JP5370844B2 - Allyl isothiocyanate volatilization formulation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a preparation capable of suitably preserving an allyl isothiocyanate-volatilizing body without preparing a barrier bag separately, and starting the volatilization by a simple method at a necessary time. <P>SOLUTION: This allyl isothiocyanate-volatilizing preparation is provided by arranging a laminate body which is as a whole the allyl isocyanate non-permeable, having in the order of an allyl isocyanate-permeable layer consisting of a single layer or a plurality of layers, a resin adhesive layer consisting of a polyester-based urethane resin, and an allyl isothiocyanate non-permeable layer consisting of a single or plurality of layers, at the part or whole of the package of closely sealing the allyl isothiocyanate-volatilizing body by facing the allyl isothiocyanate non-permeable layer to an outer side surface. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a preparation capable of arbitrarily starting volatilization of allyl isothiocyanate manually.

  Allyl isothiocyanate has volatility and exhibits a high antibacterial action, so it can be used as an antibacterial agent. However, since it has strong irritation and permeability, it has been necessary to store allyl isothiocyanate in a container with high gas barrier properties. In addition, when the allyl isothiocyanate emitter is taken out and used, there is a problem that a strong irritating odor causes pain in the eyes or a unique odor shifts when used as an antibacterial agent for foods.

  On the other hand, encapsulating a volatile agent such as a fragrance so that volatilization can be started from a necessary point is a common problem for volatile agents, and various methods are being studied. In Patent Document 1, a multilayer film produced by adhering a main film layer having gas permeability and a release film layer having gas sealing properties with a molten resin layer is manufactured, and this multilayer film is added with a fragrance. There is described a fragrance container sealed and sealed in an opening of a storage container that stores an object. When the release film layer is peeled off, the fragrance is started to evaporate.

  Patent Document 2 describes a composite film composed of a plurality of layers, in which a part of the layers is not bonded and has a space for containing a fragrance. The outer film containing aluminum foil can be peeled off from one side of the composite film, and the inner layer that remains attached to the container after the outer film is peeled off is made of expanded polypropylene and polyethylene, and transmits perfume. To do.

  Furthermore, Patent Document 3 contains a volatile substance, covers the open side of a metallic tray having an open side, and is detachably joined to a gas permeable layer made of a biaxially oriented polypropylene film. Volatile substance dispensers with lids made of foil layers are stripped.

Japanese Patent No. 3383654 Japanese Patent No. 2598605 JP-T-2005-521442

  However, if allyl isothiocyanate is sealed by the method described in Patent Documents 1 to 3, depending on the type, the adhesive is eroded, and without waiting for the allyl isothiocyanate non-permeable layer to peel off, In some cases, leakage occurred from the adhesive layer between the transmission layer. Moreover, when using the film which is a laminated body, the adhesive agent used for adhesion | attachment of the other layers may be eroded. In order to counter this, when an adhesive having resistance to allyl isothiocyanate was used, the adhesive force was too high, and the film could not be peeled off, so that volatilization could not be started.

  Therefore, the present invention has an object to allow allyl isothiocyanate emitters to be packaged and stored appropriately without preparing a separate barrier bag, and to start volatilization by a simple method when necessary. And

  This invention has an allyl isothiocyanate permeable layer composed of a single layer or a plurality of layers, a resin adhesive layer comprising a polyester urethane resin as an adhesive component, and an allyl isothiocyanate non-permeable layer composed of a single layer or a plurality of layers in this order. And a laminate that is allyl isothiocyanate impermeable as a whole, with the allyl isothiocyanate non-permeable layer facing the outer surface and a part or all of the packaging that seals the allyl isothiocyanate emitter, The problem was solved. The allyl isothiocyanate emitter includes not only allyl isothiocyanate supported on a carrier such as a porous material but also allyl isothiocyanate itself.

  The main point of this invention is not to use a polyether-based urethane resin resistant to allyl isothiocyanate, but to use a polyester-based urethane resin that can be eroded by allyl isothiocyanate. This selection is influenced by the insane properties of allyl isothiocyanate. First, it is known that a polyester-based resin adhesive is more excellent in chemical resistance than a polyether-based resin adhesive for compounds that generally cause erosion. However, with respect to allyl isothiocyanate, a polyether resin adhesive exhibits a unique characteristic that it exhibits chemical resistance rather than a polyester resin adhesive. In studying this invention, the problem can be solved for the first time by using a polyester resin adhesive that has relatively low chemical resistance due to the idea of reversal after first approaching the fact. did.

  By using a polyester-based urethane resin that is relatively inferior in allyl isothiocyanate resistance as an interlayer adhesive, allyl isothiocyanate permeates the allyl isothiocyanate permeation layer on the inner surface during the storage period, and the resin adhesive layer Adhesive strength can be reduced. However, in the case of polyester-based urethane resin, since the decrease in adhesive force stops at about 1/6 of the initial time with the amount of allyl isothiocyanate accumulated in the resin adhesive layer saturated, the adhesive state is maintained. However, the outer layer than the resin adhesive layer, that is, the allyl isothiocyanate non-permeable layer can be easily peeled off. Of course, after the allyl isothiocyanate non-permeable layer is peeled off, only the allyl isothiocyanate permeable layer and a part of the resin adhesive remain, so that allyl isothiocyanate can be volatilized through the permeation. Even if the same urethane resin is used, if the polyether urethane resin is used, the exquisite adhesive strength reduction effect does not occur in this way, so the allyl isothiocyanate non-permeable layer cannot be peeled off, or the allyl isothiocyanate permeable layer It can not be used because it will be broken. In addition, other adhesives cannot withstand the attack of allyl isothiocyanate in the first place, and the adhesive state cannot be maintained. That is, this effect can be realized only by a combination of polyester urethane resin and allyl isothiocyanate.

  The allyl isothiocyanate permeable layer may be a single layer or a plurality of layers. From the viewpoint of the permeability and strength of allyl isothiocyanate, a biaxially stretched polypropylene film is preferably included. In the case where the allyl isothiocyanate permeable layer is composed of a plurality of layers, adhesion between the layers may be performed by a polyether-based urethane resin or by thermal lamination. In the case of bonding with these, the allyl isothiocyanate does not reduce the adhesive strength too much, and the allyl isothiocyanate permeable layer itself does not peel off.

  The allyl isothiocyanate emitter may be accommodated only by the laminate, or may be accommodated in an open container that is impermeable to allyl isothiocyanate, and the laminate may be attached to the opening and sealed. However, when laminating the laminates or laminating the laminate and the opening container, allyl isothiocyanate is obtained by using a polyether urethane resin as an adhesive or by adhering by heat welding or the like. It is possible to suppress a decrease in the adhesive force due to. In addition, when using as a part at the time of sealing the said laminated body, sealing cannot be implement | achieved unless the other part, for example, the container which sticks a laminated body, is allyl isothiocyanate non-permeable.

  When the laminate is used by being attached to the open container, the laminate has a tab that protrudes from the opening edge of the open container, and the allyl isothiocyanate non-permeable layer is peeled off from the tab. Good. In order to make it easy to peel off, if a half cut cut from the allyl isothiocyanate permeation layer side to the vicinity of the allyl isothiocyanate non-permeation layer is provided on the tab, by picking the tip from the half cut and pulling it up, The allyl isothiocyanate non-permeable layer can be easily peeled off.

  From the preparation according to the present invention, allyl isothiocyanate can be easily volatilized from the required time. Thereby, even if it does not use the gas barrier bag which was required conventionally, the sealing at the time of storage is realizable only by it. In addition, since there is no space between the allyl isothiocyanate permeable layer and the allyl isothiocyanate non-permeable layer, the volatilization amount of allyl isothiocyanate gas can be minimized when starting the volatilization of allyl isothiocyanate. It is possible to reduce odors on objects that give strong stimulating odor and antibacterial effect.

Cross-sectional view of the first embodiment The expanded sectional view of the layered product of a first embodiment (A) The figure seen from the laminated body side of 1st embodiment, (b) Sectional drawing of the tab vicinity which put the half cut, (c) Sectional drawing after peeling an allyl isothiocyanate non-permeable layer Sectional drawing of the example which did not provide an allyl isothiocyanate permeation | transmission layer and a resin adhesive layer in a tab part in 1st embodiment. Cross-sectional view of the second embodiment

Hereinafter, the present invention will be described in detail with specific embodiments.
FIG. 1 is a cross-sectional view of the first embodiment. This embodiment is an allyl isothiocyanate volatilized preparation in which the laminate 11 is attached and sealed to an opening 33 of an open container 32 that houses an allyl isothiocyanate emitter 31. In the following description, allyl isothiocyanate is abbreviated as “AITC”. The detail of the laminated body 11 which comprises this embodiment, and its manufacturing method are demonstrated.

  The laminate 11 includes an AITC transmission layer 12, an AITC non-transmission layer 14, and a resin adhesive layer 13 for bonding the layers, and the AITC transmission layer 12 side faces the open container 32.

  The AITC transmission layer 12 is composed of a single layer or a plurality of layers, and FIG. 2 shows an embodiment composed of two layers in which two films 15 and 16 are thermally laminated. Examples of the material of the film constituting the AITC transmission layer 12 include a biaxially stretched polypropylene film, an unstretched polypropylene film, a polyethylene film, and an unstretched polyester film. Among these, in particular, from the viewpoint of the permeability and strength of AITC, it is preferable that the biaxially stretched polypropylene constitutes at least one layer. When the film 15 does not have heat weldability, the laminate 11 is heated in another container. A configuration in which an unstretched polypropylene film, a polyethylene film, or the like is bonded as the innermost layer facing the open container 32 as the heat welding layer 17 for welding is preferable. In addition, when the AITC transmission layer 12 is composed of a plurality of layers, either adhesion between the films constituting the individual layers is performed using a polyether urethane resin as an adhesive or by thermal lamination. Is desirable. When using an adhesive such as vinyl, acrylic, or polyester urethane resin other than polyether urethane resin, the adhesive force decreases due to the AITC that passes between the films, and peeling occurs between the layers. There is a risk that. Note that both thermal lamination and thermal welding are bonded by heating, but in the present application, the entire bonding between films is referred to as thermal lamination, and partial heat sealing is referred to as thermal welding. When it is composed of a plurality of layers, there is an advantage that it is easy to control the amount of AITC permeation, and even when the film used mainly does not have heat-weldability, the heat-weldability is not hindered without inhibiting the required amount of AITC permeation. Can also be given.

  The thickness of the AITC transmission layer 12 varies depending on the material of the film to be used, but the entire layer is preferably 40 μm or more and 200 μm or less. If it is less than 40 μm, the strength is too low and the possibility of tearing cannot be ignored. On the other hand, if it exceeds 200 μm, the welding strength may be insufficient, the AITC non-permeable layer 14 may be adversely affected depending on the welding conditions, and a sufficient amount of transmission may not be ensured. Moreover, when using a biaxially stretched polypropylene film for part, it is good to use the thickness of a biaxially stretched polypropylene film by 20 micrometers or more and 100 micrometers or less. If the thickness is less than 20 μm, the strength is too low to break and the possibility of tearing cannot be ignored. Further, since the versatility is poor, there is a disadvantage that it is difficult to obtain. On the other hand, if it exceeds 100 μm, sufficient transparency may not be ensured.

The AITC permeation amount of the entire AITC transmission layer 12 needs to be 100 mg / m ² · 24 hr or more under 30 ° C., and is preferably 200 mg / m ² · 24 hr or more and 20000 mg / m ² · 24 hr or less. If it is less than 100 mg / m ² · 24 hr, the amount of transmission as the transmission layer is insufficient. If the value is less than 200 mg / m ² · 24 hr, sufficient antibacterial effect may not be obtained depending on the use environment. On the other hand, the amount of transmission exceeding 20000 mg / m ² · 24 hr is not realistic.

The AITC non-permeable layer 14 is composed of a single layer or a plurality of layers, and the AITC permeation amount of the whole layer is 50 mg / m ² · 24 hr or less under 30 ° C. conditions. FIG. 2 shows an embodiment composed of three layers in which two films 18 and 19 are bonded with an adhesive layer 20. Examples of the material of the film constituting the AITC non-permeable layer 14 include a barrier film coated with polyester resin such as polyethylene terephthalate, ethylene-vinyl alcohol copolymer resin, polyvinylidene chloride (PCDC), and aluminum foil. It is preferable to stack a plurality of these films because pinholes due to piercing and the like can be prevented and tearing when peeling can be prevented. In particular, when an aluminum foil is used as a lower layer side film (corresponding to the film 18 in FIG. 2) in contact with the resin adhesive layer 13, the AITC that passes through the AITC transmission layer 12 and the resin adhesive layer 13 and rises. It is preferable because it has a high resistance to the above and can be blocked without causing denaturation.

The thickness of the film in which the AITC permeation amount is 50 mg / m ² · 24 hr or less in a single layer differs depending on the material. In the case of an aluminum foil, the thickness may be 7 μm or more, and in the case of an ethylene-vinyl alcohol copolymer resin, the thickness may be 12 μm or more.

  In addition, when the film 18 on the resin adhesive layer 13 side has high AITC resistance and AITC barrier properties like aluminum foil or ethylene-vinyl alcohol copolymer resin, the film laminated on the surface side than that, It does not necessarily have to be non-permeable to AITC. This is because it is possible to almost certainly prevent the AITC from entering the surface layer with only one layer having a high barrier property. When the film 18 having a high barrier property is provided as the film on the resin adhesive layer 13 side, the layer on the surface side (corresponding to the film 19 in FIG. 2) is a printed layer made of ink or the printed layer. A laminate layer or the like for protecting the film may be included.

  In addition, when the AITC non-permeable layer 14 is composed of a plurality of layers, the allyl isothiocyanate non-permeable film that directly contacts the resin adhesive layer 13 and forms a surface that is peeled off from the resin adhesive layer 13 in use. In the case where 18 has high AITC resistance and AITC barrier properties such as aluminum foil and ethylene-vinyl alcohol copolymer, the adhesive used for the plurality of adhesive layers 20 need not be particularly limited.

  The resin adhesive constituting the resin adhesive layer 13 needs to have a polyester urethane resin as an adhesive component. The number average molecular weight of the resin adhesive is preferably 1000 or more and 15000 or less. If the number average molecular weight is less than 1000, the adhesive force is insufficient, and it may be easily peeled off more than necessary. On the other hand, when it exceeds 15000, coating is difficult, and peeling may not be easy enough even after long-term storage. This average molecular weight is not realized from the beginning by the prepared material, but may be realized by causing a curing reaction by mixing the main agent and the curing agent.

  In order to obtain the laminate 11 by forming the resin adhesive layer 13, a brush or roller is applied to the surface of a single layer film constituting the AITC transmission layer 12 or to the surface of the laminate of a plurality of layers. This is realized by applying a polyester-based urethane resin by transfer or the like, and then laminating a single-layer film or a multi-layer laminate to be the AITC non-permeable layer 14. On the contrary, after applying a polyester-based urethane resin on the film or laminate that becomes the AITC non-permeable layer 14, the film or laminate that becomes the AITC transparent layer 12 may be bonded. In addition, you may use a solvent in the case of coating.

The coating amount of the polyester-based urethane resin constituting the resin adhesive layer 13 is preferably 3 g / m ² or more and 20 g / m ² or less when wet. If it is less than 3 g / m ² , the initial adhesive strength between the AITC transmissive layer 12 and the AITC non-transmissive layer 14 becomes insufficient, and the adhesive strength is reduced by the AITC accumulated between the layers, so that the originally required adhesive strength cannot be maintained. End up. On the other hand, when the coating exceeds 20 g / m ² , it takes time to dry, which slows the production rate and increases the possibility of residual solvent, which is useless.

  Specifically, the peel strength of the lowered bonded portion that should be realized to achieve the object of the present invention is preferably 0.01 N / 15 mm or more and 0.1 N / 15 mm or less. If it is less than 0.01 N / 15 mm, there is a high possibility that the AITC non-permeable layer 14 will be peeled off during storage, that is, when volatilization is not required, and if it exceeds 0.1 N / 15 mm, the AITC non-permeable layer 14 will be peeled off. When doing so, the AITC transmissive layer 12 may be torn or difficult to peel off. This adjustment can be realized by the above-mentioned coating amount, the amount of the curing agent added to the adhesive to be used, and the selection of the polyester urethane involved in the adhesion of the adhesive to be used.

  The laminated body 11 formed in this way is pasted so as to cover and seal the opening 33 of the opening container 32 containing the AITC emitter 31. The opening container 32 should just be formed with the resin etc. which distribute | arranged the resin which has AITC tolerance, such as a polyethylene terephthalate and ethylene-vinyl alcohol copolymer resin, to the whole surface at least one layer. Here, the entire surface layer may be a single layer made of the above-mentioned resin, or may occupy at least one layer among a plurality of laminated layers and may be in direct contact with AITC, or may be a layer that is not in contact among the plurality of layers. However, it may be included in a layer that can cover the entire circumference of the container. A flange 34 is provided in the opening 33, and the surface of the laminate 11 on the AITC transmission layer 12 side is attached to the flange 34. As a method of affixing, the method of adhering the resin film constituting the AITC transmission layer 12 by heat welding is preferable. If the adhesive is used, the adhesive force is reduced by the AITC, and the entire laminate 11 may be peeled off.

  In the preparation in which the laminate 11 is adhered and sealed, gaseous AITC is released from the AITC emitter 31 during storage, and passes through the AITC transmission layer 12 to reach the resin adhesive layer 13. FIG. 2 is an enlarged view of the vicinity of the laminate 11 in this state, and the arrow in the drawing indicates the AITC of the gas. The AITC that reaches the resin adhesive layer 13 decreases the adhesive strength of the polyester urethane resin constituting the resin adhesive layer 13 and decreases the adhesive force between the resin adhesive layer 13 and the AITC non-permeable layer 14. Let AITC is accumulated in the resin adhesive layer 13 until it is saturated, and in this saturated state, the adhesive force of the resin adhesive layer 13 is reduced to about 1/6 of the initial adhesive force. Thereby, although it does not peel by itself, it will be in the state which can be peeled easily by applying human power. The effect of reducing the adhesive strength is that when the film (corresponding to 18 in FIG. 2) forming the layer closest to the resin adhesive layer 13 of the AITC non-permeable layer 14 is an aluminum foil, it is difficult to adhere to the resin originally. Since it is a material, it is particularly effective.

  To peel off only the AITC non-transmissive layer 14 of the laminated body 11 and keep the AITC transmissive layer 12 adhered to the opening 33 of the opening container 32, a part of the laminated body 11 is formed on the opening 33. The tab 25 protruding from the flange 34 may be formed. As a preferable form of this tab 25, the form shown in FIG. 3 and FIG. 4 as follows is mentioned, for example.

  FIG. 3A shows a view of the tab 25 as viewed from the surface of the laminate 11 in which a half cut 26 is inserted from the side of the AITC transmission layer 12. FIG. 3B shows a cross-sectional view in the vicinity of the tab 25. The half cut 26 is provided near the root of the tab 25 and along the edge of the open container 32, and the portion beyond the half cut 26 needs to have a width that can be picked. The half cut 26 inserted from the AITC transmissive layer 12 side needs to reach at least the resin adhesive layer 13, and may be cut into the AITC non-transmissive layer 14 as long as it is halfway. If the AITC non-transparent layer 14 is cut, when the tab 25 is picked and pulled up when peeling off, the half cut 26 is formed on the opposite side of the AITC non-transparent layer 14, that is, on the surface of the laminate 11. It is necessary to have a depth that does not cause tearing.

  After the AITC is saturated in the resin adhesive layer 13 as described above and the adhesive force is reduced, the tab 25 having the above configuration is picked and pulled in the direction to peel off the laminate 11, and the tab 25 is entirely However, the AITC non-transmissive layer 14 is peeled off and the AITC transmissive layer 12 remains on the flange 34 side of the half cut 26. A cross-sectional view of this state is shown in FIG. In this state, it is possible to emit gaseous AITC while preventing the AITC emitter 31 from spilling out due to the remaining AITC transmission layer 12.

  FIG. 4 shows a configuration in which the portion that becomes the tab 25 of the laminate 11 is formed only by the AITC non-permeable layer 14 without providing the AITC transmissive layer 12 in advance, and without providing the resin adhesive layer 13. A cross-sectional view is shown. In this form, since only the film constituting the AITC non-permeable layer 14 can be picked at the tab 25 portion, after the resin adhesive layer 13 is saturated and the adhesive force is reduced as described above, the film is pulled as it is. As a result, only the AITC non-permeable layer 14 can be peeled off from the entire laminated body 11, and the gaseous AITC can be released after the peeling.

  Next, a second embodiment will be described. FIG. 5 is a cross-sectional view of the AITC volatile agent which is the bag 45 according to this embodiment. In this embodiment, similarly to the laminated body 11 used in the first embodiment, a laminated body 41 in which an AITC transmissive layer 42, a resin adhesive layer 43, and an AITC non-transmissive layer 44 are laminated in this order is used. The AITC emitter 31 is enclosed in a bag 45 formed by the body 41. When forming the bag 45, the laminates 41 and 41 are such that the AITC transmission layers 42 and 42 face each other, and the resin constituting the AITC transmission layers 42 and 42 is bonded by dry lamination. In the drawing, an adhesive surface 46 indicates an adhesive surface of the dry laminate.

  In this embodiment, if the AITC non-transmissive layer 44 of at least one of the two stacked bodies 41 is peeled off, the volatilization of AITC can be started. As a specific means, one of the laminates 41 is protruded from the other, and a half cut 47 for cutting from the AITC transmission layer 42 to the resin adhesive layer 43 is provided at the base of the protruding portion. Then, the AITC non-transparent layer 44 can be peeled by picking and pulling out the protruding portion as in FIG.

Hereinafter, not only these embodiments but also the overall invention will be described.
The form of the AITC volatilization preparation according to the present invention is not limited to the above-described embodiment, but prevents AITC volatilization during storage, and when necessary, the AITC non-permeable layers 14 and 44 on the surfaces of the laminates 11 and 41 are used. What is necessary is just to start volatilization by peeling at least one part.

  When aluminum foil is used as the AITC non-permeable layers 14 and 44, the resin adhesive constituting the resin adhesive layers 13 and 43 may be optionally added with a silane coupling agent added to increase the resin adhesive force to the aluminum foil. Can be added. This is because the peel strength can be finely adjusted depending on whether or not a silane coupling agent is added.

  Hereinafter, examples of specific allyl isothiocyanate volatilization preparations of the present invention and production examples of laminated sheets as the previous stage will be described.

First, the AITC permeation amount of the film to be used was measured under 30 ° C conditions. The values are listed below.
<AITC transmission amount of the film used for the transmission layer>
-20 μm thick biaxially oriented polypropylene film: 4700 mg / m ² · 24 hr
-40 μm thick biaxially oriented polypropylene film: 2900 mg / m ² · 24 hr
-20 μm thick unstretched polypropylene film: 11000 mg / m ² · 24 hr
-40 μm thick unstretched polyethylene film: 31000 mg / m ² · 24 hr
<AITC permeation amount of film used for non-transparent layer>
-25 μm thick biaxially stretched polyester film: 25 mg / m ² · 24 hr
-12 μm thick biaxially stretched polyester film: 70 mg / m ² · 24 hr
・ Thickness 9μm aluminum foil: less than 10mg / m ²・ 24hr

(Production Example 1)
A polyester main agent (Mitsui Chemicals Polyurethanes Co., Ltd .: Takelac A-525S) and an aromatic isocyanate curing agent (Corporation: Takenate A-3) are mixed so that the blending weight ratio is 10: 1, and ethyl acetate is mixed. A 25 μm-thick biaxially stretched polyester film (manufactured by Toyobo Co., Ltd .: T-4200, so that the coating amount after drying is 3 g / m ² in terms of solid content). Abbreviated as “biaxially stretched PET”). The biaxially stretched polyester film is an AITC non-permeable layer, and the layer formed by coating is a resin adhesive layer. In addition, an uncoated part was provided in part during application. Further, on the resin adhesive layer formed by the coating, a 20 μm unstretched polypropylene film (manufactured by Toyobo Co., Ltd .: P-1128, abbreviated as “unstretched PP” in the table) serving as an AITC transmission layer. Bonding and aging were performed at 40 ° C. for 3 days. The obtained laminate was cut into a width of 15 mm and a length of 40 mm (of which 10 mm was an uncoated part), and a gas barrier together with 500 mg of cellulose particles (Rengo Co., Ltd .: Viscopearl AH-4050L) carrying AITC 100 mg. The film was sealed in an aluminum bag having a width of 80 mm and a length of 120 mm, stored at 60 ° C. for 7 days, and then peel strength was measured according to JISZ1702. The values are shown in Table 1.

単位：Ｎ／１５ｍｍ

Unit: N / 15mm

(Production Example 2)
Instead of the 25 μm biaxially stretched polyester film (manufactured by Toyobo Co., Ltd .: T-4200) used in Production Example 1, a 12 μm thick biaxially stretched polyester film and a 9 μm thick aluminum foil were bonded to a polyether urethane resin. A laminate was obtained in the same manner except that the adhesive layer was adhered, and the peel strength was measured in the same procedure. The values are shown in Table 1.

Example 1
Two sheets having the same layer structure as the laminate obtained in Production Example 2 were stacked so that the 20 μm-thick unstretched polypropylene films were inside each other, and a bag body having a side of 100 mm was produced by heat welding. . The bag was filled with 500 mg of the AITC-supported cellulose particles used in Production Example 1, stored at 60 ° C. for 7 days, and then peel strength was measured with a tensile tester. The values are shown in Table 1.
The obtained bag was allowed to stand in an environment of 30 ° C., and the change in weight was measured over time. The decrease in weight was defined as the AITC leak amount (permeation amount). The permeation amount obtained by converting the surface area of the bag body per m ² was less than 10 mg / m ² · 24 hr.

(Example 2)
A three-layer structure of co-extruded polypropylene / ethylene-vinyl alcohol copolymer resin / polypropylene, and vacuum forming a 0.8 μm thick laminated sheet, the inner part is formed as a recess at the center, and the rectangular opening A molded container having an edge around the periphery and having one edge of 100 mm was obtained. The molded container itself is impermeable to AITC. In this molding container, 500 mg of cellulose particles carrying AITC used in Production Example 1 were placed, and the laminate produced in Production Example 2 was used as a 20 μm unstretched polypropylene film (manufactured by Toyobo Co., Ltd .: P-1128) side, that is, the AITC permeable layer side is directed to the molding container, overlapped with the entire circumference of the opening of the molding container, sealed by thermal welding, stored at 60 ° C. for 7 days, and then pulled by a tensile tester. The peel strength was measured. The values are shown in Table 1.

(Example 3)
In Example 2, instead of the 20 μm-thick unstretched polypropylene used for the AITC transmission layer, a 40 μm-thick unstretched polyethylene film (manufactured by Toyobo Co., Ltd .: L6102, abbreviated as “unstretched PE” in the table). A test similar to Example 1 was carried out except that it was used. However, although material destruction did not occur at the time of peeling, the polyethylene film was stretched, the value of the tensile test could not be measured, and an appearance problem was exhibited. However, the volatilization of AITC was possible. In addition, when it peeled intentionally at the speed in the case of peeling, it was not able to extend but torn on the way.

Example 4
In Example 2, the AITC permeation layer was formed by using a polyether-based main agent (Mitsui Chemical Polyurethane Co., Ltd .: Takelac A-969) and an aromatic isocyanate-based curing agent (Mitsui Chemical Polyurethane Co., Ltd .: Takenate A-5). Example 2 except that the laminate was made by adhering a 20 μm-thick biaxially stretched polypropylene film and a 20 μm-thick unstretched polypropylene film with a resin adhesive mixed so that the blended weight ratio was 3: 1. A similar test was conducted. The results are shown in Table 1.

(Example 5)
In Example 1, except that the AITC non-permeable layer was made of an AITC non-permeable layer consisting only of a 12 μm-thick biaxially stretched polyester film except that the 9 μm-thick aluminum foil and the polyether resin adhesive were removed. A similar test was conducted. The results are shown in Table 1. The obtained bag was allowed to stand in an environment of 30 ° C., and the change in weight was measured over time. The decrease in weight was defined as the AITC leak amount (permeation amount). The permeation amount obtained by converting the surface area of the bag body per m ² was 95 mg / m ² · 24 hr.

(Example 6)
Example 1 is the same as Example 1 except that the AITC non-permeable layer is made of an AITC non-permeable layer composed of only 9 μm thick aluminum foil except for the 12 μm thick biaxially stretched polyester film and the polyether resin adhesive. A similar test was conducted. The results are shown in Table 1. The obtained bag was allowed to stand in an environment of 30 ° C., and the change in weight was measured over time. The decrease in weight was defined as the AITC leak amount (permeation amount). The permeation amount obtained by converting the surface area of the bag body per m ² was 21 mg / m ² · 24 hr, and it was found that the aluminum foil alone had less leakage than the biaxially stretched polyester film alone. .

(Comparative Example 1)
Instead of the resin adhesive used in Production Example 1, a polyether-based main agent (Mitsui Chemical Polyurethane Co., Ltd .: Takelac A-969) and an aromatic isocyanate-based curing agent (Mitsui Chemical Polyurethanes Co., Ltd .: Takenate A-) A laminate was obtained in the same manner as in Production Example 1 except that the resin adhesive mixed so that the blending weight ratio of 5) was 3: 1 was used, and the same test was performed. The values are shown in Table 1. In the table, “material breakage” indicates that the 20 μm unstretched polypropylene film was torn and means that the adhesive strength was not fully reduced. The same applies hereinafter.

(Comparative Example 2)
Instead of the resin adhesive used in Production Example 2, the same test as in Production Example 1 was performed using the resin adhesive used in Comparative Example 1. The results are shown in Table 1.

(Comparative Example 3)
A test similar to that of Example 1 was performed except that the laminate obtained in Comparative Example 2 was used instead of the laminate used in Example 1. The results are shown in Table 1.

(Comparative Example 4)
A test similar to that of Example 2 was performed except that the laminate obtained in Comparative Example 2 was used instead of the laminate used in Example 2. The results are shown in Table 1. As described above, Comparative Examples 1 to 4 show that even when a polyether-based urethane resin is used to form an adhesive layer by dry lamination using a solvent, the peelable adhesive force does not decrease.

(Comparative Example 5)
Instead of the resin adhesive used in Production Example 1, a polyether main agent (Mitsui Chemical Polyurethane Co., Ltd .: Takelac A-244B), which is an adhesive for solvent-free lamination, and an aromatic isocyanate curing agent (Mitsui Chemical Polyurethane) Co., Ltd .: Takenate A-244A) was used in the same manner as in Production Example 1 except that the mixture was used so that the blending weight ratio was 5:10 and the solvent was not used. The same test as in Production Example 1 was performed. The results are shown in Table 1. As a result, it was found that when a polyether-based urethane resin is used for the adhesive layer, the peelable adhesive force does not decrease even in the solvent-free non-solvent laminating method.

(Comparative Example 6)
A test similar to that of Example 2 was performed except that a synthetic rubber adhesive (manufactured by Konishi Co., Ltd .: G17) was used instead of the resin adhesive of the laminate used in Example 2. As a result, delamination was observed in a part of the adhesive layer during storage. Further, the value was less than 0.01 N / 15 mm which is the measurement limit.

(Reference example)
In each of the above examples, the same number of days was stored without interposing the cellulose particles supporting AITC 100 mg used in Production Example 1, and the same test as in Production Example 1 was performed. It was found that the unstretched polyethylene film was broken and the adhesive strength was kept sufficiently high.

11, 41 Laminated body 12, 42 AITC permeable layer 13, 43 Resin adhesive layer 14, 44 AITC non-permeable layer 15, 16 (AITC permeable) film 17 Thermal welding layer 18 (AITC non-permeable) film 19 Film 20 Adhesive layer 25 Tabs 26, 47 Half cut 31 AITC emitter 32 Open container 33 Open part 34 Flange 46 Adhesive surface

Claims (6)

It has an allyl isothiocyanate permeable layer composed of a single layer or multiple layers, a resin adhesive layer comprising a polyester urethane resin as an adhesive component, and an allyl isothiocyanate non-permeable layer composed of a single layer or multiple layers in order, Placing the allyl isothiocyanate impermeable laminate on part or all of the package sealing the allyl isothiocyanate emitter, with the allyl isothiocyanate impermeable layer facing the outer surface;
During the storage period, the allyl isothiocyanate-permeable layer on the inner surface passes through the allyl isothiocyanate, by reducing the adhesive strength of that in the polyester urethane resin of the resin adhesive layer is allyl isothiocyanate erodes An allyl isothiocyanate volatilization preparation that allows the outer layer of the resin adhesive layer to be easily peeled off while maintaining the adhesive state, and enables the volatilization of allyl isothiocyanate after peeling.   The allyl isothiocyanate volatilization preparation according to claim 1, wherein at least one layer constituting the allyl isothiocyanate permeable layer is a layer made of biaxially oriented polypropylene.   Allyl isothiocyanate according to claim 1 or 2, wherein the allyl isothiocyanate permeable layer is a laminate of a plurality of layers, and the adhesion between the films constituting the plurality of layers is a polyether-based urethane resin or a thermal laminate. Volatile formulation.   4. The allyl isothiocyanate non-permeable layer that is in contact with the resin adhesive layer of the allyl isothiocyanate non-permeable layer and forms a surface that is peeled off from the resin adhesive layer when used is made of an aluminum foil. 5. The allyl isothiocyanate volatilization preparation according to claim 1.   The said laminated body was affixed by heat welding so that the opening part of the open container which is allyl isothiocyanate non-permeable which accommodated the allyl isothiocyanate discharge | release body might be covered. Allyl isothiocyanate volatilization preparation. The laminate has a tab that protrudes from the opening edge of the open container, and on the tab, from the allyl isothiocyanate permeable layer side to between the resin adhesive layer and the allyl isothiocyanate non-permeable layer. The allyl isothiocyanate volatilization preparation according to claim 5, wherein the allyl isothiocyanate permeation layer has a cut half cut or the tab is excluded from the allyl isothiocyanate permeation layer.

Images