KR20240018969A - Semi-incombustible resin composition and semi-incombustible molded article comprising same - Google Patents

Abstract

The semi-non-flammable resin composition of the present invention includes a non-halogen flame retardant including a phosphorus-based flame retardant, a melamine-based flame retardant, an inorganic flame retardant, and a polyol-based flame retardant, and further includes an inorganic flame retardant and a graphite-based flame retardant, and a conventional non-halogen-based flame retardant. In addition to being able to achieve significant flame retardancy or semi-incombustibility compared to resins containing It can achieve excellent dispersibility, preventing deterioration of physical properties and processability.

Description

Semi-incombustible resin composition and semi-incombustible molded article comprising same}

The present invention provides a semi-non-combustible resin composition that realizes high flame retardant performance at a semi-non-combustible level and a semi-non-combustible molded article manufactured including the same.

Currently, the world is transitioning from an industrial system that generates carbon dioxide to an industrial system that reduces or zeroizes carbon dioxide in order to fundamentally solve global warming that is threatening the survival of humanity.

As a result, fossil fuels are being replaced with electric energy not only in the United States but also in developed countries such as Europe and Asia. In order to solve the problem of carbon dioxide emitted from automobiles, electric vehicle research and market size are increasing and increasing further. It is expected that it will be.

However, in order to replace fossil fuels, secondary batteries require high capacity and high output, resulting in fire and explosion risk problems due to thermal runaway of secondary batteries due to high capacity and high output, and automobile parts or secondary batteries made of conventional polyolefin resin. Battery parts were vulnerable to fire due to thermal runaway of secondary batteries, so there was a problem of very low safety for users.

Accordingly, in the field where secondary batteries requiring high capacity and high output are used, a highly flame retardant resin that implements excellent flame retardancy is required to ensure user safety, and the conventional high flame retardant resin is a halogen-based flame retardant to achieve high flame retardancy. It was common to include .

However, highly retardant resins containing halogenated flame retardants may have excellent flame retardancy, but in the event of a fire, the halogenated flame retardants thermally decompose to generate toxic gas, thereby failing to ensure user safety.

Therefore, recent flame retardant resins contain non-halogen flame retardants and realize flame retardancy, but their flame retardancy is not as good as flame retardant resins containing halogen flame retardants, so they cannot completely replace halogen flame retardants and are used by mixing halogen flame retardants. there is.

In addition, flame retardant resins containing conventional non-halogen flame retardants must contain a large amount of non-halogen flame retardants to achieve excellent flame retardancy, so their miscibility with the resin is very poor and processability is very low, making them difficult to apply in various industrial fields. It was difficult.

To solve this problem, an attempt was made to coat the surface of the thermoplastic polymer resin with a flame retardant resin or a flame retardant, or to provide a flame retardant molded product composed of several layers of a metal plate such as aluminum and a thermoplastic polymer resin. However, in the event of an actual fire, the thermoplastic polymer ignites due to high heat, causing 2 Due to the secondary fire and toxic gas being generated, it was not effective in preventing secondary fire.

As a result, the flame retardant resin not only secures stability from toxic gases by including new non-halogen flame retardants that exclude or minimize halogen flame retardants, but also provides a new technology that can realize remarkable flame retardancy and processability even with non-halogen flame retardants. Development is needed.

One embodiment of the present invention seeks to provide a semi-non-flammable resin composition containing a mixed non-halogen-based flame retardant in order to solve the problem of induced gas generation due to combustion of a conventional flame-retardant composition containing a halogen-based flame retardant.

In one embodiment, in order to solve the problem that flame retardant resins containing conventional non-halogenated flame retardants have lower flame retardancy than flame retardant resins containing halogenated flame retardants, significant flame retardancy or semi-incombustibility that exceeds flame retardancy is realized even by including only non-halogenated flame retardants. The goal is to provide a semi-non-combustible resin composition as possible.

The semi-non-flammable resin composition according to one embodiment is capable of realizing remarkable miscibility between the resin and the non-halogen-based flame retardant even though it contains a large amount of non-halogen-based flame retardant, thereby realizing remarkable mechanical properties and processability, making it applicable to various industrial fields. It can be manufactured as a non-combustible molded product.

According to one implementation, the semi-non-combustible molded product can be applied to fields with a high risk of fire, such as secondary battery covers, and can achieve remarkable stability against secondary fire.

The semi-cleavable resin composition of the present invention includes a matrix resin containing an ethylene-vinylacetate copolymer and a polyethylene-propylene-diene copolymer, a phosphorus-based flame retardant, a melamine-based flame retardant, an antimony-based flame retardant, a clay-based flame retardant, or an inorganic flame retardant that is a mixture thereof, Includes graphite-based flame retardants and polyol-based flame retardant auxiliaries.

As one embodiment, the matrix resin may include 50 to 90% by weight of ethylene-vinylacetate copolymer and 10 to 50% by weight of ethylene-propylene-diene copolymer.

As an embodiment, the semi-non-flammable resin composition may include 200 to 400 parts by weight of an ammonium polyphosphate-based flame retardant based on 100 parts by weight of the matrix resin.

As one embodiment, the semi-non-flammable resin composition may include 50 to 150 parts by weight of a melamine-based flame retardant based on 100 parts by weight of the matrix resin.

As one embodiment, the semi-non-flammable resin composition may include 5 to 60 parts by weight of an inorganic flame retardant based on 100 parts by weight of the matrix resin.

As one embodiment, the semi-non-flammable resin composition may include 10 to 70 parts by weight of a polyol-based flame retardant adjuvant based on 100 parts by weight of the matrix resin.

As one embodiment, the semi-non-combustible resin composition may further include 30 to 150 parts by weight of glass fiber chop based on 100 parts by weight of the matrix resin.

As one embodiment, the semi-non-combustible resin composition includes 1 to 20 parts by weight of a reactive flame retardant monomer based on 100 parts by weight of the matrix resin.

As one embodiment, the semi-non-flammable resin composition may include 5 to 100 parts by weight of a graphite-based flame retardant based on 100 parts by weight of the matrix resin.

As one embodiment, the semi-non-combustible resin composition may further include 10 to 150 parts by weight of a metal hydroxide based on 100 parts by weight of the matrix resin.

As an embodiment, the semi-non-combustible resin composition may have a total heat emission of 50 MJ/㎡ or less for 10 minutes as measured by ISO 5660-1.

As an embodiment, the semi-non-combustible resin composition may have a maximum heat release rate exceeding 200 kW/m2 for less than 10 seconds as measured by ISO 5660-1.

As one embodiment, the semi-non-combustible resin composition may have a char formation rate of 70% or more as measured by ISO 5660-1.

The present invention provides a semi-non-combustible molded article manufactured including the semi-non-combustible resin composition.

As an embodiment, the semi-non-combustible molded product may be a fireproof structure, an aviation part, a battery module cover, or an automobile part.

The fire-safe battery module of the present invention includes a battery module, a semi-non-combustible molded product on the battery module, and a battery module cover on the semi-non-combustible molded product.

As an embodiment, the fire safety battery module may be included in an electric vehicle secondary battery.

The semi-non-flammable resin composition according to one embodiment includes a phosphorus-based flame retardant, a melamine-based flame retardant, and an inorganic flame retardant, and has a significantly higher char formation rate, superior char strength, and melting or crack generation rate after combustion than a flame retardant resin containing a conventional non-halogen-based flame retardant. As this is small, remarkable flame retardancy can be realized.

The semi-nonflammable resin composition according to one embodiment includes a matrix resin including polyethylene-vinylacetate copolymer (EVA) and polyethylene-propylene-diene copolymer (EPDM), and includes a large amount of non-halogen-based flame retardant, By realizing excellent miscibility, processability and mechanical properties can be realized.

The semi-non-combustible resin composition according to one embodiment further includes glass fiber chops, so that it can realize more remarkable char strength, and thus its stability against secondary fire can be more remarkable than that of conventional flame-retardant resins.

As an embodiment, the semi-non-combustible resin composition has a total heat release rate of 50 MJ/m 2 or less for 10 minutes in a concalometer test, a maximum heat release rate exceeding 200 kW/m ² for less than 10 seconds, and a cone calometer test. Even when burned, harmful cracks, holes, and melting may not occur in fire protection, and thus, it is possible to realize remarkable flame retardancy compared to flame retardant resins containing conventional non-halogen-based flame retardants.

The semi-non-combustible resin composition according to one embodiment has excellent miscibility between the matrix resin and the flame retardant, and can realize remarkable mechanical strength and processability, so it can be applied to various fields such as fire protection structures, aviation parts, automobile parts, and especially secondary battery covers. Non-combustible molded products can be provided.

Therefore, the semi-non-flammable resin composition of the present invention contains a phosphorus-based flame retardant, a melamine-based flame retardant, and an inorganic flame retardant, and forms a hard char at high heat, so that not only does it not generate toxic gas in the event of a fire, but it can also achieve remarkable flame retardancy or semi-incombustibility. , it can be usefully used in fields that require significant fire safety, such as aviation, ships, construction, automobiles, or nuclear power.

Hereinafter, the semi-non-combustible resin composition according to the present invention and the semi-non-combustible molded article manufactured including the same will be described in detail. At this time, if there is no other definition in the technical and scientific terms used, they have meanings commonly understood by those skilled in the art to which this invention pertains, and the following description will not unnecessarily obscure the gist of the present invention. Descriptions of possible notification functions and configurations are omitted.

As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly dictates otherwise.

In addition, the numerical range used in this specification includes the lower limit and upper limit and all values within the range, increments logically derived from the shape and width of the defined range, all double-defined values, and the upper limit of the numerical range defined in different forms. and all possible combinations of the lower bounds. Unless otherwise specified in the specification of the present invention, values outside the numerical range that may occur due to experimental error or rounding of values are also included in the defined numerical range.

The term “comprises” in this specification is an open description with the same meaning as expressions such as “comprises,” “contains,” “has,” or “characterized by” elements that are not additionally listed; Does not exclude materials or processes.

In order to solve the toxic gas problem of flame retardant resins containing conventional halogen-based flame retardants, an attempt was made to solve the above problems by including non-halogen-based flame retardants.

However, conventional flame retardant resins containing non-halogenated flame retardants have lower flame retardancy than flame retardant resins containing halogenated flame retardants, so they have no choice but to contain a large amount of non-halogenated flame retardants or be mixed with halogenated flame retardants.

In addition, flame retardant resins containing conventional non-halogen-based flame retardants were very difficult to apply to various fields because the resin and the non-halogen-based flame retardants had poor miscibility and poor processability.

In order to solve the problem of low processability of the flame retardant resin containing the non-halogen flame retardant, a flame retardant polymer coated with a flame retardant resin or flame retardant on the surface of a thermoplastic polymer molded product was conventionally provided. However, the thermoplastic resin inside the coating was combusted in a high temperature environment. Safety against secondary fires has still not been achieved.

Accordingly, as a result of intensifying research in order to solve the problem of the conventional flame retardant resin, the present inventors found that a semi-non-flammable resin composition containing a phosphorus-based flame retardant, a melamine-based flame retardant, an inorganic flame retardant, and a polyol-based flame retardant auxiliary agent is better than the conventional halogen-containing flame retardant resin. Significant flame retardancy can be achieved, and surprisingly, even if the matrix resin containing polyene-vinylacetate copolymer and poly-ethylene-propylene-diene copolymer contains a large amount of the above flame retardant, it is more flame retardant than the flame retardant resin containing conventional non-halogenated flame retardants. The goal was to achieve remarkable processability and complete the present invention.

Hereinafter, the semi-non-flammable resin composition of the present invention will be described in detail.

The present invention includes a matrix resin containing polyethylene-vinylacetate copolymer (EVA) and polyethylene-propylene-diene copolymer (EPDM), a phosphorus-based flame retardant, a melamine-based flame retardant, an inorganic flame retardant, a graphite-based flame retardant, and a polyol-based flame retardant auxiliary agent. A semi-non-combustible resin composition is provided.

As an embodiment, the matrix resin may contain 50 to 90% by weight of EVA and 10 to 50% by weight of EPDM, preferably 70 to 90% by weight of EVA and 10 to 30% by weight of EPDM. .

The matrix resin containing EVA and EPDM in the weight percentage of the above range can achieve excellent miscibility with flame retardants even if it contains a large amount of flame retardant, and the semi-non-flammable resin composition containing it contains a large amount of flame retardant to improve physical properties and processability. This deterioration can be prevented, and the char generated during combustion does not generate harmful cracks, making it possible to achieve even more remarkable flame retardancy.

The EVA may have a weight average molecular weight of 40,000 to 300,000 g/mol, but this is not limited as long as it does not impair the physical properties of the semi-incombustible resin composition.

The EPDM may be polymerized containing 4 to 8 mol% of diene comonomer, and examples of the diene comonomer include one or two selected from ethylidene norbornene, dicyclopentadiene, and vinylnorbornene. It may be more than this, but it is not limited as long as it contains a carbon double bond that can be crosslinked.

In another embodiment, the matrix resin is low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), polypropylene (PP), polytetrafluoroethylene (PTFE), polyvinyl fluoride ( It may be possible to supplement the mechanical properties, optical properties, and thermal properties by further including one or two or more polyolefin-based polymers selected from PVF), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), and polystyrene (PS). , it does not limit this.

As one embodiment, the semi-non-flammable resin composition may contain 200 to 400 parts by weight of a phosphorus-based flame retardant, preferably 250 to 350 parts by weight, based on 100 parts by weight of the matrix resin.

Examples of the phosphorus-based flame retardants include triphenyl phosphate, trialkylphenyl phosphate, tricrecylphosphate, propylated triphenylphosphate, and butylated triphenyl phosphate ( butylated triphenyl phosphate, triethylphosphate, tributyl phosphate, resorcinoldiphosphate, bisphenoldiphosphate, dimethyl methyl phosphonate, polyphosphate ester ( It may be one or two or more selected from the group consisting of polyphosphate ester, oligomeric organophosphate, ethyl pyrocadechol phosphate, dipyrocadechol biphosphate, and polyethylene ethyleneoxy phosphate, preferably ammonium. It may be dihydrogen phosphate, ammonium polyphosphate, or mixtures thereof, and better, ammonium polyphosphate may be used alone.

The phosphorus-based flame retardant is a flame retardant that does not contain halogen, and a semi-non-flammable resin composition containing it not only provides excellent flame retardancy, but also prevents the generation of harmful gases in the event of a fire, and has excellent char formation, preventing secondary fires. It can be prevented.

As one embodiment, the semi-non-flammable resin composition may contain 50 to 150 parts by weight of a melamine-based flame retardant, preferably 70 to 120 parts by weight, based on 100 parts by weight of the matrix resin.

Examples of the melamine-based flame retardant include compounds having a triazine structure such as melamine, melamine cyanurate, and triphenyl isocyanurate, melamine phosphate, and melamine pyrophosphate. ) and piperazine acid polyphosphate, etc., may be phosphorus-nitrogen containing compounds, preferably having a triazine structure that can achieve more remarkable flame retardancy and char formation rate by mixing with the phosphorus-based compound. It may be advisable to use melamine cyanurate, but this is not limited.

A semi-non-flammable resin composition containing a melamine-based flame retardant in the above range can realize better miscibility between the matrix resin and the melamine-based flame retardant, and can realize excellent flame retardancy without impairing mechanical properties.

As an embodiment, the inorganic flame retardant may include an antimony-based flame retardant, a clay-based flame retardant, or a mixture thereof. Preferably, using the antimony-based flame retardant and the clay-based flame retardant simultaneously results in a more significant char formation rate and excellent char strength. And it may be preferred because it can prevent continuous combustion by suppressing the free radical reaction in the vapor phase of the semi-non-combustible resin composition.

As an example, the antimony-based flame retardant may be any one or two or more selected from sodium antimonate, potassium antimonate, pyroanthimate, antimony trioxide, and antimony pentoxide, and preferably, when the semi-non-flammable resin composition burns, radicals are generated. It may be antimony trioxide or antimony pentoxide, which can further inhibit the reaction, but this is not limiting.

The clay-based flame retardant may be one or two or more selected from diatomaceous earth, montmorillonite, nontronite, badelite, vermiculite, halloysite, hectorite, and saponite, and diatomaceous earth may be used alone, but this is not limited. .

As one embodiment, the semi-non-flammable resin composition may include 5 to 100 parts by weight of a graphite-based flame retardant based on 100 parts by weight of the matrix resin.

As an example, the graphite-based flame retardant may include any one or two or more selected from carbon nanotubes (CNT), carbon fiber, expanded graphite, and fullerene. Preferably, expanded graphite is used because it has lower production costs and better flame retardancy. However, this is not limited.

The semi-non-combustible resin composition may include both an inorganic flame retardant and a graphite-based flame retardant, so that not only can it have excellent molding processability, but it can also achieve semi-non-flammable performance and heat shielding performance at the same time, which is preferable.

As an embodiment, the semi-incombustible flame retardant resin composition may contain 10 to 70 parts by weight of a polyol-based flame retardant auxiliary, preferably 20 to 50 parts by weight, based on 100 parts by weight of the matrix resin.

The polyol-based flame retardant auxiliary agent may be a compound containing a large amount of hydroxyl groups, and as an example, it is selected from pentaerythritol, dipentaerythritol, tripentaerythritol, polyvinyl alcohol, starch, sorbitol, mannitol, tannic acid, and dextrin. Including one or more than one, preferably pentaerythritol and dipentaerythritol, and more preferably using pentaerythritol alone can achieve excellent flame retardancy due to interaction with the phosphorus-based flame retardant, but this is not limited. .

As an embodiment, the semi-non-flammable resin composition includes a matrix resin containing 50 to 90% by weight of EVA and 10 to 50% by weight of EPDM, a non-halogen flame retardant including a phosphorus-based flame retardant, a melamine-based flame retardant, and an inorganic flame retardant, and polyol It may contain a flame retardant auxiliary agent.

The semi-non-combustible resin composition can suppress the decline in processability and physical properties caused by the excellent miscibility with flame retardants of the matrix resin and the inclusion of a large amount of flame retardants.

In addition, the semi-non-flammable resin composition surprisingly mixes a phosphorus-based flame retardant, a melamine-based flame retardant, and an inorganic flame retardant, further includes a polyol-based flame retardant auxiliary agent, and adjusts their composition, thereby providing significantly greater flame retardancy than a flame retardant resin containing a conventional non-halogen flame retardant. It has technical significance in that it can achieve semi-incombustibility beyond flame retardancy.

As one embodiment, the semi-non-combustible resin composition may further include 30 to 150 parts by weight of glass fiber chop based on 100 parts by weight of the matrix resin.

The semi-non-combustible resin composition further containing glass fiber chops in the above range not only prevents the char from generating harmful cracks after combustion, but also maintains the strength of the char more firmly, allowing the char to continuously prevent continuous fire. By being able to provide more significant stability against secondary fire, it can be preferred.

The glass fiber chops may have an average diameter of 3 to 30 ㎛ and a length of 3 to 15 mm. A semi-incombustible resin composition containing glass fiber chops with an average diameter in the above range may realize more remarkable miscibility, but There is no limitation as long as it does not impair the physical properties of the non-combustible resin composition.

As one embodiment, the semi-non-flammable resin composition may include 1 to 20 parts by weight of a reactive flame retardant monomer based on 100 parts by weight of the matrix resin.

A semi-non-flammable resin composition containing a reactive flame retardant equivalent in the above range can be preferred because it can more significantly disperse the phosphorus-based flame retardant, melamine-based flame retardant, inorganic flame retardant, and polyol-based flame retardant auxiliary agent in the matrix resin, while also realizing excellent flame retardancy.

The reactive flame retardant monomer may be, for example, phosphoric acid-modified hydroxyethyl methacrylate, melamine-modified methacrylate, or a mixture thereof, preferably phosphoric acid-modified hydroxyethyl methacrylate and melamine-modified methacrylate in a ratio of 1:1. It is possible to achieve better flame retardancy and dispersibility at the same time by mixing at 1:2 parts by weight, but this is not limited.

As an embodiment, the semi-non-combustible resin composition may further include 10 to 150 parts by weight of a metal hydroxide, preferably 30 to 100 parts by weight, and more preferably 50 to 100 parts by weight, based on 100 parts by weight of the matrix resin. It may be.

A semi-incombustible resin composition containing a metal hydroxide in the above range can achieve better heat release-related performance in the event of a fire, and thus can realize better flame retardancy or semi-incombustibility.

For example, the metal oxide may be aluminum trihydrate, magnesium dihydrate, or a mixture thereof. Better, the surface of the metal hydroxide may be coated with an organic material to achieve more remarkable miscibility, but it may be miscible with the matrix resin. This does not limit it as long as it does not cohere with each other.

As one embodiment, the semi-non-flammable resin composition may further include a compatibilizer and additives.

As one embodiment, the semi-incombustible resin composition may include 1 to 10 parts by weight of a compatibilizer based on 100 parts by weight of the matrix resin.

A semi-nonflammable resin composition containing a compatibilizer in the above range may be preferred because the phosphorus-based flame retardant, melamine-based flame retardant, and inorganic flame retardant may have better dispersion.

The compatibilizer may be a compound in which maleic anhydride is grafted onto the backbone of a polyolefin polymer (polyolefin-g-maleic anhydride), for example, ethylene vinyl alcohol-g-maleic anhydride, ethylene vinyl acetate- It may be one or two or more selected from g-maleic anhydride, low-density polyethylene-g-maleic anhydride, polyolefin elastomer-g-maleic anhydride, and linear low-density polyethylene-g-maleic anhydride, and may be limited to those recognized by a person skilled in the art. It's not like that.

As one embodiment, the semi-incombustible resin composition may include 1 to 10 parts by weight of an additive based on 100 parts by weight of the matrix resin.

A semi-non-combustible resin composition containing additives in the above range is preferred because it can prevent the matrix resin and flame retardant contained in the semi-non-combustible resin composition from being oxidized during the process of kneading or processing at a high temperature to produce a semi-non-combustible molded product to be described later. It can be.

The additive may include one or two or more selected from antioxidants, heat stabilizers, lubricants, ultraviolet stabilizers, foaming agents, viscosity regulators, processing aids, enhancers, and pigments, provided that they do not impair the physical properties of the semi-non-flammable resin composition. This is not intended to limit this.

As another embodiment, the additive is not included in the semi-non-combustible resin composition, and may be added through a different inlet from the semi-non-combustible resin composition in the semi-non-combustible molded product manufacturing process to be described later.

Hereinafter, the physical properties of the semi-non-combustible resin composition according to one embodiment will be described in detail.

According to one embodiment, the semi-non-flammable resin composition includes a matrix resin including EPDM, and includes a phosphorus-based flame retardant, a melamine-based flame retardant, an inorganic flame retardant, and a polyol-based flame retardant auxiliary agent, and by adjusting their contents, surprisingly, it has high flame retardancy or semi-flammability. It has technical significance in realizing non-combustible properties.

As an embodiment, the semi-non-combustible resin composition may have a total heat release of 50 MJ/m2 or less for 10 minutes as measured by ISO 5660-1, preferably 20 MJ/m2 or less, and more preferably 8 MJ/m2 or less. Or, as a specific example, the lower limit may be 5 MJ/m2 or more, preferably 3 MJ/m2 or more.

A semi-non-flammable resin composition realizing a total heat release within the above range can prevent continuous fires and achieve a lower total heat release than a conventional flame retardant resin, thereby providing greater safety against fire.

As an embodiment, the semi-non-combustible resin composition may have a maximum heat release rate exceeding 200 kW/m2 for less than 10 seconds as measured by a cone calorimeter test (ISO 5660-1), and preferably less than 150 kW/m2. , more preferably 100 kW/m2 or less, preferably 90 kW/m2 or more, preferably 50 kW/m2 or more, and these numerical ranges can be satisfied.

A semi-non-combustible resin composition with a maximum heat release rate in the above range can be preferred because it can prevent the spread of fire by preventing secondary fire by implementing superior ignition retardancy and low heat release rate than conventional flame retardant resins.

As an embodiment, the semi-non-combustible resin composition may not generate cracks, holes, or melting that are harmful to fire prevention through penetrating fire.

That is, according to one embodiment, the semi-non-flammable resin composition not only implements excellent processability even if it contains a non-halogen-based flame retardant and can be applied to various industrial fields, but also has a total heat release of 8 MJ/㎡ or less for 10 minutes, and a maximum heat The emission rate exceeds 200 kW/m2 for less than 10 seconds and no harmful cracks, holes, or melting may occur in the event of a fire, so it can satisfy the semi-non-flammable grade of the KS standard.

As an embodiment, the semi-non-combustible resin composition may have a char formation rate of 70% or more, preferably 75% or more, and more preferably 80% to 90%, as measured by the Concalimeter test (ISO 5660-1).

A semi-non-combustible resin composition having a char formation rate in the above range can form char excellently when combusted, thereby blocking oxygen and preventing secondary fires caused by flames.

Hereinafter, a semi-non-combustible molded article manufactured including the semi-non-combustible resin composition will be described in detail.

A semi-non-combustible molded product according to one embodiment is manufactured from a semi-non-combustible resin composition with excellent processability, and can be processed into various processing processes and shapes even if the semi-non-combustible resin composition contains a large amount of flame retardant, so that it can be used in various industrial fields. It has technical significance in terms of applicability.

The present invention provides a semi-non-combustible molded article manufactured including a semi-non-combustible resin composition.

The semi-non-combustible molded article may be manufactured including a semi-non-combustible resin composition and additives, and the additives may be the same or different from those described above.

As another embodiment, the semi-non-combustible molded product can also be used in fields that require a semi-incombustible or flame retardant rating, such as fire doors, cookware, electronic product covers, home appliance heat insulation, battery module covers, and defense products.

The semi-non-combustible molded product made from the semi-non-combustible resin composition can realize excellent processability even if it contains an excessive amount of non-halogen flame retardant, so that it can be molded to be applicable to various fields and can also satisfy the semi-non-combustible grade. It can be usefully used in a wider range of fields.

The present invention provides a fire-safe battery module including a battery module, the semi-non-combustible molded product on the battery module, and a battery module cover on the semi-non-combustible module.

As an embodiment, the battery module may be an electric vehicle secondary battery battery module.

In a situation where high capacity and high output are currently required, the battery module is preferred because it can prevent the risk of fire due to thermal runaway of secondary batteries, thereby ensuring time for drivers to evacuate even if a fire occurs in a battery-powered vehicle. You can.

The semi-non-combustible resin composition according to the present invention and the semi-non-combustible molded article manufactured therefrom will be described in more detail through examples below. However, the following examples are only a reference for explaining the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms. Additionally, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. Additionally, the terms used in the description in the present invention are only intended to effectively describe specific embodiments and are not intended to limit the present invention.

[measurement method]

1. Measurement of total heat released (THR) and maximum heat release rate (PHRR)

It was measured in accordance with ISO 5660-1, and the sample was heated with radiant heat at 780°C for 10 minutes using a cone calorimeter tester (Fire Testing Technology, FFT0402), and the mass of oxygen consumed was measured to determine the total amount of heat released. and the maximum heat release rate was obtained.

2. Measurement of char formation rate

Measurements were made according to ISO 5660-1, and the initial sample weight was measured and recorded using an electronic scale. The sample was burned in a cone calorimeter tester in the same manner as the total heat release and maximum heat release rate measurements, and the char formation rate was measured using the weight loss value of the sample measured in the cone calorimeter during combustion.

[ceremony]

Char formation rate (%) = (initial sample weight - weight loss value of sample (g) / initial sample weight (g)) × 100

3. Observe for hazardous cracks, holes or melting.

The sample after the char formation rate measurement method was visually inspected to determine whether harmful cracks, holes, or melting occurred.

4. Formability measurement

Samples were prepared from the semi-non-flammable resin compositions prepared in the following Examples and Comparative Examples using a hot place, and the dimensions of the prepared samples were measured. If the measured dimension is less than ±0.1 mm, it is marked as ◎, if the dimension error is less than 0.5 mm, it is marked as ○, if the dimension error is between 0.5 and 1 mm, it is marked as △, and if the dimension error exceeds 1 mm, it is marked as X.

[Examples 1 to 5]

The weights of ethylene-vinylacetate (EVA, density: 0.935 g/cm ³ , Lotte Chemical, VC 590, VA 28 wt%) and ethylene-propylene-diene copolymer (EPDM, Kumho Polychem, KEP510) are shown in Table 1 below. The matrix resin mixed in % was added to the melt mixer.

For 100 parts by weight of matrix resin in the melt mixer, polyammonium phosphate (APP, Exolit® AP 422, average particle size: 17 μm, Clariant), melamine cyanurate (MC, MCA50, average particle size: 5 μm, Hangzhou) Mei Wang Chemical), pendaerythritol, antimony trioxide, expanded graphite, and diatomaceous earth were added to the melt mixer in parts by weight shown in Table 1 below.

In addition, for 100 parts by weight of the matrix resin in the melt mixer, 20 parts by weight of phosphoric acid-modified hydroxyethyl methacrylate (phosphoric acid-modified HEMA), 100 parts by weight of glass fiber chop, and a compatibilizer (EVA-g-MAH (Fusabond C250, Dow) ) 5 parts by weight of additives (Irganox 1010, BASF) and 50 parts by weight of surface-coated alumina trioxide (ATH) were added, melted at 170°C, sufficiently mixed, and kneaded to prepare a semi-non-flammable resin composition.

Afterwards, samples of the prepared semi-non-flammable resin composition were prepared using a hot press (Qmesys, Korea).

Afterwards, the prepared sample was measured using the above measurement method and is shown in Table 2 below.

[Example 6]

The semi-non-flammable resin composition and sample were prepared in the same manner as in Example 2, except that phosphoric acid-modified HEMA was not added.

Afterwards, the prepared sample was measured using the above measurement method and is shown in Table 2 below.

[Example 7]

In Example 2, the semi-non-flammable resin composition and sample were prepared in the same manner, except that glass fiber chop was not added.

Afterwards, the prepared sample was measured using the above measurement method and is shown in Table 1 below.

[Example 8]

In Example 2, the semi-nonflammable resin composition and sample were prepared in the same manner, except that surface-coated alumina trioxide (ATH) 50 was not added.

[Comparative Example 1]

In Example 2, a semi-non-flammable resin composition and sample were prepared in the same manner as in Example 2, except that the matrix resin was made only of EVA.

Afterwards, the prepared sample was measured using the above measurement method and is shown in Table 2 below.

[Comparative Example 2]

In Example 2, a semi-non-flammable resin composition and sample were prepared in the same manner as in Example 2, except that the matrix resin was made only of EPDM.

Afterwards, the prepared sample was measured using the above measurement method and is shown in Table 2 below.

[Comparative Example 3]

In Example 2, the semi-noncombustible resin composition was prepared in the same manner as in Example 2, except that the matrix resin was prepared by mixing 90% by weight of EVA and 10% by weight of high-density polyethylene (HDPE, density: 0.952 g/cm ³ , Lotte Chemical, 5305E). and samples were prepared.

Afterwards, the prepared sample was measured using the above measurement method and is shown in Table 2 below.

[Comparative Examples 4 to 7]

In Example 2, the same procedure was performed except that the included polyammortium phosphate, melamicyanurate, pentaerythritol, antimony trioxide, expanded graphite, and diatomaceous earth were added or not added in the weight parts shown in Table 1 below. Nonflammable resin compositions and samples were prepared.

Afterwards, the prepared sample was measured using the above measurement method and is shown in Table 2 below.

matrix resin
(weight%) Flame retardants and flame retardant supplements
(part by weight) Other additives
(part by weight) EVA EPDM HDPE APP MC PER Antimony trioxide expanded graphite diatomaceous earth ATH Phosphoric acid modified HEMA Fiberglass Chop Example 1 80 20 100 30 5 2 One One 50 20 100 Example 2 80 20 - 200 70 20 20 10 5 50 20 100 Example 3 80 20 - 300 100 50 30 20 10 50 20 100 Example 4 80 20 - 400 150 70 30 20 10 50 20 100 Example 5 80 20 - 500 300 100 60 40 20 50 20 100 Example 6 80 20 - 200 70 20 30 20 10 50 - 100 Example 7 80 20 - 200 70 20 30 20 10 50 20 - Example 8 80 20 - 200 70 20 30 20 10 - 20 100 Comparative Example 1 100 0 - 200 70 20 30 20 10 50 20 100 Comparative Example 2 0 100 - 200 70 20 30 20 10 50 20 100 Comparative Example 3 90 10 200 70 20 30 20 10 50 20 100 Comparative Example 4 80 20 - - 70 20 30 20 10 50 20 100 Comparative Example 5 80 20 - 200 - 20 30 20 10 50 20 100 Comparative Example 6 80 20 - 200 70 - 30 20 10 50 20 100 Comparative Example 7 80 20 - 200 70 20 - - - 50 20 100

THR
(MJ/㎡) PHRR
(kW/㎡) Char formation rate
(%) harmful cracks Tsar Hardness Formability Example 1 28.2 168 75.2 Not occurred stiffness ◎ Example 2 7.1 63 85.5 Not occurred stiffness ◎ Example 3 7.8 98 84.2 Not occurred stiffness ○ Example 4 4.0 50 83.6 Not occurred stiffness ○ Example 5 3.8 30 78.2 Not occurred stiffness ○ Example 6 7.1 65 71.8 Not occurred stiffness X Example 7 38.5 132 77.8 Not occurred middle ◎ Example 8 40.8 158 74.5 Not occurred stiffness ◎ Comparative Example 1 42.5 192 76.2 generation stiffness X Comparative Example 2 37.1 132 71.1 generation stiffness X Comparative Example 3 58.6 292 37.5 generation stiffness X Comparative Example 4 60.5 385 32.0 generation Char Formation ◎ Comparative Example 5 54.5 230 35.1 Not occurred Char Formation ◎ Comparative Example 6 50.5 221 38.1 Not occurred Char Formation ◎ Comparative Example 7 50.1 208 54.1 generation middle ◎

In Table 2, Examples 1 to 5 are measurement values for semi-non-combustible resin compositions and samples to which different amounts of APP, MC, PER, antimony trioxide, expanded graphite, and diatomaceous earth were added.

From Table 2, it can be seen that Example 5 realizes the best amount of heat release and maximum amount of heat release, but it was confirmed that the moldability decreases as the content of the non-halogen-based flame retardant included increases.

This suggests that a semi-non-flammable resin composition containing excessive flame retardants causes the included flame retardants to aggregate together, resulting in low processability.

In Table 2, Example 6 was not as good in flame retardancy as Example 2, had similar total heat release, maximum heat release rate, and char formation rate as Example 5, and the formability was measured as X.

This suggests that in the case of Example 6, which does not contain phosphoric acid-modified HEMA, the effect of the diluent on the flame retardant monomer is not observed, resulting in lower dispersibility of the flame retardants and a significantly lower rate of char formation.

In Table 2, Example 7 is a semi-non-combustible resin composition that does not contain glass fiber chops, and was confirmed to have a higher total heat release amount and a higher maximum heat release rate than Example 2. In particular, Example 7 had a medium hardness. By forming a strong char, the stability against secondary fire may be lower than that of Example 2.

In Table 2, Example 8 was a semi-non-flammable resin composition that did not contain surface-coated ATH, and it was confirmed that the total amount of heat released and the maximum heat release rate were higher than those of Example 2.

Looking at Comparative Example 1 and Comparative Example 2 in Table 2, it was confirmed that not only was lower flame retardancy achieved than Example 2, but also the moldability was very poor.

This suggests that the semi-non-flammable resin composition that does not contain both EVA and EPDM does not contain the included flame retardant with excellent dispersibility, and thus flame retardancy and moldability are significantly reduced.

Looking at Comparative Example 3 in Table 2, it was confirmed that flame retardancy and processability were lower than those of Example 2, similar to Comparative Examples 1 and 2, even if HDPE was included.

Comparative Examples 4 to 7 are semi-non-flammable resin compositions containing non-halogen flame retardants excluding APP, MC, PER, antimony trioxide, expanded graphite, or diatomaceous earth, respectively, and have a total heat release rate exceeding 50 MJ/m2 and a maximum heat release rate. It was confirmed that this exceeded 200 kW/m2, and in particular, it was confirmed that the char formation rate in Comparative Examples 2 to 5 was 60% or less.

In other words, the semi-non-flammable resin composition includes all of the phosphorus-based flame retardant, melamine-based flame retardant, inorganic flame retardant, and polyol-based flame retardant auxiliary agent, thereby suggesting that it can simultaneously realize a remarkable char formation rate, low total heat release amount, and maximum heat release rate.

In addition, by controlling the content of the non-halogen-based flame retardant and including EVA and EPDM as the matrix resin, remarkable moldability can be realized, so the semi-incombustible resin composition of the present invention not only realizes semi-incombustibility, but also realizes remarkable moldability. , the limited use due to the low moldability of resin compositions containing conventional non-halogen-based flame retardants can be solved.

As described above, the present invention has been described with specific details and limited examples and comparative examples, but these are provided only to facilitate a more general understanding of the present invention, and the present invention is not limited to the above examples. Those skilled in the art can make various modifications and variations from this description.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and the scope of the patent claims described below as well as all modifications that are equivalent or equivalent to the scope of this patent claim shall fall within the scope of the spirit of the present invention. .

Claims (17)

(A) Matrix resin containing ethylene-vinylacetate copolymer and polyethylene-propylene-diene copolymer, (B) phosphorus-based flame retardant, (C) melamine-based flame retardant, (D) antimony-based flame retardant, clay-based flame retardant, or mixtures thereof. A semi-non-flammable resin composition comprising a phosphorus inorganic flame retardant, (E) a graphite-based flame retardant, and (F) a polyol-based flame retardant auxiliary agent. According to clause 1,
The matrix resin is a semi-non-combustible resin composition comprising 50 to 90% by weight of ethylene-vinylacetate copolymer and 10 to 50% by weight of ethylene-propylene-diene copolymer. According to clause 1,
The semi-non-combustible resin composition includes 200 to 400 parts by weight of an ammonium polyphosphate-based flame retardant based on 100 parts by weight of the matrix resin. According to clause 1,
The semi-non-combustible resin composition includes 50 to 150 parts by weight of a melamine-based flame retardant based on 100 parts by weight of the matrix resin. According to clause 1,
The semi-non-combustible resin composition includes 5 to 60 parts by weight of an inorganic flame retardant based on 100 parts by weight of the matrix resin. According to clause 1,
The semi-non-combustible resin composition includes 10 to 70 parts by weight of a polyol-based flame retardant adjuvant based on 100 parts by weight of the matrix resin. According to clause 1,
The semi-non-combustible resin composition further includes 30 to 150 parts by weight of glass fiber chop based on 100 parts by weight of the matrix resin. According to clause 1,
The semi-non-combustible resin composition includes 1 to 20 parts by weight of a reactive flame retardant monomer based on 100 parts by weight of the matrix resin. According to clause 1,
The semi-non-combustible resin composition includes 5 to 100 parts by weight of a graphite-based flame retardant based on 100 parts by weight of the matrix resin. According to clause 1,
The semi-non-combustible resin composition further includes 10 to 150 parts by weight of a metal hydroxide based on 100 parts by weight of the matrix resin. According to clause 1,
The semi-non-combustible resin composition is a semi-unknown resin composition with a total heat release of 50 MJ/㎡ or less for 10 minutes as measured by ISO 5660-1. According to clause 1,
The semi-non-combustible resin composition is a semi-non-combustible resin composition in which the maximum heat release rate measured by ISO 5660-1 exceeds 200 kW/m2 for less than 10 seconds. According to clause 1,
The semi-non-combustible resin composition has a char formation rate of 70% or more as measured by ISO 5660-1. A semi-non-combustible molded article manufactured including the semi-non-combustible resin composition of any one of claims 1 to 13. According to clause 14,
The semi-non-combustible molded product is a semi-non-combustible molded product that is a fireproof structure, aircraft part, battery module cover, or automobile part. battery module;
The semi-non-combustible molded product of claim 14 on the battery module; and
A fire-safe battery module comprising a battery module cover on the semi-non-combustible molded product. According to clause 16,
The fire safety battery module is a fire safety battery module included in an electric vehicle secondary battery.