JPH0623274B2 - Antibacterial polyolefin composition - Google Patents

Description

The present invention relates to a polyolefin composition having antibacterial properties,
In particular, a polyolefin composition that does not discolor due to the incorporation of an antibacterial agent and has excellent antibacterial properties in terms of long-term weather discoloration resistance, hue stability at high temperature molding (for example, 230 ° C or higher), thermal stability, and molding processing stability. Regarding

[Problems to be Solved by Prior Art and Invention]

Plastic has been generally considered to be a material that has excellent resistance to microorganisms such as fungi (fungi) and bacteria, but recently various types of damage caused by mold on plastic have been reported, and anti-mold treatment is specified. The plastics in them have come into circulation.

Further, plastic molded articles such as polyolefins are widely used for kitchen appliances, bath utensils and other water supply articles, but since water is often attached, they tend to darken due to mold. It is desired to impart antibacterial properties in order to prevent this.

In order to impart antibacterial properties, it is generally necessary to blend an antibacterial agent, but as an antibacterial agent that has been conventionally used,
There are organic compounds such as organometallic compounds containing copper and tin. However, this organic antibacterial agent has a problem that antibacterial property, durability, and heat resistance are not sufficient.

On the other hand, recently, as an inorganic antibacterial agent, a zeolite carrying a metal having a bactericidal action has been proposed (Japanese Patent Laid-open No. Sho 61-206).
62-241832).

In addition, Japanese Examined Patent Publication No. 63-28402 discloses that a carbonate of an alkaline earth metal and a zeolite ion-exchanged and adsorbed with an antibacterial metal ion selected from silver ion, zinc ion, copper ion or a mixture thereof. An antibacterial composition suitable for water treatment has been proposed, which comprises a molded product of a mixture.

It has been found that the inclusion of such a zeolite-based antibacterial agent in the polyolefin improves the antibacterial property of the polyolefin. However, it was found that some polyolefins turn yellow due to the addition of an antibacterial agent. As a result of various investigations on what kind of polyolefin causes yellowing, yellowing was observed in the polyolefin (containing chlorine compound-based residue) polymerized by the Ziegler catalyst, and other non-chlorine compound-based catalysts (eg Phillips catalyst) were used. It was found that even the polymerized polyolefin containing the chlorine-containing additive showed yellowing.

As a measure against yellowing, low temperature molding or a method of adding a high concentration of pigment to suppress the initial level of discoloration or conceal the color, etc., but it cannot be said to be a highly effective method.

Therefore, an object of the present invention is to provide a chlorine compound-containing polyolefin composition which has sufficient antibacterial properties, does not discolor even when molded at high temperature, and has a stable hue for a long period of time.

[Means for Solving the Problems]

As a result of earnest research in view of the above problems, the present inventors have found that if a hindered amine-based polysiloxane compound and a neutralizing agent are added together to a polyolefin containing a chlorine compound together with an antibacterial agent, molding stability and heat processability are obtained. Further, they have found that the discoloration resistance, in particular, the weather discoloration resistance can be significantly improved without impairing the antibacterial property, and have arrived at the present invention.

That is, the antibacterial polyolefin composition of the present invention, based on 100 parts by weight of the polyolefin resin containing a chlorine compound, (a) one or more metals selected from the group consisting of silver, copper, zinc and tin. 0.1-5.0 parts by weight of an antibacterial agent retained on porous zeolite, (b) 0.01-0.5 parts by weight of a hindered amine-based polysiloxane compound, (c) hydrotalcites, calcium aluminum silicate, Periodic Table II 0.01 to 0.5 part by weight of one or more neutralizing agents selected from the group consisting of oxides and hydroxides of group III metals.

The present invention will be described in detail below.

The polyolefin that changes color by blending the antibacterial agent contains a chlorine compound. As the chlorine compound,
Ziegler-Natta catalyst chlorine compound residue (TiCl ₄ , TiC
l ₃ ), chlorine-containing additives such as flame retardants such as chlorinated paraffin, chlorinated polyethylene, and perchloropentacyclodecane, and chlorine-containing polymers such as polyvinyl chloride.

As the polyolefin itself, ethylene, propylene, butene-1, hexene-1, 4-methylpentene-
Examples thereof include homopolymers of α-olefins such as 1, copolymers of ethylene and propylene or other α-olefins, and copolymers of two or more of these α-olefins. Among these, polyethylene such as low density polyethylene, linear low density polyethylene, medium density polyethylene and high density polyethylene and polypropylene are preferable.
Polypropylene is not limited to a homopolymer, and a random or block copolymer with another α-olefin containing a propylene component in an amount of 50 mol% or more, preferably 80 mol% or more can also be used. As a comonomer copolymerized with propylene, there are ethylene and other α-olefins,
Ethylene is particularly preferred. Therefore, the term "polypropylene" as used herein should be understood to include not only homopolymers of propylene but also copolymers.

The antibacterial polyolefin composition of the present invention contains an antibacterial agent and a discoloration preventing additive in the following mixing ratio with respect to 100 parts by weight of a chlorine resin-containing polyolefin resin.

(a) 0.1 to 5.0 parts by weight of antibacterial agent (b) 0.01 to 0.5 parts by weight of hindered amine polysiloxane compound, and (c) 0.01 to 0.5 parts by weight of neutralizing agent.

In the present invention, the antibacterial agent (a) is one in which one or more metals selected from the group consisting of silver, copper, zinc and tin are held in the porous zeolite in an ionic state.

As such an antibacterial agent, for example, zeolite having a metal having an antibacterial action proposed in JP-B-63-28402 can be mentioned.

As a zeolite suitable as a base material for holding an antibacterial agent, a porous zeolite having an ion exchange capacity of 1 meq / g (anhydrous standard) or more and a large specific surface area is preferable. For example, synthetic zeolites are A type and X type. Alternatively, Y-type zeolite, synthetic mordenite and the like are preferable, while as natural zeolite, mordenite, chronobutylolite, chabazite and the like are preferable.

Since the zeolite is contained in the polyolefin in the present invention, a powdery product having a particle size as small as possible is preferable, and particularly active zeolite powder having an average particle size of 15 μm or less is suitable for uniform dispersion. It is preferable that the above-mentioned powder has as little secondary aggregation as possible.

Further, it is preferable that the cation exchange capacity of the zeolite is large, but as described above, at least 1 meq / g
It is preferably (anhydrous basis) or more and has a high ion exchange rate.

By using the zeolite having such properties, it is possible to adjust the amount of the antibacterial metal ion, alone or a plurality of the antibacterial metal ions, to be adjusted by an ion exchange method to prepare an antibacterial agent having a desired antibacterial property. .

The amount of the bactericidal metal compounded is 0.
The amount is 005% by weight to the saturated amount. Here, the saturation amount is the saturation value of the ion exchange capacity of the zeolite used. 0.005
When the metal content is lower than wt%, sufficient antibacterial action cannot be obtained. A preferable metal compounding amount is 0.10 to 5.0% by weight.

The antibacterial agent used in the present invention has a cation exchange capacity of 1 meq /
To a porous zeolite of g (anhydrous basis) or more, 0.005% by weight or more of a metal having a bactericidal action is added in an ionic state,
It is activated by heating to reduce the water content to 5% by weight or less. If the water content is larger than this, discoloration is caused, which is not preferable. The heat activation is usually performed at 250 to 500 ° C (in air atmosphere), but it can be performed at 150 to 350 ° C under reduced pressure. Further, the zeolite which is mixed with a metal and activated by heating is appropriately pulverized to obtain an average particle size of 15 μm or less.

The content of the antibacterial agent is 0.1 to 5.0 parts by weight, preferably 0.15 to 1.0 part by weight, based on 100 parts by weight of the polyolefin. When the content of the antibacterial agent is less than 0.1 parts by weight, the antibacterial property is not sufficient, and even when it exceeds 5.0 parts by weight, not only the effect corresponding to that cannot be obtained but also the degree of discoloration becomes large.

Further, examples of the hindered amine-based polysiloxane compound added to the polyolefin in the present invention include those represented by the following general formula. Specific examples thereof include polymethylpropyl-3-oxy [4- (2,2,6,6-tetramethyl) piperidyl] siloxane.

[Wherein x is a positive integer of 1 to 8 and n is 2 to 12]
Is a positive integer and R is a methyl group or hydrogen. The content of the hindered amine polysiloxane compound is 0.01 to 0.5 part by weight, preferably 0.015 to 0.3 part by weight, based on 100 parts by weight of the polyolefin. If the content of the hindered amine-based polysiloxane compound is less than 0.01 parts by weight, the effects of suppressing discoloration, improving heat resistance, etc. and the thermal stability are insufficient, and even if it exceeds 0.3 parts by weight, the effect corresponding to it is improved. I can't get it.

The neutralizing agent (c) is one or more selected from the group consisting of hydrotalcites, calcium aluminum silicate, oxides and hydroxides of metals of Group II of the periodic table. The hydrotalcites do not contain a water-containing basic carbonate such as magnesium, calcium, zinc, aluminum, bismuth, etc. or its crystal water, and include natural products and synthetic products. As a natural product, Mg ₆ Al ₂ (O
H) ₁₆ CO ₃ .4H ₂ O structure. In addition, as synthetic products, Mg _0.7 Al _0.3 (OH) ₂ (CO ₃ ) _0.15・ 0.54H ₂ O, Mg
_4.5 Al ₂ (OH) ₁₃ CO ₃ / 3.5H ₂ O, Mg _4.2 Al ₂ (OH) _12.4 CO ₃ , Zn ₆ A
_{l 2 (OH) 16 CO 3} · 4H 2 O, Ca 6 Al 2 (OH) 16 CO 3 · 4H 2 O, Mg 14 Bi
₂ (OH) _29.6 / 4.2H ₂ O and the like can be mentioned. Further, as the metal of Group II of the periodic table, magnesium, calcium,
Zinc or the like is preferable.

The content of the neutralizing agent is 0.01 to 0.5 part by weight, preferably 0.015 to 0.3 part by weight, based on 100 parts by weight of the polyolefin. If the content of the neutralizing agent is less than 0.01 part by weight, the effect of reducing discoloration is not sufficient, and if it exceeds 0.5 part by weight, the corresponding improvement in effect cannot be obtained.

In the present invention, (d) a phosphorus-based antioxidant and / or (e) a phenol-based antioxidant can be added in order to further improve thermal stability and thermoformability.

(d) Examples of phosphorus-based antioxidants include phosphorus-based stabilizers such as alkyl phosphite, alkylallyl phosphite, allyl phosphite, and alkylphosphonite, and specifically, distearyl pentaerythritol diphosphite. , Tris (2,4-di-t-butylphenyl)
Phosphite, tetrakis (2,4-di-t-butylphenyl)
-4,4'-biphenylene phosphonite, bis (2,4-di-t-
Butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite, 1,1,3-tris (2-methyl-4-ditridecylphosphite- Examples thereof include 5-t-butylphenyl) butane.

The content of the phosphorus-based antioxidant is polyolefin 100
With respect to parts by weight, preferably 0.01 to 0.5 parts by weight, particularly 0.0
15 to 0.3 parts by weight is preferred. When the content of the phosphorus-based antioxidant is less than 0.01 part by weight, the effect of improving the thermal stability and thermoformability is not sufficient, and even when it exceeds 0.5 part by weight, the corresponding effect cannot be obtained. .

Further, (e) phenolic antioxidants include 2,6-di-t-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-t-butyl). -4-hydroxyphenyl) propionate, distearyl (3,5-di-
t-Butyl-4-hydroxybenzyl) phosphonate, 2,2 ′
-Methylenebis (4-methyl-6-t-butylphenol), 2,
2'-methylenebis (4-ethyl-6-t-butylphenol), bis [3,3-bis (4-hydroxy-3-t-butylphenyl) butyric acid] glycol ester, 4,4 '
-Butylidene bis (6-t-butyl-m-cresol), 2,2 '
-Ethylidene bis (4,6-di-t-butylphenol), 2,
2'-ethylidene bis (4-sec-butyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, bis [2-t- Butyl-4-methyl-6-
(2-Hydroxy-3-t-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, 1,
3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-
(Hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,
5-tris [(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 2-t-butyl-4-methyl-
6- (2'-acryloyloxy-3'-t-butyl-5'-methylbenzyl) phenol, 3,9-bis (1 ', 1'-dimethyl-2'-hydroxyethyl) -2,4,8 Examples include 10,10-tetraoxaspiro [5,5] undecane and bis [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate. Among these, 1,3,5-tris (2,6-dimethyl-
3-hydroxy-4-t-butylbenzyl) isocyanurate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and the like are preferable.

The content of the phenolic antioxidant is preferably 0.01 to 0.3 parts by weight, and particularly preferably 0.015 to 0.07 parts by weight, based on 100 parts by weight of the polyolefin. If the content of the phenolic antioxidant is less than 0.01 part by weight, the effect of improving thermal stability and thermoformability is not sufficient, and if it exceeds 0.3 part by weight, the corresponding effect cannot be obtained. .

In addition, in order to add the above-mentioned antibacterial agent, hindered amine-based polysiloxane compound, neutralizing agent, and phosphorus-based antioxidant and phenol-based antioxidant that are added as necessary to the polyolefin, a commonly used method is used. You can use it. For example, a method in which an antibacterial agent and these additives are mixed with polyolefin, premixed, and then kneaded with an extruder is suitable.

The antibacterial polymer composition of the present invention has other additives for the purpose of modification thereof, such as inorganic fillers such as talc, mica and wollastonite, heat stabilizers, light stabilizers, flame retardants. , A plasticizer, an antistatic agent, a release agent, a foaming agent, a nucleating agent and the like can be added.

As described in detail above, in the present invention, an antibacterial agent, a hindered amine-based polysiloxane compound, a neutralizing agent, and a phosphorus-based antioxidant added as necessary to a polyolefin containing a chlorine compound, and Since the phenolic antioxidant is added in combination, the antibacterial polyolefin composition of the present invention has very little discoloration such as yellowing due to the incorporation of the antibacterial agent, and further, the hue stability in high temperature molding is improved and the weather resistance is improved. Discoloration, molding process stability and thermal stability are also improved. Therefore, it has a high commercial value in a wide range of applications.

〔Example〕

Hereinafter, examples show the hue stability, weather discoloration resistance, molding process stability, heat stability and antibacterial property of the antibacterial polyolefin composition in high temperature molding.

Examples 1-7, Comparative Examples 1-5 Homopolypropylene (HP
P, J209, Tonen Petrochemical Co., Ltd., 100 parts by weight
As shown in the table, antibacterial agent, hindered amine-based polysiloxane compound, hydrotalcite or MgO as a neutralizing agent,
Phosphorus antioxidant, phenolic antioxidant, and other additives were added respectively, premixed with 40 Henschel mixer, and then this mixture was mixed with an extruder (50 mm
(φ, single screw), and melt-kneaded at 70 rpm under N ₂ blow to pelletize. The resin temperature in the extruder was 190 ° C. at the rear of the cylinder (hopper side), 200 ° C. in the middle of the cylinder, 220 ° C. at the front of the cylinder, and 220 ° C. at the die.

The additives used are as follows.

(1) Antibacterial agent An ₁ : Antibacterial agent containing Ag and Zn ions, trade name: BACTEKILLER (manufactured by Kanebo Co., Ltd.) (2) Hindered amine polysiloxane compound HA: Polymethylpropyl-3-oxy [4- (2, 2,6,6-Tetramethyl) piperidyl] siloxane, trade name: UVASIL 299
(Manufactured by Enichem Synthesis) (3) Hydrotalcites D ₁ : basic magnesium / aluminum / hydroxy / carbonate / hydrate Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ /
3.5H ₂ O, product name: DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) (4) Magnesium oxide MgO: product name: Micromag (manufactured by Kyowa Chemical Industry Co., Ltd.) (5) Phosphorus antioxidant P ₁ : Tris (2,4-di-t-butylphenyl) phosphite, trade name: Mark2112 (manufactured by ADEKA ARGUS CORPORATION) (6) Phenolic antioxidant Ph ₁ : Tetrakis [methylene-3- (3,5 - di -t- butyl-4-hydroxyphenyl) propionate] methane, trade name: Irganox1010 (Ciba Geigy) Ph _2: 1,3,5-tris (2,6-dimethyl-3-hydroxy -4-t- Butylbenzyl) isocyanurate Product name: CYANOX1790 (A.C.C.) (7) Others A: Calcium stearate (Nitto Kasei Co., Ltd.) B: 2- (3-t-butyl-5-methyl-2-) Hydroxyphenyl) -5
-Chlorobenzotriazole Product name: TINUVIN 326 (manufactured by Ciba Geigy) Color hue meter (digital colorimetric color difference meter) manufactured by Suga Test Instruments Co., Ltd.
It was measured at.

Next, the pellets were molded into a test piece of 80 mm × 80 mm × 2 mm at an injection temperature of 240 ° C. by an 8 ounce injection molding machine manufactured by Sumitomo Heavy Industries Ltd., and then the hue of the test piece was measured in the same manner.

Moreover, a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.) was used for this test piece to measure the black panel temperature 60
Irradiate with ultraviolet rays for 200 hours under conditions of ℃ and no rain,
The hue after irradiation was measured in the same manner.

Furthermore, this test piece was placed in an Escherichia coli suspension, and the number of viable bacteria in the solution before and after shaking for 1 hour was measured to check the antibacterial property.

The antibacterial property was evaluated according to the following criteria.

⊚: E. coli reduction rate> 99.9%.

○: Escherichia coli reduction rate is 80 to 99.9%.

Δ: Escherichia coli reduction rate <80%.

X: Not decreased.

The pellets were molded into 20 mm × 30 mm × 2 mm test pieces, and the test pieces were left in a 150 ° C. gear oven, and the time until deterioration crazing was measured to check the thermal stability.

The thermal stability was evaluated according to the following criteria.

⊚: 14 hours ≦ degradation start time.

◯: 7 hours <degradation start time <14 hours.

X: Degradation start time ≦ 7 hours.

Furthermore, using a 50 mmφ extruder, each composition was extruded three times in succession (resin temperature: 240 ° C.).
From the FR (melt flow rate, 230 ° C, 2.16 kg load) and the initial MFR value, the change rate of MFR (ΔMFR) according to the following formula
Then, the molding processing stability was checked.

The molding processing stability was evaluated according to the following criteria.

⊚: ΔMFR ≦ 20%.

○: 20% <ΔMFR ≤ 40%.

Δ: 40% <ΔMFR <60%.

X: 60% ≤ ΔMFR The results are shown in Table 1.

In addition, as a comparative example, the same measurement and evaluation were performed for a hindered amine-based polysiloxane compound and one in which any one of the neutralizing agents was omitted. The results are also shown in Table 1.

Examples 8 to 11, Comparative Examples 6 and 7 100 parts by weight of propylene-ethylene random copolymer (RPP: ethylene content 0.01 to 5% by weight, J415T, manufactured by Tonen Petrochemical Co., Ltd.) manufactured using a Ziegler catalyst. First
As shown in the table, antibacterial agent, hindered amine-based polysiloxane compound, hydrotalcite or MgO as a neutralizing agent,
A phosphorus-based antioxidant, a phenol-based antioxidant, and other additives were added, respectively, in the same manner as in Example 1,
Pelletized.

The initial hue of the obtained pellets after molding was measured in the same manner as in Example 1.

Next, the pellets were molded into a test piece of 80 mm × 80 mm × 2 mm at an injection temperature of 240 ° C. by an 8 ounce injection molding machine manufactured by Sumitomo Heavy Industries Ltd., and then the hue of the test piece was measured in the same manner.

Moreover, a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.) was used for this test piece to measure the black panel temperature 60
Irradiate with ultraviolet rays for 200 hours under conditions of ℃ and no rain,
The hue after irradiation was measured in the same manner.

Further, this test piece was subjected to the same antibacterial check as in Example 1.

Further, the pellets were molded into a test piece of 20 mm × 30 mm × 2 mm, and this test piece was checked for thermal stability in the same manner as in Example 1.

Further, the molding processing stability was evaluated by the same method as in Example 1.

The results are also shown in Table 1.

In addition, as a comparative example, the same measurement and evaluation were performed for the one in which the hindered amine-based polysiloxane compound was omitted. The results are also shown in Table 1.

Examples 12 to 15, Comparative Examples 8 and 9 Propylene-ethylene block copolymers (BPP: ethylene content 5 to 20% by weight, B
100 parts by weight of J309, manufactured by Tonen Petrochemical Co., Ltd., as shown in Table 1, antibacterial agent, hindered amine polysiloxane compound, hydrotalcite or MgO as neutralizing agent, phosphorus antioxidant, phenolic antioxidant The agent and other additives were each mixed and pelletized in the same manner as in Example 1.

The initial hue of the obtained pellets after molding was measured in the same manner as in Example 1.

Next, the pellets were molded into a test piece of 80 mm × 80 mm × 2 mm at an injection temperature of 240 ° C. by an 8 ounce injection molding machine manufactured by Sumitomo Heavy Industries Ltd., and then the hue of the test piece was measured in the same manner.

Moreover, a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.) was used for this test piece to measure the black panel temperature 60
Irradiate with ultraviolet rays for 200 hours under conditions of ℃ and no rain,
The hue after irradiation was measured in the same manner.

Further, this test piece was subjected to the same antibacterial check as in Example 1.

Further, the pellets were molded into a test piece of 20 mm × 30 mm × 2 mm, and this test piece was checked for thermal stability in the same manner as in Example 1.

Further, the molding processing stability was evaluated by the same method as in Example 1.

The results are also shown in Table 1.

In addition, as a comparative example, the same measurement and evaluation were performed for the one in which the hindered amine-based polysiloxane compound was omitted. The results are also shown in Table 1.

Examples 16 to 19 and Comparative Examples 10 and 11 High-density polyethylene (HD
No. 1 in 100 parts by weight of PE, J6311, Tonen Petrochemical Co., Ltd.
As shown in the table, antibacterial agent, hindered amine-based polysiloxane compound, hydrotalcite or MgO as a neutralizing agent,
Phosphorus antioxidant, phenolic antioxidant, and other additives were added respectively, premixed with 40 Henschel mixer, and then this mixture was mixed with an extruder (50 mm
(φ, single screw), and melt-kneaded at 70 rpm under N ₂ blow to pelletize. The resin temperature in the extruder was 160 ° C in the rear part of the cylinder (hopper side), 180 ° C in the middle part of the cylinder, 200 ° C in the front part of the cylinder, and 200 ° C in the die.

The initial hue of the obtained pellets after molding was measured in the same manner as in Example 1.

Next, the pellets were molded into a test piece of 80 mm × 80 mm × 2 mm at an injection temperature of 240 ° C. by an 8 ounce injection molding machine manufactured by Sumitomo Heavy Industries Ltd., and then the hue of the test piece was measured in the same manner.

Moreover, a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.) was used for this test piece to measure the black panel temperature 60
Irradiate with ultraviolet rays for 200 hours under conditions of ℃ and no rain,
The hue after irradiation was measured in the same manner.

Further, for this test piece, in the same manner as in Example 1,
The antibacterial property and the molding processing stability were evaluated.

The results are also shown in Table 1.

In addition, as a comparative example, the same measurement and evaluation were performed for the one in which the hindered amine-based polysiloxane compound was omitted. The results are also shown in Table 1.

Examples 20 to 23, Comparative Examples 12 and 13 100 parts by weight of linear low-density polyethylene (LLDPE, NUCG-5381, manufactured by Nippon Unicar Co., Ltd.) produced using Ziegler catalyst was added to the antibacterial agent as shown in Table 1. , Hindered amine-based polysiloxane compound, hydrotalcite or MgO as a neutralizing agent, a phosphorus-based antioxidant, a phenol-based antioxidant, and other additives, respectively, and premixed with a 40 Henschel mixer, then Then, this mixture was melt-kneaded with an extruder (50 mmφ, single screw) at 70 rpm under N ₂ blow to form pellets. The resin temperature in the extruder is 160 ° C at the rear of the cylinder (hopper side).
180 ° C in the middle of the cylinder, 200 ° C in the front of the cylinder, with a die
It was set to 200 ° C.

The initial hue of the obtained pellets after molding was measured in the same manner as in Example 1.

Next, the pellets were molded into a test piece of 80 mm × 80 mm × 2 mm at an injection temperature of 240 ° C. by an 8 ounce injection molding machine manufactured by Sumitomo Heavy Industries Ltd., and then the hue of the test piece was measured in the same manner.

Moreover, a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.) was used for this test piece to measure the black panel temperature 60
Irradiate with ultraviolet rays for 200 hours under conditions of ℃ and no rain,
The hue after irradiation was measured in the same manner.

Further, for this test piece, in the same manner as in Example 1,
The antibacterial property and the molding processing stability were evaluated.

The results are also shown in Table 1.

In addition, as a comparative example, the same measurement and evaluation were performed for the one in which the hindered amine-based polysiloxane compound was omitted. The results are also shown in Table 1.

As is clear from Table 1, the antibacterial polyolefin composition of the present invention has good antibacterial properties, molding processing stability, and thermal stability, and the degree of yellowing and discoloration after thermoforming is reduced. There is. Moreover, the degree of yellowing and discoloration is kept low even after long-term irradiation with ultraviolet rays.

〔The invention's effect〕

The antibacterial polyolefin composition of the present invention has sufficient antibacterial properties, molding stability, and thermal stability, and yellowing and discoloration due to the incorporation of an antibacterial agent are suppressed to a sufficiently satisfactory level, Moreover, the weather discoloration resistance is also improved. The antibacterial polyolefin composition having such characteristics is suitable for various kitchen utensils, bath utensils, and other water-related products.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location // (C08L 23/00 83:08) (C08K 13/06 3:00 5:13 5:54 5:49 9:12) (72) Inventor Go Kawauchi 3-1, Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Tonen Petrochemical Co., Ltd. Technology Development Center (72) Toru Matsumura Chidori, Kawasaki-ku, Kawasaki-shi, Kanagawa 3-1, Machi Tonen Petrochemical Co., Ltd. Technical Development Center (72) Inventor Masahiro Shoda 10-5 Uenomachi, Ibaraki-shi, Osaka (72) Inventor Yoshikazu Kimura 1-chome, Senbonminami, Nishinari-ku, Osaka-shi, Osaka 15-31 (56) References Japanese Patent Laid-Open No. 63-265958 (JP, A)

Claims (7)

[Claims] 1. A polyolefin resin containing a chlorine compound.
With respect to 100 parts by weight, (a) 0.1 to 5.0 parts by weight of an antibacterial agent obtained by allowing a porous zeolite to hold one or more metals selected from the group consisting of silver, copper, zinc and tin, ( b) 0.01 to 0.5 parts by weight of a hindered amine-based polysiloxane compound, and (c) a kind selected from the group consisting of hydrotalcites, calcium aluminum silicate, oxides and hydroxides of metals of Group II of the periodic table. Or two or more neutralizing agents 0.01
The antibacterial polyolefin composition is characterized by containing 0.5 to 0.5 parts by weight. 2. The antibacterial polyolefin composition according to claim 1, further comprising (d) 0.01 to 0.5 parts by weight of a phosphorus-based antioxidant, and / or 100 parts by weight of the polyolefin.
Alternatively, (e) an antibacterial polyolefin composition comprising 0.01 to 0.3 part by weight of a phenolic antioxidant. 3. The antibacterial polyolefin composition according to claim 1 or 2, wherein the chlorine compound is a residue of a Ziegler catalyst. 4. The antibacterial polyolefin composition according to any one of claims 1 to 3, wherein the chlorine compound is a chlorine-containing additive. 5. The antibacterial polyolefin composition according to any one of claims 1 to 4, wherein the hindered amine-based polysiloxane compound is polymethylpropyl-3-oxy [4- (2,2,6,6- An antibacterial polyolefin composition, which is tetramethyl) piperidyl] siloxane. 6. The antibacterial polyolefin composition according to claim 2, wherein the phosphorus-based antioxidant is tris (2,4-di-t-butylphenyl) phosphite.
Selected from bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-t-butylphenyl) butane An antibacterial polyolefin composition comprising one or more kinds. 7. The antibacterial polyolefin composition according to claim 2, wherein the phenolic antioxidant is 1,3,5-tris (2,6-dimethyl-3-hydroxy-4).
An antibacterial polyolefin composition, which is -t-butylbenzyl) isocyanurate and / or tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane.