JPH0941266A - Fiber or fiber assembly with metallic luster and its production - 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 fibers or fiber assembly with a metallic thin film followed by forming a colored copolyester resin layer thereon. SOLUTION: First, a copolyester resin containing 20-2000meq/kg of ionic group 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 incorporated with an oily dye, disperse dye or metal-free dye 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, thus obtaining the objective fiber or fiber assembly 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, mainly gold and silver threads and an assembly thereof, and a method for producing the same.

[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. The present inventors have arrived at the present invention as a result of earnest studies for obtaining fibers or fiber aggregates having metallic luster such as environmentally friendly gold and silver threads.

[0005]

That is, the present invention provides a metallic luster characterized by forming a metal layer as a reflective film on a fiber or a fiber aggregate, and further forming a copolymerized polyester resin layer on the metal layer. Is a fiber or a fiber assembly having a metallic luster, characterized in that the copolyester resin is colored with a pigment, wherein the pigment is classified into an oil dye and / or a disperse dye. A fiber or a fiber assembly having a metallic luster characterized by being a dye
A fiber or a fiber aggregate having a metallic luster characterized in that the pigment is a non-metal-containing dye, wherein the copolyester resin contains 20 to 2000 mm equivalent / kg of an ionic group. A metal or a fiber aggregate having metallic luster, characterized in that the copolymerized polyester resin layer is formed by using an aqueous dispersion of a copolymerized polyester resin (colored with a hydrophobic dye as necessary) A method for producing a fiber or a fiber aggregate having a luster, wherein the fiber or the fiber aggregate is a non-woven fabric made of a synthetic fiber, and a fiber or a fiber aggregate having a metallic luster and a method for producing the same.

The present invention relates to a fiber or a fiber assembly having a metallic luster and a method for producing the same. The fiber in the present invention means a natural fiber, a chemically synthetic fiber, a semi-chemical synthetic fiber and the like, and a fiber assembly means a multifilament yarn, a twisted yarn, a cloth, a woven cloth, a knitted fabric, a 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 paper making can be used, and synthetic fibers include polyester, polyamide, polypropylene,
Polyethylene, polyacrylic, aramid, polyimide, polyamideimide, regenerated 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 0.0
The thickness is 5 to 50 μm, preferably 0.1 to 10 μm, and 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.

The most important essential requirement of the present invention is that the resin layer formed on the metal layer as the reflection film is made of a copolyester resin. 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 and
Aromatic dicarboxylic acids such as isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and diphenic acid, p-oxybenzoic acid,
Aromatic oxycarboxylic acids such as p- (hydroxyethoxy) benzoic acid, hexahydrophthalic acid and tetrahydrophthalic acid, aromatic unsaturated polycarboxylic acids such as phenylenediacrylic acid, succinic acid, adipic acid, azelaic acid, sebacine Acids, aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid,
Unsaturated polycarboxylic acids such as citraconic acid and dimer acid,
And, cyclohexanedicarboxylic acid, alicyclic dicarboxylic acid and the like such as cyclohexene dicarboxylic acid, and other polyvalent carboxylic acid, trimellitic acid, trimesic acid,
Examples thereof include 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 polyethylene terephthalate used for fibers, films, plastic bottles, etc.
It is a method used for polymerizing polyester and the like, and 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, more preferably 50 ° C or higher, still more preferably 60 ° C or higher, and further 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 metals, ammonia, and other organic amines can be used, and in the present invention, it is particularly preferable to use organic amines.

As a method for introducing a carboxyl group into a polyester resin, in a vacuum polymerization method, a polyvalent carboxylic acid anhydride such as trimellitic anhydride, phthalic anhydride or pyromellitic anhydride is introduced into the system at the final stage of polymerization of polyester. The method of introduction 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.
Examples of the alkanolamine include monoalkanolamine, dialkylmonoalkanolamine, dialkanolamine, monoalkyldialkanolamine, trialkanolamine, and preferably trialkanolamine, and more preferably 2,
2 ′, 2 ″ -nitrile triethanol, tripropanolamine, triisopropanolamine, tributanolamine, trihexanolamine can be used.

The content of these ionic groups is required to be 20 to 2000 mm equivalent / 1000 g, preferably 20 to 1000 mm equivalent / 1000, relative to the polyester resin.
g, more preferably 50 to 500 mm equivalent / 1000 g,
Still more preferably 50 to 200 mm 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. In the present invention, the polyester resin fine particles are colored with a dye as required. As the coloring matter, either a pigment or a dye may be used. More specifically, as a pigment, C.I. I. Pigment Yellow 3, 13, 1
4, 15, 16, 17, 185, C.I. I. Pigment Red 47, 48, 58,
81, 95, 122, 184, 185 C.I. I. Pigment Violet 23 C.I. I. Pigment Blue 15, 16 carbon black and the like can be preferably used.

Further, the dye is not particularly limited as long as it can dye polyester resin fast. When the polyester resin contains an anionic group, it is dyed with a cationic dye such as a basic dye, and when it contains a cationic group, it is dyed with an anionic dye such as an acid dye, a direct dye or a reactive dye. can do. Further, disperse dyes, oil dyes, some vat dyes, reactive disperse dyes and the like used for dyeing polyester fibers can be used. Examples of the acid dye in the present invention include C.I. I. Known acid dyes classified as Acid Color can be used. In addition, some C.I. I. A dye classified as Direct Color can also be used as an acid dye. These are azo, anthraquinone, quinophthalone, triallylmethane, xanthene, phthalocyanine, and other dye skeletons to which about 1 to 4 anionic groups (mostly sodium sulfonate groups) are introduced. For process color use, C.I. I. Acid Yell
Of ow, Hue is Green Yellow,
Alternatively, a dye classified as Bright Greenish Yellow may be C.I. as magenta. I. Acid
Of Red, Hue is Bluish Red or B
dyes classified as light Blue Red,
And / or C.I. I. H in Acid Violet
ue is Reddish Violet, or Brig
A dye classified as ht Reddish Violet is C.I. I. H in Acid Blue
ue is Greenish Blue, or Bright
t Greenish Blue, and / or C.I.
I. Hue is Bluish in Acid Green
Green or Bright Bluish G
Dyes classified as reen are preferably used alone or appropriately mixed.

The basic dyes in the present invention include acridine-based, methine-based, polymethine-based, azo-based, azomethine-based, xanthene-based, thioxanthene-based, oxazine-based,
Known basic dyes such as thioxazine type, triallylmethane type, cyanine type, anthraquinone type and phthalocyanine type can be used. Especially for the three primary colors of process color, C.I. I. Basic Yel
low 11, 12, 13, 21, 23, 24, 33,
40, 51, 54, 63, 71 and 87 are C.I. I. Basic Red 13, 14, 45, 1
9, 26, 27, 34, 35, 36, 38, 39, 4
2, 43, 45, 46, 50, 51, 52, 53, 5
6, 59, 63, 65, 66, 71, C.I. I. Basi
c Violet 7, 11, 14, 15, 16, 1
8, 19, 20, 28, 29, 30, 33, 34, 3
5, 36, 38, 39, 41, 44 are C.I. I. Basic Blue 3, 22, 33, 4
1, 45, 54, 63, 65, 66, 67, 75, 7
7,85,87,88,109,116 are preferably used. Such an ionic dye can be used in the range of 1 to 98 mol%, preferably 20 to 90 mol% based on the ionic group equivalent contained in the polyester resin.

In the present invention, it is preferably colored with "a dye which is insoluble or slightly soluble in water and soluble in an organic solvent". The "dye that is insoluble in water or sparingly soluble in water and soluble in an organic solvent" in the present invention is an oil-soluble dye,
Disperse dyes and some bath dyes can be exemplified. These are "Solve" in the color index.
nt Dye "," Disperse Dye "," V
at Dye ”. "Solve
It is particularly preferable to use a non-chromium metal-containing dye of "nt Dye". Chemically, anthraquinone dye, azo dye, disazo dye, triazo dye, phthalocyanine dye, indigo dye, methine dye, nitro dye, quinophthalone dye, quinoline dye, cyanomethine dye, A triphenylmethane dye, a xanthene dye, etc. can be used. More specifically, as an oil-soluble dye, C.I. I. Solvent Yellow 96 C.I. I. Solvent Yellow 162 C.I. I. Solvent Red 49 C.I. I. Solvent Blue 25 C.I. I. Solvent Blue 35 C.I. I. Solvent Blue 38 C.I. I. Solvent Blue 64 C.I. I. Solvent Blue 70 C.I. I. Solvent Black 3 etc. can be illustrated.

As a disperse dye, C.I. I. Disperse Yellow 33 C.I. I. Disperse Yellow 42 C.I. I. Disperse Yellow 54 C.I. I. Disperse Yellow 64 C.I. I. Disperse Yellow 198 C.I. I. Disperse Red 60 C.I. I. Disperse Red 92 C.I. I. Disperse Violet 26 C.I. I. Disperse Violet 35 C.I. I. Disperse Violet 38 C.I. I. Disperse Blue 56 C.I. I. Disperse Blue 60 C.I. I. At least one dye selected from Disperse Blue 87 is preferably used. These are particularly excellent in light fastness, sublimation fastness, hue, and saturation.

In the present invention, the yellow dye used for the gold thread is particularly important, but it is preferable to use a pyridone azo dye. I. Solvent Yellow 162 C.I. I. The use of Disperse Yellow 198 is particularly preferred. Such a dye is blended in the range of 0.2 to 30% by weight with respect to the polyester resin, more preferably 2 to 25% by weight, still more preferably 5 to 20% by weight, still more preferably 10 to 20% by weight.
It is compounded in the range of weight%. 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 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. 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 the fiber or fiber assembly having the metallic luster of the present invention, first,
It can be obtained by subjecting a fiber or a fiber aggregate to metal vapor deposition, and then coating with a solution consisting of a dye and a solvent of a copolyester resin and drying. 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 copolyester resin is made into an aqueous dispersion to form a coating material and used for coating can be exemplified.

More specifically, metal or metal is vapor-deposited on at least one surface of a fiber or a fiber assembly, and further coated with an aqueous dispersion of a copolyester resin (which is colored with a hydrophobic dye as necessary) and dried. Manufacturing method. A production method in which metal is vapor-deposited on at least one side of a synthetic resin film, which is further coated with an aqueous dispersion of a copolyester resin (which is optionally colored with a hydrophobic dye), dried, and then cut. A manufacturing method in which metal is vapor-deposited on at least one surface of a fiber or a fiber assembly, which is further coated with an aqueous dispersion of a copolyester resin, dried and then wet-dyed. The production methods such as the above can be preferably used.

In the present invention, when the polyester resin is an ionic group-containing polyester resin, the polyester resin has a self-emulsifying property, so that an aqueous dispersion of polyester resin fine particles can be prepared by the phase inversion self-emulsification method. The fine particle dispersion of the polyester resin is prepared by mixing the ionic group-containing polyester resin and the water-soluble organic compound in advance and then adding water, or the ionic group-containing polyester resin, the water-soluble organic compound and water are mixed and heated all at once. It can be obtained by a method or the like. At that time, a surfactant or the like can be used together. An aqueous dispersion of a colored polyester resin can be obtained by simultaneously mixing a dye when mixing the water-soluble organic compound and the copolyester resin. Ethanol as the water-soluble organic compound,
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.

[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 copolymerized polyester resin used in the present invention is excellent in compatibility with dyes, particularly oily dyes, and is particularly a basic dye when the copolymerized polyester resin contains an anionic ionic group such as a sulfonate group. They are compatible with each other, can be colored in a very high concentration, and have excellent fastness to light. 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. Furthermore, since the solubility is high, even a thin coating film can be sufficiently colored, and the touch feeling 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.

Further, according to the manufacturing method of the present invention, since the resin coating film can be formed by the water-based paint, exhaust equipment, solvent recovery equipment, etc. are not required even in the working environment, and it is industrially significant from the viewpoint of preventing fires and the like. It will be a good thing. EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples [Polymerization Example 1 of Polyester Resin] 96 parts by weight of dimethyl terephthalate and dimethyl ester of isophthalic acid in an autoclave equipped with a thermometer and a stirrer. 92 parts by weight, 6 parts by weight of 5 sodium sulfoisophthalic acid dimethyl ester, 72 parts by weight of ethylene glycol, 103 parts by weight of neopentyl glycol, 0.1 part by weight of tetrabutoxy titanate, and 150 to 220 ° C. The mixture was heated at 180 ° C. for 180 minutes for transesterification. 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 copolymerized polyester resin thus obtained 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 (mm 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 of Copolyester Aqueous Dispersion]
Four-necked 10 equipped with a thermometer, condenser, and stirring blade
Polyester resin (A
1) 200 parts by weight, 200 parts by weight of methyl ethyl ketone,
Tetrahydrofuran 100 parts by weight was charged and dissolved at 70 ° C. Next, 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. After cooling, water was added to adjust the solid content concentration to 20 wt%. Finally, 50 parts by weight of ethanol was added to obtain a copolyester aqueous dispersion (B0). [Production Example 1 of Colored Water Dispersion] 200 parts by weight of polyester resin (A1), 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, Neptune Yellow 075 as a dye (oil dye, CI Solvent Yellow 162)
[Manufactured by BASF] 9.5 parts by weight, C.I. I. Disper
se Red60 Conc Powder [Mitsui Toatsu Dyestuff Co., Ltd.]
0.5 part by weight was charged and dissolved at 70 ° C. Then 70
After adding 800 parts by weight of ion-exchanged water at ℃ to disperse in water, distill in a distillation flask until the distillate temperature reaches 103 ℃, and after cooling, add water to adjust the solid content concentration to 20 wt%, and finally 0.1 parts by weight of the fluorine-based surfactant Megafac 142D [manufactured by Dainippon Ink and Chemicals, Inc.] was added to obtain a yellow colored aqueous polyester dispersion (B1).

[Production Example 2 of Colored Water Dispersion] In a four-necked 10 liter separable flask equipped with a thermometer, a condenser and a stirring blade, 200 parts by weight of polyester resin (A2), 200 parts by weight of methyl ethyl ketone and tetrahydro were used. 100 parts by weight of furan, Neptune Yellow 075 as dye (oil dye, CI Solvent Yell
ow162) [manufactured by BASF] 9.5 parts by weight, C.I. I.
Disperse Red 60 conc powder [manufactured by Mitsui Toatsu Dyes Co., Ltd.] 0.5 part by weight as an ultraviolet absorber 2 [2'-
0.5 parts by weight of 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 Water Dispersion] In a four-necked 10 liter separable flask equipped with a thermometer, a condenser and a stirring blade, 200 parts by weight of polyester resin (A1), 200 parts by weight of methyl ethyl ketone and tetrahydro were used. 100 parts by weight of furan, as a dye, Macrolex Red Violet R (CI Dsperse Vio
Let 26) [BAYER] 10 parts by weight was charged and dissolved at 70 ° C. Next, ion-exchanged water at 70 ° C 80
After adding 0 part by weight and dispersing in water, the mixture was distilled in a distillation flask until the distillate temperature reached 103 ° C, and after cooling, water was added to adjust the solid content concentration to 20 wt%, and finally sodium dodecylbenzenesulfonate. 1 part by weight was added to obtain a reddish purple colored polyester aqueous dispersion (B3). [Production Example 4 of Colored Water Dispersion] A four-necked 10-liter separable flask equipped with a thermometer, a condenser, and a stirring blade was placed in a polyester resin (A1) 200 parts by weight, methyl ethyl ketone 200 parts by weight, and tetrahydrofuran 100.
10 parts by weight of TS turquoise 606 cake (CI Dsperse Blue 60) [Sumitomo Chemical Co., Ltd.] as a dye were charged and dissolved at 70 ° C. Next, 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 to give a solid concentration of 20 wt%.
And finally 1 part by weight of polyoxyethylene sorbitan monooleate was added to obtain a colored polyester aqueous dispersion (B4) colored in light blue.

[0031]

[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 aluminum-coated non-woven fabric (C1) is immersed in the copolyester aqueous dispersion (B0), pulled up, and dried in a dry oven at 150 ° C. for 5 minutes to obtain a non-woven fabric (S1) having a silver-white metallic luster. It was The coating amount of the copolymerized polyester resin was about 15 g / m ² , and it 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, lightness, metallic luster, transparency (above-mentioned visual evaluation), touch and light resistance of the obtained non-woven fabric are shown in Table 1 below. Shown in Since light resistance is difficult to evaluate with a non-woven fabric, the same operation was performed on an aluminum foil to prepare a sunshine fade meter (6
The color difference ΔE in CIELAB1976 before and after irradiation at 3 ° C.) for 20 hours was rated as 5 or less and was rated as bad when it exceeded 5.

[0032]

[Example 2] The aluminum-coated nonwoven fabric (C
1) Using the yellow-colored copolyester aqueous dispersion (B1), the same procedure as in Example 1 was performed to obtain a nonwoven fabric (G1) having a golden metallic luster. The results evaluated in the same manner as in Example 1 are shown in Table 1. Shown in

[0033]

[Example 3] The aluminum-coated non-woven 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

[0034]

[Example 4] The aluminum-coated non-woven fabric (C
1) Using the reddish purple copolyester aqueous dispersion (B3), the same operation as in Example 1 was carried out to obtain a nonwoven fabric (SP1) having a metallic shocking pink metallic luster. The results evaluated in the same manner as in Example 1 are shown in Table 1. Shown in

[0035]

[Embodiment 5] The aluminum-coated non-woven fabric (C
1), using the brightly colored copolyester aqueous dispersion (B4), the same operation as in Example 1 is carried out, and a nonwoven fabric having a metallic light blue metallic luster (LB
1) was obtained. The results evaluated in the same manner as in Example 1 are shown in Table 1. Shown in

[0036]

Example 6 Basic dye Eisencatilone Brilliant Yellow 5GLH (CI Basic Yellow
w13) [Hodogaya Chemical Co., Ltd.] 95 parts by weight, basic dye Eisencatilon Pink BGH (CI Basic)
Red 27) [Hodogaya Chemical] 5 parts by weight was dissolved in 1000 parts by weight of deionized water and the temperature was raised to 80 ° C. Next, the non-woven fabric (S1) having a silver-white metallic luster obtained in Example 1 was dip dyed for 30 minutes, washed with water and dried to obtain a non-woven fabric (G3) having a golden metallic luster. Example 1 below
The results evaluated in the same manner as in Table 1. Shown in

[0037]

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 was 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 (G4). 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 (G4) is the gold-colored non-woven fabric (G1) (G2) (G
Compared to 3), it looked a little darker and the reflectance was lower.

[0038]

Comparative Example 2 A nonwoven fabric (G5) having a golden metallic luster was obtained by using the clear lacquer having the following composition ratio and by the same procedure as in Comparative Example. 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 (G5) lacked transparency and had a dull metallic luster as compared with the gold-colored non-woven fabrics (G1) (G2) (G3) obtained in the examples.

[0039]

[Comparative Example 3] Using a urethane paint having the following composition ratio,
Thereafter, the same operation as in Comparative Example was performed to obtain a nonwoven fabric (G6) 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 (G6) looks slightly darker than the golden non-woven fabrics (G1) (G2) (G3) obtained in the examples,
I felt the reflectance was low.

[0040]

Comparative Example 4 Clear lacquer 40 used in Comparative Example 2
Neptune Yellow 0 as a non-metal-containing dye in 00 parts by weight
75 (oil dye, CI Solvent Yellow
w162) [manufactured by BASF] 47.5 parts by weight, C.I. I.
Disperse Red 60 conc powder [manufactured by Mitsui Toatsu Dye Co., Ltd.] (2.5 parts by weight) was dissolved to obtain a yellow lacquer, and the same procedure as in Comparative Example 1 was performed to obtain a nonwoven fabric (G7) 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 (G7) lacked transparency and appeared dull in metallic luster as compared with the gold-colored non-woven fabrics (G1) (G2) (G3) obtained in the examples. When the resin layer was cut into ultra-thin sections with a microtome and observed with a transmission electron microscope, precipitation of dye microcrystals was observed. Similar fine crystals were similarly observed in the nonwoven fabrics obtained in Comparative Examples 1 to 3. However, nothing was observed for those obtained in Examples 1-6.

[0041]

[Table 1]

[0042]

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. Further, according to the production method of the present invention, it is not necessary to use an organic solvent or the like in a work environment, an exhaust facility, a solvent recovery facility, etc. are unnecessary, and it is industrially significant from the viewpoint of preventing fires 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.

Claims (10)

[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 copolyester resin layer thereon. 2. A fiber assembly having a metallic luster, which comprises a metal layer as a reflection film on the surface of fibers forming the fiber assembly, and a copolyester resin layer on the metal layer. 3. The fiber according to claim 1, wherein the copolyester resin is colored with a dye. 4. The fiber assembly according to claim 2, wherein the copolyester resin is colored with a dye. 5. The fiber assembly according to claim 2, wherein the pigment is a dye classified as an oil dye and / or a disperse dye. 6. The fiber assembly according to claim 2, wherein the pigment is a non-metal-containing dye. 7. The copolymerized polyester resin is 20 to 200.
The fiber assembly according to claim 2, which is a copolyester resin containing 0 mm equivalent / kg of an ionic group. 8. A metal thin film is formed on the surface of a fiber, and a polyester resin layer is formed on the film by using an aqueous dispersion of a polyester resin (colored with a hydrophobic dye if necessary). A method for producing a fiber having a metallic luster. 9. A metal thin film is formed on the fiber surface of the fiber assembly, and a polyester resin layer is formed on the film by using an aqueous dispersion of polyester resin (which is colored with a hydrophobic dye as necessary). A method for producing a fiber assembly having a metallic luster characterized by the above. 10. The fiber assembly is a synthetic fiber non-woven fabric,
The method for producing a fiber assembly having a metallic luster according to claim 9.