WO2010117669A1 - Epoxy resin based core filler material developing low exothermic heat - Google Patents
Epoxy resin based core filler material developing low exothermic heat Download PDFInfo
- Publication number
- WO2010117669A1 WO2010117669A1 PCT/US2010/028778 US2010028778W WO2010117669A1 WO 2010117669 A1 WO2010117669 A1 WO 2010117669A1 US 2010028778 W US2010028778 W US 2010028778W WO 2010117669 A1 WO2010117669 A1 WO 2010117669A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- curable composition
- epoxy resin
- weight
- amine
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
- C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
- C08K5/1539—Cyclic anhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- this disclosure relates to one-part epoxy resin based curable and cured filler compositions.
- the compositions are in particular suitable as filler material for honeycomb structures, in particular those used in aircraft, watercraft and automobiles.
- the curable filler compositions have improved fire resistance, and develop only little exothermic heat during the curing.
- the cured compositions display a good compressive strength also at elevated temperatures.
- honeycomb structures are employed to replace solid structures more and more frequently.
- the size of the void cells in a honeycomb structure influences the mechanical properties of the structure. The bigger the size the greater the weight reduction but the greater may be the loss of mechanical strength.
- Void cells in honeycomb structures may typically range from 5 mm up to 10 cm in at least one or all three dimensions.
- One approach is to partially or completely fill some or all of the void cells of the honeycomb structure with filler materials. Epoxy resin based compositions may be used for this purpose.
- thermally foaming powder that can be used as filler in honeycomb panels.
- the thermally foaming powder contains
- Araldite GY260 (a bisphenol A epoxy resin), dicyandiamide, chlorotoluron, 3,3'-dimethyl
- the powdery precursor is obtained by mixing the starting compounds at temperatures below the onset temperature of the epoxy compound and below the temperature where expansion of the unexpanded thermoplastic microspheres occurs.
- the powders are filled in a honeycomb structure and heated thereby expanding, foaming and curing the powder.
- the powders of US'202 may not be easily used in vertical bonding geometries, which limits their applicability.
- curable epoxy resins when using curable epoxy resins as core fillers the curing reaction is typically exothermic. Generally, this is not a problem in standard applications of curable epoxy resin formulations where the epoxy resins are used to bond components together. In such applications curable epoxy resin compositions are typically applied as thin layers between the substrates to be joined and bonded. However, the exothermic reaction may become noticeable when curing thick layers of epoxy resins as may be the case when using curable epoxy resins as filler materials, for example, in honeycomb structures. Due to the comparatively large size of the cells, the epoxy resin compositions may have to be applied in a thickness of greater than 30 or even greater than 50 mm.
- Heat generated by the exothermic curing reaction of substantial amounts of epoxy resins may thermally damage the epoxy resin composition and impact on its mechanical properties. It may also affect the honeycomb structure or components attached to the honeycomb structure. Therefore, there is a need for providing curable epoxy resin compositions that develop little exothermic heat during the curing reaction.
- WO 2006/071820 In international patent application WO 2006/071820 an epoxy-based filler composition is disclosed. WO 2006/071820 teaches to avoid amine based hardeners for overcoming exothermic heat generation upon curing the epoxy composition.
- curable filler compositions are also desired that can be cured to provide compositions having good compressive strength not only at room temperature but also at elevated temperatures, such as for example 135°C or even at 150°C.
- curable filler compositions desirably are extrudable pastes to allow easy application to honeycomb structures.
- curable filler compositions are desired that have in addition to the properties mentioned above a good shelf-life at room temperature.
- an epoxide hardener system comprising (a) a carboxylic acid anhydride,
- a second amine having a melting point of from about 50°C to about 180 0 C and having at least one primary amine group, wherein the first and second amines are selected such that they have a difference in melting points of at least 10°C and wherein the first and second amines are contained in minor amounts by weight as compared to the carboxylic acid anhydride;
- composition further comprises (ii) a filler capable of reducing the density of the curable composition and, optionally, (iii) a fire-retardant system that includes a mixture of:
- a process for filling cells of a honeycomb structure comprising applying a curable composition as above to the honeycomb structure and curing the composition.
- any numerical range recited herein is intended to include all values from the lower value to the upper value of that range.
- a concentration range of from 1% to 50% is intended to be an abbreviation and to expressly disclose the values between the 1% and 50%, such as, for example, 2%, 40%, 10%, 30%, 1.5 %, 3.9 % and so forth.
- Average particle sizes as referred to herein are number averages. In case of particles that are only substantially spherical the particle size is determined by adding the length of the two main (largest orthogonal) axes of the particle and dividing it by two. "Substantially spherical” means one or all main axes (x-, y- or z-axis) may deviate from the required length to form a perfect sphere by up to 50 %, preferably up to 25%.
- the curable compositions provided herein are extrudable pastes.
- extrudable paste refers to compositions which have an initial extrusion rate measured as described in the test section below which is at least 50 g/min. More preferably, the initial extrusion rate is from 50 g/min up to 300 g/min.
- the curable and cured compositions comprise: at least one organic epoxide compound, an epoxide hardener system comprising
- compositions may further include a fire-retardant system that includes a mixture of:
- Organic epoxides as used herein are epoxy resins.
- Epoxy resins are polymeric organic compounds having one or more oxirane ring polymerizable by a ring opening reaction. The epoxy-functionalities allow the resin to undertake cross-linking reactions.
- Such materials broadly called epoxides, can be cycloaliphatic or aromatic, which means they have one or more unit that is cycloaliphatic or aromatic.
- Useful materials generally have at least two polymerizable epoxy groups per molecule and, more preferably, from two to four polymerizable epoxy groups per molecule.
- the epoxy resins may have an average epoxy-functionality of at least 1 , greater than one, or of at least 2, or from about 1 to 4.
- the epoxy resin is preferably free or essentially free of aromatic amine moieties.
- essentially free means that trace amounts may be present, for example, due to impurities present in the starting materials or as a result of production process. Such trace amounts include less than 10,000 ppm, preferably less than 5,000 ppm, based on the total amount of the composition.
- the epoxy resins typically contain repeating units derived from monomers having an epoxy-functionality as described above but epoxy resins can also include, for example, silicone-based polymers that contain epoxy groups or organic polymer particles coated with or modified with epoxy groups or particles coated with, dispersed in, or modified with epoxy-groups-containing polymers.
- Epoxy resins may be selected from the group consisting of alkylene oxides, alkenyl oxides, glycidyl esters, glycidyl ethers, epoxy novolacs, copolymers of acrylic acid esters of glycidol and copolymerizable vinyl compounds, polyurethane polyepoxides, and mixtures thereof.
- the epoxy resins contain moieties of the glycidyl, diglycidyl or polyglycidyl ether type.
- Such epoxy resins may be obtained, for example, by the reaction of a hydroxyl functionality (for example but not limited to dihydric or polyhydric phenols or aliphatic alcohols including polyols) with an epichlorohydrine-functionality.
- dihydric phenols are phenols containing at least two hydroxy groups bonded to the aromatic ring (also referred to as "aromatic" hydroxy groups) of a phenol -or in case of polyphenols at least two hydroxy groups are bonded to an aromatic ring.
- dihydric phenols is not limited to phenols or polyphenols containing two "aromatic” hydroxy groups but also encompasses polyhydric phenols, i.e. compounds having more than two "aromatic" hydroxy groups.
- dihydric phenols examples include resorcinol, catechol, hydroquinone, and polyphenols including p,p'-dihydroxydibenzyl, p,p'-dihydroxyphenylsulfone, p,p'- dihydroxybenzophenone, 2,2'-dihydroxyphenyl sulfone, p,p'-dihydroxybenzophenone, 2,2-dihydroxy-1 ,1-dinaphrhylmethane, and the 2,2', 2,3', 2,4', 3,3', 3,4', and 4,4' isomers of dihydroxydiphenylmethane, dihydroxydiphenyldimethylmethane, dihydroxydiphenylethylmethylmethane, dihydroxydiphenylmethylpropylmethane, dihydroxydiphenylethylphenylmethane, dihydroxydiphenylpropylenphenylmethane, dihydroxydiphenylbutylphenylmethan
- Preferred epoxy resins include epoxy resins containing or consisting of glycidyl ethers or polyglycidyl ethers of monohydric, dihydric or polyhydric phenols, such as for example, but not limited to bisphenol A, bisphenol F, including polymers comprising repeating units of these phenols.
- Preferred epoxy resins include epoxy novolacs. Epoxy novolacs are the reaction product of an epoxy group- introducing agent, such as for example epichlorohydrin, with a condensation product of a mono- di or polyhydric phenol (which may be alkylsubstituted (e.g. cresol) or non-substituted) and an aldehyde, such as for example, formaldehyde.
- Typical epoxy novolacs are polymers containing glycidyl ether groups and further comprising repeating units derived from bisphenol F or another reaction product of a phenol with an aldehyde.
- the phenol may be monohydric, dihydric or trihyidric and may be non-substituted or alkyl substituted.
- aromatic epoxy resins described above also their fully or partially hydrogenated derivatives (i.e. the corresponding cycloaliphatic compounds) may be used.
- the epoxy resins may be liquid at room temperature or solid.
- the epoxy resins may have a viscosity of from about 400 mPa.s at 20 0 C to about 40,000 mPa.s at 50 0 C.
- the resin has a viscosity of at least 8,000 mPa s at 20°C up to 5,000 mPa s at 50 0 C.
- the epoxy resin preferably does not contain an -NH 2 or -NH 3 + functionality.
- the epoxy resin preferably does not contain an aromatic amine moiety, such as for example a unit derived from an aminophenol.
- Examples of commercially available epoxy resins include diglycidylether of bisphenol A (e.g. available under the trade designation EPON 828, EPON 830 or EPON 1001 from Hexion Speciality Chemicals GmbH, Rosbach, Germany, or under the trade designation D.E.R-331 or D.E.R-332 from Dow Chemical Co,); diglycidyl ether of bisphenol F (e.g. EPICLON 830 available from Dainippon Ink and Chemicals, Inc. or D. E. R. -354 from Dow Chemical Co, Schwalbach/Ts., Germany); silicone resins containing diglycidyl epoxy functionalities; flame retardant epoxy resins (e.g.
- DER 580 a brominated bisphenol type epoxy resin available from Dow Chemical Co.
- Other epoxy resins based on bisphenols are commercially available under the trade designations EPIKOTE (Hexion Speciality Chemicals, Rosbach, Germany), or EPILOX (Leuna Epilox GmbH, Leuna, Germany).
- Epoxy novolacs are available under the trade designation D.E.N, from Dow Chemical Co, Schwalbach/Ts., Germany, such as for example D.E.N 431 (a novolac resin with an average epoxy functionality of 2.8 and a viscosity of from 1 100 to 1700 mPa s at 51.7°C) , D.E.N.
- compositions provided herein comprise 10 to 70 percent by weight, preferably from 15 to 60 percent by weight, more preferably from 15 to 55 percent by weight and especially preferably from 15 to 50 percent by weight of one or more epoxy resin.
- Epoxy-hardener system
- compositions further contain a system of epoxy hardeners.
- Epoxide hardeners are compounds that react with the oxirane ring of the epoxide to cause cross-linking. Epoxide hardeners are known in the art also as curing agents and accelerators. In the art, the term "curing agent" often denotes an epoxide hardener that is predominantly used to carry out the cross-linking agent, i.e. it is present in the hardening system as the major component (i.e. in major amounts).
- accelerating agent has been used in the art for compounds that are also able to cross-link epoxides but that are present in smaller amounts than the curing agents, such that the cross-linking network predominantly contains units derived from the curing agent as compared to units derived from the accelerating agent.
- Typical accelerators known in the art include boron trifloride or trichloride amine complexes, imidazoles, imidazole derivatives, imidazole-like compounds and the like. Specific examples include, for example, 2-(2-(2 methylimidazolyl)-ethyl)-4,6- diamino-s-triazine.
- the curable compositions according to the invention include the following epoxy hardeners: one or more carboxylic acid anhydrides, a first amine and a second amine, wherein the first amine is an amine having a melting point of from about 30 0 C up to 180 0 C, and the second amine is an amine having a melting point of from about 40°C up to about 190 0 C.
- the first and second amines are chosen such that they have a difference in melting points of at least 10°C.
- the anhydrides, the first amines and the second amines are all capable of reacting with the epoxide groups of the resin by way of a cross-linking reaction.
- the individual components of the epoxy hardener system are described in greater detail below.
- Carboxylic acid anhydrides are known hardeners in the field of epoxy resin-based curable compositions.
- Typical carboxylic acid anhydrides include, but are not limited to, phthalic acid anhydrides, such as, for example, tetrahydroxy phthalic acid anhydrides or norbornenephthalic acid anhydrides.
- the amounts of anhydrides to epoxy resin are chosen such that they have about equal equivalent weights, i.e. the molar amounts of reactive anhydride groups to reactive epoxy groups is about 1 : 1 or from 0.8: 1 to about 1 : 0.8.
- the first amines used in the epoxy hardener system are amines having a melting point of from about 30°C up to about 100 0 C, preferably from about 40°C up to about 90°C, more preferably from about 60 0 C to about 80°C.
- the first amines are preferably aliphatic amines, meaning they do not contain an aromatic residue.
- the first amines preferably contain at least one primary amine residue (i.e. an -NH 2 residue).
- the first amines may be linear or branched, cyclic or acyclic.
- the first amines may be linear or branched amines of the general structure:
- R 2 R 4 wherein the residues R 1 , R 2 , and R 4 , independently from each other, may represent hydrogen or a hydrocarbon (such as an alkyl) or an alkoxy or a polyoxyalkyl residue.
- R 3 represents a hydrocarbon, an alkylether or a polyether alkyl residue. More preferably R 3 is a polyetheralkyl residue.
- the residues R 1 , R 2 , and R 4 are chosen such that the amine contains at least one or two primary amine groups; n represents an integer.
- Suitable polyether amines include those that can be derived from polypropylene oxide or polyethylene oxide.
- the residues and integers are chosen such that the amine has a melting point within the range as described above.
- First amines as described above are commercially available, for example, within the JEFFAMINE series from Huntsman Chemicals, or within the ANCAMINE series from Airproducts.
- the second amines are amines having a melting point of from about 50 0 C up to about 180 0 C, preferably from about 70 0 C to less than about 150°C, more preferably from about greater than 80 0 C to less than about 129°C.
- the second amines may be of the same or different chemical type than the first amines.
- the second amines are aliphatic, more preferably, cycloaliphatic (which means they do contain aliphatic or cycloaliphatic moieties but do not contain aromatic moieties).
- the cycloaliphatic amines as used herein mean that the amine contains one or more than one cycloaliphatic residues.
- the cycloaliphatic amines are preferably primary amines and contain at least one primary amine group.
- Typical examples of cycloaliphatic amines include primary amines containing one or two or more than two cyclic residues (such as, for example, cyclohexyl, cycloheptyl, or cyclopentyl residues or combinations thereof).
- compositions as provided herein may typically comprise from about 10 to about 40% weight based on the weight of the total composition of hardeners.
- the second amines are used in equal amount or in excess with respect to the first amines.
- the first and second amines are used in minor amounts compared to the anhydrides, such as for example from 0.5 to 20% or from 1 to 12% by weight based on the total amount of anhydrides used in the hardening system, or based on the total amount of hardeners used in the composition.
- the first and second amines are chosen such that they have a difference in melting points of at least 10 0 C.
- the curing system is preferably selected such that the precursor can be cured by subjecting it to a temperature between 120 0 C and 180°C.
- compositions may further comprise a fire retardant system as described below.
- compositions may further comprise a filler material as described below.
- the compositions may further comprise a filler capable of reducing the density of the composition. Capable of reducing the density of the composition as used herein means the filler has a lower density than the composition without the filler. Typically, the compositions may comprise 15 to 60 weight percent of such a filler.
- Fillers capable of reducing the density of the precursor includes low density inorganic fillers, (i.e., fillers having a density of between 0.1 to 0.5 g/cm 3 ), low density organic fillers (i.e., fillers having a density of between 0.01 to 0.30 g/cm 3 ) but low density inorganic fillers are preferred over organic fillers because the letter tend to negatively influence the compressive strength.
- a combination of organic and inorganic fillers may be used but the inorganic low density fillers are preferably used in excess over the organic fillers.
- the low-density inorganic fillers are preferably selected from inorganic particles, inorganic microspheres and in particular hollow inorganic microspheres.
- the microspheres may be selected from a variety of materials including by way of example glass, silica, ceramic (including sol-gel derived) or zirconia.
- the fillers are preferably selected so that they allow for an advantageous density of the cured composition without sacrificing its compressive strength.
- the hollow inorganic microspheres exhibit a density of less than 0.5 g/cm 3 , more preferably of between 0.12 and 0.42 g/cm 3 .
- the fillers may have an average particle size typically of less than 500 ⁇ m, or between 10 and 100 ⁇ m.
- Preferred hollow inorganic microspheres include glass microspheres which are commercially available, for example, from 3M Company under the trade designation
- Unexpanded organic hollow microsphere fillers are available, for example, from Akzo Nobel under the trade designation "Expancel(R)".
- Unexpanded organic hollow microspheres are sometimes also referred to as expandable organic microballoons which are also available, for example, from Lehmann and Voss, Hamburg, Germany under the trade designation Micropearl.
- Pre-expanded organic hollow microspheres are commercially available, for example, from Lehmann & Voss, Hamburg, Germany under the trade designation Dualite.
- the concentration and the nature of the fillers used in the curable compositions is preferably selected such that the density of the cured composition is less than 1g/cm 3 , more preferably less than 0.9 g/cm 3 and most preferably between 0.5 and 0.8 g/cm 3 .
- the precursors and cured compositions of the present invention may further comprise a fire-retardant system that includes a mixture of: (1 ) at least one compound selected from the group comprising alkaline earth metal hydroxides and aluminium group hydroxides, and (2) at least one phosphorous-containing material.
- the precursors and cured compositions typically comprise the fire-retardant system of (1 ) and (2) above from 5 to 50 weight percent and preferably from 10 to 50 weight percent based on the total composition.
- the compounds of group (1 ) comprising alkaline earth metal hydroxides and aluminium group hydroxides are often referred to as smoke suppressants.
- the phosphorous-containing material (2) may be selected from a group comprising, for example, elemental red phosphorous, melamine phosphate, dimelamine phosphate, melamine pyrophosphate and inorganic phosphinates such as, for example, aluminium phosphinates. Elemental red phosphorous and inorganic phosphinates are preferred.
- the fire-resistant system may also include an optional boron-containing material, such as those selected from the group consisting of barium metaborates, calcium metaborates, zinc metaborates and mixtures thereof. These materials may provide up to 25 weight percent with respect to the mass of the precursor.
- composition of the present invention may comprise further ingredients, adjuvants, which may be used to further regulate rheological properties or mechanical properties, adapt the visual appearance of the compositions or may help to prevent premature degradation of the compositions.
- additional materials include, for example, fillers other than those described above, thixotropic agents, reactive diluents, pigments, antioxidants, adhesion promoters and the like.
- Reactive diluents and thixotropic agents may be added to control the flow characteristics of the adhesive composition.
- Thixotropic agents typically are particulate materials having particle sizes of less than 50 nm.
- Preferred thixotropic agents include fumed silica.
- Thixotropic agents are commercially available under the trade designation Cab-O-Sil from Cabot, Schwalbach im Taunus, Germany, or Aerosil from Degussa Evonik GmbH, Frankfurt, Germany.
- Reactive diluents are typically monomeric epoxy-containing molecules. Preferably, they have a saturated or unsaturated cyclic backbone. Preferred reactive terminal ether portions include glycidyl ether. Examples of suitable diluents include the diglycidyl ether of resorcinol, diglycidyl ether of cyclohexane dimethanol, diglycidyl ether of neopentyl glycol, triglycidyl ether of trimethylolpropane.
- Further materials include wetting agents, which are preferably selected from the group consisting of titanates, silanes, zirconates, zircoaluminates, phosphoric ester(s) and mixtures thereof.
- the wetting agent improves the mixability and processability of the composition and can also enhance the composition's handling characteristics.
- An especially useful wetting agent is commercially available as Coatex DO-UP6L from Coatex, Genay, France.
- the concentration of the wetting agent component comprising one or more wetting agents is typically lower than 6 percent by weight and more preferably not more than 5 percent by weight.
- Pigments may include inorganic or organic pigments including ferric oxide, brick dust, carbon black, titanium oxide and the like.
- compositions may further comprise toughening agents.
- Toughening agents are polymers, other than the epoxy resins, capable of increasing the toughness of cured epoxy resins compared to the same composition not containing them (the difference in amount in such comparison studies is made up by the epoxy resin) and which are otherwise treated identically.
- Typical toughening agents include, for example, core-shell polymers or liquid butadiene-nitrile rubbers.
- the curable compositions of the invention can be readily prepared by a number of techniques.
- the various components may be added under ambient conditions to a suitable mixing vessel, such as a Mogul mixer.
- the vessel is preferably cooled to prevent reaction of the components during preparation and to facilitate removal of any heat generated during manufacture.
- the curable composition (also referred to herein as "precursor") is mixed at a temperature of less than 35°C. Additionally, slow mixing speeds are generally used to help prevent heat build-up in the mixer. Mixing is continued until the components form a homogeneous mixture, after which time the precursor is removed from the mixer.
- the precursors can be applied by conventional application equipment such as extruders or equipment providing pumps.
- the precursors of the present invention preferably are one-part compositions, i. e. they already comprise the hardener component as compared to two-part composition, where the hardening components are kept separated from the epoxy resin until use of the compositions.
- One-part precursors of the present invention preferably exhibit a good shelf life time at room temperature.
- One-part compositions contain a reactive system and are therefore, preferably kept at low temperatures for storage.
- a good shelf life at room temperature as referred to herein can be determined by measuring the time (from preparing the composition or from the time it has reached room temperature (20 0 C) after having been kept at -73°C) until the composition thickens such that it becomes more difficult or impossible to extrude. A slow rate of thickening is acceptable.
- a composition is considered to have a good shelf life at room temperature, if its extrusion rate (as measured according to the methods described below) is greater than 60 g/min after storage for 5 days at room temperature.
- the curable compositions can be applied to various substrates such as, for example, metals (for example, Al, Al alloys, titanium or stainless steel) or other substrates comprising, for example, glass, boron, carbon, Kevlar fibers, epoxy, phenols, cyanate esters and polyester matrices.
- substrates such as, for example, metals (for example, Al, Al alloys, titanium or stainless steel) or other substrates comprising, for example, glass, boron, carbon, Kevlar fibers, epoxy, phenols, cyanate esters and polyester matrices.
- the curable compositions may be applied, for example, as a thin coating but are preferably used for the preparation of bulky articles like, for example, filled honeycomb panels for the construction of composite floor panels or walls used in watercraft or aircrafts.
- the precursor compositions are subsequently cured, preferably by thermal curing.
- the curing conditions can be widely varied depending on the specific application.
- the curing temperature is typically chosen between 80 and 180 0 C, preferably at 175°C and the curing time typically amounts to between 15 and 180 minutes, preferably 2 hours.
- compositions can be cured at 175°C for a curing time of 120 minutes.
- Curing can be determined by testing the compositions for the mechanical properties described herein.
- the curable epoxy-based compositions can be prepared the exhibit a good processability and exhibit both an advantageous initial viscosity (evaluated, for example, in terms of initial extrusion rate) and a low increase of viscosity with time (evaluated, for example, in terms of initial extrusion rate and extrusion rates after 3 days or 5 days, respectively, as described in the methods below).
- compositions can be prepared that exhibit low exothermicity upon curing (evaluated, for example, in terms maximum exothermic peak during the curing reaction according to the method described below). Compositions are considered to have a low exothermicity if their exothermicity is less than 60 0 C, preferably less than 55°C.
- Epoxy-based compositions which are obtainable by curing the corresponding curable precursors compositions can be prepared that exhibit advantageous mechanical properties evaluated, for example, in terms of compressive strength.
- the cured compositions have good compressive strength at room temperature but also at elevated temperatures.
- the precursor compositions contain the above-mentioned ingredients in such amounts that upon curing the desired chemical and mechanical properties will be achieved.
- curable compositions having one or more or all of the following properties can be prepared: a) curable compositions having an initial extrusion rate measured as described in the method section below of between from 50 g/min to about 300 g/min; b) curable compositions having an initial extrusion rate measured as described in the method section below after 3 days storage at room temperature of from about 50 g/min up to about 200 g/min and after 5 days storage at room temperature of from about 50 g/min and up to 150 g/min; c) curable compositions having an exothermic peak of less than 60 0 C measured as described in the method section below; d) curable compositions that when cured have a compressive strength of at least 25 MPa at 135°C.
- curable compositions that when cured have a compressive strength of at least 20 MPa at 150 0 C.
- curable compositions having properties a) and b) or a), b) and c), or a), b), c), and d), or a), b), c), d) and e) or a), b), c) ,d), e), f) and g).
- curable compositions further containing the fire retardant system as described above can be prepared that exhibit when cured a burn length of less than 200 mm, an after flame time of less than 15 s, an after flame drip of less than 5 s at a vertical Bunsen burner at 12 s as measured as described below.
- curable compositions further containing the fire retardant system as described above can be prepared that exhibit when cured a burn length of less than 150 mm, an after flame time of less than 15 s, an after flame drip of less than 3 s at a vertical Bunsen burner at 60 s as measured according to the methods described below.
- curable compositions further containing the fire retardant system as described above can be prepared that when cured exhibit an optical smoke density as measured according to the methods described below of less than 200.
- the curable precursor and the cured compositions of the present invention are, in particular, useful as filler or bonding material in aircrafts because they are easily applicable, lightweight and fire-resistant materials which are capable of withstanding the forces encountered when used at the interface of a pressurized and non-pressurized zone.
- the curable compositions are particular useful as filler for honeycomb structures because of their low exothermicity and mechanical strength.
- a particularly preferred precursor composition comprises about 10 to 70 % by weight of the organic epoxide, about 1 to 55 % by weight of the epoxide hardener system, about 5 to 50 % by weight of the fire retardant system and about 10 to 60 % by weight of the filler capable of reducing the weight of the composition, wherein the percentages by weight are based on the total amount of the composition and the total amount of the weight percentages gives 100%.
- the invention is furthermore illustrated by the examples described below. Prior to that some test methods used to characterize the precursors and cured epoxy- based composition will be described. Unless specified otherwise, percentages are percentages by weight with respect to the mass of the precursor or the cured epoxy-based composition, respectively. Above and below, the mass percentages of all components of a precursor or a cured composition, respectively, add up in each case to 100 weight percent.
- the processability of the precursor of the low-density epoxy-based composition was evaluated at room temperature (23 0 C) by extruding it through standard equipment using the following procedure.
- An air driven application pistol (available from SEMCO, East Kilbride, U. K) was fitted with a 150 ml disposable cartridge and a nozzle having an aperture of 6.35 mm.
- the disposable cartridge was filled with precursor and by applying an air pressure of 5 bars the low-density epoxy composition was extruded.
- the extrusion rate was determined by measuring the quantity extruded in 60 seconds.
- test results are averages from three measurements.
- 200 g of the precursor were cast into a release-coated mould having the dimensions of 12.5 mm (height) x 12.5 mm (width) x 25mm (length) and being open on one major side.
- the mould was placed in a forced air oven and subjected to a curing program comprising two curing cycles.
- the oven temperature was raised from 23 0 C to 125 0 C using a heating rate of 3 °C/min. Then the temperature was held at 125 0 C for 1 hour and then the temperature was cooled down to 23 0 C over a period of 45 minutes.
- the oven temperature was raised from 23 0 C to 175 0 C using a heating rate of 3 °C/min. Then the temperature was held at 175 0 C for 1 hour and then temperature was cooled down to 23 0 C over a period of 45 minutes.
- test specimens were compressed along their 25 mm axis at a rate of 0.5 mm/min by using a Zwick Model Z030 Tensile Tester (Zwick GmbH & CO., UIm, Germany), equipped with heating capability.
- Compressive strength was measured at 23 0 C (room temperature), 80 0 C, 120 0 C and 135°C.
- the test specimens were preconditioned in the heated equipment for at least 30 minutes before testing at 80 °, 120 0 C and 135°C.
- a sheet having a thickness of 3 - 5 mm was prepared by pouring the composition into an aluminium release-treated mould and curing it in an air forced oven using the same curing cycle from 23 0 C to 125°C as described previously for the compressive strength test. Samples having the dimensions of 3 mm x 75 mm x 75 mm were then cut from this large sheet. The surface of one side was abraded with sandpaper to insure that the exposed resin was representative of the overall composition.
- NBS National Bureau of Standards
- Airbus Directive ABD 0031 "Fireworthiness Requirements, Pressurised Section of Fuselage", Issue D, Sept. 2002, section 5.4 "smoke-density”.
- a sample of the epoxy-based composition was placed over a gas flame of specific dimension. Smoke generated in the chamber was measured by light transmission of a vertical light beam through the air space in the oven. Three samples of each epoxy-based composition were tested and the results averaged.
- the vertical burn test was performed according to Airbus Directive ABD 0031 , Issue September 2002.
- Three test specimens with a dimension of 3mm x 75 mm x 300 mm were cut off a 3 mm x 400 mm x 400 mm panel of epoxy composition cured in an aluminium mould.
- the epoxy composition was extruded in the mould of a SEMCO cartridge.
- the mould was cured in an air forced oven for 60 minutes at 125 0 C with a heat-up rate of 3 °C/min.
- the specimens were then tested in a flammability chamber to the 12 -seconds and 60-seconds Vertical Burn Test. The burn length was recorded in mm. Three samples of each epoxy-based composition were tested and the results averaged.
- 100g of the precursor composition were filled into a stainless steel round bottom cup having a diameter of 100 mm and a height of 35 mm.
- An electrical thermocouple was placed in the center of the precursor.
- the precursor was then cured by placing it into a forced air oven and running a curing cycle where the oven temperature was raised from
- thermocouple 0 C for 1 hour.
- the peak exotherm was calculated by subtracting the oven heat from the maximum heat recorded by the thermocouple in the precursor composition, i.e. the maximum temperature recorded by the thermocouple minus 175°C.
- DMTA V Rheometer For DMTA testing a DMTA V Rheometer was used commercially available by Rheometric Scientific Inc., Piscataway, NJ 08854, USA.
- the precursor was coated between 2 silicone release liners to a thickness of about 0.3mm and cured in an air forced oven using a curing cycle from 23°C to 175°C at a heating rate of 2-5°C minutes. Then the temperature was held at 175 0 C for 1 hour, in order to completely cure the epoxy-based composition. After the curing for 1 hour at 175 0 C was completed, the cured epoxy-based composition was cooled down to 23 0 C over a period of 45 minutes.
- Test specimens were then cut out having a dimension of 5 mm x 10 mm and subjected to DMTA testing for the evaluation of the glass transition temperature (Tg).
- Tg glass transition temperature
- Samples of the epoxy-based composition were prepared by casting the corresponding precursors into moulds and curing in a forced air oven using a temperature program as described under the test method "Compressive Strength", as described previously.
- the cured samples of the epoxy-based composition were removed from the moulds and their exact dimensions recorded. Each sample was weighed and the density calculated and recorded in grams per cm 3 .
- Epoxy-based compositions were prepared by combining in each case the compounds listed below in Table 1 in a 2.0 litre mechanical mogul type mixer commercially available by Linden GmbH, Germany. In Table 1 , all concentrations are given as weight percent.
- a temperature of less than 35 0 C was maintained during the mixing process, using water- cooling.
- the epoxy resin was mixed at 20 to 40 rpm with the encapsulated red phosphorus, the aluminium trihydrate and the zinc borate for about 20 minutes until a homogeneous blend was achieved.
- the hardener system was added followed by mixing for an additional 15 minutes. Hollow glass microspheres were then stirred in followed by an additional mixing of 20 minutes.
- the homogeneous blend was degassed by applying a 100 mbar vacuum for 5 minutes.
- the precursor formulations were stored -18°C.
- the precursors were cured by subjecting them to the curing cycle from 23°C to 125°C as described in the test method section above, sub-section "Compressive strength".
- Table 3 Toxic gas emissions of the formulation of example 1 after submission to the emission test
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL10723411T PL2414425T3 (en) | 2009-03-30 | 2010-03-26 | Epoxy resin based core filler material developing low exothermic heat |
CN201080014967.5A CN102378772B (en) | 2009-03-30 | 2010-03-26 | Epoxy resin based core filler material developing low exothermic heat |
CA2756886A CA2756886C (en) | 2009-03-30 | 2010-03-26 | Epoxy resin based core filler material developing low exothermic heat |
ES10723411.4T ES2473968T3 (en) | 2009-03-30 | 2010-03-26 | Core loading material based on epoxy resin that develops under exothermic heat |
EP10723411.4A EP2414425B1 (en) | 2009-03-30 | 2010-03-26 | Epoxy resin based core filler material developing low exothermic heat |
BRPI1014695A BRPI1014695A2 (en) | 2009-03-30 | 2010-03-26 | Epoxy resin-based core loading material that generates low exothermic heat. |
JP2012503527A JP5508516B2 (en) | 2009-03-30 | 2010-03-26 | Low exothermic epoxy resin core filler |
KR1020117025459A KR101709360B1 (en) | 2009-03-30 | 2010-03-26 | Epoxy resin based core filler material developing low exothermic heat |
US13/258,665 US8779032B2 (en) | 2009-03-30 | 2010-03-26 | Epoxy resin based core filler material developing low exothermic heat |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0905362.0 | 2009-03-30 | ||
GBGB0905362.0A GB0905362D0 (en) | 2009-03-30 | 2009-03-30 | Fire resistant epoxy resin based core filler material developing low exothermic heat |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010117669A1 true WO2010117669A1 (en) | 2010-10-14 |
Family
ID=40671879
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2010/028778 WO2010117669A1 (en) | 2009-03-30 | 2010-03-26 | Epoxy resin based core filler material developing low exothermic heat |
Country Status (12)
Country | Link |
---|---|
US (1) | US8779032B2 (en) |
EP (1) | EP2414425B1 (en) |
JP (1) | JP5508516B2 (en) |
KR (1) | KR101709360B1 (en) |
CN (1) | CN102378772B (en) |
BR (1) | BRPI1014695A2 (en) |
CA (1) | CA2756886C (en) |
ES (1) | ES2473968T3 (en) |
GB (1) | GB0905362D0 (en) |
PL (1) | PL2414425T3 (en) |
PT (1) | PT2414425E (en) |
WO (1) | WO2010117669A1 (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130184379A1 (en) * | 2011-07-15 | 2013-07-18 | Basf Se | Polyether amines useful as accelerants in epoxy systems |
EP2653486A1 (en) * | 2012-04-20 | 2013-10-23 | 3M Innovative Properties Company | Low density epoxy composition with low water uptake |
US8779032B2 (en) | 2009-03-30 | 2014-07-15 | 3M Innovative Properties Company | Epoxy resin based core filler material developing low exothermic heat |
EP2818490A1 (en) | 2013-06-28 | 2014-12-31 | 3M Innovative Properties Company | Use of an epoxy resin-based composition as a filler for honeycomb cells |
CN105000129A (en) * | 2015-04-08 | 2015-10-28 | 江苏宏强船舶重工有限公司 | Construction technology for small ship lubricating oil circulating tank protecting structure |
EP3333211A1 (en) | 2016-12-09 | 2018-06-13 | 3M Innovative Properties Company | Hot/wet resistant low density epoxy compositions |
CN108350149A (en) * | 2015-10-29 | 2018-07-31 | 3M创新有限公司 | Rapid curing and high thixotropic epoxy adhesive composition |
EP3666812A1 (en) | 2018-12-13 | 2020-06-17 | 3M Innovative Properties Company | Room temperature stable one-part void filler |
US10882947B2 (en) | 2014-06-17 | 2021-01-05 | 3M Innovative Properties Company | Rapid curing epoxy adhesive compositions |
RU2747941C1 (en) * | 2020-03-03 | 2021-05-17 | Общество с ограниченной ответственностью "Архитектурно-конструкторское бюро Монолит" (ООО "АКБ Монолит") | Cellular non-flammable epoxy composition |
EP3180393B1 (en) | 2014-08-12 | 2021-09-29 | 3M Innovative Properties Company | Film adhesive |
EP4310127A1 (en) | 2022-07-19 | 2024-01-24 | 3M Innovative Properties Company | Low density potting adhesive |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2470583A1 (en) * | 2009-08-27 | 2012-07-04 | ABB Research Ltd. | Curable epoxy resin composition |
JP6200715B2 (en) * | 2013-07-24 | 2017-09-20 | ナミックス株式会社 | Epoxy resin composition, underfill agent, adhesive, and semiconductor device |
US10662302B2 (en) * | 2014-09-23 | 2020-05-26 | The Boeing Company | Polymer nanoparticles for improved distortion capability in composites |
EP3239207B1 (en) | 2016-04-27 | 2021-07-28 | 3M Innovative Properties Company | Curable epoxy compositions |
CA3054787A1 (en) * | 2017-03-01 | 2018-09-07 | Purdue Research Foundation | Epoxy tannin reaction product compositions |
US20210221971A1 (en) * | 2018-08-21 | 2021-07-22 | Evonik Operations Gmbh | Fast curing epoxy system for producing rigid foam and use of the foam in composites or as insulation material |
CN112646521B (en) * | 2020-12-18 | 2022-02-11 | 深圳市彩田化工有限公司 | Preparation process of low-heat-release epoxy resin adhesive |
CN113789034B (en) * | 2021-10-13 | 2023-07-14 | 航天特种材料及工艺技术研究所 | Low-heat-release epoxy resin composition and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0671427A1 (en) * | 1994-03-10 | 1995-09-13 | Ciba-Geigy Ag | Heat-curable epoxy resin composition having good reactivity/stability behaviour |
WO1997019124A1 (en) * | 1995-11-18 | 1997-05-29 | Ciba Specialty Chemicals Holding Inc. | Powderable reactive resin compositions |
US20020006515A1 (en) * | 2000-03-27 | 2002-01-17 | Luttrull David K. | Styrene-maleic anhydride copolymer and epoxy resin blend crosslinked with multifunctional amine compounds |
US6635202B1 (en) | 1998-10-23 | 2003-10-21 | Vantico Inc. | Method for filling and reinforcing honeycomb sandwich panels |
WO2006071820A1 (en) | 2004-12-23 | 2006-07-06 | 3M Innovative Properties Company | Fire-retardant low-density epoxy composition |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3205914B2 (en) * | 1991-09-13 | 2001-09-04 | 大倉工業株式会社 | Epoxy resin composition |
US5679719A (en) * | 1993-03-24 | 1997-10-21 | Loctite Corporation | Method of preparing fiber/resin composites |
JPH07216057A (en) * | 1994-01-27 | 1995-08-15 | Bridgestone Corp | Epoxy resin composition |
US5597886A (en) * | 1994-03-10 | 1997-01-28 | Ciba-Geigy Corporation | Heat-curable epoxy resin systems having a good reactivity/stability ratio |
US8475694B2 (en) * | 2005-10-25 | 2013-07-02 | Zephyros, Inc. | Shaped expandable material |
GB0905362D0 (en) | 2009-03-30 | 2009-05-13 | 3M Innovative Properties Co | Fire resistant epoxy resin based core filler material developing low exothermic heat |
-
2009
- 2009-03-30 GB GBGB0905362.0A patent/GB0905362D0/en not_active Ceased
-
2010
- 2010-03-26 BR BRPI1014695A patent/BRPI1014695A2/en not_active Application Discontinuation
- 2010-03-26 PT PT107234114T patent/PT2414425E/en unknown
- 2010-03-26 US US13/258,665 patent/US8779032B2/en active Active
- 2010-03-26 ES ES10723411.4T patent/ES2473968T3/en active Active
- 2010-03-26 JP JP2012503527A patent/JP5508516B2/en not_active Expired - Fee Related
- 2010-03-26 PL PL10723411T patent/PL2414425T3/en unknown
- 2010-03-26 KR KR1020117025459A patent/KR101709360B1/en active IP Right Grant
- 2010-03-26 EP EP10723411.4A patent/EP2414425B1/en active Active
- 2010-03-26 WO PCT/US2010/028778 patent/WO2010117669A1/en active Application Filing
- 2010-03-26 CN CN201080014967.5A patent/CN102378772B/en not_active Expired - Fee Related
- 2010-03-26 CA CA2756886A patent/CA2756886C/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0671427A1 (en) * | 1994-03-10 | 1995-09-13 | Ciba-Geigy Ag | Heat-curable epoxy resin composition having good reactivity/stability behaviour |
WO1997019124A1 (en) * | 1995-11-18 | 1997-05-29 | Ciba Specialty Chemicals Holding Inc. | Powderable reactive resin compositions |
US6635202B1 (en) | 1998-10-23 | 2003-10-21 | Vantico Inc. | Method for filling and reinforcing honeycomb sandwich panels |
US20020006515A1 (en) * | 2000-03-27 | 2002-01-17 | Luttrull David K. | Styrene-maleic anhydride copolymer and epoxy resin blend crosslinked with multifunctional amine compounds |
WO2006071820A1 (en) | 2004-12-23 | 2006-07-06 | 3M Innovative Properties Company | Fire-retardant low-density epoxy composition |
Non-Patent Citations (1)
Title |
---|
J. KLEE: "Hybridnetzwerke-Möglichkeiten der Carbonsäureanhydridmodifizierung und Nachvernetzung von Epoxid-Amin-Prepolymeren", DIE MAKROMOLEKULARE CHEMIE, vol. 190, no. 11, 11 November 1989 (1989-11-11), Jena, pages 2673 - 2681, XP002593711, Retrieved from the Internet <URL:http://www3.interscience.wiley.com/journal/104075553/abstract> * |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8779032B2 (en) | 2009-03-30 | 2014-07-15 | 3M Innovative Properties Company | Epoxy resin based core filler material developing low exothermic heat |
US20130184379A1 (en) * | 2011-07-15 | 2013-07-18 | Basf Se | Polyether amines useful as accelerants in epoxy systems |
EP2653486A1 (en) * | 2012-04-20 | 2013-10-23 | 3M Innovative Properties Company | Low density epoxy composition with low water uptake |
WO2013158517A1 (en) * | 2012-04-20 | 2013-10-24 | 3M Innovative Properties Company | Low density epoxy composition with low water uptake |
US9765215B2 (en) | 2013-06-28 | 2017-09-19 | 3M Innovative Properties Company | Epoxy resin-based composition as a filler honeycomb cells |
EP2818490A1 (en) | 2013-06-28 | 2014-12-31 | 3M Innovative Properties Company | Use of an epoxy resin-based composition as a filler for honeycomb cells |
WO2014210292A1 (en) | 2013-06-28 | 2014-12-31 | 3M Innovative Properties Company | Epoxy resin-based composition as a filler honeycomb cells |
US10882947B2 (en) | 2014-06-17 | 2021-01-05 | 3M Innovative Properties Company | Rapid curing epoxy adhesive compositions |
EP3180393B1 (en) | 2014-08-12 | 2021-09-29 | 3M Innovative Properties Company | Film adhesive |
CN105000129A (en) * | 2015-04-08 | 2015-10-28 | 江苏宏强船舶重工有限公司 | Construction technology for small ship lubricating oil circulating tank protecting structure |
CN108350149A (en) * | 2015-10-29 | 2018-07-31 | 3M创新有限公司 | Rapid curing and high thixotropic epoxy adhesive composition |
EP3333211A1 (en) | 2016-12-09 | 2018-06-13 | 3M Innovative Properties Company | Hot/wet resistant low density epoxy compositions |
EP3789418A1 (en) | 2016-12-09 | 2021-03-10 | 3M Innovative Properties Company | Hot/wet resistant low density epoxy compositions |
US11091629B2 (en) | 2016-12-09 | 2021-08-17 | 3M Innovative Properties Company | Hot/wet resistant low density epoxy compositions |
EP3666812A1 (en) | 2018-12-13 | 2020-06-17 | 3M Innovative Properties Company | Room temperature stable one-part void filler |
WO2020121196A1 (en) | 2018-12-13 | 2020-06-18 | 3M Innovative Properties Company | Room temperature stable one-part void filler |
RU2747941C1 (en) * | 2020-03-03 | 2021-05-17 | Общество с ограниченной ответственностью "Архитектурно-конструкторское бюро Монолит" (ООО "АКБ Монолит") | Cellular non-flammable epoxy composition |
EP4310127A1 (en) | 2022-07-19 | 2024-01-24 | 3M Innovative Properties Company | Low density potting adhesive |
WO2024018387A1 (en) | 2022-07-19 | 2024-01-25 | 3M Innovative Properties Company | Low density potting adhesive |
Also Published As
Publication number | Publication date |
---|---|
JP2012522113A (en) | 2012-09-20 |
CA2756886A1 (en) | 2010-10-14 |
CA2756886C (en) | 2017-06-13 |
EP2414425A1 (en) | 2012-02-08 |
GB0905362D0 (en) | 2009-05-13 |
JP5508516B2 (en) | 2014-06-04 |
CN102378772A (en) | 2012-03-14 |
EP2414425B1 (en) | 2014-04-23 |
KR101709360B1 (en) | 2017-02-22 |
PL2414425T3 (en) | 2014-09-30 |
CN102378772B (en) | 2014-07-09 |
BRPI1014695A2 (en) | 2016-04-12 |
PT2414425E (en) | 2014-06-25 |
US20120022185A1 (en) | 2012-01-26 |
KR20120013349A (en) | 2012-02-14 |
US8779032B2 (en) | 2014-07-15 |
ES2473968T3 (en) | 2014-07-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2414425B1 (en) | Epoxy resin based core filler material developing low exothermic heat | |
US9765215B2 (en) | Epoxy resin-based composition as a filler honeycomb cells | |
EP1838776B1 (en) | Fire-retardant low-density epoxy composition | |
EP2957584B1 (en) | Rapid curing epoxy adhesive compositions | |
EP3275915B1 (en) | Non-halogeneous fast curing two-component epoxy adhesive with flame retardant properties | |
US11091629B2 (en) | Hot/wet resistant low density epoxy compositions | |
EP3275914A1 (en) | Flame retardant adhesive composition | |
EP3666812B1 (en) | Room temperature stable one-part void filler | |
WO2024018387A1 (en) | Low density potting adhesive |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080014967.5 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10723411 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13258665 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010723411 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2756886 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012503527 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20117025459 Country of ref document: KR Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: PI1014695 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: PI1014695 Country of ref document: BR Kind code of ref document: A2 Effective date: 20110929 |