CN1863951A - Vinyl chloride based fiber and method for production thereof - Google Patents
Vinyl chloride based fiber and method for production thereof Download PDFInfo
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- CN1863951A CN1863951A CNA2004800287275A CN200480028727A CN1863951A CN 1863951 A CN1863951 A CN 1863951A CN A2004800287275 A CNA2004800287275 A CN A2004800287275A CN 200480028727 A CN200480028727 A CN 200480028727A CN 1863951 A CN1863951 A CN 1863951A
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- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- 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
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
- D01F6/10—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polyvinyl chloride or polyvinylidene chloride
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/04—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons
- D10B2321/041—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons polyvinyl chloride or polyvinylidene chloride
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
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- Textile Engineering (AREA)
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- Artificial Filaments (AREA)
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Abstract
A vinyl chloride based fiber which comprises a vinyl chloride based resin composition comprising 100 parts by mass of (a) a vinyl chloride based fiber, 0.2 to 5.0 parts by mass of (b) a hydrotalcite based heat stabilizer and 0.2 to 10.0 parts by mass of (c) an epoxy compound. Incorporation of 0.2 to 10.0 parts by mass of (c) an epoxy compound into the above vinyl chloride based resin composition improves the dispersibility of the hydrotalcite based heat stabilizer, which results in the securement of a long-running continuous operation of a melt spinning process and in the achievement of good and stable productivity in the case of the use of a hydrotalcite based heat stabilizer, and also allows the production of a vinyl chloride based fiber exhibiting reduced discoloration when heated in a step of curling.
Description
Technical field
The present invention relates to vinyl chloride based fiber in the gloss with the hair that is similar to the people, color and the feel making wig sheath (wig), part wig (hairpiece), plait (braid), use when refuting clockwork spring hair decorated articles such as (extension hair).
Background technology
In the past, vinyl chloride resin carried out spinning and the vinyl chloride based fiber that obtains because the transparency and flexibility excellence, therefore mostly as the fiber for artificial hair use that constitutes the hair decorated articles.This fiber for artificial hair of industrial manufacturing has the method for using solvent and the method for not using solvent.As above-mentioned the method for solvent " use ", known have wet type spin processes and a dry spinning method, and in addition, as above-mentioned " not using the method for solvent ", known have a melt spinning method.
Because vinyl chloride resin melt viscosity height, and stringiness is extremely low, therefore, has the problem that is difficult to the melt spinning vinyl chloride resin and makes the vinyl chloride fibers of certain quality.And, because vinyl chloride resin fractures under hot environment, perhaps tanned by the sun in daylight or ultraviolet following time, in the vinyl chloride-base polymer that constitutes vinyl chloride resin, produce dehydrochlorination reaction, therefore, there is following problem in the vinyl chloride based fiber that is made of vinyl chloride resin: (1) initial coloring is poor, (2) make commodity value reduce in strong fiber, (3) of yellowing accent easily sometimes.
Therefore, in order to solve such problem, a kind of vinyl chloride based fiber has been proposed, this vinyl chloride based fiber comprises vinyl chloride resin composition, described vinyl chloride resin composition is polyvinyl chloride-base mixture 100 weight portions that constitute with respect to by 100～60 weight % vinyl chloride resins and 0～40 weight % chlorinated vinyl chloride resins, cooperates the ethene-vinyl acetate resinoid of (a) 1～35 weight portion, the heat stabilizer of (b) 0.2～5.0 weight portion, the lubricant of (c) 0.2～5.0 weight portion to form (with reference to patent documentation 1).And, in above-mentioned patent documentation 1, disclose, as above-mentioned heat stabilizer (b), use at least a kind that from tin type thermal stabilizing agent, Ca-Zn type thermal stabilizing agent, hydrotalcite heat stabilizer and zeolites stabilizing agent, selects.
Patent documentation 1: the spy opens flat 11-100714 communique
Summary of the invention
; when the vinyl chloride resin composition that contains the tin type thermal stabilizing agent of enumerating as above-mentioned " heat stabilizer " (organic tin stabilizing agent) in use carries out melt spinning; when the organic tin stabilizing agent is discharged in the environment; can produce the ecosystem is brought harmful effect, perhaps emit the problem of unique foul smell.And, when the vinyl chloride resin composition that contains above-mentioned " tin type thermal stabilizing agent " heat stabilizer in addition in use carries out melt spinning, there is the fracture of wire when making, can not be met the problem of the vinyl chloride based fiber of aspect performances such as initial coloring.
In addition, when the vinyl chloride resin composition that use contains above-mentioned " hydrotalcite heat stabilizer " carries out melt spinning, be full of the carbide of vinyl chloride resin in the woven wire in melt spinning machinery, therefore, the fracture of wire frequency is accelerated more, and it is difficult that spinning becomes, therefore, there are continuous fusion spinnability, promptly, the problem of the long-term continuity variation of melt spinning.In addition, in constituent, contain the vinyl chloride based fiber of this hydrotalcite heat stabilizer, when applying heat and make it to curl, also have the problem of variable color.
The present invention is a purpose to address these problems.
Promptly, the object of the present invention is to provide a kind of vinyl chloride based fiber and manufacture method thereof, described vinyl chloride based fiber uses the hydrotalcite heat stabilizer, can guarantee the long-term continuity of melt spinning, thereby can obtain good and stable productivity, and, in giving curling operation, even the heat of applying, variable color are also few.
The inventor finds when furtheing investigate the reason that produces the problems referred to above, when 1) using the vinyl chloride resin composition that contains above-mentioned " hydrotalcite heat stabilizer " to carry out melt spinning, be full of the carbide and 2 of vinyl chloride resin in the woven wire in melt spinning machinery) when the vinyl chloride based fiber that contains above-mentioned " hydrotalcite heat stabilizer " in to constituent applied heat and makes it to curl, the such problem of this vinyl chloride based fiber variable color was because the bad generation of dispersion of hydrotalcite heat stabilizer.And, the inventor finds based on this, also find: containing (a) vinyl chloride resin 100 parts by mass and (b) when containing (c) epoxide 0.2～10.0 parts by mass in the vinyl chloride resin composition of hydrotalcite heat stabilizer 0.2～5.0 parts by mass, use the hydrotalcite heat stabilizer even can provide, also can guarantee the long-term continuity of melt spinning, thereby obtain good and stable productivity, and, in giving curling operation, even the heat of applying, the vinyl chloride based fiber that variable color is also few is so that finished the present invention.
Promptly, to achieve these goals, the invention of claim 1 record is a kind of vinyl chloride based fiber, it is characterized in that, described vinyl chloride based fiber be by contain (a) vinyl chloride resin 100 parts by mass, (b) hydrotalcite heat stabilizer 0.2～5.0 parts by mass and (c) vinyl chloride resin composition of epoxide 0.2～10.0 parts by mass constitute.
The feature of the invention of claim 2 record is, in the invention of claim 1 record, above-mentioned epoxide is from epoxidised soybean oil, epoxidised linseed oil, epoxidation tung oil, epoxidation fish oil, the epoxidation tallow oil, the epoxidation castor oil, epoxidation safflower wet goods epoxidation vegetable and animals oils, the methacrylic compound that contains epoxide group, the epoxidation methyl stearate, epoxidized polybutadiene, cyamelide three (glycidyl) ester, epoxidation tall oil fatty acid ester, the epoxidised linseed oil fatty acid ester, vinyl cyclohexene diepoxide (PVC ニ Le Network ロ ヘ キ セ Application ジ エ Port サ イ De), two cyclohexene carboxylate esters, bisphenol A diglycidyl ether, the glycerol polyglycidyl ether, and at least a epoxide of selecting in the cyclohexanedimethanol polyglycidyl ether.
The feature of the invention of claim 3 record is in the invention of claim 1 or 2 records, also to contain polyalcohol 0.01～2.0 parts by mass that (d) contains nitrogen in the above-mentioned vinyl chloride resin composition.
The feature of the invention of claim 4 record is, in the invention of claim 3 record, the above-mentioned polyalcohol that contains nitrogen is cyamelide three (2-hydroxyethyl) ester, cyamelide three (3-hydroxypropyl) ester or cyamelide three (4-hydroxybutyl) ester.
The feature of the invention of claim 5 record is, will contain (a) vinyl chloride resin 100 parts by mass, (b) hydrotalcite heat stabilizer 0.2～5.0 parts by mass and (c) vinyl chloride resin composition of epoxide 0.2～10.0 parts by mass under 170～190 ℃, carry out melt spinning.
The feature of the invention of claim 6 record is, in the invention of claim 5 record, keeping temperature is under 90～120 ℃ the air atmosphere gas, after above-mentioned vinyl chloride based fiber through melt spinning is stretched to 2～4 times, keeping temperature is under 110～140 ℃ the air atmosphere gas, makes 60～100% length of the lax fibre length until the fiber that is punctured into drawn of the vinyl chloride based fiber heat of this drawn.
The feature of the invention of claim 7 record is that in the invention of claim 5 or 6 records, above-mentioned vinyl chloride resin composition also contains polyalcohol 0.01～2.0 parts by mass that (d) contains nitrogen.
Invention according to claim 1,2 records, a kind of vinyl chloride based fiber can be provided, since this vinyl chloride based fiber by contain (a) vinyl chloride resin 100 parts by mass, (b) hydrotalcite heat stabilizer 0.2～5.0 parts by mass and (c) vinyl chloride resin composition of epoxide 0.2～10.0 parts by mass constitute, therefore, even use the hydrotalcite heat stabilizer, also can guarantee the long-term continuity of melt spinning, thereby obtain good and stable productivity, and, in giving curling operation, even the heat of applying, variable color are also few.
Invention according to claim 3,4 records, because above-mentioned vinyl chloride resin composition also has polyalcohol 0.01～2.0 parts by mass that (d) contains nitrogen, therefore, because synergy with above-mentioned epoxide, in giving curling operation, can further improve the effect that applies the inhibition variable color when hot.
Invention according to claim 5,6 records, since will contain (a) vinyl chloride resin 100 parts by mass, (b) hydrotalcite heat stabilizer 0.2～5.0 parts by mass and (c) vinyl chloride resin composition of epoxide 0.2～10.0 parts by mass under 170～190 ℃, carry out melt spinning, therefore, use the hydrotalcite heat stabilizer even can provide, also can guarantee the long-term continuity of melt spinning, thereby obtain good and stable productivity, and, in giving curling operation, even the vinyl chloride based fiber that the heat of applying, variable color are also few.
Invention according to claim 7 record, because above-mentioned vinyl chloride resin composition also has polyalcohol 0.01～2.0 parts by mass that (d) contains nitrogen, therefore, because synergy with above-mentioned epoxide, in giving curling operation, can further improve the effect that applies the inhibition variable color when hot.
The specific embodiment
Vinyl chloride based fiber of the present invention be by contain (a) vinyl chloride resin 100 parts by mass, (b) hydrotalcite heat stabilizer 0.2～5.0 parts by mass and (c) vinyl chloride resin composition of epoxide 0.2～10.0 parts by mass constitute.
Therefore, containing (a) vinyl chloride resin 100 parts by mass and (b) when containing (c) epoxide 0.2～10.0 parts by mass in the vinyl chloride resin composition of hydrotalcite heat stabilizer 0.2～5.0 parts by mass, use the hydrotalcite heat stabilizer even can provide, also can guarantee the long-term continuity of melt spinning, thereby obtain good and stable productivity, and, in giving curling operation, even the vinyl chloride based fiber that the heat of applying, variable color are also few.
Above-mentioned " vinyl chloride resin ", can enumerate (1) bulk polymerization by vinyl chloride, polymerisation in solution, suspension polymerization, the material that emulsion polymerisation etc. obtain, but its polymerization is not particularly limited, for example, polyvinyl chloride, chliorinated polyvinyl chloride, Vingon, haloflex, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, VCP, vinyl chloride-styrol copolymer, vinyl chloride-isobutylene copolymers, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-phenylethylene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chloropropene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleate copolymer, vinyl chloride-methacrylate copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-chlorine-containing resins such as various vinyl ether co-polymers; (2) their mutual mixture; (3) these chlorine-containing resins and other not chloride synthetic resin, for example, with the admixture of acrylonitritrile-styrene resin, acrylonitrile-styrene-butadiene terpolymer, ethylene-vinyl acetate copolymer, ethene-(methyl) ethyl acrylate copolymer, polyester etc.; Or (4) polymerization and contain the block copolymer, polymerization of vinyl chloride and contain graft copolymer of vinyl chloride etc.
In above-mentioned " fiber vinyl chloride resin composition ", can also be engaged in the known additive that uses in the polyvinyl chloride-base composition in the past.These additives are, for example, plasticizer, lubricant, phase solvent, processing aid, reinforcing agent, ultra-violet absorber, antioxidant, antistatic additive, filler, fire retardant, pigment, initial coloration improver, electric conductivity imparting agent, surface conditioning agent, light stabilizer and spices.
Vinyl chloride based fiber of the present invention, preferred 20～100 DENIER of the thickness of one root are more preferably 50～80 DENIER.Like this, when the thickness of a vinyl chloride fibers is 20～100 DENIER, become material, and when the thickness of a vinyl chloride fibers was 50～80 DENIER, in addition, sense of touch and feel were improved also no less than natural hair.
The section configuration of vinyl chloride based fiber of the present invention can be an arbitrary shape, for example, can be circle, ellipse, spectacle, star, H font, T font, Y-shaped, triangle, quadrangle, cross, heart, the shape of a hoof or their combination.In addition, can also be their ducted body.
" hydrotalcite heat stabilizer " of the present invention do not have the such microorganism in the environment of organic tin heat stabilizer to bring harmful effect, or produces problem such as foul smell, and do not have toxicity.Particularly, such " hydrotalcite heat stabilizer " is hydrotalcite compound, more specifically, is the complex salt compound that comprises magnesium and/or alkali metal and aluminium or zinc, magnesium and aluminium.In addition, in these complex salt, the material that the compound crystallization water is sloughed is arranged also.In addition, hydrotalcite compound can be a natural goods, also can be composite, as the synthetic method of composite, can be known method in the past.
In the present invention, the use level of above-mentioned hydrotalcite heat stabilizer than 0.2 parts by mass after a little while, the fracture of wire frequency increases, yet, the use level of above-mentioned hydrotalcite heat stabilizer than 5.0 parts by mass for a long time, the initial coloring deterioration.Therefore, in the present invention, preferred 0.2～5.0 parts by mass of the use level of above-mentioned hydrotalcite heat stabilizer is more preferably 0.5～3.0 parts by mass.
" epoxide " among the present invention is preferably from epoxidised soybean oil, epoxidised linseed oil, epoxidation tung oil, epoxidation fish oil, the epoxidation tallow oil, the epoxidation castor oil, epoxidation safflower wet goods epoxidation vegetable and animals oils, the methacrylic compound that contains epoxide group, the epoxidation methyl stearate, epoxidized polybutadiene, cyamelide three (glycidyl) ester, epoxidation tall oil fatty acid ester, the epoxidised linseed oil fatty acid ester, the vinyl cyclohexene diepoxide, two cyclohexene carboxylate esters, bisphenol A diglycidyl ether, the glycerol polyglycidyl ether, and at least a epoxide of selecting in the cyclohexanedimethanol polyglycidyl ether, but only otherwise violate purpose of the present invention, also can be epoxides beyond these epoxides.
In the present invention, the use level of above-mentioned " epoxide " than 0.2 parts by mass after a little while, the color changeable effect of the vinyl chloride based fiber that improves the long-term successional effect of melt spinning or suppress to make diminishes, yet, the use level of above-mentioned epoxide than 10.0 parts by mass for a long time, the fracture of wire frequency increases.Therefore, in the present invention, preferred 0.2～10.0 parts by mass of the use level of above-mentioned epoxide is more preferably 0.5～3.0 parts by mass.
In the present invention, above-mentioned vinyl chloride resin composition preferably can further contain polyalcohol 0.01～2.0 parts by mass that (d) contains nitrogen.Like this, above-mentioned vinyl chloride resin composition also has (d) when containing polyalcohol 0.01～2.0 parts by mass of nitrogen since with the synergy of above-mentioned epoxide, in giving curling operation, can further improve the effect that applies the inhibition variable color when hot.
The above-mentioned polyalcohol that contains nitrogen, preferred cyamelide three (2-hydroxyethyl) ester, cyamelide three (3-hydroxypropyl) ester or cyamelide three (4-hydroxybutyl) ester, but, also can be these polyalcohol epoxides in addition that contain nitrogen as long as without prejudice to purpose of the present invention.
In the present invention, the use level of the above-mentioned polyalcohol that contains nitrogen than 0.01 parts by mass after a little while, in giving curling operation, applying the effect that the variable color when hot reduces diminishes, yet, the use level of the above-mentioned polyalcohol that contains nitrogen than 2.0 parts by mass for a long time, the fracture of wire frequency increases.Therefore, in the present invention, above-mentioned preferred 0.01～2.0 parts by mass of use level that contains the polyalcohol of nitrogen is more preferably 0.02～1.0 parts by mass.
Vinyl chloride based fiber of the present invention preferably by will contain (a) vinyl chloride resin 100 parts by mass, (b) hydrotalcite heat stabilizer 0.2～5.0 parts by mass and (c) vinyl chloride resin composition of epoxide 0.2～10.0 parts by mass under 170～190 ℃, carry out melt spinning and make.Like this, to contain (a) vinyl chloride resin 100 parts by mass, (b) hydrotalcite heat stabilizer 0.2～5.0 parts by mass and (c) when the vinyl chloride resin composition of epoxide 0.2～10.0 parts by mass carries out melt spinning under 170～190 ℃, use the hydrotalcite heat stabilizer even can provide, also can guarantee the long-term continuity of melt spinning, thereby obtain good and stable productivity, and, in giving curling operation, even the vinyl chloride based fiber that the heat of applying, variable color are also few.
In the manufacturing of vinyl chloride based fiber of the present invention; can use single shaft extruder, incorgruous biaxial extruder, taper biaxial extruder etc. to melt extrude machine, under 170～190 ℃ temperature, will use mixers such as Henschel blender, ribbon blender to mix the mixture of powders of above-mentioned " vinyl chloride resin composition " or the granulate mixture after its melting mixing is carried out melt spinning make.
In the manufacturing of vinyl chloride based fiber of the present invention, keeping temperature is under 90～120 ℃ the air atmosphere gas, after the vinyl chloride based fiber of above-mentioned melt spinning is stretched to 2～4 times, keeping temperature is under 110～140 ℃ the air atmosphere gas, makes lax 60～100% the length before handling of the vinyl chloride based fiber heat of this stretching.
In the manufacturing of vinyl chloride based fiber of the present invention, above-mentioned vinyl chloride resin composition preferably can further contain polyalcohol 0.01～2.0 parts by mass that (d) contains nitrogen.Like this, above-mentioned vinyl chloride resin composition also has (d) when containing polyalcohol 0.01～2.0 parts by mass of nitrogen since with the synergy of above-mentioned epoxide, in giving curling operation, can further improve the effect that applies the inhibition variable color when hot.
Embodiment
(embodiment 1)
To contain (a) and cooperate (the ocean polyvinyl chloride Co., Ltd. manufacturing of 80 parts by mass vinyl chloride resins, TH-1000), (Sekisui Chemical Co., Ltd makes 10 parts by mass chlorinated vinyl chloride resins, HA-24K), (Sekisui Chemical Co., Ltd makes 10 parts by mass ethylene-vinyl acetate/vinyl chloride graft copolymerization resin, TGH-1100) vinyl chloride resin 100 parts by mass that obtain, (b) (consonance chemical company makes the hydrotalcite heat stabilizer, ALCAMIZER-1) 2 parts by mass, (c) (Nof Corp. makes epoxide, Off ア Le パ Star Network 75ASV) 0.8 parts by mass, (d) polyalcohol that contains nitrogen (is produced chemical company's manufacturing daily, NF-SE) 0.5 parts by mass, (e) (rising sun electrification company makes bi-ester of phosphite, ADKSTAB PEP-8) 0.5 parts by mass, (f) zinc soap (daily output chemical company makes NF-12Zn) 0.8 parts by mass, (g) calcium soap (daily output chemical company makes NF-12Ca) 1.0 parts by mass, and (h) vinyl chloride resin composition of ester series lubricant agent (Riken Vitamin company make EW-100) 0.7 parts by mass, from cross-section area of nozzle 0.06mm
2, 175 ℃ of hole count 120 and mold temperatures the spinning mould carried out melt spinning with extrusion capacity 10Kg/ hour, obtain the vinyl chloride based fiber that average fineness is 135 DENIER.Then, with this vinyl chloride based fiber after being stretched to 300% under 105 ℃ the air atmosphere gas, under 110 ℃ air atmosphere gas, make 75% length of the lax fibre length until the fiber that is shrunk to drawn of the fiber heat of this drawn, obtain the vinyl chloride based fiber that average fineness is 60 DENIER.
(embodiment 2)
Except in vinyl chloride resin composition, do not contain the polyalcohol that (d) contain nitrogen (daily output chemical company makes, NF-SE) beyond 0.5 parts by mass, with the foregoing description 1 similarly, obtain vinyl chloride based fiber.
(embodiment 3)
Except in vinyl chloride resin composition, contain the polyalcohol that (d) contain nitrogen (daily output chemical company makes, NF-SE) beyond 5 parts by mass, with the foregoing description 1 similarly, obtain vinyl chloride based fiber.
(comparative example 1)
To contain (a) and cooperate (the ocean polyvinyl chloride Co., Ltd. manufacturing of 80 parts by mass vinyl chloride resins, TH-1000), (Sekisui Chemical Co., Ltd makes 10 parts by mass chlorinated vinyl chloride resins, HA-24K), (Sekisui Chemical Co., Ltd makes 10 parts by mass ethylene-vinyl acetate/vinyl chloride graft copolymerization resin, TGH-1100) vinyl chloride resin 100 parts by mass that obtain, (b) (consonance chemical company makes the hydrotalcite heat stabilizer, ALCAMIZER-1) 0.1 parts by mass, (c) (Nof Corp. makes epoxide, Off ア Le パ Star Network 75ASV) 0.8 parts by mass, (e) (rising sun electrification company makes bi-ester of phosphite, ADKSTABPEP-8) 0.5 parts by mass, (f) zinc soap (daily output chemical company makes NF-12Zn) 0.8 parts by mass, (g) calcium soap (daily output chemical company makes NF-12Ca) 1.0 parts by mass, and (h) vinyl chloride resin composition of ester series lubricant agent (Riken Vitamin company make EW-100) 0.7 parts by mass, from cross-section area of nozzle 0.06mm
2, 175 ℃ of hole count 120 and mold temperatures the spinning mould carried out melt spinning with extrusion capacity 10Kg/ hour, obtain the vinyl chloride based fiber that average fineness is 135 DENIER.Then, with this vinyl chloride based fiber after being stretched to 300% under 105 ℃ the air atmosphere gas, under 110 ℃ air atmosphere gas, make 75% length of the lax fibre length until the fiber that is shrunk to drawn of the fiber heat of this drawn, obtain the vinyl chloride based fiber that average fineness is 60 DENIER.
(comparative example 2)
Except in vinyl chloride resin composition, contain (b) hydrotalcite heat stabilizer (consonance chemical company makes, ALCAMIZER-1) beyond 10 parts by mass, with the foregoing description 1 similarly, obtain vinyl chloride based fiber.
(comparative example 3)
(consonance chemical company makes except contain (b) hydrotalcite heat stabilizer in vinyl chloride resin composition, ALCAMIZER-1) 2 parts by mass and (c) epoxide (Nof Corp.'s manufacturing, Off ア Le パ Star Network 75ASV) beyond 0.1 parts by mass, with the foregoing description 1 similarly, obtain vinyl chloride based fiber.
(comparative example 4)
(consonance chemical company makes except contain (b) hydrotalcite heat stabilizer in vinyl chloride resin composition, ALCAMIZER-1) 2 parts by mass and (c) epoxide (Nof Corp.'s manufacturing, Off ア Le パ Star Network 75ASV) beyond 20 parts by mass, with the foregoing description 1 similarly, obtain vinyl chloride based fiber.
Estimate (1) long-term continuity, (2) discolouration, (3) fracture of wire frequency and (4) initial coloring of the vinyl chloride based fiber that obtains in above embodiment 1～3 and the comparative example 1～4.Evaluation result is shown in following table 1.
[table 1]
| Embodiment | Comparative example | ||||||
| 1 | 2 | 3 | 1 | 2 | 3 | 4 | |
| Long-term continuity | ◎ | ◎ | ◎ | × | ◎ | ○ | × |
| Discolouration | ◎ | ○ | ◎ | ○ | ○ | × | ○ |
| The fracture of wire frequency | ◎ | ◎ | ○ | × | ◎ | ◎ | × |
| Initial coloring | ○ | ○ | ○ | ○ | × | ○ | ○ |
Fracture of wire often takes place because the woven wire mesh blocks when melt spinning, and " the long-term continuity " of above-mentioned (1) is if be expression up to the continuous fusion spinning time of not changing the state that woven wire just can not make, and its metewand is as follows:
◎: the continuous spinning time surpasses 96 hours does not have the fracture of wire problem yet, therefore, can improve effect more aspect the operability productivity
Zero: the continuous spinning time produced the fracture of wire of trace at 96～48 hours, but no problem as making continuously for a long time
*: the continuous spinning time just produced a large amount of fracture of wires less than 48 hours, therefore, can not keep long-term manufacturing continuously.
" discolouration " of above-mentioned (2) is the characteristic value of judging the variable color degree when giving curling operation.Should " discolouration " be after in 105 ℃ gear drying box (ギ ア オ one Block Application), carrying out heat treatment in 1 hour under the state that makes the vinyl chloride based fiber tension, (the Cangfu textile company is made with colour difference meter, high accuracy spectral photometric colour measuring machine COLOR-7X) color of the vinyl chloride based fiber before and after the heat treatment is measured, with the b value before the heat treatment (in addition, above-mentioned b value is the value that measured by optical condition in the illumination according to the condition b of JIS Z 8722) as b
1, and, with the b after the heat treatment as b
2The time, use b
1And b
2Difference Δ b, i.e. Δ b=b
1-b
2Estimate, its metewand is as follows:
◎: Δ b＜0.5, use visualization less than variable color
Zero: 0.5≤Δ b＜1.0 have variable color slightly, but no problem as product
*: 1.0≤Δ b, even it is visualization also can be seen variable color, defective
" the fracture of wire frequency " of above-mentioned (3) is the number of times that the monofilament segment takes place when carrying out melt spinning, is converted into per 1 hour fracture of wire frequency (number of times/hour), and estimates according to following metewand.
◎: 0 time, no problem fully as long-term continuous manufacturing object product
Zero: 1～2 times, no problem as long-term continuous manufacturing object product
*: more than 3 times or 3 times, problem is arranged as long-term manufacturing object product continuously
" initial coloring " of above-mentioned (4) is by the visual valuation color of the silk thread behind the melt spinning just, and its metewand is as follows:
Zero: do not have xanthochromia
*: xanthochromia is arranged
As shown in Table 1.
The all characteristic of the vinyl chloride based fiber that embodiment 1 obtains is all good, can obtain the vinyl chloride based fiber as target.
The vinyl chloride based fiber that embodiment 2 obtains is the fiber that does not cooperate the polyalcohol among the embodiment 1, and deficiency is arranged on discolouration slightly, but other characteristic value all is in as the no problem scope of product.
The vinyl chloride based fiber that embodiment 3 obtains is compared with the vinyl chloride based fiber that embodiment 1 obtains, and the fracture of wire frequency has deficiency slightly, but other characteristic value all is in as the no problem scope of product.
The vinyl chloride based fiber that comparative example 1 obtains is because the use level of hydrotalcite heat stabilizer is few, and it is many that the fracture of wire frequency becomes, difficulty in spinning, long-term poor continuity.
The vinyl chloride based fiber that comparative example 2 obtains is because the use level of hydrotalcite heat stabilizer is too much, and initial coloring is poor.
The vinyl chloride based fiber that comparative example 3 obtains is because the use level of epoxide is few, and long-term continuity and discolouration are poor.
The vinyl chloride based fiber that comparative example 4 obtains is because the use level of epoxide is too much, and it is many that the fracture of wire frequency becomes, difficulty in spinning, long-term poor continuity.
Industrial applicibility
Vinyl chloride based fiber of the present invention for example can be formed in, and wig sheath, part wig, plait, refutes the vinyl chloride based fiber of the gloss with the hair that is similar to the people, color and the style used in the manufacturing of the hair decorated articles such as clockwork spring.
Claims
(according to the modification of the 19th of treaty)
1. (revise afterwards) a kind of vinyl chloride based fiber, it is characterized in that this vinyl chloride based fiber is by the vinyl chloride resin composition formation that contains (a) vinyl chloride resin 100 parts by mass, (b) hydrotalcite heat stabilizer 0.2～5.0 parts by mass, (c) epoxide 0.2～10.0 parts by mass and (d) contain polyalcohol 0.01～2.0 parts by mass of nitrogen.
2. the described vinyl chloride based fiber of claim 1, it is characterized in that above-mentioned epoxide is from epoxidised soybean oil, epoxidised linseed oil, epoxidation tung oil, epoxidation fish oil, the epoxidation tallow oil, the epoxidation castor oil, epoxidation safflower wet goods epoxidation vegetable and animals oils, the methacrylic compound that contains epoxide group, the epoxidation methyl stearate, epoxidized polybutadiene, cyamelide three (glycidyl) ester, epoxidation tall oil fatty acid ester, the epoxidised linseed oil fatty acid ester, the vinyl cyclohexene diepoxide, two cyclohexene carboxylate esters, bisphenol A diglycidyl ether, the glycerol polyglycidyl ether, and at least a epoxide of selecting in the cyclohexanedimethanol polyglycidyl ether.
3. (deletion).
4. claim 1 or 2 described vinyl chloride based fibers is characterized in that, the above-mentioned polyalcohol that contains nitrogen is cyamelide three (2-hydroxyethyl) ester, cyamelide three (3-hydroxypropyl) ester or cyamelide three (4-hydroxybutyl) ester.
5. method of making vinyl chloride based fiber, it is characterized in that the vinyl chloride resin composition that will contain (a) vinyl chloride resin 100 parts by mass, (b) hydrotalcite heat stabilizer 0.2～5.0 parts by mass, (c) epoxide 0.2～10.0 parts by mass and (d) contain polyalcohol 0.01～2.0 parts by mass of nitrogen carries out melt spinning under 170～190 ℃ temperature.
6. the method for the described manufacturing vinyl chloride based fiber of claim 5, it is characterized in that, keeping temperature is under 90～120 ℃ the air atmosphere gas, after the vinyl chloride based fiber of above-mentioned melt spinning is stretched to 2～4 times, keeping temperature is under 110～140 ℃ the air atmosphere gas, makes lax 60～100% the length before handling of the vinyl chloride based fiber heat of this drawn.
7. (deletion).
Claims (7)
1. vinyl chloride based fiber, it is characterized in that, this vinyl chloride based fiber by contain (a) vinyl chloride resin 100 parts by mass, (b) hydrotalcite heat stabilizer 0.2～5.0 parts by mass and (c) vinyl chloride resin composition of epoxide 0.2～10.0 parts by mass constitute.
2. the described vinyl chloride based fiber of claim 1, it is characterized in that above-mentioned epoxide is from epoxidised soybean oil, epoxidised linseed oil, epoxidation tung oil, epoxidation fish oil, the epoxidation tallow oil, the epoxidation castor oil, epoxidation safflower wet goods epoxidation vegetable and animals oils, the methacrylic compound that contains epoxide group, the epoxidation methyl stearate, epoxidized polybutadiene, cyamelide three (glycidyl) ester, epoxidation tall oil fatty acid ester, the epoxidised linseed oil fatty acid ester, the vinyl cyclohexene diepoxide, two cyclohexene carboxylate esters, bisphenol A diglycidyl ether, the glycerol polyglycidyl ether, and at least a epoxide of selecting in the cyclohexanedimethanol polyglycidyl ether.
3. claim 1 or 2 described vinyl chloride based fibers is characterized in that, above-mentioned vinyl chloride resin composition also contains polyalcohol 0.01～2.0 parts by mass that (d) contains nitrogen.
4. the described vinyl chloride based fiber of claim 3 is characterized in that, the above-mentioned polyalcohol that contains nitrogen is cyamelide three (2-hydroxyethyl) ester, cyamelide three (3-hydroxypropyl) ester or cyamelide three (4-hydroxybutyl) ester.
5. method of making vinyl chloride based fiber, it is characterized in that, will contain (a) vinyl chloride resin 100 parts by mass, (b) hydrotalcite heat stabilizer 0.2～5.0 parts by mass and (c) vinyl chloride resin composition of epoxide 0.2～10.0 parts by mass under 170～190 ℃ temperature, carry out melt spinning.
6. the method for the described manufacturing vinyl chloride based fiber of claim 5, it is characterized in that, keeping temperature is under 90～120 ℃ the air atmosphere gas, after the vinyl chloride based fiber of above-mentioned melt spinning is stretched to 2～4 times, keeping temperature is under 110～140 ℃ the air atmosphere gas, makes lax 60～100% the length before handling of the vinyl chloride based fiber heat of this drawn.
7. the method for claim 5 or 6 described manufacturing vinyl chloride based fibers is characterized in that, above-mentioned vinyl chloride resin composition also contains polyalcohol 0.01～2.0 parts by mass that (d) contains nitrogen.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003345440 | 2003-10-03 | ||
| JP345440/2003 | 2003-10-03 |
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|---|---|
| CN1863951A true CN1863951A (en) | 2006-11-15 |
| CN100451188C CN100451188C (en) | 2009-01-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800287275A Active CN100451188C (en) | 2003-10-03 | 2004-09-10 | Vinyl chloride based fiber and method for production thereof |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20070009735A1 (en) |
| JP (1) | JPWO2005033383A1 (en) |
| KR (1) | KR20060065725A (en) |
| CN (1) | CN100451188C (en) |
| WO (1) | WO2005033383A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103403236A (en) * | 2011-03-31 | 2013-11-20 | 柳寅植 | Synthetic fiber containing plant fatty acids, and method for manufacturing same |
| CN108395643A (en) * | 2018-03-23 | 2018-08-14 | 邵阳学院 | Modification hydrocalumite and its clean method for preparing for PVC heat stabilizer |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007052570A1 (en) * | 2005-11-02 | 2007-05-10 | Denki Kagaku Kogyo Kabushiki Kaisha | Fiber with modified cross section and fiber for artificial hair formed of the same |
| WO2007099858A1 (en) * | 2006-02-28 | 2007-09-07 | Denki Kagaku Kogyo Kabushiki Kaisha | Vinyl chloride resin fiber and method for producing same |
| CN103073830B (en) * | 2013-02-16 | 2015-04-29 | 哈尔滨中大型材科技股份有限公司 | Preparation method of maleic anhydride grafted chlorinated polyvinyl chloride composite material |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5836012B2 (en) * | 1980-11-07 | 1983-08-06 | アデカ・ア−ガス化学株式会社 | Halogen-containing resin composition |
| WO1998040545A1 (en) * | 1997-03-11 | 1998-09-17 | Kaneka Corporation | Vinyl chloride fibers and process for preparing the same |
| JP3791177B2 (en) * | 1997-07-31 | 2006-06-28 | 株式会社カネカ | Vinyl chloride fiber and method for producing the same |
| JP2000328358A (en) * | 1999-05-11 | 2000-11-28 | Toray Ind Inc | Soft polyester fiber and fabric |
| JP2000328355A (en) * | 1999-05-20 | 2000-11-28 | Kanegafuchi Chem Ind Co Ltd | Vinyl chloride-based fiber and its production |
| JP3797847B2 (en) * | 2000-03-29 | 2006-07-19 | 電気化学工業株式会社 | Vinyl chloride resin composition for fiber and stabilizer composition for vinyl chloride resin for fiber |
| US7629048B2 (en) * | 2003-04-04 | 2009-12-08 | Denki Kagaku Kogyo Kabushiki Kaisha | Polyvinyl chloride fiber, process for producing the same, and use thereof |
| CN101031676B (en) * | 2004-09-29 | 2010-05-12 | 钟渊化学工业株式会社 | Polyvinyl chloride fiber reduced in initial coloration |
| CN101035935A (en) * | 2004-09-30 | 2007-09-12 | 钟渊化学工业株式会社 | Polyvinyl chloride fiber and process for production thereof |
-
2004
- 2004-09-10 WO PCT/JP2004/013215 patent/WO2005033383A1/en active Application Filing
- 2004-09-10 CN CNB2004800287275A patent/CN100451188C/en active Active
- 2004-09-10 JP JP2005514381A patent/JPWO2005033383A1/en active Pending
- 2004-09-10 KR KR1020067006414A patent/KR20060065725A/en not_active Application Discontinuation
- 2004-09-10 US US10/574,178 patent/US20070009735A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103403236A (en) * | 2011-03-31 | 2013-11-20 | 柳寅植 | Synthetic fiber containing plant fatty acids, and method for manufacturing same |
| CN108395643A (en) * | 2018-03-23 | 2018-08-14 | 邵阳学院 | Modification hydrocalumite and its clean method for preparing for PVC heat stabilizer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100451188C (en) | 2009-01-14 |
| US20070009735A1 (en) | 2007-01-11 |
| WO2005033383A1 (en) | 2005-04-14 |
| KR20060065725A (en) | 2006-06-14 |
| JPWO2005033383A1 (en) | 2007-11-15 |
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