DE4219772A1 - 1,4-Bis(cyano styryl) mixts. for optical brighteners - esp. for natural or (semi)synthetic high molecular organic material partic. polyester fibres - Google Patents

Abstract

Mixt. of at least three different cpd.s of formula (I) contains 30-90 wt% o,p-ionomers or 20-90 wt%, m,p-isomers are two other symmetrically and/or asymmetrically, substd. ionomers, p,p'-ionomers. Also claimed is the prepn. of the mixt. contg. below 5-50 wt% o,o'-, o,p'= and o,m'-ionomers of (I) by reacting terephthaldialdehyde (TPADA) with cpds. of formulae (II), (III) and (IV). Q = -CH2P(O)(OR2), -CH2-P(O)R(OR), -CH2-P(O)-R2 or -CH2-P+R3X; R = opt. substd. 1-6(1-4)C alkyl or aryl; and X = Cl or Br. 1 mol. equiv. TPADA is reacted with 1.05-1.5 and equiv. (II) then 0.05-0.5 (0.005-0.7) mol. equiv. (III) and 0.45-0.9 (0.25-0.7) mol. equiv. (IV). USE/ADVANTAGE - Used as optical brightness in natural or (semi)synthetic high monomer organic materials, partic. polyester fibres (claimed), as well as granulates, foams, fibre e.g. for use in textile webs, paper etc., coatings, etc.. Whitener is good and icd nuauces can be observed. Further uses include scintillators for e.g. electrophotography, spin-bath prepn. in the mfr. of e.g. wash-and-wear clothing and in mixts. contg. pigments for printing dyebaths.

Description

The use of compounds of formula I.

As an optical brightener is known from the literature, the compounds often are used as mixtures of two or three different isomers, because such mixtures show a synergistic effect by the Whiteness of the mixture is higher than the whiteness of the same amount of respective individual component.

EP-B 064 303 is a mixture of three 1,4-bis (cyanostyryl) benzenes known from 27 wt .-% of the o, p'-isomer, 13 wt .-% of the o, o'-isomer and 60 wt .-% of the o, m'-isomer.

DE-A 38 02 204 names mixtures of three 1,4-bis (cyanostyryl) benzenes, which consists of 51-98.5% by weight of the p, m′-isomer, 48.5-1% by weight of the o, p′- Isomers and 0.5-5 wt .-% of the p, p'-isomer exist.

DE-A 29 29 599 describes mixtures of 1,4-bis (cyanostyryl) benzenes, from 0-80% by weight of the p, p'-isomer, 20-100% by weight of the p, o'-isomer and 0-80 wt .-% of the o, o'-isomer exist.  

EP-B 030 917 describes mixtures of 1,4-bis (cyanostyryl) benzenes called that from 51-99 wt .-% of an asymmetrically substituted Compound of formula I and 49-1 wt .-% of a symmetrically substituted Compound of formula I exist.

It has now been found that with the correct choice of the mixing ratios Mixtures of three 1,4-bis (cyanostyryl) benzenes can be obtained which show a pleasing reddish shade with good whiteness.

The invention thus relates to mixtures of at least three various compounds of formula I.

containing
30-90 wt .-% of the o, p'-isomer or
20-90 wt .-% of the m, p'-isomer and
two further symmetrically and / or asymmetrically substituted isomers, except for the p, p'-isomer, the sum of the isomers giving 100% by weight.

The mixtures of three isomers of 1,4-bis (cyanostyryl) benzene of the formula I according to the invention can each
5-70% by weight of two symmetrically substituted isomers,
5-50 wt .-% of two asymmetrically substituted isomers or
Contain 5-65 wt .-% of a symmetrically substituted and 5-75 wt .-% of an asymmetrically substituted isomer.

Mixtures (% by weight) of the following composition are advantageous

(Table 1)

Mixtures of the following composition are particularly preferred

(Table 2)

Mixtures of the following composition are very particularly preferred

(Table 3)

It is understood that the composition of the mixture within the various limits specified above are chosen so that the sum of all individual compounds is 100% by weight.  

The mixtures according to the invention are usually obtained by that the individual isomers of 1,4-bis (cyanostyryl) benzene in pure form be produced and then in the desired mixing ratio be mixed. The individual isomers can be Synthesis methods such as z. B. from DE-A 11 12 072 and EP-A 23 027 known are, manufacture.

Mixtures No. 1, No. 5 and No. 12 are preferably obtained in that one mole equivalent of terephthalaldehyde with a total of 2.0-2.6 mole Equivalents of a mixture of the compounds of formulas II, III and IV implements

where Q is a group of formulas
-CH ₂ P (O) (OR) ₂ , -CH ₂ -P (O) R (OR), -CH ₂ -P (O) R ₂ or -CH ₂ PR⊕ ₃ X⊖
R is an optionally substituted alkyl radical having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms or an aryl radical and
X is chlorine or bromine.

With mixture No. 5 or No. 12 is a mole equivalent of terephthalaldehyde with 1.05-1.5 molar equivalents of the compound of formula II implemented and then 0.05 to 0.5 mole equivalent of the compound of formula III and 0.45 to 0.9 mole equivalent of the compound of formula IV added.

With mixture No. 1 becomes a mole equivalent of terephthalic dialdehyde at 1.05-1.5 Mol equivalents of the compound of formula III implemented and then 0.05-0.7 mole equivalent of the compound of formula II and 0.25-0.9 mole  Equivalent to the compound of formula IV added. The process for the preparation of this mixture is preferably in Solvents carried out in the presence of a proton acceptor.

Examples of solvents are hydrocarbons such as toluene and Xylene, and alcohols, such as methanol, ethanol, isopropanol, butanol, glycols, Hexanols and cyclohexanols as well as ethers such as diisopropyl ether, tetrahydrofuran and dioxane, and dimethyl sulfoxide and mixtures of these solvents called. Polar organic solvents, such as Formamide, dimethylformamide and N-methylpyrrolidone, with dimethylformamide and dimethylformamide / alcohol mixtures are particularly noteworthy.

Basic compounds, such as, are primarily suitable as proton acceptors Alkali or alkaline earth metal hydroxides, alcoholates or amides, strongly basic amines and anion exchange resins in the hydroxide form. The use of is preferred Alkaline alcoholates and hydroxides, especially sodium methoxide. The reaction temperature depends on the type of compounds to be reacted Formula II-IV. It is between -10 ° C and + 100 ° C, advantageous between 0 ° -50 ° C. A preferred embodiment is that Reactants react at lower temperatures and the reaction to finish at a higher temperature.

The claimed method can be carried out, for example, in such a way that the proton acceptor in the solvent and a solution of the Reaction components terephthalaldehyde and compounds of formula II to IV added dropwise, but it is also possible to use a solution of terephthalaldehyde and to present compounds of the formulas II to IV and the proton acceptor to admit. Another embodiment is either To present terephthalaldehyde or the compounds of the formulas II to IV, then first the proton acceptor and then the remaining one Add component. The implementation is generally under strong Development of heat, so that you may have to cool. The workup  the reaction mixture is carried out in a known manner, for. B. by adding Methanol or ethanol and separation of the precipitated products. The so product mixtures obtained can be determined by GC (gas chromatography) analyze and characterize.

The starting compounds of the formulas II to IV are known and can be according to known methods can be produced.

The mixtures according to the invention can, for example, without the The following overview should be used to express any restriction Brightening of the groups of organic mentioned in DE-A 29 29 599 Materials are used.

The following may be mentioned in detail:
I. Synthetic organic high molecular materials:

• a) Polymerization products based on at least one polymerizable Organic compounds containing carbon-carbon double bond.
• b) polymerization products obtainable by ring opening.
• c) polycondensation products or precondensates based on bi- or polyfunctional compounds with condensable groups, their homo- and Mixed condensation products and post-treatment products.
• d) polyaddition products such as polyurethanes (crosslinked and uncrosslinked) and Epoxy resins.

II. Semi-synthetic organic materials
III. Natural organic materials of animal or vegetable origin
The organic materials to be optically brightened can belong to the most varied of processing conditions (raw materials, semi-finished or finished products). On the other hand, they can be in the form of a wide variety of shaped structures, for example as predominantly three-dimensionally expanded bodies such as plates, profiles, injection moldings, various workpieces, chips, granules or foams, and also as predominantly two-dimensional bodies such as films, foils, lacquers, coatings, impregnations and coatings or as predominantly one-dimensional bodies such as threads, fibers, flakes, wires. On the other hand, the said materials can also be in unshaped states in the most varied of homogeneous or inhomogeneous forms of distribution, such as, for example, B. as powders, solutions, emulsions, dispersions, latices, pastes or waxes.

Fiber materials can, for example, as endless threads (stretched or undrawn), staple fibers, flakes, stranded goods, textile threads, yarns, threads, Non-woven fabrics, felts, wadding, flocking structures or as textile fabrics or textile composites, knitted fabrics and as papers, cardboards or paper pulps available.

The compounds to be used according to the invention come u. a. Meaning of the treatment of textile organic materials, especially textile Fabrics such as B. as powders, solutions, emulsions, dispersions, latices, Pastes or waxes are present.

If fibers, which are staple fibers or continuous threads, in the form of strands, Woven, knitted, non-woven, flocked substrates or composites can be present, are to be optically brightened according to the invention, this happens with Advantage in an aqueous medium, in which the compounds in question finely divided form (suspensions, so-called microdispersions,  if necessary solutions) are available. If necessary, during treatment Dispersing, stabilizing, wetting and other auxiliaries are added.

Depending on the brightener connection type used, it can be as prove beneficial in neutral or alkaline or acid bath work. The treatment is usually carried out at temperatures of about 20 to 140 ° C, for example, at or near the boiling point of the bath (approx 90 ° C). For the finishing of textile substrates according to the invention solutions or emulsions in organic solvents also come in Consider how this happens in dyeing practice in the so-called solvent dyeing (Foulard thermosetting application, pull-out dyeing process in dyeing machines) is practiced.

The new optical brighteners according to the present invention can also added or incorporated into the materials before or during their deformation will. So you can, for example, in the production of films, foils (e.g. rolling in polyvinyl chloride in the heat) or moldings of Add molding compound or injection molding compound.

If the shape of fully or semi-synthetic organic materials done by spinning processes or spinning masses, the optical Brighteners can be applied using the following methods:

• - Addition to the starting substances (e.g. monomers) or Intermediate products (e.g. precondensates, prepolymers), d. H. before or during the polymerization, polycondensation or polyaddition,
• - powdering onto polymer chips or granules for spinning masses,
• - Bath coloring of polymer chips or granules for spinning masses
• - metered addition to spinning melts or spinning solutions,
• - Application on spinning cable before stretching.

The new optical brighteners according to the present invention can can also be used in the following forms of application, for example:

• a) Mixtures with dyes (shading) or pigments (dyes or especially z. B. white pigments) or as an additive to dye baths, Printing, etching or reserve pastes. Also for the aftertreatment of Dyeing, printing or etching printing.
• b) in mixtures with so-called "carriers", wetting agents, plasticizers, Swelling agents, antioxidants, light stabilizers, heat stabilizers, chemical bleaches (chlorite bleach, bleach bath additives).
• c) in mixtures with crosslinking agents, finishing agents (e.g. starch or synthetic finishes) as well as in combination with various Textile finishing processes, especially synthetic resin finishing (e.g. Crease-resistant equipment such as "wash-and-wear", "permanent-press", "non-iron"), also flame-resistant, soft-grip dirt release ("anti-soiling") - or antistatic equipment or antimicrobial equipment,
• d) Incorporation of the optical brightener in polymeric carrier materials (Polymerization, polycondensation or polyaddition products) in dissolved or dispersed form for use e.g. B. in coating, Impregnating or binding agents (solutions, dispersions, emulsions) for Textiles, fleeces, paper, leather,
• e) as additives to so-called "master batches",
• f) as additives to a wide variety of industrial products to the same make it more marketable (e.g. improvements to the aspect of soaps, Detergents, pigments),
• g) in spin bath preparations, d. H. as additives to spinning baths, such as for Improvements in lubricity for the further processing of synthetic Fibers are used, or from a special bath before Stretching the fiber
• h) as scintillators, for various purposes of a photographic nature, such as. B. for electrophotographic pure production or supersensitization,
• i) depending on the substitution as laser dyes.

The lightening process with textile treatment or finishing methods combined, the combined treatment can in many cases advantageously with the help of appropriate stable preparations, which the optically brightening compounds in such a concentration contain that the desired brightening effect is achieved.

In certain cases, the brighteners become full after treatment Brought effect. This can be, for example, a chemical (e.g. acid Treatment), a thermal (e.g. heat) or a combined chemical / represent thermal treatment. This is how you do things with the optical brightening of a number of fiber substrates, e.g. B. of polyester fibers, with the brighteners according to the invention expedient in such a way that these fibers with the aqueous dispersions (possibly also solutions) of Whitening agent at temperatures below 75 ° C, e.g. B. at room temperature, impregnated and dry heat treatment at temperatures above Subjects 100 ° C, it is generally advisable to the fiber material beforehand at a moderately elevated temperature, e.g. B. at at least 60 ° C to about To dry at 130 ° C. The heat treatment in the dry state then takes place advantageous by heating in a drying chamber, by ironing in the specified temperature interval or also by treatment with dry, superheated steam. The drying and dry heat treatment can also be carried out one after the other or in a single Operation can be merged.

The amount of new optical brighteners to be used according to the invention, based on the material to be optically brightened, can be used within wide limits vary. Even with very small quantities, in certain cases e.g. B. such of 0.001% by weight, a clear and durable effect can be achieved will. However, amounts of up to about 0.8 percent by weight and optionally up to about 2 percent by weight are used. For most practical concerns are preferably between 0.005 and 2, preferably 0.1 to 0.5 weight percent of interest.  

For various reasons, it is often advisable not to use the brightener as such, d. H. to be used purely, but mixed with a wide variety of auxiliary and coupling agents, such as anhydrous sodium sulfate, sodium sulfate decahydrate, Sodium chloride, sodium carbonate, alkali metal phosphates, such as sodium or Potassium orthophosphate, sodium or potassium pyrophosphate and sodium or Potassium tripolyphosphates or alkali metal silicates.

The new optical brighteners have the particular advantage that they also Presence of active chlorine donors, such as. B. hypochlorite, are effective and without significant loss of effects in washing baths with nonionic Detergents such as B. alkylphenol polyglycol ethers can be used.

In the following example, percentages are always percentages by weight:

example 1

In a mixture of 54 ml dimethylformamide (DMF) and 11 ml methanol 10.2 g of terephthalic dialdehyde and 25.0 g of diethyl-o-cyanobenzyl dissolved phosphonic acid ester. To do this, drop by drop at temperatures of 0-5 ° C 21 ml 30% sodium methylate solution in methanol. After 15 Minutes are 6.2 g of diethyl-m-cyanobenzylphosphonic acid ester and 9.2 g Diethyl p-cyanobenzylphosphonic acid ester added and in the course of 15 Minutes at approx. 20 ° C 11 ml of a 30% solution of sodium methylate in Methanol was added dropwise. The mixture is then stirred for one hour at room temperature with 135 ml Diluted methanol, suction filtered, first with methanol and then with water washed. After drying, 21.3 g (84%) of a yellow powder are obtained Formula I, which according to GC analysis consists of 27% of the o, m′-isomer, 45% of the o, p′- Isomer and 28% of the o, o'-isomer. This mixture shows a pleasing red shade with good whiteness.

Claims (8)

1. Containing mixtures of at least three different compounds of the formula I. 30-90 wt .-% of the o, p'-isomer or
20-90 wt .-% of the m, p'-isomer and
two further symmetrically and / or asymmetrically substituted isomers, except for the p, p'-isomer, the sum of the isomers giving 100% by weight. 2. Mixtures according to claim 1, characterized in that they each Contain 5-70 wt .-% of symmetrically substituted isomers. 3. Mixtures according to claim 1, characterized in that they each Contain 5-70 wt .-% of symmetrically substituted isomers. 4. Mixtures according to claim 1, characterized in that they contain 5-65% by weight of the symmetrically substituted isomer and
Contain 5-75 wt .-% of the asymmetrically substituted isomer. 5. A process for the preparation of mixtures according to claim 1, containing in addition to 5-50 wt .-% of the o, o'-isomer, the o, p'-isomer and the o, m'-isomer of the formula I, by reacting Terephthalaldehyde with compounds of the formula II, III and IV, where Q is a group of formulas
-CH ₂ -P (O) (OR ₂ ), -CH ₂ -P (O) R (OR), -CH ₂ -P (O) -R ₂ and -CH ₂ -P⊕R ₃ X⊖,
R is an optionally substituted alkyl radical having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms or an aryl radical and
X is chlorine or bromine, characterized in that 1 mol equivalent of terephthalaldehyde is reacted with 1.05 to 1.5 mol equivalents of the compound of the formula II and then with 0.005 to 0.5 mol equivalent of the compound of the formula III and 0.45 to 0.9 mol equivalent of the compound of formula IV is reacted. 6. A process for the preparation of mixtures according to claim 1, containing in addition to 5-50% by weight of the m, m'-isomer, the o, m'-isomer and the m, p'- Isomers of formula I, by reacting terephthalaldehyde with Compounds of the formula II, III and IV, characterized in that 1 mol Equivalent terephthalaldehyde with 1.05 to 1.5 molar equivalents of Compound of formula III, is reacted and then with 0.005 to 0.7 Mol equivalent of the compound of formula II and 0.25 to 0.7 mol equivalent the compound of formula IV is implemented.   7. Use of the mixtures according to one of claims 1 to 4 as optical Brightener. 8. Use according to claim 7 for natural, semi-synthetic or synthetic highly monomeric organic materials, in particular from Polyester, especially polyester fiber.