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    • 专利摘要:
    The present invention relates to a composite material comprising a flame retardant resin and gelcoat. The present invention also relates to the process for the production of a composite material and the use of the composite material, in transport means, preferably railways, and construction. The present invention also relates to a part of a rail transport comprising the composite material. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2739431A1
    申请号:ES201830787
    申请日:2018-07-30
    公开日:2020-01-31
    发明作者:Nogues Antonio Torrelles
    申请人:Polynt Composites Spain SL；
    IPC主号:
    专利说明:

    [0001]
    [0002] COMPOSITE MATERIAL, MANUFACTURING PROCEDURE AND USE OF THE SAME
    [0003] Field of the Invention
    [0004]
    [0005] The present invention relates to the field of resin-based composite materials, to its manufacturing and use process, in particular its use in the fields of transport, construction, civil engineering and public works, leisure and urban furniture, more particularly to its use in railroad materials that meet the specifications established in the UNE EN 45545-2: 2013 + A1: 2015 standard, as well as to the finished products obtained from said composite materials.
    [0006]
    [0007] Background of the invention
    [0008]
    [0009] At European level since 1975 there is the association European Committee for Standardization best known by its acronym in French: CEN (Committee Européen de Normalisation) based in Brussels. CEN has been publishing standards in various fields of activity. The first standard published in relation to the requirements against the fire of railway vehicles was CEN TS 45545: 2009, which is structured in 7 parts on the protection of fire in railroad cars. In 2012, CEN approved the EN (European Standard) version, moving from Technical Instruction to European Standard. The latest version published in Spain by AENOR (Spanish Association for Standardization and Certification) is January 2016: UNE-EN 45545-2: 2013 + A1: 2015 “Railway applications. Fire protection of railway vehicles. Part 2: Requirements for fire behavior of materials and components ”.
    [0010]
    [0011] In Spain, the European Standardization for Railways is initiated by means of the Resolution of July 10, 2009, of the General Directorate of Railway Infrastructures, which approves the “ Technical Specification for Approval of Rail Rolling Stock: Self-Propelled Units”. Provision 13539, BOE 197 of August 15, 2009 (3). Prior to this date, each CEN member state had its own Rules, which were also not equivalent to each other. In Spain, the Norms with which I worked in the railway sector were:
    [0012] - Fire reaction test:
    [0013] UNE 23727: 1990. “Fire reaction tests of construction materials. Classification of materials used in construction ” .
    [0014] UNE 23721: 1990. “Fire reaction tests of construction materials. Radiation test applicable to rigid or similar materials of any thickness and flexible materials with a thickness greater than 5 mm ”.
    [0015] UNE EN 13501-1: 2002. “Classification according to the fire behavior of construction products and building elements. Part 1: Classification based on data obtained in fire reaction tests ”.
    [0016] - Smoke density and toxicity test, for which French Standards are adopted (4):
    [0017] NF X 10702: 2006. Determination of smoke density
    [0018] NF X 70100: 2006. Determination of toxic gases.
    [0019]
    [0020] In other European countries such as Germany, England and Italy, there are also national standards of their own:
    [0021] Germany: DIN 5510, DIN 4102. England: BS 6853, BS 476.France: NF F 16-101, NF P 92-501, NF X 10702: 2006, NF X 70100: 2006. Italy: UNI 11170-3: 2005.
    [0022] There are also standards in the USA (ASTM), etc. Even at the enterprise level there are established standards, such as the RENFE DT PCI / 5A technical guideline.
    [0023]
    [0024] The incorporation of Standard UNE UN 45545-2: 2013 + A1: 2015 has meant three fundamental advantages in terms of the fire behavior of materials used in rail vehicles:
    [0025] a) The existence of a supranational standard, such as the current EN 45545-2: 2013 + A1, is imposed as a necessity, since with a single homologation there is access to the markets of the 27 countries that make up the CCE, and which are also members attached to the CEN: Croatia, Turkey, Iceland, Norway and Switzerland.
    [0026] b) Although not explicitly cited in the Standard, the specifications required are not met with halogenated resins, the use of alternative flame retardant agents, more environmentally friendly, is imposed.
    [0027] c) The rule, contemplated in its entirety, implies a very important change in terms of safety, since not only the fire behavior of the materials that are part of the railways (in part 2) is addressed, but also aspects such as fire barriers (in part 3), design (in part 4), safety requirements are extended to trolleybuses and magnetic levitation vehicles (in part 5), safety systems fire control and management (in part 6) and also address fire safety requirements in installations of flammable liquids and gases (in part 7).
    [0028]
    [0029] The UNE EN 45545-1 standard defines 4 operational categories depending on the road infrastructure of the routes (underground route, elevated structures, tunnels, diaphanous paths, etc.). It also defines 4 types of vehicles according to the ease of lateral evacuation and the accessibility to areas or stations of definitive safety:
    [0030] N: normal vehicles. A: vehicles without driver. D: two-story vehicles. S: bed cars.
    [0031]
    [0032] Additionally, it establishes three levels of risk, from less to more severe are: HL1, HL2, HL3; Identify and classify all components of the rail vehicle; and define 26 Requirements.
    [0033]
    [0034] For example, the typical requirements for composite materials based on thermosetting resins and reinforcing fibers:
    [0035] R1 interior components (structure and lining). Luggage carrier. Console Console
    [0036] R2 tables and sinks.
    [0037] R3 bands.
    [0038] R6 base structure of the passenger seat.
    [0039] R7 interior surfaces of the aisles. Walls of the external structure of the vehicle. R17 front of the train.
    [0040]
    [0041] For each Requirement, specifications based on 17 ISO standards are established. From the operational categories and the types of vehicles, the risk level matrix is generated, which appears in EN 45545 Part 2. This matrix contemplates three levels of risk, the HL3 being the most demanding. Thus, for example, a railway vehicle destined for a tram will enter within the risk level HL1, while another one destined for one meter will enter the risk level HL3.
    [0042]
    [0043] Table 1: Risk matrix.
    [0044]
    [0045] A: VEHICLE S: BED CAR V
    [0046] TRAINED COVERED DEAF
    [0047] one
    [0048] two
    [0049] 3
    [0050]
    [0051]
    [0052] For each Requirement, the specifications that the material to be tested must be established according to the Risk level. For example, for Requirement 1:
    [0053]
    [0054] Table 2: Specifications established for requirement R1 (indoor panels) for the three established risk levels HL1, HL2 and HL3.
    [0055]
    [0056] Test results
    [0057] REQUIREMENT 1
    [0058]
    [0059]
    [0060] Among the most relevant trials are:
    [0061] ISO 5658-2: 2006. "Lateral propagation of the flame." Background: Critical heat flux (CFE) (kW / m2) is measured, to which a flame that spreads laterally is extinguished, is applied to interior panels located vertically. 800mm x 155mm pieces and a maximum thickness of 70mm are required for the test.
    [0062] ISO 5660-1: 2015. "Calorimetric Cone". Background: the parameter called MARHE is measured, which is the average value of the maximum heat emission rate (KW / m2). The calorimetric cone also gives information on:
    [0063] The variation of the mass loss of the test specimen over time.
    [0064] The heat generated per unit of lost mass
    [0065] The variation of the fumes generated over time
    [0066] The variation in the time of gases such as: CO, CO2, O2, even HCl and HBr
    [0067] ISO 5659-2: 2013. "Density chamber and smoke toxicity". Background: optical density and toxicity of the gases generated are measured by burning a 75 mm x 75 mm specimen up to a maximum thickness of 25 mm by a 50 KW / m2 heat source without pilot flame, and a source of 25 can also be used KW / m2 in the presence of pilot flame, for tests where a heat source of this power is prescribed. The parameters that are measured are:
    [0068]
    [0069] Ds ( 4): Optical smoke density 4 minutes after starting the test. It is obtained from the ratio between transmittance measured by the photometric detector in an instant "t" and the initial reference value. It is a dimensionless number.
    [0070]
    [0071] Ds max: It is the maximum density recorded during the test.
    [0072]
    [0073] VOF4 : It is the area of the graph Ds (optical smoke density) as a function of time, until it reaches 4 minutes.
    [0074]
    [0075] CITg: Conventional Toxicity Index. It is a dimensionless number obtained, following the guidelines of the standard, when applying the following expression:
    [0076]
    [0077]
    [0078] 3 c i is the concentration of the gas "i" in the ISO 5659-2 chamber expressed in mg / m
    [0079] C i is the reference concentration of the gas "i".
    [0080]
    [0081] Table 3: Reference concentration values Ci
    [0082]
    [0083]
    [0084]
    [0085]
    [0086] The list of components of a railway vehicle is very extensive, however, as indicated above, the UNE EN 45545-1 Standard allows grouping them into 26 requirements, for which 17 ISO standards are applied, existing for each level of risk a different specification, the most severe being the one corresponding to the level of risk HL3. The components that constitute a railway vehicle are listed and classified by the UNE EN 45455-1 standard. Such components, be they panels for interior lining, seats, tables, etc. They consist of one or more materials that have previously been homologated based on the specifications established for each requirement.
    [0087]
    [0088] The state of the art has made it clear that halogenated resins fail to reach the density-toxicity specifications of fumes and in the best case the calorimetric cone test is passed just under the risk levels HL1 and perhaps HL2, but in no case HL3 for the different requirements established by the standard. The present inventors have shown that with flame retardant systems based on phosphorus / nitrogen and generating an intumescent layer, the specifications established by the UNE ISO 45545-2: 2013+ standard can be achieved more efficiently than in the prior art. A1: 2015 for the different requirements and levels of risk, including the maximum level of risk HL3
    [0089] There are patents on materials that meet the specifications established by the UNE EN 45545-2 standard for some or some requirements and risk levels:
    [0090] - For cables, see JP20171888248A.
    [0091] - For rubber, see CN106280020A
    [0092] - For seats, see US9266541B2
    [0093] - For polycarbonate, see US20160347952, US8969447B2 and US9365729B2
    [0094] - For polyurethane, see EP2726528A1
    [0095] - For composites with thermosetting resins and reinforcing fibers, see WO2010069465A2, which refers to a system for improving the reaction to fire by intumescence through a formulation that satisfies the different requirements and risk classes established by the UNE EN 45545-2 standard .
    [0096]
    [0097] It is important to be clear about intumescence, how it is formed and what it is for. It is said that a coating is "intumescent" when it has the ability to swell when heated above a certain temperature generating an insulating layer of heat around the elements that cover.
    [0098]
    [0099] In the formation of intumescence there are three main materials:
    [0100] - Ammonium polyphosphate, which decomposes above 250 ° C, releasing ammonia gas, which causes an expansive process of the material, similar to that of baking bread. With enough oxygen and temperature, the ammonia gas can burn, generating more gases. After the release of ammonia, polyphosphoric acid is essentially available. Polyphosphoric acid is a powerful dehydrant, capable of dehydrating polyhydroxy compounds.
    [0101]
    [0102] - Polyhydroxy compounds, such as polysaccharides, for example starch, disaccharides, for example sucrose, even compounds of lower molecular weight, for example, pentaerythrite, or derivatives, for example, dipentaerythrite. These polyhydroxy compounds have the property of being carbonized by dehydration with polyphosphoric acid, which is hydrolyzed to diphosphoric acid or pyrophosphoric acid.
    [0103] The carbonaceous layer that is generated after the previous dehydration reaction is known as "char" and consists of structured carbon. See J. Troitzsch, Plastics Flammability Handbook. Principles, regulations, testing and approval. Munich: Hanser publishers. 2004
    [0104] - Melamines as enhancers of the expansive effect by the ammonia gas released in its thermal decomposition, enhancing the ammonia gas released by the ammonium polyphosphate.
    [0105]
    [0106] In most of the tests established for the requirements in which composites of thermosetting resins and reinforcing fibers are applied, ISO 5660-1: 2015 is applied, for example, to treat the calorimetric cone test with a heat of 50 kW for tests that affect the requirements for thermosetting resin composites reinforced with fibers. After the test, which lasts 20 minutes, the specimen is completely destroyed. Under these test conditions the only strategy that allows obtaining the best possible classification is through the formation of an intumescent layer that protects the innermost areas of the test tube from heat energy.
    [0107]
    [0108] Brief description of the drawings
    [0109]
    [0110] Figure 1 shows the resin reactivity curve. A) Vinyl ester resin: catalyzed with 0.3% Co 6% and 2% PMEK 50%. B) Vinyl ester resin: catalyzed with 0.3% Co 6% 2% PMEK 50% and 0.1% pTBC 10%, in which:
    [0111] In general terms, and before a standard resin, we can have a gel time of about one hour when using 0.1-0.2% cobalt salt, such as cobalt octoate with a content of 6% in cobalt, and 1% methyl ethyl ketone peroxide.
    [0112] When 0.4-0.5% cobalt and 2% methyl ethyl ketone peroxide are used, we can have a gel time of about 20 minutes. When we also add a promoter, the gel time drops to 4-6 minutes.
    [0113] Always starting at 23 ° C.
    [0114] The catalytic system allows the gel time to be modulated from a few minutes to more than 1 hour.
    [0115] - Tg is the time in minutes that corresponds to the gel time, which coincides with the moment when the temperature increases exponentially.
    [0116] - You are the time in minutes that corresponds to the hardening time, which coincides with the point of the maximum temperature reached.
    [0117] - PIC is the maximum temperature in ° C that is reached.
    [0118]
    [0119] Figure 2A shows the appearance of halogenated resin according to the test of the examples. Figure 2B shows the appearance of an intumescent P / N base resin.
    [0120] Figure 3 shows the height of the intumescent layer formed after the calorimetric cone test for the G, H and I specimens.
    [0121]
    [0122] Figure 4 shows the correlation graph of the height of the intumescent layer versus the% fiber of the composite glass.
    [0123]
    [0124] Summary Description of the Invention
    [0125]
    [0126] In a first aspect, the present invention relates to a composite material comprising a flame retardant resin and gelcoat as indicated in the claims.
    [0127]
    [0128] In a second aspect, the present invention relates to the process for the production of a composite material, according to the first aspect of the invention.
    [0129]
    [0130] In a third aspect, the present invention relates to the use of the composite material, according to the first aspect of the invention in transport means, preferably railway, and construction.
    [0131]
    [0132] In a fourth aspect, the present invention relates to a part of a rail transport comprising the composite material, according to the first aspect of the invention.
    [0133]
    [0134] Description of the invention
    [0135]
    [0136] The present invention relates to a composite material comprising:
    [0137] a) a flame retardant resin consisting of
    [0138] - 50 parts by weight of a resin which is an unsaturated polyester resin of DCPD base in dilution of styrene, a vinyl ester resin in dilution of styrene obtained by reaction between epoxybisphenol-A and methacrylic acid, or a mixture of both resins in any proportion;
    [0139] - from 20 to 40 parts by weight of ammonium polyphosphate;
    [0140] - from 20 to 5 parts by weight of melanin;
    [0141] - 10 to 5 parts by weight of dipentaerythrite;
    [0142] provided that the parts by weight of ammonium polyphosphate, melanin and dipentaerythrite add up to 50 parts by weight;
    [0143] b) gelcoat formed by a resin that is an unsaturated polyester resin of DCPD base in dilution of styrene and a vinyl ester resin in dilution of styrene obtained by reaction between epoxybisphenol-A and methacrylic acid, or a mixture of both resins in any proportion ; said resin or resins being thixotroped with pyrogenic silica.
    [0144]
    [0145] In a preferred embodiment, said composite material further comprises
    [0146] c) finishing paint based on an isocyanate crosslinked hydroxylated acrylic resin containing per 100 parts by weight of a component A up to 25 parts by weight of HDI (hexamethylene diisocyanate), wherein said component A comprises:
    [0147] - Hydroxylated acrylic resin
    [0148] - Rheological additives
    [0149] - Surface additives
    [0150] - Solvent
    [0151] - Pigments
    [0152] - Flame retardants (ammonium polyphosphate, melamine and dipentaerythrite).
    [0153]
    [0154] In another preferred embodiment, said composite material additionally comprises fibers selected from glass fiber, aramid fiber and carbon fiber, or a mixture thereof. Preferably, said fibers are glass fibers.
    [0155]
    [0156] In another preferred embodiment, said composite material additionally comprises between 1 and 4% by weight of flexible unsaturated polyester resins containing maleic anhydride, adipic acid and hexanediol.
    [0157]
    [0158] In another preferred embodiment, the gelcoat in said composite material has a thickness of 500 mm. A greater thickness, apart from not being economically satisfactory, can cause problems of pick-up and cracking. With this standard thickness the specifications of the standard are passed.
    [0159]
    [0160] In another preferred embodiment, the melanin and ammonium polyphosphate in said composite material are in the form of particles of 8 to 15 mm in size, which allows sedimentation to be minimized.
    [0161]
    [0162] It should be understood that any of the embodiments relating to the composite material can be combined with each other.
    [0163] The present invention also relates to a part of a rail transport comprising the composite material, according to any of the embodiments described herein. By "rail transport" means any system of transport of people and goods guided on a railroad track, such as for example train, subway, tram, etc.
    [0164]
    [0165] In a preferred embodiment, said part of a rail transport comprising the composite material, is the structure and lining, the luggage rack, the control console, tables and sinks, bands, base structure of the passenger seat, interior surfaces of the aisles, walls of the external structure of the vehicle or the front of the train.
    [0166]
    [0167] Detailed explanation of composite material to achieve the objective of the invention
    [0168]
    [0169] The resins required for the composite material of the present invention should be as reactive as possible, since they will be mixed with flame retardants, and the resulting mixture should harden properly when catalyzed. In addition, the formulations must be stable over time, at least three months, in order to be transported where required without problems of gelation due to the interaction between resin and flame retardants. It is also required that the resin, formulated with flame retardant additives, be stable to the decantation of flame retardants within the resin. To avoid this problem, the viscosity must be adjusted with rheological additives so that the resin is as fluid as possible, so that it is easily applied, but at the same time has sufficient viscosity to prevent sedimentation of flame retardant additives . The addition of rheological additives such as pyrogenic silica or BYK 605 allows the resin viscosity to be slightly increased, without conflict with its application. 0.2-03% pyrogenic silica or 0.15% BYK 605 is sufficient. Obviously, the content of flame retardant additives must allow the specification of reaction to fire and the required density and toxicity of fumes to be achieved, without all this detrimental to the mechanical properties of the composite material to be obtained.
    [0170]
    [0171] As guidance on the extent to which the resins are to be added with flame retardants, generally the maximum limit is 50% so that the above expectations can be met.
    [0172] There are two types of interesting resins for our purposes:
    [0173]
    [0174] - Unsaturated polyester resins based on DCPD. Dicyclopentadiene (DCPD) is previously reacted with maleic anhydride to give an adduct with which polyester is manufactured by polymerization with a diol, such as 1,2-propylene glycol, 1,4-butanediol, etc. This type of unsaturated polyester in dilution of styrene, as a reactive monomer, produces lower viscosities than those obtained by reaction with maleic anhydride. DCPD resins thus have the advantage that they are fluid. In addition, they can still be diluted with some more styrene, generating composites with good mechanical properties after curing.
    [0175]
    [0176] - Vinyl ester resins. Vinyl ester resins are obtained by reaction between epoxybisphenol-A with methacrylic acid giving rise to the difunctional monomer epoxybisphenol-A-methacrylate. The dilution of this in styrene, as a reactive monomer, is known as vinyl ester resin. There are more vinyl ester resins, but in the present invention only epoxybisphenol-A reacted with methacrylic acid will be considered as being very reactive and at the same time sufficiently stable for our purposes, presenting very low viscosities.
    [0177]
    [0178] Apart from styrene, used as a reactive diluent par excellence in unsaturated polyester, due to its good price / quality ratio in relation to the mechanical properties of the final composite material manufactured, reactive acrylic diluents should be considered, which in some cases may be useful: Pentaerythritoltetramethacrylate (PETTMA), Hexanodioldimethacrylate (HDMA, Trimethylolpropane triacrylate (TMPTA). Also useful are allylic di- and / or tri-functional monomers, such as diallyl phthalate, diallylamaletate, triallyltrimethalate and triallyltronate).
    [0179]
    [0180] The resin curing system, that is how they harden or polymerize, is generally carried out by the use of cobalt salts, such as cobalt octoate dissolved in a solvent, such as "white spirit", with a cobalt content of the 6%, called accelerant, and an organic peroxide, such as methyl ethyl ketone peroxide, with an active oxygen content of 9%.
    [0181]
    [0182] The mechanism of curing, hardening or polymerization consists in that the organic peroxide at levels of 1.5 to 2.5% dissolved in the resin containing the flame retardant additives is decomposed by the cobalt salt, which usually contains the resin about 0.5%. The reaction between peroxide and cobalt generates organic radicals derived from peroxide that cause polymerization of the resin.
    [0183]
    [0184] During the polymerization an exothermic reaction occurs. The time it takes for the resin to polymerize depends on the proportions of cobalt salt and organic peroxide (catalytic system), as well as the starting temperature and even the humidity conditions. The exotherm of polymerization can condition the amount of resin that can be polymerized in one operation. The time it takes to cure depends on the catalytic system.
    [0185]
    [0186] The polymerization of the resin can be modulated, to some extent, by variants in the catalytic system of organic peroxide and cobalt salt. More peroxide, between 1.5 and 2.5%, for a given% of cobalt salt makes the curing time shorter. For a fixed% of organic peroxide between 1.5 and 2.5%, the higher the% of cobalt salt added, the shorter the cure time. In addition to the% organic peroxide and cobalt salt, there are other substances that affect the catalytic system. Substances such as dimethylacetoacetamide, diethylparatoluidine, dimethylaniline, and others of the same nature, act as promoters of the catalytic system at levels of 0.1% to 0.2% on the resin, shortening the time spent in curing. Other substances, such as para-tert-butylcatechol (p-TBC), at the level of a few g / Tn are capable of lengthening the time spent in curing, as well as improving the thermal stability of the resin. These substances have as common denominator that they are compounds with phenolic structure, capable of reacting with radicals forming very stable radicals. That is, the presence of phenolic compounds, such as p-TBC, inhibits the reaction of the resin with radicals, lengthening the cure time when used in small doses. At higher doses, it could totally inhibit cure.
    [0187]
    [0188] In the polymerization process, the resin thickens until it becomes a solid, at first not very rigid, but after a few hours, it becomes rigid. In the polymerization process, the radicals generated by the decomposition of the organic peroxide by the cobalt salt are responsible, when the viscosity of the polymerizing mass becomes high, the mobility of the radicals is limited and as a consequence the polymerization reaction It runs slower. It is accepted that 95% of the polymerization takes place in several tens of minutes, while to achieve complete polymerization it may take several days. In practice, polyester and / or vinylester resin composite materials undergo a cycle of several hours of heating at about 60 ° C to ensure polymerization is complete. In the case of the resin formulations presented in the present invention, it has been found that the same surface hardnesses of 40 barcol are achieved both by subjecting the pieces to a heating cycle, and bypassing said heating. In general, this treatment allows to improve the mechanical performance of the composite material, in particular when resins of medium or low reactivity have been applied.
    [0189]
    [0190] In resin formulations with flame retardants, and in general those containing a high percentage of added solids, the reactivity of the resin is an important parameter to take into account. The more unsaturated the resins are, the greater the cross-linking that is achieved by copolymerizing with the reactive monomer in which they are diluted, usually styrene, giving a more cross-linked final polymer, that is, with a greater number of carbon-carbon bonds between the styrene and unsaturated polyester.
    [0191]
    [0192] The more maleic anhydride the polyester contains, the greater the number of unsaturations it will have and therefore more styrene bridges can be formed. Styrene bridges contain between two and three styrene molecules, and this is conditioned by the relative rates of copolymerization between the styrene radicals and the unsaturated polyester radicals.
    [0193]
    [0194] In accordance with the above, and by degradation analysis of the final polyester polymer, it is known that for every two maleic unsaturations present in unsaturated polyester molecules, between two and three styrene molecules are required to achieve a final polymer that has the best possible mechanical performance, so, the higher the percentage of the unsaturated polyester in maleic anhydride, the more styrene is required for polymerization, and therefore the dissolution of the unsaturated polyester in styrene will be more fluid. It should be considered that the molecular weights of the polyester molecule generally range between 1000 and 2000 g / mol. Obviously, the lower the molecular weight, the less viscous the unsaturated base polyester will be, and the more fluid its dissolution in styrene.
    [0195]
    [0196] The same comments made for styrene unsaturated polyester can be applied in the case of vinyl ester resins also diluted in styrene.
    [0197] The most reactive resins are, therefore, generally more fluid, that is, they allow more flame retardants to be added, up to the maximum possible depending on the criteria of applicability, mechanical performance and stability.
    [0198]
    [0199] If the resin is formulated with many loads, its appearance will be pasty, and its practical applicability will be limited. Depending on the resin application system, it can be more or less tolerant, but, in general, resins formulated with flame retardants with viscosities between 1000 and up to 1500 cPs do not usually present application problems.
    [0200]
    [0201] The more reactive the resin, that is, the higher its content in maleic anhydride, the greater the hardness it will have and also the greater the toughness, which is excellent for mechanical performance, but also more crystalline, therefore, less resistant to flexotraction To minimize this inconvenience, the use of flexible resins can be used in a small proportion, which can range between 1 and 4% by weight. Flexible unsaturated polyester resins obviously contain little maleic anhydride, the major diacid is adipic acid and the diol is hexanediol. These resins have elongations at the break of the order of 100% and even 200%. Flexible resins are the simplest solution to find a point of balance between tenacity and flexotraction.
    [0202]
    [0203] Resins with a high content of maleic anhydride are therefore very reactive, which means that their half-life is shorter in relation to those of standard medium-reactivity resins. When formulated with flame retardants, the resulting product must be usable for at least 3 months. To maintain the viscosity of the resin formulated with flame retardants as constant as possible during its useful life, it is usual to inhibit it with the minimum dose of para-Tert-butylcatechol for certain conditions of use. The higher the dose of inhibitor, the longer the gel time is and at the same time its thermal stability (stable over time). The practical limit is that in which the customer's gel time to which the resin is delivered is practical and productive. If the inhibitor goes into excess, the resin does not cure.
    [0204]
    [0205] Reactivity is a property that can be easily measured. 100 g of resin are taken in a low-weight plastic cup, catalyzed with cobalt octoate with a cobalt content of 6% and with an organic peroxide, for example 0.5% octobalt and 2% methyl ethyl ketone peroxide with an active oxygen content of 9%. I know Place the plastic cup inside an adiabatic container, such as a porexpan box. A temperature probe connected to a Temperature / time recorder is placed and the graph is recorded during the polymerization process (see Figure 1).
    [0206]
    [0207] The composite material, or composite, resulting from applying the resin, optionally with fiber reinforcements, on a mold in which a gelcoat has been previously applied, has a toughness close to metals, but with a lower density and without corrosion problems. By choosing resins and fibers properly, materials with on-demand resistances are designed, from components for the aeronautical industry, aerospace industry, engineering and construction. The fiber most used for its good strength and low price is fiberglass. There are other fibers with better performance such as aramid fiber and carbon fiber with which the best mechanical performance is obtained.
    [0208]
    [0209] The most common application systems for resins formulated with flame retardants are:
    [0210] - Manual laminate. The resin is applied manually with the help of rollers on the mold containing the fibers.
    [0211] - Wash. Direct addition of resin on a mold
    [0212] - RTM (Resin Transfer Molding). Pumping into the closed mold inside which the fibers are, vacuum suction can be helped from the opposite end.
    [0213] - Filament winding. The fibers embedded in resins are wound on a mold of cylindrical geometry.
    [0214]
    [0215] In manual and RTM laminating processes, a paint is usually applied first on the mold known as gelcoat, on which the optional fiber sheets are deposited, which are laminated with resin. In casting processes, the resin that is applied to the mold without reinforcement fibers is usually pigmented.
    [0216]
    [0217] The gelcoat is a formulation of nature and composition similar or equal to the resin that is pigmented and constitutes the color finish of the composite piece once finished. The gelcoat catalyzes like the resin with cobalt salts and an organic peroxide.
    [0218]
    [0219] Resins with improved fire reaction, or fire resistant, are formulations in which flame retardant additives are incorporated. These formulations must pass Successfully fire reaction tests, case of the calorimetric cone test according to ISO 5660-1: 2015 and smoke density and toxicity, case of the smoke chamber test according to ISO 5659-2: 2013. If the content of flame retardants in a formulation is not enough, then the test will not pass. If, on the contrary, flame retardants are formulated in excess, to ensure success in the test, then we run the risk that the formulation is not applicable because it has a percentage in solids that makes its application unfeasible. It is necessary to look for an equilibrium point in which there is a minimum of flame retardants and a maximum of resin so that the mechanical properties are sufficient for the performance required of the composite piece. This equilibrium point can be placed in 50% flame retardants and 50% resin.
    [0220]
    [0221] The mixture of flame retardants, generally solids, with the resin, in proportions of the order of 50% for each one, must be stable to decantation, that is, to the formation of a gradient of solids from the bottom to the mouth of the container in which it is stored. The viscosity of the resin, at a certain temperature, and the particle size distribution of the flame retardants condition the decay stability of the formulation. The larger the particle size of the flame retardants, the higher its sedimentation rate, for the same viscosity of the resin. The higher the viscosity of the resin, the lower the decantation rate of the larger particles. A very fine particle size is not advantageous because it tends to thicken the resin. A very fluent resin admits a higher proportion of flame retardants than a more viscous one, but it has the disadvantage that for the same particle size its decantation rate is greater than that which would occur in a more viscous resin. As a summary, the experience acquired in the tests carried out below, allows us to establish the general conclusions indicated below.
    [0222]
    [0223] Fine particles of up to 8 microns have a thickening effect, the thinner they are, the more thickening capacity and they also have a slow decanting speed.
    [0224]
    [0225] The particles of approximately 15 microns have the best behavior, are not very thickening and their decantation rate is still low. Formulations with average particle sizes of approximately 15 microns easily stabilize at settling.
    [0226] As the particle size grows above 15 microns, its thickening effect is poor, but they decay more easily. For example, medium-sized particles of 40 microns decant easily when they are suspended in resins of the order of 1000 cPs of viscosity at 25 ° C. Obviously the decantation depends strongly on the temperature due to the drop in viscosity of the resins as the temperature increases.
    [0227]
    [0228] Starting from reactive resins with low viscosity, for example from 40 to 400 cPs maximum at 23 ° C, with a percentage of resin of the order of 50% and 50% of flame retardants with a particle size centered over 15 microns, viscosities are obtained end of the order of 800 to 1000 cPs. These formulations slightly additive with thixotropant agents, such as progenic silices or other liquid rheological agents such as BYK 605, allow stabilization processes to stabilize quite well, unless the storage temperature is high, for example of the order of 30 ° C. As it has been commented, these products act like yogurt, at rest they give viscosity, in movement they allow creep, they increase the viscosity of the resin a little, without hindering its application. They are effective in limiting the sedimentation of loads.
    [0229]
    [0230] The formulation of the resin and the flame retardants must also be stable at the temperature, the formation of gelation cores that extend until they gel completely must be delayed as much as possible. To improve thermal stability, taking into account that the most suitable resins are the most reactive, the inhibitors must be used and certain precautions taken. If formulated with catalyst system promoter it becomes even more unstable. If possible, it is better not to accelerate them with cobalt salts, or in their presence, avoid the entry of oxygen, which is not easy. In the presence of oxygen, unsaturated compounds can form reactive intermediates, such as oxetanes, epoxies and organic peroxides of the hydroperoxide type, which in the presence of cobalt salts decompose giving radicals that cause polymerization of the resin. In the presence of small amounts of inhibitor, such as para-tert-butylcatechol (pTBC), stability is improved, at the level of a few hundred grams per ton of resin. The more inhibitor is added, the greater thermal stability is achieved. When the resin is to be catalyzed, some more cobalt salt and organic peroxide must be added to counteract the effect of the inhibitor.
    [0231]
    [0232] The thermal stability of a pure resin or a resin formulation with flame retardants is easily evaluated by monitoring the evolution of viscosity keeping the test sample at a temperature of 40 ° C or 50 ° C (accelerated test). By adding 100 to 1000 g / Tn of p-TBC, good thermal stability results are achieved, at the expense of using a higher percentage of cobalt salt and organic peroxide when catalyzed for polymerization. The use of promoters such as dimethylacetoacetamide, dimethylaniline, toluidines, etc. It is contraindicated. Stability may vary with seasonality, depending on storage temperatures. In winter, 3 months of stability can be guaranteed, in summer, depending on the temperatures reached, at least 2 months can be guaranteed, always keeping the resin below 30 ° C and not exposed to the sun. The storage temperature for a life of 3 months is 18 ° C and 25 ° C maximum.
    [0233]
    [0234] With respect to flame retardant additives, the following compounds mentioned above are required to generate an intumescent layer:
    [0235]
    [0236] - Ammonium polyphosphate: high degree of polymerization, n> 100, has a low water absorption capacity. It is a highly efficient additive to retard flames and to generate an intumescent layer without producing dense and toxic fumes. When heating, it decomposes above 240 ° C producing ammonia gas and polyphosphoric acid, which acts as a dehydrant for certain polyols, such as polysaccharides, etc. that end up generating a carbon layer called Char.
    [0237]
    [0238]
    [0239]
    [0240] ammonium polyphosphate structure.
    [0241]
    [0242] - Melamine: It acts as a foaming agent by releasing ammonia when it decomposes by heating, giving condensed products of analogous structure but of greater molecular weight, to form as a stable decomposition product -g (C3N4) - or graffiti carbon nitride. Help foam the dough. Graffiti carbon nitride is part of the Char.
    [0243] There are other melamine compounds used as flame retardants, such as melamine cyanurate, melamine phosphates, melamine borate, which have been tested but have not yielded better results than melamine at the same percentage.
    [0244]
    [0245] - Dipentaerythrite: it is dehydrated by the phosphoric acid generated by the ammonium polyphosphate generating the carbon layer called Char.
    [0246]
    [0247]
    [0248]
    [0249]
    [0250] Structure of dipentaerythrite.
    [0251]
    [0252] Starches, cellulose, pentaerythrite act similarly to dipentaerythrite providing carbon to form the Char, but the optimal compound would be dipentaerythrite since less is needed. Char is the solid material that is generated, from an organic material, after a combustion process.
    [0253]
    [0254] Procedures and uses of the composite material of the invention
    [0255]
    [0256] The present invention also relates to a process for the production of a composite material, according to any of the embodiments indicated above, comprising the steps of:
    [0257] a) apply gelcoat on a previously waxed mold to allow the gelcoat to cure; b) apply layers of flame retardant resin and, optionally, fibers until the desired thickness is obtained;
    [0258] c) let the layered material cure from step b);
    [0259] d) unmold the mold piece; and, optionally;
    [0260] e) apply finishing paint.
    [0261]
    [0262] The foreseeable applications of the composite material of the present invention are those in which an improved fire reaction material is required that gives a low smoke density with a low toxicity index, for example for road, sea, aeronautical transport and obviously for rail, since the trials to Those of us who are going to submit the composites are standardized for railway applications. Its use in construction is also foreseeable when materials with improved fire reaction are required.
    [0263]
    [0264] Thus, the present invention also relates to the use of composite material, according to any of the embodiments indicated above, in means of transport and construction.
    [0265]
    [0266] In a preferred embodiment, said means of transport is rail transport. "Rail transport" means as defined above.
    [0267]
    [0268] In a more preferred embodiment, said rail transport comprises the components of a rail transport according to the requirements indicated in the UNE EN 45545-1 standard (see above).
    [0269]
    [0270] Next, a series of examples that reflect the tests performed for the composite material developed in the present invention will be indicated. Said examples are merely illustrative and are not intended to limit the scope of the invention, which is established by the accompanying claims.
    [0271]
    [0272] EXAMPLES
    [0273]
    [0274] Previous trials
    [0275]
    [0276] Next, the materials used to study their fire behavior are detailed in order to define resin formulations, flame retardant additives and other additives that meet the specifications established by the UNE EN 45545-2: 2013 + A1: 2015 standard .
    [0277]
    [0278] Table 4. List of materials used in the formulation of resin and gelcoat
    [0279]
    [0280]
    [0281]
    [0282]
    [0283]
    [0284]
    [0285] (*) These materials were discarded after previous tests with the selected resins.
    [0286]
    [0287] Next, the previous tests carried out to obtain a resin formulation, flame retardant additives and other additives that comply with the specifications established by the UNE EN 45545-2: 2013 + A1: 2015 standard are detailed.
    [0288]
    [0289] With these previous tests it is intended to have an overview of how the composition of the composite that is tested is correlated with the results of reaction to fire, density and toxixcity of fumes. It is studied which additives have the greatest effect and which ones are less in the reaction to fire and smoke. It is studied whether there is a correlation between the P / N ratio and the results obtained. The applicability and stability criteria of the formulation and other aspects, such as the mechanical properties of the composite material, are not taken into account in these previous tests.
    [0290]
    [0291] Table 5: Results of previous trials 20 - 24.
    [0292]
    [0293]
    [0294]
    [0295]
    [0296] Table 6: Results of previous trials 27-34.
    [0297]
    [0298]
    [0299]
    [0300]
    [0301] Table 7: Results of previous trials 35 - 41
    [0302]
    [0303]
    [0304] Table 8: Results of previous trials 43 - 49.
    [0305]
    [0306]
    [0307]
    [0308] Table 9: Results of previous trials 50-58.
    [0309]
    [0310]
    [0311]
    [0312]
    [0313]
    [0314]
    [0315]
    [0316] The resins used were Prester VE 2355 from Cromogenia Units, SA and DCPD resin from Ashland (Aropol FS series) and Polynt (Distriton 100 series), as well as flexible Polynt resin (Norsodine B73233). The results obtained using the vinyl ester resin, those of DCPD, or mixtures of both types of resin are equivalent. The observable differences focus on catalyzing, due to its different inhibition. Depending on the inhibitor content, its gel time can be modified from several minutes to one hour. Vinyl ester resin is inhibited with pTBC and has a gel time using as a catalyst system 0.4% cobalt octoate with 6% cobalt content and 2% methyl ethyl ketone peroxide of the order of a minimum of 45 minutes. Under these same conditions, the DCPP resin has a gel time of less than 10 minutes.
    [0317]
    [0318] Resin or resin formulations with flame retardants according to their inhibitor content have a longer gel time the more inhibitor has been added. For stability, a gel time of the order of 45 to 60 minutes assumes that the formulation will be thermally stable for a longer period of time, usually 3 months or more, if it has been stored at temperatures below 25 ° C. The DCPD resin needs to be inhibited to be used in formulations with the flame retardants described, that is to say it is added in the order of p-TBC to lengthen its gel time and its shelf life, without gelling in the container. In any case and as a general recommendation, the resin should be stored below 30 ° C, the stability at that temperature is about 30 days.
    [0319]
    [0320] When the resin is catalyzed with methyl ethyl ketone peroxide and cobalt salt, we observe that if a poorly inhibited resin is used, with the usual doses of cobalt and peroxide, we obtain relatively short gel times, similar to other resins, but if the resin is inhibited, the dose of cobalt salt can reach up to 1%, or even more. It all depends on the thermal stability that we want to give to the resin formulation with flame retardants, the more inhibitor, the more cobalt salt will be required to reach the same reference gel time.
    [0321]
    [0322] The most relevant conclusions drawn from the previous trials detailed in Tables 5, 6, 7, 8 and 9 are:
    [0323] 1. - Little effectiveness in reducing the density of fumes by adding with a smoke suppressor, of proven efficacy in formulations with halogenated resins.
    [0324] 2. - Little effectiveness of alumina hydrate, which has given high values of both Marhe and smoke density
    [0325] 3. - The P / N ratio does not correlate with Mahre values. If there are very clear indications that a percentage in both P and N high gives better Marhe values and lower smoke densities.
    [0326] 4. - Very good effectiveness of the additive BYK 980 as a viscosity depressant in the formulations tested.
    [0327] 5. - Fiberglass, used in proportions of 25 to 34% in prepared composites, does not correlate with Marhe values. That is, in principle a higher percentage of fiber, read as a lower percentage of resin in the composite, should give smaller Marhe values, but we see that it is not.
    [0328] 6. - Some results are not easily interpretable, unless we accept lack of cure in some specimens.
    [0329] 7. - Percentages of ammonium polyphosphate (APP) of the order of 40% and at least 15% of melamine polyphosphate seem to be required to obtain Marhe values between 55 and 65 kW / m2, but in this case the percentage in resin is reduced around 35%, which seems low input.
    [0330] 8. - Alumina hydrates (ATH), smoke suppressants used in halogenated resins, zinc borate and liquid organic phosphates are not effective in the formulations tested.
    [0331] 9.- The non-dependence of the Marhe value obtained with respect to the percentage of fiberglass in a range of 25 to 34% invites us to think that the resin content could be increased from 35 to 45% or more, for example 50% improving the effectiveness of flame retardant additives ammonium polyphosphate (APP) and melamine polyphosphate, in general melamine, and the dipentaerythrite introduced in tests 50-58 of Table 9.
    [0332]
    [0333] Comparison of the results obtained with the M1F1 resin
    [0334]
    [0335] An M1F1 resin is the one that meets the specifications established by the UNE 23727: 2006, NF X 10702: 2006 and NF X 701100: 2006 standards, effective before the entry into force of the current UNE EN 45545-2: 2013+ standard A1: 2015.
    [0336]
    [0337] M1F1 resins are formulated with halogenated resins, either with chloric acid and / or with tetrabromophthalic acid, they may also contain, or not, brominated flame retardant additives, such as tetrabromo-1,2-di-phenylethane, antimony oxide and suppressors. fumes such as zinc hydroxystannate. These resins have a good reaction to fire, but the density and toxicity of smoke is quite high.
    [0338]
    [0339] Following the line of the previous tests, the resin was formulated with the three components required to form the intumescent layer:
    [0340] - Ammonium polyphosphate, generator of polyphosphoric acid, which dehydrates the carbon donor polyol to generate the char layer.
    [0341] -Melamine, or melamine derivative, foam enhancer and that contributes to the formation of char by generating [g-C3N4] or graffiti carbon nitride.
    [0342] -Dipentaerythrit as carbon donor to form char
    [0343]
    [0344] Unlike halogenated resins, which after testing in the calorimetric cone to determine the Marhe of the composite are reduced to inconsistent white ashes, the phosphorus and nitrogen based resins, intumescent, generate a very hard black char crust (see Figures 2A and 2B).
    [0345]
    [0346] Table 10 compares the results obtained by subjecting an M1F1 resin to the requirements of Requirement 1 of the UNE EN 45545-2: 2013 + A1: 2015 standard, against a halogen-free and antimony-based resin formulated with retardants of flame based on phosphorus and nitrogen, developed from the previous results obtained in the previous section of previous tests.
    [0347] Table 10: Comparison between halogenated resin M1F1 and Prester Resin 1165 according to UNE EN 45545-2: 2013 + A1: 2015
    [0348]
    [0349]
    [0350]
    [0351]
    [0352] Table 11: Composite material formulation
    [0353]
    [0354]
    [0355]
    [0356]
    [0357] The results obtained in table 10 with the formulation established in table 11, show that by combining ammonium polyphosphate, melamine and dipentaerythrite properly, good results are obtained in the tests formulating with 50% resin percentages, as discussed in the conclusions of the section previous of the previous tests. The resin composition used, whether unsaturated polyester based on DCPD, or vinyl ester, both in styrene monomer solution as a reactive monomer, or mixtures of both resins, does not affect the reaction results to fire obtained in the calorimetric cone and those of density and toxicity of fumes obtained in the smoke chamber, as we have evidenced in tests in which the resin has been modified.
    [0358]
    [0359] Influence of the arrangement of fiberglass layers in the reaction to composite fire
    [0360]
    [0361] Composites are prepared with the HL gelcoat reference H12-291016 and the Prester 1165 resin reference 200916 applying a glass fiber percentage of 25 / - 1% on the composite. The gelcoat is spread on a waxed glass mold with an applicator to form a 750 micron thick layer. Three specimens A, B and C are prepared. Each specimen has a different arrangement of glass fibers. In the test tube A a fiberglass veil is applied to the gelcoat, in the test tube B a 100 g glass fiber mat, in the test tube C a 200 g glass fiber mat. Once this first layer is applied, all the specimens are completed by rolling with two 450g fiberglass mats. With this test we want to see if the fiber affects intumescence and it affects the test result.
    [0362]
    [0363] Table 12: Design and test data
    [0364]
    [0365]
    [0366]
    [0367]
    [0368] Table 13: Composition of the composite formulation tested
    [0369]
    [0370]
    [0371]
    [0372]
    [0373]
    [0374] Table 14: Results obtained.
    [0375]
    [0376]
    [0377]
    [0378]
    [0379] Definition of the parameters listed in table 14:
    [0380] MARHE (kW / m2): maximum value of the ARHE (t) in the 1200 s test.
    [0381] THR 1200s (MJ / m2): total heat generated in the 1200 s test
    [0382] q.max (kW / m2): peak of maximum heat generation in the 1200 s test
    [0383] MLR: average speed of mass loss (g / m2.s)
    [0384] TMLR 1200 s (g / m2): mass loss in the 1200 s test.
    [0385]
    [0386] The Marhe results obtained show that the arrangement of the layers does not alter the values obtained from the Marhe, although it is clearly observed that the rate of mass loss and the corresponding combustion energy increase as the weight of the first fiberglass layer, therefore, although it does not alter the value of the Marhe because it is obtained in the first minutes of the test, it is clear that the intumescent layer is generated with more difficulty in the presence of fiber layers of greater weight. Marhe values obtained for Requirement 1 would be classified within the HL risk level. This is something not described in the state of the art.
    [0387]
    [0388] Influence of gelcoat layer thickness on composite fire reaction Composites are prepared with the reference gelcoat HL13-290916 and the Prester 1165 reference resin by applying a percentage of glass fiber in the composite of 25 / -1%. The gelcoat is spread on a waxed glass mold with an applicator to form a layer of different thickness in each specimen. Three specimens are prepared, D, E and F. In each specimen the arrangement of the glass fibers is the same; After the gelcoat has hardened, a fiberglass mat of 100 g / m2 is applied, and then during rolling another two mats of 450 g are applied. The thickness of the composite is 3 mm. In this test we want to see if the thickness of the gelcoat layer affects the fire reaction of the composite.
    [0389]
    [0390] Table 15: Design and test data.
    [0391]
    [0392]
    [0393]
    [0394]
    [0395] Table 16: Composition of the composite formulation tested
    [0396]
    [0397]
    [0398] Table 17: Results obtained
    [0399]
    [0400]
    [0401]
    [0402]
    [0403] The Marhe results obtained show that the thickness of the gelcoat layer does not significantly alter the values obtained from Marhe. Given that the tolerance of the Marhe results allowed by the standard is 10%, the determined values are within the standard. It is observed that even in the absence of fiberglass the Marhe value does not vary less than the tolerance established by the standard. In this case the formulations used do not meet the specifications established for Requirement 1 for the HL2 risk level, it is only met for the HL1 risk class because the proportions of ammonium polyphosphate and melamine have been changed in the gelcoat formulation. Despite the poor result, it is clear which proportions of polyphosphate and melamine are adequate and which are not. As for the thickness of gelcoat layer thicknesses of less than 500 microns are not usually applied. More than 750 microns requires the application of two successive layers to avoid problems of pick-up and cracking.
    [0404]
    [0405] The gelcoat formulation used for this test (ref. HL13-290916) is different from that used in the previous series test. With respect to the gel coat HL12-290916 with which a Marhe of 72 / - 2 kW / m2 was obtained, it is now Marhe 96 / - 6. The difference found, since the composition of the resin formula of the laminate is It is due to the gelcoat formulation. See that the gelcoat HL13-290916 contains less ammonium polyphosphate and more melamine, therefore the formulation of the gelcoat HL12-290916 contains percentages of ammonium ammonium polyphosphate and melamine that allow a better classification of the composite.
    [0406]
    [0407] The most important conclusion is that thicknesses of 500 microns are sufficient to meet the specifications required by the standard. It can also be inferred that the formulation changes in the gelcoat could affect more than the resin, since the layer The intumescent gelcoat can generate is not limited by the presence of layers of glass fibers that constrain its expansion.
    [0408]
    [0409] Influence of the percentages of resin and fiberglass on the results of the reaction to fire of the composite material
    [0410]
    [0411] From the previous results it is intuited that a lower percentage of fiberglass could affect little, or even not affect the Marhe and the rest of the reaction parameters to fire measured during the calorimetric cone test on the test specimen of 10x10 cm2, because favor the development of the intumescent layer. The fiber layers act as a bandage that constrains the formation of the intumescent layer. We will try to elucidate this issue in this essay:
    [0412]
    [0413] Table 18: Design and test data.
    [0414]
    [0415]
    [0416]
    [0417]
    [0418] Table 19: Composition of the formulation of the composite material tested.
    [0419]
    [0420]
    [0421] Table 20: Results obtained.
    [0422]
    [0423]
    [0424]
    [0425]
    [0426] MARHE (kW / m2): maximum value of the ARHE (t) in the 1200 s test.
    [0427] THR 1200s (MJ / m2): total heat generated in the 1200 s test
    [0428] q.max (kW / m2): peak of maximum heat generation in the 1200 s test
    [0429] MLR: average speed of mass loss (g / m2.s)
    [0430] TMLR 1200 s (g / m2): mass loss in the 1200 s test.
    [0431]
    [0432] The results obtained show that the percentage of composite fiberglass does not affect Marhe. With a percentage of fiberglass of 22.8% or without fiberglass in the composite, Marhe's recorded values differ less than 2 kW / m2, that is, the composites present in practice the same Marhe. The test results are within the range 76 / - 4 kW / m2, values acceptable by the standard, which allow establishing the independence of the presence of fiberglass in the Marhe value of the tested composite.
    [0433]
    [0434] Recall that the Marhe (Maximum Average Rate of Heat Emission) is the maximum value of the heat emission rate over time. This maximum can be located at different times, depending on the material, always within the first minutes of the test. Marhe is a derivative, it is not an integral, it does not give information about the total energy released in forced combustion. Let's see that the total heat generated at 20 minutes, at the end of the test, is greater in the case that the composite does not contain fiberglass, that is, having a higher resin content, has burned to a greater extent therefore generating more energy. Indeed, the TMLR values recorded at 20 minutes show the facts by showing a greater loss of mass for the composite that contains a higher percentage of resin. According to the facts, the Marhe value depends on the resin formulation and the flame retardants selected, it does not depend on the percentage of fiber applied in the composite, as a priori one might think according to the state of the art Layers fiberglass, as indicated, constitute a bandage that prevents free expansion of the intumescent layer, since the Marhe does not depend on the percentage of fiber glass, according to the results we have registered, then the formation of a higher intumescent layer height should depend on the percentage of fiberglass. (See Figure 3 and Figure 4)
    [0435]
    [0436] In conclusion, the height of the intumescent layer depends on the percentage of fiberglass in the composite, but the Marhe value is not affected by that percentage, therefore depends on the resin formulation and flame retardant.
    [0437]
    [0438] Influence of the origin and surface treatment of ammonium polyphosphate on the results of the reaction to fire of the composite
    [0439]
    [0440] There are different manufacturers of ammonium polyphosphate that offer different types to the market. The most effective are those that are called encapsulated, that is, coated with barrier-acting polymers, regulating the release rate of ammonia and the diffusion of the product in the composite under a temperature gradient when a flame strikes it. It is expected that different types of ammonium polyphosphate will give different results in the calorimetric cone test. If with the encapsulation it is possible to alter the kinetics of the decomposition of the ammonium polyphosphate, it is possible that certain encapsulated types allow us to obtain a more favorable Marhe.
    [0441]
    [0442] Table 21: Design and test data.
    [0443]
    [0444]
    [0445]
    [0446]
    [0447] Table 22: Composition of the composite formulation tested.
    [0448]
    [0449]
    [0450]
    [0451]
    [0452]
    [0453] Table 23: Results obtained.
    [0454]
    [0455]
    [0456]
    [0457]
    [0458] For the same formulation and preparation procedure of a composite, different Marhe values are obtained depending on the type of encapsulation of the ammonium polyphosphate used. Encapsulation is important because it allows us to modify the Marhe or maximum heat emission rate that is reached during the test in the calorimetric cone. A priori, even knowing the type of polymer with which ammonium polyphosphate is encapsulated, only through a test in the calorimetric cone can we obtain practical information on how encapsulation alters the value of Marhe, being able to select those types of ammonium polyphosphate that They allow us to obtain a better classification for the composite under test.
    [0459]
    [0460] In this example, the tested ammonium polyphosphate, APP 262, allows us to reach the HL3 risk level for Requirement 1, since the Marhe obtained is below 60 kW / m2 established by the UNE EN 45545: 2013 + A1: 2015 standard for that requirement.
    [0461]
    [0462] Formulation and testing of a finishing paint for composite material
    [0463] For those situations in which a finishing paint is required, either because of the characteristics of the color, or because it is impossible to reproduce the color on a gelcoat, a finishing paint is formulated and the degree of compliance with the UNE EN standard is tested. 45545-2: 2013 + A1: 2015.
    [0464]
    [0465] Table 24: Design and test data.
    [0466]
    [0467]
    [0468]
    [0469]
    [0470] Table 25: Composition of the formulation of the tested compound.
    [0471]
    [0472]
    [0473] .
    [0474] Component A
    [0475]
    [0476]
    [0477]
    [0478]
    [0479] Component B: Desmodur N75 (HDI).
    [0480] 100 parts of component A are mixed with 20 parts of component B and the resulting spray paint is applied. The addition of 5 to 10% butyl acetate may be necessary to adjust the viscosity to 50 sec. in Ford Cup 4.
    [0481]
    [0482] Table 27: Results obtained.
    [0483]
    [0484]
    [0485]
    [0486]
    [0487] Although the paint incorporates the same flame retardants and the low thickness applied, the contribution to the Marhe is 12 kW / m2. To apply finishing paints on composite for risk level HL3 we should have a Marhe of the gelcoat finished composite of 45 kW / m2, a value that does not seem easy to achieve.
    [0488] Detailed preparation of the tested composites
    [0489]
    [0490] The composites described in Tables 5, 6, 7, 8 and 9 and all the examples presented corresponding to the previous tests and those described later, are prepared incorporating the accelerator, cobalt octoate with a content of 6% in Cobalt, on the resin, followed by liquid flame retardant additives, if any, then flame retardant additives that are solids are added, according to the order established in each tabulated formulation. For this purpose, a metal container is used, type can of 500 to 1000 ml of capacity fixed on a support. The ingredients are dispersed using a cowless shaker of maximum diameter half the diameter of the can with variable speed from 0 to 1500 rpm. To ensure good dispersion, stirring is maintained at 1500 rpm for at least 20 minutes. The temperature of the dispersion should not exceed 30 ° C, with which it is required to cool externally with a water container. Once the dispersion is homogenized, the final additives such as BYK 980 are added to decrease the viscosity of the formulation. The viscosity is measured with a Brokfield RV DVE viscometer.
    [0491]
    [0492] The prepared resin or gelcoat prepared is tested by catalyzing an aliquot of the formulation with methyl ethyl ketone peroxide. The mixture is stirred so that it is incorporated homogeneously. A gelcoat layer of about 500 microns is applied with an applicator for this thickness and allowed to polymerize at room temperature for a few hours, until it has hardened, while maintaining a certain tacking or tack. A first fiberglass sheet is applied, and it is manually laminated with a special roller for resin and fiber laminate, incorporating resin that has previously been catalyzed. The rolling operation is repeated by applying at least three sheets of 400 g / m2 fiberglass, between each laminated layer the previous layer is allowed to harden enough to apply the next layer with ease. Depending on the amount of resin applied, proportions of 25 to 30% of fiberglass are obtained in the composite with regular thicknesses of 3 mm. The composite is subjected to a post-cure of 6 hours at 50 ° C so that the polymerization process is exhausted. Before testing the composite, it is left at least 24 hours in a room with a constant humidity of 50% and at 23 ° C. The composite is cut to the required means, according to the standards corresponding to each test. The test is carried out.
    [0493] Conclusions
    [0494]
    [0495] a) Resinous systems:
    [0496]
    [0497] 1) Fire retardant resin systems based on DCPD resins, modified with styrene monomer have an adequate behavior. To ensure adequate thermal stability, it is necessary to inhibit the resin with p-TBC, which means that it is necessary to catalyze with more peroxide and accelerate with more cobalt salt, even use some promoter of the catalytic system. This inhibition is necessary to improve thermal stability (shelf life), but as a counterpart the gel time is longer (less production). You have to reach a balance.
    [0498]
    [0499] 2) Fire retardant resin systems based on the PRESTER 2355 vinyl ester resin have adequate cure. The resin is very reactive and is inhibited so that its gel time is about 45 minutes catalyzing with 2% methyl ethyl ketone peroxide and 0.4% cobalt octoate with 6% cobalt content.
    [0500] 3) In general, ammonium polyphosphate, which is the flame retardant that is used to a greater extent, inhibits the catalytic system. It is convenient to adjust the catalytic system with the appropriate percentages of cobalt octoate, methyl ethyl ketone peroxide, or other more active ones such as acetylacetone peroxide. You can also use the promoters.
    [0501]
    [0502] b) Flame retardants and smoke suppressors:
    [0503]
    [0504] 4) In most of the tests, FR CROS 484 ammonium polyphosphate has been used. FR CROS S 10 dramatically increases the viscosity of the resinous system. The APP 201 type considerably increases the viscosity of the resinous system and complicates the subsequent impregnation of the glass fiber. In particular, APP type 262 has the best results.
    [0505] 5) LEVAGARD DMPP inhibits the cure of the vinyl ester resin in an apparent way, however, the TEPZ does not, but was no longer used as a plasticizer.
    [0506] 6) Melanin polyphosphate (BUDIT 3141) and melamine orthophosphate (BUDIT 312) have a similar behavior, but they do not give better results than melamine in our resins.
    [0507] 7) N o s e h a a p r e c i a d o u n m e j o r c o m p o r t a m i e n t o i g n i f u g a n t e c u a n d o s e h a u t i l i z a d o d e r i v a d o s d e l b o r o c o m o s o n e l o t o d o b e n o r e o b e n o r b o r
    [0508] 8) L s m e l a m i n a s p r o b e d s t i e n e n u n c to R c t e r i g n i f u g n t e d is t in t o s e g o n s u r ig e n, s i and n d m u c h or m to s e f i c to z m e l a n i n a m o l t u r e d d e 40 and 15 m ic r to s c o m e r c i a l i z e d s p o r W e s t e r f e ld.
    [0509] 9) L or s d s h i d r or x id or s d e lu m i n e n a l i z e d s (O N 310 and M I C R A L 932) c or n l l e v n f o r m u l a t i o n s q u e g e n e r n a l t a d e n s i d a d d e h u m or s d e b i d or the o p a c i d a d d e l v a p o r d e to g u a d e s p r e n d i d or d u r a n t e s u d e s c o m p o s i t i o n. E l u s o d e A T H e s t á, p u e s, c o n t r a in d ic a d o.
    [0510] 10) L a D I P E N T A 85 a y u d a d e f o r m a c l a r a a l f e n o m e n o i n t u m e s c e n c i a e n e l s i s t e m a r e s in o s o y e n lo s g e l c o a t s q u e s e h a n e s t u d o
    [0511] 11) E n lo s e n s a y o s p r e v io s, n o s e h a a p r e c i a d o u n a m e j o r a n o t o r ia p o r e l h e c h o d e a ñ a d i r n a n o p a r t í c u l a s (D E L L I T E 67 n) L o q u e s s e a p r e c i a e s u n a u m e n t o o s t e n s i b l e n la v is c o s id a d d e l s i s t e m a r e s in o s o d e b i d o a p e q u e ñ a g r a n u l o m e t r a n a r a n a r
    [0512] 12) T a m p o c o s e a p r e c i a u n a m e j o r a o s t e n y
    [0513] 13) S i b i e n e n r e s i n a s h a l or g and n to s f u n c i o n a m u and b e n, n or s e h to a p r e c i a d o u n d e s c e n s e n o p a c i d a d / d e n s i t y th e s h s m o s c u a n d s e a n d e u n 0, 5% - 1% d e h i d r o x i e s t a n n a t o d e z in c.
    [0514] 14) D e lo s d o s e s p u m a n t e s a ñ a d i d o s e n la f o r m u l a c i o n d e l g e l - c o a t e l q u e m e j o r e s r e s u l t a d o s h a g e n e r a d o e s la a z o d i c a r o m S in e m b a r g o s u a d ic ió n d e r i v a e n g e l-c o a t s a m a r i l l n n t o s (h e c h o q u e p u e e e r s o l v e n t a d o c o n the p o s t e r io r a p l i c a t o p a t o r E l o t r o a g e n t e e s p u m a n t e u t i l i z a d o, e l H Y D R O C E R O L, in h ib e e l c u r a d o d e l s i s t e m a r e s in o s o b a s e d e l g e l - c o a t.
    [0515] 15) L o s d e r i v a d o s h a l o g e n a d o s (D B D F E) and S b 2 O 3 f u e r o n d e s a
    [0516] Approvals
    [0517]
    [0518] C O M P O S I T E D E R E S I N A I G N I F U G A C O N F I B R A D E V I D R I O. A C A B A D O E N G E L C O A T:
    [0519] M a t e r i a l e s: R e s i n a: P r e s t e r 1165, G e l c o a t: U n ig e l 2 H L.
    [0520] C o m p o s i t e: P o l i e s t e r r e f o r z a d o c o n f ib r a d e v id r io. C o n t i e n e u n v e l o d e s u p e r f i c i e y d o s m a t s d e 450 g / m 2. E s p e s o r 4 m m. P e s o p o r u n id a d d e s u p e r f i c ie 5, 86 K g / m 2. E s p e s o r g e l c o a t 600 m ic r a s.
    [0521] Classification according to Standard UNE EN 45545-2: 2013 + A1: 2015.
    [0522]
    [0523]
    [0524]
    [0525]
    [0526] Report: P17-19879 / 2. IK4 Gaiker. 4/4/2018.
    [0527]
    [0528] COMPOSITE RESIN IGNIFUGA WITH GLASS FIBER, COAT GEL AND FINISH PAINT:
    [0529] Materials: Resin: Prester 1165, Gel coat: Unigel 2HL, Paint: Unilak 2Fignifuga. Composite: Fiberglass reinforced polyester. It contains a surface veil and two mats of 450 g / m2. Thickness 4 mm. Weight per unit area 5.86 Kg / m2. Thickness gel coat 600 microns. Thick paint finish 40 microns.
    [0530]
    [0531] Classification according to Standard UNE EN 45545-2: 2013 + A1: 2015
    [0532]
    [0533]
    [0534]
    [0535]
    [0536] Report: P17-19880 / 2. IK4 Gaiker. 1/25/2018.
    权利要求:
    Claims (13)
    [1]
    1. Composite material comprising:
    a) flame retardant resin consisting of
    - 50 parts by weight of a resin which is an unsaturated polyester resin of DCPD base in dilution of styrene, a vinyl ester resin in dilution of styrene obtained by reaction between epoxybisphenol-A and methacrylic acid, or a mixture of both resins in any proportion;
    - from 20 to 40 parts by weight of ammonium polyphosphate;
    - from 20 to 5 parts by weight of melanin;
    - 10 to 5 parts by weight of dipentaerythrite;
    provided that the parts by weight of ammonium polyphosphate, melanin and dipentaerythrite add up to 50 parts by weight;
    b) gelcoat formed by a resin that is an unsaturated polyester resin of DCPD base in dilution of styrene and a vinyl ester resin in dilution of styrene obtained by reaction between epoxybisphenol-A and methacrylic acid, or a mixture of both resins in any proportion ; said resin or resins being thixotroped with pyrogenic silica.
    [2]
    2. Composite material according to claim 1, further comprising
    c) finishing paint based on an isocyanate crosslinked hydroxylated acrylic resin containing per 100 parts by weight of a component A up to 25 parts by weight of HDI (hexamethylene diisocyanate), wherein said component A comprises:
    - Hydroxylated acrylic resin
    - Rheological additives
    - Surface additives
    - Solvent
    - Pigments
    - Flame retardants (ammonium polyphosphate, melamine and dipentaerythrite).
    [3]
    3. Composite material according to claim 1 or 2, further comprising fibers selected from glass fiber, aramid fiber and carbon fiber, or a mixture thereof.
    [4]
    4. Composite material according to claim 3, wherein said fibers are glass fibers.
    [5]
    5. Composite material according to any of the preceding claims, further comprising between 1 and 4% by weight of flexible unsaturated polyester resins containing maleic anhydride, adipic acid and hexanediol.
    [6]
    6. Composite material according to any of the preceding claims, wherein the gelcoat has a thickness of 500 pm.
    [7]
    7. Composite material according to any of the preceding claims, wherein the melanin and ammonium polyphosphate are in the form of particles of 8 to 15 pm in size.
    [8]
    8. Method for the production of a composite material, according to any of the preceding claims, comprising the steps of:
    a) apply gelcoat on a previously waxed mold to allow the gelcoat to cure; b) apply layers of flame retardant resin and, optionally, fibers until the desired thickness is obtained;
    c) let the layered material cure from step b);
    d) unmold the mold piece; and, optionally;
    e) apply finishing paint.
    [9]
    9. Use of the composite material, according to any of claims 1 to 7, in means of transport and construction.
    [10]
    10. Use of the composite material according to claim 9, wherein said means of transport is rail transport.
    [11]
    11. Use of the composite material according to claim 10, wherein said rail transport comprises the components of a rail transport according to the requirements indicated in the UNE EN 45545-1 standard.
    [12]
    12. Part of a rail transport comprising the composite material according to any one of claims 1 to 7.
    [13]
    13. Part according to claim 12, which is the structure and covering, the luggage rack, the control console, tables and sinks, bands, base structure of the passenger seat, interior surfaces of the aisles, walls of the external structure of the vehicle or the front of the train.
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    同族专利:
    公开号 | 公开日
    WO2020025845A1|2020-02-06|
    ES2739431B2|2020-06-29|
    EP3831883A1|2021-06-09|
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