DE1719357A1 - Process for the treatment of molded articles made of synthetic polyesters or polyamides - Google Patents

Description

Description based on patent application of

Ieperial Chemical Induetries Ltd., London, Great Britain

concerning

Procedure «ar treatment of Foregettoden from synthetic polyesters or polyaides

Priorities: 9.2.1967 and 31.5 * 1967 - Great Britain

They refer to the treatment of porous substances made from fiber-forming eye-aesthetic poly.

Surface treatment of porous objects, the main components of which are linear, crystallizable polyesters and Polyaaddan are known · Bin wlrkeaeee Procedure for the nodification of eolo porno items in Font from fibers, thread, pil wen and fabrics en »um

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lend them an antistatic and hydrophilic surface ea rtr, hesteht therein "the surface of the object * With a polyethylene oxide or a PolyäthylenoxydderiTat optionally together with a compound treat au, welohe old the polyethylene oxide or its derivative under Bildnng a polymeric film reacted Although these treatments generally direct the application of the Reaktionenfeo naoh effective ffe, but they are not very durable to longer wash treatments, Reinigungebehandlungen or to UV light ·

The invention relates to a method for treating molded objects in the form of threads, fibers, textile fabrics or films made of synthetic fiber-forming polyesters or polyamides to give them a permanently modified To provide surface in which the molded objects at a temperature below the melting temperature of the material

a heat treatment rials of the molded article / be subjected while the shaped objects are in intimate contact with a reactive polymeric compound that has a molecular weight of at least 600, at least one reactive group as defined below contains and at least contains a surface-modifying polymeric group, characterized in that the treatment in the presence of an inorganic catalyst

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* 3-

running, making said reactive mere connection in the wee lent without networking ohemieeh is attached to the surface of the molded article.

The inorganic catalyst is preferably in one Quantity of at least 1. wt ^, absorbed by the reaction »- capable polymer compound, Torhanden "

The surface modification that occurs in a form object Also polyester or polyamide may be retained in the charge has been eating, lat permanently, i.e. it is opposed to repeated washing, even to cleansing and also to resistant to degradation by UV light »

Examples of inorganic catalysts that can be used according to the invention are iodine, compounds of sisens in bivalent or trivalent Zuetendt Selendioxyd, Kallumthiooyanat, Hatriu ^ ihydrogenphoephat, chromium-containing compounds, hydriodic acid, iodine & ure » Periodic acid, PhosphormolyMäaeäure and the Salae of these Acids.

In the non-metallic state, Bisen can be in the form of its Salae or their solutions or in the form of their coordination complexes either in the divalent or in the trivalent

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State of being present · The reactive group of the reactive polymeric compound is an amine group, a carboxylic acid group or a salt or a Seter thereof or an isocyanate group

The surface modifying polymeric group comprises at least one of the following: water-soluble polyoxyalkylene group, liquid-repellent group, the siloxane or fluorocarbon segmentβ contains, or a Group containing a variety of alcoholic hydroxyl radicals "

The molded articles consist of synthetic fiber-forming polyesters, such as b.B. Polyethylene terephthalate, poly-1,4-biB-Äethylen-cyolohexan-terephthalat, Polyäthylenoxybeneoat and their copolymers, or from synthetic fiber-forming polyamides "such as s" B. Hylon-6 and Nylon-66. Treatment with amines is particularly suitable for polyamides.

The treatment can be carried out in the presence of antioxidants, namely contains, in the case of treatment with a reactive polymeric compound "a PoIyozyalkylengruppe, _θ it is carried out particularly in the presence of a linked by sulfur or methylene bridges and from bisphenol Peroxydeersetzern

10983 7/1638

The treatment with possibly white amines can be carried out in the presence of a dye or an optical brightener ο «,.

The invention will now be elucidated by means of the following examples in which all files and percentages are expressed in weight, unless otherwise stated The examples are not intended to be limiting.

Examples 1-7

Manufacture of compound. Bis (2-hydroxy-3-oC- “ethylcyclohexyl-5-afethylphenyl) methane was added to an aqueous solution of polyethylene glycol diamine (prepared by reacting polyethylene glycol (molecular weight 1540) with thionyl chloride and then with aqueous ammonia) (0.5 wt - #, based on the weight of the Polyäthylenglycoldiamins)? 30 & ge (weight) solution given in an Äthylenoxydköndensat of nonylphenol, followed by the addition of an aqueous solution of various catalysts (2 wt _o - # solids based, on the weight of the Polyglycoldiamina), as they are given in Table 1 below, connected

109832/1638

the Ve rMiHUawft uses textile fabrics

The concentration of polyethylene glycol is 1 nminl ttaung «ar such that when padding on a polyethylene terephtha latte textile in a juice structure 3 & ew, «ji from the poly-

• ■ -diainin ethylene glycol / when the textile material is absorbed » The fabric was then dried in air and 5 min in an air oven at 20O ⁰ C heated "Sr was to stu 50 times in a Heimwaschmasohine with a 0.077 & lgen aqueous solution of a Detergenaes at 60 ⁰ C washed ₀ samples of the fabric were determined by the Vasohen 10 a rinsed in an aqueous solution of potassium bromide (1.4 g / i), rinsed for 2 min in a centrifuge and then vortex-dried at 60 ° 0 o The electrical resistance in Längerich-

tion of strips with a size of 19.8 χ 3.8 om was made measured after conditioning at 65 # relative humidity

The results shown in the following table were obtained.

10983? / 1R3 8

- Tab 1 Electrical resistance log 10,
Ablution 30th
Ablution ₀ (Ä « example
Mr. catalyst Ablution 9.36 10.23 90 » 1 K ₄ Pe (CH) ₆ 9.23 9.08 9.23 11.06 2 K ₅ Pe (OT) ₆ 9.11 9.46
9.34
9.54 10.48
10.11
11.49 9.95 3
4th
5 PeSO ₄ , (HH ₄ J ₂ SO ₄
Ha ₄ Pe (OK) ₅ HH ₂
Na ₂ Fe (NO) (CN) ₅ 9.53
9.28
9.48 9.48 10.23 11.46
11.23
11.74 6th (BH ₄ ) ₂ SO ^. ₂ 9.56 9.71 10.75 11.32 7th PeSO ₄ 9.61 12.90 > 13.3 11.66 Ver
equal
beiepo A nothing 12.60 > 13.3

Various amounts of potassium iodide (Biene label 2) were given to a 5% (by weight) aqueous solution of the amine made from a folyethylene oyd condecate with an average molecular weight of 1540, and the solution was then padded onto a polyethylene terephthalate fabric with a dried taffeta structure Containing 3 Gev .- # of the amine derivative was heated in an oven to 200 ° 0 for 5 minutes and then washed once, by weight

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of the amine derivative remaining on the fabric and the electrical resistance of the fabric were measured before the fabric was washed an additional 50 times. From Table 2 it can be seen that the potassium iodide at a concentration of at least 1.0 wt des iiainderivate, has a pronounced effect on the effectiveness of the treatment _e

All samples of the catalytically treated fabric were β hydrophilic, which was shown by the rapid rejection of oil discolouration when the samples are immersed in water « This effect was still very good even after 50 washes ο

Table 2

Potassium iodide
GeWo-jt, be—
like on
the weight
▼ on PoIy-
ethylene oxide Polyethy-
lenoxide
diandn,
that after
a wa
research on
the textile Resistance to the textile -
log ₁₀ ohm 10 Wa
sung 20 Wa
sung 30 Wa
sung 50 Wa
schung fabric ver
remain 1 wa
schung 10.71 - 12.04 13.00 (a) » 0.00 0.0 10.20 - 11.02 12.40 (b) 0.01 0.0 10 _v 00 10.75 11.18 12.08 12.04 (ο) 0.50 0.17 9.61 9.72 9.91 10.70 10.89 (d) 1.00 0.49 '9.51 8.95 - 9.23 10.30 (e) 1.10 0.59 9.18 9.10 9.04 9.36 9.38 (f) 2.00 1.02 9.04 9.06 8.98 9.20 9.20 (β) 3.00 1.43 8.92 9.42 9.48 9.74 9.85 (H) 5.00 0.71 8.86 9.42 9.40 9.48 9.48 (i) 10.00 1.05 9.04 8.95

Comparative example

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Example 9

Polyethylene terephthalate textile fabric was treated as in Example 8, with the difference that the potassium iodide was replaced by the catalysts given in Table 3. From the table it can be seen that iodine, hydriodic acid and the salts of hydriodic acid are effective catalysts.

Table 3

Kataly Kataly Polyethy- Resistance of the textile « 10 Wa- _{! 0} ohm 30 Wa- 50 Wa- sator sator lenoxide stcffs - log schg. IV / schg. schgo Gew »—S ^, diamine, based that after 1 Wa- on the
weight a wa-
sohung on 80hg c. by PoIy- the textile 10.71 12.04- 13.00 ethylene fabric ver 8.98 9.85 10.26 oxyddiarain remain 9.23 9.25 9.57 nothing * 0.00 10.00 iodine 2.25 0.71 9 _a 15 8.99 9.26 9.51 sodium 2.85 1.58 9.11 iodide 9.15 9.53 9.91 Idthium ~ 2.70 1.35 9.20 9.18 9.59 10.04 iodide Copper {I) -
3odid 1.95 0.67 9.20 Iodine water 2.70 0.86 9.08 etoffic acid

♦ Comparative example

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- ίο -

Example 10

Polyethylene oxide diamines with different molecular weights were prepared, and potassium iodide was added to the aqueous solutions as shown in Table 4. the Solutions were applied to polyethylene terephthalate textile as in Example 8 and the electrical resistance of the The fabric was cleaned periodically for 50 cycles in one Masohine measured. The resistances that it. Table 4 is given, «peculiar that polyethylene oxide diamines, which are formed from polyethylene oxide condensates with a molecular weight of and are manufactured above, result in an effective treatment »

Table 4

Molecular weight of the zur
Manufact.
d. Diamines
▼ used
Polyethylene oxide

Gtew, -% potassium iodide, based on polyethylene oxide diamine

Polyethylene oxide diamine, which appears after washing the fiber remains (wt .- ^)

Fabric resistanceβ

log ₁₀ ohm

1 wash

10 wash cycles

30 washing go

50 Waechgo

300 *

600

1540

4000

20000

3.0 3.0 3.0 3.0 3.0

0.00

1.19 1.43 1.28 0.96

11.50 9.40 8.86 9.48 9.43

12.90

9.53 9.06 9.56 9.80

9.90 9.20 9.48 9.42

* Comparative example

10.79 9.20 9.46 9.83

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BelsptejL 11

Polyäthylenterophthalattextilstoff as in Example 8 with the polyethylene oxide derivatives given in Table 5 Bind, treated From the table it can be seen that the derivatives applied without a catalyst are not really any permanent anti-btatic treatment results, whereas with Presence of potassium iodide made them permanent treatment

Table 5

Derivative of polyethy lenoxyd

catalyst

Wt .- # catalyst, b

Polyethylene oxide

Resistance of the textile material log ₁₀ ohms

1 Wa- j 10 Waachgo scorching.

30 wash cycles,

Carboxymethoxy derivative of polyethylene oxide
(brushed molecular weight 1540)

Sodium carboxy derivative of polyethylene oxide
(through molecular weight 1540)

Garboxymethoxy derivative of polyethylene oxide
(by "molecular weight 20,000")

Gaxboxymethoxy derivative of polyethylene oxide
(average molecular weight 6000

* not a KJ

13.30 j - 9.69 »10.54

10.86

11.86

KJ

* not c KT

*niece

* 0.93 j

^ 2.60 9.70

11.61

13.00 9.48

10 * 40

12.20 10.05

11.85 10.49

12 90 11/59

12.48 10.40

♦ Comparative examples

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BeiflPleJ. 12th

Chain-knitted fabric β made of nylon-6,6, which contained stabilizers against thermal degradation, were padded with aqueous solutions of polyethylene oxide diamine with a molecular weight of 1540, which was 3 wt .- #, weighted on the weight of the diamine, which is listed in the table 6 specified organic compounds contained. The dried textiles, which withheld 3 wt .- ^ of the Polyäthylenoxyddiamine, were ^{heated for 5 minutes in an oven to 200 or 215 0} O and then washed once. The weight of the amine compound remaining on the fabric and the electrical resistance of the fabric were measured. The fabric was then cleaned for 1 hour in an aqueous solution of sodium carbonate (2 g / l) and sodium oleyl sulfate (1 g / l). The table shows that iron (II) sulfate, potassium iodide and phosphonaolybdic acid are effective catalysts for the purposes of the invention.

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Table 6

catalyst Back
tempe
rature
⁰ C Polyethy
lenoxide,
that after
1 wash
on the
Textile fabric
remains behind
(«Jew.-S *) Resistance of the textile
substance s - log ^ ohm after the Rei
inclination at
100OQ Bisen (II) -
sulfate
It
Potassium iodide
η
Phosphorus-
aolybdenum
öäura
π
nothing* 200
215
200
215
200
215
215 1.77
1.74
0.93
0.72
2.16
1.74
0 after 1 wa
schung 11.00
10.71
11.71
11.85
11.59
10.28
13.0 10.11
9.97
10.34
10.23
10.18
9.97
10.43

* Tergleioh example

Example 1?

Example 12 was repeated using potassium iodide as a catalyst, a warp knitted fabric made of nylon -6 and a baking temperature of 200 ⁰ C for 5 min uses. The resistance (log ^ ohm) of the textile after a wash
was 10.00; after 10 washes 9 * 38; after 30 washes
10.78 and after 50 washes 10.42.

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Example 14

A fabric was prepared according to the example in Table 2 (d) Br treated had after a Haschinenwaschung a resistance of (log ₁₀ ohms) 8.72 Br _O was dried at 100 ⁰ C with an aqueous solution of sodium carbonate (2 g / l) and Natriumoleyleulfat (1 g / l) cleaned. Table 7, which gives the resistance of the fabric at various times, shows that the fabric is stable to extended laundering ",

Table 7

!Since the
Ablution at
100OC (st) 1 2 3 4th 7th 8th 10K2 11K2 resistance
(log _io öha) 9.08 9.00 9.11 9.11 9.40 9.15 9.92 9.65

Example 15

I am a blocked isocyanate derivative of polyethylene oxide with a average molecular weight of 20,000 was produced by the fact that the polyethylene oxide in benzene solution with two equivalents of methylene-bia (phenyl-4 ~ isocyanate) and then reacted with o-phenylphenol.

An aqueous solution (5% by weight) of the dried product was determined by Susatz of 0.5 oew. ~? S based on weight

109837Π638

the product, stabilized on BiB (2-hydroxy-5-ooethylcyolohexyl-5-n »thylphenyl) methane and then padded onto a polyethylene terephthalate textile in a quantity of 3%. The two fabric samples were 5 min at 200 ⁰ C in an air of s baked, whereupon a Maschinenvaschung was durohgefUhrt with them. After the electrical resistance was measured, the fabrics were washed an additional 49 times. From Table 8 it can be seen that the addition of potassium iodide has a profound influence on the effectiveness of the treatment "

In the previous examples the polyethylene oxide derivative used was Stabilized against heat by adding 0.5% bis (2-hydroxy-3-OCn9thylcyclohexyl-5-methyl-phenyl) * methane were added.

' Table 8

Without potassium iodide *
Kit potassium iodide Electrical resistance - log ^ ohms 10 Wa-
schg. 30 Wa-
ochg. 50 Wa-
echg. 1 Wa-
sohg. 12.23
9.72 10.16 11.92 10.06
9.58

Terglelchs example

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Example Ifi

PcJ ^ ethylene terephthalate textiles earthen with iü3r? .Gen solutions of polyethylene oxide diamine with a molecular weight το ». 1540, which contained 3% by weight of dianine of the inorganic compounds given in Table 9, padded. The getrooknt · ten fabric e, the 5 Oev .- ^ dee diamines zurückbehielten were erhite.t 3 minutes in an oven at 200 ⁰ C and then einaal gswaeohece the Qevichte the Aainverbindungen remaining on the Sextlletoffen were measured. The fabrics were then cleaned and tested as described in Example 12.

Table Q

catalyst Polyethylene dexyd,
dos after a
Ablution on the
Fabric ver
remains (<tew.-9 () Resistance of the
Textile fabric
(log ₁₀ 0hm)
a ^u cleaning
currency at 100 ⁰ C ~
rend I st Hatriuodihydrogen
phoephate
Potassium thlocyanate
Selenium dioxide
Phosphomolybdic acid
Potassium chromate
niohtB * 0.33
0.39
0.93
1.44
1.74
0 9.61
10.68
10.23
9.38
11.82
12.21

“Comparative example

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The results show that the above inorganic compounds fertilize effective catalysts for surface treatment of polyethylene terephthalate articles according to the invention are.

Example 17

This example illustrates a permanent surface modification cation of polyethylene terephthalate by diamino-pelydimethylsiloxane, either selenium dioxide or phosphomolybdic acid any catalyst is used.

0 (CJ-Diaminodiphenylpolydiiaethylsiloxan with a content of 20 dimethylfliloxane units per molecule, i.e. with a molecular weight of 1600-1700, and selenium dioxide (3 wt .- #, based on the weight of the polysiloxane) were dissolved in ethanol. The resulting solution was applied to a Polyäthylenterephthalattextiletoff by padding, such that 2 3EW .- $ i Polyeiloxan remaining on the fabric, and the coated fabric was then 5 min in an oven at 200 ⁰ C baked. Am further Polyäthylenterephthalattextilstoff was treated in a similar manner, wherein Phosphomolybdic acid was used in place of selenium dioxide Examples of the treated fabrics were washed 10 and 50 times and then subjected to the Bundesmann absorption test

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indicates that were obtained with an untreated textile fabric and with a textile etoff _t with the polyslloxane, but without an inorganic catalyst.

Table 10

catalyst Samples with
10 washes (ml) 98 Samples with
50 washes Penetrated
supply (ml) %
absorption 12th %
absorption * Tfab «traded
Textile fabric 45 2 12th niohte * 12th 3 19th 1 Selenium dioxide 8th 8th 1 Phosphorus·
molybdenic acid 9 7th

♦ Comparative example

It can be seen from the above results that the process according to the invention gives a durable water-repellent surface on a polyester molded article.

Aue Tables 4 and 10 it can be seen that reactive polymeric compounds having a molecular weight of 1500-1700 are particularly suitable for the present invention.

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Claims (2)

Claims · Procedure eur treatment of forum objects In Fora ▼ on threads «Fibers, textile fabrics or films made from synthetic fiber-forming polyethers or polyamides in order to provided with a permanently modified surface eu, at which the molded objects at a temperature below the peeling temperature of the material «of the molded object etner, heat treatment Standes / be subjected, meanwhile the Pormgegen are in intimate contact with a reactive polymeric compound which has a molecular weight of at least 600, contains at least one reactive group as defined above and at least a surface-modifying polymeric group such as ) ben defined, contains, characterized in that the treatment in the presence of a inorganic catalyst is carried out, whereby the said reactive polymeric compound is chemically linked to the surface of the molded article essentially without crosslinking. 2. The method according to Anspruoh 1, characterized in that the catalyst in an amount of clay at least 1 (tew. -5 £, based on the reactive polymeric compound, is present <, 109832/1638 7 ' Process according to Claim 1, characterized in that the reactive polymeric compound has a molecular weight of 1500-1700. MTMTANWMTt HMN6.H. RNCKE. DIfI - (NO. H. K) Ht Ml-INQ. S. STAEGH 109832/1638