JPH0941267A - Fiber or fiber assembly with metallic luster - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject fiber or fiber assembly excellent in durability and decorative effect by providing the surface of fiber or fiber assembly with a metallic thin film followed by forming a copolyester resin layer colored with a pyridone azo dye thereon. SOLUTION: First, a copolyester resin is prepared by copolymerization between dicarboxylic acid component (i.e., dimethyl terephthalate, dimethyl isophthalate and dimethyl 5-sodium sulfoisophthalate) and diol component (i.e., ethylene glycol and neopentyl glycol), and the copolyester resin is then dispersed in water and colored with a pyridone azo dye such as a liposoluble dye (C.I. Solvent Yellow 162) or a disperse dye (C.I. Disperse Yellow 198) to prepare a colored copolyester resin aqueous dispersion. Next, metallic aluminum is vacuum-deposited on the surface of polyester fibers or fiber assembly such as a fabric comprising the polyester fibers followed by providing the above aqueous dispersion thereon to effect formation of a resin film thereon, thus obtaining the objective fiber or fiber assembly such as a nonwoven fabric with metallic luster.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber or a fiber assembly having metallic luster, which has durability and a high decorative effect, and mainly to gold and silver threads.

[0002]

2. Description of the Related Art Kijyaku, costumes, belts, braids, embroidery, brocades, wool, surface cloths, ornaments, interior goods, etc.
Gold and silver threads have been used to give handicraft articles a high-class feel. The gold-silver thread is produced by depositing a metal such as aluminum or silver on a synthetic resin film having a thickness of 6 to 25 μm and coating it with a colorless or colored transparent resin to give a golden color, a metallic red or indigo color, It has been obtained by cutting with a slitter to a width of about 0.15 to 2 mm. In addition, recently, as a similar technique, a metal aggregate is similarly vapor-deposited on paper, woven fabric, non-woven fabric, etc., and further coated with a transparent colored resin, so that a more highly decorative gold-silver thread-like fiber aggregate or fiber structure can be obtained. Has been obtained. Solvent-based paints are used for forming colorless or colored transparent resin layers provided on metal layers including fibers having a metallic luster, fiber aggregates, films, gold-silver paper, etc. Examples of such solvent-based paints include so-called clear lacquer consisting of alkylated melamine resin, nitrocellulose, alkyd resin and the like and organic solvent, so-called acrylic resin lacquer consisting of methacrylic resin and the like and organic solvent, polyol, organic solvent, isocyanate curing So-called urethane resin coatings composed of agents and the like, and as the organic solvent, methyl cellosolve, alkyl acetate, alcohols, methyl ethyl ketone, methyl isobutyl ketone, xylene, toluene and the like are used.

As a pigment used for coloring, an oil-soluble dye is mainly used because of the need for transparent coloring. Many oil-soluble dyes, especially yellow dyes used for producing a golden color, have low sublimation fastness, and the dye may diffuse due to bleeding or the like to contaminate the surrounding area. Due to many problems, metal-containing complex salt type oily dyes are mainly used as dyes for gold and silver threads.

[0004]

As described above, the organic solvent contained in the transparent paint which is also used for processing the gold and silver threads should be reduced in use in view of recent environmental problems. It's obvious. From a similar perspective,
Most of the heavy metals contained in the gold-containing dyes used for coloring, especially the central metal used in the yellow, red, and purple metal-containing dyes, are chromium, and everyone wants to reduce the amount used. By the way. In the case of a combination of a resin for transparent coating that has been conventionally used with such a metal-containing complex salt type dye, or a non-metal-containing dye, the solubility of the dye in the resin is small, and therefore the coating thickness is required in order to obtain the required coloring density. Therefore, it is only possible to obtain a product with a thick and stiff texture. Also, when a dye is added in excess of the solubility in order to increase the coloring density, microcrystals of the dye occur in the coating film, impairing the transparency of the coating film, resulting in low reflectance and a dark metal tone with a dull metallic luster. The product quality is significantly reduced. The present inventors have developed a fiber or a fiber assembly that is environmentally friendly, has a good touch, has a bright and transparent color tone with excellent metallic luster, and has a metallic luster such as gold and silver threads that achieves a high decorative effect. The present invention has been achieved as a result of earnest researches for obtaining it.

[0005]

That is, the present invention has a metal layer as a reflective film on a fiber or a fiber assembly,
A fiber or fiber assembly having a metallic luster, further comprising a resin layer colored with a pyridone azo dye, wherein the pyridone azo dye is C.I.
I. A fiber or a fiber aggregate having a metallic luster, which is an oil-soluble dye classified as Solvent Yellow 162, wherein the pyridone azo dye is C.I. I. A fiber or a fiber aggregate having a metallic luster characterized by being classified as Disperse Yellow 198, wherein the resin layer is made of a copolyester resin. is there.

The present invention relates to a fiber or a fiber assembly having a metallic luster. The fiber in the present invention means a natural fiber, a chemical synthetic fiber, a semi-chemical synthetic fiber, etc.,
A fiber assembly is a multifilament yarn, twisted yarn, cloth,
It means woven cloth, non-woven cloth, paper and the like. It also includes a thin and long cut synthetic resin film such as a conventional gold and silver thread. The fiber assembly is preferably a non-woven fabric made of synthetic fibers. As the non-woven fabric, a material obtained by a known method such as a melt blow method, a spun bond method, or papermaking can be used, and synthetic fibers include polyester, polyamide, polypropylene, polyethylene, polyacryl, aramid, polyimide, polyamide imide, and recycled. Cellulose, cellulose acetate and the like can be used alone and / or in combination as required. Preferred brands include Shanfine, Ekule, Bonden, Dynac, Balcompo (all manufactured by Toyobo Co., Ltd.), and the like.

The metal layer provided on the surface of the fiber or the fiber assembly as a reflective film is formed by a dry method such as a vacuum deposition method, a sputtering method, a thermal spraying method and / or an electroless plating method, a combination of electroless plating and electroplating, a dry method and an electrical method. It can be formed by a method such as combined use of plating. Of these, the vacuum deposition method is particularly preferable. The thickness of the metal layer is 0.05
˜50 μm, preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm. The metal that can be used is not particularly limited, but aluminum, titanium, chromium, iron, cobalt, nickel,
Copper, zinc, ruthenium, rhenium, palladium, silver,
Tin, osmium, platinum, gold, etc. alone or copper /
It can be used in combination like zinc.

In the present invention, the resin layer formed on the metal layer serving as the reflection film is an alkylated melamine resin, a cellulose derivative, a polymethacrylic resin, a polystyrene resin, a urethane resin, an epoxy resin, a urea-formalin resin. Known polymer materials such as melamine / formalin resin, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, and modified products thereof can be used. However, in the present invention, it is preferable to use the polyester resin described below. The copolyester resin is obtained by polycondensation of polyvalent carboxylic acid and polyhydric alcohol. Examples of the polycarboxylic acid used in the polyester resin include dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and diphenic acid. Aromatic dicarboxylic acids such as group dicarboxylic acids, p-oxybenzoic acid, p- (hydroxyethoxy) benzoic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and aromatic unsaturated polycarboxylic acids such as phenylenediacrylic acid, Aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, unsaturated polycarboxylic acids such as dimer acid, and Alicyclic rings such as cyclohexanedicarboxylic acid and cyclohexenedicarboxylic acid The dicarboxylic acids and the like, also can be exemplified other trimellitic acid as a polycarboxylic acid, trimesic acid, and the like trivalent or higher polyvalent carboxylic acids such as pyromellitic acid.

Examples of polyhydric alcohols used in the polyester resin include aliphatic polyhydric alcohols, alicyclic polyhydric alcohols, aromatic polyhydric alcohols and the like.
Examples of the aliphatic polyhydric alcohols include ethylene glycol
, Propylene glycol, 1,3-propanedioe
2,3-butanediol, 1,4-butanediol
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylol heptane, diethylene glycol, dipropylene glycol,
2,2,4-trimethyl-1,3-pentanediol,
Polyethylene glycol, polypropylene glycol,
Aliphatic diols such as polytetramethylene glycol,
Examples thereof include trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, and other triols and tetraols. As the alicyclic polyvalent alcohols, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, spiroglycol, hydrogenated bisphenol A and ethylene oxide of hydrogenated bisphenol A Adducts and propylene oxide adducts,
Examples thereof include tricyclodecanediol and tricyclodecane dimethanol.

As the aromatic polyhydric alcohols, paraxylene glycol, metaxylene glycol, orthoxylene glycol, 1,4-phenylene glycol, 1,
Examples thereof include an ethylene oxide adduct of 4-phenylene glycol, bisphenol A, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct. Further, as a polyester polyol, ε
Examples thereof include lactone-based polyester polyols obtained by ring-opening polymerization of lactones such as caprolactone. The polyester resin preferably used in the present invention is an aromatic dicarboxylic acid and / or an alicyclic dicarboxylic acid as a polyvalent carboxylic acid component, and an aliphatic diol and / or an alicyclic diol as a polyvalent alcohol component. Is used. The copolyester resin of the present invention comprises a polyvalent carboxylic acid containing 50 mol% or more of an aromatic polyvalent carboxylic acid and / or an alicyclic polyvalent carboxylic acid, an aliphatic polyhydric alcohol and / or an alicyclic polyhydric alcohol.
Those obtained by condensation with polyhydric alcohols containing 0 mol% or more are preferable. In the present invention, it is preferable to use a polyester resin obtained from an aromatic dicarboxylic acid and an aliphatic diol, or a polyester resin obtained from an alicyclic dicarboxylic acid, an aliphatic diol and an alicyclic diol.

The polyester resin can be obtained by a conventional method such as a vacuum polymerization method or a reduced pressure polymerization method. The former is a method used for polymerizing polyethylene terephthalate or the like, which is used for fibers, films, plastic bottles and the like, and a polyester having a relatively high molecular weight can be obtained. The latter is a method used when polymerizing an unsaturated polyester resin such as an alkyd resin, and a polyester having a relatively low molecular weight is obtained. In addition to these conventional methods, the polyester resin can be obtained by an acid chloride method or the like. The softening temperature or glass transition temperature of the polyester resin in the present invention is preferably 40 ° C. or higher,
Further, 50 ° C or higher, still more preferably 60 ° C or higher,
Furthermore, it is more preferably 70 ° C. or higher. If the glass transition temperature is too low, tackiness may occur, which may be inconvenient for some applications. The number average molecular weight of the polyester resin in the present invention is preferably 2,000 to 100,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 100,000.
If the molecular weight is low, the resulting coating film may have insufficient physical properties.

The polyester resin preferably contains an ionic group in view of the production method described later. Examples of the ionic group that may be introduced into the polyester include alkali metal sulfonates or ammonium sulfonates, alkali metal carboxylates or ammonium carboxylates, carboxylic acid organic amine salt groups, sulfuric acid groups, phosphoric acid groups, Anionic groups such as phosphonic acid groups, phosphinic acid groups or their ammonium salts, organic amine salts, alkali metal salts, or cationic groups such as primary to tertiary amine groups can be used. The ionic group can be introduced by using an ionic group-containing monomer. In order to introduce a cationic group, 2-aminopropane 1,3 diol, nitrile monoalkanol, nitrile dialkanol and nitrile trialkanol can be preferably used. To introduce a sulfonate alkali metal base or ammonium sulfonate base into the polyester, sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7 dicarboxylic acid, 5 [4- Sulfophenoxy] isophthalic acid, metasulfobenzoic acid, etc. may be copolymerized with the polyester such as an alkali metal salt or ammonium salt of a mono- or polyvalent carboxylic acid having a sulfonic acid group. Counter cations include Li, Na, K,
Examples thereof include salts with alkali metal ions, alkaline earth metal ions, ammonium ions, primary to quaternary alkylammonium ions, alkanolamines and the like.
The carboxylate group can be obtained by introducing a carboxyl group into the polyester resin and then neutralizing it with a base.

As the base, alkali metal, ammonia,
Other organic amines can be used, and in the present invention, it is particularly preferable to use organic amines. As a method of introducing a carboxyl group into the polyester resin, in the vacuum polymerization method, a method of introducing a polyvalent carboxylic acid anhydride such as trimellitic anhydride, phthalic anhydride, pyromellitic anhydride into the system at the final stage of polymerization of the polyester Can be illustrated. Further, in the vacuum polymerization method, the carboxyl group remaining at the end of the polyester can be used as it is. As the organic amine, alkylamine, alkanolamine, alkylalkanolamine, aromatic amine, cyclic amine, alkylenediamine and the like can be used, and alkanolamine is particularly preferable. As an alkanolamine,
Monoalkanolamine, dialkylmonoalkanolamine, dialkanolamine, monoalkyldialkanolamine, trialkanolamine can be exemplified, and preferably trialkanolamine,
More preferably, 2,2 ′, 2 ″ -nitrile triethanol, tripropanolamine, triisopropanolamine, tributanolamine and trihexanolamine can be used.

The content of these ionic groups is required to be 20 to 2000 m equivalent / 1000 g, preferably 20 to 1000 m equivalent / 1000, relative to the polyester resin.
g, more preferably 50 to 500 m equivalent / 1000 g,
Still more preferably 50 to 200 m equivalent / 1000 g
It is. As the ionic group, it is preferable to use a group of sulfonic acid alkali metal salt. The ionic group has a function of imparting water dispersibility to the polyester resin, and when the content of the ionic group is less than the predetermined amount, sufficient water dispersibility may not be obtained, and the ionic group If the content of is too large, the polyester resin may become water-soluble and the desired colored aqueous dispersion may not be obtained.

The most important essential requirement of the present invention is that the resin layer provided on the reflective metal layer is colored with a pyridone azo dye. As the pyridone azo dye used in the present invention, it is preferable to use a dye insoluble or hardly soluble in water. Pyridone azo dyes preferably used in the present invention include C.I. I. Solvent Yellow 162 C.I. I. Disperse Yellow 198. Such a dye is blended in the range of 0.2 to 30% by weight, more preferably 1 to 25% by weight, still more preferably 2 to 20% by weight, still more preferably 3 to 15% by weight. It is blended in the range of%. If the blending amount is too small, a sufficient coloring density cannot be obtained, and it becomes necessary to increase the coating thickness, which impairs the texture and feel of the fiber or fiber assembly. On the contrary, if the blending amount is too large, it may cause bleeding and the like. In addition to these pyridoneazo dyes, other known dyes and pigments may be combined for the purpose of adjusting color tone.

Particularly in the case of expressing a golden color, it is preferable to add a slightly reddish dye. To 100 parts by weight of such a pyridoneazo dye, C.I. I. Disperse Red 60 C.I. I. Disperse Red 92 C.I. I. It is preferable to use a red dye such as Solvent Red 149 in an amount of about 0.1 to 10 parts by weight. Further, it is possible to add a fluorescent whitening agent or the like to obtain a brighter color tone.

In the present invention, an ultraviolet absorber, an antioxidant and the like can be added to the copolyester resin for the purpose of improving light resistance and heat resistance. As the ultraviolet absorber and the light stabilizer, a salicylate compound, a benzophenone compound, a benzotriazole compound, etc. can be used. As the radical chain inhibitor (primary antioxidant), a phenol compound, an amine compound, an ascorbic acid compound or the like can be used. Sulfur compounds can be used as the peroxide decomposer (secondary antioxidant), and citric acid, phosphoric acid, etc. can be used as the synergist. As a UV absorber and a light stabilizer, salicylate compounds such as phenyl salicylate, monoglycol salicylate, and t-butyl phenyl salicylate, 2-hydroxy-4
-Benzophenone compounds such as alkoxybenzophenone, 2 (2'-hydroxy-5'-methylphenyl) benzotriazole, 2 (2'-hydroxy-5'-octylphenyl) benzotriazole, 2 [2-hydroxy-3 −
(3,4,5,6-Tetrahydrophthalimido-methyl) -5-methylphenyl] benzotriazole, 2
[2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenyl] -2H-benzotriazole, 2
(2'-Hydroxy-3 ', 5'-di-charamylphenyl) benzotriazole, 2 (2'-hydroxy-3',
5'-di-tert-butylphenyl) benzotriazo-
2 (2'-hydroxy-3'-tert-butyl-5'-
Methylphenyl) benzotriazole, 2 (2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-
Benzotriazol such as 5-chlorobenzotriazol
Compounds, other than resorcinol monobenzoene
2'-ethylhexyl-2-cyano-3-phenylcinnamate, bis (2,2,6,6-tetramethyl-4)
-Piperidine) sebacate or the like can be used.

In the present invention, it is preferable to use at least one ultraviolet absorber selected from the group consisting of benzotriazole type, benzophenone type and benzosalicylate type. The blending amount of these antioxidants is 0.01 to the binder resin.
It is about 5.0% by weight, preferably about 0.02 to 1.0% by weight, and more preferably about 0.05 to 0.5% by weight. Further, in the present invention, a higher effect can be obtained by using these ultraviolet absorbers and a singlet oxygen quencher together. As the singlet oxygen quencher, nickel complex compounds, DABCO: diazabiscyclooctane and the like are used. Can be used. The above is the fiber or fiber assembly having the metallic luster of the present invention.

Next, a method for producing the fiber or fiber assembly having metallic luster of the present invention will be described. In order to obtain a fiber or a fiber assembly having a metallic luster of the present invention, first, a fiber or a fiber assembly is subjected to metal vapor deposition, and then, it is obtained by coating with a solution consisting of a dye, a resin and a solvent and drying. I can do things. However, in such a method, it is necessary to use an organic solvent as a solvent, which leaves a problem in working environment or fire prevention. In the present invention, as a preferred production method, a method in which a resin is made into an aqueous dispersion to form a paint and used for coating can be exemplified. More specifically, it is a production method in which metal is vapor-deposited on at least one surface of a fiber or a fiber aggregate, and the coating is dried with an aqueous dispersion of a resin. A method in which metal is vapor-deposited on at least one surface of a synthetic resin film, which is further coated with a resin aqueous dispersion, dried, and then cut. A manufacturing method in which metal is vapor-deposited on at least one surface of a fiber or a fiber aggregate, which is further coated with an aqueous dispersion of a resin, dried and then wet-dyed. The production methods such as the above can be preferably used.

In the present invention, when the resin, preferably the polyester resin, contains an ionic group, the resin has a self-emulsifying property, so that an aqueous dispersion of resin fine particles can be prepared by the phase inversion self-emulsification method. For the fine particle dispersion of the ionic group-containing resin, a method of adding water after previously mixing the ionic group-containing resin and the water-soluble organic compound, heating the ionic group-containing resin, the water-soluble organic compound and water all together It can be obtained by a method such as. At that time, a surfactant or the like can be used together. When a water-soluble organic compound and a resin are mixed, a hydrophobic fluorescent dye is mixed at the same time to obtain an aqueous dispersion of fluorescently colored resin. Here, the resin is preferably an ionic group-containing copolyester resin. Examples of water-soluble organic compounds include ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, methyl cellosolve,
Ethyl cellosolve, butyl cellosolve, tertiary butyl cellosolve, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane and the like can be used. The water-soluble organic compound is preferably one that can be removed by azeotropic distillation after the ionic group-containing polyester resin is dispersed in water.

The water-based medium may contain various water-soluble additives. As the additive, a water-soluble organic compound can be exemplified. As the water-soluble organic compound, methanol, ethyl alcohol, propanol, isopropanol, butanol, benzyl alcohol, ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol, neopentyl glycol, polypropylene glycol, Butyl cellosolve, tertiary butyl cellosolve, diethylene glycol, triethylene glycol, polyethylene glycol, thiodiglycol, glycerin, 2,2 ', 2''-nitrile triethanol, ethylenediamine, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Examples thereof include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, alkylene glycol monoalkyl ether, N-methylpyrrolidone, and the like. The water-soluble organic compound is 50% of the aqueous medium.
It can be added as appropriate within the range not exceeding. A fluorine-based or silicone-based antifoaming agent can be added to the aqueous medium of the present invention. Furthermore, various fungicides and fungicides, and if necessary, inorganic and organic pigments may be added to the extent that transparency is not impaired.

[0022]

[Function] In the combination of the resin for transparent paint which has been conventionally used with such a metal-containing complex salt type dye and a general non-metal-containing dye, the solubility of the dye in the resin is small, so that the required coloring density is obtained. Therefore, it is necessary to increase the coating thickness, and as a result, only a product with a thick and stiff texture can be obtained. Also, when a dye is added in excess of the solubility in order to increase the coloring density, microcrystals of the dye occur in the coating film, impairing the transparency of the coating film, resulting in low reflectance and a dark metal tone with a dull metallic luster. The product quality is significantly reduced. The pyridone azo dye used in the present invention has a lighter color than the metal-containing complex salt dye. Furthermore, such pyridone azo dyes are superior in heat resistance, sublimation resistance and bleeding resistance to other oily yellow dyes, and their fastness is not inferior to that of metal-containing complex salt dyes. This makes it possible to obtain an environment-friendly gold and silver thread that does not contain heavy metals. The copolymerized polyester resin particularly preferably used in the present invention has excellent compatibility with dyes, particularly oily fluorescent dyes, and particularly when the copolymerized polyester resin contains an anionic ionic group such as a sulfonate group. It is also compatible with basic fluorescent dyes, can be colored in very high concentrations, and has excellent light fastness. As a result, it is not necessary to use the metal-containing complex salt type dye that has been unavoidably used for securing the light resistance, and it is possible to use a general non-metal-containing dye, which is preferable in terms of environmental hygiene.

Further, since the solubility is high, even a thin coating film can be sufficiently colored, and the tactile sensation of the product is improved. Furthermore, since fine dye crystals are not deposited in the coating film, a bright and transparent color tone having excellent metallic luster can be obtained, and a high decorative effect can be realized. Furthermore, according to the preferred production method using the water dispersion exemplified in the present invention, the resin coating film can be formed with the water-based paint, so that exhaust equipment, solvent recovery equipment, etc. are not required even in the working environment, and the prevention of fire etc. It will be more meaningful in terms of industry than the point of view.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to Examples [Polymerization Example 1 of Polyester Resin] 96 weight parts of dimethyl terephthalate in an autoclave equipped with a thermometer and a stirrer. Parts, isophthalic acid dimethyl ester 92 parts by weight, 5 sodium sulfoisophthalic acid dimethyl ester 6 parts by weight, ethylene glycol 72 parts by weight, neopentyl glycol 103 parts by weight, tetrabutoxy titanate 0.1 parts by weight, Was charged and heated at 150 to 220 ° C. for 180 minutes to carry out a transesterification reaction. Then, after raising the temperature to 240 ° C.,
Gradually reduce the system pressure to 10 mmHg after 30 minutes,
The reaction was continued for 240 minutes. Copolyester resin (A
1) was obtained. The obtained copolyester resin had an average molecular weight of 15,000, an acid value of 2 eq./ton, a glass transition temperature of 62 ° C., a specific gravity of 1.26, and a sodium sulfonate group equivalent of 98 eq.ton (m equivalent / kg). It was

[Polyester Resin Polymerization Example 2] Thermometer,
In an autoclave equipped with a stirrer, 196 parts by weight of dimethyl ester of cyclohexanedicarboxylic acid, 102 parts by weight of ethylene glycol, 99 parts by weight of tricyclodecane dimethanol, 0.1 part by weight of tetrabutoxy titanate. , Were heated for 180 minutes at 150 to 220 ° C. to carry out a transesterification reaction. Then, after raising the temperature to 240 ° C.,
Gradually reduce the system pressure to 10 mmHg after 30 minutes,
The reaction was continued for 240 minutes. After that, the atmosphere in the autoclave was replaced with nitrogen gas and the pressure was adjusted to atmospheric pressure. Keeping the temperature at 200 ° C, add 4 parts by weight of trimellitic anhydride and react for 60 minutes to prepare a copolyester resin (A2).
I got The obtained copolyester resin had an average molecular weight of 12,000, an acid value of 210 eq./ton, a glass transition temperature of 71 ° C. and a specific gravity of 1.18.

[Production Example 1 of Colored Water Dispersion] 200 parts by weight of polyester resin (A1), 200 parts by weight of methyl ethyl ketone, and tetrahydro were placed in a four-necked 10 liter separable flask equipped with a thermometer, a condenser and a stirring blade. 100 parts by weight of furan, "CI Disperse Y
10 parts by weight of a conquer cake of "ellow 198" were charged and dissolved at 70 ° C. Next, ion-exchanged water at 70 ° C 8
After adding 100 parts by weight to disperse in water, distill in a distillation flask until the distillate temperature reaches 103 ° C., and after cooling, add water to adjust the solid content concentration to 20 wt%, and finally to a fluorine-based surfactant. MegaFac 142D [Dainippon Ink and Chemicals]
0.1 part by weight was added to obtain a colored polyester aqueous dispersion (B1) colored yellow. [Production Example 2 of Colored Water Dispersion] 200 parts by weight of polyester resin (A2), 200 parts by weight of methyl ethyl ketone, and 100 parts of tetrahydrofuran were placed in a four-necked 10 liter separable flask equipped with a thermometer, a condenser and a stirring blade.
Parts by weight, “CI Disperse Yellow 1
98 "Conk cake 10 parts by weight, 2 as UV absorber
2 parts by weight of [2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenyl] -2H-benzotriazole was charged and dissolved at 70 ° C. Next, after adding 6 parts by weight of triethylamine as a base, 800 parts by weight of ion-exchanged water at 70 ° C was added to disperse the water, and then distilled in a distillation flask until the distillate temperature reached 103 ° C, and after cooling, water was added. Was added to adjust the solid content concentration to 20%, and finally 50 parts by weight of ethanol was added to the colored polyester aqueous dispersion (B
2).

[Production Example 3 of Colored Aqueous Dispersion] In Production Example 1 of a colored aqueous dispersion, the dye was replaced with "CI Solvent".
A colored water dispersion (B3) was obtained by performing the same operation except that the color was changed to Yellow 162. [Production Example 4 of Colored Water Dispersion] In the production example 2 of colored water dispersion, the dye was replaced with "CI Solvent Yellow".
The same procedure as described above was repeated except that the color water dispersion (B) was changed to 162.
4) was obtained. [Preparation Example 5 of Colored Water Dispersion] Colored water dispersion was prepared in the same manner as in Preparation Example 1 of colored water dispersion except that the dye was changed to the metal-containing complex salt type oil dye "Aizenspirone Yellow GRLH Special". (B5) was obtained.

[0028]

[Example 1] Polyester non-woven fabric Balconpo HP60
Aluminum was vacuum-deposited on both sides of 50G [manufactured by Toyobo Co., Ltd.] to obtain an aluminum-coated nonwoven fabric (C1). The vapor deposition film thickness varied depending on the orientation of the fiber surface with respect to the vapor deposition direction, but was generally within the range of 1.2 to 2.5 μm. Then, the obtained aluminum-coated non-woven fabric (C1) is dipped in the fluorescent polyester aqueous dispersion (B1) colored in fluorescent yellow, pulled up, and then dried in a dry oven at 150 ° C. for 5 minutes to obtain a golden metallic luster. A nonwoven fabric (G1) having Coated polyester resin coating amount is about 15g
/ M ² , which was about 2 to 4 μm in terms of the thickness on the fiber surface. The coating amount was adjusted to be the same in the examples described below. The color tone, brightness, metallic luster, transparency (above-mentioned visual evaluation), touch, light resistance and heat resistance of the obtained nonwoven fabric are shown in Table 1 below. Shown in Since the light resistance is difficult to evaluate with a non-woven fabric, the same operation was performed on an aluminum foil, and the color difference ΔE in CIELAB1976 before and after irradiation for 20 hours with a sunshine fade meter (63 ° C.) was good at 5 or less, and exceeded 5. The thing was bad. Heat resistance rating is 2
The resulting non-woven fabric was allowed to stand in an oven at 00 ° C. for 5 minutes, and a product in which the color tone and the feeling of transparency were clearly changed was determined to be defective.

[0029]

[Example 2] The aluminum-coated nonwoven fabric (C
1) Using the yellow-colored copolyester aqueous dispersion (B2), the same operation as in Example 1 was performed to obtain a nonwoven fabric (G2) having a golden metallic luster. Example 1 below
The results evaluated in the same manner as in Table 1. Shown in

[0030]

[Example 3] The aluminum-coated non-woven fabric (C
1) Using the yellow-colored copolyester aqueous dispersion (B3), the same operation as in Example 1 was performed to obtain a nonwoven fabric (G3) having a golden metallic luster. Example 1 below
The results evaluated in the same manner as in Table 1. Shown in

[0031]

[Example 4] The aluminum-coated non-woven fabric (C
1) Using the yellow-colored copolyester aqueous dispersion (B4), the same operation as in Example 1 was performed to obtain a nonwoven fabric (G4) having a golden metallic luster. Example 1 below
The results evaluated in the same manner as in Table 1. Shown in

[0032]

[Example 5] Clear lacquer 40 having the following composition ratios
To 100 parts by weight of "CI Disperse Yellow
w198 ”Conk Cake [Mitsui Toatsu Dye Co., Ltd.] 49.0
Parts by weight, C.I. I. Disperse Red 60 conc powder [manufactured by Mitsui Toatsu Dyes Co., Ltd.] was dissolved in an amount of 1.0 part by weight (5 wt% with respect to the resin component) to give a yellow clear lacquer. Clear lacquer composition Alkylated melamine resin 15 parts by weight, nitrocellulose 10 parts by weight, methyl cellosolve 5 parts by weight-n-butyl acetate 10 parts by weight ethyl acetate 10 parts by weight n-butyl alcohol 15 parts by weight methyl isobutyl ketone 10 parts by weight xylene 25 Parts by weight The aluminum-coated non-woven fabric (C1) used in Example 1 is dipped in the obtained lacquer, pulled up, and then dried in an explosion-proof dryer at 50 ° C. to give a non-woven fabric having a golden metallic luster (G5). Got The results evaluated in the same manner as in Example 1 are shown in Table 1. Shown in

[0033]

[Example 6] Clear lacquer and dye "CI Solvent Yellow 162" having the following composition ratios [B
Manufactured by ASF Co., Ltd.], and the same operation as in Example 5,
A non-woven fabric (G6) having a golden metallic luster was obtained. Clear lacquer composition Polymethylmethacrylate resin 25 parts by weight, ethyl alcohol 1 part by weight, toluene 41 parts by weight Acetic acid-n-butyl 22 parts by weight Ethyl acetate 11 parts by weight The results evaluated in the same manner as in Example 1 are shown in Table 1. Shown in

[0034]

Comparative Example 1 Clear lacquer 40 having the following composition ratios
Aizenspirone, a metal-containing complex salt type oil dye, is added to 00 parts by weight.
47.5 parts by weight of Yellow GRLH Special and 2.5 parts by weight of Eisenspiron Red GRLH Special (5 wt% with respect to the resin component) were dissolved to obtain a yellow clear lacquer. Clear lacquer composition Alkylated melamine resin 15 parts by weight, nitrocellulose 10 parts by weight, methyl cellosolve 5 parts by weight-n-butyl acetate 10 parts by weight ethyl acetate 10 parts by weight n-butyl alcohol 15 parts by weight methyl isobutyl ketone 10 parts by weight xylene 25 Parts by weight The aluminum-coated non-woven fabric (C1) used in Example 1 is dipped in the obtained lacquer, pulled up, and dried in an explosion-proof dryer at 50 ° C. to give a golden metallic luster (G7). Got The coating amount of dry resin is about 15g /
It was adjusted to be m ² . The results evaluated in the same manner as in Example 1 are shown in Table 1. Shown in The obtained non-woven fabric (G7) is the golden non-woven fabric (G1) (G2) (G
Compared to 3), it looked a little darker and the reflectance was lower.

[0035]

[Comparative Example 2] A clear lacquer having the following composition ratio was used, and thereafter the same operation as in Comparative Example was carried out to obtain a nonwoven fabric (G8) having a golden metallic luster. Clear lacquer composition Polymethylmethacrylate resin 25 parts by weight, ethyl alcohol 1 part by weight, toluene 41 parts by weight Acetic acid-n-butyl 22 parts by weight Ethyl acetate 11 parts by weight The results evaluated in the same manner as in Example 1 are shown in Table 1. Shown in The obtained non-woven fabric (G8) lacked transparency and felt a dull metallic luster as compared with the gold-colored non-woven fabrics (G1) (G2) (G3) obtained in the examples.

[0036]

[Comparative Example 3] Using a urethane paint having the following composition ratio,
Thereafter, the same operation as in Comparative Example was carried out to obtain a nonwoven fabric (G9) having a golden metallic luster. Urethane coating composition Desmophen 800 7 parts by weight, Desmophen 1100 8 parts by weight, Ethyl acetate 15 parts by weight, Coronate L 20 parts by weight, Toluene 50 parts by weight, Methylcellosolve 50 parts by weight, Acetate-N-butyl 50 parts by weight, the following examples. The results evaluated in the same manner as in Table 1 are shown in Table 1. Shown in The obtained non-woven fabric (G9) looks slightly darker than the golden non-woven fabrics (G1) (G2) (G3) obtained in the examples,
I felt the reflectance was low.

[0037]

[Comparative Example 4] The aluminum-coated non-woven fabric (C
1) Using the yellow-colored copolyester aqueous dispersion (B5), the same operation as in Example 1 was carried out to obtain a nonwoven fabric (G10) having a golden metallic luster. The results evaluated in the same manner as in Example 1 are shown in Table 1. Shown in The obtained non-woven fabric (G10) is the golden non-woven fabric (G10) obtained in the example.
1) Compared with (G2) and (G3), it looked a little darker and the reflectance was lower.

[0038]

Comparative Example 5 Clear lacquer 4000 used in Comparative Example 1
As a dye, "CI Solvent Yel" is added to parts by weight.
low 96 ”, followed by the same operation as in Comparative Example 1,
A non-woven fabric (G11) having a golden metallic luster was obtained. The results evaluated in the same manner as in Example 1 are shown in Table 1. Shown in The obtained non-woven fabric (G11) was inferior in heat resistance to the gold-colored non-woven fabric obtained in the examples, and particularly the change in color tone after heating was large. It is considered that the inner wall surface of the oven used for the heat resistance evaluation was contaminated by the yellow dye, and the sublimation of the dye component lowered the color tone of the nonwoven fabric. The same phenomenon was confirmed in Comparative Examples 6 to 9 below.

[0039]

[Comparative Examples 6 to 9] Clear lacquer 40 used in Comparative Example 1
As a dye, "CI Disperse"
Using the “Yellow 33” conc cake, the same operation as in Comparative Example 1 was performed, and a nonwoven fabric having a golden metallic luster (G
12) was obtained. The results evaluated in the same manner as in Example 1 are shown in Table 1. Shown in Hereinafter, the dyes: C.I. I. Disperse Yellow 42 C.I. I. Disperse Yellow 54 C.I. I. Disperse Yellow 64 It changed into each conk cake and it operated similarly, and obtained the nonwoven fabric (G13)-(G15) which has metallic luster of gold. The results evaluated in the same manner as in Example 1 are shown in Table 1. Shown in

[0040]

[Table 1]

[0041]

As described above, according to the present invention, it is not necessary to use a metal-containing complex salt type dye, a good tactile sensation and a bright and transparent color tone excellent in metallic luster can be obtained, which is high. It is possible to achieve a decorative effect. Furthermore, according to the preferred production method of the present invention, it is not necessary to use an organic solvent or the like in a work environment, exhaust equipment, solvent recovery equipment, etc. are unnecessary, and it is industrially significant from the viewpoint of prevention of fire and the like. .

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yozo Yamada 2-1-1 Katata, Otsu City, Shiga Toyobo Co., Ltd. (72) Inventor Tomomasa Yamada 17-9 Nihombashi Koamicho, Chuo-ku, Tokyo No. Toyo Spinning Co., Ltd. Tokyo branch office

Claims (8)

[Claims] 1. A fiber having a metallic luster characterized in that it has a metal layer as a reflection film on the surface of the fiber, and further has a resin layer colored with a pyridone azo dye on the metal layer. 2. A metallic luster characterized by having a metal layer as a reflection film on the surface of fibers forming a fiber assembly, and further having a resin layer colored with a pyridoneazo dye on the metal layer. Fiber aggregate. 3. A pyridone azo dye is C.I. I. Solv
The fiber having a metallic luster according to claim 1, which is an oil-soluble dye classified as ent Yellow 162. 4. A pyridone azo dye is C.I. I. Solv
The fiber assembly having a metallic luster according to claim 2, which is an oil-soluble dye classified as ent Yellow 162. 5. The pyridone azo dye is C.I. I. Di
The fiber having a metallic luster according to claim 1, which is a product classified as sperse Yellow 198. 6. The pyridone azo dye is C.I. I. Di
The fiber assembly having a metallic luster according to claim 2, which is a product classified as sperse Yellow 198. 7. The fiber having a metallic luster according to claim 1, wherein the resin layer is a layer made of a copolyester resin. 8. The fiber assembly having metallic luster according to claim 2, wherein the resin layer is a layer made of a copolyester resin.