JPH0597480A - Coloring method for inorganic fiber and colored inorganic fiber - Google Patents

Abstract

(57) [Summary] [Structure] An inorganic fiber is treated with an acidic metal salt solution containing a metal element in which metal ions can have a plurality of charges, and then treated with an alkali or irradiated with an energy wave. This is a method for coloring an inorganic fiber, in which a metal, an oxide thereof, or a hydroxide thereof is stably attached, and then a coloring agent is used if necessary. [Effects] Inorganic fibers such as glass fibers can be colored without lowering the incombustibility and used as various interior materials for construction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for coloring an inorganic fiber, such as a glass fiber, which can be used as an interior material for a building by coloring it without lowering the incombustibility and coloring. Regarding the inorganic fiber.

[0002]

2. Description of the Related Art Conventionally, building interior materials have been required to be nonflammable materials, and at least flame retardant materials. In particular, in the case of a high-rise house, it is important to make the interior material non-combustible when considering the safety of people living in the house against fire. For example, a ceiling decorative plate is made of a combination of inorganic materials such as inorganic fibers and gypsum. This requires performance such as design, sound absorption, and moisture absorption, but since humans do not touch it with their hands or body,
Even a material having low strength can be used. On the other hand, the wall material is frequently brought into contact with the human body (particularly hands and arms) and furniture, and is required to have strength (especially abrasion resistance and scratch resistance) that can withstand this. Therefore, a flame-retardant resin such as vinyl chloride is used as such a wall material,
A molded body (wallpaper) having a design property is used.
Further, as the floor material, the human body (particularly the foot) and furniture are often in contact with each other. Therefore, a material such as a vinyl tile in which a resin and a filler are combined and which has a design property is often used.
Further, some cloth materials belong to the category of curtains, and are required to have sufficient flexibility, flexibility and abrasion resistance.

A nonflammable material can be easily obtained by using inorganic fibers such as glass fiber whose material itself is flame-retardant as a constituent main component of the interior material. However, glass fibers and the like have not been put into practical use although they have a basic function (property) as an interior material. This is because not only the basic function (property) as an interior material but also aesthetics and design are required. That is,
At present, there is no method for coloring glass fiber into a bright color easily and economically, and various coloring methods have been studied. Hereinafter, some of the glass fiber coloring methods proposed in recent years will be illustrated.

A method in which glass is mixed with a pigment and then formed into fibers. This method can be carried out relatively easily, and an aesthetically excellent product can be produced. A pigment rubbing method in which a pigment and a resin are fixed to glass fiber.
This method can also be performed relatively easily. The method of JP-A-60-65199. In this method, a fibrous inorganic compound is immersed in a metal compound solution and then baked to obtain a metal oxide (TiO ₂ , Fe ₂ O).
₃ , Al ₂ O ₃ etc.) film is formed and electroless plating is performed on this. Ion sputtering and vapor deposition methods. This method is a method in which a metal is made into a gas state and attached to a base material. An alkoxysilane compound having an aminoalkyl group and a guanidine alkyl group is attached to the surface of the glass fiber, and then an acid dye is used for dyeing.

[0005]

However, the above-mentioned methods (1) to (3) have not been applied to the interior materials for construction because of the following reasons. With this method, it is not possible to use various colors in small quantities. The method (1) has problems in terms of fastness to rubbing and texture of color. Further, as the amount of resin increases, the incombustibility decreases. In the above method, the color to be colored is the color of the metal or the metal oxide, and the range of the color to be colored is extremely narrow. Further, since the adhesion is stabilized only after firing, it is extremely troublesome in operation. According to the method (1), a uniform metal coating layer can be formed, but since the method itself is expensive, it is not profitable to apply it to an interior material for construction. The method (1) is expensive because the silane compound used is special. Therefore, there has been a strong demand for a method of easily and economically coloring the glass fiber to obtain a nonflammable building interior material having aesthetics and design.

[0006]

The present invention has been proposed in view of the above, and an inorganic fiber is treated in an acidic metal salt solution containing a metal element whose metal ion can have a plurality of charges. The present invention relates to a method for coloring an inorganic fiber, which comprises subsequently performing an alkali treatment and then coloring with a dye if necessary.

The present invention also provides, in the above method,
Energy waves may be irradiated instead of the alkali treatment.

The present inventors have already found that in the electroless plating method, iron ions can be deposited on the surface of the target substrate as a useful catalyst at high temperature, but by promoting this technology, Completed the invention. That is, the present invention comprises the following means.

(1) Chemical Etching Treatment The inorganic fiber is heated in an alkali (basically strong alkali) or a reactive acid solution such as hydrofluoric acid. Depending on the deposits of the inorganic fibers, heat treatment or treatment with an organic solvent may be performed in advance. Incidentally, this chemical etching treatment, in addition to the role of eroding the surface of the inorganic fiber, also serves to remove the resin and other fouling components adhering to the surface of the inorganic fiber, there is no fear of that. In some cases it is not necessary.

(2) Acid metal salt treatment Inorganic fibers are treated with acid metal salts (Fe ²⁺ and Fe ³⁺ , Co ²⁺ and Co).
³⁺ , Ni ²⁺ and Ni ³⁺ , Cu ⁺ and Cu ²⁺ , Zn ²⁺ and Z
n ⁴⁺ , a combination of Sn ²⁺ and Sn ⁴⁺ ) and heat treatment with an aqueous solution. Thereafter, the inorganic fibers are taken out of the solution and subjected to an alkali treatment (immersing in an alkali solution) to stabilize the adhesion of the metal salt. Stabilize the attachment of metal salts by keeping the metal ions in the high-order side abundant and applying an energy wave without removing them from the liquid or removing them from the liquid and the liquid adhering to the surface. It may be allowed to. In the case of irradiating with the energy wave described above, it is possible to stabilize the adhesion of the metal salt without performing the etching treatment of (1). In addition, in the acidic metal salt solution,
Resins and dyes may be dispersed or dissolved, and the resin or dye may be co-deposited with the metal salt. Then, when no organic substance is present in the system, the adhesion can be stabilized by heating.

(3) Coloring Treatment A coloring matter such as a dye or a pigment is attached to the inorganic fiber treated with the above-mentioned acidic metal salt to obtain a desired color. At that time, the pigment does not adhere to the inert inorganic fiber,
Since the above-mentioned acidic metal salt treatment adheres to the metal, the metal oxide, or the metal hydroxide adhered (on the surface of the inorganic fiber), stable coloring is performed.

It is considered that the following actions are performed in each of the steps of the present invention described above. (1)
In (1), by chemically etching the surface of the inorganic fiber, the surface is chemically roughened (the glass fiber having a roughness of 7 to 10 Å becomes a roughness of 100 to 150 Å), and the surface layer is an old layer. Instead, a new layer is obtained. This is confirmed by the discoloration of the color of the treatment liquid that has been subjected to the chemical etching treatment. In the above (2), metal ions in a state of being activated at a high temperature and in a state of being activated by an energy wave are attached to the surface of the inorganic fiber, and thereafter, a hydroxide having a low solubility and a metal oxide It is considered that stable attachment is performed by changing to a substance or a metal. Further, the surface of the inorganic fiber becomes more uneven due to the size of the constituent units of the adhered metals. In the above (3), a coloring treatment can be performed by selecting a material (dye) that is strongly adhered (adhered) to the metal, metal oxide, or metal hydroxide adhered (generated) to the surface of the inorganic fiber.

The colored inorganic fiber thus obtained can be easily made into a nonflammable material having a design property by molding. That is, since it has a function (property) such that it can be used in places such as a ceiling, a wall, and a floor, and has nonflammability, it is extremely useful as an interior material for construction.
In this case, it is not necessary to mold only colored inorganic fibers, and unprocessed inorganic fibers or organic fibers may be combined and molded. Of course, in the latter case, it is difficult to make the material incombustible, but the amount of smoke generated during combustion can be reduced.

Further, the metallized fibers or colored inorganic fibers according to the present invention can be used as a non-combustible inorganic filler or can be made into a non-combustible material. That is, a resin dissolved in an organic solvent, a resin dispersed in water (emulsion), an uncured thermosetting resin is applied and dispersed, and a resin film is used to form an adhesive layer on the surface. It is also possible to create. In this case, it is possible to obtain a flexible material that does not become a completely incombustible material but has extremely few combustible substances. Further, by setting the amount of resin to 5% or less, a composition that substantially passes the nonflammability test can be obtained.

Further, the inorganic fibers (as a raw material) to be treated according to the present invention are not limited to single fibers, and untreated inorganic fibers preformed may be used.
In the following examples, glass fibers are used as the inorganic fibers, but it has been confirmed that similar results can be obtained with slag wool, alumina fibers, and stainless fibers in addition to glass fibers.

[0016]

EXAMPLES Examples of the present invention will be shown below. [Raw materials used] Inorganic fiber; Glass fiber (diameter 20 mmφ, length 15 mm) Chemical etching solution; Hydrofluoric acid (5%) solution Acidic metal salt solution; Fe ²⁺ solution: FeCl ₂ (5%) solution Fe ^{3 +} Liquid: FeCl ₃ (5%) liquid Fe ²⁺ / Fe ³⁺ liquid: FeCl ₂ (5%) FeCl ₃ (5%) liquid Cu ²⁺ liquid: CuCl ₂ (5%) liquid Resin; Epotite (amine curing) Type epoxy resin, Showa Highpolymer Co., Ltd.) High-mol emulsion (ethylene vinyl acetate resin, Showa Denko KK) Dye (dye); rhodamine β (tetraethylrhodamine) alkali treatment liquid; NaOH (1%, 10%) liquid SnCl ₂ liquid

[Adhesion and Stabilization of Metal Salt] First, the glass fiber was chemically etched with a hydrofluoric acid (5%) solution at 50 ° C. for 1 hour. Next, treatment was performed with the above-mentioned four types of acidic metal salt solutions at 95 to 100 ° C. for 1 hour. Further, any one of the following processes (a) and (b) was performed. (A) The glass fiber was taken out of the liquid, drained, and then immersed in a NaOH (1%) liquid for 1 hour. (B) When the glass fiber is immersed in the liquid, electromagnetic waves (2
(450 kHz) was irradiated and processed. Then, this was dehydrated and dried.

[Coloring (staining)] (a) and (b) described above
A glass fiber that has been subjected to any of the treatments, and (a),
Glass fibers washed with water instead of the treatment of (b) (Comparative Examples 1 and 2) and glass fibers not subjected to the adhesion of a metal salt (Comparative Example 3) were colored (dyed) with the above-mentioned dye and compared.

The following evaluation tests were conducted on the obtained glass fibers. [Evaluation Test] (Color Adhesion) The adhesion of the metal salt to the glass fiber was visually confirmed. Those with sufficiently colored glass fibers were evaluated as ◯, and those with slightly colored glass fibers were determined as Δ, and the results are shown in Table 1. (Washing stability) The stability of coloring of the dye on the glass fiber was visually confirmed. Those that were not discolored even after being immersed in 1% soapy water for 10 days were evaluated as ○. (Cooling stability) (20 ° C. × 1 hour → 80 ° C. × 1 hour) was set as one cycle, and 10 cycles were repeated, and those having no color change were judged as ◯ and shown in Table 1. (Chemical stability) Immersion in 50% C. HCl (3%) or NaOH (3%) solution for 1 hour without any change. ○ After immersing in normal temperature HCl (3%) solution for 1 hour, change Those that did not exist were judged as Δ and are shown in Table 1.

[0020]

[Table 1]

[Papermaking] Using the glass fibers of Examples 1, 2 and 4 and the untreated glass fibers, a papermaking paper having a basis weight of 300 g was obtained by an ordinary papermaking method.

[Coating] This paper was coated or impregnated with the above resin.

The following evaluation test was conducted on the obtained papermaking paper. [Evaluation Test] (Coloring Stability) After molding, the molded product was treated with 1% soapy water at 50 ° C. for 30 minutes, and the presence or absence of decolorization was observed. (Combustion test) No smoke was emitted ◎ Odor was found and the shape was retained. ○ Smoke was emitted, but shape was retained. △ Smoke was emitted and the shape was not retained. It was judged and shown in Table 2.

[0024]

[Table 2]

[0025]

As described above, according to the method for coloring an inorganic fiber of the present invention, glass fiber or the like, which has been difficult to be colored in the past, can be colored easily and inexpensively. That is, in the present invention, since it is only necessary to attach (dye) an ordinary dye using an ordinary method, it is possible to use various colors little by little, and the range of colors to be colored is extremely wide. become. Further, it does not require expensive chemicals or special processing equipment and does not require complicated operations, so that it is economically profitable.

Further, the colored inorganic fiber of the present invention can be used as an almost completely non-combustible material since no resin is basically used. Alternatively, by using this fiber for papermaking and woven fabric, and by allowing a resin component to exist on the surface or inside thereof, it can be used as a flexible material having a hard surface and less scratching. In this case, the incombustibility is slightly reduced, and although it cannot be said that it is a completely incombustible material,
It can be a material that has a shape even after burning and emits a small amount of smoke. As described above, the inorganic fiber of the present invention is appropriately molded, dispersed or added to other materials, and various materials, for example, various building interior materials (for example, flexible nonflammable materials). Sheet, flexible non-combustible plate)
Can be used as As mentioned above,
Although there was no building interior material having aesthetics and designability, by using the colored inorganic fiber of the present invention as described above, it is extremely aesthetically excellent as an interior material for a high-rise housing and has designability. Material can be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location D06P 3/874 7306-4H D21H 13/40

Claims (3)

[Claims] 1. An inorganic fiber is treated in an acidic metal salt solution containing a metal element whose metal ion can take a plurality of charges, then treated with an alkali, and then colored with a dye if necessary. A method for coloring an inorganic fiber, comprising: 2. An inorganic fiber is treated with an acidic metal salt solution containing a metal element in which a metal ion is capable of taking a plurality of charges, followed by irradiation with an energy wave, and then using a dye if necessary. A method for coloring an inorganic fiber, characterized in that it is colored. 3. A method in which a metal element capable of having a plurality of charges of metal ions, an oxide thereof, or a hydroxide thereof is stably attached to the surface of the inorganic fiber, and a dye is attached if necessary. Characterized colored inorganic fiber.