CN100518503C - Novel laminates for blocking ethylene response in plants, methods of making or using same - Google Patents

Abstract

The invention discloses a non-woven fabric laminate for blocking ethylene reaction of plants, which comprises at least one layer of thermoplastic composition and at least one layer of non-woven fabric, wherein the thermoplastic composition comprises an agent for blocking ethylene binding sites of plants and a thermoplastic polymer or copolymer. A method of making the nonwoven laminate and a method of inhibiting ethylene response in a plant are also disclosed. The invention further discloses an aluminum foil laminate or corrugated board laminate for inhibiting plant ethylene reaction, which comprises at least one layer of thermoplastic composition and at least one layer of aluminum foil or corrugated board, wherein the thermoplastic composition comprises an agent for inhibiting plant ethylene binding sites and a thermoplastic polymer or copolymer.

Description

Novel laminates for blocking the ethylene response in plants, methods of making or using them

technical field

The present invention relates to a novel laminate for the regulation of plant physiology, in particular for the inhibition of the ethylene response, comprising an inhibitor which has the ability to inhibit the binding sites of ethylene in plants. In particular, the present invention relates to a nonwoven laminate, a method of making the nonwoven laminate, and a method of inhibiting various ethylene reactions by applying the laminate of the present invention.

Background technique

Ethylene is known to cause yellowing of vegetable leaves, fruit ripening and flower decline. Since ethylene is associated with premature maturation of plants, the commercial value of fresh produce is often reduced by excess ethylene gas. Much research has been devoted to the control of ethylene gas for post-harvest preservation of fresh produce.

For example, US Patent No. 5,518,988 discloses the use of cyclopropene and its derivatives, such as 1-methylcyclopropene (1-MCP), as an ethylene binding site blocker. However, 1-MCP is generally unstable due to its high chemical activity. US Patent No. 6,017,849 discloses a method of gas-encapsulating methylcyclopropene with a carrier. Carriers such as alpha-cyclodextrin can be used to stabilize the reactivity and instability of cyclopropene gas, thereby providing a convenient and safe method of storing, transporting, applying or delivering this gas to plants.

Commercial 1-MCP powder products are usually added to water or buffer solutions to release 1-MCP gas into the atmosphere where the agricultural products to be treated are stored. The effective concentration of 1-MCP varies with application time, temperature and method. Generally speaking, in the atmospheric environment around agricultural products, the treatment concentration is between 0.1 and 1.0 million concentration (vol/vol).

Powder products are far more convenient to use than gaseous products, but they are still not conducive to users. It still has the disadvantages of this field with respect to powder handling. PCT Published Patent Application No. WO02/24171 A1 discloses an effervescent lozenge formulation that alleviates the disadvantages of the mixing process associated with the powder form. This tablet form product is easier to measure and has a controlled release mechanism not possible with powder form formulations. The lozenge is user-friendly for non-technical consumers, florists and wholesalers compared to powdered products.

However, like powders, lozenges still have their application limitations, as air circulation is usually required to ensure uniform distribution of the active agent, which is sometimes not possible in field situations. The non-uniform concentration of 1-MCP in the atmospheric environment will cause non-uniform ripening reactions, which will detract from its commercial application benefits. Therefore, the present invention is based on a completely novel concept, creating a novel laminate to solve this problem, which not only allows the uniform delivery of 1-MCP to plants, but also The novel laminate is even more user friendly. The present invention provides a major improvement to post-harvest preservation technology that could not be realized before the present invention came into the market.

Contents of the invention

Therefore, the object of the present invention is to provide a non-woven fabric laminate for hindering plant ethylene reaction, which comprises at least one layer of thermoplastic composition and at least one layer of non-woven fabric, wherein the thermoplastic composition comprises hindering plant ethylene binding sites pharmaceuticals and thermoplastic polymers or copolymers.

Another object of the present invention is to provide a process for preparing the nonwoven laminates of the present invention.

A further object of the present invention is to provide a method for inhibiting ethylene response in plants.

The object of the present invention is also to provide an aluminum foil laminate or corrugated board laminate for hindering plant ethylene reaction, which comprises at least one layer of thermoplastic composition and at least one layer of aluminum foil or corrugated board, wherein the thermoplastic composition comprises Agents and thermoplastic polymers or copolymers that block ethylene binding sites in plants.

Description of drawings

Figure 1 shows the structure of a multilayer laminate according to the invention.

Symbolic meaning

1 Non-woven fabric

2 Moisture semi-permeable membrane

3 1-MCP-releasing laminates

4 Moisture evaporated from agricultural products

Detailed ways

The present invention provides a nonwoven fabric laminate comprising at least one layer of thermoplastic composition and at least one layer of nonwoven fabric, wherein the thermoplastic composition comprises an agent (ie, an ethylene blocker) that blocks ethylene binding sites in plants and a thermoplastic polymer or copolymer.

According to the present invention, ethylene inhibitors used to block ethylene binding sites in plants include all compounds conventionally used to inhibit ethylene responses in plants such as, but not limited to, cyclopropene, 1-methyl-cyclopropene (1-MCP), 3,3 - Dimethylcyclopropane, methylenecyclopropane, diazocyclohexadiene, trans-cyclooctene, cis-cyclooctene, 2,5-protobornadiene, derivatives thereof and mixtures thereof. Related background art, such as U.S. Patent Nos. 3,879,188, 5,100,462, 5,518,988, and 6,017,849, and Plant Growth Reg.9 by Sisler et al., 157-164, 1990 are fully incorporated herein in the manner already mentioned in the manual. A preferred agent to block ethylene binding sites in plants is 1-methylcyclopropene (1-MCP).

Many thermoplastic polymers or copolymers are suitable for use in the present invention, including, but not limited to, generally solid-state oxyalkanoyl polymers or dialkanoyl polymers, optionally blended with polyvinyl alcohol or starch polymers. olefin-based polymers, including the most common ethylene- or propylene-based polymers, such as polyethylene and polypropylene; and olefin-based copolymers, such as Ethylene-vinyl acetate (EVA), ethylene-methyl acrylate (EMA), and ethylene acrylic acid (EAA); and copolymers of the foregoing polyolefins.

The ethylene blocker releasable thermoplastic composition of the present invention comprises a thermoplastic polymer or copolymer and an ethylene blocker, such as 1-MCP commercially encapsulated in any powder form. The weight ratio of the polymer or copolymer to the ethylene blocker is between 2000:1 and 1:1, preferably between 100:1 and 1:1, more preferably between 20:1 and 1:1 between.

The thermoplastic composition of the present invention may further comprise fillers for conventional tablet or powder forms. Suitable additional fillers include, but are not limited to, antimicrobial agents, polymeric absorbents, polyglucosamine, dextrins, clays, and montmorillonites.

The non-woven fabric used in the present invention is any non-woven fabric generally used by those skilled in the art. Suitable nonwovens include, but are not limited to, fibers of polyethylene, polypropylene, polyester, rayon, cellulose, and nylon, and blends of such fibers. The term "nonwoven" as used herein is used to generally define a planar structure that is relatively flat, elastic, porous, and composed of short or continuous filaments. In the present invention, the weight of the nonwoven fabric used should depend on the actual application. Preferably, the weight of the non-woven fabric used in the present invention is between 20 and 300 g/m2, preferably between 30 and 150 g/m2.

The basis weight of the nonwoven laminates of the present invention will depend upon the desired dosage of ethylene blocker for the treatment. Generally, the layer of thermoplastic composition releasable with ethylene blocker applied to the nonwoven layer has a basis weight of about 7 to 50 grams/square meter, preferably about 10 to 35 grams/square meter.

The main advantages of the novel nonwoven laminate of the present invention are that it provides an ethylene blocker that can block ethylene binding sites in plants, and that it is flexible and easy to apply. The novel nonwoven laminates of the present invention alleviate the disadvantages of the mixing process associated with powder formats, as well as the limitations associated with tablet formats.

The present invention further provides a process for preparing the novel nonwoven laminates of the present invention comprising bonding a layer of a thermoplastic composition to a nonwoven layer, wherein the thermoplastic composition comprises an agent that blocks ethylene binding sites in plants and a thermoplastic polymer compounds or copolymers.

Methods of bonding thermoplastic layers to nonwoven layers have been known for some time. Additionally, methods of bonding thermoplastic layers to nonwovens by fusion bonding or extrusion lamination are also known to those skilled in the art. However, no one has tried to apply the above concept to the field of post-harvest preservation technology for agricultural products.

Broadly speaking, any method can be used to manufacture the nonwoven fabric laminate of the present invention, and the method capable of forming the laminate in an integrated form is not particularly limited. For example, a layer of a thermoplastic composition of the present invention comprising a thermoplastic polymer or copolymer and an ethylene blocker may be bonded to a nonwoven layer by melt-bonding lamination or extrusion lamination.

The present invention further provides a method of using the nonwoven fabric laminate of the present invention to inhibit the ethylene response of plants. For example, the novel nonwoven laminate of the present invention may be cut to size for use as a cover sheet for fruits or vegetables stored in containers, or alternatively, the nonwoven laminate of the present invention may be The edges of the bags are joined together to form a bag for storing fruits and vegetables. In such a container or bag, moisture evaporating from the produce causes the ethylene blocker to be released as a gas from the nonwoven laminate of the present invention.

According to the present invention, the nonwoven fabric laminate can be extended to a multilayer structure comprising more than one layer of the thermoplastic composition releasable with an ethylene blocker and more than one layer of the nonwoven fabric. The order and configuration of layers in a multi-layer structure should depend on the actual use case. Preferably, layers of thermoplastic composition releasable ethylene blocker and layers of nonwoven fabric are alternately arranged in a multilayer structure.

The nonwoven laminates of the present invention may contain additional moisture semipermeable membranes for regulating the release of moisture from the produce. In this embodiment, the moisture semi-permeable membrane is located on the outermost layer of the laminate facing the storage of agricultural products during actual use. Typical moisture vapor permeable membranes include, but are not limited to, urethane, polyamide, polyester, and nylon, and blends of these hydrophilic polymers.

In another aspect of the invention, the concept of nonwoven laminates can be applied to laminates with aluminum foil, corrugated cardboard, or other suitable substrate materials, or any other combination thereof. The layers of aluminum foil or corrugated cardboard can be laminated with a thermoplastic polymer or copolymer and an ethylene blocker by any method known to those skilled in the art, such as by fusion bonding or extrusion lamination. Thermoplastic composition layer bonding.

Thus, the present invention further provides an aluminum foil laminate for blocking ethylene reactions in plants, comprising at least one layer of a thermoplastic composition and at least one layer of aluminum foil, wherein the thermoplastic composition contains an agent that blocks ethylene binding sites in plants and a thermoplastic polymer compounds or copolymers.

The present invention also provides a corrugated cardboard laminate for blocking ethylene reaction in plants, comprising at least one layer of thermoplastic composition and at least one layer of corrugated cardboard, wherein the thermoplastic composition contains an agent for blocking ethylene binding sites in plants and a thermoplastic polymer compounds or copolymers.

According to the present invention, the term "plant" includes, in addition to woody plants, field crops, potted plants, cut flowers, harvested fruits, vegetables and ornamental plants.

Plants that are treated with the nonwoven laminates of the present invention to inhibit the ethylene response must be treated in non-phytotoxic amounts. This phytotoxic amount varies not only with the plant, but also with the cultivated plant variety.

According to the present invention, many ethylene reactions can be prevented as disclosed in US Patent Nos. 5,518,988 and 3,879,188. Ethylene reactions can be initiated by exogenous or endogenous ethylene sources. Ethylene responses include, for example, ripening and/or senescence of flowers, fruits, and vegetables; abscission of leaves, flowers, and fruit; ripening and/or shortening of lifespan in ornamentals such as potted plants, cut flowers, shrubs, and dormant seedlings; inhibition of some plant Such as the growth of peas; and stimulate the growth of some plants such as rice.

According to the present invention, plants that can be treated to inhibit senescence include green leafy vegetables, such as lettuce (e.g., Lactuea sativa), spinach (Spinaca oleracea) and cabbage (Brassica oleracea); various rhizomes, such as potato (Solanum tuberosum) , carrots (Daucus); bulbs, such as onions (Allium sp.); spice plants, such as basil (Ocimum basilicum), oregano (Origanum vulgare), and dill (Anethum graveolens); and soybeans (Glycinemax), Lima Beans (Phaseolus limensis), peas (Lathyrus sp.), maize (Zeamays), broccoli (Brassica oleracea italica), cauliflower (Brassica olefaceabotrytis) and stone cypress (Asparagus officinalis).

According to the present invention, fruits that may be treated to inhibit their ripening include tomato (Lycopersicon esculentum), apple (Malus domes tica), banana (Musasapientum), pear (Pyrus communis), papaya (Carica papya), mango (Mangiferaindica), peach (Prunus persica), Apricot (Prunus armeniaca), Nectarine (Prunuspersica nectarina), Orange (Citrus sp.), Lemon (Citrus limonia), Lime (Citrus aurantifolia), Grapefruit (Citrus paradisi), Orange (Citrus nobilis deliciosa) ), kiwi (Actinidia. ursinus), blueberries (Vaccinium sp.), green beans (Phaseolus vulgaris), members of the melon genus such as cucumbers (C. sativus) and avocados (Persea Americana).

According to the present invention, ornamentals that may be treated to inhibit senescence and/or prolong flowering and appearance (eg, delayed wilting) include potted ornamentals and cut flowers. Potted ornamental plants and cut flowers that can be processed by the method of the present invention include Rhododendron spp.; Macrophylla hydrangea, Hibiscus rosasanensis, Antirrhinum sp., Euphorbia pulcherima , cactus (e.g., Cactaceaeschlumbergera truncata), begonia (Begonia sp.), rose (Rosa sp.), tulip (Tulipa sp.), daffodil (Narcissus sp.), morning glory (Petunia hybrida), carnation (Dianthus caryophyllus ), lily (such as Lilium sp.), gladiolus (Gladiolus sp.), lily narcissus (Alstroemaria brasiliensis), anemone (such as Anemone bland), columbine (Aquilegia sp.); , Violet (such as Aster carolinianus), Jiuzhong (Bougainvillea sp.), Camellia (Camellia sp.), Campanula (Campanula sp.), Celosia (Celosia sp.), Cypress (Chamaecyparis sp.), Chrysanthemum ( Chrysanthemum sp.), clematis (Clematis sp.), primrose (Cyclamen sp.), freesia (e.g., Freesia refracta); and orchids of the family Orchidaceae.

According to the present invention, plants that can be treated to inhibit the removal of leaves, flowers and fruits include cotton (Gossypium spp.), apple, pear, cherry (Prunus avium), walnut (Carvaillinoensis), grape (Vitis vinifera), olive ( For example, dormant seedlings of Olea europaea), coffee (Coffeaarabica), bean (Phaseolus vulgaris) and weeping fig (Ficusbenjamina) and many fruit trees including apples, ornamental plants, shrubs and tree seedlings.

In addition, according to the present invention, shrubs that can be treated to inhibit leaf loss include Ligustrum sp., Photina sp., Ilex sp., ferns of the family Water Keelaceae, Schefflera sp. sp.), Dieffenbachia (Aglaonema sp.), Cotoneaster sp., Barberry (Berberris sp.), Bayberry (Myrica sp.), Abelia sp., Gum Arabic (Acacia sp.) , and pineapple (Bromeliades) of the family Bromeliaceae.

Without further elaboration, one skilled in the art can, using the above disclosure and the following examples, utilize the present invention to its fullest extent. The following examples are provided only to illustrate how a person familiar with the art can operate the method of the patent application, but in no way limit the rest of the disclosure.

Example 1: Manufacturing method

A powder blend of ethylene-vinyl acetate (EVA) and 1-methylcyclopropene having the following composition was laminated to a nonwoven.

57% ethylene-vinyl acetate

利统股份有限公司，台北，台湾，中华民国)(

 from Lytone Enterprise，Inc.Taipei，Taiwan，ROC)38% 1-methylcyclopropene powder (

Lee Tung Co., Ltd., Taipei, Taiwan, Republic of China) (

from Lytone Enterprise, Inc. Taipei, Taiwan, ROC)

5% sodium polyacrylate (a polymeric absorbent)

Using a hot-melt laminator, a non-woven fabric (polyethylene+rayon) of 50 g/m2 was laminated with the above-mentioned 1-MCP-releasing composition by hot-melt bonding. The thermoplastic coating substance powder is applied to the nonwoven using a spreading device throughout the working area of the nonwoven. The amount of powder added per unit surface area can be determined by the speed of rotation of the dosing roller. In this example, the aforementioned releasable 1-MCP substance was laminated to the nonwoven fabric in an amount of 12 g/m2.

Example 2: Release of 1-MCP from nonwoven laminates

The 1-MCP release properties of the 1-MCP releasable nonwoven laminate were measured by the following steps:

A laminate with a size of 10 cm×10 cm was placed in the room, water was sprayed on the surface of the laminate, and the concentration of 1-MCP was analyzed by gas chromatography (GC).

Table 1 shows the evolution of 1-MCP release from nonwoven laminates. It is clearly seen that the application of water to the surface of the 1-MCP releasable nonwoven laminate easily and rapidly results in the release of 1-MCP. Furthermore, even though the laminate had initially released 5% of 1-MCP, at 5 minutes, 70% of the active ingredient had been released.

Table 1

Example 3: Application

Bananas were harvested at 80% ripeness to evaluate the performance of the 1-MCP releasable nonwoven laminates of the present invention. The 1-MCP releasable non-woven laminate was cut to a size of 20 cm x 20 cm to serve as a cover sheet for the fruit.

In the experiment, the experimental group and the control group used three bunches of fruit (each bunch contains 4 to 5 pieces) for treatment. Each treatment was stored at room temperature in a closed container (relative humidity: 90 to 95%) with a volume of 36 liters for 24 hours, and then removed for quality observation.

The results show that treatment with the 1-MCP releasable cover sheet can extend the shelf life to 14 to 17 days, compared to the 7 to 9 day storage life of the control group without the 1-MCP releasable cover sheet of the present invention , longer.

Example Four: Multilayer Laminates

The multilayer laminate structure according to FIG. 1 is composed of a nonwoven fabric 1 according to the invention, a moisture vapor semipermeable membrane 2 and a 1-MCP releasable laminate 3 . Among them, the non-woven fabric 1 and the laminate 3 capable of releasing 1-MCP were prepared according to the method of Example 1. Moisture semi-permeable membrane 2 (10 g/m2) is made of urethane and coated on the outermost layer to regulate moisture 4 evaporated from agricultural products.

Use an air-permitting drum to bring all the materials together. The air temperature was 170°C.

Claims (27)

1. nonwoven layer compound that is used for counteracting ethylene response in plants, it comprises one deck thermoplastic compounds and layer of non-woven fabric at least at least, and wherein this thermoplastic compounds comprises medicament and thermoplastic polymer or the copolymer that hinders ethylene binding site in plants.

2. laminated thing according to claim 1, wherein the medicament of this obstruction ethylene binding site in plants is selected from by cyclopropylene, 1-methyl-cyclopropylene, 3,3-dimethylcyclopropane, methylene cyclopropane, diazonium cyclohexadiene, anti--cyclo-octene, suitable-cyclo-octene, 2, the set that 5-norbornadiene, its derivative and composition thereof are formed.

3. laminated thing according to claim 2, wherein the medicament of this obstruction ethylene binding site in plants is 1-methyl-cyclopropylene.

4. laminated thing according to claim 1, wherein this thermoplastic polymer is selected from by oxygen alkanoyl polymer and dioxane polymeric diacyl and the set formed based on the polymer of alkene.

5. laminated thing according to claim 4, wherein said oxygen alkanoyl polymer and dioxane polymeric diacyl are with polyvinyl alcohol or starch polymer blending.

6. laminated thing according to claim 4 should be the polymer of ethylidene or propylidene based on the polymer of alkene wherein.

7. laminated thing according to claim 6 should be polyethylene and polypropylene based on the polymer of alkene wherein.

8. laminated thing according to claim 1, wherein this thermoplastic copolymer is to be selected from by ethane-acetic acid ethyenyl ester, ethylene-methyl acrylate, ethylene acrylic to reach the set of being formed based on the copolymer of alkene.

9. laminated thing according to claim 1, wherein the weight ratio of the medicament of this thermoplastic polymer or copolymer and this obstruction ethylene binding site in plants is between between the 2000:1 to 1:1.

10. laminated thing according to claim 9, wherein this thermoplastic polymer or copolymer and this weight ratio that hinders the medicament of ethylene binding site in plants are between between the 100:1 to 1:1.

11. laminated thing according to claim 10, wherein this thermoplastic polymer or copolymer and this weight ratio that hinders the medicament of ethylene binding site in plants are between between the 20:1 to 1:1.

12. laminated thing according to claim 1, wherein this thermoplastic compounds further comprises the filler that is selected from the set of being made up of antibacterial agent, polymerism absorbent, poly-grape amine sugar, dextrin, clay and imvite.

13. laminated thing according to claim 1, wherein this nonwoven comprises the fiber that is selected from the set of being made up of polyethylene, polypropylene, polyester, rayon, cellulose, nylon and admixture thereof.

14. laminated thing according to claim 13, wherein this nonwoven is made up of short fiber.

15. laminated thing according to claim 13, wherein this nonwoven is made up of continuous fibril.

16. laminated thing according to claim 1, wherein put on this nonwoven layer this thermoplastic compounds layer basis weight between 7 to 50 the gram/square metre between.

17. laminated thing according to claim 16, wherein put on this nonwoven layer this thermoplastic compounds layer basis weight system between 10 to 35 grams/square metre between.

18. laminated thing according to claim 1, wherein the basis weight of this nonwoven layer between 20 to 300 the gram/square metre between.

19. laminated thing according to claim 18, wherein the basis weight of this nonwoven layer between 30 to 150 the gram/square metre between.

20. laminated thing according to claim 1, the medicament that wherein should hinder ethylene binding site in plants is to discharge with gas form.

21. laminated thing according to claim 1, it is a sandwich construction, and this thermoplastic compounds layer and this nonwoven layer that wherein can discharge the ethene Inhibitors are interconnected in sandwich construction.

22. laminated thing according to claim 1, it further comprises a moisture semipermeable membrane, and it is positioned at the outermost layer of this laminated thing.

23. laminated thing according to claim 22, wherein this moisture semipermeable membrane is selected from the set of being made up of amine Ethyl formate, polyamide, polyester, nylon and admixture thereof.

24. method for preparing the nonwoven layer compound that is used for counteracting ethylene response in plants, it comprises a thermoplastic compounds layer is bonded to a nonwoven layer that wherein this thermoplastic compounds comprises medicament and thermoplastic polymer or the copolymer that hinders ethylene binding site in plants.

25. method according to claim 24, wherein this thermoplastic compounds layer is bonded to this nonwoven layer for cohering laminated mode by fusion.

26. method according to claim 24, wherein this thermoplastic compounds layer is for to be bonded to this nonwoven layer by the extrusion lamination mode.

27. a method that suppresses ethylene response in plants, it comprises use nonwoven layer compound according to claim 1.