JPH0853164A - Packing material - Google Patents

Abstract

PURPOSE:To prevent penetration of malodorous substances into the contents, thereby ensure flavor and fragrance of the contents of product by providing a layer, into which specific compounds are kneaded, on the innermost side and providing a layer of polyolefin resin containing deodorant. CONSTITUTION:An innermost layer is constituted of a compound of polyolefin resin and at least one substance selected from the group consisting of natural resin tackifier, wax, polyamide resin, and polycarbonate resin. And polyolefin resin layers, at least one layer of which containing deodorant, are provided in innermost layers or other layers. At this moment, hydrophobic zeolite is preferably used as deodorant. In this case, an innermost layer, to which specific compound added, does not practically absorb flavor of contents having fragrant component, and in the case that deodorant is added to the innermost layer or the other layer, absorption, fragrance, taste can be maintained in a preferable state.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a packaging material for accommodating contents having an aroma component, and more specifically, it maintains the flavor balance of fruit juice beverages and the like in which flavor is important and impairs heat sealability. Further, the present invention relates to a packaging material suitable for accommodating contents having an aroma component, which prevents deterioration of flavor balance due to the packaging material and an odor substance from the outside.

[0002]

2. Description of the Prior Art Contents having an aroma component, for example, fruit juice drinks such as wine, coffee, tea, and orange juice, which value the aroma and flavor, are extremely sensitive to alteration of flavor. In recent years, in one-way food containers, laminated materials mainly composed of paper and a polyolefin resin have been diversified. In a paper container for juice etc.,
Usually, low density polyethylene / paper / low density polyethylene (hereinafter, low density polyethylene is abbreviated as LDPE).
For products requiring a gas barrier property for long life, aluminum foil, polyester resin, vinyl alcohol resin layer, ethylene-vinyl alcohol copolymer resin layer, etc. are added to the above structure. There is.

Furthermore, recently, ethylene has been used as the innermost layer.
A modified polyester resin layer using a vinyl alcohol copolymer resin layer has also been developed. However, these resins have physical properties such as heat seal strength lower than those of polyolefin-based resins, and a significant decrease in the function of protecting liquid foods as a packaging material is observed, which is not preferable in practice and costly. It is expensive and not economical.

Further, a packaging material having a multi-layer structure using paper is
It is also used in sake, water, whiskey, and tea, and its composition is diversifying. However, in the case of a content having an aroma component, as long as the innermost layer is the polyolefin-based resin layer, the flavor of the content is sorbed on the polyolefin-based resin layer, and the taste and odor of the food are altered.

Therefore, a technique has been proposed in which the flavor component is pre-saturated in the innermost layer to prevent the deterioration of taste and odor (Japanese Patent Laid-Open No. 59-17438). Ink and odorous substances from the outside may not be sufficiently prevented and may migrate to the contents, which may change the flavor of the contents.

[0006]

SUMMARY OF THE INVENTION In view of the above situation, the present invention allows a deodorant to absorb an odor inherent in resin or paper, or a decomposed odor generated by heat when heat sealing is performed, and an odor to the contents A packaging material that prevents the migration of substances, prevents the deterioration of the contents due to the sorption of the flavor on the polyolefin resin layer, and retains the processability and heat sealability of conventional packaging materials. Is.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that contents having an aroma component, particularly liquid food packaging materials such as fruit juice drinks in which flavor is important, The above problem is solved by providing a layer in which a specific compound is kneaded in the innermost layer so as to maintain the flavor balance, and by providing a deodorant-containing polyolefin resin layer for odor substances from the packaging material and the outside. It was found that the present invention has been completed.

That is, in the present invention, the innermost layer is a mixture of a polyolefin resin and at least one selected from the group consisting of tackifier, wax, polyamide resin and polycarbonate resin, and at least one layer. Is a polyolefin-based resin layer containing a deodorant.

The role of the innermost layer in the present invention is to prevent the volatile compounds constituting the flavor from being sorbed to the innermost layer of the packaging material and to maintain the flavor balance of the contents. One of the formulations contained in this innermost layer is
Taking orange juice as an example, it is a natural resin tackifier such as a terpene-based or rosin-based resin.
If the addition amount is less than 1% by weight, the effect is not sufficient and 2
If it exceeds 0% by weight, workability problems will occur, so 1-2
0% by weight is preferred. The above is to prevent further flavor sorption by kneading a mixture having a molecular structure similar to that of the flavor component into the innermost layer in advance and allowing it to saturate.

Another formulation included in the innermost layer is a wax. The addition amount is the same as in the above tackifier, and is preferably 1 to 20% by weight. This aims to prevent flavor sorption by filling intermolecular spaces in the innermost layer to increase the density.

Still another compound contained in the innermost layer is a compound having a hindrance effect due to a molecular structure such as an aromatic polyamide or a polycarbonate resin, and a resin having a high compatibility parameter is blended in the innermost layer to have a flavor. It is intended to prevent the sorption of. In this case, modified polyolefin or the like can be used as a compatibilizing agent with the polyolefin resin, or can be used in combination with a tackifier.
The amount of addition is such that the cost is low and the physical properties such as heat seal strength are not deteriorated. That is, it is preferable that the aliphatic polyamide is 20 to 30% by weight, and the polycarbonate resin is 30 to 40% by weight.

Next, the role of the deodorant-containing polyolefin resin layer in the present invention is to transfer the offensive odor inherent in the resin to the contents, printing ink and ink solvent, residual solvent from adhesive and paper. It is intended to prevent the transfer to the contents such as paper odor.

The deodorant refers to a physical adsorbent made of a porous active substance, a chemical decomposing agent made of a redox substance and its catalytic substance, or a combination of both. Examples of the former are activated carbon, activated clay, acid clay, natural zeolite, synthetic zeolite (hydrophilic and hydrophobic), bentonite, sepiolite,
Examples include silica, a mixture of MgO and SiO _2, and the like.
Examples of the latter include titanium-based, silica-alumina-based, iron-manganese-based, platinum-based, palladium-platinum-based,
Examples include inorganic enzymes such as (oxidized) manganese, organic enzymes, phthalocyanine artificial enzymes, and the like. These are used alone or in combination of two or more. Among these, hydrophobic zeolite is particularly preferable as the porous active substance, and titanium-based one is particularly preferable as the catalyst substance. When the active substance comes into contact with food, it is necessary to select a substance approved as a food additive, but in other cases, it is appropriately determined depending on performance, appearance (color, etc.) and the like. The particle size of the deodorant is preferably in the range of 0.1 to 10 μm (average particle size), more preferably 0.3 to 5 μm. If it is less than 0.1 μm, the deodorizing ability is not sufficient, and if it exceeds 10 μm, the film formability during processing deteriorates.

Further, the alteration of the contents due to oxidation (heat, light) (for example, the change of the vitamin C residual ratio of orange juice) and the volatilization of volatile compounds constituting the flavor to the outside are greatly related to the alteration of the contents. Therefore, it is more effective to use the gas barrier resin in combination with the above. Examples of the gas barrier resin include polyvinyl alcohol-based resin, polyamide-based resin, polyester-based resin, ethylene-vinyl alcohol copolymer resin, vinylidene chloride-based resin, and polysaccharides, which are used alone or in combination of two or more. To be

[0015]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

Example 1 As a tackifier, 10% by weight of "CLEARON P-125" (trade name, manufactured by Yasuhara Chemical Co., Ltd .; terpene hydrogenated resin, specific gravity = 0.996 (20 ° C.)) was used, and a polyolefin resin " Mirason-206P "(trade name, manufactured by Mitsui Petrochemical Co., Ltd .; LDPE, MI =
3.8 g / 10 min, density = 0.923 g / cm ³ ) 90
The mixture was dry blended with wt% and put into a KCK continuous kneading extruder (120X2-65VEX), and the mixture was kneaded at a die outlet temperature of 180 ° C. while being degassed through a vent hole, water-cooled and pelletized. Next, as the deodorant, "Absent # 3000"
(Trade name, sold by Union Showa Co., Ltd .; hydrophobic zeolite, average particle size = 3 to 5 μm) was used in an amount of 2% by weight, and after dry blending with 98% by weight of “Mirason-206P”, the die outlet temperature was Pelletization was performed in the same manner as above except that the temperature was 200 ° C.

Next, the two pelletized kneaded products were separately fed into a T-die extruder (screw diameter = 40 mm, L
/ D = 22), and the "Milason-206P" containing 2% by weight of "Absentsu # 3000" is added to the T-die outlet temperature of 32.
It was extruded on polypropylene process paper at 0 ° C., laminated to a thickness of 20 μm, and then 10% by weight of “CLEARON P-125” contained therein “MILASON-
"206P" is laminated at a T-die outlet temperature of 270 ° C. to a thickness of 40 μm, and peeled off from polypropylene polypropylene paper (hereinafter abbreviated as PP paper) to form a two-layer film packaging of the present invention. The material was made (see Table 6).

Example 2 Instead of "Clearon P-125", "Sazol Wax C-105" (trade name, sold by Kato Yoko Co., Ltd .; synthetic wax, density = 0.94 g / cm ³ ) was used as a wax.
The same operation as in Example 1 except that "Absent #
A packaging material of the invention was made up of a two-layer film with a "3000" containing layer (see Table 6).

Example 3 As a polyamide, 20% by weight of "nylon MXD-6" (trade name, manufactured by Mitsubishi Gas Chemical Co., Inc .; aromatic polyamide) was dry blended with 80% by weight of "Mirason-206P" to obtain KCK. Set the die exit temperature of the continuous kneading extruder to 2
A two-layer film with an "Absent # 3000" -containing layer was provided by the same operation as in Example 1 except that the temperature was 40 ° C, and the packaging material of the present invention was produced (see Table 6).

Example 4 As a polycarbonate, "AD-5503" (trade name,
Teijin Kasei Co., Ltd .; ultra low viscosity, specific gravity = 1.20) 4
"Absent # 3000" was contained in the same operation as in Example 1 except that 0% by weight and 60% by weight of "Mirason-206P" were dry blended and the die outlet temperature of the KCK continuous kneading extruder was 240 ° C. A two-layer film with layers was provided to make the packaging material of the present invention (see Table 6).

Example 5 "Clearon P-125" was used as a tackifier.
0% by weight, as a polyamide "nylon MXD-6" 3
In combination with 0% by weight, the above "Mirason-206P" 60
A two-layer film with an "Absent # 3000" -containing layer was provided in the same manner as in Example 1 except that the composition was dry-blended with wt% and the die outlet temperature of the KCK continuous kneading extruder was 240 ° C. Packaging materials were made (see Table 6).

Example 6 In the same manner as in Example 1, the deodorant-containing polyethylene layer was mixed with 2% by weight of "Absent # 3000" and the titanium oxide catalyst "ST-01" (trade name, manufactured by Ishihara Sangyo Co., Ltd .; average particle size). = 70Å) 0.01 wt% content "Mirason-206
A packaging material of the present invention designated as "P" was prepared (see Table 6).

Example 7 "Clearon P-125" was used as a tackifier.
0% by weight and 2% by weight of "Absentu # 3000" as a deodorant were used together and dry blended with 88% by weight of "Mirason-206P", and the die outlet temperature of the KCK continuous kneading extruder was set to 200 ° C. It pelletized by the same operation as. Next, the pelletized kneaded product was put into a T-die extruder, extruded on a PP process paper at a T-die outlet temperature of 270 ° C., laminated to a thickness of 60 μm, and then peeled off from the PP process paper. A layer film was provided to produce the packaging material of the present invention (see Table 6).

Example 8 Milk carton base paper (manufactured by Warehauser Co .;
Using the basis weight = 305 g / m ² ), the "Mirason-206P" was laminated to the corona discharge treated surface of the paper which had been subjected to the corona discharge treatment in advance with a thickness of 20 μm (printing surface side, container outer surface side). ). Next, a corona discharge treatment is applied to the base paper surface on the inner surface side of the container, and 2% by weight of "Absentu # 3000" is contained by a T-die extrusion laminator.
206P ”was melt extruded at a T-die outlet temperature of 320 ° C. and 20 μm. Furthermore, T is applied to the surface of the polyethylene layer containing the deodorant.
Using a die extrusion laminator, the outlet temperature is 270 ° C, and the tackifier "CLEARON P-125" is 10% by weight.
The contained "Mirason-206P" was extruded in a thickness of 40 μm to provide the innermost layer of the container to prepare the packaging material of the present invention (Table 6).
reference).

Example 9 The same milk carton base paper as used in Example 8 was used as the paper, and the above-mentioned "Absent # 30" was applied to the corona discharge treated surface of the paper which had been subjected to the corona discharge treatment in advance with a thickness of 20 μm.
Lamination was performed with "Mirason-206P" containing 2% by weight of "00" as the outer surface of the container. Next, "Adv Coat 335A" [trade name, manufactured by Toyo Morton Co., Ltd.] was previously formed on "BOBRON EX" (trade name, manufactured by Nichigo Film; biaxially stretched polyvinyl alcohol resin film, thickness = 12 μm) as a gas barrier layer. Anchor coating agent (hereinafter referred to as AC agent), urethane-based] solution having a concentration of 5% by weight (solvent is 1: 1 of methyl ethyl ketone and toluene)
Mixing), coating and drying to form an AC agent layer having a coating amount of 0.5 g / m ² , and the surface of this AC agent layer and the milk carton base paper are processed using a T-die extrusion laminator to produce “Mirason M-2
06P ”was extruded at an outlet temperature of 310 ° C. and a thickness of 20 μm, and laminated by a polysand laminating method. Further, an AC agent layer having a coating amount of 0.5 g / m ² was provided on the gas barrier layer by the same operation as described above, and 2% by weight of “Absentu # 3000” was contained on the surface of the AC agent layer “Mirason-2”.
06P ”was laminated to a thickness of 20 μm. Next, a tackifier "CLEARON P-125" 10% by weight was applied to the surface of the deodorant-containing polyethylene layer with a T-die extrusion laminator at an outlet temperature of 270 ° C. and a thickness of 40 μm.
Containing "Mirason-206P" as the innermost layer of the extrusion container,
The packaging material of the present invention was prepared for long-term storage (see Table 6).

COMPARATIVE EXAMPLE 1 In Example 1, "Mirason-206P" which does not contain "Absent # 3000" was used as a low density polyethylene layer at an outlet temperature of 320 ° C. and a thickness of 20 μm using a T-die extrusion laminator, and the innermost layer was also used. Outlet temperature 27 by the same operation
A packaging material having a low-density polyethylene layer containing 0 ° C. and a thickness of 40 μm and containing no “CLEARON P-125” was prepared (see Table 7).

COMPARATIVE EXAMPLE 2 The procedure of Example 1 was repeated except that "Mirason-206P" containing no "Absent # 3000" was formed into a low density polyethylene layer at an outlet temperature of 320 ° C. and a thickness of 20 μm using a T-die extrusion laminator. A packaging material was prepared in the same manner as in Example 1 (see Table 7).

Comparative Example 3 In Example 1, except that "Milason-206P" containing no "Clearon P-125" was formed into a low density polyethylene layer at an outlet temperature of 270 ° C and a thickness of 40 µm using a T-die extrusion laminator. A packaging material was prepared in the same manner as in Example 1 (see Table 7).

Comparative Example 3 "Mirason-2" containing no "Absent # 3000" or "Clearon P-125" in Example 8
A packaging material was prepared in the same manner as in Example 8 except that "06P" was used (see Table 7).

Evaluation of the packaging materials obtained in Examples 1 to 9 and Comparative Examples 1 to 4 (odor / sorption test, aroma retention test, pack check test, d-limonene quantitative analysis, P
H change value) was measured by the following method.

(1) Odor test and sorption test (a) Test sample preparation method Odor test: Two square samples each having a side of 10 cm from the material films produced in Examples 1-7 and Comparative Examples 1-3. The pieces were cut out, placed in a closed container, stored at room temperature for 1 week, and then subjected to a sensory test. Sorption test: The material films produced in Examples 1 to 7 and Comparative Examples 1 to 3 were cut to A4 size, and folded from the center so that the surface containing the specific compound of the present invention was the innermost layer. Bend to A5 size. Two of the three A5 size mating surfaces are heat-sealed (temperature = 120
℃, pressure = 2Kg / cm ² , pressure bonding time = 2sec) to make a bag by heat sealing, pour 80ml of 100% orange juice into this bag, and heat the remaining open side with a heat sealing machine. Seal it. This orange pack is put in a refrigerator and opened one week later to be used for a test.

(B) Evaluation method Odor test: According to the above-mentioned preparation method, a sensory test was performed on the odor of only the material film from the closed container stored at room temperature for 1 week. Sorption test: According to the above preparation method, the sample was stored in a refrigerator for 1 week, then opened, the contents of orange juice were discarded, two square samples with a side of 10 cm were cut out from the material film, and these were immersed in water for a certain time (20 sec). After that, it was wiped off lightly, placed in another closed container, and a sensory test of fragrance was conducted by 6 panelists every 10 minutes. The above is evaluated according to the following four-step criteria. Average the total scores of the 6 panelists, if the average score is 0 to less than 1 point x, if it is less than 1 to 2 points △, if less than 2 to 3 points ○, 3 points In case of ◎. The results of the above odor test and sorption test are shown in Table 1. No odor on the film itself (odor test) and no scent of orange (sorption test) 3 points Slight odor on the film itself (odor test) and slight scent of orange (sorption test) 2 Dot The film itself has a slight odor (odor test) and has a little scent of orange (sorption test) 1 point The film itself has a considerable odor (odour test) and has a scent of orange (sorption test) ) 0 points

[0033]

[Table 1]

(2) Aroma retention test (a) Test sample preparation method The material films prepared in Examples 1 to 7 and Comparative Examples 1 to 3 were cut into two square samples of 10 cm from one side,
These two sheets are piled up and a heat sealing machine (temperature =
Heat seal at 120 ° C, pressure = 2 kg / cm ² , pressure bonding time = 2 sec) to make a bag, inject 20 ml of 100% orange juice into this bag, and heat the remaining open side with a heat seal machine. Heat seal. Put the filled sample in a weighing bottle and cover. After storing at room temperature for 6 hours, a sensory test was conducted.

(B) Evaluation method The lid of the weighing bottle is opened, and the scent of orange is evaluated by a sensory test according to the following four-step criteria. Average the total scores of the 6 panelists, if the average score is 0 to less than 1 point x, if it is less than 1 to 2 points △, if less than 2 to 3 points ○, 3 points In case of ◎. The results of the above aroma retention test are shown in Table 2. No orange scent: 3 points Slight orange scent: 2 points Slight orange scent: 1 point Slight orange scent: 0 points

[0036]

[Table 2]

(3) Pack check test (a) Test sample preparation method The material films prepared in Examples 1 to 9 and Comparative Examples 1 to 4 were cut into A4 size and bent from the center to A5 size. To do. Of the three A5 size mating surfaces, two sides are heat-sealed (Examples 1 to 7 and Comparative Examples 1 to 1).
3 is temperature = 120 ° C., pressure = 2 kg / cm ² , pressure bonding time = 2
sec) (Temperature = 130 ° C. in Examples 8 and 9 and Comparative Example 4,
After making a bag by heat sealing at a pressure of 5 kg / cm ² and a pressure bonding time of 5 sec, sterilize and dry the bag with hydrogen peroxide, and then inject 50 ml of 100% orange juice,
The remaining one side that was open is also heat-sealed with a heat-sealing machine. This orange juice pack is placed in a refrigerator and opened one week later.

(B) Evaluation method Orange juice is poured out from the pack, and the odor and taste are evaluated by sensory test according to the following four-step criteria. The average of the scores of the 6 panelists is averaged, and the average score is 0 to 1.
If it is less than the point, it is x, if it is 1 to less than 2 points it is Δ, if it is less than 2 to 3 points it is o, and if it is 3 points it is o. The results of the above pack check test are shown in Table 3. Orange juice has a good taste and aroma: 3 points Orange juice has a slightly off-taste or odor: 2 points Orange juice has a slight off-taste or odor: 1 point Orange juice has a considerable off-taste or off-odor: 0 points

[0039]

[Table 3]

(4) PH change value (a) Test sample preparation method The materials prepared in Examples 1 to 9 and Comparative Examples 1 to 4 were treated under the same conditions for one week under the same conditions as the test sample preparation method of the pack check test. I left it in the refrigerator.

(B) Evaluation method Orange juice is poured from a pack into a weighing bottle, covered with a lid, and left at room temperature for 1 hour. Then, it measured with the PH measuring device (Hanna Instruments Japan Co., Ltd. make; pocket type PH meter PICCOLO2). The results of the above PH change values are shown in Table 4.

[0042]

[Table 4]

(5) Quantitative analysis of d-limonene (a) Test sample preparation method "Mirason-206P", "Clearon P-125 1"
0% by weight of Mirason-206P "was added to the T-die outlet temperature 2
A single layer of 30 μm was extruded into a film at 70 ° C., and left in a refrigerator at 10 ° C. for 1 week under the same conditions as in the test sample preparation method of the “pack check test”.

(B) Evaluation method The residual amount of d-limonene in the orange juice in the film bag was measured in comparison with 100% orange juice in a bottle. The results of the above d-limonene quantitative analysis are shown in Table 5.

[0045]

[Table 5]

Among the above evaluation results of the packaging materials of Examples and Comparative Examples, the results of sorption, aroma retention and taste are shown in Tables 6 and 7.

[0047]

[Table 6]

[0048]

[Table 7]

From the results of Tables 6 and 7, as in Examples 1 to 7, when a specific formulation was added to the innermost layer and a deodorant was added to the innermost layer or other layers, the sorption property was determined. It can be seen that the fragrance, the aroma retaining property and the taste are all good. Further, it can be seen that by providing the gas barrier layer as in Example 9, transfer of odor to the contents and volatilization to the outside of the flavor can be prevented more effectively.

[0050]

The innermost layer to which the specific composition according to the present invention is added hardly sorbs the flavor of the content having an aroma component, and the deodorant-containing polyolefin resin layer is a packaging material and an odorous substance from the outside. It is possible to provide a good packaging material because it prevents the invasion of the contents into the product and does not change the flavor and aroma of the product contents.

Claims (2)

[Claims] 1. The innermost layer comprises a mixture of a polyolefin resin and at least one selected from the group consisting of natural resin tackifiers, waxes, polyamide resins and polycarbonate resins, and at least one layer comprises A packaging material, which is a polyolefin resin layer containing a deodorant. 2. The packaging material according to claim 1, wherein the deodorant is a hydrophobic zeolite.