JPH03181538A - Antifungal polyolefin composition - Google Patents

Abstract

PURPOSE:To prove the title composition excellent in antifungal performance, molding processing stability, thermal stability and weathering discoloration resistance, suitable for kitchen and bath utensils, etc., comprising a chlorine compound-contg. polyolefin resin, antifungal agent, hindered amine compound and neutralizing agent at specified proportion. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100 pts.wt. of a chloride compound-contg. polyolefin resin with (B) 0.1-5.0 (pref. 0.15-1.0) pts.wt. of an antifungal agent (pref. zeolite carried with an antifungal metal like silver, copper, zinc or tin), (B) 0.01-0.5 (pref. 0.015-0.3) pts.wt. of a hindered amine compound {pref. polymethylpropyl-3-oxy[4-(2,2,6,6- tetramethyl)piperidyl]siloxane} and (C) 0.01-0.5 (pref. 0.015-0.3) pts.wt. of a neutralizing agent (e.g. a hydrotalcite).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polyolefin composition having antibacterial properties,
In particular, a polyolefin composition with antibacterial properties that does not discolor due to the combination of antibacterial agents, has long-term weather resistance, and has excellent hue stability, thermal stability, and molding stability during high temperature molding (e.g., 230°C or higher). relating to things.

[Prior art and problems to be solved by the invention] Plastics have generally been considered to be materials with excellent resistance to microorganisms such as fungi and bacteria, but recently plastic molds have caused various types of problems. Cases of damage have been reported, and plastics with anti-mold treatment are now on the market.

In addition, plastic molded products such as polyolefin are widely used for kitchen items, bath utensils, and other plumbing products, but because they are often contaminated with water, they tend to darken due to mold. To prevent this, it is desired to impart antibacterial properties.

In order to impart antibacterial properties, it is generally necessary to incorporate an antibacterial agent, but the antibacterial agents that have traditionally been used include:
There are organic compounds such as organometallic compounds containing copper, tin, etc. However, this organic antibacterial agent has problems in that it does not have sufficient antibacterial properties, durability, or heat resistance.

On the other hand, recently, a zeolite containing a metal having a bactericidal action has been proposed as an inorganic antibacterial agent (Japanese Patent Application Laid-Open No. 62-241832).

In addition, Japanese Patent Publication No. 63-28402 describes a zeolite in which one alkaline earth gold carbonate and an antibacterial metal ion selected from silver ions, zinc ions, copper ions, or a mixture thereof are adsorbed by ion exchange. An antibacterial composition suitable for water treatment consisting of a molded mixture of

It has been found that by incorporating such a zeolite-based antibacterial agent into a polyolefin, the antibacterial properties of the polyolefin are improved. However, it has been found that some polyolefins yellow due to the addition of antibacterial agents. As a result of various studies to determine which types of polyolefins cause yellowing, it was found that yellowing was observed in polyolefins polymerized using Ziegler catalysts (containing chlorine compound residues), and in addition, yellowing was observed in polyolefins polymerized using Ziegler catalysts (containing chlorine compound residues). It was found that yellowing was observed even in polymerized polyolefins containing chlorine-containing additives.

Possible countermeasures against yellowing include low-temperature molding and adding high-concentration pigments to suppress or hide the level of initial discoloration, but these methods cannot be said to be highly effective.

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

[Means for Solving the Problems] In view of the above problems, as a result of intensive research, the present inventors have found that if a compound of a hindered amine compound and a neutralizing agent is added to a polyolefin containing a chlorine compound along with an antibacterial agent, molding can be achieved. The present inventors have discovered that it is possible to significantly improve discoloration resistance, particularly severe discoloration, without impairing stability, heat processability, and antibacterial properties, and have conceived the present invention.

That is, the antibacterial polyolefin composition of the present invention contains (a) 0.1 to 5.0 parts by weight of an antibacterial agent and (b) 0.01 to 0.01 to 5.0 parts by weight of a hindered amine compound, based on 100 parts by weight of a polyolefin resin containing a chlorine compound. 0.5 parts by weight and (c
) 0.01 to 0.5 parts by weight of a neutralizing agent.

The present invention will be explained in detail below.

Polyolefins that change color due to the addition of antibacterial agents contain chlorine compounds. The above chlorine compounds include:
Chlorine compound residue of Ziegler-Natsuta catalyst (T+Cfl
4, T+ (j! 3), chlorine-containing additives such as flame retardants such as chlorinated halaffin, chlorinated polyethylene, perchloropentacyclodecane, and other chlorine-containing polymers such as polyvinyl chloride.

The polyolefins themselves include ethylene, propylene, butene-1, hexene-1,4-methylpentene-
Examples include homopolymers of α-olefins such as No. 1, copolymers of ethylene and propylene or other α-olefins, and copolymers of two or more of these α-olefins. Among these, polyethylene and polypropylene such as low density polyethylene, linear low density polyethylene, medium density polyethylene, and high density polyethylene are preferred.

Polypropylene is not limited to a homopolymer, and random or block copolymers with other α-olefins containing a propylene component of 50 mol% or more, preferably 80 mol% or more can also be used.

Comonomers copolymerized with propylene include ethylene and other α-olefins, with ethylene being particularly preferred. Therefore, the term "polypropylene" used herein is not limited to homopolymers of propylene, but should be understood to include copolymers as well.

The antibacterial polyolefin composition of the present invention contains an antibacterial agent and an additive for preventing discoloration in the following proportions.

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

In the present invention, as the antibacterial agent (a), it is preferable to use an inorganic agent such as zeolite containing a metal having a bactericidal effect, from the viewpoint of antibacterial properties when blended with the polyolefin. Particularly preferred is one in which one or more metals from the group consisting of silver, copper, zinc, and tin are retained in a porous zeolite in an ionic state.

Such antibacterial agents include, for example, Japanese Patent Publication No. 63-28
Zeolite that retains metals and has an antibacterial effect is proposed in No. 402.

Zeolites suitable for holding antibacterial agents are preferably porous ones with an ion exchange capacity of 1 meq/g or more (anhydrous standard) and a large specific surface area.For example, synthetic zeolites include type A, type Type or Y type zeolite, platform mordenite, etc. are suitable, while as natural zeolites, mordenite, talonobutyrolite, chabasite, etc. are suitable.

Since the zeolite is contained in the polyolefin in the present invention, it is preferably a powdered product with a particle size as small as possible. In particular, active zeolite powder with an average particle size of 15 or less is suitable for uniform dispersion. The above powder preferably has as little secondary agglomeration as possible.

Furthermore, it is preferable that the cation exchange capacity of the zeolite is large, but in particular, as mentioned above, it is at least 1 meq/
g (anhydrous standard) or more and has a high ion exchange rate.

By using a zeolite having such characteristics, the amount of the antibacterial metal ion retained alone or in combination can be arbitrarily adjusted by an ion exchange method to prepare an antibacterial agent having desired antibacterial properties. .

The amount of metal with bactericidal properties is 0 for the entire antibacterial agent.
．． 0.005% by weight to saturation amount. Here, the saturated amount is the saturated value of the ion exchange capacity of the zeolite used. 0
．． If the metal content is lower than 0.005% by weight, sufficient antibacterial action cannot be obtained. The preferred metal content is 0. lO~5.
It is 0% by weight.

The antibacterial agent used in the present invention has a cation exchange capacity of Ime.
q/g (anhydrous standard) or more of porous zeolite is added with 0.005% by weight or more of a metal having a bactericidal effect in the form of ions, and activated by heating to reduce the water content to 5% by weight or less. If the water content is higher than this, it may cause discoloration and is not preferable. In addition, heating activation is usually performed at 250 to 500℃.
(in air atmosphere), but under reduced pressure it is 150 to 350
It can be done at ℃.

Furthermore, the zeolite blended with metal and activated by heat is appropriately ground to give an average particle size of 15 um or less.

The content of the antibacterial agent is 0.1 to 5.0 parts by weight, preferably 0.15 to 1 part by weight, per 100 parts by weight of the polyolefin.
．． It is 0 parts by weight. If the content of the antibacterial agent is less than 0.1 parts by weight, the antibacterial properties will not be sufficient, and if it exceeds 5.0 parts by weight, not only will the effect be not commensurately improved, but the degree of discoloration will increase.

Further, examples of the hindered amine compound added to the polyolefin in the present invention include those represented by the following general formula. Specifically, polymethylpropyl-3
Examples include hindered amine polysiloxane compounds such as -oxy(4-(2,2,6,6-tetramethyl)piperidylcosiloxane).

[However, in the formula, X is a positive integer of 1 to 8, and n is 2 to 1
is a positive integer of 2, and R is a methyl group or hydrogen.

] The content of the hindered amine compound is 0.01-0.5 parts by weight, preferably 0.015-0.3 parts by weight, based on 100 parts by weight of the polyolefin. If the content of the hindered amine compound is less than 0.01 parts by weight, effects such as suppressing discoloration and improving heat resistance and thermal stability will not be sufficient, and even if the content exceeds 0.3 parts by weight, the effects will not improve commensurately. is not obtained.

Further, as the neutralizing agent (c), hydrotalcites, calcium aluminum silicate, oxides and hydroxides of metals of group Ⅰ of the periodic table, etc. can be used. The above-mentioned hydrotalcites include water-containing basic carbonates such as magnesium, calcium, zinc, aluminum, and bismuth, or those that do not contain crystal water, and include natural products and synthetic products.

As a natural product, iJgsA122 (DH) l 6
Examples include those having the structure CO3.4 H20. Also, as a synthetic product, Mgo.

7AAo, 3(OH)2(cO3)O,Is' 0
．． 54H20, Mg,, s AL(ON),, Co3
・ 3.5H20, Mg<, 2 Aj22 (O
)l) I 2□C03, Zo, ノ\n 2 (DH>
, ecL・4H20, Cat+A, g 2
(Off) l 6CO3' 4820,! J
Examples include gzBiz(OR) 29.6 and 4.21120. Further, as the above-mentioned metal of Group Ⅰ of the periodic table, magnesium, calcium, zinc, etc. are preferable.

The content of the neutralizing agent is 0.01 to 0.5 parts by weight, preferably 0.01 parts by weight, based on 100 parts by weight of the polyolefin.
It is 5 to 0.3 parts by weight. If the content of the neutralizing agent is less than 0.01 parts by weight, the effect of reducing discoloration will not be sufficient, and
, even if it exceeds 5 parts by weight, no commensurate improvement in effects can be obtained.

In the present invention, in order to further improve thermal stability and thermoformability, (d) an IJ compound and/or (e)
Phenolic compounds can be added.

(d) As the phosphorus compound, alkyl phosphite,
Examples include phosphorus stabilizers such as alkylaryl phosphite, allyl phosphite, and alkyl phosphonite, specifically distearyl pentaerythritol diphosphite and tris(2,4-di-t-butylphenyl) phosphite. , tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylenephosphonite,
Bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2゜5-sheet t-'':
Butyl-4-methylphenyl)pentaerythritol-
diphosphite, 1.1.3- ) lis(2-methyl-
Examples include 4=ditridecylphosphite-5-t-butyl)butane.

The content of the phosphorus compound is preferably 0.01 to 0.5 parts by weight, and preferably 0.15 to 0.3 parts by weight, based on 100 parts by weight of the polyolefin. If the content of the phosphorus compound is less than 0.01 part by weight, the effect of improving thermal stability, thermoformability, etc. will not be sufficient, and even if it exceeds 0.5 parts by weight, the effect will not be commensurately improved. I can't do it.

In addition, (e) phenolic compounds include 2.6-sheet t-butyl-p-cresol, 2.6-diphenyl-4-
Octadesiloxyphenol, 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[343-bis(4-hydroxy-3-t-
butylphenyl) butyric acid coglycol ester, 4,4'-butylidene bis(6-t-butyl-m
-cresol), 2,2°-ethylidene bis(4,6-
di-t-butylphenol), 2.2゛ethylidenebis(4-sec-butyl-6-t-butylphenol),
1. ], 3-) Lis(2-methyl-4-hydroxy-5-t-butylphenyl)butane, Bis I: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-)lis(3, 5-dit-butyl-4-
Hydroxybenzyl)isocyanurate, 1.3.5-
) Lis(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-tristilbenzene, 1,3°5-tris[(3,5-di-savetyl-4-hydroxyphenyl) ) propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3,5-di-t-
Butyl-4-hydroxyphenyl)propionate comethane, 2-t-butyl-4-methyl-6-(2'-acryloyloxy-3'-t-butyl-5'-methylbenzyl)phenol, 3.9bis (1',1°-dimethyl-
2°-hydroxyethyl)-2,4-8°10-tetraoxaspiro[5,5] undecane bis[t(3-t
-butyl-4-hydroxy-5-methylphenyl) propionate and the like. Among these, 1, 3
．． 5-) Lis(2,6-dimethyl-3-hydroxy-
Preferred are 4-t-butylbenzyl) isocyanurate, tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane, and the like.

The content of the above phenolic compound is polyolefin 1
0.01 to 0.3 parts by weight, particularly preferably 0.015 to 0.07 parts by weight.

If the content of the phenolic compound is less than 0.01 parts by weight, the effect of improving thermal stability, thermoformability, etc. will not be sufficient, and even if it exceeds 0.3 parts by weight, the effect will not be commensurately improved. I can't do it.

Note that a commonly used method may be used to add the above-mentioned antibacterial agent, hindered amine compound, neutralizing agent, and optionally added phosphorus compound and phenol compound to the polyolefin. For example, a suitable method is to blend polyolefin with an antibacterial agent and these additives, premix them, and then knead them in an extruder.

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

As detailed above, in the present invention, a polyolefin containing a chlorine compound is combined with an antibacterial agent, a hindered amine compound, a neutralizing agent, and a phosphorus compound and a phenol compound added as necessary. As a result, the antibacterial polyolefin composition of the present invention has extremely little discoloration such as yellowing due to the combination of antibacterial agents, and has improved hue stability during high temperature molding, and has excellent weather resistance and molding process stability. and thermal stability has also been improved. Therefore, it has a high commercial value in a wide range of applications.

〔Example〕

Hereinafter, the hue stability in high-temperature molding, weather resistance, molding process stability, thermal stability, and antibacterial properties of antibacterial polyolefin compositions will be shown in Examples.

Examples 1 to 7, Comparative Examples 1 to 5 Homopolypropylene (H
PP 5J209, manufactured by Toshin Petrochemical @), 100 overlapping parts, as shown in Table 1, antibacterial agents, hindered amine compounds, hydrotalcite or MgO as neutralizing agents, IJ compounds, phenolic compounds, and other The additives were blended and premixed using a 4H Henschel mixer, and then this mixture was melt-kneaded using an extruder (50mmφ, single screw) at 70 rpm under N2 blowing to form pellets 7). did. The resin temperature in the extruder was 190°C at the rear of the cylinder (hopper side), 200°C at 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 n1; 8 g,
゜6.6-Tetramethyl)piperidylcosiloxane, trade name: UVASrL 299 (EnichemSy
(manufactured by nthesis) Dl: Salt magnesium aluminum hydroxy carbonate hydrate Mg<,
sAA 2 (OH) I 3CO3・3. 5
H20, Product name: DI (T-4A (Kyowa Chemical Industry @
(manufactured by Kyowa Chemical Industry) (4) Magnesium oxide MgO: Product name: Micromag (manufactured by Kyowa Chemical Industry @) (
5) Phosphorous compound P1 nidris (2,4-di-t-butylphenyl) phosphite, trade name: Mark2112 (ADEKA ARGUS@!A) (
6) Phenolic compound ph: Tetrakis [methylene-3-(3,5-di-butyl-4-hydroxyphenyl)propionate]
Methane, trade name: IrganoxlOlo (manufactured by Ciba Geigy) Ph2: 1.3.5-) Lis(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate trade name: CYANOX1790 (A, C, C (manufactured by Nitto Kasei) (7) Other A Calcium stearate (manufactured by Nitto Kasei) B:
2-(3-t-Butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole Trade name: Tinuvin 326 (manufactured by Ciba Geigy) The initial hue (b value) of the resulting pellet after molding was Measured with a color meter (digital colorimeter) manufactured by Suga Test Instruments ■.

Next, the pellet was molded into a size of 80 mm x 30 mm at an injection temperature of 240° C. using an 8-ounce injection molding machine manufactured by Sumitomo Heavy Industries @.
After molding into a test piece of X2m+++, the hue of this test piece was measured in the same manner.

In addition, this test piece was tested with a Sunshine Weather-Ometer (
Black panel temperature 60℃ using Suga Test Instruments ■)
, irradiated with ultraviolet rays for 200 hours under no rain conditions,
The hue after irradiation was measured in the same manner.

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

Note that antibacterial properties were evaluated based on the following criteria.

◎: Large intestine slowdown rate>99.9%.

○: Escherichia coli reduction rate 80-99.9%.

△: E. coli reduction rate <80%.

×：＠Not a little.

Also, the above-mentioned beret is 20m+n x 30w x 2
This test piece was molded into a + m test piece, and this test piece was left in a gear oven at 150°C, and the time until deterioration crazing occurred was measured to check thermal stability.

The thermal stability was evaluated based on the following criteria.

◎: 14 hours ≦ time start time.

Opens at 017:00 Deterioration start time <14 hours.

X: Deterioration start time≦7 hours.

Furthermore, using a 50 mmφ extruder, each composition was extruded three times in succession at a resin temperature of 240°C>, and at that time! JFR (melt flow rate, 230°C, 2.
The rate of change in MFR (ΔMPR) was determined by the following formula from the values of 16 kg load) and the initial MFR, and molding stability was checked.

In addition, the molding stability was evaluated based on the following criteria.

◎：△! JF R520%.

0120% 6M P R240%.

△:40% △MPR<60%.

×: 60%≦△M　P　R The respective results are shown in Table 1.

In addition, as a comparative example, similar measurements and evaluations were performed for a sample in which either one of the hindered amine compound and the neutralizing agent was omitted. The results are also listed in Table 1.

Examples 8 to 11, Comparative Example 6.7 Propylene-ethylene random copolymer (RPP: ethylene content 0.01
~5% by weight, J415T, manufactured by Tonen Petrochemical ■) 100
Parts by weight include antibacterial agents, hindered amine compounds, and hydrotalcite as a neutralizing agent as shown in Table 1. JgO
, an IJ compound, a phenol compound, and other additives, and pelletized in the same manner as in Example 1.

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

Next, the pellets were molded into 80mm x 80n at an injection temperature of 240°C using an 8oz injection molding machine manufactured by Sumitomo Heavy Industries, Ltd.
After molding into a test piece of uu×2 mm, the hue of this test piece was measured in the same manner.

In addition, this test piece was tested with a Sunshine Weather-Ometer (
Black panel temperature 60℃ using Suga Test Instruments ■)
, irradiated with ultraviolet rays for 200 hours under no rain conditions,
The hue after irradiation was measured in the same manner.

Furthermore, the same antibacterial property check as in Example 1 was performed on this test piece.

In addition, the pellets were placed in a size of 20mm x 30w x 2m.
The test piece was molded into a test piece of 500 m in diameter, and the same thermal stability check as in Example 1 was performed on this test piece.

Furthermore, the molding stability was evaluated in the same manner as in Example 1.

The results are also shown in Table 1.

Furthermore, as a comparative example, similar measurements and evaluations were performed on a sample in which the hindered amine compound was omitted. The results are also listed in Table 1.

Examples 12-15, Comparative Example 8.9 Probylene-ethylene bronze copolymer produced using Ziegler catalyst (BPP: ethylene content 5-20% by weight, B, +309, manufactured by Tonen Petrochemical ■) 100 As shown in Table 1, antibacterial agents, hindered amine compounds, and neutralizing agents such as hydrotalcite or MgO, IJ
A phenolic compound, a phenolic compound, and other additives were blended, and pelletized in the same manner as in Example I.

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

Next, the pellets were molded into a size of 80 mm x 80 mm at an injection temperature of 240° C. using an 8-ounce injection molding machine manufactured by Sumitomo Heavy Industries @.
After molding into a 2 mm test piece, the hue of this test piece was measured in the same manner.

In addition, this test piece was tested with a Sunshine Weather-Ometer (
Black panel temperature 60℃ using Suga Test Instruments ■)
, irradiated with ultraviolet rays for 200 hours under no rain conditions,
The hue after irradiation was measured in the same manner.

Furthermore, this test piece was subjected to the same antibacterial check as in Example I.

In addition, the pellets were 20w x 30+++m x 2
This test piece was molded into a test piece with a diameter of mm, and the same thermal stability check as in Example 1 was performed on this test piece.

Furthermore, the molding stability was evaluated in the same manner as in Example 1.

The results are also shown in Table 1.

Furthermore, as a comparative example, similar measurements and evaluations were performed on a sample in which the hindered amine compound was omitted. The results are also listed in Table 1.

Examples 16 to 19, Comparative Example 10111 High-density polyethylene produced using Ziegler catalyst (
100 parts by weight of HOP Mi, +6311, manufactured by Toshin Petrochemical H), as shown in Table 1, an antibacterial agent, a hindered amine compound, and a hydrotalcite or MgO as a neutralizing agent.
, a phosphorus compound, a phenol compound, and other additives, premixed in a 40ffi Henschel mixer, and then transferred to an extruder (50ffi).
mmφ, axle screw), 70 pm, jl=l nib blow, melt kneaded and pelletized.The resin temperature in the extruder was 160°C at the rear of the cylinder (hopper side).
, 180℃ in the middle of the cylinder, 2 in the cylinder tl'1 part
00°C and 200°C with a die.

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

Next, the pellet was molded into a size of 80mm x 80+n at an injection temperature of 240°C using an 8oz injection molding machine manufactured by Sumitomo Heavy Industries@.
After molding into a test piece of m×2m+n, the hue of this test piece was measured in the same manner.

In addition, using a Sunshine Weatherometer (manufactured by Suga Test Instruments) on this test piece, the black panel temperature was set at 60°C.
Under no rain conditions, ultraviolet rays were irradiated for 200 hours, and the hue after irradiation was measured in the same manner.

Furthermore, for this test piece, in the same manner as in Example 1,
Antibacterial properties and molding stability were evaluated.

The results are also shown in Table 1.

Furthermore, as a comparative example, similar measurements and evaluations were performed on a sample in which the hindered amine compound was omitted. The results are also listed in Table 1.

Examples 20 to 23, Comparative Example 12.13 To 100 parts by weight of linear low-density polyx-tyrene (LLDPE, NUCG-5381, manufactured by Nippon Unicar Wa) produced using a Ziegler catalyst, an antibacterial agent as shown in Table 1 was added. Hindered amine compound, hydrotalcite or 1AFrO as a neutralizing agent, phosphorus compound, phenol compound,
and other additives, premixed using a 401 Henschel mixer, and then this mixture was mixed using an extruder (50+no+φ, single screw). Orp
m, The mixture was melted and kneaded under N2 blowing to form pellets. The resin temperature in the extruder was 160°C at the rear of the cylinder (hopper side), 180°C at the middle of the cylinder, 200°C at the front of the cylinder, and 200°C at the die.

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

Next, the pellet was molded into 80+ nm x 80 m at an injection temperature of 240°C using an 8 oz injection molding machine manufactured by Sumitomo Heavy Industries ■.
After molding into a test piece of mX 2 m+n, the hue of this test piece was measured in the same manner.

In addition, this test piece was tested with a Sunshine Weather-Ometer (
Black panel temperature 60℃ using Suga Test Instruments @)
, irradiated with ultraviolet rays for 200 hours under no rain conditions,
The hue after irradiation was measured in the same manner.

Furthermore, for this test piece, in the same manner as in Example 1,
Antibacterial properties and molding stability were evaluated.

The results are also shown in Table 1.

Furthermore, as a comparative example, similar measurements and evaluations were performed on a sample in which the hindered amine compound was omitted. The results are also listed in Table 1.

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

〔Effect of the invention〕

The antibacterial polyolefin composition of the present invention has sufficient antibacterial properties, molding stability, and thermal stability, and yellowing and discoloration due to the addition of antibacterial agents are suppressed to a sufficiently satisfactory level. Moreover, weather resistance and discoloration resistance are also improved. Antibacterial polyolefin materials having such characteristics are suitable for various kitchen utensils, bath utensils, and other bathroom utensils.

Applicant: Tonen Petrochemical Co., Ltd. Kanebo Kasei Co., Ltd. Kanebo Co., Ltd.

Claims (9)

[Claims] (1) Polyolefin resin containing chlorine compound 100
Based on parts by weight, (a) 0.1 to 5.0 parts by weight of an antibacterial agent, (b) 0.01 to 0.5 parts by weight of a hindered amine compound, and (c) 0.01 to 0.0 parts by weight of a neutralizing agent. 5 parts by weight of an antibacterial polyolefin composition. (2) In the antibacterial polyolefin composition according to claim 1, based on 100 parts by weight of the polyolefin, further (d) 0.01 to 0.5 parts by weight of a phosphorus compound and/or
or (e) an antibacterial polyolefin composition containing 0.01 to 0.3 parts by weight of a phenolic compound. (3) The antibacterial polyolefin composition according to claim 1 or 2, wherein the antibacterial agent is a zeolite retaining a metal having a bactericidal effect. (4) In the antibacterial polyolefin composition according to claim 3, the metal having a bactericidal effect is one or more metals selected from the group consisting of silver, copper, zinc, and tin, and the zeolite is An antibacterial polyolefin composition characterized in that the metal is retained in an ionic state. (5) The antibacterial polyolefin composition according to any one of claims 1 to 4, wherein the chlorine compound is a residue of a Ziegler catalyst. (6) The antibacterial polyolefin composition according to any one of claims 1 to 4, wherein the chlorine compound is a chlorine-containing additive. (7) The antibacterial polyolefin composition according to any one of claims 1 to 6, wherein the hindered amine compound is polymethylpropyl-3-oxy[4-(2,2,
An antibacterial polyolefin composition characterized in that it is 6,6-tetramethyl)piperidyl]siloxane. (8) The antibacterial polyolefin composition according to any one of claims 2 to 7, wherein the phosphorus compound is tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)phosphite, -t-butylphenyl) pentaerythritol diphosphite, 1,1,3-tris(2-methyl-4-ditridecylphosphite-5-t-butyl)
An antibacterial polyolefin composition characterized by containing one or more types selected from butane. (9) The antibacterial polyolefin composition according to any one of claims 2 to 8, wherein the phenolic compound is
1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate and/or
or an antibacterial polyolefin composition characterized in that it is tetra-scratched [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane.