KR20110087966A - Resin composition using phyllite fine powder - Google Patents

Abstract

PURPOSE: A resin composition is provided to avoid the reduction of mechanical properties such as impact strength, to decrease the amount of halogens, phosphorous-based retardants and/or antimony trioxide, and to reduce the generation of dioxine and furan. CONSTITUTION: A resin composition using phyllite micropowder compises: 30~95 parts by weight of a resin; 1~60 parts by weight of one kind or more selected from a flame retardant and a flame-retardant aid; and 0.5~20 parts by weight of phyllite micropowder having the maximum particle size of 1251~15,000 mesh. The flame retardant is one kind or more selected from the group consisting of a phosphorous-based flame retardant, brome-based flame retardant, chlorine-based flame retardant, zinc-based flame retardant, nitrogen-containing flame retardant, nitrogen-phosphorous-containing flame retardant, aluminum hydroxide and magnesium hydroxide.

Description

Resin Composition Using Phyllite Fine Powder

The present invention relates to a resin composition, and more particularly, to a resin composition using a fine particulate rock powder and a method for producing the same.

Thermoplastics used in the housing of offices and home appliances, such as computers, copiers, facsimiles, etc., are typically 1.6mm thick and must pass the V0 rating of the 20mm vertical combustion test of Underwriter's Library (UL) 94. As the flame retardant thermoplastic resin exhibits self-extinguishing, it is required from the viewpoint of safety to secure fire prevention and escape time. In addition, flame-propagation speed and smoke-density must pass certain standards in the UL 910 test called Steiner Tunnel Test in the field of flame retardant wires and power cables. As described above, the flame-retardant thermoplastic resin should not be burned well in a fire, self-extinguishing, and should not emit a large amount of toxic gas. To this end, various flame retardants are used in the resin.

Currently used flame retardants are classified into organic and inorganic based on the constituents, organic is mainly classified into phosphorus, bromine, chlorine, inorganic is classified into aluminum hydroxide, magnesium hydroxide and the like. In addition, it is classified into additive type and reactive type by usage. The additive type physically adds flame retardant to plastic to improve flame retardancy, but reactive type improves flame retardancy of resin by adding some flame-retardant monomer to chemical reaction during resin synthesis. It is a way. In general, flame retardant is mainly due to the addition of a flame retardant. In recent years, brominated flame retardants are mainly used.

Bromine-based flame retardants have adverse effects on humans and ecosystems through exposure to workers in production and processing, consumer exposure due to the use of final products and fires, environmental exposure such as air, water and soil, and environmental exposure through food chains. It is known to form dioxins or furans known as carcinogens when heated. Recently, the use of penta, octa, deca and polybrominated biphenyl (PBB) has been banned in Europe, but there is no further movement for TBBPA or BEO.

In addition, antimony trioxide, which is added to enhance the flame retardant effect of bromine-based flame retardants, has been reported to be carcinogenic, and antimony oxide is known to catalyze the formation of dioxins or furans during incineration. Moreover, the use of antimony oxide deteriorates the thermal stability and weather resistance of the plastics, and thus has the disadvantage of rapidly deteriorating physical properties when staying in the injection molding machine.

As the harmful problems of brominated flame retardants have been raised for a long time, researches on high-quality flame retardants and flame retardants (or flame retardant aids) such as low toxicity and low smoke have continued.

Techniques for use of feldspar for flame retardant resins are already known in Korean Patent Laid-Open Publication Nos. 10-2007-0084897 and 10-2007-0085175. However, the feldspar powder used in the above technique has a particle size of 1250 mesh (maximum particle size of 10 μm) when mixed with a thermoplastic resin so that the particles are relatively large and the impact strength is very large and dispersion is not so good that the flame retardancy increase is not large.

SUMMARY OF THE INVENTION An object of the present invention is to add a fine particulate rock powder having a very small particle size to a resin composition to which a flame retardant is added, thereby greatly improving flame retardancy, thereby providing a resin composition having the same or better flame retardancy while reducing the content of flame retardant aids and / or flame retardants. It is.

Another object of the present invention is to add a fine particulate rock powder to the resin composition to provide a resin composition having excellent antimicrobial properties.

Still another object of the present invention is to reduce the amount of addition of halogen-based, phosphorus-based flame retardants and / or flame retardant aids conventionally used for flame retardancy by using fine particulate rock powder in the resin composition, and exhibits almost no effect on mechanical properties including impact strength. In addition, to provide a resin composition that can reduce the generation of dioxins and furans during processing and incineration, and obtain a deodorizing and anti-fungal effect.

In order to achieve the above object, the present invention provides a resin composition in which at least one selected from a flame retardant and a flame retardant aid is contained in the resin, wherein the resin composition comprises fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh. It provides a resin composition using fine particulate rock powder, characterized in that.

The flame retardant in the present invention may be at least one selected from the group consisting of a phosphorus flame retardant, bromine flame retardant, chlorine flame retardant, zinc-based flame retardant, nitrogen-containing flame retardant, nitrogen-phosphorus-containing flame retardant, aluminum hydroxide, and magnesium hydroxide.

Flame retardant adjuvant in the present invention, antimony trioxide (Sb ₂ O ₃ ), antimony pentoxide (Sb ₂ O ₅ ), zinc tin hydroxide (Zinc hydroxystannate), iron oxide (Fe ₂ O ₃ ), anhydrous alumina (Anhydrous Al ₂ O ₃ ), And tin oxide (SnO ₂ ) It may be one or more selected from the group consisting of.

In the present invention, the resin composition using the fine particulate rock powder is 30 to 95 parts by weight of the resin; 1 to 60 parts by weight of at least one selected from a flame retardant and a flame retardant aid; And 0.5 to 20 parts by weight of fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh.

The present invention provides a resin composition using fine particulate rock powder, wherein the resin is polyvinyl chloride (PVC), and includes fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh in place of the flame retardant or flame retardant aid.

In the present invention, the resin is polypropylene (PP), polyethylene (PE), ethylene vinyl acetate (EVA), polystyrene (PS), acrylonitrile butadiene styrene (ABS), styrene acrylonitrile (SAN), polycarbonate (PC) , Polyvinyl chloride (PVC), styrene butadiene styrene (SBS), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), nylon (Nylon), polyester, polyurethane (PU), epoxy And it may be one or more selected from the group consisting of a mixture thereof.

The present invention provides a resin composition using fine particulate rock powder having an antimicrobial activity by including fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh in the resin.

In the present invention, the resin composition using the fine particulate rock powder is characterized in that it further comprises at least one member selected from the group consisting of plasticizers, stabilizers, drip inhibitors, lubricants, and antioxidants.

The present invention provides a product in which fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh is contained in any one selected from thermosetting resin, thermoplastic resin, paper, fiber, building material, pigment, paint and rubber product.

The present invention comprises the steps of preparing a composition material comprising at least one selected from a resin, a flame retardant and a flame retardant aid, and fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh;

Mixing ingredients:

Injecting the mixed composition material into the extruder;

It provides a method for producing a resin composition using the fine granite rock powder comprising the step of kneading the composition material introduced into the extruder for 1 to 5 minutes at a temperature of 160 ~ 300 ℃.

The resin composition using the fine particulate rock powder according to the present invention greatly improves the flame retardancy by adding the fine particulate rock powder to the resin composition and shows the same or better flame retardancy while reducing the content of the flame retardant aid or flame retardant.

In addition, the resin composition using the fine particulate rock powder according to the present invention has excellent antimicrobial properties by adding the fine particulate rock powder to the resin composition.

In addition, the resin composition using the fine particulate rock powder according to the present invention, by using the fine particulate rock powder in the resin composition, the amount of halogen-based, phosphorus-based flame retardants and / or flame retardant agents conventionally used for flame retardancy is reduced, and mechanical properties including impact strength are reduced. In addition, it can additionally reduce the occurrence of dioxins and furans during processing and incineration, and deodorizing and antifungal effects can be obtained.

In addition, the method for producing a resin composition using the fine particulate rock powder according to the present invention can provide conditions for producing a resin composition having the above-described effect.

The present invention relates to a resin composition using fine particulate rock powder and a method for producing the same.

The resin composition using the fine particulate rock powder according to the present invention is a resin composition in which at least one selected from a flame retardant and a flame retardant aid is contained in the resin, wherein the resin composition comprises fine particulate rock powder.

Suzy( resin )

A thermosetting resin or a thermoplastic resin may be used to prepare a resin composition using the fine particulate rock powder according to the present invention, and more preferably, polypropylene (PP), polyethylene (PE), ethylene vinyl acetate (EVA), and polystyrene (PS). ), Acrylonitrile butadiene styrene (ABS), styrene acrylonitrile (SAN), polycarbonate (PC), polyvinyl chloride (PVC), styrene butadiene styrene (SBS), polybutylene terephthalate (PBT), polyethylene tere Phthalate (PET), nylon (Nylon), polyester, polyurethane (PU), epoxy (epoxy) or mixtures thereof may be used alone or in combination of two or more.

Flame retardant  And flame retardant supplements

According to the present invention, in order to improve the flame retardancy of the resin, halogen-based flame retardants (bromine-based and chlorine-based), halogen-containing phosphorus-based flame retardants, phosphorus-based flame retardants (phosphate esters, red, etc.), zinc-based flame retardants, nitrogen or nitrogen-phosphorus-containing flame retardants ( Melamine, melamine phosphate, melamine cyanurate, ammonium polyphosphate, polyphosphazene and the like), metal hydroxide flame retardant (such as aluminum trihydroxide or magnesium hydroxide) may be used alone or in combination of two or more thereof. As the brominated flame retardant, TBBPA (Tetrabromobisphenol A), BEO (brominated epoxy oligomer) or bistribromophenoxy ethane (bis) may be used.

The resin composition using the fine particulate rock powder of the present invention may include 1 to 60 parts by weight of a flame retardant and / or flame retardant aid. If the content of the flame retardant and / or flame retardant adjuvant is less than 1 part by weight, the flame retardancy is insufficient, and if it exceeds 60 parts by weight, it is not preferable because the mechanical properties are low.

The resin composition using the fine particulate rock powder of the present invention may include a flame retardant aid to further improve flame retardancy.

Antimony trioxide (Sb ₂ O ₃ ), antimony pentoxide (Sb ₂ O ₅ ), zinc tin hydroxide (Zinc hydroxystannate), iron oxide (Fe ₂ O ₃ ), anhydrous alumina (Al ₂ O ₃ ), or Tin oxide (SnO ₂ ) may be used alone or in combination of two or more thereof.

The resin composition using the fine particulate rock powder of the present invention may include fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh in place of the flame retardant aid or the flame retardant when polyvinyl chloride (PVC) is used as the resin. Therefore, there is an effect of reducing the use of flame retardant aids by replacing the flame retardant or flame retardant aids with fine particulate rock powder.

Fine Filbert  powder

The fine particulate rock powder according to the present invention can be applied to all flame retardant resins using a flame retardant.

The feldspar used in the present invention is also called Phyllite, and is an ore that is formed through a process of hydrolysis due to hydrothermal alteration, denaturation, weathering, corrosion, and the like, of sediment of clay. Constituents, pore characteristics, antibacterial activity, far-infrared emission amount, and deodorizing ability (formaldehyde) of cheonmaelam are introduced in detail in Korean Patent Publication No. 10-2007-0084987.

The feldspar is mainly composed of quartz and feldspar and is mixed with various minerals such as biotite, dolomite, biotite, chlorite and calcite (see Table 1).

division SiO ₂ Al ₂ O ₃ CaO MgO K ₂ O Na ₂ O TiO ₂ MnO P ₂ O ₃ weight% 73.2 20.20 0.84 1.82 1.82 2.45 0.54 0.01 0.16

Natural feldspars (pilites) have a dark brown color and convenience surfaces give a strong luster due to the small particles of the mica.

Aphrodisiac forms many nano-sized spaces inside, so it is excellent in physical adsorption and chemical cation repair. The reason for this is as shown in Table 2, that the phyllite and zeolite have almost the same porosity, but the pore has a smaller pore area, and the pores are not evenly distributed. Formed. Absorption rate and porosity have a clear linear relationship, and it is reported that the larger the porosity, the higher the water content. That is, the pores formed in the cultivated rock can be expected to increase the adsorptive force due to the large volume and area.

division
Total pore Median pore Volume (ml / g) Area (㎥ / g) Volume (ml / g) Area (㎥ / g) Filbert 0.648 21.6 8.742 0.0061 zeolite 0.641 137.4 0.602 0.0043

Therefore, it is known to be effective for deodorization and humidity control because it has a unique characteristic of absorbing and adsorbing moisture and gas, and storing it slowly and then discharging itself. It emits far infrared rays and has a content of germanium (Ge) of 0.1 ppm. It is superior to the germanium content of ginseng and hot spring water (see Table 3).

division Deodorization effect (%)
(Formaldehyde) Far infrared ray emission amount
(40 ℃) germanium
(ppm) Filbert 97.0 0.924 0.11

The feldspar is considered to be excellent as a flame retardant aid as it has a lot of fine pores and has a very large surface area and contains various kinds of metal oxides.

The constituents, porosity, deodorizing effect, far-infrared emission amount, germanium content, etc., of the chalcedony rock are for general feldspar and do not limit the feldspar used in the present invention.

The fine particulate rock powder used in the present invention is prepared using a pulverization process and a classification process, and has a maximum particle size of 1251 mesh (maximum particle size of 10 μm) to 15,000 mesh (maximum particle size of about 0.8 μm) of dispersibility in resin. It is desirable to be able to improve. If the maximum particle size of the fine particulate rock of the present invention is less than 1251 mesh, the degree of impact strength reduction is not preferable, and if it exceeds 15,000, the manufacturing cost greatly increases and is not preferable.

It is preferable that the resin composition of this invention contains 0.5-20 weight part of natural stone powders whose maximum particle size is 1251 mesh (maximum particle size 10 micrometers)-15,000 mesh (maximum particle size about 0.8 micrometers). If the content of the fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh is less than 0.5 parts by weight, the replacement effect of the feldspar powder with the flame retardant and / or the flame retardant aid is insufficient and the flame retardant effect is not preferable. In this case, the mechanical strength such as impact strength deteriorates, which is not preferable.

The flame retardant ABS (acrylonitrile-butadiene-styrene terpolymer) resin using the fine particulate rock powder according to the present invention is as follows.

Halogen-based flame retardant ABS resin is 30 to 50 parts by weight ABS resin having a polybutadiene content of 30 to 80 wt%, SAN copolymer 30 to 60 parts by weight, brominated flame retardant 12 to 20 parts by weight, antimony trioxide 2 to 5 parts by weight and fine It is composed of 0.5 to 3 parts by weight of the natural stone powder.

Non-halogen flame-retardant PC / ABS resin is a blend of PC (polycarbonate) and ABS in order to maintain the flame retardancy of UL 94 V-0 grade 50 to 80 parts by weight of PC, 10 to 20 parts by weight of ABS with 30 to 80wt% polybutadiene content 10 parts by weight of TPP (triphenylphosphate) and 0.5 to 3 parts by weight of fine granite powder are used as the phosphorus-based flame retardant.

In the case of flame-retardant soft PVC (polyvinyl chloride), 40 to 60 phr of plasticizer (DOP, DINP, etc.), 1 to 4 phr of antimony oxide, 1 to 6 phr of stabilizer, and 1 to 50 phr of fine granite powder for 100 phr of PVC Flame retardant PVC compound with high oxygen index, low smoke density and excellent mechanical properties. In the case of adding fine particulate rock to PVC, since it is softer than the existing flame retardant, the amount of plasticizer added can be reduced, thereby reducing the toxicity of the product.

The fine particulate rock powder of the present invention has an effect of greatly increasing the flame retardancy when added to the resin and hardly decreasing the impact strength, thereby reducing the addition amount of the flame retardant and / or flame retardant aid, thereby significantly reducing the manufacturing cost of the flame retardant thermoplastic resin. Could get

The resin composition using the fine particulate rock powder of the present invention can retain the antimicrobial power by including the fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh, and more preferably 5 to 90 parts by weight based on 10 to 95 parts by weight of the resin. By including it can retain the antimicrobial activity.

The resin composition using the fine particulate rock powder of the present invention may further include at least one of a plasticizer, a stabilizer, an anti-drip agent, a lubricant, and an antioxidant.

According to the present invention, it is possible to provide a product in which fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh is contained in any one selected from thermosetting resin, thermoplastic resin, paper, fiber, building material, pigment, paint and rubber product. have.

According to the present invention, a composition material comprising a resin, a flame retardant and / or a flame retardant adjuvant, and a fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh is prepared, and after mixing the composition materials, the mixed composition materials are introduced into an extruder, And kneading at a temperature of 160 to 300 ° C. for 1 to 5 minutes to prepare a resin composition using fine particulate rock powder.

In the present invention, the kneading temperature and time of the twin screw extruder are determined according to the type of resin and flame retardant used.

In the method for preparing a resin composition using the fine particulate rock powder according to the present invention, the compositional material is the same as that described in the resin composition using the fine particulate rock powder.

Hereinafter, the present invention will be described in detail with reference to Examples.

The following examples are intended to illustrate the invention and should not be construed as limiting the invention.

[Example]

Example  1 to 4

Brominated Epoxy Oligomer (BEO) produced by LG Chem's DP 270 product as acryl butadiene styrene (ABS), 81HF by LG Chem as styrene acrylonitrile (SAN), and Kukdo Chemical as brominated flame retardant KB-563H, antimony is ANTIS-W of Ilsung antimony with particle size of 0.8 ~ 1.5μm, ethylene bis stearamide (EBS) as lubricant and primary and secondary oxidation as antioxidant Songnox 21B of Songwon Industrial Co., Ltd., which is a 1: 2 blend of inhibitors, was used as titanium dioxide (TiO ₂ ) as Dupont's R-350 and Dupont's Teflon 800J was used as it was.

The fine granite powder is FR-2000 and FR-5000 produced by Jewon Nano Materials Co., Ltd., and the grinding and classification process is performed with 2000 mesh (maximum particle size 6.5μm) and 5000 mesh (maximum particle size 2.6μm), respectively. The product prepared through was used. These products are characterized by fine particles and improved dispersibility in the resin.

Kneading was carried out with the composition given in Table 4, followed by a twin screw extruder at a maximum temperature of 230 ^° C. The kneaded resin was pelletized and dried, and each test specimen was prepared by an injection molding machine and tested.

Comparative example  One

It was mixed to the composition given in Table 4, and only antimony oxide was applied without using the fine particulate rock powder.

Comparative example  2 and 3

Mixed with the composition given in Table 4, the used Cheonam Rock powder is PCS-1250 produced by Jewon Nano Co., Ltd., which has a maximum particle size of 10μm.

The composition and physical property measurement results of Examples 1 to 4 and Comparative Examples 1 to 3 are shown in Table 4 below.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Of composition
Configuration
(Parts by weight) ABS 36 36 36 36 36 36 36 SAN 42.3 42.3 43.3 43.3 42.3 42.3 42.3 BEO 16 16 15 15 16 16 16 Lubricant 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Antioxidant 0.6 0.6 0.6 0.6 0.6 0.6 0.6 TiO ₂ 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Teflon 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Sb ₂ O ₃ 3 3 2 2 4 3 2 Thousand Rock PCS-1250 - - - - - One 2 Thousandstone FR-2000 One - 2 - - - - Thousandstone FR-5000 - One - 2 - - - Properties Tensile strength ^{1 )}  330  322 341 325 310 340 342 Tensile modulus ^{1 )}  16,510  16,370 16,700 16,830 16,010 16,350 16,470 Tensile Elongation ^{1 )} 11.6 11.9 10.1 13.1 12.0 6.5 5.7 Flexural Strength ^{2 )}  463  475 489 468 436 462 480 Flexural modulus ^{2 )} 13,950  14,350   15,350 14,920 13,080 14,310  14,830 Impact strength ^{3 )} 12.0 13.1 10.5 12.0 14.0 9.7 8.1 Flame retardant grade ^{4 )} (seconds) VO (11) VO (6) VO (29) VO (18) V1 (95) VO (47) VO (30) MI ^{5 )} 2.3 2.4 2.5 2.8 2.2 2.4 2.6

The final physical properties of the halogen-based flame retardant ABS compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were measured by the methods given below.

1) Tensile test

According to the test method of ASTM D 638 was measured at a strain rate of 5mm / min. Physical properties of tensile strength and modulus are kg _f / cm ² .

2) Flexural test

According to the test method of KS M ISO 178 was tested on a 1/4 inch thick specimen at a speed of 2mm / min. The property unit for flexural strength and modulus is kg _f / cm ² .

3) impact strength

It was measured in a notched Izod manner for specimens 1/8 inch thick by ASTM D 256. The property unit is kg _{f ˙} cm / cm.

4) Flame retardant test

 Evaluation was made according to UL 94's 20 mm vertical burning test method and grading criteria.

5) MI ( Melt Index , Melt index)

The flowability was measured by ASTM D 1238 at a load of 2.16 kg at 230 ^° C. and is in g / 10 min.

Examples 5-8

Polycarbonate (PC) is LG Chem's 300-15 product, acryl butadiene styrene (ABS) is LG Chem's DP 255 product, phosphorus-based flame retardant TPP is Duksan's CP grade reagent, a second blend of Songwon industrial Co., Ltd. a Songnox 21B, titanium dioxide (TiO ₂₎ is DuPont R-350's,: Note) the EBS (ethylene bis stearamide), first and second one of the antioxidant as an antioxidant As a drip prevention agent, Dupont Teflon 800J was used as it was obtained.

The fine granite powder is FR-2000 and FR-5000 produced by Jewon Nano Materials Co., Ltd., and the grinding and classification process is performed with 2000 mesh (maximum particle size 6.5μm) and 5000 mesh (maximum particle size 2.6μm) It is a product manufactured through.

The kneading process was carried out by mixing with the composition given in Table 5 and then using a twin screw extruder at a maximum temperature of 250 ^o C. The kneaded resin was pelletized and dried, and each test specimen was prepared by an injection molding machine and tested.

Comparative Example 4

The composition shown in Table 5 increased the content of PC by the same instead of using the fine particulate rock powder.

Comparative Examples 5 and 6

In the composition shown in Table 5, PCS-1250 (maximum particle size 10 μm in 1250 mesh) was used as the general feldspar powder instead of the particulate feldspar powder.

The physical property measurement results of Examples 5 to 8 and Comparative Examples 4 to 6 are shown in Table 5 below.

division Example 5 Example 6 Example 7 Example 8 Comparative Example 4 Comparative Example 5 Comparative Example 6 Of composition
Configuration
(Parts by weight) PC 71.5 71.5 71.0 71.0 72.5 71.5 70.5 ABS 15 15 15 15 15 15 15 TPP 10.5 10.5 10.0 10.0 10.5 10.5 10.5 Lubricant 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Antioxidant 0.6 0.6 0.6 0.6 0.6 0.6 0.6 TiO ₂ 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Teflon 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Thousand Rock PCS-1250 - - - - - One 2 Thousandstone FR-2000 One - 2 - - - - Thousandstone FR-5000 One - 2 - - - Properties Tensile strength ^{1 )} 557 550 549 570 560 575 583 Tensile modulus ^{1 )} 19,520 19,730 19,980 20,190 19,500 21,300 23,700 Tensile Elongation ^{1 )} 52 57 49 52 60 50 43 Flexural Strength ^{2 )} 610 607 632 645 605 575 598 Flexural modulus ^{2 )} 17,170 17,230 17,740 17,890 17,050 16,930 17,200 Impact strength ^{3 )} 56 57 50 52 59 36 28 Flame retardant grade ^{4 )} (seconds) VO (10) VO (7) VO (30) VO (21) V1 (75) VO (41) VO (25) MI ^{5 )} 18 17 21 19 18 19 20

The final physical properties of the non-halogen flame retardant PC / ABS compositions of Examples 5 to 8 and Comparative Examples 4 to 6 were measured in the same manner as in the measurement methods of the physical properties of Examples 1 to 4 and Comparative Examples 1 to 3.

Examples 9-12

Polyvinyl chloride (PVC) is Hanwha Chemical's P-1000 product, plasticizer is DOP of LG Chemical, epoxy stabilizer is E-700 of Songwon Industrial Co., and Ca / Zn stabilizer is KP-110 of Y & J. Antimony oxide was used as ANTIS-W of Ilsung antimony having a particle size of 0.8-1.5 μm, and KH-25R manufactured by KC Co., Ltd. for aluminum hydroxide.

The fine granite powder is FR-2000 and FR-5000 produced by Jewon Nano Materials Co., Ltd., and the grinding and classification process is performed with 2000 mesh (maximum particle size 6.5μm) and 5000 mesh (maximum particle size 2.6μm), respectively. The product prepared through was used. These products are characterized by fine particles and improved dispersibility in the resin.

Cheonmae Rock Powder is PCS-1250 produced by Jewon Nano Materials Co., Ltd. and is manufactured through the grinding and classification process with 1250 mesh (maximum particle size 10μm).

Kneading was carried out by mixing with the composition given in Table 5 and then using a single screw extruder at a maximum temperature of 190 ° C. The kneaded resin was pelletized and dried, and each test specimen was prepared by an injection molding machine and tested.

Comparative Example 7

A resin composition was prepared in the same manner as in Examples 9 to 12, except that the fine granite powder was not used.

Comparative Examples 8 and 9

A resin composition was prepared in the same manner as in Examples 9 to 12, except that the feldspar powder PCS-1250 was used in the composition given in Table 6 instead of the particulate feldspar powder.

Comparative Examples 10 and 11

A resin composition was prepared in the same manner as in Examples 9 to 12, except that aluminum hydroxide was used in the composition given in Table 6 instead of the fine particulate rock powder.

The measurement results of the physical properties of Examples 9 to 12 and Comparative Examples 7 to 11 are shown in Table 6 below.

division Example Comparative example 9 10 11 12 7 8 9 10 11 Of composition
Configuration
(Parts by weight) PVC 100 100 100 100 100 100 100 100 100 DOP 50 50 50 50 50 50 50 50 50 E-700 3 3 3 3 3 3 3 3 3 KP-110 2 2 2 2 2 2 2 2 2 Sb ₂ O ₃ 3 3 3 3 3 3 3 3 3 Thousand Rock PCS-1250 - - - - - 10 20 - - Thousandstone FR-2000 10 20 - - - - - - - Thousandstone FR-5000 10 20 - - - - - Aluminum hydroxide - - - - - - - 10 20 Properties Oxygen index
(OI) 30.5 30.8 31.5 31.8 28.7 29.3 29.6 28.5 28.8

Oxygen index of the final physical properties of the PVC composition of Examples 9, 10 and Comparative Examples 7 to 11 was measured by the KS M ISO 4589-2 method.

In the case of adding fine particulate rock to PVC, since it is softer than the existing flame retardant, the amount of plasticizer added can be reduced, thereby reducing the toxicity of the product.

When the fine particulate rock powder is mixed with more than 5 parts by weight of resin such as polyethylene (PE) and polypropylene (PP) to manufacture films, containers, non-woven fabrics, foams, etc., it can be used for food storage and distribution. Freshness lasts longer than before, prevents mold, and suppresses the growth of various bacteria can be seen an excellent effect on the contents.

Example 13

30 parts by weight of fine particulate rock powder FR-2000 is added to 100 parts by weight of Samsung Total's PP HJ750, and an antioxidant (using 0.2 parts by weight of Songnox 21B) and a lubricant (0.5 parts by weight of PP wax 502N from Lion Chemtech) are used. The mixture was extruded and kneaded at 230 ^° C. with a twin screw extruder, pelletized, and then compressed into a sheet having a thickness of 1 mm to prepare a 10 mm × 10 mm specimen.

Comparative Example 12

A specimen was prepared in the same manner as in Example 13 except that 30 parts by weight of talc powder KCA-2000 produced by KOCH Co., Ltd. was used instead of the fine particulate rock powder.

In Example 13 and Comparative Example 12, an antimicrobial test was conducted according to the antimicrobial activity test method of Part 1 shake flask method (KS J 4206: 2008). Strains are Escherichia Coli and Staphylococcus aureus ) were used and the number of cells after incubation for 24 hours is summarized in Table 7.

 Strain Control Example 13
(Decrease rate) Comparative Example 12
(Decrease rate) Escherichia coli (g-) 2.85 ± 0.13x10 ⁹ 1.02 ± 0.18x10 ⁹
(64.2%) 2.54 ± 0.09x10 ⁹
(10.9%) Staphylococcus aureus (G +) 3.34 ± 0.44x10 ⁹ 1.26 ± 0.28x10 ⁹
(62.3%) 3.20 ± 0.41x10 ⁹
(4.2%)

What has been described above is only an embodiment for carrying out the thermoplastic resin using the fine particulate rock powder according to the present invention, the present invention is not limited to the above-described embodiment, may have various embodiments.

In addition, not limited to the thermoplastic resin, when the thermosetting resin, paper, fiber, building materials, paints, etc., when the product is added 5 ~ 90 parts by weight of the fine grained rock powder to the weight of the product has a flame retardant and antibacterial properties, it is very It has excellent antimicrobial activity.

As described above, the halogen-based flame retardant ABS resin using the fine particulate rock powders (FR-2000 and FR-5000) according to the present invention is relatively reduced in impact strength while reducing the amount of conventional bromine-based flame retardant and antimony trioxide. As less effective. Examples 1 and 2 each contained 1 part by weight of fine particulate rock FR-2000 and FR-5000, and the flame retardancy was increased from the V1 grade to the V0 grade compared to Comparative Example 1, and the impact strengths were 14.3% (Example 1) and It only decreased by 6.4% (Example 2). In addition, Examples 3 and 4 each contained 2 parts by weight of fine particulate rock FR-2000 and FR-5000, and showed a V0 grade even when the BEO flame retardant was reduced by 1 part by weight, and the impact strength reduction was 25% (Example 3) and 14.3% (Example 4).

Non-halogen flame-retardant PC / ABS resins use fine grainstone powders (FR-2000 and FR-5000) with a size of 2000 mesh or 5000 mesh, which greatly increases the flame retardancy and decreases the impact strength with a margin of error. Showed. Examples 5 and 6 contained 1 part by weight of fine particulate rock FR-2000 and FR-5000, respectively, the flame retardancy was increased from the V1 grade to V0 grade compared to Comparative Example 4 and the impact strength was 5.1% (Example 5) and It only decreased by 3.4% (Example 6). In addition, Examples 7 and 8 contained 2 parts by weight of fine particulate rock FR-2000 and FR-5000, respectively, and showed a V0 grade even when 0.5 parts by weight of TPP flame retardant was reduced, and the impact strength was 15.3% (Example 7). Only 11.9% (Example 8) decreased. This effect is believed to be due to the smaller particle size and the improved dispersion in the resin.

Fine grain powders (FR-2000 and FR-5000) exhibited better flame retardancy and mechanical properties than aluminum hydroxide or untreated natural rock powder (PCS-1250) in soft PVC compounds containing DOP plasticizers and antimony trioxide. Example 9 containing 10 phr of fine grain powder (FR-2000) had an oxygen index of 30.5 and a 4.1% increase over that of the same amount of feldspar powder (PCS-1250) (comparative example 8 with an oxygen index of 29.3). 7.0% was higher than 28.5 of Comparative Example 10 containing 10 phr of aluminum. In addition, Example 10 containing 20 phr of fine grainstone powder (FR-2000) had an oxygen index of 30.8, which was 4.1% higher than that of the same amount of feldspar powder (PCS-1250) (comparative example 9 with an oxygen index of 29.6). And 6.9% higher than 28.8 of Comparative Example 11 containing the same amount of aluminum hydroxide. Example 11 containing 10 phr of fine particulate rock powder (FR-5000) had an oxygen index of 31.5 and 7.5% higher than that of the same quantity of fine rock powder (PCS-1250) (comparative example 8 with an oxygen index of 29.3). 10.5% was higher than 28.5 of Comparative Example 10 containing 10 phr of aluminum. In addition, Example 12 containing 20 phr of fine grainstone powder (FR-5000) had an oxygen index of 31.8, which was 7.4% higher than that of the same amount of feldspar powder (PCS-1250) (comparative example 9, which had an oxygen index of 29.6). 10.4% compared with 28.8 of Comparative Example 11 containing the same amount of aluminum hydroxide.

In addition to flame retardancy and impact strength, tensile properties, flexural properties and flowability were slightly decreased or increased.

The fine granite powder showed excellent antimicrobial effect similarly to the powder itself even when added to the plastic resin. E. coli killed 64.2% and Staphylococcus aureus killed 62.4% within 24 hours in a PP compound containing 30 parts by weight of particulate feldspar powder (FR-2000). In addition, the fine particulate rock powder showed a greater degree of impact strength increase in the PP compound than the large particulate rock powder. This is a remarkable property, which makes it possible to apply particulate chalcedony powder to environmentally friendly and more economical materials for textiles, food products and hygiene products.

Claims (10)

A resin composition, wherein the resin composition comprises fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh, wherein at least one selected from a flame retardant and a flame retardant aid is contained in the resin. The flame retardant according to claim 1, wherein the flame retardant is at least one selected from the group consisting of phosphorus flame retardants, bromine flame retardants, chlorine flame retardants, zinc flame retardants, nitrogen-containing flame retardants, nitrogen-phosphorus-containing flame retardants, aluminum hydroxide, and magnesium hydroxide. Resin composition using fine grained rock powder. The flame retardant auxiliary agent according to claim 1 or 2, wherein the flame retardant aid is antimony trioxide (Sb ₂ O ₃ ), antimony pentoxide (Sb ₂ O ₅ ), zinc tin hydroxide (Zinc hydroxystannate), iron oxide (Fe ₂ O ₃ ), anhydrous alumina (Al ₂ O ₃ ), and tin oxide (SnO ₂ ) is a resin composition using a fine particulate rock powder, characterized in that at least one selected from the group consisting of. The resin composition of claim 1 or 2, wherein the resin composition comprises 30 to 95 parts by weight of a resin; 1 to 60 parts by weight of at least one selected from a flame retardant and a flame retardant aid; And 0.5 to 20 parts by weight of fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh. 3. The granulated fine rock powder according to claim 1, wherein the resin is polyvinyl chloride (PVC) and comprises fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh in place of the flame retardant aid or flame retardant. 4. Resin composition used. The method of claim 1 or 2, wherein the resin is polypropylene (PP), polyethylene (PE), polystyrene (PS), acrylonitrile butadiene styrene (ABS), styrene acrylonitrile (SAN), polycarbonate (PC) , Polyvinyl chloride (PVC), styrene butadiene styrene (SBS), polyester, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyurethane (PU), nylon (Nylon) and mixtures thereof Resin composition using a fine particulate rock powder, characterized in that at least one selected from the group consisting of. A resin composition using fine particulate rock powder having an antimicrobial activity by including fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh in the resin. 8. The resin composition according to claim 1 or 7, wherein the resin composition further comprises at least one member selected from the group consisting of a plasticizer, a stabilizer, an anti-drip agent, a lubricant, and an antioxidant. Thermosetting resin, thermoplastic resin, paper, fiber, building materials, pigments, paints and rubber products containing fine particulate rock powder with a maximum particle size of 1251 to 15,000 mesh. Preparing a composition material comprising at least one selected from a resin, a flame retardant, and a flame retardant adjuvant, and fine particulate rock powder having a maximum particle size of 1251 to 15,000 mesh;
Mixing ingredients:
Injecting the mixed composition material into the extruder;
A method for producing a resin composition using fine particulate rock powder comprising the step of kneading the composition raw material introduced into the extruder at a temperature of 160 to 300 ℃ for 1 to 5 minutes.