JPH0718097B2 - Colorant - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION This invention relates to a synthetic resin molded product,
The present invention relates to a coloring agent to be added to paper, paint, etc., and more particularly to a coloring agent for showing a pattern to show the color tone of fibers as a pattern and a method for producing the same.

[0002]

2. Description of the Related Art Generally, an inorganic pigment, an organic pigment or a dye is known as a colorant added to synthetic resins, paper, paints and the like. Of these, the pigment is dispersed and blended with the substrate to be colored, reflects and absorbs light to impart a predetermined color tone, and normally, the substrate to be colored is colored in a uniform tone without a pattern.
Most of this type of colorant is usually particles of about 10 μm, but the smaller the particle size, the larger the surface area.
It is widely used that the coloring power is efficiently increased to about 0.02 μm to 5 μm.

Further, among the colorants, the dye is used after being dissolved, and the particles of the dye are not visible on the substrate to be colored, and the dye is uniformly colored without a pattern. It is the same as the pigment.

The inventor of the present application has disclosed a coloring agent for pattern expression which can enhance the commercial value and meet various demands by making a spotted or thread-like pattern appear on the surface of a colored object. No. 2-68373.

This coloring agent is made of cellophane film of viscose derivative or viscose rayon as a raw material, and the fibers dyed with a reactive dye in order to prevent water absorption, which is a drawback thereof, are cut into appropriate lengths. In this case, it is possible to cause a spotted or thread-like pattern to appear in the thermoplastic resin molded product that has been mixed and added.

Of the above-described coloring agents for pattern expression, when the thickness of the fiber such as rayon is 50 denier or less, 1
Fine and short filaments of mm or less are unique because the fibers can be randomly arranged on the surface of the molded product and colored in a dot-drawing manner when mixed with a colored substrate such as a synthetic resin. It was possible to obtain a molded product having a color tone and being extremely rich in decorativeness.

[0007]

However, the aforesaid colorant for the appearance of a dot-like pattern, when stirred with a material to be colored in a mixer, violently generates static electricity and strongly adheres to the tank wall of the mixer. Therefore, there is a problem that the addition efficiency is extremely poor.

[0008] Further, this colorant, after being cut by a dry method, is entangled in a lump form with each other to form a so-called thread ball, which does not function efficiently as a colorant.

It is difficult to use such a colorant as a colorant for coating materials and plastics, which are required to have stable quality even with time.

In view of the above, the present invention solves the above-mentioned problems and prevents the coloring agent for pattern expression using organic fibers having a predetermined thickness and length from adhering to the mixing container. It is an object of the present invention to provide a colorant capable of efficiently coloring a molded article or the like in a dot-drawing style, as a material that does not cause such agglomerated aggregation.

[0011]

In order to solve the above problems, in the present invention, an undyed or dyed organic fiber having a fiber diameter of 5 to 100 μm and a fiber length of 0.1 to 2 mm is used as a material, and an antistatic material is used. The coloring agent is made of the above-mentioned organic fiber, the surface of which is treated with an agent, a lubricant, or a treating agent which is a combination of both.

The colorant has a fiber diameter of 5 to 100.
It can be produced by impregnating a tow of undyed or dyed organic fiber of μm with water, cutting the tow to a fiber length of 0.1 to 2 mm, and then surface-treating it with an antistatic agent, a lubricant, or a treatment agent in which both are used in combination. . The details will be described below.

The organic fiber used in the present invention can be used without particular limitation as long as it has a predetermined fiber diameter (diameter) and fiber length, and specifically, cotton, silk, cabot,
Natural fibers such as wool, flax, cannabis, lami, jute, and palm, polyester, polyamide, polyacetal, polyurethane, polyethylene, polypropylene, polyvinyl chloride, acrylic, aramid, and other synthetic fibers, acetate and other semi-synthetic fibers, rayon, vinylon Regenerated fibers such as

Of these, fibers such as rayon, vinylon, polyester and acetate can be stretched to obtain
At first glance, it becomes a colorant with a silky luster, and it can be used for pearlescent coloring. Further, it is also possible to obtain a matte color tone by dyeing a thread such as jute or using a matte thread.

As such organic fibers, those having a fiber diameter (diameter) of 5 to 100 μm and a fiber length of 0.1 to 2 mm are used. The reason is that if the diameter is smaller and shorter than the above-mentioned predetermined range, it is not preferable because it cannot be colored in a dot-drawing style and becomes a single color. This is because the fibers are juxtaposed on the surface and cannot be colored like a dot drawing. In addition,
As for the fiber diameter, rayon having a specific gravity of about 1.5, 1.38
In case of polyester of 1.14, nylon of 1.14, etc., commonly used fiber thickness is 1 to 50 denier (hereinafter, d
Abbreviated).

The antistatic agent used in the present invention is a so-called antistatic agent that forms a dense molecular layer on the surface of the organic fiber to reduce the surface leakage resistance of electricity, and various surfactants can be used. In addition, a water-soluble inorganic substance may be used, which has an action of physically preventing contact between fibers as well as antistatic property. Specific examples include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and water-soluble inorganic substances such as sodium silicate, magnesium sulfate, sodium chloride, and sodium sulfate.

The lubricant used in the present invention is a so-called external lubricant that adheres to the surface of the organic fibers and acts to prevent the fibers from being entangled with each other. Fatty acids or salts thereof known as lubricants, higher aliphatic alcohols, and fats are known. Group amides, metal soaps, or silicone oils, fluorine oils, vegetable oils, mineral oils, synthetic oils can be used. Of these, aliphatic amides, aliphatic bisamides, and metal soaps have been used as aqueous emulsions with favorable results, and
It has been found that the blending ratio of the lubricating oil is preferably 20% by weight or less.

The above-mentioned antistatic agent and lubricant may be used alone or in combination. This is because the generation rate of static electricity varies depending on the type of fiber, or the degree of entanglement between fibers varies depending on the fiber diameter, so it is desirable to appropriately select the treatment agent so as to achieve the optimum state. In particular, for fine fibers having a diameter of 10 d or less, it is usually necessary to use an antistatic agent and a lubricant together.

It is needless to say that a well-known filler may be added to the colorant of the present invention, or a general-purpose pigment may be used in combination, as long as the desired effect is not impaired.

[0020]

When the tongue-cutting colorant of the present invention is made to be in a water-containing state during the cutting of the tow, the water during the cutting lubricates the fibers or the fibers and the cutting blade to suppress the generation of static electricity. Also, when agitated with the base material to be colored in the mixer, the added antistatic agent makes it difficult for the organic fiber to generate static electricity, so it does not adhere to the tank wall of the mixer or scatter, improving the addition efficiency. To be done. Since the cut organic fibers are lubricated with each other through the lubricant, they are not entangled in a lump and so-called thread balls do not occur.

Therefore, as an extremely fine fibrous colorant having a predetermined thickness and fiber length, the fibers are dispersed at random on the surface of the molded product, and the colorant has an extremely excellent function of coloring in a dot-drawing style. Further, such a colorant maintains stable quality as a colorant for adding paint.

[0022]

【Example】

Example 1 Rayon fiber (manufactured by Daiwa Spinning Co., Ltd .: 38 μm)
(15d)) was made to contain water to give a product containing about 50% by weight, and this was cut into a length of 0.5 mm with a cutting machine.

Dyeing was performed using the above-mentioned cut fibers as a material according to the following procedures and composition ratios.

(A-1) Dyeing process 20 g of sodium silicate and 30 g of sodium sulfate were dissolved in 800 g of water to prepare a solution, and 400 g of the above-mentioned cut fiber (water content 50% by weight) was added.

After heating to 40 ° C., 5 g of a reactive dye (manufactured by Nippon Kayaku Co., Ltd .: Blue RS) was added and stirred.

After dehydrating this, 1000 g of water was added and washed with water, and then 16 g of a fixing agent (Kayafix manufactured by Nippon Kayaku Co., Ltd.) was added together with 500 g of warm water at 40 ° C. to obtain 1
The mixture was mixed for 0 minutes and subjected to a fixing treatment.

After dehydration and washing with water (twice), the water was further dehydrated to 50% by weight.

To 400 g of the cut and dyed fibers described above, the materials were added in the following composition ratios and mixed by stirring for 5 minutes to treat the surface, and then dehydrated and dried to obtain a colorant.

Antistatic agent (Nippon Yushi Co., Ltd .: Elegan T0F100 aqueous solution) 5 g Metal soap (Asahi Denka Co., Ltd .: ADEKA FINE FCODE SUPER Z, 10 g 45% water dispersion product) Modified silicone oil (Toray Co., Ltd .: SH3746, Emulsified product) 5 g [Example 2] In Example 1, except that rayon fiber (manufactured by Daiwa Spinning Co., Ltd .: 17 μm (3d)) was used instead of rayon fiber (manufactured by Daiwa Spinning Co., Ltd .: 38 μm (15d)). Dyeing and surface treatment were carried out in the same manner as in Example 1 to obtain a colorant.

Example 3 Instead of rayon fiber (manufactured by Daiwa Spinning Co., Ltd .: 38 μm (15d)), rayon fiber (manufactured by Daiwa Spinning Co., Ltd .: 17 μm (3d)) was used, and the reactivity was obtained in the dyeing step (a). Dyeing and surface treatment were carried out in exactly the same manner as in Example 1 except that a reactive dye (Nippon Kayaku Co., Ltd .: Micasion Scarlet GS) was used in place of the dye (Nippon Kayaku Co .: Blue RS). , A colorant was obtained.

Example 4 Rayon fibers (manufactured by Daiwa Boshoku Co., Ltd .: 38 μm (15d)) were moistened to prepare a water-containing product of about 50% by weight, which was cut into a length of 0.5 mm by a cutting machine.

Dyeing was carried out using the above-mentioned cut fibers as a material according to the following procedures and composition ratios.

(A-2) Dyeing process 30 g of sodium sulfate and 14 g of sodium carbonate were dissolved in 600 g of water to prepare a solution, and 400 g of the above-mentioned cut fiber (dry weight 200 g) was added.

After heating to 90 ° C., 15 g of a direct dye (Nippon Kayaku Co., Ltd .: Green GG, Brown MA) was added,
Stir for 40 minutes.

To this, 10 g of a fixing agent (Nippon Kayaku Co., Ltd .: Kayafix M) was added and mixed for 10 minutes to carry out a fixing treatment.

After dehydration, 1000 g of water was added and washed with water, and then further dehydrated to a water content of about 50% by weight.

To 500 g of the above-mentioned cut and dyed fibers, the materials were added in the following composition ratios and mixed by stirring for 5 minutes to treat the surface, and then dehydrated and dried to obtain a colorant.

Antistatic agent (Nippon Yushi Co., Ltd .: Elegan T0F100 aqueous solution) 10 g Low molecular weight polyethylene wax (Sanyo Chemical Co., Ltd .: Permarin PN) 25 g Metal soap (Asahi Denka Co., Ltd .: calcium stearate, ADEKA FINE FCODE SUPER C) 25 g [Example 5] Rayon fiber (manufactured by Daiwa Spinning Co., Ltd .: 38 μm)
(15d)) instead of rayon fiber (manufactured by Daiwa Spinning Co., Ltd .:
Dyeing and surface treatment were carried out in the same manner as in Example 4 except that 17 μm (3d)) was used to obtain a colorant.

Example 6 Polyester fiber (Unitika Co., Ltd .: 32 μm (10d), black-dyed product) was moistened to give a water-containing product of about 20% by weight, which was cut with a cutting machine to a length of 1
It was cut into mm.

For 1000 kg of the fiber that has been cut,
Each material was added in the following composition ratio, and mixed by stirring for 5 minutes to treat the surface, and then dehydrated and dried to obtain a colorant.

Antistatic agent (Nippon Oil and Fats Co., Ltd .: Elegan T0F100 aqueous solution) 2.5 g Lauric acid (Nippon Oil and Fats Co., Ltd .: NAA-312 emulsion) 25 g Low molecular weight polyethylene wax (Sanyo Kasei Co., Ltd .: Permarin PN) 50 g [ Example 7] Nylon 6 fiber (manufactured by Toray Industries, Inc .: 61 μm (3
0d), a yellow dyed product) was made to contain water to give a product containing about 20% by weight of water, which was cut into a length of 2 mm by a cutting machine.

For 1000 kg of the fiber that has been cut,
Each material was added in the following composition ratio, and mixed by stirring for 5 minutes to treat the surface, and then dehydrated and dried to obtain a colorant.

Calcium stearate (Adeka Fine Fukode Super C) 30 g Magnesium sulfate 80 g Table 1 shows the types of the organic fibers and the color tones of the dyes of Examples 1 to 7 described above.

[0044]

[Table 1]

A plastic molded product was manufactured in the following manner using Example 1, 3, 6 or 7, and its color tone was examined.

[Experimental Example 1] 0.3 part by weight of liquid paraffin was mixed in 3 parts by a mixer with 100 parts by weight of polypropylene.
Mix for 1 minute, then add 1 part by weight of Example, and 0.3 of Example 3.
3 parts by weight, 0.5 parts by weight of titanium oxide R dispersed with zinc stearate were added and mixed for 15 minutes, and a plate-shaped molded article was manufactured by injection molding by a conventional method.

[Experimental Example 2] 2 parts by weight of Example 6 and 0.3 part by weight of carbon black were dry-mixed, 100 parts by weight of polystyrene was mixed, and 0.3 part by weight of liquid paraffin was placed in a mixer. And mixed for 3 minutes to produce a plate-shaped molded product by injection molding according to a conventional method.

[Experimental Example 3] 1 part by weight of Example 1, 1 part by weight of Example 3, 1 part by weight of Example 7, and 0.5 part by weight of titanium oxide were dry-mixed to obtain a low content. 100 parts by weight of molecular weight polyethylene was mixed in a Henschel mixer, 0.3 parts by weight of liquid paraffin was further mixed in a mixer for 3 minutes, and a plate-shaped molded article was manufactured by injection molding at a molding temperature of 180 ° C.

As a result, in Experimental Example 1, blue color and scarlet color single fibers were respectively confirmed, and the color tone was like a dot drawing, and the mixed color was a violet color depending on the viewing angle.

Further, in Experimental Example 2, the black carbon fiber as a whole was black, and the glossy black single fiber was colored in a unique color tone which is clearly recognized in a dot-drawing style.

In Experimental Example 3, single colors of yellow, blue, and scarlet could be discriminated, and the color tone looked green or violet depending on the viewing angle.

Examples of the paint for showing pattern of the present invention will be described below.

[Embodiment 8] The raw materials of the coating material and the blending ratio (% by weight) are collectively shown below.

(1) Thickening component: carboxymethyl cellulose 12% by weight (manufactured by Daicel Chemical Co., Ltd .: 0.5% by weight of CMC-1150 dissolved in 99.5% by weight of tap water at 50 ° C. with stirring) (2) Mixed colorant; Example 1 0.2% by weight Example 7 0.3 〃 Titanium oxide R type (manufactured by Sakai Chemical Co., Ltd.) 0.5 〃 Corn starch (manufactured by Japan Corn Starch Co.) 1.0 〃 (3 ) Film forming component: Styrene / acrylic emulsion (Net.49%) 20.4 〃 (Sanden Chemical Co., Ltd .: Cybinol E-16) Water 1.8 〃 Emulsifier (Kao: Rebenol WZ) 0.03 〃 Film forming Auxiliary agent (benzyl alcohol) 1.8 〃 (water previously emulsified with styrene-acrylic emulsion, emulsifier, film forming auxiliary was gradually added) (4) Antifreezing agent; ethylene glycol 0.5 〃 (Five) Antiseptic; (ICI: Proxel GXL) 0.04〃 (6) Antiseptic; (ICI: Densil S-25) 0.02〃 (7) Defoamer; (San Nopco: Nopco 8034L) 0.02〃 (Method for producing paint) Put the viscous agent (1) in the mixing tank containing the above-mentioned film-forming component (3), and mix it with the colorant (2) while stirring.
Then, the raw materials (4), (5), (6) and (7) were sequentially mixed to obtain an acrylic emulsion paint.

[Example 9] An acrylic emulsion paint was obtained in the same manner as in Example 8 except that the mixed colorant was replaced with the following component (8).

(8) Mixed colorant; Example 3 0.2% by weight Example 4 (green) 0.3 〃 Example 4 (brown) 0.1 〃 [Example 10] Paint raw materials and blending ratio ( weight%)
Are collectively shown below.

(1) Mixed colorant; Example 3 0.1 wt% Example 5 0.1 〃 Example 6 0.1 〃 White dispersion color (manufactured by Towa Chemical Co., Ltd .: White AE) 0.4 〃 (2) Pulp (Sanyo Kokusaku Pulp Co., Ltd .: W200) 6.0 〃 (3) Defoamer; (San Nopco Co .: Nopco 8034) 0.32 〃 (4) Thickener; Carboxymethylcellulose 60 〃 (Daicel Chemical) Company: 0.5% by weight of CMC-1150 mixed and dissolved in 99.5% by weight of tap water at 50 ° C. with stirring) (5) Film-forming agent: urethane emulsion 40 〃 (Bayer: DLP , Net.46%) (6) Preservative; (ICI: Proxel GXL) 0.24〃 (7) Antifungal agent: (ICI: Dencel S-25) 0.24〃 (Paint manufacturing method ) The mixed colorant (1) and pulp (2) are dry-mixed, and the raw materials (3), (4), and (5) are added to the mixing tank. The charged was the mixed with stirring (1) and (2) were charged and mixed for 10 minutes, further preservatives (6), with the addition of an antifungal agent (7) 3
Mixing for minutes gave a urethane paint.

[Experimental Examples 4 to 6] In order to examine the color tones of the coating films of Examples 8 to 10, the clean surface of hard vinyl chloride was coated with the paint of each Example by air spraying, and at 20 ° C at 20 ° C. It was dried and painted for a minute.

As a result, Experimental Example 4 (paint of Example 8)
Formed a highly decorative coating film in which each color of blue and yellow was recognized in a dot-drawing style and looked green depending on the viewing angle.

In Experimental Example 5 (paint of Example 9), scarlet, green, and brown monofilaments can be visually confirmed, and depending on the viewing angle, a brown-based or green-based black coating with high decorativeness. A film was formed.

In Experimental Example 6 (paint of Example 10), black, brown, and scarlet monofilaments can be visually confirmed, and a highly decorative coating film that looks blackish red or brown depending on the viewing angle is used. Formed.

[0062]

As described above, the present invention provides an organic fiber having a predetermined fiber diameter and fiber length as a raw material, and an antistatic agent or a slip agent, or a colorant comprising an organic fiber surface-treated with a combination of both. Therefore, when it is mixed with a base material for coloring such as synthetic resin, paper, paint, etc., it does not adhere to the mixing tank and the addition efficiency is good, and it does not cause agglomerate aggregation which is itself called a thread ball. Thus, it can be said that the finely-divided fibers are randomly arranged on the surface of the object to be colored, and the coloring agent has an excellent decorative property and can be colored in a dot-drawing color tone, and has high industrial utility value.

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Claims (2)

[Claims] 1. Undyed or dyed fiber diameter 5 to 10
Made from organic fibers with a fiber length of 0 μm and a fiber length of 0.1 to 2 mm,
A coloring agent comprising the above-mentioned organic fiber, the surface of which is treated with an antistatic agent, a lubricant, or a treating agent which is a combination of both. 2. A tow of an undyed or dyed organic fiber having a fiber diameter of 5 to 100 μm is hydrated, and the tow is cut into a fiber length of 0.1 to 2 mm, and then an antistatic agent or a lubricant or both are used in combination. A method for producing a colorant, which comprises surface-treating with a treatment agent.