KR19980043158A - Soundproofing resin composition for building interior materials and automobiles - Google Patents

Abstract

The present invention is 100 parts by weight of a polyolefin mixture consisting of 10 to 90% by weight of polyethylene and 90 to 10% by weight of an elastomer composed of ethylene-α-olefin copolymer, 100 to 300 parts by weight of inorganic filler, flame retardant additives and antimony oxide mixture 50 to 150 parts by weight, and relates to a resin composition, it characterized in that the stabilizer comprises 0.5 to 3 parts by weight of the composition while Genie the cold resistance, durability, heat resistance and mechanical properties of the combustible material, UL 94V ₀ there is no combustion at the time of melt drops The present invention provides a carpet backing agent and a soundproofing resin composition for automobiles having a flame retardancy of a grade and excellent in forming retention (dimension stability) and fluidity, processability, and sound insulation during extrusion molding, unlike general polyethylene resins.

Description

Soundproofing resin composition for building interior materials and automobiles

The present invention relates to a polyethylene interior resin, to an elastomer, an inorganic filler, a flame retardant additive and a resin stabilizer, to a building interior material and a vehicle sound insulation resin composition excellent in cold resistance, mechanical properties, shape retention, soundproofing and flame retardant.

The resin composition according to the present invention is usefully used in the carpet industry for applications such as door panels, engine room and vehicle interior covers, trunk and seat barrier walls, etc. .

Conventionally, asphalt, rubber-based synthetic resins, urethane foam, polyvinyl chloride, and the like have been used as carpets, backing agents and soundproofing materials for automobiles. For example, Japanese Patent Laid-Open No. 2-31952 (1990) proposed a resin composition prepared by mixing an elastomer and an inorganic filler with a polypropylene or ethylene vinyl acetate copolymer. In this case, heat resistance, dimensional stability, and sound insulation are improved, but the addition of a large amount of inorganic filler results in poor compatibility with the main material, resulting in poor tensile properties, poor hinge characteristics, and flammability. There is this. On the other hand, Japanese Patent Application Laid-Open No. 5-269906 (1993) improves the fluidity, flexibility, and tensile properties of a material by using a mixture of ethylene-1-butene-olefin and thermoplastic elastomer, but has problems in complicated vacuum forming and regeneration. There is a disadvantage that is a flammable material. European Patent Publication No. 338693 A1 (1989) discloses a sound insulation resin composition for automobiles prepared by mixing silicone foam, inorganic filler, stabilizer, etc. In this case, flame retardancy and heat resistance of the material are recognized, but durability and tensile properties are There is a disadvantage that the economy is low, because the raw material is expensive and the regeneration is impossible. Korean Patent Publication No. 91-2584 discloses a vehicle insulation composition prepared by mixing synthetic rubber, ethylene vinyl acetate copolymer, inorganic filler, asphalt, plasticizer, stabilizer, surfactant, anti-aging agent, liquid rubber, etc. It did not mention the effect on the heat resistance, tensile properties, and the use of silica, alumina, and the like as a filler may cause a decrease in soundproofing effect, there is a flammable material disadvantages.

Accordingly, an object of the present invention is to solve the above problems, having the cold resistance, durability, heat resistance, mechanical properties of the combustible material, has a flame retardancy of UL 94V ₀ grade without melt-fall during combustion, unlike the general polyethylene resin formation and maintainability It is to provide a carpet backing agent and a soundproofing resin composition for automobiles which are excellent in (dimension stability) and fluidity, processability and soundproofing properties in extrusion molding.

The resin composition according to the present invention comprises 100 parts by weight of a polyolefin mixture composed of 10 to 90% by weight of polyethylene and 90 to 10% by weight of an elastomer composed of an ethylene-α-olefin copolymer, 100 to 300 parts by weight of an inorganic filler, and a flame retardant additive. 50 to 150 parts by weight of antimony oxide mixture, 0.5 to 3 parts by weight of a stabilizer comprising a cold-resistance, mechanical properties, shape retention, sound insulation and flame retardancy excellent in building interior materials and automotive sound insulation material composition. In addition, the composition may further comprise 5 to 30 parts by weight of polyethylene wax.

The polyethylene component used in the polyolefin mixture of the present invention has a melt flow index measured by the ASTM D-1238 method of 0.05 to 5.0 g / 10 min, and a density measured by the ASTM D-792 method of 0.890 to 0.970 g / cm 3, preferably. Preferably from 0.890 to 0.950 g / cm 3, high density polyethylene, low density polyethylene, linear low density polyethylene or mixtures thereof may be used.

Elastomers have a Moycy viscosity (measured at ML _{1 + 4} at 121 ° C) of 10 to 70, preferably 10 to 50, and a density of 0.850 to ASTM D-792, as measured by ASTM D-1646. 0.920 g / cm 3.

When the elastomer is an ethylene-α-olefin copolymer, the content of α-olefin monomer is less than 10% by weight of ethylene-propylene, ethylene-butene, ethylene-hexene, ethylene-octene or a mixture thereof of 10 to 50% by weight. When a large amount of the inorganic filler is added, tensile strength and impact resistance are not good, and when it is more than 50% by weight, elongation is improved, but surface hardness and thermal stability are inferior.

The composition of the present invention includes calcium carbonate, barium sulfate or a mixture thereof as an inorganic filler to improve the sound insulation effect and surface hardness, 100 to 300 parts by weight, preferably 120 to 250 parts by weight based on 100 parts by weight of the polyolefin mixture If it is less than 100 parts by weight, the soundproofing effect of the composition is inferior, and if it exceeds 300 parts by weight, mechanical properties are deteriorated. It is preferable that the average particle diameter of an inorganic filler is about 0.7-10.0 micrometers, The thing surface-treated with silane or fatty acid can be used. An average particle diameter of less than 0.7 μm results in poor dispersibility with the base material, resulting in poor tensile properties. An average particle diameter of more than 10.0 μm has a problem in that dispersion is difficult and impact resistance is poor.

In the composition of the present invention, as a flame retardant component, a mixture of a flame retardant additive and antimony oxide is used in an amount of 50 to 150 parts by weight based on 100 parts by weight of the polyolefin mixture. . These are used by mixing 20 to 80 parts by weight of antimony oxide based on 100 parts by weight of the flame retardant additive. Examples of flame retardant additives include, for example, decabromodiphenyl ether, tetrabromodiphenoxybenzene, polydibromophenylene oxide, ethylene bistetrabromophthalimide, tetrabromophenol-A-bis (2, 3-dibromopropyl ether), aromatic and cycloaliphatic halogen compounds such as hexabromosoxy clododecane, or mixtures thereof may be used, and antimony trioxide or antimony pentoxide may be used as the antimony oxide.

The composition of the present invention is used as an additive 0.5 to 3 parts by weight based on 100 parts by weight of the polyolefin mixture in order to give the antioxidant effect of the composition during molding process and pentaerythryl-tetrakis (3- (3, 5-di -Tetrabutyl-4-hydroxyphenyl) -propionate, 4, 4'-thio-bis (6-t-butyl-3-methylphenol), phenol, 2, 4-bis (1, 1-dimethylethyl ) -Phosphite or mixtures thereof are selected and used.

In addition, the composition of the present invention may further include polyethylene wax in the composition of the present invention in order to improve the dispersion of the inorganic filler, 0.5 to 30 parts by weight of polyethylene wax can be used based on 100 parts by weight of the polyolefin mixture.

In addition to the other additives can be used by mixing the adhesive (Tackifier) in order to improve the adhesion performance of the sheet (Sheet), black powder containing a pigment, for example carbon black can be added, wherein the average particle diameter of the powder is 10 60 nm, Preferably it is 10-30 nm. If the average particle diameter of the powder is less than 10 nm or more than 60 nm, there is a problem of lowering dispersibility. In addition, carbon black may also serve as an ultraviolet absorber, and if necessary, a pigment other than black may be used, and in this case, may include a UV stabilizer.

The resin composition according to the present invention can be prepared by mixing at a temperature of 160 ~ 230 ℃ using a conventional mixing equipment such as a kneader, a Banbury mixer, or a twin screw extruder.

The resin composition according to the present invention prepared as described above has the cold resistance, durability, heat resistance, mechanical properties of the combustible material, has a flame retardancy of UL 94V ₀ grade without melting drop during combustion, and maintains the shape unlike general polyethylene resin Performance It has the property of excellent fluidity, processability and sound insulation in extrusion molding.

Therefore, the resin composition according to the present invention is useful for a backing agent in the carpet industry and an application product which is used for noise prevention purposes such as door panels, engine compartments and interior walls of vehicles, and barrier walls of trunks and seats in automobiles. Used.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, this invention is not limited by the following Example and a comparative example. In the examples and comparative examples below, polyethylene, elastomers, inorganic fillers, flame retardant additives, stabilizers and polyethylene waxes are used.

1. Polyethylene

PE: Density is 0.901 g / cm 3 and melt flow index is 0.9 g / 10 min (measured at 190 ° C / 2.16 kg) (Daelim Industrial Co., Ltd., Daelim Pori LV-05)

2. Elastomer

EL: density 0.88 g / cm 3, melt flow index 1.2 g / 10 min (measured at 190 ° C./2.16 kg), pattern viscosity 40 (measured at ML _{1 + 4} , 100 ° C.), butene content 20% Phosphorus ethylene-butene copolymer (Misui Petrochemical.Ind., Ltd. TAFMER A-1085)

3. Inorganic filler

MF (1): calcium carbonate (large product) with an average particle diameter of 6.8 mu m and a specific gravity of 4.2

MF (2): barium sulfate (large product) with an average particle diameter of 1.00 μm and a specific gravity of 4.2.

4. Flame retardant additive

FR (1): Bromine-containing aromatic compound (Albemarle Corp. Saytex) having a bromine content of 80% and a specific gravity of 3.25.

FR (2): Antimony trioxide with an average particle diameter of 0.7 µm and specific gravity of 5.6 (Cheil Flame Retardant Chemical Co., Ltd., HS)

5. Stabilizer

AO: pentaerythryl-tetrakis (3- (3,5-di-tetrabutyl-4-hydroxyphenyl) -propionate) (Ciba-Geigy, irganox)

6. Wax

WAX: Non-emulsified polyethylene wax (Lion Chemical, L-C 101 N) with specific gravity 0.916, softening point 150 ℃, average molecular weight 1,700

Example 1

120 parts by weight of MF (1), 120 parts by weight of MF (2), 90 parts by weight of FR (1), 30 parts by weight of FR (2), based on 100 parts by weight of a polyolefin compound composed of 40% by weight of PE and 60% by weight of EL, 1 part by weight of AO and 10 parts by weight of WAX were mixed in a dry mixer (Hensel mixer) having a temperature control, followed by melt mixing using a twin screw extruder. The barrel of the twin-screw extruder is capable of temperature control in 10 parts, the temperature range is 180 ~ 230 ℃, screw rotation speed was adjusted to 200 ~ 230rpm. The strand, which passed through the die of the extruder, was cooled in a cooling water tank, and cut into pellets that were easily secondary processed by a pelletizer. These pellets were fabricated using a compression molding machine (IKEGAI, screw diameter: 65 mm) to prepare specimens for molding, tensile properties test, cold resistance test, flame resistance test, and soundproof test. Extruded specimens were prepared. Physical properties were measured by the following test method.

(1) Tensile strength and elongation

Tested according to ASTM D-638. (Test piece: Type VI, Tensile speed: 50㎜ / min)

(2) cold resistance

The specimens were placed in a constant temperature bath at -20 ± 2 ° C, cooled for 24 hours, then taken out and left for about 30 minutes at room temperature, and then visually observed for abnormalities such as cracking and deformation. (Test piece: 100 × 100 mm, thickness: 1.5 mm)

(3) flame retardant

Five specimens (127 x 127 mm, thickness: 2 mm) were retrofitted by UL 94 vertical combustion test to determine flame retardancy and melt drop.

(4) acoustic transmission loss

The SAE Practice JI400 of ASTM E 90-87 was used to determine the average value of the acoustic transmission loss (dB) at a frequency of 1000 Hz.

In the measurement results of the physical properties, the tensile property is a factor related to the toughness of the composition. Cold resistance shows the shape retention characteristics of the composition at a constant temperature, flame retardancy is a measure of the self-extinguishability of the composition, V ₀ is superior to V ₂ and that flammability is not self-extinguishing. Acoustic transmission loss (dB) is a measure of the anti-noise effect according to the frequency of the composition. The larger this value, the better the sound insulation effect. The results of measuring the properties of the composition as described above were as Table 1 below.

TABLE 1

As can be seen from the above results, shape retention and tensile properties are excellent, and flame retardancy is maintained without melting drop.

EXAMPLES 2-6

Except that the amount and type of the composition used as Table 2 was carried out in the same manner as in Example 1, the results were as shown in Table 3.

TABLE 2

TABLE 3

[Comparative Examples 1-5]

Except that the amount and type of the composition used as shown in Table 4 was carried out in the same manner as in Example 1, the results were as shown in Table 5.

TABLE 4

TABLE 5

As can be seen from the above examples and comparative examples, the resin composition of the present invention prevents noise by adding an elastomer and a polyethylene wax, so that even when a large amount of inorganic filler is mixed, excellent shape retention and high acoustic transmission loss due to frequency are prevented. It was found that the effect was excellent and that the flame retardancy was maintained without melting drop by appropriately blending the flame retardant additive.

The resin composition of the present invention was excellent in noise-preserving effect due to its excellent shape retention and high acoustic transmission loss according to frequency even when a large amount of inorganic filler was mixed by adding an elastomer and polyethylene wax. It was found that no melt drop occurred and flame retardancy was maintained. Therefore, it has the cold resistance, durability, heat resistance and mechanical properties of flammable materials, and has flame retardancy of UL 94 V ₀ grade without melting drop during combustion, and unlike general polyethylene resin, shape retention (dimension stability) and fluidity during extrusion molding, It can be used as a carpet backing agent excellent in workability and soundproofing and a soundproofing material for automobiles.

Claims (10)

100 parts by weight of a polyolefin mixture consisting of 10 to 90% by weight of polyethylene and 90 to 10% by weight of an elastomer composed of an ethylene-α-olefin copolymer, 100 to 300 parts by weight of an inorganic filler, and 50 to 150 parts by weight of a flame retardant additive and an antimony oxide mixture. A resin composition having excellent cold resistance, mechanical properties, shape retention, sound insulation and flame retardancy, comprising 0.5 to 3 parts by weight of a stabilizer. The resin composition according to claim 1, wherein the polyethylene component is a high density polyethylene, a low density polyethylene, a linear low density polyethylene, or a mixture thereof having a melt flow index of 0.05 to 5.0 g / 10 minutes and a density of 0.890 to 0.970 g / cm 3. The method of claim 1, wherein the elastomer is an ethylene-α-olefin copolymer having a Moony viscosity of 10 to 70 and a density of 0.850 to 0.920 g / cm 3, wherein the content of the α-olefin monomer is 10 to 50% by weight. Resin composition characterized in that ethylene-propylene, ethylene-butene, ethylene-hexene, ethylene-octene or a mixture thereof. The resin composition according to claim 1, wherein the inorganic filler is calcium carbonate, barium sulfate or a mixture thereof having an average particle diameter of about 0.7 to 10 .mu.m. The resin composition according to claim 1, wherein the mixture of the flame retardant additive and antimony oxide is a mixture of 20 to 80 parts by weight of antimony oxide based on 100 parts by weight of the flame retardant additive. The flame retardant additive according to claim 5, wherein the flame retardant additive is decabromodiphenyl ether, tetrabromodiphenoxybenzene, polydibromophenylene oxide, ethylene bistetrabromophthalimide, tetrabromophenol-A-bis (2 , 3-dibromopropyl ether), aromatic and alicyclic halogen compounds such as hexabromocyclododecane or a mixture thereof. The resin composition according to claim 5, wherein the antimony oxide is antimony trioxide or antimony pentoxide. The method of claim 1, wherein the stabilizer is pentaerythryl-tetrakis (3- (3,5-di-tetrabutyl-4-hydroxyphenyl) -propionate, 4,4'-thio-bis (6- t-butyl-3-methylphenol), phenol, 2,4-bis (1,1-dimethylethyl) -phosphite or mixtures thereof. The resin composition according to any one of claims 1 to 8, wherein 0.5-30 parts by weight of polyethylene wax is added based on 100 parts by weight of the polyolefin mixture. 10. A molded article for building interior materials and automotive soundproofing materials having excellent cold resistance, mechanical properties, shape retention, soundproofing and flame retardancy prepared from the resin composition of claims 1 to 9.