KR100241804B1 - Packing materials for fruits and vegetables - Google Patents

Abstract

The present invention relates to a semi-sealed to sealed fruits and vegetables fresh preservation container, a fresh preservation method, and a fresh preservation package made of resin coating. Corrugated cardboard, which is a conventional package of fruits and vegetables, could not be prepared in a fresh state. The present invention uses a corrugated box made by laminating a liner material of resin composition on the inner and outer surfaces of the corrugated cardboard, and after filling the fruits and vegetables, sealing the engagement portion or the overlapped portion of the bottom and the lid with an I-shaped or H-shaped sealing adhesive tape Seal the edges or seal them as necessary, leaving the ventilation zone in place.The packing material and the packing material at a temperature of 27 ° C have a carbon dioxide permeation coefficient of PCO ² of 5 x 10 ^-10 cm ³ (STP) cm / (cm ² It is an inner liner of cmHg) or more, a water vapor permeability is an inner liner of 100 g / m ² or less at 27 ° C, and is composed of a wavy pin-shaped intermediate core in the middle. Fresh preservation package made of single-pack paper made of such packing materials and preservation method of the fruits and vegetables when preserving fruits and vegetables can be oxygen-free breathing, yellowing, wilting, crushing, moisture loss, good packaging without crushing or ruining the box , Package, packing method.

Description

Fresh-sealed containers for half-sealed and sealed fruits and vegetables, fresh preservation methods, and fresh preservation packages

1 is a partial cross-sectional view of the wall of the corrugated container of the present invention.

2 is a perspective view of the assembled corrugated container of the present invention.

3 is a perspective view showing an example of a sealed corrugated container of the present invention.

Figure 4 is a partial cross-sectional view of the star of the corrugated container of the comparative example, Figure 5 is an explanatory view showing the seal of the corner.

* Explanation of symbols for main parts of the drawings

1: outside liner 2: center shim

3: inner liner 4: resin coating layer

5: moisture-proof resin coating layer 6: groove

7: corrugated container 8: rod palm tape

9: edge 10: corrugated end

11: joining surface 13-15: container surface

The present invention is a packaging container and a method for preserving the freshness of fruits and vegetables using a packaging material consisting of a special cardboard (hardboard paper) and a packaging paper and a container composed of the paper, and a container made of paper, to keep freshness of fresh fruits and vegetables The present invention relates to a method for sealing fresh fruits and vegetables for preserving freshness of fruits and vegetables using a special sealing method using a wrapping paper, and a fresh preservative packaging for fruits and vegetables packaged in this way.

Various attempts have been made to protect the freshness of fruits and vegetables. For example, each method has been proposed to prevent evaporation of moisture by reducing the moisture-permeable packaging material, to lower the storage temperature, to inhibit respiration by using an oxygen scavenger, or to prevent aging by adsorbing ethylene gas.

For example, Japanese Unexamined Patent Publication No. 38-2757 describes the use of a high pressure polyethylene film to package and refrigerate fruits and vegetables to prevent the evaporation and further maturation of moisture. In addition, Japanese Patent Application Laid-Open No. 61-216640 discloses that the ratio (QCO ₂ / QO ₂ ) of carbon dioxide gas and oxygen permeability is preserved by controlling the respiration by packing fruits and vegetables using 3 to 4 synthetic resin films. However, the use of such a film could not achieve sufficient freshness protection effect. In addition, Japanese Patent Application Laid-Open No. 1-317354 describes a method of cooling and preserving the inside of a cardboard box as a storage gas composition. Although Japanese Patent Application Laid-Open No. 2-233381 describes a box in which the permeability of oxygen and carbon dioxide gas in the corrugated sheet is controlled, the composition of the atmosphere gas is not necessary because only the permeability of both gases is limited. There was no.

In the prior art, the freshness of fruits and vegetables is lost, and the basic problem of the freshness is insufficient. Therefore, the problem of freshness preservation has not been solved to a satisfactory level.

According to the researches of the present inventors, fruits and vegetables exhibit life reactions during respiration, breathe, and act on plant hormones and enzymes. Therefore, for example, when ethylene gas is present in a storage atmosphere, aging hormone is actively secreted to accelerate aging. In addition, the preservation atmosphere changes its composition due to the respiration of fruits and vegetables, and the oxygen content is too low. When the carbon dioxide gas increases, the inorganic fermentation proceeds, and alcohol fermentation proceeds, generating aldehydes and ethanol. On the other hand, if there is a lot of oxygen, the breathing proceeds vigorously and matures.

As such, the composition of the storage atmosphere plays an important role in maintaining the freshness of fruits and vegetables, and the amount of oxygen as well as carbon dioxide gas should be controlled to an appropriate value.

In addition, fruits and vegetables have a high water content of almost 80 to 95% of all crops, and when they are left at a low temperature, violent moisture is increased in tissues such as peels and leaves, and the loss of water immediately causes wilting and lower freshness.

Usually, more than 5% of moisture is lost, causing some cosmetic changes. The present inventors have studied the adjustment of the composition of the gas in the preservation atmosphere, paying attention to the physiology of such plants. As a result, in order to protect freshness of fruits and vegetables, 1) suppress the evaporation of water, ② adjust the amount of oxygen in the storage atmosphere to be 1 ~ 16%, preferably 2 ~ 12%, ③ carbonic acid in the storage atmosphere. It was found that it was necessary to make the amount of gas present as small as possible in the range of 0-20%, preferably 2-15%.

The inventors of the present invention have a carbon dioxide gas permeability coefficient PCO ₂ of 15 × ^{10 −10} cm ³ (STP) cm / (cm ² · S · cmHg) or higher at 27 ° C. as a packaging material for forming the storage atmosphere. Fruit and vegetable freshness protective packaging material made of synthetic resin film with ratio of ₂ and oxygen permeability PO ₂ and above 4.2 and water vapor permeability coefficient PH ₂ O below 80 x 10 ^-9 cm ³ (STP) cm / (cm ² · S · cmHg) Has completed the invention.

This is invention of Japanese Patent Application Laid-Open No. 2-103131.

The present inventors further pushed forward the research and succeeded in improving the fruit and vegetable fresh preservation action with paper, especially paper, which is a packaging material widely used. In addition, it was clear that the corrugated container using the paper in the sealing container such as a bag, a box, a tray, etc. using the paper which forms this special storage atmosphere, or the liner of an outer layer also showed the outstanding storage property.

The present inventors further pursued the present invention to find out that the container made of the corrugated plate could not be sealed by the conventional seal method according to the configuration of the corrugated plate.

Conservation atmosphere changes in composition by the breathing of fruits and vegetables, and the composition moves in a direction that maintains equilibrium.

This equilibrium does not allow for inorganic breathing, low hormonal secretion, no aging, and even breathing, but a low volume of freshness keeps fresh fruit fresh. In other words, the carbon dioxide gas generated by the respiration of the preservation atmosphere is released as much as possible to the outside, and an appropriate amount of oxygen is introduced into the preservation atmosphere from outside to maintain the equilibrium in the above-mentioned range. This is to protect the freshness.

As a result of various studies to produce such a state, the present inventors have found a new fact that fruits and vegetables cannot be dormant unless the packaging material is improved, thereby improving the packaging material to complete the present invention. . As the container made of cardboard of the present invention,

① If the carbon dioxide gas permeation coefficient PCO ₂ of the outer liner is not more than 5 x 10 ^-10 cm ³ (STP) cm / (cm ² · S · cmHg), the preservation atmosphere may not be satisfied even if other conditions are changed. ,

( ₂₎ The ratio of the carbon dioxide gas permeation coefficient PCO ₂ to the vessel is then effective. 1.5 or less, the carbon dioxide and oxygen concentration is not controlled enough to keep the fruits and vegetables in a sufficient state,

③ If the moisture permeability of the liner is not less than 100g / m ² · day, the release of moisture to the outside of the packaging material increases, so that the water evaporation of the fruits and vegetables in the package becomes violent and wilting, so the freshness of the fruits and vegetables is not kept protected and evaporated. Moisture was transferred to the liner and the center core to reduce the box strength, thus completing a container excellent in freshness.

In the packaging container, (a) the paper must be covered with a resin layer, but from the packaging properties, a copolymer of a low density ethylene having a density of 0.917 g / cm ³ or less and an α-olefin having 3 to 12 carbon atoms is used. That there is a need. (b) the resin layer coated on the paper

① If the carbon dioxide permeation coefficient PCO ₂ is not more than 8 x ^{10 -10} cm ³ (STP) cm / (cm ² · S · cmHg), the storage atmosphere will not be satisfied even if other conditions are changed.

( ₂₎ The ratio of carbon dioxide permeation coefficient PCO ₂ to oxygen permeability coefficient PO ₂ should be 3.5 or more, and below 3.5, carbon dioxide and oxygen concentrations are not sufficiently controlled and fruits and vegetables cannot be maintained in sufficient dormant state. .

③ In addition, if the water vapor transmission coefficient PCO ₂ is not less than 80 x 10 ^-9 cm ³ (STP) cm / (cm ² · S · cmHg), the water evaporates to the outside of the packaging material, so that the moisture evaporation of the fruits and vegetables in the package is intense. As a result of withering, it was found that freshness of fruits and vegetables is not protected and completed the invention of wrapping paper with excellent freshness. Therefore, the present invention is a combination of all of the above conditions to achieve a synergistic effect of fresh preservation of fruits and vegetables.

Further, the present inventors have made various studies to produce such a state, and have obtained a new fact that fruits and vegetables cannot be dormant unless the packaging material is improved, thereby improving the corrugated packaging material. However, it was difficult for the container made of corrugated board to keep confidential. As a result of various studies, it has been found that the cause lies in the configuration consisting of the outer line, the inner line, and the center of the corrugated sheet.However, the airtightness is broken even by blocking the air permeability caused by this structure. Knowing that the negative seal was insufficient, the sealing method and packaging invention were completed.

Therefore, the present invention,

1. (a) Outer liner whose carbon dioxide gas permeability coefficient PCO ₂ at 27 ° C. is 5 × ^{10 −10} cm ³ (STP) cm / (cm ² · S · cmHg) or higher, (b) Center core (c) Moisture permeability 27 A fresh fruit preservation container consisting of a corrugated cardboard with an inner liner of 100 g / m ² , day or less at < RTI ID = 0.0 > C, < / RTI >

2. The fresh fruit or vegetable preserved according to the container and carbon dioxide gas permeability coefficient ratio PCO ₂ / PO ₂ of 1.5 or more times the one of an oxygen transmission coefficient of the container.

3. Fresh fruit storage container according to the above item 1 or 2, wherein the inner liner is composed of a liner material having a moisture permeability of 100 g / m ² · day or less at 27 ° C.

4. The freshwater storage container according to item 3, wherein the inner liner is made of a liner material in which a resin layer having a moisture permeability of 100 g / m ² · day or less at 27 ° C. is disposed on the innermost layer.

5. The outer liner is composed of a liner material in which the carbon dioxide permeability coefficient at 27 ° C. is PCO ₂ having a resin coating of 5 × ^{10 −10} cm ³ (STP) cm / (cm ² · S · cmHg) or more in the outermost layer. Fresh fruit storage container described in No. 3.

6. The outer liner contains a copolymer having a density of 0.917 g / m ³ or less of ethylene and an α-olefin having 3 to 12 carbon atoms, and the carbon dioxide permeability coefficient at 27 ° C. is 8 x 10 ^-10 cm ³ (STP). cm / (cm ² · S · cmHg) or more, transmission coefficient ratio PCO ₂ / PO ₂ is 3.5 or more, and water vapor transmission coefficient is 80 x 10 ^-9 cm ³ (STP) cm / (cm ² · S · cmHg) The fruit and vegetable fresh storage container of the said 3rd comprised from the liner material which excavated the following resin layer.

7. The freshwater storage container according to item 6, wherein the copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms is an ultra low density LLDPE having a density of 0.912 or less.

8. Sealing tape of the bottom, cover and corners of the end of the corrugated cardboard is completely sealed, and the exposed end of the joint of the side is sealed with leaving the ventilation portion, and the fresh fruit container according to item 3 above. .

9. The outer surface of the container consisting of corrugated cardboard consisting of (a) an outer liner with a carbon dioxide permeation coefficient of 5 x 10 ^-10 cm ³ (STP) cm / (cm ² · ScmHg) at 27 ° C and (b) an inner liner. a corrugated end the sealing tape is substantially greater than the carbon dioxide permeability coefficient and the ratio PCO ₂ / PO ₂ of 1.5 in the oxygen permeability coefficient product of the containment vessel, fresh preserved in containers exposed _to, (c) a corrugated bottom portion and the lid portion of the container The sealing sheet of the abutting part and the overlapping part of the sheet is adhered to seal the inside, and the sealing sheet is adhered to both sides of the container and to the upper surface of the lid or the bottom of each corner at a length longer than the length of each side. The non-adhesive end is bonded to room temperature to form an adhesive surface to seal the corner part, and the adhesive surface is adhered and fixed to the container by using the sealing sheet end that protrudes without sticking the adhesive surface. point Outer sealing a sprocket fresh fruits and vegetables storage containers to leave an air passage, the control area with a sealing adhesive tape as needed, the cardboard of the end to expose the portion.

10. The edge of the sealing sheet is bent the end of the sealing sheet adhered to one side of the container, and a part of the sealing sheet is adhered to the other side and the remaining portion is affixed to the end of the sealing sheet adhered to the surface to form a triangular adhesive piece. The fresh fruit storage container according to No. 9, which is a seal surrounding the corner portion.

11. The fresh fruit storage container according to No. 9 or No. 10, wherein the fruit or vegetable fresh storage container according to No. 9 or No. 10 is adhered to and fixed to the back surface of the sealing sheet adhered to the container by using the sealing sheet end portion which is pulled out without sticking the adhesive surface.

12. The freshwater storage container according to item 11, wherein the inner liner uses a corrugated container made of a liner material having a moisture permeability of less than 100 g / (m ² · day) at 27 ° C. disposed in the innermost layer.

13. A corrugated container consisting of a liner material having an outer liner having a resin coating having a carbon dioxide gas permeability of 5 x 10 ^-10 cm ³ (STP) cm / (cm ² · S · cmHg) at 27 ° C. The additive storage container of the said 11th used.

14. A container consisting of corrugated cardboard consisting of (a) an outer liner and (b) an inner liner having a carbon dioxide gas permeation coefficient at 27 ° C of not less than 5 x 10 ^-10 cm ³ (STP) cm / (cm ² · S · cmHg). The bottom of the container is stored in an additive fresh preservation container having a ratio of at least 1.5 carbon dioxide permeation coefficient and oxygen permeability coefficient of PCO ₂ / PO ₂ of the vessel substantially sealed by a sealing tape. A sealing sheet is attached to the abutment portion and the overlapping portion of the corrugated cardboard of the lid portion to seal the inside, and a sealing sheet longer than the length of each side portion at each corner portion is indigenous to both sides of the container and the upper surface of the lid or bottom, The article adheres these non-stick ends to each other to form an adhesive piece, seals it around the corners, and adheres and fixes the container to the container by using a sealing sheet end that protrudes without sticking. A fruit and vegetable fresh preservation package in which the end portion of the corrugated cardboard exposed to the outer surface of the joint portion on the side surface corrugated sheet is left as an aeration control region as necessary, and is sealed by applying a sealing tape.

15. (a) Outer liner with carbon dioxide gas permeability coefficient PCO ₂ of at least 5 x 10 ^-10 cm ³ (STP) cm / (cm ² · S · cmHg); and (b) Center core and (c) Moisture permeability. Is stored in a container made of corrugated cardboard consisting of an inner liner of 100 g / (m ² · day) or less at 27 ° C., and the sealing tape is attached to the end of the cardboard exposed to the bottom of the container and the outer surface of the lid. In addition, the corners are also sealed with a sealing tape, and the exposed end of the side corrugated joint portion is left with a ventilation control area as necessary, and is sealed with a sealing tape so that the ratio of the ratio of PCO ₂ / PO ₂ between the carbon dioxide permeation coefficient of the container and the pickling coefficient is 1.5. Fruit and vegetable packaging body characterized by the above.

16. (a) The core and (C) moisture permeability of the outer liner (B) with a carbon dioxide permeation coefficient PCO ₂ of 27 ° C. or greater of 5 × 10 ⁻¹⁰ cm ³ (STP) cm / (cm ² · S · cmHg) At 27 ° C, the fruit and vegetable of the container consisting of corrugated cardboard with inner liner of 100 g / cm ² · dya or less is stored, and the sealing tape is adhered to and sealed at the end of the cardboard exposed to the bottom of the container and the outer surface of the lid. sealed with sealing tape and the exposed end of the corrugated that the engagement side is adhesive for the sealing tape leaving the air control area as necessary, and that the ratio PCO ₂ / PO ₂ of the carbon dioxide gas permeability coefficient and the oxygen transmission coefficient of the container by less than 1.5 Fresh fruit preservation method characterized by.

17. Carbon dioxide gas permeation coefficient at 27 ° C. containing a copolymer of ethylene and a α-olefin having 3 to 12 carbon atoms of 0.917 g / cm ³ or less, 8 × 10 ⁻⁹ cm ³ (STP) cm / (cm A fruit and vegetable packaging paper obtained by covering at least one side with a resin layer of ² · S · cmHg) or less.

18. The additive packaging paper according to item 17, wherein the ethylene and an ultra low density LLDPE having a density of 0.912 or less with an α-olefin having 3 to 12 carbon atoms are used.

19. Fruit and vegetable packaging paper for internal bending processing which consists of resin coating paper of said 17 or 18.

20. A greengrocer packaging container using the packaging vessel of item 17 or 18 as a base.

21. A cardboard box for storing fruits and vegetables, wherein the packaging paper according to 17 or 18 is used as at least an outer liner material.

22. Outside the container consisting of corrugated cardboard consisting of (a) an outer liner having a carbon dioxide gas permeation coefficient at 27 ° C. of at least 5 × ^{10 −10} cm ³ (STP) cm / (cm ² · S · cmHg), and (b) an inner liner. the corrugated end portions exposed to a surface substantially sealed to by the sealing tape, and the carbon dioxide gas permeability coefficient and the ratio PCO ₂ / PO ₂ of 1.5 or more fruits or vegetables, fresh storage containers of the oxygen transmission coefficient of the container, (c) the bottom of the container and A sealing sheet is attached to the abutment portion and the overlapping portion of the corrugated plate of the lid to seal the inside, and a sealing sheet longer than the length of each side is attached to both sides of the container and three sides of the lid or the bottom at each corner portion. The non-adhesive ends of the upper articles are mutually bonded to form an adhesive piece and sealed by enclosing the corner portion, and the adhesive piece is fixed to the container by using a sealing sheet end portion protruding without sticking, Corrugated board Encapsulation method of the fresh fruit or vegetable storage containers, characterized in that the seal to the vent control adjustment region leaving the adhesive with a sealing tape as needed, the ends of cardboard is exposed to the outer surface of the engagement point.

23. The end of the sealing sheet adhered to one side of the container by bending the corner portion is bent and the part is adhered to the other side, and the remaining portion is affixed with the end of the sealing sheet adhered to the surface to form a triangular adhesive piece. The sealing method for fresh fruits and vegetables fresh storage as described in said 22 which makes a sealing enclosed a corner part.

24. The sealing method of the fresh fruit storage container of Claim 22 or 23 which adhered and fixed to the back surface of the sealing sheet which adhered to the container using the sealing sheet edge which protruded without sticking an adhesive piece.

25. The method for sealing a blue water fresh storage container according to item 24, wherein the inner liner uses a corrugated container composed of a liner material having a moisture permeability of 100 g / (m ² · day) or less at 27 ° C. disposed on the innermost side. .

26. Using a corrugated container composed of a liner material having an outer liner having a resin coating having a carbon dioxide gas permeability of 5 x 10 ^-10 cm ³ (STP) cm / (cm ² · S · cmHg) at 27 ° C. It relates to the sealing method of the fruit and vegetable storage container of the said 24th.

First, the invention of a cardboard container is demonstrated.

The corrugated plate consists of an outer liner, a center shim and an inner liner, and the center shim is formed in a corrugated plate shape in order to bring about a shock absorbing action. This corrugated structure has a significant impact on the formation and maintenance of a conservation atmosphere that is important for the freshness of fruits and vegetables. In addition, since the type of the corrugated plate has moisture permeability and air permeability, the storage atmosphere changes through the walls of the container. For this reason, the inventors of the present invention performed processing of each group on the inner wall of the container after sealing the end exposed to the outside.

As a result of further study, the container was assembled with corrugated board, and the corrugated plate groove 6 of the cross-section opened in the container of the corrugated plate communicated with the wall of the outer liner, so that the outer liner had no interior or resin coating. It was found that the atmosphere was changed through the ditch in the middle of the forest.

This is a novel fact first identified by the inventor.

As a result, even if the inner surface of the corrugated container is anyly processed, the gas in the container escapes from the wall of the outer liner through the groove of the center shim and the outside air enters the container through the reverse course.

Based on this new aspect, the present inventors need to seal at least the external exposed end in order to apply the corrugated container to fresh preservation of the fruits and vegetables, and the carbon dioxide permeability coefficient PCO ₂ at 27 ° C. x 10 ^-10 cm ³ (STP) cm / (cm ² · S · cmHg) or more outer liner. Thus, it was found that it is effective to set the ratio PCO ₂ / PO ₂ of carbon dioxide gas permeation coefficient and oxygen permeability coefficient to 1.5 or more in a sealed container and solved all the problems.

Further, the inner liner is less than 100g / (m ² · day) at 27 ℃ because when water is released absorbs this reduced my humidity vessel as well as the strength of the container decreases and promotes the dehydration of the fruit or vegetable by the living reaction of fruits or vegetables When the resin layer is composed of a liner material disposed on the innermost layer, an inner liner that satisfies the required performance is obtained.

The liner material may be resin-processed to obtain the above-mentioned moisture permeability. As the resin layer, other foamed resin coating layers of uniform coating are also used. In addition, the outer liner is required to have a carbon dioxide permeability coefficient of 27 × 5 at 10 x 10 ^-10 cm ³ (STP) cm / (cm ² · S · cmHg) or more with a liner material in which the outermost layer is formed of a liner material. It becomes an outer liner which satisfies.

That is, if the outermost layer is the carbonic acid gas permeation coefficient, the entry and exit of gas through the wall of the container is controlled, and when the corrugated end exposed to the outside is sealed with a sealing tape, the inflow of gas through the groove of the center seam can be blocked. have. In addition, moisture absorption of the corrugated board is also prevented.

When assembled, the corrugated container is usually sealed with adhesive tape, but the sides of the top and bottom are easily sealed. By the way, the side portion of the corrugated cardboard is bonded to the outside, but the cross section of the corrugated cardboard to the outside is exposed to the outside, the gas in and out is performed in the same form on the back.

The present invention is characterized in that, by using the corrugated cross section of the haptic portion of this side, the sealing of the cross section can be adjusted according to the fruits and vegetables to be stored in the container, and the change in gas composition due to the breathing of the fruits and vegetables in the container can be adjusted. In order to preserve the fruits and vegetables using the container, the present invention stores the fruits and vegetables of the container and seals the end surface exposed to the outside with a sealing tape and seals the sealing tape to the corner portion where the sealing is most likely to be broken. by the like to the vent control area as required corrugated open end portion bongjeop adjusting the ratio PCO ₂ / PO ₂ of the carbon dioxide gas permeability coefficient and the oxygen permeation coefficient of less than 1.5 in a container, to a fruit or vegetable with a sufficient dormant fresh for a long period of time the fruit or vegetable I can preserve it.

Although described in a comparative test below, when the ratio of the carbon dioxide permeation coefficient of the outer liner, the moisture permeability of the inner liner, and the ratio of the carbon dioxide permeation coefficient and the oxygen permeability coefficient of the container is not within the specific range of the present invention, It doesn't work.

Next, the resin layer used for this invention is demonstrated.

As the outer liner characteristic, the carbon dioxide gas permeability coefficient is 5 x 10 ^-10 cm ³ (STP) cm / (cm ² · ScmHg) or more, and the ratio of the carbon dioxide gas permeability coefficient and the oxygen permeability coefficient of the vessel is PCO ₂ / PO. _The outer liner must be formed of a fine resin layer that is not porous in the necessity of ₂ or more to 1.5.

As a resin layer which satisfies these requirements, resin which has low density polyethylene or ethylene, (alpha) -olefin, a crude vinyl acid, acrylic acid, methacrylic acid, etc. as a component is used. Ethylene-alpha-olefin copolymer, an ethylene vinyl acetate copolymer, an ethylene acrylic acid copolymer, an ethylene methacrylic acid copolymer, a polystyrene, a styrene butadiene copolymer, etc. are mentioned. Moreover, in order to improve the permeability of resin and adhesiveness with a paper base material, these base resins may be graft-modified with silicone, maleic anhydride, etc. in some cases.

The resin layer that satisfies the requirements of the permeation characteristics of the present invention may be formed of a single synthetic resin, but is preferably composed of a plurality of synthetic resins in the necessity of satisfying each of the requirements for varying the above characteristics independently.

Representative examples of such synthetic resins include ethylene and α-olefin copolymers having 3 to 12 carbon atoms, such as ethylene-butylene-1 copolymer, ethylene-hexane-1 copolymer, ethylene-4-methylpentene-1 copolymer, Ethylene-octene-1 copolymer etc. are mentioned, It is good to use it as at least 2 or more types of brands chosen from these resin. Moreover, these ethylene, C3-C12 alpha-olefin copolymer, and low density polyethylene brand products can be used.

In particular, in order to obtain a high carbon dioxide permeability coefficient, the main component is a low density ethylene-α-olefin copolymer having a relatively high copolymerization ratio of α-olefin or a high copolymerization ratio of α-olefin, that is, an ultra low density ethylene-α-olefin copolymer. It is preferable to use at least two or more kinds of resins composed of other monomers in the above resin groups, such as low density polyethylene, ethylene-hexene-1 copolymer, and ethylene-butene-1 copolymer, in order to obtain high selectivity. And an ethylene-hexane-1 copolymer may be selected and used.

As another method for obtaining a resin layer that satisfies the requirements of the permeation characteristics of the present invention, the resin alone or a plurality of resin brands may be used as a base polymer, and ethylene-vinyl acetate copolymer (EVA) and ethylene may be used. Ethylene copolymers such as acrylic acid copolymers and ethylene-methyl methacrylate copolymers, ethylene or α-olefin-propylene-non-conjugated diene polymers, or ethylene-butadiene flock copolymers, styrene / isoprene ratios Resin of the hydrogenated substance of a copolymer can also be used as a brand.

When these resins are used as single resins, it is difficult to satisfy all of the permeability requirements of the present invention, and the lamination strength with paper decreases, and cracks and cracks due to bending after lamination tend to occur. It is necessary to use it as a brand ratio of 90:10-50:50 with respect to said base polymer.

As described above, the detailed transmission ratio of carbon dioxide gas and oxygen is increased by branding resins having different complex reduction units, but the present inventors have a region in which molecular chains having different molecular mobility are present at different concentrations. This is because the hydrophilic permeability of both changes depending on the molecular chain concentration.

As the characteristics of the inner liner, any resin may be used as long as the moisture permeability at 27 ° C. is 100 g / (m ² · day) or less, and a relatively high density resin mainly containing ethylene among the resins used for the outer liner is preferable. High-density polyethylene, polypropene, copolymer resins based on propylene, foams and the like are used.

At this time, in order to more effectively prevent the lowering of the box compressive strength due to moisture absorption, it is preferable to select a material and a thickness configuration in which the moisture permeability of the inner liner can be smaller than that of the outer liner. When the liner material having these resin layers is processed into a corrugated box, the resin layer is not cracked, cracked, or used in this kind of defects and delamination. It is important in this respect. In particular, when the resin layer of the outer liner is cracked, terami, etc., it becomes difficult to preserve the permeability coefficient ratio PCO ₂ / PO ₂ of the container to 1.5 or more.

These resin layers include lubricants, antifoaming agents, charging agents such as phenolic, organic sulfuric acid, organic nitrogen, organic solvents such as antioxidants or thermal stabilizers, and fatty acid derivatives such as metal soaps and other fatty acid esters according to its own known prescription. Inorganic fillers or other coloring agents such as calcium carbonate, white carbon, plywood white, magnesium carbonate, magnesium silicate, carbon black, various clays, natural to synthetic zeolites, or other coloring agents, It can mix | blend with a compounding ratio.

The thickness of the coating resin layer needs to be appropriately set in consideration of the type of resin used and its physical strength, the relationship between the properties of the paper used, and sometimes the type of additive to be packaged and the storage temperature. Generally 5 to 60 µm, preferably 10 to 40 µm is appropriate.

Although there is no restriction | limiting in particular in the melt index (MI) of resin used by this invention, For example, it is good to use about 0.1-30 g / 10min of MI value, Preferably it is about 0.1-10g / 10min (based on JIS 6760).

In general, the numerical layer of the present invention can be formed by extrusion lamination or laminates such as resin films and sheets. In addition, for the purpose of improving the adhesion to paper and the surface characteristics of the resin coating layer, lamination using a multilayer board or a multilayer film made of a multilayer film in advance may be used. In addition, although a predetermined resin coating layer is preferably provided on the outermost layer of each liner material, a porous plastic film or a relatively low basis weight paper is disposed on the outermost layer within a range of maintaining the earth-to-ceil ratio ratio PCO ₂ / PO ₂ of 1.5 or more. Alternatively, a layer made of synthetic paper may be provided by a method such as side lamination or dry lamination.

In addition to the above method, the resin layer can be formed by drying the film, which has been formed in advance, using a pressure-sensitive adhesive, or coating the film on the liner paper with a solution or dispersed paint, impregnating or drying the film. have.

Examples of the paper used for the corrugated board of the present invention include papers made of cellulose pulp, such as graft paper, art paper, general printing paper and roll paper, thin paper or corrugated paper, and white paper such as manila balls and white balls. Used. Furthermore, for pulp, paper mixed with synthetic resin fibers such as polyethylene is also used. Printing on the surface of the resin layer provided on the corrugated paper is desirable in terms of securing the cosmetic properties of the packaging container and forming a resin layer on the paper. It may be printed on paper before the bin. As a printing method, known printing methods such as gravure, fresco, silk screen, etc. are possible. Since the thickness of the printing layer is thin and not a continuous film, the influence on the permeability is extremely small. In the case of printing on the surface of the resin layer, from the viewpoint of increasing the adhesion of the ink to prevent scratch resistance, after the resin coating or in the case of the film, the treatment such as corona discharge treatment is usually performed by a known method. It is effective.

In the use of the corrugated plate of the present invention, a means effective for maintaining freshness protection of a known fruit or vegetable can be used. For example, the gas adsorbent and moisture control of the generated gas such as ethylene aldehyde and the like of the fruits and vegetables may also have a more effective effect on maintaining the freshness of the desiccant, the desiccant, the deoxidizer, or the carbon dioxide remover. These auxiliaries are usually used in the form of separate bags inside the packaged cardboard of the present invention, but sometimes when the liner of the present invention is coded or liner papered, it is impregnated with pulp or the like It is effective also by the method of mixing.

After filling the contents, the corrugated box is used for sealing, such as I-sealing and H-sealing, which are known per se, and a manual machine such as an automatic handheld. In the case of room H, research is needed to close the space gap at the corner of the cardboard box. Incomplete sealing of the corners makes it difficult to maintain the permeability ratio PCO ₂ / PO ₂ of the container to 1.5 or more. Moreover, the oxygen and carbon dioxide concentration in a container can be adjusted to an appropriate range by changing the exposed edge | side sealing bag of the side gluing part. This method is effective for relatively high respiratory contents. As the material of the tape used for sealing, those having gas permeability less than the value of the outer liner are suitable, but not limited thereto, biaxially stretched polypropylene, salt ratio, biaxially stretched polyethylene terebutate, biaxially stretched nylon, high density polyethylene, etc. The material of is suitable, 20-80 micrometers Preferably the thickness of 30-50 micrometers and the width of 20-80 mm are preferable.

In order to accommodate a fruit or vegetable, it is preferable that it is water-resistant as an adhesive, and it is desirable to have cold resistance suitable for low temperature storage or distribution.

Next, the sealing method is demonstrated.

As described above, the corrugated plate is composed of an outer liner, a center core, and an inner liner, and the center core is formed in a wavy plate shape in order to absorb shocks. In addition, the paper constituting the corrugated sheet has moisture permeability and air permeability, and changes in the storage atmosphere occur through the walls of the container. For this reason, the present inventors applied various processing to the wall of the container after sealing the end exposed to the outside, but it was ineffective. A further study of why it was not sealed revealed that it was due to the structure of the cardboard.

When the container is assembled from the corrugated plate, the groove of the corrugated plate in the center of the cross section opening in the container of the corrugated plate communicates with the wall of the outer liner. Let's do it.

This is a fact first identified by the inventor.

As a result, even if the inner surface of the corrugated container is treated, the gas in the container escapes from the wall of the outer liner through the groove of the center shim and the outside air enters the reverse course into the container.

In view of this new aspect, the present inventors need to seal at least the end exposed to the outside in order to be suitable for fresh preservation of fruits and vegetables of the corrugated container, and the carbon dioxide permeability coefficient PCO ₂ of the outer liner of the corrugated plate at 27 ° C. The outer liner of 5 x 10 ^-10 cm ³ (STP) cm / (cm ² · S · cmHg) and thus the ratio of carbon dioxide gas permeability and oxygen permeability coefficient of the sealed container to PCO ₂ / PO ₂ of 1.5 or more We solved this problem by finding out that it is necessary.

In addition, the inner liner releases moisture due to the life reaction of fruits and vegetables, and absorbing it lowers the strength of the container as well as lowers the humidity in the container and encourages the dehydration of the fruits and vegetables. Therefore, the inner liner is less than 100 g / (m ² · day) at 27 ° C. It is preferable to comprise a liner material at the moisture permeability of.

For example, when the inner liner is composed of a liner material having a resin layer having a moisture permeability of 100 g / (m ² · day) at 27 ° C. or less disposed on the innermost layer, it becomes an inner liner that satisfies the required performance. Of course, the moisture permeability may be adjusted by processing such as converting the liner material into resin. If the outer liner is made of a liner material in which a resin coating having a carbon dioxide permeation coefficient of 5 x 10 ^-10 cm ³ (STP) cm / (cm ² · S · cmHg) at 27 ° C. or more is disposed on the outermost layer, It becomes an outer liner that satisfies the required performance. What is important here is to arrange | position the said coating | cover to the outermost layer. Even if the coating is disposed on the inner layer, gas is released through the outer layer liner and flows into the reverse course. Therefore, gas permeation must be controlled to the outermost layer of the outer liner.

That is, if the outermost layer is the carbonic acid gas permeability coefficient, the entry and exit of gas through the wall of the container is controlled, and if the corrugated end portion exposed to the outside is sealed with a sealing sheet, the inflow of gas through the center core can be blocked. . In addition, by limiting the moisture permeability of the innermost layer to the inner liner, the moisture absorption of the bone plate and the dehydration of fruits and vegetables can be prevented.

When assembled, the corrugated container is usually sealed with an adhesive sheet while the upper and lower bottoms and the lid parts are easily sealed. By the way, corrugated cardboard is formed in the side part to form a container, but a predicted cross section of the corrugated cardboard is exposed to the outside, and gas flows in and out through the groove of the center core from the back side.

The present invention has a feature that the change in gas composition due to the breathing of the fruits and vegetables in the container can be adjusted by adjusting the sealing of the fruits and vegetables in the container according to the fruits and vegetables to be stored in the container using the corrugated cardboard section. Of course, you may seal completely.

Next, the sealing of the corner part which is the most important characteristic of this invention is demonstrated.

Even when a container satisfies all of the above factors, it is often seen that the sealing is insufficient. As a result of the inventor's study on the advantages, it was found that the corrugated container has a part that is easily broken in the sealing. Each corner of the corrugated container is there. Since the corner portion of the corrugated container has many end faces of the corrugated plate due to the structure in which the three sides are orthogonal, and because the material is paper, the corner is often not sealed by precise bonding and the gap is generated anyway.

Further, even when the sealing sheet is adhered, since the corner portion is composed of three surfaces crossing at right angles, the sealing sheet does not adhere to the corner portion of the corner tip.

In addition, since a sheet is adhered to three surfaces of such a container, wrinkles are likely to occur, and therefore, corner portions at the corners are easily communicated with the outside.

Therefore, the present invention first bends the edges of the sealing sheet adhered to both sides or one side of the corner and the lid or the bottom by bending on the other side, and the sheet end portion adhered to both sides of the bent portion and its vicinity and adhered to both sides. When the unsettled portions of each other are bonded together, a triangular junction piece is formed so that the corner edge portion is completely enclosed and sealed by the sealing sheet, and there is no occurrence of wrinkles in the sealing sheet. However, when such an affixation is performed, the affix pieces of the agglomerated sheets rise to the left from the corners and are difficult to handle, and also remain in contact with each other, so that these parts adhere to other articles and are torn. There is a danger.

Then, the adhesive pieces of the mutually mutually sealed sealing sheets are adhesively fixed to the container or the sealed sealing sheet of the container by using the remaining adhesive layer. Thus, when preserving the fruits and vegetables using the container of the present invention, in the corrugated container used in the present invention, the fruits and vegetables are stored in the corrugated container, and the corrugated end face exposed to the outside is sealed with a sealing sheet, and then the opening end of the side plate of the cardboard is sealed. Depending on the type, leave the appropriate ventilation control area and seal and adjust the ratio of carbon dioxide permeation coefficient and oxygen permeability coefficient and PCO ₂ / PO ₂ ratio of the container to 1.5 or more, so that the fruits and vegetables can be kept dormant for a long time. have.

Although described by comparative experiments below, the fresh preservation of fruits and vegetables cannot be preserved unless the ratio of the carbon dioxide permeation coefficient of the outer liner of the present invention or the carbon gas permeability coefficient and oxygen permeability coefficient of the container is within the specific range of the present invention. In addition, if the sealing method of the corner is changed to other than the sealing method of the present invention, fresh preservation of fruits and vegetables is impossible.

Next, although the wrapping paper of this invention is demonstrated, the resin layer which coats a wrapping paper is demonstrated first.

The resin layer that satisfies the requirements of the permeation characteristics of the present invention may be formed of a single synthetic resin as described above. However, it is preferable to constitute a plurality of synthetic resins in order to satisfy the requirements different from each other independently. Examples of such synthetic resins are as described above.

In addition, another method for obtaining a resin layer that satisfies the requirements of the permeation characteristics of the present invention is to use the resin alone or a plurality of resin brands as a base polymer. Ethylene copolymers such as acrylic acid copolymers, ethylene-methyl methacrylate copolymers, ethylene or α-olefin-propylene-non-conjugated diene polymers, or styrene / butadiene prop copolymers, styrene / isopropylene floc copolymers Resin, such as hydrogenated additives, can be used as a brand.

As shown in the following examples, when these resins are used as the sole resins, the above-described problems are used. Therefore, it is necessary to use the resin in a brand ratio of 90:10 to 50:50 with respect to the base polymer.

As mentioned above, these resin layers can be mix | blended with a well-known compounding ratio according to the well-known formulation itself. The thickness of the coating resin layer needs to be appropriately set depending on the type of resin used and its physical strength, and also considering the relationship between the properties of the paper used, sometimes the type of fruit or vegetable to be packaged, and the storage temperature. About 5 ~ 60μ, preferably 10 ~ 40μm is appropriate.

Although the resin used in this invention does not have a restriction | limiting in particular in melt index (MI), For example, it is good to use what is MI value about 0.1-10 g / 10min (based on JISK6760).

The resin layer of the present invention can be formed by extrusion or laminate such as a resin film or sheet. In order to improve the adhesion to paper and the surface characteristics of the resin coating layer, lamination using a multilayer plate or a multilayer film previously formed from a multilayer plate can be used. In this case, these multilayer resin layers are defined in the claims. Of course it meets the permeability.

Printing on the surface of these resin layers is, of course, desirable in terms of securing the cosmetic properties of the packaging container, and may also be printed prior to forming the resin layer on paper. Since the thickness of the printed layer is thin and not a continuous film, the influence on the permeability is extremely small. In particular, in the former case, it is effective to perform a corona discharge treatment or the like by a known method after coating the resin or before coating the film in the case of increasing the adhesiveness of the ink to prevent scratch resistance.

The paper of the present invention is used as a paper impregnated with cellulose pulp, such as graft paper, art paper, general printing paper, roll paper, thin paper, or liner, corrugated paper such as center core, manilable, white paper of valve, or the like. do. Moreover, the paper which mixed the synthetic resin fiber, such as polyethylene, with respect to pulp is also used. The wrapping paper of the present invention may be packaged by sealing the abutting portion of the wrapping paper like a normal wrapping paper, or may be sealed by sealing the opening or closing the opening by storing the fruits and vegetables as a bag or box-shaped container. When sealed in this way, the atmosphere inside becomes an appropriate atmosphere and the freshness of a fruit or vegetable is maintained.

In the use of the packaging paper of the present invention, it is possible to modify a means effective for freshness of the fruits and vegetables known per se. For example, in the case of generated gases such as ethylene and aldehydes of fruits and vegetables, a moisturizing agent, an absorbent material or a deoxidation material, and a carbon dioxide remover may also have a more effective effect on maintaining freshness in controlling gas adsorption and moisture in bags.

These auxiliaries are usually used in the form of a separate bag inside the packaging paper of the present invention, but in some cases, the packaging paper of the present invention may be coded or impregnated or mixed with pulp or the like at the time of papermaking, or mixed in a resin. It is also valid in the way.

Briefly, the gas flow generated between the atmosphere in the package and the outside air during the storage of fruits and vegetables is briefly described. Carbon dioxide (CO _2), produced by the breathing of fruits and vegetables, penetrates the wrapping paper and is released into the outside air. On the other hand, oxygen, O ₂ consumed by the respiration of fruits and vegetables penetrates the package from outside air and invades into the package. Here, in order to create an atmosphere in which fruits and vegetables are kept in a dormant state, carbon dioxide gas in the package is released to the outside as much as possible, and the abundance is controlled as little as possible to control the invading oxygen. It is important to control the amount as much as you can. In addition, another effect of using the packaging paper of the present invention is that the packaging paper of the present invention has high gas permeability and also releases ethylene gas generated by fruits and vegetables to the outside with great efficiency, thereby suppressing an increase in the concentration of ethylene gas inside the package. It is effective in preventing aging of fruits and vegetables.

Although the detailed effect is shown as a comparative test in the term of the Example, the extension of the fresh preservation days of 150% or more compared with the package was recognized by adjustment of the atmosphere of this invention. The wrapping paper of the present invention should have a ratio of the carbon dioxide permeation coefficient PCO ₂ , the carbon dioxide gas permeation coefficient PCO ₂ oxygen permeation coefficient PO ₂ , and the water vapor permeation coefficient PH ₂ O to be within a specific range.

This is explained in detail in the section of the following examples.

Moreover, the wrapping paper of this invention is excellent in the possibility of bending, and even if it is bend | processed, no adverse influence will arise in gas permeability and water vapor permeability. This performance is very effective for the formation of containers such as boxes.

The following examples will be described in detail, but the most appropriately preserved articles of the present invention include citrus fruits such as citron citrus and starch (SUDATI FRUIT), apples, corn, and leek, in addition to the items illustrated in the examples. In addition, there are vegetables such as tomato, broccoli, asparagus, broccoli, which are effective for inhibiting transpiration, raw shiitake mushrooms and cherries. For crops that require cold storage, coolant, dry ice and ice may also be used.

As an effect of the present invention, by using a corrugated plate in addition to the above, the contents are set freely by the ratio between the surface area and the content of the container according to the amount of respiration, thereby optimizing the gas composition in the container. ) Free space, not filling, packing materials according to the contents, especially the pinhole of the outer liner is prevented.

EXAMPLE

First, a description will be given for an example of a fresh fruit fresh storage container and a fresh storage packaging, and then the sealing method will be described with respect to the wrapping paper.

1 is a partial cross-sectional view of the wall in the corrugated container of the present invention.

(1) is an outer liner, and since the resin coating layer 4 is arrange | positioned at the outermost layer, inflow and outflow of gas through the wall surface of an outer liner is controlled by the resin coating layer.

(2) is a center core, wavy, and a communication groove (6) is formed.

(3) is an inner liner, and since the moisture proof resin coating layer 5 is arrange | positioned at the innermost side, the movement of moisture through a resin layer is controlled.

2 is a perspective view of the assembled corrugated container 7 of the present invention.

The corrugated end exposed portion of the lid and the bottom is sealed by a sealing tape 8. It can be appreciated that the edge 9 is sealed.

Figure 3 shows that the end of the corrugated container of the present invention sealed the end of the corrugated plate 10 exposed to the outside of the corrugated adhesive. In Fig. 3, all of the corrugated board ends are sealed, but some of them may be left as ventilation control areas.

4 is a corrugated container of a comparative example in which the resin coating layer 4 is provided on the inner shaft of the outer liner 1 and the resin coating layer 5 is provided on the center of the inner liner 3.

5 shows the seal of the corner.

The sealing tape is adhered to the surfaces 13, 14, and 15 to seal the sealing tape. The end portion of the sealing tape adhered to the surface 13 at the corner of the container is bent and adhered leaving some corner periphery on the surface 14 side, so that the end of the sealing tape protruding from the surface 13 is closed. When the sheet is bent and adhered to the surface 15 side, and the remaining portions are bonded to each other, a four-sided bonded piece 11 is formed. In this way, the locking portion 12 of the adhesive face is formed. This locking portion 12 is adhered to the surface 14 to fix the viscous piece 11. Thus, the corner is completely surrounded by the sealing tape so that the end of the sealing tape is also fixed and does not protrude. Although the sealing tape adhered to the surface 13 has been described in this embodiment, the same is true for the sealing sheets on the surfaces 14 and 15, and the triangular shape of the seal portion 12 is somewhat changed and the adhesive portion of the adhesive piece is The only difference is the effect.

Next, evaluation of the permeation characteristics of gas and water vapor at 27 ° C. of various films and corrugated vessels used in the following examples and the compressive strength of the corrugated vessels will be described.

(1) gas permeability of film

For the measurement, a mixed gas permeability measuring device (LYSSY GPM-200) using commercially available gas chromatography as a detector was used. On the inlet side of the film, carbon dioxide and air are flowed at atmospheric pressure in a mixing ratio of volume ratio 1: 4, and on the outlet side, helium gas is used as a carrier gas, and the gas composition on the sales side is measured at every moment, and the coefficients of the respective gases are prepared in advance. The amount of permeation at each time is corrected by a line, and the difference is determined by the least-square method from before them, and the permeation system PCO ₂ {cm ³ ( STP) cm / (cm ² · S ⁻¹ · cmHg ⁻¹ } The measurement measured that the permeation cell and chamber were constantly protected at 27 ° C.

(2) water vapor permeability

For measurement, a moisture vapor permeability tester (LYSSY L80-4000 type) was used, and as a standard sample, a 25 μm two-sided stretched polyethylene thilephthalate film was measured and used in advance by a couple method. According to this method, the permeability of water vapor was determined in units of g / m ² · day, and this was used as an index of water vapor permeability of the coated liner.

(3) Gas Permeability of Corrugated Containers

After the corrugated container was sealed in an empty state, the permeation characteristics at 27 ° C. were measured. In the case of carbon dioxide gas, the permeability at a pressure difference of 0.2 atm is determined from a curve obtained by substituting a mixed gas of nitrogen 80: carbon dioxide gas (volume ratio) for the inside of the container and measuring the change in time of the gas adjustment by chromatography. It was. In the case of oxygen, after completely replacing the inside with nitrogen, a time-varying curve of oxygen concentration was measured in the same manner, and the permeability at a pressure difference of 0.2 atm was obtained. The unit of permeability thus obtained is cc (STP) -hr (standard state conversion), but considering the effective surface area which hindered the thickness of the coating resin and the portion used for sealing the end to the corner, the permeability coefficient PCO _2, PCO ₂ { cm ³ (STP) cm / (cm ² · S ⁻¹ · cmHg ⁻¹ ), and the transmission coefficient ratio PCO ₂ / PO ₂ was obtained from the values of both. The arithmetic mean of time measurement was made into the measured value.

(4) compressive strength of corrugated container

The measurement was carried out in accordance with JIS 0212 using a commercial compression tester (CTM-1-5000 type). The compression direction was directed toward the surface and the compression speed was tested at 10 mm / min, and the maximum compressive load (Kgf) was used as the compressive strength of the corrugated container. In any of the above measurements, the arithmetic mean of three measurements was taken as the measured value.

(5) Water vapor permeability of synthetic resin coating package

For the measurement, a commercial vapor permeability tester (Lyssy L80-4000 type) was used, and the standard sample used a 25 μm biaxially stretched polyethylene terephthalate film by measuring the water vapor permeability by the capping method in advance. According to this method, it is calculated | required in the unit of g / (m <^2> * day) as water vapor permeability. So, from this measurement, the film permeability and the moisture vapor permeability (2.67 mHg) at 27 ° C. are converted into units of cm ³ (STP) cm / (cm ² · S · cmHg), indicating the water vapor permeability of the coated paper. It was set as. For example, in the case of a coated paper having a thickness of 20 μm and a permeability of 50 g / (m ² · day), the transmission coefficient of 54 × 10 ⁻⁹ cm ³ (STP) cm / (cm ² · S · cmHg) in terms of do. The permeability of the actual package can be estimated using the permeability tester of the resin coating obtained by the measurement by the above method.

For example, in the corrugated board of Example 1 described later (length l = 228, width w = 190, height H = 111 mm external dimension), the effective surface area excluding the portion used for sealing the end to the corner is 1650 cm ² . When the pressure difference between carbon dioxide and oxygen in the package is 0.2 atm, when the resin coating of the present invention 1 of the embodiment is used, PCO ₂ 86cc (STP) hr, PCO ₂ / PO ₂ 3.7, PH ₂ O is calculated to be 2.5 g / day.

On the other hand, after sealing this package empty, the permeation | transmission characteristic to 27 degreeC was carried out. In the case of carbon dioxide gas, the permeability at a pressure difference of 0.2 atm in the curve obtained by replacing the inside of the package with a mixed gas of nitrogen 80: carbon dioxide gas (volume ratio) and measuring the change in time of the gas composition by gas chromatography. Was obtained. In addition, in the case of oxygen, after completely nitrogen-substituting the inside, the time change curve of oxygen concentration was measured by the same method, and the permeability in the pressure difference 0.2atm was calculated | required. In the case of steam, a package in which a saturated salt solution capable of maintaining a relative temperature (RH) of 97% at 27 ° C. is kept inside a chamber at 27 ° C. RH 25%, and a time variation of its weight is measured to measure steam. Permeability was obtained by converting the concentration difference. It was confirmed that the measured values obtained in this way and the previous calculated values agree well with each other by a maximum of 10%, and the permeation characteristics of the package can be accurately measured by the permeation characteristics of the resin coating used.

(6) Permeability after Low Temperature Bending Process

Bending resistance of the resin coating was carried out with the resin coated surface on the outside of the 100 x 100 mm test piece according to the evaluation method of the limit of (5) and (6) during JFS-J1514 polyethylene processing.

After two-way bending in the perpendicular direction, gas permeability and water vapor permeability were measured by the method described above. In any of the above measurements, the arithmetic mean of three measurements was taken as the measured value.

[Comparative Examination 1]

Example 1

It is a container using the corrugated board of FIG.

The gerbil by high-pressure polymerization in the bone panyong liner surface sheet having a basis weight of 220g / m ² is also polyethylene (Low density polyethylone; LDPE), and ethylene and a weight ratio of 60 that is the very low density polyethylene (LLDPE) by copolymerizing butene-1: brand of 40 Water was compressed to a resin film thickness of 20 탆 and laminated. As conditions, the plate direct resin temperature 320-325 degreeC, lamination speed 100m / min, and the liner surface corona treatment 5Kw were used.

Using the resin coated liner as an outer surface, using a water-based bond as a corrugayer, the center seam of a basis weight of 180 g / m ² firstly processed, followed by a basis weight of 220 g coated with a film thickness of 30 μm with LDPE on the inner surface side The liners of / m ² were each matched to give a corrugated cardboard.

In this paperboard, a normal mold is drawn, and the joints are joined using a hot-melt adhesive material, and the specified A-1 corrugated board (length l = 288, width w = 190, according to JIS J-1507). Height h = 115 mm). PCO ₂ of the resin coated outer liner was 15.0 × 10 ⁻¹⁰ (cm ³ (STP) cm ⁻² · S ⁻¹ · cmHg ⁻¹ ) and the moisture permeability of the resin coated inner liner was 32.5 (g / m ² · day).

Comparative Example 1

The configuration of the outer liner was the same as in Example 1, and the inner liner was used without a resin coating.

Comparative Example 2

The outer liner is used without a resin coating as it is and the configuration of the inner liner is the same as in Example 1.

Comparative Example 3

The conventional corrugated container was used as it is. There is no resin coating layer.

[Comparative Example 4]

It is a container using the corrugated board of FIG.

The coated resin layers of the outer liner and the inner liner were the same as in Example 1.

[Test Methods]

In the above five kinds of corrugated boards, the KABOSU FRUIT harvested in mid-September (preparation No. 1 of Owache) was put in advance and filled with Kg, respectively, and the adhesive tape based on biaxially stretched polypropylene having a width of 40 mm. Sealed completely as shown in FIG. Five cases of each kind were prepared and stored in an atmosphere of 20 ° C. and 65% RH. After storage for about one month, the oxygen and carbon dioxide concentrations in the corrugated plate were measured, and the compressive strength was measured by the method described above. After that, the quality of the caboose

① Green is sufficiently protected and the skin is taut quantity (%)

② For defective products, a: sulfide, b: cherries, and c: wither. d: incidence of mold and other defects (%)

③ The weight reduction rate (%) was evaluated based on the total initial weight.

Table 1 shows the composition of the gas in the corrugated plate, the compressive strength of the container (the ratio when the maximum compressive load of the conventional corrugated sheeting machine is 100 before storage, and the results of the carbos storage test by each of them). It was.

TABLE 1

In the table of defective items, a, b, c, d is a sulfide, b is dull, c is wilted and d is moldy (%).

In the corrugated sheet coated with resin only on the outer liner of Comparative Example 1, since the gas exchange with the outside of the container is controlled through the outer liner surface, the gas composition in the container is consistent with the Cargo's CA storage condition, but the green color of the skin is maintained. The compressive strength of the container became extremely small because the transpiration portion of the was transferred to the liner and the center. In addition, the weight of the fruit was also reduced and the wilting was apparent. In the corrugated sheet coated with resin only in the inner liner of Comparative Example 2, the compressive strength of the container was preserved and the weight loss of the fruit was also suppressed because no transpiration was transferred. Since the gas exchange with the outside was freely performed through the outer liner, the gas composition in the container was almost the same as that of the atmosphere, and there was an extremely high amount of sulfation and sedimentation.

In the conventional corrugated sheet without the resin coating of Comparative Example 3, the weight loss was extremely severe and almost withered. In addition, there were many yellowing fruits because they did not inhibit respiration. In the corrugated plate of Comparative Example 4, since the gas was freely introduced through the liner at the portion engaged with the flap of the outer liner, respiratory control was not performed, and thus there were many sulfide fruits. Moreover, since the inner liner had the resin layer 5 outside, it was exposed in the container, absorbed the moisture which evaporates from fruit, the intensity | strength fell, and the moisture evaporation of fruit was also accelerated. On the other hand, in the corrugated sheet coated with resin on both side liners of Example 1, the greenness of the skin was maintained due to the breathing control by the simple CA effect, and the satisfactory preservation was achieved with little weight loss. In addition, the strength of the vessel was not lowered as compared with the initial stage, and the results were practical.

[Comparative Test 2]

Example 2

Laminate was extruded at 25μm of film thickness using a 40:60 brand of LDPE (density ρ = 0.918) and ultra-low density LLDPE (density ρ = 0.995) on a corrugated liner base surface of 280 g / m ² basis weight. . Used by the side of the outer surface of these resin-coated surface to the outer liner and an inner liner having a basis weight of 180g / m ² of turmeric, a basis weight of coating the LDPE (density ρ = 0.918) on the inner surface side to a thickness of 25μm 280g / m ² of Corrugated board was obtained by sticking with an aqueous bond as follows. In addition, molds and boxes were made and made into A-1 corrugated board (length l = 288, width w = 190, height h = 115mm). PCO ₂ of resin coated outer liner is 13.5 x 10 ^-10 cm ³ (STP) cm / (cm ² · S ^-1 · cmHg ^-1 ), and the moisture permeability of resin coated inner liner is 39.0 (g / m ² · day Was. In the above-mentioned corrugated sheet, 2 kg of fresh medium (cheong mae: cultivar Minami Takaume) refrigerated at 10 ° C. for 8 hours after harvesting were filled, and then the adhesive tape based on biaxially stretched polypropylene having a width of 40 mm was used as shown in FIG. 2. The exposed end of the corrugated sticky side of the side was sealed leaving the ventilation area.

[Comparative Example 5]

The same procedure as in Example 2 was carried out except that the adhesive tape was applied only to the portion where the bottom plate and the lid portion were in contact with the corrugated plate.

Comparative Example 6

The same procedure as in Example 2 was carried out except that the corner portions 9 were not sealed.

Comparative Example 7

The conventional corrugated board without the bark was sealed as shown in FIG.

[Test Methods]

Ten cases of each kind were prepared and stored in an atmosphere of 20 ° C. and 65% RH. Five days after harvest, they were opened for evaluation of ① yellowing, ② withering, and ③ weight loss of young hawks.

① and ② represent the percentage of change in the total population (%), and ③ represents the percentage of reduction based on the total initial weight. The results are shown in Table 2.

TABLE 2

In the sealing method of the comparative example 5 and the comparative example 6, since gas flows in freely and especially oxygen is supplied through the flap overlap part and corner part of a corrugated board, the gas permeability ratio of a container is small, and the sulfide fruit was produced by about half. In addition, although weight loss was suppressed compared with the resin coating of the comparative example 7, by transpiration, about 20% withering was seen.

On the other hand, in the sealing method of Example 2, since the gas exchange with the outside of the container is controlled by the exposed end of the corrugated plate joint of the side opened to the outer liner surface and the ventilation control area, many carbonic acid gases accompanied by high gas permeability ratio Emissions and adequate oxygen supply resulted in a significant suppression of yellowing even on the 5th day after harvesting, and no browning and no weight loss.

[Comparative Test 3]

Example 3

Lamination was carried out by compressing a film thickness of 20 μm using a 60:40 brand of LDPE (density ρ = 0,918) and ultra low density LLDPE (density = 0.905) on a corrugated liner base surface of 220 g / m ² . This resin is used as the outer liner with the resin coated surface as the outer surface, and the inner core with a basis weight of 220g / m ² coated with LDPE (density ρ = 0.915) with a film thickness of 30 μm on the center core of the basis weight 160g / m ² and the inner surface side. It bonded with a bond and obtained the corrugated board board material. In addition, by making a draw box, A-1 corrugated board (length 1 = 400, width w = 140, height h = 100mm) was made. The PCO ₂ of the resin coated outer liner was 16.0 × 10 ⁻¹⁰ cm ³ (STP) cm-2 · S ⁻¹ · cmHg ⁻¹ , and the moisture permeability of the resin coated inner liner was 37.5 (g / m ² · day).

Comparative Example 8

In the corrugated plate of Example 3, the film thickness of the coating resin LDPE (density p = 0.915) of the inner liner was 10 μm. The water vapor transmission rate of the resin coated inner liner was 112.5 (g / m ² · day).

Comparative Example 9

The conventional corrugated container is used as it is. There is no resin coating layer. The basis weight of the liner and the size of the container are the same as in Example 3.

[Test Methods]

The three kinds of corrugated plates were filled with 500 g of spinach cooled by vacuum pre-cooling at 5 ° C. for 2 hours after harvesting, and then completely sealed as shown in FIG. 3 by using an adhesive tape based on biaxially stretched polypropylene having a width of 40 mm. Five kinds of each kind were made and 20 degreeC. Stored in an atmosphere of 60% RH. After 6 days of storage, the percentage of decay was determined by opening up the total initial weight to the quality of the spinach.

[result]

In the conventional corrugated sheet without the resin coating of Comparative Example 9, the weight loss rate was 61.5% after 6 days of harvest, and it was completely withered. In addition, in the corrugated plate using the thinner inner liner of the resin coating layer of Comparative Example 8, the moisture permeability was large, so that the weight loss was insufficient, and the weight loss rate after 6 days was 14.4%, and the commerciality was lost. Moreover, the maximum compressive load of the container tended to fall to 35%. On the other hand, in the corrugated plate of Example 3, since the moisture permeability of the inner liner was small, the weight loss rate after 6 days was also low at 2.3%, and there was little withering. In addition, since the PCO ₂ of the outer liner was moderately large, sufficient freshness-protective effect was obtained without the occurrence of yellowing, rounding, and off-flavor (odor) of leaves. Moreover, the fall of container strength was also small and favorable.

[Comparative Test 4]

Example 4

Laminate was extruded to a film thickness of 25 μm using an 80:20 brand of LDPE (density p = 0.918) and ultra low density LLDPE (density p = 0.995) on a base liner surface of a corrugated liner having a basis weight of 280 g / m ² . Subsequent to evaluating the gas permeation characteristics of the resin coated liner material, the resin coated surface was used as an outer liner with the outer surface axis, and LDPE (density ρ = 0.918) at the center core and inner surface side of the basis weight of 180 g / m ² . Corrugated cardboard was obtained by joining with an aqueous bond like the inner liner with a basis weight of 280 g / m ² coated with a film thickness of 30 µm. In addition, a drawer box was made to produce a-1 type corrugated board (length l-288, width w = 190, height h = 115m). The water vapor transmission rate of the resin coated inner liner was 32.5 (g / m ² · day).

Comparative Example 10

Except having changed the brand of LDPE and LLDPE into poly-4-methyl benzene 1: TPX, it carried out similarly to Example 4, and set it as the cardboard.

Comparative Example 11

The brand of LDPE and LLDPE was changed to polypyrene derephthalate, which was used as one corrugated board as in Example 4.

[Test Methods]

In the above three kinds of corrugated boards, the caboose harvested in mid-September was put in advance and filled with 2Kg, respectively, and the adhesive tape based on biaxially stretched polypropylene was 40mm wide. Fully sealed as shown in FIG. After about 2 months of storage, it is opened and the quality of Caboose

① Yield of green enough and tight skin (%)

② For defective products, A: sulfide B: pitting C: browning, D: mold incidence (%), and ③ weight reduction rate (%) based on the total initial weight was evaluated. (Storage I)

Subsequently, for good storage, it was sealed again in anticipation of the distribution using the box, leaving the exposed end of the sideboard corrugated joint part as the air-conditioning atmosphere as shown in FIG. After 2 weeks at 20 ° C and 65% RH, they were reopened for quality evaluation (Storage II).

Table 3 shows the permeation characteristics of each resin coated and corrugated container, and the results of the storage test of the carbos by those corrugated plates.

TABLE 3

_{^{* PCO 2 x 10 -10 cm 3}} (STP) cm / (cm 2 · S · cmHg)

** A: Sulfide, B: Fitting, C: Browning D: Mold Others (%)

When poly 4-methylpentene 1 having a large carbon dioxide permeation coefficient of Comparative Example 10 was used as a coating, the permeability ratio of the resin itself was relatively large, but when the container was processed, cracks occurred and even if sealed as shown in Fig. 3 (Storage I Since the permeability ratio of the vessel is reduced, the oxygen permeability coefficient is also significantly increased. Reflecting this characteristic of permeation coefficient, in the preservation test on the corrugated board, there is almost no control of breathing, so about 70% of sulfide fruit is produced in 2 months of cold storage. In addition, when the exposed end of the corrugated sticky side of the side is opened to the ventilation control area as in 2e for distribution, the permeability ratio of the container is further reduced and almost all of the sulfur is sulfed in two weeks at room temperature storage.

As apparent from Comparative Example 11, as the coating of polyethylene terephthalate, the carbonic acid gas permeation coefficient was remarkably small, so that the carbon dioxide concentration in the corrugated plate was extremely high, and inorganic respiration occurred, resulting in many fruits in the gas field. On the other hand, in the coating made of the LDPE and the ultra-low density LLOPE brand of Example 4, yellowing is suppressed much after 2 months of low-temperature storage and browning is possible due to the moderate oxygen supply accompanied by the high carbon dioxide permeation coefficient and the high permeability coefficient of the container. There is no occurrence of and the weight loss is extremely small, thus ensuring sufficient preservation. At room temperature, where the actual circulation was expected, browning occurred due to an increase in respiratory volume, but as shown in FIG. It was suitable and there were few gas faults.

In the following, a specific example is shown and demonstrated about the sealing method.

Example 5

On the base surface of the corrugated liner for a basis weight of 220 g / m ² , the laminate was extruded to a thickness of 20 μm using a 60:40 brand of LDPE (density ρ = 0.918) and ultra low density LLDPE (density ρ = 0.005). This is used as the outer liner on the outer surface side of the resin coated surface, and the inner liner of the basis weight 220 g / m ² coated with the center core of the basis weight 160 g / m ² and the LDPE (density ρ = 0.915) of the inner surface side with a film thickness of 30 μm; It corrugated together with an aqueous bond to obtain corrugated cardboard. In addition, a drawing box was made to create an A-1 corrugated plate (length L = 400, width W = 140, height H = 100mm). The PCO ₂ of the resin coated outer liner is 16.0 × 10 ⁻¹⁰ cm ³ (STP) cm / (cm ² · S · cmHg)). The moisture permeability of the resin coated inner reamer was 37.5 g / (m ² · day). In the above corrugated plate, 500 g of the leek cooled for 2 hours by vacuum pre-cooling at 5 ° C. after harvesting was filled, and then completely sealed as shown in FIG. 3 by using an adhesive tape based on two-side stretched polypropylene having a width of 40 mm. The corner part was sealed as in FIG.

Comparative Example 12

The same procedure as in Example 1 was carried out except that only the joints of the corrugated plate of the bottom part and the lid part were attached with adhesive tape and sealed in a straight shape.

Comparative Example 13

It carried out like Example 5 which did not seal the corner part 9. As shown in FIG.

Comparative Example 14

The conventional corrugated board without the resin coating was sealed as shown in FIG.

[Test Methods]

Five cases of each type were prepared and preserved in an atmosphere of 20 ° C. and 60% RH. After 6 days of storage, they were opened and evaluated for ① yellowing and crushing, ② withering, and ③ weight loss of leeks. ①, ② For the percentage of change in the total population, the percentage is expressed as percentage reduction based on the total initial weight. The results are shown in Table 4.

TABLE 4

In the sealing method of the comparative example 12 and the comparative example 13, since the gas inflow, especially oxygen supply, was freely performed to the flap of the corrugate through the polymerization part and the corner part, the gas permeability ratio of the container was small, and yellowing and rounding were many. In addition, the weight loss due to transpiration is suppressed in comparison with that in which the resin coating of Comparative Example 14 was not performed. On the other hand, in the sealing method of Example 5, since the gas exchange with the outside of the container is controlled by the outer liner surface, a large amount of carbon dioxide with high gas permeability ratio is discharged and a suitable oxygen supply is performed, so that yellowing occurs even after 6 days of harvest. It was considerably suppressed, and there was no occurrence of off-flavor, and the integrity of the balance with very little weight reduction was ensured.

[Comparative Test 2]

Example 6

Laminate was extruded to a film thickness of 30 μm using an 80:20 brand water of LDPE (density ρ = 0.918) and ultra-low density LLDPE (density ρ = 0.005) on a base liner surface of a corrugated liner having a basis weight of 280 g / m ² . With respect to the resin-coated liner material to the side of outer surface of the plain, yisuji coated surface to evaluate the transmission characteristics of the gas used as the outer liner, pyeongrang center of 180g / m ² core, side inner surface of 30μm to LDPE (density ρ = 0.918) Corrugated cardboard was obtained by bonding together with a quartz bond like an inner inner with a basis weight of 280 g / m ² coated with a film thickness. In addition, a-1 type corrugated board (length l = 288, width w = 190, height h = 115mm) was made by drawing and box making. The PCO ₂ of the resin coated outer liner is 7.5 × 10 ⁻¹⁰ cm ³ (STP) cm / (cm ² · S · cmHg). The water vapor transmission rate of the resin coated inner liner was 37.5 g / cm ² · day. Following the corrugated plate, the harvested in early September was sealed and packed with LDPE bags and filled with 2kg of healthy Caboose (Buak Oake No. 1) stored for 2 months in a cold store. Pyrene-based adhesive tape was used to seal the exposed end portion of the corrugated adhesive portion on the side surface as shown in FIG. The corner part was sealed as in FIG.

Example 7

Except the sealed end of the corrugated joint portion of the side was sealed as in Fig. 3 except that it was as in Example 5.

Example 8

The same procedure as in Example 6 was carried out except that the exposed ends of the side face corrugated portions were sealed as shown in FIG.

[Test Methods]

Ten cases of each type were prepared and placed in two weeks at 20 ° C and 65% RH in anticipation of distribution using this box.

① Yield of green enough and tight skin (%)

② For defective products, A: sulfide B: pitching C: browning, D: mold occurrence rate (%), and ③ weight reduction rate (%) based on the total initial weight was evaluated. Table 5 summarizes the results of the gas permeability of each corrugated container, the gas composition in the corrugated board, and the results of the storage test of the carboose due to them.

TABLE 5

* A: sulfide B: pitching C: browning D: mold Others (%)

In Examples 6, 7, and 8, the carbon dioxide permeability coefficient of the outer liner, the moisture permeability of the inner liner, and the ratio of the carbon dioxide permeability coefficient and the oxygen permeability coefficient of the container are within the specific range of the present invention, respectively, It can be understood that the gas composition in the corrugated sheet varies according to the difference in the sealing method at the exposed ends. That is, in the corrugated plate completely sealed in the exposed end as in Example 7, when the crop with a large respiratory volume such as storage caboose was lowered, the oxygen concentration in the corrugated plate was lowered, and pitching and browning were generated by inorganic respiration. Moreover, in the corrugated board which did not seal the exposed end like Example 8, the oxygen concentration in the corrugated board became high, and the yellowing fruit was produced. On the other hand, as the sealing method of Example 6, the gas exchange with the outside air and the breath of the carbohydrates in the corrugated board are well balanced through the 50 mm wide exposed end opened as the ventilation control area, and the gas composition in the corrugated board is preserved. It was suitable for the gas, and there were almost no gas obstruction fruit, sulfide fruit and the like. Thus, it is useful to suture the corrugated opening at the side of the crop according to the respiration volume of the crop as the ventilation control area.

Next, the resin-coated wrapping paper will be described with specific examples.

[Comparative Examination 5]

Example 9

Low density polyethylene (density = 0.918) polymerized by high pressure method on the corrugated liner base surface at a basis weight of 280 g / m ² and copolymerized with ethylene and butene -1, i.e., ultra low density LLDPE (density ρ = 0.905) with a weight ratio of 60:40 Resin film thickness (5 micrometers) and weight conversion per unit area were extruded to 13.7 g / m with brand water, and lamination was carried out. As the conditions, the wave bottom resin temperature was 320 to 325 ° C., the lamination speed was 100 m / min, and the liner surface corona treatment 5 Kw was used.

Comparative Example 15

LDPE for comparison (density ρ = 0.918)

Example 16

Poly 4-methylpentene 1: TPX

[Comparative Example 17]

Polyethylene terephthalate: PET was extruded and laminated according to the above conditions so as to have a resin film thickness of 15 µm. These resin coated liner materials were evaluated for the permeation characteristics of gas and water vapor according to the above-described methods, while the resin coated liner was subjected to the short process using an aqueous bond by a colloid with an outer surface of the resin coated liner and having a basis weight of 180 g / m ² . The middle core was then covered with LDPE (density rho = 0.918) on the inner surface side with a film thickness of 20 µm, and the liners each having a basis weight of 280 g / m ² were bonded to each other to obtain a corrugated sheet material. These sheet materials were drawn in the usual mold, and the joints were joined using a hotmet adhesive, and an A-1 corrugated board (length l = 288, width w = 190, height h = 115 mm) specified in JIS-J1507 was prepared. . In order to compare the above-mentioned corrugated plates, two kinds of conventional corrugated boards (Comparative Example 18) without resin coating were added, and after filling, 2Kg of blue-green (breed Minami-Tagaume), which were refrigerated at 10 ° C. for 8 hours, were then filled in width. Using the adhesive tape based on 40-mm biaxially-stretched polypropylene, the flap end part including the up-and-down flap joint part and the corner part was sealed in H shape, and the seam was again sealed by sealing the edge part again. Ten cases of each kind were prepared and stored in an atmosphere of 20 ° C. and 65% RH. After harvesting, 5 cases were opened on the 3rd day and the remaining 5 cases on the 6th day were evaluated for ① yellowing ② browning or softening and ③ weight loss rate of the young medium. As for ① and ②, the percentage (%) of the change in skin was recognized as a decrease (%) based on the total initial weight. The results are shown in Table 6.

TABLE 6

_{^{* PCO 2 x 10 10 cm 3}} (STP) cm / (cm 2 · S · cmHg), PH 2 Ox 10 9 cm 3 (STP) cm / (cm 2 · S · cmHg)

According to the results of Table 6, when poly 4-methylpentene 1 having a large carbon dioxide permeability coefficient of Comparative Example 16 was not used as a coating, the permeability of oxygen was also significantly increased because of the small permeability ratio. In addition, since the coating cracked and cracked at low temperature bending, PCO ₂ was large and PCO ₂ / PO ₂ tended to be smaller. Reflecting this permeation property, the preservation test on the corrugated board showed little respiration inhibition, so yellowing was observed for 3 days after harvesting. This tendency showed an effect in preventing the increase in reduction by transpiration compared with that in the resin coating of Comparative Example 4, but there was little effect of preventing yellowing. In the coating of polyethylene terephthalate, the carbon dioxide gas permeability was remarkably low as apparent from Comparative Example 3, while the PH ₂ O was remarkably large, so that the microcracks of craze were formed due to low temperature bending, and the permeability was slightly changed. This was not enough.

In this case, the concentration of carbon dioxide gas in the corrugated board was remarkably high, and inorganic respiration occurred, and browning of the skin occurred a lot after 3 days of harvest, and almost all of them became gas barrier fruits on the 6th day. In addition, the water vapor permeability was remarkably large, indicating a large weight loss. It is difficult to realize the more effective ratio of PCO ₂ / PO ₂ in the low density polyethylene (LDPE) coating by the general high pressure method of the comparative example 15, and the permeability accompanying the fine gray in low temperature bending processing Changes were also slightly recognized, with a slight but browning fruit on day 3 post-harvest, tended to increase further on day 6. Here, the fruits evaluated at the time of opening the corrugate were left at room temperature for about 3 days, and yellowing was recognized even in the fruit which was considered healthy. The effects of respiratory disorders were found to be quite large. On the other hand, in the coating made of the LDFE and the ultra low density LLDPE water of Example 9, yellowing was considerably suppressed even after 6 days since the proper oxygen supply was performed with high carbon dioxide permeability and high PCO ₂ / PO ₂ ratio. In addition, no browning occurred, the weight loss was extremely low, the balance was preserved, and no sign of respiratory failure was observed even after opening. Moreover, this coating resin was excellent in bending workability, and the change of permeability after processing was hardly recognized.

[Comparative Examination 6]

Example 10 uses 80:20 brand water of LDPE (density ρ = 0.918) and very low density LLDPE on a corrugated liner base surface of 220 g / m ² basis weight, and Example 11 changes the ratio of the brand to 60:40. Example 12 uses a brand having a blend ratio of 40:60, and Example 13 uses a very low density LLDPE (C 4, density ρ = 0.003), each having a thickness of 25 μm, and Example 9 Extrusion was carried out according to the method of lamination. They evaluated the permeation characteristics of gas and water vapor on the resin-coated liner material, while using them as outer liners, and coated LLPE (density ρ = 0.918) with a film thickness of 25 μm on the center core and inner surface of a basis weight of 180 g / m ² . A liner with a basis weight of 220 g / m ² was then bonded with an aqueous bond (Gonnis # No. 645) to obtain corrugated cardboard. In addition, flattening and box making were performed according to the above-described method, and an A-1 type corrugated plate (length l = 288, width w = 190, height h = 115 mm) was prepared. As a comparative example, Comparative Example 20 uses 60:40 brand water of LDPE (ρ = 0.918) and LLDPE (C 8, ρ = 0.927), and Comparative Example 7 uses LDPE (ρ = 0.928) and ultra low density LLDPE (C4). , p = 0.903).

For comparison, in seven types including the conventional corrugated plate comparative example 19 without resin coating, the carboose harvested in mid-September was cooled beforehand and filled with 20 kg each, and filled with a width of 40 mm. Sealing the upper and lower flap engaging portions and the corners of the flap including the corners are H-shaped by using double-stretched polypropylene adhesive tape, and then the ends of the seam are sealed and completely sealed and stored at 5 ° C. and 60% RH. It was.

After about 2 months of storage, open the caboose quality

① Yield of sufficient green color and tight skin (%) and ② for defective product respectively A: sulfide B: pattern C: browning, D: incidence of mold and others (%), and ③ initial weight per box Based on the weight loss rate (%) was evaluated. (Storage Category Ⅰ)

Subsequently, in the case of good storage, it was sealed by the method of recharging in anticipation of the distribution using the box, it was left for 2 weeks at 20 degreeC and 65% RH, and it was opened again, and quality evaluation was carried out (storage classification II).

Table 7 summarizes the resin coating permeation characteristics of each resin coating and the results of the storage test of the carbos with the corrugated sheets prepared using them.

TABLE 7

_{^{* PCO 2 x 10 10 cm 3}} (STP) cm / (cm 2 · S · cmHg), PH 2 Ox 10 9 cm 3 (STP) cm / (cm 2 · S · cmHg)

** A: Sulfide B: Pattern C: Browning, D: Mold Others (%)

In the conventional corrugated plate without the resin coating of Comparative Example 19, since the respiration was not suppressed, almost all of the sulfides were sulfided even at low temperature storage, showing a considerable weight loss. In addition, even if a brand LLDPE is used as the coating resin of Comparative Example 20 or a brand of comparatively small amount of ultra low density LLDPE of Comparative Example 21, the permeation coefficient of carbon dioxide gas is remarkably low, and microcracks are applied to the coating layer by processing. As a result, the permeability ratio became small, and it was difficult to sufficiently suppress the respiration of fruits and vegetables in the sealed container.

Therefore, the storage and storage of the caboose caused a lot of fitting and browning caused by respiratory disorders. Especially, when it was opened in low temperature storage and returned to room temperature and then sealed again, the breathing became vigorous. Significant quality degradation such as mold development accompanied by softening of was recognized.

On the other hand, in the case of the composition of the coating resin layers of Examples 10 to 13, a relatively large amount of ultra low density LLDPE is used in combination, a relatively large carbon dioxide permeation coefficient and permeation coefficient ratio are obtained, and their values are less fluctuated by processing. Therefore, it is possible to keep the inside of the sealed corrugated container using these resin coatings in a respiratory inhibition state in the storage of the cabot, and to obtain a practically satisfactory shelf life in any storage category.

[Comparative Test 7]

Using brand water at 40: 60 of LDPE (ρ = 0.918) and ultra low density LLDPE (C6, ρ = 0.910) in Example 14 on the surface of a blended paper made of pulp and PE-based synthetic pulp having a basis weight of 400 g / m ² , Example 15 uses LDPE (density ρ = 0.918), ultra-low density LLDPE (C6, ρ = 0.910), and a brand of 40: 30: 30 of the SB copolymer abutment, and Example 16 uses LDPE (ρ = 0.918). And 40 of ultra low density LLDPE (C 6, p = 0.910) and ethylene vinyl acetate copolymer (VA 20%); 30; The film thickness was 20 micrometers using 30 brand-name articles, and it extruded according to the method of Example 1, and laminated. For these resin coatings, the permeation characteristics of the gas and the water vapor were evaluated according to the above method, and a tray (110 mm wide, 160 mm long and 30 mm high) having a heat seal flange by the press molding method was used. ).

In Comparative Example 23, LLDPE (C4, ρ = 0.920) was used for five kinds of trays without resin coating and Comparative Example 22 for comparison with the coated paper obtained in the same manner as in Example 1 with a film thickness of 20 µm. 300g each of the zodiacal immediately after harvesting, and a low-density LLDPE (ρ = 0.905) vs. LLDPE (ρ = 0.920), 70: 30, anti-destructive film, tray flange Was sealed by heat seal.

Trays of each type n = 10 were stored for 10 days in an atmosphere of 22 ° C and a relative temperature of 65% to maintain a quality protection state. Yield rate, defective rate (a; wither b: deterioration c: browning d: mold development, etc.) The weight loss rate was evaluated.

In the case of using the tray without the usual resin coating of Comparative Example 22, since the breathing is vigorous, the wilting and accompanying shafts are progressed by preservation for 10 days, and a large amount of debris is generated, and the weight is also greatly reduced. It shows the tendency of aging and lost a lot of merchandise. In addition, in the case of using general LLDPE as the coating resin of Comparative Example 23, there is a tendency that the press molding processability is inferior and cracks of the coating resin layer are generated at corner corners of the tray. In the preservation test, the concentration of carbon dioxide gas in the package is significantly increased, and the browning of the skin caused by respiratory disorder is generated in the preservation test reflecting these characteristics, resulting in significant alcohol odor and softening of the flesh. The occurrence of mold can also be seen, and the quality value is lost.

On the other hand, in Examples 14 to 16 using ultra-low density LLDPE as a component of the coating resin, not only the press formability was excellent, but also the high CO2 permeability and the high permeation ratio required for proper oxygen supply, it was possible to suppress proper respiration of the contents. Good preservation was shown.

When the hydrogenated styrene butadiene fluoropolymer and the ethylene co-vinyl vinyl copolymer (20 mol% of the crude oil content) of Example 16 were used as the component of the coated resin of Example 15, in particular, the effect of improving the permeability was preserved when the permeation ratio increased. Was admitted. The experimental results are shown in Table 8.

TABLE 8

_{^{* PCO 2 x 10 10 cm 3}} (STP) cm / (cm 2 · S · cmHg), PH 2 Ox 10 9 cm 3 (STP) cm / (cm 2 · S · cmHg)

** A: Sulfide B: Fitting C: Browning, D: Mold Others (%)

[Comparative Examination 8]

Example 17

50 g / m ² thin wool paper with a basis weight of 50:50 of LDPE (ρ = 0.919) and ultra low density LLDPE (C4, ρ = 0.905) was injected in the same manner as in the above example so that the coating thickness was 16 μm. It was. The permeability of this coated paper is PCO ₂ : 15.6 x 10 ^-10 cm ³ (STP) cm / (cm ² ScmHg), PCO ₂ / PO ₂ : 3,7, P ₂ O: 13.2x 10 ^-9 cm ³ (STP) cm / (cm ² · ScmHg).

Using this coated paper as a cover material, -50 cmHg was filled with a pre-pre-deposited caboose in a fillable package of a spherical additive having a diameter of 60 mm made by vacuum tendency with a 120 μm-thick LLDPE (C4, ρ = 0.918) film. The heat seal was performed under the degassing of.

500 packages of these were stored at 5 ° C. for 3 months. However, some of the packages were defective due to cuts of the skin, but the yield was extremely good at 98.6%.

Subsequently, 10 g of the package was packed in corrugated cardboard and transported to a mixed truck of about 1000 kg, and then stored at room temperature for 2 months under the conditions of distribution. Green has been sufficiently maintained, and leading protection has been recognized for its great effectiveness.

[Comparative Examination 9]

Example 18

Three directions were applied to the coated paper of Example 17 to prepare tpo bags having dimensions and length of 280 mm and width of 120 mm to fill the caboose, and after degassing, the mouth of the bag was wrapped with adhesive tape and sealed. The permeability of the blood is well-being _{^{PCO 2: 15.6x 10 -10 cm 3}} (STP) cm / (cm 2 · S · cmHg), PCO 2 / PO 2: 3.7, PH 2 O: 13.2 x 10 -9 cm 3 ( STP) cm / (cm ² · ScmHg).

500 pieces of these packages were stored at 5 ° C for 3 months, but some of them were defective due to damage of the skin, but the yield was 98.6%. Subsequently, this package was packed into 10Kg of corrugated board and transported by truck mix of about 100Kg, and stored at room temperature for 2 weeks in anticipation of distribution conditions. Retention was recognized for its great effect.

The preservation tool composed of the corrugated plate of the present invention is remarkably excellent in the freshness preservation effect of fruits and vegetables and can be preserved by preventing the degradation of freshness for a long time.

The sealing of the corner part by the sealing method of this invention is complete and can protect and protect the gas composition in a container.

In addition, by using the wrapping paper of the present invention, the fruits and vegetables are in a dormant state, the fresh state is preserved, and the shelf life is greatly extended.

In addition, the present invention exhibits an excellent effect of protecting the freshness of the packaged fruits and vegetables for a long time by forming a gas composition in a storage atmosphere in the container.

Claims (26)

(a) Outer liner 1 coated with a resin layer having a carbon dioxide gas permeation coefficient PCO ₂ of 27 ° C. of ₅ × 10 ⁻¹⁰ cm (STP) cm / (cm ² · S · cmHg) or higher, and (b) Shim (2) and (c) The end 10 of the corrugated cardboard exposed to the outer surface of the container is composed of a corrugated cardboard consisting of the inner liner (3) coated with a resin layer of less than 100g / m ² · day at 27 ℃ Fresh fruit and vegetable containers, sealed with tape. The freshwater storage container according to claim 1, wherein the ratio of the carbon dioxide gas permeation coefficient and the oxygen permeability coefficient of the container to PCO ₂ / PO ₂ is 1.5 or more. The freshwater storage container according to claim 1 or 2, wherein the inner liner is made of a liner material having a moisture permeability of 100 g / m ² · day or less at 27 ° C. 4. The product freshness storage container according to claim 3, wherein the inner liner is made of a liner material in which a resin layer having a water vapor transmission rate of less than 100 g / m ² · day at 27 ° C. is disposed in the innermost layer. The outer liner is a liner material in which the outer liner has a resin coating having a carbon dioxide permeation coefficient of 5x10 ^-10 cm ³ (STP) cm / (cm ² · S · cmHg) at 27 ° C. in the outermost layer. Fresh fruit container consisting of fresh fruits and vegetables. The method of claim 3, wherein the outer liner is a carbon dioxide gas permeability coefficient of the ethylene contained in the copolymer of the density 0.917g / cm ³ or less of the α- olefin having a carbon number of 3-12 and, 27 ℃ 8x 10 ^-10 cm ³ (STP) cm / (cm ² · ScmHg) or less, the transmission coefficient ratio PCO ₂ / PO ₂ is 3.5 or more, and the water vapor transmission coefficient is 80x 10 ^-9 cm ³ (STP) cm / (cm ² · S · Fresh fruit and vegetable preservation container composed of a liner material having a resin layer of cmHg) or less. The fruit and vegetable fresh storage container according to claim 6, wherein the copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms is ultra low density polyethylene (LLOPE) having a density of 0.912 or less. 4. The fresh fruit preservation container according to claim 3, wherein the sealing tape is sealed with the bottom, the lid, and the edge exposed surface of the corrugated cardboard at the corners, and the exposed end portion of the side surface is sealed while leaving the ventilation adjustment portion. (a) Outer liner (1) and (b) Inner liner (3) coated with a resin layer having a carbon dioxide gas permeability of 5 × 10 ⁻¹⁰ cm ³ (STP) cm / (cm ² · S · cmHg) at 27 ° C. Fresh fruit storage container containing a carbon dioxide gas permeation coefficient and an oxygen permeability coefficient of PCO ₂ / PO ₂ of 1.5 or more, sealed with corrugated cardboard, and (c) the abutment portion of the bottom plate and the lid of the container (7) The sealing sheet of the overlapped portion is adhered to seal the inside, and at each corner portion 9, a sealing sheet longer than the length of each side is adhered to both sides of the container and three sides of the lid or bottom, and the sheet-shaped article is adhered to them. Adhesion to the container is carried out at room temperature to form an adhesive piece, and the corner part 9 is enclosed and sealed. The adhesive sheet is fixed to the container by using a sealing sheet end portion protruding from the block without sticking the adhesive piece. Pass the end of the corrugated cardboard exposed to the outer surface of the corrugated portion of the corrugated sheet as needed. Fresh-keeping container for fruits and vegetables sealed with adhesive tape (8), leaving a controlled area. 10. The triangular pressure-sensitive adhesive piece of claim 9, wherein the corner portion seals the end of the sealing sheet adhered to one side of the container by bending the end portion of the sealing sheet to adhere to the other side and the remaining portion adheres to the end portion of the sealing sheet adhered to the sea surface. Fresh fruit fresh storage container that is sealed to form a corner portion. The fresh fruit preservation container according to claim 9 or 10, which is adhered to and fixed to the rear surface of the sealing sheet adhered to the container by using the sealing sheet end portion protruding from the adhesive pieces without sticking. The freshwater fruit storage container according to claim 11, wherein the inner layer liner is a corrugated container made of a liner material in which a resin layer having a moisture permeability of 100 g / (m ² · day) at 27 ° C. or less is disposed on the innermost layer. 12. The liner according to claim 11, wherein the outer liner is composed of a liner material having a carbon coating coefficient of at least 5x10 ^-10 cm ³ (STP) cm / (cm ² · S · cmHg) at 27 ° C. Fruit and vegetable preservation container using a corrugated container. (a) Outer liner 1 and (b) Inner liner coated with a resin layer having a carbon dioxide gas permeability of at least 5 × 10 ⁻¹⁰ cm ³ (STP) cm / (cm ² · S · cmHg) at 27 ° C. ) ratio PCO ₂ / PO ₂ of 1.5 or higher of carbon dioxide gas permeability coefficient and the oxygen permeation coefficient by a sealing tape (8) made of cardboard end portion which is exposed to the container outer surface configured to be waro corrugated substantially sealed, the container 7 Fruits and vegetables are stored in fresh fruit storage containers, and the sealing sheet is adhered to the abutment portion and the overlapping portion of the corrugated plate at the bottom of the container, and the inside is sealed, and the corners 9 are sealed longer than the length of each side. The sheet is indigenous to both sides of the container and the three sides of the lid or the bottom, and the sheet-like article is mutually bonded to the non-stick end portions 10 to form an adhesive piece to surround and seal the corner portion 9, Contact the container using the end of the sealing sheet sticking out without sticking the adhesive pieces A fruit and vegetable fresh preservative packaging material which is fixed and adhered to the corrugated plate of the side surface of the container (7), leaving the end of the corrugated cardboard exposed to the outer surface of the joining portion as a ventilation control area as necessary, and is sealed by adhering the sealing tape (b). (a) Outer liner (1) and (b) center core coated with a resin layer of carbon dioxide gas permeation coefficient PCO ₂ at 27 ° C of not less than 5x10 ^-10 cm ³ (STP) cm / (cm ² · S · cmHg) (2) and (c) fruits and vegetables are stored in the container 7 which consists of corrugated cardboard which consists of an internal-strength liner 3 coated with a resin layer of 100 g / cm <^2> or less at 27 degreeC, and the moisture permeability of the container 7 The sealing tape 8 is adhered and sealed at the end of the corrugated cardboard exposed to the bottom and the outer surface of the lid, and the corner 9 is also sealed with the sealing tape, and the corrugated joint at the side leaves a ventilation control area as necessary. A fruit and vegetable packaging agent characterized in that the ratio of carbon dioxide permeation coefficient and oxygen permeability coefficient of the container to the PCO ₂ / PO ₂ 1.5 or more by sticking with the sealing tape (8). (a) Outer liner coated with a resin layer having a carbon dioxide gas permeation coefficient PCO ₂ of at least 5 × 10 ⁻¹⁰ cm ³ (STP) cm / (cm ² · S · cmHg) at 27 ° C., and (b) Center core (c) ) Fruits and vegetables of the container made of corrugated cardboard, which is made of an inner liner coated with a resin layer of 100 g / cm ² · day or less at 27 ° C., and adhered to the end of the corrugated cardboard exposed to the bottom of the container and the outer surface of the lid portion Seal the corners with a sealing tape, and the exposed end of the corrugated joint on the side is left as an air-conditioning area, sticking the sealing tape, and reducing the ratio of CO2 and oxygen permeation coefficients of the container to PCO ₂ / PO. Fresh fruit preservation method, characterized in that ₂ to 1.5 or more. It contains a copolymer having a density of 0.917 g / cm ³ or less of ethylene and an α-olefin having 3 to 12 carbon atoms, and the carbon dioxide gas permeation coefficient at 27 ° C. is ⁸ × 10 ⁻¹⁰ cm ³ (STP) cm / (cm ² At least one resin layer having a permeability ratio of at least S · cmHg) and a permeability ratio of at least PCO ₂ / PO ₂ 3.5 and a water vapor transmission coefficient of 80 × 10 ⁻⁹ cm ³ (STP) cm / (cm ² · S · cmHg) or less. Fruit and vegetable wrapper coated with cotton. 18. The greengrocer packaging paper according to claim 17, which is an ultra low density polyethylene (LLDPE) having a density of 0.912 or less of ethylene and an α-olefin having 3 to 12 carbon atoms. The fruit and vegetable packaging paper for internal bending processing of Claim 17 or 18 which consists of resin coating paper. 20. The fruit or vegetable packaging container according to claim 17 or 18, wherein the packaging container is used for the wall. 19. The cardboard box for storing fruits and vegetables according to claim 17 or 18, wherein the packaging paper is used as at least an outer liner material. (a) Outer liner 1 coated with a resin layer having a carbon dioxide gas permeability of 5 × 10 ⁻¹⁰ cm ³ (STP) cm / (cm ² · S · cmHg) at 27 ° C., and (b) Inner liner 3 ) ratio PCO ₂ / PO of the carbon dioxide gas permeability coefficient and the oxygen transmission coefficient of the end portion 10 of the corrugated exposed to the outside of the container (7) is configured as a waro cardboard is by a sealing tape (8) is substantially cut off, the container ₂ is 1.5 or more fresh fruit storage container, (c) attaching a sealing sheet to the abutment portion and the overlapping portion of the corrugated plate of the bottom part and the lid part of the container to seal the inside and seal the inside of each corner portion 9 than the length of each side. The long sealing sheet is adhered to both sides of the container and the three sides of the lid or the bottom, and the non-adhesive ends of the sheet-shaped articles are mutually bonded to form an adhesive piece, and the corner portion 9 is enclosed and sealed. By sticking to the container using the end of the sealing sheet protruding And, the fruit or vegetable encapsulation method of the fresh storage containers, characterized in that the seal to the vent control adjustment region leaving the adhesive as a sealing tape 8, as needed to end the cardboard is exposed to the outer surface of that the engagement of the wife side of the container corrugated. 23. The triangular pressure sensitive adhesive piece according to claim 22, wherein the corner portion seals the end portion of the sealing sheet adhered to one surface of the container and adheres a portion of the sealing sheet to the other surface, and the sealing sheet adheres the remaining portion to the surface of the seal with the end portion. Method for sealing fresh fruit and vegetables fresh preservation container to form a seal to surround the corner portion. 24. The sealing method according to claim 22 or 23, wherein the fresh fruit storage container according to claim 22 or 23 is adhered to and fixed to the rear surface of the sealing sheet adhered to the container by using the sealing sheet end portion protruding without sticking the adhesive pieces. 25. The sealing method according to claim 24, wherein the inner liner is made of a corrugated container composed of a liner material in which a resin layer having a moisture permeability of 100 g / (m ² · day) at 27 ° C. or less is disposed on the innermost side. 25. The corrugated sheet according to claim 24, wherein the inner liner is formed of a liner material having a resin coating having a carbon dioxide permeation coefficient of at least 5 × 10 ⁻¹⁰ cm ³ (STP) cm / (cm ² · S · cmHg) at 27 ° C. Method for sealing fruit and vegetable storage container using a container.