HUE034897T2 - Keményíthetõ epoxi készítmények - Google Patents

Description

(12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C08L 63100 (2006 01> 06.09.2017 Bulletin 2017/36 (86) International application number: (21) Application number: 14772553.5 PCT/US2014/055888 (22) Date of filing: 16.09.2014 (87) International publication number: WO 2015/047799 (02.04.2015 Gazette 2015/13)

(54) CURABLE EPOXY COMPOSITIONS hArtbare epoxidzusammensetzungen

COMPOSITION D’EPOXY DURCISSABLE (84) Designated Contracting States: · XIE, Rui AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Pearland, TX 77584 (US) GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO · WILSON, Mark B. PL PT RO RS SE SI SK SM TR Clute, TX 77531 (US) (30) Priority: 26.09.2013 US 201361882940 P (74) Representative: Glansdorp, Freija Gwendolyn

Greaves Brewster LLP (43) Date of publication of application: Copa House 03.08.2016 Bulletin 2016/31 Station Road

Cheddar (73) Proprietor: Blue Cube IP LLC Somerset BS27 3AH (GB)

Midland Ml 48674 (US) (56) References cited: (72) Inventors: · DATABASE WPI Week 201415 Thomson • LIANG, Yi Ling Scientific, London, GB; AN 2013-T01776

Pearland, TX 77584 (US) XP002734691, & CN 103 182 831 A (SHANNXI • FAN, William W. SHNEGYI SCI & TECHNOLOGY CO LTD) 3 July

Lake Jackson, TX 77566 (US) 2013 (2013-07-03) • MOORE, Stanley E.

Michigan 48674 (US)

Description BACKGROUND OF THE INVENTION Field of the Invention [0001] Embodiments of the present disclosure relate to epoxy compositions and in particular to epoxy compositions that are combined with hardeners to form curable compositions. The curable compositions can be used to prepare prepregs.

Description of Background and Related Art [0002] Epoxy thermosets have been used as the resin matrix to embed reinforced fibers to prepare lightweight and high strength composite articles for structural purposes. Among various composite manufacturing processes, the hot-melt prepreg process is a preferred process because it provides consistent properties and ease of use for composite fabricators, particularly in sporting goods, aerospace, automotive and other applications.

[0003] "Hot-melt" prepregs presented herein refer to fibers impregnated with solvent free, un-cured or slightly cured epoxy formulations. A typical manufacturing procedure involves (1) film manufacture and (2) film impregnation.

[0004] Many different types of high functional epoxy resins have been used to achieve high glass transition temperatures (Tg) of the cured epoxy thermosets to shorten de-molding time. However, the usage of these high functional epoxy resins may also cause a loss of adequate tackiness, and an increase in the melt viscosity of the resin blend, which can lead to insufficient resin wetting of the impregnated fibers, the formation of voids between the layered structures in composite articles, and a difficulty of preparing melt-epoxy-resin blends.

[0005] Therefore, a curable composition useful for preparing hot-melt prepregs which provides (1) adequate tack to serve as a semi-permanent adhesive (2) high glass transition temperature (Tg) and (3) an adequate viscosity profile for hotmelt prepreg processing is desired.

SUMMARY OF THE INVENTION

[0006] In one broad embodiment of the present invention, there is disclosed a curable composition comprising, consisting of, or consisting essentially of: a) an epoxy mixture comprising i) a first epoxy component comprising epoxy phenol novolac oligomers having a content of 2-functional monomers of less than 10 weight percent based on the total weight of the first epoxy component and having an epoxide equivalent weight in the range of 170 to 200 and ii) a second epoxy component comprising epoxy resin oligomers having monomers with an average functionality of at least 2 and b) a hardener.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Figure 1 is a plot of temperature versus heat flow.

DETAILED DESCRIPTION OF THE INVENTION

[0008] In various embodiments, the curable composition comprises an epoxy mixture; and b) a hardener.

Epoxy Mixture [0009] The composition contains an epoxy mixture. The mixture comprises i) a first epoxy component comprising epoxy phenol novolac oligomers having a content of 2-functional monomers of less than 10 weight percent based on the total weight of the first epoxy component and having an epoxide equivalent weight in the range of 170 to 200 and ii) a second epoxy component comprising an epoxy resin having monomers with an average functionality of at least 2.

[0010] The first epoxy component comprises epoxy phenol novolac oligomers. In an embodiment, the epoxy phenol novolac is phenol novolac (EPN) and is a bisphenol-F epoxy novolac in yet another embodiment.

[0011] The general structure of an epoxy phenol novolac is shown in Formula I, below.

Formula I

[0012] In an embodiment, the first epoxy component comprises epoxy novolac oligomers having less than 10 weight percent of 2-functional monomers (2-functional, n=0 in Formula I, above), and has less than 5 weight percent of 2-functional monomers in another embodiment.

[0013] Generally, the first epoxy component averages in the range of from 4.0 to 5.0 epoxide groups per molecule (n=2.0 to 3.0 in Formula I above), and having an epoxide equivalent weight in the range of 150 to 220, has in the range of 4.2 to 4.8 epoxide groups per molecule (n=2.2 to 2.8 in Formula I above) and has an epoxide equivalent weight in the range of 170 to 200 in another embodiment.

[0014] The first epoxy component is generally present in the epoxy mixture in the range from 3 weight percent to 96 weight percent and is present in an amount in the range of from 10 weight percent to 90 weight percent in other embodiments, based on the total weight of the epoxy mixture. Concentrations of lower than 3 weight percent may lead to a low Tg which is insufficient to reduce the de-molding time, while concentrations of higher than 96 weight percent may lead to insufficient tack performance for composite manufacturing.

[0015] In various embodiments, the epoxy mixture further comprises a second epoxy component comprising an epoxy resin having monomers with an average functionality of at least 2. In an embodiment, the second epoxy component can have an average functionality of 2.8.

[0016] The second epoxy component may vary and can include conventional and commercially available epoxy resins, which may be used alone or in combinations of two or more. In choosing epoxy resins for compositions disclosed herein, consideration should not only be given to properties of the final product, but also to viscosity and other properties that may influence the processing of the resin composition.

[0017] Particularly suitable epoxy resins include epoxy resins based on reaction products of polyfunctional alcohols, phenols, cycloaliphatic carboxylic acids, aromatic amines, or aminophenols with epichlorohydrin. A few embodiments include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, resorcinol diglycidyl ether, and triglycidyl ethers of para-aminophenols. Other examples of suitable epoxy resins include reaction products of epichlorohydrin with o-cresol and, respectively, phenol novolacs. Further epoxy resins include epoxides of divinylbenzene ordivinylnaphtha-lene. It is also possible to use a mixture of two or more epoxy resins.

[0018] The epoxy resins useful in the present invention for the preparation of the curable compositions may be selected from commercially available products; for example, D.E.R®. 331, D.E.R.® 332, D.E.R®. 383, D.E.R.® 334, D.E.R®. 580, D.E.N®. 431, D.E.N.® 438, D.E.R®. 736, or D.E.R®. 732, epoxy resins available from The Dow Chemical Company or Syna 21 cycloaliphatic epoxy resin from Synasia. As an illustration of the present invention, the additional epoxy resin may be a mixture of a liquid epoxy resin, such as D.E.R. 383, an epoxy novolac D.E.N. 438, a cycloaliphatic epoxide Syna 21, and a divinylarene dioxide, divinylbenzene dioxide (DVBDO) and mixtures thereof.

[0019] The second epoxy component is generally present in the epoxy mixture in the range of from 0 weight percent to 97 weight percent, based on the total weight of the epoxy mixture, and is present in the range of from 10 weight percent to 90 weight percent, based on the total weight of the epoxy mixture in various other embodiments.

Hardener [0020] A hardener can be added to the mixture to form a curable composition.

[0021] Any suitable epoxy hardener can be used. Examples of epoxy hardeners that can be used include aliphatic amines, modified aliphatic amines, cycloaliphatic amines, modified cycloaliphatic amines, amidoamines, dicyanopolya-mide, polyamide, tertiary amines, aromatic amines, anhydrides, mercaptans, cyclic amidines or isocyanates cyanate esters. Suitable hardeners include Dicyandiamide (DICY), bis(4-aminocyclohexyl)methane (AMICURE® PACM), dieth-ylenetriamine (DETA), triethylenetetramine (TETA), aminoethylpiperazine (AEP), isophorone diamine (IPDA), 1,2-di-aminocyclohexane (DACH), 4,4’-diaminodiphenylmethane (MDA), diaminodiphenylsulfone (DDS), m-phenylenediamine (MPD), diethyltoluenediamine (DETDA), meta-xylene diamine (MXDA), bis(aminomethyl cyclohexane), dicyandiamide, phthalic anhydride (PA), tetrahydrophthalic anhydride (THPA), methyltetrahydrophthalic anhydride (MTHPA), methyl hexahydrophthalic anhydride (MHHPA), hexahydrophthalic anhydride (HHPA), nadic methyl anhydride (NMA), benzo-phenonetetracarboxylic dianhydride (BTDA), tetrachlorophthalic anhydride (TCPA), and mixtures thereof.

[0022] Phenolic hardeners can also be used in the thermosetting composition. Suitable phenolic hardeners include the Rezicure ® 3XXX product line, Meiwa’s MEH-XXXX product line or other phenolic hardeners known to those skilled in the art..

[0023] Generally, the hardener is present in the curable composition in the range of from 1 to 35 parts per hundred parts epoxy resin (phr), and from 3 to 30 phr in another embodiment. A hardener content of less thanl phr may lead to insufficiently-cured thermosets that are not capable of providing desired composite performance

OPTIONAL COMPONENTS

Solvents [0024] In various embodiments, the curable composition can optionally further comprise one or more solvents. Examples of solvents that can be used include methyl ethyl ketone (MEK), dimethylformamide (DMF), ethyl alcohol (EtOH), propylene glycol methyl ether (PM), propylene glycol methyl ether acetate (DOWANOL™ PMA) and mixtures thereof.

[0025] In various other embodiments, no solvent is used.

Catalysts [0026] Optionally, catalysts can be added to the curable composition to facilitate the curing of the formulation. The type of catalyst depends on the desired end use.

[0027] Exam pies of catalysts that can be used include phenyl dimethyl urea (Omicure U405, CVC Thermoset Specialty), 4,4’ methylene bis phenyl dimethyl urea (Omicure U415, CVC Thermoset Specialty), cycloaliphatic dimethyl urea (Omicure U35, CVC Thermoset Specialty), 3, 4 dichlorophenyl dimethyl urea (Diuron, CVC Thermoset Specialty), and 4 chlorophenyl diemthyl urea (Monuron, CVC Thermoset Specialty). Other catalyst examples include at least one tertiary amine, including phenolic substituted ones; at least one boric acid-amine complex; at least one boron trifluoride-amine complex; at least one imidazole or substituted imidazole; at least one metal acetylacetonate); at least one transition metal (for example cobalt, nickel, zinc, chromium, iron, copper) salt; at least one quaternary ammonium or phosphonium salts; at least one phosphine or substituted phosphine compound; or a combination thereof.

[0028] Generally, the catalyst is present in the curable composition in the range of from 0.5 to 10 parts per hundred parts epoxy resin (phr), and in the range of from 1 to 8 phr in another embodiment.

Toughening agents [0029] The curable composition can also contain a toughening agent. In an embodiment, the toughening agent is a core shell rubber.

[0030] A core shell rubber is a polymer comprising a rubber particle core formed by a polymer comprising an elastomeric or rubbery polymer as a main ingredient, optionally having an intermediate layer formed with a monomer having two or more double bonds and coated on the core layer, and a shell layer formed by a polymer graft polymerized on the core. The shell layer partially or entirely covers the surface of the rubber particle core by graft polymerizing a monomer to the core.

[0031] Generally the rubber particle core is constituted from acrylic or methacrylic acid ester monomers or diene (conjugated diene) monomers or vinyl monomers or siloxane type monomers and combinations thereof.

[0032] The shell layer provides compatibility to the formulation and has limited swellability to facilitate mixing and dispersion of the core shell rubber particles in the resin or hardener of the current invention. In one embodiment the shell does not have reactive groups towards the epoxy resin or the hardener of the present invention. Yet in another embodiment the shell might have reactive groups towards the epoxy resin or the hardener, for example epoxide or carboxylic acid groups.

[0033] The core shell rubber may be selected from commercially available products; for example, Paraloid EXL 2650A, EXL 2655, EXL2691 A, each available from The Dow Chemical Company, or Kane Ace® MX series from Kaneka Corporation, such as MX 120, MX 125, MX 130, MX 136, MX 551, or METABLEN SX-006 available from Mitsubishi Rayon.

Polymeric additives [0034] Polymeric additives can also be present in the curable composition. Examples of suitable polymeric additives include polyvinylformals (such as Vinylec K and Vinylec L from Chisso Corp.), polymethylmethacrylates (such as Dianal BR-73 and BR-80 from Dianal America Inc.), polyethersulfones (such as Sumika Excel 3600P and 5003P from Sumitomo Chemical Co. Ltd.), polysulfones (such as Ultrason S2010 from BASF), polyimides (such as Extern Resin VH1003 from Sabic Innovative Plastics), and polyetherimides (such as Ultem 1010 and ULTEM 1040 from Sabic Innovative Plastics).

[0035] The curable or thermosettable composition of the present invention may optionally contain one or more other additives which are useful for their intended uses. For example, the optional additives useful in the present invention composition may include reactive or non-reactive diluents, stabilizers, surfactants, flow modifiers, pigments or dyes, matting agents, degassing agents, flame retardants (e.g., inorganic flame retardants, halogenated flame retardants, and non-halogenated flame retardants such as phosphorus-containing materials), curing initiators, curing inhibitors, wetting agents, colorants or pigments, thermoplastics, processing aids, UV blocking compounds, fluorescent compounds, UV stabilizers, inert fillers, fibrous reinforcements, antioxidants, impact modifiers including thermoplastic particles, and mixtures thereof. The above list is intended to be exemplary. The preferred additives for the, formulation of the present invention may be optimized by one skilled in the art.

[0036] The curable composition can be prepared by any suitable method known to those skilled in the art, such as, for example, distillation or solvent extraction. The curable composition can then be mixed with a hardener, another epoxy resin, and any other component described above to form the curable composition in any combination or subcombination.

END USE APPLICATIONS

[0037] The curable composition can be used to prepare hot-melt prepregs, where fibers are impregnated with solvent free, un-cured or slightly cured epoxy formulations. A typical manufacturing procedure involves (1) film manufacture and (2) film impregnation. In film manufacture, the epoxy resin(s) are mixed at elevated temperature (eg., from 50-150°C) with additive(s), catalyst(s), hardener(s) and fabricated to the particular film format. The formulations are mainly in the pre-polymer state with a limited curing level (if any), and the films are protected by paper/polyethylene release sheets. In film impregnation, the woven or unidirectional fabrics are impregnated with the epoxy films under heat to form prepregs. Prior to the curing, the prepregs are somewhat similar to those sticky tapes covered with protective sheets. Once the protective sheets are removed, multiple layers or plies of the prepregs are stacked into a mold, or onto a mandrel to form the desired shapes of the composite articles. Then the prepreg materials undergo a thermal curing process under vacuum and/or pressure to consolidate the laminates. A higher curing temperature usually leads to rapid curing reaction kinetics, but may require additional mold-cooling time, which enables the consolidated laminates regain the sufficient stiffness for their removal from the hot molds.

[0038] In various embodiments, the prepregs prepared from the curable compositions have a glass transition temperature (Tg) that is equal to or greater than the final curing temperature when the prepreg is cured for less than two hours. In various embodiments, the curing conditions include a curing temperature in the range of from 80°C to 200°C. In various embodiments, the Tg is in the range of from 115°C to 215°C.

[0039] Tack is the property of a semi- permanent adhesive that allows it to adhere to another surface on immediate contact. With regards to tack, the desired complex shear modulus (G*) ranges from about 0.3 MPa to 0.03 MPa under 25°C, 1 rad/s. When G* is larger than 0.3 MPa, the uncured epoxy composition may lack of adequate wetting capability to attach to the adherent. When G* is smaller than 0.03 MPa, the uncured epoxy composition may lack of adequate shear resistance to hold the prepreg on the vertical adherent.

[0040] In an embodiment, prepregs are manufactured as follows: sheets of carbon-fiber fabric pre-impregnated with somewhat sticky, solvent-free, epoxy formulations are supplied in rolls. A silicone-treated paper and/or polyethylene protective sheet is sandwiched between the layers on the roll to prevent the pre-preg from sticking to itself during storage and to facilitate handling during the fabrication process.

[0041] The acceptable impregnation temperature ranges of the hot-melt (solvent free) prepreg fabrication from about 60°C to about 80°C, which is at least 20°C lower than the onset temperature of the exothermic curing reaction shown in Figure 1. Such impregnation temperature range is supposed to reduce the undesired epoxy gelation prior to the composite fabrication. The recommended processing viscosity level with the aforementioned temperature range is from about 10 to about 3 Pa*s, such that the fibers are still capable of being impregnated with the epoxy composition with a good fiber wetting, even with the presence of optional solid and viscous fillers, but without resin dripping.

[0042] Examples of uses for the composite articles that can be prepared with the hotmelt prepregs include sporting goods, aircrafts, and automobiles.

EXAMPLES

[0043] The following raw materials were used:

Experimental EPN - (E-EPN), high functional epoxy phenol novolac with averages in the range of from 4.0 to 5.0 epoxide groups per molecule (n=2.0 to 3.0 in Formula I above), with less than 5 weight percent based on the of 2.0 epoxide groups per molecule (2-functional). D.E.N.™ 438- ("DEN 438"), an EPN having an average of 3.6 epoxide groups per molecule, available from the Dow Chemical Company. D.E.N.™ 431- ("DEN 431"), an EPN having an average of 2.8 epoxide groups per molecule, available from the Dow Chemical Company. D.E.R.™ 662 -("DER 662"), a solid epoxy resin available from the Dow Chemical Company. D.E.R.™ 383 - ("DER 383"), a bisphenol A liquid epoxy resin available from the Dow Chemical Company.

Epon SU-8-("eBPAN"), epoxy bisphenol A novolac, a multifunctional epoxy, available from the Momentive. CG-1200- ("DICY"), dicyandiamide, a latent curing agent available from the Air Product and Chemical Inc. U415 M-("UREA"), 2,4-toluene bis dimethyl urea, a catalyst, available from the Emerald Performance, CVC Thermoset Specialities.

[0044] In Examples 1 and 2, DEN 431 was heated to 70°C and DICY and UREA were then added and mixed together by a SpeedMixer™ (DAC150.1 FVZ-K, FlackTeK Inc.) at 2,300 rpm for 2 min, at least three runs or more, to obtain the homogeneous blend, Blend-1. The E-EPN, DER 383 and DER 662 were heated to 120°C and were mixed by the above SpeedMixer™ at 2,300 rpm for 2 min, at least three runs or more, to obtain the homogeneous blend, Blend-2. Blend-1 was then poured into Blend -2, and the two blends were mixed together using the above-mentioned SpeedMixer™ at 800 rpm for 30 sec, and then at 1,600 rpm for 1 min to obtain a well-mixed formulation. The whole formulation was poured into a pre-heated mold (about 120°C) to cast the 3 mm thick plaques for further curing. The amounts of the components used in Examples 1 and 2 are shown in Tables 1 and 2, respectively.

[0045] In comparative examples A and B, DEN 431 was heated to 70°C and DICY and UREA were then added and the components were mixed using the above-mentioned SpeedMixer™ with 2,300 rpm, 2 min, at least three runs or more, to obtain the homogeneous blend, Blend-1. DER 383 and DER 662 and epoxy bisphenol A novolac (EBPAN) (EBPAN is used in Comparative Example B only) heated to 120°C and mixed together with the above SpeedMixer™ with 2,300 rpm, 2 min, at least three runs or more, to obtain the homogeneous blend, Blend-2. Blend-1 was then poured into the Blend -2, and the two blends were then mixed by the above SpeedMixer™ at 800 rpm for 30 sec, and then at 1,600 rpm for 1 min to obtain a well-mixed formulation. The whole formulation was poured into the pre-heated mold (about 120°C) to cast the 3 mm thick plaques for further curing. The components were used in the amounts shown in Table 1.

[0046] In comparative example C, DEN 431 was heated to 70°C and DICY and UREA were then added and the components were mixed using the above-mentioned SpeedMixer™ at 2,300 rpm for 2 min, at least three runs or more, to obtain the homogeneous blend, Blend-1. DEN 438 was heated to 120°C and was mixed with Blend-1 using the above SpeedMixer™ (DAC150.1 FVZ-K, FlackTeK Inc.) at 800 rpm for 30 sec, and then at 1,600 rpm for 1 min to obtain a well-mixed formulation. The whole formulation was poured out into the pre-heated mold (about 120°C) to cast the 3 mm thick plaques for further curing.

[0047] For Comparative Examples A and B and Example 1, the curing schedule used was 2 hours of 140°C isotherm curing in an air circulation oven.

[0048] For Example 2 and Comparative Example C, the curing schedule used was 2 hours of 160°C isotherm curing in an air circulation oven.

Table 1

(continued)

Table 2

Characterizations [0049] The functionality was determined by the GPC using a Viscotek GP Max equipped with a TDA 302 detector array which included a refractive index detector, a viscosity detector, and a RALLS (right angle laser light scattering detector). Separation was achieved using 2 PL gel 3um mixed E, 300 x 7.5 mm analytical columns. Tetrahydrofuran (THF), inhibited with 250 ppm BHT was used as the mobile phase. The sample was dissolved in mobile phase (1%) and filtered. The instrument was calibrated using Viscotek 115K polystyrene standards.

[0050] A differential scanning calorimeter (TA Instruments Q2000) was used for thermal analysis. The onset temperature of the exothermic curing reaction, Tonset, was obtained by conducting a temperature sweep of 2°C/min under nitrogen atmosphere (flow rate = 80 ml/min).

[0051] The dynamic mechanical thermal analysis (DMTA) was conducted by using an advanced rheometric expansion system (ARES G2, TA Instruments). The nominal dimension of the testing specimen was 12.7 mm x 3.0 mm x 40.0 mm. The testing temperature ranged from 25 to 250 °C and with a ramp rate of 3°C/min. The fixed testing frequency was 1Hz and the strain amplitude was 0.1%. The peak of tan δ was reported as the Cured Tg.

[0052] A rotational rheometer (AR2000 ex. TA Instruments) was used for the rheological study. The investigations were conducted by using a stainless steel parallel plate (50 mm diameter, gap=800 μ(η). The viscosity-temperature profile of the tested formulation was monitored with the fixed ramp rate, oscillation frequency and oscillation strain (2°C/min, 1Hz, and 0.5%, respectively). A frequency sweep (0.1 to 100 Hz) at 25°C was conducted to monitor the variation of the complex shear modulus for the tack measurement.

[0053] The fracture toughness (K|C) and flexure modulus were determined by following the testing guidance of ASTM D5045 and ASTM D790, respectively.

Claims 1. A curable composition comprising: a) an epoxy mixture comprising i) a first epoxy component comprising epoxy phenol novolac oligomers having a content of 2-functional monomers of less than 10 weight percent based on the total weight of the first epoxy and having an epoxide equivalent weight in the range of 170 to 200 ii) a second epoxy component comprising an epoxy resin having monomers with an average functionality of at least 2 wherein the first epoxy is present in the range of from 10 weight percent to 90 weight percent and the second epoxy is present in the range of from 0 weight percent to 97 weight percent, based on the total weight of the epoxy mixture; and b) a hardener. 2. A curable composition in accordance with claim 1 wherein the first epoxy component comprises less than 5 weight percent of 2-functional monomers based on the total weight of the first epoxy component. 3. A curable composition in accordance with claims 1 or 2 wherein thefirst epoxy component has an average functionality of from 4.0 to 5.0 epoxy groups per molecule. 4. A curable composition in accordance with any of the preceding claims wherein the first epoxy component has an average functionality of from 4.2 to 4.8 epoxy groups per molecule. 5. A curable composition in accordance with any of the preceding claims wherein the first epoxy component comprises less than 5 weight percent of 2-functional monomers, in the range of from 15 weight percent to 20 weight percent of 3-functional monomers, in the range of from 10 weight percent to 20 weight percent of 4-functional monomers, in the range of from 10 to 20 weight percent of 5-functional monomers, and in the range of from 50 weight percent to 60 weight percent of 6-functional monomers, based on the total weight of the first epoxy component. 6. A curable composition in accordance with any of the preceding claims wherein the hardener is selected from the group consisting of aliphatic amines, modified aliphatic amines, cycloaliphatic amines, modified cycloaliphatic amines, amidoamines, dicyanopolyamide, polyamide, tertiary amines, aromatic amines, anhydrides, mercaptans, cyclic amidines, isocyanate cyanate esters, phenolic hardeners and combinations thereof. 7. A curable composition in accordance with any of the preceding claims wherein the curable composition does not contain a solvent. 8. A curable composition in accordance with any of the preceding claims further comprising a catalyst. 9. A curable composition in accordance with any of the preceding claims having a complex shear modulus in the range of from 0.3 MPa to 0.03 MPa at conditions of under 25°C and 1 rad/s and a glass transition temperature (Tg) that is equal to or greater than the final curing temperature when the prepreg is cured for less than two hours. 10. A hot melt prepreg prepared from the curable composition of any of the preceding claims.

Patentansprüche 1. Härtbare Zusammensetzung, umfassend: a) eine Epoxidmischung, umfassend i) einen ersten Epoxidbestandteil, der Epoxyphenol-Novolak-Oligomere mit einem Gehalt an 2-funktionalen Monomeren von weniger als 10 Gewichtsprozent, bezogen auf das Gesamtgewicht des ersten Epoxids, und mit einem Epoxidäquivalentgewicht im Bereich von 170 bis 200, ii) einen zweiten Epoxidbestandteil, derein Epoxidharz mit Monomeren mit einer durchschnittlichen Funktionalität von mindestens 2 umfasst, wobei, bezogen auf das Gesamtgewicht der Epoxidmischung, das erste Epoxid im Bereich von 10 Gewichtsprozent bis 90 Gewichtsprozent vorliegt und das zweite Epoxid im Bereich von 0 Gewichtsprozent bis 97 Gewichtsprozent vorliegt, und b) einen Härter. 2. Härtbare Zusammensetzung nach Anspruch 1 .wobei der erste Epoxidbestandteil, bezogen auf das Gesamtgewicht des ersten Epoxidbestandteils, weniger als 5 Gewichtsprozent an 2-funktionalen Monomeren umfasst. 3. Härtbare Zusammensetzung nach Anspruch 1 oder 2, wobei der erste Epoxidbestandteil eine durchschnittliche Funktionalität von 4,0 bis 5,0 Epoxidgruppen pro Molekül aufweist. 4. Härtbare Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei der erste Epoxidbestandteil eine durchschnittliche Funktionalität von 4,2 bis 4,8 Epoxidgruppen pro Molekül aufweist. 5. Härtbare Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei der erste Epoxidbestandteil, bezogen auf das Gesamtgewicht des ersten Epoxidbestandteils, weniger als 5 Gewichtsprozent an 2-funktionalen Monomeren, im Bereich von 15 Gewichtsprozent bis 20 Gewichtsprozent an 3-funktionalen Monomeren, im Bereich von 10 Gewichtsprozent bis 20 Gewichtsprozent an 4-funktionalen Monomeren, im Bereich von 10 bis 20 Gewichtsprozent an 5-funktionalen Monomeren und im Bereich von 50 Gewichtsprozent bis 60 Gewichtsprozent an 6-funk-tionalen Monomeren umfasst. 6. Härtbare Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei der Härter ausgewählt ist aus der Gruppe, bestehend aus aliphatischen Aminen, modifizierten aliphatischen Aminen, cycloaliphatischen Aminen, modifizierten cycloaliphatischen Aminen, Amidoaminen, Dicyanpolyamid, Polyamid, tertiären Aminen, aromatischen Aminen, Anhydriden, Mercaptanen, cyclischen Amidinen, Isocyanatcyanatestern, phenolischen Härtern und Kombinationen davon. 7. Härtbare Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei die härtbare Zusammensetzung kein Lösemittel enthält. 8. Härtbare Zusammensetzung nach einem der vorhergehenden Ansprüche, ferner umfassend einen Katalysator. 9. Härtbare Zusammensetzung nach einem der vorhergehenden Ansprüche mit einem komplexen Schubmodul im Bereich von 0,3 MPa bis 0,03 MPa bei Bedingungen unter 25 °C und 1 rad/s und einer Glasübergangstemperatur (Tg), die gleich der oder größer als die endgültige Härtetemperatur ist, wenn das Prepreg für weniger als zwei Stunden gehärtet wird. 10. Aus der härtbaren Zusammensetzung nach einem der vorhergehenden Ansprüche hergestellter Heißschmelz-Pre-preg.

Revendications 1. Composition durcissable comprenant : a) un mélange époxy comprenant i) un premier composant époxy comprenant des oligomères époxy phénol novolac ayant une teneur en monomères difonctionnels de moins de 10 pourcent en poids sur la base du poids total du premier composant époxy et ayant un poids en équivalent époxyde dans la plage de 170 à 200 ii) un deuxième composant époxy comprenant une résine époxy ayant des monomères avec une fonctionnalité moyenne d’au moins 2, dans laquelle le premier composant époxy est présent dans la plage de 10 pourcent en poids à 90 pourcent en poids et le deuxième composant époxy est présent dans la plage de 0 pourcent en poids à 97 pourcent en poids, sur la base du poids total du mélange époxy ; et b) un durcissant. 2. Composition durcissable selon la revendication 1, dans laquelle le premier composant époxy comprend moins de 5 pourcent en poids de monomères difonctionnels sur la base du poids total du premier composant époxy. 3. Composition durcissable selon les revendications 1 ou 2, dans laquelle le premier composant époxy a une fonctionnalité moyenne de 4,0 à 5,0 groupes époxy par molécule. 4. Composition durcissable selon l’une quelconque des revendications précédentes, dans laquelle le premier composant époxy a une fonctionnalité moyenne de 4,2 à 4,8 groupes époxy par molécule. 5. Composition durcissable selon l’une quelconque des revendications précédentes, dans laquelle le premier composant époxy comprend moins de 5 pourcent en poids de monomères difonctionnels, dans la plage de 15 pourcent en poids à 20 pourcent en poids de monomères trifonctionnels, dans la plage de 10 pourcent en poids à 20 pourcent en poids de monomères tétrafonctionnels, dans la plage de 10 à 20 pourcent en poids de monomères pentafonc-tionnels et dans la plage de 50 pourcent en poids à 60 pourcent en poids de monomères hexafonctionnels sur la base du poids total du premier composant époxy. 6. Composition durcissable selon l’une quelconque des revendications précédentes, dans laquelle le durcissant est choisi dans le groupe consistant en amines aliphatiques, amines aliphatiques modifiées, amines cycloaliphatiques, amines cycloaliphatiques modifiées, amidoamines, dicyanopolyamide, polyamide, amines tertiaires, amines aromatiques, anhydrides, mercaptans, amidines cycliques, ester d’isocyanate cyanate, durcissants phénoliques et leurs combinaisons. 7. Composition durcissable selon l’une quelconque des revendications précédentes, dans laquelle la composition durcissable ne contient pas de solvant. 8. Composition durcissable selon l’une quelconque des revendications précédentes, comprenant en outre un catalyseur. 9. Composition durcissable selon l’une quelconque des revendications précédentes, ayant un module complexe de cisaillement dans la plage de 0,3 MPa à 0,03 MPa dans des conditions de moins de 25 °C et 1 rad/s et une température de transition vitreuse (Tg) qui est supérieure ou égale à la température de durcissement finale lorsque le pré-imprégné est durci pendant moins de deux heures. 10. Pré-imprégné thermofusible préparé à partir de la composition durcissable selon l’une quelconque des revendications précédentes.

Claims (3)

1. KEMÉNfftílETÖ EPÖXI KÉSEÍTMÉNYEK Szabadalmi igénypontok L fCeméayítitető készítmény, amely a kővetkezőket tartalmazza; ab egybpoxi keveréket, amely tartalmaz: ;) egy első epoxi-komponenst, amely tartalmaz epoxvfe«<>E«ovolik-#%omereket ahol az egy olyan bifunkeiós (kétionkeiős) monomer 'tartalommal rendelkezik, amely kisebb, mint 10 tőmegszázalék, az első epoxi^ompooensoék az össztőmegére vonatkoztatva, és egy olyan sípoxid-egyeialrtlktőömggei rendelkezik, amely a Π0-40Ι200-ig terjedő tartományban található, it) egy második époxi-komponenst, amely tartalmaz egy epoxi gyantát amely olyan monomerekkel rendelkezik, amelyek átlagos ő.mkciona!itása legalább 2, ahol az ólai ejmxi a 11) tömegszáza lék tői 90 tömegszázaiéklg terjedő tartományban van jelé», és a második epoxi a 0 tőmegszá2&amp;lektdl 9? tömegszáxalékig tetjeőő tartötnányhen van jelen, az epoxi-ke verébnek az őssztőmegere vonatkoztatva; és b) egy keményítőt
2. 2. Keményít beid készítmény az 1, igénypont szerint slel m első epoxidmnípooens kevesebb, mini 5 tömepzáztdek NfUnkvios (kértünk ms) monomert tartalmaz, a/ első epox hkompoímnsnek az összíömegére vonatkozóivá, &amp; Keményíthető készítmény az 1. vagy 2. igénypontok szerint ahol az. első epoxí-komponens egy olyan átlagos ímikuonaliblssal rendelkezik, amely 4,0461 $2>4g epoxb csoport moícknőmként, 4>. Keményíthető készítmény az előző igénypontok bénnelyike szerint, ahol az első epoxi-kompomns eg\ olyan athmox őmvommhussaí tcnneíkeztk. amely 4J^tőll4J4gepo«E csoport molekulánként.
3. 5, Keményíthető készítmény az előző igénypontok bármelyike szerint, ahol az első epoxi-komponens kevesebb, mint 5 iőmrgszázalék bi funkciós (kétíunkeiős) monomert, a 15 tömegszázaléktól 20 tőmegszázalékig terjedő tartományban ttibmkcíós (hámndtmkeiősl monomert, a 10 tdmegszá/aléktól 20 tőmegszázaléklg terjedő tartományba?} nitrátunkéi (négyfunkciős) monomert, a 10 tősnegszázaiéktől 20 tőmegszázalékig terjedő tartományban pentafunkciós (Őt funkciós) monomert és az 511 tőmepzázalektől őö tőmegszázaléklg terjedő tartományban hexafunkclős íhatfnnkelós) rnónotnert tartalmaz, az első epox (-komponensnek az ossztőmegére vonatkoztatva, #, Keményíthető készítmény az előző igényporttok bármelyike szerint, ahol a keményítő a kővetkezőkből állő csoport bői van választva; alifás atrbnpk, módosított áiíis aminek, eikloaíifás a minők, módosított cikloaíifás atomok, amido-antinok, diciano-poíiamid, poiíamid, tercier aminek, aromás aminok, aalddridek, mérkaptánok, ciklusos mrádinek, tsocínnát-einríát-észterbk, lenoíos keményítők é$ azok kombinációi. f, Keményíthető készítmény m előző igénypontok bármelyike szedni, ahol a keményíthető készítmény nem tartalmaz oldószert, $. Keményíthető készítmény az előző lgét$ypontok bármelyike szerint, amely továbbá tartalmaz egy katalizátort %. Keményíthető készítmény az előző igénypontok bármelyike szerint, amely egy olyan komplex nyitási modulussal (angolul: „contplcx sfcear modulus”) rmddkezik, amely a 'λ3 MPa-iói 0,03 MPa-ig terjedő tartományban található, 250€ és I tad/s alatti körülmények között, és egy olyan üvegesedé·*? átmeneti hőmérsékletté! (Tg, angolul: „gkss transition temperature’') rendelkezik, amely egyenlő' a végleges keményítési hőmérséklettel (angolul: „final curing temperature") vagy annál nagyobb, amikor ív prepreg kevesebb, mint két óráig van keményítve. !i< Hím-ón olvasztott (tőrré olvadék módszerrel előállított, angolul „hot. melt'd prepreg, amely az előző igénypontok bármelyike szerinti keményíthető készítményből vaut előállítva.