Composition of epoxy resin, low glass transition temperature copolymer, latent hardener and carboxy-terminated polyamide and/or polyamide
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08K-003/36
C08L-009/02
C08L-063/02
C08L-067/00
C08L-077/00
출원번호
US-0257308
(2001-03-31)
우선권정보
DE-0017784 (2000-04-10); DE-0017783 (2000-04-10)
국제출원번호
PCT/EP01/03699
(2003-03-07)
§371/§102 date
20030307
(20030307)
국제공개번호
WO01/94492
(2001-12-13)
발명자
/ 주소
Schoenfeld, Rainer
Schenkel, Hubert
Kuester, Harald
출원인 / 주소
Henkel Kommanditgesellschaft auf Aktien
인용정보
피인용 횟수 :
36인용 특허 :
38
초록▼
Condensation products prepared from cyclic carboxylic anhydrides of dicarboxylic acids, tricarboxylic anhydrides or tetracarboxylic anhydrides and difunctional polyamines, in particular polyoxyalkyleneamines, are suitable as a builder component for epoxy resin compositions. The reaction products bas
Condensation products prepared from cyclic carboxylic anhydrides of dicarboxylic acids, tricarboxylic anhydrides or tetracarboxylic anhydrides and difunctional polyamines, in particular polyoxyalkyleneamines, are suitable as a builder component for epoxy resin compositions. The reaction products based on tricarboxylic anhydrides or tetracarboxylic anhydrides are distinguished by having on average more than one imide group and carboxyl group per molecule. The compositions may optionally also contain condensation products obtained from tri- or poly-functional polyols and/or tri- or poly-functional amino-terminated polymers and cyclic carboxylic anhydrides, wherein the latter reaction products contain on average more than one carboxyl group per molecule. These compositions additionally contain conventional rubber-modified epoxy resins together with liquid and/or solid polyepoxy resins and conventional hardeners and accelerators and optionally fillers and rheology auxiliaries. Such compositions are particularly suitable as impact-resistant, impact/peel-resistant and peel-resistant adhesives in vehicle construction and in electronics. Particularly at very low temperatures, these adhesives exhibit very good impact and peel properties combined with very good corrosion resistance and ageing resistance of the adhesive bond.
대표청구항▼
1. A thermally curable composition comprising:(A) at least one epoxy resin having on average more than one epoxy group per molecule; (B) a copolymer having a glass transition temperature of ?30° C. or lower and epoxy-reactive groups or a reaction product of such copolymer with a stoichiometric exces
1. A thermally curable composition comprising:(A) at least one epoxy resin having on average more than one epoxy group per molecule; (B) a copolymer having a glass transition temperature of ?30° C. or lower and epoxy-reactive groups or a reaction product of such copolymer with a stoichiometric excess of at least one epoxy resin according to (A); (C) at least one latent hardener activatable at elevated temperature, for component (A); and either (D) a reaction product obtained from a difunctional amino-terminated polymer and a tri- or tetra-carboxylic acid anhydride having on average more than one imide group and carboxyl group per molecule; or (E) a reaction product produced from a tri- or poly-functional polyol or a tri- or poly-functional amino-terminated polymer and a cyclic carboxylic anhydride, which reaction product contains on average more than one carboxyl group per molecule, or (F) a mixture of the reaction products according to (D) and (E). 2. A composition as claimed in claim 1 wherein component (B) is a copolymer based on butadiene.3. A composition as claimed in claim 1 wherein component (B) is (a) a copolymer containing carboxyl groups based on butadiene/acrylonitrile copolymer, butadiene/(meth)acrylic acid ester copolymer, butadiene/acrylonitrile/styrene copolymer, or butadiene/(meth)acrylate/styrene copolymer or (b) a dendrimer.4. A composition as claimed in claim 1 wherein component (B) is a core/shell polymer, the core of which is a diene polymer or a (meth)acrylic polymer having a glass transition temperature of ?30° C. or lower and which may optionally be crosslinked with 0.01 to 5 wt. % of a diolefinic comonomer and the shell of which has a glass transition temperature of 60° C. or higher and is synthesised from one or more monomers selected from the group consisting of alkyl (meth)acrylate, (meth)acrylonitrile, (methyl)styrene, olefinically unsaturated carboxylic acids, carboxylic anhydrides and mixtures thereof.5. A composition as claimed in claim 1 wherein component (D) is produced by a condensation reaction from:(a) a carboxylic anhydride selected from the group consisting of citric anhydride, 1,2,3-propane tricarboxylic anhydride, aconitic anhydride, 1,2,3-benzenetricarboxylic anhydride, 1,2,4-benzenetricarboxylic anhydride, mellophanic anhydride, pyromellitic anhydride, 1,8:4,5-naphthalenetetracarboxylic dianhydride, 2,3:6,7-naphthalenetetracarboxylic dianhydride, perylene dianhydride, biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, diphenylmethanetetracarboxylic dianhydride, 2,2-diphenylpropanetetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride and mixtures thereof; and (b) a diamine seiected from the group consisting of polyethylene glycol diamine, polypropylene glycol diamine, polyoxytetramethylene diamine and polybutadiene diamine; wherein the reaction product contains on average more then one cyclic imide group and carboxyl group per molecule.6. A composition as claimed in claim 1 wherein component (E) is produced from:(a) a carboxylic anhydride selected from the group consisting of citric anhydride, 1,2,3-propanetricarboxylic anhydride, aconitic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, suberic anhydride, azelaic anhydride, sebacic anhydride, phthalic anhydride, 1,2,3-benzenetricarboxylic anhydride, 1,2,4-benzenetricarboxylic anhydride, mellophanic anhydride, pyromellitic anhydride, 1,8:4,5-naphthalenetetracarboxylic dianhydride, 2,3:6,7-naphthalenetetracarboxylic dianhydride, perylene dianhydride dianhydride, biphenyltetracarboxylic anhydride, diphenyl ether tetracarboxylic dianhydride, diphenylmethanetetracarboxylic dianhydride, 2,2-diphenyl-propanetetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride and mixtures thereof; and (b) a polymer selected from the group consisting of polyethylene glycol triamine, polypropylene glycol triamine, polyoxytetramethylene triamine polybutadiene triamine, trifunctional polyoxyethylene polyol, trifunctional polyoxypropylene polyol, trifunctional polyoxytetramethylene polyol, copolymers thereof and OH-functional polybutadiene; ?wherein the reaction product contains on average more than one carboxyl group per molecule. 7. A composition as claimed in claim 5 wherein said component (D) is dissolved in at least one liquid polyepoxide.8. A composition as claimed in claim 6 wherein said component (E) is dissolved in at least one liquid polyepoxide.9. A composition as claimed in claim 5 wherein said component (D) is reacted with a stoichiometric excess of at least one polyepoxide.10. A composition as claimed in claim 6 wherein said component (E) is reacted with a stoichiometric excess of at least one polyepoxide.11. A composition as claimed in claim 1 wherein said latent hardener (C) is at least one compound selected from the group consisting of dicyandiamide, guanamines, guanidines, aminoguanidines solid aromatic diamines and a curing accelerator.12. A composition as claimed in claim 1 additionally comprising one or more auxiliaries selected from the group consisting of plasticizers, reactive diluents, rheology auxillaries, fillers, wetting agents, antioxidants and stabilizers.13. A composition as claimed in claim 1 which has been cured by heating the composition to temperatures of between 80 and 210° C.14. A process for adhesive bonding a first substrate to a second substrate comprising:(1) applying to at least one of the substrate surfaces to be joined a thermally curable adhesive as claimed in claim 1; (2) joining the first substrate and the second substrate; and (3) curing the thermally curable adhesive by heating. 15. A process according to claim 14 additionally comprising cleaning or surface treating or both cleaning and surface treating the substrate surface to which the thermally curable adhesive is applied prior to applying the thermally curable adhesive.16. A process according to claim 14 wherein the thermally curable adhesive is heated to temperatures between 80 and 210° C.17. A process according to claim 14 wherein the thermally curable adhesive is pregelled prior to curing.
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이 특허에 인용된 특허 (38)
Rinde James A. (Fremont CA) Lopez Eugene F. (Sunnyvale CA) Glover Leon C. (Los Altos CA), Adhesives and devices coated therewith.
Mlhaupt Rolf (Freiburg DEX) Rfenacht Werner (Marly CHX), Composition of epoxy resin, butadiene-acrylonitrile copolymer and segmented copolyester, copolyamide or copolyesteramide.
Schmid Rolf (Schwarzenburg CHX) Eldin Sameer H. (Fribourg CHX), Curable epoxy resin compositions of matter containing a thermoplastic which has phenolic end groups.
Kimball ; deceased Michael E. (late of Westbrook ME by Edward A. Kimball ; legal representative), Epoxy adhesives and methods of using cured compositions therefrom.
Waddill Harold G. (Austin TX) Dominguez Richard J. G. (Austin TX), Epoxy resin containing a combination of high and low molecular weight polyoxyalkylene polyamine curing agents.
Mlhaupt Rolf (Marly CHX) Powell Jeremy H. (Horseheath GB2) Adderley Christopher S. (Hardwick GB2) Rfenacht Werner (Marly CHX), Phenol-terminated polyurethane or polyurea(urethane) with epoxy resin.
Kiyohara Osamu (Shizuoka JPX) Taruishi Tomohiro (Shizuoka JPX), Polyamide resin which can be dissolved in alcohol solvent, composition thereof, and method of use thereof.
Garcia Gilbert (Westchester CA) Domnikov Larissa (Los Angeles CA), Reacting novolac and bisphenol F epoxy resins with carboxy-terminated butadiene-acrylonitrile.
Ming, Ming; Feng, Shaoguang; Liu, Yan Fei; Froese, Robert D J; Lutz, Andreas; Eagle, Glenn G.; Jialanella, Gary L.; Cole, Eric E.; Golden, Michael R., Storage-stable heat-activated tertiary amine catalysts for epoxy resins.
Ming, Ming; Feng, Shaoguang; Liu, Yan Fei; Lutz, Andreas; Froese, Robert D.; Eagle, Glenn G.; Jialanella, Gary L.; Cole, Eric E.; Golden, Michael R., Storage-stable heat-activated tertiary amine catalysts for epoxy resins.
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