JPH0632099A - Manufacture of art decorative material using fish scales - Google Patents

Abstract

PURPOSE:To provide a novel colored transparent decorative material by using special shape of fish scales and transparency. CONSTITUTION:Calcium of fish scales purified on its surface is removed by 1/4-2/3, colored with acidic dye or gold-containing dye, then chemically modified at part of collagen in the scale with basic chromium complex salt or basic aluminum salt to fix the shape of the scale, thereby obtaining a decorative material having a colored transparency and high reflectivity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a novel shaped decorative material having a high degree of transparency which can be used for decoration of a floor material, an inner wall of a building or a surface plate of a table.

[0002]

2. Description of the Related Art The main protein of fish scale is collagen belonging to type I, but it is detached and accumulated in large quantities at the time of landing of sardines, saury, etc. in fishing ports. After drying, these fish scales are only partially used as fertilizer and feed.

[0003]

In recent years, collagen has been widely developed as a biopolymer and its application has been widely developed. Fish scales are considered to be important as one of the raw materials of this kind, and fish scales have a unique shape. The present invention is intended to provide a colored decorative material having an excellent transparency by utilizing the holding.

[0004]

SOLUTION: The present invention provides a modeling material having an excellent transparency, which is obtained by purifying fish scales (accumulation in a dry state) and then fixing the shape by dyeing the dried fish scales. After that, dip it in a mild alkaline solution and then dip it in a sodium chloride solution to remove foreign matters, and dilute acid treatment to reduce the total calcium content in fish scales to about 1/4 to 2/3. Second step of removal and after dyeing with acidic or metal-containing dyes, a small amount of basic chromium complex salt or basic aluminum salt is used to chemically modify part of the carboxyl groups of collagen in fish scales to fix the shape of fish scales. It consists of a third step.

[0005]

[Test Example] A dried fish scale is mildly alkali-treated, that is, soaked in a calcium hydroxide solution, and then adhering calcium is removed and neutralized with an ammonium chloride solution, followed by a 10% sodium chloride solution. Impregnation was removed by immersion. After the above treatment, the chemical analysis values of fish scales degreased and dehydrated with cold acetone were as shown in Table 1.

[0006]

[Table 1] Chemical analysis value of fish scale (%) Sample Water Protein Total ash Oil Oil Dry fish scale 16.21.8 19.8 ± 1.2 57.2 ± 1.4 4.7 ± 0.9 [Mawashi] (23.6) (68.3) (5.6) Treated fish scale 34.8 ± 2.4 62.3 ± 3.2 [Degreasing / dehydration] The value in parentheses () is the value converted to the anhydride, which is the average SD of 5 measurements.

Comparing the protein contents of livestock bones and fish scales after defatting treatment, bovine bone: 35.9 ± 3.2%,
Pork bone: 48.2 ± 4.3%, Chicken bone: 60.3 ± 5.8%
The fish scale shows the lowest value and the total ash content is 62.3 ± 3.2.
%, The dyeability was poor, and calcium removal treatment was required. As a result of immersion treatment in a 1% hydrochloric acid solution at 20 ° C for 1 hour, the residual ash content was 0.24%, and it was completely decalcified (calcium), and as shown in Table 2, the amino acid composition was also purified. Became.

[0008]

[Table 2] Numerical values indicate amino acid residues

Acid dyes (CI Acid Red7
A dyeing experiment according to 3) showed that the fish scales that were not subjected to the calcium removal treatment had a very poor dyeing property, and that the purified fish scales that had been completely decalcified under the same conditions gave a thick dyed product. Then, the original shape of the fish scale could not be retained. Therefore, 1/4 amount of total calcium in fish scale, 1/3
The amount of 1/3% of the above dye was adjusted by changing the dipping time with the above-mentioned 1% hydrochloric acid solution to adjust the amount and 2/3 amount.
After dyeing with a solution and drying, the spectral reflectance curves were compared (Fig. 1). All of them have higher reflectance than the completely decalcified fish scales, indicating low dyeing property.
However, since the one-third amount and the two-third amount removed have almost the same reflectance, at least 1/4 to 1
It is estimated that up to / 3 amount of calcium removal treatment is necessary. In order to maintain the original shape of fish scales, it is possible to achieve the intended purpose by chemically modifying the carboxyl groups of collagen in fish scales with basic chromium sulfate or basic aluminum sulfate following the dyeing treatment. It was

[0010]

【Example】

First step: Using sardine fish scales as a raw material, water-washed for 24 hours, washed with running water for 2 hours, drained (30 minutes), and weighed. Dip in 20% volume of 2% calcium hydroxide solution (containing 0.1% nonionic surfactant) for 2 days, 20-2
5 ° C, renew the immersion liquid, soak for 1 day, drain for 30 minutes,
Further, it was washed with running water for 2 hours and drained for 30 minutes. 2%
It was immersed in an ammonium chloride solution for 2 hours to remove the adhered calcium and perform a neutralization treatment. After washing with running water for 2 hours, drain for 30 minutes. Then, soak in a 10% sodium chloride solution for 1 day, drain for 30 minutes, and wash with running water for 2 hours.
Soak in cold acetone, change acetone twice every 2 hours,
Subsequently, it was soaked for 24 hours and air-dried.

Second step Fish scales obtained after the first step are placed in a 0.1% hydrochloric acid solution at 20 °
It was immersed in C for 6 hours to remove about 1/3 of the total calcium content. The 0.1% hydrochloric acid solution used was 50 times the weight of the fish scale. The fish scales that had been subjected to the calcium removal treatment were washed with running water for 2 hours and drained for 30 minutes. After immersing the fish scale in 50 times the amount of distilled water (35 ° C) for 30 minutes, a small amount of sodium bicarbonate solution was added to adjust the pH of the solution to 5.8 to 6.0, followed by draining.

Third step Immerse in 50 times volume of distilled water (55 ° C.) and immediately add 1% of the acid dye (CI Acid Red7) to the weight of the fish scale.
3) was added with stirring and stirring was continued for another 40 minutes. Then, dilute formic acid (1:10) was added and bath PH was added.
Was adjusted to 4.2. Furthermore, a solution of basic chromium sulfate corresponding to 0.5% of the fish scale weight was added, and after stirring and soaking for 30 minutes, the bath was drained, washed with running water for 30 minutes, air-dried, and a transparent red-dyed fish scale foil was obtained. Obtained.

[0013]

Industrial Applicability According to the present invention, it becomes possible to use fish scales, which have been poorly used in the past, as a novel colored decorative material having high transparency. For example, by fixing this material on the surface of a table top or floor material and then covering it with a transparent paint or the like, a decorative effect different from that of a conventional decorative material containing a colored reflective piece is obtained.

[Brief description of drawings]

FIG. 1 is a graph showing a reflectance curve according to the degree of deashing treatment.

[Explanation of symbols] None

Claims (1)

[Claims] After allowing the dried fish scale to absorb water sufficiently, soak it in a mild alkaline solution and then soak it in a sodium chloride solution to remove contaminants, and dilute acid treatment to reduce the total calcium content in the fish scale to 1 The second step of removing about / 4 to 2/3 and after dyeing with an acid dye or a metal-containing dye, a small amount of basic chromium complex salt or basic aluminum salt is used to chemically remove a part of the carboxyl groups of collagen in fish scales. A method for producing a shaped decorative material using fish scales, which comprises the step of modifying the scales to fix the shape of the fish scales.