Co-extruded sheet and article manufactured therefrom

Abstract

Provided is an co-extruded sheet comprising: (A) a polyalkyl(meth)acrylate resin sheet; and (B) a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition sheet, wherein the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition comprises: (a) 20-30 wt % of a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer; (b) 35-50 wt % of an aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109-113 ℃; and (c) 20-35 wt % of an N-phenyl maleimide-based copolymer having a glass transition temperature of 195-200 ℃, and the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition has a Vicat softening temperature of 113 ℃ or higher as measured according to ISO 306 and a melt flow index of 3.5-6 g / 10 min as measured according to ISO 1133 under conditions of 220 ℃ / 10 kg.

Description

Coextruded sheets and molded articles manufactured therefrom

[0001] It relates to a coextruded sheet and a molded product manufactured therefrom.

[0002] Thermoplastic resins have lower specific gravity than glass or metal and possess superior physical properties, including excellent formability and impact resistance. Driven by the recent trend toward lower costs, larger sizes, and lighter weight in electrical and electronic products, thermoplastic resin-based plastic products are rapidly replacing traditional glass and metal products, expanding their applications from electrical and electronic devices to automotive components. In particular, the recent trend toward lighter automobiles is leading to attempts to replace steel sheets, traditionally used in automotive exterior materials, with plastics.

[0003] However, in order to use plastic as an automobile exterior material instead of steel plate, it must have melt strength that can withstand the vacuum forming process, high heat resistance, and excellent appearance after forming.

[0004] Recently, there have been attempts to use coextruded sheets manufactured using the coextrusion method as automotive exterior materials, but the general coextruded sheets widely used in the home appliance and industrial materials fields have low heat resistance, making them impossible to use as automotive exterior materials.

[0005] Therefore, there is a need to develop a coextruded sheet that has melt strength, high heat resistance, and appearance properties that can withstand the vacuum forming process.

[0006] Provided are coextruded sheets having excellent fluidity, heat resistance and appearance properties and molded products manufactured therefrom.

[0007] According to one embodiment, there is provided a composition comprising: (A) a polyalkyl (meth)acrylate resin sheet; and (B) a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition sheet, wherein the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition comprises: (a) 20 to 30 wt% of a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer; (b) 35 to 50 wt% of an aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature (Tg) of 109 to 113°C; And (c) 20 to 35 wt% of an N-phenyl maleimide copolymer having a glass transition temperature of 195 to 200°C, wherein the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition has a Vicat softening temperature (VST) of 113°C or higher measured according to ISO 306 and a melt flow index (MI) of 3.5 to 6 g / 10 min measured according to ISO 1133 under 220°C / 10 kg conditions.

[0008] The above polyalkyl (meth)acrylate resin may have a melt flow index of 3.5 to 6 g / 10 min measured according to ISO 1133 under conditions of 220°C / 10 kg.

[0009] The above polyalkyl (meth)acrylate resin may be a polymethyl methacrylate (PMMA) resin.

[0010] The above (a) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may have a core-shell structure including a core comprising a butadiene-based rubber polymer, and a shell formed by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound onto the core.

[0011] The above butadiene-based rubber polymer may have an average particle diameter of 0.2 to 1.0 ㎛.

[0012] The above (a) butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer (g-ABS).

[0013] The aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C (b) above may have an oligomer content of less than 0.5 wt% based on 100 wt%.

[0014] The above (b) aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C may have a weight average molecular weight (Mw) of 80,000 to 300,000 g / mol.

[0015] In the above (b) aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C, the aromatic vinyl-vinyl cyanide copolymer may be a styrene-acrylonitrile copolymer (SAN).

[0016] The above (c) N-phenyl maleimide copolymer having a glass transition temperature of 195 to 200°C may contain 20 to 55 wt% of a component derived from N-phenyl maleimide based on 100 wt%.

[0017] The above (c) N-phenyl maleimide copolymer having a glass transition temperature of 195 to 200°C may have a weight average molecular weight of 150,000 to 250,000 g / mol.

[0018] In the above (c) N-phenyl maleimide copolymer having a glass transition temperature of 195 to 200°C, the N-phenyl maleimide copolymer may be an N-phenyl maleimide-styrene-maleic anhydride copolymer.

[0019] The difference in glass transition temperature between the aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C and the N-phenyl maleimide copolymer having a glass transition temperature of 195 to 200°C may be less than 90°C.

[0020] In one embodiment, a molded product is provided by vacuum forming the coextruded sheet and then manufacturing the same through a long fiber injection molding (LFI) method.

[0021] A coextruded sheet having excellent fluidity, heat resistance and appearance properties and a molded product manufactured therefrom can be provided.

[0022] Figure 1 shows the criteria for evaluating the appearance of a coextruded sheet.

[0023] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention. The present invention is defined solely by the scope of the claims set forth below.

[0024] Unless specifically stated herein, “copolymerization” means block copolymerization, random copolymerization, and graft copolymerization, and “copolymer” means block copolymer, random copolymer, and graft copolymer.

[0025] Unless otherwise specified herein, the average particle size of a rubber polymer is a volume average diameter and refers to the Z-average particle size measured using a dynamic light scattering analyzer.

[0026] Unless otherwise specified herein, the weight average molecular weight is measured by dissolving a powder sample in an appropriate solvent and using Agilent Technologies' 1200 series Gel Permeation Chromatography (GPC) (Shodex polystyrene is used as the standard sample).

[0027] According to one embodiment, a coextruded sheet comprises (A) a polyalkyl (meth)acrylate resin sheet; and (B) a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition sheet, wherein the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition comprises (a) 20 to 30 wt% of a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer; (b) 35 to 50 wt% of an aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C; And (c) 20 to 35 wt% of an N-phenyl maleimide copolymer having a glass transition temperature of 195 to 200°C, wherein the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition is characterized in that the Vicat softening temperature (VST) measured according to ISO 306 is 113°C or higher, and the melt flow index (MI) measured according to ISO 1133 under 220°C / 10kg conditions is 3.5 to 6 g / 10 min.

[0028] Hereinafter, each component included in the above co-extruded sheet will be described in detail.

[0029] (A) Polyalkyl (meth)acrylate resin sheet

[0030] According to one embodiment, a co-extruded sheet includes (A) a polyalkyl (meth)acrylate resin sheet. The (A) polyalkyl (meth)acrylate resin sheet can impart scratch resistance, moldability, etc. to the co-extruded sheet.

[0031] In the above (A) polyalkyl (meth)acrylate resin sheet, the polyalkyl (meth)acrylate resin can be obtained by polymerizing an alkyl (meth)acrylate compound by a known polymerization method such as suspension polymerization, bulk polymerization, or emulsion polymerization.

[0032] The above alkyl (meth)acrylate compound may be at least one selected from methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, butyl methacrylate, and butyl acrylate, but is not limited thereto. The poly alkyl (meth)acrylate resin may be a polymethyl methacrylate resin, and the polymethyl methacrylate resin may be produced by copolymerizing a monomer mixture containing 80 to 99 wt% of methyl methacrylate and 1 to 20 wt% of methyl acrylate.

[0033] The above polyalkyl (meth)acrylate resin may have a melt flow index of 3.5 to 6 g / 10 min, for example, 4 to 6 g / 10 min, for example, 4 to 5 g / 10 min, as measured according to ISO 1133 under conditions of 220°C / 10 kg. When the above range is satisfied, the fluidity of the polyalkyl (meth)acrylate resin and the butadiene-based rubber-modified aromatic vinyl-cyanide vinyl copolymer resin described below may be similar, so that processability and moldability may be excellent when producing a coextrusion sheet.

[0034] In one embodiment, the (A) polyalkyl (meth)acrylate resin sheet may be transparent or translucent.

[0035] (B) Butadiene-based rubber-modified aromatic vinyl-cyanide vinyl copolymer resin composition sheet

[0036] A co-extruded sheet according to one embodiment includes (B) a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition sheet. The (B) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition sheet can impart impact resistance, moldability, heat resistance, etc. to the co-extruded sheet.

[0037] In the above (B) butadiene-based rubber modified aromatic vinyl-vinyl cyanide copolymer resin composition sheet, the butadiene-based rubber modified aromatic vinyl-vinyl cyanide copolymer resin composition may have a Vicat softening temperature measured according to ISO 306 of 113°C or higher, for example, 114°C or higher, for example, 115°C or higher, for example, 116°C or higher.

[0038] The above butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition may have a melt flow index of 3.5 to 6 g / 10 min, for example, 4 to 6 g / 10 min, for example, 4 to 5 g / 10 min, as measured according to ISO 1133 at 220°C / 10 kg. When the above range is satisfied, the fluidity of the polyalkyl (meth)acrylate resin and the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition may be similar, so that processability and moldability may be excellent when producing a coextrusion sheet.

[0039] In one embodiment, the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition may include (a) a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer; (b) an aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C; and (c) an N-phenyl maleimide-based copolymer having a glass transition temperature of 195 to 200°C.

[0040] (a) Butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer

[0041] The above (a) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may have a core-shell structure including a core comprising a butadiene-based rubber polymer, and a shell formed by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound onto the core.

[0042] According to one embodiment, (a) a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer can be produced by graft polymerizing a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound onto a butadiene-based rubber polymer. The polymerization can be carried out using a conventional production method, such as emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization.

[0043] The above butadiene-based rubber polymer may be selected from the group consisting of polybutadiene rubber polymer, butadiene-styrene rubber polymer, butadiene-acrylonitrile rubber polymer, butadiene-acrylate rubber polymer, and mixtures thereof.

[0044] The above aromatic vinyl compound may be selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, and mixtures thereof.

[0045] The above vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile and mixtures thereof.

[0046] The average particle size of the above butadiene-based rubber polymer may be 0.2 to 1.0 μm, for example 0.2 to 0.8 μm, for example 0.25 to 0.50 μm. When the above range is satisfied, excellent impact resistance and appearance properties can be exhibited.

[0047] With respect to 100 wt% of the (a) butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer, the butadiene-based rubber polymer may be included in an amount of 40 to 70 wt%, for example, 40 to 60 wt%, for example, 50 to 60 wt%. Meanwhile, the weight ratio of the aromatic vinyl compound and the cyanide vinyl compound graft-polymerized onto the core including the butadiene-based rubber polymer may be 6:4 to 8:2.

[0048] In one embodiment, the (a) butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer.

[0049] In one embodiment, the (a) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may be included in an amount of 20 to 30 wt%, for example, 20 to 25 wt%, for example, 25 to 30 wt%, based on 100 wt% of the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition.

[0050] (b) Aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C

[0051] The above (b) aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C has a small difference in glass transition temperature from the component (c) N-phenyl maleimide copolymer described below, and thus can improve the coextrusion molding stability and heat resistance of a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin containing them.

[0052] The above (b) aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C has an oligomer content of less than 0.5 wt% based on 100 wt%, which is lower than that of a typical aromatic vinyl-vinyl cyanide copolymer having an oligomer content of about 2 wt%. This enables it to have a glass transition temperature higher than that of a typical aromatic vinyl-vinyl cyanide copolymer, for example, a typical styrene-acrylonitrile copolymer (SAN), which has a glass transition temperature of about 106°C.

[0053] In one embodiment, the aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C (b) may have a weight average molecular weight of 80,000 to 300,000 g / mol, for example, 85,000 to 250,000 g / mol, for example, 90,000 to 200,000 g / mol.

[0054] In one embodiment, the aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C (b) can be prepared by a conventional polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization of a monomer mixture containing an aromatic vinyl compound and a cyanide vinyl compound.

[0055] The above aromatic vinyl compound may be selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, and mixtures thereof.

[0056] The above vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile and mixtures thereof.

[0057] The above (b) aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C may contain 55 to 85 wt%, for example 60 to 80 wt%, for example 65 to 75 wt%, of a component derived from the aromatic vinyl compound based on 100 wt%.

[0058] In addition, the aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C (b) may contain 15 to 45 wt%, for example 20 to 40 wt%, for example 25 to 35 wt%, of a component derived from the vinyl cyanide compound based on 100 wt%.

[0059] In one embodiment, in the aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C, the aromatic vinyl-vinyl cyanide copolymer may be a styrene-acrylonitrile copolymer (SAN).

[0060] In one embodiment, the (b) aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C may be present in an amount of 35 to 50 wt%, for example, 35 to 45 wt%, for example, 40 to 50 wt%, based on 100 wt% of the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition.

[0061] (c) N-phenyl maleimide copolymer having a glass transition temperature of 195 to 200°C

[0062] The above (c) N-phenyl maleimide copolymer having a glass transition temperature of 195 to 200°C can impart excellent heat resistance to a butadiene-based rubber-modified aromatic vinyl-cyanide vinyl copolymer resin containing the copolymer.

[0063] In one embodiment, the difference in glass transition temperatures between the aromatic vinyl-vinyl cyanide copolymer (b) having a glass transition temperature of 109 to 113°C and the N-phenyl maleimide copolymer (c) having a glass transition temperature of 195 to 200°C may be less than 90°C. By reducing the glass transition temperature difference to the above range, processability during coextrusion molding can be improved, and appearance characteristics and overall physical properties can also be further improved.

[0064] In one embodiment, the N-phenyl maleimide copolymer having a glass transition temperature of 195 to 200°C (c) may contain 20 to 55 wt% of a component derived from N-phenyl maleimide.

[0065] The above (c) N-phenyl maleimide copolymer having a glass transition temperature of 195 to 200°C may have a weight average molecular weight of 150,000 to 250,000 g / mol, for example, 15,000 to 200,000 g / mol.

[0066] In one embodiment, the N-phenyl maleimide copolymer having a glass transition temperature of 195 to 200°C (c) may be included in an amount of 20 to 35 wt%, for example, 20 to 30 wt%, for example, 25 to 35 wt%, based on 100 wt% of the butadiene-based rubber-modified aromatic vinyl-cyanide vinyl copolymer resin composition. If the amount exceeds the above-described range, coextrusion moldability may be significantly reduced.

[0067] (d) additives

[0068] The above butadiene-based rubber-modified aromatic vinyl-cyanide vinyl copolymer resin composition may further include one or more additives necessary to exhibit excellent flame retardancy, antibacterial properties, antistatic properties, weather resistance, light resistance, fluidity, mold release properties, impact resistance, heat resistance, and appearance properties, or depending on the final use.

[0069] Specifically, as the additives, flame retardants, nucleating agents, coupling agents, fillers, plasticizers, lubricants, antibacterial agents, release agents, heat stabilizers, antioxidants, ultraviolet stabilizers, pigments, dyes, etc. can be used, and these can be used alone or in combination of two or more.

[0070] These additives may be appropriately included within a range that does not impair the physical properties of the resin composition, and specifically, may be included in an amount of 20 parts by weight or less per 100 parts by weight of components (a) to (c), but are not limited thereto.

[0071] In one embodiment, a molded product is provided by vacuum forming the coextruded sheet and then manufacturing the same using a long fiber injection molding (LFI) method.

[0072] The LFI method is a method of forming a molded product having the shape of a desired part by vacuum forming a coextruded sheet, and then spraying a mixture of polyurethane resin and glass fiber on the opposite side (or inside) of the molded product that is not exposed to the outside to impart rigidity. Molding using the LFI method is possible only when the coextruded sheet and the resin constituting the sheet have excellent heat resistance. As described above, the coextruded sheet of the present invention and the resin constituting the sheet have excellent heat resistance by including the above components, and therefore molding using the LFI method is possible.

[0073] Meanwhile, molding using the LFI method offers the advantage of being environmentally friendly, as it does not require a painting process. Therefore, molded products manufactured using the coextruded sheet of the present invention exhibit excellent heat resistance, fluidity, and appearance properties, while also being environmentally friendly.

[0074] Hereinafter, preferred embodiments of the present invention will be described. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to the following embodiments.

[0075] Examples 1 and 2, and Comparative Examples 1 to 3

[0076] Polyalkyl (meth)acrylate resin (polymethyl methacrylate resin (Lotte Chemical Co.) used, melt flow index of about 4.2 g / 10 min measured according to ISO 1133 at 220℃ / 10kg) and butadiene-based rubber modified aromatic vinyl-vinyl cyanide copolymer resin composition were fed into the feed section of a co-extrusion machine, and then the molten polyalkyl (meth)acrylate resin and butadiene-based rubber modified aromatic vinyl-vinyl cyanide copolymer resin composition were co-extruded into a sheet having a thickness of 1.5 mm or less. Subsequently, the co-extruded sheet was dried at about 80℃ for about 2 hours, placed in a mold of a separate standard, heated, and vacuum-formed. A mixture of polyurethane resin and glass fiber was sprayed on the inside of the vacuum-formed molded product to manufacture a final molded product. At this time, the butadiene-based rubber modified aromatic vinyl-vinyl cyanide copolymer resin composition includes components (a), (b), (b') and / or (c), and the weight % of the components relative to 100 weight % of the butadiene-based rubber modified aromatic vinyl-vinyl cyanide copolymer resin composition is shown in Table 1 below.

[0077] The butadiene-based rubber-modified aromatic vinyl-cyanide vinyl copolymer resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were prepared according to the component content ratios described in Table 1 below.

[0078] Specifically, the components described in Table 1 below were mixed in a conventional mixer and extruded at a barrel temperature of approximately 230°C using a twin-screw extruder with L / D = 29 and Φ = 45 mm to manufacture pellets. The manufactured pellets were dried in a dehumidifying dryer at approximately 80°C for approximately 3 hours before injection molding, and then a 6 oz. injection molding machine was used to manufacture a specimen for Vicat softening temperature (VST) evaluation by setting the cylinder temperature to approximately 230°C and the mold temperature to approximately 60°C.

[0079] Classification Implementation Preliminary Comparison Example 12123(a)2520223025(b)5050---(b')--783050(c)2530-4025

[0080] (a) Butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer

[0081] An acrylonitrile-butadiene-styrene graft copolymer (Lotte Chemical Co.) having a core-shell structure comprising a core (average particle diameter: about 0.3 ㎛) made of a polybutadiene rubber polymer and a shell formed by graft polymerization of acrylonitrile and styrene (acrylonitrile: styrene weight ratio = about 2.5: about 7.5) onto the core was used.

[0082] (b) Aromatic vinyl-vinyl cyanide copolymer

[0083] A styrene-acrylonitrile copolymer (Lotte Chemical Co., Ltd.) having a weight average molecular weight of about 117,000 g / mol, an oligomer content of about 0.4 wt%, and a glass transition temperature of about 110°C, copolymerized from a monomer mixture containing about 28 wt% of acrylonitrile and about 72 wt% of styrene, was used.

[0084] (b') Aromatic vinyl-vinyl cyanide copolymer

[0085] A styrene-acrylonitrile copolymer (Lotte Chemical Co., Ltd.) having a weight average molecular weight of about 97,000 g / mol, an oligomer content of about 2.0 wt%, and a glass transition temperature of about 106°C, copolymerized from a monomer mixture containing about 27 wt% of acrylonitrile and about 73 wt% of styrene, was used.

[0086] (c) N-phenyl maleimide copolymer

[0087] An N-phenyl maleimide-styrene-maleic anhydride copolymer (Denka) was used, having a glass transition temperature of approximately 196°C, an N-phenyl maleimide-derived component content of approximately 49 wt%, and a weight average molecular weight of approximately 125,000 g / mol.

[0088] Experimental example

[0089] The experimental results are shown in Table 2 below.

[0090] (1) Fluidity (unit: g / 10min)

[0091] The melt flow index (MI) of a pellet-type butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition was measured according to ISO 1133 under conditions of 220℃ / 10kg.

[0092] (2) Heat resistance (unit: ℃)

[0093] The Vicat softening temperature (VST) of a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition was measured according to ISO 306.

[0094] (3) Appearance of co-extruded sheet

[0095] The appearance of the sheet after co-extrusion was judged based on the degree of surface wrinkles or pinholes on the sheet. The appearance was evaluated by placing the co-extruded sheet under LED light and visually observing the LED light reflected from the surface of the co-extruded sheet, and the evaluation criteria are shown in Fig. 1. As shown in Fig. 1, if no wrinkle defects or pinhole defects appeared and the appearance was normal, the appearance performance was evaluated as O, and if wrinkle defects and / or pinholes appeared, the appearance performance was evaluated as X.

[0096] (4) Whether vacuum forming is possible

[0097] The possibility of vacuum forming of coextruded sheets was determined by visually checking for cracks after vacuum forming. If no cracks occurred, it was evaluated as O, and if cracks occurred, it was evaluated as X.

[0098] (5) Whether LFI is applicable

[0099] After spraying a mixture of polyurethane resin and glass fiber on the inside of a vacuum-formed molded product using the LFI method, if no sink occurs on the surface of the molded product at the boss area, it was evaluated as O, and if sink occurs, it was evaluated as X.

[0100] Classification Preliminary Comparative Example 12123 Resin Composition Properties MI 3.9 4.7 7.0 2.5 4.0 VST 117 115 95 120 111 Co-extruded Sheet Properties Co-extruded Sheet Appearance OOOXO Vacuum Forming Possible OOOXXLFI Applicability OOOXXX

[0101] As can be seen from Tables 1 and 2, the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin compositions of Examples 1 and 2 have excellent fluidity and heat resistance, and the coextruded sheet using the resin composition has an excellent appearance, and it is possible to manufacture a final molded product by both vacuum forming and the LFI method after vacuum forming. On the other hand, the resin composition of Comparative Example 1 does not contain an N-phenylmaleimide-based copolymer, and thus has significantly poor heat resistance, and although the coextruded sheet using it was possible to vacuum form, there was a problem of sinking occurring due to low heat resistance when the vacuum-formed product was manufactured as a final molded product by the LFI method. Meanwhile, the resin composition of Comparative Example 2 used an N-phenylmaleimide copolymer in an excessive amount, which significantly lowered the fluidity of the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition, resulting in a large difference in the fluidity of the polyalkyl (meth)acrylate resin sheet and the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition sheet, which resulted in poor appearance of the coextruded sheet, cracks occurring in the vacuum-molded product using the coextruded sheet, and sinking occurring on the surface of the molded product when the LFI method was applied to the vacuum-molded product. In addition, the resin composition of Comparative Example 3 used an aromatic vinyl-vinyl cyanide copolymer having a lower glass transition temperature than Examples 1 and 2, which resulted in low heat resistance of the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition, resulting in poor vacuum-molding of the coextruded sheet using the same, and resulting in poor sinking of the vacuum-molded product when the LFI method was applied.

[0102] Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the present invention defined in the appended claims also fall within the scope of the present invention.

Claims

1. (A) a polyalkyl (meth)acrylate resin sheet; and (B) a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition sheet, wherein the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition comprises (a) 20 to 30 wt% of a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer; (b) 35 to 50 wt% of an aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C; and (c) 20 to 35 wt% of an N-phenyl maleimide-based copolymer having a glass transition temperature of 195 to 200°C. The above butadiene-based rubber-modified aromatic vinyl-vinyl cyanide copolymer resin composition is a coextruded sheet having a Vicat softening temperature of 113°C or higher as measured according to ISO 306 and a melt flow index of 3.5 to 6 g / 10 min as measured according to ISO 1133 under 220°C / 10 kg conditions.

2. In paragraph 1, The above polyalkyl (meth)acrylate resin is a coextruded sheet having a melt flow index of 3.5 to 6 g / 10 min as measured according to ISO 1133 under 220°C / 10 kg conditions.

3. In paragraph 1 or 2, A coextruded sheet wherein the above polyalkyl (meth)acrylate resin is polymethyl methacrylate resin.

4. In any one of paragraphs 1 to 3, The above (a) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is a coextruded sheet having a core-shell structure including a core comprising a butadiene-based rubber polymer, and a shell formed by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound onto the core.

5. In paragraph 4, The above butadiene-based rubber polymer is a coextruded sheet having an average particle diameter of 0.2 to 1.0 ㎛.

6. In any one of paragraphs 1 to 5, A coextruded sheet, wherein the above (a) butadiene-based rubber-modified aromatic vinyl-cyanide vinyl graft copolymer is an acrylonitrile-butadiene-styrene graft copolymer.

7. In any one of paragraphs 1 to 6, A coextruded sheet, wherein the aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C has an oligomer content of less than 0.5 wt% based on 100 wt%.

8. In any one of paragraphs 1 to 7, A coextruded sheet, wherein the aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C has a weight average molecular weight of 80,000 to 300,000 g / mol.

9. In any one of paragraphs 1 to 8, A coextruded sheet, wherein the aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C in the above (b) is a styrene-acrylonitrile copolymer.

10. In any one of paragraphs 1 to 9, A coextruded sheet, wherein the above (c) N-phenyl maleimide copolymer having a glass transition temperature of 195 to 200°C contains 20 to 55 wt% of a component derived from N-phenyl maleimide based on 100 wt%.

11. In any one of paragraphs 1 to 10, A coextruded sheet, wherein the above (c) N-phenyl maleimide copolymer having a glass transition temperature of 195 to 200°C has a weight average molecular weight of 150,000 to 250,000 g / mol.

12. In any one of paragraphs 1 to 11, A coextruded sheet, wherein the N-phenyl maleimide copolymer having a glass transition temperature of 195 to 200°C in the above (c) is an N-phenyl maleimide-styrene-maleic anhydride copolymer.

13. In any one of paragraphs 1 to 12, A coextruded sheet, wherein the difference in glass transition temperatures between (b) an aromatic vinyl-vinyl cyanide copolymer having a glass transition temperature of 109 to 113°C and (c) an N-phenyl maleimide copolymer having a glass transition temperature of 195 to 200°C is less than 90°C.

14. A molded product manufactured by vacuum-forming a coextruded sheet according to any one of claims 1 to 13 and then using a long fiber injection molding method.

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