JPH07109681A - Reversibly color-variable coloring method by padding and colored textile product - Google Patents

Abstract

PURPOSE:To color continuous textile products in high uniformity and efficiency with reversibly color-variable microcapsule fine particles through preventing both tailing and reverse-tailing phenomena. CONSTITUTION:Continuous textile products are treated continuously by padding method using a water-based liquid containing thermo/optoreversibly color- variable microcapsule fine particles 0.5-15mum in median diameter on a volume basis and a thermoplastic resin.

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 a continuous product of textiles with reversible color-changing microcapsule particles and a colored product obtained by the method.

[0002]

BACKGROUND OF THE INVENTION The inventors of the present invention have previously proposed, as a method for efficiently coloring a continuous product of textiles with a reversible color-changing material, the continuous product was previously subjected to a nitrogen-cationic compound. And a reversible color-changing material is supported by a padding method after the treatment (Japanese Patent Application No. 5-60959).

If the above coloring method can be applied padding legally to a reversible color-changing material, which has hitherto been considered impossible due to the fact that a uniform colored product in the length direction cannot be obtained. From the point of view, the usefulness for industrial use was extremely large, but on the other hand, compared with the usual padding method, it was necessary to separately perform pretreatment with a nitrogen-cationic compound, so that the process operation was It was multistage.

Further, this nitrogen-cationic compound was originally used for the purpose of preventing the reverse tailing phenomenon that appears during the padding operation, but depending on the type of textile products and the type of nitrogen-cationic compound, In some cases, the tailing phenomenon may occur because the deposition rate of the non-vehicle component such as the reversible color-changing material is so accelerated.

The present invention has been made in view of the above problems existing in the prior art, and an object of the present invention is to make a continuous product of textile products into a tailing phenomenon and a reverse tailing phenomenon. The present invention is to provide a reversible color-changing coloring method by padding and a colored product thereof, which can prevent the above-mentioned problems, and can be colored with the reversible color-changing microcapsule particles with high uniformity and efficiency.

[0006]

The present inventors have found that the above-mentioned tailing phenomenon and reverse tailing phenomenon occur extremely strongly depending on the particle size of various fine particles which are non-vehicle components present in the padding bath. It was Further research shows that the use of reversible color-changing microcapsule particles having a specific range of particle size prevents the reverse tailing phenomenon without pretreatment with a nitrogen-cationic compound, and avoids the tailing phenomenon. The present inventors have completed the present invention by finding that it is possible to obtain a reversibly discolorable colored product which is highly uniformly colored by the microcapsule fine particles.

That is, in the coloring method of the present invention, fibers are prepared by using an aqueous liquid containing thermo- and / or photo-reversible color-changing microcapsule fine particles having a volume-based median diameter of 0.5 μm to 15 μm and a thermoplastic resin. It is characterized in that a continuous product is continuously treated by a padding method.

When the volume-based median diameter of the heat- and / or photo-reversible color-changing microcapsule particles is less than 0.5 μm, the microcapsule particles are easily supported on the textile products, and at least the reverse tailing phenomenon is prevented. Since the proportion of the non-coloring component in the microcapsule particles increases, the coloring density of the colored product becomes extremely low,
Practicality is poor.

On the other hand, when the volume-based median diameter of the heat- and / or photo-reversible color-changing microcapsule particles exceeds 15 μm, the reverse tailing phenomenon cannot be prevented unless the pretreatment with the nitrogen-cationic compound is carried out, and thus the present invention can be used. It does not meet the purpose. One of the reasons is that the microcapsule particles are easily removed from the textile products when the solution is squeezed. The volume-based median diameter can be measured by, for example, a laser diffraction / scattering type particle size distribution measuring device.

The reversible color-changing microcapsule particles used in the present invention include both so-called thermochromic type microcapsule particles which are reversibly discolored by heat and so-called photochromic type microcapsule particles which are reversibly discolored by light. And those exhibiting a hysteresis phenomenon in the color change cycle are also included. Of course, for the purpose of enriching the color variations of the obtained textile products and increasing the added value, one or more kinds of microcapsule particles of the type that changes color by heat and microcapsule particles of the type that changes color by light are used in combination. It is also possible.

More specific examples of these microcapsule microparticles will be given. First, as thermochromic type thermoreversible color-changing microcapsule microparticles, an acid represented by a leuco dye for pressure-sensitive and thermosensitive copying paper is used. Two-component composition comprising a color-developing substance and an acidic substance such as phenols having the ability to develop and decolor it; organic compounds such as alcohols and esters in addition to the acid-developing substance and the acidic substance A three-component composition containing a solvent; and a conventionally known thermoreversible discoloration material such as a cholesteric liquid crystal or a mixed liquid crystal composition composed of a chiral nematic liquid crystal, an interfacial polymerization method, an in situ polymerization method, and a submerged curing coating. Method, coacervation method, spray-drying method, or other known means for encapsulating a film-forming polymer compound in the form of fine particles. Examples thereof include fine particles obtained by solidifying the thermoreversible color-changing material with a child compound, and fine particles obtained by dispersing the thermoreversible color-changing material in a synthetic resin matrix.

Next, photochromic photoreversible color-changing microcapsule microparticles are obtained by dispersing a so-called organic photochromic compound such as spiropyran, spirooxazine, naphthopyran or fulgide in a synthetic resin matrix. Fine particles obtained by encapsulating matrix fine particles with the film-forming polymer compound, a mixture in which the organic photochromic compound is dissolved or dispersed in a medium such as hindered amines, hindered phenols, plasticizers, high-boiling solvents and synthetic resins. Examples thereof include fine particles obtained by encapsulating or forming a solid solution with the above-mentioned film-forming polymer compound.

The above-mentioned microcapsule microparticles are dispersed singly or in combination of two or more kinds in water to form an aqueous liquid together with a thermoplastic resin. As the thermoplastic resin used in the present invention, acrylic ester resin, methacrylic ester resin, vinyl acetate resin,
Any polyurethane resin, polyester resin, styrene butadiene latex, polyolefin resin or the like that is known as an adhesive component in a padding bath may be used. This thermoplastic resin can be applied singly or in combination of two or more in the form of an aqueous solution or an aqueous emulsion.

The thermoplastic resin has a function of adhering the heat and / or photo-reversible color-changing microcapsule fine particles onto the textile products. A part of the thermoplastic resin used may be crosslinkable, or another crosslinkable resin may be used in combination. Needless to say, in such a case, a necessary crosslinking catalyst is added and used.

In addition to the ultraviolet absorber, the antioxidant, the antistatic agent, the flame retardant,
Preservatives, repellents, insect repellents, resin cross-linking agents, surfactants, viscosity modifiers, wetting agents, plasticizers, softeners, fragrances, antibacterial deodorants, general dyes and pigments, ultraviolet-emitting dyes, fluorescent pigments, phosphorescent pigments. Any of the above-mentioned materials such as a luminescent pigment, a fluorescent whitening agent, an extender pigment, an electrolyte, an anti-discharge printing agent, a thermosetting resin, a drying regulator, etc. can be used in combination as long as they are used in an ordinary mixture for padding. As long as the above-mentioned microcapsule fine particles do not impair the discoloring property, the above-mentioned substances may coexist in the fine particles.

According to the coloring method of the present invention, for example, a continuous fiber product is continuously immersed in a padding bath in a padding machine filled with the above-mentioned aqueous liquid material through a guider or the like. By applying a coloring treatment,
The fiber products that have undergone such treatment are dehydrated (squeezed) by applying them to a mangle or the like, and then dried by a tentering machine, etc.
That is, the colored product of the present invention can be obtained. In addition, this aspect is only an example of an aspect in which the coloring method of the present invention is further embodied. In addition to this, for example, by passing through the first padding bath and then pre-drying, and then passing through a second padding bath containing microcapsule fine particles as coloring seeds different from the first time, the color variations are enriched. Alternatively, it is of course possible to further enhance the friction fastness of the colored product by passing it through a second padding bath containing only the above-mentioned thermoplastic resin as a main constituent.

Examples of the fiber species constituting the continuous product of the textile products used in the present invention include cellulosic fibers such as cotton and hemp, protein fibers such as wool and silk, recycled fibers such as viscose rayon and cupra, Semi-synthetic fibers such as acetate and triacetate, and polyamide, polyester,
Examples thereof include synthetic fibers such as polyurethane, polyolefin, and acrylic. You may combine 2 or more types of these. Next, examples of the continuous product of the fiber products constituted by these include the following sheet-like products and bundle-like products.

The term "sheet-like material" as used herein is a term used relative to the term "bundle material" described below, and specifically, a woven fabric, a knitted fabric, which can be used in a single continuous process, It refers to a fabric in the form of long fabric such as non-woven fabric. From the viewpoint of improving productivity, those having a width of several tens of cm to several m and a length of several tens of m or more are preferably used. However, each fabric shorter than this is easily sewn into a long piece of fabric. It is also possible to use the prepared one.

Next, the term "bundle" is a term relatively used to the term "sheet-like article" described above, and as long as it can be used in a continuous coloring step, it is particularly preferable. It is not limited. In particular,
A thread, a string, a rope, or the like having a linear shape is shown, and several to hundreds of them are bundled or twisted. Although those having a length of several tens of meters or more are preferably used, it is also possible to lightly connect linear bodies shorter than that and to use them as an appropriate length. Furthermore, these textile products may be pre-colored. As the object of the present invention, a continuous product of fiber products having uniformity in the length direction is desirable.
Textile products particularly suitable as objects of the present invention include knitted fabrics.

[0020]

INDUSTRIAL APPLICABILITY According to the present invention, by using reversible color-changing microcapsule fine particles having a volume-based median diameter within a specific range, padding is performed on textile products without pretreatment with a nitrogen-cationic compound. The continuous product of the textile products is directly colored by the method by the reversible color change microcapsule fine particles, of course, in the width direction.
It is possible to color with high uniformity in the length direction as well, and in addition, the obtained colored product has almost the same excellent feeling and texture as the original products of textile products, and also has abrasion resistance and washing resistance. Also excellent in sex. Therefore, pretreatment with a nitrogen-cationic compound can greatly simplify the multi-step process operation and further improve the production efficiency, and this and the non-use of the nitrogen-cationic compound combine to produce a reversible discolorable colorant. The production cost can be significantly reduced.

[0021]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In the following description, “part by weight” is abbreviated as “part”.

Production Example of Microcapsule Particles with Thermoreversible Color Change Crystal Violet Lactone (acid-developing substance) 1
Part Bisphenol A (acidic substance) 3 parts myristyl alcohol (solvent) 25 parts

A mixture of the above-mentioned compounds, which was heated and melted, was used as CMC.
5 parts and anion activator (Brand name: Demol N made by Kao Co.)
The mixture was put into 200 parts of an aqueous solution of 80 parts at a temperature of 80 ° C. containing 0.1 parts with stirring and emulsified so as to have an average particle size of about 3 μm by visual confirmation (microscopic observation) (basic emulsification). A 20% aqueous solution of a melamine-formalin prepolymer obtained by initial polymerization of 30 parts of a granular melamine resin with 10 parts of formalin was added to this emulsion.
5 parts were added, pH was adjusted to 5 by adding 10% acetic acid aqueous solution, 5 parts formalin was subsequently added, the liquid temperature was raised to 95 ° C., and stirring was continued for 2 hours, then, the reaction was terminated. .

The thus obtained dispersion of thermoreversible color-changing microcapsule fine particles was applied to a laser diffraction / scattering type particle size distribution measuring device (product number: LA-700, manufactured by Horiba, Ltd.), and the volume-based median diameter was measured. Was measured to be 2.25 μm. The dispersion was filtered, and the filtered material was dried to obtain about 30 parts of thermoreversible color-changing microcapsule fine particles having a volume-based median diameter of 2.25 μm (thermoreversible color-changing microcapsule fine particles A).

Further, the particle sizes at the time of basic emulsification are about 0.1 μm, 0.3 μm, 0.5 μm, 1 μm and 5 respectively.
μm, 8 μm, 12 μm, 15 μm, 17 μm, 25 μ
The thermoreversible color-changing microcapsule fine particles B to K were obtained in the same manner as described above except that the m was adjusted to m. Table 1 shows the results of measuring the volume-based median diameter of these microcapsule fine particles.

[0026]

[Table 1]

Production Example of Photoreversible Color- changing Microcapsule Fine Particles 3,3-diphenyl-3H-naphtho [2,1-b] pyran (organic photochromic compound) 1 part Methyl methacrylate-butyl methacrylate-acrylonitrile 1: 1: 1 Copolymer resin (molecular weight about 150,000)
10 parts Diisononyl phthalate 20 parts Xylene 15 parts Epoxy resin (trade name: Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) 4 parts

A mixture obtained by heating and melting the above-mentioned compound was heated to 60 ° C.
The resulting mixture was added to 700 parts of 10% aqueous gelatin solution under agitation and emulsified by visual confirmation (microscopic observation) so that the average particle size was about 3 μm (basic emulsification). To this emulsion, 2 parts of a curing agent for epoxy resin (trade name: Epomate-B-002 manufactured by Yuka Shell Epoxy Co., Ltd.) was added, and the liquid temperature was adjusted to 8
After the temperature was raised to 0 ° C. and stirring was continued for 1 hour, the reaction was terminated.

The thus obtained dispersion of photoreversible color-changing microcapsule fine particles was applied to a laser diffraction / scattering type particle size distribution measuring device (product number: LA-700 manufactured by Horiba, Ltd.), and the volume-based median diameter was measured. Was measured to be 2.08 μm. The dispersion was filtered and the filtered material was dried to obtain about 50 parts of photoreversible discolorable microcapsule microparticles having a volume-based median diameter of 2.08 μm (photoreversible discolorable microcapsule microparticle A).

Further, the particle diameters at the time of basic emulsification are approximately 0.1 μm, 0.3 μm, 0.5 μm, 1 μm, and 5 μm, respectively.
μm, 8 μm, 12 μm, 15 μm, 17 μm, 25 μ
Photoreversible color-changing microcapsule microparticles B to K were obtained in the same manner as above except that the fineness was adjusted to m. Table 2 shows the results of measuring these volume-based median diameters.

[0031]

[Table 2]

Example 1 50 kg of a cotton knitted fabric (tenjiku 50 cm width × 300 m length) circularly knitted with 20 w of previously scoured cotton yarn was opened, and this was put into a padding bath in a roll padder [water 100 parts, thermo-reversible color change micro 10 parts of capsule fine particles A, 20 parts of acrylic ester copolymer (thermoplastic resin) emulsion [50% aqueous emulsion of a 2: 1: 1 copolymer of ethyl acrylate: butyl acrylate: 2-ethylhexyl acrylate] Mix in a ratio], and then dehydrate (squeeze liquid) with a mangle to obtain a squeezing rate of 100%.
After that, the knitted fabric was subjected to a thermoreversible discoloration coloring treatment by drying in a non-touch method at a temperature of 100 to 120 ° C. with a tentering machine.

The cotton knitted fabric colored with the thermoreversible color-changing microcapsule fine particles A in this manner exhibits a deep blue color at 22 ° C. or lower, while it exhibits the original white color of the cotton knitted fabric at 32 ° C. or higher. I could reversibly repeat as many times as I wanted. In addition, this cotton knitted fabric shows substantially no difference in hue and density in the width direction and the length direction,
In addition to being highly uniform, it also had excellent feel, feel, abrasion resistance, and wash resistance.

Examples 2 to 7 The same procedure as in Example 1 was carried out except that the thermoreversible color-changing microcapsule fine particles A were replaced with the same D, E, F, G, H and I, respectively. Thermoreversible discoloration cotton knitted fabrics were obtained.

The thus obtained cotton knitted fabric exhibits a deep blue color at 22 ° C. or lower, as in Example 1, while 32
At above ℃, the original white color of the cotton knit was exhibited, and this discoloration phenomenon could be reversibly repeated any number of times. Various properties of these cotton knits are shown in Table 3 below together with those of the cotton knit of Example 1.

Comparative Examples 1 to 4 Thermoreversible color-changing cotton knitted fabrics were treated in the same manner as in Example 1 except that the thermoreversible color-changing microcapsule fine particles A were replaced with the same B, C, J and K. Got Various properties of these cotton knits are shown in Table 3 below. As is clear from Table 3, these cotton knits had poor color density at 22 ° C. or lower, uneven coloring, poor abrasion resistance and washing resistance, etc. Through 7
The product value was poorer than that of the thermoreversible discoloration cotton knit.

The maximum color density in Table 3 is 20.
The value was measured using a CR121 color difference meter manufactured by Minolta Co. at 0 ° C., and the numerical value converted based on the measured value of Example 1 as 100% is shown. Regarding the color difference, the value measured at 20 ° C. using the above color difference meter was used. The abrasion resistance test is based on AATCC8-1979 and is determined in gray scale, and the washing resistance test is JIS L-08.
Based on the 44 A-2 method, it was judged in gray scale.

[0038]

[Table 3]

Example 8 300 m of 90 cm wide fabric of 100% pre-scoured silk
(100 kg), using a roll padder, water 100
Part, 8 parts of photoreversible color-changing microcapsule fine particles A, 15 parts of polyurethane resin (thermoplastic resin) emulsion (trade name: Hydran HW311 manufactured by Dainippon Ink and Chemicals), and 3 parts of urea Then, the product was dehydrated (squeezed liquid) with a mangle so that the squeezing ratio would be 100%, and then dried by a non-touch method at a temperature of 100 to 120 ° C. using a tentering machine.

The photo-reversible color-changing silk fabric thus obtained is
In the room where it was not exposed to direct sunlight, it had the original white color of silk,
It showed a deep yellow color near a window exposed to direct sunlight, outdoors or under the irradiation of a fluorescent lamp emitting ultraviolet rays, and such a discoloration phenomenon could be repeated many times. In addition, this silk fabric is
In the width direction and the length direction, there is substantially no difference in hue and density, and it shows a uniform coloration state, and it is also excellent in feel, feel, abrasion resistance and washing resistance. It was

Examples 9 to 14 Except that the photo-reversible color-changing microcapsule fine particles A were replaced with the same D, E, F, G, H, and I, all were treated in the same manner as in Example 8, respectively. A silk fabric having photoreversible discoloration was obtained. The silk knitted fabric thus obtained exhibited the same photo-reversible discoloration phenomenon as in Example 8, and was also excellent in touch, feel, abrasion resistance and washing resistance. Various properties of these silk fabrics are shown in Table 4 below together with those of Example 8.

Comparative Examples 5 to 8 The photo-reversible color-changing silk fabric was treated in the same manner as in Example 8 except that the photo-reversible color-changing microcapsule fine particles A were replaced with the same B, C, J and K. Got Various properties of these silk fabrics are shown in Table 4 below.

As is clear from Table 4, these silk fabrics are inferior in color density during photo-coloring, non-uniformly colored, inferior in abrasion resistance and wash resistance, etc. The product value was poor as compared with those of Examples 8 to 14. In addition, the maximum color density in Table 4 was measured using a CR121 color difference meter manufactured by Minolta Co., Ltd. at the time of light irradiation, and the value obtained by converting the measured value of Example 8 as 100% is shown. Regarding the color difference, the numerical value measured at the time of light irradiation using the above color difference meter was used. The abrasion resistance and the washing resistance were determined in the same manner as in Table 3.

[0044]

[Table 4]

Example 15 35% polyester / 65% cotton dyed in pink
90k width mixed circular knitted fabric (Tenjiku 200m) 50k
g of padding bath [water 10
0 part, thermoreversible color-changing microcapsule fine particles F 8 parts,
Photoreversible color-changing microcapsule fine particles F 8 parts, acrylic ester copolymer resin (thermoplastic resin) emulsion [Kanebo NSC Co., Ltd. trade name: Iodozol MR-9
6] Compounded at a ratio of 10 parts and 3 parts of a higher fatty acid ester type softener (Meisei Chemical Co., Ltd., trade name: Eleganol HAS).
After dipping it in water and dehydrating (squeezing) it with a mangle so that the squeezing rate will be 100%, then using a tentering machine,
It was dried by a non-touch method at a temperature of 0 to 120 ° C.

This knitted fabric was further subjected to a padding bath [water 10
0 parts, acrylic ester copolymer resin (thermoplastic resin)
It is immersed in an emulsion [commercial name: Boncoat R-3360 manufactured by Dainippon Ink and Chemicals, mixed at a ratio of 10 parts], dehydrated (squeezed) to a squeezing ratio of 100% with a mangle, and then 100 to 100 using a tentering machine. It was dried by a non-touch method at a temperature of 120 ° C.

The knitted fabric thus obtained undergoes multi-stage discoloration into pink, purple, orange, brown, etc. depending on the presence or absence of light irradiation and temperature changes, and such discoloration phenomenon can be reversibly repeated many times. I was able to. The shirt obtained by cutting and sewing this knitted fabric exhibits a variety of discoloration phenomena as described above, has a good feel and feel, and is further excellent in abrasion resistance and washing resistance, It had excellent commercial value.

Example 16 Using a padding machine, 1 kg of rayon yarn obtained by combining 10 yarns of 100% rayon and having a thickness of 2 denier was combined.
Padding bath [100 parts of water, 0.2 part of phthalocyanine blue (organic pigment), 12 parts of photoreversible color-changing microcapsule fine particles F, 5 parts of glycerin, acrylic acid ester copolymer (thermoplastic resin) emulsion [Matsui Dye Chemical Industry Company name: Matsuminzor MR conc]
15 parts, 0.5 parts of ethylene urea-based condensate (trade name: Fixer F, manufactured by Matsui Pigment & Chemical Industry Co., Ltd.)]
After immersing in water and dehydrating (squeezing liquid) with a mangle to obtain a squeezing ratio of 100%, 100 to 12 using a hot air dryer.
Non-touch drying was performed at a temperature of 0 ° C.

This rayon yarn was further padded using a padding machine [100 parts of water, silicone softening agent (trade name: Softener AQ, manufactured by Matsui Pigment Chemicals Co., Ltd.) 2
Part of the mixture], followed by dehydration (squeezing solution) with a mangle to a squeezing ratio of 80%, followed by drying with a hot air dryer at a temperature of 100 to 120 ° C. and winding. .

The rayon yarn having photo-reversible discoloration obtained in this manner was blue in a room not exposed to direct sunlight, but was green in a window exposed to direct sunlight or outdoors, and such a discoloration phenomenon occurred. It could be reversibly repeated any number of times. Furthermore, this rayon yarn had a uniform coloring density in the length direction, was excellent in fastness to rubbing and washing, and had good feeling and feel.

Claims (2)

[Claims] 1. A volume-based median diameter of 0.5 μm to 15
A continuous product of textiles is continuously treated by a padding method with an aqueous liquid containing microcapsule particles of thermo- and / or photo-reversible discoloration of μm and a thermoplastic resin. Coloring method. 2. A colored product obtained by the coloring method according to claim 1.