CN103403237A - Stain-resistant fibers, textiles and carpets - Google Patents
Stain-resistant fibers, textiles and carpets Download PDFInfo
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- CN103403237A CN103403237A CN2011800588450A CN201180058845A CN103403237A CN 103403237 A CN103403237 A CN 103403237A CN 2011800588450 A CN2011800588450 A CN 2011800588450A CN 201180058845 A CN201180058845 A CN 201180058845A CN 103403237 A CN103403237 A CN 103403237A
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- diamine
- fiber
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- polyamide
- polymer composition
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Classifications
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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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
-
- 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
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
- D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
-
- 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
- D01F1/04—Pigments
-
- 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
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
- D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
-
- 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
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
-
- 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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
-
- 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
- Y10T428/249921—Web or sheet containing structurally defined element or component
-
- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
- Y10T442/2893—Coated or impregnated polyamide fiber fabric
Abstract
The present invention relates to stain- or dye-resistant fibers, textiles and carpets made of a polymer composition (C) comprising at least one semi-aromatic polyamide comprising recurring units resulting from the condensation of terephthalic acid and at least one aliphatic diamine selected from the group consisting of 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine, methylcyclohexanediamine, isophoronediamine and mixtures thereof, wherein the color of said fiber has a lightness (L*) of at least 50 in the CIE 1976 (L*, a*, b*) color space when measured according to ASTM E308-08.
Description
Quoting of related application
The application requires the priority of the U. S. application of submitting on October 13rd, 2010 number 61/392864, for all purposes are combined in this by reference by the full content of this application.
Technical field
The present invention broadly relates to light fiber, textiles and the carpet that comprises semiaromatic polyamide composition, it is characterized in that unexpected anti-dyeing property.The present invention also is particularly related to a kind of semiaromatic polyamide composition with regard to its anti-dyeing property and the purposes in the manufacture of fiber, textiles and carpet.
Background of invention
Polyamide-based (as derived from those of Phthalic acids and aliphatic diamine class, namely, the polyphthalamide class, perhaps derived from those of aromatic diamines and aliphatic diacid class) be to have excellent machinery, the polymer of physics and chemistry characteristic, it is all useful for diversified different application that these characteristics make them.
Polyamide fiber is relatively inexpensive and the combination of desirable quality is provided, and these qualities are such as durability, comfort level and are easy to manufacture diversified color, pattern and textiles.Therefore, polyamide fiber is widely used as carpet, curtain account material, interior ornaments and clothing in family and industry.Carpet and the blanket by polyamide fiber, made are popular floor coverings in house and business application.
Polyamide fiber easily passes through dye coloring.Consequently, the fiber of polyamide, textiles and carpet have significant shortcoming: they do not have a tolerance for the coloring agent that often contacts placement with these article.Typical coloring agent comprises: artificial or natural colouring agent (such as in soft drink, coffee, red wine, food, find those) and cosmetics (such as lipstick, lip gloss, lip line, rich lip frost, lip gloss, foundation cream, loose powder and rouge).When with these coloring agents, contacting, the article of prior art are easy to be colored.
Resulting stain can not easily be removed under conventional clean conditions.Serious carpet dyeing is user's subject matter.In fact, investigate and show because the carpet that dyeing causes is changed more than what because of wearing and tearing, cause.Therefore, the polyamide fiber that is to provide anti-common household wares and common stain of hope, increase life-span of carpet and textiles thus.
People have made a lot of effort so that a kind of stain-fast polyamide carpet and textiles to be provided.For example, avoiding a kind of mode of this kind dyeing is that a kind of special anti-coloring agent is coated on the surface of this polyamide filament material partly.US6 for example, 488,893 provide a kind of condensation product that comprises sulfonated naphthalene sulfonic acid and aldehyde and the dihydroxydiphenylsulisomer scheme together with a kind of methacrylate polymer, this methacrylate polymer as the stain retarding agent in order to prevent that stain is forever painted to yarn.Yet the processing of discussing is expensive and be impermanent (washing off with one or more cleaning solutions) often.
Still need to have overcome polyamide fiber, carpet and textiles restrictive condition discussed above, anti-dyeing or anti-dyestuff.
Therefore, another object of the present invention is to provide anti-coloured fibre, woollen blanket and the textiles of polyamide.
Detailed description of the invention
in first aspect, the present invention relates to a kind of fiber that contains polymer composition (C), this polymer composition comprises at least a semiaromatic polyamide composition, this semiaromatic polyamide composition comprises by terephthalic acid (TPA) and closes the repetitive that obtains with at least a aliphatic diamine condensation, this aliphatic diamine is to be selected from lower group, this group is comprised of the following: 1, the 8-octamethylenediamine, 1, the 9-nonamethylene diamine, the 2-methyl isophthalic acid, the 8-octamethylenediamine, 1, the 10-decamethylene diamine, 1, 12-dodecane diamines, 2, 2, 4-trimethyl-1, the 6-hexamethylene diamine, 2, 4, 4-trimethyl-1, the 6-hexamethylene diamine, the 5-methyl isophthalic acid, the 9-nonamethylene diamine, the methyl cyclohexane diamines, isophorone diamine, and composition thereof, the color of wherein said fiber when according to ASTME308-08, measuring at CIE1976(L*, a*, b*) brightness that has in the colour space (L*) is at least 50.
Another aspect of the present invention is for the textiles that contains with good grounds fiber of the present invention and carpet, it is characterized by excellent anti-dyeing property.
in a specific embodiment, the present invention relates to have stain-fast fiber with respect to dyestuff or pigment, textiles, and carpet, these fibers, textiles, and carpet is made by a kind of polymer, this polymer comprises the repetitive by aromatic diacid (such as terephthalic acid (TPA)) and at least a aliphatic diamine formation greater than 50mol%, this aliphatic diamine is to be selected from lower group, this group is comprised of the following: 1, the 8-octamethylenediamine, 1, the 9-nonamethylene diamine, the 2-methyl isophthalic acid, the 8-octamethylenediamine, 1, the 10-decamethylene diamine, 1, 12-dodecane diamines, 2, 2, 4-trimethyl-1, the 6-hexamethylene diamine, 2, 4, 4-trimethyl-1, the 6-hexamethylene diamine, the 5-methyl isophthalic acid, the 9-nonamethylene diamine, the methyl cyclohexane diamines, isophorone diamine, and composition thereof.
again aspect another, the present invention relates to a kind of for to fiber, textiles or carpet are given the method for anti-dyeing property, the method comprises with a kind of semiaromatic polyamide composition manufactures described fiber, textiles, or carpet, this semiaromatic polyamide composition comprises by terephthalic acid (TPA) and at least a aliphatic diamine condensation and the repetitive that obtains, this aliphatic diamine is selected from lower group, this group is comprised of the following: 1, the 8-octamethylenediamine, 1, the 9-nonamethylene diamine, the 2-methyl isophthalic acid, the 8-octamethylenediamine, 1, the 10-decamethylene diamine, 1, 12-dodecane diamines, 2, 2, 4-trimethyl-1, the 6-hexamethylene diamine, 2, 4, 4-trimethyl-1, the 6-hexamethylene diamine, the 5-methyl isophthalic acid, the 9-nonamethylene diamine, the methyl cyclohexane diamines, isophorone diamine, and composition thereof.
According to these fibers of the present invention, carpet and textiles, demonstrate outstanding anti-dyeing property.More precisely, according to these fibers of the present invention, carpet and textiles, on the dyeing grade scale of dyeing method of testing described below, having is 1 anti-dyeing grade.Dyeing this be intended to represent by the coloring agent that has penetrated material produce painted.In many cases, stain can received heat and the impact of moisture, and can become enough reactive and combine with subsurface material.Extreme heat can, originally on removable stain, causing chemical reaction, make it become a kind of chemical compound that can't remove.
This coloring agent is intended to represent to cause any reagent of dyeing material contacted with it.Typically, coloring agent comprises at least a dyestuff or pigment.Dyestuff and dyestuff seem it is all coloured, because their preferential absorption and reflect the light of some wavelength.Typical coloring agent comprises: cosmetics (such as, lipstick, lip gloss, lip line, rich lip frost, lip gloss, foundation cream, loose powder and rouge), artificial and natural colouring agent (such as, those that find in soft drink, coffee, red wine, mustard and catsup), dyestuff and pigment (such as in the textiles and leathers that is being colored, find those).
Fiber, textiles and carpet
According to fiber of the present invention, textiles and carpet when according to ASTM E308-08, measuring at CIE1976(L*, a*, b*) advantageously have at least 50 brightness (L*) in the colour space.For the program of measuring brightness, describe in detail hereinafter:
Use a CE7000Gretag MacBeth spectrophotometer with cold white fluorescent (F2) illuminator, 10 ° of observers, 10nm wavelength interval, from 360 to 700nm spectral region and with the D/8 optics geometric configurations of passband calibration, use on the 22nd page of ASTM E308-08() table 5.27 measure brightness (L*).On CIE Lab coordinate, a plurality of values have been measured.Three coordinates of CIELAB have represented that (L*=0 is the white that black and L*=100 represent diffusion for the brightness of color; The white of mirror reflection may be higher), its position between redness and green (a*, negative value represents green and red on the occasion of expression) with and position between yellow and blueness (b*, negative value represents blueness and yellow on the occasion of expression).
The brightness (L*) that has according to fiber of the present invention, textiles and carpet is preferably at least 60, more preferably at least 65, still more preferably at least 70, even more preferably at least 75, and most preferably be at least 80.
Fiber is intended to be expressed as continuous filament or is similar to a class material that is discontinuous elongated bodies of line length.According to the length of fiber of the present invention, can vary widely.It normally from 2 to 50mm, preferably from 10 to 40mm, more preferably from 20 to 30mm.The diameter of this fiber can change equally to a great extent.It is from 1.10 generally
-6M to 1.10
-4M, preferably from 5.10
-6M to 5.10
-5M, be more preferably approximately 1.10
-5M.
According to fiber of the present invention, textiles and carpet, can manufacture by distinct methods known in the art.
Textiles is intended to represent a kind of flexible material that is comprised of the network of natural or artificial fibre (often being called as line or yarn).Yarn normally produce to produce by fibrous raw material being carried out to spinning on a spinning wheel by long yarn thigh.Textiles by fiber is woven, knitting, crocheted, twisting together or forcing together forms.
Carpet is intended to represent a kind of textiles floor covering, the upper strata " pile " that is attached on backing, consists of.This pile is comprised of the tufting products of twisting usually, this tufting products often through heat-treated in order to remain its structure.
Fiber of the present invention, textiles and carpet can be coloured to different colours.
Semiaromatic polyamide composition
Semiaromatic polyamide composition according to the present invention comprises the repetitive (R) that is produced by terephthalic acid (TPA) and at least a aliphatic diamine condensation, this aliphatic diamine is to be selected from lower group, this group is comprised of the following: 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 2-methyl isophthalic acid, 8-octamethylenediamine, 1,10-decamethylene diamine, 1,12-dodecane diamines, 2,2,4-trimethyl-1,6-hexamethylene diamine, 2,4,4-trimethyl-1,6-hexamethylene diamine, 5-methyl isophthalic acid, 9-nonamethylene diamine, methyl cyclohexane diamines, isophorone diamine, and composition thereof.
Preferably, this at least a aliphatic diamine is to be selected from lower group, and this group is comprised of the following: 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 2-methyl isophthalic acid, 8-octamethylenediamine, 1,10-decamethylene diamine, 1,12-dodecane diamines, 2,2,4-trimethyl-1,6-hexamethylene diamine, 2,4,4-trimethyl-1,6-hexamethylene diamine, 5-methyl isophthalic acid, the 9-nonamethylene diamine, and composition thereof.More preferably, this at least a aliphatic diamine is to be selected from lower group, and this group is comprised of the following: 1,9-nonamethylene diamine, 2-methyl isophthalic acid, and 8-octamethylenediamine, 1,10-decamethylene diamine, 1,12-dodecane diamines, and composition thereof.Also more preferably, this at least a aliphatic diamine is to be selected from lower group, and this group is comprised of the following: 1,9-nonamethylene diamine, 2-methyl isophthalic acid, and 8-octamethylenediamine, 1, the 10-decamethylene diamine, and composition thereof.Most preferably, this at least a aliphatic diamine is to be selected from lower group, and this group is comprised of the following: 1,9-nonamethylene diamine, 1, the 10-decamethylene diamine, and composition thereof.
In a specific embodiment, this aliphatic diamine that has more than 8 carbon atoms is the C9 diamines.In this case, this diamines can be 1,9-nonamethylene diamine (NDA) and/or 2-methyl isophthalic acid, 8-octamethylenediamine (MODA).This 2-methyl isophthalic acid, 8-octamethylenediamine (MODA) can be pressed from 0 to 50 % by mole of existence based on the total mole number of diamines.When having aliphatic diamine more than 8 carbon atoms while being the mixture of NDA and MODA, mol ratio [(NDA): (MODA)] advantageously is at least 1, preferably at least 2, more preferably at least 3, and more preferably at least 4; In addition, it is advantageously maximum 9, and is preferably maximum 7, and more preferably is 6 to the maximum.
When the chief component of polyamide of the present invention is following, obtained excellent result:
-a kind of diamine components (a), its chief component are 1,9-nonamethylene diamine and 2-methyl isophthalic acid, and the 8-octamethylenediamine is pressed the approximately mixture of 1.5 or 5.6 mol ratio [(NDA): (MODA)], and
-a kind of dicarboxylic acid component (b), its chief component is terephthalic acid (TPA).Preferred polyamide is the mixture that often is called as those and they of PA9T, PA10T, PA12T.
PA9T is a kind of polyamide with repetitive of following structure when using 1,9-nonamethylene diamine to manufacture:
PA10T is a kind of polyamide with repetitive of following structure:
PA10T can be prepared by different modes.It is advantageously prepared by the decamethylene diamine derived from renewable raw materials (such as castor bean) at least in part.
According to semiaromatic polyamide composition of the present invention, can comprise other repetitives except repetitive (R).
According to semiaromatic polyamide composition of the present invention, can obtain by the ring-opening polymerization product of one or more dicarboxylic acids of condensation and one or more diamines and/or one or more amino carboxylic acids and/or one or more cyclic lactames.
Except terephthalic acid (TPA) (economizing slightly " T " in the polyamide name), the dicarboxylic acids that is suitable for also includes but not limited to: butanedioic acid, glutaric acid, decanedioic acid, adipic acid, azelaic acid, 1,6-cyclohexane dicarboxylic acid, naphthalene dicarboxylic acids and M-phthalic acid (in the polyamide name, economizing slightly " I ").Preferably, based on the total mole number of this diacid component, the amount that adipic acid exists is 30mol% at the most, more preferably 20mol%, even more preferably 10mol% at the most at the most.More preferably, this diacid component is not contain adipic acid.
The diamines that is suitable for includes but not limited to: tetra-methylenedimine, hexamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, ten dimethylene diamines, 2 methyl pentamethylenediamine, 2-methyl octamethylenediamine, trimethylhexamethylenediamine, two (p-aminocyclohexyl) methane, isophthalic two methanediamines and terephthaldehyde's diamines.
in a specific embodiment, fiber is obtained by a kind of polymer composition (C), in this polymer composition, this at least a semiaromatic polyamide composition except above-mentioned repetitive (R) (by terephthalic acid (TPA) and at least a be selected from lower group aliphatic diamine condensation and produce, this group is comprised of the following: 1,8-octamethylenediamine, 1,9-nonamethylene diamine, the 2-methyl isophthalic acid, the 8-octamethylenediamine, 1,10-decamethylene diamine, 1,12-dodecane diamines, 2,2,4-trimethyl-1, the 6-hexamethylene diamine, 2,4,4-trimethyl-1, the 6-hexamethylene diamine, the 5-methyl isophthalic acid, the 9-nonamethylene diamine, the methyl cyclohexane diamines, isophorone diamine, and composition thereof) outside also comprise other repetitives (R '), these other repetitives are to be produced by the condensation of dicarboxylic acids and diamines, this dicarboxylic acids is to be selected from: butanedioic acid, glutaric acid, decanedioic acid, adipic acid, azelaic acid, 1,6-cyclohexane dicarboxylic acid, naphthalene dicarboxylic acids, and M-phthalic acid, this diamines is to be selected from: tetra-methylenedimine, hexamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, ten dimethylene diamines, 2 methyl pentamethylenediamine, 2-methyl octamethylenediamine, trimethylhexamethylenediamine, two (p-aminocyclohexyl) methane, isophthalic two methanediamines, and terephthaldehyde's diamines.
When using hexamethylene diamine, obtained excellent result, for example caused having obtained following copolymer: PA6T/10T, PA6T/10T/6I/10I, PA6T/6,6, PA10T/10,10, PA10T/6T/6,10/10,10.
Semiaromatic polyamide composition according to the present invention comprises preferred 20wt.% at least, more preferably 40wt.%, even more preferably 50wt.%, also more preferably 60wt.% and the most preferably repetitive of 80wt.% (R) at least at least at least at least based on the gross weight of this semiaromatic polyamide composition.At this semiaromatic polyamide composition, be to be substantially free of or to have obtained while not containing other repetitives except repetitive (R) even fully excellent result.
In this polymer composition (C), can exist more than a kind of semiaromatic polyamide composition.In this case, contain by terephthalic acid (TPA) and at least a above semiaromatic polyamide composition that contains the repetitive that produces more than the aliphatic diamine condensation of 8 carbon atoms that describes in detail preferably based on the gross weight of this semiaromatic polyamide composition by 20wt.% at least, more preferably 40wt.%, even more preferably 50wt.%, also more preferably 60wt.% and most preferably 70wt.% and existing at least at least at least at least.
According to semiaromatic polyamide composition of the present invention, advantageously has high-melting-point.Its fusing point preferably at 200 ° more than C, more preferably at 240 ° more than C, even more preferably at 280 ° more than C and most preferably at 300 ° more than C.The semiaromatic polyamide composition of the fusing point by being characterized as 316 ° of C has obtained excellent result.
According to semiaromatic polyamide composition of the present invention, advantageously has high heat deflection temperature.Its heat deflection temperature preferably at 200 ° more than C, more preferably at 250 ° more than C, even more preferably at 270 ° more than C and most preferably at 290 ° more than C.The semiaromatic polyamide composition of the heat deflection temperature by being characterized as 295 ° of C has obtained excellent result.
According to semiaromatic polyamide composition of the present invention, advantageously have high heat deflection temperature and high-melting-point, therefore it is characterized by excellent heat-resisting quantity.
Semiaromatic polyamide composition according to the present invention is based on this polymer composition (C) in this polymer composition (C) gross weight with 10wt.% at least, more preferably at least 20wt.%, also more preferably at least 30wt.% and most preferably at least the amount of 40wt.% exist.On the other hand, the semiaromatic polyamide composition according to the present invention gross weight that is based on this polymer composition (C) in this polymer composition (C) with 99wt.% at the most, more preferably at the most 95wt.%, also more preferably at the most 90wt.% and most preferably at the most the amount of 85wt.% exist.When the gross weight that for example is based on this polymer composition (C) at semiaromatic polyamide composition according to the present invention in this polymer composition (C) exists with about 50wt.%, obtained excellent result.
The optional member of polymer composition (C)
This polymer composition (C) may further include at least a filler that is selected from lower group, and this group is comprised of the following: fiber filling agent, particulate filler, and composition thereof.The example of this type of filler includes but not limited to: glass fibre, carbon fiber, the glass fibre with noncircular cross section, glass flake, carbon fiber, wollastonite, calcined clay, kaolin, etc.
In a specific embodiment of the present invention, this filler is a kind of particulate filler preferably.The example of this based fine particles filler comprises: carbon black, talcum, glass marble, calcium silicates, calcium metasilicate, kaolin, chalk, flint, mica, barium sulfate, alumina silicate, calcium carbonate, clay etc.
In a specific embodiment of the present invention, this filler is a kind of fiber filling agent preferably.
This fiber filling agent can have circular or non-circular cross section, have with the vertical perpendicular of this reinforcing agent and with cross section in longest linear apart from a corresponding major axis.This noncircular cross section has a minor axis corresponding with the longest linear distance in this cross section on the direction perpendicular to major axis.The length ratio of this jitty of Length Ratio of this major axis is preferably approximately between 1.5:1 and about 6:1.This ratio is more preferably approximately between 2:1 and 5:1 and more preferably approximately between the extremely about 4:1 of 3:1.
This fiber enhancer can be glass, carbon fiber or other materials.Glass fibre preferably.Form or other suitable forms known to persons of ordinary skill in the art of the short glass fiber that this fiber enhancer can be long glass fibres, the rope strand that minces, grind.According to the present invention, particularly preferably be fibre diameter between 7 and 18 μ m, the glass fibre between 9 and 15 μ m preferably.
In a specific embodiment of the present invention, this filler is the mixture of particulate filler and fiber filling agent preferably.
In a preferred embodiment, this polymer composition (C) comprises based on the gross weight of this polymer composition (C) and is 20wt.% at least, more preferably 30wt.%, also more preferably 40wt.% and the most preferably filler of 45wt.% at least at least at least.On the other hand, this polymer composition (C) comprises based on the gross weight of this polymer composition (C) and is preferred 80wt.% at the most, more preferably 70wt.%, also more preferably 60wt.% and the most preferably filler of 55wt.% at the most at the most at the most.
This polymer composition (C) may further include at least a pigment.
This type of pigment can be to be selected from inorganic pigment and organic pigment.This type of pigment is well known to those skilled in the art and notably is selected from: titanium dioxide, zine sulfide pigment, iron oxide pigment, chrome oxide green, lead chromate-molybdate pigment, cadmium pigment, metal oxide hybrid pigment, ultramarine blue, etc.
These pigment according to the present invention are based on this polymer composition (C) in this polymer composition (C) gross weight preferably with 1wt.% at least, more preferably at least about 2wt.%, also more preferably at least about 3wt.% or more preferably at least about the amount of 4wt.%, exist again.On the other hand, these pigment according to the present invention in this polymer composition (C), be based on said composition gross weight preferably with 15wt.% at the most, more preferably at the most 10wt.%, also more preferably at the most 8wt.% or again more preferably at the most the amount of 6wt.% exist.When these pigment exist with about 5wt.% based on the gross weight of this polymer composition (C) in this polymer composition (C), obtained excellent result.
This polymer composition (C) preferably includes at least a Chinese white.Among Chinese white, Chinese white according to the present invention preferentially is selected from: titanium dioxide, barium sulfate and zinc sulphide.More preferably, this Chinese white is titanium dioxide or zinc sulphide.
This polymer composition (C) may further include one or more other polymer.specifically, this polymer composition (C) can further wrap other polyamide, comprise fatty polyamide, such as polyamide 6, polyamide 6, 6, polyamide 4, 6, polyamide 6, 10, polyamide 6, 12, polyamide 11, polyamide 12, polyamide 9, 10, polyamide 9, 12, polyamide 9, 13, polyamide 9, 14, polyamide 9, 15, polyamide 6, 16, polyamide 9, 36, polyamide 10, 10, polyamide 10, 12, polyamide 10, 13, polyamide 10, 14, polyamide 12, 10, polyamide 12, 12, polyamide 12, 13, polyamide 12, 14, polyamide 6, 14, polyamide 6, 13, polyamide 6, 15, polyamide 6, 16, polyamide 6, 13, and semiaromatic polyamide composition, such as poly-(m-xyxylene adipamide) (polyamide MXD, 6), poly-(ten dimethylene terephthalamides) (polyamide 12, T), poly-(nine methylene terephthalamides) (polyamide 9, T), cyclohexane adipamide/hexa-methylene terephthalamide copolyamide (polyamide 6, T/6,6), hexa-methylene terephthalamide.This polymer composition (C) further preferably includes at least a fatty polyamide, such as polyamide 6, and 6.
This polymer composition (C) can further randomly comprise other additive, such as UV light stabilizing agent class, heat stabilizer class, antioxidant, processing aid class, lubricant class, fire retardant class and/or conductive additive class, such as carbon black and carbon nanometer fibril.
In a preferred embodiment, this polymer composition (C) preferably includes:
-20wt.% at least, more preferably 30wt.% at least, and at least a semiaromatic polyamide composition of 40wt.% at least most preferably, this semiaromatic polyamide composition comprises by terephthalic acid (TPA) and at least a repetitive that is selected from the aliphatic diamine condensation of lower group and produces, this group is comprised of the following: 1, the 8-octamethylenediamine, 1, the 9-nonamethylene diamine, the 2-methyl isophthalic acid, the 8-octamethylenediamine, 1, the 10-decamethylene diamine, 1, 12-dodecane diamines, 2, 2, 4-trimethyl-1, the 6-hexamethylene diamine, 2, 4, 4-trimethyl-1, the 6-hexamethylene diamine, the 5-methyl isophthalic acid, the 9-nonamethylene diamine, the methyl cyclohexane diamines, isophorone diamine, and composition thereof, and
-based on the gross weight of this polymer composition (C) be at least 1wt.%, more preferably at least about 2wt.%, also more preferably at least about the pigment of 3wt.%.
In a further advantageous embodiment, this polymer composition (C) preferably includes:
-20wt.%, more preferably 30wt.% and the most preferably at least a semiaromatic polyamide composition that is selected from PA9T, PA10T and PA12T of 40wt.% at least at least at least;
-based on the gross weight of this polymer composition (C) for 1wt.% at least, more preferably at least about 2wt.%, also more preferably at least about at least a Chinese white that is selected from titanium dioxide, barium sulfate and zinc sulphide of 3wt.%.
The polymer composition (C) that is molded as substrate when according to ASTM E308-08, measuring at CIE1976(L*, a*, b*) brightness (L*) that has in the colour space is preferably at least 60, more preferably at least 65, also more preferably at least 70, even more preferably at least 75 and most preferably be at least 85.
If any afoul degree of description of quoting disclosure content in patent, patent application and the publication that is combined in this and the application is to causing term unclear, this explanation should be preferential.
Example
Cosmetics are used as coloring agent.Or rather, these cosmetics are the romantic plum rouge of Maybelline rouge 10 (Maybelline Blush10Romantic Plum blush).
This coloring agent is tested on the thick mold substrate of being made by following different materials of different 0.3cm:
PA6,6: by E.I.Du Pont Company (E.I.du Pont de Nemours and Company), released
101
PA6T/6,6: by the Polymer Co., Ltd such as Su Weigao (SOLVAY ADVANCED POLYMERS, L.L.C), released
A-4122L WH905
PA6T/6I/6,6: by the Polymer Co., Ltd such as Su Weigao (SOLVAY ADVANCED POLYMERS, L.L.C), released
A-1133NL WH505
PA10,10: commercially available from ShanDong DongChen Engineering Plastic Co., Ltd. (Shandong Dongchen Engineering Plastic Co., Ltd.)
PA10.12: commercially available from ShanDong DongChen Engineering Plastic Co., Ltd. (Shandong Dongchen Engineering Plastic Co., Ltd.)
PA9T: by the C9 aliphatic diamine that is provided by cruel Ai Rui (Kuraray) company and the polymer that condensation obtains to the toluene dioctyl phthalate
PA10T: by the Vicnyl700 of golden hair company (Kingfa) release
Glass fibre: by the CSG3PA-820 of Buddhist nun's wave transparent company (Nitobo) release
Coloured dyestuff: a kind of pigment composition is used to color matching.
Chinese white I: zinc sulphide: released by German Sha Haliben chemistry Co., Ltd (Sachtleben Chemie GmbH)
HD-L
Chinese white II: titanium dioxide: by the R-105 of titanium white scientific & technical corporation of Du Pont (DuPont Titanium Technologies) release
Talcum: released by French Lu Zi Nanogram Corp. (Talc de Luzenac France)
OOS
Sebum: by the synthetic sebum of scientific service company (Scientific Services) release.
Table 1: the material of selection
| ? | CE1 | CE2 | CE3 | CE4 | CE5 | E1 | E2 |
| Polyamide | ? | ? | ? | ? | ? | ? | ? |
| PA?6,6 | 50 | ? | ? | ? | ? | ? | ? |
| PA?6T/6,6 | ? | 66 | ? | ? | ? | ? | ? |
| PA?6T/6I/6,6 | ? | ? | 58,7 | ? | ? | ? | ? |
| PA?10,10 | ? | ? | ? | 46,22 | ? | ? | ? |
| PA?10,12 | ? | ? | ? | ? | 46,22 | ? | ? |
| PA?9T | ? | ? | ? | ? | ? | 46,22 | ? |
| PA?10T | ? | ? | ? | ? | ? | ? | 46,22 |
| Filler | ? | ? | ? | ? | ? | ? | ? |
| Glass fibre | 50 | 21 | 34,5 | 47,26 | 47,26 | 47,26 | 47,26 |
| Pigment | ? | ? | ? | ? | ? | ? | ? |
| Colored pigment | ? | ? | ? | 0,025 | 0,025 | 0,025 | 0,025 |
| Chinese white I | ? | ? | ? | 4,755 | 4,755 | 4,755 | 4,755 |
| Chinese white II | ? | 12 | 6 | ? | ? | ? | ? |
| Additive | ? | ? | ? | ? | ? | ? | ? |
| Typical PA additive | ? | 1 | 0.5 | 0,74 | 0,74 | 0,74 | 0,74 |
| Talcum | ? | ? | 0,3 | 1 | 1 | 1 | 1 |
The dyeing method of testing
As described in detail above, use a CE7000 Gretag MacBeth spectrophotometer to test the color of these substrates with cold white fluorescent (F2) illuminator and 10 ° of observers and measured particularly the brightness (L*) of these samples.
With following test program, measure the anti-dyeability of example of the present invention, this method of testing has been simulated the colouring method in potential real-life, and the people who has smeared thus cosmetics can cause colouring agent on the mobile phone component of plastics with its mobile phone speech the time.Use synthetic face cream (sebum) to simulate possible carrier or the solvent of these pigment.
One by the heating sebum until it becomes liquid then the sebum through heating of 3 parts is sneaked in a cosmetics and finally heated this mixture in order to remain mobility, prepared a kind of coloring agent mixture.
With cotton swab, prepared coloring agent mixture is applied on the surface of mold substrate.These substrates were placed 24 hours in the environmental chamber of 65 ° of C and 90% humidity.Then these mold substrates were placed under room temperature before with its surface of isopropyl alcohol.In case through clean, the coloration of these substrates of final inspection.
The color of the fiber of being made by polymer composition according to the present invention (C) always when on substrate, measuring the color of same composition (C) shallow.Yet this anti-coloration is can be than on fiber, more easily and more accurately detecting on substrate.
Check that step comprises the measurement to brightness (L*) as described in detail above.Calculate L* and the dyeing of initial measurement and processed the difference between the rear L* that measures.
Dyeing grade scale: these stains are classified according to following standard:
1=dye-free=Δ L≤0.5
2=moderate dyeing=0.5<Δ L<5
3=severe dyeing=Δ L > 5
In other words, be that 1 dyeing grade is excellent, shown good anti-dyeability, and 3 are poor grades, shown the persistence of severe dyeing.Be considered to have suitable anti-chromatic substrate for one, it should have on above-mentioned dyeing grade scale is 1 grade.
Table 2: dyeing test result
| ? | CE1 | CE2 | CE3 | CE4 | CE5 | E1 | E2 |
| Initial L* value | 61.6 | 91.0 | 93.9 | 90.9 | 90.8 | 89,7 | 89.4 |
| L* value is afterwards processed in dyeing | 58.4 | 90.0 | 92.7 | 84.3 | 84 | 89.7 | 89.0 |
| The dyeing grade | 2 | 2 | 2 | 3 | 3 | 1 | 1 |
Claims (13)
1. fiber that contains polymer composition (C), described polymer composition comprises at least a semiaromatic polyamide composition, this semiaromatic polyamide composition comprises by terephthalic acid (TPA) and at least a aliphatic diamine condensation and the repetitive that obtains, described aliphatic diamine is selected from lower group, this group is comprised of the following: 1, the 8-octamethylenediamine, 1, the 9-nonamethylene diamine, the 2-methyl isophthalic acid, the 8-octamethylenediamine, 1, the 10-decamethylene diamine, 1, 12-dodecane diamines, 2, 2, 4-trimethyl-1, the 6-hexamethylene diamine, 2, 4, 4-trimethyl-1, the 6-hexamethylene diamine, the 5-methyl isophthalic acid, the 9-nonamethylene diamine, the methyl cyclohexane diamines, isophorone diamine and composition thereof, wherein when according to ASTM E308-08, measuring the color of described fiber at CIE1976(L*, a*, b*) brightness that has in the colour space (L*) is at least 50.
2. fiber according to claim 1, wherein when according to ASTM E308-08, measuring the color of described fiber at CIE1976(L*, a*, b*) brightness (L*) that has in the colour space is at least 70.
3. fiber according to claim 1 and 2, wherein said at least a aliphatic diamine is selected from lower group, and this group is comprised of the following: 1,9-nonamethylene diamine, 2-methyl isophthalic acid, 8-octamethylenediamine, 1,10-decamethylene diamine, 1,12-dodecane diamines and composition thereof.
4. fiber according to claim 3, wherein said at least a aliphatic diamine is selected from lower group, and this group is comprised of the following: 1,9-nonamethylene diamine, 1,10-decamethylene diamine and composition thereof.
5. according to the described fiber of any one in above claim, wherein said semiaromatic polyamide composition is selected from lower group, and this group is comprised of the following: PA9T, PA10T, PA12T and composition thereof.
6. according to the described fiber of any one in above claim, wherein said polymer composition (C) comprises based on the gross weight of this polymer composition (C) the described semiaromatic polyamide composition greater than 30wt.%.
7. according to the described fiber of any one in above claim, wherein said polymer composition (C) further comprises based on the gross weight of this polymer composition (C) one or more pigment of 1wt.% at least.
8. fiber according to claim 7, wherein said pigment comprises Chinese white.
9. fiber according to claim 8, wherein said Chinese white is selected from titanium dioxide, barium sulfate and zinc sulphide.
10. textiles that comprises according to the described fiber of any one in above claim.
11. carpet that comprises according to the described fiber of any one in above claim.
12. according to the described fiber of any one in above claim, it has 1 anti-dyeing grade on the dyeing grade scale of dyeing method of testing.
13. for to fiber, textiles or carpet are given the method for anti-dyeing property, the method comprises with semiaromatic polyamide composition manufactures described fiber, textiles or carpet, described semiaromatic polyamide composition comprises the repetitive that is obtained by the condensation of terephthalic acid (TPA) and aliphatic diamine, described aliphatic diamine is selected from lower group, this group is comprised of the following: 1, the 8-octamethylenediamine, 1, the 9-nonamethylene diamine, the 2-methyl isophthalic acid, the 8-octamethylenediamine, 1, the 10-decamethylene diamine, 1, 12-dodecane diamines, 2, 2, 4-trimethyl-1, the 6-hexamethylene diamine, 2, 4, 4-trimethyl-1, the 6-hexamethylene diamine, the 5-methyl isophthalic acid, the 9-nonamethylene diamine, the methyl cyclohexane diamines, isophorone diamine and composition thereof.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US39286410P | 2010-10-13 | 2010-10-13 | |
| US61/392,864 | 2010-10-13 | ||
| EP11157969 | 2011-03-11 | ||
| EP11157969.4 | 2011-03-11 | ||
| PCT/EP2011/067902 WO2012049254A1 (en) | 2010-10-13 | 2011-10-13 | Stain-resistant fibers, textiles and carpets |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103403237A true CN103403237A (en) | 2013-11-20 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800588450A Pending CN103403237A (en) | 2010-10-13 | 2011-10-13 | Stain-resistant fibers, textiles and carpets |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20130309928A1 (en) |
| EP (1) | EP2627806B1 (en) |
| JP (1) | JP5933566B2 (en) |
| KR (1) | KR20130117790A (en) |
| CN (1) | CN103403237A (en) |
| BR (1) | BR112013008851A2 (en) |
| WO (1) | WO2012049254A1 (en) |
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| WO2012049252A2 (en) | 2010-10-13 | 2012-04-19 | Solvay Specialty Polymers Usa, Llc | Stain-resistant articles |
| US10053799B2 (en) | 2014-01-31 | 2018-08-21 | Shakespeare Company, Llc | Nylon based filaments, yarns, and fabrics |
| EP3099745A4 (en) * | 2014-01-31 | 2017-09-27 | Shakespeare Company, LLC | Novel nylon blend for improved mechanical properties of monofilaments and multifilament fibers |
| JP2018508663A (en) * | 2015-02-23 | 2018-03-29 | ディーエスエム アイピー アセッツ ビー．ブイ． | High strength polyamide yarn |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20130309928A1 (en) | 2013-11-21 |
| WO2012049254A1 (en) | 2012-04-19 |
| KR20130117790A (en) | 2013-10-28 |
| EP2627806B1 (en) | 2015-09-16 |
| BR112013008851A2 (en) | 2016-06-21 |
| EP2627806A1 (en) | 2013-08-21 |
| JP2013540909A (en) | 2013-11-07 |
| JP5933566B2 (en) | 2016-06-15 |
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