KR20100079610A - The composition of glass fiber reinforced polyamide resin - Google Patents

Abstract

PURPOSE: A glass fiber-reinforced polyamide resin composition is provided to economically produce the composition, and to secure the mechanical strength and the shock resistance. CONSTITUTION: A glass fiber-reinforced polyamide resin composition contains 100 parts of polyamide resin by weight, 10~130 parts of glass fiber by weight, 3~26 parts of thermoplastic elastomer by weight, 0.1~0.7 parts of benzotriazole based or benzophenone based ultraviolet ray-absorbing agent by weight, and 0.1~0.7 parts of hindered amine-based radical scavenger by weight. The polyamide resin is polyamide 6, polyamide 66, or their mixture.

Description

The composition of Glass fiber reinforced Polyamide resin

The present invention is a composition comprising a polyamide resin, a glass fiber, a thermoplastic elastomer, a benzotriazole-based or a benzophenone-based ultraviolet absorber, and a hindered amine-based radical scavenger, light and various physical properties, in particular excellent weather resistance A glass fiber reinforced polyamide resin composition suitable for use in various outdoor moldings.

Techniques for producing high-performance polyamide resins include techniques to alloy with other polymers or to reinforce inorganic materials. In particular, inorganic reinforced polyamide resins have been widely used in various moldings for a long time due to the advantage of good flexural modulus and heat resistance due to the addition of glass fibers or minerals used as inorganic materials, and low molding shrinkage. come. In addition, alloys with other polymers include alloys with general-purpose plastics or thermoplastic elastomers, and alloys with other enpras. The alloys for alloys include polypropylene-based, polystyrene-based and olefin-based elastomers. Due to its low compatibility with amides, techniques for producing functional polyamides through commercialization techniques have been applied to various industrial fields. However, such an alloy composition alone can not achieve the desired purpose has been proposed to improve the heat resistance, dimensional stability by reinforcing the inorganic material after alloying.

U.S. Pat.No. 5,028,262 or European Patent No. 1312647 describes a technique for reinforcing inorganic fillers after the addition of polyolefin elastomers. They propose a method to improve the functionality by adding an elastomer to the impact resistance caused by the inorganic filler reinforcement, the impact resistance and toughness is improved due to the addition of the elastomer, but the heat resistance is lowered and the surface is poor during molding There is a disadvantage in that it is difficult to apply only to limited use, and the addition of glass fiber alone has a disadvantage in that the dimensional stability is poor, there was a limit to apply for the manufacture of automotive exterior products.

On the other hand, current rain gutters or manholes on the road are most of the metal material, but replacing them with a polymer resin composition is economical and easy to install, it is required to have a performance equal to or higher than the metal material in strength / rigidity.

Japanese Patent Laid-Open Publication No. 1999-071779 proposes a technology that uses glass fiber reinforced resin with unsaturated polyester as a basic polymer, which is proposed as a technology for plastic materials used in rain gutters or manhole products on roads. Patent Publication No. 2007-103825 also proposed a technique of reinforcing waste materials and glass fibers in unsaturated polyester, and Korean Patent Publication No. 2002-72346 describes mating of glass fibers in polypropylene resin (PP resin). ), A technique having a feature of manufacturing using the GMT technique, which is a technique of impregnating into weaving, has been proposed. In addition, Korean Utility Model Application No. 2003-25037 proposes a feature using a thermosetting resin which is a fiber-reinforced plastic material.

As described above, most of the prior art proposes a technique of manufacturing glass fiber by using a thermosetting resin or mentioning a rain gutter or a manhole as a structural feature of the structure. However, in the case of thermosetting resins, the composition is excellent in terms of stiffness, strength, and weather resistance, which is an important requirement for outdoor parts.However, the manufacturing cost is high, the molding is difficult, and the thermosetting resin is not an eco-friendly material, which causes environmental problems and impact resistance. Due to its weak characteristics, it is difficult to see an advantage over the rigid metal materials which are widely used at present. In addition, due to structural limitations during molding, there are disadvantages such as odors such as sewage and dirt are exposed as it is after installation.

Accordingly, the present inventors have conducted research to develop an excellent glass fiber reinforced thermoplastic polyamide resin composition which is economical, easy to install, and has a performance equal to or higher than that of a metallic material even in strength / rigidity. Increasing the mechanical strength, improving the shrinkage of the resin in the product during molding, adding olefin elastomer to improve impact resistance, and adding UV stabilizer to ensure weather resistance, rain gutter or manhole for road The present invention has been completed by knowing that a composition suitable for various outdoor moldings such as a product can be manufactured.

Accordingly, an object of the present invention is to provide a resin composition containing polyamide resin, glass fiber, thermoplastic elastomer, ultraviolet absorber, and hindered amine radical scavenger in a predetermined amount.

The present invention is based on 100 parts by weight of polyamide resin, 10 to 130 parts by weight of glass fiber, 3 to 26 parts by weight of thermoplastic elastomer, 0.1 to 0.7 parts by weight of benzotriazole-based or benzophenone-based ultraviolet absorber, and hindered amine radical radicals Characterized in that the glass fiber reinforced polyamide resin composition containing 0.1 to 0.7 parts by weight as a cabin.

In the present invention, the impact strength measured by ASTM evaluation method D256 is 8 kgcm / cm or more, the flexural modulus measured by ASTM evaluation method D790 is 40,000 kg / cm ² or more, and the xenon arc weather meter measured by ASTM evaluation method D2565. It is characterized by the molded article manufactured from the said polyamide resin composition whose (DELTA) E value is 3 or less after 3000 hours.

The glass fiber-reinforced polyamide resin composition of the present invention is light in weight, low in manufacturing cost, satisfies rigidity and impact resistance with various physical properties, and there is no warpage or deformation due to problems in forming a product, and also secures a good appearance molded article. As it is a composition having excellent weather resistance when applied to outdoor use, it is very suitable to be used for various outdoor moldings, rain gutters or manholes for roads, and thus it can replace metal materials or thermosetting materials that are currently used in large quantities.

Hereinafter, the present invention will be described in detail.

The present invention is characterized by a glass fiber reinforced polyamide resin composition comprising a polyamide resin, a glass fiber, a thermoplastic elastomer, a benzotriazole-based or a benzophenone-based ultraviolet absorber, and a hindered amine-based radical scavenger.

Although the kind in particular is not restrict | limited in the polyamide resin used by this invention, Polyamide 6, polyamide 66, or the mixture of the said polyamide 6 and polyamide 66 can be used. It is also preferred that the relative viscosity of the polyamide resin is in the range of 2.1 to 3.5 (measured with a solution of 1 g of polymer in 100 ml of 96% sulfuric acid at 20 ° C.). When the viscosity of the polyamide resin is less than the above range, the flexural modulus and impact resistance are lowered, and when the viscosity of the polyamide resin is exceeded, problems of surface expression and molding of the inorganic material used as poor fluidity occur.

Glass fiber used in the present invention is a glass fiber in the form of chop (Chop) commonly used as "G" or "K" glass, the main component is CaO · SiO ₂ · Al ₂ O ₃ and CaO is 10 to 20% by weight 50 to 70% by weight of SiO2 and 2 to 15% by weight of Al ₂ O ₃ are preferably coated with a silane (Siup) on the glass fiber surface for interfacial adhesion with the final composition. It is preferable to use the fiber of 3-6 mm in length and 10-13 micrometers in diameter. It is preferable that the glass fiber is used in an amount of 10 to 130 parts by weight based on 100 parts by weight of the polyamide resin, and when the glass fiber is less than 10 parts by weight, the flexural modulus is lowered. There is a disadvantage that the molding is not good or the surface is poor.

Thermoplastic elastomers are added as impact and water resistant modifiers of polyamide resins, from one or more unsaturated monomers such as α-olefins containing ethylene, acrylic acid and its derivatives, aromatic vinyl monomers, vinyl cyanide monomers, or diene monomers, and the like. As the polymer to be produced, one obtained by grafting α, β-unsaturated carboxylic acid, α, β-unsaturated anhydride or a derivative thereof can be used. In particular, a polymer made of a random or block copolymer of the aromatic vinyl monomer and the vinyl cyanide monomer may be used.

The α-olefins are saturated with ethylene, propylene, butylene, 1-pentene, isobutylene, isoprene, 1-hexene, 1,3-hexadiene, 1-heptene, and vinyl acetate or propionate. Vinyl esters of carboxylic acids.

The acrylic acid and its derivatives are methacrylate, methyl acrylate, butyl acrylate, glycidyl acrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, hydryl ethyl methacrylate, amino methacrylate and greasy Dimethyl methacrylate or maleimide compounds such as N-phenylmaleimide, N-methylmaleimide, and N-cyclohexylmaleimide.

Examples of the aromatic vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, tetrabutylstyrene, dimethylstyrene, chlorostyrene, dichlorostyrene, vinylnaphthalene, and the like.

Examples of the vinyl cyanide monomers include acrylonitrile, methacrylonitrile or fumaronitrile.

The diene monomers include butadiene, 1.3-cyclohexadiene, 1,4-cyclohexadiene, cyclopentadiene, or 2,4-hexadiene.

Also, the grafted α, β-unsaturated carboxylic acids or α, β-unsaturated anhydrides and derivatives thereof are functional groups having excellent reactivity with amide groups, maleic acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, allyl succinic acid, 2 Dicarboxylic acid, maleic acid, fumaric acid, or anhydrides or derivatives thereof may be used, and more specifically, maleic anhydride, itaconic anhydride, citraconic anhydride, acrylic acid, methacrylic acid, allyl succinic acid , 2-dicarboxylic acid, maleic acid, fumaric acid, diethyl maleate, dimethyl maleate, maleic anhydride, itaconic anhydride, citraconic anhydride, allylsuccinic anhydride, or 4-methyl-4-cyclohexene-1 have.

In particular, the thermoplastic elastomer of the present invention is an ethylene propylene copolymer, an ethylene propylene diene copolymer, styrene ethylene, butadiene styrene (SEBS) copolymer, styrene butadiene styrene (SBS, Styrenebutadiene styrene) copolymer, or 0.4-3 parts by weight of a methacrylate butadiene styrene (MBS) copolymer and an ethylene ethyl acrylate copolymer with α, β-unsaturated carboxylic acid or α, β-unsaturated anhydride and derivatives thereof Preferably, the ethylene octene copolymer containing 0.4-3 parts by weight of maleic anhydride in the α, β-unsaturated carboxylic acid compound and ethylene is used.

When the grafted α, β-unsaturated carboxylic acid or α, β-unsaturated anhydride and its derivatives are grafted to less than 0.4 part by weight, compatibility with the polyamide resin is inferior, and when grafted to more than 3 parts by weight, the viscosity becomes high and kneaded. This becomes difficult.

The thermoplastic elastomer is preferably used 3 to 26 parts by weight based on 100 parts by weight of polyamide resin. If the content of the thermoplastic elastomer is less than 3 parts by weight, the effect of improving the impact strength is insignificant. If the content of the thermoplastic elastomer exceeds 26 parts by weight, heat resistance and stiffness are reduced, mold shrinkage is increased, and shrinkage anisotropy is increased.

In the present invention, the ultraviolet absorber and the hindered amine radical scavenger are used in parallel. Photoaging is the main cause of UV energy in the wavelength range of 290 to 400 nm, which breaks down the chemical bonds of polymers, creating free radicals, causing discoloration, cracking, and deterioration of physical properties. Absorbers and blockers, radical scavinzers and peroxide decomposers, quenchers and the like are known, but in the present invention, a UV absorber and a hindered amine radical scavinzer were used in parallel. When the present invention is secured to the desired level of weathering performance was found to be excellent in preventing physical property degradation and discoloration when used outdoors.

As the ultraviolet absorber, a benzotriazole compound or a benzophenone compound may be used. In the present invention, the benzotriazole compound may be used as a 2- (2-hydroxy-3,5-di (1,1). -Dimethylbenzyl) phenyl) 2H-benzotriazole ultraviolet absorber is used. In addition, as a hindered amine radical scavenger, poly (6-((1,1,3,3-tetramethylbutyl) amino) -1,3,5-triazine-2,4-diyl)-(( 2,2,6,6-tetramethyl-4-piperidyl) imino) -1,6-hexamethylene- (2,2,6,6-tetramethyl-4-piperidyl) imino)) Can be used. Each of these is preferably used 0.1 to 0.7% by weight relative to the polyamide resin composition, less than 0.1% by weight of the weather resistance effect is insignificant, and more than 0.7% by weight more than the weather resistance according to the increase in the addition amount It may not show an improvement effect, but rather the weather resistance may be lowered, and gas may be generated during molding to generate a flow mark on the surface of the product, which is undesirable and accompanied by a decrease in impact resistance.

Further, tris- (2,4-dibutylbutylphenyl) -phosphate and N-N'-hexamethylene bis (3.5-dibutylbutyl-4-) having an amide group as a heat-resistant agent within a range not impairing the object of the present invention. Iganox B1171 (manufactured Sibagaiki), which is a 1: 1 mixture of hydroxy-hydrocinamide, can be used.

By using the polyamide resin composition of the present invention, outdoor molded products such as rain gutters and manholes for roads, pipes, firefighting, water tanks, drains, signs, and the like can be manufactured.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are intended to illustrate the present invention and do not limit the present invention.

Raw materials used in Examples and Comparative Examples are as follows.

As the polyamide resin, polyamide 6 or 66 having a relative viscosity of 2.8 was used, and glass fibers (gold steel chemical, trade name "CS311") having a length of 3 mm and a diameter of 13 mu m and surface-treated with silane; Thermoplastic elastomers include ethylene octene elastomer (TPE 1) grafted with 1 part by weight of maleic anhydride, ethylene octene elastomer (TPE 2) with 2 parts by weight of maleic anhydride (TPE 2) or ethylene octene elastomer with 2.5 parts by weight of maleic anhydride (TPE 3). )); 2- (2-hydroxy-3,5-di (1,1-dimethylbenzyl) phenyl) 2H-benzotriazole (UV-1, trade name "tinuvin234") as an ultraviolet absorber; Poly (6-((1,1,3,3-tetramethylbutyl) amino) -1,3,5-triazine-2,4-diyl)-((2, as a hindered amine radical scavenger 2,6,6-tetramethyl-4-piperidyl) imino) -1,6-hexamethylene- (2,2,6,6-tetramethyl-4-piperidyl) imino)) (UV -2, trade name "Schimasorb 944") was used.

Production Example

Using a twin screw extruder, the cylinder barrel was melt kneaded at 275 ° C to 285 ° C for polyamide 66 and 245 ° C to 255 ° C for polyamide 6, and then chipped to 90 ° C, 5 ° C. After drying using a time dehumidifying dryer, each specimen was produced at the same temperature as melt kneading using a heated screw-type injection molding machine.

The raw materials are added according to the composition of Table 1 and Table 2, but in order to maximize the physical properties of the resin composition, the polypropylene resin and UV stabilizer are blended into the primary inlet by using an extruder having three inlets, and the thermoplastic in the secondary inlet. Elastomers and glass fibers were introduced into the third inlet. The third inlet is preferably located as close to the discharge part of the extruder as possible to minimize the damage of inorganic material by the shear of the screw in the extruder. In addition, it is desirable to minimize the residence time as part of maximizing the physical properties of the composition during melt kneading, and a pressure reducing device called vent (Vent) is installed near the tertiary inlet and outlet to reduce the pressure to 150 mmHg or less.

Experimental Example

The impact strength, the flexural modulus and the weather resistance of the Examples 1 to 12 and Comparative Examples 1 to 6 of the preparation were measured and shown in Tables 3 and 4.

Flexural modulus was measured after fabricating 1/8 inch specimens in accordance with ASTM D790, and values less than 40,000 kg / cm ² were judged as defective.

Impact strength was measured by Izod Notched impact strength at room temperature with 1/4 inch specimen according to ASTM D256 and 8 kgcm / cm. Less than judged that the impact resistance is poor

The weather resistance (△ E value) is 83 ° C, 50% absolute using Xenon arc weather-O-meter evaluation equipment after fabricating 1/8 inch specimens in accordance with ASTM D2565. The change of L, a, b value, which is each color evaluation value, was calculated by the following Equation 1 by evaluating 3,000 hours in a humidity atmosphere, and when ΔE value was greater than 3, it was judged as defective.

As shown in Tables 3 and 4, Examples 1 to 12, which are compositions according to the present invention, maintain high flexural modulus and impact strength, and have excellent weather resistance ΔE of less than 3. However, Comparative Examples 1 to 6, but not the composition according to the present invention was not good balance of flexural modulus and impact strength, in particular, it was confirmed that the poor in terms of weather resistance.

In particular, in the case of Comparative Examples 1, 2, 5, the weather resistance is maintained to some extent, Comparative Example 1 is too low flexural modulus and impact strength, Comparative Examples 2 and 5 are too low impact strength.

Claims (8)

With respect to 100 parts by weight of polyamide resin, 10 to 130 parts by weight of glass fiber, 3 to 26 parts by weight of thermoplastic elastomer, 0.1 to 0.7 parts by weight of benzotriazole- or benzophenone-based ultraviolet absorber, and a hindered amine radical scavenger Glass fiber reinforced polyamide resin composition comprising 0.1 to 0.7 parts by weight. The polyamide resin composition according to claim 1, wherein the polyamide resin is polyamide 6, polyamide 66, or a mixture thereof. The polyamide resin composition according to claim 1, wherein the glass fiber has a length of 3 to 6 mm and a diameter of 10 to 13 m. The polyamide resin composition of claim 1, wherein the thermoplastic elastomer is an ethylene-octene copolymer having 0.4-3 parts by weight of maleic anhydride monomer. The polyamide resin composition according to claim 1, wherein the ultraviolet absorber is 2- (2-hydroxy-3,5-di (1,1-dimethylbenzyl) phenyl) 2H-benzotriazole. The method of claim 1, wherein the hindered amine radical scavenger is poly (6-((1,1,3,3-tetramethylbutyl) amino) -1,3,5-triazine-2,4-diyl )-((2,2,6,6-tetramethyl-4-piperidyl) imino) -1,6-hexamethylene- (2,2,6,6-tetramethyl-4-piperidyl) Imino)), polyamide resin composition. The impact strength measured by ASTM evaluation method D256 is 8 kgcm / cm or more, the flexural modulus measured by ASTM evaluation method D790 is 40,000 kg / cm ² or more, and after 3000 hours of xenon arc weather ome measured by ASTM evaluation method D2565 E-value is 3 or less, The molded article manufactured from the polyamide resin composition of any one of Claims 1-6 characterized by the above-mentioned.  8. The molded article according to claim 7, wherein the molded article is a rain gutter or a manhole for road use.