JP2001192602A - Colorant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colorant homogeneously producible in large quantities, excellent in color fastness to dyeing, weather resistance and the like and suitable for dying fibers and coloring woods. SOLUTION: This highly industrially valuable colorant is homogeneously producible in large quantities by dissolving a solution or paste of soluble lignocellulose in a solvent and is capable of dying fibers and coloring woods excellently in color fastness to dyeing, weather resistance and the like wherein the lignocellulose is obtained by adding a phenol to sawdust of cryptomeria or wood flour and thermally reacting the resultant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colorant containing a soluble lignocellulosic substance as a coloring component, which is used for dyeing fibers, coloring wood, and the like. The present invention further relates to a method of using the soluble lignocellulosic material for dyeing fibers, coloring wood, and the like. According to the present invention, a solution or paste-like substance of a lignocellulosic substance obtained by adding a phenol such as phenol to various lignocellulose materials such as wood flour and heating the mixture is suitable for coloring or dyeing. Based on new findings. In the present specification, the lignocellulose material means various raw materials derived from plants containing celluloses, lignins and the like as main components, and the soluble lignocellulose material is obtained by a heat reaction between the lignocellulose material and phenols. Solution or paste-like substance to be obtained. Further, the coloring agent means a coloring agent used for dyeing fibers and the like, and coloring wood and the like.

[0002]

2. Description of the Related Art As a dyeing method using plants such as wood and plants as raw materials, plant dyeing is known. Plant dyeing is a method in which extracts such as leaves, stems, bark, and flowers of plants are used as coloring agents. Plant dyeing of fibers and yarns has been practiced since ancient times and is commonly used. However, the extracts of countless vegetation in nature include bark, leaves, flowers,
It differs greatly depending on the parts such as the wood part and the timing of the sampling, and it is difficult to produce them uniformly and in large quantities. It has also been proposed to use as a coloring agent a cationic lignin derivative in which a quaternized nitrogen-containing aliphatic group is bonded to lignin isolated from wood as a fractional component of wood (Japanese Patent Application Laid-Open No. 7-215988). ). However, this method is difficult to put into practical use because of the complicated processing steps and high cost. Although a method using a solubilized lignocellulose substance as a coloring agent using polyhydric alcohols as a solvent has been attempted, it has not been put to practical use due to poor weather resistance and solvent solubility.

[0003]

The following problems (1) to (5) can be cited as problems which are likely to occur in plant dyeing. (1) Since plant dyeing is extracted from plants, it is quantitatively limited as a coloring agent. (2) Since the plant dye is extracted from the plant, there is a variation in hue, and it is difficult to adjust the concentration and the like. (3) Since the dyeing of plants and plants is colored by a chemical bond with a mordant, the coloring may be different due to subtle differences in the components. (4) The coloration of plant dyes differs depending on the environmental temperature and humidity. In addition, since there are two steps, management of each is required. (5) Since plant dyeing is usually performed with an aqueous solution,
Fluff is likely to occur when coloring wood or the like.

There are the following problems (1) and (2) in the technology using a cationic lignin derivative as a coloring agent. (1) Each step of isolating lignin from wood, derivatizing the isolated lignin with a cationizing agent, and purifying the reaction product requires high costs due to the use of expensive chemicals and complicated processes. Bring. (2) The weather resistance of the colored material to light and moisture is not clear and there is a concern.

[0005] An object of the present invention is to solve the above problems by using lignocellulose, which is a main constituent of plants, as a raw material and subjecting it to a substance obtained by subjecting it to a simple chemical treatment and purification treatment. The present invention provides a plant-derived coloring agent which is a coloring agent used as a coloring component and which is far less expensive than currently used general-purpose chemically synthesized coloring agents and which has excellent performance such as weather resistance.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a coloring agent containing, as a coloring component, a soluble lignocellulosic substance obtained by adding a phenol to a lignocellulose material and subjecting it to a heat reaction. In the colorant of the present invention, a metal salt is used together with a soluble lignocellulose substance for the purpose of enhancing the dyeing property and the color fastness with the article to be dyed, or for enhancing the colorability and weather resistance with the article to be dyed. Is preferred. Further, in the coloring agent of the present invention, using an acid or an alkali together with a soluble lignocellulose substance,
Depending on the object to be colored or the object to be dyed,
It is preferred to adjust the pH value. In addition, the present invention provides a method of immersing an object to be dyed in a solution obtained by dissolving a soluble lignocellulosic substance obtained by adding phenols to a lignocellulose material and heating and reacting the same in a solvent, or coating the solution with the solution. The present invention relates to a method of using the soluble lignocellulose substance as a coloring agent, which is applied to a coloring matter.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As a lignocellulose material which is a starting material of a coloring component in a coloring agent of the present invention,
Sawdust, wood flour, wood chips, veneer chips, plywood cuttings,
Examples of the material include plant fiber materials such as bark, and various plant-derived materials mainly containing celluloses such as straw, peach, coffee bean scum, bagasse scum, and beet pulp, and lignins. The phenols used in the present invention include phenol, o-, m-, p-cresol, 3,5
-, 2,3-, 2,6-xylenol, o-, m-, p-
Propylphenol, o-, m-, p-butylphenol, o-, m-, p-secondary butylphenol,
o-, m-, p-tert-butylphenol, hexylphenol, phenylphenol, octylphenol, monohydric phenols such as naphthol; catechol,
Divalent phenols such as resorcinol, quinol, bisphenol A, bisphenol B, bisphenol F;
Pyrogallol, phloroglucyl, trihydrobenzene,
Trivalent phenols such as gallic acid; and chlorides thereof. These phenols can be used alone or as a mixture. In the present invention, it is particularly preferable to use phenol from the viewpoint of price and performance. Furthermore, in order to lower the solution viscosity, alleviate the runaway reaction due to the heat generated in the initial stage of the reaction, and remove the water in the lignocellulose substance out of the system, an organic solvent azeotropic with water is used.
It may be used together with phenols. In addition, other organic solvents can be added and used together within a range in which the object of the present invention is achieved.

As a method for producing the solution or paste soluble lignocellulosic substance as the coloring component of the present invention, known methods such as a non-catalytic method, an acid catalyzed method and an alkali catalyzed method can be adopted. As the non-catalytic method, Japanese Patent Application Laid-Open No.
No. 61358, that is, a lignocellulose material is added to phenols,
A method of producing a solution of a lignocellulosic substance such as wood by heating to 0 ° C. Specifically, for example, 4.5 g of dry wood flour and 4.5 g of phenol are weighed in a beaker, mixed well, put into a 20 ml pressure-resistant container, packed, and sealed, then heated at 250 ° C. for 2 to 3 hours. It is a method of processing. The acid catalyzed method is disclosed in Japanese Patent Application Laid-Open No. 57-36113.
In other words, there is a method introduced in Japanese Patent Application Publication No. H10-15064, that is, a method in which phenol is reacted with pulverized wood in the presence of a small amount of a mineral acid. Specifically, for example, phenol 940 g
And 9.4 g of concentrated sulfuric acid are weighed into a beaker, heated to 150 ° C., 400 g of wood flour is fed in over 1 hour, and further heat-treated at the same temperature for 1 hour. As the alkali catalyst method, a method introduced in JP-A-7-188568 and the like, that is, a soluble lignocellulosic substance is obtained by adding a phenol to a lignocellulose material and subjecting it to a heat reaction in the presence of an alkaline additive. And a method for producing Specifically, for example, 120 g of wood flour (water content 71%), 47 g of phenol, and 2.3 of sodium hydroxide
5 g is weighed into a 2 L pressure-resistant reaction vessel equipped with a stirrer,
This is a method of performing heat treatment at 250 ° C. for 1 hour in an oil bath. By the above-mentioned method, a lignocellulosic material such as wood flour is converted into a solution, and a solution or paste-like, normally black-brown, soluble lignocellulosic substance can be obtained. In the present invention, any of the above methods may be used.

In the above-mentioned method, it is desired that the compounding ratio of the lignocellulose material and the phenol is such that the compounding ratio of the lignocellulose material is as large as possible and the undissolved residue is small. In the case of the non-catalytic method, 5 to 2 phenols are added to 10 parts by weight of the lignocellulose material.
0 parts by weight, preferably about 10 parts by weight, is added. The reaction temperature is in the range of 200 to 300 ° C, preferably about 250 ° C, and the reaction time is in the range of 15 minutes to 1 hour. In the case of adding an acid catalyst, 10 to 100 parts by weight, preferably 20 to 40 parts by weight of a phenol is added to 10 parts by weight of the lignocellulose material. The amount of the acid catalyst used is 0.2 to 10 parts by weight, preferably 0.5 to 2.5 parts by weight, based on 10 parts by weight of the lignocellulose material. The reaction temperature is in the range of 100 to 200 ° C, preferably about 150 ° C,
The reaction time ranges from a few minutes to one hour. In the case of adding an alkali catalyst, 3 to 20 parts by weight, preferably 10 parts by weight of phenol is added to 10 parts by weight of the lignocellulose material.
Add about parts by weight. The amount of the alkali catalyst used is 0.1 to 10 parts by weight, preferably 0.2 to 2.0 parts by weight, based on 10 parts by weight of the lignocellulose material. The reaction temperature is in the range of 200 to 300C, preferably about 250C,
The reaction time ranges from 15 minutes to 1 hour. Soluble lignocellulose material in the form of a solution or paste obtained by the above-described method, preferably after further removing undissolved residues by filtration or centrifugation, a water-soluble unreacted solvent such as phenol, and hydrolysis, By washing with water to remove water-soluble reactants by-produced by oxidative decomposition, a viscous soluble lignocellulosic substance that separates from water is obtained. Preferably, the water in the material is further removed by drying, distillation under reduced pressure, or the like, to obtain a soluble lignocellulosic material that is desirable for use as the coloring component of the present invention.

The soluble lignocellulosic material thus obtained can be used as a colorant as it is. Soluble lignocellulosic substances are soluble in alcohol solvents such as methanol and ethanol; ketone solvents such as acetone; ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve. A coloring agent is prepared by dissolving in a solvent as a coloring component. The concentration of the solution is adjusted depending on the degree of coloring or dyeing, but it is usually desirable to use the solution as a 1 to 50% by weight solution. In the present invention, it is preferable to use a metal salt together with the soluble lignocellulosic substance for the purpose of improving the dyeing property and the color fastness to the material to be dyed and for enhancing the weather resistance of the material to be colored. Metal salts include potassium carbonate, alum, copper sulfate, iron sulfate, ferrous chloride, stannous chloride, cupric chloride, anhydrous cupric chloride, cupric ammonium chloride, copper acetate, ferric acetate Aluminum acetate, iron acetate, cupric bromide, copper nitrate, copper naphthenate, sodium stannate, slaked lime, potassium bichromate, lye, titanium salts, etc. can be used for alum, cupric chloride, Anhydrous cupric chloride, copper sulfate and the like are desirable. Among them, cupric chloride and anhydrous cupric chloride, which are soluble in acetone or the like, are most desirable. By forming a complex salt using these metal salts, for example, an increase in affinity with a material to be dyed is considered to be a cause of good dyeing properties. The amount of the metal salt used is usually 0.1 to 100 parts by weight of the coloring component.
It is 1 to 50 parts by weight, preferably 2 to 20 parts by weight.

In the present invention, it is preferable to adjust the pH of the colorant by using an acid or an alkali together with soluble lignocellulose as a coloring component according to the purpose of use. Adjustment of the pH is usually performed by adding an aqueous acid solution or an aqueous alkali solution to the coloring agent. Alternatively, a coloring agent may be further added to a solution in which the above-mentioned solvent is dissolved. The acid used includes at least one selected from inorganic acids, organic acids, and Lewis acids. As the inorganic acid, a common mineral acid such as hydrochloric acid, sulfuric acid, phosphoric acid, and hydrobromic acid is used.As the organic acid, carboxylic acids such as formic acid, acetic acid, oxalic acid, tartaric acid, and benzoic acid, and Organic sulfonic acids such as phenolsulfonic acid and p-toluenesulfonic acid, and sulfinic acids such as phenolsulfinic acid, and uric acids are included. Examples of the Lewis acid include compounds such as aluminum chloride, titanium chloride, and boron trifluoride, and complexes thereof. The alkali used includes at least one selected from alkali metal hydroxides, alkaline earth metal hydroxides, alkaline earth metal carbonates and amines. Alkali metal hydroxides include sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides include calcium hydroxide, alkaline earth metal carbonates include calcium carbonate, and amines include monoethanolamine. Can be exemplified. It is also possible to use a buffer. Examples of the buffer include Clark-Labs buffer, Seirsensen buffer, McKilbain buffer, and Walpole buffer.

In the present invention, the material to be dyed is usually immersed in a solution obtained by dissolving a soluble lignocellulosic substance or a coloring agent containing the same in a solvent, or the solution is applied to the material to be colored. Coloring is performed. For example, in the case of fiber dyeing, one of the above-mentioned solvents is selected, and the bath ratio (concentration) is such that the weight ratio of the coloring component to the solvent is from 1: 1 to 1: 100, preferably about 1:40, and the weight of the fiber to be dyed. About 50 times the solution is prepared. Dyeing is generally used for dyeing. As for the dyeing temperature, the higher the temperature, the higher the dyeing speed and the larger the amount of dyeing, but usually at room temperature. The dyeing time is adjusted in the range from 5 minutes to several hours. The dyeing process may be repeated for deep dyeing. For the solution, adjusting the appropriate pH as described above is also effective. All are determined by the degree of coloring of the target fiber.

For example, in the case of dyeing silk cloth and wool, it is desirable to add an acid (weakly acidic system pH 3 to 5), and in the case of cotton cloth, it is desirable to add an alkali (weakly alkaline system pH 9 to 11). In the former case, the ionization of the constituent proteins of silk and wool is promoted under weak acidity, and in the latter case, the ionization of the functional groups in the molecules of the coloring component is promoted under weak alkalinity and the constituent components of cotton cloth It is considered that the occurrence of the surface activation of cellulose which is a cause of good dyeability. The pH of the dyeing solution is desirably 3 to 5 in the case of silk cloth or wool, and desirably 9 to 11 in the case of cotton cloth. It is also possible to carry out pre-treatment or post-treatment of the fiber with a mordant containing a metal salt as described above in order to effect dyeing or improve weather resistance, and to wet the dye solution. , Penetrant, dissolution, solubilizer,
It is also possible to add various auxiliaries used for ordinary dyeing, such as level dyeing, slow dyeing agents and deep dyeing agents. Alternatively, other vegetable dyes, synthetic dyes, pigments, and the like can be mixed or dyed and laminated. For example, the coloring component of the present invention is mixed with an alcoholic coloring agent or NGR stain in a weight ratio of 100: 0.
It is mixed and used depending on the degree of coloring of the target fiber in the range of 100 to 500.

When, for example, wood coloring is carried out using the coloring component of the present invention, one of the above-mentioned solvents is selected, and the weight ratio of the coloring component: solvent is from 1: 1 to 1: 200, preferably 1: 1:
Adjust to about 30. The coloring method is brush painting, spraying,
The same process as that for general wood coloring such as a roll coater may be used. The amount of application is adjusted according to the desired degree of coloring of the wood. In order to improve the weather resistance, it is also possible to add the above-mentioned metal salts dissolved in a solvent, for example, cupric chloride, cupric acetate, cupric bromide, copper naphthenate and the like. The amount of addition is 1 to 30 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the coloring component. Usually, the metal salt is added to the solution in which the coloring component is dissolved, but it is also possible to mix the metal salt with the coloring component in advance. It is also possible to use a commercially available ultraviolet absorber or light stabilizer in the coloring component solution or in the coloring component. It is also possible to use the coloring component of the present invention or a solution thereof mixed in an oil paint, or to use a mixture of an oil paint in the coloring component solution.

Hereinafter, the present invention will be described in more detail with reference to examples. Example 1 120 g of cedar sawdust (water content: 71%) and phenol 47
g (wood flour / phenol = 6/4) and 2.35 g of sodium hydroxide are weighed into a 2 liter pressure-resistant container equipped with a stirrer, and are weighed in an oil bath until the temperature in the container reaches 180 ° C. ± 5 ° C. It takes about 30 minutes to raise the temperature.
The temperature was raised in 5 to 30 minutes, kept at 250 ° C. for 1 hour, and then cooled to obtain a black solubilized substance. G
The mixture was filtered through the glass filter No. 3 to obtain a black product with a yield of about 99%. Distilled water was added to the obtained liquid substance and washed with water while stirring. The washing with water was repeated several times until completely separated from water. The liquid material completely separated was taken out and dried with a drier to obtain a coloring component. Acetone was added to this coloring component to make a 10% solution, and a coloring solution for cotton cloth was obtained as a coloring agent. 2 g of cotton cloth was immersed in 100 g of a coloring solution for about 30 minutes, and then washed with water to obtain a cotton cloth A dyed brown. Further, 2 g of cotton cloth was previously immersed in boiling water of 200 g of 1% alum solution for 30 minutes, and then immersed in 100 g of a coloring solution adjusted to pH 10 with an aqueous hydrochloric acid solution and an aqueous sodium hydroxide solution for about 30 minutes to obtain a cotton cloth dyed brown. B was obtained. JIS L 0848-1996 (sweat test), JIS L 0845-1975 (hot water test), JIS L 0844-1997
Table 1 shows the dye fastness performance based on the (washing test).

[0016]

[Table 1]

As shown in Table 1, it is clear that both cotton fabrics have excellent color fastness and can be used in the same manner as ordinary coloring agents. Example 2 132 g of cedar sawdust (water content 10%) and phenol 28
0 g (wood flour / phenol = 3/7) and sulfuric acid 8.4 g,
Weigh out into a 2 L pressure vessel equipped with a stirrer and raise the temperature in an oil bath to 180 ° C. ± 5 ° C. in 15-30 minutes, then to 250 ° C. 15-30 minutes After heating at 250 ° C. for 1 hour, the mixture was cooled to obtain a black solubilized substance. The liquid was filtered through a G3 glass filter to give a black product with a yield of about 98%. Distilled water was added to the obtained liquid substance and washed with water while stirring. The washing was repeated many times until the water and liquid were completely separated. The liquid material completely separated was taken out and dried with a drier to obtain a coloring component. Acetone was added to this coloring component to make a 20% solution, and a coloring solution for wood was obtained as a coloring agent. This solution was spray-coated on a medium fiber board (MDF) to give a predetermined color tone, and a brown colorant C was obtained. Next, cupric chloride was added to the coloring solution for wood in an amount of 5% by weight based on the coloring component, and then spray-coated on MDF to obtain a predetermined color tone to obtain a brown coloring material D. Further, 0.5% by weight of a light stabilizer LS-770 manufactured by Sankyo Co., Ltd. was added to the coloring solution to which cupric chloride was added, based on the solution.
The MDF was spray-painted and finished to a predetermined color tone to obtain a brown colorant E. Sunshine Ink Senon Long Life Weather Meter (WEL-6XS-HC B)
In Ec), irradiation was performed for 85 hours using sunshine carbon. Table 2 shows changes in color difference before and after irradiation measured by a color difference meter.

[0018]

[Table 2]

As shown in Table 2, it is clear that the weather resistance is excellent and that it can be used as a coloring agent.

[0020]

The plant-based coloring agent of the present invention described above can be produced more homogeneously and in large quantities, and is excellent in fastness such as discoloration and fading, as compared with plant dyes. It is a coloring agent having an affinity for natural fibers such as silk, wool, cotton, and wood, and the industrial value of the present invention is extremely high. In addition, as the main raw material of the coloring agent of the present invention, waste materials such as unused materials such as thinning materials and branch materials which are by-products of forest trees, construction waste materials, demolition materials of wooden houses, waste chips and the like can be used. The present invention contributes to the development of environmentally friendly technologies in terms of recycling, expansion of new uses, and energy saving effects.

Continued on front page F-term (reference) 4J038 BA021 HA096 HA106 HA176 HA216 HA286 HA326 HA366 HA406 HA476 JA37 JB01 JB09 JC03 JC10 JC13 JC37 JC38 KA08 LA03 MA06 MA10 NA03 NA11 PB14 PC06 PC10

Claims (4)

[Claims] 1. A colorant containing, as a coloring component, a soluble lignocellulose substance obtained by adding a phenol to a lignocellulose material and subjecting it to a heat reaction. 2. The colorant of claim 1 which comprises metal salts with the soluble lignocellulosic material. 3. A colorant according to claim 1, which contains an alkali or an acid together with the soluble lignocellulosic material. 4. A dyeing material is immersed in a solution obtained by dissolving a soluble lignocellulosic substance obtained by adding a phenol to a lignocellulose material and heating and reacting in a solvent, or coloring the solution. A method of using the soluble lignocellulosic substance as a colorant, which is applied to an object.