KR20010044796A - Thermochromic accessories with the incorporated decoration of plant - Google Patents

Abstract

PURPOSE: Thermochromic accessories capable of being well preserved in its natural form without discoloration and deformation for a long period of time by fixing a reversible thermochromic resin composition impregnated with natural plant to accessories are provided, which can be applied to a lighter, a bracelet or the like as well as a key ring. CONSTITUTION: In accessories impregnated with a dried natural plant into transparent synthetic resin, a composition containing 100 parts by weight of epoxy resin and 0.001 to 10 parts by weight of a reversible thermochromic mixture of an electron-donation coloration compound and an electron accepting compound in a ratio of 1:1 to 1:10 as synthetic resin is impregnated with natural plant such as a four-leaf clover.

Description

Thermochromic accessories with the incorporated decoration of plant}

The present invention relates to thermochromic ornaments using plants, and more particularly, to thermochromic ornaments attached to natural plants so that they are preserved as they are without being discolored and deformed for a long time.

For example, many accessories such as key chains, bracelets, lighters, necklaces, earrings, rings, tie pins, watches, wall hangings, hairpins, frames, business card cases, etc., must be classy as they stand out for beauty, and more unique if they are interesting.

In recent years, many attempts have been made to introduce natural plants such as flowers, trees and grasses as a means of elevating ornaments. Normally, natural plants are susceptible to water, light, heat, etc., and are easily discolored and deformed when used as they are. Therefore, technology development for high-quality jewelry that utilizes natural flavor for a long time by appropriate physical and chemical treatment is active.

For example, coating synthetic resin such as transparent epoxy resin on natural plants such as dried four-leaf clover and applying them to ornaments (Korean Utility Model Publication No. 20-190633, 20-210221), hygroscopicity on the back of undried plants A paper is placed, and a front surface is provided with a transparent resin layer (Korean Patent Laid-Open Publication No. 2001-475), at a temperature of 50 to 90 ° C. under pressurization of a plant at a pressure of 5 to 30 kg / cm 2. The dried plant obtained by heating is coated with a slurry mixture composed of 5 to 40% by weight of ultrafine hygroscopic inorganic material having a particle size of 10 to 1,000 nm and 60 to 95% by weight of liquid epoxy resin, without discoloring and deforming for a long time. Plants that are preserved and ornaments using them (Korean Patent Application No. 2001-11439) are good examples.

However, while the above-mentioned prior art is obviously a means of improving the quality, there is not enough as a unique material that can cause the interest that the jewelry should have. In particular, modern people who are pursuing sensuous and diverse changes have been continuously asked for the appearance of jewelry that can trigger interest with new functions. In particular, as the temperature changes over the four seasons like in Korea, the appearance of interesting ornaments that can be changed differently is more urgent.

Accordingly, an object of the present invention is to provide a new function of the so-called 'reversible thermochromic phenomenon' that reversibly repeats the color change based on a specific temperature, the ornaments using natural plants that can induce interest to consumers To provide.

In order to solve the above problems, the present inventors earnestly researched, by fixing a natural plant to the ornament body as a reversible thermochromic resin composition is preserved as it is without discoloring and deforming for a long time, 'reversible thermochromic phenomenon The present invention has been completed by knowing that it can provide amazing ornaments with interesting interest.

1 is a photograph showing Example 1 (when the temperature was 14 ° C. or more) applied by applying a dry plant to a key ring with a thermochromic resin composition according to the present invention.

FIG. 2 is a photograph showing Example 1 (when the temperature was 14 ° C. or lower) applied to a key ring with a thermochromic resin composition according to the present invention.

FIG. 3 is a photograph showing Example 2 (when it was 14 ° C. or more) by applying a dry plant to a lighter with a thermochromic resin composition having a different composition according to the present invention.

4 is a photograph showing Example 2 (when the temperature was 14 ° C. or less) applied to a lighter as a thermochromic resin composition according to the present invention.

FIG. 5 is a photograph showing Example 2 (when it was 14 ° C. or more) by applying a dry plant to a bracelet with a thermochromic resin composition having a different composition according to the present invention.

FIG. 6 is a photograph showing Example 2 (when the temperature was 14 ° C. or less) applied to a bracelet with a dry plant as a thermochromic resin composition according to the present invention.

That is, the present invention is a thermochromic material comprising a composition in which a natural plant is immobilized to a body with a synthetic resin, and a composition containing 0.001 to 10 parts by weight of a reversible thermochromic compound is added to 100 parts by weight of an epoxy resin as the synthetic resin. To provide sex ornaments.

In the present invention, the reversible thermochromic compound is usually composed of an electron-donating coloring compound (I) and an electron-accepting compound (II).

Examples of the electron donating colorimetric compound (I) include so-called leuco dyes such as diaryl phthalides, polyaryl carbinols, leucooramines, aryloramines, rhodamine B lactams, indorins, spiropyranes, and huroreans. Specific examples thereof include spiro [12-H-benzo-α-chianthene-12-1 (3H) -isobenzopyran-3-one, 9- (diethylamine) -spiro [isobenzofuran-1 (8H), 9- (9H) chianthene] -3-one, 2-chloro- (diethylamino) -3-methyl-spiro [isobenzofuran-1 (3H) -9- (9H) chianthene] -8-one, 6-diethylamino-2- [cyclohexyl (phenylmethyl) amino], etc. are mentioned.

Electron-accepting compound (II) is a compound that accepts electrons from the above leuco dyes to color the leuco dyes, such as nonylphenol, dodecylphenol, 4,4-thiobis (6-t-butyl-8-methylphenol) , Compounds having a phenolic hydroxyl group such as bisphenol A, and metal salts thereof, aromatic carboxylic acids such as maleic acid, phmalic acid, benzoic acid, and phthalic acid, and their metal salts such as metal salts, acetic acid and propionic acid, aliphatic carboxylic acids having 2 to 5 carbon atoms, acid salts thereof and acid phosphate esters and the like Metal salts, 1,2,3-triazole and derivatives thereof, and hydropyridine and derivatives thereof having 2 to 5 carbon atoms;

The mixing ratio of the electron-donating colorimetric compound (I) and the electron-accepting compound (II) is preferably in the range of 1: 1 to 1:10.

The epoxy resin used as the synthetic resin in the present invention is a conventional compound having two or more epoxy groups in a molecule, and for example, a resin produced by the reaction of bisphenol A and epichlorohydrin. In order to impart thermosetting properties to such epoxy resins, catalysts such as tertiary amines and boron fluoride, or curing agents such as first amines, second amines, and acid anhydrides are generally added, followed by mixing the thermochromic compounds well. Good to do.

In the present invention, for example, acrylic resins and polycarbonate resins having good transparency may be used as the synthetic resins, but polycarbonates are expensive and difficult to process, and acrylic resins are inexpensive. Thermosetting epoxy resin having excellent chemical resistance and transparency and good moldability is optimal.

In this invention, it is preferable to add 0.001-10 weight part of reversible thermochromic compounds with respect to 100 weight part of epoxy resins, and it is more preferable to add 0.01-1 weight part. The addition amount is adjusted in consideration of thermochromic sensitivity, molecular weight and the like of the thermochromic compound. The color of the thermochromic compound varies depending on the molecular structure, in particular, the substituent, and may be selected in consideration of the type, design, and color of jewelry to be applied.

Plants that can be used in the present invention may be any of natural flowers, such as flowers, trees, grass, etc., for example, flowers include horticultural plants, wildflowers, and any part of the plants such as leaves, stems, roots. It is also possible to use undried plants as they are, but it is preferred to use dried plants.

As a method of obtaining dried plants, for example, vacuum drying (Japanese Patent Publication No. 57-11881), freeze drying (Japanese Patent Publication No. 52-2650), and high frequency drying (Japanese Patent Publication) 61-30642), a method of inserting a plant into a microsphere of a heat-resistant inorganic material (Japanese Patent Publication No. Hei 4-257501), a method of heating and drying the plant under pressure (Japanese Patent Laid-Open Application No. Hei 2-178201). 5 to 40% by weight of ultrafine hygroscopic inorganic material having a particle size of 10 to 1,000 nm in a dried plant obtained by heating the plant to a temperature of 50 to 90 ° C. under pressure of 5 to 30 kg / cm 2. It is suitable to coat the slurry mixture composed of% and 60 to 95% by weight of the liquid epoxy resin (Korean Patent Application No. 2001-11439) so that it does not discolor and deform for a long time and is preserved as it is.

In addition, UV absorbers, antioxidants, flame retardants and the like can be added to the epoxy resin to improve the quality according to the purpose.

Through the following examples will be described in more detail the present invention. The following examples are merely illustrative and the present invention is not limited to the following examples.

Example 1

Four-leaf clover was used as a plant, and a dried plant was manufactured by using a continuous drying device that was dried while pressurized with a rotary heating drum installed in a hot air heating tank. First, the leaves of the four-leaf clover were properly collected, and dried under the conditions of drying at a temperature of 75 ° C., a pressure of 15 kg / cm 2 and a time of 2 minutes to prepare dried four-leaf clover. On the other hand, a slurry mixed with 25 wt% of 50 nm zeolite (trade name Advera, PQ Co., Ltd.) and 80 wt% of epoxy resin of liquid bisphenol A having an epoxy value of 0.50 and epichlorohydrin was dispersed with a homogenizer for 40 minutes. To produce a clear particulate / epoxy slurry mixture. 6 parts by weight of a room temperature curing agent diethylenetriamine was added to the slurry mixture and mixed to prepare a slurry mixture coating solution. The prepared dried four-leaf clover was coated with the prepared fine particle / epoxy slurry mixture coating solution to prepare a final dried plant sample.

Electron-donating color-compounding compound (I) Spiro [12-H-benzo-α-chianthene-12-1 (3H) -isobenzopyran] -3-one, 9- (diethylamine) -spiro [isobenzofuran -1 (8H), 9- (9H) chianthene] -3-one and the electron-accepting compound (II) 4,4-thiobis (6-t-butyl-8-methylphenol) in a 1: 3 ratio To prepare a reversible thermochromic compound that changes from colorless to pink starting at 14 ℃. Subsequently, the thermochromic resin composition was prepared by adding 0.3 parts by weight of the reversible thermochromic compound obtained above to 100 parts by weight of the epoxy resin of liquid bisphenol A and epichlorohydrin having an epoxy of 0.50.

The obtained dried plant sample was attached to the key ring, and the thermochromic resin composition was coated to prepare a key ring sample decorated with four-leaf clover. The state at the time of leaving the obtained sample at 14 degreeC or more is shown in FIG. 2 shows that the key ring sample is discolored by being left at a temperature of 14 ° C. or lower.

Example 2

Using the dried plant obtained in Example 1 and the reversible thermochromic resin composition was applied to the lighter in the same manner. The state which left the obtained sample to 14 degreeC or more and the temperature below is shown to FIGS. 3 and 4, respectively.

Example 3

Using the dried plant obtained in Example 1 and the reversible thermochromic resin composition was applied to the bracelet in the same manner. The state which left the obtained sample to 14 degreeC or more and the temperature below is shown to FIGS. 5 and 6, respectively.

As can be seen in the above embodiment it can be seen that the reversible discoloration based on a specific temperature, this can be seen that it can be applied to a variety of applications, such as a key ring, lighters, bracelets.

The ornament of the present invention is a thermochromic resin composition, which holds natural plants in the ornament body, thereby retaining its natural appearance without being discolored and deformed for a long time, and is expected to be useful as an amazing ornament that causes the interest of 'reversible thermochromic phenomenon'. do.

Claims (5)

In the decorative material impregnated with dried natural plants in a transparent synthetic resin, Natural plants using a composition comprising 100 parts by weight of epoxy resin and 0.001 to 10 parts by weight of a reversible thermochromic mixture in which the electron donating colorimetric compound and the electron-accepting compound are mixed at a ratio of 1: 1 to 1:10. Thermochromic decorative material impregnated with a natural plant, characterized in that impregnated. The method of claim 1, wherein the electron-donating color-compound compound comprises diaryl phthalides, polyaryl carbinols, leucooramins, aryloramins, rhodamine B lactams, indorins, spiropyranes, or huroranes. A thermochromic decorative material impregnated with a natural plant, characterized in that one or more leuco dyes selected from the group are used alone or in combination. The phenolic hydroxyl group according to claim 1, wherein the electron-accepting compound is selected from the group consisting of nonylphenol, dodecylphenol, 4,4-thiobis (6-t-butyl-8-methylphenol) and bisphenol A. Branched compounds and metal salts thereof; Aromatic carboxylic acids and metal salts thereof selected from the group consisting of maleic acid, fric acid, benzoic acid and phthalic acid; Aliphatic carboxylic acids having 2 to 5 carbon atoms and metal salts thereof selected from acetic acid or propionic acid; Acidic phosphate esters and metal salts thereof; 1,2,3-triazole and its derivatives; And a compound selected from the group consisting of hydropyridine and a derivative thereof having 2 to 5 carbon atoms, alone or in combination, wherein the thermochromic decorative material is impregnated with a natural plant. The method of claim 3, wherein the electron-accepting compound is selected from spiro- [12-H-benzo-α-chianthene-12-1 (3H) -isobenzopyran-3-one, 9- (diethylamine) -spiro [ Isobenzofuran-1 (8H), 9- (9H) chianthene] -3-one, 2-chloro- (diethylamino) -3-methyl-spiro [isobenzofuran-1- (3H), 9- (9H) -chixanthene] -8-one or 6-diethylamino-2- [cyclohexyl (phenylmethyl) amino]. A compound characterized in that it is used alone or in combination. Thermochromic decorative material impregnated with plants. Jewelry with a thermochromic decorative material impregnated with the natural plant according to any one of claims 1 to 4.