JPS6220311B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has a light wavelength order of 0.2 on the surface of synthetic fibers.
By forming a multi-layer irregular unevenness including unevenness of ~1.0 micron (hereinafter abbreviated as μ), the amount of adhesion of printing paste (dyeing amount) is increased and the dyeing density (color development) is improved by reducing the surface reflection of light. The present invention relates to a printed material with good fastness and a method for producing the same. Conventional dyeing methods for synthetic fibers include the dyeing method, the printing method, the Patsudo high-pressure steam method, and the Patsudo thermosol method, all of which have advantages and disadvantages. The textile printing method and the paddo heat treatment (color development) method are continuous, easy to handle, and low cost, but have the disadvantage that as the color becomes darker, the dye is adsorbed on the surface and the fastness tends to decrease. In particular, in the case of polyester, due to the smooth surface characteristic of synthetic fibers and the low coloring properties of disperse dyes, there is a lot of reflection of white light (specular reflection), which tends to result in dull, dull colors.Increasing the concentration of dye used reduces fastness and costs. Invite high. Against this background, the present inventors investigated various ways to obtain deep, dark-colored printed materials with good fastness. As a result, the inventors of the present invention found that unevenness on the order of the wavelength of light (0.2 to 1.0 μ) was created by changing the plane distance in the direction perpendicular to the fiber axis. It has been found that the presence of 10 or more particles per 10μ reduces the surface reflection of white light and increases the color development (deep color effect) with the same amount of dyeing. In addition, by creating irregular multilayer unevenness including the above-mentioned unevenness, the amount of printing paste attached increases, and the build-up property (dyeing amount) of the dye increases, making it easier to obtain a deep color. It has been found that the fastness is good, probably because the adsorbed dye is less likely to fall off or sublimate. On the other hand, as a method of making the fiber surface uneven, there is a method of adding inert fine particles or a crystallizing agent to a polymer to make the fiber surface uneven, as shown in Japanese Patent Publication No. 43-14186 and Japanese Patent Publication No. 46-26887. Kosho 43-
As in No. 16665, there is a method of adding fine particles and then treating the fine particles with a solvent to create unevenness, but these methods create unevenness on the fiber surface that is several to several tens of times the wavelength of light and has a deep texture. It is difficult to obtain deep colors. Furthermore, as shown in Japanese Patent Application Laid-open No. 52-99400, it has been disclosed that plasma irradiation can be used to create unevenness with a height of 0.1 to 0.5μ to produce a deep color effect. The present invention is better in terms of increased build-up properties and fastness, since unevenness is not obtained. Furthermore, there are methods of imparting irregularities to the fiber surface by mineral acid treatment of polyamide fibers or alkali treatment of polyester fibers, but these irregularities are scattered with a diameter of 2μ or more, and are outside the range of the wavelength order of light. Therefore, even though it has effects such as improving water absorption and improving texture, it does not lead to a deep color effect that adds depth to the color. The present invention has been developed in view of the above points, and has a random surface with irregular irregularities. The printing surface is made of synthetic fibers having unevenness that is not spaced at regular intervals with a planar distance between vertices of 0.2 to 0.7μ, and in which there are 10 or more unevenness per 10μ of the planar distance in the direction perpendicular to the fiber axis. The present invention provides an invention for a printed product that is robust and has a large dark color effect, characterized in that 20% by weight or more of the total fibers constituting the surface of the fabric is occupied by the synthetic fibers, and at least fine particles with a particle size of 0.2 microns or less are used. After constructing a fabric so that the synthetic fibers containing 0.5 to 10% by weight account for 20% or more of the total fibers forming the surface of the fabric that will be the printing surface, at least the fibers are dissolved or Either the synthetic fibers are reduced in weight with a decomposing solvent to give surface irregularities, or the synthetic fibers are reduced in weight with a solvent to give surface irregularities, and then the fibers account for 20% by weight or more of the total fibers forming the fabric surface. This invention relates to a method for producing a printed product that is robust and has a large dark color effect, which is characterized by forming a fabric and then printing. The synthetic fibers referred to in the present invention refer to synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyvinyl alcohol, polyethylene, polyvinyl chloride, and polyurethane.
Also included are those obtained by copolymerizing modifying components such as 5-metal sulfoisophthalic acid, and those to which a matting agent, heat stabilizer, pigment, antistatic property improver, disaster prevention property improver, etc. are added. In particular, polyesters in which 80% or more of the repeating units are polyethylene terephthalate are particularly preferred because the effects of the present invention are remarkable. In addition, the synthetic fiber is composed of one or more types of polymers, and the fiber cross section may be circular or irregularly shaped, such as spun mixed fiber yarn, drawn mixed fiber yarn, air mixed fiber yarn,
It may take any fiber form such as spun yarn, false twisted crimped yarn, rubbed crimped yarn, or twisted yarn. In order to exhibit the effects of the present invention, when obtaining synthetic fibers, it is necessary to include a particle size of 0.2 in the polymer forming the fibers.
It is necessary to contain at least 0.5 to 10% by weight of fine particles having a particle size of less than μ, preferably less than 0.1 μ, more preferably less than 0.06 μ. Fine particles include oxides and salts of group elements such as zinc oxide, cadmium oxide, calcium carbonate, barium carbonate, barium phosphate, and magnesium phosphate, or silicon-containing substances such as colloidal silica, silica organosol, and sodium orthosilicate. Alternatively, titanium oxide, kaolinite, alumina sol, etc. may be used as long as they have a particle size of 0.2 μ or less after fiber formation, but it is preferable that 50% by weight or more of the fine particles be a silicon-containing inert substance with a particle size of 0.1 μ or less. It is more preferable in terms of properties and unevenness formation. Also, the particle size is 0.2
There is no problem even if the fiber contains particles exceeding 0.2 μm, but if the fiber does not contain particles of at least 0.2 μm or less, the present invention has 10 or more irregularities of 0.2 to 1.0 μ per 10 μ in plane distance perpendicular to the fiber axis. It is difficult to make it exist, and as a result, the specular reflection of visible light increases, making it impossible to obtain a deep color effect. In addition, the content of fine particles is 0.5 to 10% by weight, preferably 2 to 7% by weight, and if it is less than 0.5%, irregularities of 0.2 to 1.0 μm or more are present on the entire fiber surface. Unevenness is difficult to obtain and reduces the effect of the present invention. If it exceeds 10%, the spinning and drawing properties will decrease and the cost will increase. As mentioned above, the size of the unevenness (0.2 to 1.0μ) in the present invention refers to the distance on a plane from the apex of the protrusions that are adjacent to each other in the direction perpendicular to the fiber axis. It's not the height (depth). Further, in the present invention, the planar distance between the vertices is naturally not constant, and the unevenness exists at irregular intervals. In addition, irregular multilayer unevenness is defined as 0.2 μm within the above 0.2 to 1.0 μ
This means that there are fine irregularities smaller than μ. As mentioned above, in the present invention, surface elution is carried out by treating synthetic fibers in which fine particles of 0.2μ or less in size are well dispersed with a solvent, and the density is reduced as well as the relatively large irregularities caused by the areas with high particle density. Fine irregularities due to the low parts exist on the entire surface of the large irregularities, and this presence is also thought to contribute to this effect. This structure of this fiber increases the build-up of the printing paste and increases the diffuse reflection of light, resulting in a greater dark color effect. Next, in the present invention, it is necessary to reduce the weight of the microparticle-containing microfiber obtained by using a solvent that dissolves or decomposes the fiber alone or the fiber and the microparticle by at least 1.0% by weight, preferably 3 to 30% by weight, and less than 1.0%. Satisfactory surface roughness cannot be obtained. Examples of solvents include alkaline solutions and dimethylformamide for polyester fibers, mineral acids and phenols for polyamide fibers, acetone and dimethylformamide for polyacrylonitrile fibers, formic acid and phenols for polyvinyl alcohol fibers, and hydrocarbons and phenols for polyethylene fibers. Any material that dissolves or decomposes fibers, such as chlorinated hydrocarbons, may be used. Further, the solvent treatment may be carried out in the form of fibers, after forming a two-dimensional object such as a knitted fabric or non-woven fabric, or before or after printing, but it is preferable to carry out the solvent treatment before printing in order to prevent the dye from falling off and decomposing. The above method causes heterogeneous elution of the synthetic polymer and fine particles, resulting in fine irregularities on the fiber surface.
Irregular multi-layered unevenness is formed in which 10/10μ or more of unevenness of ~1.0μ is present, and as a result, unprecedented deep color printing with low surface reflection of light and high dye build-up ability is possible. On the other hand, in the present invention, other fibers other than the textured surface fibers may be blended, twisted, mixed knitted, etc., but the textured fibers account for at least 20% by weight of the fibers forming the surface of the fabric that will be the printing surface. Unless the fabric is formed so as to occupy the same area, it is not possible to obtain a printed product that is strong and has a large dark color effect as described in the present invention. Further, the present invention is particularly effective in medium to deep colors, and in very dark colors, it shows a deep color that has not been seen before. On the other hand, the improvement in color development of the present invention can be seen even in the case of light to medium colors, but when improving the color development in light to medium colors, increasing the concentration of the dye used is sufficient and the fastness is not a problem. Conventionally, in the case of medium to very dark colors, there was a problem with fastness, and only certain dyes could produce deep colors. Particularly in very dark colors, there are limits to the amount of printing paste attached (dye build-up ability) and color development, and it has not been possible to obtain printed materials with good fastness and large color development (deep color effect) as in the present invention. The printed materials referred to in the present invention include mechanical printing methods such as roller, screen, and heat transfer printing, manual printing methods such as paper pattern printing, tie-dyeing, and Yuzen dyeing, and methods other than dyeing such as Patsudo steam method and Patsudo thermosol method. Contains everything dyed with.
Furthermore, the printing paste may be obtained by a general method in which a natural paste, a processed paste, or a synthetic paste is added in order to prevent liquid splatter, color tearing, scale spots, ground spots, etc. without any problem. Furthermore, an auxiliary agent such as a surfactant or urea or a fiber swelling agent may be added to the printing paste to improve the permeability and fluidity of the printing paste and to improve antifoaming properties, hygroscopicity, and desizing properties. However, the fiber swelling agent may reduce fastness, so it is best to use it in as small a quantity as possible. As for the printing method, any method such as direct printing, discharge printing, resist dyeing, molded dyeing method, padding method, etc. may be used.The internal penetration and fixation of the dye is caused by steaming or dry heat treatment using a conventional method, and the sizing agent is applied in post-processing. Wash off. The present invention will be specifically explained below using Examples. Example 1 Particle size when polymerizing polyethylene terephthalate
0.07μ or 0.5μ silica ethylene glycol dispersion, each containing 5% by weight of silica particles based on the polymer.
Each polymer was extruded through a nozzle, rolled up, and then stretched to obtain a 75d/36f multifilament. The untwisted silica-containing filaments were alternately used as warp yarns, and the 2000T/M S and Z twists were alternately used as weft yarns to form a deshin fabric with a 1/1 flat structure. It was immersed in a caustic soda aqueous solution of % by weight to reduce the weight by about 5%. Next, plain dyeing was performed on one side using the following printing paste using a roller printing machine with a rubber drum pattern, followed by drying, steaming at 130° C., water washing, and reduction washing in a conventional manner to obtain a dark-colored printed fabric.

[Table] Color development (K/S) was determined from the reflectance of the dyed material using a Hitachi self-recording spectrophotometer model EPR-2. In addition, the uneven shape of the fiber surface was determined from the scanning electron micrograph and the results are shown in Table 1 together with the color fastness results.

[Table] When the silica particle size is 0.07μ, the fiber surface has a large irregular layer of irregularities including fine irregularities of 0.2 to 1.0μ.
The unevenness was present at a density within the range of 30 to 50 pieces/10μ. Therefore, the pick-up amount of the printing paste was larger than that of the control product containing no silica. In addition, a deep navy blue dechine fabric with great color development and a depth not seen in conventional products was obtained. Furthermore, the color fastness of each product was good, at grade 3-4 or higher, making it a product with high added value. On the other hand, when the silica particle size is as coarse as 0.5μ, it is 0.2 to 1.0.
The unevenness of μ was minimal, and large unevenness was scattered, and the color development, depth of color, and fastness were at the same level or lower than the control product. Example 2 10% by weight of alumina with a particle size of 0.12μ in nylon 6
75d/72f fine denier filament is used for the front yarn, and 75d/24f high shrinkage polyester drawn yarn with a hot water shrinkage rate of 20% is used for the back yarn to create a 28G single tricot yarn with a 1/3 satin weave. The edition was composed. The fabric was then immersed in a 40% by weight aqueous formic acid solution at 85°C and dried, continuously rolled up to obtain a knitted fabric with a weight loss of 15%, and the front yarn, nylon 6, was raised for needlework. A geometric pattern was printed on the raised side of the raised tricot knit using a traveling automatic screen printing machine using the following printing paste.

[Table] The obtained fine denier brushed knit printed material
When it was steamed at 100°C, washed with water, and dried, it had a deep hue despite being fine denier. Also, according to the scanning electron micrograph, the unevenness of 0.2 to 1.0μ is 15 to 30.
It has multi-layered unevenness including microscopic unevenness, has good fastness, and has a unique suede-like texture. Example 3 To a copolymer resin consisting of 40% by weight of acrylonitrile monomer and 60% by weight of vinyl chloride monomer, 1.0% by weight of calcium carbonate and 2.5% by weight of 0.02μ silica were added and dry-spun. The resulting spun fibers were bundled into a 500,000 denier tow and stretched 2.4 times, then fed at low speed into a sealed dimethylformamide bath at 60°C to reduce the weight by 7.0% and create unevenness on the fiber surface. was granted. Next, oil-crimping-drying-cutting was performed to obtain a cut fiber of 3D x 51mm, which was then mixed with 30% wool to make a spun yarn with a worsted count of 50 to form a 30G circular knit. The knitted fabric was unfolded and roller printing was performed using the following printing paste.

[Table] The surface of the obtained acrylic fiber has 20 to 40 irregularities of 0.2 to 1.0μ/10μ, and 5 to 10 irregularities of 1.5 to 3μ.
The result is a marbled-like knitted fabric with unprecedented color development and fastness. Example 4 The fiber cross section is 〓, and the white part is silica with a particle size of 0.10μ.
It is polyethylene terephthalate containing 10% by weight [η] = 0.65 dl/g, and the shaded area is the sulfonic acid sodium salt of dimethyl isophthalic acid.
A drawn multifilament of 50d/24f made of polyethylene terephthalate copolymerized with 2.5 moles was prepared. Then the filament and 75d/36f or
After twisting 225d/108f polyester drawn yarn at 300T/M to create a fabric with a 2/2 twill texture in both the vertical and horizontal directions, it was twisted with an 8% alkali aqueous solution.
℃ x 20 minutes to give unevenness to the fine particle-containing fiber at a weight loss rate of 25%, and at the same time divide the above hatched area and white area based on the difference in alkali dissolution rate to form a single yarn of 0.3 to 0.7 dr.
It was made into ultrafine fibers. The resulting fabric was dip-nipped in a dye bath having the following composition, heat treated at 200°C for 60 seconds, and reduced and washed to obtain a dyed product.

[Table] A product with a blending ratio of about 35% of ultrafine fibers with uneven surfaces produced a deep, extremely dark brown color with a K/S of 19.2 and good fastness. On the other hand, for those with a blending rate of approximately 15%, K/S is
12.1 and the fastness was lower than grade 3, which lowered the commercial value.

Claims (1)

[Claims] 1. It has a random surface with irregular irregularities, and the irregularities forming the random surface have at least a plane distance of 0.2 between the vertices of adjacent convex portions existing in the outer circumferential direction perpendicular to the fiber axis. A fabric surface that is made of synthetic fiber and has irregularities that are not spaced at a constant interval of ~0.7 microns, and in which there are 10 or more irregularities per 10 microns of planar distance in the outer circumferential direction perpendicular to the fiber axis, and that is the printing surface. 20% by weight or more of the total fibers constituting the synthetic fibers are comprised of the synthetic fibers. 2. A robust printed material with a large dark color effect according to claim 1, characterized in that ultrafine irregularities smaller than 0.2 microns are present within the irregularities forming the random surface. 3. A robust printed product with a large dark color effect as claimed in any one of claims 1 to 2, characterized in that the synthetic fiber having a random surface is a polyester fiber. 4 At least fine particles with a particle size of 0.2 microns or less
The synthetic fiber contains 0.5 to 10% by weight,
After structuring the fabric so that it accounts for 20% or more by weight of all the fibers forming the surface of the fabric that will become the printing surface, it is reduced in weight with a solvent that at least dissolves or decomposes the fibers, or the surface is made uneven. After reducing the amount of synthetic fibers with a solvent and making the surface uneven, 20% of the total fibers forming the fabric surface are used.
A method for producing a printed article that is robust and has a large dark color effect, characterized by composing a fabric so that it accounts for more than % by weight, and then printing. 5. The method for producing a printed product that is robust and has a large dark color effect according to claim 4, wherein the synthetic fiber that imparts unevenness to the surface is a polyester fiber. 6. Production of a durable printed product with a large dark color effect as claimed in any one of claims 4 to 5, characterized in that 50% by weight or more of the fine particles are silica particles with a particle size of 0.1 micron or less Law.