Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/34—Material containing ester groups
  • D06P3/52—Polyesters
  • D06P3/54—Polyesters using dispersed dyestuffs
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
  • D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/82—Textiles which contain different kinds of fibres
  • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
  • D06P3/8214—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing ester and amide groups
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/82—Textiles which contain different kinds of fibres
  • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
  • D06P3/8223—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups
  • D06P3/8238—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using different kinds of dye
  • D06P3/8252—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using different kinds of dye using dispersed and reactive dyes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/82—Textiles which contain different kinds of fibres
  • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
  • D06P3/8276—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing ester groups
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/22—Effecting variation of dye affinity on textile material by chemical means that react with the fibre

Definitions

• This invention relates to a polyester fiber dyeable with a disperse dye at a temperature of 95°C or less, and especially to a polyester fiber capable of effecting an even and ample dye absorptions of various dyes from a dye mixture making up a dye combination whereby the dyeing of the fiber can produce a superb color development with a dye combination (especially, a black dye combination) as good as the color development intended before dyeing.
• This invention also relates to a productive polyester fiber able to provide a superb color fastness to dry-cleaning, color fastness to light and superb thermal and mechanical properties with high productivity.
• This invention relates also to a piece dyed fabric of a fiber composite having excellent color development, color fastness and hand, in which the fiber composite is composed of the above-mentioned polyester fiber in combination with at least one fiber selected from a group consisting of cellulosic fiber, wool fiber, silk, stretch fiber, polyamide fiber and acetate fiber.
• the polyester fiber of the invention as well as the fabric of a fiber composite thereof affords useful textile materials for lining cloth, women's outer garments and women's underwears (foundation garments and lingerie).
• a fabric composed of a fiber composite in which a known polyester fiber is incorporated is difficult to dye by means of a one bath one step dyeing process because the dyeing temperatures for the respective fibers are far apart.
• the only conventionally practiced method is; a knitted or woven union fabric is first prepared by making use of polyester fiber dyed in the form of yarn or fiber, and thereafter wool fiber or silk is dyed with acid dyes.
• this dying system has a serious drawback in productivity and cost of dyeing because the method requires extremely complicated works to obtain diverse color effect. If dyeing is carried out under the normal pressure paying a due consideration to thermal stability of wool fiber or silk, polyester fibers cannot be dyed into a heavy or deep shade because conventional polyester fibers lacks dyeability.
• polyamide fiber has a soft hand and is dyeable under normal pressure.
• polyamide fiber is conventionally mixed with a stretch fiber as typified by polyurethane fiber and has been applied to making knitted sport wears, women's underwear including foundation garments and lingerie, swimwear, socks and the like.
• polyamide fiber has disadvantageous features: the fiber is susceptible to gases and/or light which readily give rise to yellowing of the fiber; when the fiber is used as covering yarn, slippage of the covering yarn is liable to occur due to its poor constraining force; the fiber lacks dimensional stability and a shape retention property or the like.
• a fiber mixture of a polyester fiber with a stretch fiber is used.
• Acetate fiber is a modified cellulosic fiber in which the hydroxyl groups are acetylated. Although the basis of its molecular structure is similar to cellulose, acetate fiber is not dyeable with direct and reactive dyes. Conventionally, dyeing of acetate fiber is done with disperse dyes under the normal pressure dyeing system. In the case high pressure dyeing at a temperature at above 100°C should be applied, thermaldegradation due to the hydrolysis of acetyl group tends to occur causing the fiber to lose its transparency (become milky white colored). It is known that this phenomenon tends to occur especially with diacetate fiber.
• polyester fiber To obtain a fabric of acetate fiber composite having an improved mechanical strength, dimensional stability with economical production, the combined uses of polyester fiber have been considered.
• a conventional polyester fiber of which dyeing temperature is high there are, however, problems in that acetate fiber becomes milky white colored (devertified turbid color) and stiff.
• dyeing carried out under normal pressure in which acetate fiber is thermally stable heavy shade dyeing of polyester fiber cannot be attained because a conventional polyester fiber lacks dyeability.
• any of the known polyester fibers having an improved dyeability with a disperse dye can exhaust only a certain specific dye from a dye combination in which various dyes are compounded, even though the fiber exhibits good dyeing properties with a specific single dye.
• the respective dye compounded in a dye combination differs in rate of dye exhaustion.
• the consequent color of a dyeing comes to differ in effect from the color which has been intended on the basis of a mixing ratio of respective dye components before dyeing. This problem is especially remarkable with a black dye.
• the known polyester fibers improved in dyeing properties have a problem in that black color development of dyeing differs from that intended before dyeing.
• polyester fibers in which copolyesters are used as a raw material.
• fibers composed of a polymer produced by copolymerizing with a polyoxyethylene glycol or adipic acid.
• Japanese Unexamined Patent Publications (Kokai) No. 3-40880, No. 3-174076, No. 4-41732 and No. 4-41738 there are disclosed polyethylene terephthalate fibers composed of a polymer in which only a polyoxyethylene glycol is copolymerized.
• the known fibers are polyester fibers composed of a polymer, in which 6 to 10% by weight of a polyoxyethylene glycol is copolymerized, and the fibers can be dyed at 98°C.
• the fiber has a low color fastness to light and a low dry-cleaning fastness because of the use of a high copolymerizing ratio of polyoxyethylene.
• the fiber can be dyed at 98°C, it cannot be dyed at 95°C. It may be said that there exists a serious difference between the dyeability at 98°C and the dyeability at 95°C in the sense of a commercial dyeing practice.
• Fine denier yarns are an unavoidably necessary product item with a view to provide the essential descriptions for applications such as linings or women's garments where a soft hand is very much required.
• the field of application will be very much limited due to the difficulty of preparing fine denier yarns. It is, therefore, to be noted that the known easily dyeable fiber yarns referred to above are still problematic in dyeability, color fastness to light, whiteness, polymerizing properties and spinnability.
• a polyester fiber from a polymer obtained by copolymerizing adipic acid and polyethylene glycol is also known (for examples, Japanese Unexamined Patent Publications (Kokai) No. 63-85111 and No. 63-235536).
• Japanese Unexamined Patent Publication No. 63-85111 there is disclosed a polyester fiber composed of a copolyester in which 0.5 to 10% by weight of polyether unit, and 0.5 to 10% by weight of dicarboxylic acid unit are copolymerized.
• a polyester fiber composed of a polymer in which 4% by weight of polyethylene glycol and 4% by weight of adipic acid is copolymerized, and there is further described that the fiber achieve a high rate of dye exhaustion with an anthraquine dye.
• the dye is easily adsorbed on the fiber since its molecular weight is relatively small (molecular weight: 349) among the conventional disperse dyes.
• the attainment of the high rate of dye exhaustion with this dye does not mean that the fiber can exhibit a high rate of dye exhaustion with all dyes.
• the fiber contains a smaller percentage by weight of adipic acid/by weight of polyethylene glycol, the fiber is difficult to dye with a dye combination of various dyes and has a tendency to have a poor color yield especially when the fiber is dyed with a black dye.
• the fiber exhibits a relatively high peak temperature (herein after called Tmax (°C) of the loss tangent values determined by measuring dynamic viscoelasticity of a fiber.
• Tmax peak temperature
• the parameter represents a relative magnitude of density of molecule in the amorphous portion of fiber.
• the fiber does not exhibit ease of dyeing with a dye combination of various component dyes, but it exhibits an ease of dyeing only with a limited single dye. For the reason set forth above, the fiber has still serious problems in conventional use.
• Japanese Unexamined Patent Publication (Kokai) No. 63-235536 there is described a polyethylene terephthalate fiber in which 6% by weight of polyethylene glycol and 5.1% by weight of adipic acid are polymerized.
• the fiber can have as high a rate of dye exhaustion with a single dye as the aforesaid fiber.
• the fiber still has problems in color fastness to dry-cleaning of the dyed fiber, whiteness, polymerizing properties, dyeability with a combination of various dyes, spinnability because of its high polymerizing ratio of polyethylene glycol and a high Tmax (°C) value.
• copolymerized polyester fibers from a copolymer obtained by copolymerizing glycols such as tetra-methylene glycol and 1, 4-cyclohexane diol(Japanese Unexamined Patent Publication No. 58-120815) and a polyester fiber obtained by high speed spinning of a copolymer copolymerized with 2, 2-bis [4-(2-hydroxy) phenyl] propane (Japanese Unexamined Patent Publication (Kokai) No. 59-199814).
• These polyester fibers obtained by those method mentioned above cannot be dyed at 95°C, though they are improved in dyeability.
• the carrier dyeing technique As attempts to modify dyeing methods or finishing methods, the carrier dyeing technique is known.
• the carrier dyeing technique itself has drawbacks in that it makes the waste dye bath treatment and dyeing work difficult because high boiling point organic substances such as phenol derivatives, chlorinated aromatic compound or biphenyl must be used.
• polyester fiber which has not only a capability of being dyed at 95°C or less with disperse dyes, but also has an excellent dyeability with a dye combination of various dyes. Even with known polyesters improved in rate of dye exhaustion to a certain degree, they still have problems in color fastness to dry-cleaning, thermal properties, polymerization properties and the spinnability.
• the object of the invention is to provide a polyester fiber capable of being dyed at 95°C or less with disperse dyes and having an excellent dyeability with a combination of various dyes and; further, a polyester having good properties pertaining to color fastness to dry-cleaning and to light, thermal and mechanical properties and; a polyester fibers capable of being converted by wet-processing including dyeing and finishing at an excellent productivity and; a piece dyed polyester fabric of polyester fiber composite exhibiting an superb color yield (color development), color fastness and hand in which the polyester fiber composite is composed of at least one fiber selected from the group consisting of cellulosic fiber, wool fiber, silk, stretch fiber and polyamide fiber.
• the objectives of the invention can be achieved by a fiber having a specific range of Tmax determined by measurement of the dynamic viscoelasticity which indicates the molecular density of the amorphous portion in a fiber, and making use of a polyethylene terephthalate copolymerized with a polyethylene glycol and dicarboxylic acid from which adipic acid is specifically selected in a an extremely limited range of copolymerizing ratios.
• the invention is embodied on the basis of this knowledge.
• the first feature of the invention is a polyester fiber characterized in that a copolymerized polyethylene terephthalate comprises 1.5 to 4.5% by weight of a polyethylene glycol having a molecular weight of 500 to 4000 and 9 to 6% by weight of adipic acid in a ratio satisfying 1.3 ⁇ % by weight of adipic acid/% by weight of polyethylene glycol ⁇ 6, and that the fiber satisfies a peak temperature of the loss tangent of 90 to 100°C.
• the second feature of the invention is a piece dyed fabric of a composite fiber containing the above-mentioned polyester fiber combined with cellulosic fiber.
• the third feature of the invention is a piece dyed fabric of a composite fiber containing the above-mentioned fiber and wool or silk.
• the fourth feature of the invention is a piece dyed fabric of a fiber composite containing the above-mentioned polyester fiber and a stretch fiber.
• the fifth feature of the invention is a piece dyed fabric of a fiber composite containing the above-mentioned polyester fiber and polyamide fiber.
• the sixth feature of the invention is a piece dyed fabric characterized in that a piece dyed fabric is composed of the above-mentioned polyester fiber and acetate fiber.
• a polymer constituting the polyester fiber in accordance with the invention is a copolymerized polyester comprising a polyethylene terephthalate copolymerized with 1.5 to 4.5% by weight of a polyethylene glycol having a molecular weight of 500 to 4000 and 9 to 6% by weight of adipic acid in a ratio satisfying 1.3 ⁇ % by weight of adipic acid/% by weight of polyethylene glycol % ⁇ 6.
• the two copolymerized components namely a polyethylene glycol and adipic acid are necessary.
• the dyeability herein is defined as dye the property of a fiber capable of developing a heavy shade dyeing in which a dye is absorbed adequately on the fiber; stated most simply, a dyeability can be estimated by a relative magnitude of rate of dye exhaustion from a dye bath containing the dye as exemplified in the Examples hereinafter.
• a polyethylene glycol used as a copolymerizing component is an extremely effective component for improving the dyeability.
• the molecular weight of the polyethylene glycol is less than 500, a content of the polyethylene glycol unit in the resultant polymer cannot be kept at a prescribed content because a fairly large amount of low molecular weight polyethylene glycol contained in a conventionally available raw polyethylene glycol fractionally removed in the course of polymerization under a high vacuum.
• the resulting fiber as an ultimate product tends to fluctuate in properties such as tensile properties, dyeability, thermal properties or the like.
• the mean molecular weight exceeds 4000, the dyeability and color fastness to light deteriorate due to an increase in high molecular weight polyethylene glycol which remains unpolymerized in the resultant polymer.
• Adipic acid used as the copolymerizing component can do much towards producing adequate disorder in the amorphous structure of the fiber. It is needless to say that an aliphatic dicarboxylic acid component other than adipic acid (number of carbon atoms 6) can be effective as a comonomer which can produce disorder in the amorphous portion for improving the dyeability. However, with an aliphatic dicarboxylic acid having 5 carbon atoms, thermal stability of the polymer deteriorates and the whiteness is lowered. It may be said in this connection that the deterioration in thermal stability becomes greater in proportion to the mole number of the ethylene group adjacent to carboxyl group.
• adipic acid is an extremely excellent copolymerizing component is effective in a limited range narrow range. It may be postulated that the whole length of 4 methylene groups contained in adipic acid is substantially equal to the length of the benzene nucleus of telephthalic acid.
• the amorphous structure is disordered by the presence of bendable group in the polyester fiber used in the invention, the degree of the disorder is brought to a minimum whereby the polyester fiber used in the invention becomes a modified polyester fiber of which the properties such as the thermal property are most closely alike those of a polyethylene terephthalate fiber.
• the amount of polyethylene glycol required to ensure a sufficient dyeability with a disperse dye ranges from 1.5 to 4.5% by weight. When the amount of polyethylene glycol is less than 1.5% by weight, the dyeability become impaired. When the amount of polyethylene glycol exceeds 4.5% by weight, color fastness to light becomes deteriorated, and, in addition, the polymer is difficult to polymeric due to the occurrence of discoloration of the polymer in the course of polymerization and the occurrence of a bumping or bubbling phenomenon in the polymerization vessel under a high vacuum. Still further problems in spinnability with this polymer are the difficulty of spinning fine denier yarn and the occurrences of yarn breakage and the high rate of forming fluffy yarn. The most preferred amount in which the dyeability, color fastness, operability of polymerization and spinnability are all compatible with each other, ranges from 2 to 4% by weight.
• the most suitable amount of adipic acid is 9 to 6% by weight, though it varies depending on the amount of polyethylene glycol. Where the amount of adipic acid is less than 6% by weight, the dyeability at 95°C is not satisfactory. However, where the amount exceeds 9% by weight, thermal resistance deteriorates and the resultant fabric has a stiff handling.
• a practically advantageous polymer cannot be attained unless selection is made of a polymerization ratio by which the resulting polymer can exhibit a balance between the dyeability and color fastness concurrently with a good polymerizability and spinnability.
• the deterioration in color fastness to light, color fastness to dry cleaning, dyeability, polymerizability and spinnability and reduced polymerizability can be successfully suppressed by carrying out a copolymerization in which a suitable amount of adipic acid, instead of using a large quantity of a polyethylene glycol is used.
• the ratio of adipic acid to a polyethylene glycol is extremely critical condition for attaining an enhanced dyeability not only with a single dye, but also with a dye combination in which various disperse dyes are compounded.
• Such a copolymerization composition needs to satisfy a ratio of 1.3 ⁇ % by weight of adipic acid/% by weight of polyethylene glycol ⁇ 6 (hereinafter called R value). With an R value less than 1.3, color fastness to light as well as color fastness to dry-cleaning deteriorates due to an increased ratio of polyethylene glycol in the case where a polyethylene glycol and adipic acid are copolymerized in amounts sufficient to attain a dyeing property under normal pressure dyeing.
• a preferred value for R is 1.7 to 6, more preferably 1.7 to 4.
• polyester fiber used in the invention other copolymerizable components capable of forming a polyester such as another kind of diol and oxycarboxylic acid can be incorporated in an amount of 10% or less, preferably 5% or less by weight.
• these optionally incorporated components should not deteriorate in color fastness of a dyed fiber.
• additives for example, a delustering agent, a thermal stabilizer, an antifoaming agent, a flame retardant, an ultra-violet absorbing agent, an infra-red ray absorbing agent, a nucleating agent and a fluorescent whitening agent can be incorporated by colymerizing or blending if case of needed.
• the polymer forming the polyester fiber of the invention can be prepared using a conventional process for polymerization of a polyethylene terephthalate; by copolymerizing by mean of adding, for example, a polyethylene glycol and adipic acid in itself or in the form of its lower alkylester such as monomethyl ester, dimethyl ester, diethyl ester, bis (oxyethyl) ester and the like to the reaction system at any stage before the termination of condensation polymerization.
• these copolymerizing components can be added in the component compounds in themselves or in a dissolved or dispersed form in a suitable solvent such as ethylene glycol, after being heat-treated as the case may be.
• a representative process of polymerization is herein described; an ester exchange reaction between dimethyl terephthalate and dimethyl adipate is carried out in ethylene glycol in the presence of a catalytic amount of manganese acetate, calcium acetate or cobalt acetate at a temperature of 200 to 240°C to ethoxylate the respective terminal groups of telephthalic and adipic acids.
• the termination is determined by the moment when the theoretical amount of methanol is liberated.
• a polyethylene glycol and antimony trioxide which is a catalyst for condensation polymerization and the polymerization is carried out at a temperature of 260 to 290°C under a vacuum.
• the polyester fiber of the invention must have a peak temperature of the loss tangent of 90 to 108°C which is determined by dynamic viscoelasticity measurement. The reason for this is that a dyeability as intended by the invention can be ensured in this range. Since Tmax corresponds to a density of molecule in the amorphous portion, the smaller the value becomes, the smaller the density of molecule in the amorphous portion widening the gap (interstices) for the easy entry of dye which causes a rate of dye exhaustion to increase.
• a polyester of the invention not only attains the dyeability at 95°C with a single dye, but also exhibits an excellent dyeability with every diverse disperse dye when dyeing is carried out with a dye combination of various disperse dyes; and a color development as intended prior to dyeing can be attained in consequence. Especially, a black color development becomes extremely superb when dyeing is carried out with a black dye.
• Tmax value represents the fiber structure
• value of Tmax is brought to be different depending not only on spinning conditions such as spinning temperature, spinning speed and draw ratio and but also textile converting processes conditions such as heat-treatment, scouring and alkali reduction processing even when copolymer is composed of the same composition.
• the Tmax value is broadly changed by heat setting temperature, it is important to keep the Tmax range within the above range.
• Tmax becomes gradually higher with a heat setting temperature within the range from room temperature to 160°C, however, it lowers remarkably as temperature exceeds about 160°C. Since the proportion of these changes differs from copolymerization composition to composition, Tmax should be determined by considering the relationship between Tmax and the heat-setting temperature. In accordance with the invention, when Tmax become greater than 108°C, improvement in the dyeability is too small to attain an adequate dyeability at 95°C. However, not all low Tmax values are acceptable because of disadvantage to the effect that the ease of entry of dye into the fiber and ease of stripping off of dye occurs concurrently due to the formation of loose amorphous portions.
• Tmax ranges from 90 to 110°C, preferably from 95 to 105°C.
• the melting point of the polyester fiber of the invention is in a range from 230°C to 245°C.
• the polyester fiber suffers from a thermal degradation in conventional processing or daily use as typified by heat-setting or ironing where the fiber is changed in its physical properties and hand. If the melting point exceeds 245°C, the spinnability is deteriorated. Since the polymer forming the polyester of the invention is of a special composition, the spinning temperature for attaining satisfactory spinning needs to be maintained in a range from about 255°C to about 250°C at the spinneret face. When a melting point of a polymer exceeds 245°C, it becomes difficult to maintain this temperature at the spinneret face, because the temperature of extruder for melting the polymer should be raised.
• the polyester fiber of the invention can be prepared either by a conventional process in which an undrawn yarn is draw-twisted at a draw ratio ranging from about 2 to 3.5 times at a winding speed of 1,500 m/min., or by a spin-draw process in which spinning stage and draw-twisting are continuously coupled.
• the fiber may be prepared by making use of a high speed spinning process in which a winding speed of 5,000 m/min or more is used, however this process may not be preferred because the orientation of amorphous portion becomes much lowered (hence, Tmax is much lowered) so that color fastness is much lowered.
• the spinning conditions are not limitative. Spinning can be carried out using any known condition except that the spinneret face temperature needs to be regulated.
• the spinneret face temperature is in a range from about 255°C to about 270°C.
• the temperature is less than 255°C, the spinning at such a low temperature results in the occurrence of slub in the yarn which creates a number of yarn breakages.
• spinning is possible at a temperature between from about 270°C to about 300°C, the spinning at such range of temperature, however, encounteres a number of yarn breakages with an increased rate of development of fluffy yarn because of the occurrence of yarn bending.
• a K/S which represents a color yield obtained when the fiber is dyed at 95°C is 20 or more.
• the method for measuring K/S is in accordance with that described in the Examples of the invention.
• the dye used for estimation of dyeability has a large molecular structure (molecular weight of 518). Accordingly, if an enhanced dyeability is attained with the use of this dye, an enhanced dyeablity can be ensured regardless of the kinds of disperse dye.
• an enhanced dyeability is meant a K/S of 20 or more in this case.
• a dyeing having a K/S of 20 or more exhibits a color development as good as the polyester fiber that has been dyed at 130°C.
• Such a color development can generally be attained when a rate of dye exhaustion reaches about 75% or more.
• color fastness to dry-cleaning is evaluated in reference to liquid staining.
• the method for the evaluation is discussed in Example.
• the items of color fastness cover a variety of evaluation items including color fastness to water, color fastness to laundry, color fastness to sublimation, color fastness to rubbing and the like.
• the color fastness of all the various items required in practice including color fastness to water, laundry, sublimation, rubbing and the like excepting color fastness to light for the polyester fiber of the invention can be rated as having ratings satisfying the commercially acceptable level in the case where the color fastness to dry-cleaning is rated at grade 3 or higher. Accordingly, the color fastness to dry-cleaning can be an index representing the entire color fastness properties of the polyester fiber of the invention. Therefore, a dyed article of which color fastness is rated as grade 3 or higher is determined to have a good color fastness properties in practice. For a dyed article enabling use for outer garments, color fastness to light should be rated as being grades 3 to 4, preferably 4 or higher under the dyeing conditions specified in the invention.
• the dyed fabric of a fiber composite of the invention is characterized in that a dyed fabric is composed of polyester fiber of the invention and at least one kind of fiber selected from the group consisting of cellulose fiber, wool fiber, silk, stretch fiber, polyamide fiber acetate fiber.
• the form of the polyester fiber of the invention and mixing method of the fiber of the invention are not specifically limited; namely, any known method can be used.
• a method for preparation of the fiber composite includes, for example, a woven fabric such as union in which the polyester fiber is used either in warp yarns or in weft yarns, reversible woven fabric, knitted fabric such as tricot and rashel fabric, and further use of doubling of yarn, plaiting and entangling can be employable.
• Cellulosic fiber used in the invention is not specifically limited, and includes natural fibers such as cotton fibers, linen or ramie, cuprammomium rayon, viscose rayon, polynosic and the like.
• the ratio of the polyester fiber component is not limited and a preferred content of the polyester fiber is in a range from 25% to 75% to make the best use of the characteristic hand, hygroscopicity, water absorbency and anti-electricity provided by cellulosic fibers.
• Wool fiber and silk used in the invention can be of the fiber as conventionally available.
• the content of the polyester fiber is not specifically limited in a fabric of the fiber composite, however, a preferred content of the polyester fiber is in a range from 25% to 75% to make the best use of the characteristic nature of wool fibers such as the hand touch, warmness and bulkiness or the characteristics of silk such as the hand and kishimi sound.
• the stretch fiber usable in the invention is not specifically limited, and includes dry- or melt-spun polyurethane fiber, polybutylene telephthalate fiber, polyester type elastic fiber which are typified by polytetramethylene glycolether copolymerized polybutylene telephthalate fiber and the like.
• a preferred content of the polyester fiber is in a range from about 60% to about 98%.
• a content of the polyester fiber exceeds 70%, it can be used for producing outer garments and casual wear because the stretch properties become suppressed.
• a content of the polyester is less than 70%, it can be used for producing such end-use articles as women's underwears, foundation garments, swimwear and the like.
• the polyamide fiber usable in the invention can be nylon 66 and nylon 6 in which an amide group is substantially contained; and as conventionally available fiber can be used.
• Content of the polyester fiber is not specifically limited in the fabric of the fiber composite, however, a preferred content of the polyester fiber is in a range from 25% to 75% for making the use of characteristic hand touch peculiar to polyamide.
• the acetate fiber usable in the invention can be either diacetate fiber or cellulose triacetate fiber.
• the best use of the advantageous merit of the invention can be made by a fiber composite containing diacetate fiber which lacks thermal stability. Since acetate fiber is dyed with a disperse dye as in the dyeing of polyester fiber, a fiber composite composed of acetate fiber combined with the polyester fiber of the invention can be dyed at a temperature below 95°C to attain a processed article with a good hand touch at a reduced dyeing cost.
• content of the polyester fiber in the composite fiber fabric is not limited, it is preferred that the content of the polyester fiber is preferably in a range from 25% to 70% for making the best use of the hand, brightness of color and luster provided by acetate fiber.
• the dyed fabric of the fiber composite of the invention can be incorporated with a fiber other than the fibers not specified in the invention unless the object of the invention is impaired. It is permissible that a small amount of wool fiber, silk, viscose rayon, cuprammonium rayon, polyamide fiber, polyacryl fiber, acetate fiber or acrylic fiber may be jointly used. In this case, it is possible that an addition of physical properties characteristic of a jointly used fiber can be made.
• the dyeing of fabric of the fiber composite can be obtained by carrying out knitting or weaving the fabric followed by a conventional scouring and subsequent dyeing.
• the fabric may be processed by a conventional caustic reduction treatment after scouring and before dyeing.
• the scouring is carried out at a temperature between 60 and 98°C.
• scouring is carried out while allowing relaxation to ensure an improvement in elasticity.
• Dyeing is carried out without use of carrier at a temperature of 95°C or less with a disperse dye for the polyester fiber of the invention; with a direct dye or reactive dye for a cellulosic fiber; with a disperse dye for acetate fiber; with an acid dye for wool fiber, silk or polyamide fiber.
• the most preferred method is the one bath one step dyeing at a temperature of 95°C or less in order to give the advantageous merits full play.
• a one-bath two step dyeing system as well as two-bath two step dyeing system may be used. After dyeing is terminated, a conventional soaping or reduction clearing is applied.
• a disperse dye staining the polyurethane fiber should have to be fully removed by application of a reduction cleaning.
• these methods can be known methods. If there is required a heat-setting treatment before or after dyeing, the heat-setting treatment is done at a temperature between 140 to 190°C, preferably between 160 and 180°C under dry setting conditions.
• the dyeing of a fabric of fiber composite can be obtained by carrying out dyeing at a temperature of 95°C or less. For this reason, the troubles with deterioration in strength of wool fiber and silk, the yellowing of polyamide fiber, the thermal degradation of polyurethane fiber and the devetrification (delustering) of acetate fiber are eliminated. Besides, dyeing can be carried out at a temperature of 95°C or less where no degradation of the dyes takes place, and, as a result, a bright color dyeing can be attained.
• the loss tangent (tan ⁇ ) and dynamic elasticity were measured at respective temperatures at a measuring frequency of 110 Hz in a dried air while temperature was raised at a rate of 5°C/min. From the results, a loss tangent-temperature curve was drawn to find a Tmax which is the peak temperature Tmax (°C) of a loss tangent on the curve. The measurement was performed at a rate of at a rate of 5°C/min. and at a measuring frequency of 110 Hz.
• the melting point was measured in a nitrogen gas flowing at a flow rate of 100 ml/min., while the temperature was raised at a rate of 20°C/min. The peak value of fusing was determined as the melting point.
• a one feeder single circular knitted fabric was used as a specimen.
• the knitted fabric was scoured at 70°C in a lukewarm water containing Scourol 400 at 2 g/l for 20 minutes, and dried in a tumbling dryer, and subsequently heat-set at 180°C for 30 seconds on a pin tenter.
• the rate of dye exhaustion was estimated by finding the dye exhaustion in a dye bath which had been maintained for 1 hour after the bath temperature was raised from 40°C to 95°C.
• the dye used was Kayalon Polyester Blue 3RSF (a product available from Nippon Kayaku Co., Ltd.: molecular weight, 518; Color Index Blue 257).
• the dyeing was carried out in a dye bath containing 6% owf of the dye with a liquor to goods ratio 50:1.
• the dye bath contained Nicca Sunsalt 7000 (a dispersing agent from Nicca Chemical Co., Ltd.) at 0.5 g/l and acetic acid 0.25 g/l and sodium acetate at 1 g/l were added to adjust the pH to 5.
• a one feeder single circular knitted fabric of polyester fiber was used for a specimen. Three pieces of the same knitted specimen were laid one on top of another. A measurement was performed on the three thickness using a color computer (SM-4) available from Suga Test Instruments Co., Ltd.
• a test piece having a size of 16 cm length by 2.5 cm width was fixedly secured between chucks at a distance of 10 cm on a tensile tester.
• An elongation-recovery curve was drawn up to an elongation of 80%, from which a residual elongation (L') was read. The value was determined according to the following formula in which L is defined as 80%.
• PEG1000 polyethylene glycol having a molecular weight of 1000
• PEG1000 polyethylene glycol having a molecular weight of 1000
• 0.1 parts of titanium dioxide as a delustering agent 0.16 parts of antimony trioxide as a condensation polymerization catalyst
• prepolymerization was then carried out over 50 minutes.
• the composition of the obtained polymer contained a PEG 1000 component of 2% by weight and DMA of 7% by weight.
• the dried chips were spun at a spinning temperature of 270°C at a spinning speed of 1500 m/min using a spinneret having 36 holes each having a circular cross section to prepare an undrawn yarn.
• the resultant undrawn yarn was then draw-twisted at a draw ratio of 2.8 times over a hot roll at 80°C and hot plate at 160°C at a winding speed of 800 m/min to produce a drawn yarn of 75 denier/36 filaments; the yarn had a strength of 5.1 g/d, an elongation of 31% and a Tmax of 103°C.
• the dyeability of the polyester of the invention can be evaluated by comparing it with the dyeability exhibited by a polyethylene terephthalate fiber (Tmax: 136°C) spun by a commonly accepted spinning (so called conventional process in which the undrawn yarn which is once wound is drawn) which is dyed at 130°C for 60 minutes with a blue disperse dye.
• Tmax polyethylene terephthalate fiber
• conventional process spun by a commonly accepted spinning (so called conventional process in which the undrawn yarn which is once wound is drawn) which is dyed at 130°C for 60 minutes with a blue disperse dye.
• the dyeing does not show color degradation and liquid staining was evaluated as grade 4. Moreover, the dyeing had a good color fastness of the dye in various items of evaluations; color fastness to light (grade 4), color fastness to dry and wet rubbing (grade 5), color fastness to water (grade 5), color fastness to laundering (grade 5) and color fastness to sublimation (grade 4).
• Example 1 was repeated with varied molecular weights of polyethylene glycols; 2000, 3000 and 4000.
• the resultant polyester had the same properties as those in Example 1.
• the range of K/S is from 21.5 to 21. 7 showing no significant difference from those in Example 1.
• both color fastness to dry-cleaning and color fastness to light were rated as grade 4.
• Polyester fibers composed of various copolymerized compositions as given in Table 1 were prepared and subjected to various items of evaluations. Any copolymerized composition out of the scope of the invention exhibits cannot be acceptable for practical use because these fibers lack dyeability, color fastness or other properties.
• Comparative Example 2 and 5 there were often encountered bumping phenomena in the polymerization under an extremely high vacuum, and the content in the vessel moved into the vacuum pipe line. In the event where bumping was violent, the apparatus needed to be disassembled for cleaning. Yellowing also occurred in the obtained polymer.
• the one feeder single circular knitted fabric in Examples 3 and 4 were dyed with 5% owf of Sumikalon Black S-BF (a disperse dye, available from Sumitomo Chemical Co. Ltd.) in a dye bath at a pH of 6 with a liquor to fiber ratio of 50:1 in the presence of Nicca Sunsalt 7000, a dyeing auxiliary (available from Nicca Chemical Co., Ltd.).
• the dyeing was carried out at 95°C. L values (brightness) of the resultant dyeings were 15.5 and 15.3 respectively presenting good black dyeing in adequate heavy shade.
• a black dye is generally a dye combination (dye compounded mixture) in which three kinds of dyes have different respective maximum peak absorbencies at 400 nm, 500 nm and 580 nm.
• the spectroscopic absorbency of the dye bath at the termination of dyeing was measured and it was found that almost no peak absorbencies remained at the three spectrums.
• the polyester fiber of the present example when being dyed with a dye combination, exhibits a good rate of dye exhaustion with respective component dyes.
• the fiber out of the scope of the invention does not show a fluctuation of high rate of dye exhaustion with respective component dyes.
• a plain weave woven fabric was prepared using a polyester fiber of 75d/72f produced in the same manner as in Example 1 for warp yarn and cuprammonium rayon of 75d/44f for filling yarn.
• the fabric was scoured by a conventional method and then mercerized.
• the mercerizing treatment was carried out by dipping the fabric in a caustic soda solution containing 75% of sodium hydroxide at room temperature. After neutralization, washing with water and subsequently heat-setting at 180°C for 30 seconds, one bath one step dyeing with a disperse dye and a reactive dye was carried out in the absence of a carrier.
• a dye bath was prepared by adding the dyes in a solution adjusted at pH 11 containing Disper TL, a dispersing agent (available from Meisei Chemical Works, Ltd.) at 1 g/l, sodium sulfate at 50 g/l and of sodium carbonate at 15 g/l. Dyeing was carried out at 95°C with a bath containing 2 owf of the dye in 50:1 liquor ratio for 1 hr.
• the dyed fabric was soaped at 80°C in a bath containing Granup P (available from Sanyo Chemical Industries Ltd.) at a concentration of 1 g/l with a bath ratio of 50:1 for 10 minutes.
• Granup P available from Sanyo Chemical Industries Ltd.
• the dyed fabric was finally finished in a conventional manner.
• the resultant dyed fabric was evenly dyed and had a nice hand; the K/S value was 21.5; and the color fastness to dry-cleaning and color fastness to light were both rated as grade 4.
• Example 7 Using the polyester fiber in Comparative Example 4, Example 7 was repeated. The resultant dyeing was not an even dyeing. This is because the polyester fiber has a low developability of color due to its low dyeability.
• Example 7 Using the polyester fiber in Example 6, Example 7 was repeated. The resultant dyeing was evenly dyed. However, color fastness to dry-cleaning as well as color fastness to light was evaluated as grade 2 - 3 which is not acceptable in commercial practice. Since the fiber is a fine denier fiber of 75d/72f, a lot of fluff occurred in the resultant dyeing.
• a polyethylene terephthalate fiber copolymerized with 4% by weight of PEG 1000 and 7% by weight of DMA was twisted under heat to produce a torque type bulked textured yarn.
• the conditions for texturizing were: heating plate temperature, 195°C; number of twists at twisting, 3400 times/m; feeding ratio, -0.2%.
• the obtained textured yarn was doubled to form a yarn having a denier of 150, and was knitted with a wool yarn having a yarn count of 48 Nm to produce a reversible double-faced union fabric with polyester on top and wool on the back.
• the mixed ratio of the polyester fiber in the union fabric was 48% by weight.
• the knitting conditions are: 20 gauge; diameter of needle bed, 20 inches.
• the knitted fabric was, then, dyed according to a conventional method.
• Dianix Black BGFS (200% grade; available from Dystar Japan Co. Ltd.) as the disperse dye and Kayalon Black BGL (Nippon Kayaku Co. Ltd.) as the acid dye were used.
• One bath one step dyeing was carried out at 95°C applying 7% owf of the respective dyes in a slightly acidic bath in the presence of a dispersing agent. After dyeing, the dyeing was soaped at 70°C in a slightly alkaline bath containing soda ash at 1 g/l and nonionic detergent at 0.5 g/l for 20 minutes. The resulting dyeing had a L value (brightness) of 11.8, a superb value. The lower the brightness, the heavier the shade of black dyeing is obtained. The dyeing was rated as grade 4 in both color fastness to dry-cleaning and color fastness to light.
• Polyester fibers having the copolymerizing composition given in Table 2 were subjected to various items of evaluations.
• the fibers in which copolymerizing compositions were outside the invention had problems with either dyeability or their color fastness.
• Examples Compositions (% by weight) R value L value Color fastness to light (grade) Color fastness to dry-cleaning (grade) PEG1000 DMA 9 4 7 1.8 11.8 3 - 4 4 10 2 8 4.0 11.9 4 4 11 3 7 2.3 11.9 4 4 12 2 7 3.5 11.8 4 4 4
• a plain weave fabric was made using silk yarn (21d/2f) as filling yarns.
• Dianix Black BGFS (200% grade; available from Dystar Japan Co. Ltd.) as the disperse dye and Kayalon Black BGL (Nippon Kayaku Co., Ltd.) as the acid dye were used.
• One bath one step dyeing was carried out at 95°C applying 7% owf of the respective dyes in a slightly acidic bath in the presence of a dispersing agent. After dyeing, the dyeing was soaped at 70°C in a slightly alkaline bath containing soda ash at 1 g/l and nonionic detergent at 0.5 g/l for 20 minutes. The resulting dyeing had a L value (brightness) of 11.1, a superb value. The lower the brightness, the heavier the shade of black dyeing is obtained. The dyeing was rated as grade 4 in both color fastness to dry-cleaning and color fastness to light. The dyed goods had the superb hand peculiar to silk.
• Example 13 With the exception that a polyethylene terephthalate fiber was used, Example 13 was repeated. An L value of 15.3 was obtained. The polyester fiber was dyed only to a pale shade. When dyeing was done at a dyeing temperature of 130°C, an L value of 11.5 was reached; the dyed goods lost the hand peculiar to silk and had a stiff hand.
• a knitted fabric was produced using a polyurethane stretch fiber having a denier of 210, Roica (a product of Asahi Chemical Industries Co., Ltd.) and a polyethylene terephthalate fiber (50d/36f) having a trilobal shaped cross section comprising 4% by weight of PEG 1000 and 7% by weight of DMA as copolymerizing components.
• the knitting particulars were: a knitting gauge of 28GG and a loop length of 1080 mm/480 courses for the normal pressure dyeable yarn and 112 mm/480 courses for the stretch fiber.
• the mixed ratio of the polyester fiber was selected at 75.5%.
• the grey knitted fabric was scoured in a relaxed state at 90°C for 2 minutes and thereafter dried at 160°C for 1 minute.
• Dyeing was carried out at 95°C for 60 minutes with 8% owf of Dianix Black FS (available from Dyestars Japan Co., Ltd.) in the presence of Nicca Sunsalt 1200, a dyeing assistant, at a concentration of 0.5 g/l in a dye bath at a pH of 6 adjusted by acetic acid with a bath ratio of 30:1.
• the resulting dyeing had a value (black brightness value) of 12.3, and adequate color development.
• the dyeing had an elastic recovery of 95.3%, and color fastness to laundering was rated as grade 5 and color fastness to light was rated as grade 4.
• the resulting dyed goods had a soft, pliable and resilient hand.
• Example 14 was repeated by varying the copolymerizing compositions. In every case, the resultant dyed goods exhibited a superb color development, good color fastness and a good elastic recovery and had a soft, pliable and resilient hand.
• Example 14 was repeated using polyethylene glycols differing in their molecular weights; 2000, 3000 and 4000.
• the properties of the resultant dyed goods were almost the same with those of Example 14.
• black lightness value of the resultant dyeing fell within a range from 12.8 to 12.4 showing sufficient development of color.
• the dyeing had an elastic recovery of 95%, and color fastness to laundering was rated as grade 5 and color fastness to light was rated as grade 4.
• the resultant dyed goods had a soft, pliable and resilient hand.
• a warp knitted fabric was made from Roica and a polyethylene terephthalate fiber obtained by a conventional spinning process and dyeing was carried out at 95°C for 60 minutes.
• the resultant dyeing had an L value of 18.3 showing an inadequate black color development.
• an L value of 12.4 was attained.
• the magnitude of bursting strength of the dyed fabric fell to as low as 2/3 of that of the grey fabric and that the elastic recovery fell to as low as 65% of that of the grey fabric.
• a plain weave fabric was made using the yarn as warp and a folded yarn consisting of 3 ends of nylon 66 yarn having a denier of 50d/96f as filling yarn.
• One bath one step dyeing was carried out at 95°C applying 5% owf of the respective dyes in a slightly acidic bath in the presence of a dispersing agent. After dyeing, the dyeing was soaped at 70°C in a slightly alkaline bath containing soda ash at 1 g/l and nonionic detergent at 0.5 g/l for 20 minutes. The resultant dyeing had a K/S value of 21.0, a superb value. The ratings of both color fastness to dry-cleaning and color fastness to light were grade 4. The dyeing had a soft hand touch and a superb match of color with that of nylon 66 was obtained.
• Example 19 Except that a fiber (75d/72f) composed of a polyethylene terephthlate copolymerized with 2% by weight of PEG 1000 and 8% by weight of polyethylene terephthalate fiber, Example 19 was repeated.
• the obtained dyeing has a K/S of 21.0 and the rating of color fastness to dry-cleaning was grade 4 and that of color fastness to light was grade 5.
• Hand of the dyeing was superb. It exhibited a soft hand touch and superb match of color with nylon 66 was attained.
• One bath one step dyeing was carried out at 95°C applying 5% owf of the respective dyes in a slightly acidic bath in the presence of a dispersing agent. After dyeing, the dyeing was soaped at 70°C in a slightly alkaline bath containing soda ash at 1 g/l and nonionic detergent at 0.5 g/l for 20 minutes. The resultant dyeing had a K/S value of 21.1, a superb value. The ratings of both color fastness to dry-cleaning and color fastness to light for the dyeing were grade 4. The dyeing had a soft hand touch and was superb in vividness of color.
• Example 21 Except that a fiber (75d/72f) composed of a polyethylene terephthalate copolymerized with 2% by weight of PEG 1000 and 8% by weight of DMA, Example 21 was repeated.
• the obtained dyeing has a K/S of 20.2 and the rating of color fastness to dry-cleaning was grade 4 and that of color fastness to light was grade 5.
• the hand of the dyed goods was superb.
• the ratings of color fastness to dry-cleaning and color fastness to light of the dyed goods were grade 4.
• the dyeing had a soft hand and was superb in vividness of color.
• Example 21 Except that use was made of polyethylene terephthalate fiber and that dyeing was carried out at 130°C, Example 21 was repeated. Although the obtained dyed goods has a K/S of 21.5, the dyeing presented a dull color development and its hand lacked softness.
• the polyester fiber of the invention can be dyed with a disperse dye at a temperature of 95°C or less in a depth of shade required in the commercial dyeing practice.
• the thermal properties and color fastness of the dyed goods can be matched for the level obtainable by a dyeing of the conventional polyester fiber, for example, in color fastness to dry-cleaning and color fastness to light.
• the polyester fiber of the invention can exhaust individual dye components composing a dye combination evenly without effecting differential dye exhaustion in dyeing with a disperse dye combination in which various disperse dyes are compounded thereby enabling a fabric to be dyed in a color and depth of shade identical with those normally intended by a dye combination commercially available, for example, a black dye for black dyeing.
• the composite fiber fabric composed of the polyester fiber of the invention mixed with cellulosic fiber, wool fiber, silk, polyamide fiber or stretch fiber in combination can be piece-dyed substantially at a normal practical dyeing temperature for any of the mixed fibers whereby all the fiber composing the fabric can be dyed. Accordingly, the piece dyed goods of polyester fiber composite in which properties of fiber having a poor thermal stability remain undamaged can be provided by an exceedingly productive means.

Landscapes

• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Dispersion Chemistry (AREA)
• Artificial Filaments (AREA)
• Coloring (AREA)

Applications Claiming Priority (3)

Publications (2)

Family

ID=16323904

Family Applications (1)

Country Status (4)

Cited By (7)

Families Citing this family (2)

Citations (2)

Family Cites Families (3)

• 1996
  • 1996-07-30 TW TW085109411A patent/TW320655B/zh active
  • 1996-07-31 EP EP96925962A patent/EP0843030A4/fr not_active Withdrawn
  • 1996-07-31 WO PCT/JP1996/002160 patent/WO1997005308A1/fr active IP Right Grant
  • 1996-07-31 KR KR1019980700674A patent/KR19990036010A/ko active IP Right Grant

Patent Citations (2)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events