JP2010248655A - Colored paper, colored paper mold and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide colored paper used for packaging food, medicines, beverages or the like, a colored paper mold used as cushioning material for transporting the food or the like and a method for manufacturing them. <P>SOLUTION: Conventionally, basic dyes or the like for industrial dyes are mainly used as coloring agents of a packaging material or cushioning material of food. Packaging paper or colored paper molds colored by these dyes cause problems of contamination or the like of the food contacting them when color bleeding or fading of dye components occurs by water such as rain. In this invention, they are colored with chlorophyllin salt, which is a pigment component. The problems are solved by a technique for insolubilizing to water and fixing, and safety or environmental aspects are also improved. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

The present invention relates to a colored paper using a paper raw material, a colored paper mold, and a method for producing the same.
More specifically, it is highly safe to be used as a food additive for coloring products such as wrapping paper for products that come into direct contact with foods, pharmaceuticals, and beverages, and paper molds for protecting and fixing products as cushioning materials. The present invention relates to a colored paper, a colored paper mold, and a method for producing them, which are colored using iron chlorophyllin sodium, which is a coloring matter, and are further fixed to improve water resistance, thereby preventing color flow and color transfer.

Conventionally, synthetic dyes (organic dyes, organic pigments) and natural pigments (plant pigments, animal pigments, etc.) are often used for coloring paper and pulp. However, many of the dyes or pigments used are water-soluble, and coloring of papers and pulps using these dyes is not sufficient. For example, basic dyes for industrial dyes are used for packaging of agricultural products such as apples and paper molds. Colored wrapping paper and paper molds have color flow and color transfer of dyes due to rainwater, and contact with them. Color fixing technology to papers such as pulp with dyes or pigments, such as causing stains by transferring colors to apples and the like that are still not sufficient.

In food packaging using dyes or pigments, the colored surface does not come into direct contact with food because the colored paper adheres to the food and there are concerns about health issues. It is used via packaging materials. In addition, it is used for protection and immobilization as a cushioning material for fragile agricultural products (for example, fruits) and foods (for example, eggs) that are easily broken or crushed by impact, etc. during handling during transportation or movement. The above dyes or pigments are also used in paper molds and the like.

Copper chlorophyllin Na or iron chlorophyllin Na in which magnesium (magnesium located at the center of the chlorophyll molecule) in chlorophyll extracted from raw leaves (green leaves) of plants such as Kumazasa is substituted with copper or iron, taking advantage of the characteristics of natural pigments A manufacturing method (see Patent Document 1) relating to pulp and paper yarn containing the above pigment is disclosed.
In addition, a technique relating to functional hygiene paper (see Patent Document 2) having a pharmacological effect such as a deodorizing effect and an antibacterial effect by containing a salt of copper chlorophyllin or iron chlorophyllin in toilet paper, towel paper, paper diaper, etc., and copper chlorophyllin A technology relating to deodorized filter paper (see Patent Document 3) in which Na salt is treated with a weak acid having a pH of 1 to 2 (fixing by acid treatment) and copper chlorophyllin that is insoluble in water is adsorbed to the fiber of the paper is also disclosed. Yes.
In addition, a technology relating to ink jet recording ink (see Patent Document 4) using copper chlorophyllin Na and / or iron chlorophyllin Na as green dyes is also disclosed. Suitable for fonts.
JP 2002-37789 A JP-A-5-168570 JP 62-215100 A JP 59-230071

The present invention solves the above-mentioned problems existing in colored paper molds used as packaging materials for foods, pharmaceuticals, beverages and the like, and used as a cushioning material when transporting foods, etc. An object of the present invention is to provide a colored paper and a colored paper mold in which color flow and color transfer from a substrate are prevented. Furthermore, it aims at providing the manufacturing method of these colored paper and a colored paper mold.

The present invention for solving the above-described problems has the following contents.

In the first aspect of the present invention, the paper raw material is colored with a dye composition liquid containing iron chlorophyllin Na, and the iron chlorophyllin Na present on the surface of the paper raw material or in the paper raw material is converted into a paper raw material with a dye fixing agent containing calcium ions. It is a colored paper characterized in that it is fixed on the paper.

According to a second aspect of the present invention, a paper raw material is colored with a dye composition liquid containing iron chlorophyllin Na, and iron chlorophyllin Na present on the surface of the paper raw material or in the paper raw material is converted into a paper raw material with a dye fixing agent containing calcium ions. It is a colored paper mold characterized by being fixed to.

According to a third aspect of the present invention, the paper raw material is colored with a dye composition liquid containing iron chlorophyllin Na, and the iron chlorophyllin Na present on the surface of the paper raw material or in the paper raw material is converted into a paper raw material with a dye fixing agent containing calcium ions. A method for producing a colored paper, characterized in that the colored paper is fixed.

According to a fourth aspect of the present invention, a paper raw material is colored with a dye composition liquid containing iron chlorophyllin Na, and iron chlorophyllin Na present on the surface of the paper raw material or in the paper raw material is converted into a paper raw material with a dye fixing agent containing calcium ions. It is the manufacturing method of the colored paper mold characterized by making it fix to.

The colored paper and colored paper mold of the present invention and the production method thereof are specified as iron chlorophyllin Na designated as a food additive as a pigment component, and the pH value of the pigment composition liquid containing the pigment and the aqueous medium is 6 or more. It is adjusting. In particular, when the pH value of the dye composition solution becomes acidic at 4 or less, the terminal carboxylate salt becomes free and changes to chlorophyllin insoluble in water.

When the pH value of the dye composition solution is adjusted to 6 or more, the dye composition solution exhibits a yellowish green color. The dye composition solution is dipped or spray-coated on the base paper produced in the target papermaking process, and then the colored paper is used as a calcium chloride aqueous solution of a dye fixing agent ( It is immersed in about 3 to 5%), taken out, and dried to obtain a colored paper ion-exchanged with a calcium salt. This colored paper is excellent in water resistance without causing color shift or color transfer with water.

Conventionally, basic dyes of industrial dyes are mainly used as coloring materials for food packaging materials and buffer materials, and wrapping paper and colored paper molds colored with these dyes are dye components with water such as rainwater. There were problems such as contamination of food that was in contact due to color flow and color transfer. According to the present invention, the problem can be solved by a technique of coloring with iron chlorophyllin Na, which is a pigment component, and further insolubilizing and fixing in water, and also in terms of safety and environment.

In addition, iron chlorophyllin Na is excellent in light resistance because it has a robust chemical structure against sunlight. By taking advantage of this characteristic and ion-exchange to the terminal carboxylic acid calcium salt, it has a stable dye fixing ability to cellulose such as paper. This characteristic is the same for the use of the colored paper mold.

“[Color transfer test] was performed on Example 1 (Test body 1) to Comparative example 2 (Test body 3), and the state of migration of the dye onto the filter paper was photographed.”

Iron chlorophyllin Na used in the dye composition solution of the present invention is described in the food additive list (designated additive), and is a dye that forms a Na salt at the terminal of the carboxyl group of iron chlorophyllin.

The pigment iron chlorophyllin Na is preferably contained in an amount of 0.1 to 10% by mass in the pigment composition solution. A more preferable pigment content is 0.2 to 5% by mass. If the blending amount of the dye is less than 0.1% by mass, it may be difficult to sufficiently exhibit the blending effect (toning effect). On the other hand, even if it exceeds 10% by mass, no further compounding effect can be expected.

The surfactant of the dye composition liquid of the present invention is not an essential component, but when used, it may be used as a food additive or a pharmaceutical and has no safety problem, and is not particularly limited. Specific examples include stearyl alcohol, polyoxyethylene glycol fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyethylene glycol fatty acid ester.

It is preferable that the amount of the surfactant is 0.01 to 15% by mass in the dye composition solution. If the blending amount of the surfactant is less than 0.01% by mass, it may be difficult to sufficiently exhibit the blending effect (dispersion effect). On the other hand, even if it mixes exceeding 15 mass%, the further blending effect cannot be expected. Preferably, it is 0.05-10 mass%.

In the present invention, a pH adjuster is used as necessary to adjust the pH. Examples of the pH adjuster include citric acid, sodium citrate, phosphoric acid, trisodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium carbonate, sodium hydrogen carbonate, hydrochloric acid, sodium hydroxide and the like.

In the present invention, a preservative can be added if necessary. Examples of the preservative include benzoic acid, sodium benzoate, ethanol, citric acid, salicylic acid, sodium salicylate, D-sorbitol, sorbic acid, methyl paraoxybenzoate, and the like.

The amount of these preservatives used is preferably in the range of 0.1 to 5% by mass relative to the total amount of the dye composition solution. If the amount used is less than 0.1% by mass, there is no storage effect, and even if it exceeds 5% by mass, there is no further effect.

The dye composition liquid in the present invention can be produced by a usual formulation method. For example, iron chlorophyllin Na and, if necessary, a surfactant are dissolved in water and mixed, and other adjunct preservatives and the like are added, and the pH is adjusted to 6 or more with a pH adjuster to produce a dye composition solution.

The dye fixing agent in the present invention is not particularly limited as long as it is a compound salt that can be dissolved in water containing calcium ions. Specific examples of calcium salts include calcium chloride, calcium hydroxide, calcium nitrate, calcium sulfate, calcium hydrogen phosphate, calcium lactate, and calcium oxalate. As the dye fixing agent of the present invention, calcium chloride is particularly preferable because it is remarkably effective in preventing color migration and color transfer from colored paper or the like.

The colored paper and colored paper mold of the present invention can be produced as follows.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, the scope of the present invention is not limited to these Examples. In the examples and comparative examples, “%” indicates “% by mass”.

1 g of iron chlorophyllin sodium (manufactured by Tama Seikagaku) is dissolved in 99 g of ion-exchanged water,
A mass% dye aqueous solution was prepared. This dye aqueous solution was weighed 1.5 g, which is 30 times the mass of the filter paper. 0.05 g of filter paper (manufactured by ADVANTEC) was immersed in the weighed dye aqueous solution and left for 5 minutes. The colored filter paper is taken out and placed on a Kimwipe (manufactured by Nippon Paper Crecia) for 30 seconds to dehydrate it. Separately, 3 g of calcium chloride is dissolved in 97 g of ion-exchanged water to prepare a 3 mass% calcium chloride aqueous solution, and 1.5 g, which is 30 times the mass of the filter paper, is weighed, and the above colored filter paper is soaked for 3 minutes. I left it alone. The soaked filter paper was placed on a Kimwipe for 30 seconds to dehydrate and dried. This was designated as test body 1, and the following [bleeding test], [color transfer test] and [light resistance test] were performed.

[Bleeding test]
0.025g of ion-exchanged water was dropped on the test body 1 using a Pasteur pipette from a height of 1 cm from the test body. After leaving as it is for 10 minutes, the degree of bleeding from the spread of the droplets dropped on the test body 1 was measured.

[Color transfer test]
The test body 1 was placed on a new filter paper, and 0.15 g of ion-exchanged water was dropped on the test body 1 using a Pasteur pipette. The sample was allowed to stand for 10 minutes, covered with a new filter paper from above, a certain pressure was applied, and how much the dye had transferred to the new filter paper covered was measured with the following color difference meter. The constant pressure is 0.12 MPa.

[Light resistance test]
The test body 1 was irradiated for 40 hours with ultraviolet rays using an ultraviolet long life fade meter (trade name; FAL-5H, manufactured by Suga Test Instruments Co., Ltd.). Subsequently, the specimen body irradiated with ultraviolet rays and the specimen not irradiated with ultraviolet rays were measured with the following color difference meter, and the color difference (ΔE) before and after the test of the specimen 1 was obtained.

[Color difference measurement method]
The color difference measurement is a color difference (ΔE) between a test piece that has been transferred using a spectroscopic color difference meter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. and a new filter paper before the test that is a blank.

The smaller the color difference ΔE is, the better the color transfer is.

[Comparative Example 1]
1 g of iron chlorophyllin sodium (manufactured by Tama Seikagaku) is dissolved in 99 g of ion-exchanged water,
A mass% dye aqueous solution was prepared. This dye aqueous solution was weighed 1.5 g, which is 30 times the mass of the filter paper. 0.05 g of filter paper (manufactured by ADVANTEC) was immersed in the weighed dye aqueous solution and left for 5 minutes. The colored filter paper was taken out, placed on Kimwipe for 30 seconds, dehydrated and dried.
This was designated as test body 2, and [bleeding test], [color transfer test] and [light resistance test] were conducted in the same manner as in Example 1.

[Comparative Example 2]
1 g of iron chlorophyllin sodium (manufactured by Tama Seikagaku) is dissolved in 99 g of ion-exchanged water,
A mass% dye aqueous solution was prepared. This dye aqueous solution was weighed 1.5 g, which is 30 times the mass of the filter paper. 0.05 g of filter paper (manufactured by ADVANTEC) was immersed in the weighed dye aqueous solution and left for 5 minutes. The colored filter paper was taken out and placed on a Kimwipe for 30 seconds for dehydration.
Separately, 1.5 g of pH 3 citrate buffer prepared by the following method is 30 times the filter paper mass.
Weighed, soaked the colored filter paper, and left for 3 minutes. 30 soaked filter paper on the Kimwipe
It was dehydrated for 2 seconds and dried.
This was designated as test body 3, and [bleeding test], [color transfer test] and [light resistance test] were carried out in the same manner as in Example 1.

[Method for preparing pH 3 citrate buffer]
Solution 1: Add ion-exchanged water to 21 g of citric acid and dissolve to make 1000 ml.
Second liquid: Dissolve by adding ion-exchanged water to 71.6 g of disodium phosphate to make 1000 ml.
This 1st liquid (159 volume) and 2nd liquid (41 volume) are mixed uniformly, and a citrate buffer solution (pH 3) is prepared.

Table 1 shows the results of [bleeding test], [color transfer test] and [light resistance test]. In addition, a photograph [Fig. 1] of the color transfer test result is presented.

From the test results of [Table 1], the fixing treatment with Ca ions in Example 1 was compared with Comparative Example 1 (without fixing treatment) and Comparative Example 2 (fixing with acid treatment) [color transfer test]. Excellent results have been obtained in [Light resistance test]. In particular, in the [light resistance test], the result is considerably better than the fixing technique by acid treatment [Comparative Example 2].

The present invention improves the water resistance and light resistance, which are conventional problems, by coloring and fixing papers and paper molds using iron chlorophyllin, which is a food additive and a highly safe pigment. By doing so, color flow and color transfer from a substrate such as paper could be prevented and the problems could be solved.
The technique of insolubilizing the iron chlorophyllin and Ca ion pigments of the present invention and fixing them to a substrate such as paper can be used in other fields because it does not require special equipment and can reduce capital investment. Think of things.

Claims (6)

The paper raw material is colored with a dye composition liquid containing iron chlorophyllin Na, and iron chlorophyllin Na present on the surface of the paper raw material or in the paper raw material is fixed to the paper raw material with a dye fixing agent containing calcium ions. Colored paper. The colored paper according to claim 1, wherein the dye composition solution contains 0.1 to 10% by mass of iron chlorophyllin Na and is adjusted to pH 6 or more. The paper raw material is colored with a dye composition liquid containing iron chlorophyllin Na, and iron chlorophyllin Na present on the surface of the paper raw material or in the paper raw material is fixed to the paper raw material with a dye fixing agent containing calcium ions. Colored paper mold. The colored paper mold according to claim 3, wherein the dye composition liquid contains 0.1 to 10% by mass of iron chlorophyllin Na and is adjusted to pH 6 or more. The paper raw material is colored with a dye composition liquid containing iron chlorophyllin Na, and iron chlorophyllin Na present on the surface of the paper raw material or in the paper raw material is fixed to the paper raw material with a dye fixing agent containing calcium ions. To produce colored paper. The paper raw material is colored with a dye composition liquid containing iron chlorophyllin Na, and iron chlorophyllin Na present on the surface of the paper raw material or in the paper raw material is fixed to the paper raw material with a dye fixing agent containing calcium ions. A method for producing a colored paper mold.

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