TWI402395B - Light-fast dyeings on bicomponent fibres - Google Patents

Description

Lightfast dyeing on bicomponent fibers

The present invention relates to a method of dyeing multi-component fibers, particularly dyed two-component and three-component fibers, which is distinguished by excellent light fastness. The invention further relates to a dyed, light-resistant multicomponent fiber.

Unmodified polyolefin fibers, especially polypropylene (PP) fibers, can be dyed using general disperse dyes, but can only be dyed to very low light fastness. The prior art methods for improving dyeability include, on the one hand, chemically modified polyolefin fibers (especially polypropylene (PP) fibers) and on the other hand the use of modified or newly synthesized dyes.

JP 10-331034 relates to a fiber having excellent hygroscopicity and relaxation properties, which is suitable as a fiber of a fabric which is improved in heat resistance and light resistance of the fiber itself, and is used in a core component comprising a specific amount of a phenol antioxidant and The sheath component includes a specific amount of a benzotriazole-based ultraviolet absorber. There is no relevant disclosure of lightfast dyeing of bicomponent fibers.

EP445076 benzotriazole ultraviolet (UV) absorber using a modified lignosulfonate as a dispersant, a stable dispersion, a method of dispersing the benzotriazole UV absorber, and a method for protecting a fabric using the stabilized dispersion And the fabric treated with the stable dispersion, to avoid any undispersed UV absorbent being filtered out to produce deposits. There is no relevant disclosure of lightfast dyeing on bicomponent fibers.

EP 474 595 relates to a stable dispersion aqueous solution of a UV-absorbing benzotriazole compound, wherein the dispersion is an excellent composition for improving the light fastness of dyeing on synthetic fibers, especially polyester fibers or acid-modified poly Ester fiber. However, there is no relevant disclosure of lightfast dyeing on bicomponent fibers.

US 5,221,287 relates to a method for the photochemical and thermal stabilization of polyamine fibers having an affinity for acids and basic dyes and blends of the fibers with each other and with other fibers. However, there is no relevant disclosure of lightfast dyeing on bicomponent fibers.

Appropriate process treatments and suitable dye dispersions which can also be used for dyeing polyester fibers are now available so that good lightfast dyeing results can be obtained with the dyeing, which treatment is carried out in particular using benzotriazole derivatives.

Now, it has been found that the dyeing of multi-component fibers, especially the disperse dyes, after dyeing the bicomponent fibers composed of the thermocompatible polyolefin and the polyamidamine, when the multicomponent fiber is treated with the benzotriazole derivative, It has high light fastness.

The invention further relates to a light-resistant multicomponent fiber dyed by the method of the invention.

The invention also relates to the use of benzotriazole derivatives to enhance the light fastness of dyed multicomponent fibers, especially after dyeing of bicomponent fibers consisting of thermally compatible polyolefins and polyamides.

The multicomponent fiber of the present invention is a side-by-side fiber (two or more different polymers side by side, not a blend, nor a fiber fiber - thus a binder and thus a single fiber), a sheath-core fiber (the first polymer) Forming a core portion and the second polymer forms a sheath surrounding the first polymer, and optionally another polymer forming a sheath surrounding the inner core-and-sheath-structure or a star-like shape A fiber in which a plurality of core portions of a polymer are surrounded by a second sheath polymer. The sheath-core fiber and the star-shaped fiber are preferred multi-component fibers, and the sheath-core fiber is a better fiber. In preferred sheath-core fibers, the sheath is concentrically arranged around the core portion.

Preferred multi-component fibers, especially bi-component fibers, are comprised of a thermally compatible polyolefin and a polyamidamine, especially polypropylene, modified polyamine (PA) and polydecylamine.

Preferred multi-component fibers, or more specifically bi-component fibers, have multifilament properties.

More preferred multi-component fibers, especially bi-component fibers, are formed by coating the outer core of a polymer, preferably polyamine, with another polymer, preferably a polyolefin. A fiber composed of a thermocompatible polypropylene and a polyamidamine, especially polypropylene and nylon 6 (PP/N6), is produced by a spinning method to produce a polymer (preferably polyfluorene). The elongated filaments of the amine are formed in a matrix of another polymer, preferably a polyolefin. When the two melts are simultaneously fed to the spinning holes, bicomponent filaments are produced. A spinneret having two concentric holes produces a sheath-nuclear filament (two-component sheath-core fiber) from both melts.

In order to improve the adhesion between PA and PP, an ionomer copolymer (IM), maleic anhydride or polyester may be used. These agents for enhancing the compatibility between the various components may be present in an amount up to 10% by weight, but preferably from 3 to 8 % by weight.

Preferably, the multicomponent fibers, especially the multicomponent fibers, are dyed in one component and the benzotriazole derivative is applied to the other component of the multicomponent fiber or bicomponent fiber. The dye and the benzotriazole derivative are not located in the same component of the multicomponent fiber.

The preferred multicomponent fibers of the present invention, especially bicomponent fibers, are dyed in the core portion and the benzotriazole derivative is applied to the sheath portion of the multicomponent fiber or bicomponent fiber. Preferred multicomponent fibers of the present invention are bicomponent fibers.

Preferred benzotriazole derivatives are benzotriazole derivatives of formula (I) Wherein R ₁ is a halogen atom, R ₂ is a C ₁ to C ₆ alkyl group, and R ₃ is a C ₁ to C ₆ alkyl group. Preferably, R ₃ is a branched chain C3 to C6 hydrocarbon group. Preferably, in the benzotriazole of the formula (I), R ₁ is chlorine or fluorine, R ₂ is methyl, ethyl or propyl, and R ₃ is methyl, ethyl or propyl, isopropyl or Third butyl.

Excellent formula (I) benzotriazole has the formula (I') Wherein R ₁ is a halogen atom, R ₂ is a C ₁ to C ₆ alkyl group, and R ₃ is a C ₁ to C ₆ alkyl group.

Preferably, in the benzotriazole of the formula (I'), R ₁ is chlorine or fluorine, R ₂ is methyl, ethyl or propyl, and R ₃ is methyl, ethyl or propyl, isopropyl. , the third butyl group.

An excellent one is a benzotriazole derivative of the formula (I') wherein R ₁ is chlorine, R ₂ is methyl and R ₃ is a third butyl group.

The benzotriazole is used in the process of the invention in an amount of from 0.01 to 20% by weight, based on the dry matter, preferably from 0.01 and especially from 0.1 to 15% by weight on a dry basis, but particularly from 0.1 to 10% by weight on a dry basis. percentage.

Treatment with a benzotriazole derivative can be carried out simultaneously after dyeing or during dyeing. The dyeing of the present invention includes printing.

The disperse dyes used in the process of the present invention are those which have conventionally been used for dyeing polyester materials but also have high light fastness to polyamidoamines.

Preferred disperse dyes for use in the process of the invention are disperse dyes having formula (1) Wherein R ₄ and R ₄ are each phenyl or benzene substituted by halogen - especially -Cl or -Br, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH base.

A more preferred disperse dye for use in the process of the invention is a disperse dye having formula (2), (3) or (4)

Wherein R ₅ , R' ₅ and R" ₅ are each halogen - especially -Cl or -Br, phenyl or halogen - especially -Cl or -Br, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or phenyl substituted by -OH.

A more preferred disperse dye for use in the process of the invention is a disperse dye having formula (5)

Wherein R ₆ is halogen - especially -Cl or -Br, phenyl or via halogen (especially -Cl or -Br), -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or a phenyl group substituted with -OH, a phenoxy group or a benzene substituted with a halogen (especially -Cl or -Br), -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH Oxy, R ₇ is phenyl or phenyl substituted by halogen (especially -Cl or -Br), -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH, R ₈ is -NH ₂ or -NHR ₉ , wherein R ₉ is halogen, especially -Cl or -Br, phenyl or halogen (especially -Cl or -Br), -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH substituted phenyl, phenoxy or halogen (especially -Cl or -Br), -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or a phenoxy group substituted by -OH, or R ₉ is a group of the formula SO ₂ -phenyl group, wherein the phenyl group of the SO ₂ -phenyl group is unsubstituted or is halogenated ( In particular, phenyl substituted by -Cl or -Br), -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH.

A more preferred disperse dye for use in the process of the invention is a disperse dye having formula (6)

Wherein R ₁₀ is -H or halogen, especially -H, -Cl or Br.

Particularly suitable formula (1), (2), (3), (4), (5) or (6) disperse dyes for use in the process of the invention are CI Disperse Orange 41 and/or CI Disperse Orange 41: 1 and/or CI Disperse Violet 36 and/or CI Solvent Yellow 163 and/or CI Disperse Blue 73 and/or CI Disperse Blue 56 and/or CI Disperse Red 86 and/or CI Disperse Red 60 and/or CI Disperse Violet 27 And/or CI disperse yellow 64 and/or CI disperse yellow 54.

The dye of the formula (1), (2), (3), (4), (5) or (6) may be used in the method of the present invention alone or in the form of a mixture comprising one of the foregoing disperse dyes.

The dyeing or printing in the process of the invention is carried out according to methods known per se, for example as described in French Patent No. 1445371. Conventional dyeing methods which can be dyed and/or printed with disperse dyes by the method of the invention are also described, for example, in M. Peter and HK Rouette: "Grundlagen der Textilveredelung; Handbuch der Technologie, Verfahren und Maschinen", thirteenth, revised edition, 1989, In Deutscher Fachverlag GmbH, Frankfurt/Main, Germany, ISBN 3-87150-277-4, the following precautions are particularly relevant: pages 460 to 461, pages 482 to 495, pages 556 to 566 and pages 574 to 587 . The possibilities of mats and blankets include continuous or batch dyeing methods, including non-contact dyeing or dye or dye formulations by typical printing or dyeing by the ChromoJet method or other methods (M. Peter and HKRouette: "Grundlagen der Textilveredelung; Handbuch der Technologie, Verfahren und Maschinen", thirteenth, revised edition, 1989, Deutscher Fachverlag GmbH, Frankfurt/Main, Germany, ISBN 3-87150-277-4, pp. 484-492 (7.221.1) Chapter) and page 846 and Figure 8.70).

The dyeing obtained has comprehensive fastness; in particular, it refers to light fastness, heat setting and pleating fastness and excellent wet fastness, after heat setting (heat absorbing fastness), and especially high light resistance Fastness.

The fabric materials mentioned may be in various processing forms, such as fibers, yarns or webs, woven or looped knit fabrics or blankets. It has been found that such fabrics can be applied to automotive parts or techniques that are commonly used in transportation engineering such as trains, airplanes and/or trams, building structures or more specifically in or on building structures and/or leisure parts.

Disperse dyes are applied to the fabric material by known dyeing methods. For example, the polyolefin-polyamine polycomponent fiber or bicomponent fiber material is self-dispersing in the presence of an anionic or nonionic dispersant with or without a conventional carrier at a temperature between 70 and 140 °C. The aqueous solution is exhausted.

The polyolefin-polyamide-based fibrous material is preferably dyed at pH 3 to 7, especially 3 to 6. The dyeing temperature is preferably in the range of 70 to 110 ° C, especially 80 to 105 ° C.

Baths are more dependent on the device, substrate and supplemental form. However, the bath ratio can be selected within a wide range, for example from 4:1 to 100:1, preferably from 5:1 to 30:1.

The disperse dyes used in the present invention can be applied by conventional dyeing methods such as, for example, dyeing, continuous, printing or non-printing, such as, for example, ink jet or spray/jet printing particularly suitable for blankets (Chromojet) )method.

The disperse dyes used in the present invention are also suitable for dyeing from small bath ratios, for example, for continuous dyeing methods or batch and continuous foam dyeing methods.

The dye liquor or printing paste may contain, in addition to water and dyes, other additives such as wetting agents, defoamers, leveling agents or agents which affect the properties of the fabric material, such as fabric softeners, flame retardants or antifouling agents, Water and oil repellents and water softeners and natural or synthetic thickeners such as alginate and cellulose ethers.

The amount of disperse dye used in the dye bath or printing paste can vary widely depending on the desired color density. The preferred amount is usually in the range of 0.01% (0.001% by weight to 20% by weight) to 15% by weight, especially 0.1% by weight to 10% by weight, based on the weight of the fiber and the printing paste.

Various dyeing and printing methods for use in blankets are preferably carried out by preparing a dye liquor having the following composition for use in a continuous process: 0.001 to 30 g/liter disperse dye 1 to 15 g/liter thickener, such as Polyprint M225 , polysaccharide, guar gum, tamarind gum 0.1 to 10 g / liter wetting and anti-matting agent, such as Sandogen WAF liq., Sandogen AFB liq., 0.1 to 10 g / liter acid donor, such as Sandcid VS liq., Sandacid VAN liq. 0.1 to 10 g/liter buffer system, such as Sandacid PB liq., Sandacid PBBK liq. 0.1 to 30 g/L of the benzotriazole derivative of formula (I).

The material to be dyed is padded in a padder mill at 100 to 600% wet pick-up (preferably 400%), and fixed in saturated hot steam at about 102 ° C for 8 minutes. 20 minutes; or may be fixed by dry heat or superheated steam during the aforementioned period. Thereafter, the material is rinsed with cold water and, if appropriate, further processed or further processed as is customary in the industry.

A dye solution having the following composition is prepared for use in an exhaust dye method: 0.001 to 20% disperse dye 0.1 to 10 ml/liter dispersant, such as Lyocol RDN Liq., Lyocol OU Liq. 0.1 to 5 g/liter ammonium sulfate 0.1 to 30 g/L of the benzotriazole derivative of formula (I).

The pH is adjusted to a value of from 3 to 7, preferably from pH 4.5 to 6. The dyeing is carried out at 70 to 140 ° C for 30 to 90 minutes, followed by rinsing with water, and if appropriate, further processing or further processing as is customary in the industry.

A printing paste having the following composition is prepared for use in a non-printing printing method: 0.001 to 30 g/liter of disperse dye 2 to 20 g/kg of synthetic thickener, such as Tanaprint ST 160, Prisulon 200, Texipol 675031 0.1 to 10 g / Kilograms of dispersing, wetting, anti-matting agents, such as Sandogen WAF liq., Sandogen AFB liq., Tanaspers CF liq. 0.1 to 10 g / kg of acid for pH adjustment, such as 0.1 to 10 g / kg of defoamer For example, Nofome 1125 liq., Antimussol UP liq., Antimussol SF liq. 0.1 to 30 g/L of the benzotriazole derivative of the formula (I).

The material to be printed and dyed in the non-printing printing method is sprayed with the printing paste to a liquid absorption rate of 100 to 600% by dry weight of the material to be printed, preferably 300%, and is fixed with saturated hot steam at about 102 ° C. After 2 to 20 minutes (preferably 8 minutes), it is only possible to use dry heat or superheated steam for fixing. Thereafter, the material is rinsed with cold water and, if appropriate, further processed or further processed as is customary in the industry.

Further processing or further processing in the industry may include finishing with fluorinated chemicals, other antifouling and/or water repellent chemicals, and/or applying a blanket backing layer.

The following examples are intended to illustrate the invention. Percentages are by weight unless otherwise stated.

Example

The dyeing example was a small piece of blanket made of bicomponent fiber (PP/PA) from Aquafil Textile Yarns S.p.A., Via Parma, 45, IT-46041 Asola-Mantova (Italy).

Example 1 (not according to the invention)

The small piece of blanket in the padding machine contains 0.25 g / liter CI Solvent Yellow 163, 0.06 g / liter CI Disperse Red 86 and 0.009 g / liter CI Disperse Blue 73, 100 g / liter of 3.5% Polyprint M225 solution, 3 g / liter Sandogen WAF liq., 2 g/L Sandacid VS liq. and padding in the dye bath of Sandacid PB liq. which is sufficient for the pH5 dye bath to reach 400% absorbance (dry weight), padded blanket The color was fixed in saturated hot steam at 102 ° C for 8 minutes and then washed with cold water. A beige stain was obtained on the mat. The light fastness of the resulting mat was tested (see below).

Example 2 (not according to the invention)

The small piece of blanket was dyed as in Example 1, but the dye bath additionally contained 5 g/L of 10% suspension of the compound of the formula

The mat was dyed in beige. The light fastness of the resulting mat was tested (see below).

Example 3

The small piece of blanket was dyed as in Example 1, but the dye bath additionally contained 5 g/L of 25% suspension of the compound of the formula

The mat was dyed in beige. The light fastness of the resulting mat was tested (see below).

Example 4 (not according to the invention)

The small piece of blanket was dyed as in Example 1, but the dye bath additionally contained 5 g/L of 20% suspension of the compound of the formula

The mat was dyed in beige. The light fastness of the resulting mat was tested (see below).

Example 5 (not according to the invention)

The small piece of blanket was dyed as in Example 1, but the dye bath additionally contained 5 parts per liter of 35 parts of the compound of the formula And 35 parts of the compound of the formula

Suspension. The mat was dyed in beige. The light fastness of the resulting mat was tested (see below).

Example 6 (not according to the invention)

The small piece of blanket was dyed as in Example 1, but the dye bath additionally contained 5 g/L of 10% suspension of the compound of the formula

The mat was dyed in beige. The light fastness of the resulting mat was tested (see below).

Light fastness measurement of Examples 1 to 7

Light fastness is measured according to ISO 105 Method 2. The mat samples to be tested were exposed halfway with a blue light fastness standard, which was a wool cloth. The color fastness was evaluated by comparing the color change of the sample with the color change of the light fastness standard used. The sample was exposed to a specific amount of light energy and was evaluated on a fifth-order gray scale instead of the eighth-order blue scale. A dye fastness to light rating of 1 to 5 is produced.

Example 8

A small piece of blanket in a padder containing 0.30 g/L CI Disperse Blue 73, 100 g/L 3.5% Polyprint M225 solution, 3 g/L Sandogen WAF liq., 5 g/L 25% compound suspension 2g/L Sandacid VS liq. and padding in a dye bath of Sandacid PB liq. which is sufficient for the pH5 dye bath to reach 400% liquid absorption (dry weight). The padded blanket is at 102 ° C. The color was fixed in saturated hot steam for 8 minutes, and then washed with cold water to obtain a mat with excellent light fastness and reddish yellow.

Examples 9 to 16

The small piece of blanket was dyed as in Example 8, but the dye bath contained 0.32 g/L of dye (F) instead of 0.30 g/L CI Disperse Blue 73: A mat is obtained which is dyed in the color and has excellent light fastness.

Claims (9)

A method for improving the light fastness of dyeing of a disperse dye on a multicomponent fiber composed of a thermocompatible polyolefin and a polyamidamine, characterized in that the multicomponent fiber is treated with a benzotriazole derivative. Wherein the benzotriazole derivative has the formula (I) Wherein R ₁ is a halogen atom, R ₂ is a C ₁ to C ₆ alkyl group, and R ₃ is a C ₁ to C ₆ alkyl group; and characterized in that the disperse dye has the formula (1) Wherein R ₄ and R′ ₄ are each a phenyl group or a phenyl group substituted by halogen, —CH ₃ , —CH ₂ CH ₃ , —OCH ₃ , —OCH ₂ CH ₃ or —OH, or has the formula (2) , (3) or (4) Wherein R ₅ , R′ ₅ and R′ ₅ are each a halogen, a phenyl group or a phenyl group substituted by halogen, —CH ₃ , —CH ₂ CH ₃ , —OCH ₃ , —OCH ₂ CH ₃ or —OH, Or have the formula (5) Wherein R ₆ is halogen, phenyl or phenyl substituted by halogen, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH, phenoxy or halogen, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH substituted phenoxy, R ₇ is phenyl or halogen, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ a phenyl group substituted with -OCH ₂ CH ₃ or -OH, wherein R ₈ is -NH ₂ or -NHR ₉ , wherein R ₉ is halogen, phenyl or halogen, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH substituted phenyl, phenoxy or substituted by halogen, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH A phenoxy group, or R ₉ is a group of the formula SO ₂ -phenyl group, wherein the phenyl group of the SO ₂ -phenyl group is unsubstituted or is halogen, -CH ₃ , -CH ₂ CH ₃ , a phenyl group substituted with OCH ₃ , -OCH ₂ CH ₃ or -OH, or having the formula (6) Wherein R ₁₀ is -H or halogen. The method of claim 1, wherein the multicomponent fiber is composed of a thermally compatible polyolefin and polyamine. The method of claim 2, wherein the multicomponent fiber is comprised of polypropylene, modified polyamine, and polyamine. The method of claim 2 or 3, wherein the multicomponent fiber has a multifilament feature. The method of claim 1, wherein the multicomponent fiber is composed of a core of polyamine and the core is coated with a polyolefin. The method of claim 1, wherein the benzotriazole derivative is used in an amount of from 0.01 to 20% by weight based on the dry multicomponent fiber. A light-resistant dyed multicomponent fiber consisting of a thermally compatible polyolefin and a polyamidamine dyed with a disperse dye, characterized in that it has been treated with a benzotriazole derivative, wherein the benzoate Triazole derivatives have the formula (I) Wherein R ₁ is a halogen atom, R ₂ is a C ₁ to C ₆ alkyl group, and R ₃ is a C ₁ to C ₆ alkyl group; and characterized in that the disperse dye has the formula (1) Wherein R ₄ and R′ ₄ are each a phenyl group or a phenyl group substituted by halogen, —CH ₃ , —CH ₂ CH ₃ , —OCH ₃ , —OCH ₂ CH ₃ or —OH, or has the formula (2) , (3) or (4) Wherein R ₅ , R′ ₅ and R′ ₅ are each a halogen, a phenyl group or a phenyl group substituted by halogen, —CH ₃ , —CH ₂ CH ₃ , —OCH ₃ , —OCH ₂ CH ₃ or —OH, Or have the formula (5) Wherein R ₆ is halogen, phenyl or phenyl substituted by halogen, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH, phenoxy or halogen, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH substituted phenoxy, R ₇ is phenyl or halogen, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ a phenyl group substituted with -OCH ₂ CH ₃ or -OH, wherein R ₈ is -NH ₂ or -NHR ₉ , wherein R ₉ is halogen, phenyl or halogen, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH substituted phenyl, phenoxy or substituted by halogen, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH A phenoxy group, or R ₉ is a group of the formula SO ₂ -phenyl group, wherein the phenyl group of the SO ₂ -phenyl group is unsubstituted or is halogen, -CH ₃ , -CH ₂ CH ₃ , a phenyl group substituted with OCH ₃ , -OCH ₂ CH ₃ or -OH, or having the formula (6) Wherein R ₁₀ is -H or halogen. A use of the lightfast dyed multicomponent fiber of claim 7 for the manufacture of blankets and/or fabric carpets. A use of a benzotriazole derivative for enhancing the light fastness of a multicomponent fiber dyed by a disperse dye composed of a thermocompatible polyolefin and a polyamine, wherein the benzotriazole derivative Object type (I) Wherein R ₁ is a halogen atom, R ₂ is a C ₁ to C ₆ alkyl group, and R ₃ is a C ₁ to C ₆ alkyl group; and characterized in that the disperse dye has the formula (1) Wherein R ₄ and R′ ₄ are each a phenyl group or a phenyl group substituted by halogen, —CH ₃ , —CH ₂ CH ₃ , —OCH ₃ , —OCH ₂ CH ₃ or —OH, or has the formula (2) , (3) or (4) Wherein R ₅ , R′ ₅ and R′ ₅ are each a halogen, a phenyl group or a phenyl group substituted by halogen, —CH ₃ , —CH ₂ CH ₃ , —OCH ₃ , —OCH ₂ CH ₃ or —OH, Or have the formula (5) Wherein R ₆ is halogen, phenyl or phenyl substituted by halogen, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH, phenoxy or halogen, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH substituted phenoxy, R ₇ is phenyl or halogen, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ a phenyl group substituted with -OCH ₂ CH ₃ or -OH, wherein R ₈ is -NH ₂ or -NHR ₉ , wherein R ₉ is halogen, phenyl or halogen, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH substituted phenyl, phenoxy or substituted by halogen, -CH ₃ , -CH ₂ CH ₃ , -OCH ₃ , -OCH ₂ CH ₃ or -OH A phenoxy group, or R ₉ is a group of the formula SO ₂ -phenyl group, wherein the phenyl group of the SO ₂ -phenyl group is unsubstituted or is halogen, -CH ₃ , -CH ₂ CH ₃ , a phenyl group substituted with OCH ₃ , -OCH ₂ CH ₃ or -OH, or having the formula (6) Wherein R ₁₀ is -H or halogen.