resin system, composite material, and, method to retain the morphology of the ilt thermoplastic poly

专利摘要:
RESIN SYSTEM, COMPOSITE MATERIAL, AND, METHOD FOR RETENTING THE MORPHOLOGY OF ILT THERMOPLASTIC POLYAMIDE PARTICLES AND / OR REDUCING OR ELIMINATING MI-CROFISSURES AND / OR COMPRESSION PERFORMANCE IN A CURED RESIN A resin system containing: (i) a component of a resin of a thermosetting resin precursor comprising one or more multifunctional epoxy resin precursors having a functionality of at least three, preferably wherein said precursors are selected from a trifunctional epoxy resin precursor and / or a tetrafunctional epoxy resin precursor, ( ii) a thermoplastic polyamide particle component in which the polyamide particles have a melting temperature TPA; and (iii) one or more curing agents, in which the resin precursor component, the thermoplastic particle and curing agents are selected so that the gelation of the epoxy matrix during the curing cycle of the resin system occurs at a TGEL gelation temperature which is at or below TPA.
公开号:BR112015008662B1
申请号:R112015008662-4
申请日:2013-11-01
公开日:2021-01-05
发明作者:Vincent J.J.G. Aerts；Mark Bonneau；Judith ELDER；Emiliano Frulloni；James Martin Griffin
申请人:Cytec Industries Inc.；
IPC主号:

专利说明:

[001] The present invention relates to composite materials comprising thermoplastic interlaminating (ILT) hardening particles to provide morphological stabilization and to reduce or eliminate microfissures during curing. FUNDAMENTALS
[002] Composite materials comprising fiber-reinforced thermosetting resins are used in the manufacture of load-bearing components suitable for use in transport applications (including aerospace, aeronautical, nautical and land vehicles) and in construction applications. Thermosetting materials such as cured epoxy resins are known for their thermal and chemical resistance. They also have good mechanical properties, but often lack strength and tend to be very fragile. This is especially true as the crosslinking density increases or the monomer functionality increases above two.
[003] For high performance applications, the composite material comprising a continuous resin matrix and continuous reinforcement fibers is typically used in the form of a pre-preg, in which the reinforcement fibers are pre-impregnated with a controlled amount of uncured resin, which is suitable for molding and curing for the final composite part. The reinforcement fibers can be woven in a multidirectional fabric or oriented in parallel in a unidirectional (UD) ribbon. In the aerospace industry, prices are the preferred materials for critical load-bearing applications, including, but not limited to, wings and fuselage, which at the same time require high specific strength, impact resistance, and damage tolerance.
[004] In general terms, the mechanical performance of the cured composite is a function of the individual properties of the reinforcing fiber and the matrix resin, and the interaction between these two components. The resin content is also an important factor.
[005] The mechanical performance of pre-preg systems is usually measured in terms of tensile performance (open hole tensile strength (OHT)), compression performance (open hole compression strength (OHC)), resistance to impact (compressive strength after impact (CSAI)) and damage tolerance (GI / IIC: resistance to interlaminar fracture in mode I and mode II, respectively).
[006] Another important property of pre-preg systems is the performance of hot-humid compression (resistance to hot-humid open hole compression (HW-OHC)), which is why the OHC resistance decreases at temperatures after prolonged exposure to moisture. The OHC resistance of existing pre-preg systems is usually quite constant below room temperature (for example, from room temperature (21 ° C) to about -55 ° C), but it can get significantly worse at elevated temperatures (for example , 70 ° C) when saturated with moisture.
[007] In many applications, it is desirable to maximize tensile strength. Unfortunately, the increase in OHT resistance is generally accompanied by a decrease in OHC resistance, and in particular, HW-OHC resistance, which is a critical design value for aerospace applications. Likewise, the increase in HW-OHC resistance is generally accompanied by a decrease in OHT resistance, but more importantly, it generally impacts negatively on impact resistance (CSAI) and / or damage tolerance (GI / IIC) which are requirements critical to critical flight parts in aerospace applications.
[008] In order to improve CSAI and GI / IIC performances of pre-preg systems, two main strategies have been used over the last few decades: increasing the hardness of the intrinsic resin and hardening of the interlaminar region.
[009] To improve the hardness of the intrinsic resin, the addition of rubber and / or thermoplastic to the resin formulation has been used for many years. For example, US 3,926,904 and US 4,500,660 disclose that functionalized acrylonitrile-butadiene rubbers are efficient hardening agents for epoxy resin systems. These rubbers were initially shown to be soluble in uncured epoxy resin systems and undergo RIPS (reaction-induced phase separation) during curing to form rcrtiewncu tkecu go dqttcejc “kp situ” pqu ukuVgocu ewtcfqUo Godqtc guVcu rubbers have been proven effective agents hardening, they generally decreased the HW-OHC resistance of pre-pregs, which limited their use for aerospace applications.
[0010] Alternatively, US 4,656,207 discloses that thermoplastics, such as polyethersulfones, could advantageously be used instead of the aforementioned rubbers to increase the hardening of epoxy resin systems without significant loss of hot-wet performance. This makes these thermoplastics the preferred hardening agents for epoxy resin systems for aerospace applications. Like the aforementioned rubbers, these thermoplastics are initially soluble in uncured epoxy resins and subsequently undergo RIPS during curing.
[0011] Regarding the targeted hardening of the interlaminar region itself, US 3,472,730 discloses that the interleaving of the reinforcement fiber layers with a rubber-hardened resin system can significantly improve the impact resistance of the pre-pregs. Hirschbuehler et al. US 4,539,253 also discloses that a key aspect to achieve high impact resistance is the maintenance of the integrity of this discrete interlaminar layer (also known as interlayer). Hirschbuehler et al. discloses that continuous or light discontinuous fibrous mats or diffusers can be used to control the integrity of this interlaminar region, providing pre-pregs with better impact resistance and damage tolerance. However, the use of rubber as a hardening agent in the interlaminar layer significantly impacted the hot-humid performances.
[0012] US 4,783,506 and US 4,999,238 disclosed another approach to enhance the impact resistance through the insertion of infusible rubber particles with a diameter between 10 to 75 microns in the interlaminar region. These rubber particles were large enough to be filtered on the surface of the reinforcement fiber layer during the manufacture of pre-pregs. Although infusible, they were capable of swelling in the resin. US 5,266,610 and US 6,063,839 disclose core-shell rubber particles for the same purpose.
[0013] Evans et al. US 4,604,319 showed that by concentrating thermoplastic in the interlaminar layer instead of rubber as a hardening agent, impact resistance can be improved without significant impact on hot-humid performances. According to this concept, Evans et al. disclosed the use of a thermoplastic interlaminar layer, the latter optionally comprising up to 40% by weight of a modifying thermosetting resin system. The thermoplastic can be selected from a range of engineering thermoplastics such as polyamide, polyimide or imide polyester. In addition, Evans et al also discloses the potential use of reinforcement additives in the thermoplastic interlaminar layer as a diffuser, chopped fibers and particulates.
[0014] US 5,276,106 discloses the use of soluble thermoplastic particles that would remain mainly insoluble at pre-preg manufacturing temperatures, but would later dissolve in the resin system at curing temperatures. These particles are large enough to be filtered on the surface of the reinforcement fibers during manufacture and their dissolution occurring during curing enriches the layer interspersed in the thermoplastic. The use of thermoplastic in the form of particles, instead of an interleaved layer, provides much better grip and fit. These thermoplastic particles can be selected from a range of amorphous thermoplastics, having a Tg above 140 ° C, such as polyether sulfone or polyether imide.
[0015] In US 4,957,801, Maranci et al. discloses the use of insoluble thermoplastic particles. Thermoplastic particles comprise between 20% and 80% by volume of the interlaminar region and are characterized by a diameter ranging from 2 to 100 microns. These particles remain insoluble during the pre-preg manufacture and the curing cycle and are large enough to be filtered on the surface of the reinforcement fiber layer. The insolubility of these thermoplastic particles helps to maintain the integrity of a discrete interlaminar layer to achieve greater impact resistance. These thermoplastic particles can be selected from a range of engineering thermoplastics such as polyether sulfone, polyamide or polyimide.
[0016] In US 5,242,748, Folda et al. discloses the use of polyimide which must remain insoluble at the processing temperature but must swell or partially dissolve at the curing temperature, maintaining a certain integrity. Folda et al discloses that if partial dissolution or swelling does not occur, or if complete dissolution occurs as proposed by Turpin in US 4,954,195, only a minor increase in impact strength will be achieved.
[0017] In WO-2010/136772, Baidak et al. discloses the use of partially cross-linked polyether sulfone particles to better control the swelling and partial dissolution of the thermoplastic particles while maintaining the integrity of the particle during curing.
[0018] Polyamide particles are also exploited for their hardening capacity. US 5,028,478 discloses the use of transparent amorphous polyamide particles. In US 5,169,710 and US 5,268,223, Qureshi et al. discloses the use of porous polyamide particles. US 7,754,322 discloses the use of a mixture of non-amorphous polyamide particles, one having a melting temperature above the curing temperature and the other having a melting temperature at or below the curing temperature.
[0019] In US 5,087,657, Qureshi et al. discloses the use of polyphenylene ether thermoplastic particles. However, experience has shown that these thermoplastic particles are prone to micro-cracking that greatly limits their applicability.
[0020] Microfissures can occur within thermoplastic or at the interfaces between the thermosetting resin matrix and a thermoplastic component of the resin system (ie, disconnection between the matrix and the thermoplastic domain). Resistance to micro cracking is another key property of pre-pregs. Microcracks tend to be associated with reduced fatigue resistance and reduced fluid resistance since the presence of microcracks increases the percolation paths for, for example, moisture or solvent.
[0021] Another important property of pre-preg systems is their “xkfc gzVgmc”. swg §u xgzgu fi tguqnxkfc go woc “ocpkrwnc>« q fg xkfc gzVgmc ”g woc“ ogeâpkec fg xkfc gzVgmc ”External life manipulation is the period of time in which an uncured pre-preg can be stored at room temperature ( around 21 ° C) and maintain sufficient adhesion. Uncured “cfgtêpekc” fg wo rtg-preg is a measure of an uncured pre-preg's ability to adhere to itself and to shape surfaces, and is an important factor during molding and laying operations, where pregs are formed in laminates that are subsequently cured to form the composite part. External life mechanics is the period of time that an uncured pre-preg can be stored at room temperature (around 21 ° C) and maintain sufficient flow to allow the manufacture of composite parts of acceptable quality.
[0022] The standard and preferred pre-preg curing agent based on go gr „zk rctc crnkec> õgu cgtqgurcekcku fg cnvq fgugorgpjq fi 6.6" - diaminodiphenyl sulfone (DDS), which is known to offer good OHT resistance performance at the same time, CSAI and GI / CII in relation to other healers, as well as good external life.
[0023] While some conventional pre-preg systems containing crystalline polyamide particles were able to increase impact resistance (CSAI) and damage tolerance (GI / IIC) simultaneously, this negatively affected hot-humid compression performance (OHC resistance). Other pre-preg systems have optimized compression performance (OHC resistance) at the expense of impact resistance (CSAI) and damage tolerance (GI / IIC). In conventional resin systems, it has proved to be extremely difficult to optimize these aspects simultaneously. It would be desirable to maximize the compression performance without prejudice to at least CSAI, and preferably, without detriment to CSAI and GI / IIC.
[0024] Another problem with conventional resin systems comprising crystalline polyamide particles is the degree to which mechanical performance may be dependent on the rate of temperature ramp used during curing. In particular, the inventors observed that the mechanical performance, morphology and micro-cracking in these systems depend heavily on the cure rate used during the manufacture of the pre-preg laminates. This temperature dependence is very disadvantageous, particularly for large structures, and this lack of robustness in the process greatly limits the use of particles as interlaminate hardening agents in conventional pre-pregs, despite the attractiveness of these ILT particles in terms of improving CSAI and GI / IIC. It would be highly desirable to provide a resin system that cures in substantially the same manner over a range of temperature ramp rates.
[0025] Thus, pre-pregs having excellent or improved impact resistance and damage tolerance combined with excellent or improved compression performances would present a useful advance in the technique, particularly if the morphology necessary to achieve these performances can be maintained over a period of time. wide range of process conditions, which would eliminate the need for an impractical degree of control during part manufacturing, as well as ensuring performance reliability. These improved pre-pregs could find rapid acceptance, particularly in the aerospace industry, displacing today's less robust pre-preg systems. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] FIG. 1 provides DSC thermograms showing the “mpqemfqyn” effect fc rtgugn> c fc tguknc gr „zk o-TGAP on the melting peak of a polyamide particle.
[0027] FIGS. 2 and 3 are optical microscopy images showing the cross-sectional views of composite laminates prepared according to an example.
[0028] FIGS. 4A, 4B, 5A, 5B, 6A, 6B, 7A, 7B are optical microscopy images showing the cross views of composite laminates prepared according to another example.
[0029] FIG. 8 shows the viscosity profiles (continuous lines) and DSC thermograms (dashed lines) for three resins prepared according to another example DETAILED DESCRIPTION
[0030] It is an object of the present invention to provide a composite material exhibiting excellent or better compression performance (OHC resistance), particularly hot-humid OHC resistance, without significant detriment to CSAI performance and / or GI / IIC performance, particularly where a microfissure in the interlaminar region is reduced or eliminated.
[0031] It is another object of the present invention to provide a composite material exhibiting excellent or improved CSAI performance simultaneously with excellent or improved GI / IIC performance without significant damage to the compression performance (OHC resistance), particularly hot-wet OHC resistance, particularly in that microfissure in the interlaminar region is reduced or eliminated.
[0032] Thus, it is another object of the present invention to provide a composite material exhibiting excellent or improved CSAI performance simultaneously with excellent or improved GI / IIC performance in combination with excellent or improved compression performance (OHC resistance), particularly hot-wet OHC resistance , particularly where microfissure in the interlaminar region is reduced or eliminated.
[0033] It is another object of the present invention to provide a resin system comprising ILT particles that is capable of providing this mechanical performance in which the dependence on the temperature ramp rate normally used during curing is reduced or eliminated.
[0034] Accordingly, the present invention provides a resin system comprising: (i) a thermoset resin precursor component comprising one or more multifunctional epoxy resin precursors having a functionality of at least three, preferably wherein said precursor is selected from a tri-functional epoxy resin precursor and / or a tetrafunctional epoxy resin precursor; (ii) a thermoplastic particle component comprising particles having a melting temperature TPA; and (iii) one or more curing agents, wherein said resin precursor component, said thermoplastic particle and said curing agent are selected so that the gelation of the epoxy matrix during the curing cycle of the resin system occurs at a TGEL gelling temperature that is at or below TPA.
[0035] Thus, for a resin system that is thermally curable using a TC cure temperature, which is achieved with an RCR cure rate, gelation of the epoxy matrix during the cure cycle occurs at a TGEL gelation temperature which is at or below TPA, particularly for RCR cure rate up to about 3.0 ° C / min (particularly up to about 2.5 ° C / min, and in a mode up to about 2.0 ° C / min, and particularly in the range of 0.05 ° C / min to 3.0 ° C / min, particularly in the range of 0.05 ° C / min to 2.5 ° C / min, and in a mode in 0.05 ° C / min to 2.0 ° C / min), particularly for TC cure temperatures in the range of 140 ° C to 200 ° C (particularly from 160 ° C to 195 ° C, and more preferably from 170 ° C to 190 ° C). Preferably, the RCR cure rate is at least about 0.1 ° C / min, and preferably at least 0.5 ° C / min. Preferably, the gelation of the epoxy matrix during the curing cycle of the resin system occurs at a TGEL gelation temperature below TPA.
[0036] The particular combination of the resin system components of the present invention provides morphology stabilization and resistance to micro-cracking, which is surprisingly insensitive to the temperature ramp rate during curing (as used, for example, during part manufacturing) . Thus, the resin systems of the present invention allow processing at the high and low cure rate (and, particularly, at the RCR cure rate mentioned above), thus providing robustness to the process.
[0037] In particular, the combination of a highly cross-linked epoxy resin matrix with a relatively high reactivity curing agent has been shown to reduce or eliminate the temperature ramp rate dependency on interlaminar morphology, in a way that stabilizes and preserves particulate morphology (which is used here to refer to the mechanical integrity and particle shape) of the polyamide ILT particles and reduces or eliminates micro-cracking, even when cured at a high heating rate (for example, up to about 3.0 ° C / min ).
[0038] The combination of highly cross-linked epoxy resin matrix with a relatively high reactivity curing agent promotes gelation of the resin matrix before any melting of the polyamide particle during curing, which the inventors believe is the essential mechanism in the establishment particle morphology and reducing / eliminating micro cracks, even at high temperature ramp rates. Thus, the use of a curing agent with relatively high reactivity in combination with the formulation of a highly cross-linked system is capable of achieving the object of the present invention.
[0039] The resin systems containing particles of the present invention maintain the excellent mechanical performance in terms of CSAI and GI / IIC, offering improved OHC, in particular HW-OHC and reducing or eliminating the temperature ramp rate dependence during curing , thus providing the significant advantage of the robustness of the process in terms of morphology and microfissure.
[0040] According to the general meaning of the term in the art, the term TGEL gelling temperature (also referred to here as gel temperature or gel point) is the temperature at which the viscosity of the resin system tends to infinity, and can be identified by dynamic rheology. In a preferred embodiment of the present invention, the term TGEL gelling temperature is taken to be the temperature at which the viscosity of the ukuVgoc fg tgukna cVkPig 3222 Ra * Uo Go wo pixgn oqngewnct. gelation is the incipient formation of a reticulated network, and a thermosetting resin loses its ability to flow above its gel point. The kinetics of gelation depends on the functionality, reactivity and stoichiometry of the reagents, and can be modulated by the temperature profile of the curing cycle. Thus, for example, increasing the functionality of an epoxy resin precursor will increase the crosslink density, usually leading to an earlier gelation, all other factors being equal. Likewise, the increase in the stoichiometry of the curing agent in relation to the amount of epoxy resin precursor (for example, from 0.9 to 1.0), usually results in an earlier gelation. The macroscopic consequence of gelation is the rapid approach to infinite viscosity, and it is the viscosity that can be measured to identify the gel point. In a dynamic rheology measure, the point fg ign fi q etwzcogpVq fqu o „fwnqu xkueququ * I” + g gnáuVkequ * ff + Cuuko. I7I ’@ 3 fgfmg wo eqorqrtcogpVq xkuequq (liquid): q rqpVq fg ign fi definkfq eqoq c VcPigpVg fg rgtfc * Van h + I7I ’ 3 = g I7I '> 3 fgfmg q elastic behavior (solid). The thermoplastic particle component
[0041] The resin systems of the present invention achieve a high concentration of thermoplastic particles locally in the interlaminar region, thus increasing the hardening of the pre-preg laminate. The particles can be detected using scanning electron microscopy (SEM) or optical microscopy.
[0042] The combination of the components of the resin system of the present invention promotes gelation of the resin matrix before the melting of the thermoplastic polyamide particles, even at high cure rate. The thermoplastic particles described here for use in the resin systems of the present invention remain insoluble in the epoxy resin matrix during the curing cycle and maintain their initial particle morphology, which increases the tolerance to hardening and damage of the thermosetting resin and composite material. The particles retain their mechanical integrity during the process of mixing, curing and maintaining the resin and pre-preg. The prevention of coalescence of the fused polyamide particle within the epoxy matrix reduces or eliminates the formation of micro-fissures at the particle / matrix interface. In addition, the retention of discrete polyamide particles instead of a continuous phase or coalesced polyamide mesh is beneficial for the hot-wet performance of the cured resin.
[0043] The amount of thermoplastic particles in the resin system is preferably in the range of about 2.5 to about 30% by weight, more preferably in the range of about 5 to 25% by weight, relative to the total weight of the resin system (ie the total weight of the thermosetting resin precursors, the ILT thermoplastic particles, curing agents and any optional additional hardening agents).
[0044] The thermoplastic particles used in the resin system preferably have an average particle size of about 2 to about 75 μm, preferably about 5 to about 50 μm and usually preferably about 10 to about 30 μm.
[0045] Thermoplastic polyamide particles are suitably prepared from an aliphatic polyamide selected from polymers of n-polyamide-n, m, where neither are independently selected from 10, 11 or 12. Thus, polyamide is preferably selected from polyamide-10, polyamide-10.10, polyamide-11, polyamide-11.11, polyamide-12, polyamide-12.12 and polyamide-10-12, and more preferably polyamide-11, polyamide-12 , polyamide-10.10 and polyamide-10.12. In a preferred embodiment, polyamide is selected from polyamide-10,10 and polyamide-12 and particularly polyamide-12. In one embodiment, only one type of polyamide from the above list is present in the thermoplastic polyamide particle component. Preferably, the aforementioned thermoplastic polyamide material is the only thermoplastic polyamide present in the thermoplastic polyamide particle component.
[0046] The aliphatic polyamides used in the present invention have increased sensitivity to moisture, for example, in relation to the highest melting point of polyamide-6, polyamide-6.6, polyamide-6.10 and polyamide-6.12. However, the polyamides used in the present invention tend to have a lower effective melting temperature than polyamide-6, polyamide-6.6, polyamide-6.10 and polyamide-6.12 and those effective melting temperatures more low overlap with the curing temperature range normally used for epoxy resins, which can result in coalescence of the polyamide within the epoxy resin matrix during the curing cycle and the formation of a continuous or semi-continuous polyamide network within the resin matrix. As noted above, the inventors noted that this morphology results in microfissure and is detrimental to the hot-wet compressive performance. However, the present inventors have found that the advantageous properties of these polyamides can be used to facilitate gelation of the epoxy matrix prior to any melting of the polyamide during a curing cycle, thereby maintaining particulate morphology. The inventors believe that, once the resin matrix reached the gel point during the curing cycle, the rigid structure of the resin matrix substantially restricts the expansion of the melting polyamide particles at temperatures above the gel point subsequently experienced during the healing cycle. Therefore, during the cooling phase of the curing cycle, cooling the molten polyamide does not result in shrinkage of the discrete polyamide phases that would otherwise result in micro cracks or cavities being generated for the polyamide / epoxy interfaces.
[0047] In addition, the polyamides used in the present invention result in composite materials with superior compression performance, damage tolerance and impact resistance (CSAI), for example, compared to polyamide-6 (which is characterized by a much higher fusion).
[0048] The molecular weight of the polyamide is typically in the range of about 2,000 to about 60,000 g / mol, suitably in the range of about 5,000 to about 50,000 g / mol.
[0049] The melting temperature (TPA) of the polyamide particles is preferably at least about 160 ° C, preferably at least about 165 ° C, and preferably not more than about 200 ° C. In a preferred embodiment, the melting temperature (TPA) of the polyamide particles is not less than 30 ° C below the nominal cure temperature, preferably not less than 20 ° C below the nominal cure temperature, preferably not less than than 10 ° C below the rated curing temperature. Preferably, the melting temperature (TPA) of the polyamide particles is no more than 20 ° C above the nominal curing temperature, and in one embodiment it is no more than the nominal curing temperature. Preferably, all thermoplastic particles in the resin system have a melting temperature (TPA) that is more than 20 ° C above the rated cure temperature, and in one embodiment, no more than the rated cure temperature.
[0050] Eqoq wucfq cswk. q Vgtoq “VeoretcVutc fg fuu« q * VPA) from rqnkcokfc ”is effected at the effective melting temperature which is defined here as the position in degrees Celsius of the endothermic melting peak present in the DSC thermogram (acquired at 10 ° C / min under nitrogen) of a mixture of 25% by weight of the polyamide in meta-substituted tri-glycidyl amino phenol (m-TGAP; available as Araldite® MY0610 from Huntsman). This measurement of TPA is illustrated in FIG. 1. The skilled person will therefore appreciate that the effective melting temperature is different from the intrinsic melting temperature Tm of the polyamide which is defined as the position in degrees Celsius of the endothermic melting peak present in the DSC thermogram of the polyamide itself. The effective melting temperature is typically 5 to 15 ° C below the intrinsic melting temperature Tm, as illustrated in Table (A) below. Table (A)

[0051] Ugtá crtgekcfq rgnq gurgekcnkuVc swg q Vgtoq “VeoretaVwta fg ewtc pqokpal” is set at the programmed curing temperature of the curing cycle. The cure temperature TC as used here refers to the rated cure temperature.
[0052] As noted above, the gelation of the epoxy matrix during the curing cycle occurs at a TGEL gelation temperature that is at or below TPA, and is preferably below TPA. Preferably, TGEL is at least 5 ° C, preferably at least 10 ° C, less than TPA. Preferably Tgel is no more than 200 ° C, when measured with a 2 ° C / min reference ramp.
[0053] The aliphatic polyamide particles used in the resin system of the present invention are preferably crystalline or semi-crystalline, that is, non-amorphous. A crystalline or semi-crystalline polymer is defined here as one having a degree of crystallinity of at least 5%, preferably at least 10%, as measured using differential scanning calorimetry (DSC).
[0054] The polyamide particles mentioned above can be pure, that is, the particles can consist or consist essentially of said polyamide material. Alternatively, the aforementioned polyamide particles can be formulated, that is, the particles comprise polyamide material and further comprise additives, such as fillers or other functional additives.
[0055] The thermoplastic polyamide particles can be manufactured by any conventional method known in the art, for example, by anionic polymerization, by coextrusion, precipitation polymerization, emulsion polymerization or cryogenic grinding. Thermoplastic polyamide particles are also commercially available, for example, XguVqukpV ™ * Gxqpkm +. TüucpTM * Ctmgoc + qw Qticuqn ™ * Ctmgoc + o The thermosetting resin precursor
[0056] The resin system of the present invention comprises one or more multifunctional epoxy resin precursors having a functionality of three or more, preferably selected from an epoxy resin precursor having three epoxide groups per molecule and / or a precursor of epoxy resin having four epoxide groups per molecule. In one embodiment, said epoxy resin precursors are selected from multifunctional epoxides having three, four or more epoxide groups per molecule. The epoxy resin precursor is suitably liquid at room temperature. The epoxy resin precursor can be saturated, unsaturated, cycloaliphatic or heterocyclic. In one embodiment, the precursor comprises a phenyl meta ring substituted in its structure.
[0057] Suitable multifunctional epoxy resins include: epoxy phenol and cresol novolacs; glycidyl ethers of phenolaldehyde adducts; aromatic epoxy resins; dialytic triglycidyl ethers; aliphatic polyglycidyl ethers; epoxidized olefins; brominated resins; aromatic glycidyl amines and glycidyl ethers; heterocyclic imidines and glycidyl amides; glycidyl ethers; fluorinated epoxy resins; and combinations thereof.
Preferred epoxy resin precursors include glycidyl derivatives of one or more of the group of compounds consisting of aromatic diamines, aromatic monoprimary amines, aminophenols, polyhydric phenols, polyhydric alcohols, polycarboxylic acids and the like, or a mixture of the same.
[0059] Preferred epoxy resin precursors are selected from: a. bisphenol A glycidyl ethers, bisphenol F, dihydroxydiphenyl sulfone, dihydroxybenzophenone and dihydroxy diphenyl; B. epoxy resins based on novolacs; and c. glycidyl functional reaction products of m- or p-aminophenol, m- or p-phenylene diamine, 2,4-, 2,6 or 3,4-vqnwkngpq "fkcokpc." 5.5Ó- qw "6.6Ó- diaminodiphenyl methane, wherein the epoxy resin precursor has three or four, and in one embodiment at least three epoxy groups per molecule.
[0060] Particularly preferred epoxy resin precursors are selected from O, N, N-triglycidyl-para-aminophenol (TGPAP); O, N, N-triglycidyl-meta-cokpqhgpqn "* VIOCR + =" g "P.P.PÓ.PÓ-tetraglycidyldiaminodiphenyl methane (TGDDM).
[0061] The proportion of active hydrogen equivalent in the curing agent to epoxy equivalent, known as stoichiometry, is preferably in the range of 0.5 to 1.5. More preferably, the stoichiometry is in the range of 0.75 to 1.25.
[0062] Commercially available epoxy resin precursors crtqrtkcfqu rctc wuq pc rtgugpVg kpxgp> 'q kpenwgo P.P.pó.pó-tetraglicidil diamino diphenylmethane (e.g. MI 9663, MI 720 or MI 721; Ciba-Geigi); P.P.PÓ.PÓ-tetraglycidyl-bis (4-aminophenyl) -1,4-diiso-rtqrüdgpzgpq * rqt gzgornq. GRQP 3293 = Ujgnn Ejgokecn Eqo + = P.P.pó.po-tetraclycidyl-bis (4-amino-3,5-dimethylphenyl) -1,4-diisopropylbenzene, (for example, EPON 1072; Shell Chemical Co.); triglycidyl ethers of p-aminophenol (for example, MI 0510; Ciba-Geigi); triglycidyl ethers of m-aminophenol (for example, MI 0610; Ciba-Geigi); glycidyl ethers of Novolac phenol resins (for example, DEN 438 or DEN 439; Dow); phenolic novolac based on cyclopentadiene (eg, Tactix 556, Huntsman).
[0063] The present invention can use a mixture of epoxy resin precursors of a certain functionality, that is, one or more epoxy resin precursors having three epoxide groups per molecule (hereinafter referred to as P3 precursors), and / or one or more epoxy resin precursors with four epoxide groups per molecule (hereinafter referred to as P4 precursors) and / or one or more epoxy resin precursors having more than four epoxide groups per molecule (hereinafter referred to as PP precursors).
[0064] In one embodiment, only P3 precursors are present. In an alternative embodiment, only P4 precursors are present. In another embodiment, P3 precursors and P4 precursors are present, and in one embodiment, the resin precursor component comprises: a. from about 5 phr to about 95% epoxy resin precursors (P3); and b. from about 5 phr to about 95 epoxy resin precursors (P4), where the phr amounts are the parts in grams of said resin precursor per hundred grams of the total resin precursor component (ie excluding curing agents, curing agents, and other additives).
[0065] In one embodiment, the resin system does not contain epoxy resin precursors with a functionality of less than three, that is, it does not contain monofunctional or bifunctional epoxy resin precursor components (two or a functional epoxy group, respectively), in order to maximize the hot-humid performance of the cured resin. If monofunctional and / or bifunctional epoxy resin precursors are present, then the total amount of these precursor components is preferably less than 10% by weight, preferably not more than 7.5% by weight, preferably not more than 5% by weight, preferably not more than 2.5% by weight, preferably not more than 1% by weight, preferably not more than 0.5% by weight, preferably not more than 0.1% by weight, in relation to the total weight of the resin (ie, the combined weight of the thermosetting resin precursor component, the thermoplastic particle component, curing agents and optional curing agent component or other additives, in other words, Vgtoq “ukuVeoc fg yoursinc” fi wucfq cswk rctc ug tefetkt c woc eqorquk> "q swg excludes reinforcing agents. Preferably, the thermosetting resin precursor component comprises not more than 1% by weight, preferably not more than 0.5% by weight, preferably not more in 0.1% by weight of said epoxy resin precursors with a functionality of less than three, in relation to the total weight of the thermosetting resin precursor component.
[0066] Preferably, the amount of thermosetting resin component in the resin system is in the range of about 20 to about 80% by weight, more preferably in the range of about 30 to about 70% by weight, with respect to the total weight of the resin system (ie the total weight of the thermosetting resin precursors, the ILT thermosetting polyamide particles, the curing agents and any additional optional curing agents or other additive). The healing agent.
[0067] The resin system of the present invention can be cured by conventional means, for example, autoclave or infrared radiation or microwave, and must be thermally curable. The addition of one or more curing agents increases the curing rate and / or reduces the curing temperatures. In one embodiment, one or more catalysts can also be used.
[0068] Curing agents are well known in the art, and are disclosed in, for example, EP-A-0311349, EP-A-0486197, EP-A-0365168 or in US-6013730, which are incorporated herein by reference. Known curing agents include an amino compound having a molecular weight of up to 500 per amino group, for example, an aromatic amine or a guanidine derivative. An aromatic amine curing agent is of particular utility for epoxide resin systems, particularly aromatic amines having at least two amino groups per molecule and particularly diaminodiphenyl sulfones, for example, where the amino groups are in the meta- or para- position tgnc> «q cq itwrq uwnfopCo Gzgornqu rcrtkedctgu u« q 5,5'- and 4-.6'1- diaminodiphenylsulfone (DDS); methylenedianiline; bis (4-amino-3,5-dimethylphenyl) -1,4-diisopropylbenzene (available as EPON 1062 from Shell Chemical Co.); bis (4-aminophenyl) -1,4-diisopropylbenzene (available as GRQP 3283 fg Ujgnn Ejgokecn Eq0 + = 6,6Óogvkngpqdku- (2,6-diethyl) -aniline * OFGC = Nqnzc + = 6,6óogtügpqdku- (3-chloro 2 , 6-diethyl) -aniline (MCDEA; Nqnzc + = 6,6óogtingpqdku- (2,6-diisopropyl) -amlma (M-DIPA; Lonza); 3,5-diethyl toluene-2,4 / 2,6-diamine ( D-GVFC: 2 = Nqnzc + = 6,6óogtügpqdku- (2-isopropyl-6-methyl) -aniline (M-MIPA; Lonza); 4-chlorophenyl-N, N-dimethyl-urea (for example, Monuron); 3 , 4-dichlorophenyl-N, N-dimethyl-urea (eg DiuronTM) and dicyandiamide (AmicureTM CG 1200; Pacific Anchor Chemical). Bisphenol chain extenders, such as bisphenol-S or thiodiphenol, are also useful as curing agents for epoxy resins. Another class of curing agents known for epoxy resins is hydrazides, as disclosed in, for example, US 2010/0222461-A1, the disclosure of which is incorporated herein by reference. Thus, a hydrazide curing agent can be selected from the group consisting of hydrazides, dihydrazides, trihydrazides and te tra-hydrazides. Dihydrazides, for example, are represented by the active group [H2NHNC (= O) -RC (= O) NHNH2] where R is any polyvalent organic radical, for example, carbodihydrazide (R = CH2), and preferably derived from a carboxylic acid and exemplified by adipic acid dihydrazide (ADH), sebacic acid dihydrazide (SDH), valine dihydrazide (VDH), isophthalic acid dihydrazide (HDI), dihydrazide phthalic, terephthalic dihydrazide and naphthalene dicarboxylic acid dihydrazide. Other hydrazide curing agents include 1,2,3-benzene-tricarbonic trihydrazide, trimellitic trihydrazide, trimethic trihydrazide, aromatic monohydrazides, aliphatic monohydrazides, aliphatic dihydrazides, aliphatic trihydrazides, tetra -aliphatic hydrazides, aromatic monohydrazides, aromatic dihydrazides, aromatic trihydrazides, aromatic tetrahydrazides and naphthanoic acid hydrazide.
[0069] In the present invention, a single curing agent can be used, or a combination of curing agents can be used. When a combination of curing agents is used, curing agents can be referred to as a primary curing agent and one or more secondary curing agents. When a combination of curing agents is used, curing agents preferably have different relative reactivity, and the curing agent with relatively higher reactivity is referred to here as the primary curing agent, and curing agents with relatively low reactivity are referred to here as secondary curing agents.
[0070] When a primary curing agent is used in combination with one or more secondary curing agents, the relative proportions are such that the primary curing agent is normally present in a stoichiometry of at least 50%, preferably at least about 60%, preferably at least about 70% and preferably at least about 80% of the total amount of curing agent present in the resin system. However, the resin systems of the present invention also include the use of a highly reactive primary curing agent that is used in a relatively minor proportion, with respect to said one or more low reactive secondary curing agents, so that said highly reactive primary curing agent is present in a stoichiometry of less than 50%, preferably not more than 40%, preferably not more than 30%, preferably not more than 20%, preferably not more than 10% of the total amount of the curing agent curing present in the resin system.
[0071] In a first preferred embodiment, a single curing agent is used. In this embodiment, the curing agent is preferably ugngekqpcfq "fg" 5.5Ó-FFU "g" 6.6Ó-FFU "g" go "woc" oqfcnkfcfg "fg" 5.5Ó-DDS.
[0072] In a second preferred embodiment, a combination of curing agents is used in which the primary curing agent is rtghgtgpekcnogpvg "ugngekqpcfq" c "rctvkt" fg "5." 5-diaminodiphenyl sulfone (DDS) and dihydrazide isophthalic acid (HDI). In this embodiment, the curing agent ugewpfátkq fi rtgfetgpekcnogpVg ugngekqpcfq fg 6.6Ó-DDS, particularly where the main curing agent is the HDI.
[0073] Thus, in a preferred embodiment, a combination of KFJ "g" 6.6Ó-DDS is used as curing agents in resin systems of the kpxgp> «q. and the KFJ swe fi q cigpVe fe ewtc rtkoátkq e 6.6 "-DDS is the secondary curing agent. In this case, however, the primary HDI curing agent is of such high reactivity that it is used in relatively high proportions qduetxcfcu cekoc, and the tenc > «Q cq cigpVe fg ewtc ueewpfáriq 6.6" - DDS, and particularly where the HDI is present in a stoichiometry of not more than 10% of the total amount of curing agent present in the resin system. The inventors have found that this combination is particularly suitable for providing the kinetics to achieve gelation of the resin matrix before melting the polyamide particles.
[0074] Go qwVtc oqfcnkfcfe, woc eqodkpc> «q fe 5.5" -FFU and 6.6 "- DDS is used as a curing agent in resin systems of the present kpxgp>« q. go swg 5.50-FFU fi q cigpVg fg ewtc rtkoátkq g 6.6Ó-DDS is the secondary curing agent, preferably in the proportions noted above in which the primary curing agent is present as a large proportion of the total amount of curing agent present in the resin system.
[0075] In another embodiment, a curing agent selected from hydrazides is used in combination with a curing agent selected from amines, and the relative proportions are such that the hydrazide-based curing agent is present in less 50% of stoichiometry based on the weight of epoxy resin equivalent; and the amine-based curing agent is present in more than 30% of stoichiometry based on the weight of epoxy resin equivalent.
[0076] Curing agents are normally present in stoichiometry in the range of 0.5 to 1.5, more preferably in the range of 0.75 to 1.25.
[0077] More generally, curing agents are usually present at about 5-60% by weight, preferably about 20-50% by weight, usually about 25-40% by weight, relative to the total combined weight of the precursor component of thermosetting resin plus curing agents of the resin system. The total amount of curing agents in the resin system is preferably in the range of about 5 to about 60% by weight, more preferably in the range of about 20 to about 50% by weight, usually about 25-40% by weight, relative to the total weight of the resin system (ie the total weight of the thermosetting resin precursor component, the thermoplastic polyamide particle component, curing agents and any optional additional hardening agents or other additive) .
[0078] When a catalyst is used, for example, to accelerate the curing reaction, appropriate catalysts are well known in the art and include Lewis acids or bases. Specific examples include compositions comprising boron trifluoride, such as the etherates or amine adducts therefor (for example, the boron trifluoride and ethylamine adduct), particularly where epoxy resin precursors are used in conjunction with the aforementioned amine curing agents .
[0079] According to the present invention, the components of the resin system are selected so that the gelation of the epoxy matrix during the curing cycle of the resin system occurs at a TGEL gelation temperature that is at or below TPA . In this regard, particularly preferred combinations are: (i) a resin precursor component comprising tri and / or tetrafunctional epoxy resin precursors, 12 g "5.5Ó-DDS polyamide particles; (ii) a resin precursor component; comprising triple and / or tetrafunctional epoxy resin precursors, 11 g "5.5Ó-DDS polyamide particles; (iii) a resin precursor component comprising tri and / or tetrafunctional epoxy resin precursors, 32.32 "g" 6.6Ó-DDS polyamide particles; and (iv) a resin precursor component comprising tri and / or tetrafunctional epoxy resin precursors, polyamide-34 particles. "g" 6.6Ó-DDS and HDI. Uses of curable polymer compositions and cured thermoset resin compositions
[0080] The resin systems described here define compositions that can be used to manufacture cast or molded structural materials, in pre-pregs. These compositions are particularly suitable for the manufacture of structures, including load-bearing or impact resistance structures. The compositions can be used neat, or as fiber-reinforced composite materials or fillers.
[0081] Thus, according to another aspect of the invention, a molded or cast article is provided, comprising, or derived from the resin systems defined herein.
[0082] According to another aspect of the invention, a composite material is provided comprising, or derived from the resin systems described above, particularly wherein the composite material is, or comprises, a pre-preg.
[0083] Molded products are obtainable from compositions comprising the resin systems defined here by the general steps of mixing the uncured resin precursor component with (optional, but preferred) additional curing agents (preferably thermoplastic curing agents discussed below, and homogenizing the mixture thus obtained, which is then cooled. The thermoplastic polyamide particle component and curing agents (and, optionally, a catalyst, if necessary) are then added, the mixture is melted in a mold to obtain a product molded, and the molded product is cured at an elevated temperature, as described here to form a cured molded product.
[0084] In a preferred embodiment, particularly for the manufacture of load-bearing or impact-resistant structures, the compositions are composite materials comprising the resin systems defined herein and further comprising fiber reinforcing agents or fillers.
[0085] The fibers can be added short or chopped normally of the average length of the fiber no more than about 2 cm, for example, about 6 mm. Alternatively, and preferably, the fibers are continuous and can, for example, be fibers unidirectionally arranged or woven or braided, knitted or non-woven to form a pre-preg. Eqpfotog wucfq cswk. q Vgtoq “rte-rtei” is used for pre-preg composite materials with reinforced uncured fiber. A pre-preg usually comprises continuous fibers, but combinations of short and / or cut fibers and continuous fibers can be used. For some applications, pre-impregnated fibers can be selected from short unidirectional fibers and / or cut alone.
[0086] The fibers can be sized or not sized. The fibers can normally be added at a concentration of at least 20%, especially from 30% to 70%, more especially 50 to 70% by volume, in relation to the total volume of the composition comprising the resin system defined herein and reinforcing agents. For structural applications, it is preferable to use continuous fiber, for example, glass or carbon.
[0087] The fiber can be organic, especially of rigid polymers such as poly paraphenylene terephthalamide, or inorganic. Among inorganic fibers, cu hkdtcu fg xiftq eqoq “E” qw “U” rqfgo ugt wucfcu. qw cnwokpc. zite »pic. silicon carbide, other ceramic compounds or metals. A very suitable reinforcement fiber is carbon, especially as graphite. Graphite fibers that have been shown to be especially useful in the invention are intermediate module carbon fibers (IM).
[0088] The organic or carbon fiber is preferably not dimensioned or is dimensioned with a material that is compatible with the resin systems defined here, in the sense of being soluble in the composition of the liquid precursor without adverse reaction or of bonding to the fiber and to the thermoset / thermoplastic composition described here. In particular, carbon or graphite fibers that are not dimensioned or with resin precursor are preferred. The inorganic fiber is preferably sized with a material that binds to the fiber and the polymer composition; examples are organosilane coupling agents applied to glass fiber.
[0089] In a preferred embodiment, the resin systems of the present invention still contain conventional curing agents such as engineering high-Tg thermoplastic curing agents, such as aromatic thermoplastic polymers having relatively high Tg (for example, at least about 150 ° C) and having a divalent aromatic radical repetition unit (or of greater valence) that is inside, instead of hanging, in the polymer structure. These aromatic polymers are preferably selected from the group consisting of polyethers, polyether sulfones, polyether imides, polyimides, polyether ketones, polycarbonates, polysulfones, polyketones, mixed poly-sulfone ketones, polyether sulfone-mixed ketones, polyesters, polyethersters, polyamides , polyetheramides and polysulfides and copolymers thereof, most preferably selected from the group consisting of aromatic polyether sulfones, aromatic polyether ketones, aromatic polyether imides and aromatic polysulfide sulfones and most preferably selected from the group consisting of polyethersulfones, for example as defined in US 2004/0044141, US 6437080 and international patent application copending by depositor number PCT / GB2012 / 051779, whose disclosure of aromatic polymers is incorporated here by reference. Preferred polyether sulfones include poly-1,4-phenylene-oxy-1,4-phenylene-sulfone; polyether sulfone prepared from bisphenol A and dichlorodiphenyl sulfone; and poly-bis (1,4-phenylene) -oxy-1,4-phenylene sulfone. Alternatively, or in addition, resin systems may contain curing agents that are block copolymers, for example, those disclosed in WO-2006/077153-A or, more preferably, the block copolymers disclosed in the copending international patent application of the depositor number PCT / GB2012 / 051779, whose disclosure of block polymers is hereby incorporated by reference.
[0090] A particularly preferred group of aromatic thermoplastic polymers for use as curing agents in the resin systems of the present invention are the aromatic polyether sulfones selected from polyarylsulfones comprising repeating units linked to the ether, optionally still comprising repeating units attached to the thioether, the units being selected from: - [ArSO2Ar] n- and optionally from: - [Ar] a- where: Ar is phenylene; n = 1 to 2 and can be fractional; a = 1 to 3 and can be fractional and when it exceeds 1, said phenylene groups are linearly linked through a single chemical bond or a divalent group other than -SO2- (preferably where the divalent group is a -C group (R1 ) 2- where each R1 can be the same or different and selected from H and C1-8 alkyl (particularly methyl)), or are fused together, as long as the repeat unit - [ArSO2Ar] n- is always present in the polyarylethersulfone in a proportion that, on average, at least two of the said - [ArSO2Ar] n- units are in sequence in each polymer chain present, and in which the polyarylsulfone has one or more pending and / or reactive end groups, as disclosed in greater detail in prior art mentioned above, and the disclosure that is incorporated herein by reference.
[0091] Preferably the polyarylsulfone comprises a combination of - [ArSO2Ar] n- and repeating units - [Ar] a-, linked by ether and / or ether-thio bonds, preferably by ether bonds. Thus, preferably polyarylsulfone comprises a combination of repeating units linked to polyethersulfone ether (PES) and polyetherethersulfone (PEES). Preferably, the preferred repetition units in said polyarylsulfones are: (I): -X-Ar-SO2-Ar-X-Ar-SO2-Ar- (here called as woc “wpkfcfg RGU” + and (II): -X - (Ar) aX-Ar-SO2-Ar- (called here eqoq woc “wpkfcfg RGGU” + where: X is O or S (preferably O) and may vary from unit to unit, and the proportion of units I: II it is preferably in the range of 10:90 to 80:20, as disclosed in the aforementioned prior art.
[0092] Alternatively, or in addition, resin systems can comprise other additives, including preformed particulate hardening agents known as glass granules, rubber particles and rubber coated glass granules, filler such as polytetrafluoroethylene, silica, nanotubes carbon, graphite, boron nitride, mica, talc and vermiculite, pigments, nucleating agents and stabilizers, such as phosphates. Liquid rubbers with reactive groups can also be used. Preferably, however, the curing agents present in the composition are selected from the group consisting of block copolymers and high Tg engineering thermoplastics referred to above.
[0093] The total amount of curing agents and any fiber reinforcing agent in the resin systems of the present invention is typically at least 20% by volume, as a percentage of the total volume of the composition comprising the resin system defined herein and reinforcement. The percentages of fibers and other materials are calculated on the total composition after curing at the temperatures described below.
[0094] Curing agents, particularly the thermoplastic aromatic polymers having relatively high Tg observed above, are preferably present in the resin system defined here in an amount of about 5 to about 40% by weight, preferably in an amount of about 7.5 to about 32.5% by weight, by the weight of the resin system (ie the total weight of the thermosetting resin precursor component, the thermoplastic polyamide particle component, the curing agent and hardening and other optional additive).
[0095] Composites are obtained from a curable polymer composition prepared by combining the resin precursor component and the thermoplastic polyamide particle component with fiber reinforcing agent and / or other materials. For instance, the manufacture of a prep usually comprises the steps of mixing the resin precursor component and the thermoplastic particle, adding one or more curing agents (and optional catalyst as needed), homogenizing the mixture thus obtained, and applying the homogenized mixture for a bundle or ribbon of fibers parallel to or woven or knitted or nonwoven fabrics to form the pre-preg. A solvent may be present to aid processing, as is known in the art.
[0096] More specifically, the manufacture of articles and composites of the resin systems of the present invention is as follows. Curing is suitably carried out at an elevated temperature using a curing temperature (TC) of up to 200 ° C, preferably at least 140 ° C, preferably at least 160 ° C, preferably in the range 160 to 195 ° C, more preferably 170 at 190 ° C and more preferably from 175 to 185 ° C. Curing can be carried out at temperature in an autoclave at elevated temperatures to restrict the effects of deformation of the exhaust gases, or to restrict the formation of voids, appropriately at pressure up to 10 bar, preferably in the range of 3 to 7 bar abs. Alternatively, curing can be carried out outside the autoclave only under vacuum. The curing temperature (TC) is reached by heating at a curing ramp rate (RCR) which is preferably at least about 0.05 ° C / min, preferably at least about 0.1 ° C / min, preferably at least about 0.5 ° C / min and usually up to about 3.0 ° C / min, more usually up to about 2.5 ° C / min and in an embodiment up to about 2.0 ° C / min , and in an embodiment in the range of about 0.1 ° C / min to about 2.5 ° C / min, usually from about 0.5 ° C to about 2.0 ° C / min. The curing temperature is maintained for the necessary period of up to 6 hours, preferably above 2 hours.
[0097] According to another aspect of the invention, a composite is provided comprising laminates pre-pregs joined together by heat and pressure, for example by autoclave, compression molding, or by heated rolls, at a temperature above the curing temperature of the composition of curable polymer comprising the resin system defined here.
[0098] The resin systems of the present invention find particular utility in the manufacture of components suitable for use in transportation applications (including aerospace, aeronautical, nautical and land vehicles and including the automotive, railway and bus industries), in construction or other commercial applications. In the aerospace and aeronautical industry, resin systems can be used for primary and secondary parts of the aircraft and particularly for primary parts (eg wing, fuselage, pressure shield, etc.).
[0099] In accordance with another aspect of the present invention, use is made of a combination of the thermosetting resin precursor component as defined herein and the curing agents defined herein, in a resin system comprising ILT thermoplastic polyamide particles with the purpose of retaining the morphology of said particles and / or reducing or eliminating microcracks and / or improving compression performance (OHC resistance and particularly hot-humid OHC resistance) in a cured resin produced from said resin system. In another aspect, said retention of the morphology of said particles and / or reduction or elimination of microcracks and / or improvement of the compression performance (OHC resistance and particularly hot-humid OHC resistance) is achieved without significant damage CSAI and / or GI / IIC (preferably CSAI and GI / IIC).
[00100] According to another aspect of the present invention, a method is provided to retain the morphology of the ILT thermoplastic polyamide particles and / or to reduce or eliminate micro-cracks and / or to improve the compression performance (OHC resistance, particularly hot- wet) into a cured resin produced from a resin system comprising said particles, said method comprising (i) selecting a thermoset resin precursor component comprising one or more multifunctional epoxy resin precursors as defined herein, (ii) combining said thermosetting resin precursor component with the ILT thermoplastic polyamide particle component as defined herein, (iii) curing the combination of said thermosetting resin precursor component and said thermoplastic polyamide particle component with curing agents, as defined here. In another aspect, said retention of the morphology of said particles and / or reduction or elimination of microcracks and / or improvement of the compression performance (OHC resistance and particularly hot-humid OHC resistance) is achieved without significant damage CSAI and / or GI / IIC (preferably CSAI and GI / IIC).
[00101] The use and method described above are of particular use to retain the morphology of said particles and / or to reduce or eliminate micro-cracks and / or to improve the compression performance (OHC resistance, particularly hot-wet OHC resistance) in a system of resin that is suitable to be cured at any temperature ramp rate in the range up to 3.0 ° C / min (and particularly the cure ramp rates described here above).
[00102] Eqoq wucfq cswk. q Vgtoq "ugo rtgjwizq ukipkfiecvkxq rctc CSAI and / or GI / CΠ" ukiPkfiec swg c tgukpc ewtcfc ocpVfio rtqrtkgfcfgu EUCK and / or GI / CII suitable for use in particularly primary and secondary parts (primary and secondary).
[00103] Preferably, the composite materials of the present invention have an interlaminar fracture hardness value in mode ii (Giic) which is at least 10 in-lb / in2 through the wide and preferred RcR cure rate seen above, and particularly at RcR curing rates in the range of 0.05 to 2.5 ° c / min, particularly where RcR is at least about 0.1 ° c / min, particularly at least about 0.5 ° c / min
[00104] In accordance with another aspect of the present invention, a process is provided for the production of a cured thermoset resin comprising the steps of: a. selecting a thermosetting resin precursor component comprising one or more multifunctional epoxy resin precursors having a functionality of at least three, preferably wherein said precursor is selected from a trifunctional epoxy resin precursor and / or a tetrafunctional epoxy resin precursor; B. combining said resin precursor component with a thermoplastic polyamide particle component wherein the polyamide particles have a melting temperature TPA, and c. cure the combination of said curing precursor component and said thermoplastic particle component with one or more curing agents, wherein said resin precursor component, said polyamide particle component and said curing agents are selected so that the gelation of the epoxy matrix during the curing cycle occurs at a TGEL gelation temperature which is below TPA, particularly where gelation of the epoxy matrix during the curing cycle occurs at a TGEL gelation temperature which is below TPA for rates cure rate in the range of 0.05 ° C / min to 3.0 ° C / min (and particularly the cure rate described above).
[00105] The invention is now illustrated in a non-limited manner with reference to the following examples. Examples
[00106] The physical properties and behavior of the resin systems described here can be measured according to the following techniques Glass transition temperature
[00107] The glass transition temperature is defined as the temperature where the sample shows a dramatic change in mechanical behavior and damping with increasing temperature when subjected to an oscillating displacement. The appearance of Tg is defined as the intersection of the extrapolated tangents taken from the points of the storage module curve before and after the start of the glass transition event. The test was performed using TA Q800 in a single cantilever bending mode in the temperature range between about 50 ° C and 300 ° C, with a heating rate of 5 ± 0.2 ° C / min and the frequency of 1 Hz Particle size
[00108] The particle size distribution was measured by laser diffraction, using a Malvern Mastersizer 2000 operating in the range of 0.02μm to 2000μm. Mechanical properties
[00109] Interlaminar fracture hardening in the way that I (GIC) was measured in a unidirectional tray (UD) in double-beam cantilever coupons (DCB) according to the BSS7273 test method.
[00110] Hardening of interlaminar fracture in mode II (GIIC) was measured in a unidirectional tray (UD) in coupons notched at the end loaded in 3-point flexion mode (ENF) according to the BMS8-276 test method.
[00111] Compressive strength after impact (CSAI; in kiloliters per square inch (ksi)) was measured according to the BSS7260 test method. The coupon to be tested is subjected to an energy impact previously defined for compression load. The coupon is then loaded in compression into an anti-tongue mold and the strength of the coupon is measured.
[00112] Open hole compression (OHC; in kilo-pounds per square inch (ksi)) was measured according to the ASTM D6484 test method. The hot-humid performance was assessed by measuring the OHC resistance at 160 ° F (approx. 71.1 ° C) after immersing the coupons for 14 days in water at 160 ° F (approx. 71.1 ° C).
[00113] Open hole traction (OHT; in kilo-pounds per square inch (ksi)) was measured according to the ASTM D5766 test method. Morphology
[00114] Normally, a coupon is cut perpendicular to its zero direction and then polished to obtain a cross section revealing the interlaminar region. The coupon is then observed using optical microscopy (OM). Since the polyamide particles are larger than 5 μm and are characterized by a refractive index sufficiently different from the surrounding thermosetting matrix, OM can be used to observe interlaminar morphology. Microfissure
[00115] The presence and extent of microcracks can be assessed using optical microscopy (OM) or scanning electron microscopy analysis (SEM). Typically, a coupon is cut perpendicular to its zero direction and then polished to obtain a cross section revealing the interlaminar region. The coupon is then observed by SEM or OM Microfissures can be reinforced by subjecting the coupon to cold-hot thermal cycling. Rheology and thermodynamics of resin systems during curing
[00116] Rheometry and DSC were used to evaluate the rheology and thermodynamics of resin systems during a curing cycle, in order to measure the gelation temperature of the resin system and the melting point of the polyamide particles in it. DSC thermograms were purchased on a TA Q2000 DSC under a nitrogen environment. The rheology curves were acquired in an ARES under compressed air, using parallel stainless steel plates, a frequency of 10rad / s and a tension of 10% and a gap between 0.6 and 1.3 mm.
[00117] The following resin systems were prepared and analyzed according to the test procedures described above. Example 1
[00118] A series of resin systems have been formulated using the components shown in Table 1 below to produce a 2.5 kg composition. Table 1
Caption: MY721 is TGDDM tetraglycidyldiaminodiphenylmethane (Araldite MY721; Huntsman) MY610 is triglycidyl m-aminophenol (Araldite MY0610; Huntsman) PES5003P is polyethersulfone (Sumitomo Chemical Co. Ltd) added as a soluble hardening agent of 12-fold polycarbonate (217) 10 μm; Evonik Industries) 6.6Ó-FFU "fi" 6.6.6Ó-diaminodiphenyl sulfone (Huntsman) 5.5Ó-FFU "fi" 5.5Ó-diaminodiphenyl sulfone (Huntsman)
[00119] For resin systems 1 and 2, the epoxy resin precursors, MY721 and MY610 were heated to 75 ° C and mixed thoroughly. The PES5003P hardening agent was added at 75 ° C and dissolved for 20 minutes, and the temperature of the mixture then increased to 125 ° C until complete dissolution. The mixture was then cooled to 85 ° C, and the curing agent * 6.6Ó-FFU "qw" 5.5Ó-DDS) was then added to 85 ° C, and the mixture dissolved for another 25 minutes at this temperature.
[00120] For resin systems 3 and 4, the epoxy resin precursors, MY721 and MY610 were heated to 75 ° C and mixed thoroughly. Half of the PES5003P hardening agent was added at 75 ° C and dissolved for 20 minutes, and the temperature of the mixture then increased to 125 ° C until complete dissolution. The mixture was then cooled to 85 ° C, and the second half of the PES5003P hardening agent added to 85 ° C and the mixture dissolved for 15 minutes at this temperature. The curing agent * 6.6Ó-FFU "qw" 5.5Ó-DDS) was added at 85 ° C, and the mixture dissolved for another 15 minutes at this temperature. Vestasint 2159 particles were added at 85 ° C and dissolved until complete dispersion was achieved.
[00121] The compositions thus produced were then filmed to an air weight of 25.5 gsm on paper support. The carbon fibers of the intermediate module (IM) were spread on a pre-impregnated machine with an air weight of 190gsm. The resin films were then applied to each side of the propagation fibers to obtain a pre-preg with a fiber sand weight (FAW) of 190 gsm and a resin content of 35% by weight.
[00122] To manufacture laminate 1, the prepared films of resin 1 were applied to each side of the propagation fibers followed by the application of the prepared films of resin 3 to obtain a pre-preg with a sandy fiber weight (FAW) of 190 gsm, a resin content of 35% by weight.
[00123] To manufacture laminate 2, the prepared films of resin 2 were applied to each side of the propagation fibers followed by the application of the prepared films of resin 4 to obtain a pre-preg with a sandy fiber weight (FAW) of 190 gsm, a resin content of 35% by weight.
[00124] The laminates were then cured at 180 ° C, using a cure rate of 2 ° C / min. The laminates were then tested according to the procedures described here, and the results shown in Table 2 below. Table 2

[00125] The results of Table 2 demonstrate that cured laminates 5.5Ó-DDS present increased OHC resistance and hot-uokfq compression performance. go tgnc> «q cqu ncokpcfqu ewtcfqu 4,4’-DDS, maintaining excellent CSAI resistance and GIIC performance.
[00126] Preferably, the composite materials of the present invention have a mode II interlaminar fracture hardening value (GIIC) that is at least 10 in-lb / in2.
[00127] From the panel used to measure GIIC performance, small samples perpendicular to the direction of the fibers were cut, polished and observed by optical microscopy. The optical microscopy images are shown in FIGS. 2 and 3 for the cross-sectional view of Laminates 1 and 2, respectively, which generate the thicknesses of the resin established in Table 3 below. Table 3

[00128] The greater thickness of the resin in Laminate 2 demonstrates that the resin system cured with 3,3-DDS according to the invention is better able to create and maintain an interlaminar gap between the layers of reinforcement fibers. It is apparent from the optical micrograph in Figure 1 that some coalescence of the fused polyamide particles occurred in the interlaminar region of Laminate 1, while little or no coalescence occurred in the interlaminar region of Laminate 2. The gelation of the epoxy resin matrix in Laminate 2 before melting of the polyamide particles during the curing cycle, resulted in the retention of discrete polyamide particles rather than a continuous coalesced polyamide phase or network. As a result, microcracks at the particle / matrix interface are reduced, and the hot-wet compression performance of the cured composite material is improved. Example 2
[00129] Two other laminates (Laminates 3 and 4) were prepared similarly to Laminate 1 above, but using curing ramp rates of 0.5 ° C / min and 2.5 ° C / min, respectively. In addition, two other laminates (Laminates 5 and 6) were prepared similarly to Laminate 2 above, but using curing ramp rates of 0.5 ° C / min and 2.5 ° C / min, respectively. The samples were analyzed as described here. The results of the optical microscopy are shown in Figures 3 and 4 here. FIGS. 4A, 4B, 5A, 5B show optical microscopy images for the cross-sectional view of laminates cured at 0.5 ° C / min. laminate 3 (4, 6O-DDS) is shown in Fig. 4A and an exploded view of a respective interlaminar region is shown in Fig. 4B. Q "Ncokpcfq" 7 "* 5.5Ó-DDS) is shown in Figure 5A, and an exploded view of an interlaminar region thereof is shown in Figure 5B. Figures 6A, 6B, 7A, 7B show microscopic images optics for cross-sectional views of laminates cured at 2.5 ° C / min. Q "Ncokpcfq" 6 "* 6.6Ó-DDS) is shown in FIG. 6A, and an exploded view of an interlaminar region thereof is shown in FIG. 6B. The Ncokpcfq "8" * 5.5Ó-DDS) is shown in FIG. 7A, and an exploded view of an interlaminar region thereof is shown in FIG.7B.
[00130] Optical microscopy demonstrates that the interlaminar morphology fcu rcrtiewncu fg rqnkcokfc KNV go ncokpcfq ewtcfq 6.6Ó-DDS was strongly influenced by the cure rate used during the manufacture of laminates, as follows: (i) in the slower heating rate ( 0.5 ° C / min), there was no indication of coalescence of the polyamide particles and the particulate morphology was maintained, but (ii) at the higher heating rate (2.5 ° C / min), a semi-continuous polyamide network coalescence within the resin phase was observed, in which the polyamide particles melted and coalesced during the curing cycle, with the loss of the particulate morphology of the polyamide particles.
[00131] Go eqpvtcuvg. qu gzrgtkogpvqu eqttgurqpfgpvgu eqo q 5.5Ó- DDS more reactive as the curing agent showed particulate morphology without coalescence at both low and high heating rates. The largest tgcvkxkfcfg fq 5.5Ó-DDS allowed the resin matrix around the polyamide particles to gel before the melting of the rqnkcmifc, cuuko particles. “Eqpigncogpto” c rqnkcokfc go uwc oqtfbnqikc rcrtkewncfc original.
[00132] Optical microscopy also revealed that when a particulate morphology was maintained after curing, there was no sign of the microfissure. However, a semi-continuous coalesced morphology was accompanied by a significant amount of microfissure, even before any thermal cold / heat cycling. Example 3
[00133] A resin system similar to that described for Experiment 1 was formulated using the components in Table 4 below. Pguvg "gzgornq." q "cigpvg" fg "ewtc" 6.6Ó-DDS is complemented, rather than replaced, with a curing agent having relatively high reactivity, in order to promote the previous gelation of the epoxy matrix. Table 4
Legend: HDI is isophthalic dihydrazide
[00134] The MY721 and MY610 epoxy resin precursors were heated to 75 ° C and mixed thoroughly. Half of the PES5003P hardening agent was added at 75 ° C and dissolved for 20 minutes, and the temperature of the mixture was then increased to 125 ° C until complete dissolution. The mixture was then cooled to 85 ° C, and the second half of the PES5003P hardening agent added to 85 ° C and the mixture dissolved for 15 minutes at this temperature. The HDI curing agent was added at 85 ° C, and the mixture dissolved for an additional 15 minutes at this temperature. The 6.6Ó-DDS curing agent was added at 85 ° C, and the mixture dissolved for another 15 minutes at this temperature. Vestasint® particles were added at 85 ° C and dissolved until complete homogeneous mixing was achieved.
[00135] The compositions of resin systems 3, 4 and 5, that is, the eqorquk> õgu eqo 6.6Ó-FFU. 5.5 'FFU and 4.4 "FFU1KFJ eqoq cigpVgu fg curing, respectively, were then analyzed by rheometry and DSC as described above, during a curing cycle at a temperature ramp rate of 2.5 ° C / min to determine the influence of the relative rates of epoxy gelling and the melting of the polyamide particles The results are summarized in FIG.
[00136] The viscosity versus temperature graphs illustrate the sharp increase in viscosity at the gel point in each of the resin systems, and also that the temperature of the gel point differs in the three systems (177, 178 and 192 ° C; at 1000Pa.s they are 175, 175.5 and 190 ° C, respectively). The heat flow versus temperature graphs are used to identify the melting points of the polyamide particles in each of the resin systems. FIG. 8, therefore, illustrates that the temperature of the point fg "ign" go "ukuvgocu" fg "tgukpc" 6 "g" 7 "* wucpfq" 5.5Ó-FFU "g" 6.6Ó-DDS / HDI as curing agents, respectively ) is significantly lower than the peak temperature of the fusion endotherm, while the temperature of the rqpvq "fg" ign "pq" ukuvgoc "fg" tgukpc "5" * wucpfq "6.6Ó-DDS as a curing agent) is higher than that of the melting peak. Example 4
[00137] A series of resin systems were formulated using the components shown in Table 5 below to produce a 2.5 kg composition. Table 5
Caption: MY0510 is triglycidyl p-aminophenol p-TGAP (Araldite MY0510; Huntsman) PY306 is diglycidyleter of bisphenol-F DGEBF (Araldite PY306; Huntsman) PES5003P is polyethersulfone (Sumitomo Chemical Co. Ltd) added as a soluble hardening agent 6.6 FFU "fi" 6.6.6Ó-diaminodiphenyl sulfone (Huntsman) Orgasol ® 1002D is polyamide-6 particles (Arkema Industries) Orgasol ® 2002D is polyamide-6 particles (Arkema Industries) Vestosint ® Z2640 is polyamide-10-10 particles (Evonik Industries)
[00138] For resin system 6, the epoxy precursors MY0510 and PY306 were heated to 70 ° C and mixed thoroughly. The PES5003P hardening agent was added at 70 ° C and dissolved for 20 minutes, and the temperature of the mixture was then increased to 125 ° C until complete dissolution. The mixture was then cooled to 80 ° C, and the curing agent * 6.6 (-DDS) was then added to 80 ° C, and the mixture dissolved for an additional 25 minutes at this temperature.
[00139] For resin systems 7, 8 and 9, the epoxy precursors MY0510 and PY306 were heated to 70 ° C and mixed thoroughly. Three-quarters of the hardening agent PES5003P was added at 70 ° C and dissolved for 20 minutes, and the temperature of the mixture was then increased to 125 ° C until complete dissolution. The mixture was then cooled to 80 ° C, and the last quarter of the PES5003P hardening agent added to 80 ° C and the okuvwtc "fkuuqnxkfc" rqt "37" okpwvqu "c" guvc "vgorgtcvwtc0" Q "cigpvg" fg "ewtc" * 6.6-DDS) was added at 80 ° C, and the mixture dissolved for another 15 minutes at this temperature. The particles (Orgasol1002D or Orgasol2002D or VestosintZ2640) were added at 80 ° C and dissolved until complete dispersion was achieved.
[00140] The compositions thus produced were then filmed to an air weight of 25.5 gsm on paper support. The carbon fibers of the intermediate module (IM) were spread on a pre-impregnated machine with an air weight of 190gsm. The resin films were then applied to each side of the propagation fibers to obtain a pre-preg with a fiber sand weight (FAW) of 190 gsm and a resin content of 35% by weight.
[00141] To manufacture laminate 3, the prepared films of resin 6 were applied to each side of the IM propagation fibers followed by the application of the prepared films of resin 7 to obtain a pre-preg with a 190gsm fiber sand weight and a resin content of 34% by weight.
[00142] To manufacture laminate 4, the prepared films of resin 6 were applied to each side of the IM propagation fibers followed by the application of the prepared films of resin 8 to obtain a pre-preg with a 190gsm fiber sand weight and a resin content of 34% by weight.
[00143] To manufacture laminate 5, the prepared films of resin 6 were applied to each side of the IM propagation fibers followed by the application of the prepared films of resin 9 to obtain a pre-preg with a fiber weight of 190gsm and a resin content of 34% by weight.
[00144] The laminates were then cured at 180 ° C using a cure rate of 2 ° F / min (1.1 ° C / min) or 4 ° F / min (2.2 ° C / min). The laminates were then tested according to the procedures described here, and the results shown in Table 6 below. Table 6

[00145] The results in Table 6 demonstrate that the cured laminates 4 and 5 containing the long chain PA particles (PA12 and PA10-10) show increased CSAI and GIIC performances, compared to the cured laminate 3 containing the PA-6 particles of short chain.
[00146] The results in Table 6 further demonstrate that the hardening of a resin with a lower crosslink density ewtcfcu "rqt" 6.6Ó-DDS of low reactivity with PA12 particles (where the melting temperature (TPA) is lower than the nominal cure temperature TC) results in a lack of robustness for variation in the cure temperature ramp rates. This is best illustrated by the drop in GIIC performances in faster heating rates by laminate 4.
[00147] The results in Table 6 further demonstrate that, when wucpfq woc tguknc eqo woc ognqt fgnukfcfg fg tgVkewnc> õgu ewtcfc rqt 6.6 "- Low reactivity DDS then the selection of particles PA10-10 (where the TPA fusion temperature is greater than the nominal cure temperature TC) provides a resin system that is robust to the variation in ramp rates of cure temperature, which is best illustrated by the GIIC robustness for faster heating rates presented by laminate 5. In this case , TGEL = TC <TPA.
[00148] According to the present invention, therefore, PA10-10 is the preferred polyamide for crosslinked low density resins cured by cwtc agents "fg" tgcvkxkfcfg "tgncvkxcogpvg" dckzc "eqoq" 6.6Ó- DDS, when cured in nominal TC cure temperature preferred in the range of 170 ° to 190 ° C.

权利要求:
Claims (15)
[0001]
1. Resin system, characterized by the fact that it comprises: (i) a thermosetting resin precursor component comprising one or more multifunctional epoxy resin precursors having a functionality of at least three and less than 10% by weight, based on in the total weight of the resin system, of epoxy resin precursors with a functionality of less than three, in which said multifunctional precursor (s) is (are) selected from an epoxy resin precursor tri-functional and a precursor of tetrafunctional epoxy resin; (ii) a thermoplastic polyamide particle component comprising polyamide particles having a melting temperature TPA; where TPA is the effective melting temperature which is defined as the position in degrees Celsius of the endothermic melting peak present in the DSC thermogram (acquired at 10 ° C / minute in nitrogen) of a mixture of 25% by weight of the polyamide in meta-substituted triglycidyl aminophenol (m-TGAP); and (iii) one or more curing agents, wherein said resin precursor component, said thermoplastic particle and said curing agents are selected so that the gelation of the epoxy matrix during the curing cycle of the resin system occurs at a TGEL gelation temperature which is at or below TPA, where TGEL is the temperature at which the viscosity of the resin system tends to infinity; and where the resin system is curable using a TC cure temperature in the range of 140 to 200 ° C and all thermoplastic particles in the resin system have a TPA melting temperature that is not higher than the TC cure temperature.
[0002]
2. Resin system, according to claim 1, characterized by the fact that it is thermally curable using a curing temperature Tc, in which said curing temperature is reached with a rate of cure RCR, and gelation of the matrix of epoxy during the curing cycle of the resin system occurs at a TGEL gelling temperature which is at or below TPA for RCR cure ramp rates in the range of 0.05 ° C / min to 3.0 ° C / min .
[0003]
3. Resin system according to claim 1 or 2, characterized by the fact that the resin system is curable in the range of 170 to 190 ° C.
[0004]
Resin system according to any one of claims 1 to 3, characterized in that the resin system does not contain epoxy resin precursors with less than three functionality, including difunctional and monofunctional epoxy resin precursors.
[0005]
Resin system according to any one of claims 1 to 4, characterized in that a curing agent is used and said curing agent is 3,3'-diaminodiphenyl sulfone.
[0006]
Resin system according to any one of claims 1 to 5, characterized in that a plurality of curing agents is used, wherein the curing agents are isophthalic dihydrazide and 4,4'-diaminodiphenyl sulfone.
[0007]
7. Resin system according to any one of claims 1 to 6, characterized in that said multifunctional epoxy resin precursors are selected from glycidyl derivatives of one or more of the group of compounds consisting of aromatic diamines, monoprimary amines aromatics, aminophenols, polyhydric phenols, polyhydric alcohols, polycarboxylic acids and the like, or a mixture thereof.
[0008]
Resin system according to any one of claims 1 to 7, characterized in that said multifunctional epoxy resin precursors are selected from O, N, N-triglycidyl-para-aminophenol (TGPAP); O, N, N-triglycidyl-meta-aminophenol (TGMAP); and N, N, N ', N'-tetraglycidyldiaminodiphenyl methane (TGDDM).
[0009]
Resin system according to any one of claims 1 to 8, characterized in that said polyamide is selected from polyamide-11 and polyamide-12, polyamide 10,10 and polyamide 10,12.
[0010]
Resin system according to any one of claims 1 to 9, characterized in that the resin system comprises a combination of resin precursor component, thermoplastic particle and curing agent (s) selected from a group consisting of : (i) a resin precursor component comprising tri and / or tetrafunctional epoxy resin precursors, polyamide-12 and 3,3'-DDS particles; (ii) a resin precursor component comprising tri and / or tetrafunctional epoxy resin precursors, polyamide-11 and 3,3'-DDS particles; (iii) a resin precursor component comprising triple and / or tetrafunctional epoxy resin precursors, polyamide-10,10 and 4,4'-DDS particles; and (iv) a resin precursor component comprising tri and / or tetrafunctional epoxy resin precursors, polyamide-12 particles, and 4,4'-DDS and HDI.
[0011]
Resin system according to any one of claims 1 to 10, characterized in that said thermoplastic particles are present in the resin system in the range of about 2.5 to about 30% by weight, in relation to the weight combined total of the thermosetting resin precursor component plus thermoplastic particle component of the resin system.
[0012]
12. Resin system according to any one of claims 1 to 11, characterized in that it further comprises a curing agent selected from aromatic thermoplastic polymers having a Tg of at least about 150 ° C, and selected from of aromatic polyethersulfones.
[0013]
13. Composite material, characterized by the fact that it comprises a resin system as defined in any of claims 1 to 12 in combination with reinforcing agents selected from the group of reinforcing fibers and fillers.
[0014]
14. Composite material according to claim 13, characterized by the fact that it is in the form of a pre-preg or laminates thereof.
[0015]
15. Method for retaining the morphology of ILT thermoplastic polyamide particles and / or reducing or eliminating micro-cracks and / or compression performance (OHC resistance and particularly hot-wet OHC resistance) in a cured resin produced from a resin system comprising said particles, said method characterized by the fact that it comprises (i) forming a resin system of claim 1, and (ii) curing the resin system at RCR cure ramp rates in the range of 0.05 ° C / min at 3.0 ° C / min.

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同族专利:

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公开号 | 公开日

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AU2013345179A1|2015-04-02|

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KR20150086270A|2015-07-27|

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EP2888306B1|2019-09-25|

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US10815373B2|2020-10-27|

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JP2018066016A|2018-04-26|

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US20140135443A1|2014-05-15|

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JP2015535037A|2015-12-07|

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MX2015005378A|2015-07-21|

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RU2641004C2|2018-01-15|

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TW201433600A|2014-09-01|

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EP2888306A2|2015-07-01|

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BR112015008662B8|2021-03-16|

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WO2014078095A3|2014-07-03|

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CN104736590B|2017-08-01|

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WO2014078095A2|2014-05-22|

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CN107778854A|2018-03-09|

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AU2013345179B2|2016-08-25|

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RU2015122411A|2017-01-10|

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JP6621457B2|2019-12-18|

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MX371000B|2020-01-13|

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CA2891378A1|2014-05-22|

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US20210002476A1|2021-01-07|

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CN104736590A|2015-06-24|

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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优先权:

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申请号 | 申请日 | 专利标题

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US201261726596P| true| 2012-11-15|2012-11-15|

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US61/726,596|2012-11-15|

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PCT/US2013/067966|WO2014078095A2|2012-11-15|2013-11-01|Thermoset resin composite materials comprising inter-laminar toughening particles|

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