EP4065655A1 - Zusammensetzung aus (meth)acrylatmonomeren - Google Patents

Zusammensetzung aus (meth)acrylatmonomeren

Info

Publication number
EP4065655A1
EP4065655A1 EP20820503.9A EP20820503A EP4065655A1 EP 4065655 A1 EP4065655 A1 EP 4065655A1 EP 20820503 A EP20820503 A EP 20820503A EP 4065655 A1 EP4065655 A1 EP 4065655A1
Authority
EP
European Patent Office
Prior art keywords
composition
meth
acrylate
family
chosen
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.)
Pending
Application number
EP20820503.9A
Other languages
English (en)
French (fr)
Inventor
Guillaume Michaud
Frédéric Simon
Stéphane Fouquay
Jacques Lalevee
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.)
Centre National de la Recherche Scientifique CNRS
Bostik SA
Universite de Haute Alsace
Original Assignee
Centre National de la Recherche Scientifique CNRS
Bostik SA
Universite de Haute Alsace
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 Centre National de la Recherche Scientifique CNRS, Bostik SA, Universite de Haute Alsace filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP4065655A1 publication Critical patent/EP4065655A1/de
Pending 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2491/00—Presence of oils, fats or waxes

Definitions

  • the present invention relates to a composition based on (meth) acrylate monomer.
  • the invention also relates to the use of said composition for the repair and / or semi-structural or structural bonding of materials in the field of transport, marine, assembly, electronics or construction.
  • Acrylic compositions are known reactive systems crosslinking by radical polymerization. They are used as adhesives, sealants and coatings. Radical polymerization is typically initiated by a redox system which through an oxidation-reduction reaction results in the production of radicals.
  • the majority of acrylic systems are two-component systems.
  • the first component traditionally contains the reducing agent and reactive monomers, and the second component contains the oxidizing agent. Once the two components are mixed, the reducing agent induces the cleavage of the 0-0 bond of organic peroxide, for example, and initiates polymerization.
  • oxygen inhibition one of the problems with this technique is oxygen inhibition.
  • the oxygen present in the air in its triplet state will interact with the radicals formed on the surface of the sample, thus preventing them from initiating polymerization.
  • This inhibition is expressed mainly on the surface since the oxygen penetrates little or no depth depending on the weight deposited.
  • the polymerization reaction is often slow for surfaces exposed to atmospheric oxygen which, partially cured, often remain sticky.
  • the present invention relates to a two-component composition
  • a two-component composition comprising:
  • composition A comprising:
  • composition B comprising:
  • composition being characterized in that:
  • composition A comprises at least one radical photoinitiator in composition A and / or B;
  • It comprises at least one polymerization inhibitor in a content of less than or equal to 0.3% by weight relative to the total weight of said composition.
  • the reducing agent can be selected from tertiary amines, sodium metabisulfite, sodium bisulfite, transition metals, azo compounds, alpha-aminosulfones, and mixtures thereof.
  • azo compounds there may be mentioned, for example, azoisobutyric acid.
  • alpha-sulfones mention may for example be made of bis (tolylsulfonymethyl) benzylamine.
  • DIIPT diisopropanol-p-toluidine
  • dimethyl-p-toluidine dipropoxy-p-toluidine
  • dimethylaniline N, N-dimethylaminomethylphenol
  • N, N-diisopropanol-p-chloroaniline N, N-diisopropanol-p-bromoaniline
  • N N-dimethyl-p-chloroaniline
  • N-dimethyl-p-bromoaniline N, N-diethyl-p-chloroaniline
  • N, N-diethyl-p-bromoaniline N, N-diethyl-p-bromoaniline
  • the amines having the following formulas (I) or (II); and their mixtures: in which :
  • - m and n are, independently of one another, an integer ranging from 1 to 150, preferably from 1 to 100, preferably from 1 to 72, advantageously from 1 to 36, even more advantageously from 1 to 18 ;
  • - r is an integer ranging from 1 to 200, preferably from 1 to 104, preferably from 1 to 72, advantageously from 1 to 36;
  • R 1 represents a radical chosen from the group consisting of an alkyl, linear or branched, saturated or unsaturated, comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms; a (hetero) aryl comprising from 6 to 12 carbon atoms; a cycloalkyl comprising from 3 to 12 carbon atoms;
  • - v represents an integer ranging from 0 to 5;
  • R 2 and R 3 represent, independently of one another, a halogen atom, a hydrogen atom or an alkyl group, linear or branched, comprising from 1 to 12 carbon atoms, said alkyl group being optionally interrupted by at least one oxygen atom;
  • R 4 represents a hydrogen atom, an arylalkyl group, or an alkyl group, linear or branched, comprising from 1 to 20 carbon atoms, preferably an alkyl group comprising from 1 to 12 carbon atoms, advantageously from 1 to 6 carbon atoms;
  • v is preferably 1, and R 1 is preferably in the para position.
  • the amines of formula (I) are preferably chosen from those in which:
  • R 1 represents an alkyl, linear or branched, saturated or unsaturated, comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, preferably R 1 represents methyl;
  • - m and n represent, independently of one another, an integer ranging from 1 to 18, preferably from 1 to 9, advantageously from 1 to 5;
  • - R 2 and R 3 represent, independently of one another, a hydrogen atom or an alkyl group, linear or branched, comprising from 1 to 12 carbon atoms, said alkyl group being optionally interrupted by at least one oxygen atom, preferably R 2 and R 3 each represents a hydrogen atom;
  • the amines of formula (I) are those in which:
  • R 1 represents an alkyl, linear or branched, comprising from 1 to 5 carbon atoms, preferably R 1 represents methyl;
  • - m and n represent, independently of one another, an integer ranging from 1 to 18, preferably from 1 to 9, advantageously from 1 to 5;
  • R 2 and R 3 represent a hydrogen atom
  • amines of formula (I) mention may be made, for example, of “BISOMER® PTE” (CAS number: 878391-30-1) sold by GEO SPECIALITY CHEMICALS, “Accelerator PT25E” (CAS number: 878391-30-1 ) marketed by LANXESS, N, N- Bis (2-hydroxypropyl) -p-aniline (CAS number: 3077-13-2) available from BIOSYNTH, N, N- Bis (2-hydroxypropyl) -p-toluidine ( CAS number: 38668-48-3) marketed by BASF, “ETHOX ANA-10” (CAS number: 36356-83-9) available from ETHOX CHEMICAL.
  • v is preferably 1, and R 1 is preferably in the para position.
  • the amines of formula (II) are preferably chosen from those in which:
  • R 1 represents an alkyl, linear or branched, saturated or unsaturated, comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, preferably R 1 represents methyl;
  • - R represents an integer ranging from 1 to 36, preferably from 1 to 18, advantageously from 1 to 10;
  • R 3 represents a halogen atom, a hydrogen atom or an alkyl group, linear or branched, comprising from 1 to 12 carbon atoms, said alkyl group being optionally interrupted by at least one oxygen atom,
  • R 4 represents a hydrogen atom, an arylalkyl group, or an alkyl group, linear or branched, comprising from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms.
  • composition A comprises at least one tertiary amine as reducing agent, and even more preferably an amine of formula (I) mentioned above.
  • Composition A may comprise a total content of reducing agent (s) ranging from 0.5% to 5%, preferably from 1% to 3%, by weight relative to the total weight of said composition A.
  • the oxidizing agent can be chosen from peroxides, organic salts of transition metals, compounds containing labile chlorine, and mixtures thereof.
  • the peroxide can be chosen from organic peroxides, inorganic peroxides, and mixtures thereof.
  • Mention may be made, among inorganic peroxides, of peroxydisulfuric acid and their salts, such as ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate.
  • organic peroxides mention may be made of cumene hydroperoxide, para-menthane hydroperoxide, tert-butyl peroxyisobutyrate, tert-butyl peroxybenzoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, acetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, 1,3-bis- (t-butylperoxyisopropyl) benzene, diacetyl peroxide, t-butylcumyl peroxide, tert-butyl peroxyacetate, cumyl, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butyl-peroxyhex-3-yne, 4-methyl-2,2 -di-t-butylperoxypentane, and mixture
  • composition B comprises benzoyl peroxide as an oxidizing agent.
  • Composition B can comprise a total content of oxidizing agent (s) ranging from 0.5% to 5%, preferably from 1% to 3%, by weight relative to the total weight of said composition B.
  • composition according to the invention can typically comprise a redox system, a reducing agent being included in composition A and an oxidizing agent being included in composition B.
  • a redox system a reducing agent being included in composition A
  • an oxidizing agent being included in composition B.
  • composition according to the invention can be polymerized or crosslinked under electromagnetic radiation.
  • the composition according to the invention may comprise from 0.1% to 5% by weight, preferably from 0.5% to 3% by weight, even more preferably from 1% to 2% by weight, of photoinitiator (s ) radical (s) relative to the total weight of the composition.
  • the radical photoinitiator is preferably contained in composition A.
  • the free radical photoinitiator can be any free radical photoinitiator known to those skilled in the art. Under the action of UV-visible radiation, the radical photoinitiator generates radicals which will be responsible for initiating the photopolymerization reaction, and in particular makes it possible to increase the efficiency of the photopolymerization reaction . This is of course chosen as a function of the light source used, according to its capacity to efficiently absorb the selected radiation.
  • the appropriate radical photoinitiator can be chosen from its visible UV absorption spectrum.
  • the radical photoinitiator is suitable for working with sources of irradiation emitting in the region close to the visible.
  • the source of UV or visible radiation can be an LED.
  • said at least one radical photoinitiator is chosen from the group consisting of:
  • acetophenones and alkoxyacetophenones such as, for example, 2,2-dimethoxy-2-phenyleacetophenone and 2-diethyl-2-phenyleacetophenone;
  • hydroxyacetophenone family such as for example 2,2-dimethyl-2-hydroxyacetophenone, 1-hydroxycyclohexylephenyl ketone, 2-hydroxy-4 '- (2-hydroxyethoxy) -2-methyl-propriophenone and 2- hydroxy-4 '- (2-hydroxypropoxy) -2-methyl-propriophenone;
  • alkylaminoacetophenones such as for example 2-methyl-4'- (methylthio) -2-morpholino-propriophenone, 2-benzyl-2- (dimethylamino) -4-morpholinobutyrophenone and 2- (4- ( methylbenzyl) -2- (dimethylamino) -4-morpholino-butyrophenone;
  • benzoin ethers such as, for example, benzyl, methyl benzoin ether and isopropyl benzoin ether;
  • phosphine oxides such as for example diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide (TPO), ethyl- (2,4,6-trimethylbenzoyl) phenylphosphine oxide ( TPO-L) and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylphenyl phosphine oxide (BAPO);
  • the metallocene family such as, for example, ferrocene, bis (eta 5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro) -3- (1 H-pyrrole-1-yl ) -phenyl) titanium and iron (cumene) cyclopentadienyl hexafluorophosphate;
  • - type II radical photoinitiators chosen from: - the benzophenone family, such as for example 4-phenylbenzophenone, 4- (4'-methylphenylthio) benzophenone, 1- [4 [(4-benzoylphenyl) thio] phenyl] -2-methyl-2 - [( 4-methylphenyl) sulfonyl] -1 -propanone;
  • thioxanthone family, such as for example isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxantone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone;
  • ITX isopropylthioxanthone
  • 2,4-diethylthioxanthone 2,4-diethylthioxanthone
  • 2,4-dimethylthioxantone 2,4-dimethylthioxantone
  • 2-chlorothioxanthone 2-chlorothioxanthone
  • 1-chloro-4-isopropylthioxanthone 1-chloro-4-isopropylthioxanthone
  • the quinone family such as, for example, anthraquinones including 2-ethylantraquinone and camphroquinones;
  • benzoyl formate esters such as, for example, methylbenzoylformate
  • dibenzylidene ketones such as, for example, p-dimethylaminoketone
  • the coumarin family such as, for example, 5-methoxy and 7-methoxy coumarin, 7-diethylamino coumarin and N-phenyleglycine coumarin;
  • - radical photoinitiators of the family of dyes such as, for example, triazines, fluorones, cyanines, safranins, 4,5,6,7-tetrachloro-3 ', 6'-dihydroxy- 2', 4 ', 5', 7'-tetraiodo-3H-spiro [isobenzofuran-1, 9'-xanthen] -3-one, pyrylium and thiopyrylium, thiazines, flavins, pyronines, oxazines, rhodamines;
  • said at least one radical photoinitiator is chosen from the group consisting of:
  • acetophenones and alkoxyacetophenones such as, for example, 2,2-dimethoxy-2-phenyleacetophenone and 2-diethyl-2-phenyleacetophenone;
  • hydroxyacetophenone family such as for example 2,2-dimethyl-2-hydroxyacetophenone, 1-hydroxycyclohexylephenyl ketone, 2-hydroxy-4 '- (2-hydroxyethoxy) -2-methyl-propriophenone and 2- hydroxy-4 '- (2-hydroxypropoxy) -2-methyl-propriophenone;
  • alkylaminoacetophenones such as for example 2-methyl-4'- (methylthio) -2-morpholino-propriophenone, 2-benzyl-2- (dimethylamino) -4-morpholinobutyrophenone and 2- (4- ( methylbenzyl) -2- (dimethylamino) -4-morpholino-butyrophenone;
  • benzoin ethers such as, for example, benzyl, methyl benzoin ether and isopropyl benzoin ether;
  • phosphine oxides such as, for example, diphenyl- (2,4,6-trimethylbenzoyl) phosphine (TPO) oxide, ethyl- (2,4,6-) trimethylbenzoyl) phenylphosphine (TPO-L) and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylphenyl phosphine (BAPO) oxide;
  • the metallocene family such as, for example, ferrocene, bis (eta 5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro) -3- (1 H-pyrrole-1-yl ) -phenyl) titanium and iron (cumene) cyclopentadienyl hexafluorophosphate;
  • the benzophenone family such as for example 4-phenylbenzophenone, 4- (4'-methylphenylthio) benzophenone, 1- [4 [(4-benzoylphenyl) thio] phenyl] -2-methyl-2 - [( 4-methylphenyl) sulfonyl] -1 -propanone;
  • thioxanthone family, such as for example isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxantone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone;
  • ITX isopropylthioxanthone
  • 2,4-diethylthioxanthone 2,4-diethylthioxanthone
  • 2,4-dimethylthioxantone 2,4-dimethylthioxantone
  • 2-chlorothioxanthone 2-chlorothioxanthone
  • 1-chloro-4-isopropylthioxanthone 1-chloro-4-isopropylthioxanthone
  • benzoyl formate esters such as, for example, methylbenzoylformate
  • dibenzylidene ketones such as, for example, p-dimethylaminoketone
  • the coumarin family such as, for example, 5-methoxy and 7-methoxy coumarin, 7-diethylamino coumarin and N-phenyleglycine coumarin;
  • - radical photoinitiators of the family of dyes such as, for example, triazines, fluorones, cyanines, safranins, 4,5,6,7-tetrachloro-3 ', 6'-dihydroxy- 2', 4 ', 5', 7'-tetraiodo-3H-spiro [isobenzofuran-1, 9'-xanthen] -3-one, pyrylium and thiopyrylium, thiazines, flavins, pyronines, oxazines, rhodamines;
  • radical photoinitiator is chosen from the following radical photoinitiators:
  • phosphine oxides such as for example diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide (TPO), ethyl- (2,4,6-trimethylbenzoyl) phenylphosphine oxide ( TPO-L) and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylphenyl phosphine oxide (BAPO);
  • the thioxanthone family such as for example isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxantone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone;
  • the radical photoinitiator being even more preferably chosen from diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide (TPO), ethyl- (2,4,6-trimethylbenzoyl) phenylphosphine oxide (TPO) -L) and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylphenyl phosphine oxide (BAPO).
  • the radical photoinitiator can be chosen from 2,4,6-trimethylbenzoyldiphenylphosphine or TPO available for example from LAMBSON under the commercial reference SPEEDCURE® TPO ( CAS: 75980-60-8), ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate or TPO-L available for example from LAMBSON under the trade reference SPEEDCURE® TPO-L (CAS: 84434-11-7), Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide or BAPO (CAS: 162881-26-7) available for example from BASF under the trade reference IRGACURE® 819, 2-Benzyl-2-dimethylamino-1- (4 -morpholinophenyl) -1- butanone (CAS: 119313-12-1) available for example from BASF under the trade reference IRGACURE® 369, 2-methyl-1- [4- (
  • composition according to the invention comprises at least one polymerization inhibitor. Its content in the composition is therefore strictly greater than 0 ppm (part per million by weight).
  • the total content of polymerization inhibitor (s) is preferably less than or equal to 0.25%, preferably less than or equal to 0.20% by weight, and advantageously less than or equal to 0.10% by weight relative to the weight total of said composition.
  • the composition comprises from 0.01% to 0.20% by weight of polymerization inhibitor (s) relative to the total weight of said composition.
  • the polymerization inhibitor can be any type of polymerization inhibitor known to those skilled in the art.
  • hydroquinone hydroquinone monomethyl ether (4-hydroxyanisole, MEHQ), 1, 4-benzoquinone, 1, 4-napthoquinone, catechol, pyrogallol, bisphenol A, para -tertiobutylphenol, phenothiazine, and mixtures thereof.
  • the polymerization inhibitor is hydroquinone monomethyl ether (MEHQ).
  • the (meth) acrylate monomers in composition A and in composition B may be the same or different.
  • the (meth) acrylate monomers can comprise one (monofunctional) or more (meth) acrylate (polyfunctional) functions.
  • the (meth) acrylate monomer (s) can be chosen from the group consisting of:
  • H2C C (R 5 ⁇ -COOR 8 (111) in which:
  • R 5 represents a hydrogen atom or a methyl group
  • R 6 is chosen from the group consisting of alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls, said alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls which may be optionally substituted and / or interrupted by at least one silane, silicone, oxygen, halogen, carbonyl, hydroxyl, ester, urea, urethane, carbonate, amine, amide, sulfur, sulfonate, or sulfone;
  • R 7 represents H or methyl
  • R 8 represents H or ethyl
  • the (meth) acrylate monomer is chosen from methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate , 2-tert-butylheptyl (meth) acrylate, octyl (meth) acrylate, 3-isopropylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, ( undecyl meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, tridecyl (meth) acrylate, 5 (meth) acrylate -methyltridecyl, tetradecyl (meth) acrylate, pentadecyl (
  • the (meth) acrylate monomer is chosen from the monomers of formulas (IV) and (V), and mixtures thereof.
  • composition A may comprise a total content of (meth) acrylate monomer (s) greater than or equal to 30%, preferably greater than or equal to 40%, even more preferably greater than or equal to 60% by weight relative to the total weight of composition A.
  • composition B comprises a (meth) acrylate monomer
  • its content may be greater than or equal to 40% by weight, preferably greater than or equal to 50% by weight, and advantageously greater than or equal to 60% by weight relative to the weight total of composition B.
  • composition B comprises at least one (meth) acrylate monomer.
  • the two-component composition according to the invention can comprise at least one additive chosen from the group consisting of catalysts, fillers, antioxidants, light stabilizers / UV absorbers, metal deactivators, antistats, anti-fog agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, modifiers impact, adhesion promoters, optical brighteners, flame retardants, anti-seepage agents, nucleating agents, solvents, and mixtures thereof.
  • additives chosen from the group consisting of catalysts, fillers, antioxidants, light stabilizers / UV absorbers, metal deactivators, antistats, anti-fog agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, modifiers impact, adhesion promoters, optical brighteners, flame retardants, anti-seepage agents, nucleating agents, solvents, and mixtures thereof.
  • composition A and / or composition B of the composition according to the invention may be present in composition A and / or composition B of the composition according to the invention.
  • plasticizer As an example of a plasticizer that can be used, there may be mentioned any plasticizer usually used in the field of adhesives such as, for example, epoxy resins, phthalates, benzoates, trimethylolpropane esters, trimethylolethane esters. , trimethylolmethane esters, glycerol esters, pentaerythritol esters, naphthenic mineral oils, adipates, cyclohexyldicarboxylates, paraffinic oils, natural oils (possibly epoxidized), polypropylenes, polybutylenes, hydrogenated polyisoprenes and hydrogenated polyisoprenes their mixtures.
  • adhesives such as, for example, epoxy resins, phthalates, benzoates, trimethylolpropane esters, trimethylolethane esters. , trimethylolmethane esters, glycerol esters, pentaerythritol esters, naphthenic mineral oils,
  • diisodecyl phthalate such as for example marketed under the name PALATINOL TM DI DP by the company BASF
  • an ester of alkylsulphonic acid and of phenol such as for example marketed under the name MESAMOLL® by the company LANXESS
  • diisononyl-1 such as for example marketed under the name MESAMOLL® by the company LANXESS
  • diisononyl-1 such as for example marketed under the name HEXAMOLL DINCH® by the company BASF
  • pentaerythritol tetravalerate such as for example marketed under the name PEVALEN TM by the company PERSTORP
  • the oil epoxidized soybean such as, for example, sold under the name VIKOFLEX® 7170 by the company ARKEMA.
  • rheological agent (s) which can be used, there may be mentioned any rheological agent usually used in the field of adhesive compositions.
  • the thixotropic agents are chosen from: PVC plastisols, corresponding to a suspension of PVC in a plasticizer miscible with PVC, obtained in situ by heating at temperatures ranging from 60 ° C to 80 ° C.
  • PVC plastisols can be those described in particular in the work “Polyurethane Sealants”, Robert M. Evans, ISBN 087762-998-6, fumed silica, such as for example sold under the name HDK® N20 by WACKER; urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such as 4,4'-MDI with an aliphatic amine such as butylamine.
  • urea derivatives is described in particular in application FR 1 591 172; micronized amide waxes, such as CRAYVALLAC® SLT or CRAYVALLAC® SLA sold by ARKEMA.
  • composition according to the invention can further comprise at least one organic and / or inorganic filler.
  • the usable mineral filler (s) is (are) advantageously chosen so as to improve the mechanical performance of the composition according to the invention in the crosslinked state.
  • mineral filler As an example of usable mineral filler (s), it is possible to use any mineral filler (s) usually used in the field of adhesive compositions. These fillers are typically in the form of particles of various geometry. They can be for example spherical, fibrous, or have an irregular shape.
  • the filler (s) is (are) chosen from the group consisting of clay, quartz, carbonate fillers, kaolin, gypsum, clays, and their mixtures, preferably the filler (s) is (are) chosen from carbonate fillers, such as carbonates of alkali or alkaline earth metals, and more preferably calcium carbonate or chalk.
  • These fillers can be untreated or treated, for example using an organic acid such as stearic acid, or a mixture of organic acids consisting mainly of stearic acid.
  • hollow mineral microspheres such as hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or of aluminosilicate.
  • composition according to the invention can also comprise at least one adhesion promoter, preferably chosen from silanes, such as aminosilanes, epoxysilanes or acryloylsilanes, or adhesion promoters based on phosphate ester.
  • adhesion promoter preferably chosen from silanes, such as aminosilanes, epoxysilanes or acryloylsilanes, or adhesion promoters based on phosphate ester.
  • a solvent in particular a volatile solvent
  • its content is preferably less than or equal to 5% by weight, more preferably less than or equal to 3% by weight, relative to the total weight of the product. composition.
  • the content of solvent (s) in the composition is between 0% and 5% by weight.
  • a pigment is present in the composition, its content is preferably less than or equal to 3% by weight, more preferably less than or equal to 2% by weight, relative to the total weight of the composition.
  • the pigment may for example represent from 0.1% to 3% by weight or from 0.4% to 2% by weight of the total weight of the composition.
  • the pigments can be organic or inorganic pigments.
  • the pigment is T1O2, in particular KRONOS® 2059 sold by the company KRONOS.
  • the composition can comprise an amount of 0.1% to 3%, preferably 1% to 3% by weight, of at least one UV stabilizer or antioxidant.
  • UV stabilizer or antioxidant typically introduced to protect the composition from degradation resulting from a reaction with oxygen which may be formed by the action of heat or light.
  • These compounds can include primary antioxidants which scavenge free radicals. Primary antioxidants can be used alone or in combination with other secondary antioxidants or UV stabilizers.
  • IRGANOX® 1010 Mention may be made, for example, of IRGANOX® 1010, IRGANOX® B561, IRGANOX® 245, IRGAFOS® 168, TINUVIN® 328 or TINUVIN TM 770 sold by BASF.
  • the composition can comprise at least one acrylic block copolymer.
  • Acrylic block copolymers are typically impact modifiers.
  • the acrylic block copolymers can be copolymers comprising:
  • the copolymers are rigid block / flexible block / rigid block triblocks, in which:
  • the flexible block (B) advantageously contains:
  • the rigid block (A) preferably comprises monomer units derived from methyl methacrylate monomers.
  • the rigid block (A) can also comprise at least one dialkylacrylamide monomer whose alkyl groups, linear or branched, comprise from 1 to 10 carbon atoms, such as N, N-dimethylacrylamide.
  • the flexible block (B) preferably comprises monomer units derived from at least one monomer chosen from butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, 2-ethylhexyl methacrylate, l n-octyl acrylate and mixtures thereof.
  • the copolymer is a polymethyl methacrylate / n-butyl polyacrylate / polymethyl methacrylate block copolymer.
  • the acrylic block copolymers mention may be made, for example, of the Nanostrength® marketed by Arkema (M52 comprising 52% by weight of n-butyl polyacrylate, or M75 comprising approximately 75% by weight of n-butyl polyacrylate or M65 comprising about 65% by weight of n-butyl polyacrylate).
  • M52 comprising 52% by weight of n-butyl polyacrylate
  • M75 comprising approximately 75% by weight of n-butyl polyacrylate
  • M65 comprising about 65% by weight of n-butyl polyacrylate
  • the composition may comprise at least one urethane-acrylate having a number-average molecular weight greater than or equal to 2000 g / mol, preferably greater than or equal to 4000 g / mol.
  • Urethane acrylates can be obtained by reacting a polyol with a polyisocyanate, followed by functionalization with, for example, hydroxymethyl methacrylate.
  • Composition B can comprise at least one epoxy resin.
  • the epoxy resin can be aliphatic, cycloaliphatic, heterocyclic or aromatic.
  • the epoxy resin can be monomeric or polymeric.
  • the epoxy resins can be chosen from polyglycidyl ethers of polyphenolic compounds, preferably comprising from 2 to 6 glycidyl ether functions per mole of resin.
  • a phenolic compound is a compound having at least two aromatic hydroxyl groups.
  • the phenolic compounds can be selected from the group consisting of resorcinol, catechol, hydroquinone, bisphenol A (2,2-bis- (4-hydroxyphenyl) propane), bisphenol AP (1, 1-bis- (4 -hydroxyphenyl) -1-phenylethane), bisphenol AF (2,2-bis- (4-hydroxyphenyl) - hexafluoropropane), bisphenol B ((2,2-bis- (4-hydroxyphenyl) butane), bisphenol BP (bis- (4- hydroxyphenyl) -diphenylmethane), bisphenol C (2,2-bis- (3-methyl-4-hydroxyphenyl) propane), bisphenol Cil (bis (4-hydroxyphenyl) -2,2-dichloroethylene), bisphenol E ( 1, 1 -bis- (4- hydroxyphenyl) ethane), bisphenol F (bis (4-hydroxyphenyl) -2,2-dichloroethylene), bisphenol FL (4,4 '- (9H-fluoren-9-yliden
  • the epoxy resin can have an epoxy functional content ranging from 0.3 to 10.8 meq per gram of resin.
  • epoxy resins are typically available commercially. Mention may be made, for example, of the DER TM 331 and DER TM 383 resins marketed by the company DOW CHEMICALS, the EPON 862 resin marketed by HEXION SPECIALITY CHEMICALS, the EPOSIR® resins based on bisphenol A marketed by SIR INDUSTRIAL (for example EPOSIR® 7120, EPOSIR® resins based on bisphenol A / bisphenol F (for example EPOSIR® F556).
  • composition B does not include an epoxy resin.
  • the volume ratio of composition A / composition B in the composition of the invention ranges from 20/1 to 1/1, preferably from 10/1 to 1/1.
  • the present invention preferably relates to a two-component composition comprising:
  • composition A comprising:
  • composition B comprising:
  • composition being characterized in that:
  • composition A comprises at least one radical photoinitiator in composition A and / or B;
  • radical photoinitiator chosen from the following radical photoinitiators:
  • phosphine oxides such as for example diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide (TPO), ethyl- (2,4,6-trimethylbenzoyl) phenylphosphine oxide ( TPO-L) and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylphenyl phosphine oxide (BAPO);
  • TPO diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide
  • TPO-L ethyl- (2,4,6-trimethylbenzoyl) phenylphosphine oxide
  • BAPO bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylphenyl phosphine oxide
  • thioxanthone family such as for example isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthi
  • R 7 represents H or methyl
  • - R 8 represents H or ethyl
  • - p represents 0 or 1
  • Ready-to-use kit comprising composition A as defined above on the one hand and composition B as defined above on the other hand, packaged in two separate compartments. It may for example be a two-component cartridge.
  • composition according to the invention may be in a two-component form, for example in a ready-to-use kit, comprising composition A on the one hand in a first compartment or drum and composition B d. '' elsewhere in a second compartment or drum, in proportions suitable for direct mixing of the two components, for example using a metering pump.
  • the kit further comprises one or more means allowing the mixing of compositions A and B.
  • the mixing means are chosen from metering pumps, static mixers of diameter adapted to the quantities. used.
  • the present invention also relates to the use of a composition as defined above, as an adhesive, mastic or coating, preferably as an adhesive.
  • the invention also relates to the use of said composition for the repair and / or structural or semi-structural bonding of materials in the field of transport, automobile (car, bus or truck), assembly, marine, etc. electronics, or construction.
  • the invention also relates to the use of said composition for the repair and / or structural or semi-structural bonding of materials in the field of transport, automobile (car, bus or truck), assembly, marine, etc. or construction.
  • the present invention also relates to a method of assembling two substrates by bonding, comprising: coating on at least one of the two substrates to be assembled with a composition obtained by mixing compositions A and B as defined above; then the effective contacting of the two substrates; crosslinking the composition by subjecting it to electromagnetic irradiation.
  • the crosslinking step can be carried out at a temperature between 0 ° C and 200 ° C, preferably between 10 ° C and 150 ° C, preferably between 23 and 80 ° C and in particular between 20 ° C and 25 ° C.
  • Electromagnetic irradiation can be carried out with a UV radiation source or with an LED.
  • the electromagnetic irradiation crosslinking step can be performed at a wavelength ranging from 200 to 500 nm.
  • the electromagnetic irradiation step is carried out with an intensity less than or equal to 300 mW / cm 2 , preferably less than or equal to 200 mW / cm 2 , for example less than or equal to 100 mW / cm 2 .
  • Suitable substrates are, for example, inorganic substrates such as concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and painted composites.
  • compositions according to the invention advantageously allow rapid polymerization and polymerization which takes place at the surface and at depth.
  • the surface of the crosslinked compositions dries quickly and are not "tacky", which advantageously makes it possible to increase the productivity of industrial processes.
  • compositions according to the invention advantageously allow a good compromise between storage stability and high reactivity.
  • compositions of the invention makes it possible to crosslink at the surface and depth the shadow zones which have not been irradiated.
  • compositions according to the invention advantageously exhibit, after crosslinking, good adhesive properties.
  • between x and y or “ranging from x to y” is meant an interval in which the limits x and y are included.
  • the range “between 0% and 25%” notably includes the values 0% and 25%.
  • ARKEMA is a micronized amide wax used as a rheological agent
  • - VISIOMER® GLYFOMA (CAS: 1620329-57-9) marketed by EVONIK Industries and with a molar mass equal to 172.2 g / mol, mixture of isomers of formal glycerol methacrylate, comprising a content of MEHQ (4-hydroxyanisole or hydroquinone monomethyl ether) of 200 ppm;
  • - AEROSIL ® R202 (CAS number: 67762-90-7): a hydrophobic fumed silica (post-treated PDMS) with a specific surface area (BET) equal to 100 ⁇ 20 m 2 / g marketed by EVONIK;
  • MBS Clearstrength ® XT100 marketed by ARKEMA: a “core-shell” impact modifier based on MBS (MMA-butadiene-styrene);
  • - VIKOFLEX® 7170 marketed by ARKEMA is an epoxidized soybean oil used as a plasticizer
  • - urethane-acrylate U1 obtained by reacting a polypropylene glycol diol of molar mass of 2000 g / mol with MDI, followed by functionalization with hydroxymethyl methacrylate.
  • the weight average molecular mass is 6500 g / mol and the polydispersity is 2.9.
  • Component A and component B above were mixed in a 1: 1 volume ratio.
  • the mixing is carried out at a temperature of approximately 23 ° C., according to the volume ratio given with a static mixer, then was irradiated under LED at 405 nm with an intensity of 100 mW / cm 2 .
  • Component A and component B above were mixed in a 1: 1 volume ratio.
  • the mixing is carried out at a temperature of approximately 23 ° C., according to the volume ratio given with a static mixer.
  • This optical pyrometry test is used to determine the exothermicity of the reaction and the latency time, that is, the time it takes for the sample to begin to polymerize. This time is freezing time.
  • FIG. 1 shows that comparative composition No. 2 (absence of photoinitiator, curve a) does not polymerize in the absence of photoinitiator and irradiation with an LED.
  • composition No. 1 according to the invention (curve b) polymerizes very quickly because an exotherm (temperature peak) is observed from the first seconds of irradiation.
  • the polymer obtained is advantageously dry on the surface (“tack-free”).
  • Example 3 Composition No. 3
  • the Crayvallac® and the VISIOMER GLYFOMA are mixed at 55 ° C. for 1 h.
  • the reaction mixture is then cooled to 23 ° C and the other ingredients constituting component A are added in the proportions indicated in the following table at a temperature of 23 ° C.
  • component B In a reactor maintained under constant stirring and under nitrogen, the various ingredients constituting component B are mixed in the proportions indicated in the following table at a temperature of 23 ° C. Component A and component B above were mixed in a 1: 1 volume ratio.
  • gel time 30 s.
  • the polymer obtained is advantageously dry on the surface (“tack-free”) so the oxygen has not had time to inhibit the surface.
  • the combination of the photoactivated redox system advantageously makes it possible to improve the surface polymerization in air.
  • composition A of composition no. 1 of example 1 was placed in a study at 50 ° C for 12 days.
  • compositions A and B of composition n ° 1 were made in a volume ratio 1: 1 at 23 ° C with a static mixer, then was irradiated under LED at 405 nm with an intensity of 100 mJ / cm 2 .
  • composition No. 1 according to the invention is almost identical with composition No. 1 which has undergone accelerated aging (temperature peak at 101 ° C. with a gel time of 32 s).
  • the reactivity of composition no. 1 is advantageously stable over time.
  • compositions No. 1 (Example 1) and No. 3 (Example 3) were tested for polymerization in the shadow zones. Part of the sample (mixture) is hidden to act as a barrier to light. The other part is irradiated for two minutes with an LED at 405 nm with an intensity of 100 mW / cm 2 . The sample is then left in the dark and checked at different times to see the propagation of the polymerization in the non-irradiated zone thanks to the second mechanism of the redox reaction which does not require light. Complete polymerization (shadow areas included) of the samples was observed within 1 hour 30 minutes.
  • Example 6 bonding tests - compositions n ° 4 and n ° 5
  • the CRAYVALLAC® and the VISIOMER GLYFOMA are mixed at 55 ° C. for 1 h. Then the mixture is brought down to 23 ° C and the other ingredients constituting component A are added in the proportions indicated in the following table at a temperature of 23 ° C.
  • Component A and component B above were mixed, in a 1: 1 volume ratio.
  • the mixing is carried out at a temperature of about 23 ° C, according to the given volume ratio with a static mixer, then was irradiated under LED at 405 nm with an intensity of 100 mW / cm 2 .
  • Bonding tests Bonding is carried out on aluminum sterigmas from the company Rocholl. On a sterigma, an area of 25 * 12.5mm was delimited using Teflon wedges 250 ⁇ m thick, an area of 25 * 12.5mm. This zone was filled with the composition to be tested, then a second sterigma of the same material was laminated. The whole was held by forceps and placed in an air-conditioned room at 23 ° C or 100 ° C and 50% RH (relative humidity) for one week before traction on a dynamometer. Insolation on the edge for 30 seconds.
  • RH relative humidity
  • the purpose of traction on a dynamometer is to evaluate the maximum force (in MPa) to be exerted on the assembly to separate it.
  • the use of a traction machine makes it possible to subjecting a single lap joint placed between two rigid supports to a shear stress until failure by exerting a tension on the supports parallel to the surface of the assembly and to the principal axis of the specimen.
  • the result to be recorded is the force or stress at break.
  • the shear stress is applied via the movable jaw of the tensile machine with displacement at the speed of 5 mm / min. This traction method is carried out as defined by standard EN 1465 of 2009.
  • Figure 2 shows that composition No. 4 according to the invention (curve 1) exhibits a faster increase in cohesion than comparative composition No. 5 (curve 2).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP20820503.9A 2019-11-25 2020-11-24 Zusammensetzung aus (meth)acrylatmonomeren Pending EP4065655A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1913176A FR3103487B1 (fr) 2019-11-25 2019-11-25 Composition à base de monomères ( méth )acrylate
PCT/FR2020/052154 WO2021105603A1 (fr) 2019-11-25 2020-11-24 Composition a base de monomeres (meth) acrylate

Publications (1)

Publication Number Publication Date
EP4065655A1 true EP4065655A1 (de) 2022-10-05

Family

ID=70295219

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20820503.9A Pending EP4065655A1 (de) 2019-11-25 2020-11-24 Zusammensetzung aus (meth)acrylatmonomeren

Country Status (7)

Country Link
US (1) US20230022325A1 (de)
EP (1) EP4065655A1 (de)
JP (1) JP2023503475A (de)
CN (1) CN114729231A (de)
FR (1) FR3103487B1 (de)
TW (1) TW202128793A (de)
WO (1) WO2021105603A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3122881B1 (fr) * 2021-05-17 2024-04-19 Bostik Sa Composition à base de monomères (méth)acrylate
FR3125055A1 (fr) * 2021-07-12 2023-01-13 Bostik Sa Composition à base de monomères ( méth )acrylate
FR3125056A1 (fr) * 2021-07-12 2023-01-13 Bostik Sa Composition à base de monomères (méth)acrylate
FR3129402B1 (fr) * 2021-11-22 2023-10-27 Bostik Sa Composition à base de monomères (méth)acrylate
FR3135984A1 (fr) * 2022-05-31 2023-12-01 Bostik Sa Composition à base de composés (méth)acrylate

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3547848A (en) 1967-11-03 1970-12-15 Armour Ind Chem Co Thixotropic coating compositions comprising a varnish and a di-substituted urea
JPS5258315A (en) 1975-11-10 1977-05-13 Hitachi Denshi Ltd Portable tv camera
US20080023131A1 (en) * 2006-07-28 2008-01-31 Pressley Mark W Dual cure adhesive formulations
CN102898963B (zh) * 2012-10-18 2014-03-26 上海康达化工新材料股份有限公司 一种丙烯酸酯结构胶及其制备方法
CN104781358B (zh) * 2012-10-26 2017-03-29 汉高知识产权控股有限责任公司 粘合剂组合物
US9771501B2 (en) * 2013-02-20 2017-09-26 Illinois Tool Works, Inc. Galvanized metal bonding adhesive formulation and process for the use thereof

Also Published As

Publication number Publication date
US20230022325A1 (en) 2023-01-26
WO2021105603A1 (fr) 2021-06-03
TW202128793A (zh) 2021-08-01
FR3103487A1 (fr) 2021-05-28
JP2023503475A (ja) 2023-01-30
CN114729231A (zh) 2022-07-08
FR3103487B1 (fr) 2022-03-04

Similar Documents

Publication Publication Date Title
WO2021105603A1 (fr) Composition a base de monomeres (meth) acrylate
KR20120001817A (ko) 경화성 수지 조성물, 접착제 조성물, 경화체 혹은 복합체
EP3947497A1 (de) Methacrylatmonomerbasierte zusammensetzung
EP3947502A1 (de) Methacrylatmonomerbasierte zusammensetzung
CA3013936A1 (fr) Composition polymerisable de faible viscosite precurseur de materiaux renforces a l'impact
EP4341306A1 (de) Zusammensetzung auf basis von (meth)acrylatmonomeren
EP4341313A1 (de) Zusammensetzung auf basis eines (meth)acrylatmonomers und zinksalz
EP4308616A1 (de) Zusammensetzung auf basis von (meth)acrylatmonomeren
FR3120872A1 (fr) Composition à base de monomères ( méth )acrylate
WO2023233100A1 (fr) Procede d'assemblage de deux substrats par collage
US20240240063A1 (en) Composition based on a (meth)acrylate monomer and zinc salt
WO2023285760A1 (fr) Composition a base de monomeres (meth)acrylate
FR3108908A1 (fr) Matériaux élastiques préparés à partir de compositions liquides durcissables
WO2022117940A1 (fr) Composition adhesive bicomposante a base de monomere itaconate
WO2020128325A1 (fr) Composition (méth)acrylique comprenant un polyuréthane modifié
WO2023233099A1 (fr) Composition à base de composés (méth)acrylate
EP4370563A1 (de) Zusammensetzung auf basis von (meth)acrylatmonomeren
WO2023105177A1 (fr) Compositions acryliques bi-composantes pour la formulation de produits de marquage routier
WO2023089252A1 (fr) Composition à base de monomères (méth)acrylate
WO2023105152A1 (fr) Formulation adhesive bicomposante a base de (meth)acrylate pour l'assemblage de pales d'eoliennes

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20220427

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20240523