DE1940660A1 - Thread made from a polymer mixture of polyester and polyamide with an organic phosphorus compound - Google Patents

Description

Priority? dated August 15, 1968 under serial no. 752 789 in F S A

The invention relates to a thread of increased white value, in particular a method for increasing it the white value of a thread made from a polymer mixture of polyamide and polyester using a organic phosphorus compound, which is an organic phosphite, phosphinate, phosphate / polymeric phosphite, polymeric phosphate, the corresponding © acid or a ' Can be a mixture of these.

009808/186

Carpets and fabrics made from fibers comprising a polyamide base with polyester microfibers dispersed therein; have found considerable interest in the textile industry, and their splendid own! shafts have made them more popular than carpets and fabrics made from other fibers. These fibers, which have a polyamide base with polyester dispersed therein ^; Microfibers contain a possible disadvantage in that they are sometimes very yellow in color; if they are manufactured in the usual way. For example, the apparel industry prefers a white fiber and pays an excessive price for such a fiber.

Therefore it is extremely desirable for the

\ - - "■ '■■ ■'. ''■ ■■ ■■ "' ■ ■

f buy and for reasons other than that these fibers white

- ■ -'-'- ■

Γ are.

According to the invention it was found that the white value a thread made of a polymer mixture of polyamide and " Polyester can be increased by being in the Pölymergeaisch a small amount of an organic one Phosphorus compound like an organic phosphite? Phosphinate, phosphate, polymeric phoaphite, polymeric Phosphatef, the corresponding acid or a mixture

of this, brings in. According to the invention, the Weis value is one of ei "em Polymergemiacli of polyester u ä polyamide ▼ extorted thread increased by a process ₅ which consists in" that, in the /; Polymergemisc & ■ before its ■; a small amount of ox ■ Strangv®rpres8uiig ^ gaadsokea. '"■ -

.. 'Phßsphörvarbinduiig' brings in one of the following all- - - ■■; ■■■ -009808 / 166-7-- ^: ■ ^; " _: . "'. _ ■ ~

BAD ORiG (NAL

can have common formulas:

(I)

(II) R «-, 0-P-O-R« . ι

(III) R'-0-POR ' t

(IV) R'-O-P-O

0 »

R «-0-P-0»

R ¹

Ri-O-P-O t

0 »

R «-Q-P-O

Mixtures of these can also be used. In the formulas, R can be an aryl group of up to about 12 carbon atoms, alkyl of up to about 25 carbon atoms, or aralkyl of up to about 30 carbon atoms. R ¹ can be hydrogen, aryl with up to 12 carbon atoms, alkyl with up to about 25 carbon atoms, aralkyl with

up to about 30 carbon atoms or an alkali metal

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and R "can be a divalent aliphatic or aromatic · be a shear radical with up to about 12 carbon atoms, while X is an integer from 1 to about 25. In a preferred embodiment of the invention, the thread contains a polyamide base component dispersing polyester microfibers "

The threads produced according to the invention can be made from mixtures of polyester and polyamide as described in the United States patent 3,369,057 to Twilley. Also for the purposes of the invention üiwei-atomic threads suitable from other mixtures spun from polyester and polyamide, for example as described in U.S. Patents 3,378,0551 British Patent 3,378,056, 3,378,602 and 3,382,305 1 097 068, Belgian patent specification 702 and Dutch patent specification 66 06838 and 66 12628. are described. In the preferred Embodiment of the invention produced threads, the polyester component is dispersed as distributed microfibers through the whole polyamide, which forms a continuous phase as the basic component. The polyester microfibers have an average diameter of no more than one j / u preferably no more than about 0.5 yu. In your The microfibers vary considerably in length, however they are they are all essentially elongated. The microfathe can within the basic component continuously or the-

00980871667

be continuous «Xm means they are at least 5 times and usually at least 20 times longer than the middle one Durohmesser, with an advantageous mean value in the length at about 250 times their mean diameter ' lies. The microfibers are predominant in the threads in the direction of the thread hook. The dispersion of microfibers in the threads is convenient both lengthways; as uniformly across each thread. "Preferably through- ' put at least 100 microfibers each cross section each Thread. The microfibers generally have substantially. , round cross-section, although it is buried lengthways can fluctuate and they can become theirs. Ends out as a result of the shear forces applied during the train can rejuvenate. .

According to the preferred embodiment of the invention The threads produced contain ge j per 100 parts by weight velvet polyamide and polyester about 50 to 90 parts poly-: amide as a basic component and dispersed in it «about 50 up to 10 parts polyester ".

For the purposes of the invention, for example, those polyamides are suitable which are manufactured by condensation of hexylene: diamine and adipic acid (known as nylon 6-6) or by _: polymerization of e-caprolactam (known as nylon 6) "' _? " .,

The poly-

. 009808/166 7 _0R , _ei HAL i.specteo

Esters can generally by condensation reactions between dicarboxylic acids or their derivatives and compounds with two hydroxyl groups or substances that both an alcohol group and a garbosylic acid group own or are a derivative thereof, or are produced by condensation polymerization of lactones. Among the dicarboxylic acid derivatives that can be used include esters, salts, anhydrides, and acid halidinides. the Types of monomers used in making the polyesters are preferably not more functional than difunctional in their ability to react, the more we sent-- " borrowed linear non-crosslinked polymer structures produce.

Suitable for use in the invention are those polyesters in which one of the recurring units in the polyester chain of the diazylaromatres-Ir of terephthalic acid, isophthalic acid, 5-t-butylxsophthalic acid, a ' haphthalenedicarboxylic acid such as haphthalene-2 _? 6- and -2,6-dicarboxylic acid, a diphenyldicarboxylic acid, a diphenylether dicarboxylic acid, a diphenylalkylenedicarboxylic acid © ,. a® diphenylsulfondiearboxylic acid, a® azodibenzoic acid, a pyridinedicarboxylic acid, iron oleine dicarboxylic acid, or a similar aromatic type, including the sulfon ™ acid © analogue B. by "alkyl" or halogen substituents substituted Eeste "-

ORiGlNAL INSPECTED

_ ₇ . - ■ / .. "■■■" ■ 134066Q

The dioxy residue, which is the other main recurring unit in the polyester chain can be an open aliphatic chain such as ethylene glycol or its ether z. B. be the Blather, or it can contain the Hing ©, how they form part of the above-mentioned diazyl radicals. The carboxy and / or the oxy chain links can attached directly to a ring or removed from it by one or more carbon atoms, such as

methyl
in the 1 _t 4-dioxycyclohexane residue.

The organic phosphorus compound may be an organic one

I- '

Phosphite, phosphinate, phosphate, polymeric phosphite, polymeric phosphate, the corresponding acid or a. Mixture thereof with one of the above general formulas.

Basically 0.1 to 5 »0 percent by weight of organic phosphorus compound, based on the weight of the polyamide and polyester, the desired white value of bathing, but 0.1 to 1.0 percent by weight is preferred. The organic phosphorus compound contains at least one aryl, alkyl or aralkyl group ^ and preferably it consists of aryl such as phenylOther suitable aryls include, for example, phenyl, T-naphthyl, 2-raphthyl> biphenyl, anthracyl, phenanthyl and the like. To suitable alkylene include, for example, methyl, ethyl, k-propyl, isopropyl, t-butyl, decyl, hexadecyl, cyclohexyl and the like. Suitable aralkylenes include, for example

00S808 / 1667

_ ₈ _ 194Q66Q

wise nonylphenyl, benzyl, ToIy 1 and the like. Suitable divalent aliphatic or aromatic radicals include, for example, ethylene, propylene, butylene, phenylene and the like. Thus the alkali preferably consists of sodium, and sodium compounds such as disodium phenylphosphinate are particularly preferred _; however, other alkalis W such as lithium and potassium are also suitable. Organic phosphites, phosphinates, phosphates, polymeric phosphites, polymeric phosphates and their corresponding acids suitable for use in the invention are, for example, triphenyl phosphite, didecylphenyl phosphite, diethylphenyl phosphite, phosphinic acids, disodium phenylphosphinate, disodium phenyl.

: phosphate, sodium diphenyl phosphate, sodium diethyl phosphate, Tris (4-nonyl) phenyl phosphite, trihexadecyl phosphate,

ϊ "triphenyl phosphate, tribenzyl phosphate, trilauryl phosphate, ; Triethyl phosphite, poly (ethylene butyl phosphite), poly (ethylene

phenyl phosphate) and the like.

The organic phosphorus compound can be either in the Polyamide or the polyester, or both, or both during the polymerizations in question dry with the polyamide and polyester granules the melting of the polymer blend by conventional addition and dry blending methods. The organic Phosphorus compound can also be in the melt mixture of

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. ■ '■. ORIGINAL INSPECTED-

Polymers are introduced by si © for example in the mixer part of the extruder during the Injected melt compression of the thread. ^

The thread produced according to the invention can be processed into conventional knitted, woven or also slightly woven fabrics. If desired, the filaments containing these fibers can be fused together by the method described in U.S. Patent Application Serial Io. 727 327 of May 7, 1968 to produce fibers that are durable in the dimension "which retain their original" fibrous appearance ^{23O 0} O has been shown to be effective for at least partial fusion when a softer fabric is desired. Melting times of up to about 10 minutes and longer at about 225 ° O can be used, but the breaking strength of the fabric will then be somewhat reduced.

The following examples illustrate preferred embodiments of the invention in a more fundamental and practical manner Respect.

EXAMPLE 1

Synthetic multifilament yarns were made according to "the process that in Example 1 of U.S. Patent 3,369

009808/186?

used by Twilley. It was granulated Polyäthylenterephthalatpolymer having a melting point obeimlh 255 ⁰ C (DTA) and about 265 ⁰ C (optical), ö a Siehte in the amorphous state of about 1.55 g / cm ⁵ b © i 25 ° and about 1V38g / enr \ in Shape of the drawn thread, with a reduced viscosity of about 0.58 and a 3L, of about 65 ° 0 yer-. applies "The polyester in the form of the drawn thread, stretched to a final length not exceeding 20 #, will have a tensile modulus (elasticity modulus) in the range of about 70 to 140 g / denier, depending on the extrusion conditions used"

There are mixtures of 50 parts of granular polyester ver _r mixed with 70 parts of granulated lylon 6 (Polycabroamid) of a reduced viscosity of about 1.04, a T "of about 55 G and a density of about 1.14 g / cm at 25 G Prepared «The amine groups in nylon 6 (polycabroamide) were blocked by reaction with sebacic acid,. The analysis showed that the amine group was 11 milliequivalents of NHg groups per kg of polymer.Bylon 6 (polycaproamide) contained 50 ppm Ku $ sr as gupriacetate as a heat stabilizer.Different amounts of triphenyl phosphite were cut dry with the chemicals from polyamide and polyester granules.

The blends of polyamide and Poljestergranalien and triphenylphosphite were durehgemisctt in a Boppelkegelmisclier an hour · - Di © granulated -Sftmisolie were "f to a moisture content of more than niciit 0 ^ 01 ~; ■ ■■ -... 00-9338 /1S6.7- 'bad original

_ _n _ * 194Ö66Ö

dried, then ^{melted at 285 Q} 0 in a screw press about 89 mm (3 1/2 inches) in diameter operating at an orbital speed of about 39 rpm to produce an exit pressure of about 210 kg / cm (3000 psig) to create. A dry nitrogen atmosphere was used to protect the mixtures against the absorption of moisture. The dwell time in the extruder was 8 minutes *

The thus obtained molten mixtures were Schmäzviskositäten of about 2000 poises at 285 ⁰ C, the polyester was uniformly dispersed throughout the mixture and had an average Teilchendurohmesser of about 2 / Mj as in cooling and solidifying a melt sample Auilaugung of the polyamide component with formic acid and examination of the remaining polyester material was observed.

The molten mixtures thus obtained were ' a spinneret plate with 14 holes of circular Cross-section pressed out, and the resulting fibers were, pulled and coiled. The ribbon yarn generally had a denier of about 63 · The polyethylene terephthalate microfibers had a mean, diameter of not more than 1 / u and an average length of at least 20 times their mean diameter. The microfibers were predominantly in the direction of the thread axis. The own

009808/1667

19-0660

find shafts of the multifilament yarn according to this example Table I. The yarns with triphenyl phosphite were white, while the one containing no triphenyl phosphite Control was yellow.

TABLE I. control - Triphenyl phosphite 0.25 Organic
Phosphite no 0.1 51.9 Weight- ^
organic
Phosphite be
pulled up
entire
Polyester and
polyamide 51.8 56.1 4.0 extreme stretch
(UE) in # 3.7 4.2 252 outermost tensile strength
capacity (UTS) g / denier 254 254 60
58 Breaking strength,
G 65
65 60
70 65 Breaking strength
conservation, aged
100 hours in
Atlas fadeometer,
in 1 °
Coal arc
Xenon arc. 65 70 White
* denier strong
yellowish White 115.5 physical appereance 122.7 114.4 Yellow index

* Measured on a reflection colorimeter. The reflection was measured at 420 _r 550 and 576 nyu; the yellowness index was then calculated in a manner customary in the art,

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EXAMPLE 2

Synthetic multifilament yarns were made in the same way as produced in example 1. .Triphenyiphosphite and Tris ^ (. 4-Nonoyl) -phenylphosphit were rated. The yarns »containing triphenyl phosphite and trinonyl phenyl phosphite, were white, while the controls with no organic phosphorus compound were yellow. The results can be found in Table II.. .

TABLE II control Triphenyl
Phosphite nonylj-
Phenyl
phoaphite Organic
Phosphite no 0.3 ί .. ""
0.25 Weight- ^
organic.
Phosphite be
moved on to poly
ester and poly
amide total 63 ■, 61 '■■ 77 ■'. '■ denier strong
yellowish White White external end
see 125 117 mm Yellow index

see table I.

EXAMPLE 3

Synthetic multifilament yarns were produced in the same manner as in Example 1. It was disodium phenyl

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phosphinate rated »The disodium phenyl phosphate., containing Yarns were white, while those were not disodium phenylphosphinate containing controls were yellow. The results can be found in Table III.

TABLE III control Disodium phenylphosphate
phinate W "'Ό * 3 ·"' - ': Organic
phosphate none none 0.5 j *,.; ■, - ■■ Weight- ^
organic
Phosphite be
moved on to poly
ester and poly
amide total 63 64 65 White denier strong yellowish White 118 external end
see 125 125 118 Yellow index *

* see table I.

EXAMPLE 4 - - .'.'......

Synthetic multifilament yarns were made in the same manner as produced in example 1. It became tripheny! Phosphate evaluated. The yarn containing triphenyl phosphate was white, while the control without triphenyl phosphate was yellow was. The results are given in Table IV.

TABLE IV

Organic phosphate

control

0098087Ί667

Triphenyl phosphate

• t ,.

Weight - ^ '.
organic
Phosphate "^;<
moved on to poly
ester and poly
amide overall no extreme stretch
(UE) in i * 31.5 extreme rupture
strength (UTS)
g / denier 3.7 Breaking strength
in g 239 Breaking strength
preservation after
100 hours of aging
in atlas fadeometer
in? 6
Xenon arc 84

Denier external appearance Yellow index

64

strong yellow 125

0.3
20.4

4.7 279

white 117

♦ see table I.

EXAMPLE

The synthetic Meh ^ filament yarn produced according to Example 1 with triphenylphasphite and a control yarn without Triphenylphosphii; which otherwise produces the same world war became single-walled fabrics at 19 Weft threads woven each inch in the weft and warp directions. The Grame contained 14 strands each and were in a draw ratio of about 3.0 times to a final denier number been drawn by about 63. Thirteen ends of the yarn of Example 1 were plied to make a plied yarn of about Get 840 denier before weaving. The fabrics were

194066O

the method according to bound by melting on a tenter names with 30 <fo overfeed, 3 minutes at 25O ⁰ C, in the United States Patent Application Serial No. 727 327 of May 7, 1968. The molten material with triphenyl phosphite was only yellowed while the control without triphenyl phosphite was brown. The results can be found in Table V.;

TABLE V control Triphenyl
phosphite Organic
Phosphite no 0.25 Weight- ^
organic
Phosphite be
moved on to poly
ester and poly
amid Overall 63 63 denier Brown yellowed external end
see 158.1 126.9 Yellow index

♦ see table I.

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Claims (1)

.; ...--. '. λ PATENT CLAIMS .. ■ ■. -;. -.... ■ ^. - Process for increasing the whitenessa "a atrangver- -pfö'asHretf '" thread made of a polymer mixture of polyester and polyacid, characterized in that one in the
Polymer aggregate a small before it is extruded
Amount of an organic phosphorus compound in one of the following general formulas: (I) Rt-O-P-O-R ' (II) R1-0-POR '
» (in) (IV) (V) Rt-0-P-O-R »· - ■
ι O ^
RM-OPO
I. R. O
i ..-. Rt-OPO
t _ R - 0
1 I. R. O
I. Rt -O-P-O
» R. O
I. R. -J X or a Gremiaoh thereof ^ · "-, ■ ■ ;: 009808/1667 - ίσο incorporated, where R from aryl with up to about 12 carbon atoms, alkyl with up to about 25 carbon atoms or aralkyl with up to about 30 carbon atoms, R ¹ from hydrogen, aryl with up to 12 carbon atoms, alkyl with up to 25 carbon atoms, Aralkyl with up to 30 carbon atoms or an alkali metal, R "is a divalent aliphatic or aromatic radical with up to about 12 carbon atoms and X is an integer from 1 to about 25. 2ο method according to claim 1, characterized in that the thread has a polyamide base with dispersed therein Has polyester microfibers. ^. Method according to claim 2, characterized in that the phosphorus compound consists of triphenyl phosphite » 4 * Method according to claim 2, characterized in that the phosphorus compound from tris (4-nonyl) phenyl phosphite consists. 5. The method according to claim 2, characterized in that ■ - * -... , - /: ^ - ^ - v '-> ■ λ ■■■ -, -; ■ ► · _ ■; ■ - ../ ... .-.-. ■■ ^ phenyl-, _ ■: ;; ■ - ^ V - ^ '>' .: the phosphorus compound consists of disodium phosphinate. 6. The method according to claim 2, characterized in that the phosphorus compound consists of triphenyl phosphate. 7. The method according to claim 2, characterized in that 009808/186 1 the phosphorus compound from poly (ethylene butyl phosphite) ateht. 8. The method according to claim 2, characterized in that the phosphorus compound from poly (ethylene phenyl phosphate) consists. 9 · The method according to claim 2, characterized in that the amount of incorporated phosphorus compound about 0.1 to 5.0 weight percent of the weight of the polyamide and polyester. 10. The method according to claim 9 »characterized in that the amount of the phosphorus compound is about 0.1 to 1.0 percent by weight of the weight of the polyamide and polyester 11 · Method according to claim 2, characterized in that the polymer mixture 100 parts by weight of polyamide and poly ^ ester total of about 50 to 90 parts by weight of polyamide with about 50 to 10 parts of polyester dispersed therein having. , 12, method according to claim 11, characterized in that the polyamide consists of nylon 6. 13. The method according to claim 11, characterized in that ** the polyester consists of polyethylene terephthalate. 009808/1667 14. The method according to claim 2, characterized in that the phosphorus compound is dry mixed with polyamide and polyester granules. 15. The method according to claim 2, characterized in that the phosphorus compound in a molten polymer. a mixture of polyester and polyamide is incorporated. 16. The method according to claim 2, characterized in that the phosphorus compound in one of the polymers during this Polymerization is incorporated. 17. Thread made from a polymer mixture of polyester and polyamide, characterized by a small amount of an organic compound corresponding to one of the following general formeini - (I) R'-OPOR ¹ . - ■ ι (II) R'-O-P-O-R 0 t (III) R'-O-P-O-R ' Ü 0 9 8 0 8 / -1 6 6 (IT) (V) O Ri-O-P-O Rt-O-P-O 0 -P t 0 » RH-O-P-O I 0 - R—. R ¹ R ¹ or contains a semi-mixture of where R is selected from aryl of up to about 12 carbon atoms, alkyl of up to about 25 carbon atoms, or aralkyl of up to about 30
Carbon atoms, R ¹ from hydrogen, aryl of up to about 12 carbon atoms, alkyl of up to about 25
Carbon atoms, aralkyl of up to about 30 carbon atoms, or an alkali metal, R "is a divalent aliphatic or aromatic radical of up to 12 carbon atoms, and X is an integer from 1 to about 25. 18. Thread according to claim 17> characterized in that the polymer mixture has a polyamide base therein
dispersing polyester microfibers. 19o thread according to claim 18, characterized in that the phosphorus compound consists of triphenylphosphite. 20. Thread according to claim 18, characterized in that I 009808/166 7 the phosphorus compound from tri- (4-nonyl) -phenylphöaphit consists· 21. Thread according to claim. 18, characterized in that the phosphorus compound consists of disodium phenylphosphinate. 22. Thread according to claim 18, characterized in that the phosphorus compound consists of fripheyl phosphate. 23 «thread according to claim 18, characterized in that the phosphorus compound from poly (ethylene butyl phosphite) consists. 24. Thread according to claim 18, characterized in that the Phoaphorverbindungen also consists of poly (ethylene phenyl phosphate). - 25. Thread according to claim 18, characterized in that the amount of phosphorus contained therein about 0.1 to 5 percent by weight the weight of polyamide and polyester. 26. Thread according to claim 25, characterized in that / the amount of deyäarin contained-sen phosphorus compound approximately Is 0.1 to 1.0 percent by weight of the weight of the polyamide and polyester. 27. Thread according to claim 18, characterized in that 009808/16 6 1 he per 100 parts by weight of polyamide and polyester a total of about 50 to 90 parts of polyamide with dispersed therein contains about 50 to 100 parts Polyeste'r. 28. Thread according to claim 27, characterized in that the polyamide consists of nylon 6 " 29. Thread according to claim 27, characterized in that the polyester consists of polyethylene terephthalate. 30. Textile made of threads according to claim 18, characterized in that that the threads are fused together to form a dimensionally stable substance. 003808/1 6 t