JP3444834B2 - Colorant - Google Patents

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Plant dyeing is known as a dyeing method using a plant such as wood or plants as a raw material. Plant dyeing is a method of using extracts of plant leaves, trunks, bark, flowers and the like as coloring agents. The dyeing of fibers and threads with plants has been performed since ancient times and is generally used. However, the extracts of the myriad of plants that exist in nature include bark, leaves, flowers,
It varies greatly depending on the parts such as the timber and the time of the sampling, and it is difficult to produce them uniformly and in large quantities. It has also been proposed to use a cationic lignin derivative obtained by binding a quaternized nitrogen-containing aliphatic group to lignin isolated from wood as a coloring agent as a fractionation component of wood (Japanese Patent Laid-Open No. 7-215988). ). However, this method is difficult to put into practical use due to the complicated process steps and high cost. Although a method of using a solubilized lignocellulosic material as a colorant with a polyhydric alcohol as a solvent has been attempted, it has not been put to practical use because of poor weather resistance and solvent solubility.

[0003]

Problems (problems to be solved by the invention) include the following problems (1) to (5) which are likely to occur in plant dyeing. (1) Since plant dyes are extracted from plants, they are limited in quantity as colorants. (2) Since the plant dye is extracted from the plant, there are variations in hue and it is difficult to adjust the concentration and the like. (3) Since vegetation is colored by chemical bonding with a mordant, the color may differ due to subtle differences in its components. (4) The coloring of plant dyeing differs depending on the environmental temperature and humidity. In addition, since the process has two stages, each must be managed. (5) Since plant dyeing is usually performed with an aqueous solution,
Fluffing tends to occur when coloring wood or the like.

Problems with the technique of using a cationic lignin derivative as a colorant include the following (1) to (2). (1) The steps of isolating lignin from wood, the reaction of derivatization of isolated lignin with a cationizing agent, and the purification of reaction products are expensive due to the use of expensive chemicals and the complexity of the steps. Bring (2) There is concern that the weather resistance of the colored material to light and moisture is not clear.

In order to solve the above problems, the object of the present invention is to provide a substance obtained by using lignocellulose, which is a main constituent of plants, as a raw material as it is and subjecting it to simple chemical treatment and purification treatment. The present invention provides a colorant as a coloring component, which is far cheaper than currently used general-purpose chemically synthesized colorants and which is excellent in performance such as weather resistance.

[0006]

The present invention relates to a coloring agent containing a soluble lignocellulosic material obtained by adding phenols to a lignocellulosic material and reacting it by heating as a coloring component. In the colorant of the present invention, a metal salt is used together with a soluble lignocellulosic substance for the purpose of enhancing the dyeability and dyeing fastness with the material to be dyed, or for the purpose of enhancing the colorability and weather resistance with the material to be dyed. Is preferred. Further, in the colorant of the present invention, using an acid or alkali together with the soluble lignocellulosic material,
Depending on the object to be colored or the object to be dyed,
It is preferable to adjust the pH value. In addition, the present invention, a soluble lignocellulosic material obtained by adding phenols to a lignocellulosic material and reacting by heating is immersed in a solution obtained by dissolving it in a solvent, or the solution to be dyed is immersed in the solution. It relates to a method of applying the soluble lignocellulosic material as a colorant, which is applied to a colorant.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As a lignocellulosic material which is a starting material for a coloring component in the coloring agent of the present invention,
Scraps, wood powder, wood chips, veneer scrap, plywood scrap,
Examples thereof include plant fiber materials such as bark, and various plant-derived materials containing cellulose, lignins and the like as main components, such as straw, chaff, coffee bean dregs, bagasse squeezed dregs and beet pulp. Phenols used in the present invention include phenol, o-, m-, p-cresol, and 3,5.
-2,3-, 2,6-xylenol, o-, m-, p-
Propylphenol, o-, m-, p-butylphenol, o-, m-, p-secondary butylphenol,
Monohydric phenols such as o-, m-, p-tertiary butylphenol, hexylphenol, phenylphenol, octylphenol, 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 in a mixture. In the present invention, it is particularly preferable to use phenol in terms of price and performance. Furthermore, in order to reduce the solution viscosity, to mitigate the runaway reaction due to heat generation in the initial stage of the reaction, and to remove the water in the lignocellulosic material from the system, water and an azeotropic organic solvent are added,
It may be used together with phenols. It is also possible to add and coexist with another organic solvent within the range in which the object of the present invention is achieved.

As a method for producing a soluble or pasty soluble lignocellulosic material which is a coloring component of the present invention, known methods such as a non-catalytic method, an acid catalyst method and an alkali catalyst method can be adopted. As a non-catalytic method, there is JP-A-61-2.
No. 61358, for example, a lignocellulosic material is added to phenols,
A method of producing a solution of a lignocellulosic material such as wood by heating to 0 ° C can be mentioned. Specifically, for example, 4.5 g of dried wood powder and 4.5 g of phenol are weighed out in a beaker, mixed well, put in a 20 ml capacity pressure vessel and packed, then sealed, and heated at 250 ° C. for 2 to 3 hours. It is a method of processing. The acid catalyst method is disclosed in JP-A-57-36113.
The method introduced in Japanese Patent Laid-Open Publication No. 2003-242242, that is, a method of reacting phenol with finely chopped wood in the presence of a small amount of mineral acid can be mentioned. Specifically, for example, 940 g of phenol
And 9.4 g of concentrated sulfuric acid are weighed in 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 Japanese Patent Laid-Open No. 188568/1995, that is, a soluble lignocellulosic material is obtained by adding phenols to a lignocellulosic material and heating the mixture in the presence of an alkaline additive. The method of manufacturing is mentioned. Specifically, for example, 120 g of wood flour (water content 71%), 47 g of phenol and 2.3 of sodium hydroxide.
Weigh 5g into a 2L pressure resistant reactor equipped with a stirrer,
It is a method of heat-treating at a system temperature of 250 ° C. for 1 hour in an oil bath. By the above-mentioned method, the lignocellulosic material such as wood flour is solubilized to obtain a solution-like or paste-like soluble brown lignocellulosic material. In the present invention, any of the above methods may be used.

In the above-mentioned method, the blending ratio of the lignocellulosic material and the phenols is desired to be as high as possible and to have as little undissolved residue as possible. In the case of the non-catalytic method, 5 to 2 phenols are added to 10 parts by weight of the lignocellulosic material.
Add 0 parts by weight, preferably about 10 parts by weight. The reaction temperature is 200 to 300 ° C, preferably about 250 ° C, and the reaction time is 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 phenols are added to 10 parts by weight of the lignocellulosic 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 lignocellulosic material. The reaction temperature is in the range of 100 to 200 ° C., preferably about 150 ° C.,
The reaction time is several minutes to 1 hour. When an alkali catalyst is added, 3 to 20 parts by weight of phenols, preferably 10 parts by weight, is added to 10 parts by weight of the lignocellulosic material.
Add about 1 part 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 lignocellulosic material. The reaction temperature is in the range of 200 to 300 ° C, preferably about 250 ° C.
The reaction time is 15 minutes to 1 hour. The solution-like or paste-like soluble lignocellulosic material obtained by the above-mentioned method, preferably, after removing undissolved residue by further filtration or centrifugation, a water-soluble unreacted solvent such as phenol, and hydrolysis, By washing with water to remove a water-soluble reaction product produced by oxidative decomposition, a viscous soluble lignocellulosic substance that separates from water is obtained. Preferably, the water content of this substance is further removed by drying or distillation under reduced pressure to obtain a soluble lignocellulosic substance desirable for use as the coloring component of the present invention.

The soluble lignocellulosic material thus obtained can be used as it is as a colorant. 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, ethyl cellosolve, etc. A coloring agent is prepared by dissolving it in a solvent as a coloring component. Although the solution concentration is adjusted depending on the degree of coloring or dyeing, it is usually desirable to use a 1 to 50% by weight solution. In the present invention, it is preferable to use a metal salt together with the soluble lignocellulosic material for the purpose of enhancing the dyeing property with the article to be dyed and the dye fastness, and the weather resistance of the article to be colored. Metal salts include potassium carbonate, alum, copper sulfate, iron sulfate, ferrous chloride, stannous chloride, cupric chloride, anhydrous cupric chloride, ammonium cupric chloride, copper acetate, ferric acetate. , Aluminum acetate, iron acetate, cupric bromide, copper nitrate, copper naphthenate, sodium stannate, slaked lime, potassium dichromate, lye, titanium salt, etc. can be used, but alum, cupric chloride, Anhydrous cupric chloride, copper sulfate, etc. are desirable. Of these, cupric chloride and anhydrous cupric chloride, which are soluble in acetone and the like, are most desirable. It is considered that when a complex salt is formed using these metal salts, for example, an increase in affinity with the material to be dyed brings about good dyeability. The amount of the metal salt used is usually 0.
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 using an acid or an alkali together with soluble lignocellulose which is a coloring component, depending on the purpose of use. The pH is usually adjusted by adding an aqueous acid solution or an aqueous alkali solution to the colorant. Alternatively, the colorant may be added to the solution further dissolved in the above-mentioned solvent. The acid used includes at least one selected from inorganic acids, organic acids, and Lewis acids. As the inorganic acid, usual mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and hydrobromic acid are used, and as the organic acid, carboxylic acids such as formic acid, acetic acid, oxalic acid, tartaric acid, and benzoic acid, and It includes organic sulfonic acids such as phenolsulfonic acid, p-toluenesulfonic acid, and sulfinic acids such as phenolsulfinic acid, and uric acids. Examples of the Lewis acid include compounds such as aluminum chloride, titanium chloride and boron trifluoride, and their complexes. 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 are sodium hydroxide, potassium hydroxide, alkaline earth metal hydroxides are calcium hydroxide, alkaline earth metal carbonates are calcium carbonate, amines are monoethanolamine, etc. Can be illustrated. It is also possible to use a buffer solution. Examples of the buffer solution include Clark-Labus buffer solution, Sorensen buffer solution, McKilvein buffer solution, and Walpole buffer solution.

In the present invention, a dye to be dyed is immersed in a solution obtained by dissolving a soluble lignocellulosic substance or a colorant containing the dye in a solvent, or the solution is applied to the dye to be colored, Coloring is done. For example, in the case of fiber dyeing, one of the above-mentioned solvents is selected, and the bath ratio (concentration) is a coloring component: solvent weight ratio of 1: 1 to 1: 100, preferably about 1:40, and the weight of the fiber to be dyed. A solution of about 50 times is prepared. Dyeing is generally used for dyeing. Generally, the higher the temperature, the faster the dyeing speed and the larger the amount of dyeing, but the normal temperature may be normal temperature. The dyeing time is adjusted within the range of 5 minutes to several hours. Further, the dyeing process may be repeated for deep dyeing. It is also effective to adjust the pH of the solution as described above. All are determined by the desired degree of fiber coloring.

For example, in the case of dyeing silk cloth and wool, it is desirable to add an acid (weakly acidic at pH 3 to 5 of the system), and in the case of cotton cloth, addition of alkali (weakly alkaline at pH 9 to 11 of the system). 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 constituents of cotton cloth. It is considered that the interfacial activation of cellulose, which is the above, causes good dyeability. The pH of the dyeing solution is preferably 3 to 5 for silk cloth, wool, etc., and 9 to 11 for cotton cloth. It is also possible to pretreat or posttreat the fiber with a mordant containing a metal salt as described above in order to effectively carry out dyeing or improve weatherability, 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 overlapped. For example, the weight ratio of the coloring component of the present invention to the alcoholic coloring agent or NGR stain is 100: 0.
It is used by mixing in the range of 100: 500 depending on the desired coloring degree of the fiber.

When wood is colored using the coloring component of the present invention, for example, one kind is selected from the above-mentioned solvents, and the weight ratio of coloring component: solvent is 1: 1 to 1: 200, preferably 1 :.
Adjust to about 30. The coloring method is brushing, spraying,
The same process as general wood coloring such as a roll coater may be used. The coating amount is adjusted according to the desired coloring degree of the wood. In order to improve the weather resistance, it is possible to add the above-mentioned metal salts dissolved in a solvent, such as cupric chloride, cupric acetate, cupric bromide and copper naphthenate. The addition amount is 1 to 30 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the coloring component. The metal salt is usually added to the solution in which the coloring component is dissolved, but it is also possible to mix it in advance with the coloring component. It is also possible to add a commercially available ultraviolet absorber or light stabilizer to the coloring component solution or the coloring component and use them together. It is also possible to use both of them, such as mixing the coloring component of the present invention or a solution thereof in an oil paint, or mixing 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 were weighed out in a 2 liter pressure vessel equipped with a stirrer and kept in an oil bath at a temperature of 180 ° C ± 5 ° C for 15 It takes 1 to 30 minutes to raise the temperature, and then to 250 ° C for 1
The temperature was raised for 5 minutes to 30 minutes, the temperature was kept at 250 ° C. for 1 hour, and then cooled to obtain a black solubilized substance. This liquid is G
Filtration with a glass filter of No. 3 gave a black product with a yield of about 99%. Distilled water was added to the obtained liquid substance and washed with water while stirring. Washing with water was repeated many times until completely separated from water. The completely separated liquid material was taken out and dried in a dryer to obtain a colored 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 the cotton cloth was immersed in 100 g of the coloring solution for about 30 minutes and then washed with water to obtain a cotton cloth A dyed in brown color. In addition, 2 g of cotton cloth was previously immersed in 200 g of 1% alum solution in boiling water 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 dye the cotton cloth in brown color. B was obtained. JIS L 0848-1996 (sweat test), JIS L 0845-1975 (hot water test), JIS L 0844-1997
The dyeing fastness performance based on (washing test) is shown in Table 1.

[0016]

[Table 1]

As shown in Table 1, it is clear that both of these cotton fabrics have excellent fastness to dyeing and can be used in the same manner as conventional colorants. Example 2 Sugi sawdust 132 g (water content 10%) and phenol 28
0g (wood flour / phenol = 3/7) and sulfuric acid 8.4g,
Weigh it in a 2L pressure resistant container equipped with a stirrer, heat the container in an oil bath to 180 ° C ± 5 ° C in 15 to 30 minutes, and then raise it to 250 ° C in 15 to 30 minutes. The temperature was raised, and the temperature was maintained at 250 ° C. for 1 hour, followed by cooling to obtain a black solubilized substance. The liquid was filtered through a G3 glass filter to obtain a black product with a yield of about 98%. Distilled water was added to the obtained liquid substance and washed with water while stirring. Washing with water was repeated many times until water and liquid were completely separated. The completely separated liquid material was taken out and dried in a dryer to obtain a colored 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-quality fiberboard (MDF) to give a predetermined color tone to obtain a brown colorant C. Next, 5% by weight of cupric chloride was added to the coloring solution for wood, and then spray-painted on MDF to obtain a predetermined color tone to obtain a brown colorant D. Furthermore, after adding 0.5 wt% of the light stabilizer LS-770 manufactured by Sankyo Co., Ltd. to the colored solution to which cupric chloride was added,
The MDF was spray-painted to a predetermined color tone to obtain a brown coloring material E. Sunshine incenon long life weather meter (WEL-6XS-HC B for weather resistance test)
It was irradiated for 85 hours using sunshine carbon in Ec). Table 2 shows changes in color difference before and after irradiation, which were measured by a color difference meter.

[0018]

[Table 2]

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

[0020]

As described above, the plant-derived coloring agent of the present invention is homogeneous and can be produced in a large amount as compared with a dye for plant dyeing, and is excellent in fastness such as discoloration and fading. It is a colorant having an affinity for natural fibers such as silk, wool and cotton, and wood, and the industrial utility value of the present invention is extremely high. Further, as the main raw material of the colorant of the present invention, unused materials such as thinned wood and branch materials which are by-products of forest trees, construction waste materials, waste materials such as wooden house dismantling materials, waste chips, and the like can be used. The present invention contributes to the development of a technology that is friendly to the global environment in terms of recycling use, expansion of new applications, and energy saving effects.

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Claims (4)

(57) [Claims] 1. A colorant containing a soluble lignocellulosic material obtained by adding phenols to a lignocellulosic material and heating and reacting it as a coloring component. 2. The colorant of claim 1, which contains metal salts with the soluble lignocellulosic material. 3. The coloring agent according to claim 1, which contains an alkali or an acid together with the soluble lignocellulosic material. 4. A solution to be dyed is immersed in a solution obtained by dissolving a soluble lignocellulosic material obtained by adding phenols to a lignocellulosic material and heating and reacting the solution, or coloring the solution. A method of using the soluble lignocellulosic material as a colorant, which is applied to an object.