JP2006131858A - Artificial amber and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an artificial amber having also physicochemical properties which amber has, e.g. transparency, gloss, insulating properties, processability, melting point, color tone or hardness. <P>SOLUTION: The artificial amber is produced by crosslinking an exocyclic methylene group in a resin having peak tops in 108 ppm and 148 ppm based on spectrum obtained by measurement of<SP>13</SP>C-NMR. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention includes building materials such as wall materials and floor materials, furniture such as desks and shelves, furniture such as clocks, fountain pens, cups, plates and lamps, electrical parts such as outlets, cultural assets such as wall paintings and paintings, and art. The present invention relates to an artificial amber having effects such as decorative value, electrical insulation, and long-term storage stability by forming or coating a product.

  Kohaku is a transparent or translucent and glossy resin that has been buried in the ground and fossilized from the resin of trees that flourished during the geological period. Because of its preciousness and beauty, it has been prized as an ornament of walls, furniture and furniture since ancient times. In addition, since it is easy to process, light and highly insulating, highly airtight, and resistant to chemical reactions, it is used for industrial applications such as the development of radar insulators and ship paints. . In addition, it is used for incense, incense sticks, and pharmaceuticals.

  However, the production area of kohaku is limited worldwide, and its industrial use was limited. On the other hand, the resin used as a basis for agitation can be easily obtained in a large amount in the form of rubber plantation cultivation, and if agitation can be artificially made using resin, agitation was used. New industrial development becomes possible.

Many products that resemble kohaku have been manufactured so far. For example, a product is known that imitates an amber containing insects and includes various memorabilia such as animals and plants and minerals with an acrylic resin. Obviously, it has a different texture such as gloss and has little value as a decorative product.
Therefore, Patent Document 1 discloses a method of manufacturing an artificial succinze by mixing a finely crushed shell and curing a polyester resin.

  JP 7-1113021 A   Srebrodrisky's “The Secret of its Charm” New Reading Company 1993

What is described in Patent Document 1 is only imitation because of its molecular structure, and physicochemical characteristics equivalent to those of agitation cannot be expected.
Non-Patent Document 1 introduces a production method by polymerizing abietic acid, which is a diterpene as a main component of pine resin, but it has not been put into practical use because the product is brittle. These do not have physicochemical properties characteristic of agitation such as transparency, gloss, insulation, processability, melting point, color tone, and hardness.

  An object of the present invention is to provide an artificial coral having a high decorative value that combines the physicochemical properties of the coral, such as transparency, gloss, insulation, processability, melting point, color tone, and hardness.

The present invention is an artificial amber produced by crosslinking exocyclic methylene groups in a resin.
And as said resin, resin which has a peak top in 108 ppm and 148 ppm in the spectrum obtained by < ¹³ > C-NMR measurement is used.
Moreover, it is an artificial succinic acid produced by crosslinking exocyclic methylene groups of the resin, and peak tops are 108 ppm and 148 ppm with respect to the total area of peaks appearing from 100 ppm to 160 ppm in solid ¹³ C-NMR measurement by CP _- MAS method. A ratio of the peak area is 0.4 or less.

Furthermore, the present invention is a method for producing an artificial succinic acid characterized in that crosslinking of an exocyclic methylene group is advanced by heat-treating a resin.
Further, the present invention is a method for producing an artificial succinic acid characterized in that crosslinking of an exocyclic methylene group is advanced by subjecting a resin to light irradiation treatment.

According to the present invention, it is possible to provide an artificial coral having a high decorative value that combines the physical and chemical properties of the coral, such as transparency, gloss, insulation, workability, melting point, color tone, and hardness.
The present invention includes building materials such as wall materials and floor materials, furniture such as desks, bookcases and cupboards, furniture such as clocks, fountain pens, ballpoint pens, cups, plates and lamps, electrical parts such as outlets, murals, paintings, etc. By coating or processing the cultural assets of the building, it can be stored stably for a long period of time, coating materials such as walls and furniture that have increased decorative value of art, and murals that are stable and highly transparent for a long period of time. It is most suitable for the field of preservation materials such as protective materials for cultural properties such as electrical insulation materials and ornaments, and building materials that require decorative value.

BEST MODE FOR CARRYING OUT THE INVENTION

  Hereinafter, embodiments of the present invention will be described in detail by way of examples.

As a result of solid state ¹³ C-NMR measurement of a compound related to a plant resin such as amber, pine ani, and damar resin, the present inventors have found that an exocyclic methylene group is used for the succination of a resin collected from the plant. Found that it is important to form an intermolecular cross-linked structure. The resin having an exocyclic methylene group is subjected to a heat treatment or a light irradiation treatment to advance the crosslinking reaction of the exocyclic methylene group contained in the resin component, so that the transparency, gloss, insulation, workability are increased. It has been found that an artificial amber can be produced that also has the physicochemical properties of the amber such as melting point, color tone and hardness.

As the resin used in the present invention, one having an exocyclic methylene group is selected. As a resin having an exocyclic methylene group, a resin having peak tops at 148 ppm and 108 ppm by directly measuring by a solid ¹³ C-NMR method, or by measuring by a liquid ¹³ C-NMR method after dissolving in an alcohol or the like It is characterized by using. Here, the resin refers to an oil and fat component secreted by plants, and means both a solution-like or latex-like one immediately after secretion and a solidified one. Further, it is assumed to include a resin called copal which is buried in the upper stone together with the vegetation and solidified in the sediment after being detached from the vegetation.

  Plants that produce such resins include the genus Agathis, Araucaria, Cunninghamia, Methesequoia, Cyptomeria, Cyptomae, and Cyptomae. (Hymenaea), preferably Kagami pine species (Agathis australaris), Agithis dammara species, New Caledonian kauri species (Agathis lancisata species), South Queens kauri species (Agathis robasiga species) Borneensis species (Agathis bornenesis) ), Agathis microphylla species, Agathis palmerstonii species, Agathis microstasis species, Agathis microstasis species, Agathis lombodias species moorei), Agathis robusta species (Agathis robusta), Agathis labiadieri species (Agathis labrarderi), Agathis obtusa species (Agathis obtusa) species (Agathis vitensis species) inghamia lanceolata), Raidashisugi species (Cunninghamia konishii), Kuningamia Kawakami species (Cunnighamia kawakamii), Metasequoia species (Metasequoia glyptostoboides), cedar species (Cryptomeria japonica), it is more desirable that the cypress species (Chamaecyparis obtusa), limited to these It is not something that can be done.

When the cross-linking reaction of the exocyclic methylene group proceeds by heat treatment or light irradiation treatment, the peak areas of 148 ppm and 108 ppm on the spectrum obtained by performing measurement by solid ¹³ C-NMR method decrease. Therefore, by calculating the ratio of the peak area with 108 ppm and 148 ppm as the peak top to the total area of the peak appearing from 100 ppm to 160 ppm in the solid NMR measurement by CP _- MAS method for the artificial amber produced by heat treatment or light irradiation treatment The progress of the crosslinking reaction can be confirmed, and this ratio is 0.4 or less.

  In addition, when this ratio is small, it is difficult to obtain the integrated intensities of the signals of 108 ppm and 148 ppm, but this is not a limitation.

The resin collected from the plant may be used as it is, or may be used after pulverizing and making the particle size uniform by sieving, removing impurities such as the woody part, or washing with water.
In addition, after the resin is dissolved in a solvent capable of dissolving the resin, impurities such as a woody part are removed by filtration, and then the residue recovered by precipitation by adding the residue obtained by distilling off the solvent or water may be used. . Examples of the solvent include alcohol, ketone, ether, furan, aliphatic hydrocarbon, aromatic hydrocarbon, pyridine, pyrrolidone, chloroform, and more preferably methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butanol, heptanol. , Hexanol, acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, tetrahydrofuran, chloroform, dichloromethane, diethyl ether, pyridine, dimethylformamide, dimethyl sulfoxide, and may be a mixed solvent composed of these, but not limited thereto is not. Furthermore, you may use the essential oil component obtained by distilling resin under pressure reduction.

  The heat treatment is performed by heating at a temperature of 40 ° C. or higher and 420 ° C. or lower. The heat treatment time varies depending on the reaction temperature. When heat treatment is performed at 120 ° C. or higher and 420 ° C. or lower, it is desirable to perform the heat treatment under a reduced pressure condition of 800 hPa or lower, or in an inert gas atmosphere. Inert gases include, but are not limited to, helium, argon, nitrogen, and carbon dioxide. The light irradiation treatment is performed by irradiating ultraviolet rays having a wavelength of 180 nm to 400 nm. The light irradiation may be in the air, but it is desirable to perform the treatment in an inert gas atmosphere. Inert gases include, but are not limited to, helium, argon, nitrogen, and carbon dioxide. Further, the heat treatment and the light irradiation treatment may be performed simultaneously or continuously.

  A resin of Metasequoia species (Metasequoia glyptostrobodies) 1 g of powder prepared using a mortar was placed in a test tube having a diameter of 1 cm, and the inside of the test tube was replaced with nitrogen gas, followed by heat treatment at 350 ° C. for 1 hour.

  After the resin of Kaurimatsu species (Agathis australaris) was washed with distilled water to remove bark components, 1 g of powder prepared using a mortar was placed in a test tube having a diameter of 1 cm, and the inside of the test tube was replaced with helium gas. For 36 hours.

  A resin of Metasequoia species is dissolved in a solution in which methanol and dichloromethane are mixed in a volume ratio of 1: 1, and after removing impurities by filtration, the solvent is distilled off and powdered in a mortar. 1 g of the prepared resin was placed in a test tube having a diameter of 1 cm, and the inside of the test tube was replaced with nitrogen gas, followed by heat treatment at 200 ° C. for 30 hours.

  1 g of a powder prepared using a mortar and a resin of Cunninghamia lanceolata was placed in a beaker and irradiated with light in the atmosphere for 120 hours at room temperature with an ultraviolet lamp having a wavelength of 254 nm.

  After washing the resin of hinoki seeds (Chamaecypalis obtusa) with distilled water to remove the bark component, 1 g of the powder prepared using a mortar was placed in a quartz glass tube, the inside of the glass tube was replaced with nitrogen gas, and then sealed Then, light irradiation treatment was performed at room temperature for 60 hours with an ultraviolet lamp having a wavelength of 254 nm.

(Comparative example 1) Natural amber produced from Kuji City, Iwate Prefecture was powdered.
(Comparative Example 2) Natural agate produced from Hachioji City, Tokyo was powdered.
(Comparative Example 3) Natural amber produced from the Baltic region of Poland was powdered.
(Comparative Example 4) Resin of Cunninghamia lanceolata was powdered.
(Comparative Example 5) Resin of Metasequoia species (Metasequoia glyptostromoids) was powdered.
(Comparative Example 6) A resin of Kagami pine species (Agathis australaris) was powdered.

For solid state ¹³ C-NMR measurement, Bruker Avance DRX-600 NMR spectrometer is equipped with a 4 mm solid MAS probe, MAS rotational frequency 9 kHz, π / 2 pulse width 6 μs, CP contact time 2 ms, waiting time 4 s, 2400- Obtained after 3000 times of integration. Using a VACP pulse sequence, ¹ H decoupling was performed at tppm (two-pulse phase modulation). The standard for ¹³ C chemical shift was set to 29.5 ppm (with tetramethylsilane (TMS) at 0 ppm) with adamantane as the external standard and the high magnetic field peak. The solid ¹³ C-NMR spectra of the artificial amber shown in Examples 1 and 3 measured under these conditions, the natural amber shown in Comparative Examples 1 and 2 and the resin shown in Comparative Example 5 are shown in FIGS. It was.

  Table 1 shows the artificial amber obtained in Examples 1 to 5 and the natural amber shown in Comparative Examples 1 to 6 and the peaks of 108 ppm and 148 ppm relative to the total area of peaks appearing at 100 to 160 ppm in the NMR spectrum of the resin. The ratio of peak areas is shown. In the NMR spectrum of the artificial amber obtained in Examples 1 to 5, the signals of 108 ppm and 148 ppm are reduced in intensity compared to the signals of 108 ppm and 148 ppm in the NMR spectra of the resins of Comparative Examples 4 to 6 used as raw materials. It was shown that the cross-linking reaction of the exocyclimethylene group proceeded. As a result, it was confirmed that the artificial amber obtained in Examples 1 to 5 had undergone the exocyclimethylene group crosslinking reaction to the same extent as the natural amber shown in Comparative Examples 1 to 3.

  It is known that kohaku has a characteristic transparent and glossy color called amber, emits fluorescence when irradiated with ultraviolet rays, has a high melting point, and does not dissolve in an organic solvent. Therefore, Table 2 shows the results of measuring the color tone, melting point, fluorescence emission, and solubility of the artificial amber obtained in Examples 1 to 5 and the natural amber and resins shown in Comparative Examples 1 to 6 in Table 2. It was. The fluorescence emission was irradiated with ultraviolet rays of 302 nm, and the presence or absence of emission was observed. The solubility was observed by adding 1 ml of a mixed solution of methanol and dichloromethane in a volume ratio of 1: 1 to 10 mg of the sample and dissolving. The melting point was measured by heating the capillary tube containing the sample in an oil bath to completely melt it. As shown in Table 2, the artificial ambers of Examples 1 to 5 are different from the resins of Comparative Examples 3 to 6 used as raw materials, and have the same properties as the natural ambers shown in Comparative Examples 1 to 3. showed that.

FIG. 3 is a diagram showing a solid ¹³ C-NMR spectrum of the artificial amber obtained in Example 1. FIG. 4 is a diagram showing a solid ¹³ C-NMR spectrum of the artificial amber obtained in Example 3. The diagram which shows the solid ¹³ C-NMR spectrum of the natural amber obtained in Comparative Example 1. The diagram which shows the solid ¹³ C-NMR spectrum of the natural amber obtained in Example 2. FIG. The diagram which shows the solid ¹³ C-NMR spectrum of the resin succinol obtained in Comparative Example 5.

Claims (5)

  Artificial agate produced by crosslinking exocyclic methylene groups in a resin. An artificial agglomeration characterized in that a resin having a peak top at 108 ppm and 148 ppm in a spectrum obtained by ¹³ C-NMR measurement is used as the resin. An artificial succinic acid produced by crosslinking the exocyclic methylene group of the resin, with the peak top being 108 ppm and 148 ppm relative to the total area of peaks appearing from 100 ppm to 160 ppm in solid ¹³ C-NMR measurement by the CP _- MAS method. An artificial shale having a peak area ratio of 0.4 or less.   A method for producing an artificial succinic acid characterized in that crosslinking of an exocyclic methylene group is advanced by heat-treating a resin.   A method for producing an artificial succinic acid characterized in that crosslinking of an exocyclic methylene group is advanced by light irradiation treatment of a resin.

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