AU619792B2 - Sulfonated 2-(2'-hydroxyaryl)-2h-benzotriazoles and their use to improve stain resistance and dye lightfastness - Google Patents

Description

i i

IP

OPI DATE 23/05/89 AOJP DATE 29/06/89 WOKL.tional Bure.....

International Bureau APPLN. ID 27974 89 PCT NUMBER PCT/US88/03547

PCT

INTERNATIONAL APPLICAT PUIQ D DEA4HEY TENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 (11) Internationa Publication Number: WO 89/ 03826 C07D 249/20, 6PD06M 13/34

A

l (43) International Publication Date: 5 May 1989 (05.05.89) (21) International Application Number: PCT/US88/03547 Morristown, NJ 07960 BLAND, Karen, Marie 144 Heritage Lane, Hamburg, NJ 07419 (US).

(22) International Filing Date: 12 October 1988 (12.10.88) (74) Agent: WINTER, Richard, Allied-Signal Inc., Law Department McNally), P.O. Box 2245-R, Morristown, (31) Priority Application Number: 111,873 NJ 07960 (US).

(32) Priority Date: 21 October 1987 (21.10.87) (81) Designated States: AT (European patent), AU, BE (European (33) Priority Country: US patent), CH (European patent), DE (European patent), DK, FR (European patent), GB (European patent), IT (European patent), LU (European patent), NL (European patent), (71) Applicant: ALLIED-SIGNAL INC. [US/US]; Law Department NO, SE (European patent).

McNally), P.O. Box 2245-R, Morristown, NJ 07960

(US).

Published (72) Inventors: BERENBAUM, Morris, Benjimin 59 Crest Drive, With international search report.

Summit, NJ 07901 BONFIELD, John, Henry 183 Ly- Before the expiration of the time limit for amending the claims ons Drive, Basking Ridge, NJ 07920 COLE, Charles, and to be republished in the event of the receipt of amend- Jayroe 11560 Teterling Road, Chester, VA 23831 ments.

HARRIS, Paul, Wesley 2321 Hey Road, Richmond, VA 23224 IZOD, Thomas, Paul 112 Victoria Drive, Basking Ridge, NJ 07920 ULMER, Harry, Edwards Route 2, Box 3, Cameron, SC 29030 HOPF, Frederick, Robert 350 Parsippany Road, Parsippany, NJ 07054 (US).

YARDLEY, James, Thomas 40 Macculloch Avenue, (54) Title: SULFONATED 2-(2'-HYDROXYARYL)-2H-BENZOTRIAZOLES ,f.t F2RIM1A EH-DE C-t -N eS S AND THEIR USE TO IMPROVE STAIN RESISTANCE AND DYE LIGHTFASTNESS (57) Abstract A new class of sulfonated 2-(2'-hydroxyaryl)-2H-benzotriazole compounds and method for using them and other sulfonated hydroxyaryl benzotriazoles on nylon fibers to improve stain resistance and dye lightfastness has been discovered. A process is provided for improving stain resistance of nylon fibers by treatment with sulfonated aromatic-formaldehyde condensate and fluorinated dry soil resist agents.

la SULFONATED 2-(2'-HYDROXYARYL)-2H-BENZOTRIAZOLES AND THEIR USE TO IMPROVE STAIN RESISTANCE AND DYE LIGHTFASTNESS BACKGROUND OF THE INVENTION This invention relates to new sulfated 2-(2'-hydroxyaryl)-2H-benzotriazoles and their use to improve stain resistance and dye lightfastness in nylon fibers.

DESCRIPTION OF THE PRIOR ART The prior art is replete with compositions and processes for improving the stain resistance of polyamide (nylon) fibers. The advantages of stain resistance is apparent for many of the uses of nylon, especially when 0 used in carpets. U.S. Patents 3,663,157 and 3,519,669 s ee* disclose certain formaldehyde condensation products S useful as stain resists. The use of fluorine containing S* agents to impart soil resistance of nylons is well known 20 as illustrated by U.S. Patents 4,414,277; 4,209,610; 4,195,105 and 4,192,754. U.S. Patent 3,844,712 to sO Frickenhaus discloses a method of improving the wet fastness of polyamides dyed with cationic dyes by treatment with the salts of condensation products of S 25 formaldehyde and sulfonated diphenyl ethers. However, Frickenhaus does not disclose or recognize any 0 improvement in stain resistance and especially, ,I f Frickenhaus does not recognize that his condensation SeI *products would increase the stain resistance of a 1* 30 polyamide fiber treated with a dry soil release agent.

The unsulfated precursor 2-(2'-hydroxyaryl)-2Hi benzotriazoles (hereinafter sometimes called hydroxy S* benzotriazole or aryl benzotriazole) are disclosed for use to protect organic substances from light-induced deterioration in U.S. 4,226,763 and U.S. 4,278,589. Use of sulfonated 2-(2'-hydroxyaryl)-2H-benzotriazoles as photostabilizing agents for natural and synthetic fibers is disclosed in a published international application under the Patent Cooperation Treaty (PCT), Publication 4/'Q 40 No. WO 84/02365 and in U.S. 4,668,235.

2 1 -2- SUMMARY OF THE INVENTION In accordance with this invention there is provided compounds having the structure

N

N/

N-'

S'--so R'-O-SOG M 3.where R is a secondary alkyl, tertiary alkyl group, and M hydrogen or metal, especially 6@sS Seag

"C

Ce, g.e.

C C 0

CO

080 S. C 6

N

N

C-CH3 ST-1130

CH

3

CH

2

-CH

2 -4 -CH 2

-CH

2 O-SO Na 0

S

C

4* S ft wherein the ionic sulfate group is located at the terminus of an oxygen containing heteroaliphatic chain of 5 to 69 atoms (preferably about 15 to 24 atoms) afford a surprising increase of photostability to polyamides relative to compounds VI and VII

VI

30 N

'N,

VII

N

N-N

HO SO Na

CH

3

CH

3 w The invention also provides methods for improving resistance to staining by anionic staining compounds and improving lightfastness of dyes on nylon material which 911030,immdatl28,a:\27974alLres,2 -3comprises treating the nylon material with an effective amount of an aqueous solution of the above described sulfonated benzotriazole at mild temperatures.

The preferred method of treatment is an aftertreatment at a pH of between about 2 and 5. The preferred treatment temperature is between about 30°C and The preferred time to aftertreat the fiber is after dyeing, preferably from about 10 to 30 minutes in duration. The compounds are also useful to improve properties of nylon materials in other forms, such as film.

The terms nylon and pol amide as used herein denote those synthetic long chain polyamides having recurring o amide groups as an integral part of the polymer chain.

6 15 Exemplary of such polyamides are nylon 6, nylon 66, nylon 12, etc.

goes When not otherwise defined, as used in this specification alkyl means a paraffin hydrocarbon radical *e* derived from an alkane by dropping at least one hydrogen atom, such radicals containing from one to about thirty carbon atoms.

Advantageously the compounds of the present invention are used in conjunction with sulfonated aromatic-formaldehyde condensation products having the S* 25 following structure (hereinafter called the "preferred $e.se DPE condensate"): 0*

S

3 0 0 H 5 L Jm ILJ wherein m is 0 to 4, n is 0 to 3 and x is 1 to 5. Most preferred are the compounds wherein m is 0 or 1, n is 0 to 2 and x is 1 to 3, except the nonpreferred species are 911031,mmdaLl28,a:\27974alLres,3 rIJ -4compounds wherein m n 0 or 1 along with x m n i, or wherein m 0, n 1 and x 2. A particularly wellperforming compound is when m 1, n 0 and x 2.

These agents are described more fully in International Publication No. WO 88 02042.

The method of the invention can be advantageously combined with the use of fluorinated dry soil release agents. Although the use of fluorinated dry soil release (DSR) agents have been previously employed to impart stain resistance to polyamide carpet fibers, it has been found in accordance with this invention, that the use of such DSR agent in conjunction with the sulfonated aromatic condensate results in a synergistic effect producing a superior stain resistance than either 15 treatment agent alone. Additionally, the resistance of such fibers to ozone fading is surprisingly improved.

°The term fluorinated dry soil release agent as used herein is intended to denote those agents known and used in the art to impart increased soil resistance to polyamide fibers, particularly, carpet fibers.

Particularly useful in the process of this invention are the fluorinated dry soil release agents of the types disclosed in U.S. Patent Nos. 4,191,754; 4,604,316 and 4,605,587, which are incorporated herein by reference.

25 It is preferred that the fiber first be treated with the a ge* fluorinated dry soil release agent and thereafter with the inventive compounds although that sequence may be reversed.

The use of the compounds of the present invention 4 30 are preferentially concentrated near the surface of e.g., S" fibers of nylon to ensure optimum effective absorption of wave lengths of radiation which cause photo degradation of nylon and dyes in nylon. The anionic portion of these molecules ensures that they will be strongly attracted to nylon under the application conditions. However, the relatively hydrophobic remainder of the molecules will not readily migrate into the bulk of nylon. This unique 911031,immdat 128,a: 27974a]Lres,4 balancing of effects results in optimal near-surface concentration of these light screens. This renders them remarkably effective both as UV light screens and as stain repelling agents.

The inventive compounds useful in accordance with this invention are water soluble and can be applied to nylon in a variety of ways. Typically, the compounds are applied to dyed fiber from either a dilute or concentrated aqueous solution with a concentration range between 0.001 and 75 weight percent. The solution is contacted with the polyamide fiber for 5 seconds to minutes at temperatures ranging from room temperature to about 100 0 C. The pH of this solution should be between 1.0 and 5.0, preferably about 2.0. It has been found 0 15 that when the pH of the solution is at the lower pH values the percent exhaust and stain resist property of the treated fiber is significantly improved. For this reason, it is preferred to employ sulfonated inventive compounds with -S03H groups instead of sulfonate salts.

@0 After treatment, the fiber is water extracted and oven dried at 120*C. The sulfonated condensates useful in this invention can be applied to dry or wet fiber either as a concentrate or dilute solution. The treated fibers will generally contain the inventive compounds in amounts of between 0.05 and 10% OWF (on the weight of fibers) and the treatment bath conditions should be maintained accordingly.

The method for applying the optional fluorinated dry soil release agent (DSR) to polyamide fibers is known in 9 30 the art and is thus not necessary to describe in detail.

In general, the fibers may be contacted with a spin finish containing the DSR agent in a known matter or other suitable procedures may be employed. The amount of DSR on the fibers resulting from the process of this invention should be between 0.05 and 1.0% on weight of fabric (OWF).

911030,immdat.28,a:\27974alLres,5 v jo -6- The treated nylon carpet fibers are tested for stain resistance in the following manner: A treated sample of nylon carpet yarn in circular knit sleeve form is placed on a non-absorbent surface and a small (10 ml) beaker containing 2 ml of staining solution Cherry Kool-Aid™ is inverted on the fabric and slowly agitated in such a manner that the liquid is retained within the beaker and in contact with the fabric until the termination of the test, or absorption of the staining solution by the fabric takes place. After 5 minutes, or other suitable period of time, the beaker and remaining solution are removed and any excess liquid on the fabric is blotted away with absorbent paper towels. The depth of the stained area is then visually assessed by use of a. 15 the AATCC Gray Scale for staining, the AATCC Chromatic Transference Scale, or other suitable comparative method.

Traditional agents employed to enhance photostability of dyed polyamides include compounds of structures such as

HO

I 25 N rC T~

H

S N I!O N 3 3 N 33C-C-CH 3 Tinuvin- P Ile o i Tinuvin 234 911030,inundatl28,a\27974alLres6 -7-

HO

N

CH CH N O 3 f 3 N -C-CH -C-CH 2 3

CH

3

CH

3 Cyasorb UV-54 Since these compounds are generally soluble only in organic solvents, the incorporation of such material into *V nylon poses serious problems. Surface application from organic solvents is a hazardous process and may result in a non-uniform coating of poor durability. Addition of these materials during extrusion may result in thermal degradation, may result in an ineffectiveness distribution of material, and may result in loss of material due to volatility under extruder conditions.

It has been proposed to sulfonated hydroxyaryl benzotriazoles to ameliorate some of these deficiencies.

For example, sulfonated Tinuvin P (STP) having the structure HO SO Nao 3 I* 30 N STP CH3 911030,immdat.128,a:\27974alL.res,7 9 p..

P.S.C

p 0s *0

S

SS S 0 9

P

PP 55 5 S S -8 may be effectively incorporated into nylon fiber from aqueous solution at relatively low pH (preferably pH 3) and at modest temperatures (0°C 100 0 C, preferably 70°C). Nylon fibers or dyed nylon fibers treated with this material (0.05 5 percent, preferably 0.1 1 percent by weight) either before or after dyeing show dramatically enhanced photostability relative to untreated materials. In addition, these fibers demonstrate increased resistance to staining by certain common stains, especially those containing anionic groups.

Example 1 (Comparative) Synthesis of Sulfonated Tinuvin P or STP.

HO

N Q Cl-SO 3

H

CH

3 i. Cl 25 2. Reflux two hours 3. Neutralize to pH 6 with Na 2

CO

3 30 HO SO 3 Na 0 NN CH3 911030immdat.28,a:\27974altres,8 -9- A solution of 53.5 grams (0.238 mole) of Tinuvin-P in 650 milliliters of chlorobenzene was added to a 1 liter round bottom one-neck flask equipped with a magnetic stirrer and heating mantle and set up for reflux under an atmosphere of nitrogen. Then 15.85 milliliters (0.238 mole) of reagent grade chlorosulfonic acid was slowly added to the stirred solution over a period of approximately twenty minutes. The resulting mixture was brought to reflux and maintained at reflux for 1-k hours.

e 9 U

C

S..

j I 911030,imrda. 128,a:W\2974a1.res,9 Example 2 (Comparative)

NH

2 O NO2 SO 3( 2 3 Aq.NaN 2

+MG

Alkaline aq. Solution of

CH

j3 *0

S

Sb 0

OS

S

CH

3

OH

N=QC-CH3 CH3 0 3 NO 2 3 CH 3 CH 3 H 3

C-C-CM

3

HO

ii

N

N aD00 3 S -fa 1. Reflux in aq/alcoholic solution of thiourua dioxide 2. Neutralize to pH 6

CH

3 911030,immdatL28a: \27974alures,10 fZ T WO 89/03826

N

N

N

N%

where x ;t 6-7 PCrIUS8$I03547 Example %pa

-CCH

3

C

3 CiSO3 H CH -CH -C('OCH -CH4 OH 0(0

N

CHi I3

CHR

3 -CuC -S Na0 1. Q S Cl, R.T.

2. Neutralize to pH 6 with Ma 2

CO

3 Or other base 3. Evaporate solvent to dryness The same procedure can also be used when X =8-9 or 12-13 or the entire radge of 6-30.

~D C~CSt cxa0ta~,cJYO"' WO 89/03826 WO 8903826PCT/US88/03547

N

Example V Ij 4 o~ (Prospective example)

CH

33 CH 2- CH -C('OCH 3 -CH jOH 0 N

N

CC,,N

CH

f 3 I3

C

3 ~-CH 2

-C('-CH

3 -CH jO-s0 3 0 NaG 2 01 where x 6-8 1. Q Cl, R. T.

2. Neutralize to pH 3. Remove solvent The same procedure can also be used when x 16-22 or the entire range of 6-30. Example t: Photostability of UV Light Screens Dissolved in Po Film Matrices.

1 ym er 771 Light Screen Agent Tinuvin P Tinuvin P

STP

STP

T inuvin Tinuvin ST-1130 ST-1130 Polymer

PMMA

Nylon-6 2MMA Nylon-6

PMMA

Nyon-6

PMMA

Nylon-6 Destruction, 9 9 <13 1130 1130 L6.

WO 89/03826 PCT/US88/03547 )3 Twenty-one hours of irradiation in a Rayonet Photochemical eactor equipped with RPR-3000 lamps at temperatures of 46-52*C and ambient humidity. Amount of destruction determined by ultraviolet spectrophotometry.

This example demonstrates that hydroxybenzotriazoles lose photostability in a polyamide environment. It also demonstrates that incorporation of bulky hydrophobic groups near the intramolecular hydrogen bond (especially in the ortho position relative to the hydroxyl group) effectively provides for a high degree of photostability.

Example 4 Protective Effects of Water-Soluble UV Light Screens on Undyed Nylon-6 Khitted Sleeves.

AdditiveL pH 2 Irradiation Irradiation 3 Control White Yellow STP 2 >95 White Light Yellow ST-1130 *2 >95 White Slightly Yellow STP 5 25 Light Yellow Yellow ST-1130 5 55 White Slightly Yellow 1 Applied at 71*C from 20:1 liquor ratio bath. Nominal loading 0.1-2.0%.

2 Percent bath exhaustion.

3 Irradiation for 12 hours in a Rayonet Photochemical Reactor with RPR-3000 Lamps at 46-52 0 C temperature and ambient humidity.

This example illustrates that uptake and color of nylon sleeves treated with anionic, sulfated UV light screens is vastly superior for application at pH 2 relative to application at pH 5. Also, the superior performance of ST 1130 relative to STP is demonstrated.

7 Example Protective Effects of Water-Soluble UV Light Screens on Dyedl Nylon-6 Knitted Sleeves.

4- Ii, SWO 89/03826 Additive 2 Control

STP

ST-1130

STP

Exhaustion, 2 >95 >95 25 Color Before Irradiation Normal Slightly Offshade Normal Off-shade Yellow Coloration Normal PCT/US88/03547 Color After Irradiation 4 Severly Faded Good Protection Excellent Protection Good Protection Excellent Protection ST-1130 1 Dyed with 0.1% (OWF) argent grey 15 2 Applied at 71°C from 20:1 liquor ratio, 0.1-2% (OWF) loading on non-DSR knitted sleeves.

3 Percentage bath exhaustion, by spectrophotometric determination.

4 After 12 hours irradation in a Rayonet Photochemical Reactor with RPR-3000 lamps at temperatures of 48-52°C and ambient humidity.

This example demonstrates that UV screens which are rendered anionic by sulfation and which posses a bulky hydrophobic group near the intramolecular H-bond (such as ST-1130) may be effectively applied to dyed nylon sleeves and that such materials provide superior light screening capability compared to similar compounds without such a hydrophobic group STP).

Claims (7)

1. A sulfonated 2-(2'-hydroxyaryl)-2H-benzotriazole of the chemical structure N 1- N R' -0-soG M 3 0000 S S. S 005 S. S 0* S SS S S OS S S *155 0* *5 S 0000 S @555 0 *.S.SS 4 0 00554S S OS 0 5 0 wherein R is secondary alkyl, tertiary alkyl group, R' is an oxygen containing heteroaliphatic chain of 5 to 69 atoms and M is hydrogen or a metal ion.

2. The benzotriazole of claim 1 wherein the structure N'- N CH C-CE I 3 E 3 CH -CH R" -j o-SoO N wherein x is 1 to 22 and R" is -CH 2 CH 2 or -CHCH 2 CH1 2

3. A sulfonated 2-(2'hydroxyaryl)-2H-benzotriazole as defined in claim 1 and substantially as hereinbef ore described with reference to the Examples.

4. A method for improving resistance to staining by anionic staining compounds and improving lightfastness of dyes on nylon material which comprises treating the nylon material with an effective amount of an aqueous solution 911030,immdat.128,a:\27974al.res,15 16 of sulfated 2-(2'hydroxyaryl)-2H--benzotriazole as defined in claim 1, 2 or 3 at mild temperatures.

The method of claim 4 wherein the material treated is film.

6. The method of claim 4 wherein the material treated is fiber.

7. The method of claim 4, 5 or 6 wherein the treatment is carried out at a temperature in the range to 90 0 C. a. A method according to claim 4 and substantially as hereinbefore described with reference to the Examples. DATED this 30th day of October, 1991. ALLIED-SIGNAL INC. By Its Patent Attorneys DAVIES COLLISON 0s** S S *5 S. S SSS SB S SO OS S 00555S S Ob @5 6 5500 S S 6 55*66 0 6* 6 0 0 0 911030,ixmmdatL 28,a:M2974 lares, 16 V- i i- i 4 I INTERNATIONAL SEARCH REPORT International Aoolicatnon No PCT/US 88/03547 I. CLASSIFICATION OF SUDJECT MATTER (It several classiiic3lon symools aooly, Indicate all) According to Intarnational F'tont Clasification (IPC) or to both National Classification and IPC IPC4: C 07 D 249/20; D 06 M i3/34; D 06 P 1/62 II. FI.aLDA C tSAlICHS3 Minimum Documentation Searched 7 Classificati.n jttem I Classification Symbols IPC4 C 07 D; D 06 P Documentation Searched other than Minimum Documentation to the Extent that such DoLuments are included In the Fields Searched I III. DOCUMENTS CONSIDERED TO BS RELEVANT' Calegory I Citation of Document. with Indication, where appropriate, of the relevant passages i Relevant to Claim No. J A US, A, 4 226 763 DEXTER ET AL.) 7 October 1980, see the whole document A US, A, 4 278 589 DEXTER ET AL.) 14 July 1981, see the whole document A US, A, 4 668 235 (NEIL A. EVANS ET AL.) 26 May 1987, see the whole document A,P WO, A2,' 8800942 (ALLIED CORPORATION) 11 February 1988, see the whole document Special categories of cited documents: lo later document published after the International filing date document defining the general state of the art which is not or priority date and not in conflict with the apolication but considered to oe ol particular relevance cited to understand the principle or theory underlying the invention earlier document but publshed on or after the Internationlal E" alier document but pubhed on or ar the nternational document of particular relevance; the claimed Invention filig de cannot be considered novel or cannot be considered to document which may throw doubts on priorlty claim(s) or involve an inventive step which is cited to establi h the puolication datr of another document of articular relevance; the clamed invention citation or olher Ioecial reaion (a ipilned) document of OartIcular relevance; the claimed invention n or o e a s cannot be considered to Involve an inventive steo when the document referring to an oral disclosure, use, exhibition or document ia combined with one or more otner such docu- other means ments, sucn combination being obvious to a person skilled document oublished prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International 'iearch Report 23rd February 1989 2 0. 03. 8Y International Searching Authority Signatutei cer EUROPEAN PATENT OFFICE D PUTTE Form PCTIISA/2D0 scond sht) Jnuy 5ER P Form PCT/ISA/I210 Iecond iheet) (January 1iO5) -7 P ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. PCT/US 88/03547 SA 25695 Tis anncx lists the patent family mcmherc relating to the pontent dociimente cited in the ahovc-mentiooedi international crarch report. The mcmhere. are as contained in the Furopean Patent Officr FlIP File on 12/01/89 The Fliropean Patent Otfice is in no way liahle for thece portietilarn ihich ore m~erely given far the piirpocc of information. Patent document Plilleation Paten t familv ulcto cited in cearch report date heter(c) d.oteC US-A- 4 226 763 07/10/80 EP-A-B- JP-A- US-A- US-A- CA-A- CA-A- 0006564 55007292 4275004 4278589 1146948 1168655 US-A- 4 278 589 14/07/81 EP-A-B- US-A- JP-A- US-A- CA-A- CA-A- US-A- EP-A- WO-A- ~JP-T- AU-A- US-A- 0006564 4226763 55007292 4275004 1146948 1168655 4315848 0112120 84/02365 60500137 568110 4770667 09/01/80 19/01/80 23/06/8i 14/07/81 24/05/83 05/06/84 09/01/80 07/10/80 19/01/80 23/06/81 24/05/83 05/06/84 16/02/82 27/06/84 2 1/06/84 3 1/0 1/85 17/12/87 13/09/8 US-A- 4 668 235 26/05/87 WO-A2- 8800942 11/02/88 AU-FJ- 77027/87 24/02/88 w For more detuilq ahoitt thic anncx see OfMcinl Jouirnal of flte Fliropen I'ltent Office, No. t 2 1 g2