DE1235254B - Optical brightening of materials made of polyolefins - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN mjtim PATENT OFFICE

EDITORIAL

t ~> 7

Int Cl D06c

-CJ8 L 23/02

P 'ί

German class. 8i-l

Number 1235 254

File number: C 26026IV c / 81

Filing date January 18, 1962

Opening day 2 March 1967

It has been found that 2,5 - di - [benzoxazolyl- (2 ')] - thiophene compounds the general formula

Z C-

C-C

-C

Il,

C-C

O'

(1)

where X and Xi are the same or different and a Denote hydrogen atom or a methyl group and Z and Zi are identical or different and each a hydrogen atom or a hydrocarbon radical with 1 to 10 carbon atoms, ζ Β one Methyl or phenyl groups, advantageously for the optical brightening of materials made of polyolefins, especially polyethylene or polypropylene, are suitable

Among the 2,5 - di - [benzoxazolyl - (2 ')] - thiophene compounds to be used according to the invention of the formula (1), for example, the following can be mentioned

Optical brightening of materials made from polyolefins

Applicant CIBA Aktiengesellschaft, Basel (Switzerland)

Representative Dr-Ing Dr jui F Redies, Dr rer nat B Redies, Dr rei nat D Turk and Dipt -Ing Ch GiHe, patent attorneys, Opladen, Rennbaumstrasse 27

Named as Erhndei Dr Erwin Maeder, Munchenstem, Di Jose! Lanter, Basel, Dr Peter Liechti, Binningen, Dr Max Dunnenberger, Birsfelden, Dr Adolf-Emil Siegnst, Basel (Switzerland)

Claimed priority Switzerland from January 19, 1961 (639)

(2)

2,5-di- [benzoxazolyl- (2 ')] thiophene HC CH

(3)

2- [Benzoxazolyl- (2 ')] - 5- [5'-methyl-benzoxazolyl- (2')] thiophene HC CH

H ₃ C

(4)

ο / ^x s ^x

2,5-di- [5'-methylbenzoxazolyl- (2 ')] thiophene HC CH

H ₃ C

<N

CH ₃

(5)

0 ^{/ X} S / ^x

2,5-di- [6'-methyl-benzoxazolyl- (2 ')] -tluophen

H ₃ C

CH,

Λ / ^Ν \

HC

CH

', N

2,5-di- [4'-methyl-benzoxazolyl- (2 ')] thiophene

H ₃ C

HC

-CH

y N

CH ₃ 2,5-di [7'-methyl-benzoxazolyl- (2 ')] thiophene

H ₃ C CH ₃

C C

, N

v \ ₀ / \ _s / ν

3,4-dimethyl-2,5-di- [benzoxazolyl- (2 ')] thiophene H ₃ C CH ₃

VA ₀ / \ _s / \ _O 3,4-dimethyl-2,5-di- [5'-methyl-benzoxazolyl- (2 ') -thiophene

H ₃ CC

H ₃ C

I. c-

⁵ CC

CH ₃ -C

Il

c - c

CH ₅

3,4-Dimethyl-2,5-di- [6'-methyl-benzoxazolyl- (2 ^/ )] thiophene

H ₃ C

H ₃ C
C-

CH ₃ C

CH ₃

<N

3,4-dimethyl-2,5-di- [4'-methyl-benzoxazolyl- (2 ')] thiophene

/ T

CH ₃ C

; N

V ^ N ₀ / \ _s / \ _v

H ₅ C CH ₅

3,4-dimethyl-2,5-di- [7'-methyl-benzoxazolyl- (2 ')] thiophene (6)

(10)

(H)

(12)

3,4-diphenyl-2,5-di- [benzoxazolyl- (2 ') -thiophene

H ₃ C

c - c

\ _s / \ ₀

3,4-diphenyl-2,5-di- [5'-methyl-benzoxazolyI- (2 ')] thiophene

3-phenyl-2,5-di- [benzoxazolyl- (2 ')] thiophene

CH,

w ^{HC c}

(T C C C C

SA ₀ / \ _s /

3-methyl-2,5-di- [benzoxazolyH2 ')] thiopliene

The 2,5-di- [benzoxazolyl- (2 ')] thiophene dci Foimel (2) and the 2,5-di- [5'-methyl-benzoxazolyl- (2 ')] thiophene of formula (4) are known from French patent specification 1,233,914

The thiophendenvates to be used according to the invention of the formula (1) can be obtained by methods known per se by o-Oxyainmobenzenes, optionally on the benzene nucleus can still carry a methyl group as a further substituent at elevated temperatures and preferably in the face of catalysts with dicarboxylic acids of the formula

HOOC - R - COOH

worm R one in the 2- and 5-position to the carboxyl groups bonded thiophene radical means odei with functional derivatives of these dicarboxylic acids implements

For asymetic thiophene bonds the 1-formula (1) in which the two benzo \ azoly Ii este are different, one can get / B in the way that one mole / weici \ eisehiedenci o-Oxyaminobenzenes with 1 mol of thiophene-2,5-dicarboxylic acid in the presence of catalysts higher Temperdtuien implemented and from the et IuI-tenen Reaction mixture the asymmetrical connection isolated

If fiber made of polyolefins, in particular Polyethylene or polypropylene, which can be used as staple fibers or continuous fibers in unbcaibeitem condition can be present in the form of strands or fabrics, according to the invention, to be optically brightened are, this is done with Voiteil in watery Medium in which the compounds in question are suspended Dispersants added willow, such as /. B.

Soaps, polyglycol ethers of fatty alcohols, fatty amines or alkylphenols, cellulose sulphite waste liquor or condensation products of optionally alkylated naphthalenesulphonic acids with formaldehyde to 100 ° C, for example at boiling temperature of the bath or in whose near (about 9O ⁰ C.) for ίο the inventive finishing are also solutions in organic solvents into consideration

The 2,5-difbenzoxazolyl- (2 ')] thiophene compounds to be used according to the invention of formula (1) can also consist of polyolefin materials before or during their deformation they can be added or incorporated the production of films, foils, tapes or mold bodies of the molding compound add or before Spinning loosely or finely distribute in the spinning mass The thiophendenvates of the formula (1) can finer added before or during the polymerization of the monomers of the polymerization mass will

Attention has already been drawn to the fact that methylgi uppen-substituted dibenzoxazolylthiophenes can lead to Vergrunungserschemungen, but this effect is with substrates thin layers (fibers, thin foils) cannot be observed

The amount of the invention to be used 2,5-di- [benzoxazolyl- (2 ')] - thiophene compounds of Formula (1), based on the material to be optically brightened, can vary within wide limits with very successful quantities, in certain cases ζ Β those of 0.01 ° / o, can be a clearer and more durable Effect can be achieved, however, amounts of up to about 1% can also be used

In the examples, parts are parts by weight and percentages are percentages by weight

example 1

Polypropylene fibers or polyethylene fibers are used with a liquor ratio of 1 40 for 60 minutes treated at 60 to 100'C in a bath which per liter 5 g of an adduct of about 35 moles of ethylene oxide with 1 mole of octadecyl alcohol, 0.5 g of sodium phosphate and 0.02 to 0.4 "/ 0 2,5-di- [benzoxazolyl- (2 ')] thiophene of the formula (2) (based on the fiber material) then the material is spooled and dried Polyolefin fibers thus retained have an essential higher whiteness than the untreated fasci η

If 1 g of 85% formic acid is used instead of 0.5 g of trisodium phosphate, one obtains a similar effect

Example 2

100 parts of polyethylene are placed on a warm Calender rolled into a homogeneous foil this film becomes 0.02 part of 2,5-di- [benzoxazolyl- (2 ')] thiophene of formula (2) and 0.5 parts of titanium dioxide incorporated The detached from the calender Foil is then pressed between 130 and 135 ° C hot steel plates to form a smooth on both sides Surface

The opaque polyethylene film obtained in this way has a significantly higher whiteness than a film which does not contain the thiophendenvate

Example 3

Polypropylene fibers or polyethylene fibers are used with a liquor ratio of 1. 40 treated for about 60 minutes at 50 to 100 ⁰ C in a bath containing 2 g per liter of an adduct of about 35 mol of ethylene oxide with 1 mol of octadecyl alcohol and 0.05% of 2,5-di- [5'-methyl-benzoxazolyl - (2 ')] thiophene of the formula (4) or 0.05% 3,4-dimethyl-2,5-di [5'-methyl-benzoxazolyl- (2')] thiophene of the formula (9) (based on the fiber material) then the material is rinsed and dried

The polyolefin fibers obtained in this way have a significantly higher whiteness than the untreated ones Fibers

Example 4

100 parts of polyethylene are rolled out on a 130 ⁰ C hot calender to form a homogeneous film in this film are slowly 0.02 parts of 2,5 - di - [5 '- methyl - benzoxazolyl - (2')] - thiophene of formula (4 ) or 3,4-dimethyl-2,5-di- [5'-methyl-benzoxazolyl- (2 ')] - thiophene of the formula (9) or 3,4-diphenyl - 2,5 - [benzoxazolyl - (2 ')] - thiophene of the formula (13) incorporated after the optical brightening agent has distributed evenly, the film is peeled from the calender and then pressed on a hot press at 130 to 135 ⁰ C to plates

In all three cases there are strong neutral casts Get lightening effects

Claims (1)

Claim Use of 2,5-di- [benzoxazolyl- (2 ')] -thiophene compounds the general formula χ-ίΥ ¹ f I SA ₀ / Z Zi ι ι c-c c-c ^ s / ^χ ο »■ wherein X and X] are the same or different and represent a hydrogen atom or a methyl group, and Z and Zi are the same or different and a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms represent, for the optical brightening of materials made of polyolefins Documents considered
British Patent No. 824,659 When the application was announced, a table with explanations was displayed