JP4624367B2 - Coloring accelerator for persimmon - Google Patents

Description

The present invention relates to a persimmon color development accelerator, a persimmon color development promotion method, and a persimmon astringent paint manufacturing method .

In wooden buildings such as wooden houses, pillars, beams, flooring, paneling, handrails, counters, doors, furniture, etc. are often painted to protect the wood and improve the beauty. . Most of the paints used today are synthetic paints based on petroleum-based synthetic resins because of their excellent performance and ease of handling. Typical examples of such synthetic resins include lacquer resin, polyurethane resin, acrylic resin, fluorine resin, polyester resin, silicone resin, acrylic silicone resin, etc., but these are problems of resource depletion and global warming. We have environmental problems such as gas emission problems.
In addition, organic solvents are mainly used as the solvent for the synthetic resin paint, and these are volatile organic compounds. Therefore, it is pointed out that they may contribute to sick house syndrome.

Until now, due to the efforts of the paint industry, the amount of organic solvents contained in these synthetic resin paints has been reduced, and water-based aqueous paints or water-based emulsion resin paints have been developed and marketed. Not a few organic solvents are included. In addition, various chemical substances are often added as additives in order to solve various problems that occur with the aqueousization.
In recent years, there has been an increase in the momentum for active use of natural materials due to the growing awareness of environmental protection and safety of familiar substances.

One of the traditional natural paints in Japan is Kashiwabu.
As a technique using amber astringency, after applying amber astringency to lumbered wood, it is burnt with a flame, and by applying amber astringency, the technique of coloring the surface of the wood to show an ancient color over time It is known (see Patent Document 1).

JP 2003-53707 A

When applied to wood, cotton, paper, etc. and dried and cured, persimmon astringent color develops slowly and takes on a unique reddish brown to brown color over several weeks to more than half a year.
The color and texture peculiar to this astringent have been loved as a finishing method to bring out the texture of wood in the history of Japanese architecture.
However, in recent years, since the color development is slow, it is difficult to adjust the hue of the indoor design, it is inconvenient that the color development precedes only the part that is exposed to sunlight, or the color development from the beginning is desired, half a year or a year Some people say that they can't wait for the color development to take time.
In order to develop amber astringency, it is exposed to sunlight and promotes the coloration of the amber astringent component by ultraviolet rays, or is artificially irradiated with ultraviolet rays, or an oxidizing agent is added to the amber in advance, It may be oxidized. However, exposure to sunlight or artificial UV irradiation takes time, is affected by the weather, requires a large area or dedicated equipment, and produces less color. Not early. In addition, many oxidizers are not suitable in the same manner because they are problematic in terms of the safety of their components or are synthetic compounds that do not conform to the gist of natural paints.
It should be noted that coloring by adding a pigment or a dye is not suitable for the purpose of the present invention for promoting the color development of astringency.

Accordingly, an object of the present invention is to provide a color developing accelerator for persimmon, which can easily and quickly color the persimmon.
Another object of the present invention is to provide a method for facilitating color development of strawberries that can easily and quickly color the strawberries.
Moreover, the objective of this invention is providing the manufacturing method of the astringent astringent paint whose color is stabilized early.

The present inventors diligently studied to solve the above problem, and found that color development can be promoted by adding a basic water-soluble compound to the persimmon.
The present invention has been completed based on these findings and further studies.

The present invention comprises a basic water-soluble compound that is a salt of a carboxylic acid (excluding citric acid) and an alkali metal or an alkaline earth metal, or an aqueous solution thereof, and is used by mixing with astringent astringent color accelerator. The above-mentioned object is achieved by providing an agent (hereinafter referred to as this invention when referred to as the first invention).

The present invention also provides a basic water-soluble compound which is a salt of a carboxylic acid (excluding citric acid) and an alkali metal or alkaline earth metal, or an aqueous solution thereof, after the addition of the persimmon astringent The above-mentioned object is achieved by providing a method for promoting color development of persimmon astringency, characterized in that it is painted on (hereinafter referred to as the second invention).

In addition, the present invention applies a water solution of a basic water-soluble compound, which is a salt of a carboxylic acid and an alkali metal or an alkaline earth metal , to the object to be coated after applying amber astringency to the object to be coated. after applying the aqueous solution of the water-soluble compound to the coating material, characterized by applying a persimmon thereon is obtained by achieving the above object by providing a color method of promoting persimmon (hereinafter, third The term invention refers to this invention).
The present invention also relates to a method for producing a persimmon astringent paint by obtaining a persimmon astringent paint by coating the persimmon astringency on the object to be coated, and promoting the color development of the painted persimmon astringent by the color development promoting method of the second or third invention. It is intended to provide a method for producing an astringent astringent paint.

According to the color development accelerator and method for promoting color development of the present invention, it is possible to easily and quickly color the persimmon.
According to the method for producing a persimmon painted product of the present invention, it is possible to provide a persimmon painted product whose color is stabilized at an early stage.
In the present invention, it is not necessary to use a dye or a pigment.

Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.
The color development accelerator for persimmons of the first invention comprises a basic water-soluble compound or an aqueous solution thereof, and is used by mixing with persimmons.
In the second aspect of the present invention, the basic water-soluble compound or an aqueous solution thereof is added to the persimmon and then the persimmon is painted on the object to be coated.

The basic water-soluble compound in the present invention functions as a color development accelerator that promotes color development of persimmons.
Basic water-soluble compound used as color enhancer (hereinafter, simply referred to as color enhancer) may be an aqueous solution thereof is present use those which show a basic. Examples of basic water-soluble compounds include salts of alkali metal hydroxides and weak acids typified by sodium hydroxide, alkali earth metal hydroxides and weak acids typified by calcium hydroxide, Examples include amines (such as ammonia) and weak acid salts. In the present invention, a basic water-soluble compound that is a salt of a carboxylic acid and an alkali metal or alkaline earth metal is used as the color development accelerator. A basic water-soluble compound can be used individually by 1 type or in combination of 2 or more.

Although strong bases such as sodium hydroxide and weak bases such as sodium carbonate are effective in promoting color development, these bases, especially strong bases, must be added as a sufficiently dilute solution. Gelling of astringent astringent or denatured precipitate occurs. Therefore, these strong bases and weak bases with relatively strong basicity are inconvenient when you do not want to add water to the astringent fruit.
From this point of view, sodium acetate, sodium citrate, sodium adipate, weak alkali metal salts or alkaline earth metal salts such as salicylic acid sodium (however, the aqueous solution is limited to those showing alkalinity) are preferred, weak acid A metal salt which is a carboxylic acid is more preferable, and sodium acetate is particularly preferably used from the viewpoint of safety and cost.

The persimmon astringent used in the present invention is a fermented liquid material obtained by squeezing persimmon, and various known persimmons can be used without particular limitation. Commercially available persimmon astringents can also be preferably used. There are no particular restrictions on the variety of persimmon, the fermentation years of persimmon, the species of bacteria used for fermentation, the tannin content of persimmon, baume, acidity, the presence or absence of additives, and the like.
As an example of the persimmon astringent used preferably, the cultivar is Tenno koji, which has a fermentation period of half a year, a tannin content of 5%, and an acidity of 3-4. It is preferable to use the persimmon astringent so as to adjust the content ratio of tannin to 0.5 to 10% by weight, particularly 1 to 5% by weight.

The addition amount of the color accelerator for the persimmon varies depending on the target persimmon astringency, the concentration and the content, and cannot be defined uniformly, but as an example, 0.1 to 10 parts per 100 parts persimmon astringent More preferably, it is 0.5-5 parts, More preferably, it is 1-3 parts. In addition, as for the addition amount of the color development accelerator in the case of adding as aqueous solution, it is preferable that the weight part converted before melt | dissolution is in said range.
Here, “part” is “part by weight”. Further, when the color accelerator is added as an aqueous solution, the amount of the aqueous solution added is preferably 0.1 to 300 parts.

  The color development accelerator may be added in a solid state such as a powder to the persimmon astringent, or may be added as an aqueous solution. It is preferable to mix after the addition. As the mixing method, various known methods can be adopted without particular limitation, and various stirrers, mixers, and the like can be used, and after adding astringency and color accelerator to the container, the container may be shaken. .

  In the second invention, after the color accelerator is added to the persimmon, the persimmon is painted on the object to be coated. As the object to be coated, cellulose materials such as wood, paper, and cotton are preferable. The wood may be various kinds of wooden materials in addition to the solid materials. Examples of the wood material include plywood, single plate laminate (LVL), particle board, MDF, and the like. As the coating method, various known coating methods can be used without particular limitation in wood coating. As the paper, various known papers such as Japanese paper and kraft paper can be used. The painted astringency of the present invention is obtained, for example, by painting a coated astringency with a coloring accelerator added to an object to be coated and then drying it. As the drying method, various known drying methods can be used without particular limitation in wood coating, and examples thereof include natural drying and hot air drying.

The persimmon astringent modified by the addition of a color accelerator has drastically improved color developability compared with the conventional persimmon astringency, and the desired degree of persimmon color development can be obtained very simply and quickly. . Such an effect can also be obtained by using only an additive that is highly safe for the human body, such as sodium acetate, as a color accelerator. In addition, unlike natural paints that have been marketed on the market, it is not necessary to include an organic solvent, which is unlikely to cause an incidental organic compound.
It should be noted that the mixture of the color accelerator and the astringent is not limited to the effect of the present invention, but other additives such as a pH adjuster, a buffer, an alcohol that accelerates drying, and an inorganic filler that enhances coating performance. May be included.

  According to the third aspect of the present invention, a method for promoting color development of astringent astringents is applied to an object to be coated, and then an aqueous solution of a basic water-soluble compound is applied thereon, or an aqueous solution of a basic water-soluble compound is applied to an object to be coated. After applying, apply astringency from above. The points that are not particularly described with respect to the third invention are the same as those of the first or second invention, and the descriptions of the first or second invention described above are appropriately applied to the points that are not particularly described.

(1) After applying persimmon astringent to the object to be coated, when applying an aqueous solution of a basic water-soluble compound from above, the aqueous solution is applied in a state where the amber astringent previously applied to the object to be coated is dry. It is preferable.
(2) After applying an aqueous solution of a basic water-soluble compound to an object to be coated, and then applying an amber astringency from above, the application of the anther is an aqueous solution of a basic water-soluble compound previously applied to the object to be coated. Is preferably performed in a dry state.
In both cases (1) and (2), the ratio of the water-soluble compound in the aqueous solution of the water-soluble compound is such that the weight of the water-soluble compound before dissolution is 0.1 parts per 100 parts of water as the solvent. It is preferably 1 to 50 parts, and preferably 0.5 to 30 parts.

Also by the color development promoting method of the third invention, it is possible to easily and quickly develop the color of persimmon astringency.
The second invention has the advantage that only one painting operation is required compared to the third invention, and the third invention has the advantage that the coloring can be adjusted after painting compared to the second invention. is there.
The persimmon astringent paint obtained by applying the amber astringent and an aqueous solution of a basic water-soluble compound to the object to be coated by the method of the third invention and drying it is also an embodiment of the amber astringent painted of the present invention.

  As mentioned above, although one Embodiment of this invention (1st-3rd invention) was demonstrated, each invention is not restrict | limited to said embodiment, It can change suitably.

  Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples. In this example, “parts” is “parts by weight” unless otherwise specified.

Example 1
[Verification of the relationship between the amount of color development accelerator (weakly basic salt) added and the degree of color development]
The following evaluation was performed using a commercially available strawberry shibu (made by Tomiyama Co., Ltd., liquid).
The commercially available strawberry astringent was a liquid containing about 5% by weight of tannin, and in the following examples, it was used as a strawberry astringent liquid without dilution.
0 parts, 1.5 parts or 3 parts of sodium acetate (solid) was added to 100 parts of persimmon juice, and stirred until they were sufficiently mixed. The obtained aqueous solutions were designated as aqueous solutions 1, 2 and 3 in ascending order of sodium acetate (coloring accelerator) addition.
Next, aqueous solutions 1, 2, and 3 were applied to a cedar board and allowed to dry naturally. This coating and drying operation was repeated three times to obtain a sample of astringent astringent paint corresponding to each aqueous solution.
About each sample, the change of each color was measured over time using the color difference meter (CR-200 by Minolta), and color difference (DELTA) E was calculated.
ΔE was calculated from the L ^* a ^* b ^* colorimeter as ΔE = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2 (where L ^* : brightness, a ^* , b ^* : saturation).

Changes in color (L ^* , a ^* , b ^* ) and ΔE are shown in Table 1 and FIG.
In Table 1 and FIG. 1, “control” is a sample obtained by applying and drying aqueous solution 1 (sodium acetate addition amount 0 part), and “1.5 parts” is aqueous solution 2 (sodium acetate addition amount). 1.5 parts) is a sample obtained by applying and drying, and “3.0 parts” is a sample obtained by applying and drying the aqueous solution 3 (sodium acetate addition amount: 3.0 parts).

As is apparent from Table 1, the color change of the control sample was extremely slow. On the other hand, samples obtained by adding sodium acetate to persimmon (“1.5 parts” and “3.0 parts”), although there is little difference in color among the three specimens immediately after the addition (day 0). From the third day onward, the lightness (L ^* ) is remarkably lowered and the chroma (a ^* , b ^* ) is also lowered at the same time when sodium acetate is added. That is, it can be said that the color development (browning) of persimmon astringency is effectively promoted.
As is clear from FIG. 1, even when a very small amount of sodium acetate was added (1.5 parts), color development was sufficiently promoted, and color development was completed in a very short time compared to the conventional (control). is doing.
Sodium acetate itself is a transparent crystal, and its aqueous solution is also colorless and transparent. Moreover, wood is not discolored only by applying an aqueous solution of sodium acetate to wood. Therefore, it is clear that the color development observed in this test is a phenomenon caused by the action of sodium acetate on the persimmon.
In Example 1, the color after 60 days of the application of the persimmon astringent to which sodium acetate was added and the sample dried was the same as the color after the long-term passage of the conventional persimmon astringent coating obtained by coating only the persimmon astringent The red-brown to brown-brown color peculiar to amber shibu.

Example 2
Ion-exchanged water, an aqueous solution obtained by dissolving 1.5 parts of sodium acetate in 100 parts of ion-exchanged water, and an aqueous solution obtained by dissolving 3.0 parts of sodium acetate in 100 parts of ion-exchanged water (in order) Aqueous solutions 1, 2, and 3) were respectively applied to cedar plates and allowed to dry naturally. This operation (application and drying) was repeated three times.
Next, under the condition that the surface of the cedar board coated with the aqueous solutions 1 to 3 is naturally dried, a commercially available strawberry (manufactured by Tomiyama Co., Ltd., liquid) is applied to the one surface of each cedar board and dried naturally. I let you. The operation of applying and drying the persimmon astringent was repeated three times to obtain a persimmon astringent paint sample.
These samples were evaluated in the same manner as in Example 1.
Changes in color (L ^* , a ^* , b ^* ) and ΔE are shown in Table 2 and FIG.
In Table 2 and FIG. 2, “control” is a sample obtained by applying astringency after applying aqueous solution 1 (sodium acetate addition amount 0 parts), and “1.5 parts” is aqueous solution 2 (sodium acetate). "3.0 parts" is a sample obtained by applying and drying the aqueous solution 3 (3.0 parts of sodium acetate added).

  As can be seen from Table 2 and FIG. 2, the color development of the persimmon was also effectively promoted even when the persimmon was applied after the aqueous sodium acetate solution was applied.

Example 3
In Example 2, a sample of persimmon painted material was obtained in the same manner as in Example 2 except that the order of application of persimmon astringent and aqueous solutions 1, 2, and 3 was reversed. In addition, the persimmon astringent repeated application | coating and natural drying 3 times. Moreover, application | coating of the aqueous solutions 1-3 was performed 3 times, and it dried naturally after that.
The obtained sample was evaluated in the same manner as in Example 1.
The changes in color (L ^* , a ^* , b ^* ) and ΔE are shown in Table 3 and FIG.
In Table 3 and FIG. 3, “control” is a sample obtained by applying aqueous solution 1 (sodium acetate addition amount 0 parts) after applying persimmon astringent, and “1.5 parts” after applying persimmon astringent This sample was obtained by applying aqueous solution 2 (sodium acetate addition amount 1.5 parts). “3.0 parts” was applied after applying astringent astringent solution 3 (sodium acetate addition amount 3.0 parts). It is a sample obtained.

  As can be seen from Table 3 and FIG. 3, even when the persimmon astringent was applied after the sodium acetate aqueous solution was applied, the color development of the persimmon astringent was effectively promoted.

Reference example 1
[Verification of the relationship between the amount of color development accelerator (strongly basic salt) added and the degree of color development]
In Example 1, instead of sodium acetate, sodium hydroxide (solid) was added in the same manner as in Example 1 except that 0 part, 1.5 part, or 3 parts was added to 100 parts of persimmon astringent (liquid). Samples of coated products were obtained, and those samples were evaluated in the same manner as in Example 1.
Changes in color (L ^* , a ^* , b ^* ) and ΔE are shown in Table 4 and FIG.
In Table 4 and FIG. 4, “control” is a sample obtained by applying and drying aqueous solution 1 (sodium hydroxide addition amount 0 parts), and “1.5 part” is aqueous solution 2 (sodium hydroxide). “3.0 parts” is a sample obtained by applying and drying aqueous solution 3 (sodium hydroxide addition amount: 3.0 parts).

  As can be seen from Table 4 and FIG. 4, when a strong base is used as the color developing accelerator, the change in color difference is small, but the color is also small. That is, it can be said that it is colored immediately after the addition. In addition, reaction precipitates are easily formed.

Reference example 2
[Verification of the relationship between the amount of color development accelerator (strong weak basic salt) added and the degree of color development]
In Example 1, instead of sodium acetate, sodium carbonate (solid) was added in the same manner as in Example 1 except that 0 part, 1.5 parts, or 3 parts of sodium carbonate (liquid) was added to 100 parts Product samples were obtained and evaluated in the same manner as in Example 1.
Changes in color (L ^* , a ^* , b ^* ) and ΔE are shown in Table 5 and FIG.
In Table 5 and FIG. 5, “control” is a sample obtained by applying and drying aqueous solution 1 (sodium carbonate addition amount 0 part), and “1.5 parts” is aqueous solution 2 (sodium carbonate addition amount). 1.5 parts) is a sample obtained by coating and drying, and “3.0 parts” is a sample obtained by coating and drying the aqueous solution 3 (sodium carbonate addition amount: 3.0 parts).

  As can be seen from Table 5 and FIG. 5, when a strong weak base is used as the color developing accelerator, the change in color difference is small, but the color is also small. That is, it can be said that it is colored immediately after the addition. In addition, reaction precipitates are easily formed.

Comparative Example (Verification of the relationship between the amount of neutral salt added and the degree of color development)
In Example 1, a sample of an astringent painted material in the same manner as in Example 1 except that ammonium acetate is added in place of sodium acetate in an amount of 0, 1.5 or 3 parts per 100 parts of an astringent (liquid) These samples were evaluated in the same manner as in Example 1.
Changes in color (L ^* , a ^* , b ^* ) and ΔE are shown in Table 6 and FIG.
In Table 6 and FIG. 6, “control” is a sample obtained by coating and drying aqueous solution 1 (ammonium acetate addition amount 0 part), and “1.5 parts” is aqueous solution 2 (ammonium acetate addition amount). 1.5 parts) is a sample obtained by coating and drying, and “3.0 parts” is a sample obtained by coating and drying the aqueous solution 3 (amount of ammonium acetate added: 3.0 parts).

As apparent from the above examples, the addition of or contact with a basic water-soluble compound, particularly sodium acetate, can effectively promote the color development of the persimmon in a very short time. On the other hand, as can be seen from Table 6 and FIG. 6, the neutral salt hardly promotes color development, which is the same as “control”.
By facilitating the color development, the color of the amber astringent paint stabilizes early or the tendency of the change is known, making it easy to adjust the color of the interior design, and the color of the amber astringent paint desired by the customer can be quickly Can be provided. Further, since the operation is easy to promote color development and the necessary apparatus is simple, it is possible to provide an astringent paint with a stable color at a low cost.

FIG. 1A is a graph showing the relationship between the amount of sodium acetate added and the color difference, and FIG. 1B is a graph showing the relationship between sodium acetate and color. FIG. 2 (a) is a graph showing the change in color difference when the amber astringency is applied after applying sodium acetate, and FIG. 2 (b) is the color change when the amber astringency is applied after applying sodium acetate. It is a graph. FIG. 3 (a) is a graph showing a change in color difference when sodium acetate is applied after application of strawberries, and FIG. 3 (b) shows a change in color when sodium acetate is applied after application of strawberries. It is a graph. FIG. 4A is a graph showing the relationship between the amount of sodium hydroxide added and the color difference, and FIG. 4B is a graph showing the relationship between sodium hydroxide and the color. FIG. 5A is a graph showing the relationship between the amount of sodium carbonate added and the color difference, and FIG. 5B is a graph showing the relationship between sodium carbonate and the color. FIG. 6A is a graph showing the relationship between the added amount of ammonium acetate and the color difference, and FIG. 6B is a graph showing the relationship between ammonium acetate and color.

Claims (6)

Carboxylic acid (except citric acid) and a basic water-soluble compound is an alkali metal or alkaline earth salts of the metal or made of an aqueous solution thereof, characterized by being used are mixed persimmon juice, color of persimmon Accelerator. 2. The color developing accelerator for persimmon astringency according to claim 1, wherein the water-soluble compound is sodium acetate. A basic water-soluble compound which is a salt of a carboxylic acid (excluding citric acid) and an alkali metal or alkaline earth metal or an aqueous solution thereof is added to the amber and then the amber is applied to the object to be coated. And a method for promoting the color development of persimmons. After coating the object to be coated persimmon, or applying the aqueous solution of a basic water-soluble compound is a salt of the carboxylic acid from above and an alkali metal or alkaline earth metal, or the water-soluble to the object to be coated A method for promoting color development of strawberries, comprising applying an aqueous solution of a compound and then applying strawberries on the top. The method for promoting color development of persimmon astringency according to claim 3 or 4 , wherein the water-soluble compound is sodium acetate. It is a method for manufacturing a strawberry astringent paint to obtain a strawberry astringent paint by painting the strawberry astringent on the object to be painted,
6. A method for producing an amber painted product , characterized in that the color development of the painted astringent astringent is promoted by the method for promoting color development according to any one of claims 3 to 5 .

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