WO2024010072A2

WO2024010072A2 - Ornamental plant production method and ornamental plant

Info

Publication number: WO2024010072A2
Application number: PCT/JP2023/025178
Authority: WO
Inventors: 美和子堺
Original assignee: 美和子堺
Priority date: 2022-07-08
Filing date: 2023-07-06
Publication date: 2024-01-11
Also published as: WO2024010072A3

Abstract

An ornamental plant production method according to the present invention comprises a drying step for drying a plant and a film formation step for forming a film of a resin composition on the surface of the dried plant. The resin composition is a coating material consisting of a prepolymer solution that is composed of a (E) polyurethane resin and has active isocyanate terminal groups, said (E) polyurethane resin being obtained by reacting a (A) polyol component and a (B) polyisocyanate component in a (D) solvent in the presence of a (C) catalyst. The (A) polyol component is a liquid carbonate polyol having two functional groups and a number average molecular weight of 2,000-3,000, and has active hydroxyl terminal groups. The (B) polyisocyanate component is an alicyclic polyisocyanate having two functional groups, and has isocyanate terminal groups. The hydroxyl equivalent (OH) of the (A) polyol component is less than the isocyanate equivalent (NCO) of the (B) polyisocyanate component. In the film formation step, a film of the (E) coating material is formed on the surface of the dried plant, and reacts with water vapor in the air to form urea bonds.

Description

Ornamental plant manufacturing method and ornamental plants

The present invention relates to a method for producing an ornamental plant and an ornamental plant.

Patent Document 1 describes a step of putting a plant into a container, a step of putting into the container a ceramic body obtained by applying silica gel, shirasu, and glaze to a spherical ceramic and a desiccant containing oil, and a step of putting the entire container into the container. A method for producing a dried ornamental plant is disclosed, which includes the step of drying at 27 to 32°C.

Patent No. 5564142

By the way, in order to extend the period during which ornamental plants such as flowers and leaves can be admired, the ornamental plants are sometimes subjected to a drying treatment to produce so-called dried flowers. However, as dried ornamental plants dry, their flexibility decreases, and for example, they tend to break when subjected to external pressure.　

Therefore, the present invention aims to suppress damage to dried ornamental plants.

For this purpose, the technology disclosed herein includes a drying step of drying a plant, and a film forming step of forming a film of a resin composition on the surface of the dried plant. In the resin composition, (A) the polyol component is a liquid carbonate polyol having a functional group number of 2 and a number average molecular weight of 2,000 to 3,000, and has an active hydroxy group at the terminal, and (B) The polyisocyanate component is an alicyclic polyisocyanate having two functional groups and has an isocyanate group at the terminal, and the hydroxyl equivalent (OH) of the polyol component (A) is equal to that of the polyisocyanate component (B). The polyol component of (A) and the polyisocyanate component of (B) are reacted in the presence of (C) a catalyst (D) in a solvent (E) This is a prepolymer solution paint composed of polyurethane resin and having active isocyanate groups at the end. In the film forming step, a film of the paint (E) is formed on the surface of the dried plant, and the paint is exposed to air. This is a method for producing ornamental plants in which a urea bond is formed by reacting with water vapor.　

Here, the equivalent ratio (NCO/OH) between the hydroxyl equivalent (OH) of the polyol component (A) and the isocyanate equivalent (NCO) of the polyisocyanate component (B) is 1.95 to 2.5. Good. Furthermore, the alicyclic polyisocyanate is preferably methylene bis(4,1-cyclohexylene) diisocyanate or isophorone diisocyanate. Further, the film of the resin composition has a tensile stress at 100% elongation of 1.0 to 1.1 MPa, a tensile elongation at break of 1,000% or more, and a tensile strength at break of 17.6 to 18.7 MPa. It would be good if it were. Furthermore, it is preferable that the paint (E) be dry to the touch within 30 seconds after forming a film of the paint on the dried plant. Further, the solvent (D) is preferably an ethyl acetate solvent, and the resin concentration of the paint used in the touch drying step is preferably 5 to 10%. Further, the step of drying to the touch is performed by placing the dried plants on an absorbent body that absorbs the paint of (E), and after the step of drying to the touch, the dried plants are hung to absorb the paint. It is advisable to further dry the membrane. It is also preferable that the plant is provided with a flower receptacle, and that the frozen plant is vacuum-dried in the drying step. Furthermore, it is preferable that the plant is dried in the drying step without being pressed into a flat shape after being harvested.　

From another perspective, the technology disclosed in this specification includes a drying step of freezing and vacuum drying a plant provided with flower receptacles, and a film forming step of forming a film of a resin composition on the surface of the dried plant. and, in the resin composition, (A) the polyol component is a liquid carbonate polyol having a functional group number of 2, a molecular weight of 2,000 to 3,000, and an active hydroxyl group at the end, and (B) a polyol component. The isocyanate component is methylene bis(4,1-cyclohexylene) diisocyanate or isophorone diisocyanate having two functional groups and an isocyanate group at the terminal, and the hydroxyl equivalent (OH) of the polyol component (A) and the polyol component (B) are The equivalent ratio (NCO/OH) of the isocyanate component to the isocyanate equivalent (NCO) is 1.95 to 2.5, and the polyol component of (A) and the polyisocyanate component of (B) are combined into (C) It is a coating of a prepolymer solution having an active isocyanate group at the end, which is composed of (E) a polyurethane resin reacted in (D) an ethyl acetate solvent in the presence of a catalyst, and in the film forming step, the drying A film of the paint of (E) is formed on the surface of the dried plant, and is reacted with water vapor in the air to form a urea bond, and the paint of (E) forms the film on the dried plant. The film of the resin composition is dry to the touch within 30 seconds after being applied, and the film of the resin composition has a 100% elongation tensile stress of 1.0 to 1.1 MPa, and a tensile elongation at break of 1,000% or more. This is a method for producing an ornamental plant having a tensile strength at break of 17.6 to 18.7 MPa.　

Viewed from another perspective, the technology disclosed herein is an ornamental plant produced by the above production method.　

Viewed from yet another perspective, the technology disclosed herein includes a dried plant and a film of a resin composition formed on the surface of the plant, and the film of the resin composition has a It is an ornamental plant having a % elongation tensile stress of 1.0 to 1.1 MPa, a tensile elongation at break of 1,000% or more, and a tensile strength at break of 17.6 to 18.7 MPa.

According to the present invention, damage to dried ornamental plants can be suppressed.

FIG. 1 is a schematic configuration diagram of a dried flower to which this embodiment is applied. It is a figure showing the manufacturing process of dried flowers. (A) is a flowchart showing a manufacturing process of dried flowers, and (B) is a flowchart showing another manufacturing process of dried flowers.

Embodiments of the present invention will be described below with reference to the accompanying drawings. <Dried Flower 10> FIG. 1 is a schematic configuration diagram of a dried flower 10 to which this embodiment is applied. As shown in FIGS. 1A and 1B, the dried flower 10 includes a plant body 20 and a resin film 30 that is a protective layer formed on the surface of the plant body 20.　

The plant body 20 is not particularly limited as long as it is a plant that can be subjected to drying treatment or resin forming treatment, which will be described later. For example, the plant body 20 is an ornamental plant such as a rose, a carnation, a viola, a snapdragon, a julienne, a pentus denfare (orchid), a dianthus (diana), a cherry blossom, a cosmos, a carrot leaf, a basil, or a chervil. The plant body 20 has a stem 11, a leaf blade 13, petals 15, a flower receptacle 17, and a calyx 19.　

Note that the plant body 20 in the illustrated example is a rose. Here, dried flowers refer to ornamental plants that have been subjected to drying treatment. For example, the moisture content of the plant body 20 is, for example, 20% or less, preferably 10% or less, and more preferably 5% or less. Additionally, dried flowers include not only petals and leaf blades, but also dried stems, fruits, and the like.　

Moreover, the plant body 20 has a three-dimensional shape. In other words, the plant body 20 is not a so-called pressed flower. Here, pressed flowers are harvested flowers and leaves that are pressed into a flat shape and dried. In addition, the plant body 20 is manufactured without being pressed into a flat shape from the harvested state.　

Here, since dried flowers such as the plant body 20 have been subjected to a drying process, they are easily damaged when subjected to external pressure. Therefore, in the past, dried flowers were sometimes reinforced by applying resin or the like to the surface of the dried flowers. However, when the resin is applied, a so-called shine or luster occurs, and the appearance of the dried flowers becomes different from the natural texture before the resin is applied. To explain further, if the entire resin is formed thickly in a thin part such as a flower petal, gloss may occur and the appearance may differ from the natural finish.　

In addition, even if ornamental plants are dried in a form similar to fresh flowers while retaining their flexibility, for example by freeze-drying (freeze-drying), the ornamental plants can be dried along with the resin by applying a highly rigid resin. There were times when it became easy to crumble (become brittle).　

In this embodiment, the thickness of the resin film 30 can be suppressed by using a resin liquid to be described later. As a result, even when the resin film 30 is formed on the surface of the plant body 20, gloss is suppressed, and an ornamental plant with a natural-looking finish can be formed.　

Further, the illustrated resin film 30 is flexible. Therefore, even with the resin film 30 formed, deformation of the plant body 20 can be allowed, and it is possible to suppress deformation and cracking of the dried flower 10. In other words, in this embodiment, the durability of the dried flowers 10 is improved, and the dried flowers 10 can be made to last for a long time.　

Further, by forming the resin film 30, the dried flowers 10 can be made to last for a long time even when the dried flowers 10 are displayed in a humid environment, for example. Further, since the resin film 30 reflects light such as ultraviolet rays, it becomes possible to maintain bright colors for a long period of time.　

Furthermore, in this embodiment, by forming the resin film 30 on the surface of the plant body 20, it is possible to suppress a portion of the dried flower 10, that is, a petal or a leaf blade, from falling.　

Further, in this embodiment, the deformable resin film 30 can be formed on the surface of the plant body 20. This can prevent the dried flowers 10 from collapsing even when external force is applied.　

Further, in this embodiment, the resin film 30 is formed on the surface of the plant body 20 in a shape corresponding to the irregularities of the plant body 20. In other words, the resin film 30 is formed to smooth the surface of the plant body 20. To explain further, as shown in FIG. 1(B), the resin film 30 is formed in a thick film part 31 formed in the concave part 18 of the plant body 20 and a thick film part 31 formed in the convex part 16 of the plant body 20. It has a thin film portion 33 with a small thickness. By having different thicknesses of the resin film 30, generation of gloss due to the resin film 30 can be suppressed.　

<Manufacturing process of dried flower 10> FIG. 2 is a diagram showing a manufacturing process of dried flower 10. Next, the manufacturing process of the dried flower 10 will be explained with reference to FIG. 2. As shown in FIGS. 2(A) to 2(D), in this manufacturing process, drying treatment, dipping treatment, temporary drying treatment, and main drying treatment are performed. Here, the dipping treatment, temporary drying treatment, and main drying treatment are resin forming treatments that form the resin film 30 on the surface of the plant body 20.　

First, as shown in FIG. 2(A), the plant body 20 is dried. In the illustrated drying process, the plant body 20 and the desiccant 4 are placed in the drying container 3, and the plant body 20 is dried. To explain further, a predetermined amount of desiccant 4 is placed at the bottom of the drying container 3, for example. Then, the plant body 20 is placed on the desiccant 4, and the desiccant 4 is further added into the drying container 3. As a result, the outer periphery of the plant body 20 is covered with the desiccant 4. In this state, the plant body 20 is dried over a predetermined period (for example, 3 days to 1 week). Note that the drying container 3 may be placed in a dryer to control the drying of the plant body 20. There is no particular limitation on the type of desiccant 4 that can be used in this embodiment, but examples include silica gel, calcium chloride, and magnesium chloride.　

Next, as shown in FIG. 2(B), a resin film 30 is formed on the surface of the dried plant body 20. To explain further, the dried plant body 20 is immersed in a resin liquid 6 (described later) contained in a resin container 5. The time for immersing the plant body 20 in the resin liquid 6 may be any length that allows the resin liquid 6 to adhere to the entire surface of the plant body 20. The immersion time is, for example, 1 second to 60 seconds.

Next, as shown in FIG. 2(C), the resin liquid 6 adhering to the plant body 20 is temporarily dried. To explain further, the plant body 20 with the resin liquid 6 adhered to its entire surface is placed on a nonwoven fabric 7 that is an absorbent body. The temporary drying time may be long enough for the resin liquid 6 attached to the plant body 20 to be dry to the touch. The temporary drying time is, for example, 3 seconds to 3 hours. Note that drying to the touch refers to touching the surface of the resin liquid 6 (resin film 30) adhering to the plant body 20 with a fingertip so that the resin liquid 6 does not stick to the fingertip. Further, by temporarily drying on the nonwoven fabric 7, formation of an excessive resin film 30 on the plant body 20 is suppressed. To explain further, for example, formation of a pool of the resin liquid 6 on the lower side of the plant body 20 and formation of an excessive resin film 30 on the plant body 20 is suppressed.　

Next, as shown in FIG. 2(D), the resin liquid 6 adhering to the plant body 20 is dried. To explain further, the plant body 20 with the resin liquid 6 adhered to its entire surface is suspended by the hanging tool 9. The main drying time may be long enough for the resin liquid 6 attached to the plant body 20 to be completely dried. The main drying time is, for example, 2 hours to 5 days. Note that main drying refers to pressing the surface of the resin liquid 6 (resin film 30) with a fingertip to make it free from fingerprints. In other words, main drying is a process for bringing the resin of the resin film 30 into a more stable state than drying to the touch.　

Now, when performing decorations using the dried flowers 10, etc., it is preferable to perform the main drying process to stabilize the resin film 30. For example, by performing the main drying process for 24 hours, damage to the dried flowers 10 is suppressed. Further, for example, by performing the main drying treatment for 24 hours, the odor of the resin liquid 6 can be reduced.　

Furthermore, as shown in FIG. 2(D), the posture in which the plant body 20 is hung by the hanging tool 9 in the main drying process is such that the plant body 20 is in the opposite growth state in the vertical direction, that is, the petals 15 are on the lower side. Place it like this. This makes it easier for the excess resin film 30 adhering to the plant body 20 to fall from the plant body 20. Moreover, it becomes possible to make the thickness of the resin film 30 formed on the plant body 20 uniform.　

In the manufacturing process (manufacturing method) of a dried ornamental plant in the present embodiment, the plant body 20 such as a flower is dried, and an ornamental plant such as a dried flower can be manufactured. Here, the method of disposing the resin liquid 6 on the surface of the plant body 20 may be other methods such as spraying or hand painting. Note that by immersing the entire plant body 20 in the resin liquid 6 as shown in FIG. 2(B), it is possible to suppress the occurrence of uncoated resin liquid 6 and unevenness in the film thickness of the resin liquid 6.　

<Other manufacturing steps for the dried flower 10> FIG. 3(A) is a flowchart showing the manufacturing process for the dried flower 10, and FIG. 3(B) is a flowchart showing another manufacturing step for the dried flower 10.　

Although it has been explained above that drying treatment, dipping treatment, temporary drying treatment, and main drying treatment are performed, the present invention is not limited thereto. For example, some of these processes may be omitted. To explain further, for example, an embodiment may be adopted in which either the temporary drying process or the main drying process is omitted. Moreover, in the drying process, a well-known drying process method such as a hanging method, dry-in-water method, freeze-vacuum drying, vacuum drying, or hot air drying may be used.　

Below, an example of another manufacturing process for the dried flower 10 will be explained with reference to FIGS. 2 and 3. First, in the dried flower 10 manufacturing process explained with reference to FIG. 2 above, as shown in FIG. ) and the main drying process (S304) are performed in this order.　

On the other hand, in the other manufacturing process shown in FIG. 3(B), the following processing is performed. Specifically, first, the plant body 20 is subjected to a drying process (S311). In this drying process, a desiccant 4 (see FIG. 2(A)) is used. The plant body 20 dried by the desiccant 4 is then frozen by a freezing device (not shown) (S312). Then, the frozen plant body 20 is vacuum dried by a vacuum drying device (not shown) (S313). That is, in this manufacturing process, the plant body 20 is dried in two stages: a drying process using the desiccant 4 and a freeze-vacuum drying process.　

Next, the plant body 20 that has been vacuum dried is subjected to a dipping treatment (S314). In this immersion process, the plant body 20 is immersed in the resin liquid 6 (see FIG. 2(C)). Then, the main drying process is performed on the plant body 20 to which the resin liquid 6 has adhered (S315). In this main drying process, the plant body 20 is held in a suspended state (see FIG. 2(D)).　

Here, in the freezing process (see S312), for example, the temperature inside the refrigerator is set to -80° C. to -60° C. and maintained for 12 hours to 24 hours. This ensures that the plant body 20 is frozen. Note that the internal temperature of the freezing device (-80°C to -60°C) and the freezing period (3 hours to 24 hours) required for the freezing process are based on the appearance of the plant body 20 after the vacuum drying process. This is derived from the test results that determine pass/fail.　

Further, the vacuum drying process (see S313) is performed by, for example, keeping the interior of the vacuum drying device at room temperature for 12 hours to 3 days. To explain further, holding at a temperature of 40° C. or less, preferably 30° C. or less, more preferably 20° C. or less at a pressure of 50 Pa or less, preferably 5 Pa or less, more preferably 1 Pa or less for about 12 hours to 3 days. is executed. This ensures that the plant body 20 is dried. The moisture content of the plant body 20 becomes, for example, 5% or less after vacuum drying. In addition, the pressure inside the vacuum drying device decreases as time passes in the vacuum drying process, but the plant body 20 may be dried when the pressure inside the storage becomes 5 Pa or less. . The processing period (12 hours to 3 days), which is the period required for this vacuum drying process, was derived from the test results that determined the quality of the appearance of the processed flower plant body 20.　

Here, for example, the plant body 20 includes the flower receptacles 17 and calyxes 19 (see FIG. 1), so that the flower receptacles 17 and calyxes 19 support the petals 15, and deformation of the petals 15 is suppressed. On the other hand, the flower receptacle 17 (see FIG. 1) is a portion with a large diameter in the plant body 20, and is a portion in which it is difficult to dry water in the plant body 20 compared to other portions. For such a portion, it is preferable to perform freeze-vacuum drying treatment as shown in FIG. 3(B). This allows the plant body 20 to be dried more reliably. Additionally, by making the drying more reliable, the occurrence of mold on the dried flowers 10 can be suppressed. Note that as shown in FIG. 3(B), freeze-vacuum drying treatment may be performed together with drying treatment using desiccant material 4, or unlike FIG. 3(B), drying treatment using desiccant material 4 is not performed. may be subjected to freeze-vacuum drying treatment.　

Further, the plant body 20 is suppressed from changing its appearance such as color and shape due to the freeze-vacuum drying process, and has an appearance and flexibility similar to that of a fresh flower. Further, the resin film 30 formed on the plant body 20 is thin and deformable. This makes it possible to give the dried flower 10 the appearance and feel of a fresh flower.　

<Resin film 30> The resin film 30 has, for example, the following properties. The resin film 30 is soft and has a tensile stress of 1.0 to 1.1 MPa at 100% elongation. Furthermore, the resin film 30 has a tensile elongation at break of 1,000% or more and is excellent in displacement followability. Further, the resin film 30 has a tensile strength at break of 17.6 to 18.7 MPa. In addition, the resin film 30 is a soft coating or a coating composition.　

Here, as a non-yellowing soft paint, a method is known in which two liquids, a specific polyol component and a specific isocyanate component for imparting flexibility, are mixed in a solvent and applied. The coating workability of this two-liquid mixed reaction type paint sometimes depends on the reaction rate. In addition, since this two-component mixed reaction type coating material imparts softness, the toughness (tensile elongation or tensile strength) of the coating film sometimes decreases. On the other hand, although the resin liquid 6 of this embodiment is a one-component moisture-curable non-yellowing soft paint, the resin film 30 is soft with low elongation and tensile stress at 100%, and has excellent tensile elongation at break. It can form a tough coating film with excellent displacement followability and high tensile strength at break.　

<Resin liquid 6> The resin liquid 6 described above in FIG. 2(B) is a one-component moisture-curable non-yellowing soft paint. This resin liquid 6 is a solvent solution of a prepolymer having active isocyanate groups at the terminals obtained from the reaction of a less than stoichiometric amount of a specific polyol component and a stoichiometric amount of a specific polyisocyanate compound component. To explain further, in the resin liquid 6, the hydroxyl equivalent (OH) of the polyol component is smaller than the isocyanate equivalent (NCO) of the polyisocyanate compound component. This resin liquid 6 is applied as a paint to the surface of the plant body 20 as an adherend, and in parallel with the volatilization of the solvent, it reacts with water vapor in the air to form urea bonds, thereby forming a resin film 30. is formed as.　

Here, for example, in the resin liquid 6, the polyol component (A) is a carbonate polyol with a functional group number of 2 and a number average molecular weight of 2,000 to 3,000, and has an active hydroxyl group at the terminal, ( B) The polyisocyanate component is an alicyclic polyisocyanate having two functional groups and has an isocyanate group at the terminal, and the hydroxyl equivalent (OH) of the polyol component of (A) above is the same as the polyisocyanate component of (B) above. smaller than the isocyanate equivalent (NCO) of the isocyanate component, the polyol component of (A) above and the polyisocyanate component of (B) above are reacted in the presence of (C) a catalyst and (D) a solvent ( E) It is a prepolymer solution paint composed of a polyurethane resin and has active isocyanate groups at the end. It is a quick-drying paint that reacts with water vapor in the air to form urea bonds and is dry to the touch in about 30 seconds.　

The polyol component (A) is a liquid carbonate polyol having two functional groups, a molecular weight of 2,000 to 3,000, and an active hydroxyl group at the end. Here, since the number of functional groups is 2, it becomes easier to obtain a linear polymer. When the number of functional groups is less than 2, the composition tends to be uncured. Moreover, when the number of functional groups is larger than 2, a network-like crosslinked structure is created in the polymer structure, which is not preferable because the tensile elongation rate of the coating film decreases. Moreover, when the number of functional groups is less than 2, it is not preferable because the liquid viscosity of the (E) prepolymer solution increases or the prepolymer solution gels. Furthermore, if the molecular weight is less than 2,000, the tensile elongation at break will be small and the displacement followability will be poor. If the molecular weight is greater than 3,000, the liquid viscosity becomes high, and the liquid viscosity of the prepolymer solution (E) becomes high, which is not preferable.　

As a specific example of the polyol component (A), known carbonate polyols that are liquid at room temperature are preferred from the viewpoint of achieving the desired properties of the coating film, long-term stability, and adjusting the liquid viscosity, molecular weight, and number of functional groups. That is, the liquid carbonate polyol can maintain the resin of the coating film in an amorphous state, that is, as a transparent coating film, because of its structure of repeating alkyl carbonate bonds having branches such as methyl groups. In addition, a carbonate-bonded coating film has excellent weather resistance, thermal history and heat shock resistance, and is therefore preferable for a coating film with a linear structure that is soft and stretches well, such as this coating film.　

The liquid carbonate polyol can be obtained, for example, by a known method by polycondensation reaction of diphenyl carbonate and 3-methyl-1,5-pentanediol in the presence of a transesterification catalyst. As the liquid carbonate polyol, for example, Clapol C3090 (manufactured by Kuraray Co., Ltd.) may be used. Further, as the liquid carbonate polyol, known carbonate polyols, ε-caprolactone polyols, polytetramethylene polyoxyglycol, β-methyl-δ-valerolactone polyols, etc. may be used, or two of these polyols may be used. The above may be used in combination.

(B) The polyisocyanate component is an alicyclic polyisocyanate having two functional groups and an isocyanate group at the terminal. Since the number of functional groups is 2, it becomes easier to obtain a coating film of a linear polymer. When the number of functional groups is less than 2, the composition tends to be uncured. If the number of functional groups is greater than 2, it is not preferable because a network-like crosslinked structure is created in the polymer structure, resulting in a decrease in the tensile elongation rate of the coating film. Further, (E) is not preferable because the liquid viscosity of the prepolymer solution increases and the prepolymer solution gels.　

(B) As an example of the polyisocyanate component, a general alicyclic compound can be used. For example, methylene bis(4,1-cyclohexylene) diisocyanate or the like may be used as the polyisocyanate component, or two or more of these may be used in combination. Further, as the polyisocyanate component, known hexamethylene diisocyanate (HDI) or its derivatives, xylidene diisocyanate, norbornene diisocyanate, etc. may be used, or two or more of these may be used in combination.　

(C) The catalyst causes a urethanization reaction between the isocyanate component (B) and a less than stoichiometric amount of the polyol component (A) to obtain a prepolymer having an active isocyanate group at the end and is composed of a polyurethane resin. In this process, a predetermined urethanization catalyst can be used. As this urethanization catalyst, known catalysts such as tertiary amine compounds and organometallic compounds can be used. In addition, examples of urethanation catalysts include triethylenediamine, N,N-dimethylhexamethylenediamine, N,N-dimethylbutanediamine, diazabicyclo(5,4,0)-7-undecene (DBU) and DBU salt, bismuth Preferred are tris(2-ethylhexanoate), diisopropoxybis(ethyl acetoacetate)titanium, lead octylate, dibutyltin laurate, and the like.　

(D) Solvents include ester solvents, ketone solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, and polyhydric alcohol derivatives, preferably ester solvents, ketone solvents, and polyhydric alcohol derivatives. Derivatives of alcohols are preferred because of their low toxicity. For example, ester solvents include ethyl acetate, butyl acetate, etc., ketone solvents include acetone, methyl ethyl ketone, etc., and polyhydric alcohol derivatives include propylene glycol monomethyl ether acetate.　

Here, when obtaining a prepolymer solution having an active isocyanate group at the terminal and composed of the polyurethane resin (E), the reaction ratio between the isocyanate component (B) and the polyol component (A), which is 1/2 of the theoretical amount, is The equivalent ratio of the isocyanate groups (NCO) of the prepolymer to the hydroxyl groups (OH) of the polyol, that is, the NCO/OH ratio, is 1.95 to 2.5, more preferably 2.0 to 2.1. If this equivalent ratio exceeds 2.5, a large amount of unreacted active isocyanate remains in the coating material (E), which is undesirable because dryness to the touch after coating becomes slow. Furthermore, if this equivalent ratio is less than 1.95, the viscosity of (E) the paint becomes high, and the workability of (E) the manufacturing and coating operations of the paint may deteriorate. In addition, when this equivalent ratio is 2.0 to 2.1, all of the (B) isocyanate components react and become a prepolymer, and there is no unreacted (B) isocyanate component in the paint, so the (E) paint Ingredient safety is increased.　

(E) The prepolymer solution coating composed of polyurethane resin and having an active isocyanate group at the end can be used alone, but the following components can be added. First, pigments can be added. The amount of this pigment is preferably less than 5 parts by weight, preferably less than 1 part by weight, per 100 parts by weight of the total amount of the isocyanate component (B) and the polyol component (A) as main components. When this pigment is added, the hardness of the resulting coating film decreases as the amount added increases. As an example of the pigment, there is no particular limitation as long as it is a pigment for urethane resin, but a paste in which the pigment is kneaded using a polyol as a vehicle is preferred for use. For example, each color of the paste coloring agent FTR (manufactured by Dainichiseika Chemical Co., Ltd.) can be used.　

In addition, in order to improve the durability and stability of the composition, one type of stabilizer, such as a heat stabilizer, antioxidant, ultraviolet absorber, ultraviolet stabilizer, filler, etc., may be added as long as there is no problem. Alternatively, two or more kinds can be mixed and used. Furthermore, in addition to those mentioned above, pigments, dyes, flame retardants, antifoaming agents, dispersants, surface modifiers, water adsorbents, etc. can also be added as appropriate.　

Now, a solvent is put into a reaction tank equipped with a mixing device, then (A) polyol component used as a raw material is added and mixed and dispersed in the solvent, (B) polyisocyanate component is added and mixed and dispersed, and then ( C) After adding the catalyst and mixing and dispersing it, stirring is continued under a nitrogen atmosphere, and the urethanization reaction is carried out for a predetermined time at room temperature or in a heated state, respectively. (E) Active isocyanate is added to the terminals composed of polyurethane resin A coating of prepolymer solution with groups is obtained. When mixing additives, they may be mixed with the polyol component in advance, or may be added at the time of mixing the main components.　

As a result, a one-component moisture-curable non-yellowing soft paint is obtained. This can be achieved by diluting the obtained paint with a solvent or the like and adjusting the resin concentration in the paint depending on the purpose of finishing the paint film to be "glossy" or "non-glossy."　

The above-obtained paint (E) is quick-drying and can be dry to the touch in about 30 seconds. Here, it is preferable to apply the paint (E) to the precursor and allow it to react with water vapor at room temperature to 120° C. for several tens of seconds to 2 hours or more in order to obtain the final strength of the coating film. After that, the paint becomes a soft, tough, transparent film. Alternatively, it can be applied to a polypropylene plate (PP plate), and after reacting with water vapor, the coating film can be peeled off from the PP plate and taken out.

EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples.　

<Example 1> 350 g of dehydrated ethyl acetate was added to a four-necked separable flask equipped with a stirring blade, a reflux device, and a heating device in a nitrogen gas atmosphere, and then methylene bis(4,1- 17.86 g (0.139 equivalents) of cyclohexylene diisocyanate were added, and then 100 g (0.067 g. Then, 0.1 g of dibutyl-tin-laurate as a reaction catalyst was charged into the reaction tank, and the reaction was carried out for 4 hours while the temperature of the reaction solution was maintained at 40° C. or lower. Then, the mixture was refluxed at 80° C. for 4 hours. After the reaction was completed, when the reaction solution was returned to room temperature, 0.9 g of dibutyl-tin-laurate was added and mixed with stirring to obtain a prepolymer solution coating composed of polyurethane resin and having active isocyanate groups at the terminals. Ta. The obtained coating material was a liquid having a viscosity of 0.3 Pa·s at 25°C. This is indicated by the symbol “Example-1”.　

The obtained paint (E) of "Example-1" was applied to a PP board, and the solvent quickly evaporated and the paint film was dry to the touch after 30 seconds. Furthermore, by leaving it at room temperature for 2 hours, a reaction with water vapor is caused, after which the paint becomes a soft, tough, transparent coating. This coating film was left at room temperature for 3 days and then peeled off from the PP board to obtain a soft, tough and transparent film. The coating film has a soft tensile stress of 1.1 MPa at 100% elongation (for example, natural rubber 0.5 MPa), a tensile strength of 18.7 MPa (for example, natural rubber 5 MPa), and a tensile elongation rate of 1,300% (for example, natural rubber 5 MPa). 600% rubber) and strong. When this coating film was exposed for 10 days in a constant temperature bath at 100° C., no change was observed in the appearance of the coating film and it exhibited excellent durability (natural rubber melted due to decomposition within one day).　

<Example 2> A coating material of a prepolymer solution was obtained in the same manner as in Example 1 except that 15.26 g (0.139 equivalents) of isophorone diisocyanate was added. The obtained coating material was a liquid having a viscosity of 0.2 Pa·s at 25°C. The coating film has a soft tensile stress of 1.0 MPa at 100% elongation, and is strong with a tensile strength of 17.6 MPa and a tensile elongation rate of 1,200%. When this coating film was exposed for 10 days in a constant temperature bath at 100° C., no change was observed in the appearance of the coating film, and it showed excellent durability. (Natural rubber melts due to decomposition within one day).　

<Example 3> 100 g of the obtained (E) paint of "Example-1" (resin concentration (NV) 25%) and 150 g of ethyl acetate solvent were added and mixed to obtain a diluted paint (NV 10%). Ta. Dried flowers were dipped in this diluted solution and air-dried for 30 seconds to dry to the touch to obtain shiny coated dried flowers. This dried flower was confirmed to be flexible. Moreover, this dried flower had a glossy (glossy) appearance compared to before coating. In addition, the growth of mold was suppressed in this dried flower compared to when it was not coated.　

<Example 4> 300 g of ethyl acetate solvent was added to 100 g (resin concentration 25%) of the obtained paint (E) of "Example-1" and mixed to obtain a diluted paint (NV 5%). Dried flowers were dipped in this diluted solution and air-dried for 30 seconds to dry to the touch to obtain matte coated dried flowers. This dried flower was confirmed to be flexible. Additionally, this dried flower had an appearance with no significant change in gloss compared to before coating. In addition, the growth of mold was suppressed in this dried flower compared to when it was not coated.　

<Example 5> 0.5 g of pigment (FTR Red; manufactured by Dainichiseika Kaisha, Ltd.) and 300 g of ethyl acetate solvent were added to 100 g (NV 25%) of the obtained (E) paint of "Example-1" and mixed. A red colored diluted paint (NV5%) was obtained. Dried rose flowers were dipped in this diluted solution and air-dried for 30 seconds to dry to the touch to obtain a matte coated dried flower colored red. This dried flower was confirmed to be flexible. Furthermore, compared to before coating, this dried flower had a reddish appearance with no significant change in glossiness. In addition, the growth of mold was suppressed in this dried flower compared to when it was not coated.　

<Measurement conditions, etc.> The above "liquid viscosity" is the numerical value measured using a BH type liquid viscometer, and the coating limit is set to 8/Pa・s or less, and a viscosity higher than that is considered difficult to coat. .　

In addition, "100% elongation tensile stress", "tensile strength", and "tensile elongation rate" are determined by performing a tensile test using a dumbbell-shaped No. 3 test piece according to JIS K6301, and calculating the stress at 100% elongation. (unit: MPa), stress at break (unit: MPa), and elongation at break (unit: %).　

The one-component, moisture-curable, non-yellowing soft paint of the present invention dries quickly to the touch in 30 seconds after application, and has excellent workability.It reacts with water vapor to create a soft, tough coating with excellent displacement followability. A transparent coating can be provided.　

For example, a soft composition deforms under load and easily breaks due to stress concentration, but it would be extremely advantageous if it were covered with a strong coating that is soft and has excellent displacement followability. For example, in the case of dried flowers, by coating or dipping the dried flowers with the one-component moisture-curable non-yellowing soft paint, it is possible to prevent petals and leaf blades from falling or breaking.　

<Modification> In the above description, it has been explained that the resin film 30 is formed on the entire surface of the plant body 20, but the present invention is not limited to this. For example, the resin film 30 may be formed on a part of the surface of the plant body 20, such as only on the petal portion of the plant body 20.　

Although various embodiments and modifications have been described above, it is of course possible to combine these embodiments and modifications. Further, the present disclosure is not limited to the above-described embodiments, and can be implemented in various forms without departing from the gist of the present disclosure.

The plant body 20 is an example of a plant. The dipping treatment, the temporary drying treatment, and the main drying treatment are examples of film forming steps. The nonwoven fabric 7 is an example of an absorbent material.

4... Desiccant, 6... Resin liquid, 10... Dried flower, 15... Petal, 17... Flower receptacle, 20... Plant body, 30... Resin film

Claims

The resin composition comprises a drying step of drying the plant, and a film forming step of forming a film of the resin composition on the surface of the dried plant. It is a liquid carbonate polyol with a number average molecular weight of 2,000 to 3,000 and has an active hydroxy group at the terminal, and (B) the polyisocyanate component is an alicyclic polyisocyanate having a functional group number of 2. and has an isocyanate group at the terminal, the hydroxyl equivalent (OH) of the polyol component (A) is smaller than the isocyanate equivalent (NCO) of the polyisocyanate component (B), and the polyol (A) A prepolymer solution having an active isocyanate group at the end and composed of (E) a polyurethane resin in which the component and the polyisocyanate component of (B) are reacted in the presence of (C) a catalyst in (D) a solvent. In the film forming step, a film of the paint of (E) is formed on the surface of the dried plant, and the film is reacted with water vapor in the air to form a urea bond. Production of ornamental plants. Method.
Claim 1: The equivalent ratio (NCO/OH) between the hydroxyl equivalent (OH) of the polyol component (A) and the isocyanate equivalent (NCO) of the polyisocyanate component (B) is 1.95 to 2.5. Method for producing the described ornamental plants.
The method for producing an ornamental plant according to claim 1, wherein the alicyclic polyisocyanate is methylene bis(4,1-cyclohexylene) diisocyanate or isophorone diisocyanate.
The film of the resin composition has a 100% elongation tensile stress of 1.0 to 1.1 MPa, a tensile elongation at break of 1,000% or more, and a tensile strength at break of 17.6 to 18.7 MPa. A method for producing an ornamental plant according to claim 1.
2. The method for producing an ornamental plant according to claim 1, wherein the paint (E) is dry to the touch within 30 seconds after forming a film of the paint on the dried plant.
The method for producing an ornamental plant according to claim 5, wherein the solvent (D) is an ethyl acetate solvent, and the resin concentration of the paint used in the touch drying step is 5 to 10%.
The drying to the touch step is carried out by placing the dried plants on an absorbent body that absorbs the paint of (E), and after the drying to the touch step, the dried plants are hung to form a film of the paint. The method for producing an ornamental plant according to claim 6, further comprising drying.
2. The method for producing an ornamental plant according to claim 1, wherein the plant includes a flower receptacle, and in the drying step, the frozen plant is vacuum-dried.
9. The method for producing an ornamental plant according to claim 8, wherein the plant is dried in the drying step without being pressed into a flat shape after being harvested.
A drying step of freezing and vacuum drying a plant with flower receptacles, and a film forming step of forming a film of a resin composition on the surface of the dried plant, the resin composition comprising (A) a polyol component. is a liquid carbonate polyol having an active hydroxyl group at the end with a functional number of 2 and a molecular weight of 2,000 to 3,000, and (B) the polyisocyanate component is a methylene bis(4) having a functional number of 2 and an isocyanate group at the end. , 1-cyclohexylene) diisocyanate or isophorone diisocyanate, and the equivalent ratio (NCO/OH) between the hydroxyl equivalent (OH) of the polyol component (A) and the isocyanate equivalent (NCO) of the polyisocyanate component (B). is 1.95 to 2.5, and the polyol component of (A) and the polyisocyanate component of (B) are reacted in the presence of (C) a catalyst and (D) in an ethyl acetate solvent. (E) A prepolymer solution coating composed of polyurethane resin and having an active isocyanate group at the end, and in the film forming step, a film of the coating of (E) is formed on the surface of the dried plant. , reacts with water vapor in the air to form urea bonds, the paint of (E) becomes dry to the touch within 30 seconds after forming the film on the dried plant, and the resin composition The film of the product has a 100% elongation tensile stress of 1.0 to 1.1 MPa, a tensile elongation at break of 1,000% or more, and a tensile strength at break of 17.6 to 18.7 MPa. manufacturing method.
An ornamental plant formed by the production method according to claim 1.
It has a dried plant and a film of a resin composition formed on the surface of the plant, and the film of the resin composition has a 100% elongation tensile stress of 1.0 to 1.1 MPa, and a tensile elongation at break of 1.0 to 1.1 MPa. is 1,000% or more and has a tensile breaking strength of 17.6 to 18.7 MPa.