JPH0278433A - Gaseous ethylene absorbing composition - Google Patents

Abstract

PURPOSE:To enhance the ability of selectively absorbing gaseous ethylene in the title absorbing compsn. by blending 5-95 pts.wt. resin with 95-5 pts.wt. activated carbon-metal oxide mixture as a gaseous ethylene absorbent and preparing the compsn. CONSTITUTION:A gaseous ethylene absorbing compsn is prepared by blending and mixing 5-95 pts.wt. resin with 95-5 pts.wt. activated carbon-metal oxide mixture as a gaseous ethylene absorbent. The resin may be polyolefin resin, PVC or polyester. The metal oxide may be ZnO, Al2O3, Sb2O3 or CaO. The gaseous ethylene absorbent is preferably composed of 50-99 pts.wt. activated carbon and 1-50 pts.wt. metal oxide. The absorbing compsn. can be molded into plastic film and sheet packing materials, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an ethylene gas absorbing composition, and more particularly to an ethylene gas absorbing composition useful for preserving the freshness of fresh foods such as vegetables and fruits.

(Conventional technology and its problems) Conventionally, large quantities of fresh foods such as vegetables and fruits have been preserved by low-temperature storage or frozen storage, but when they are displayed and sold in small portions at retail stores, etc. , it is impossible to store such a large amount as described above.

Therefore, in retail stores, these fresh foods and the like are often stored in simple dish-shaped containers, wrapped in synthetic resin film, and displayed and sold at the store.

In such cases, fresh foods such as vegetables and fruits.

Fresh food that generates ethylene gas due to its own physiological action and is placed in an ethylene gas atmosphere accelerates ripening and deterioration due to the action of ethylene gas, and has a very long shelf life when displayed and sold in stores. There is a problem with whether it is bad or not. Of course, similar problems exist at home.

Known methods to solve these problems include placing activated carbon, which has excellent gas adsorption properties, inside the container or encapsulating it in the container wall to absorb ethylene gas, but using a large amount of activated carbon Activated carbon has a large adsorption power and has no adsorption selectivity for gas components, so it absorbs not only ethylene gas, which is harmful to maintaining the freshness of the food contained therein.
Because it also absorbs desirable aroma and flavor components of foods,
There is a problem in that when the consumer opens the package, the aroma and flavor components of the food that the consumer expects are lost, giving the consumer a bland feeling.

On the other hand, if the amount of activated carbon used is reduced in order to solve these problems, ethylene gas cannot be sufficiently adsorbed and removed, resulting in insufficient freshness maintenance.

Therefore, an object of the present invention is to provide an ethylene gas absorbing composition that efficiently absorbs ethylene gas generated by fresh foods and is effective in maintaining the freshness of fresh foods.

(Means for solving problems) The above objects are achieved by the present invention as follows.

That is, the present invention provides an ethylene gas absorbing composition comprising 5 to 95 parts by weight of a resin and 95 to 5 parts by weight of an ethylene gas absorbent, characterized in that the ethylene gas absorbent is a mixture of activated carbon and a metal oxide. This is an ethylene gas absorbing composition.

(Function) By using a mixture of activated carbon and metal oxide as an ethylene gas absorbent, the ethylene gas generated by fresh foods can be selectively and efficiently absorbed, and a small amount of activated carbon can maintain sufficient freshness. becomes.

(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments.

The resin used in the present invention includes various conventional molded products,
For example, plastic film, plastic sheet,
Synthesized or modified polyethylene and polypropylene used in the molding of plastic containers and fibers, polyolefin resins such as binders for paints and printing inks, polyvinyl chloride, vinylon, polystyrene, polyamide, polyester, cellulose acetate, vinyl resins, etc. These resins are all readily available on the market and can be used, and these resins may be in solid, paste, or liquid form such as a solution or emulsion.

The individual ethylene gas absorbents themselves used in the present invention are all known compounds, and the activated carbon that has been conventionally used as a deodorizing agent or adsorbent may be used, and the metal oxide used in combination with it may be , for example, zinc oxide (ZnO)
, aluminum oxide (^1203), antimony oxide (sbzo3), calcium oxide (Cab), calcium peroxide (CaOz), silver oxide (^g20), (
8go), cobalt oxide ([:oO), (CO203
), zirconium oxide (Zr02), tin oxide (Sn
O) , (SnO,), Cere oxide: / (Sea□)
, (SeOa), tungsten oxide (102),
(103), titanium oxide (TiO2), iron oxide (Fe
20+), (Fe30J, copper oxide ((:uJ)
, nickel oxide (Nip) vanadium oxide (V2O3)
, barium oxide (Bad), magnesium oxide (Mg
O), manganese oxide (MnO), germanium oxide (GeO2), etc., and particularly preferred oxides are oxides of calcium, magnesium, zinc, and germanium.

In the above-mentioned ethylene gas absorbent consisting of activated carbon and metal oxide, the ratio of their usage is also important.If the total amount is 100 parts by weight, the activated carbon is 50 to 99 parts by weight, and the oxide is The proportion is 50 to 1 part by weight, and in such a combination and blending ratio, the object of the present invention is best achieved. If the amount of activated carbon used is too small, the absorption of ethylene gas will be insufficient, and if the amount of metal oxide used is too small, the selective absorption of ethylene gas will be insufficient.

When the total amount of the ethylene gas absorbent and the resin is toogB, a suitable ratio is 5 to 95 ffl parts of the resin and 95 to 5 parts by weight of the ethylene gas absorbent, and if the amount of the resin is too small, shape retention will be difficult. On the other hand, if the amount of resin is too large, the ethylene gas absorption effect will be insufficient.

The ethylene gas absorption composition of the present invention has the above three components as essential components, and in addition, various conventionally known additives for resins,
For example, solvents, colorants, fillers, extender pigments, plasticizers, stabilizers, ultraviolet absorbers, etc. may be optionally blended as necessary.

The ethylene gas absorbing composition of the present invention can be obtained by simply mixing the above-mentioned components, or may be obtained by melt-kneading the mixture and granulating it into a pellet shape or the like. Furthermore, it may be in the form of a masterbatch containing a high concentration (for example, 10 to 50% by weight) of ethylene gas absorbent for later use by diluting with additive-free resin, or it may be shaped into a film or container. It may also be in the form of a paint or printing ink dispersed in a medium.

The embodiment of the resin molded body will be described below.

The ethylene gas-absorbing molded product of the present invention is a molded product of the above-mentioned ethylene gas-absorbing composition in various shapes, such as a packaging material made of a plastic film or sheet, or an arbitrary molded product made by molding the ethylene gas-absorbing composition by various methods. These are shaped containers, fibers, and other molded objects.

Forming of such films, sheets, containers, etc. is carried out under various conventionally known conditions using conventionally known inflation devices, presses, calendars, extrusion molding machines, spinning machines, blow molding machines, injection molding machines, vacuum forming machines, etc. The process can be carried out using the method as it is, and the ethylene gas absorbing molded product of the present invention can be easily obtained.

The embodiment as a paint or printing ink will be explained below.

This embodiment is obtained by mixing the ethylene gas absorbent as described above with a binder resin as a resin and a liquid medium.

As the binder resin, for example, acrylic pA,
Vinyl acetate resins and other resins used as binder resins in various conventional water-based or oil-based paints and printing inks are preferred, and these binder resins may be thermoplastic or thermosetting.

Further, as the liquid medium, water, alcohol-based, ketone-based, ester-based, aromatic-based, aromatic-based, other organic solvents, or mixtures thereof can be used.

The concentration of the binder resin may be any value, but is generally preferably about 10 to 30% by weight. These binder resins may be dissolved in a liquid medium, or -
It may be in a dispersed or emulsified state.

In the present invention, about 10% of the above ethylene gas absorbent is added to a liquid medium containing such a conventionally known binder resin.
It can be obtained by dissolving or dispersing it to a concentration of 30% by weight.

The ethylene gas absorbing paint or printing ink of the present invention as described above is applied and/or printed on one or both sides of a sheet such as general wrapping paper, plastic sheet, woven fabric, nonwoven fabric, or a composite material thereof to absorb ethylene gas. It can be made into a sex sheet.

There is no particular limit to the amount of coating and/or printing of the ethylene gas absorbing paint, but it is generally about 5 to 20 g/m in solid content.
By keeping it within this range, it is possible to impart an excellent ethylene gas absorption effect to sheets such as wrapping paper, plastic sheets, woven fabrics, non-woven fabrics, etc., without losing their breathability. The coating area of the ethylene gas absorbing paint and printing ink, the printing method, and the drying method may be any conventionally known method.

The embodiment of the granular ethylene gas absorbent will be explained below.

The granular ethylene gas absorbent of the present invention can be obtained by simply mixing the above-mentioned components and compression molding, but in terms of cost, it is better to melt-knead and extrude the mixture and granulate it into pellets or the like. The particle size of the resulting granular ethylene gas absorbent is preferably about 1 to 5 mm, but may be finer or coarser depending on the application.

(Effects) By using a mixture of activated carbon and metal oxide as an ethylene gas absorbent, the ethylene gas generated by fresh foods can be efficiently and selectively absorbed, making it possible to maintain sufficient freshness with activated carbon for a short period of time. Become.

(Example) Next, the present invention will be described in more detail with reference to Examples. In the text, parts or percentages are based on weight unless otherwise specified.

Example 1 99 parts of low-density polyethylene was blended with 1 part of a mixture of activated carbon and calcium oxide in a weight ratio of 10=3, mixed in a mixer, and heated in a 40IIIffi extruder (L/D=2
8, C, R, = 3.1, screw with dullage, cylinder temperature 130°C, screw rotation speed 70 rpm)
The mixture was kneaded to obtain a pellet-shaped ethylene gas absorbing composition of the present invention.

Next, the above ethylene gas absorption composition was passed through an inflation device (30 mm extruder, inner diameter 50 m1 inflation die, cylinder temperature 140°C, screw rotation speed 60).
rpm) to obtain a polyethylene film with a thickness of about 50 microns. The ethylene gas absorption properties of this ethylene gas absorption sheet were investigated and the results were as follows.

Put one sheet of the polyethylene film (50 x 200 ma+) described in ■ into a 300 mj! Erlenmeyer flask, inject 10 ppra of ethylene into it, leave it at 25°C, and measure the residual ethylene concentration (ppm) after a predetermined period of time. did.

1st time dish, 1st part, 1st time dish, 10th birthday, 10th birthday
9 8 6.5 Note blank is a sheet without the addition of ethylene gas absorbent (hereinafter referred to as "interval").

In addition, bags were made from each of the above-mentioned blank and the film of the invention product, tomatoes with a slight bluish tinge were placed in the bags and left to stand, and when the bag was opened after 7 days, 0% was found from the film of the invention product. The deterioration of the tomatoes in the prepared bag was slight, whereas in the case of the blank, there was no significant deterioration of the tomatoes.

Example 2 - Value 4 A plastic packaging material of the present invention was obtained using the following components and in the same manner as in Example 1, and its performance was measured in the same manner as in Example 1, and the results were as follows. .

High-density polyethylene 95 parts Activated carbon and magnesium oxide 8/2 part compound 5 parts - Ucho Sarayari Tsukiru Shin 1st publication Betsushima blank 10 10 10 Kimitsu ■ Eggplant
8 6 5 Example 1 95 parts polypropylene 5 parts 5 parts mixture of activated carbon and zinc oxide - 5 parts mixture 10 10 101
8 6.5 5.5 Real Ml Polystyrene 98 parts 7/3 part compound of activated carbon and germanium oxide 2 parts Upper and lower parts LL value 10. 10 10 moxibustion songs
75.5 4 Example 5 Activated carbon and calcium oxide mixture with a city itt ratio of 9:1, A
15 parts of product i were dissolved in ethyl acetate/isopropyl alcohol (
3/1'>60 parts and 25 parts of nitrocellulose/alkyd resin (5/1) to obtain the ethylene gas absorbing paint of the present invention.

Next, apply this ethylene gas absorbing paint to kraft paper.
/rrf by gravure printing and dried to obtain an ethylene gas absorbing sheet of the present invention. The ethylene gas absorbency of this ethylene gas absorbent sheet was tested in the same manner as in Example 1.

1st Place Plate "And the same fish special visit" Zuyu no Yuu 10 10 10 Trees ■ Eggplant
8 6 5 Examples 6 to 8 An ethylene gas absorbing sheet of the present invention was obtained using the following components and in the same manner as in Example 5, and its performance was measured in the same manner as in Example 1. The following results were obtained. Met.

Jodomaru j Tokisararei on 8=2 mixture of activated carbon and magnesium oxide
10 10 10 wood 1 egg
8 6 4 Inu Arashi Example 7.3 Mixture of activated carbon and germanium oxide
``Ranjido''l±Tokioka'' Blank 10 10 10 Ki＾Tomo,
￥, 75.5 4-pointed 9=1 mixture of mutually activated carbon and magnesium oxide.
1 Jihobi l±Tokioka Reizu no 7 10 10 10 Kihatsu Tomokai
8 7 6 Actual Mi Example 9 To 50 parts of low density polyethylene, the amount ratio of Bli is lo: 3
50 parts of a mixture consisting of activated carbon and zinc oxide are blended,
Mix with a mixer and use a 40mm extruder (L/D=28, C
, R, = 3.1, screw with dullage, cylinder temperature 130℃, screw rotation speed? The ethylene gas absorbing composition of the present invention in the form of pellets with a particle size of approximately 3 mm was obtained. The ethylene gas absorbency of this ethylene gas absorbing composition was evaluated in the same way as in Example 1.
When the mixture was cooled down, the result was 7 as shown below.

Tokisaragi and Tokioka box l Dotokusarani It was my evening.

Kibatsu Eggplant 6 3 1 Examples 10 to 12 An ethylene gas absorption composition of the present invention was obtained using the following ingredients and in the same manner as in Example 9, and its performance was measured using Example 9 and the same company. The results were as follows.

45 parts of high-density polyethylene in memory of the fire tribe 55 parts of an 8=2 mixture of activated carbon and calcium oxide.

Eggplant for grove 6 4 2.5X 5 cases ± polypropylene 6 o parts 40 parts of a 7:3 mixture of activated carbon and strontium oxide
97.5 7 parts Δ■ 1 polystyrene 70 parts 30 parts of a 6:4 mixture of activated carbon and aluminum oxide.

1 item 9 8 7.5 Patent applicant Okuchi Kaika Kogyo Co., Ltd.

Claims (6)

[Claims] (1) 5 to 95 parts by weight of resin and 9 parts by weight of ethylene gas absorbent
An ethylene gas absorbing composition comprising 5 to 5 parts by weight, wherein the ethylene gas absorbent is a mixture of activated carbon and metal oxide. (2) The ethylene gas absorbing composition according to claim 1, wherein the ethylene gas absorbent comprises 50 to 99 parts by weight of activated carbon and 50 to 1 part by weight of a metal oxide. (3) The ethylene gas absorbing composition according to claim 1, wherein the metal oxide is an oxide of calcium, magnesium, zinc or germanium. (4) The ethylene gas absorbing composition according to claim 1, which is a resin molded article. (5) Claim 1, which is a coating composition or a printing ink composition.
The ethylene gas absorbing composition described in . (6) The ethylene gas absorbing composition according to claim 1, which is in granular form.