KR820000789B1 - Mixtures of optical brighteners - Google Patents

Abstract

A whitening and brightening agent contg. 0.05-0.95 part I(X = O, S; R1 and R2 are H, F, Cl, Ph, C1-9 alkyl, etc-; A = cyano, -COOR3, -CONR3; R3 = H, alkenyl, C1-18 alkyl, etc.) and 0.95-0.05 part II or III was obtained. For example, polyester fabric impregnated with a soln. contg. 0.6 g/ I and 0.2 g/ II, squeezed, dried 20 sec at 120oC, and thermosoled 30 sec at 190oC had whiteness degress 162(Berger) and 158(Stensby).

Description

Photo Brightener Mixture

The present invention relates to a mixture of optical brighteners composed of 0.05 to 0.95 parts by weight of a compound of formula (I) and 0.95 to 0.05 parts by weight of a compound of formula (II) or (III).

In the general formulas (I), (II) and (III), X, R ¹ , R ² , A, and B have the following meanings.

X is oxygen or sulfur atom,

R ¹ and R ² independently of one another are hydrogen, fluorine or chlorine, phenyl, C ₁ -C ₉ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -dialkylamino, acylamino radicals, or any Functionally modified carboxy or sulfo groups of the same or different groups selected from adjacent groups, adjacent R ¹ and R ² together represent a benzocyclic lower alkylene or 1,3-dioxa-propylene group;

A is a cyano, a group of formula -COOR ³ or -CONR ³ ₂ , wherein R ³ is hydrogen, alkenyl, C ₁ -C ₁₈ -alkyl, cycloalkyl, aryl, alkylaryl, halogennoaryl, Two alkyl or alkenyl groups in which alkyl, alkoxyalkyl, halogenoalkyl, hydroxy-alkyl, alkylamino-alkyl, carboxyalkyl or carboalkoxy alkyl and R ^{3 represent a} morpholine, piperidine or pipette with a nitrogen atom Can form a ragin ring)

A is a group of the following general formula

또는

or

[Wherein R ⁴ is 1 to 18 carbon atoms optionally substituted by hydroxy group, halogen atom, lower alkoxy, dialkylamino, lower alkylmelcapto, chloro-aryloxy, aryloxy, arylmelcapto, aryl group Is a 1 to 6 straight or branched alkyl group (when R ⁴ is a dialkylamino-alkyl group these two alkyls may together optionally form a morpholine piperidine or piperazine ring), or R ⁴ is general Is a group of the formula- (CH ₂ CH ₂ O) nR wherein n is 1,2 or 3 and R is hydrogen, lower alkyl, dialkylamino-alkoxyalkyl or alkylthio-alkoxyalkyl and dialkylamino-alkoxyalkyl And alkyl groups together may optionally form a piperidine, pyrrolidine, hexamethylene-imine, morpholine or piperazine ring). Or R ⁴ is a group of the general formula (CH ₂ ) m-CH = CH-R (m is an integer of 0 to 5) or the following general formula:

Wherein R ⁵ and R ⁶ are the same or different and are each selected from hydrogen, fluorine or chlorine atom, phenyl, lower alkyl, lower alkoxy, (C ₁ -C ₄ ) -acylamino group or optionally modified carboxy or sulfo group Two adjacent R ⁵ and R ⁶ groups together are optionally a lower alkylene group, a fused benzo ring or a 1,3-dioxapropylene group);

B is a group of the following general formula.

or

Wherein R ⁷ and R ⁸ are independently of each other a hydrogen, fluorine or chlorine atom or a C ₁ -C ₄ alkyl group. Of particular interest are compounds of formula I, wherein A, X, R ¹ and R ² are as defined above and R ⁴ is the following group. (C ₁ -C ₆ ) -alkyl, (C ₁ -C ₆ ) -chloroalkyl, dimethyl- or diethylamino (C ₁ -C ₄ ) alkyl, morpholinoethyl, N-β-piperidinoethyl N -β- (N'- methyl-piperazino) -ethyl, benzyl, phenoxy - (C ₁ -C ₄₎ alkyl, chloro, phenoxy - (C ₁ -C ₄₎ alkyl, (C ₁ -C ₄₎ alkyl Melcapto- (C ₁ -C ₄ ) alkyl, phenylmelcapto- (C ₁ -C ₄ ) alkyl, phenyl, (C ₁ -C ₆ ) alkylphenyl, di- (C ₁ -C ₆ ) alkylphenyl, chloro Phenyl, dichlorophenyl, (C ₁ -C ₆ ) alkoxypiphenyl or β-naphthyl or a general formula- (CH ₂ -CH ₂ O) nR where n is 1,2 or 3 and R is a hydrogen atom, (C ₁ -C ₇ ) alkyl group, (C ₁ -C ₄ ) alkylmelcapto- (C ₁ -C ₄ ) alkyl, dimethyl- or diethylamino- (C ₁ -C ₄ ) alkyl or morpholino ( C ₁ -C ₄ ) alkyl group.

Preferred compounds include X being oxygen or sulfur, R ¹ and R ² independently of one another are hydrogen or chlorine atoms in the 5-6, 7-, or 7-position, (C ₁ -C ₄ ) alkyl, phenyl or R ¹ , R ² is a benzo ring fused together and R ⁴ in group A is (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) chloroalkyl, (C ₁ -C ₄ ) alkoxy,-(C ₁ -C ₄ ) Alkyl, hydroxy (C ₁ -C ₄ ) alkyl or a group of the formula-(CH ₂ CH ₂ O) n-R ', n is 2 or 3 and R' is hydrogen or (C ₁ -C ₄ ) alkyl Phosphorus is a compound of formula (I).

Also of particular interest are subgroups where X is an oxygen atom, R ¹ at the 5-position is a hydrogen or chlorine atom, methyl or phenyl group, and R ² is hydrogen or R ¹ and R ² together are 5,6- Or form a methyl group at the 5,7-position;

R ₄ in group A is methyl-ethyl-n- or i-propyl, -n or i-butyl, pentyl, chloromethyl, β-chloroethyl, β-hydroxyethyl, β-methoxyethyl, β-ethoxy Of general formula (I) which is ethylbenzyl, phenyl, o-tolyl, p-tolyl, 2,4-dimethylphenyl, o-chlorophenyl, p-chlorophenyl, 2,4-dichlorophenyl or p-methoxyphenyl group Compound.

Preferred compounds of formula (II) are benzo in which R ¹ and R ² are hydrogen or chlorine, (C ₁ -C ₄ ) alkyl, phenyl or R ¹ and R ² are fused together in the 5-, 6- or 7-positions; Compounds in cyclic form, particularly preferred are those wherein R ¹ is hydrogen or a chlorine atom, methyl or phenyl group at the 5-position and R ² is a hydrogen atom or both R ¹ and R ² are methyl at the 5,6- or 5,7-position; Compound that is a group.

Preferred general formula (III) compounds are benzo rings in which R ¹ and R ² are hydrogen or chlorine, (C ₁ -C ₄ ) alkyl, phenyl or R ¹ and R ² are fused together in the 5-6- or 7-position; And R ⁷ and R ⁸ are each independently hydrogen or methyl.

By functionally modified carboxy group is meant a carboxylic acid derivative which is a compound in which one carbon atom is linked to three heteroatoms, in particular oxygen, nitrogen and sulfur. In a narrower sense, they are salts with colorless cations, preferably alkali metal or ammonium ions and cyano, carboxylic ester or carboxylic acid amide groups. Carboxylic acid esters are in particular the general formula of COOQ ¹ wherein Q ¹ is a phenyl group or any branched lower alkyl group. The carboxylic acid amide group is in particular the general formula CONQ ² Q ³ wherein Q ² and Q ³ are hydrogen atoms or an optionally substituted lower alkyl group capable of forming a hydroaromatic ring with nitrogen.

A functionally modified sulfo group similarly to the above means a sulfo group linked to a heteroatom, ie a salt with a colorless cation, preferably an alkali metal or ammonium ion and also sulfonic acid esters and sulfonamide groups. The sulfonic acid esters are in particular general formula SO ₂ OQ ¹ where Q ¹ is as defined above and the sulfonamide group is general formula SO ₂ NQ ² Q ³ where Q ² and Q ³ are as defined above.

Acyl groups are in particular general formula COQ ⁴ wherein Q ⁴ is an optionally substituted, preferably lower alkyl or phenyl group, in particular an unsubstituted C ₁ -C ₄ alkanoyl group or benzoyl group. Preferred substituents R ³ are C ₁ -C ₆ alkyl, halogeno-alkyl or alkoxy. In addition to the above-described subgroups, other subgroups may be formed using groups represented by X, R ¹ , R ² , A, and B, respectively. Of course, the formation of such subgroups does not mean the introduction of new materials in accordance with 35U.SC 132. Unless defined otherwise, alkyl groups and their derivatives each contain 1 to 4 carbon atoms.

Specifically, examples of R ¹ and R ² include the following groups. Methyl ethyl, n- or i-propyl, n- or i-butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, hexoxy, dimethylamino, diethylamino, trimethylammonium, acetylamino, cya Furnace, -SO ₃ H, carboxyl, carbo-methoxy, -ethoxy, -propoxy, -butoxy and sulfonic acid alkylesters of corresponding groups, methyl, ethyl, propyl and butyl, carbon amide and alkylsulfonamides Corresponding groups of the family and corresponding dialkyl-carbonamide and dialkylsulfonamide groups. Two adjacent groups R ¹ and R ² may together form a fused phenyl or cyclo hexyl ring. Regarding X, all compounds containing a benzoxazolyl group (X = 0) are preferred.

Examples of R ⁴ are the following groups. Methyl, ethyl, n- or i-propyl n- or i-butyl, pentyl, hexyl or chloroalkyl, hydroxyalkyl, dimethylaminoalkyl, diethyl-aminoalkyl, methoxyalkyl, ethoxyalkyl, propoxyalkyl, Butoxyalkyl, methylmecaptoalkyl, ethylmelcaptoalkyl, chlorophenoxyalkyl, phenoxyalkyl, phenylmelcaptoalkyl, phenylalkyl or a naphthalalkyl group derived therefrom and is also of the general formula-(CH ₂ CH ₂ O n is a 1,2 or 3 and R is a dimethyl or diethylamino-alkoxyalkyl group having 1 to 4 carbon atoms at the hydrogen, methyl, ethyl, propyl, or butyl group alkyl or alkoxy moiety Or an alkylthio-alkoxy-alkyl group having 1 to 4 carbon atoms in the alkyl or alkoxy moiety and examples of the structural formulas of these groups are as follows.

R ₄ is also an unsubstituted or mono- or di-substituted phenyl group, alkyl, alkoxy, acyl, carboalkoxy, alkylcarbonamide, alkylsulfonamido and sulfonic acid alkylester groups, each optionally containing 1 to 4 carbon atoms . Bisubstituents R ⁵ and R ⁶ together form a fused benzo or cyclo-hexyl ring.

Compounds of the general formula (I) which do not contain an oxadiazole ring are described in the following Japanese patent specification.

ShO 43-7045; ShO 44-6980; ShO 44-6981; ShO 44-6982; ShO 42-21013.

The compound of formula (I) wherein A is an oxadiazole ring can be prepared by reacting a compound of formula (IV) with a compound of formula (V) by the method of German Publication 27 09 924.

Wherein R ¹ , R ² and R ⁴ are as defined above and Y is a group of formula (IV)

Z is a group of the formula

Or Y is a group of formula (VII) and Z is a group of formula (VI).

In the former case, a compound of general formula (I) containing 1,2,4-dioxazolyl-3 group is obtained. In the latter case, a compound containing 1,2,4-dioxazolyl-5 group is obtained. To obtain. This reaction is preferably carried out at 20 to 200 ° C. in the presence of an acid binder in an inert solvent.

Starting compounds of the general formula (V), wherein Z is a group of the formula (IV), were selected from Chem. Rev. 62 (1962), p. 155 et sequ. It may be prepared according to the process described in. According to this process, starting compounds of the general formula (IV), wherein Y is a group of the structural formula (IV), can be obtained by a similar method.

Compounds of general formula (III) are known in the patent specification below. German Publication No. 1,255, 077; 1,288,608; 1,445,694, German Publication No. 1,469,207 and Belgian Patent No. 648,674.

The compound of the general formula (III) can be obtained by reacting the carboxylic acids or their acid chlorides of the following general formula (1) with the compound of the general formula (2) according to a known method.

Wherein R ¹ , R ² , R ⁷ , R ⁸ and Z are as defined above and Z is an amino group, Y is a hydroxy group or Y is an amino group and Z is a hydroxy or chlorine atom. This reaction is carried out at high temperature, for example 120 to 330 ° C., without intermediate separation or separation of the acyl compound obtained first, preferably in the presence of an acid catalyst such as zinc chloride or polyphosphoric acid. Optionally, this reaction can be carried out in a high boiling point inert organic solvent, unlike the above (German publication 2,712,942).

The reaction products of the process are also known to be converted, for example starting with molecules containing sulfo or carboxyl groups to obtain functionally modified sulfo or carboxyl groups and converting such groups to other groups or free acids of the same kind. . It is also possible to introduce chloromethyl groups or to oxidize methyl groups.

Likewise halogenated and introduced halogen atoms can be further reacted, for example chlorine or bromine can be replaced by an aminak vessel.

The mixing ratio of each component is 0.05 to 0.95 parts by weight of compound (I) and a corresponding amount of (0.95 to 0.05 parts by weight) of compound (II) and (III) mixture.

Preferable mixing ratio is the ratio which adds 0.05 to 0.95 weight part of compound (I), compound (II), and (III) to 1 weight part. The optimum mixing ratio depends in each case on the type of compounds of formulas (I), (II) and (III), which can be easily determined by simple preliminary experiments. The ratio of compounds (II) and (III) to each other is not critical at all and varies within the range of 0 to 1 parts by weight; That is, you may mix compound (I) and said quantitative range independently in compound (II) and (III).

In general, the optical brightener is a commercial application by dispersing the individual components in a solvent. These components disperse each and then combine the corresponding dispersions into one or mix and disperse them together. Dispersion is usually carried out in a spherical mill, colloid mill, bead mill, or dispersion hardener.

The mixtures of the present invention are particularly conjugated to optical brighteners of straight polyester, polyamide or acetyl cellulose fabrics. The mixture can also be used for blends of straight polyesters, and other synthetic or natural fiber materials, inter alia, fibres, including hydroxy groups, in particular cotton, for good results. The optical brightener mixture is applied under normal conditions, for example at 90 to 130 ° C., by means of an evacuation process or by a heat treatment process with or without adding a carrier. In addition, the optical brightener insoluble in water and the mixture of the present invention can be applied in the form of a solution in an organic solvent such as perchloroethylene or fluorohydrocarbon. In the latter case, the fabric is treated with a solvent liquid containing a dissolved optical brightener by heat treatment or immersed, surface-sucked or sprayed with a solvent containing the optical brightener and dried at 120 to 220 ° C. to completely fix the optical brightener. Fabric is obtained.

The advantage of this mixture over the individual components is the unexpected synergistic effect of increasing the degree of whiteness. That is, a mixture of compounds of formula (I), (II) and / or (III) is higher than when only one compound of the same amount of compound of formula (I), (II) or (III) It exhibits whiteness and is also effective for the glossiness of brigtening. Furthermore, the brightener obtained by using the mixture of the present invention is a slightly red shiny white matter obtained using only the compound of formula (I) or green color when using a single compound of formula (II) or (III). It has a pleasant bluish-purple hue to the human eye compared to the white matter.

The following examples illustrate the invention.

Parts and percentages are by weight and temperatures are in degrees Celsius. The degree of whiteness was measured according to the format of Stansby (Soap and Chemical Specailities, April 1967, p. 41ft) and Berger (Die Farbe 8 (1959) p.187et sequ.).

Example 1

The polyester fiber fabrics are washed, rinsed in jigs and dried at 120 ° C. in a conventional manner. This pre-treated material is immersed in a solution containing 0.8 g / l of the optical brightener of general formula (I) or 0.8 g / l of the mixture of the optical brightener of the general formula (II) or the head optical brightener of 0.8 g / l. Let's do it.

The immersed material is squeezed on a roller to adjust the moisture content to 80% and then dried in a stenter for 20 seconds at 120 ° C. and heat treated at 190 ° C. for 30 seconds. The degree of whiteness measured is described in the following table.

TABLE 1

The above table shows that the use of the mixture is of a higher degree of whiteness than the use of the individual components.

Example 2

Knitted pieces of polyester fibers are pre-washed in a conventional manner and whitened for 30 minutes at 120 ° C. in a dyeing apparatus under high temperature conditions. The liquid contains general formula (I) or (II) of 0.08% of the fabric weight, respectively. To compare, use this brightener as a mixture of itself and in the proportions shown in Table 2. After rinsing and drying, the degree of whiteness measured is described in Table 2.

TABLE 2

This example also demonstrates that the mixture significantly enhances the whiteness of the corresponding monocomponent material.

Example 3

The polyester curtain of Raschel-tulle weaving is pre-washed in a conventional manner by a continuous washer and dried at 120 ° C. in a stenter and wound on a dyeing beam. After being placed in a high temperature dyeing apparatus, the solution contains 0.05% (of fabric weight) of the optical brightener shown in Examples 1 and 2, or the optical brightener mixture of the ratio shown in Table 3, or 3 g / L of 50% sodium chloride, respectively. Treat the fabric. The pH of the liquid is adjusted to pH 4 using formic acid. The curtain is bleached or bleached at 120 ° C. for 45 minutes, then rinsed and dried to heat-fix at 180 ° C. The degree of whiteness obtained is described in Table 3.

TABLE 3

It can be seen that the degree of whiteness when using the mixture of the optical brightener is clearly superior to that of the white when the optical brightener of each component is used.

Example 4

The fabric of the polyester fibers is washed, rinsed in a conventional jigger and treated with 0.08% of the brightener of formulas (I) and (II). For comparison, the light brightener itself and the mixture are applied.

The polyester was treated with a commercially available propellant having a diphenyl group at a boiling point in a ratio of 1: 6 propellant: liquid at a boiling point for 60 minutes, then rinsed and dried at 120 占 폚. The degree of each white obtained is described in Table 4.

TABLE 4

Also in this case, the mixture clearly increased the whiteness of the individual components.

Example 5

A piece of fabric of polyester staple fiber is washed, dried in a conventional manner, and then immersed in a solution containing 8 g / l of the optical brightener of general formula (II) on a printing base.

The absorbed material is dried in a stenter at 120 ° C. for 30 seconds and heat-treated at 190 ° C. for 30 seconds. The following whiteness is obtained, but also when the mixture is used, the gloss is higher than when the individual components are used.

Claims (1)

A mixture of 0.05 to 0.95 parts by weight of a compound of formula (I) and 0.95 to 0.05 parts by weight of formula (II) or (III).

Wherein X, R ¹ , R ² , A and B have the following meanings. X is oxygen or sulfur atom and R ¹ and R ² are independently of each other hydrogen, fluorine or chlorine atom, phenyl, C ₁ -C ₉ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -dialkylamino, R ¹ and R ² , which are the same or different groups selected from acylamino groups or any functionally modified carboxy or sulfo groups, together optionally represent a benzo ring, a lower alkylene or a 1,3-dioxy-propylene group A is a cyano, a group of formula -COOR ³ or CONR ³ ₂ , wherein R ³ is hydrogen, alkenyl, C ₁ -C ₁₈ -alkyl, cycloalkyl, aryl, alkylaryl, halogenoaryl, Alkyl, alkoxyalkyl, halogenoalkyl, hydroxy-alkyl, alkyl-amino-alkyl, carboxyalkyl or carboalkoxyalkyl, or two alkyl or alkenyl groups meaning R ³ , together with the nitrogen atom, make morpholine, piperidine Or piperazine ring) or A is Is a group of expressions

or

[Wherein R ⁴ is 1 to 18 carbon atoms optionally substituted by a hydroxy group, a halogen atom, a lower alkoxy, a dialkylamino, a lower alkyl melcato, a glolo-aryloxy, an aryloxy, an arylmelcapto or an aryl group Preferably a 1 to 6 straight or branched chain alkyl group (when R ⁴ is a dialkylamino-alkyl group, two alkyl groups may optionally form a morpholine, piperidine or piperazine ring). Or R ⁴ is a group of the formula — (CH ₂ CH ₂ O) nR where n is 1,2 or 3 and R is hydrogen, lower alkyl, dialkylamino-alkoxyalkyl or alkylthio-alkoxyalkyl and dialkyl In the case of amino-alkoxyalkyl, the alkyl groups together may optionally form a piperidine, hexamethylene-imine, morpholine or piperazine ring). Or R ⁴ is a group of the general formula- (CH ₂ ) m-CH = CH-R (m is an integer of 0 to 5) or a general formula

Wherein R ⁵ and R ⁶ are the same or different and are each hydrogen, fluorine or chlorine atom, phenyl, lower alkyl, lower alkoxy, (C ₁ -C ₄ ) -acylamino group or optionally modified carboxy or sulfo group And two adjacent R ⁵ and R ⁶ together may optionally be a lower alkylene group, a fused benzo ring or a 1,3-dioxypropylene group). B is a group of the following general formula.

or

Wherein R ⁷ and R ⁸ are independently of each other a hydrogen, fluorine or chlorine atom or a C ₁ -C ₄ alkyl group