KR20070032419A - Thermoplastic Resin Compositions having Excellent Impact Resistance - Google Patents

Abstract

Provided is a thermoplastic resin composition, which uses an impact resistance reinforcing agent applicable to both olefinic resins and styrenic resins, and has improved impact resistance. The thermoplastic resin composition comprises: a thermoplastic base resin; and 0.1-60 wt% of an impact resistance reinforcing agent. The impact resistance reinforcing agent comprises: (A) styrene-butadiene-styrene copolymer/ ethylene vinyl acetate; (B) styrene-butadiene-styrene copolymer/ ethylene-ethyl acrylate; (C) styrene-butadiene-styrene copolymer/alpha-olefin copolymer; (D) styrene-butadiene-styrene copolymer/ethylene-octene copolymer (polyolefin elastomer); (E) styrene-butadiene copolymer/ethylene-vinyl acetate; (F) styrene-butadiene copolymer/ethylene-ethyl acrylate; (G) styrene-butadiene copolymer/ alpha-olefin copolymerl or (H) styrene-butadiene copolymer/ethylene-octene copolymer (polyolefin elastomer), wherein each component is used in a weight ratio of 99:1 to 1:99.

Description

Thermoplastic Resin Compositions having Excellent Impact Resistance

Figure 1 is an electron micrograph of the impact reinforcement modifier pellet prepared using the SBS / EVA (60/40) blend according to the present invention. (Example 3)

Figure 2 is an electron micrograph of the impact reinforcement modifier pellet prepared using the SBS / EEA (60/40) blend according to the present invention. (Example 3)

Figure 3 is an electron micrograph of the impact reinforcement modifier pellets prepared using the SBS / alpha-olefin copolymer (60/40) blend according to the present invention. (Example 3)

Figure 4 is an electron micrograph of the impact reinforcement modifier pellet prepared using the SBS / ethylene- octene copolymer (60/40) blend according to the present invention. (Example 3)

5 is an electron micrograph of the impact reinforcement modifier pellet prepared using the SBC / EVA (60/40) blend according to the present invention. (Example 3)

The present invention relates to a thermoplastic resin compound composition having excellent impact resistance.

Generally, styrene- as an impact modifier for high density polyethylene (HDPE), homo polypropylene (HPP), general polystyrene (GPPS), high impact polystyrene (HIPS), flame retardant high impact polystyrene (HIPS), styrene acrylonitrile (SAN) Butadiene-styrene copolymer (SBS), hydrogenated styrene butadiene styrene block copolymer (SEBS), ethylene-ethyl acrylate (EEA), α-olefin copolymer, polyolefin elastomer, ethylene-propylene monomer (EPM) and ethylene propylene diene Copolymer resin (EPDM) and the like are used.

However, according to the related art, an olefinic impact modifier is used in an olefinic polymer, and a styrene impact modifier has a disadvantage of being used only in a styrene impact modifier. Hydrogenated styrene butadiene styrene block copolymers (SEBS) can be used in both olefins and styrenes, but are not widely used because they are expensive. In particular, low cost impact modifiers with good performance in both olefinic and styrene based polymers have not been developed.

Accordingly, it is an object of the present invention to provide an impact modifier that can be used in both olefinic and styrenic polymers and an improved impact resistant thermoplastic resin composition comprising the same, in order to solve the problems of the prior art as described above.

The above object of the present invention is an amount of (A) styrene-butadiene-styrene copolymer (SBS) / ethylene-vinyl acetate (EVA), (B) styrene-butadiene-styrene copolymer (SBS) / ethylene-ethyl as an impact modifier. Acrylate (EEA), (C) styrene-butadiene-styrene copolymer (SBS) / alpha-olefin copolymer, (D) styrene-butadiene-styrene copolymer (SBS) / ethylene-octene copolymer (polyolefin elastomer), (E) styrene-butadiene copolymer (SBC) / ethylene-vinyl acetate (EVA), (F) styrene-butadiene copolymer (SBC) / ethylene-ethyl acrylate (EEA), (G) styrene-butadiene copolymer ( Surprisingly by the present inventors it can be achieved by thermoplastic resin compositions containing SBC) / alpha-olefin copolymers, or (H) styrene-butadiene copolymers (SBC) / ethylene-octene copolymers (polyolefin elastomers). Found.

The base resin of the impact resistant thermoplastic resin composition of the present invention may be selected from polyethylene polymers, polypropylene polymers, polystyrene polymers, polyester polymers or polyamide polymers, and preferred examples thereof include high density polyethylene (HDPE) and low density polyethylene. (LDPE), linear low density polyethylene (LLDPE), homopolypropylene (HPP), polypropylene copolymer (PPC), general polystyrene (GPPS), high impact polystyrene (HIPS), styrene acrylonitrile (SAN), polyethylene terephthalate (PET), nylon 6, nylon 66 or polycarbonate (PC).

The ratio between the two components constituting the impact modifier according to the invention is selected in the range of 99: 1 to 1:99, preferably 5: 1 to 1: 5, more preferably 5: 1 to 1: 1. It can be appropriately selected by those skilled in the art within the range that the impact resistance of the obtained thermoplastic resin composition is reinforced to a desired degree while not adversely affecting other physical properties.

The amount of impact modifier in the resin composition according to the present invention is selected from an amount of 0.1 to 60% by weight, preferably 0.5 to 50% by weight, more preferably 1 to 30% by weight, based on the weight of the total composition. It can be appropriately selected by those skilled in the art in consideration of the production cost in a range that does not adversely affect other physical properties of the resin while reinforcing the impact resistance of the thermoplastic resin composition to a desired degree.

According to the present invention, the resin composition (A), (B), (C), (D), (E), (F), (G) or (H) as an impact resistant reinforcing agent is homopropylene (HPP), Thermoplastic resins having improved impact resistance by physically mixing thermoplastic resins such as general polystyrene (GPPS), high impact polystyrene (HIPS), and styrene acrylonitrile (SAN) without applying heat, and then compounding the mixture by melting. It can be obtained <Method I>.

Otherwise, the resin composition (A), (B), (C), (D), (E), (F), (G) or (H) as the impact reinforcing agent is first melted to give a modifier for impact reinforcement. High density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), homopolypropylene (HPP), polypropylene copolymer (PPC), ordinary polystyrene (GPPS), high impact polystyrene (HIPS) , Styrene acrylonitrile (SAN), polyethylene terephthalate (PET), nylon 6, nylon 66 or polycarbonate (PC) or the like can be mixed to obtain an impact resistant thermoplastic resin (method II).

The impact resistant thermoplastic resin composition of the present invention obtained by the aforementioned method I or II is preferably composed of a matrix.

During the preparation of the compound resin composition described above, minerals such as calcium carbonate, blowing agents, flame retardants, lubricants, dispersants, antistatic agents, UV stabilizers, thermal stabilizers, antioxidants, ultraviolet absorbers, lubricants, crosslinkers, conductive agents, fillers, reinforcing agents, carbon Impact resistant thermoplastics may be obtained by adding one or more components selected from various additives such as blacks, colorants, reactive catalysts, and the like.

The flame retardant may comprise a chlorine-based flame retardant and an inorganic flame retardant, in a preferred embodiment a mixture of 0.1-50% by weight of chlorine-based flame retardant and 0.1-50% by weight of inorganic flame retardant is used as flame retardant.

The chlorine-based flame retardant may be preferably selected from hexachlorocyclopentadiene, methylcyclopentadiene, dicyclopentadiene, cyclohexadiene, chlorinated polyethylene resin, chlorinated paraffin and cyclodecadiene having a chlorine content of 10 to 90% by weight. have.

The inorganic flame retardant is phosphorus, nitrogen, stearic acid, oleic acid, silane coupling agent, titanate, zirconium, magnesium hydroxide, alumina hydrate compound, antimony oxide, sodium antimonate, iron oxide, zinc oxide, triphenylphosphate , Decabromodiphenyl-based, brominated epoxy, polytribromostyrene, poly (dibromophenylene oxide), ethylenebispentabromodiphenyl and tetrabromobisphenol A can be preferably selected. .

In a preferred embodiment, the thermoplastic resin composition, in addition to the flame retardant, 0.1 to 30% by weight of the flame retardant synergist and 0.1 to 60% by weight of the impact modifier of the rubber component, 0.1 to 40% by weight of the olefinic impact supplement; And further containing foaming agent, wax, antistatic agent, UV stabilizer, antioxidant, ultraviolet absorber, lubricant, crosslinking agent, conductive agent, filler, reinforcing agent, dispersant, thermal stabilizer, reactive catalyst and colorant in amounts of 0.001 to 20% by weight, respectively. Can be.

The wax is at least one metal stearate selected from calcium, zinc, magnesium or barium stearate, ethyl acrylate copolymer, polypropylene or polyethylene polyhydric alcohol fatty acid, polydimethylsiloxane, stearic acid, ethylenebis stearamide, bis It may be preferably selected from the group consisting of (stearoyl) ethylenediamine and chlorate paraffin, but is not limited thereto.

The flame retardant synergist may be preferably selected from the group consisting of antimony trioxide, phosphorus compound, zinc oxide, titanium dioxide, silica and carbon black, but is not limited thereto.

In one exemplary embodiment of the above method I, SBS or SBC and EVA, α-olefin copolymer or ethylene-octene copolymer or ethylene-ethyl acrylate (EEA) is 99: 1 to 1:99, preferably 5: 1 to 1: 5, more preferably 5: 1 to 1: 1 weight ratio physically mixed without applying heat to prepare a shock-resistant reinforcing agent, high density polyethylene (HDPE), low density polyethylene (LDPE), linear Low Density Polyethylene (LLDPE), Homopolypropylene (HPP), Polypropylene Copolymer (PPC), General Polystyrene (GPPS), High Impact Polystyrene (HIPS), Styrene Acrylonitrile (SAN), Polyethylene Terephthalate (PET), Nylon 6, nylon 66 or polycarbonate (PC), in an amount of 0.1 to 60% by weight, preferably 0.5 to 50% by weight, more preferably 1 to 30% by weight, based on the weight of the total thermoplastic composition, Double screw The extruder is melt blended at an extruder temperature of 130 to 300 ° C. at a raw material feed rotation speed of 0 to 100 rpm and a screw rotation speed of 0 to 500 rpm and using a cutter, an impact resistant thermoplastic resin composition is obtained in the form of pellets.

In another exemplary embodiment of Method I, SBS or SBC and EVA, α-olefin copolymer or ethylene-octene copolymer or ethylene-ethyl acrylate (EEA) are thermally heated at a weight ratio of 5: 1 to 1: 5. Physically mixing without addition of a modifier for impact modifiers is prepared, which is high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), homopolypropylene (HPP), polypropylene copolymer (PPC), In general polystyrene (GPPS), high impact polystyrene (HIPS), styrene acrylonitrile (SAN), polyethylene terephthalate (PET), nylon 6, nylon 66 or polycarbonate (PC), the modifier is based on the weight of the entire thermoplastic composition. In an amount of 1 to 30% by weight, and the resulting mixture is mixed with the above-mentioned minerals, blowing agents, flame retardants, lubricants, dispersants, antistatic agents, UV stabilizers, heat stabilizers, antioxidants, Raw material feed rotation speed at the extruder temperature 130-300 ° C. using a double screw extruder with at least one component selected from various additives such as sun absorbers, lubricants, crosslinkers, conductive agents, fillers, reinforcing agents, carbon blacks, colorants, reactive catalysts, etc. To 100 rpm, screw rotational speed from 0 to 500 rpm to melt blend and use a cutter to obtain an impact resistant thermoplastic resin composition in the form of pellets with flame retardancy.

In one embodiment of the above method II, SBS or SBC and EVA, α-olefin copolymer, ethylene-octene copolymer or EEA are 99: 1 to 1:99, preferably 5: 1 to 1: 5, more Preferably, the mixture is mixed at a weight ratio of 5: 1 to 1: 1, and melt blended using a double screw extruder at an extruder temperature of 130 to 300 ° C. at a raw material feed rotation speed of 0 to 100 rpm and a screw rotation speed of 0 to 500 rpm. To obtain a modifier for impact modifiers as pellets.

0.1 to 60% by weight, preferably 0.5 to 50% by weight, more preferably 1 to 1, of the modifier in HDPE, LDPE, LLDPE, HPP, PPC, GPPS, HIP, SAN, PET, Nylon 6, Nylon 66 or PC. 30 wt% of the mixture, melt blended at an extruder temperature of 130 to 300 ° C. with a double screw extruder at a raw material feed rotation speed of 0 to 100 rpm, a screw rotation speed of 0 to 500 rpm, and using a cutter to form pellets. A thermoplastic resin composition is obtained.

In another embodiment of Method II, the modifier is preferably in an amount of 1 to 30% by weight in HDPE, LDPE, LLDPE, HPP, PPC, GPPS, HIP, SAN, PET, Nylon 6, Nylon 66 or PC. Mixed with an inorganic resin such as calcium carbonate, foaming agent, flame retardant, lubricant, dispersant, antistatic agent, UV stabilizer, thermal stabilizer, antioxidant, carbon black, colorant, reactive catalyst, etc. A screw extruder is used to melt blend at an extruder temperature of 130 to 300 ° C. at a raw material feed rotation speed of 0 to 100 rpm and a screw rotation speed of 0 to 500 rpm, and a cutter is used to obtain a thermoplastic resin composition in pellet form.

In the methods I and II for preparing the resin composition according to the present invention, the conditions such as the type and form of the device for mixing or melt blending, the feed rotation speed, the screw speed and the extrusion temperature are in accordance with conventional methods used in the art It may be appropriately selected by those skilled in the art.

In the above methods I and II, the thermoplastic resin or flame retardant thermoplastic resin composition is preferably ethylene-vinyl acetate (EVA) containing 1 to 99% by weight of vinyl acetate, ethylene containing 1 to 99% by weight of ethyl acrylate. -Ethyl acrylate (EEA), ethylene-octene copolymer, alpha-olefin copolymer or polyolefin elastomer component in an amount of 0.1 to 60% by weight.

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the present invention thereto.

Example 1

HPP, GPPS, HIPS, and SAN resins containing impact modifier component (A) composed of various ratios were prepared by Method I, and the thermoplastic resin containing no modifier component of the present invention, impact strength, flexural modulus, tensile strength, Physical properties such as elongation at break and melting point were compared (Table 1 to Table 4).

In addition, HIPS resins containing the impact modifier components (A), (B), (D), (E), and (G) of the present invention, respectively, in a proportion, are prepared to contain only SBS instead of the modifier component of the present invention. The resin composition was compared with physical properties such as impact strength, flexural modulus, tensile strength, elongation at break and melting point (Table 5).

The raw material feed rotation speed is 0-300 at a compound melting temperature of 130-300 ° C after physically mixing the impact modifier components as described in Tables 1 to 4 without applying heat with thermoplastic base resins (HPP, GPPS, HIPS, SAN). Melt blending was performed at 100 rpm, screw rotation speed of 0 to 500 rpm, and a resin composition was obtained in pellet form using a cutter.

Properties of HPP Containing Impact Resistant (A) ingredient weight% Izod impact strength (kgcm / cm) ⁽¹⁾ Flexural Modulus (kg / cm ² ) ⁽²⁾ Tensile Strength (kg / cm ² ) ⁽³⁾ Elongation at Break (%) ⁽⁴⁾ Melting point (℃) HPP 100 3 16,000 350 10 165 SBS 100 NB - 380 650 - EVA 100 NB - 220 700 87 HPP / SBS / EVA 80/10/10 20 9,010 265 520 165, 86 HPP / SBS / EVA 80/12/8 30 9,870 260 550 165, 87 HPP / SBS / EVA 80/14/6 35 9,800 256 540 165, 88 ⁽¹⁾ measured according to ASTM D256 / ⁽²⁾ measured according to ASTM D790 / ⁽³⁾ measured according to ASTM D638 / ⁽⁴⁾ measured according to ASTM D638

Properties of HPP by Types of Impact Resistant ingredient weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting Point (℃) HPP / SBS / EVA 80/14/6 33 6,797 265 > 500 87 HPP / SBC / EVA 80/14/6 30 6,872 268 > 500 87 HPP / SBS / EEA 80/14/6 54 6,787 261 > 500 98 HPP / SBS / α-olefin copolymer 80/14/6 65 6,651 259 > 500 66 HPP / SBS / ethylene-octene copolymer 80/14/6 68 6,511 256 > 500 76 HPP / SBS (Compare) 80/20 56 6,815 262 > 500 - HPP / SEBS (Compare) 80/20 77 6,872 229 > 500 - HPP / ethylene-octene copolymer (comparative) 80/20 64 5,910 238 > 500 76 ⁽¹⁾ measured according to ASTM D256 / ⁽²⁾ measured according to ASTM D790 / ⁽³⁾ measured according to ASTM D638 / ⁽⁴⁾ measured according to ASTM D638

It can be seen from the experimental results shown in the table that the impact strength was improved by the impact resistance modifier according to the present invention, the impact resistance modifier using the ethylene-octene copolymer had the highest impact strength, and the composition of the present invention The use of the impact reinforcing agent having an excellent impact strength compared to the case of the comparative example using only SBS or ethylene-octene copolymer. In addition, in the case of the comparative example using the SEBS, the impact strength is somewhat lowered, but when using the impact-resistant reinforcing agent having the composition of the present invention showed an excellent tensile strength.

Physical Properties of GPPS Containing Impact Resistant (A) ingredient weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) GPPS 100 One 33,200 470 4 - GPPS / SBS / EVA 80/10/10 7.5 26,500 300 15 88 GPPS / SBS / EVA 80/12/8 10.6 27,800 315 24 87 GPPS / SBS / EVA 80/14/6 11.0 28,300 320 28 86

Properties of HIPS Containing Impact Resistant (A) ingredient weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) HIPS 100 11 23,500 255 63 - HIPS / SBS / EVA 100 / 1.5 / 1.5 15.4 22,700 240 100 88 HIPS / SBS / EVA 100 / 1.8 / 1.2 19.4 23,000 245 120 87 HIPS / SBS / EVA 100 / 2.1 / 0.9 18.7 23,400 248 136 88

Physical Properties of SAN Containing Impact Resistant (A) ingredient weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) SAN 100 One 53,000 755 6 - SAN / SBS / EVA 80/10/10 7.2 38,500 510 18 88 SAN / SBS / EVA 80/12/8 9.5 37,000 535 19 87 SAN / SBS / EVA 80/14/6 9.8 38,000 540 25 87

Properties of HIPS According to the Type of Impact Resistant ingredient weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) HIPS / SBS / EVA (A) 100 / 1.8 / 1.2 18.4 23,000 245 120 87 HIPS / SBC / EVA (E) 100 / 1.8 / 1.2 15.5 23,700 247 100 87 HIPS / SBS / EEA (B) 100 / 1.8 / 1.2 18.6 22,900 230 125 98 HIPS / SBS / α-olefin copolymer (G) 100 / 1.8 / 1.2 19.8 23,100 235 124 66 HIPS / SBS / ethylene-octene copolymer (D) 100 / 1.8 / 1.2 20.3 22,900 237 140 76 HIPS / SBS (Compare) 100/3 15.6 23,500 245 90 -

It can be seen from the experimental results of Tables 1 to 4 that the impact strength is improved by the impact reinforcing agent according to the present invention, and that the impact strength is improved as the butadiene content is increased.

From the results in Table 5, the impact modifier (G) using the ethylene-octene copolymer had the highest impact strength, and the impact modifier having the composition of the present invention had a better impact than the comparative example using only SBS. Strength is shown.

The use of SBS in the components of the impact modifier composition resulted in better impact resistance than the use of SBC.

Example 2

As shown in Table 6 to Table 10, the impact reinforcing agent is mixed with the base resin, and 0.1 to 40% by weight of chlorine-based flame retardant, 0.1 to 30% by weight of inorganic flame retardant, 0.1 to 30% by weight of flame-retardant synergist, and the impact of rubber component Example 1 except for the physical mixing of 0.1 to 40% by weight, and 0.001 to 10% by weight of each of wax, carbon black, colorant, reactive catalyst, antistatic agent, UV stabilizer, antioxidant, dispersant and heat stabilizer In the same manner as in the thermoplastic resin composition was obtained. The result is as follows.

Properties of Flame Retardant HPP Containing Impact Resistant (A) ingredient weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) Flame Retardant ⁽⁵⁾ HPP / SBS / EVA 80/10/10 15 12,238 254 200 166 V2 HPP / SBS / EVA 80/12/8 24 11,563 235 240 165 V2 HPP / SBS / EVA 80/14/6 28 10,876 224 250 166 V2 ⁽⁵⁾ measured according to ASTM UL94

Properties of Flame Retardant HPP According to Types of Impact Resistant ingredient weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) Flame Retardant ⁽⁵⁾ HPP / SBS / EVA 80/14/6 25 7,659 232 200 86 V2 HPP / SBC / EVA 80/14/6 45 7,457 238 212 87 V2 HPP / SBS / EEA 80/14/6 48 7,683 230 220 98 V2 HPP / SBS / α-olefin copolymer 80/14/6 53 7,821 227 245 67 V2 HPP / SBS / ethylene-octene copolymer 80/14/6 60 7,365 229 235 75 V2 HPP / SBS (Compare) 80/20 48 7,935 231 232 - V2 HPP / SEBS (Compare) 80/20 65 7,365 197 243 - V2 HPP / ethylene-octene copolymer (comparative) 80/20 57 7,216 195 246 76 V2 ⁽¹⁾ measured according to ASTM D256 / ⁽²⁾ measured according to ASTM D790 / ⁽³⁾ measured according to ASTM D638 / ⁽⁴⁾ measured according to ASTM D638

It can be seen from the experimental results shown in the table that the impact strength was improved by the impact resistance modifier according to the present invention, the impact resistance modifier using the ethylene-octene copolymer had the highest impact strength, and the composition of the present invention The use of the impact reinforcing agent having an excellent impact strength compared to the case of the comparative example using only SBS or ethylene-octene copolymer. In addition, in the case of the comparative example using the SEBS, the impact strength is somewhat lowered, but when using the impact-resistant reinforcing agent having the composition of the present invention showed an excellent tensile strength.

Properties of Flame Retardant GPPS Containing Impact Resistant (A) ingredient weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) Flame Retardant ⁽⁵⁾ GPPS / SBS / EVA 80/10/10 5.5 26,500 278 15 88 V2 GPPS / SBS / EVA 80/12/8 8.8 24,800 305 17 87 V2 GPPS / SBS / EVA 80/14/6 8.5 25,300 310 20 87 V2

Properties of Flame Retardant HIPS Containing Impact Resistant (A) ingredient weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) Flame Retardant ⁽⁵⁾ HIPS / SBS / EVA 100 / 1.5 / 1.5 8.5 22,100 225 87 87 V0 HIPS / SBS / EVA 100 / 1.8 / 1.2 9.5 22,900 226 85 87 V0 HIPS / SBS / EVA 100 / 2.1 / 0.9 9.8 22,800 229 88 87 V0

Properties of Flame Retardant SAN Containing Modifier (A) ingredient weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) Flame Retardant ⁽⁵⁾ SAN / SBS / EVA 80/10/10 6.2 36,000 500 14 88 V2 SAN / SBS / EVA 80/12/8 7.8 36,500 510 15 87 V2 SAN / SBS / EVA 80/14/6 7.5 37,000 515 18 87 V2

Properties of Flame Retardant HIPS According to the Type of Modifier ingredient weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) Flame retardant HIPS / SBS / EVA (A) 100 / 1.8 / 1.2 9.5 22,900 226 85 87 V0 HIPS / SBC / EVA (E) 100 / 1.8 / 1.2 8.5 23,400 238 65 87 V0 HIPS / SBS / EEA (B) 100 / 1.8 / 1.2 9.2 22,300 224 87 99 V0 HIPS / SBS / α-olefin copolymer (G) 100 / 1.8 / 1.2 9.9 22,500 230 89 66 V0 HIPS / SBS / ethylene-octene copolymer (D) 100 / 1.8 / 1.2 10.2 22,700 231 86 76 V0 HIPS / SBS (Compare) 100 / 3.0 8.6 23,300 237 72 - V0

It can be seen from the experimental results shown in the table that the impact strength was improved by the impact resistant reinforcing agent according to the present invention, and the impact strength was improved as the content of butadiene was increased.

From the results in Table 10, the impact modifier (G) using the ethylene-octene copolymer had the highest impact strength, and the impact modifier having the composition of the present invention had a better impact than the comparative example using only SBS. Strength is shown.

The use of SBS in the components of the impact modifier composition resulted in better impact resistance than the use of SBC.

Example 3

The impact feed agent component (A), (B), (C), (D), (E) or (G) according to the present invention is supplied at a feed rate of 0 to 100 rpm at an extruder temperature of 130 to 300 °, Melt blended at a screw rotation speed of 0 to 500 rpm and using a cutter to obtain a modifier for impact resistance reinforcement in pellet form. The electron micrograph is shown in FIGS.

As a result of the electron microscope observation of FIGS. 1 to 5, it can be seen that the interface shape is a single surface in all compounds, and the compatibility between the compounds is excellent.

Example 4

20 parts by weight of the impact reinforcing modifier (A) having a weight ratio of 60/40 of the two components obtained in Example 3, together with the base resin HPP, GPPS, HIPS or 80 parts by weight of SAN, was supplied with raw materials at an extruder temperature of 130 to 300 ° C. Melt blended at a rotational speed of 0 to 100 rpm and a screw rotational speed of 0 to 500 rpm and prepared in pellet form using a cutter. The results are shown in Tables 11 to 14.

HIPS resins containing the modifier components (A), (B), (D), (E) and (G) for impact reinforcement of the present invention prepared in the same manner, respectively, were prepared to produce a modifier component of the present invention. Instead, the resin composition containing only SBS and physical properties such as impact strength, flexural modulus, tensile strength, elongation at break and melting point were compared (Table 15).

Properties of HPP Containing Modifier for Impact Reinforcement (A) HPP weight% Modifier weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) 80 20 40 9,950 258 568 165, 87

Properties of HPP by Types of Impact Resistant ingredient weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) HPP / SBS / EVA (A) 80/20 35 6,697 267 > 500 86 HPP / SBC / EVA (E) 80/20 33 6,831 265 > 500 88 HPP / SBS / EEA (B) 80/20 58 6,821 265 > 500 98 HPP / SBS / α-olefin copolymer (C) 80/20 68 6,735 260 > 500 65 HPP / SBS / Ethylene-Octene Copolymer (D) 80/20 73 6,648 257 > 500 77 HPP / SBS (Compare) 80/20 56 6,815 262 > 500 - HPP / SEBS (Compare) 80/20 77 6,872 229 > 500 - HPP / ethylene-octene copolymer (comparative) 80/20 64 5,910 238 > 500 77 ⁽¹⁾ measured according to ASTM D256 / ⁽²⁾ measured according to ASTM D790 / ⁽³⁾ measured according to ASTM D638 / ⁽⁴⁾ measured according to ASTM D638

It can be seen from the experimental results shown in the table that the impact strength was improved by the impact resistance modifier according to the present invention, the impact resistance modifier using the ethylene-octene copolymer had the highest impact strength, and the composition of the present invention The use of the impact reinforcing agent having an excellent impact strength compared to the case of the comparative example using only SBS or ethylene-octene copolymer. In addition, in the case of the comparative example using the SEBS, the impact strength is somewhat lowered, but when using the impact-resistant reinforcing agent having the composition of the present invention showed an excellent tensile strength.

And all the physical properties were higher than in the case of Example 1. Therefore, the impact modifier according to the present invention, rather than the compound after physical mixing, the impact modifier resin composition (A), (B), (C), (D), (E), (F), (G) ) Or (H) can be compounded first and then compounded with HPP.

Physical Properties of GPPS Containing Modifiers for Impact Reinforcement (A) HPP weight% Modifier weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) 80 20 11.2 28,800 320 34 87

Physical Properties of HIPS Containing Modifier (A) for Impact Reinforcement HPP weight% Modifier weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) 80 20 20.2 23,300 240 135 87

Physical properties of SAN containing impact modifier (A) HPP weight% Modifier weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) 80 20 9.8 37,200 530 21 87

Physical properties of HIPS according to the type of modifier for impact resistance Ingredient (60/40) HIPS weight% Modifier weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) SBS / EVA (A) 80 20 20.2 23,300 240 135 87 SBC / EVA (E) 80 20 18.5 23,500 246 127 87 SBS / EEA (B) 80 20 20.6 23,000 235 130 98 SBS / α-olefin copolymer (G) 80 20 20.8 23,300 237 136 66 SBS / ethylene-octene copolymer (D) 80 20 21.2 23,000 235 145 75 SBS (Compare) 80 20 18.4 23,000 230 125 -

From the experimental results shown in the above table, it can be seen that the impact strength was improved by the impact resistance modifier according to the present invention, and the impact resistance modifier (G) using the ethylene-octene copolymer had the highest impact strength. The use of the impact reinforcing agent having the composition of the invention showed superior impact strength compared to the case of the comparative example using only SBS.

The use of SBS in the components of the impact modifier composition resulted in better impact resistance than the use of SBC.

Example 5

When mixing the impact-resistant reinforcement modifier obtained in Example 3 with the base resin, 0.1 to 40% by weight of chlorine-based flame retardant, 0.1 to 30% by weight of inorganic flame retardant, 0.1 to 30% by weight of flame retardant synergist, the impact of rubber components Example 1 except for the physical mixing of 0.1 to 40% by weight, and 0.001 to 10% by weight of each of wax, carbon black, colorant, reactive catalyst, antistatic agent, UV stabilizer, antioxidant, dispersant and heat stabilizer In the same manner as in the thermoplastic resin composition was obtained. The result is as follows.

Properties of Flame Retardant HPP Containing Modifier for Impact Reinforcement (A) HPP weight% Modifier weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) Flame retardant 80 20 31 10,100 237 120 165, 87 V2

Properties of Flame Retardant GPPS Containing Modifier (A) for Impact Reinforcement HPP weight% Modifier weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) Flame retardant 80 20 8.0 23,500 300 15 87 V2

Properties of Flame Retardant HIPS Containing Modifier (A) for Impact Reinforcement HPP weight% Modifier weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) Flame retardant 80 20 9.8 22,500 228 96 87 V0

Properties of flame retardant SAN containing impact modifier (A) HPP weight% Modifier weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) Flame retardant 80 20 8.5 35,700 515 13 87 V2

Properties of flame retardant HIPS according to the type of modifier for impact reinforcement Ingredient (60/40) HIPS weight% Modifier weight% Izod impact strength (kgcm / cm) Flexural modulus (kg / cm ² ) Tensile Strength (kg / cm ² ) Elongation at Break (%) Melting point (℃) Flame retardant SBS / EVA (A) 100 3 9.8 22,500 228 96 87 V0 SBC / EVA (E) 100 3 8.8 22,600 229 76 87 V0 SBS / EEA (B) 100 3 9.7 22,600 227 95 99 V0 SBS / α-olefin copolymer (G) 100 3 10.0 22,400 229 93 66 V0 SBS / ethylene-octene copolymer (D) 100 3 10.2 22,600 227 96 76 V0 SBS (Compare) 100 3 8.6 23,300 229 72 - V0

From the experimental results shown in the above table, it can be seen that the impact strength was improved by the impact resistance modifier according to the present invention, and the impact resistance modifier (G) using the ethylene-octene copolymer had the highest impact strength. The use of the impact reinforcing agent having the composition of the invention showed superior impact strength compared to the case of the comparative example using only SBS.

The use of SBS in the components of the impact modifier composition resulted in better impact resistance than the use of SBC.

According to the present invention, by using a modifier for impact reinforcement having a specific component, a thermoplastic resin composition and a flame retardant thermoplastic resin composition with remarkably enhanced impact strength are obtained, and the impact modifier for impact reinforcement is both an olefin-based and styrene-based resin composition. Both can be used for the purpose of improving the impact resistance.

Claims (11)

(A) styrene-butadiene-styrene copolymer (SBS) / ethylene-vinyl acetate (EVA), (B) styrene-butadiene-styrene copolymer, each component having a weight ratio of 99: 1 to 1:99 SBS) / ethylene-ethyl acrylate (EEA), (C) styrene-butadiene-styrene copolymer (SBS) / alpha-olefin copolymer, (D) styrene-butadiene-styrene copolymer (SBS) / ethylene-octene air Copolymer (polyolefin elastomer), (E) styrene-butadiene copolymer (SBC) / ethylene-vinyl acetate (EVA), (F) styrene-butadiene copolymer (SBC) / ethylene-ethyl acrylate (EEA), (G) Styrene-butadiene copolymer (SBC) / alpha-olefin copolymer, or (H) styrene-butadiene copolymer (SBC) / ethylene-octene copolymer (polyolefin elastomer) Impact thermoplastic resin composition. The impact resistant thermoplastic resin composition according to claim 1, wherein the base resin of the thermoplastic resin is selected from the group consisting of polyethylene polymer, polypropylene polymer or polystyrene polymer, polyester polymer and polyamide polymer. The impact resistant thermoplastic resin composition according to claim 1 or 2, which is obtained by physically mixing the impact resistant agent with the base resin without applying heat and then melt blending the obtained composition. The compound according to claim 1 or 2, wherein the resin composition (A), (B), (C), (D), (E), (F), (G) or (H) as an impact modifier is first melt compounded. Modifiers for impact reinforcement have been prepared and then made into high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), homopolypropylene (HPP), polypropylene copolymer (PPC), general polystyrene (GPPS), An impact resistant thermoplastic resin prepared by melt mixing with a base resin such as high impact polystyrene (HIPS), styrene acrylonitrile (SAN), polyethylene terephthalate (PET), nylon 6, nylon 66 or polycarbonate (PC). The method of claim 3 or 4, 0.1 to 50% by weight of chlorine-based flame retardant, 0.1 to 50% by weight of inorganic flame retardant, 0.1 to 30% by weight of flame retardant synergist and 0.1 to 60% by weight of impact modifier of rubber component, olefinic impact supplement 0.1 to 40 weight percent; And flame retardant containing a foaming agent, a wax, an antistatic agent, a UV stabilizer, an antioxidant, a UV absorber, a lubricant, a crosslinking agent, a conductive agent, a filler, a reinforcing agent, a dispersant, a heat stabilizer, a reactive catalyst and a coloring agent in an amount of 0.001 to 20% by weight Impact resistant thermoplastic resin having a. (A) Styrene-butadiene-styrene copolymer (SBS) / ethylene-vinyl acetate (EVA) according to claim 3 or 4, wherein each component is a weight ratio of 5: 1 to 1: 5 as an impact modifier. Styrene-butadiene-styrene copolymer (SBS) / ethylene-ethyl acrylate (EEA), (C) styrene-butadiene-styrene copolymer (SBS) / alpha-olefin copolymer, (D) styrene-butadiene-styrene copolymer (SBS) / ethylene-octene copolymer (polyolefin elastomer), (E) styrene-butadiene copolymer (SBC) / ethylene-vinyl acetate (EVA), (F) styrene-butadiene copolymer (SBC) / ethylene-ethyl acryl 0.1 to 60% by weight of latex (EEA), (G) styrene-butadiene copolymer (SBC) / alpha-olefin copolymer, or (H) styrene-butadiene copolymer (SBC) / ethylene-octene copolymer (polyolefin elastomer) And a thermoplastic resin composition containing an impact resistant thermoplastic resin. (A) Styrene-butadiene-styrene copolymer (SBS) / ethylene-vinyl acetate (EVA) according to claim 3 or 4, wherein each component is a weight ratio of 5: 1 to 1: 5 as an impact modifier. Styrene-butadiene-styrene copolymer (SBS) / ethylene-ethyl acrylate (EEA), (C) styrene-butadiene-styrene copolymer (SBS) / alpha-olefin copolymer, (D) styrene-butadiene-styrene copolymer (SBS) / ethylene-octene copolymer (polyolefin elastomer), (E) styrene-butadiene copolymer (SBC) / ethylene-vinyl acetate (EVA), (F) styrene-butadiene copolymer (SBC) / ethylene-ethyl acryl 0.1 to 60% by weight of latex (EEA), (G) styrene-butadiene copolymer (SBC) / alpha-olefin copolymer, or (H) styrene-butadiene copolymer (SBC) / ethylene-octene copolymer (polyolefin elastomer) And a thermoplastic resin composition containing an impact resistant thermoplastic resin. 6. The chlorine-based flame retardant according to claim 5, wherein the chlorine-based flame retardant has a chlorine content of 10 to 90 wt%, hexachlorocyclopentadiene, methylcyclopentadiene, dicyclopentadiene, cyclohexadiene, chlorinated polyethylene resin, chlorinated paraffin and cyclodecadiene. Impact resistant thermoplastic resin composition selected from the group consisting of. 6. The inorganic flame retardant according to claim 5, wherein the inorganic flame retardant is phosphorus, nitrogen, stearic acid, oleic acid, silane coupling agent, titanate, zirconium, magnesium hydroxide, alumina hydrate compound, antimony oxide, sodium antimonate, iron oxide, In the group consisting of zinc oxide, triphenylphosphate, decabromodiphenyl-based, brominated epoxy, polytribromostyrene, poly (dibromophenylene oxide), ethylenebispentabromodiphenyl and tetrabromobisphenol A Impact resistant thermoplastic resin composition selected. The method of claim 5, wherein the wax is at least one metal stearate selected from calcium, zinc, magnesium or barium stearate, ethyl acrylate copolymer, polypropylene or polyethylene-based polyhydric alcohol fatty acid, polydimethylsiloxane, stearic acid , Impact resistant resin composition selected from the group consisting of ethylene bis stearamide, bis (stearoyl) ethylene diamine and chlorate paraffin. The impact resistant resin composition according to claim 5, wherein the flame retardant synergist is selected from the group consisting of antimony trioxide, phosphorus compound, zinc oxide, titanium dioxide, silica and carbon black.

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