 10 parties en poids, pour 100 parties en poids de ladite composition, d'au moins d'un adjuvant tel qu'une cire ou paraffine, comme la cire de polyéthylène.Furthermore, at least one of the compositions (A) and (B) may contain up to 10 parts by weight, per 100 parts by weight of the said composition, of at least one adjuvant such as a wax or paraffin, like polyethylene wax.
De même, au moins l'une des compositions (A) et (B) peut renfermer jusqu'à 5 parties en poids, pour 100 parties en poids de ladite composition, d'au moins une charge minérale, choisie notamment parmi la silice, l'alumine, les
silicates, aluminates et silicoaluminates minéraux et le talc.Likewise, at least one of the compositions (A) and (B) may contain up to 5 parts by weight, per 100 parts by weight of the said composition, of at least one mineral filler, chosen in particular from silica, alumina, mineral silicates, aluminates and silicoaluminates and talc.
Egalement, au moins l'une des compositions (A) et (B) peut renfermer jusqu'à 1 partie en poids, pour 100 parties en poids de ladite composition, d'au moins un antioxydant choisi notamment parmi le 2,6-ditertiobutyl- paracrésol, le bishydroxyanisol, le 2,2'-thiodiéthyl-bis-3- (3,5-ditertiobutyl-4-hydroxyphényl)propionate, le tétrakis- (méthylène 3-(3',5'-ditertiobutyl-4•-hydroxyphényl) ropio- nate) éthane, le 2,4-bis-N-octylthio-6-(4-hydroxy 3,5- ditertiobutylanilino) 1,3,5-triazine, le ditertiobutyl-3,5 hydroxy-4 phényl-3 propionate et 1'octadécyl-3,5-ditertio- butyl-4-hydroxyhydrocinnamate.Also, at least one of the compositions (A) and (B) may contain up to 1 part by weight, per 100 parts by weight of the said composition, of at least one antioxidant chosen in particular from 2,6-ditertiobutyl - paracresol, bishydroxyanisol, 2,2'-thiodiethyl-bis-3- (3,5-ditertiobutyl-4-hydroxyphenyl) propionate, tetrakis- (methylene 3- (3 ', 5'-ditertiobutyl-4) - hydroxyphenyl) ropionate) ethane, 2,4-bis-N-octylthio-6- (4-hydroxy 3,5-ditertiobutylanilino) 1,3,5-triazine, ditertiobutyl-3,5 hydroxy-4 phenyl- 3 propionate and octadecyl-3,5-ditertio-butyl-4-hydroxyhydrocinnamate.
La présente invention porte également sur des systèmes tels que définis ci-dessus dans lesquels, lorsqu'il est présent, 1*activateur (C) se trouve au moins partiel¬ lement incorporé dans la composition (A) et/ou dans la composition (B) . L'activateur (C) peut avantageusement être totalement incorporé dans la composition (A) et/ou dans la composition (B) , de manière à former un système bi-composants comme dans le cas où il est absent.The present invention also relates to systems as defined above in which, when it is present, the activator (C) is at least partially incorporated in the composition (A) and / or in the composition ( B). The activator (C) can advantageously be completely incorporated in the composition (A) and / or in the composition (B), so as to form a two-component system as in the case where it is absent.
Conformément à un mode de réalisation particulier, le système bi-composants précité comprend en outre un film de matière thermoplastique chimiquement inerte vis-à-vis de chacun des deux composants et portant sur chacune de ses faces une couche de 1'un desdits composants. Le film inerte sera constitué, par exemple, par du polyéthylène ou poly- propylène ou encore par un copolymere éthylène/acrylate d'alkyle ou éthylène/acétate de vinyle. La présente invention porte également sur un procédé de préparation d'un système bi-composants tel que défini ci-dessus. Ce procédé est caractérisé par le fait qu'on mélange séparément les constituants de la composition (A) et ceux de la composition (B) à une température suffi- santé pour obtenir des liquides homogènes, et qu'on refroidit chacun des deux mélanges liquides tout en incorporant le cas
échéant l' ctivateur (C) à au moins une desdites compositions (A) et (B) .In accordance with a particular embodiment, the aforementioned two-component system further comprises a film of thermoplastic material chemically inert with respect to each of the two components and carrying on each of its faces a layer of one of said components. The inert film will consist, for example, of polyethylene or polypropylene or also of an ethylene / alkyl acrylate or ethylene / vinyl acetate copolymer. The present invention also relates to a process for the preparation of a two-component system as defined above. This process is characterized by the fact that the constituents of composition (A) and those of composition (B) are mixed separately at a temperature sufficient to obtain homogeneous liquids, and that each of the two liquid mixtures is cooled. while incorporating the case optionally the activator (C) to at least one of said compositions (A) and (B).
De préférence, on mélange les constituants de chaque composition (A) et (B) à une température qui est supérieure d'au moins 10°C au point de ramollissement de ladite composition, par exemple entre 120°C et 170βC. La température à laquelle on incorpore le cas échéant 1*activa¬ teur (C) est notamment comprise entre 120°C et 170°C.Preferably, mixing the constituents of each composition (A) and (B) at a temperature which is higher by at least 10 ° C above the softening point of said composition, for example between 120 ° C and 170 C. The β temperature at which one incorporates if necessary 1 * activa¬ tor (C) is in particular between 120 ° C and 170 ° C.
Dans le cas où le système bi-composants comprend en outre un film de matière thermoplastique, le procédé sous indiqué comporte, après que l'on ait préparé ses deux composants, l'étape consistant à appliquer l'un d'eux sur une face dudit film et l'autre sur l'autre face. L'application d'un composant sur une face du film peut s'effectuer par coextrusion, ou par enduction, par exemple au rouleau ou au moyen d'une filière plate.In the case where the two-component system further comprises a film of thermoplastic material, the process indicated below comprises, after having prepared its two components, the step consisting in applying one of them to one face of said film and the other on the other side. The application of a component to one face of the film can be carried out by coextrusion, or by coating, for example with a roller or by means of a flat die.
La présente invention a également pour objet un procédé d'assemblage de deux'objets, caractérisé par le fait que l'on porte à une température comprise entre 120°C et 220°C chacun des composants du système bi-composants, tel que défini ci-dessus, puis : soit on les mélange intimement à cette température, puis on applique l'adhésif thermofusible résultant sur au moins l'un des deux objets à assembler, et enfin on applique l'un des deux objets à assembler contre 1'autre, soit on applique séparément les deux compositions soit l'une après l'autre sur l'un des deux objets à assem¬ bler, soit l'une sur un objet à assembler et l'autre, sur l'autre objet à assembler, puis on applique l'un contre l'autre lesdits objets.The present invention also relates to a method of assembling two ' objects, characterized in that one brings to a temperature between 120 ° C and 220 ° C each of the components of the two-component system, as defined above, then: either they are intimately mixed at this temperature, then the resulting hot-melt adhesive is applied to at least one of the two objects to be assembled, and finally one of the two objects to be assembled is applied against 1 ' other, either the two compositions are applied separately, either one after the other on one of the two objects to be assembled, or one on an object to be assembled and the other, on the other object to be assembled , then said objects are applied against each other.
Il est parfois souhaitable, après avoir appliqué les deux objets l'un contre l'autre, de chauffer l'assemblage pendant une durée suffisante pour achever la réticulation. L'invention porte également sur un procédé d'assem¬ blage de deux objets à l'aide du système comprenant un film de matière thermoplastique, ce procédé étant caractérisé par
le fait qu'on assemble les deux objets au moyen du film, pu on porte 1'ensemble à une température supérieure au point fusion du film thermoplastique, et suffisante pour permett la migration de l'un des composés (Ab) et (Bb) vers l'autr leur entrée en contact provoquant la réticulation du systèm Les exemples ci-après sont donnés à titre illustr tif et non limitatif de la présente invention.It is sometimes desirable, after applying the two objects against each other, to heat the assembly for a sufficient time to complete the crosslinking. The invention also relates to a method for assembling two objects using the system comprising a film of thermoplastic material, this method being characterized by the fact that the two objects are assembled by means of the film, or the assembly is brought to a temperature above the melting point of the thermoplastic film, and sufficient to allow the migration of one of the compounds (Ab) and (Bb) towards the other, their coming into contact causing crosslinking of the system. The examples below are given by way of illustration and without limitation of the present invention.
EXEMPLE 1EXAMPLE 1
On prépare d'abord à la température de 170°C u mélange (A) comprenant :A mixture (A) comprising:
- 9,5 parties en poids d'un polyamide à fonctions amin libres, de viscosité 26 centipoises à 25"C et ayant u taux d'aminé de 400 mg KOH/g, commercialisé par l société CRAY VALLEY PRODUCTS sous la dénominatio VERSAMIDE 140,- 9.5 parts by weight of a polyamide with free amine functions, of viscosity 26 centipoises at 25 "C and having an amine content of 400 mg KOH / g, marketed by the company CRAY VALLEY PRODUCTS under the name VERSAMIDE 140 ,
40 parties en poids d'un copolymere éthylène/acétate d vinyle commercialisé par la société DU PONT DE NEMOUR sous la dénomination ELVAX 210,40 parts by weight of an ethylene / vinyl acetate copolymer sold by the company DU PONT DE NEMOUR under the name ELVAX 210,
30 parties en poids d'une résine tackifiante commercia lisée par la société BERVIK CHEMIE sous la dénominatio BEVILITE 6285, - 20 parties en poids d'une résine tackifiante commercia lisée par la société CRAY VALLEY SA sous la marqu NORSOLENE® 1090, et - 0,5 partie en poids d'un antioxydant commercialisé pa la société CIBA-GEIGY sous la dénomination IRGANOX 1010. On prépare d'autre part à la température de 170° un mélange (B) comprenant :30 parts by weight of a tackifying resin marketed by the company BERVIK CHEMIE under the name BEVILITE 6285, - 20 parts by weight of a tackifying resin marketed by the company CRAY VALLEY SA under the brand NORSOLENE ® 1090, and - 0 , 5 parts by weight of an antioxidant sold by the company CIBA-GEIGY under the name IRGANOX 1010. On the other hand, a mixture (B) comprising:
40 parties en poids d'un terpolymère éthylène/acrylate d'éthyle/méthacrylate de glycidyle, d'indice de fluidité40 parts by weight of an ethylene / ethyl acrylate / glycidyl methacrylate terpolymer, of melt index
4 dg/ in. (mesuré selon la norme ASTM D-1238) et comprenant 7% en poids de méthacrylate, commercialisé par la société ATOCHEM sous la dénomination LOTADER® HX 8660,
20 parties en poids de la résine tackifiante NORSOLENE® 1090,4 dg / in. (measured according to ASTM D-1238) and comprising 7% by weight of methacrylate, sold by Atochem under the trademark LOTADER ® 8660 HX, 20 parts by weight of NORSOLENE ® 1090 tackifying resin,
20 parties en poids d'une résine tackifiante commercia¬ lisée par la société EXXON CHEMICAL sous la dénomination ESCOREZ® 4401,20 parts by weight of a tackifying resin commercia¬ Lisée by Exxon Chemical under the name Escorez ® 4401,
- 19,5 parties en poids d'une cire commercialisée par la société ALLIED CORPORATION sous la dénomination AC 400, et- 19.5 parts by weight of a wax sold by the company ALLIED CORPORATION under the name AC 400, and
- 0,5 partie en poids de 1'antioxydant IRGANOX 1010. A 175°C la composition préparée en premier lieu présente une viscosité de 3000 centipoises, celle préparée en second lieu une viscosité de 15000 centipoises.- 0.5 part by weight of the antioxidant IRGANOX 1010. At 175 ° C. the composition prepared in the first place has a viscosity of 3000 centipoises, that prepared in the second place a viscosity of 15000 centipoises.
Pour le système bi-composants obtenu par mélange equiponderal, à 170°C pendant 1 minute dans un mélangeur statique, des deux compositions décrites ci-dessus, on détermine les propriétés suivantes.For the two-component system obtained by equiponderal mixing, at 170 ° C. for 1 minute in a static mixer, of the two compositions described above, the following properties are determined.
- température de ramollissement >140°C après 30 heures (selon norme NFT 76 106) - contrainte à la rupture (selon norme NFT 76 107) : 2 MPa force de pelage (selon norme NFT 76 112) : 40 N.- softening temperature> 140 ° C after 30 hours (according to NFT 76 106 standard) - breaking stress (according to NFT 76 107 standard): 2 MPa peeling force (according to NFT 76 112 standard): 40 N.
EXEMPLE 2EXAMPLE 2
En procédant comme à 1'exemple 1, on prépare une première composition (A) comprenant : - 5,5 parties en poids de VERSAMIDE 140,By proceeding as in Example 1, a first composition (A) is prepared comprising: - 5.5 parts by weight of VERSAMIDE 140,
40 parties en poids de copolymere éthylène/acétate ELVAX 210,40 parts by weight of ethylene / acetate copolymer ELVAX 210,
30 parties en poids de résine tackifiante BEVILITE 6285, 20 parties en poids de résine tackifiante NORSOLENE 1090,30 parts by weight of BEVILITE 6285 tackifying resin, 20 parts by weight of NORSOLENE 1090 tackifying resin,
4 parties en poids d'aminoéthylimidazolidone, et 0,5 partie en poids d*antioxydant IRGANOX 1010.4 parts by weight of aminoethylimidazolidone, and 0.5 parts by weight of antioxidant IRGANOX 1010.
Cette composition (A) possède une viscosité à 175°C de 3900 centipoises.
En procédant dans les normes indiquées ci-après, on détermine, pour le système bi-composants obtenu par mélange equiponderal de la composition (A) décrite ci-dessus et de la composition (B) de l'exemple 1, les propriétés suivantes - température de ramollissement (selon NFT 76106) : 113°C après 4 jours. contrainte à la rupture (selon NFT 76 107) : 1,4 MPa force de pelage (selon NFT 76 112) : 4,4 N.This composition (A) has a viscosity at 175 ° C of 3900 centipoise. By proceeding in the standards indicated below, the following properties are determined for the two-component system obtained by equiponderal mixing of the composition (A) described above and of the composition (B) of Example 1 - softening temperature (according to NFT 76106): 113 ° C after 4 days. breaking stress (according to NFT 76 107): 1.4 MPa peeling force (according to NFT 76 112): 4.4 N.
EXEMPLE 3EXAMPLE 3
En procédant comme à l'exemple 1, on prépare une première composition (A) comprenant :By proceeding as in Example 1, a first composition (A) is prepared comprising:
11,5 parties en poids de VERSAMIDE 140,11.5 parts by weight of VERSAMIDE 140,
- 50 parties en poids d'un copolymere éthylène/acétate de vinyle commercialisé par la société DU PONT DE NEMOURS sous la dénomination ELVAX 240,50 parts by weight of an ethylene / vinyl acetate copolymer sold by the company DU PONT DE NEMOURS under the name ELVAX 240,
- 10 parties en poids de résine tackifiante BEVILITE 6285,- 10 parts by weight of BEVILITE 6285 tackifying resin,
- 28 parties en poids de résine tackifiante NORSOLENE 1090, et- 28 parts by weight of NORSOLENE 1090 tackifying resin, and
0,5 partie en poids d•antioxydant IRGANOX 1010.0.5 part by weight of antioxidant IRGANOX 1010.
Cette composition (A) possède une viscosité à 175βC de 30 800 centipoises.This composition (A) has a viscosity at 175 β C of 30,800 centipoise.
On prépare d'autre part une composition (B) comprenant :On the other hand, a composition (B) is prepared comprising:
40 parties en poids d'une résine époxydique, solide à température ambiante, commercialisée par DOW CHEMICAL sous la référence DER 662 et ayant pour formule :40 parts by weight of an epoxy resin, solid at room temperature, sold by DOW CHEMICAL under the reference DER 662 and having the formula:
dans laquelle n est égal à 2 ou 3,where n is 2 or 3,
10 parties en poids de la résine tackifiante ESCOREZ® 10 parts by weight of ESCOREZ ® tackifying resin
4401,
19,5 parties en poids de la cire AC 400, 10 parties en poids du copolymere éthylène/acétate ELVAX 210,4401, 19.5 parts by weight of the wax AC 400, 10 parts by weight of the ethylene / acetate copolymer ELVAX 210,
20 parties en poids de la résine tackifiante NORSOLENE® 1090, et20 parts by weight of the tackifying resin NORSOLENE ® 1090, and
0,5 partie en poids de 1'antioxydant IRGANOX 1010.0.5 part by weight of the antioxidant IRGANOX 1010.
Cette composition (B) possède une viscosité à 175°C de 1250 centipoises.This composition (B) has a viscosity at 175 ° C of 1250 centipoise.
Pour le système bi-composants obtenu par mélange equiponderal, à 150"C pendant 1 minute dans un mélangeur statique, des compositions (A) et (B) ci-dessus, on détermine la propriété suivante : contrainte au cisaillement (selon norme NFT 76 107, support aluminium) : 5,5 MPa.
For the two-component system obtained by equiponderal mixing, at 150 "C for 1 minute in a static mixer, of the compositions (A) and (B) above, the following property is determined: shear stress (according to standard NFT 76 107, aluminum support): 5.5 MPa.
Claims
REVENDICATIONS 1 - Système pour adhésif thermofusible reticulable caractérisé par le fait qu'il comporte : (A) une première composition ne renfermant pas de groupes époxy et comportant :CLAIMS 1 - System for cross-linkable hot-melt adhesive, characterized in that it comprises: (A) a first composition not containing epoxy groups and comprising:
(a) au moins un polymère choisi parmi les polymères thermoélastiques et les caoutchoucs de synthèse ;(a) at least one polymer chosen from thermoelastic polymers and synthetic rubbers;
(b) au moins un composé renfermant au moins un groupe¬ ment susceptible de réagir avec des groupes époxy; (c) au moins une résine tackifiante ; et(b) at least one compound containing at least one group capable of reacting with epoxy groups; (c) at least one tackifying resin; and
(d) le cas échéant, au moins un plastifiant ou une cire ;(d) where appropriate, at least one plasticizer or a wax;
(B) une seconde composition comportant :(B) a second composition comprising:
(a) le cas échéant au moins un polymère choisi parmi les polymères thermoélastiques et les caoutchoucs de synthèse ;(a) where appropriate at least one polymer chosen from thermoelastic polymers and synthetic rubbers;
(b) au moins un composé renfermant au moins un groupe époxy ;(b) at least one compound containing at least one epoxy group;
(c) au moins une résine tackifiante ; et (d) le cas échéant, au moins un plastifiant ou une cire ; et(c) at least one tackifying resin; and (d) where appropriate, at least one plasticizer or a wax; and
(C) le cas échéant au moins un activateur de la réaction entre les groupements réactifs du constituant (Ab) et les fonctions époxy du constituant (Bb) . 2 - Système selon la revendication 1, caractérisé par le fait que le rapport molaire des groupements réactifs du constituant (Ab) aux groupes époxy du constituant (Bb) est au moins égal à 1.(C) if necessary at least one activator of the reaction between the reactive groups of the constituent (Ab) and the epoxy functions of the constituent (Bb). 2 - System according to claim 1, characterized in that the molar ratio of the reactive groups of the constituent (Ab) to the epoxy groups of the constituent (Bb) is at least equal to 1.
3 - Système selon l'une des revendications 1 et 2, caractérisé par le fait que, pour 100 parties en poids de la composition (A) , celle-ci comprend : de 10 à 60 parties en poids du constituant (Aa) ; de 3 à 15 parties en poids du constituant (Ab) ; de 10 à 60 parties en poids du constituant (Ac) ; et - άe 0 à 40 parties en poids du constituant (Ad) .
4 - Système selon l'une des revendications 1 à 3, caractérisé par le fait que, pour 100 parties en poids de la composition (B) , celle-ci comprend : de 0 à 40 parties en poids du constituant (Ba) ; - de 20 à 60 parties en poids du constituant (Bb) ; de 10 à 60 parties en poids du constituant (Bc) ; et de 0 à 40 parties en poids du constituant (Bd) .3 - System according to one of claims 1 and 2, characterized in that, for 100 parts by weight of the composition (A), it comprises: from 10 to 60 parts by weight of the constituent (Aa); from 3 to 15 parts by weight of the constituent (Ab); from 10 to 60 parts by weight of the constituent (Ac); and - άe 0 to 40 parts by weight of the constituent (Ad). 4 - System according to one of claims 1 to 3, characterized in that, for 100 parts by weight of the composition (B), it comprises: from 0 to 40 parts by weight of the constituent (Ba); - from 20 to 60 parts by weight of the constituent (Bb); from 10 to 60 parts by weight of the constituent (Bc); and from 0 to 40 parts by weight of the constituent (Bd).
5 - Système selon la revendication 1 à 4, caracté¬ risé par le fait que le composé (Ab) renferme au moins un groupement aminé.5 - System according to claim 1 to 4, caracté¬ ized in that the compound (Ab) contains at least one amino group.
6 - Système selon la revendication 5, caractérisé par le fait que le composé (Ab) est choisi parmi les poly¬ amides à fonctions amin libres et les aminoalkylimidazoli- dones. 7 - Système selon la revendication 1, caractérisé par le fait que le composé (Bb) est choisi parmi les copoly¬ mères d'au moins un alcène avec au moins un monomère insaturé renfermant un groupement époxy et les résines époxydées présentant une fonctionnalité au moins égale à 2. 8 - Système selon la revendication 1, caractérisé par le fait qu'il comprend en outre un film de matière thermoplastique chimiquement inerte vis-à-vis de chacun des deux compositions et portant sur chacune de ses faces une couche de l'une desdites compositions. 9 - Procédé d'assemblage de deux objets, caracté¬ risé par le fait que l'on porte à une température comprise entre 120 et 220°C chacune des compositions du système de la revendication 1, puis : soit on les mélange intimement à cette température, puis on applique l'adhésif thermofusible résultant sur au moins l'un des deux objets à assembler, et enfin on applique l'un des objets à assembler contre l'autre, soit on applique séparément les deux compositions soit l'une après l'autre sur l'un des deux objets à asse - bler, soit l'une sur un objet à assembler et l'autre sur l'autre objet à assembler, puis on applique l'un contre l'autre lesdits objets.
10 - Procédé d'assemblage de deux objets à l'aide d'un système selon la revendication 8, caractérisé par le fait qu'on assemble les deux objets au moyen du film, puis on porte l'ensemble à une température supérieure au point de fusion du film thermoplastique, et suffisante pour permettre la migration de l'un des composés (Ab) et (Bb) vers l'autre, leur entrée en contact provoquant la réticulation du système.
6 - System according to claim 5, characterized in that the compound (Ab) is chosen from poly¬ amides with free amine functions and aminoalkylimidazolidones. 7 - System according to claim 1, characterized in that the compound (Bb) is chosen from copoly¬ mothers of at least one alkene with at least one unsaturated monomer containing an epoxy group and the epoxidized resins having at least one functionality equal to 2. 8 - System according to claim 1, characterized in that it further comprises a film of chemically inert thermoplastic material with respect to each of the two compositions and carrying on each of its faces a layer of l 'one of said compositions. 9 - Method of assembling two objects, caracté¬ ized in that one brings to a temperature between 120 and 220 ° C each of the compositions of the system of claim 1, then: either they are intimately mixed with this temperature, then the resulting hot-melt adhesive is applied to at least one of the two objects to be assembled, and finally one of the objects to be assembled is applied against the other, either the two compositions are applied separately or one after the other on one of the two objects to be assembled - either one on an object to be assembled and the other on the other object to be assembled, then said objects are applied against one another. 10 - A method of assembling two objects using a system according to claim 8, characterized in that the two objects are assembled by means of the film, then the assembly is brought to a temperature above the point of fusion of the thermoplastic film, and sufficient to allow the migration of one of the compounds (Ab) and (Bb) towards the other, their coming into contact causing the crosslinking of the system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92923860A EP0614481A1 (en) | 1991-11-29 | 1992-10-26 | Systems for cross-linkable hot-melt adhesives, their preparation method and an assembly method using same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR91/14770 | 1991-11-29 | ||
| FR9114770A FR2684387A1 (en) | 1991-11-29 | 1991-11-29 | SYSTEMS FOR CROSSLINKABLE HEAT MELT ADHESIVES, THEIR PREPARATION AND ASSEMBLY METHOD USING THE SAME. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1993011200A1 true WO1993011200A1 (en) | 1993-06-10 |
Family
ID=9419481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FR1992/001001 WO1993011200A1 (en) | 1991-11-29 | 1992-10-26 | Systems for cross-linkable hot-melt adhesives, their preparation method and an assembly method using same |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0614481A1 (en) |
| AU (1) | AU2948692A (en) |
| FR (1) | FR2684387A1 (en) |
| PT (1) | PT101097A (en) |
| WO (1) | WO1993011200A1 (en) |
| ZA (1) | ZA929281B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997011122A1 (en) * | 1995-09-20 | 1997-03-27 | Minnesota Mining And Manufacturing Company | Semi-interpenetrating polymer networks of epoxy and polyolefin resins, methods therefor, and uses thereof |
| US6057382A (en) * | 1998-05-01 | 2000-05-02 | 3M Innovative Properties Company | Epoxy/thermoplastic photocurable adhesive composition |
| US6077601A (en) * | 1998-05-01 | 2000-06-20 | 3M Innovative Properties Company | Coated abrasive article |
| US6136398A (en) * | 1998-05-01 | 2000-10-24 | 3M Innovative Properties Company | Energy cured sealant composition |
| US6228133B1 (en) | 1998-05-01 | 2001-05-08 | 3M Innovative Properties Company | Abrasive articles having abrasive layer bond system derived from solid, dry-coated binder precursor particles having a fusible, radiation curable component |
| US6274643B1 (en) | 1998-05-01 | 2001-08-14 | 3M Innovative Properties Company | Epoxy/thermoplastic photocurable adhesive composition |
| CN1074780C (en) * | 1995-09-20 | 2001-11-14 | 美国3M公司 | Semi-interpenetrating polymer networks of epoxy and polyolefin resins, methods therefor and uses thereof |
| KR100877087B1 (en) * | 2004-07-08 | 2009-01-07 | 아르끄마 프랑스 | Polymer material containing chains bearing imidazolidone functions |
| US20110003872A1 (en) * | 2007-12-06 | 2011-01-06 | Arkema France | Material formed from dendritic molecules containing associative groups |
| DE102012009055A1 (en) | 2012-05-08 | 2013-11-14 | Carl Freudenberg Kg | Thermally fixable fabric |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0252795A1 (en) * | 1986-06-27 | 1988-01-13 | Cray Valley Sa | Curable hot-melt adhesives, their preparation and their use |
| EP0289632A1 (en) * | 1987-05-04 | 1988-11-09 | American Cyanamid Company | High green strength induction curable adhesives |
| EP0343676A2 (en) * | 1988-05-27 | 1989-11-29 | Teroson Gmbh | Reactive hot melt structural adhesive |
| EP0442700A2 (en) * | 1990-02-14 | 1991-08-21 | Union Camp Corporation | Two-component curable hot-melt resin compositions |
-
1991
- 1991-11-29 FR FR9114770A patent/FR2684387A1/en active Granted
-
1992
- 1992-10-26 WO PCT/FR1992/001001 patent/WO1993011200A1/en not_active Application Discontinuation
- 1992-10-26 EP EP92923860A patent/EP0614481A1/en not_active Withdrawn
- 1992-10-26 AU AU29486/92A patent/AU2948692A/en not_active Abandoned
- 1992-11-27 PT PT101097A patent/PT101097A/en not_active Application Discontinuation
- 1992-11-30 ZA ZA929281A patent/ZA929281B/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0252795A1 (en) * | 1986-06-27 | 1988-01-13 | Cray Valley Sa | Curable hot-melt adhesives, their preparation and their use |
| EP0289632A1 (en) * | 1987-05-04 | 1988-11-09 | American Cyanamid Company | High green strength induction curable adhesives |
| EP0343676A2 (en) * | 1988-05-27 | 1989-11-29 | Teroson Gmbh | Reactive hot melt structural adhesive |
| EP0442700A2 (en) * | 1990-02-14 | 1991-08-21 | Union Camp Corporation | Two-component curable hot-melt resin compositions |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074780C (en) * | 1995-09-20 | 2001-11-14 | 美国3M公司 | Semi-interpenetrating polymer networks of epoxy and polyolefin resins, methods therefor and uses thereof |
| WO1997011122A1 (en) * | 1995-09-20 | 1997-03-27 | Minnesota Mining And Manufacturing Company | Semi-interpenetrating polymer networks of epoxy and polyolefin resins, methods therefor, and uses thereof |
| US6372336B1 (en) | 1998-05-01 | 2002-04-16 | 3M Innovative Properties Company | Coated abrasive article |
| US6441058B2 (en) | 1998-05-01 | 2002-08-27 | 3M Innovative Properties Company | Abrasive articles having abrasive layer bond system derived from solid, dry-coated binder precursor particles having a fusible, radiation curable component |
| US6136398A (en) * | 1998-05-01 | 2000-10-24 | 3M Innovative Properties Company | Energy cured sealant composition |
| US6228133B1 (en) | 1998-05-01 | 2001-05-08 | 3M Innovative Properties Company | Abrasive articles having abrasive layer bond system derived from solid, dry-coated binder precursor particles having a fusible, radiation curable component |
| US6258138B1 (en) | 1998-05-01 | 2001-07-10 | 3M Innovative Properties Company | Coated abrasive article |
| US6274643B1 (en) | 1998-05-01 | 2001-08-14 | 3M Innovative Properties Company | Epoxy/thermoplastic photocurable adhesive composition |
| US6077601A (en) * | 1998-05-01 | 2000-06-20 | 3M Innovative Properties Company | Coated abrasive article |
| US6359027B1 (en) | 1998-05-01 | 2002-03-19 | 3M Innovative Properties Company | Coated abrasive article |
| US6057382A (en) * | 1998-05-01 | 2000-05-02 | 3M Innovative Properties Company | Epoxy/thermoplastic photocurable adhesive composition |
| US6136384A (en) * | 1998-05-01 | 2000-10-24 | 3M Innovative Properties Company | Epoxy/thermoplastic photocurable adhesive composition |
| US6753359B2 (en) | 1998-05-01 | 2004-06-22 | 3M Innovative Properties Company | Abrasive articles having abrasive layer bond system derived from solid, dry-coated binder precursor particles having a fusible, radiation curable component |
| KR100877087B1 (en) * | 2004-07-08 | 2009-01-07 | 아르끄마 프랑스 | Polymer material containing chains bearing imidazolidone functions |
| US20110003872A1 (en) * | 2007-12-06 | 2011-01-06 | Arkema France | Material formed from dendritic molecules containing associative groups |
| US20150132239A1 (en) * | 2007-12-06 | 2015-05-14 | Centre National De La Recherche Scientigique Cnrs | Material formed from dendritic molecules containing associative groups |
| US9301912B2 (en) | 2007-12-06 | 2016-04-05 | Arkema France | Material formed from dendritic molecules containing associative groups |
| DE102012009055A1 (en) | 2012-05-08 | 2013-11-14 | Carl Freudenberg Kg | Thermally fixable fabric |
| WO2013167250A1 (en) | 2012-05-08 | 2013-11-14 | Carl Freudenberg Kg | Thermo-fusible sheet material |
| DE102012009055B4 (en) * | 2012-05-08 | 2015-06-03 | Carl Freudenberg Kg | Thermally fixable fabric, process for its preparation and its use as a lining material for fixing to an outer fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2684387A1 (en) | 1993-06-04 |
| EP0614481A1 (en) | 1994-09-14 |
| ZA929281B (en) | 1993-06-02 |
| FR2684387B1 (en) | 1994-08-19 |
| PT101097A (en) | 1994-02-28 |
| AU2948692A (en) | 1993-06-28 |
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