Thermoplastic flame-retardant resin composition and molded article

Abstract

The present invention relates to a thermoplastic flame-retardant resin composition and / or a molded article. The present invention has the effects of providing: a lightweight thermoplastic flame-retardant resin composition, which exhibits high flame retardancy while having excellent post-molding shrinkage prevention ability and processability required for a very thin, large-area lightweight molded article; and a molded article manufactured therefrom.

Description

Thermoplastic flame-retardant resin composition and molded article

[0001] 〔Cross-citation with the applicant(s)〕

[0002] This application claims the benefit of priority from Korean Patent Application No. 10-2024-0087977, filed July 4, 2024, the entire contents of which are incorporated herein by reference.

[0003] The present invention relates to a thermoplastic flame-retardant resin composition molded article, and more particularly, to a thermoplastic flame-retardant resin composition having excellent post-molding shrinkage prevention and processability required for a large-area lightweight molded article with a very thin thickness, while exhibiting high flame retardancy and being lightweight, and a molded article manufactured therefrom.

[0004] Polypropylene resin is a type of general-purpose plastic that is widely used in the fields of automobiles, building materials, and electrical components in the form of injection molded products, sheets, and blow molded products due to its excellent processing characteristics, chemical resistance, weather resistance, and high sliding properties. Recently, high-gloss grades with excellent surface gloss and wear resistance, high-weight grades with improved rigidity and damping characteristics, thermally stable heat-resistant grades, high-rigidity grades that meet various mechanical property requirements by adding glass fiber, etc. and that show tensile strength approximately 200-300% higher and flexural modulus more than 4 times higher than general polypropylene resins, high-impact grades that show excellent impact strength at low temperatures and excellent fluidity by using RTPO (Reactor-made Thermoplastic Olefin) and synthetic rubber to improve impact strength, and long-term weather-resistant grades that have excellent weather stability and do not discolor even when left outdoors for a long time, are appearing, and thus, various new uses are being attempted as multi-functionality is being achieved.

[0005] Polypropylene resin was originally classified as a combustible plastic, limiting its use as a flame retardant. However, as polypropylene resin becomes more functionalized and its applications expand, the demand for flame retardant properties is also increasing. To meet this demand, flame retardant grades of polypropylene, which are enhanced with various organic and inorganic flame retardants to impart superior flame retardancy, have been developed and are being used.

[0006] This flame-retardant polypropylene is mainly used in electrical and electronic components such as TVs, monitors, and air conditioners. Recently, in addition to flame retardancy, there is a demand for improved physical properties such as moldability and processability for these products, and lightweight is also required. For example, in the case of insulating sheets for energy storage systems that exhibit flame retardancy class V-0 of UL94, it is required to have an extremely thin thickness of less than 0.3 mm, a large area, excellent post-molding shrinkage prevention performance, high flame retardancy, improved processability, and a lightweight specific gravity of less than 1.

[0007] In general, flame retardancy of polypropylene resins tends to be inversely proportional to light weight, so that resin compositions with high flame retardancy tend to have an increased specific gravity.

[0008] The above flame-retardant polypropylene resin is disclosed in Japanese Patent Application Laid-Open No. 6-184372, which is a flame-retardant compound that is a tetrabromobisphenol A compound or a tetrabromobisphenol S compound mixed with polypropylene. Although the flame-retardant polypropylene resin can increase the flame-retardant effect by mixing a small amount of the flame retardant, it causes a problem that it is difficult to mold into a large-area product with a very thin thickness due to poor processability, etc.

[0009] In order to improve the problems such as poor processability as described above, a method is disclosed in Japanese Patent Application Laid-Open No. Hei 9-52988 in which a tetrabromobisphenol A compound or a tetrabromobisphenol S compound is added as a flame retardant and chlorinated polyethylene is mixed in, but there is a problem in that it has a somewhat low flame retardancy corresponding to UL94 V-2 grade.

[0010] In addition, thermoplastic flame-retardant resin compositions containing halogen diphenyl ether compounds such as decabromodiphenyl oxide and octabromodiphenyl oxide, and halogen bisphenol compounds such as hexabromocyclododecane as flame retardants, as described in Japanese Patent Application Laid-Open No. 2000-344973 and Japanese Patent Application Laid-Open No. 2001-220470, etc., exhibit high flame-retardant effects (UL94 V-2~V-0), but have problems with mechanical properties, heat resistance, and weather resistance.

[0011] The present invention is intended to solve the problems of the prior art as described above, and aims to provide a thermoplastic flame-retardant resin composition that exhibits high flame retardancy and is lightweight while also having excellent post-molding shrinkage prevention and processability required for a large-area lightweight molded product with a very thin thickness.

[0012] In addition, the present invention aims to provide a molded product manufactured from the thermoplastic flame-retardant resin composition described above.

[0013] The above and other objects of the present invention can all be achieved by the present invention described below.

[0014] I) The present invention provides a thermoplastic flame-retardant resin composition comprising: a resin represented by the following chemical formula 1; a resin represented by the following chemical formula 2; a post-molding shrinkage prevention agent represented by the following chemical formula 3; a halogen-based flame retardant; and a flame retardant aid; wherein the resin represented by the above chemical formula 2 and the resin represented by the above chemical formula 1 are included in a weight ratio of 1:6 to 1:7.4, and the resin represented by the above chemical formula 1 is characterized in that it includes a first resin having an n value of an integer of 1000 to 3000 and a second resin having an n value of an integer of 3000 to 6000 in a weight ratio of 1:1 to 1:3.8.

[0015] [Chemical Formula 1]

[0016]

[0017]

[0018] [Chemical Formula 2]

[0019]

[0020] [Chemical Formula 3]

[0021]

[0022] (In the above chemical formulas 1 to 2, n is an integer from 1000 to 6000, m is an integer from 2000 to 8000, and in the above chemical formula 3, the carbon (C) symbol and the carbon-hydrogen bond symbol are omitted.)

[0023]

[0024] II) In the above I), the first resin may have a melting index measured according to the ISO1133 standard under the conditions of 230°C and 2.16 kg within the range of 5 to 50 g / 10 min.

[0025] III) In the above I) to II), the second resin may have a melting index measured according to the ISO1133 standard under the conditions of 230°C and 2.16 kg within the range of 0.01 to 4 g / 10 min.

[0026] IV) In the above I) to III), the resin represented by the above chemical formula 2 and the post-molding shrinkage prevention agent represented by the above chemical formula 3 may be included in a weight ratio of 1:0.5 to 1:1.5.

[0027] V) In the above I) to IV), the halogen-based flame retardant may be a brominated flame retardant.

[0028] VI) In the above I) to V), the brominated flame retardant may be at least one selected from tetrabromobisphenol A, decabromodiphenyloxide, octabromo-1,3,3-trimethyl-1-phenylindane, tetrabromobisphenol A-bis(2,3-dibromopropyl ether), and 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine.

[0029] VII) In the above I) to VI), the flame retardant may be an antimony compound.

[0030] VIII) In the above I) to VII), the antimony compound may be at least one selected from antimony trioxide, polysiloxane compound, biotite, muscovite, iron oxide, tungsten oxide, and calcium carbonate.

[0031]

[0032] IX) In addition, the present invention comprises 19 to 29 wt% of a first resin represented by the following chemical formula 1, wherein n is an integer from 1000 to 3000 and has a melt index of 5 to 50 g / 10 min measured under the conditions of 230°C and 2.16 kg according to ISO1133; 40 to 50 wt% of a second resin represented by the following chemical formula 1, wherein n is an integer from 3000 to 6000 and has a melt index of 0.01 to 4 g / 10 min measured under the conditions of 230°C and 2.16 kg according to ISO1133; 6 to 14 wt% of a resin represented by the following chemical formula 2, wherein m is an integer from 2000 to 8000; 6 to 14 wt% of a post-molding shrinkage inhibitor represented by the following chemical formula 3; 6.5 to 11 wt% of a brominated flame retardant; and 1 to 4 wt% of an antimony-based flame retardant,

[0033] A thermoplastic flame retardant resin composition is provided, characterized in that the resin represented by the above chemical formula 2 and the resin represented by the above chemical formula 1 are included in a weight ratio of 1:6 to 1:7.4.

[0034] [Chemical Formula 1]

[0035]

[0036] [Chemical Formula 2]

[0037]

[0038] [Chemical Formula 3]

[0039]

[0040] (In the above chemical formulas 1 to 2, n is an integer from 1000 to 6000, m is an integer from 2000 to 8000, and in the above chemical formula 3, the carbon (C) symbol and the carbon-hydrogen bond symbol are omitted.)

[0041] X) In addition, the present invention provides a molded article molded from the thermoplastic flame retardant resin composition described above.

[0042] XI) In the above X), the molded product may be an energy storage system component or a large-area sheet having a thickness of 0.3 mm or less.

[0043] The thermoplastic flame-retardant resin composition according to the present invention has excellent combustion characteristics, exhibiting flame retardancy of class V-0 in the vertical combustion test of UL94, and has excellent post-molding shrinkage prevention and processability, making it particularly suitable for large-area, lightweight molded products having a very thin thickness that require such performance.

[0044] Therefore, the thermoplastic flame-retardant resin composition and / or molded article according to the present invention can be applied to various industrial fields such as electrical and electronic products and automobile parts that require the same.

[0045] Figure 1 is a drawing confirming the results of a post-molding shrinkage prevention test of a molded product manufactured according to the present invention.

[0046]

[0047]

[0048] The present invention is described in more detail below.

[0049] In the present invention, the halogen may be, for example, at least one of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), preferably at least one of chlorine and bromine, and more preferably bromine.

[0050] The thermoplastic flame-retardant resin composition according to the present invention comprises two or more different polyolefin resins, a post-molding shrinkage inhibitor, a halogen-based flame retardant, and a flame retardant aid.

[0051] The present inventors have confirmed that when a predetermined post-molding shrinkage prevention agent, a halogen-based flame retardant, and a flame retardant aid are mixed in an appropriate amount with two or more different polyolefin resins, the post-molding shrinkage problem for a molded article manufactured over a large area with a very thin thickness of 0.3 mm or less is solved without lowering the flame retardancy developed by the flame retardant and flame retardant aid included in the thermoplastic flame retardant resin composition, thereby providing the required physical properties and reliability of the molded article. As a result of continuing the research, the present invention has been completed.

[0052]

[0053] Below, each component constituting the thermoplastic flame retardant resin composition is described in more detail.

[0054] Resin represented by chemical formula 1

[0055] The resin represented by chemical formula 1 according to the present invention may have the following structure.

[0056] [Chemical Formula 1]

[0057]

[0058] In the above chemical formula 1, n is an integer from 1000 to 6000.

[0059] The resin represented by the above chemical formula 1 can provide excellent flame retardancy without increasing specific gravity when provided as a flame retardant resin composition.

[0060] The resin represented by the above chemical formula 1 may be manufactured by a method commonly used in the technical field to which the present invention pertains, or may be commercially available, within the scope consistent with the definition of the present invention, and is not particularly limited.

[0061]

[0062] The resin represented by the above chemical formula 1 may include, for example, at least one selected from a first resin having an n value of an integer from 1000 to 3000 and a second resin having an n value of an integer from 3000 to 6000.

[0063] The melt index of the first resin, measured according to the ISO1133 standard under conditions of 230°C and 2.16 kg, may be, for example, 5 to 50 g / 10 min, preferably 5 to 30 g / 10 min, and more preferably 5 to 20 g / 10 min. In this case, it is possible to provide an effect of suppressing a strong pressure increase that may occur during extrusion processing by imparting appropriate flowability.

[0064] The first resin may be included in an amount of, for example, 19 wt% or more, and specifically, 19 to 29 wt%, and more preferably, 20 to 28 wt%, of the total 100 wt% of the thermoplastic flame-retardant resin composition containing the first resin. In this case, it is possible to provide an effect of suppressing a strong pressure increase that may occur during extrusion processing by imparting appropriate flowability.

[0065] The above first resin may be manufactured by a method commonly used in the technical field to which the present invention pertains, or may be commercially available, within the scope consistent with the definition of the present invention, and is not particularly limited.

[0066]

[0067] The melting index of the second resin, measured according to the ISO1133 standard under the conditions of 230°C and 2.16 kg, may be, for example, 0.01 to 4 g / 10 min, preferably 0.01 to 3 g / 10 min, and more preferably 0.1 to 3 g / 10 min. In this case, sheet production through extrusion molding may be possible.

[0068] The second resin may be included in an amount of, for example, 50 wt% or less, and specifically, 40 to 50 wt%, and more preferably 42 to 48 wt%, of the total 100 wt% of the thermoplastic flame-retardant resin composition containing the second resin. In this case, sheet production through extrusion molding may be possible.

[0069] The above second resin may be manufactured by a method commonly used in the technical field to which the present invention pertains, or may be commercially available, within the scope consistent with the definition of the present invention, and is not particularly limited.

[0070]

[0071] The total content of the first resin having the n value of 1000 to 3000 and the second resin having the n value of 3000 to 6000 may be included in a total of 100 wt% of the thermoplastic flame-retardant resin composition containing them, for example, 50 wt% or more, specifically, 55 to 74 wt%, and more preferably, 60 to 74 wt%. In this case, there is an effect of providing appropriate insulating performance and chemical resistance.

[0072]

[0073] The first resin having the above n value being an integer of 1000 to 3000 and the second resin having the n value being an integer of 3000 to 6000 can be included in a weight ratio (first:second) of 1:1 to 1:3.8 as a specific example, and can be included in a weight ratio (first:second) of 1:1 to 1:3.4 as a preferred example, and can be included in a weight ratio (first:second) of 1:1 to 1:3 as a more preferred example. In this case, there is an effect of providing the most appropriate flowability and viscosity for continuously producing a sheet of 0.5 mm or less through extrusion processing.

[0074]

[0075] Resin represented by chemical formula 2

[0076] The resin represented by chemical formula 2 according to the present invention may have the following structure.

[0077] [Chemical Formula 2]

[0078]

[0079] In the above chemical formula 2, m is an integer from 2000 to 8000.

[0080] The resin represented by the above chemical formula 2 can provide an effect of further increasing the shrinkage prevention effect by assisting the shrinkage prevention agent represented by the chemical formula 3 described below without increasing the specific gravity of the flame-retardant resin composition implemented by the resin represented by the above chemical formula 1 and without adversely affecting the effect of providing excellent flame retardancy.

[0081]

[0082] The resin represented by the above chemical formula 2 may have a melting index measured according to the ISO1133 standard under the conditions of 190°C and 2.16 kg, for example, of 0.1 to 20 g / 10 min, preferably 0.1 to 10 g / 10 min, and more preferably 0.1 to 5 g / 10 min. In this case, by adding an anti-shrinkage agent represented by the chemical formula 3 described below, the effect of further increasing the anti-shrinkage effect can be provided.

[0083] The resin represented by the above chemical formula 2 may have an impact strength measured according to the ISO180 standard at 23°C under notched conditions of, for example, 2 to 20 kJ / m2, preferably 4 to 15 kJ / m2, and more preferably 4 to 10 kJ / m2. In this case, it may provide an effect of supplementing the impact strength and rigidity of the thermoplastic flame-retardant resin composition.

[0084] The resin represented by the above chemical formula 2 may be included in a total of 100 wt% of the thermoplastic flame-retardant resin composition containing the resin, for example, 14 wt% or less, specifically 6 to 14 wt%, and more preferably 6 to 12 wt%. In this case, there is an effect of providing impact strength or rigidity without adversely affecting the effect of providing excellent flame retardancy without increasing the specific gravity of the flame-retardant resin composition.

[0085] The resin represented by the above chemical formula 2 may be manufactured by a method commonly used in the technical field to which the present invention pertains, or may be commercially available, within the scope consistent with the definition of the present invention, and is not particularly limited.

[0086] In this description, n and m can be calculated by dividing the number average molecular weight by the molar mass of each unit, and the number average molecular weight can be measured as a relative value for a standard polystyrene sample through gel chromatography (GPC), but is not limited thereto.

[0087]

[0088] Post-molding shrinkage prevention agent

[0089] The post-molding shrinkage prevention agent according to the present invention may use a compound represented by the above chemical formula 3.

[0090] [Chemical Formula 3]

[0091]

[0092] The compound represented by the above chemical formula 3 simultaneously includes a propylene fraction, an ethylene fraction, a crosslinking fraction, etc., thereby improving compatibility with the resin represented by the above chemical formula 1, the resin represented by the chemical formula 2, and the flame retardant and flame retardant aid described later, thereby providing an effect of improving shrinkage prevention after molding even when molded over a large area with a very thin thickness of 0.3 mm or less.

[0093] In the above chemical formula 3, the carbon (C) symbol and the carbon-hydrogen bond symbol are omitted.

[0094] The resin represented by the above chemical formula 3 may be included in a total of 100 wt% of the thermoplastic flame-retardant resin composition containing the same, for example, 14 wt% or less, specifically 6 to 14 wt%, and more preferably 6 to 12 wt%. In this case, by simultaneously including a propylene fraction, an ethylene fraction, a crosslinking fraction, etc., the compatibility with the resin represented by the above chemical formula 1, the resin represented by the chemical formula 2, and the flame retardant and flame retardant aid described below is improved, so that even when molded into a large area with a very thin thickness of 0.3 mm or less, there is an effect of suppressing the tendency to shrink after molding.

[0095] The resin represented by the above chemical formula 3 may be manufactured by a method commonly used in the technical field to which the present invention pertains, or may be commercially available, within the scope consistent with the definition of the present invention, and is not particularly limited.

[0096]

[0097] Halogen-based flame retardants

[0098] The halogen-based flame retardant according to the present invention has the advantage of superior thermal stability compared to non-halogen-based flame retardants.

[0099] The above halogen-based flame retardant may be, for example, a brominated flame retardant. In this case, it can provide the effect of preventing combustion by suppressing the spread of sparks following ignition.

[0100] Specific examples of the brominated flame retardant may include at least one selected from among tetrabromobisphenol A, decabromodiphenyloxide, octabromo-1,3,3-trimethyl-1-phenylindane, tetrabromobisphenol A-bis(2,3-dibromopropyl ether), and 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine.

[0101] The halogen-based flame retardant may be included in a total of 100 wt% of the thermoplastic flame retardant resin composition containing the halogen-based flame retardant, for example, 11 wt% or less, and specifically, 6.5 to 11 wt%, and more preferably, 6.5 to 10 wt%. In this case, excellent flame retardancy and fluidity can be imparted to the thermoplastic flame retardant resin composition without deterioration of other physical properties.

[0102] The above halogen-based flame retardant may be manufactured by a method commonly used in the technical field to which the present invention pertains, or may be commercially available, within the scope of the definition of the present invention, and is not particularly limited.

[0103]

[0104] flame retardant

[0105] The flame retardant agent according to the present invention has the advantage of increasing the flame retardancy provided by the aforementioned flame retardant without deteriorating other physical properties.

[0106] The above flame retardant agent may be, for example, an antimony compound. In this case, it may provide an auxiliary effect that further enhances the flame retardant effect of the flame retardant.

[0107] As a specific example, the flame retardant may be at least one selected from antimony trioxide, polysiloxane compounds, biotite, muscovite, iron oxide, tungsten oxide, and calcium carbonate, and preferably antimony trioxide.

[0108] The flame retardant agent may be included in an amount of, for example, 4 wt% or less, and specifically, 1 to 4 wt%, and more preferably, 2 to 4 wt%, of the total 100 wt% of the thermoplastic flame retardant resin composition containing the flame retardant agent. In this case, excellent flame retardancy and fluidity can be imparted to the thermoplastic flame retardant resin composition without deterioration of other physical properties.

[0109] The above flame retardant agent may be manufactured by a method commonly used in the technical field to which the present invention pertains, or may be commercially available, within the scope consistent with the definition of the present invention, and is not particularly limited.

[0110]

[0111] Thermoplastic flame retardant resin composition

[0112] The thermoplastic flame retardant resin composition according to the present invention may contain a resin represented by the above chemical formula 2 and a post-molding shrinkage inhibitor represented by the above chemical formula 3 in a weight ratio of, for example, 1:0.5 to 1:1.5 (formula 2:formula 3), and as a specific example, in a weight ratio of, for example, 1:0.8 to 1:1.3 (formula 2:formula 3). In this case, there is an advantage of high economic efficiency while best suppressing the tendency to shrink after molding.

[0113]

[0114] The above thermoplastic flame retardant resin composition may include one or more other additives selected from the group consisting of an activator, a light stabilizer, and a release agent, within a range that does not affect the appearance properties, etc.

[0115] The above-described other additives may be included, for example, in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the thermoplastic flame-retardant resin composition. When the above-described range is satisfied, there is an effect of implementing the functions of the other additives without lowering the basic physical properties inherent to the thermoplastic flame-retardant resin composition of the present disclosure.

[0116] The above-mentioned active agent may be, for example, at least one selected from ethylene bissteramide, polyethylene oxide wax, magnesium stearate, calcium stearamide, and stearic acid, but is not limited thereto.

[0117] Examples of the above light stabilizer include, but are not limited to, Hals-based light stabilizers, benzophenone-based light stabilizers, and benzotriazole-based light stabilizers.

[0118] The above-mentioned release agent may be selected from, for example, glycerin monostearate, glycerin tristearate, polyethylene tetrastearate, etc., but is not limited thereto.

[0119]

[0120] Furthermore, a thermoplastic flame-retardant resin composition according to the present invention comprises: 19 to 29 wt% of a first resin represented by the following chemical formula 1, wherein n is an integer from 1000 to 3000 and a melt index measured under 230°C and 2.16 kg according to ISO1133 standards of 5 to 50 g / 10 min; 40 to 50 wt% of a second resin represented by the following chemical formula 1, wherein n is an integer from 3000 to 6000 and a melt index measured under 230°C and 2.16 kg according to ISO1133 standards of 0.01 to 4 g / 10 min; 6 to 14 wt% of a resin represented by the following chemical formula 2, wherein m is an integer from 2000 to 8000; 6 to 14 wt% of a post-molding shrinkage inhibitor represented by the following chemical formula 3; 6.5 to 11 wt% of a brominated flame retardant; And it is possible to provide a thermoplastic flame retardant resin composition comprising 1 to 4 wt% of an antimony-based flame retardant, characterized in that the resin represented by the above chemical formula 2 and the resin represented by the above chemical formula 1 are included in a weight ratio of 1:6 to 1:7.4 (Formula 2:Formula 1).

[0121] [Chemical Formula 1]

[0122]

[0123] [Chemical Formula 2]

[0124]

[0125] [Chemical Formula 3]

[0126]

[0127] (In the above chemical formulas 1 to 2, n is an integer from 1000 to 6000, m is an integer from 2000 to 8000, and in the above chemical formula 3, the carbon (C) symbol and the carbon-hydrogen bond symbol are omitted.)

[0128]

[0129] The above thermoplastic flame retardant resin composition exhibits flame retardancy of class V-0 in the vertical combustion test of UL94, and has excellent shrinkage prevention and processability after molding, making it particularly suitable for large-area, lightweight molded products with very thin thicknesses that require such performance.

[0130]

[0131] The method for producing the thermoplastic flame-retardant resin composition described above is described. When describing the method for producing the thermoplastic flame-retardant resin composition of the present invention, all contents of the thermoplastic flame-retardant resin composition described above are included.

[0132] A method for manufacturing a thermoplastic flame-retardant resin composition according to the present invention includes, for example, a step of introducing a resin represented by the following chemical formula 1; a resin represented by the following chemical formula 2; a post-molding shrinkage prevention agent represented by the following chemical formula 3; a halogen-based flame retardant; and a flame retardant aid into a twin-screw extruder, and melt-kneading and extruding the resin.

[0133] [Chemical Formula 1]

[0134]

[0135] [Chemical Formula 2]

[0136]

[0137] [Chemical Formula 3]

[0138]

[0139] (In the above chemical formulas 1 to 2, n is an integer from 1000 to 6000, m is an integer from 2000 to 8000, and in the above chemical formula 3, the carbon (C) symbol and the carbon-hydrogen bond symbol are omitted.)

[0140] The resin represented by the above chemical formula 2 and the resin represented by the above chemical formula 1 may be included in a weight ratio of 1:6 to 1:7.4 (Formula 2:Formula 1).

[0141] The above melt mixing step may include, for example, other additives as described above.

[0142] The above melt mixing and extruding step can be performed using, for example, at least one selected from the group consisting of a single-screw extruder, a twin-screw extruder, and a Banbury mixer, and is preferably a twin-screw extruder. By using the same, the composition is uniformly mixed and then extruded to obtain, for example, a thermoplastic flame retardant resin composition in the form of pellets. In this case, there is an excellent effect of improving product reliability, flame retardancy, and post-molding shrinkage prevention performance, thereby improving the appearance quality.

[0143] The above mixing and extrusion can be performed within a barrel temperature range of, for example, 250 to 310°C, preferably 260 to 300°C, more preferably 270 to 290°C, and even more preferably 250 to 280°C, in which case, there is an advantage in that sufficient melt mixing is possible while the processing amount per unit time is high, and problems such as thermal decomposition of the resin component do not occur.

[0144] The above mixing and extrusion can be performed under conditions where the screw rotation speed is, for example, 100 to 600 rpm, preferably 150 to 400 rpm, more preferably 100 to 350 rpm, even more preferably 150 to 320 rpm, and even more preferably 200 to 310 rpm, and within this range, the throughput per unit time is high and the process efficiency is excellent, while excessive cutting of the inorganic filler is suppressed, so that the strength of the final product is superior, etc., and so on.

[0145] The thermoplastic flame retardant resin composition obtained through the above mixing and extrusion can preferably be provided in the form of pellets.

[0146] The type of the extruder is not particularly limited, and can be appropriately selected and used if it is one commonly used in the art. For example, a single-screw extruder with one screw or a multi-screw extruder with multiple screws can be used. Considering uniform mixing of materials, ease of processing, and economy, it may be preferable to use a twin-screw extruder with two screws.

[0147] The extruder is composed of a feeder for supplying materials into a barrel, a screw for transporting and mixing the materials supplied into the barrel, and a die for extruding the mixed materials, and the screw is composed of a plurality of screw elements to provide various functions.

[0148] The above raw material feeder may be one or more, and two or more may optionally be provided as needed. For example, a main feeder and an optional auxiliary feeder may be provided, and two or more auxiliary feeders may be provided as needed.

[0149] The kneading block of the present invention is an example of the screw element, and specifically comprises a plurality of discs, preferably 3 to 7 discs, 5 to 7 discs, 3 to 5 discs, or 4 to 5 discs, and typically has a cross-section such as a polygon or an ellipse, and is arranged continuously in the direction of material transport. In addition, in the kneading block, the phase angle of the discs (meaning the movement angle between the discs) is preferably 45 to 90°.

[0150] In addition, the above-mentioned mixing block includes a forward mixing block having the ability to transport, distribute, and mix materials, a neutral mixing block having only the ability to distribute and mix materials without the ability to transport materials, and a backward mixing block that transports materials in the opposite direction to the transport direction.

[0151]

[0152] molded products

[0153] The molded article of the present invention is characterized by including, for example, the thermoplastic flame-retardant resin composition of the present invention, and in this case, compared to a conventional thermoplastic flame-retardant resin composition, it has the advantage of being able to realize excellent post-molding shrinkage prevention performance, processability, and a balance of flame retardancy properties even when molding a large area with a very thin thickness of 0.3 mm or less.

[0154] The molded article of the present invention may be, for example, molded using the thermoplastic flame-retardant resin composition of the present invention. When describing a molded article comprising the thermoplastic flame-retardant resin composition of the present invention, all of the contents of the thermoplastic flame-retardant resin composition described above are included.

[0155]

[0156] The method for manufacturing a molded article of the present invention is characterized by including a step of injection molding or sheet molding an extruded article manufactured by the method for manufacturing the thermoplastic flame-retardant resin composition, and in this case, there is an advantage in that a molded article having post-shrinkage prevention, processability, and flame retardancy can be easily manufactured even when molding a large area with a very thin thickness of 0.3 mm or less.

[0157] In the above injection or sheet molding, the injection temperature (cylinder temperature) or sheet molding temperature is preferably 200 to 300°C, more preferably 200 to 290°C, and within this range, there is an advantage in that a large-area injection molded product or sheet with a very thin thickness of 0.3 mm or less can be easily manufactured.

[0158] The above injection or sheet forming speed is preferably 10 to 100 mm / s, more preferably 10 to 80 mm / s, and even more preferably 20 to 80 mm / s, and within this range, there is an advantage in that a large-area injection molded product or sheet having a very thin thickness of 0.3 mm or less can be easily manufactured.

[0159] The pressure during the above injection or sheet molding is preferably 10 to 150 bar, more preferably 20 to 90 bar, and even more preferably 40 to 80 bar, and within this range, there is an advantage in that a large-area injection molded product or sheet with a very thin thickness of 0.3 mm or less can be easily manufactured.

[0160] The holding pressure during the above injection or sheet molding may preferably be 10 to 100 bar, more preferably 20 to 80 bar, and even more preferably 30 to 60 bar, and within this range, there is an advantage in that a large-area injection molded product or sheet having a very thin thickness of 0.3 mm or less can be easily manufactured.

[0161] The above molded product may be a product for use that requires post-shrinkage prevention, processability, and flame retardancy even when molding a large area with a very thin thickness of 0.3 mm or less.

[0162] The above molded product may be an automobile or electrical / electronic part.

[0163] The above molded product may be, for example, an energy storage system component.

[0164] The above-mentioned molded product may be, for example, a large-area sheet having a thickness of 0.3 mm or less.

[0165] The molded product of the present invention can exhibit flame retardancy of class V-0 in the vertical combustion test of UL94.

[0166] The molded product of the present invention has excellent post-molding shrinkage prevention ability, and can prevent post-molding shrinkage even after being stored at room temperature for 5 to 7 days after being molded into a large-area sheet with a very thin thickness of 0.3 mm or less.

[0167]

[0168] In describing the thermoplastic flame retardant resin composition, its manufacturing method, and molded product of the present invention, it is stated that other conditions or equipment, etc. that are not explicitly described can be appropriately selected within the range commonly practiced in the art and are not particularly limited.

[0169]

[0170] Hereinafter, preferred examples are presented to help understand the present invention, but the following examples are only 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 technical idea of ​​the present invention, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[0171]

[0172] [Example]

[0173] The components used in the following examples and comparative examples are as follows.

[0174] *Resin represented by chemical formula 1

[0175] -1st resin: SK's BX3500 product with a melting index of 10g / 10min measured according to ISO1133 standards under conditions of 230℃ and 2.16kg

[0176] - Second resin: Polymirae EP332C product with a melting index of 0.35 g / 10 min measured according to ISO1133 standards under conditions of 230℃ and 2.16 kg

[0177] *Resin represented by Chemical Formula 2: LG Chemical ME1000 product with an impact strength of 8 measured according to ISO180 standards under notched conditions at 23℃

[0178] *Resin represented by chemical formula 3: KEP-070P product from Kumho Polychem with Mooney Viscosity of 69 MU measured according to ASTM D1646 standard under ML(1+4)@100℃ conditions

[0179] *Brominated flame retardant: DAI-ICHI FR SR-743N

[0180]

[0181] Examples 1 to 3 and Comparative Examples 1 to 12

[0182] The ingredients and contents listed in Tables 2 and 3 below were melt-mixed and extruded using a twin-screw extruder [SM T40] at a temperature of 200 to 250°C and a rotation speed (rpm) of 250 revolutions / minute to manufacture pellets. The pellets were then molded into square test pieces for evaluation with dimensions of 60 mm X 60 mm X 2 mm using an injection molding machine [Engel, 80 ton].

[0183] The above twin-screw extruder has two or more total input ports, and all ingredients are input into the main input port.

[0184]

[0185] [Example Exam]

[0186] The characteristics of the specimens manufactured in Examples 1 to 3 and Comparative Examples 1 to 12 were measured by the following methods, and the results are shown in Table 2, Table 3, and Figure 1 below, respectively.

[0187] * Flame retardancy (for 0.2 mm thick specimen): Flame retardancy was evaluated for 1 / 12 inch thick specimens according to the UL94 measurement method (1.5 mm vertical) with reference to item 1.2 and Table 1 below.

[0188] 1. Roll the specimen onto a 13mm diameter rod (mandrel), tape the top, and secure it with a clamp.

[0189] 2. The burner and test method evaluate the combustion pattern of the product and the extent of flame spread to the surroundings after applying flames to the specimen twice for 3 seconds each.

[0190] Classification VTM-0 VTM-1 VTM-2 Individual combustion time (t1 or t2 of individual specimen) 10 seconds or less 30 seconds or less 30 seconds or less Total combustion time of 5 specimens (sum of t1 and t2 of 5 specimens) 50 seconds or less 250 seconds or less 250 seconds or less Combustion and spark formation time after secondary contact (sum of t2 and t3 of individual specimens) 30 seconds or less 60 seconds or less 60 seconds or less No combustion up to the clamp (125 mm mark) None None Ignition of cotton wool by dropping None None Yes

[0191] * Post-molding shrinkage resistance (dimensional deformation): The difference in size measured after 5 to 7 days of storage at room temperature after molding compared to the size immediately after molding using a 0.2 mm thick specimen was calculated as a percentage (%).

[0192] * Flow index: Measured according to ISO1133 standard under conditions of 230℃ and 10.0 kg.

[0193] *Specific gravity: Measured according to ISO1183 standards at 23℃.

[0194] Classification (weight%)Example 1Example 2Example 3First resin 242919Second resin 454050Resin expressed by chemical formula 2101010Shrinkage prevention agent after molding101010Bromide flame retardant888Flame retardant aid333Flame retardancy (0.2 mm thickness)VTM-0VTM-0VTM-0Shrinkage prevention ability after molding (dimensional deformation%)2.11.52.2Flow index (g / 10 min)303324Specific gravity (g / ml)0.960.960.96

[0195]

[0196] Classification (weight %)Comparative Example 1Comparative Example 2Comparative Example 3Comparative Example 4Comparative Example 5Comparative Example 6Comparative Example 7Comparative Example 8Comparative Example 9Comparative Example 10Comparative Example 11Comparative Example 12First Resin 302724272427242169-455Second Resin 7067566356635649-69245Resin represented by Chemical Formula 2-----10102010101069Shrinkage prevention agent after molding---1020-101010101010Bromide flame retardant-415-----8888Flame retardant aid-25-----3333Flame retardancy (0.2 mm thickness)Not measurableNot measurableNot measurableNot measurableNot measurableVTM-0VTM-0VTM-0VTM-0Shrinkage prevention ability after molding (dimensions) (Transformation%)7.37.37.42.93.07.32.12.12.12.32.326.0Flow Index(g / 10min)3535353025353030130156025Specific Gravity(g / ml)0.890.921.050.890.890.900.900.910.960.960.951.00

[0197] As shown in Tables 2 and 3 above, the thermoplastic flame-retardant resin compositions according to the present invention (Examples 1 to 3) were able to produce molded articles with a very thin thickness of 0.2 mm, compared to the thermoplastic flame-retardant resin compositions (Comparative Examples 1 to 12) that fall outside the scope of the present invention. It was confirmed that excellent physical property balance was achieved in all examples among all measured items, such as flame retardancy, post-molding shrinkage prevention, flow index, and specific gravity.

[0198] In particular, as shown in the following Figure 1, it was confirmed that excellent post-molding shrinkage prevention ability was effectively implemented in the case of Example 1 according to the present invention.

[0199]

[0200] On the other hand, in the case of Comparative Example 1, which used only two types of resin represented by Chemical Formula 1, or Comparative Example 2, which added a flame retardant and a flame retardant aid to the composition of Comparative Example 1, it was confirmed that not only was the flame retardancy poor compared to Example 1, but shrinkage occurred after molding.

[0201] In addition, in the case of Comparative Example 3, which used two types of resins represented by Chemical Formula 1 and added an excessive amount of flame retardant and flame retardant aid, flame retardancy was secured, but shrinkage occurred after molding compared to Example 1, and it was confirmed that the lightweight failed as the specific gravity exceeded 1 g / ml.

[0202] In addition, in the case of Comparative Example 4, which did not contain the resin, flame retardant, and flame retardant aid represented by Chemical Formula 2, it was confirmed that shrinkage after molding was prevented compared to Example 1, but flame retardancy was not secured.

[0203] In addition, in the case of Comparative Example 5, which used two types of resins represented by Chemical Formula 1 and added an excessive amount of shrinkage inhibitor after molding, similar processability to Example 1 was secured, but flame retardancy was confirmed to be poor.

[0204] In addition, in the case of Comparative Example 6, in which no post-molding shrinkage inhibitor, flame retardant, or flame retardant aid was added, it was confirmed that the flame retardancy was inferior to that of Example 1 and that post-molding shrinkage was not prevented.

[0205] In addition, in the case of Comparative Example 7, in which no flame retardant or flame retardant additive was added, it was confirmed that the flame retardancy was inferior to that of Example 1.

[0206] In addition, in Comparative Example 8, which used two types of resins represented by Chemical Formula 1 and an excessive amount of resin represented by Chemical Formula 2, it was confirmed that the flame retardancy was inferior to that of Example 1.

[0207] In addition, in the case of Comparative Example 9, in which the first resin represented by Chemical Formula 1 was used alone and the second resin was not used, it was confirmed that the processability for extrusion molding was poor due to the viscosity being too low compared to Example 1, even though the resin represented by Chemical Formula 2 and the post-molding shrinkage inhibitor, flame retardant, and flame retardant aid were added in appropriate amounts.

[0208] In addition, in the case of Comparative Example 10, in which the second resin represented by Chemical Formula 1 was used alone and the first resin was not used, even when the resin represented by Chemical Formula 2 and an appropriate amount of a post-molding shrinkage inhibitor, flame retardant, and flame retardant aid were added, it was confirmed that the processability for extrusion molding was poor due to a viscosity that was too high compared to Example 1.

[0209] In addition, in the case of Comparative Example 11, in which the first resin and the second resin among the resins represented by Chemical Formula 1 were used in combination at a ratio outside of the appropriate mixing ratio, it was confirmed that the processability for extrusion molding was poor due to the viscosity being too low compared to Example 1, even though the resin represented by Chemical Formula 2 and the post-molding shrinkage inhibitor, flame retardant, and flame retardant aid were added in appropriate amounts.

[0210] In addition, in the case of Comparative Example 12, in which the first and second resins represented by Chemical Formula 1 were used in combination at a ratio outside of the appropriate mixing ratio and the resin represented by Chemical Formula 2 was added in excess, even if an appropriate amount of a shrinkage inhibitor, flame retardant, and flame retardant aid was added after molding, it was confirmed that the shrinkage suppression ability after molding was poor compared to Example 1 and the weight reduction was poor due to a specific gravity of 1.0 or higher.

[0211]

[0212] In conclusion, the thermoplastic flame-retardant resin composition of the present invention, when mixing an appropriate amount of a predetermined post-molding shrinkage inhibitor, a halogen-based flame retardant, and a flame retardant aid into two or more different polyolefin resins, solves the post-molding shrinkage problem for a large-area molded product having a very thin thickness of 0.3 mm or less without lowering the flame retardancy developed by the flame retardant and flame retardant aid contained in the thermoplastic flame-retardant resin composition, and provides the reliability of the molded product, while exhibiting flame retardancy of class V-0 in the vertical combustion test of UL94, and it was confirmed that it is suitable for electrical and electronic products such as insulating sheets for energy storage systems and automobile parts that require such performance.

Claims

1. A resin represented by the following chemical formula 1; a resin represented by the following chemical formula 2; a post-molding shrinkage prevention agent represented by the following chemical formula 3; a halogen-based flame retardant; and a flame retardant aid; The resin represented by the above chemical formula 2 and the resin represented by the above chemical formula 1 are included in a weight ratio of 1:6 to 1:7.4, A thermoplastic flame retardant resin composition characterized in that the resin represented by the above chemical formula 1 comprises a first resin having an n value of an integer from 1000 to 3000 and a second resin having an n value of an integer from 3000 to 6000 in a weight ratio of 1:1 to 1:3.

8. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] (In the above chemical formulas 1 to 2, n is an integer from 1000 to 6000, m is an integer from 2000 to 8000, and in the above chemical formula 3, the carbon (C) symbol and the carbon-hydrogen bond symbol are omitted.) 2. In paragraph 1, A thermoplastic flame retardant resin composition characterized in that the first resin has a melting index within the range of 5 to 50 g / 10 min as measured according to the ISO1133 standard under the conditions of 230°C and 2.16 kg, and the second resin has a melting index within the range of 0.01 to 4 g / 10 min as measured according to the ISO1133 standard under the conditions of 230°C and 2.16 kg.

3. In paragraph 1, A thermoplastic flame retardant resin composition characterized in that the resin represented by the above chemical formula 2 and the post-molding shrinkage inhibitor represented by the above chemical formula 3 are included in a weight ratio of 1:0.5 to 1:1.

5.

4. In paragraph 1, A thermoplastic flame retardant resin composition characterized in that the above halogen-based flame retardant is a brominated flame retardant.

5. In paragraph 4, A thermoplastic flame retardant resin composition characterized in that the above brominated flame retardant is at least one selected from among tetrabromobisphenol A, decabromodiphenyloxide, octabromo-1,3,3-trimethyl-1-phenylindane, tetrabromobisphenol A-bis(2,3-dibromopropyl ether), and 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine.

6. In paragraph 1, A thermoplastic flame retardant resin composition characterized in that the flame retardant agent is an antimony-based compound.

7. In paragraph 6, A thermoplastic flame retardant resin composition characterized in that the above antimony compound is at least one selected from antimony trioxide, polysiloxane compounds, biotite, muscovite, iron oxide, tungsten oxide, and calcium carbonate.

8. 19 to 29 wt% of a first resin represented by the following chemical formula 1, wherein the value of n is an integer from 1000 to 3000 and the melting index measured according to the ISO1133 standard under the conditions of 230°C and 2.16 kg is from 5 to 50 g / 10 min; 40 to 50 wt% of a second resin represented by the following chemical formula 1, wherein the value of n is an integer from 3000 to 6000 and the melting index measured according to the ISO1133 standard under the conditions of 230°C and 2.16 kg is from 0.01 to 4 g / 10 min; 6 to 14 wt% of a resin represented by the following chemical formula 2 and having an m value of 2000 to 6000; 6 to 14 wt% of a post-molding shrinkage prevention agent represented by the following chemical formula 3; 6.5 to 11 wt% of a brominated flame retardant; and Contains 1 to 4 wt% of an antimony-based flame retardant, A thermoplastic flame retardant resin composition characterized in that the resin represented by the above chemical formula 2 and the resin represented by the above chemical formula 1 are included in a weight ratio of 1:6 to 1:7.

4. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] (In the above chemical formulas 1 to 2, n is an integer from 1000 to 6000, m is an integer from 2000 to 8000, and in the above chemical formula 3, the carbon (C) symbol and the carbon-hydrogen bond symbol are omitted.) 9. A molded article molded with the thermoplastic flame-retardant resin composition of claim 1 or claim 8.

10. In paragraph 9, A molded product characterized in that the above molded product is an energy storage system component or a sheet having a thickness of 0.3 mm or less.

Images