KR100446957B1 - Preserving Method of Dry Flower by Polymer Coating - Google Patents

Abstract

The present invention relates to a method of preserving dry flowers (dried flowers), and an object of the present invention is to provide a method of coating a polymer having moisture and oxygen barrier properties and increasing mechanical strength on the surface of a dry flower.

A pretreatment step of treating the surface of the dry flower with a polymerizable gas plasma selected from hydrocarbons, organosilicones, hydrogen fluoride or mixtures thereof, p-xylylene dimer of [Formula 1], [ A chloro-p-xylylene dimer of Formula 2, a dichloro-p-xylylene dimer of Formula 3, or a mixture thereof is 0.001 to 10 torr. Heating to 100-170 ° C. at a pressure of sublimation, pyrolysis at 600-750 ° C. to become radicals, and depositing the resulting radicals on the surface of the dry flower.

[Formula 1]

[Formula 2]

[Formula 3]

Description

Preserving Method of Dry Flower by Polymer Coating

The present invention relates to a method of preservation of dried flowers (dried flowers), in particular, to a method of coating the polymer thin film to increase moisture and oxygen barrier properties to prevent discoloration and decay and to increase the mechanical strength of the petals so that they do not crumble. It is about.

Dry flowers are made by natural drying or freeze-drying of natural flowers. Dry flowers are inherently moisture-free and are not glossy, brittle, discolored when exposed to prolonged air or sunlight, resulting in less vivid color, and moldy contact with moisture. There are disadvantages.

Therefore, in order to prevent discoloration and decay, and to maintain the freshness as possible, the polymer is coated on the surface of the dry flower. A method of spraying a water-soluble polymer on the surface of the dry flower or spraying the dry flower in the water-soluble polymer solution and then drying This is the most common.

However, the method by spraying is difficult to coat evenly, and the method by dipping is difficult to maintain the shape because it has to wet the whole once. In addition, both methods have a disadvantage in that workability is poor and takes a lot of time because they have to be done manually.

As a method of coating a polymer thin film on a dry flower, Japanese Patent Laid-Open No. Hei 7-118101 discloses gas phase polymerization of a photopolymerizable monomer and / or a silane coupling agent in the presence of a photopolymerization initiator and an ultraviolet ray to the surface of the dry flower. A method of coating is disclosed. However, this focuses on imparting water repellency to the surface of the dry flower, and the oxygen or barrier properties of the polymer thin film have not been proved, and there is a disadvantage in that ultraviolet rays which cause discoloration or decolorization of the dry flower must be irradiated to polymerize the polymer. .

Korean Patent Application No. 98-56766 discloses a method of coating a surface of a dry flower by low temperature plasma polymerization of a polymerizable gas such as hydrocarbon, hydrogen fluoride, organosilicon, and the like. However, due to the characteristics of the plasma polymerization process, it is difficult to predict the physical properties of the polymer to be polymerized, and in some cases, the moisture barrier property may not be so high.

It is an object of the present invention to provide a method of coating a polymer having high moisture and oxygen barrier properties and increasing mechanical strength on the surface of a dry flower to prevent discoloration and decay of the dry flower and to prevent chipping.

1 is a schematic diagram of a polymer coating system used in the practice of the present invention.

* Description of the symbols for the main parts of the drawings *

11: sublimation tube 12: pyrolysis tube

13: deposition chamber 14: cooling collection chamber

15: sample (dry flower) 16: pressure gauge

17: vacuum pump 18: sublimation heater

19: by pyrolysis

The present invention for achieving the above object is a pretreatment step of treating the surface of the dry flower with a polymerizable gas plasma selected from hydrocarbons, organosilicon, hydrogen fluoride or a mixture thereof, and the p-xylene dimer of the formula [1] Sieve (p-xylylene dimer), chloro-p-xylylene dimer of [Formula 2], dichloro-p-xylylene dimer of [Formula 3] ) Or a mixture thereof heated to 100 to 170 ° C. at a pressure of 0.001 to 10 torr, sublimated, pyrolyzed at 600 to 750 ° C. to become radicals, and depositing the resulting radicals on the surface of the dry flower It includes.

The dimers are sublimable and evaporate at higher temperatures, and pyrolysis at higher temperatures to decompose into two highly reactive radicals. The pyrolyzed radicals are polymerized as they deposit on the surface of the dry flower to dry the surface of the dry flower. A polymer thin film is formed in the.

The process is carried out at 0.001 ~ 10torr, preferably 0.01 ~ 0.10torr, it is preferable to proceed to move the position in one reactor.

1, 120 to 180 ^o C, the pyrolysis pipe 12 is 600 to 800 ^o C, and the deposition chamber 13 is maintained at -196 to 80 ^o C. The dimer is vaporized in the sublimation tube and moved to the deposition chamber through the pyrolysis pipe, pyrolyzed in the pyrolysis pipe to form radicals, and deposited in the deposition chamber on the surface of the dry flower to coat the polymer thin film.

Carrier gas may be used to smoothly move from the sublimation step to the pyrolysis step and the pyrolysis step to the deposition step. As a carrier gas, an inert gas such as argon or helium is used.

The temperature of each step is preferably carried out at 140 to 170 ^° C. for the sublimation step, 650 to 750 ^° C. for the pyrolysis step and -80 to 50 ^° C. for the deposition step.

The polymer thin film coated through the above process not only has very low oxygen permeability (O ₂ permeability) and moisture permeability (that is, very high moisture and oxygen barrier properties), but also mechanical properties such as tensile strength and breaking strength. High strength Moreover, since it is transparent, it does not affect the color of a dry flower.

Coating the plasma polymer of the polymerizable gas is carried out to increase the adhesion between the dry flower and the polymer to be coated, and as the polymerizable plasma gas, hydrocarbons such as methane, ethane and benzene, organosilicon, hydrogen fluoride or a mixture thereof are used. do.

In addition, in order to improve adhesion between the plasma polymer and the dry flower, a step of etching the surface of the dry flower with oxygen or air plasma, which is a non-polymeric gas, may be provided prior to the plasma polymer coating.

Coating the plasma polymer on the dry flower forms free radicals on the surface of the dry flower. Therefore, the adhesion to the polymer to be coated later is increased, and if the surface of the dry flower is treated with plasma of non-polymerizable gas, the surface of the dry flower is not only washed but also roughened to increase adhesion.

The plasma polymerization process and the etching process are well disclosed in Korean Patent Application No. 98-56766 filed by the inventor of the present invention.

The construction of the present invention will become more apparent from the following examples.

<Example 1>

P-xylylene dimer of [Formula 1] was thermally decomposed and coated on a freeze-dried rose (Little Marble, Vermilion), orchid leaf (Gun Yin, green leaf) and carnation using the reactor shown in FIG. After irradiating with UV for 1 month, the sensory test was performed.

A. Coating Process

Fill the sublimation pipe 11 with 5 g of p-xylene, place the dry flower 15 as a sample in the center of the deposition chamber 13, and operate the vacuum pump 17 to maintain the reactor pressure at 0.020 torr. While supplying electricity to the sublimation heater 18 and the pyrolysis furnace 19 to raise the temperature of the sublimation pipe 11 and the pyrolysis pipe 12 to 150 ^o C and 650 ^o C, respectively, liquid nitrogen in the cooling collector 14 The coating was performed for 40 minutes while keeping the temperature of the deposition chamber 13 low.

The dimer sublimed in the sublimation tube moved to the deposition chamber through the pyrolysis pipe throughout the process, and the vacuum pump 17 was operated to remove radicals not deposited on the sample.

B. Sensory Test

Dry flower (a) immediately after coating and dry flower (b) irradiated with ultraviolet rays for 30 months at 30cm distance with 30W ultraviolet light after coating were applied to 10 people with normal visual acuity and mixed with 10 flowers samples and 2m. Experiments were conducted to identify dry flowers at distance.

As a result, no one could identify the dry flower (a) immediately after the coating, and the dry flower (b) irradiated with ultraviolet light identified three roses and one carnation, and no orchids.

<Example 2>

Oxygen barrier and water barrier were measured for the polymer produced by pyrolyzing the chloro-p-xylylene dimer of [Formula 2].

Since it is very difficult to directly measure the oxygen barrier property and water barrier property by coating the polymer on the dry flower, the polymer was indirectly measured by coating a polyethersulfone (PES) film having a thickness of 0.2 mm.

A. Coating Process

Coating was carried out under the same conditions as in Example 1, except that chloro-p-xylylene dimer was used as the dimer. That is, the pressure of the reactor was 0.020torr, the temperature of the sublimation tube (11) 150 ^° C, the temperature of the pyrolysis tube (12) was 650 ^° C and coated for 40 minutes.

B. Test Method

Oxygen barrier was measured by the absolute pressure method (KS A 1027), which measures the rate at which the pressure on the vacuum side increases, with one side being vacuum and the other side being 2 atm. The method of measuring the rate of increase of the weight of the dehumidifying agent by using a dehumidifying agent (anhydrous CaCl ₂ ) as 0% relative humidity and the relative humidity of 90% using the so-called Desiccant method. It was.

C. Measurement Results

Oxygen permeability was measured as 7.2 (cm ³ ) (mil) / (100in ² ) (day), and water permeability was 0.2 (cm ³ ) (mil) / (100in ² ) (day). (Where 1mil = 1 / 1000inch)

Compared with polyurethane, oxygen permeability is only about 1/20 ~ 1/30 compared to 150 ~ 200 (cm ³ ) (mil) / (100in ² ) (day) (literature) of polyurethane, and moisture It can be seen that the transmittance is only about 1/10 to 1/40 compared to 2.4 to 8.7 (cm ³ ) (mil) / (100 in ² ) (day) (literature) of the polyurethane.

<Example 3>

The mechanical strength (tensile strength and breaking strength) of the polymer produced from the chloro-p-xylylene dimer of [Formula 2] was measured.

The mechanical strength was measured by ASTM D882 because it was very difficult to measure the polymer directly on the dry flower as well as the oxygen permeability and the moisture permeability. The tensile strength was about 8,500 psi and the breaking strength was about 200%, respectively.

This is a low value compared to 175 to 10,000 psi (literature) and 100 to 1,000% (literally) of polyurethane, and considering that the dry flower is very brittle, the mechanical strength will be significantly improved even with a thin coating alone. It is expected.

<Example 4-5 and a comparative example>

To test the adhesion of the polymer thin film to be coated, three 10 × 10 cm iron sheets were coated with a polymer by the following method, scraped with a pencil, and a salt spray test was performed.

A. Sample Preparation

(1) Example 4

Plasma generator was used in the form of wrapping an electrode (not shown) of 54x10x0.1cm on the outer wall of the deposition chamber 13 of the reactor of FIG. 1, supplying 40W of power at 120mmTorr of methane gas and plasma for 3 minutes. After coating, chloro-p-xylylene dimer was pyrolyzed and coated in the same manner as in Example 2.

(2) Example 5

After surface treatment with air plasma for 5 minutes at 120 mmTorr with 40 W of power, the methane plasma polymer was coated by the method of Example 4, followed by pyrolysis of chloro-p-xylene dimer in the same manner as in Example 2. By coating.

(3) Comparative Example

The chloro-p-xylylene dimer was pyrolyzed and coated in the same manner as in Example 2 without a plasma process.

B. Experiment

The surface of the sample produced through the above process was rubbed under a load of 500g on the pencil of hardness 4B, HB, 2H, 4H, respectively (scratch), and the degree of rust was observed by spraying brine.

C. Results

Example 4 was observed from the HB, Example 5 was rusted in 4H. As in Example 4, a rusted portion was observed in HB as in Example 4, but the degree was more severe than in Example 4.

According to the present invention, oxygen and ultraviolet rays in the air are blocked to prevent discoloration or discoloration of the dry flower, moisture is blocked to prevent decay, and mechanical strength such as tensile strength is prevented from being broken.

In addition, when the present invention is combined with a known method such as storing dry flowers in a closed space made of glass and filling with an inert gas such as nitrogen, the bouquets used in the wedding can be permanently preserved.

Claims (5)

A pretreatment step of treating the surface of the dry flower with a polymerizable gas plasma selected from hydrocarbons, organosilicones, hydrogen fluoride or mixtures thereof, p-xylylene dimer of [Formula 1], [ A chloro-p-xylylene dimer of Formula 2, a dichloro-p-xylylene dimer of Formula 3, or a mixture thereof is 0.001 to 10 torr. A method of coating a dry flower, comprising the steps of heating to a temperature of 100 to 170 ° C. to sublimate, pyrolyzing at 600 to 750 ° C. to become a radical, and depositing the generated radicals on the surface of the dry flower. [Formula 1] [Formula 2] [Formula 3] delete delete delete The method of claim 1, wherein the surface of the dry flower is treated with oxygen or air plasma, which is a non-polymerizable gas, prior to the polymerizable plasma treatment.