Eco-friendly ship hull and method for manufacturing same

Abstract

An eco-friendly ship hull of the present invention is characterized by comprising: high-density polyethylene; carbon material; light stabilizer; and an antioxidant. The eco-friendly ship hull has excellent eco-friendliness, weather resistance, impact resistance, rigidity, heat resistance, and balance of these physical properties.

Description

Eco-friendly ship hull and manufacturing method thereof

[0001] The present invention relates to an eco-friendly ship hull and a method for manufacturing the same. More specifically, the present invention relates to an eco-friendly ship hull with excellent environmental friendliness, weather resistance, impact resistance, rigidity, heat resistance, and a balanced physical property thereof, and a method for manufacturing the same.

[0002]

[0003] Most existing small and medium-sized ships are made of FRP (Fiber Reinforced Plastic). However, FRP is difficult to recycle and costs over 1 million won per ton to dispose of. Consequently, FRP ships that have reached the end of their useful life are often abandoned in the wild rather than recycled or disposed of, posing a significant problem. Furthermore, FRP ships generate glass dust during the manufacturing process, and the paint used on ships peels off, creating microplastics. This poses significant risks to shipyard workers and the surrounding environment.

[0004] To solve these problems, research has been conducted on materials to replace FRP materials, and attempts have been made to manufacture ships using aluminum materials, but they have not been able to establish themselves in the market due to their high price and difficulty in repair. To this day, there is no suitable alternative, and the proportion of FRP ships in Korean fishing boats is approximately 97%.

[0005] Therefore, there is a need to develop an eco-friendly ship hull that is suitable for ships in terms of weather resistance, impact resistance, and rigidity, while also being recyclable and reducing greenhouse gas emissions and worker health issues during the manufacturing process.

[0006]

[0007] The purpose of the present invention is to provide an eco-friendly ship hull having excellent environmental friendliness, weather resistance, impact resistance, rigidity, heat resistance, and a balance of these properties.

[0008] Another object of the present invention is to provide a method for manufacturing the eco-friendly ship hull.

[0009] The above and other objects of the present invention can all be achieved by the present invention described below.

[0010]

[0011] 1. One aspect of the present invention relates to an eco-friendly ship hull. The eco-friendly ship hull comprises high-density polyethylene; carbon material; a light stabilizer; and an antioxidant.

[0012] 2. In the above 1 specific example, the eco-friendly ship hull may include about 100 parts by weight of the high-density polyethylene; about 0.01 to about 4 parts by weight of the carbon material; about 0.01 to about 2 parts by weight of the light stabilizer; and about 0.01 to about 2 parts by weight of the antioxidant.

[0013] 3. In the above 1 or 2 specific examples, the high-density polyethylene may be linear high-density polyethylene.

[0014] 4. In the above 1 to 3 specific examples, the high-density polyethylene may have a weight average molecular weight of about 100,000 to about 1,000,000 g / mol.

[0015] 5. In the above specific examples 1 to 4, the carbon material may include at least one of carbon black, carbon fiber, carbon nanotube, graphite, and graphene.

[0016] 6. In the above 1 to 5 specific examples, the light stabilizer may include at least one of a UV absorber, a hindered amine light stabilizer, and a UV stabilizer.

[0017] 7. In the above 1 to 6 specific examples, the antioxidant may include at least one of a hindered phenol compound, an aromatic amine compound, a phosphite compound, a phosphonite compound, an organic sulfur-containing compound, and a dithiophosphonate compound.

[0018] 8. In the above 1 to 7 specific examples, the eco-friendly ship hull may further include an additive including at least one of a flame retardant, an anti-loading agent, an antibacterial agent, a heat stabilizer, an activator, a release agent, a nucleating agent, an antistatic agent, a dispersant, a processing aid, a commercializing agent, and a pigment.

[0019] 9. In the above 1 to 8 specific examples, the pigment may include at least one of a monoazo pigment, a diazo pigment, an anthraquinone pigment, a benzimidazole pigment, a quinacridone pigment, a quinophthalone pigment, a diketopyrrolopyrrole pigment, a dioxazine pigment, an indanthrone pigment, an isoindoline pigment, an isoandolinone pigment, a metal complex pigment, a perinone pigment, a perylene pigment, a phthalocyanine pigment, and a non-neutral pigment.

[0020] 10. In the above specific examples 1 to 9, the eco-friendly ship hull may have a tensile strength of about 24 N / mm2 or more of a 3.2 mm thick specimen measured according to ASTM D638.

[0021] 11. In the above 1 to 10 specific examples, the eco-friendly ship hull may have a notched Izod impact strength of about 196 J / m or more of a 3.2 mm thick specimen measured at -20°C according to ASTM D256.

[0022] 12. In the above 1 to 11 specific examples, the eco-friendly ship hull has a 3.2 mm thick specimen with a 340 nm, 0.35 W / m according to ASTM G155. 2 After irradiating with ultraviolet (UV) rays at 65℃ for 5,000 hours, it may not undergo brittle fracture when measured by notched Izod impact strength at -20℃ according to ASTM D256.

[0023] 13. In the above 1 to 12 specific examples, the eco-friendly ship hull has a yellowness index difference (ΔYI) before and after ultraviolet (UV) irradiation measured according to the following equation 1. 1-0) may be less than or equal to about 2.5, and the yellowness index difference (ΔYI) before and after ultraviolet (UV) irradiation measured according to Equation 2 below 1-0 ) can be less than or equal to about 2.5:

[0024] [Formula 1]

[0025] Difference in yellowness index (ΔYI) before and after UV irradiation 1-0 ) = YI1- YI0

[0026] In the above equation 1, YI0 is the yellowness index of a 3.2 mm thick specimen before UV irradiation measured according to ASTM D1925, and YI1 is the yellowness index of the specimen before UV irradiation at 340 nm, 0.35 W / m according to ASTM G155. 2 Yellowness index after UV irradiation measured according to ASTM D1925 after irradiation with ultraviolet (UV) rays at 65℃ for 12,000 hours;

[0027] [Formula 2]

[0028] Difference in yellowness index (ΔYI) before and after UV irradiation 2-0 ) = YI2-YI0

[0029] In the above equation 2, YI0 is the yellowness index of a 3.2 mm thick specimen before UV irradiation measured according to ASTM D1925, and YI2 is the yellowness index of the specimen before UV irradiation at 340 nm, 0.35 W / m according to ASTM G155. 2 This is the predicted yellowness index after UV irradiation, measured according to ASTM D1925, after irradiating with ultraviolet (UV) rays at 65℃ for 16,000 hours.

[0030] 14. In the above specific examples 1 to 13, the eco-friendly ship hull may have a tensile strength change rate before and after ultraviolet (UV) irradiation measured according to the following Equation 3 of about 12% or less, and a tensile strength change rate before and after ultraviolet (UV) irradiation measured according to the following Equation 4 of about 12% or less:

[0031] [Formula 3]

[0032] Change in tensile strength before and after UV irradiation (%) = (TS0- TS1) / TS0× 100

[0033] In the above equation 3, TS0 is the tensile strength before UV irradiation of a 3.2 mm thick specimen measured according to ASTM D638, and TS1 is the tensile strength of the specimen measured according to ASTM G155 at 340 nm, 0.35 W / m 2 This is the tensile strength after UV irradiation measured in accordance with ASTM D638 after irradiation with ultraviolet (UV) rays at 65℃ for 12,000 hours;

[0034] [Formula 4]

[0035] Change in tensile strength before and after UV irradiation (%) = (TS0- TS2) / TS0× 100

[0036] In the above equation 4, TS0 is the tensile strength before UV irradiation of a 3.2 mm thick specimen measured according to ASTM D638, and TS2 is the tensile strength of the specimen before UV irradiation at 340 nm, 0.35 W / m according to ASTM G155. 2 This is the predicted tensile strength after UV irradiation measured according to ASTM D638 after irradiating with ultraviolet (UV) rays at 65℃ for 16,000 hours.

[0037] 15. In the above specific examples 1 to 14, the eco-friendly ship hull may have an anti-slip surface shape having a cubic or grain shape.

[0038] 16. In the above 1 to 15 specific examples, the eco-friendly ship hull may have a glossy surface or a matte surface.

[0039] 17. Another aspect of the present invention relates to a method for manufacturing an eco-friendly ship hull. The method comprises the steps of mixing and melting high-density polyethylene, carbon material, a light stabilizer, and an antioxidant, and then extruding the mixture to produce pellets; extruding the pellets into sheets; cutting the sheets into ship hull component shapes according to nesting drawings; and assembling (welding) the ship hull components.

[0040] 18. In the above 17 specific examples, the pellets can be manufactured under extrusion molding temperature conditions of about 170 to about 240°C.

[0041] 19. In the above 17 or 18 specific examples, the sheet may have a thickness of about 5 mm or more and a width of about 500 mm or more.

[0042] 20. In the above 17 to 19 specific examples, the sheet may have a single-layer structure or a multi-layer structure.

[0043]

[0044] The present invention has the effect of providing an eco-friendly ship hull having excellent environmental friendliness, weather resistance, impact resistance, rigidity, heat resistance, and balance of these properties, and a method for manufacturing the same.

[0045]

[0046] Figure 1 is a nesting drawing for manufacturing an eco-friendly ship hull according to one specific example of the present invention.

[0047] Figure 2 is a cross-sectional view of an eco-friendly ship hull sheet having a single-layer structure according to one specific example of the present invention.

[0048] Figure 3 is a cross-sectional view of an eco-friendly ship hull sheet having a multi-layer structure according to one specific example of the present invention.

[0049] Figure 4 is a perspective view of an eco-friendly ship hull sheet having an anti-slip surface formed according to one specific example of the present invention.

[0050] Figure 5 is a cross-sectional view of an eco-friendly ship hull sheet having an anti-slip surface formed according to one specific example of the present invention.

[0051]

[0052] Hereinafter, the present invention will be described in detail as follows.

[0053] An eco-friendly ship hull according to the present invention comprises (A) high-density polyethylene; (B) carbon material; (C) light stabilizer; and (D) antioxidant.

[0054] In this specification, “a to b” indicating a numerical range is defined as “≥a and ≤b”.

[0055]

[0056] (A) High-density polyethylene

[0057] High density polyethylene (HDPE) according to one specific example of the present invention is used as a substitute for fiber reinforced plastic (FRP) materials and aluminum, etc. used in existing ships, thereby providing eco-friendliness (recyclability, greenhouse gas reduction, etc.) to the product. When applied together with carbon materials, light stabilizers, antioxidants, etc., it can improve the eco-friendliness, weather resistance, impact resistance, rigidity, heat resistance, and the balance of these properties, etc. of the eco-friendly ship hull.

[0058] In a specific example, the high-density polyethylene may be linear high-density polyethylene.

[0059] In a specific example, the high-density polyethylene may have a weight average molecular weight (Mw) of about 100,000 to about 1,000,000 g / mol, for example, about 120,000 to about 980,000 g / mol, as measured by gel permeation chromatography (GPC) at 160°C under TCB (1,2,4-trichlorobenzene) conditions, and a density of about 0.94 to about 0.97 g / cm 3It can be. In the above range, the rigidity, impact resistance, etc. of the eco-friendly ship hull can be excellent.

[0060]

[0061] (B) Carbon material

[0062] According to one specific example of the present invention, a carbon material is applied to high-density polyethylene together with a light stabilizer and an antioxidant, thereby improving the eco-friendliness, weather resistance, impact resistance, rigidity, heat resistance, and the balance of these physical properties of an eco-friendly ship hull.

[0063] In specific examples, the carbon material may include carbon black, carbon fiber, carbon nanotube, graphite, graphene, or combinations thereof.

[0064] In a specific example, the carbon material may have an average particle size of about 5 to about 50 nm, for example, about 10 to about 45 nm, as measured by transmission electron microscopy (TEM). Within this range, the surface area increases, UV absorption rate increases, and the weather resistance (long-term maintenance of properties) of the eco-friendly ship hull may be excellent.

[0065] In a specific example, the carbon material may be included in an amount of about 0.01 to about 4 parts by weight, for example, about 1 to about 3 parts by weight, relative to about 100 parts by weight of the high-density polyethylene. Within this range, the weather resistance (UV deterioration prevention) of the eco-friendly ship hull may be excellent.

[0066]

[0067] (C) Light stabilizer

[0068] A light stabilizer according to one specific example of the present invention can be applied to high-density polyethylene together with carbon materials and antioxidants to improve the eco-friendliness, durability, impact resistance, rigidity, heat resistance, and balance of these properties of an eco-friendly ship hull, and a commercialized light stabilizer used in a typical thermoplastic resin composition can be used.

[0069] In a specific example, the light stabilizer may include at least one of a UV absorber, a hindered amine light stabilizer, and a UV stabilizer.

[0070] In specific examples, the ultraviolet absorbent may include a benzophenone-based ultraviolet absorbent, a benzotriazole-based ultraviolet absorbent, a salicylic acid-based ultraviolet absorbent, a cyanoacrylate-based ultraviolet absorbent, a combination thereof, and the like.

[0071] Examples of the above benzophenone-based UV absorber include, but are not limited to, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxy benzophenone, 2,2'-dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis(2-methoxy-4-hydroxy-5-benzoyl phenyl)methane, and combinations thereof.

[0072] Examples of the above benzotriazole-based UV absorbers include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, Examples thereof include, but are not limited to, 2-[2'-hydroxy-3'-(3",4",5",6",-tetrahydrophthalimidemethyl)-5'-methylphenyl]benzotriazole, 2,2'methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], [2(2'-hydroxy-5'-methacryloxyphenyl)-2H-benzotriazole, and combinations thereof.

[0073] Examples of the above salicylic acid-based UV absorbent include, but are not limited to, phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and combinations thereof.

[0074] Examples of the above cyanoacrylate-based ultraviolet absorbent include, but are not limited to, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3'-diphenylacrylate, and combinations thereof.

[0075] Examples of the above hindered amine light stabilizer include, but are not limited to, [bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate], bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, methyl1,2,2,6,6-pentamethyl-4-piperidylsebacate, and combinations thereof.

[0076] Examples of the above UV stabilizer include, but are not limited to, nickel bis(octylphenyl)sulfide, [2,2'-thiobis(4-tert-octylphenolate)]-n-butylamine nickel, nickel complex-3,5-di-tert-butyl-4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyldithiocarbamate, benzoate type quenchers, nickel-dibutyldithiocarbamate, and combinations thereof.

[0077] In a specific example, the light stabilizer may be included in an amount of about 0.01 to about 2 parts by weight, for example, about 0.05 to about 1 part by weight, based on about 100 parts by weight of the high-density polyethylene. Within this range, the weather resistance (yellowness index maintenance, etc.) and impact resistance of the eco-friendly ship hull may be excellent.

[0078]

[0079] (D) Antioxidant

[0080] An antioxidant according to one specific example of the present invention is applied to high-density polyethylene together with a carbon material and a light stabilizer, etc., to improve the eco-friendliness, durability, impact resistance, rigidity, heat resistance, and the balance of these physical properties of an eco-friendly ship hull, and an antioxidant used in a typical thermoplastic resin composition can be used.

[0081] In specific examples, the antioxidant may include a hindered phenol compound, an aromatic amine compound, a phosphite compound, a phosphonite compound, an organic sulfur-containing compound, a dithiophosphonate compound, a mixture thereof, and the like.

[0082] In a specific example, the antioxidant may be a commercially available product, and may include, but is not limited to, Irganox 1010, Irgafos 168, and mixtures thereof.

[0083] In a specific example, the antioxidant may be included in an amount of about 0.01 to about 2 parts by weight, for example, about 0.05 to about 1 part by weight, based on about 100 parts by weight of the high-density polyethylene. Within this range, oxidation heat reactions, etc. may be suppressed during the production of pellets and sheets for producing eco-friendly ship hulls, and processing stability, etc. may be excellent.

[0084]

[0085] An eco-friendly ship hull according to one embodiment of the present invention may further include additives included in conventional thermoplastic resin compositions. Examples of such additives include, but are not limited to, flame retardants, anti-loading agents, antibacterial agents, heat stabilizers, lubricants, release agents, nucleating agents, antistatic agents, dispersants, processing aids, compatibilizers, pigments, and mixtures thereof.

[0086] In specific examples, the pigment may be used alone or in the form of a pigment masterbatch (MB).

[0087] In specific examples, the pigment may include a monoazo pigment, a diazo pigment, an anthraquinone pigment, a benzimidazole pigment, a quinacridone pigment, a quinophthalone pigment, a diketopyrrolopyrrole pigment, a dioxazine pigment, an indanthrone pigment, an isoindoline pigment, an isoandolinone pigment, a metal complex pigment, a perinone pigment, a perylene pigment, a phthalocyanine pigment, a non-neutral pigment, a mixture thereof, and the like.

[0088] In a specific example, when the above pigment is applied, various colors can be given to the ship without the environmental pollution problem caused by the use of paint during the manufacture of existing ships.

[0089] In a specific example, when the additive is used, the content may be about 0.001 to about 40 parts by weight, for example, about 0.01 to about 10 parts by weight, based on about 100 parts by weight of the high-density polyethylene, but is not limited thereto.

[0090]

[0091] An eco-friendly ship hull according to one specific example of the present invention can be manufactured by a manufacturing method including the steps of mixing and melting the above components and then extruding them to manufacture pellets; extruding the pellets into a sheet shape; cutting the sheets into the shape of ship hull parts according to a nesting drawing; and assembling (welding) the ship hull parts.

[0092] In a specific example, the pellets can be manufactured using a conventional twin-screw extruder at an extrusion temperature of about 170 to about 240°C, for example, about 190 to about 230°C.

[0093] In a specific example, the sheet can be manufactured using a multi-layer type twin-screw extruder at an extrusion temperature of about 170 to about 240°C, for example, about 190 to about 230°C. Such sheet extrusion methods are well known to those skilled in the art to which the present invention pertains.

[0094] FIG. 1 is a nesting diagram for manufacturing an eco-friendly ship hull according to one specific example of the present invention. The eco-friendly ship hull can be manufactured by cutting the sheet into the shape of a ship hull component according to a design (e.g., the nesting diagram illustrated in FIG. 1), and then assembling (welding) the ship hull components. Such cutting and assembly (welding) methods are well known to those skilled in the art to which the present invention pertains. Examples of the cutting method include, but are not limited to, the CNC method and the water jet method.

[0095] In a specific example, the sheet may have a thickness of about 5 mm or more, for example, about 5 to about 100 mm, and a width of about 500 mm or more, for example, about 500 to about 2,000 mm. Within the above range, depending on the hull application location, design and manufacturing of an eco-friendly ship hull may be facilitated.

[0096] Fig. 2 is a cross-sectional view of an eco-friendly ship hull sheet having a single-layer structure according to one specific example of the present invention, and Fig. 3 is a cross-sectional view of an eco-friendly ship hull sheet having a multi-layer structure according to one specific example of the present invention. As illustrated in Figs. 2 and 3, the sheet may have a single-layer structure or a multi-layer structure.

[0097] In a specific example, the sheet having the multilayer structure may be a laminated sheet (110) on at least one side of a sheet (100) having a single-layer structure, for example, a laminate film for securing flame retardancy, anti-fouling function, hull design, etc., a sheet of two or more layers, etc. may be laminated.

[0098] Fig. 4 is a perspective view of an eco-friendly ship hull sheet having an anti-slip surface formed according to one specific example of the present invention, and Fig. 5 is a cross-sectional view of an eco-friendly ship hull sheet having an anti-slip surface formed according to one specific example of the present invention. As illustrated in Figs. 4 and 5, the eco-friendly ship hull (sheet) may include an anti-slip surface (120) having a cubic or grain shape on at least one side of the sheet (100). In addition, when the sheet has a multi-layer structure, the anti-slip surface (120) may be formed on a laminated sheet (110).

[0099] In a specific example, the eco-friendly ship hull (sheet) may have a glossy surface or a matte surface, as needed.

[0100] In a specific example, the eco-friendly ship hull may have a tensile strength of about 24 N / mm2 or more of a 3.2 mm thick specimen measured according to ASTM D638.

[0101] In a specific example, the eco-friendly ship hull may have a notched Izod impact strength of about 196 J / m or more of a 3.2 mm thick specimen measured at -20°C according to ASTM D256.

[0102] In a specific example, the eco-friendly ship hull has a 3.2 mm thick specimen with a 340 nm, 0.35 W / m according to ASTM G155. 2 After irradiating with ultraviolet (UV) rays at 65℃ for 5,000 hours, it may not undergo brittle fracture when measured by notched Izod impact strength at -20℃ according to ASTM D256.

[0103] In a specific example, the eco-friendly ship hull has a yellowness index difference (ΔYI) before and after ultraviolet (UV) irradiation measured according to Equation 1 or Equation 2 below. 1-0 ) may be less than or equal to about 2.5, for example less than or equal to about 1.

[0104] [Formula 1]

[0105] Difference in yellowness index (ΔYI) before and after UV irradiation 1-0 ) = YI1- YI0

[0106] In the above equation 1, YI0 is the yellowness index of a 3.2 mm thick specimen before UV irradiation measured according to ASTM D1925, and YI1 is the yellowness index of the specimen before UV irradiation at 340 nm, 0.35 W / m according to ASTM G155. 2 Yellowness index after UV irradiation measured according to ASTM D1925 after irradiation with ultraviolet (UV) rays at 65℃ for 12,000 hours.

[0107] [Formula 2]

[0108] Difference in yellowness index (ΔYI) before and after UV irradiation 2-0 ) = YI2-YI0

[0109] In the above equation 2, YI0 is the yellowness index of a 3.2 mm thick specimen before UV irradiation measured according to ASTM D1925, and YI2 is the yellowness index of the specimen before UV irradiation at 340 nm, 0.35 W / m according to ASTM G155. 2 This is the predicted yellowness index after UV irradiation, measured according to ASTM D1925, after irradiating with ultraviolet (UV) rays at 65℃ for 16,000 hours.

[0110] In a specific example, the eco-friendly ship hull may have a tensile strength change rate of about 12% or less, for example, about 10% or less, before and after ultraviolet (UV) irradiation, as measured according to Equation 3 or Equation 4 below.

[0111] [Formula 3]

[0112] Change in tensile strength before and after UV irradiation (%) = (TS0- TS1) / TS0× 100

[0113] In the above equation 3, TS0 is the tensile strength before UV irradiation of a 3.2 mm thick specimen measured according to ASTM D638, and TS1 is the tensile strength of the specimen measured according to ASTM G155 at 340 nm, 0.35 W / m 2 This is the tensile strength after UV irradiation measured according to ASTM D638 after irradiating with ultraviolet (UV) rays at 65℃ for 12,000 hours.

[0114] [Formula 4]

[0115] Change in tensile strength before and after UV irradiation (%) = (TS0- TS2) / TS0× 100

[0116] In the above equation 4, TS0 is the tensile strength before UV irradiation of a 3.2 mm thick specimen measured according to ASTM D638, and TS2 is the tensile strength of the specimen before UV irradiation at 340 nm, 0.35 W / m according to ASTM G155. 2 This is the tensile strength after UV irradiation measured in accordance with ASTM D638 after irradiation with ultraviolet (UV) rays at 65℃ for 16,000 hours.

[0117]

[0118] The eco-friendly ship hull of the present invention is suitable for ship use due to its weather resistance, impact resistance, and rigidity. Unlike existing FRP ship hulls, it can be recycled after use and reduces greenhouse gas emissions and worker health issues during the shipbuilding process, making it environmentally friendly. Furthermore, the eco-friendly ship hull is economical compared to aluminum ships, which require high manufacturing and repair costs.

[0119]

[0120] Hereinafter, the present invention will be described in more detail through examples; however, these examples are for the purpose of explanation only and should not be construed as limiting the present invention.

[0121]

[0122] Example

[0123] Below, the specifications of each component used in the examples and comparative examples are as follows.

[0124] (A) High-density polyethylene

[0125] High-density polyethylene (HDPE, manufacturer: Lotte Chemical, product name: 5200B, weight average molecular weight: approximately 250,000 g / mol) was used.

[0126] (B) Carbon material

[0127] Carbon black (Manufacturer: Bura Carbon, Product Name: Raven UV Ultra) was used.

[0128] (C) Light stabilizer

[0129] Light stabilizer (1,6-Hexanediamine, N,N'-Bis(2,2,6,6-tetramethyl-4-4piperidinyl)-,Polymers with 2,4-Dichloro-6-(4-morpholinyl)-1,3,5-triazine, Manufacturer: Scienceco, Product name: UV3346) was used.

[0130] (D) Antioxidant

[0131] Pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate] (manufacturer: Ciba Specialty Chemicals, product name: Irganox 1010) and tris(2,4-di-t-butylphenyl)phosphite (manufacturer: Ciba Specialty Chemicals, product name: Irgafos 168) were mixed and used (mixing ratio (Irganox 101:Irgafos 1680) = 1:1.5).

[0132]

[0133] Example 1 and Comparative Examples 1 to 3

[0134] Each of the above components was added in the amounts shown in Table 1 below, and then extruded at about 220°C to produce pellets. The extrusion was performed using a twin-screw extruder with an L / D of 36 and a diameter of 45 mm. The produced pellets were dried at about 80°C for about 2 hours or more, and then injected into a 220-ton injection molding machine (molding temperature: about 220°C, mold temperature: about 40°C) to produce test pieces. The physical properties of the produced test pieces were evaluated using the following methods, and the results are shown in Table 1 below.

[0135]

[0136] Method of measuring physical properties

[0137] (1) Density (unit: g / cm) 3 ): The density of the sheet was measured by the submerged displacement method (after 24 hours) according to ISO 1183.

[0138] (2) Melt flow index (unit: g / 10 min): Melt flow index (MI) was measured at 190℃ and 2.16 kgf according to ASTM D1238.

[0139] (3) Tensile strength (unit: N / mm) 2 ): The tensile strength of 3.2 mm thick specimens was measured according to ASTM D638.

[0140] (4) Flexural strength (unit: N / mm) 2 ): The flexural strength of 3.2 mm thick specimens was measured according to ASTM D790.

[0141] (5) Flexural modulus (unit: N / mm) 2 ): The flexural modulus of 3.2 mm thick specimens was measured according to ASTM D790.

[0142] (6) Notched Izod impact strength (unit: J / m): The notched Izod impact strength of a 3.2 mm thick specimen was measured at -20℃ according to ASTM D256.

[0143] (7) Notched Izod impact strength after UV irradiation (unit: J / m): 340 nm, 0.35 W / m on 3.2 mm thick specimens according to ASTM G155 2 After irradiating the specimen with ultraviolet (UV) rays at 65°C for 5,000 hours, the weathering resistance was evaluated by measuring the notched Izod impact strength at -20°C according to ASTM D256. (NB: Non-Break)

[0144] (8) Heat distortion temperature (unit: ℃): Heat distortion temperature was measured when a deformation of 0.254 mm occurred on the specimen surface according to ASTM D640.

[0145] (9) Vicat softening point (unit: ℃): The Vicat softening point was measured when 1 mm of needle-like particles penetrated the specimen surface according to ISO 306.

[0146] (10) Weatherability evaluation: According to the following equations 1 and 2, the yellowness index difference (ΔYI) before and after ultraviolet (UV) irradiation 1-0 ) was measured.

[0147] [Formula 1]

[0148] Difference in yellowness index (ΔYI) before and after UV irradiation 1-0 ) = YI1- YI0

[0149] In the above equation 1, YI0 is the yellowness index of a 3.2 mm thick specimen before UV irradiation measured according to ASTM D1925, and YI1 is the yellowness index of the specimen before UV irradiation at 340 nm, 0.35 W / m according to ASTM G155. 2 Yellowness index after UV irradiation measured according to ASTM D1925 after irradiation with ultraviolet (UV) rays at 65℃ for 12,000 hours.

[0150] [Formula 2]

[0151] Difference in yellowness index (ΔYI) before and after UV irradiation 2-0 ) = YI2-YI0

[0152] In the above equation 2, YI0 is the yellowness index of a 3.2 mm thick specimen before UV irradiation measured according to ASTM D1925, and YI2 is the yellowness index of the specimen before UV irradiation at 340 nm, 0.35 W / m according to ASTM G155. 2 This is the predicted yellowness index after UV irradiation, measured according to ASTM D1925, after irradiating with ultraviolet (UV) rays at 65℃ for 16,000 hours.

[0153] (11) Weatherability evaluation: According to the following equations 3 and 4, the change rate in tensile strength (unit: %) before and after ultraviolet (UV) irradiation was measured.

[0154] [Formula 3]

[0155] Change in tensile strength before and after UV irradiation (%) = (TS0- TS1) / TS0× 100

[0156] In the above equation 2, TS0 is the tensile strength before UV irradiation of a 3.2 mm thick specimen measured according to ASTM D638, and TS1 is the tensile strength of the specimen measured according to ASTM G155 at 340 nm, 0.35 W / m 2 This is the tensile strength after UV irradiation measured according to ASTM D638 after irradiating with ultraviolet (UV) rays at 65℃ for 12,000 hours.

[0157] [Formula 4]

[0158] Change in tensile strength before and after UV irradiation (%) = (TS0- TS2) / TS0× 100

[0159] In the above equation 4, TS0 is the tensile strength before UV irradiation of a 3.2 mm thick specimen measured according to ASTM D638, and TS2 is the tensile strength of the specimen before UV irradiation at 340 nm, 0.35 W / m according to ASTM G155. 2 This is the predicted tensile strength after UV irradiation measured according to ASTM D638 after irradiating with ultraviolet (UV) rays at 65℃ for 16,000 hours.

[0160]

[0161] Example Comparative Example 1123 (A) (parts by weight) 100 100 100 100 (B) (parts by weight) 2.5-2.5 2.5 (C) (parts by weight) 0.2 0.1-0.1 (D) (parts by weight) 0.25 0.25 0.25 - Density 0.96 9 0.96 9 0.96 4 Melt Index 0.25 0.36 0.25 0.27 Tensile Strength 29 26 29 27 Flexural Strength 29 23 28 26 Flexural Modulus 1,38 1 1,35 0 ​​1,39 5 1,35 0 ​​Notched Izod Impact Strength 37 33 4 33 5 33 4 3 Notched Izod Impact Strength after UV Irradiation ≥ 37 3 (NB) - 33.3 - Heat Distortion Temperature 9 9 9 4 9 7 9 5 Vicat Softening point 127 125 126 127 Difference in yellowness index before and after UV irradiation (before and after 12,000 hours of irradiation) 1.68 - 3.77 Difference in yellowness index before and after UV irradiation (before and after 16,000 hours of irradiation) Approximately 2.5 - Approximately 5 - Change in tensile strength before and after UV irradiation (before and after 12,000 hours of irradiation) Approximately 8 - Approximately 20 - Change in tensile strength before and after UV irradiation (before and after 16,000 hours of irradiation) Approximately 10 - Approximately 30 -

[0162]

[0163] From the above results, it can be seen that the eco-friendly ship hull of the present invention is eco-friendly by applying high-density polyethylene instead of FRP material, and has excellent weather resistance (notched Izod impact strength after ultraviolet (UV) irradiation, difference in yellowness index before and after ultraviolet (UV) irradiation, change rate in tensile strength before and after ultraviolet (UV) irradiation), impact resistance (notched Izod impact strength), rigidity (tensile strength, flexural strength, flexural modulus), heat resistance (heat deflection temperature, Vicat softening point), and a balance of these physical properties.

[0164] On the other hand, in the case of Comparative Example 1, where no carbon material was applied, it was impossible to measure the physical properties after UV irradiation (the specimen was destroyed), and it was found that weather resistance, etc. were reduced. In the case of Comparative Example 2, where no light stabilizer was applied, it was found that weather resistance, etc. were reduced, and impact resistance, etc. were reduced compared to the examples. In the case of Comparative Example 3, where no antioxidant was applied, it was impossible to measure the physical properties after UV irradiation (the specimen was destroyed), and it was found that weather resistance, etc. were reduced, and it was confirmed that processability, etc. were reduced.

[0165]

[0166] The present invention has been described with reference to exemplary embodiments. Those skilled in the art will appreciate that the present invention can be implemented in modified forms without departing from its essential characteristics. Therefore, the disclosed embodiments should be considered illustrative rather than limiting. The scope of the present invention is set forth in the claims, not the foregoing description, and all differences within the scope equivalent thereto should be construed as being encompassed by the present invention.

Claims

1. High density polyethylene; carbon material; Light stabilizer; and An environmentally friendly ship hull characterized by including an antioxidant.

2. In the first paragraph, the eco-friendly ship hull is characterized by comprising about 100 parts by weight of the high-density polyethylene; about 0.01 to about 4 parts by weight of the carbon material; about 0.01 to about 2 parts by weight of the light stabilizer; and about 0.01 to about 2 parts by weight of the antioxidant.

3. An eco-friendly ship hull according to claim 1 or 2, characterized in that the high-density polyethylene is linear high-density polyethylene.

4. An eco-friendly ship hull according to any one of claims 1 to 3, characterized in that the high-density polyethylene has a weight average molecular weight of about 100,000 to about 1,000,000 g / mol.

5. An eco-friendly ship hull according to any one of claims 1 to 4, characterized in that the carbon material includes at least one of carbon black, carbon fiber, carbon nanotube, graphite, and graphene.

6. An eco-friendly ship hull according to any one of claims 1 to 5, characterized in that the light stabilizer comprises at least one of an ultraviolet absorber, a hindered amine light stabilizer, and an ultraviolet stabilizer.

7. An eco-friendly ship hull according to any one of claims 1 to 6, characterized in that the antioxidant comprises at least one of a hindered phenol compound, an aromatic amine compound, a phosphite compound, a phosphonite compound, an organic sulfur-containing compound, and a dithiophosphonate compound.

8. An eco-friendly ship hull according to any one of clauses 1 to 7, characterized in that it further includes an additive including at least one of a flame retardant, an anti-loading agent, an antibacterial agent, a heat stabilizer, an activator, a release agent, a nucleating agent, an antistatic agent, a dispersant, a processing aid, a commercializing agent, and a pigment.

9. An eco-friendly ship hull, characterized in that in paragraph 8, the pigment comprises at least one of a monoazo pigment, a diazo pigment, an anthraquinone pigment, a benzimidazole pigment, a quinacridone pigment, a quinophthalone pigment, a diketopyrrolopyrrole pigment, a dioxazine pigment, an indanthrone pigment, an isoindoline pigment, an isoandolinone pigment, a metal complex pigment, a perinone pigment, a perylene pigment, a phthalocyanine pigment, and a non-neutral pigment.

10. An eco-friendly ship hull according to any one of clauses 1 to 9, characterized in that the tensile strength of a 3.2 mm thick specimen measured in accordance with ASTM D638 is about 24 N / mm2 or more.

11. An eco-friendly ship hull according to any one of claims 1 to 10, characterized in that the eco-friendly ship hull has a notched Izod impact strength of about 196 J / m or more of a 3.2 mm thick specimen measured at -20°C according to ASTM D256.

12. In any one of clauses 1 to 11, the eco-friendly ship hull has a radiation intensity of 340 nm and 0.35 W / m on a 3.2 mm thick specimen according to ASTM G155. 2 An eco-friendly ship hull characterized by not undergoing brittle fracture when exposed to ultraviolet (UV) rays at 65°C for 5,000 hours and measured by notched Izod impact strength at -20°C according to ASTM D256.

13. In any one of clauses 1 to 12, the eco-friendly ship hull has a yellowness index difference (ΔYI) before and after ultraviolet (UV) irradiation measured according to the following equation 1. 1-0 ) is about 2.5 or less, and the yellowness index difference (ΔYI) before and after ultraviolet (UV) irradiation measured according to Equation 2 below 1-0 ) is characterized by an environmentally friendly ship hull of about 2.5 or less: [Formula 1] Difference in yellowness index (ΔYI) before and after UV irradiation 1-0 ) = YI1- YI0 In the above equation 1, YI0 is the yellowness index of a 3.2 mm thick specimen before UV irradiation measured according to ASTM D1925, and YI1 is the yellowness index of the specimen before UV irradiation at 340 nm, 0.35 W / m according to ASTM G155. 2 Yellowness index after UV irradiation measured according to ASTM D1925 after irradiation with ultraviolet (UV) rays at 65℃ for 12,000 hours; [Formula 2] Difference in yellowness index (ΔYI) before and after UV irradiation 2-0 ) = YI2-YI0 In the above equation 2, YI0 is the yellowness index of a 3.2 mm thick specimen before UV irradiation measured according to ASTM D1925, and YI2 is the yellowness index of the specimen before UV irradiation at 340 nm, 0.35 W / m according to ASTM G155. 2 This is the predicted yellowness index after UV irradiation, measured according to ASTM D1925, after irradiating with ultraviolet (UV) rays at 65℃ for 16,000 hours.

14. In any one of clauses 1 to 13, the eco-friendly ship hull is characterized in that the eco-friendly ship hull has a tensile strength change rate of about 12% or less before and after ultraviolet (UV) irradiation measured according to the following formula 3, and a tensile strength change rate of about 12% or less before and after ultraviolet (UV) irradiation measured according to the following formula 4: [Formula 3] Change in tensile strength before and after UV irradiation (%) = (TS0- TS1) / TS0× 100 In the above equation 3, TS0 is the tensile strength before UV irradiation of a 3.2 mm thick specimen measured according to ASTM D638, and TS1 is the tensile strength of the specimen measured according to ASTM G155 at 340 nm, 0.35 W / m 2 Tensile strength after UV irradiation measured according to ASTM D638 after irradiation with ultraviolet (UV) rays at 65℃ for 12,000 hours; [Formula 4] Change in tensile strength before and after UV irradiation (%) = (TS0- TS2) / TS0× 100 In the above equation 4, TS0 is the tensile strength before UV irradiation of a 3.2 mm thick specimen measured according to ASTM D638, and TS2 is the tensile strength of the specimen measured according to ASTM G155 at 340 nm, 0.35 W / m 2 This is the predicted tensile strength after UV irradiation, measured according to ASTM D638, after irradiating with ultraviolet (UV) rays at 65℃ for 16,000 hours.

15. An eco-friendly ship hull according to any one of claims 1 to 14, characterized in that the eco-friendly ship hull has an anti-slip surface shape having a cubic or grain shape.

16. An eco-friendly ship hull according to any one of clauses 1 to 15, characterized in that the eco-friendly ship hull has a glossy surface or a matte surface.

17. High-density polyethylene, carbon material, light stabilizer and antioxidant are mixed and melted, then extruded to produce pellets; The above pellets are extruded into a sheet shape; The above sheet is cut into the shape of a ship hull part according to the nesting drawing; and An eco-friendly ship hull manufacturing method, characterized by including a step of assembling (welding) the ship hull parts.

18. A method for manufacturing an eco-friendly ship hull, characterized in that in claim 17, the pellets are manufactured under extrusion molding temperature conditions of about 170 to about 240°C.

19. A method for manufacturing an eco-friendly ship hull, characterized in that the sheet according to claim 17 or 18 has a thickness of about 5 mm or more and a width of about 500 mm or more.

20. A method for manufacturing an eco-friendly ship hull, characterized in that the sheet has a single-layer structure or a multi-layer structure according to any one of claims 17 to 19.

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