KR20060000712A - A polyolefin resin composition for a store courage - Google Patents

Abstract

The present invention relates to a polyolefin-based composite resin composition for a storage container, and more particularly, a polyolefin-based resin, an inorganic filler having a far-infrared emissivity, and a small amount of rosin in a specific ratio, when used in combination, a composite containing a conventional far-infrared radiator It is possible to shield not only the antibacterial and deodorizing effect by far-infrared radiation of resin, but also the resin component itself and other odors generated by heat processing, and the mechanical strength such as elongation and impact strength is improved by improving compatibility. It relates to a polyolefin-based composite resin composition for storage containers that can be usefully used in the field of storage containers, packaging materials and the like.

Polyolefin resin, far infrared emissivity, inorganic filler, rosin, composite resin

Description

A polyolefin resin composition for a store courage

The present invention relates to a polyolefin-based composite resin composition for a storage container, and more particularly, a polyolefin-based resin, an inorganic filler having a far-infrared emissivity, and a small amount of rosin in a specific ratio, when used in combination, a composite containing a conventional far-infrared radiator It is possible to shield not only the antibacterial and deodorizing effect by far-infrared radiation of resin, but also the resin component itself and other odors generated by heat processing, and the mechanical strength such as elongation and impact strength is improved by improving compatibility. It relates to a polyolefin-based composite resin composition for storage containers that can be usefully used in the field of storage containers, packaging materials and the like.

Increasing standards of living and increasing interest in more healthy and well being are increasing the movement to eliminate odors. In addition, research on the alternative use of natural materials that are harmless to humans rather than artificially formed compounds is being actively conducted.

As one of these natural materials, inorganic fillers such as elvan and loess that emit far infrared rays promote perspiration, pain relief, blood circulation and metabolism promotion, heavy metal removal, sleep, deodorization, antibacterial, mold growth prevention, dehumidification, and air purification. It has excellent effects such as water purification, and is widely used in various fields such as housing and building materials, kitchen utensils, textiles, clothing, bedding, medical appliances, and jjimjilbang.

In particular, they are widely used in food containers for long-term storage of various foods, and in general, natural foods, such as various vegetables and fruits, to maintain freshness, and long-term storage for fermented foods such as kimchi and salted fish. Inhibition of odor and germ breeding has become a major requirement. However, various storage containers currently used are made of metal or plastic, and thus only perform a simple loading function to block outside air and the inside of the container.

In order to improve such a problem, recently, studies have been performed using far-infrared radiation and antibacterial deodorization of these materials by adding elvan or ocher to plastic components, and products have begun to be released. Examples of research on this are synthetic resin products containing elvan and its manufacturing method (Korean Patent Registration No. 0254945), ocher-based fibers and its manufacturing method (Korean Patent Registration No. 0231059), ocher-containing synthetic resin compositions and their preparation Method [Korean Patent Registration No. 0321290], and the Kimchi container for kimchi refrigerator as a food storage container and a manufacturing method thereof [Korea Patent Publication 2004-0000587], a yellow clay container for the kimchi refrigerator and a manufacturing method [Korea Patent Publication 2004- 0075100 ].

These products and compositions are antimicrobial and deodorant by far-infrared ray-containing inorganic fillers, and the inorganic fillers such as elvan, loess, etc., and the odors of plastic components themselves and odors caused by heat decomposition during processing into products. There is a limit.

Accordingly, the present inventors have made efforts to improve the odor of the contained composition itself as described above and the odor caused by thermal decomposition during processing, and as a result, the polyolefin resin and the inorganic filler which is a far infrared emitter of a specific range, Containing a small amount of rosin, as well as antibacterial and deodorizing effect by far-infrared radiation, as well as shielding and neutralizing effect of natural rosin can remove the resin component itself and other odor generated by heat processing, and elongation and elasticity by improving the dispersibility of inorganic filler It has been found that mechanical strength, such as impact strength, is improved to complete the present invention.

Accordingly, the present invention is polyolefin for storage containers with improved mechanical strength by antibacterial, deodorizing by far-infrared radiation, inherent odor of the components contained in the composite resin and the odor generated by heat processing and improved dispersibility of inorganic fillers The purpose is to provide a composite composite resin composition.

The present invention relates to a composite resin of (A) 80 to 95% by weight of polyolefin resin and (B) 5 to 20% by weight of inorganic filler having far infrared ray emissivity of 0.8 to 0.93, based on 100 parts by weight of the composite resin (C) natural rosin The polyolefin-based composite resin composition for storage containers containing 0.001 to 0.1 parts by weight is characterized by its characteristics.

Hereinafter, the present invention will be described in more detail.

The present invention, in the polyolefin-based composite resin containing an inorganic filler which is a far-infrared emitter, antimicrobial, deodorizing by far infrared rays at the same time to improve the shielding and mechanical properties of the odor generated during the unique odor and heat processing process of the composite resin composition It relates to a polyolefin composite resin composition using a small amount of natural rosin in order to.

In general, in the case of loess or elvan, which are far-infrared emitters, the anti-microbial, deodorizing and absorbing effects of the emitters due to the resonance of the far-infrared radiation of the emitters have an effect of promoting metabolism and blood circulation. In the case of polyolefin-based composite resins containing such far-infrared emitters, there is a certain effect on antibacterial and deodorizing properties, but the inherent odors of organic resin components and inorganic emitters and the stability to heat when processed and commercialized are reduced. Over-decomposition occurs to form a characteristic odor, and also, the inorganic compound of the far-infrared emitter does not exhibit even dispersibility, and thus mechanical properties are inferior to the commercialization.

However, the polyolefin-based composite resin composition of the present invention adds a small amount of natural rosin to the organic and inorganic-type composite resins of the organic material of the polyolefin and the inorganic material which is the far infrared emitter, thereby intrinsic to the components contained in the composite resin. Natural rosin masks the odor generated by odor and heat processing and physically wraps the odor component (Counteractants or Neutralization). In the case of the shielding or neutralization, it can be seen that the existing odor is not sensually removed rather than removing the causative substance by a chemical reaction. However, if there is only a role of shielding such as fragrance or perfume, it may be counterproductive by synergistic effect with existing smell, but it is shown to remove odor by simultaneously performing a role of neutralization. In the case of the neutralization may also have the effect of deodorization according to the physical binding force with the odor component. In addition, the rosin is a colorless transparent liquid component, has a slight viscosity over time, improves the dispersibility of the inorganic filler as the far-infrared emitter to improve the compatibility of the organic-inorganic composite resin ultimately It serves to improve mechanical properties.

Hereinafter, the components contained in the polyolefin-based composite resin composition for storage of the present invention will be described in more detail.

First, the base resin component may be a polyolefin resin, which is a thermoplastic resin which is relatively inexpensive and has good workability and is widely used for miscellaneous goods, packaging, and agriculture. Such polyolefin resins include, for example, polypropylene, polyethylene, polybutene, polyoctene, polyisoprene, polyethylene terephthalate and derivative compounds thereof. In the present invention, polypropylene is preferably used. 80-95 weight% of said polyolefin resin can be used.

In order to impart antimicrobial and deodorizing properties to the polyolefin resin, an inorganic filler having far infrared rays having a wavelength of 25 μm or more is radiated at a specific ratio. In general, emissivity is a relative value of a black body which is a perfect radiator. In the present invention, an inorganic filler having an emissivity of 0.8 to 0.93, preferably 0.85 to 0.93 may be selected. If the emissivity is less than 0.8, it is difficult to obtain the desired degree of far-infrared radiation effect, and it is more efficient to use a radiator exceeding 0.93, but it is more difficult to find such a radiator. Inorganic fillers having far-infrared emissivity used in the present invention are 40 to 70% by weight of silica (SiO ₂ ), 5 to 30% by weight of aluminum trioxide (Al ₂ O ₃ ), 1 to 15% by weight of potassium oxide (K ₂ O), It is an inorganic material containing 0.05 to 10% by weight of iron trioxide (Fe ₂ O ₃ ) and metal ions selected from Ag, Mg, Zn, Na, Zr, Mn, Sr, Ti and Ca in the range of 0.01 to 10% by weight. For example, natural inorganic substances having such a composition include feldspar rock (macbanrite), tourmaline, loess, jadeite, jadeite, purgatory and magnetic stones. The silica (SiO ₂ ) and aluminum trioxide (Al ₂ O ₃ ) mainly emits far infrared rays and potassium oxide (K ₂ O), iron trioxide (Fe ₂ O ₃ ) and trace metal ions have a strong sterilization effect on the product In addition, it plays a role of conferring antimicrobial properties, and when it has porosity along with far-infrared emissivity, it is provided with breathability so that a certain amount of moisture can be controlled. The effect of making it possible.

The inorganic filler having the far-infrared emissivity of 0.8 to 0.93 is used in 5 to 20% by weight, and if the amount is less than 5% by weight, the effect of the intended far-infrared radiation is insufficient and the dispersibility of the inorganic filler is greater than 20% by weight. It may also cause a problem such as lowering the durability of the product due to the reduction of physical properties of the composite resin.

The present invention is characterized in the technical construction of a polyolefin-based composite resin composition for storage using a small amount of natural rosin in an organic / inorganic composite resin containing an organic material of the polyolefin resin and an inorganic filler which is a far infrared emitter.

The rosin is a natural material obtained from pine and is insoluble in water, but has a property of dissolving in organic solvents such as ethanol, chloroform and acetic acid. This rosin has long been known to be effective in antibacterial and bactericidal action, and is effective in skin diseases, boils, toothaches, edema, asthma, etc. It has also been shown to be effective against toxic water removal at universities and cancer in Russia.

In the present invention, a small amount of rosin is used in a range of about 0.001 to 0.1 parts by weight based on 100 parts by weight of the mixed composition of the polyolefin-based resin and the inorganic filler which is a far-infrared emitter. And it is not effective to neutralize and if exceeding 0.1 parts by weight will cause the problem of causing the smell of rosin itself, and to comply with its usage with the use of rosin is an important factor.

In addition, a certain amount of the additive may be mixed and used within the scope without departing from the object of the present invention.

As described above, the polyolefin-based composite resin composition of the present invention is capable of removing not only the antibacterial, sterilizing and deodorizing effect by far-infrared radiation, but also removing other odors generated by the resin component itself and heat processing, and improving elongation and impact by improving compatibility. The mechanical strength, such as strength, is improved, and thus may be usefully used in fields such as medical or food storage containers, packaging materials, and the like. In particular, it is expected to be highly utilized in the field of storage food containers requiring long-term freshness such as kimchi.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

Examples 1-9 and Comparative Examples 1-5

Next, the composition shown in Table 2 and Table 3, after pre-mixing uniformly in a mixer for 10 minutes, and uniformly melt mixed using a twin extruder in the temperature range of 170 ~ 220 ℃ polyolefin-based composite resin The composition was prepared. At this time, the inorganic filler of the far-infrared emitter of the above components was used by processing to the same particle size of about 325 mesh.

The antimicrobial deodorizing effect and physical properties of the composite resin compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 5 were measured by the following methods, and the results are shown in Tables 2 and 3 below.

1. Antibacterial, Deodorant

[How to measure]

1) Far-infrared emissivity: Far-infrared emissivity having a wavelength in the range of 5 to 20 μm under an outdoor air temperature of 40 ° C. is measured as a result of comparison with a black body using an FT-IR spectrometer. The test method was performed as defined in KICM-FIR-1005.

2) Antibacterial: The cultured E. coli is stored in a storage container made of the above Examples 1 to 9 and Comparative Example compositions, and after 24 hours, the reduction rate of E. coli is measured for each container.

3) Deodorization rate: Ammonia reagent, which is a reference reagent for evaluating odor, is placed in a storage container made of the above Examples 1-9 and Comparative Example composition, and after 24 hours, the decrease rate of the reagent is measured and expressed in%. .

4) Odor rating: relates to the odor grade of the finished product itself prepared in Examples 1 to 9 and Comparative Example composition, the test method was used to evaluate the odor grade for plastic products, the evaluation method is as follows.

① Place the specimen processed to standard size into 4 L sealed glass container.

② Put the sealed glass container into the oven at 100 ± 2 ℃ and heat it for 2 hours.

③ Take out the container and leave it for 1 hour at room temperature (23 ± 2 ℃), open the container about 3 ~ 4 cm to evaluate the grade according to the criteria in Table 3.

Rating Degree of smell One Irritating and intense smell 2 Strong smell 3 Weak but detectable smell 4 Odor is detected but insignificant 5 Almost undetectable odor

2. Mechanical Properties

In order to measure the physical properties of the resin compositions of Examples 1 to 9 and Comparative Examples 1 to 5, a specimen was prepared by injection molding using a composite specimen mold in accordance with ASTM standards, and physical properties were measured by the following method.

[How to measure]

(1) Melt Flow Index (MFR): measured according to ASTM D1238 (230 ℃, 2160 g)

(2) Tensile strength: measured according to ASTM D638 (TYPE I, speed: 50 mm / min)

(3) Flexural modulus: measured according to ASTM D790 (speed: 30 mm / min)

(4) Flexural strength: measured according to ASTM D790 (Speed: 30 mm / min)

(5) Izod impact strength measured according to ASTM D256 (23 ℃, -30 ℃)

(6) Rockwell hardness: measured according to ASTM D785

(7) Heat deflection temperature: measured according to ASTM D648 (load: 4.16 kg)

division Example Comparative example One 2 3 4 One 2 3 4 5 Composition (wt%) Suzy Polypropylene 88 88 88 88 88 88 88 acryl 88 ABS 88 Inorganic compounds Fresh ocher 12 12 12 12 12 12 12 12 12 Rosin (parts by weight) 0.005 0.01 0.015 0.02 - 0.15 0.2 0.01 0.01 Antibacterial, Deodorant Far Infrared 0.894 0.894 0.894 0.896 0.894 0.894 0.894 0.891 0.892 Antibacterial (%) 85 89 90 90.5 82 89 89 83 81 Deodorization rate (%) 39 41 41 41 38 41 41 40 39 Odor rating 4 4.5 3.5 3.5 3.5 2.5 2.5 3 2 Properties Melt Index Flow (g / 10min) 21 21 21 21 21 20 20 3 3.5 Tensile Strength (kgf / ㎠) 275 276 275 277 275 276 275 660 550 Elongation (%) 68 73 72 74 62 73 73 8 10 Flexural modulus (kgf / ㎠) 21900 21900 21900 21900 21900 21900 21800 32000 29000 Flexural Strength (kgf / ㎠) 410 420 410 410 410 410 410 1260 860 Impact strength (kgfcm / cm) 23 ℃ 12 12.3 12 12.2 10.6 12.2 12.1 1.6 7.5 -30 ℃ 6.6 6.9 6.7 6.8 6.1 6.8 6.8 0.5 4.5 Rockwell Hardness (R-Scale) 94 94.2 94.5 95.8 94 94.3 94.2 88 115 Heat Deflection Temperature (℃) 131.5 132.5 131 131 131 131 131 92 88

As shown in Table 2, the polyolefin-based composite resin compositions of Examples 1 to 9 containing natural rosin according to the present invention have improved antimicrobial activity, deodorization rate, and odor grade by equivalent to or more than the resin compositions of Comparative Examples 1 to 5. It could be confirmed. In addition, the mechanical properties were also improved by more than equivalent, especially the impact strength and elongation according to the temperature showed more improved value by using rosin, the dispersibility of the inorganic filler is improved and this dispersibility improvement improves the compatibility of the composition It can be seen that it forms more improved physical properties.

Example 2 and Comparative Examples 4 and 5 show the effect of the selective use of the resin, it can be seen that the difference according to the type of resin used is also large.

In addition, in the case of Examples 1 to 4 shows the physical properties according to the change in the content of the rosin, the antibacterial and deodorization rate tends to increase as the content is increased, but the odor grade is increased but maintained after a certain range regardless of the content In the case of Comparative Examples 2 and 3 outside the range set forth in the present invention, it can be seen that rather deteriorated.

division Example 5 6 7 8 9 Composition (wt%) Suzy Polypropylene 88 88 88 88 88 Inorganic fillings Calcined ocher over 600 ℃ 12 Tourmaline 12 Feldspar rock 12 jade 12 Magnetite 12 Rosin (parts by weight) 0.01 0.01 0.01 0.01 0.01 Antibacterial, Deodorant Far Infrared 0.896 0.896 0.896 0.895 0.891 Antibacterial (%) 82 84 83 80 81 Deodorization rate (%) 39 35 40 35 35 Odor rating 4 3.5 4 4 3.5 Mechanical property Melt Index Flow (g / 10min) 21.4 22 21 21.5 21.5 Tensile Strength (kgf / ㎠) 275 274 275 276 278 Elongation (%) 71 69 74 68 70 Flexural modulus (kgf / ㎠) 22100 22000 22000 21900 22200 Flexural Strength (kgf / ㎠) 415 4420 415 410 415 Impact strength (kgfcm / cm) 23 ℃ 11.8 11.2 12.4 12.2 11.4 -30 ℃ 6.6 6.7 7.0 6.8 6.6 Rockwell Hardness (R-Scale) 95.2 95 94 94.7 95.5 Heat Deflection Temperature (℃) 131 131 132 131.5 131.5

Table 3 shows the effect data according to the type of inorganic filler, and showed the same results as in the previous example. However, Comparative Example 1, which does not contain rosin, showed the same numerical difference despite having a far-infrared emissivity almost identical to that of the inorganic filler used in the Examples, which is more effective due to the shielding and neutralizing action of the rosin contained in the Examples. It can be seen that the improved effect.

As described above, the polyolefin-based composite resin composition of the present invention shields the smell generated during the vehicle body and processing by adding a small amount of rosin as well as conventional far-infrared radiation, antibacterial and deodorizing properties, and dispersibility of inorganic materials. By improving the mechanical strength by the improvement is expected to have high utilization in the field of medical or food storage containers, packaging materials and the like.

Claims (4)

In the composite resin of 80 to 95 weight% of (A) polyolefin resin and 5 to 20 weight% of inorganic filler whose (B) far-infrared emissivity is 0.8-0.93, (C) 0.001 to 0.1 parts by weight of natural resin based on 100 parts by weight of the composite resin Polyolefin-based composite resin composition for a storage container, characterized in that it contains. The polyolefin-based composite resin composition according to claim 1, wherein the polyolefin resin is one or two or more selected from polypropylene, polyethylene, polybutene, polyoctene, polyisoprene, polyethylene terephthalate and derivatives thereof. . The method of claim 1, wherein the inorganic filler is silica (SiO ₂ ) 40 to 70% by weight; 5 to 30% by weight of aluminum trioxide (Al ₂ O ₃ ); 1-15 wt% potassium oxide (K ₂ O); Iron trioxide (Fe ₂ O ₃ ) 0.05-10 wt%; And 0.01 to 10% by weight of at least one metal ion selected from Ag, Mg, Zn, Na, Zr, Mn, Sr, Ti, and Ca. The polyolefin-based composite resin composition according to claim 1, wherein the inorganic filler is one or two or more selected from feldspar rock (macbanite), tourmaline, loess, jadeite, jadeite, nephrite, and magnetite.