JPH0860025A - Colored bead for stipple coloration of textile - Google Patents

Abstract

PURPOSE: To obtain colored beads for stipple coloration of a textile which can be produced by a simple operation, has fastness, does not hurt the drape and handle of a textile and can stably exhibit a visual effect characteristics of stipple coloration in a very high reproducibility. CONSTITUTION: These beads are obtained by spray-drying an aqueous liquid essentially consisting of a particle-forming component (A) comprising a styrene polymer, a coloring component (B) comprising a pigment and a fiber-adhering component (C) comprising an acrylic polymer or essentially consisting of components (A) to (C) and a wall surface adhesion inhibiting component (D) comprising a microparticulate filler.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to spotted colored beads which can impart a special coloring effect to fibers.

[0002]

2. Description of the Related Art As a method for coloring fibers, a special method known as pointillistic coloring is known. This technique
By providing countless colored dots for fibers,
For example, it is intended to provide a unique visual effect such as a frosted tone and a washed-out tone.

Usually, such colored dots are composed of various coloring agents processed and formed into beads, and conventionally, for example, the following method has been adopted as a processing and forming method of such coloring agents. There is.

(1) A pigment and a thermoplastic substance are dispersed in an aqueous sizing agent solution, and then an aqueous solution containing another sizing agent which is incompatible with the sizing agent in the solution is added to separate the sea-island texture into two phases. Then, a method of obtaining colored beads by adding an electrolyte to gel the island component.

(2) Addition of a curing agent to a dispersion containing various thermoplastic resins and sizing agents, as well as various polymer components such as epoxy resin, urethane resin and melamine resin, and a pigment while stirring. , A method of obtaining colored beads by adjusting the pH, heating or the like to cure or insolubilize the polymer component.

(3) A method in which a pigment and a resin or a paste having opposite charges are made into beads by ion adsorption.

(4) A method in which a molten mixture of a resin and a pigment is solidified and then mechanically pulverized to form beads.

[0008]

However, the bead-like material obtained by these methods has the following (1)-
Among the problems of (7), at least one of them has a sufficient performance, and at present, it has not yet been obtained.

(1) The strength of the obtained bead-like material is insufficient, and the beads are easily broken at the stage of actual use.

(2) The pigment-carrying power is weak, causing color bleeding and crying.

(3) It is difficult to control the particle size, and it is impossible to obtain a uniform particle having good reproducibility.

(4) In order to obtain particles having a uniform particle size, a separate classification operation is essential.

(5) Productivity is poor due to complicated work operations.

(6) The texture and feel of the fibers are impaired.

(7) A stippled colored product with poor definition.

The present invention has been made in view of these problems, and the main purpose of the present invention is that it can be manufactured by a simple processing operation, is strong, and has a feeling of fiber. It is an object of the present invention to provide colored beads for stippling coloring of fibers, which can exhibit the visual effect peculiar to stippling coloring with extremely good reproducibility and stably without damaging the touch.

[0017]

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have made a simple treatment when a so-called spray drying method is used as a processing and forming means for colored beads. We obtained the finding that colored beads capable of exhibiting the visual effect peculiar to pointillistic coloring with excellent reproducibility and stability can be obtained by operation, and as a result of further research based on this finding, specific granulation components and specific fiber adhesion In the coexistence of ingredients,
It was found that by spray-drying a dispersion liquid containing pigments, colored beads capable of eliminating the above-mentioned problems can be obtained, and finally the present invention was completed.

That is, the present invention provides the following colored beads for pointillistic coloring of fibers. 1. Average particle size 5 to 5 obtained by spray-drying an aqueous liquid containing the following three components (A) to (C) as essential components
Colored beads for stippling coloring of fibers having a size of 00 μm: (A) a granulating component composed of a styrene polymer, (B) a coloring component composed of pigments, and (C) a fiber adhesive component composed of an acrylic polymer.

2. Colored beads for pointillistic coloring of fibers having an average particle diameter of 5 to 500 μm obtained by spray drying an aqueous liquid containing the following four components (A) to (D) as essential components: (A) Styrene-based polymer A granulating component composed of (B) a coloring component composed of pigments, (C) a fiber adhesive component composed of an acrylic polymer, and (D) a wall surface adhesion preventing component composed of a fine particle filler.

The colored beads for pointillistic coloring of the fibers of the present invention will be described in more detail below.

The colored beads for stippling coloring of the fibers of the present invention are (A) a granulating component comprising a styrene polymer, (B)
It is obtained by spray-drying an aqueous liquid containing a coloring component composed of pigments and a fiber adhesive component composed of (C) an acrylic polymer as essential components. Each component contained in the aqueous liquid will be described below.

Granulation Component (A) The granulation component (A) constitutes the matrix of the colored beads obtained, and it is necessary to use a styrene polymer as the granulation component (A). is there.

In the present invention, the reasons for using the styrene-based polymer are mainly as follows. First, the first reason is that a granulated product formed using a styrene-based polymer has high transparency. Usually, in a bead-shaped colorant, a large number of pigment particles tend to be included in agglomerative manner, and thus the sharpness tends to decrease as compared with the case where the pigment particles are individually dispersed. The polymer as a matrix is required to have high transparency. Next, the second reason is that the styrene polymer is granulated with high production efficiency. That is,
When a polymer other than the styrene-based polymer is used, there is a drawback that a large amount of the polymer adheres to the wall surface of the spray drying device at the time of spray drying described later, which not only decreases the yield. Although the washing operation requires a lot of labor, such inconvenience is avoided when the styrene polymer is used. For this reason, although the detailed mechanism has not been clarified, it is presumed that the cause is probably the rigidity of the molecular chain derived from the benzene nucleus of styrene. The third reason is that the styrene polymer has the ability to form a strong granulated product. This ability is considered to be partly due to the rigidity of the above-mentioned molecular chain, but the colored beads finally obtained by this are excellent in breakage resistance at the stage of actual use, and are also described below. The pigments as the coloring component (B) can be firmly supported, and inconveniences such as color bleeding and crying can be avoided at the same time.

The styrene polymer suitable for use in the present invention is a styrene homopolymer or styrene obtained by using styrene as a monomer component in an amount of 10% by weight or more, preferably 20% by weight or more, based on the total amount of monomers. It is a system copolymer. In the styrene-based polymer, if the amount of styrene used as the monomer component is less than 10% by weight, the effect of using the styrene-based polymer as described above is not sufficiently exhibited, which is not preferable. The type of the monomer component to be copolymerized with styrene in the styrene-based copolymer is not particularly limited, but a monomer component having a high hydrophilicity such as sodium styrene sulfonate causes poor water resistance of the colored beads. You should avoid using it. Specific examples of preferred copolymerization components in the present invention include ethylene, propylene, butadiene, divinylbenzene, vinyl chloride, vinyl acetate, vinylidene chloride,
(Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol dimethacrylate, (meth) acrylonitrile, (meth) acrylamide, dimethyl (meth) ) Acrylamide, diethyl (meth) acrylamide and the like can be mentioned.

The styrene-based polymer used in the present invention is preferably prepared so that the glass transition temperature is 70 ° C to 150 ° C. This is because when the glass transition temperature is lower than 70 ° C., the amount attached to the drying device tends to increase, and
This is because if the temperature exceeds 50 ° C., the breaking strength of the colored beads after production tends to decrease. The method for producing the styrene-based polymer is not particularly limited, and a known production method may be appropriately applied.

Coloring component (B) The colored beads of the present invention must contain pigments as a coloring component. The type of pigments is not particularly limited, and any conventionally known pigment can be used. As an example, Hansa yellow, benzidine yellow, benzidine orange, pyrazolone orange,
General organic pigments such as quinacridone red, various azo red organic pigments, dioxazine violet, anthraquinone yellow, phthalocyanine blue, indanthrene blue, phthalocyanine green and aniline black; resins with fluorescent cationic dyes and disperse dyes Fluorescent organic pigments that are colored; general chromatic inorganic pigments such as chrome yellow, cadmium yellow, chrome orange, rouge, cadmium red, cobalt purple, ultramarine blue, navy blue, viridian, emerald green; black inorganic such as carbon black and iron black Pigment; white inorganic pigment such as zinc white, titanium oxide; zinc sulfide,
Calcium sulfide, zinc silicate, zinc cadmium sulfide, etc. alone or their copper, silver, manganese, bismuth, mesothorium, tritium activator, and a fluorescent pigment, a phosphorescent pigment or a mixed pigment of a metal oxide and a rare earth element, or Luminescent pigments; metal powder pigments such as gold powder, silver powder, bronze powder, copper powder, aluminum powder; mica, M.I. I. O. , Glass spheres or the like or metallic luster pigments, pearl pigments or reflection type pigments obtained by coating them with nickel, cobalt, copper, gold, silver, palladium, titanium oxide, iron oxide, etc .; thermochromic dyes, photochromic dyes, etc. Examples thereof include reversible color-changing pigments such as microcapsules, fine particles of solid solution or fine particles of matrix contained therein.

Further, as a special one which can be used as a pigment in the present invention, a disperse dye containing no dispersant, a water-insoluble dye such as oil color, and the like can be mentioned. In the granulation step, the dyes are dyed with the granulation component (A) or the fiber adhesive component (C) described below, so that the colored beads obtained have properties similar to those of the fluorescent organic pigment.

The above-mentioned pigments may be used alone,
You may use 2 or more types together.

Fiber Adhesive Component (C) The fiber adhesive component (C) is mainly used to give the colored beads themselves an affinity for fibers, and is used as the fiber adhesive component (C). It is necessary to use an acrylic polymer.

The above-mentioned two components, that is, the granulating component (A) and the coloring component (B) can be turned into colored beads by spray drying as described below even if only these two components are used, and they are used for paints and printing inks. This is enough to use, but when considering the application to fibers, which is the object of the present invention, this 2
Ingredients alone do not give sufficient results. That is,
It is well known that fibers are used for applications such as clothing products, and have many opportunities to come into contact with the human body, and the texture and feel thereof are very important. Therefore, even if the color effect is excellent, the one that impairs the feeling and the feel is not allowed. This is also the biggest problem with the colored beads of the present invention. However, since the colored beads composed of only the above-mentioned two components have no affinity for fibers, it is possible to use In order to adhere to, it is essential to use a binder component in combination, and the amount used is very large compared to the case where individual pigment particles are used alone because the beads are bulky, The result is that the texture and feel of the fibers are greatly impaired.

In the present invention, by using the fiber adhesive component (C) made of an acrylic polymer, the obtained colored beads are given an affinity for fibers, and a large amount of binder component is added at the stage of using the colored beads. It can be applied to fibers without being used in combination, and a dot-stained colored fiber having an extremely good texture and feel is provided. Further, the acrylic polymer has a good compatibility with the styrene polymer which is the above-mentioned granulating component (A), and therefore can be advantageously used for obtaining good colored beads.

The acrylic polymer suitable for use in the present invention is, as a monomer component, at least one acrylic monomer selected from (meth) acrylic acid, alkyl (meth) acrylate, (meth) acrylonitrile and (meth) acrylamide. To the total monomer weight of 20
It is a homopolymer or an acrylic copolymer of an acrylic monomer containing at least 30% by weight, preferably at least 30% by weight.
In the acrylic polymer, if the amount of the acrylic monomer used as the monomer component is less than 20% by weight, the effect of using the acrylic polymer as described above is not sufficiently exhibited, which is not preferable. Examples of the monomer component to be copolymerized with the acrylic monomer in the acrylic copolymer include ethylene glycol dimethacrylate, N-methylol acrylamide, trimethylolpropane trimethacrylate, divinylbenzene, divinyltoluene, styrene and vinyl acetate. But,
It is not limited to these.

The acrylic polymer has a glass transition temperature of 100 ° C. or lower, preferably 70 ° C. or lower. When the glass transition temperature is higher than 100 ° C, the affinity for fibers is poor, which is not preferable. The method for producing the acrylic polymer is not particularly limited, and a known production method may be appropriately applied.

In the present invention, a styrene-based polymer which is a copolymer containing both styrene and an acrylic monomer as essential monomer components and has a styrene content of the above-mentioned granulating component (A) is used. Styrene-acrylic copolymer having a styrene content within the range and an acrylic monomer content within the range of the acrylic monomer content in the acrylic polymer used as the fiber adhesive component (C) Is only this one type of polymer, and is a granulation component (A) and a fiber adhesive component (C).
It is possible to use it as a polymer exhibiting both functions of. Specifically, the monomer composition of the styrene-acrylic copolymer will be described below. The styrene content is 10 to 80% by weight, preferably 20 to 7% by weight based on the total weight of the monomers.
0% by weight and the acrylic monomer content is 20 to 90% by weight, preferably 30 to 90% by weight based on the total weight of the monomers.
80% by weight. Further, the styrene-acrylic copolymer may contain styrene and an acrylic monomer as monomer components in the above range, and may also contain other monomer components as necessary. As the other monomer component in this case, any of those described as the copolymerization component of the styrene polymer and the acrylic polymer can be used.

From the viewpoint that the glass transition temperature of the styrene-acrylic copolymer exhibits the functions of both the granulating component (A) and the fiber adhesive component (C), the above-mentioned granulating component (A) is used. ), The glass transition temperature range of the styrene polymer used as a) and the glass transition temperature range of the acrylic polymer used as the fiber adhesive component (C) overlap with each other,
That is, the wall surface adhesion preventing component (D) which is preferably in the range of 70 to 100 ° C. The colored beads for stippling coloring of the fibers of the present invention are the above-mentioned three components, that is, (A) a styrene-based polymer. Granulation ingredients,
(B) A coloring component composed of pigments and (C) a fiber adhesive component composed of an acrylic polymer are contained as essential components, and if necessary, a wall surface adhesion preventing component (D) composed of a fine particle filler is further added. May be included. The use of the wall surface adhesion preventing component (D), combined with the action of the granulation component (A), makes it possible to further reduce the amount of adhesion to the wall surface of the spray drying device during spray drying, thus improving the production efficiency. Can be further improved. Moreover, by using the fine particle filler, not only such an effect but also a secondary effect that the types and blending ratios of the above-mentioned three essential components can be selected from a wider range are exhibited. That is, usually, the amount of adhesion to the wall surface of the spray dryer is often influenced by the types of the three essential components used and the mixing ratio thereof, and in particular, when the mixing amount of the fiber adhesive component (C) increases,
Although the amount adhering to the wall surface tends to increase, even if the compounding amount of the fiber adhesive component (C) is increased by the addition of the wall surface anti-adhesion component (D), the amount adhering to the wall surface also increases. It can be prevented and the amount of the fiber adhesive component (C) used can be significantly increased as compared with the case where the wall surface adhesion preventing component (D) is not used. This makes it possible to increase the amount of the fiber adhesive component (C) used in applications in which particularly strong adhesion to fibers is required, or the amount of adhesion to a drying device tends to increase. Even when using a component having a glass transition temperature, it is possible to prevent an increase in the amount attached to the wall surface.

Further, the wall surface adhesion preventing component (D) has a relatively large particle size, in addition to the above-described excellent effects, without impairing the breaking strength and adhesive properties of the obtained colored beads. It is also useful for preparing beads.

The wall surface adhesion preventing component (D) has an average particle size in the range of about 0.01 to 50 μm, preferably 0.1.
Any fine particle filler in the range of about 1 to 20 μm, as long as it does not melt or soften at the temperature during spray drying described below, as long as it does not adversely affect the above-mentioned three essential components. There is no problem in using, and both organic fine particles and inorganic fine particles can be used. Examples of fine particle fillers suitable for use in the present invention include barium carbonate, barium sulfate, zinc sulfide, calcium carbonate, calcium phosphate, talc, alumina, gypsum, silica, activated clay, clay, glass spheres, metal powder, silicone resin, phenol. Resins, epoxy resins, melamine resins, urea resins, crosslinked styrene resins, crosslinked PMMA resins and the like can be mentioned, and these can be used alone or in appropriate combination.

Blending Ratio In the present invention, the blending ratio of each of the above-mentioned components can be adjusted within a wide range depending on the type of each polymer and pigment to be used, and is not particularly limited, but in general, granulation Pigments 0.0001 to 1 as the coloring component (B) per 1 part by weight of the styrene polymer as the component (A).
It may be appropriately selected within the range of about 0 parts by weight and about 0.1 to 2 parts by weight of the acrylic polymer which is the fiber adhesive component (C).

The specific blending amount of the coloring component (B) can be determined according to the required coloring density, and normally, the blending amount of about 0.0001 parts by weight or more is sufficient as described above. However, when ultra-light colored beads are required, there is no problem even if the amount is less than this amount. On the other hand, if the blending amount of the coloring component (B) exceeds 10 parts by weight, the granulating strength of the colored beads is lowered, the beads are easily broken, and the desired effect may not be obtained, which is not preferable. .

Regarding the blending amount of the fiber adhesive component (C),
If the amount exceeds 2 parts by weight, the amount of adhesion to the wall surface of the drying device increases at the time of spray drying described below, the production efficiency decreases, and the granulation strength of the obtained colored beads also decreases, which is not preferable. On the other hand, if the amount is less than 0.1 parts by weight, the adhesive strength to the fibers is lowered and the abrasion fastness and the fastness to washing are deteriorated.

Further, the wall surface adhesion preventing component (D) is used as necessary, but in order to sufficiently exert the above-mentioned effects, 1 part by weight of the granulating component (A) is used. On the other hand, it is appropriate that the amount used is in the range of about 0.1 to 10 parts by weight. Further, as described above, by using the wall surface adhesion preventing component (D), it becomes possible to increase the amount of the fiber adhesive component (C) used, and the granulating component (A) 1
The blending ratio of the fiber adhesive component (C) to 0.1 part by weight is 0.1.
It may be in the range of about 5 parts by weight. The mixing ratio of the coloring component (B) is about 0.0001 to 10 parts by weight with respect to 1 part by weight of the granulating component (A), as in the case where the wall surface adhesion preventing component (D) is not mixed. Good.

When the styrene-acrylic copolymer is used as a polymer having both functions of the granulating component (A) and the fiber adhesive component (C), the styrene-acrylic copolymer is used. The amount of use of the above-mentioned granulating component (A) is the same as in the case of using the three-component system of (A) to (C) and the four-component system of (A) to (D). It is appropriate that the total amount of the fiber adhesive component (C) is within the range.

Method for Producing Colored Beads Next, a method for producing the colored beads for stippling colored fibers of the present invention will be described.

First, an aqueous liquid containing the above-mentioned essential components is prepared. In this case, the granulation component (A) and the fiber adhesive component (C) can be added in the form of a solution, emulsion, suspension or the like using water or an organic solvent as a solvent or dispersion medium, and powder. It does not matter if it is added as it is. The same applies to the coloring component (B) or the wall surface adhesion preventing component (D) that is added as necessary, and the order of addition is not particularly limited.

The proportion (concentration) of the essential components in the aqueous liquid material may be arbitrarily selected according to the drying conditions and the intended particle diameter of the beads, and is not particularly limited. Usually, it is preferable to set it to about 5 to 50% by weight. The proportion of water in the total solvent or dispersion medium of the aqueous liquid is preferably 50% by weight or more.

Further, in the aqueous liquid, any additives may be used in combination, if necessary, as long as they are additives that can be blended in inks and paints of ordinary formulation. Examples of such additives include organic solvents, surfactants,
Polymer protective colloid, thermoplastic resin, thermosetting resin, oil, wax, catalyst, electrolyte, plasticizer, resin cross-linking agent, wetting agent, softening agent, ultraviolet absorber, antioxidant, antistatic agent, preservative, Deodorants, repellents, insect repellents, antibacterial agents, insecticides, fungicides, rust preventives, pH adjusters, viscosity modifiers, flame retardants, lubricants, various dyes, extender pigments, optical brighteners, discharge preventive discharges. Agents, ultraviolet light-emitting dyes, drying regulators, foaming agents, defoamers,
Examples include water repellents, fragrances, and various other stabilizers.

Next, the above-mentioned aqueous liquid is charged into a spray drying device (hereinafter referred to as a spray dryer) at a constant speed to carry out spray drying to remove volatile components (mainly solvent or dispersion medium) in the liquid. By volatilizing to obtain a composite granulated product, colored beads for point-spot coloring of the target fibers can be obtained. As the spray dryer, any of a disc rotary type, a pressure nozzle type, a two-fluid nozzle type and the like may be used, but in particular, a disc rotary type suitable for obtaining a uniform particle size. Is preferably used.

The conditions for spray drying are also not particularly limited, and spray drying may be carried out in accordance with a conventional method, and the drying temperature, disk rotation speed, nozzle injection amount, liquid feed rate, etc., of the liquid used. It may be appropriately adjusted depending on the type and the like so as to obtain a target composite granulated product.

The average particle size of the colored beads is required to be 5 to 500 μm, and by setting the average particle size within this range, the coloring effect is excellent, and the touch, feel, friction fastness, etc. are also colored. You can give things. If the average particle size of the colored beads is less than 5 μm, the visual effect as pointillistic coloring is poor, while if it exceeds 500 μm,
It is not preferable because it causes deterioration or deterioration of touch, feel, friction fastness and the like of the colored product. The particle size of the colored beads can be extremely easily adjusted by adjusting the concentration of the essential components in the aqueous liquid, the disk rotation speed of the spray dryer, the feeding speed of the liquid, and the drying temperature (spray dry temperature). It can be adjusted with good reproducibility. As described above, according to the method of the present invention, since the particle size of the colored beads can be easily and reproducibly adjusted, the colored beads having an arbitrary particle size and good uniformity can be obtained. Therefore, the colored beads of the present invention are extremely useful in pointillistic coloring in which the superiority or inferiority of the visual effect depends on the size and uniformity of the particle size.

Colored Beads for Stippled Coloring of Fibers The colored beads for stippled coloring of fibers obtained by the present invention may be prepared by using one or more kinds of the colored beads for a conventional formulation, for example, a printing paste. , Printing ink, paint, spray colorant, coating agent, etc.
By using the coloring composition to perform printing, transfer, printing, coating, dipping, spraying, brush coating, and the like according to a conventional method, a unique visual effect such as a frost effect, a colorful effect, a three-dimensional effect, and a washing effect can be obtained. Can be exerted on fibers. For example, when a printing paste is prepared by using colored beads of two or more colors and a printing cloth is obtained by printing this, a printed portion does not have a uniform mixed color pattern and two or more colors are used. It becomes a pattern with innumerable dots of, and microscopically, in addition to the single color that each dot exhibits, there is also a heavy color in the adjacent part of those dots, which exerts a colorful effect, macroscopically By mixing colors in the visual sense, the effect of mixed colors having a stereoscopic effect is exhibited. In addition, in the various colored compositions described above, a resin binder or a sizing agent as an adhesive component can be added, but the addition amount can be suppressed to be relatively lower than that of a normal formulation, and thus excellent. A stippled colored fiber having a good texture and feel can be obtained.

If necessary, the above-mentioned various additives can be added to the coloring composition, and at this time, the coloring composition is prepared by using a resin binder having an opposite potential to the beads of the present invention. To prepare the beads of the present invention.
It can also be used after being aggregated.

By using the colored beads obtained according to the present invention in combination with various ordinary dyes and pigments, the color effect of the colored product can be further varied. For example, a colored product obtained by using a colored composition obtained by using a colored bead obtained by the present invention and a general organic pigment in combination exhibits microscopically defrosting with dots dispersed in a uniform ground color, and macroscopically. Produces a three-dimensional effect in which the dot color appears to stand out independently of the ground color.
Further, by using a metal powder pigment or a pearl pigment in combination, it is possible to freely obtain a pointillized colored product having a metallic luster or a pearl luster.

The coloring composition containing the colored beads for stippling coloring of the present invention is not particularly limited as long as it is a fiber, and can be applied to a wide range. For example, as an object to be colored, a yarn, Examples thereof include sliver, raw cotton, woven fabric, knitted fabric, non-woven fabric, film-shaped product, and sewn products and molded products obtained by processing them. Also, the type of fiber constituting the object is not limited at all, and natural cellulose fibers such as cotton and hemp, natural protein fibers such as silk and wool, regenerated and semi-synthetic fibers such as rayon and acetate, acrylic and nylon. , Polyester, various kinds of synthetic fibers such as polyolefin, and the like, as the coloring object,
These fibers may be used alone or in combination of two or more kinds.

[0054]

According to the present invention, the following excellent effects are achieved.

(1) Since the styrene-based polymer as the granulating component (A) has a high transparency, it is possible to carry out pointillation coloring having a high definition. Since the styrene-based polymer is also excellent in the granulation effect, the adhesion phenomenon that occurs on the wall surface of the spray dryer during spray drying is prevented, the production efficiency is improved, and the colored beads of the present invention using it as a matrix are It has excellent breaking strength and will not be broken during actual use. At the same time, the pigments as the coloring component (B) are
Since it is strongly supported on the matrix made of a styrene polymer, it is possible to eliminate undesirable factors such as color bleeding and crying.

(2) Since the acrylic polymer, which is the fiber adhesive component (C), is added to the colored beads for stippling coloring of the present invention, excellent affinity for various fibers is exhibited. It is possible to provide a very robust stippling coloring effect without impairing the feel and feel of various fibers.

(3) When the fine particle filler as the wall surface adhesion preventing component (D) is added, the adhesion phenomenon during spray drying can be further suppressed in combination with the action of the above-mentioned styrene polymer. , The production efficiency is improved. Furthermore, by using the wall surface adhesion preventing component (D), the selection range of the types and blending ratios of the above-mentioned three essential components can be expanded, and colored beads having a relatively large particle size can be obtained.

(4) The colored beads for pointillistic coloring of the present invention can be prepared very easily by spray drying,
High productivity can be secured because no complicated operation is required for its manufacture. In addition, since the particle size is extremely uniform and can be obtained with good reproducibility, it is possible to always perform the pointillistic coloring treatment with stable properties.

[0059]

The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples.

In the following description, "part" and "%"
Means "parts by weight" and "% by weight", respectively.

Example 1 A styrene polymer obtained by using a monomer component consisting of 55% styrene, 40% methyl methacrylate, 4.6% methacrylic acid and 0.4% divinylbenzene [glass transition temperature 90 ° C.] 50% aqueous emulsion of 50% of particle component), 5 parts of 15% aqueous dispersion of phthalocyanine blue (coloring component) having an average particle size of about 0.4 μm, and 45% of methyl acrylate, 45% of ethyl acrylate and 10% of acrylic acid. An aqueous liquid was prepared by adding 10 parts of a 50% aqueous emulsion of an acrylic polymer [glass transition temperature of 60 ° C.] (fiber adhesive component) obtained by using the following monomer component to 50 parts of water and thoroughly stirring. .

Then, the aqueous liquid was fed into an L-8 type spray dryer (disc rotary type; manufactured by Okawara Kakoki Co., Ltd.) set at a spray dry temperature of 180 ° C. and a disc rotational speed of 16000 rpm. Approximately 25 parts by weight of colored beads for stippling coloring of blue fibers, which is a composite granule having a uniform particle size distribution with an average particle size of approximately 45 μm, are charged at a rate of about 97 μm (yield: about 97 μm). %) Was obtained. At the end of the operation, the inside of the spray dryer was observed, but almost no adhesion phenomenon to the wall surface was observed.

Next, 10 parts of the colored beads obtained above, 60 parts of an acrylic ester resin emulsion (binder for printing, trade name: binder 350R; manufactured by Matsui Dye & Chemical Co., Ltd.), and 2 parts of an epoxy type crosslinking agent. Was mixed to prepare a printing paste, and the paste was printed on a cotton T-shirt using an 80-mesh character pattern screen plate, and then heat-treated at 130 ° C. for 3 minutes. The printed portion of the T-shirt was composed of clear blue dots when viewed from a close distance, but exhibited a unique wash-out tone when viewed from a distance.

The printed part had a good tactile sensation as compared with the part other than the pattern, and had various fastnesses such as abrasion resistance.

Examples 2 to 8 In place of 40 parts of 50% aqueous emulsion of styrene polymer used in Example 1, 40 parts of 50% aqueous emulsion of styrene polymer having the following monomer composition was used. Except for the above, except that in the same manner as in Example 1, a cotton T-shirt having a character pattern imprinted thereon was obtained. The performance of the T-shirt thus obtained was almost the same as that of Example 1.

<Example 2> Copolymer consisting of 60% styrene and 40% methyl methacrylate [glass transition temperature 90 ° C] <Example 3> 60% styrene, 30 methyl acrylate
% And vinyl acetate 10% [glass transition temperature 95 ° C.] <Example 4> 40% styrene, 4 methylmethacrylate
Polymer consisting of 0% and acrylonitrile 20% [glass transition temperature 85 ° C.] <Example 5> 50% styrene and 50 acrylonitrile
% Copolymer [glass transition temperature 100 ° C.] <Example 6> 40% styrene, 40% dimethylmethacrylamide, 15% butyl acrylate and 5 vinyl acetate
% Copolymer [glass transition temperature 80 ° C.] <Example 7> 30% styrene, 50% acrylonitrile
And a copolymer of 20% methyl methacrylate [glass transition temperature 105 ° C.] <Example 8> 40% styrene, 30 methyl acrylate
%, Vinyl acetate 25%, butadiene 4.5%, and ethylene glycol dimethacrylate 0.5% [glass transition temperature 95 ° C.] Examples 9-14 50 of the acrylic polymer used in Example 1 %, Except that 10 parts of 50% aqueous emulsion of an acrylic polymer having the following monomer composition was used in place of 10 parts of the aqueous emulsion, and otherwise the same as in Example 1 except that a character-patterned cotton was printed. I got a T-shirt. The performance of the T-shirt thus obtained was almost the same as that of Example 1.

<Example 9> 45% of methyl acrylate,
Copolymer consisting of butyl acrylate 45% and vinyl acetate 10% [glass transition temperature 50 ° C.] <Example 10> Copolymer consisting of methyl methacrylate 50% and acrylonitrile 50% [glass transition temperature 6
5 ° C.] <Example 11> A copolymer composed of 40% methyl acrylate, 30% ethyl acrylate, 15% dimethylacrylamide and 15% vinyl acetate [glass transition temperature 60
C.] <Example 12> Copolymer consisting of 60% methyl methacrylate, 20% dimethylmethacrylamide, 15% acrylonitrile and 5% styrene [glass transition temperature 65
° C] <Example 13> Copolymer consisting of methyl acrylate 50%, butyl acrylate 30%, vinyl acetate 19% and ethylene glycol dimethacrylate 1% [glass transition temperature 70 ° C] <Example 14> acrylonitrile 60%, methyl Copolymer consisting of 20% acrylate and 20% vinyl chloride [glass transition temperature 40 ° C.] Comparative Example 1 All the same as in Example 1 except that 10 parts of a 50% aqueous emulsion of an acrylic polymer was not used. I got a cotton T-shirt imprinted with a character pattern.

The performance of the obtained T-shirt was evaluated according to the T-value of Example 1.
When compared with a shirt, the color effects were almost the same, but the rubbing fastness was inferior. This rubbing fastness was twice as high as that of the printing binder used in Example 1 (120
However, the texture and feel at that time became a little stiff and the pattern part felt uncomfortable.

Comparative Example 2 Aqueous emulsion of acrylic polymer used in Example 14 was used instead of both 40 parts of aqueous emulsion of styrene polymer and 10 parts of aqueous emulsion of acrylic polymer used in Example 1. A cotton T-shirt imprinted with a character pattern was obtained in the same manner as in Example 1 except that 50 parts were used alone.

On the way, the yield of colored beads was about 65% and a considerable amount of deposits was observed on the walls of the spray dryer.

Further, it was found that when the printed T-shirt of the obtained cotton T-shirt was rubbed with a claw, specs were generated, and the breaking strength of the beads was lower than that of Example 1.

Example 15 Fibers were prepared in the same manner as in Example 1 except that an aqueous liquid containing 20 parts of calcium carbonate having an average particle size of 0.5 μm was spray-dried as a component for preventing wall adhesion. To obtain colored beads for pointillistic coloring.

The yield of the colored beads was almost the same as that of Example 1, but it was observed that the amount of adhesion to the wall of the spray dryer was further reduced as compared with that of Example 1. The average particle diameter of the colored beads was about 48 μm, which was slightly larger than that of Example 1, but the uniformity was almost the same.

Next, 10 parts of the blue colored beads and 70 parts of a urethane-based emulsion binder (trade name: AR binder GS; manufactured by Matsui Dye & Chemical Co., Ltd.) are mixed to prepare a printing ink, and one side is made of silicone resin. The ink was printed on the polyester film treated with No. 1 by using a screen plate (70 mesh) having a floral pattern.

Subsequently, when the ink-printed surface is wet, hot-melt polyester resin powder (trade name: Byron GM90)
2, manufactured by Toyobo Co., Ltd.) on the entire surface of the film to a dry film thickness of about 20.
The powder was sprayed so as to have a particle size of 0 μm, excess powder adhering to parts other than the pattern part was removed, and the powder was dried at 25 ° C. to obtain a transfer printing sheet having a floral pattern.

The hot-melt resin surface of the transfer printing sheet was brought into contact with the back surface of an acrylic shirt dyed in pink in advance, and the polyester film was treated with a heat press machine at 140 ° C. for 5 seconds. A floral pattern was transferred to the back surface of the shirt by peeling and removing.

The pattern portion of the obtained shirt is composed of small blue dots when viewed from a close distance, but from a distance away, a blue floral pattern appears on a pink background and appears. It has a very three-dimensional visual effect.

The texture, feel, and various fastnesses of the pattern portion were all good.

Example 16 100 parts of a 40% aqueous emulsion of a styrene-acrylic copolymer obtained by using a monomer component consisting of 30% styrene, 20% acrylonitrile, 30% methyl methacrylate, and 20% butyl acrylate was prepared. It is used as a polymer that has the function of both a grain component and a fiber adhesive component, and uses 50 parts of chrome yellow with an average particle size of about 0.7 μm and 20 parts of quinacridone red with an average particle size of about 0.3 μm as coloring components to prevent wall adhesion. 40 parts of melamine fine particles having an average particle diameter of 0.8 μm were used as components, and these were mixed with 10 parts of polyethylene glycol, 0.5 part of a silicone-based defoaming agent and 200 parts of water and stirred to prepare an aqueous liquid material. .

Next, using the same spray dryer as in Example 1, a spray dry temperature of 150 ° C. and a disk rotation speed of 2 were used.
Set to 0000 rpm, the liquid material obtained above is charged at a feed rate of 2.0 liters / hour for spray drying,
Colored beads for dot-stain coloring of orange fibers having an average particle diameter of about 35 μm were obtained.

Further, an aqueous liquid obtained by replacing 50 parts of chrome yellow and 20 parts of quinacridone red in the above aqueous liquid with 70 parts of chrome yellow, and the same chrome yellow 50.
Parts and 20 parts of quinacridone red were replaced with 70 parts of quinacridone red, and aqueous liquids were prepared. Using these liquids, colored beads for yellow and red pointillization coloring were respectively produced.

Next, 200 m (50 kg) of a 90 cm wide mixed-spun circular knitted fabric made of 35% polyester / 65% cotton is used for 3 times.
It is put into a jet dyeing machine with a capacity of 000 liters, and the bath ratio is 1: 2.
After adding water to 0, the dyeing machine was operated. Next, after diluting 5% by weight of the quaternary ammonium salt type nitrogen-cationic compound (trade name: Panfix NF, manufactured by Yatasha Fat & Oil Co., Ltd.) with 100 times the amount of water in advance, the dyeing machine It was put in and treated at room temperature for 15 minutes.
Subsequently, the temperature is raised to 70 ° C. and
The mixed-spun circular knit fabric was cationized by treating for 5 minutes. Continuously, the circular knitted fabric was
Cold rinsing for 2 minutes was performed to remove excess cationic compounds. After the circulation was once stopped, water was supplied to the dyeing machine so that the bath ratio was 1:20, and the circulation was restarted.
Then, each of the three colored beads obtained above is prepared in an amount of 5% by weight with respect to the weight of the fabric, and diluted in advance with 5 times the weight of water,
After gradually introducing them into the dyeing machine, they were treated at room temperature for 20 minutes, and then gradually heated to 50 ° C. and treated for 15 minutes. Next, the colored mixed-spun circular knitted fabric was rinsed for 2 minutes in the same dyeing machine. After stopping the circulation again, water was supplied to the dyeing machine so that the bath ratio was 1:15, and the circulation was restarted. Then, 3% by weight of the fabric weight of the polyurethane resin emulsion binder (trade name: Hydran HW31
1; manufactured by Dainippon Ink and Chemicals, Inc.) was previously diluted with 20 times by weight of water, and they were put into a dyeing machine to gradually raise the temperature.
It was treated at 80 ° C. for 15 minutes. Then, the circular knit fabric was taken out from the dyeing machine, dehydrated using a centrifugal dehydrator, opened, and dried at 80 ° C to 100 ° C using a tumbler dryer. After that, the polo shirt obtained by cutting and sewing the knitted fabric has good feeling, feeling, abrasion resistance, and wash resistance, and when viewed from a distance, it is entirely orange.
When viewed closely, it had a unique color effect composed of the above-described three-color clear dots.

[0083]

Claims (2)

[Claims] 1. Colored beads for stippling coloring of fibers having an average particle diameter of 5 to 500 μm obtained by spray drying an aqueous liquid containing the following three components (A) to (C) as essential components: ) A granulating component composed of a styrene polymer, a coloring component composed of (B) pigments, and a fiber adhesive component composed of (C) an acrylic polymer. 2. Colored beads for stippling coloring of fibers having an average particle diameter of 5 to 500 μm obtained by spray drying an aqueous liquid containing the following four components (A) to (D) as essential components: ) A granulation component composed of a styrene polymer, a coloring component composed of (B) pigments, a fiber adhesive component composed of (C) an acrylic polymer, and a wall surface adhesion preventing component composed of (D) fine particle filler.