JPH0556836A - Flower box - Google Patents

Abstract

PURPOSE:To supply a flower box in which a sufficiently long appreciation interval can be obtained use of cut flowers which are fresh requires inevitably water and further in which oxygen concentration within the box can be kept sufficiently low by use of an oxygen absorbent. CONSTITUTION:This device is a flower box stuck with a laminate composed of an oxygen absorbent layer in which at least an oxygen absorbent is enveloped in a resin and an asymmetrical porous layer which is positioned at the inside of the base of the oxygen absorbent layer and in which are a densed film is formed in the thickness direction in the inside of case, at a part of the inside of a transparent enclosed case.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel flower box for ornamental cut flowers that accommodates cut flowers in a transparent case.

[0002]

2. Description of the Related Art An ornamental flower box in which an artificial flower is housed in a transparent case is well known. However, if cut flowers, which are fresh flowers, are similarly housed in a transparent case, the housed cut flowers are normally stored under an oxygen atmosphere (in the air), and therefore it takes only about two weeks at most. Therefore, even if there is an idea of storing cut flowers in a transparent case for ornamental use, such a flower box is not in practical use because the ornamental period is short as described above.

[0003]

As a result of intensive studies, the present inventors have found that when a cut flower is housed in a sealed case, the ornamental period can be greatly extended by greatly reducing the oxygen concentration in the case. I found that I could do it. Although not related to the flower box, a method of providing an oxygen absorber having an oxygen absorbing performance in the container is known as a method for reducing the oxygen concentration in the sealed container (for example, JP-A-56-2164). JP-A-57-19
4959, JP 1-167079, JP 1-308781, JP 1-315438, JP 55-161858, and JP 56-.
No. 38056). However, since cut flowers require moisture, the internal humidity becomes extremely high when the cut flowers are housed in a sealed case. Since the conventional oxygen absorbers described above have insufficient water resistance, even if they are provided in a cut flower ornamental sealed case, the oxygen absorption performance of the oxygen absorber is rapidly reduced due to the intrusion of water. And then
After all, it cannot be put to practical use. Also, oxygen absorbers are often stored in the air from the time they are manufactured until they are installed, but conventional oxygen absorbers absorb oxygen in the air during the storage period and At times, there is a problem that most of the oxygen absorption capacity may be exhausted.

An object of the present invention is to provide a novel flower box which can keep the oxygen concentration in the case sufficiently low for a long period of time by using an oxygen absorber, and at the same time, cut flowers containing a large amount of water are used. When providing the oxygen absorber inside the case to be housed, it is possible to reliably shield the oxygen absorber from moisture in the case and to keep the oxygen permeation rate to the oxygen absorber high. The purpose is to be able to maintain high oxygen absorption performance until use.

[0005]

In order to achieve this object, the flower box of the present invention is an oxygen absorbing device in which at least an oxygen absorbing agent is embedded in a resin in a part of the inside of a transparent hermetically-sealed case. From a fixed body of a laminate comprising a body layer and an oxygen permeable layer having an asymmetric porous layer located inside the case of the oxygen absorber layer and having a dense thin film layer formed inside the case in the thickness direction. Become.

"Transparent sealed case" in the present invention
At least a part of the case body is made of a substantially transparent material (for example, transparent glass, transparent plastic),
Any size and shape is not particularly limited as long as the cut flowers housed inside can be viewed from the outside and can be substantially sealed with a lid or a cap. Since the laminated body including the oxygen absorber layer and the oxygen permeable layer generally does not become a transparent body, it may be fixed to any portion in the case that does not interfere with the cut flower viewing.

The "asymmetric porous layer" in the present invention is
This layer is necessary to achieve the above-mentioned object, that is, to shield the oxygen absorber from moisture in the case while maintaining sufficient oxygen permeability. In the present invention, the asymmetric type porous layer refers to a flat membrane sheet comprising a very thin dense layer on one side and a porous layer supporting the dense layer. Since the dense thin film layer has only the angstrom level pores necessary for oxygen permeation, the shielding effect of the contents is significantly larger than that of the conventional porous film, and the dense layer is thin,
Oxygen permeability can also be significantly higher than that of conventional sheets. That is, it is possible to exhibit a sufficiently high oxygen permeability while achieving a sufficiently high moisture shielding effect (water resistance). This dense thin film layer is supported by the porous layer having high oxygen permeability. Further, when there is a possibility that a sufficient shielding effect cannot be expected with only the asymmetric type porous layer, an oxygen permeable homogeneous thin film layer is further provided on the dense thin film layer to reduce the oxygen permeability too much. It is possible to further improve the shielding effect.
Further, the oxygen permeable layer having the asymmetric porous layer may be in the form of a so-called “oxygen permeable composite membrane” supported by a woven or non-woven fabric layer.

The "oxygen absorber layer in which the oxygen absorber is embedded in the resin" in the present invention is a layer that absorbs oxygen in the case and the contents, and also achieves the above-mentioned another object, that is, oxygen. It is a layer necessary for improving the storage stability and maintaining the shape of the absorbent before it is actually used in the case. As the oxygen absorbent in the present invention, those exhibiting oxygen absorbing ability under high humidity can be preferably used.
However, such an oxygen absorbent itself is deactivated when activated to some extent by moisture in the air. Therefore, by embedding the oxygen absorbent in a resin that does not allow moisture to pass through in a normal atmosphere but allows moisture and oxygen to pass under high humidity, deactivation of the oxygen absorbent can be prevented until it is actually attached and used. .. Therefore, by using this oxygen absorber layer, it is possible to improve the storage stability until it is actually attached, and it is also possible to easily maintain the form as a laminate.

In consideration of higher storage stability, it is possible to provide an oxygen barrier film layer. The oxygen barrier film layer is located between the oxygen absorber layer and the back surface of the case when mounted inside the case.
During the pre-wearing storage period, the presence of the oxygen barrier film layer prevents the oxygen absorber layer from being directly exposed to the atmosphere, so that the deterioration of the oxygen absorbing performance of the oxygen absorber layer can be prevented more reliably. Further, since the laminated body has the oxygen barrier film layer made of resin, the laminated body can be more easily adhered and fixed to the back surface of the case. Further, when the sealed case is made of resin, oxygen penetrates into the case body and penetrates into the inside. However, the presence of the oxygen barrier film layer can suppress such oxygen penetration.

The flower box of the present invention, in particular, each part of the laminate will be described in more detail below. (1) Asymmetric Porous Layer The asymmetric porous layer is composed of a very thin dense layer on one side of a flat sheet and a porous layer supporting the dense layer. The dense layer present on one side of the layer is formed as a very thin layer having pores with a pore diameter of 0.0005 to 0.5 μm and having a thickness of up to several μm. In the asymmetric porous layer, the dense layer has a small thickness, and the subsequent porous layer has a high porosity, so that the permeation rate of gas or water vapor is very high. As a preferred embodiment of the present asymmetric porous layer, from the viewpoint of achieving both a shielding effect and an oxygen permeation rate, and in the case of providing an oxygen permeable homogeneous thin film layer, from the viewpoint of forming the oxygen permeable homogeneous thin film layer, a dense thin film The preferred pore size of the layer is 0.001-0.1 μm. The total thickness of the asymmetric porous layer is usually 1 to 300 μm in order to have practical mechanical strength and to obtain a sufficient gas permeation rate.
m, and preferably 10 to 100 μm. Although it is possible to use a symmetric structure in the film thickness direction as the film structure, an asymmetric type porous structure is necessary in order to achieve both a shielding effect and an oxygen permeation rate, and in particular, an asymmetric type porous structure By doing so, the gas permeation resistance can be reduced. The porosity of the entire membrane can be arbitrarily selected according to the purpose, but is generally selected from the range of 10 to 90%. When the porosity is high, the gas permeation rate is high, and when the porosity is low, the durability is excellent. However, in the present invention, the porosity is 70 to 85% in terms of having both of these characteristics. An asymmetric type porous layer can be mentioned as a preferable example. Further, as the asymmetric type porous layer, a layer formed by a known method, for example, a wet method, a dry / wet method, a melting method, a stretching method or the like is appropriately used. As the material for forming the asymmetric porous layer, aromatic polysulfone-based materials such as polysulfone, polyether sulfone, polyphenylene sulfide sulfone, and polyphenylene sulfone, cellulose acetate, ethyl cellulose, cellulose-based materials such as cellulose, polyacrylonitrile, polypropylene, polyethylene. Polyolefin materials such as polyvinylidene fluoride, polytetrafluoroethylene and other fluorine-containing polymer materials, polyamide materials or polyimide materials and polyurethane materials can be used, among which gas permeability is sufficient. The aromatic polysulfone-based material is preferably used because it is easy to control the pore size. Further, the gas permeability of this porous layer is 10 to 10,000 [m ³ / m ² at the air permeation rate.
.Hr.atm] is preferable.

(2) Layer Composed of Woven Fabric or Nonwoven Fabric A base layer made of woven fabric or nonwoven fabric is provided as a support layer for supporting the asymmetric type porous layer, and oxygen permeation between the asymmetric type porous layer and this support layer. You may take the form of what is called an "oxygen permeable composite film" which comprises a layer. The base material layer made of this woven or non-woven fabric preferably has sufficient air permeability and good mechanical strength. Examples of those having such characteristics include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polyamides such as nylon, and known woven or non-woven fabrics containing natural fibers as a main component. The air permeability of this woven or non-woven fabric is not particularly limited as long as oxygen that permeates the asymmetric porous layer does not have a large resistance before reaching the oxygen absorber layer. As air permeability, for example, 0.01 to 100 [ml /
cm ² · sec], and considering the film-forming property of the asymmetric porous layer and the performance of the oxygen absorber layer having a composite structure, 0.1-10 [ml / cm ² · se
c] is particularly preferable. Further, the thickness is particularly preferably 50 to 300 μm in view of the above supporting strength. In the case of non-woven fabric, as a basis weight corresponding to this performance, 10-20
A range of 0 g / cm ² can be mentioned as a suitable amount. Furthermore, when a woven or non-woven fabric having a heat-sealing property is used, it is possible to enhance the work efficiency during lamination.

(3) Oxygen-permeable homogeneous thin film layer An oxygen-permeable homogeneous thin film layer may be further provided inside the container of the oxygen-permeable layer. This oxygen-permeable homogeneous thin film layer is
It is a layer that more reliably prevents the permeation of water in the case and also permeates oxygen and water vapor. The oxygen permeability of the oxygen permeable homogeneous thin film layer is such that when the oxygen permeability coefficient P _o2 is used, P _o2 is
1 × 10 ^-10 [cm ³ (STP) · cm / cm ² · se
c · cmHg] (= volume of gas converted to standard state / film thickness / membrane area / time / pressure) or more, more preferably 1 × 10 ⁻⁹ [cm ³ (STP) · cm / cm ² · se
c · cmHg] or more is more preferable. The water vapor permeability depends on the temperature and pressure inside the case, the contents of the case, and the characteristics of the oxygen absorber, so it cannot be determined unconditionally, but as a rough guideline, 0.5 [g / m ² · atm · 24 hr]
The above can be mentioned as preferable examples.

As the polymer satisfying the above range, for example,
Polyorganosiloxanes such as polydimethylsiloxane, polymethylphenylsiloxane, cross-linked polymers of polydimethylsiloxane derivatives, polyorganosiloxane /
Polyorganosiloxane copolymers such as polystyrene copolymer, polyorganosiloxane / polycarbonate copolymer, polyorganosiloxane / polysulfone copolymer, poly (4-methylpentene-1), polyethylene / propylene copolymer, poly (4-methylpentene-
1) crosslinked polymers, polyolefins such as poly (di-tert-butyl fumarate), poly (2,6-dimethyl-1,4-phenylene oxide) and silyl modified poly (2,6-dimethyl-1, 4-phenylene oxide) and other polyphenylene oxides, poly (trimethylsilylpropyne), poly (tert-butylacetylene) and other substituted acetylene polymers, ethyl cellulose and other celluloses, poly (bisethoxyphosphazene)
Examples include polyorganophosphazenes and the like.

For forming a pinhole-free oxygen-permeable homogeneous thin film layer which enables high oxygen permeability, a polyorganosiloxane cross-linked polymer or poly (4-methylpentene-1) is used.
The cross-linked polymer can be mentioned as a preferable example.
Examples of the crosslinkable modified polyorganosiloxane include silanol modified polyorganosiloxane represented by the following chemical formulas 1 and 2.

[0015]

[Chemical 1]

[0016]

[Chemical 2]

In the above Chemical Formulas 1 and 2, R1 and R2 are methyl, ethyl, propyl or phenyl, and R3 is
Methyl group, ethyl group or propyl group, R4 has 2 carbon atoms
It represents an alkyl group up to 15 or a compound represented by the following chemical formula 3. Further, p + p ′ = 3, p is an integer of 1 to 3, 0.001 ≦ m / (m + n) ≦ 0.20,
n + m represents an integer of 50 to 3000.

[0018]

[Chemical 3]

These compounds are silane cross-linking agents having high reactivity with silanol groups such as polyfunctional acetoxy silanes, oxime silanes, alkoxy silanes, alkenyloxy silanes, amide silanes and amino silanes, and the above silane crosslinkers. It can be crosslinked with a siloxane crosslinker which is a hydrolyzate of The number of functional groups is not particularly limited, but tetrafunctional or higher functional groups are preferable in view of thin film forming property and thin film strength on a microporous support having high reactivity. Specific examples thereof include tetraacetoxysilane, tetradimethyloxime silane, ethyl orthosilicate, propyl orthosilicate, tetrakisisopropenoxysilane, ethyl polysilicate, pentadimethyloxime siloxane, hexadimethyloxime siloxane, and hexaacetoxysiloxane. This reaction may contain a catalyst to increase the reaction rate, and examples thereof include dibutyltin acetate and dibutyltin octoate.

Examples of other polydimethylsiloxane derivatives include amino-modified polydimethylsiloxanes represented by the following chemical formulas 4 and 5.

[0021]

[Chemical 4]

[0022]

[Chemical 5]

These compounds are polydimethylsiloxane derivatives obtained by polyfunctional compounds having two or more functional groups in the molecule such as acid chlorides, acid anhydrides, isocyanates, thioisocyanates, sulfonyl chlorides, epoxies, aldehydes and active halogens. It can be a cross-linked polymer.
Among them, acid chlorides, isocyanate compounds, and aldehyde compounds are particularly preferred because of their high reactivity, and examples thereof include isophthalic acid dichloride, terephthalic acid dichloride, trimesic acid chloride, fumaric acid dichloride, tolylene-2,
4-diisocyanate, diphenylmethane-4,4,-
Examples include diisocyanate, glutaraldehyde, and phthalaldehyde.

Examples of the poly (4-methylpentene-1) crosslinked polymer include trimethoxyvinylsilane graft poly (4-methylpentene-1) self-crosslinked products. However, as long as the oxygen permeability coefficient substantially satisfies the above range, the oxygen permeability coefficient is not limited to these and can be used. Further, the polymer forming the oxygen-permeable homogeneous thin film layer may be added with other polymers in a range not impairing the permeability of the thin film layer, a mixing method using two or more of the above polymers, There is a lamination method and the like.

As the method for forming the oxygen permeable homogeneous thin film layer, any method such as a polymer coating method, an interfacial polymerization method of a monomer, a method of coating a crosslinkable polymer after coating and a plasma polymerization method can be used. However, when the thickness of the thin film is too thin, the mechanical strength of the thin film layer decreases, and when it is too thick, the oxygen permeation rate decreases. Therefore, the thickness of the thin film is generally 0.01 to 3 μm, preferably 0.1. 05
It is suitable that it is ˜1 μm.

(4) Oxygen-permeable composite membrane A laminate comprising an asymmetric porous layer and a woven or non-woven support layer is referred to as an "oxygen-permeable composite membrane" in the present invention. The oxygen-permeable composite membrane may further be provided with an oxygen-permeable homogeneous thin film layer on the asymmetric type porous layer. The oxygen-permeable composite membrane is a composite membrane composed of a support layer made of a woven or non-woven fabric and an asymmetric porous layer provided on the support layer, or a support layer, and an asymmetric type provided on the support layer. A composite film composed of a porous layer and an oxygen-permeable homogeneous thin film layer provided on the asymmetric porous layer may be used, but the oxygen transmission rate Q _O2 is 0.1 to 0.1%.
50 [m ³ / m ² · hr · atm] is preferable,
More preferably 0.5 to 15 [m ³ / m ² · hr · at
m] is used. When the oxygen permeation rate is lower than the above range, the oxygen absorption rate of the oxygen absorber decreases, which is not preferable, and when the oxygen permeation rate exceeds the above range, the oxygen permeable composite membrane is formed by contact with other substances. Is easily scratched, which is not preferable. For water vapor permeability,
1.0 [g / m ² · at to activate the oxygen absorber
m · 24 hr] or more is preferable. For foods and beverages that are particularly susceptible to oxidation, 10 [g / m ² · atm
・ 24 hr] or more, more preferably 40 [g / m ² · a
It is preferable that the water vapor permeability of tm · 24 hr] or more is exhibited.

Further, in the oxygen permeable composite membrane having the oxygen permeable homogeneous thin film layer, the oxygen permeable homogeneous thin film layer is preferably a pinholeless homogeneous layer,
Oxygen / nitrogen permeation rate ratio α (= Q
_O2 / _QN2 ). When the inherent oxygen / nitrogen permeation rate ratio of the material forming the oxygen permeable homogeneous thin film layer is α ^* , α of the oxygen permeable composite membrane is preferably 0.5α ^{* to} 2.0α ^* , and Preferably 0.
8α ^{* to} 1.5α ^* . When α of the oxygen permeable composite film is lower than the above range, it is not preferable because pinholes exist in the oxygen permeable homogeneous thin film layer, and when α exceeds the above range, the oxygen permeable homogeneous thin film layer is porous. There is a risk that the layer may be impregnated, which reduces the oxygen permeation rate of the oxygen-permeable composite membrane, which is not preferable.

(5) Resin for embedding an oxygen absorber For example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, vinyl chloride type, isoprene type, butadiene type, chloroprene type, urethane type or acrylic type polymer is also used. It is possible. There is no particular limitation as long as it can hold the oxygen absorbent, but considering oxygen permeability and water vapor permeability, silicone resin can be mentioned as the most preferable example. It is desirable that the embedding resin is packed as close as possible in the sense that it holds the oxygen absorbent, but if it is desired to enhance the permeability of oxygen and water vapor for the purpose of improving the oxygen absorbing ability, a porous structure can be adopted. The oxygen absorber layer in which the oxygen absorber is embedded in the silicone resin is formed by a method of mixing the silicone compound and the oxygen absorber, applying the mixture to a constant thickness on the base material of the oxygen permeable composite film, and then curing the mixture. It is possible. Although the coating method is not particularly limited, for example, screen printing or the like is used, and the coating is performed in a form suitable for the intended use. In the case of producing a laminated body that is fixed to a cylindrical case, efficient production is possible by applying it in a strip shape on the oxygen-permeable composite membrane sheet. Alternatively, it may be coated on the entire surface of the oxygen-permeable composite membrane sheet and cut into a required size. In addition to this, various shapes such as a circle, an ellipse, a triangle, a quadrangle, a hexagon, and an amorphous shape can be adopted as the application shape. The thickness of the coating cannot be decided unconditionally because the required amount of oxygen absorber depends on the amount of oxygen inside the case, but if there is an oxygen barrier film layer, the adhesiveness with the oxygen barrier film layer and the oxygen barrier property Considering the airtightness of the film layer, 5μm-3mm
Is preferred. It is also possible to dilute the mixture of compound and oxygen absorber with a solvent to facilitate the application. As the solvent, hexane, cyclohexane, freon, ether, halogenated hydrocarbons and the like having a low boiling point and being volatile can be preferably used in the sense of retaining the form after coating, but are not particularly limited thereto. Absent. The volume ratio of the embedding resin and the oxygen absorbent is not particularly limited, but the absorbent / resin = 0.2 to
2.0 can be mentioned as a preferable example. However, considering the oxygen absorption capacity and the oxygen absorbent retention, 0.7 to 1.3 is particularly preferable.

(6) Oxygen Absorber Any known oxygen absorber can be used as it is.
For example, ascorbic acid, ascorbate, isoascorbic acid, isoascorbate, gallic acid, gallate, tocopherol, hydroquinone, catechol, resorcin, dibutylhydroxytoluene, dibutylhydroxyanisole, pyrogallol, rongalit, sorbose, glucose, lignin. Such as organic oxygen absorbers, iron powder, activated iron, ferrous oxides, iron-based oxygen absorbers such as iron salts, inorganic oxygen such as sulfites, thiosulfates, dithionates, bisulfites One kind or a mixture of two or more kinds selected from an absorbent, a redox resin, a polymeric oxygen absorbent such as a polymeric metal complex, an oxygen absorbent such as zeolite and activated carbon is appropriately used according to the use conditions. When the oxygen absorbent is in the form of powder, its particle size is not particularly limited, but in general, it is preferably smaller in terms of increasing the surface area. The oxygen absorbent may contain other substances such as a catalyst, a water retention agent and a hydrate in order to control the oxygen absorption capacity. As the oxygen absorbent, one that does not exhibit oxygen absorbing ability under normal atmosphere (room temperature, relative humidity 70% or less) and exhibits oxygen absorbing ability near the dew point is easy to produce and store the laminate of the present invention. It is particularly preferable because it has the advantage of being present, but the present invention is not limited thereto.

(7) Oxygen-barrier film layer The oxygen-barrier film layer is a layer whose main purpose is to shield the oxygen absorber from the air to suppress the reduction (deactivation) of the oxygen absorption capacity during storage. However, it may also have a function of making the oxygen-absorbing laminated sheet easily adhere to the inside of the case. Regarding the former oxygen barrier property, generally, polyvinylidene chloride-coated KOP is used as the oxygen barrier property packaging material.
(Registered trademark) / PE (K-coated polypropylene / polyethylene), KON (registered trademark) / PE (K-coated nylon / polyethylene), KPET (registered trademark) / PE (K
Coated polyester / polyethylene), EVAL (registered trademark), Saranex (registered trademark), OV (registered trademark), films such as Varianlon (registered trademark), aluminum foil / polyethylene, etc. Oxygen transmission rate at 20 to 25 ° C. 1.0 [Ml / m ² · hr · atm] or less can be mentioned, but if the oxygen absorbent has low activity under low humidity or the time from production to installation is short, this condition is not necessarily satisfied. .. Specifically, the oxygen permeation rate at 20 to 25 ° C. is 4000 [ml / m ² · hr · at
There is no particular limitation as long as it is m] or less, but when using an oxygen absorbent which is commonly called a quick-acting type, it is desirable that the oxygen permeation rate is 125 [ml / m ² · hr · atm] or less. .. The thickness of the oxygen barrier film layer is preferably 800 μm or less in consideration of adhesiveness to the oxygen permeable composite film, and is preferably 50 μm or more in consideration of mechanical strength. In addition to the above characteristics, 20 in consideration of oxygen barrier properties, adhesiveness to the back surface of the case, ease of manufacture, etc.
0 to 500 μm is particularly preferable. Regarding the latter adhesiveness, it is sufficient if it has sufficient adhesiveness to integrally bond either the woven or nonwoven fabric layer of the oxygen permeable composite membrane or the oxygen absorber layer and the back surface of the case. The term "adhesiveness" as used herein includes any method capable of adhering a polymer film, such as an adhesive, heating, and ultrasonic waves. Above all, heating and ultrasonic method with less eluate are preferable, but not limited to these. Further, the oxygen barrier film layer can effectively suppress the invasion of oxygen permeating the case body when the case is made of resin.

(8) Form of Laminated Body The laminated body produced in this manner is cut out or punched into a shape corresponding to the shape of the mounting portion of the case to be mounted, and fixed to the inner surface of the case by the above method. Since the size of the mounted laminated body also affects the oxygen absorption amount, the size may be determined as necessary. Further, in the laminate of the present invention, in order to prevent scratches in practical use, the oxygen-permeable homogeneous thin film layer side is protected by a member such as a net, a woven fabric, a non-woven fabric, a porous sheet, and a sponge that does not pose a problem in oxygen permeability. May be.

[0032]

EXAMPLES Examples of the present invention will be described below. The performance of the oxygen permeable composite membrane is as follows: the pressure on the primary side is 2 kg / cm ² , the pressure on the secondary side is 1 kg / cm ² , and the gas (oxygen or nitrogen) permeation rate is set to a precision membrane flowmeter across the composite membrane. S
It measured with F-101 (made by Standard Technology). The oxygen transmission rate Q _O2 is [m ³ / m ² ·
[hr · atm], and used as an index of gas permeability of the oxygen permeable composite membrane. The oxygen / nitrogen permeation rate ratio α of the oxygen permeable composite film was calculated by Q _O2 / Q _N2 and used as the evaluation standard for the homogeneity of the polymer thin film layer contained in the composite film.
In addition, the intrinsic oxygen of the material forming the polymer homogeneous thin film layer
The nitrogen permeation rate ratio α ^* (= P _O2 / P _N2 ) and the oxygen permeation coefficient P _O2 were measured by a decompression method at 25 ° C. using a dense film of a raw material polymer by a gas permeability measuring device manufactured by Yanagimoto Seisakusho.

Example 1 An oxygen-permeable composite membrane (A) having oxygen permeability was prepared by the following method. A 15 wt% dimethylformamide (DMF) solution of polysulfone (Udel-P3500 manufactured by Union Carbide Co., Ltd.) was applied on a polyester non-woven fabric (MF100 manufactured by Japan Vilene Co., Ltd.) having a weight of 50 μm and a basis weight of 100 g / m ² at room temperature. Polysulfone is coagulated by casting and dipping in a coagulation tank filled with water to form a membrane (I) composed of a polysulfone porous layer (porosity 75%) of 200 μm in thickness / polyester nonwoven fabric (130 μm in thickness). Obtained. 0.2 wt% of both-end silanol polydimethylsiloxane (number average molecular weight 30,000 to 50,000),
A 0.1 wt% solution of tetrakis (2-propanone oxime) silane in trichlorotrifluoroethane was coated on the membrane (I) whose surface was only drained, and the coating was performed at 130 ° C. for 10 minutes.
After heat-drying for seconds, it was dried at 100 ° C. for 10 minutes to obtain an oxygen-permeable composite membrane (A) composed of a crosslinked siloxane homogeneous thin film layer (thickness of about 0.1 μm) / polysulfone porous layer / polyester nonwoven fabric. The oxygen permeation rate Q _O2 of this oxygen permeable composite membrane is 6 [m ³ / m ² · hr · atm], the oxygen / nitrogen permeation rate ratio α (= Q _O2 / Q _N2 ) is 2.0, and the water vapor permeation rate is It was 15 [m ³ / m ² · hr · atm]. The intrinsic oxygen / nitrogen permeation rate ratio α ^* of the crosslinked siloxane forming the thin film layer is 2.0 (oxygen permeation coefficient P _O2 is 5 × 10 ^−8).
(cm ³ · cm / cm ² · sec · cmHg), it was confirmed that a uniform thin film layer without defects was formed.

An iron-based oxygen absorbent (Ageless (registered trademark) manufactured by Mitsubishi Gas Chemical Co., Inc.) as an oxygen absorbent under a nitrogen stream
FX type inclusions (2.5 g) and 1-component curing type RTV silicone (KE44 manufactured by Shin-Etsu Chemical Co., Ltd.)
After adding 2.0 g to cyclohexane and mixing well,
This mixture was applied to the polyester nonwoven fabric surface of the oxygen permeable composite membrane (A) and dried. On top of this, a polyethylene sheet (manufactured by Mitsubishi Petrochemical Co., Ltd.) having a thickness of 300 μm as an oxygen barrier film layer was placed at 140 ° C. on the oxygen absorbent coated surface side.
It was fixed by hot pressing for 10 minutes. This laminate sheet was cut into strips according to the size of the mounting portion on the back surface of the case to be mounted, and the surface of the cut laminate sheet on the oxygen barrier film layer side was ultrasonically welded to the back surface of the case. As a result, a sealed case having a transparent part, to which an oxygen permeable layer composed of an oxygen permeable composite film, an oxygen absorber layer in which an oxygen absorbent is embedded in a resin, and a laminate composed of an oxygen barrier film layer is fixed (flower box )was gotten. More detailed laminated structure of this laminate, from the inside of the case, an oxygen-permeable homogeneous thin film layer, an asymmetric type porous layer composed of a dense thin film layer and a porous layer, a support layer composed of a polyester nonwoven fabric,
This is a structure in which an oxygen absorber layer in which an oxygen absorber is embedded in a resin and an oxygen barrier film layer are sequentially laminated. In the obtained flower box, rose flowers are stored as cut flowers,
When the case was sealed and the oxygen concentration in the case was measured, the oxygen concentration, which was about 20% at the beginning, was reduced to 2% or less, and the low oxygen concentration state could be maintained for one month or more. As a result, the viewing period for rose flowers was one month (up to two weeks in the past).

Example 2 In Example 1, as the iron-based oxygen absorbent, AGELESS (registered trademark) S type manufactured by Mitsubishi Gas Chemical Co., Inc. (inclusion 2.
When an experiment was conducted in the same manner except that 5 g) was used, a low oxygen concentration state of 2% or less could be maintained for one month or more, and the rose viewing period could be extended to one month.

Example 3 Polysulfone (Udel-made by Union Carbide Corporation)
15% by weight of P3500) dimethylformamide (DM
F) A non-woven fabric made of polyester fiber having a thickness of 50 μm at room temperature (MF-11 manufactured by Nippon Vilene Co., Ltd.)
0) A film made of a polysulfone porous layer (porosity 75%) / polyester nonwoven fabric (thickness 130 μm) having a thickness of 160 μm, which is cast on the above and is immersed in a coagulation tank filled with water to coagulate polysulfone. (II) was obtained.
An amino-modified polydimethylsiloxane having the structure of the following chemical formula 6 was dissolved in trichlorotrifluoroethane to prepare a 2% by weight polymer solution.

[0037]

[Chemical 6]

Separately, a 1% by weight trichlorotrifluoroethane solution of tolylene diisocyanate / dibutyltin diacetate [= 9/1 (weight ratio)] was prepared. The two liquids were mixed 1: 1 and then diluted with trichlorotrifluoroethane to prepare a dilute solution. A part of this diluted solution was coated on the membrane (II) whose surface was only drained, dried by heating at 130 ° C. for 1 minute, and then dried at room temperature for 1 hour to form a crosslinked siloxane homogeneous thin film layer (thickness: about 0.08 μm). / Polysulfone porous layer /
An oxygen-permeable composite membrane (B) made of a polyester nonwoven fabric was obtained. The oxygen permeation rate Q _O2 of this oxygen-permeable composite membrane is 10
[M ³ / m ² · hr · atm], the oxygen / nitrogen permeation rate ratio α (= Q _O2 / Q _N2 ) is 2.1, and the water vapor permeation rate is 21 [m ³ / m ² · hr · atm]. Met. The intrinsic oxygen / nitrogen permeation rate ratio α ^* of the crosslinked siloxane forming the thin film layer is 2.1 (oxygen permeation coefficient P _O2 is 6 × 10 −8 c).
m ³ · cm / cm ² · sec · cmHg), it was confirmed that a uniform thin film layer without defects was formed.

Other than using the oxygen-permeable composite membrane (B),
A flower box using the laminate of the present invention was prepared and evaluated in the same manner as in Example 1, and it was possible to maintain a low oxygen concentration state of 2% or less for 1 month or more as in Example 1. , The rose viewing period could be extended to one month.

Example 4 Poly (4-methylpentene-1) (manufactured by Mitsui Petrochemical Industry Co., Ltd., TPX) in 250 g of anhydrous xylene under a nitrogen atmosphere.
To a solution of 25 g of RMX-001) heated and dissolved, 50 g of trimethoxyvinylsilane was added, and further 1.25 g of benzoyl peroxide was added, followed by reaction at 110 ° C. for about 4 hours. The polymer obtained was purified by repeating reprecipitation from methanol twice, and then vacuum-dried to perform methoxysilane graft poly (4-methylpentene-1).
Got The silicon content of this graft polymer is 0.
It was 13%. 1 g of synthesized methoxysilane-grafted poly (4-methylpentene-1) and dilauric acid di-n
-Butyltin 10 mg and 200 g cyclohexane were dissolved. This solution was used for the membrane prepared in Example 3 (I
I) Coated on, heat-dried at 140 ° C. for 5 minutes, and then dried at room temperature for 1 hour to form a crosslinked poly (4-methylpentene-1) homogeneous thin film layer (thickness about 0.1 μm) / polysulfone porous layer. An oxygen-permeable composite membrane (C) consisting of a polyester nonwoven fabric was obtained. The oxygen permeation rate Q _O2 of this oxygen-permeable composite membrane is 0.2 [m ³ / m ² · hr · atm], and the oxygen / nitrogen permeation rate ratio α (= Q _O2 / Q _N2 ) is 3.
8. Water vapor transmission rate is 5 [m ³ / m ² · hr · atm]
Met. The intrinsic oxygen / nitrogen permeation rate ratio α ^* of the crosslinked siloxane forming the thin film layer is 4.2 (oxygen permeation coefficient P _O2 is 1.5 × 10 ⁻⁹ cm ³ · cm / cm ² · sec ·
It was confirmed that a uniform thin film layer having no defects was formed.

Other than using the oxygen permeable composite membrane (C),
A flower box using the laminate of the present invention was prepared and evaluated in the same manner as in Example 1, and it was possible to maintain a low oxygen concentration state of 2% or less for 1 month or more as in Example 1. , The rose viewing period could be extended to one month.

[0042]

According to the flower box of the present invention, since the oxygen-absorbing laminate having water resistance is provided inside the transparent hermetically sealed case, the following effects can be obtained. (1) Since the oxygen absorber that has a high oxygen absorption rate and can keep the activity of the oxygen absorber sufficiently high until wearing, keeps the oxygen concentration in the flower box sufficiently low after storing cut flowers. The low oxygen concentration can be maintained for a long period of time, and the ornamental period can be kept sufficiently long to make the flower box for cut flowers highly practical. (2) In particular, since it can exert a sufficient shielding effect against moisture while ensuring high oxygen permeability, it does not permeate the oxygen absorber, and is suitable for cut flowers where moisture is indispensable to obtain an optimal flower box. Be done. (3) Since the moisture does not penetrate into the oxygen absorber, a phenomenon such as an offensive odor is not caused by the reaction between the oxygen absorber and the moisture. (4) Since at least the oxygen absorber layer in which the oxygen absorber is embedded in the resin and the oxygen permeable layer having the asymmetric type porous layer can be formed as a laminate, the production is easy, and a laminated sheet is obtained. Since the formed one can be cut into any size depending on the application, it is easy to miniaturize,
No special installation space is required.

Claims (3)

[Claims] 1. An oxygen absorber layer in which at least an oxygen absorber is embedded in a resin, and an oxygen absorber layer embedded in a resin in a part of the inside of the transparent hermetically sealed case, the oxygen absorber layer being located inside the case, A flower box characterized in that a laminate comprising an oxygen permeable layer having an asymmetric porous layer having a dense thin film layer formed inside the case is fixed. 2. The flower box according to claim 1, wherein the oxygen permeable layer comprises the asymmetric porous layer and a support layer that supports the asymmetric porous layer and is made of either a woven fabric or a non-woven fabric. .. 3. The flower box according to claim 1, wherein the laminated body further has an oxygen barrier film layer between the oxygen absorber layer and the back surface of the case.