JPH045790B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to highly functional fibers manufactured by a special surface modification method and structures thereof. Although various synthetic and natural fibers have been widely used in the past, they have many drawbacks, and there is a strong need for improvements to provide better and more advanced functionality. For example, depending on the application of textile products, such as dyeability, color development of dyed products, water repellency, flame retardance, antistatic properties, water absorption properties, etc., some textile products may be used tacitly or at low levels despite their serious drawbacks. The reality is that Many attempts have been made to solve these difficulties. Among these methods, the method of processing the surface of the base material of fibers and structures thereof is promising as a method that can impart high functionality and quality while retaining the characteristics of the fiber base material itself. However, in reality,
There are many problems such as loss of characteristics of the fiber base material due to surface treatment, insufficient functionality, and high processing cost. For example, in the method of applying a polymer with a desired function to the surface of a base material, the adhesion to the fiber base material is insufficient, it tends to fall off during use, and it is difficult to control the coating thickness. The disadvantage is that the original functions and texture of the material are lost. On the other hand, in the radiation grafting method, since a graft reaction occurs with the base material, there is less chance of shedding during use, and the film thickness can be reduced, making it easier to maintain the original function. However, the disadvantages of the radiation method are that the base material is easily damaged due to the high energy, and it also places a heavy burden on safety and equipment. On the other hand, in recent years there has been progress in surface processing technology using plasma irradiation. When graft polymerization is carried out by the plasma method, it is possible to considerably improve the prevention of shedding during use, maintenance of original functions, and operability. However, depending on the intended function, the level and durability are still insufficient, the processing efficiency is poor, and there are problems in terms of cost. On the other hand, the present inventors have been conducting research on a method for improving the color development and color depth of fibers by plasma irradiation. Senior researchers published a technique in JP-A-52-99400, in which organic synthetic fibers are irradiated with glow discharge plasma to form specific irregularities on the fiber surface, and these irregularities produce a darkening effect. ing. In addition, the present inventors proposed in Japanese Patent Application No. 56-180464 a technique for improving color development by forming a special uneven structure by subjecting synthetic fiber containing fine particles in a polymer base material to low-temperature plasma treatment.
Although these inventions have effects significantly superior to those of the prior art, they are still unsatisfactory in terms of product friction durability and plasma irradiation efficiency. Therefore, the inventors of the present invention continued various studies, and found that these difficulties could be greatly improved by making fine particles exist on the surface and performing plasma irradiation, and that it would be possible to obtain a product with excellent color development. (patent pending). Furthermore, as a result of deepening and developing these studies, the present inventors found that fibers irradiated with plasma with fine particles present on the surface have a very special structure.
By performing graft polymerization on this special surface, it is possible to provide higher functionality and quality than conventional plasma graft polymerization methods, and it also has good durability and high plasma processing efficiency. It has been found that the present invention is advantageous in terms of cost, and furthermore, the presence of the graft polymer protects the structure of the special unevenness, and the durability of the effect of improving color development derived from the structure is also significantly improved. In the present invention, after plasma irradiation is performed with fine particles present on the surface, the fine particles aggregate on the surface, and the base polymer component forms a granular structure with the aggregated fine particles as cores, forming convex portions. is formed. This is presumably due in part to the fact that the microparticles are more inert to plasma etching than the polymer matrix. In addition, the portions covered with fine particles are difficult to be etched, and the portions not covered with fine particles are selectively etched, so that differences in surface height are likely to be created and the etching efficiency of plasma irradiation is considered to be good. Generally, the center-to-center distance between the protrusions is 0.01 to 1 micron. Because of the special unevenness of the present invention, it is considered that when graft polymerization is subsequently performed, grafting is likely to be carried out and the graft polymer is less likely to fall off. The surface of the base material after graft polymerization in the present invention is
The structure is such that the surface layer of the irregularities created by plasma etching is coated with a graft polymer, and the voids adjacent to each other in the projections are virtually connected. It is believed that such a structure facilitates high performance, protects etching irregularities, and improves color development and durability. The target fibers of the present invention include synthetic fibers such as polyester, polyamide, acrylic, and polyurethane, natural fibers such as wool, cotton, hemp, and silk, semi-synthetic fibers such as acetate, and recycled fibers such as rayon. . The synthetic fibers may be copolymerized polymers, polymer blends, those containing pigments, modifiers, etc., or composite spun fibers. The fiber structures of the present invention include those composed of the above-mentioned fibers alone or in composites or mixtures of two or more types, and include yarns such as tows, filaments, yarns, and two-dimensional fibers such as woven/knitted and non-woven fabrics. means something. The fine particles used in the present invention may be any inorganic or organic particles that are more inert than the polymer matrix in low-temperature plasma. Among these, metal oxides, hydroxides, carbonates, phosphates, etc. are preferred, examples include silica, tin oxide, aluminum oxide, titanium oxide, antimony oxide, thorium oxide, zirconium oxide, aluminum hydroxide,
Calcium carbonate, magnesium phosphate, calcium phosphate, aluminum phosphate, boron phosphate, etc. are used. The size of the fine particles is generally 2 microns or less, preferably 0.5 microns or less as an average primary particle diameter.
More preferably, the diameter is 0.2 microns or less, and even more preferably 0.07 microns or less. The method for applying the fine particles of the present invention to fibers can be carried out in accordance with ordinary resin processing methods. For example, a fine particle dispersion is applied to a fiber structure by a method such as padding or spraying, adjusted to an appropriate adhesion amount using a mangle, and then adhered to the fiber surface by dry heat or wet heat treatment. An adhesive resin may be used together with the fine particles to firmly adhere the fine particles and the fibers. The amount of fine particles attached to the fiber is 0.001 to 10% by weight, preferably 0.01 to 6%, more preferably
0.05-4% by weight is used. Adhesion amount is 0.001%
If it is less than 10%, there is no effect, and if it exceeds 10%, the texture etc. will deteriorate significantly. The conditions for plasma irradiation with fine particles present on the surface of the present invention depend on the type and shape of the target fiber base material, the content and level of the intended function to be imparted, and the type and shape of the device, and the type of gas. , flow rate, degree of vacuum, output, processing time, etc. must be selected. As the low-temperature plasma generating gas, oxygen and air are preferred from the viewpoint of etching efficiency, while argon, helium, neon, nitrogen, hydrogen, etc. are preferred from the viewpoint of suppressing etching and inducing graft polymerization active sites. The object of the present invention can be suitably achieved by using a mixture of these gases, switching gases midway, or adjusting other conditions. Further, the plasma treatment may be performed either before or after processing such as dyeing the fibers or finishing treatment. The shape of the unevenness is less likely to change than when the fiber is not protected by the graft polymer, but if there is a particular concern about changes in the unevenness formed on the fiber surface, it is better to carry out the dyeing process after the dyeing process or the like. Further, the plasma treatment effect of the present invention does not necessarily need to be applied to the entire surface layer, interior layer, and back layer of the fibrous structure. It is sufficient that at least the surface exhibits the treatment effect, and in some cases it may be better to treat only the surface layer, and the plasma treatment conditions are selected depending on the purpose. Graft polymerization in the present invention is carried out after a special uneven structure is developed by plasma irradiation. Since active sites are formed in the base polymer by plasma irradiation when the uneven structure is formed, it is preferable to contact the radically polymerizable monomer in this state. The monomer may be in gaseous form or may be in liquid form alone or dissolved in a solvent. The monomer capable of radical polymerization in the present invention is generally a compound having a carbon-carbon double bond and which polymerizes in a chain mechanism with radicals as propagating terminals. Suitable monomers vary depending on the desired function and the plasma-irradiated polymer base material, but examples include tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, tetrahydroperfluorohexyl acrylate, 1,1',3 -Trihydroperfluoropropyl acrylate, vinyltrimethylsilane, vinyltriethylsilane, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, styrene, vinylpyridine, acrylonitrile, and the like. These monomers may be used alone, or two or more types may be used for copolymerization grafting. In the present invention, various types of high functionality can be imparted by using the radically polymerizable monomer and the type of fine particles present on the surface during plasma irradiation. For example, dyeability, color development of dyed products, water repellency, oil repellency,
It has flame retardancy, antistatic property, water absorption, sweat absorption, moisture absorption, stain resistance, low friction, melt resistance, special gloss, special texture, etc., and has excellent levels and durability. It is also possible to provide some of these functions in combination. In the present invention, for example, a fluorine-containing unsaturated compound and/or a silane compound is used as at least a part of the radically polymerizable monomer, and the refractive index of the graft polymer is 1.5 or less, and the refractive index is
By using fine particles with a particle size of 1.6 or less, it is possible to obtain a highly functional surface-treated product that has a remarkable depth of color and has a water-repellent function. Examples of the monomer include tetrafluoroethylene,
hexafluoropropylene, vinylidene fluoride,
Fluorine compounds such as vinyl fluoride and chlorotrifluoroethylene, and vinyltrimethylsilane,
Silane compounds such as vinyltriethylsilane, vinyltrimethoxysilane, and vinyltriethoxysilane are used. Furthermore, as the fine particles, silica is most suitable. In the present invention, by using at least a part of the radically polymerizable monomer containing a halogen and/or phosphorus atom, and by using specific flame-retardant inorganic particles as the fine particles, a high A functional surface-treated product can be obtained. Examples of the monomer include the above-mentioned futsuso compound, vinylidene chloride, 2-hydroxyethyl methacrylic acid,
Acid phosphate (

[Formula]:n=1-2) etc. are used. In addition, the fine particles include tin oxide, aluminum hydroxide, antimony oxide,
Aluminum phosphate, magnesium phosphate, calcium phosphate, boron phosphate, etc. are used. Furthermore, in the present invention, by using at least a part of the radically polymerizable monomers that give a highly crosslinked infusible polymer, it is possible to obtain a highly functional surface-treated product having a melt-proofing function. can. As mentioned above, the present invention is applicable to various natural or synthetic fibers, but the effect is particularly great in the case of polyester, and there is also a great demand for its high functionality. Of course, the polyester may be any conventionally used polyester such as modified polymer fibers, irregular cross-section fibers, composite spun fibers, false twisted yarns, or reduced weight yarns. Next, the present invention will be explained with reference to examples, but the present invention is not limited to the following examples. In the examples, the color depth effect was evaluated in 5 levels, with ordinary unprocessed fabric made by a conventional method being rated as 1st grade, and fabrics with a significantly deeper feeling compared to that being rated as 5th grade. In addition, the color fastness to friction of the color depth effect is
The cloths were rubbed against each other 300 times under a load of 300 g, and visually judged in 5 grades: 5th grade was when there was almost no change, and 1st grade was when there was significant deterioration or color spots. Water repellency was determined by spraying distilled water on a test cloth according to JIS L1092, and scoring 100 points for a cloth with no moisture on the surface, and 0 points for a cloth with completely wet surface, and comparing it with a comparison sample. The washing durability was measured after washing for 5 hours in a home washing machine using a 40°C washing liquid containing 1 g of neutral detergent. Example 1 From ordinary polyethylene terephthalate
A drawn yarn of 100 dr/48 f was prepared, and subjected to false twisting and weaving in a conventional manner to prepare a Kasidos fabric. This fabric is Kayalon manufactured by Nippon Kayaku Co., Ltd.
135 using Polyester Black G-SF with 12% owf
It was dyed at ℃ to obtain a black dyed product. 0.5% by weight of colloidal silica with an average primary particle size of 45 millimicrons (mμ) was added to this black-dyed fabric using a butt-dry method.
Attached. This sample was placed in an internal electrode type plasma device (electrode area 50 cm ² ), and air was used as the introduced gas.
Plasma irradiation was performed for 1 minute at 0.1 Torr and an output of 50 watts, and then the gas was switched to argon and plasma irradiation was performed for 2 minutes at 0.5 Torr. When the fiber surface of the sample after plasma irradiation is observed using a stereoscopic electron microscope, fine particles are aggregated on the surface, and the base polymer component forms a granular structure with the aggregated fine particles as the core, forming convex parts. This was recognized. The plasma-irradiated sample was immediately exposed to tetrafluoroethylene gas containing a trace amount of methyl acrylate to perform graft polymerization. When observed under an electron microscope, it was confirmed that the graft polymer layer covered the surface layer of the irregularities caused by plasma irradiation, and that the voids adjacent to each other in the convexities were virtually connected. The sample subjected to this grafting treatment had a remarkable depth of color, and the depth effect was grade 5. Water repellency was also good, scoring 100 points. It also has good durability,
The abrasion fastness for color depth effect was grade 5, and the washing durability for water repellency was 100 points, with almost no functional deterioration observed. Comparative Example 1 The sample of Example 1 after dyeing but before fine particles were attached had a first grade color depth effect and a water repellency score of 0 to 50 points. Comparative Example 2 The dyed sample of Example 1 was subjected to plasma irradiation without adhering fine particles, and the sample without graft polymerization had a color depth effect of grade 2, its abrasion fastness was grade 1, and it had a large effect due to friction. Color spots occurred. Moreover, the water repellency was 0 to 50 points. Comparative Example 3 A sample treated in the same manner as in Example 1 except that fine particles were not attached had a color depth effect of 4.
The color fastness to rubbing was grade 3, and some color unevenness occurred. Water repellency was 100 points, but it dropped to 80 points after washing. Example 2 A sample obtained by processing in the same manner as in Example 1 except that methyl methacrylate was used instead of tetrafluoroethylene containing a trace amount of methyl acrylate had a color depth effect of grade 3 to grade 4, and Rubbing fastness is 5
There was almost no occurrence of color spots in the grade. Comparative Example 4 Samples treated in the same manner as in Example 2 except that fine particles were not attached had a color depth effect of 2 to 2.
Grade 3: Its color fastness to rubbing was grade 3, with slight color spots. Example 3 After dyeing and fine particle adhesion in the same manner as in Example 1, using oxygen gas as the introduced gas,
Plasma irradiation was performed at 0.05 Torr for 1 minute, then the gas was changed to nitrogen and plasma irradiation was performed at 1.0 Torr for 2 minutes.
Subsequently, graft polymerization was carried out by exposing it to vinyltrimethylsilane gas. The color depth effect of this sample was 4th grade, its abrasion fastness was 5th grade, and the water repellency was 100 points both before and after washing. Comparative Example 5 A sample treated in the same manner as in Example 3 except that fine particles were not attached had a color depth effect of grade 3,
Its abrasion fastness is grade 3, water repellency is 100 points, and after washing it is 80 points.
It was a hot spot. Example 4 A sample obtained by processing in the same manner as in Example 3 except that acrylic acid was used in place of vinyltrimethylsilane had a color depth effect of grade 3, a rub fastness of grade 4, and When water droplets were dropped, they instantly dispersed, indicating good hydrophilicity. Comparative Example 6 A sample treated in the same manner as in Example 3 except that fine particles were not attached had a color depth effect of grade 2,
Its abrasion fastness was grade 3, and it took some time for water droplets to diffuse. Example 5 3% by weight of tin oxide with a particle size of approximately 0.15μ was attached to the dyed sample of Example 1, and after plasma irradiation was performed at 0.5 Torr for 3 minutes using a mixed gas of 10 mol% oxygen and 90 mol% argon. , 2-hydroxyethyl methacrylic acid/acid phosphate solution to carry out graft polymerization. This sample did not burn immediately, and was made flame retardant, unlike irradiated ordinary fabrics where the flame spreads quickly when a flame is brought close to the fabric. Example 6 3% by weight of aluminum phosphate with a particle size of approximately 0.15μ was attached to the dyed sample of Example 1, and after plasma irradiation was performed in the same manner as in Example 1, vinylidene chloride and a small amount of acrylic acid were applied. Graft polymerization was carried out by exposure to a mixture containing methyl. This sample did not burn immediately even when a flame was brought close to it. Example 7 4% by weight of aluminum hydroxide having a particle size of approximately 0.15 μm was attached to the dyed sample of Example 1, and after plasma irradiation was performed in the same manner as in Example 6, it was exposed to tetrahydroperfluorohexyl acrylate. This sample did not burn immediately even when a flame was brought close to it. Example 8 0.5% by weight of titanium oxide with an average particle size of 30 mμ was attached to the dyed sample of Example 1, and after plasma irradiation was performed in the same manner as in Example 1, 1,1'3-trihydroper was applied. Exposure to fluoropropyl acrylate gas. This sample has water repellency before and after washing.
It was 100 points. Example 9 0.3% by weight of aluminum oxide with an average particle size of 20 mμ was attached to the dyed sample of Example 1.
After plasma irradiation was performed in the same manner as above, the sample was exposed to tetrahydroperfluorohexyl acrylate gas. The water repellency of this sample is both before and after washing.
It was 100 points. Example 9 0.3% by weight of silica having an average particle size of 15 mμ was adhered to a dyed 6-nylon tricot knitted fabric, and plasma irradiation and grafting reaction were performed in the same manner as in Example 1. This sample had a remarkable color depth effect and its rub fastness was grade 5. In addition, water repellency is determined before washing.
Both players scored 100 points. Comparative Example 7 A sample treated in the same manner as Example 9 except that fine particles were not attached had a color depth effect slightly inferior to that of Example 9, and its abrasion fastness was grade 3. . Water repellency is 100 points before washing.
It was 80 points after washing. Example 10 A dyed wool chilimendiose fabric was subjected to particle deposition and plasma treatment as in Example 1 and then exposed to tetrahydroperfluorohexyl acrylate gas. This sample had excellent color depth and its rub fastness was grade 5. Comparative Example 8 A sample treated in the same manner as in Example 10 except that fine particles were not attached had a color depth slightly inferior to that of Example 10, and its abrasion fastness was grade 4. Example 11 A sample of a dyed rayon chilimenzioset fabric treated in the same manner as in Example 10 had excellent depth of color and a rub fastness of grade 5. Also, the water repellency is 100% before and after washing.
It was a hot spot. Comparative Example 9 A sample treated in the same manner as in Example 11 except that fine particles were not attached had slightly inferior color depth to Example 11, and its abrasion fastness was grade 4. Water repellency was 100 points before washing and 70 points after washing.

Claims (1)

[Scope of Claims] 1. A fiber structure made of roughened fibers, the fiber surface of which is formed of convex portions containing fine particles, and the convex portions aggregate to form unevenness on the fiber surface,
A highly functional surface-treated product characterized in that the surface layer of the uneven portion is coated with a graft polymer made of a radically polymerizable monomer, and voids adjacent to each other in the raised portion are virtually connected. 2 At least a part of the radically polymerizable monomer is a fluorine-containing unsaturated compound and/or a silane compound, the graft polymer thereof has a refractive index of 1.5 or less, and the fine particles have a refractive index of 1.6 or less. 2. A highly functional surface-treated product according to claim 1, which is characterized by a remarkable depth of color and a water-repellent function. 3 at least a part of the radically polymerizable monomer contains a halogen and/or phosphorus atom,
and the fine particles are one or more flame-retardant inorganic particles selected from tin oxide, aluminum hydroxide, antimony oxide, aluminum phosphate, magnesium phosphate, calcium phosphate, and boron phosphate. The highly functional surface-treated product according to claim 1, which has the following properties. 4 Plasma irradiation is performed with fine particles present on the surface of the fiber structure to form unevenness consisting of convex portions containing fine particles on the fiber surface, and then, while the fiber base polymer is in an active state, a radically polymerizable monomer is formed. A method for producing a highly functional surface-treated product, characterized by carrying out graft polymerization in contact with a polymer.