JPH06179780A - Polyolefin composition - Google Patents

Abstract

PURPOSE:To provide a polyolefin composition having excellent deodorizing and odor-eliminating functions and good color and effective for suppressing the deterioration of the taste of a food filled in or packaged with the polyolefin composition. CONSTITUTION:The polyolefin composition is produced by compounding a polyolefin with 1-1,500wt.ppm (based on the weight of the polyolefin) of a polyphenol compound extracted from natural plant and 0.02-1wt.% of a fatty acid metal salt and/or a hydrotalcite compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin composition which is excellent in deodorizing and deodorizing properties, keeps a good hue, and has an effect of suppressing the deterioration of the taste of filled and packaged foods. is there.

[0002]

2. Description of the Related Art Conventionally, polyolefins represented by polyethylene and polypropylene have been widely used in fields such as food containers and packaging materials. The sensitivities and demands of the packaging materials and containers (hereinafter referred to as packaging containers) themselves are high (the so-called poly odor).
From the viewpoint of suppressing the transfer of food to food
The current situation is that improvements are being made to enhance low taste. In response to such a demand, in the production process of polyolefin, a method for improving the contrivance for reducing easily deteriorated components due to the inclusion of low molecular weight components and impurities which are relatively likely to affect the odor and taste is merely made. Instead, a method has been proposed in which an additive such as a synthetic zeolite or a porous material such as a silicate mineral is mixed, and the adsorption effect of the porous material is utilized. However, although these improvements have been confirmed to have their respective improvement effects, they are not yet sufficient, and as a result, no effective method has been found yet.

On the other hand, in recent years, among extracts from natural plants, especially those containing a polyphenol compound as a main component, the action mechanism such as deodorization / deodorization and flavor maintenance has been found although the mechanism of action has not yet been sufficiently elucidated. It has been released and has been applied as a food additive as a part of it. Further, a proposal of blending the extracted component from this natural plant with a resin is also disclosed in JP-A-61-134232 and JP-A-2-1711.
No. 71 is reported. The above-mentioned JP-A-61-13
In the proposal by Japanese Patent No. 4232, the purpose is to obtain the deodorizing action of a sheet-shaped resin product having a design property, but when considering its application as a food packaging container, the packaging caused by the polyphenol compound itself. There is no suggestion of the effect on the deterioration of the hue of the container or the deterioration of the taste of food. Further, in the proposal of Japanese Patent Application Laid-Open No. 2-171171, there is no suggestion about the influence on the hue or the taste of food because it is intended only for the antioxidant property of the food contents. Therefore, no proposals have been made yet for using these extracts from natural plants, particularly those containing a polyphenol compound as a main component to deodorize and deodorize, and to further effectively suppress deterioration of hue and taste. The current situation is not. Such a fact is that a satisfactorily effect cannot be obtained as shown in the comparative example described below only by adding only an extract from a natural plant containing a polyphenol compound as a main component.

[0004]

DISCLOSURE OF THE INVENTION The object of the present invention is to be suitable as a material for food packaging containers, having a good hue, excellent deodorizing and deodorizing properties, and suppressing the deterioration of the taste of filled and packaged foods. Another object of the present invention is to provide a polyolefin composition which is effective.

[0005]

[Means for Solving the Problems]

[Summary of the Invention] In view of the present situation, the present inventors have conducted extensive studies to provide the above-mentioned materials, and as a result, have identified an extract from a natural plant containing a polyphenol compound as a main component and a specific compound. By blending together with the polyolefin, the dispersibility and the processing stability at the time of blending the extract are enhanced, and as a result, the hue of the resin is prevented from being lowered,
Further, they have found that a function of suppressing deodorizing / deodorizing properties and deterioration of taste can be effectively imparted to polyolefin, and the present invention has been completed. That is, the polyolefin composition of the present invention is a polyolefin containing polyphenol compounds 1-1,500 extracted from natural plants, based on the weight of the polyolefin.
It is characterized by being mixed with ppm by weight and 0.02 to 1% by weight of a fatty acid metal salt and / or a hydrotalcite compound.

[Detailed Description of the Invention] [I] Constituent Component (1) Polyolefin Resin (a) Type The polyolefin used in the polyolefin composition of the present invention includes high density polyethylene, linear low density polyethylene, and branched form. Ethylene homopolymers such as low density polyethylene or ethylene and other α-olefin copolymers, or propylene homopolymers such as homopolypropylene, propylene / ethylene copolymer, propylene / butene-1 copolymer or propylene Random or block copolymers with other α-olefins, polybutene-1,
Examples thereof include poly-4-methylbutene-1, poly-3-methylbutene-1, poly-4-methylpentene-1, propylene / ethylene copolymer rubber, propylene / butene-1 copolymer rubber, and the like. Modified coalescence,
That is, an unsaturated carboxylic acid such as maleic anhydride or a derivative thereof, an aromatic unsaturated monomer, a vinyl ester, a vinyl silane or the like may be copolymerized. Further, a blended product obtained by mixing a plurality of these may be used. Among these, preferable polyolefin resins include high density polyethylene, linear low density polyethylene, branched low density polyethylene, propylene homopolymer, propylene and other α.
-Random or block copolymers with olefins and the like can be mentioned.

(B) Olefin Produced The above polyolefin is obtained by homopolymerization or copolymerization of olefins alone or in combination in the presence of a radical initiator or a transition metal catalyst. Specifically, in the presence of a radical initiator or a transition metal catalyst,
Polymerize ethylene or propylene alone, or
It is obtained by copolymerizing ethylene with another α-olefin or propylene with another α-olefin. The α-olefin used as the comonomer is a 1-olefin having 3 to 12 carbon atoms (which is represented by the general formula R-CH = CH ₂ and R represents an alkyl group), and is, for example, propylene. , Butene-1, pentene-1, hexene-1, 4-
Methylpentene-1,4-methylhexene-1,4,4
-Dimethylpentene-1, heptene-1, octene-
1, nonene-1, decene-1 and the like. Of these, preferably propylene, butene-1, hexene-1,4-
Methylpentene-1 and octene-1 can be mentioned. Further, the α-olefin in this case is not limited to one kind, and a multi-component copolymer using two or more kinds such as a terpolymer is also included as a preferable one.

[0008] There is no particular limitation for the catalysts the catalyst and the polymerization method, for example, as a catalyst radical initiators such as oxygen and peroxide, Ziegler-type catalysts, Ziegler-Natta type catalyst, Philip catalysts, Kaminsky type catalyst Etc. can be mentioned.

Polymerization Method As for the polymerization method, in the case of the above-mentioned high-density polyethylene or linear low-density polyethylene, a gas-phase fluidized bed method (for example, see JP-A-59-23011), a solution method,
Alternatively, the pressure is 200 kg / cm ² or more, and the polymerization temperature is 150.
A high pressure ionic polymerization method at a temperature of not less than 0 ° C. can be used. In the branched low-density polyethylene, generally, using a tank reactor or a tubular reactor, in the presence of a radical initiator, a pressure of 1,400 to 2,500 kg / cm ² , and a polymerization temperature of 200 to 320 ° C. It is produced by polymerizing ethylene below. Further, a propylene homopolymer or a copolymer of propylene and another α-olefin is produced using a Ziegler-Natta catalyst in a gas phase, a liquid phase or a solvent such as heptane. Further, these polyolefins can be appropriately selected and used from commercially available products that are usually commercially available. Furthermore, these polyolefins have an MFR of 0.01 to 200 g / 10.
It is preferable that it is a resinous material in terms of moldability and effect.

(2) Polyphenol compound (a) Natural plant Examples of the natural plant extract used in the composition of the present invention include teas such as green tea, oolong tea, black tea and mate tea, camellia, mountain tea flowers, laurel Such as evergreen broad-leaved trees, kurobe, cypress, sawara, asunaro, Lawson cypress, mousse, squid, hijaxin, and other cypress plants, and paulownia,
Forsythia, holly dwarf, black pine, purple oxalis, oxalis, dokudami, tsubaki, butterbur, lilac, Chinese forsythia, chestnuts, alder trees, etc. It is preferable to use.

(B) Extraction A polyphenol compound is obtained by extracting these natural plants. As a method for obtaining an extract component from such a natural plant, the natural plant is finely chopped or crushed, and then extracted using warm water, preferably hot water, or an organic solvent such as acetone or alcohol, preferably in a water-containing state. It is extracted by a multi-stage countercurrent extraction method, etc., and the extract is filtered, and then the solvent is evaporated to dryness under reduced pressure by usual concentration / drying, or the solution is further dried under reduced pressure. Examples thereof include a method of dry-distilling under. Particularly, in order to economically obtain the above polyphenol compound, the molecular weight obtained by fractionating this extract is 6,000 to 1
Preferred methods include separation and purification by combining a method such as passing through an ultrafiltration membrane of 0,000 (JP-A-2-6499) and adsorption separation with a specific adsorbent.

(C) Structure Polyphenol compounds extracted from natural plants in this manner are specifically flavones, flavonols, isoflavones, flavanonols, anthocyanidins, catechins, aurones, chalcones, etc. based on the phenylchroman skeleton. It is a flavonoid consisting of many compounds. The polyphenol compound thus extracted from the natural plant can be appropriately selected and used from commercial products.

(3) Fatty acid metal salt and / or hydrotalcite compound (a) Hydrotalcite compound The hydrotalcite compound used in the composition of the present invention is usually a hydrous basic carbonate of magnesium or aluminum. A certain hydrotalc stone (manaceite): Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O and chemical formula: Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O
And the like.

(B) Fatty Acid Metal Salt As the fatty acid metal salt used in the composition of the present invention, for example, calcium stearate, magnesium stearate, lithium stearate, zinc stearate, barium stearate, aluminum stearate, 1, 2-hydroxystearate calcium, 1,
Examples thereof include lithium 2-hydroxystearate, calcium laurate, zinc laurate, barium laurate and the like. Of these, it is preferable to use calcium stearate, zinc stearate, lithium stearate, magnesium stearate, and calcium 12-hydroxystearate.

(C) Combined Use The hydrotalcite compound and the fatty acid metal salt may be used alone or in combination of two or more.

[II] Composition (1) Blending amount Polyphenol compound component The blending amount of the polyphenol compound extracted from the above natural plant is generally 1 to 1,500 ppm, preferably 5 ppm of polyphenols based on the weight of the polyolefin. ~
It is in the range of 1,000 ppm. If the blending ratio is less than the above range, the effect of the present invention cannot be obtained, while if it exceeds the above range, the hue of the composition is deteriorated, which is not preferable.

Fatty acid metal salt and / or hydrotalc
The compounding amount of the fatty acid metal salt and / or the hydrotalcite compound component is 0.02 to 1% by weight based on the same weight,
It is preferably 0.05 to 0.25% by weight. If the amount of the fatty acid metal salt and / or the hydrotalcite compound is less than the above range, the effect of the present invention cannot be obtained, and
If it exceeds the above range, the effect is saturated and it is not economical.

(2) Compounding method These compounding methods for producing the composition of the present invention are not particularly limited, and known methods can be adopted. That is, each of the above components is mixed in a predetermined amount and mixed by a generally known mixer such as a Henschel mixer, a V blender or a tumbler mixer, and then a single-screw kneader, a meshing co-rotating type / meshing machine. Different direction rotation type / Non-meshing same direction rotation type
Generally, a continuous melt kneading method using a biaxial kneading machine such as a non-meshing different direction rotation type or a batch type melt kneading method such as roll or Banbury is adopted. Further, the polyolefin composition is prepared by previously mixing a high-concentration masterbatch of the polyphenol compound extracted from the natural plant with a fatty acid metal salt and / or a hydrotalcite compound, and mixing the masterbatch described above with the above-mentioned mixture. A method is preferred in which it is prepared by a kneading method and then this is compounded in a polyolefin resin according to the required amount.

(3) Other compounding agents In addition to the above components, the polyolefin composition of the present invention contains an antioxidant, a colorant, an antistatic agent, an adsorbent, a lubricant, a slip agent, an ultraviolet absorber depending on the purpose of use. , Fillers and the like can be added within a range that does not significantly impair the effects of the present invention.

(4) Usage The polyolefin composition thus obtained is subjected to molding processing such as blow molding, injection molding, film molding, sheet molding, lamination molding, compression molding and vacuum molding to obtain at least one of the polyolefin compositions. It can be a packaging container that constitutes a part. This packaging container can be applied not only to foods, but also to contents where a change in odor or the like is disliked.

[0021]

EXAMPLES In order to more specifically describe the polyolefin composition of the present invention, experimental examples and evaluation methods thereof will be shown below. (1) Evaluation method (a) Melt index Melt index (MFR) is based on JIS K7210, polyethylene is 190 ° C, polypropylene is 2
It is a measured value at 30 ° C. Also, the density is JIS K
7112 (density gradient tube method).

(B) Odor evaluation Molded bottles sealed with aluminum foil were
After heat treatment at ℃ for 1 hour, sensory laboratory (room temperature, 5
In 0% RH), five panelists sniffed the smell of the air in the bottle, and scored according to the following evaluation criteria. The evaluation results were averaged. Evaluation criteria 0 point: No odor 1 point: Weak odor 2 points: Clear odor 3 points: Strong odor

(C) Taste evaluation Put 400 cc of mineral water in a molding bottle, and
After heat treatment at 0 ℃ for 3 hours, let it stand until the temperature drops to 60 ℃, and then in the sensory laboratory (room temperature, 50% R
In H), the mineral water was tasted by five panelists by the tongue, and the score was evaluated according to the following evaluation criteria. The evaluation result adopted the average value. Evaluation criteria 0 point: tasteless 1 point: slightly off-taste is understood 2 points: off-taste is clearly understood 3 points: off-taste is completely understood

(D) Hue evaluation Cut out the side surface of the molded bottle and use a photoelectric colorimeter to measure in accordance with JIS.
In accordance with K7103, yellowness index (Y
I) The value was measured.

(2) Experimental Examples Examples 1 to 10 and Comparative Examples 1 to 5 (a) Production of Polyolefin Resins In Examples 1 to 8 and Comparative Examples 1 to 3, Phillips using a chromium compound as a transition metal component. Example 1 of JP-A-55-120608 using a type catalyst
It was carried out with polymerization in a gas phase fluidized bed reactor similar to that used in 9. In addition, MFR is 0.35g / 10
An ethylene / butene-1 copolymer granule having a density of 0.953 g / cm ³ and a butene-1 content of 0.5% by weight was used. Furthermore, in Example 9 and Comparative Example 4, the MFR obtained by radical polymerization in a tubular reactor was used.
Was 0.3 g / 10 min and the density was 0.928 g / cm ³ and branched low-density polyethylene (ethylene homopolymer) was used. In addition, in Example 10 and Comparative Example 5, slurry polymerization was carried out using a Ziegler-Natta catalyst in a heptane solvent to obtain an MFR of 1.8 g / 10 minutes and a density of 0.8.
A powder made of a propylene / ethylene random copolymer having 9 g / cm ³ and an ethylene content of 3.0% by weight was used.

(B) Composition: Tea extract powder manufactured by Taiyo Kagaku Co., Ltd. (trade name: “Sanflavone”, polyphenol compound content: 30% by weight) and calcium stearate as a fatty acid metal salt (trade name of Kosei Co., Ltd.) "BK"), lithium stearate (Kosei Co., Ltd. trade name "Li-St") and hydrotalcite compound (Kyowa Chemical Co., Ltd. trade name "DHT"
-4A "), zinc stearate (Kosei Co., Ltd. trade name" Zn-St "), magnesium stearate (Co., Ltd.)
Kosei product name "Mg-St"), 12-hydroxycalcium stearate (Kosei Co., Ltd. product name "CS-6")
Were blended in the proportions shown in Table 1, respectively. Next, except for Example 9 and Comparative Example 4, after mixing with a super mixer, the mixture was granulated at a temperature of 200 ° C. using a full flight type single screw extruder to obtain pellets. Also, in Example 9 and Comparative Example 4, the same material was used, and 1% by weight of the tea extract powder was used.
The master batch of was prepared in advance with a roll kneader and a predetermined amount was mixed. The "sanflavone" is produced by a method in which sencha is extracted by stirring with hot water, the extract is subjected to an ultrafiltration device, further concentrated by a reverse osmosis membrane, and then freeze-dried.

(C) Evaluation Next, these mixtures were each subjected to hollow molding at a molding temperature of 200 ° C. using a hollow molding machine IPB10A (screw diameter 40 mm ^φ , die lip width 1.5 mm) manufactured by Ishikawajima Harima Heavy Industries Ltd. Conducted, internal volume 700 cc, wall thickness 0.5 mm
A single layer bottle of t was obtained. Immediately after this, it was sealed with aluminum foil. Then, the odor, taste, and hue of this bottle were evaluated. Table 1 shows the evaluation results of these examples.

[0028]

[Table 1]

[0029]

[Effect of the Invention] By blending a polyolefin with a polyphenol compound which is an extract from a natural plant and a fatty acid metal salt and / or a hydrotalcite compound together, the food container suitability is maintained and the deodorizing and deodorizing properties are maintained. Since it is excellent in that the hue is kept good and the effect of suppressing the deterioration of taste can be provided, it is possible to obtain a polyolefin composition suitable for a food to be filled or packaged.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shotaro Kashiwagi 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Petrochemical Co., Ltd. Yokkaichi Research Institute

Claims (2)

[Claims] (1) Polyolefin containing 1 to 1,500 ppm by weight of a polyphenol compound extracted from a natural plant and a fatty acid metal salt and / or hydrotalcite compound of 0.02, based on the weight of the polyolefin. ~ 1
A polyolefin composition, characterized by being blended in a weight percentage. 2. The polyolefin composition according to claim 1, wherein the natural plant is tea leaves.