Halogen-free flame-retardant ASA resin composition and sheet prepared therefrom

Abstract

Disclosed are a halogen-free flame-retardant ASA resin composition and a sheet prepared therefrom. The halogen-free flame-retardant ASA resin composition according to an embodiment of the present invention comprises 40-85 parts by weight of an acrylonitrile-styrene-acrylate (ASA) resin; and 15-60 parts by weight of a halogen-free flame retardant.

Description

Non-halogen flame-retardant ASA resin composition and sheet manufactured therefrom

[0001] The present invention relates to a non-halogenated flame-retardant ASA resin composition and a sheet produced therefrom, and more specifically, to a non-halogenated flame-retardant ASA resin composition having excellent flame retardancy that does not generate toxic gases and a sheet produced therefrom.

[0002] In general, acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) resin is widely used because it has excellent impact resistance and processability, making it applicable to various uses such as automobiles, electrical and electronic equipment, office equipment, home appliances, toys, and stationery.

[0003] However, the use of ABS resin as an exterior material is very limited due to its fragility; the double bonds of the butadiene rubber used as an impact modifier cause it to oxidize easily when exposed to oxygen, ultraviolet rays, light, and heat, leading to color changes and a deterioration in appearance quality. Furthermore, even in interior materials, it fails to meet consumer requirements due to discoloration.

[0004] Therefore, to compensate for these problems, methods such as post-processing like painting or plating on ABS resin molded products or adding a large amount of UV stabilizer during the extrusion process of ABS resin are used, but the former has the disadvantage of a complex process and a high defect rate, and the latter has the disadvantage of increased manufacturing costs and failure to obtain satisfactory weather resistance for a long time.

[0005] To overcome the limitations of the applications of such ABS resin, various resins known for their excellent weather resistance are being used instead of ABS resin; among these, Acrylate-Styrene-Acrylonitrile resin (hereinafter referred to as 'ASA resin') is the most widely used.

[0006] ASA resin can improve weather resistance and chemical resistance, which are the major drawbacks of ABS resin, by using acrylic rubber instead of butadiene. ASA resin has the advantage of minimal changes in product physical properties and the appearance of molded parts, even when used outdoors for extended periods or exposed to chemicals. Additionally, ASA resin offers the advantage of eliminating the painting process required to improve weather resistance and chemical resistance.

[0007] These ASA resins are generally manufactured by mixing and extruding an acrylic graft polymer, obtained by graft polymerizing a vinyl cyanide compound and an aromatic vinyl compound by an emulsion graft polymerization method on acrylic synthetic rubber, and a vinyl cyanide compound-aromatic vinyl compound copolymer, obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound.

[0008] At this time, by controlling the properties and content of the acrylic synthetic rubber, acrylic graft polymer, and the matrix polymer, vinyl cyanide compound-aromatic vinyl compound copolymer, and selectively adding a reinforcing agent with a specific role, a resin with desired properties can be obtained.

[0009] As mentioned above, the ASA resin produced in this way exhibits excellent weather resistance, light resistance, chemical resistance, and heat resistance, making it suitable for use in outdoor exterior parts subject to significant sunlight exposure, such as outdoor electrical and electronic products, automotive exterior parts, and construction materials.

[0010] When such ASA resin is produced as a particularly thin sheet or film (since it is difficult to clearly distinguish between a sheet and a film, it will be referred to as a sheet below as a term that includes both sheets and films, and its thickness may be 50㎛ to 2,000㎛), it may be used in furniture by applying an adhesive to a plywood sheet, bonding an ASA sheet thereon, applying an adhesive thereon, bonding a patterned film thereon, and forming a coating layer such as a UV coating thereon, or it may be bonded to a desired place such as a panel.

[0011] However, ASA resin itself has no resistance to combustion, and there is a problem in that when ignited by an external ignition factor, the resin itself acts as energy that aids combustion, causing the fire to spread continuously.

[0012] If a sheet made of ASA resin becomes flame-retardant, it will be possible to add flame retardancy to furniture or other panels by bonding it to desired places such as furniture or other panels, thereby enabling a different level of usability than before.

[0013] Looking at conventional technologies, most ASA resins do not have added flame retardancy, but there have also been many studies on the development of flame-retardant ASA resins. Representative examples include a technology that uses ASA resin instead of ABS resin to improve weather resistance and enhance flame retardancy by adding a halogen-containing organic compound as a flame retardant and an antimony oxide-containing inorganic compound as a flame retardant adjuvant.

[0014] However, in these conventional technologies, since halogen-containing organic compounds are used as flame retardants, toxic and corrosive gases are easily generated, which can cause harm to the human body and the environment.

[0015] Therefore, the technical problem to be solved by the present invention is to provide a non-halogenated flame-retardant ASA resin composition with excellent flame retardancy, such as possessing excellent weather resistance while generating less toxic and corrosive gases than conventional materials, and a sheet manufactured therefrom.

[0016] According to the present invention, a non-halogenated flame-retardant ASA resin composition and a sheet manufactured therefrom are provided, which possess excellent weather resistance and generate less toxic and corrosive gases than conventional materials while having excellent flame retardancy.

[0017] According to one aspect of the present invention, a non-halogen flame-retardant ASA resin composition may be provided, characterized by comprising 40 to 85 parts by weight of acrylate-styrene-acrylonitrile (ASA) resin; and 15 to 60 parts by weight of a non-halogen flame retardant.

[0018] The above-mentioned non-halogen flame retardant may comprise 55 to 80 parts by weight of any one selected from aluminum diethylphosphinate and aluminum diethylphosphinate derivatives; and 20 to 45 parts by weight of any one selected from melamine polyphosphate and melamine polyphosphate derivatives.

[0019] The above-mentioned non-halogenated flame retardant may comprise 55 to 80 parts by weight of any one selected from aluminum diethylphosphinate and aluminum diethylphosphinate derivatives; and 20 to 45 parts by weight of any one selected from ammonium polyphosphate and ammonium polyphosphate derivatives.

[0020] The above-mentioned non-halogen flame retardant may comprise 55 to 80 parts by weight of any one selected from aluminum diethylphosphinate and aluminum diethylphosphinate derivatives; 5 to 25 parts by weight of any one selected from melamine polyphosphate and melamine polyphosphate derivatives; and 5 to 30 parts by weight of any one selected from piperazine pyrophosphate and piperazine pyrophosphate derivatives.

[0021] The above-mentioned non-halogen flame retardant may comprise 55 to 80 parts by weight of any one selected from aluminum diethylphosphinate and aluminum diethylphosphinate derivatives; and 20 to 45 parts by weight of any one selected from aluminum hypophosphate and aluminum hypophosphate derivatives.

[0022] The above non-halogen flame-retardant ASA resin composition may further include 0.1 to 30 parts by weight of an impact modifier.

[0023] The above impact modifier may include styrene-ethylene-butylene-styrene (SEBS), methyl methacrylate-butadiene-styrene (MBS), and butyl acrylate-methyl methacrylate polymer.

[0024] The impact modifier may be 5 to 30 parts by weight, the acrylate-styrene-acrylonitrile (ASA) resin may be 40 to 75 parts by weight, and the non-halogen flame retardant may be 15 to 30 parts by weight.

[0025] The above non-halogen flame-retardant ASA resin composition may further include 0.5 to 4 parts by weight of a processing additive.

[0026] The above processing additive may include at least one of fatty acid wax derivatives, fatty acid amide derivatives, fatty acid ester derivatives, and mixtures thereof.

[0027] The above non-halogen flame-retardant ASA resin composition may further include 0.1 to 10 parts by weight of a metal oxide; and 0.1 to 0.5 parts by weight of an antioxidant.

[0028] The metal oxide may include at least one of titanium oxide, iron oxide, and other metal oxides or a mixture thereof.

[0029] The above non-halogen flame-retardant ASA resin composition may further include 0.1 to 0.5 parts by weight of a UV stabilizer.

[0030] According to another aspect of the present invention, a non-halogen flame-retardant ASA sheet manufactured from the non-halogen flame-retardant ASA resin composition may be provided.

[0031] The above non-halogen flame-retardant ASA sheet can have a thickness of 50㎛ to 2,000㎛.

[0032] According to another aspect of the present invention, a non-halogen flame-retardant ASA multi-sheet manufactured by co-extrusion of the non-halogen flame-retardant ASA resin composition and a different material into multiple layers can be provided.

[0033] The present invention is not limited to the embodiments disclosed below but may be implemented in various different forms, and these embodiments are provided merely to make the disclosure of the present invention complete and to fully inform those skilled in the art of the scope of the invention.

[0034] In this specification, the singular form includes the plural form unless specifically stated otherwise in the text. As used in this specification, "comprises" and / or "comprising" do not exclude the presence or addition of one or more other components, steps, and actions in addition to the mentioned components, steps, and actions.

[0035] The composition of the non-halogenated flame-retardant acrylate-styrene-acrylonitrile resin (hereinafter referred to as 'ASA resin') and the sheet produced therefrom according to the present invention will be described in detail below.

[0036] The non-halogen flame-retardant ASA sheet according to the present invention is a sheet produced from a non-halogen flame-retardant ASA resin composition created by adding and mixing a non-halogen flame retardant to an ASA resin.

[0037] As previously mentioned, sheets manufactured from conventional ASA resin have a problem in that the ASA resin itself lacks resistance to combustion, and when ignited by an external ignition factor, the resin itself acts as energy that aids combustion, causing the fire to spread continuously.

[0038] Therefore, sheets manufactured from such ASA resin cannot add flame retardancy even when attached to furniture or panels.

[0039] In the case of the present invention, to solve these problems, a non-halogen flame-retardant ASA resin composition having excellent flame retardancy that does not generate toxic gases can be produced by adding and mixing a non-halogen flame-retardant to an ASA resin, and a non-halogen flame-retardant ASA sheet can be manufactured using a twin-screw extruder or a single-screw extruder with the non-halogen flame-retardant ASA resin composition produced in this way.

[0040] The non-halogen flame-retardant ASA sheet according to the present invention may have a thickness of 50㎛ to 2,000㎛, but the scope of the present invention is not limited thereto and it is obvious that it may have various thicknesses.

[0041] As such, the non-halogen flame-retardant ASA sheet according to the present invention comprises a non-halogen flame-retardant ASA resin composition.

[0042] The non-halogen flame-retardant ASA resin composition according to the present invention comprises an acrylate-styrene-acrylonitrile (ASA) resin and a non-halogen flame retardant.

[0043] Acrylate-Styrene-Acrylonitrile resin, or ASA resin, is a thermoplastic resin of ternary copolymer made primarily of acrylonitrile, styrene, and acrylic rubber.

[0044] The ASA resin used in the present invention may have various ratios between acrylonitrile, styrene, and acrylate rubber. The melt index of such ASA resin is in the range of 2 to 10 g / 10 min (220°C, 10 kg).

[0045] And in the non-halogen flame-retardant ASA resin composition according to the present invention, the ASA resin may be configured to include 40 to 85 parts by weight.

[0046] This is because if less than 40 parts by weight of ASA resin is used, brittleness increases, making it difficult to use even if a sheet (a term including film) is manufactured, and if more than 85 parts by weight of ASA resin is used, it is difficult to achieve flame retardancy.

[0047] Next, the non-halogen flame retardant used in the present invention is described.

[0048] In the non-halogen flame-retardant ASA resin composition according to the present invention, the non-halogen flame retardant may be configured to include 15 to 60 parts by weight.

[0049] This is because using less than 15 parts by weight of non-halogenated flame retardant makes it difficult to achieve flame retardancy, and using more than 60 parts by weight of non-halogenated flame retardant makes the physical properties unsuitable for use as a sheet.

[0050] And the non-halogenated flame retardant used in the present invention is composed of a combination of aluminum diethylphosphinate (ADP), ammonium polyphosphate (APP), melamine polyphosphate (MPP), piperazine pyrophosphate (PIPP), and aluminum hypophosphite (AHP).

[0051] Aluminum diethylphosphinate (ADP) is an organophosphorus flame retardant that exhibits excellent flame retardancy and a good balance of physical properties.

[0052] In the present invention, the non-halogenated flame retardant may be configured to include 55 to 80 parts by weight of aluminum diethylphosphinate (ADP: Aluminum diethylphosphinate) and the remainder by weight of one or a combination of two of ammonium polyphosphate, melamine polyphosphate, piperazine pyrophosphate, and aluminum hypophosphate.

[0053] Ammonium polyphosphate (APP) is a representative phosphorus-nitrogen flame retardant and exists as a white crystalline powder in both water-soluble and insoluble forms. Its general function in polymers is to act as a flame retardant during combustion through surface coating, heat dissipation via the evaporation of phosphorus compounds, dilution of decomposition products, and reduction of melt viscosity. It is recognized as an excellent flame retardant due to its high phosphorus content of 30%.

[0054] Ammonium polyphosphate is a non-halogen and non-toxic flame retardant for plastics, rubber, coatings, paper, wood, paints, and wood materials; when exposed to fire or heat, it decomposes into polymeric phosphate, acid, and ammonia.

[0055] In the present invention, a non-halogenated flame retardant comprising ammonium polyphosphate (APP) may be configured to include 55 to 80 parts by weight of aluminum diethylphosphinate (ADP) and 20 to 45 parts by weight of ammonium polyphosphate (APP).

[0056] Melamine polyphosphate (MPP) can be included together with the aforementioned aluminum diethylphosphinate to further enhance flame retardancy, and can play a role in preventing the deterioration of physical properties by substantially reducing the content of aluminum diethylphosphinate, which is a flame retardant.

[0057] The inclusion of melamine polyphosphate allows the melamine to sublimate during combustion, absorbing energy and lowering the temperature of the combustion material. This generates ammonia as a decomposition product, which dilutes oxygen and combustion gases of the resin composition, thereby enhancing the flame-retardant effect.

[0058] In the present invention, a non-halogenated flame retardant containing melamine polyphosphate (MPP) may be configured to include 55 to 80 parts by weight of aluminum diethylphosphinate (ADP) and 20 to 45 parts by weight of melamine polyphosphate (MPP).

[0059] Piperazine pyrophosphate (PIPP) is a compound that combines piperazine, a common organic compound used for various purposes, with pyrophosphate, an inorganic anion, and provides flame retardancy.

[0060] In the present invention, a non-halogenated flame retardant containing piperazine pyrophosphate (PIPP) may be configured to include 55 to 80 parts by weight of aluminum diethylphosphinate (ADP), 5 to 25 parts by weight of melamine polyphosphate (MPP), and 5 to 30 parts by weight of piperazine pyrophosphate (PIPP).

[0061] Aluminum hypophosphite (AHP) is an inorganic phosphorus-based flame retardant. It is slightly soluble in water, has a high phosphorus content, and possesses good thermal stability.

[0062] In the present invention, a non-halogenated flame retardant comprising hypophosphate (Aluminum hypophosphite: AHP: Aluminum hypophosphite) may be configured to include 55 to 80 parts by weight of aluminum diethylphosphinate (ADP: Aluminum diethylphosphinate) and 20 to 45 parts by weight of hypophosphate (Aluminum hypophosphite: AHP: Aluminum hypophosphite).

[0063] Meanwhile, the non-halogen flame-retardant ASA resin composition according to an embodiment of the present invention may further include one or more additives necessary according to the non-halogen flame-retardant ASA resin composition, in addition to the above components, to balance the physical properties under conditions for improving impact resistance or flow and surface.

[0064] Specifically, as additives, impact modifiers, processing additives for flow and surface improvement, metal oxides that are coloring agents, antioxidants, ultraviolet (UV) stabilizers, etc., may be used, and these may be used alone or in combination of two or more.

[0065] The non-halogenated flame-retardant ASA resin composition according to the present invention may include 0.1 to 30 parts by weight of an impact modifier.

[0066] In the present invention, impact modifiers may include styrene-ethylene-butylene-styrene (SEBS) and its derivatives, methyl methacrylate-butadiene-styrene copolymer (MBS) and its derivatives, butyl acrylate-methyl methacrylate copolymer and its derivatives, etc.

[0067] Although impact modifiers do not directly affect flame retardancy, they improve impact strength, thereby allowing for the inclusion of a larger amount of non-halogenated flame retardant to enhance flame retardancy.

[0068] The non-halogenated flame-retardant ASA resin composition according to the present invention may further include 0.5 to 4 parts by weight of a processing additive.

[0069] In the present invention, at least one of fatty acid wax derivatives, fatty acid amide derivatives, fatty acid ester derivatives, and mixtures thereof may be used as the processing additive.

[0070] In the following examples, the processing additive used was EL840 from the applicant, Iruchem Co., Ltd. EL840 can improve flow and surface.

[0071] The non-halogenated flame-retardant ASA resin composition according to the present invention may further include 0.1 to 10 parts by weight of a metal oxide.

[0072] In the present invention, at least one of titanium oxide (TiO2), iron oxide (Fe2O3), and mixtures thereof may be used as the metal oxide, and the scope of the present invention is not limited thereto, and various metal oxides may be used.

[0073] When metal oxides are added in an amount of up to 2 parts by weight, they help to achieve flame retardancy to some extent, but if the amount increases beyond that, flame retardancy decreases. The most important reason for adding metal oxides is to brighten the color and produce a color.

[0074] The non-halogenated flame-retardant ASA resin composition according to the present invention may further include 0.1 to 0.5 parts by weight of an antioxidant.

[0075] The non-halogenated flame-retardant ASA resin composition according to the present invention may further include 0.1 to 0.5 parts by weight of a UV stabilizer.

[0076] Hereinafter, preferred embodiments are presented to aid in understanding the present invention; however, the following embodiments are merely illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, and that such variations and modifications fall within the scope of the appended claims.

[0077]

[0078] [Example 1]

[0079] A composition comprising 72.8 parts by weight of acrylonitrile-styrene-acrylate (ASA) (Rockwell hardness 103), 20 parts by weight of a non-halogenated flame-retardant compound (non-halogenated flame retardant) containing aluminum diethylphosphinate (ADP) and melamine polyphosphate (MPP) in a ratio of 2:1, 5 parts by weight of titanium oxide (TiO2), 2 parts by weight of talc, and 0.2 parts by weight of an antioxidant was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. The pellets were then dried at 90°C for 2-3 hours to ensure that the moisture content of the final compound was less than 0.03%. Then, a non-halogen flame-retardant ASA sheet was manufactured using a calendering system with a well-dried compound, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0080]

[0081] [Example 2]

[0082] A composition comprising 61.8 parts by weight of acrylonitrile styrene acrylate (ASA) (Rockwell hardness 103), 30 parts by weight of a non-halogenated flame-retardant compound containing aluminum diethylphosphinate (ADP) and melamine polyphosphate (MPP) in an ADP / MPP ratio of 2:1, 6 parts by weight of titanium oxide (TiO2), 2 parts by weight of talc, and 0.2 parts by weight of an antioxidant was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. The pellets were then dried at 90°C for 2-3 hours to ensure that the moisture content of the final compound was less than 0.03%. Then, a non-halogen flame-retardant ASA sheet was manufactured using a well-dried compound through a calender system, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0083]

[0084] [Example 3]

[0085] A composition comprising 61.8 parts by weight of acrylonitrile styrene acrylate (ASA) (Rockwell hardness 103), 30 parts by weight of a non-halogenated flame-retardant compound containing aluminum diethylphosphinate (ADP), piperazine pyrophosphate (PIPP), and melamine polyphosphate (MPP) in a ratio of 20:7:3, 6 parts by weight of titanium oxide (TiO2), 2 parts by weight of talc, and 0.2 parts by weight of an antioxidant was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. Then, the pellets were dried at 90°C for 2-3 hours so that the moisture content of the final compound was less than 0.03%. Then, a non-halogen flame-retardant ASA sheet was manufactured using a calender system with the well-dried compound, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0086]

[0087] [Example 4]

[0088] A composition comprising 61.3 parts by weight of acrylonitrile styrene acrylate (ASA) (Rockwell hardness 103), 21.5 parts by weight of a non-halogenated flame-retardant compound containing aluminum diethylphosphinate (ADP) and ammonium polyphosphate (APP) in a 2:1 ratio of aluminum diethylphosphinate (ADP) to ammonium polyphosphate (APP), 10 parts by weight of styrene-ethylene-butylene-styrene (SEBS), 6 parts by weight of titanium oxide (TiO2), 1 part by weight of EL840 (processing additive, Iruchem), and 0.2 parts by weight of an antioxidant was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. Then, the pellets were dried at 90°C for 2-3 hours so that the moisture content of the final compound was less than 0.03%. Then, a non-halogen flame-retardant ASA sheet was manufactured using a calendering system with the well-dried compound, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0089]

[0090] [Example 5]

[0091] A composition comprising 56.3 parts by weight of acrylonitrile styrene acrylate (ASA) (Rockwell hardness 103), 21.5 parts by weight of a non-halogenated flame-retardant compound containing aluminum diethylphosphinate (ADP) and ammonium polyphosphate (APP) in a 2:1 ratio, 15 parts by weight of styrene-ethylene-butylene-styrene (SEBS), 6 parts by weight of titanium oxide (TiO2), 1 part by weight of EL840 (processing additive, Iruchem), and 0.2 parts by weight of an antioxidant is thoroughly mixed in a mixer. The resulting mixture is then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range is maintained within the 200-210°C range, and the pellets are formed using a strand cutting system. Then, the pellets were dried at 90°C for 2-3 hours so that the moisture content of the final compound was less than 0.03%. Then, a non-halogen flame-retardant ASA sheet was manufactured using a calendering system with the well-dried compound, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0092]

[0093] [Example 6]

[0094] A composition comprising 51.3 parts by weight of acrylonitrile styrene acrylate (ASA) (Rockwell hardness 103), 21.5 parts by weight of a non-halogenated flame-retardant compound containing aluminum diethylphosphinate (ADP) and ammonium polyphosphate (APP) in a 2:1 ratio, 20 parts by weight of styrene-ethylene-butylene-styrene (SEBS), 6 parts by weight of titanium oxide (TiO2), 1 part by weight of EL840 (processing additive, Iruchem), and 0.2 parts by weight of an antioxidant was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. Then, the pellets were dried at 90°C for 2-3 hours so that the moisture content of the final compound was less than 0.03%. Then, a non-halogen flame-retardant ASA sheet was manufactured using a calendering system with the well-dried compound, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0095]

[0096] [Example 7]

[0097] A composition comprising 46.3 parts by weight of acrylonitrile styrene acrylate (ASA) (Rockwell hardness 103), 21.5 parts by weight of a non-halogenated flame-retardant compound containing aluminum diethylphosphinate (ADP) and ammonium polyphosphate (APP) in a 2:1 ratio, 25 parts by weight of styrene-ethylene-butylene-styrene (SEBS), 6 parts by weight of titanium oxide (TiO2), 1 part by weight of EL840 (processing additive, Iruchem), and 0.2 parts by weight of an antioxidant was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. Then, the pellets were dried at 90°C for 2-3 hours so that the moisture content of the final compound was less than 0.03%. Then, a non-halogen flame-retardant ASA sheet was manufactured using a calendering system with the well-dried compound, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0098]

[0099] [Example 8]

[0100] A composition comprising 41.3 parts by weight of acrylonitrile styrene acrylate (ASA) (Rockwell hardness 103), 21.5 parts by weight of a non-halogenated flame-retardant compound containing aluminum diethylphosphinate (ADP) and ammonium polyphosphate (APP) in a 2:1 ratio of aluminum diethylphosphinate (ADP) to ammonium polyphosphate (APP), 30 parts by weight of styrene-ethylene-butylene-styrene (SEBS), 6 parts by weight of titanium oxide (TiO2), 1 part by weight of EL840 (processing additive, Iruchem), and 0.2 parts by weight of an antioxidant was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. Then, the pellets were dried at 90°C for 2-3 hours so that the moisture content of the final compound was less than 0.03 parts by weight. Then, a non-halogen flame-retardant ASA sheet was manufactured using a calendering system with the well-dried compound, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0101]

[0102] [Example 9]

[0103] A composition comprising 65.8 parts by weight of acrylonitrile styrene acrylate (ASA) (Rockwell hardness 103), 22 parts by weight of a non-halogen flame retardant compound containing aluminum diethylphosphinate (ADP) and ammonium polyphosphate (APP) in a 2:1 ratio, 5 parts by weight of methyl methacrylate-butadiene-styrene (MBS), 6 parts by weight of titanium oxide (TiO2), 1 part by weight of EL840 (processing additive, Iruchem), and 0.2 parts by weight of an antioxidant was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. Then, the pellets were dried at 90°C for 2-3 hours so that the moisture content of the final compound was less than 0.03%. Then, a non-halogen flame-retardant sheet was manufactured using a calendering system with the well-dried compound, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0104]

[0105] [Example 10]

[0106] A composition comprising 60.8 parts by weight of acrylonitrile styrene acrylate (ASA) (Rockwell hardness 103), 22 parts by weight of a non-halogen flame retardant compound containing aluminum diethylphosphinate (ADP) and ammonium polyphosphate (APP) in a 2:1 ratio, 10 parts by weight of methyl methacrylate-butadiene-styrene (MBS), 6 parts by weight of titanium oxide (TiO2), 1 part by weight of EL840 (processing additive, Iruchem), and 0.2 parts by weight of an antioxidant was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. Then, the pellets were dried at 90°C for 2-3 hours so that the moisture content of the final compound was less than 0.03%. Then, a non-halogen flame-retardant ASA sheet was manufactured using a calendering system with the well-dried compound, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0107]

[0108] [Example 11]

[0109] A composition comprising 55.8 parts by weight of acrylonitrile styrene acrylate (ASA) (Rockwell hardness 103), 22 parts by weight of a non-halogenated flame-retardant compound containing aluminum diethylphosphinate (ADP) and ammonium polyphosphate (APP) in a 2:1 ratio, 15 parts by weight of methyl methacrylate-butadiene-styrene (MBS), 6 parts by weight of titanium oxide (TiO2), 1 part by weight of EL840 (processing additive, Iruchem), and 0.2 parts by weight of an antioxidant was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. Then, the pellets were dried at 90°C for 2-3 hours so that the moisture content of the final compound was less than 0.03%. Then, a non-halogen flame-retardant ASA sheet was manufactured using a calendering system with the well-dried compound, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0110]

[0111] [Example 12]

[0112] A composition comprising 50.8 parts by weight of acrylonitrile styrene acrylate (ASA) (Rockwell hardness 103), 22 parts by weight of a non-halogenated flame-retardant compound containing aluminum diethylphosphinate (ADP) and ammonium polyphosphate (APP) in a 2:1 ratio, 20 parts by weight of methyl methacrylate-butadiene-styrene (MBS), 6 parts by weight of titanium oxide (TiO2), 1 part by weight of EL840 (processing additive, Iruchem), and 0.2 parts by weight of an antioxidant was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. Then, the pellets were dried at 90°C for 2-3 hours so that the moisture content of the final compound was less than 0.03%. Then, a non-halogen flame-retardant ASA sheet was manufactured using a calendering system with the well-dried compound, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0113]

[0114] [Example 13]

[0115] A composition comprising 44.8 parts by weight of acrylonitrile styrene acrylate (ASA) (Rockwell hardness 103), 25 parts by weight of a non-halogenated flame-retardant compound containing aluminum diethylphosphinate (ADP) and ammonium polyphosphate (APP) in a 2:1 ratio, 20 parts by weight of methyl methacrylate-butadiene-styrene (MBS), 8 parts by weight of titanium oxide (TiO2), 2 parts by weight of EL840 (processing additive, Iruchem), and 0.2 parts by weight of an antioxidant was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. Then, the pellets were dried at 90°C for 2-3 hours so that the moisture content of the final compound was less than 0.03%. Then, a non-halogen flame-retardant ASA sheet was manufactured using a calender system with the well-dried compound, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0116]

[0117] [Example 14]

[0118] A composition comprising 54.8 parts by weight of acrylonitrile styrene acrylate (ASA) (Rockwell hardness 94), 25 parts by weight of a non-halogenated flame-retardant compound containing aluminum diethylphosphinate (ADP) and ammonium polyphosphate (APP) in a 2:1 ratio of aluminum diethylphosphinate (ADP) to ammonium polyphosphate (APP), 10 parts by weight of methyl methacrylate-butadiene-styrene (MBS), 8 parts by weight of titanium oxide (TiO2), 2 parts by weight of EL840 (processing additive, Iruchem), and 0.2 parts by weight of an antioxidant was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. Then, the pellets were dried at 90°C for 2-3 hours so that the moisture content of the final compound was less than 0.03%. Then, a non-halogen flame-retardant ASA sheet was manufactured using a calendering system with the well-dried compound, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0119]

[0120] [Example 15]

[0121] A composition comprising 49.8 parts by weight of acrylonitrile styrene acrylate (ASA) (Rockwell hardness 94), 30 parts by weight of a non-halogenated flame-retardant compound containing aluminum diethylphosphinate (ADP) and ammonium polyphosphate (APP) in a 2:1 ratio of aluminum diethylphosphinate (ADP) to ammonium polyphosphate (APP), 10 parts by weight of methyl methacrylate-butadiene-styrene (MBS), 8 parts by weight of titanium oxide (TiO2), 2 parts by weight of EL840 (processing additive, Iruchem), and 0.2 parts by weight of an antioxidant was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. Then, the pellets were dried at 90°C for 2-3 hours so that the moisture content of the final compound was less than 0.03%. Then, a non-halogen flame-retardant ASA sheet was manufactured using a calendering system with the well-dried compound, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0122]

[0123] [Example 16]

[0124] A composition comprising 54.8 parts by weight of acrylonitrile styrene acrylate (ASA) (Rockwell hardness 94), 20 parts by weight of aluminum diethylphosphinate (ADP), 5 parts by weight of aluminum hypophosphite (AHP), 10 parts by weight of methyl methacrylate-butadiene-styrene (MBS), 8 parts by weight of titanium oxide (TiO2), 2 parts by weight of EL840 (processing additive, Iruchem), and 0.2 parts by weight of an antioxidant was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. The pellets were then dried at 90°C for 2-3 hours to ensure that the moisture content of the final compound was less than 0.03 parts by weight. Then, a non-halogen flame-retardant ASA sheet was manufactured using a well-dried compound through a calender system, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0125]

[0126] [Comparative Example 1]

[0127] A composition consisting of 98 parts by weight of acrylonitrile-styrene-acrylate (ASA) and 2 parts by weight of pigment was mixed in a mixer. The resulting mixture was then fed into the main feeder of a 36 mm twin-screw extruder to produce pellets. The extruder temperature range was maintained within the 200-210°C range, and the pellets were formed using a strand cutting system. The pellets were then dried at 90°C for 2-3 hours to ensure that the moisture content of the final compound was less than 0.03%. Subsequently, ASA sheets were manufactured using a calendering system with the well-dried compound, and the thickness of the output sheet was controlled to within 0.3 mm ± 0.03 mm.

[0128]

[0129] [Test Example]

[0130] The characteristics of the specimens prepared in Examples 1 to 16 and Comparative Example 1 were measured by the following method, and the results are shown in Table 1 below.

[0131] 1) Tensile strength (MPa): Measured using the ISO 527-1 Standard Test Method with a specimen of 170 x 10 x 4 mm and a Universal Testing Machine from Qmesys.

[0132] 2) Elongation (%): Measured using the ISO 527-1 Standard Test Method with a specimen of size 170 x 10 x 4 mm (length of span between support 100 mm) and a Universal Testing Machine from Qmesys.

[0133] 3) Flexural strength (MPa): Measured using the ISO 178 Standard Test Method with a specimen of size 120 x 10 x 4 mm (length of span between support 100 mm) and a Universal Testing Machine from Qmesys.

[0134] 4) Flexural Modulus: Measured using the ISO 178 Standard Test Method with a specimen of size 120 x 10 x 4 mm (length of span between support 100 mm) and a Universal Testing Machine from Qmesys.

[0135] 5) Charpy Impact Strength (KJ / m2): Measured using the ISO 178 Standard Test Method with a specimen of 80 x 10 x 4 mm size and 1 / 4" notched at 23℃ and a Charpy Impact Strength Test Machine from Qmesys.

[0136] 6) Flame Retardancy - UL94 VTM Grade @ 0.3 millimeters: Measured using a Qmesys Flammability Tester according to UL V-0 standards.

[0137] 7) Flame Retardancy - UL94 VTM Total Burn Time(s) @ 0.3mm: Measured using a Qmesys Flammability Tester and stopwatch according to UL V-0 standards.

[0138]

[0139] Table 1

[0140]

[0141]

[0142] In Example 1, a non-halogenated flame retardant compound containing 20 parts by weight of aluminum diethylphosphinate (ADP) / melamine polyphosphate (MPP) was used, and the flame retardant grade was V-1 according to the UL-94 VTM standard.

[0143] In Example 2, after using up to 30 parts by weight of a mixture of aluminum diethylphosphinate (ADP) / melamine polyphosphate (MPP) non-halogenated flame retardants, a non-halogenated flame-retardant ASA sheet with a thickness of 0.3 mm obtained a flame retardant rating of V-0 according to the UL-94 VTM standard.

[0144] In Example 3 as well, after using up to 30 parts by weight of a non-halogenated flame retardant mixture containing aluminum diethylphosphinate (ADP) / piperazine pyrophosphate (PIPP) / melamine polyphosphate (MPP), a flame retardant rating of V-0 was obtained for an ASA sheet with a thickness of 0.3 mm according to the UL-94 VTM standard. However, the non-halogenated flame-retardant ASA sheet of this example had low impact strength due to its flame retardancy.

[0145] In Examples 4 to 8, varying amounts of the impact modifier styrene-ethylene-butylene-styrene (SEBS) were used, ranging from 10 to 30 parts by weight, to improve the impact strength of the non-halogen flame-retardant ASA sheet. However, since introducing an impact modifier into the non-halogen flame-retardant ASA resin composition degrades the flow and surface properties of the ASA resin, EL840 (processing additive, Iruchem), which acts to improve the flow and surface of the ASA resin, was added. By increasing the amount of styrene-ethylene-butylene-styrene (SEBS), the impact strength of the non-halogen flame-retardant ASA sheet was improved, but the flame retardancy of the non-halogen flame-retardant ASA sheet was reduced.

[0146] In Examples 9 to 12, methyl methacrylate-butadiene-styrene (MBS) impact modifiers were used in different amounts to improve the impact strength of halogenated flame-retardant ASA sheets. Compared to styrene-ethylene-butylene-styrene (SEBS), methyl methacrylate-butadiene-styrene (MBS) showed better impact strength improvement for non-halogenated flame-retardant ASA sheets when used in the same amount. The flame retardant ability of the non-halogenated flame-retardant ASA sheets was tested using UL-94 VTM on 0.3 mm sheets, and it was found that all samples exhibited a V-1 rating even as the total burning time increased with increasing amounts of methyl methacrylate-butadiene-styrene (MBS).

[0147] In Example 13, when the amount of non-halogen flame retardant was increased to 25 parts by weight, the flame retardancy of the non-halogen flame-retardant ASA sheet reached UL-94 VTM V-0 grade.

[0148] In Example 14, an ASA resin with a Rockwell hardness of 94 was used, and the amount of methyl methacrylate-butadiene-styrene (MBS) required to obtain the same impact strength as the non-halogenated flame-retardant ASA sheet of Example 14 could be reduced.

[0149] In Example 15, the content of the non-halogenated flame retardant was increased to 30 parts by weight, resulting in better flame retardancy even in thinner sheets.

[0150] In Example 16, a non-halogenated flame-retardant ASA sheet was prepared using an aluminum diethylphosphinate (ADP) / aluminum hypophosphite (AHP) mixture instead of using a diethylphosphinate (ADP) / melamine polyphosphate (MPP) mixture or an aluminum diethylphosphinate (ADP) / ammonium polyphosphate (APP) mixture. Although using the aluminum diethylphosphinate (ADP) / aluminum hypophosphite (AHP) flame retardant is not as good as diethylphosphinate (ADP) / melamine polyphosphate (MPP) and aluminum diethylphosphinate (ADP) / ammonium polyphosphate (APP), it is applicable depending on the required flame retardancy.

[0151]

[0152] In the above-described embodiments, the non-halogen flame-retardant ASA resin composition was manufactured using an extruder to produce the non-halogen flame-retardant ASA resin, but a non-halogen flame-retardant ASA multi-sheet can also be manufactured by co-extrusion in which the non-halogen flame-retardant ASA resin composition and a different material are simultaneously extruded in multiple layers.

[0153] As such, the present invention is not limited to the described embodiments, and it is obvious to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention. Accordingly, such modifications or variations should be deemed to fall within the scope of the claims of the present invention.

[0154] The present invention can be used in the plastic processing industry where outdoor weather resistance and flame retardancy are required simultaneously.

Claims

1. 40 to 85 parts by weight of acrylate-styrene-acrylonitrile (ASA) resin; and A non-halogen flame-retardant ASA resin composition characterized by containing 15 to 60 parts by weight of a non-halogen flame retardant.

2. In Paragraph 1, The above-mentioned non-halogen flame retardant is, 55 to 80 parts by weight of any one selected from aluminum diethylphosphinate and aluminum diethylphosphinate derivatives; and A non-halogenated flame-retardant ASA resin composition characterized by comprising 20 to 45 parts by weight of any one selected from melamine polyphosphate and melamine polyphosphate derivatives.

3. In Paragraph 1, The above-mentioned non-halogen flame retardant is, 55 to 80 parts by weight of any one selected from aluminum diethylphosphinate and aluminum diethylphosphinate derivatives; and A non-halogenated flame-retardant ASA resin composition characterized by comprising 20 to 45 parts by weight of any one selected from ammonium polyphosphate and ammonium polyphosphate derivatives.

4. In Paragraph 1, The above-mentioned non-halogen flame retardant is, 55 to 80 parts by weight of any one selected from aluminum diethylphosphinate and aluminum diethylphosphinate derivatives; 5 to 25 parts by weight of any one selected from melamine polyphosphate and melamine polyphosphate derivatives; and A non-halogenated flame-retardant ASA resin composition characterized by comprising 5 to 30 parts by weight of any one selected from piperazine pyrophosphate and piperazine pyrophosphate derivatives.

5. In Paragraph 1, The above-mentioned non-halogen flame retardant is, 55 to 80 parts by weight of any one selected from aluminum diethylphosphinate and aluminum diethylphosphinate derivatives; and A non-halogenated flame-retardant ASA resin composition characterized by comprising 20 to 45 parts by weight of any one selected from aluminum hypophosphate and aluminum hypophosphate derivatives.

6. In Paragraph 1, The above-mentioned non-halogen flame-retardant ASA resin composition is, A non-halogenated flame-retardant ASA resin composition characterized by further including 0.1 to 30 parts by weight of an impact modifier.

7. In Paragraph 6, The above impact modifier is, A non-halogenated flame-retardant ASA resin composition characterized by comprising styrene-ethylene-butylene-styrene (SEBS), methyl methacrylate-butadiene-styrene (MBS), and butyl acrylate-methyl methacrylate polymer.

8. In Paragraph 6, The above impact modifier is 5 to 30 parts by weight, and The above acrylate-styrene-acrylonitrile (ASA) resin is 40 to 75 parts by weight, and A non-halogen flame-retardant ASA resin composition characterized by containing 15 to 30 parts by weight of the above-mentioned non-halogen flame retardant.

9. In Paragraph 6, The above-mentioned non-halogen flame-retardant ASA resin composition is, A non-halogenated flame-retardant ASA resin composition characterized by further including 0.5 to 4 parts by weight of a processing additive.

10. In Paragraph 9, A non-halogenated flame-retardant ASA resin composition characterized by the above-mentioned processing additive comprising at least one of fatty acid wax derivatives, fatty acid amide derivatives, fatty acid ester derivatives, and mixtures thereof.

11. In Paragraph 9, The above-mentioned non-halogen flame-retardant ASA resin composition is, 0.1 to 10 parts by weight of metal oxide; and A non-halogenated flame-retardant ASA resin composition characterized by further including 0.1 to 0.5 parts by weight of an antioxidant.

12. In Paragraph 11, A non-halogen flame-retardant ASA resin composition characterized in that the metal oxide comprises at least one of titanium oxide, iron oxide, and mixtures thereof.

13. In Paragraph 11, The above-mentioned non-halogen flame-retardant ASA resin composition is, A non-halogenated flame-retardant ASA resin composition characterized by further including 0.1 to 0.5 parts by weight of a UV stabilizer.

14. A non-halogen flame-retardant ASA sheet manufactured from a non-halogen flame-retardant ASA resin composition of any one of claims 1 to 13.

15. In Paragraph 14, The above-mentioned non-halogen flame-retardant ASA sheet is characterized by having a thickness of 50㎛ to 2,000㎛.

16. A non-halogen flame-retardant ASA multi-sheet manufactured by co-extrusion of a non-halogen flame-retardant ASA resin composition of any one of claims 1 to 13 and a material different therefrom into multiple layers.

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