KR820000026B1 - Mixtures of optical brighteners - Google Patents

Abstract

Mixtures of fluorescent whiteners I(X = O, S; R1,R2, A = substituted group) 5-95% and II (B = >=3-ring polycyclic arom. residue; C = substituted amino group, alkoxy, acyloxy, hydro-alkoxy, alkylthio, carbalkoxythio; D = C, Cl) 95-5% give a degree of whiteness on polyester fibers greater than the individual components. For example, a typical mixture contains 0.28% I(X = O; R1 = Cl; R2 = H, A = COOCH3) and 0.012% II(B = 1-pyrenyl; C = D = CH3O) to give a degree of whiteness 143 (Berger).

Description

Mixture of fluorescent brighteners

The present invention relates to a mixture of fluorescent brighteners effective for fabrics.

German patent application p27 21048.0 relates to a mixture of fluorescent brighteners comprising 0.05 to 0.95 parts by weight of the following general formula (I) and 0.95 to 0.05 parts by weight of the following general formula (II) or (III).

(여기에서 R³는 수소, 탄소수 1내지 18의 알킬, 사이클로알킬, 아릴, 알킬아릴, 할로겐아릴, 아르알킬, 알콕시알킬, 할로겐알킬, 하이드록시알킬, 알킬아미노알킬, 카복시알킬 또는 카보알콕시알킬 또는 R³에서의 두개의 알킬 또는 알킬렌기는 질소원자와 함께 모르폴리노, 피페리디노 또는 피페라지노 환을 형성함) 또는 A는 다음 일반식의 기이고Wherein X is oxygen or sulfur and R ¹ and R ² are the same or different and hydrogen, fluorine or chlorine atom, phenyl, alkyl of 1 to 9 carbon atoms, alkoxy of 1 to 4 carbon atoms, dialkylamino of 1 to 4 carbon atoms, A group selected from an acylamino group or optionally functionally modified carboxy or sulfo group or two adjacent R ¹ and R ² together form a benzo ring or 1,3-dioxapropylene fused together and A is cyano, —COOR ³ or

Wherein R ³ is hydrogen, alkyl of 1 to 18 carbon atoms, cycloalkyl, aryl, alkylaryl, halogenaryl, aralkyl, alkoxyalkyl, halogenalkyl, hydroxyalkyl, alkylaminoalkyl, carboxyalkyl or carboalkoxyalkyl or The two alkyl or alkylene groups in R ³ together with the nitrogen atom form a morpholino, piperidino or piperazino ring) or A is a group of the general formula

Wherein R ⁴ is straight or branched chain alkyl of 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, hydroxy, halogen, lower alkoxy, dialkylamino, lower alkyl mercapto, chloroaryloxy, aryloxy, aryl mercapto Or two alkyl groups which may be substituted by an aryl group and contained in a dialkylaminoalkyl group optionally together form a morpholino, piperidino or piperazino ring, or R ⁴ is a general formula (CH ₂ CH ₂ O) n The group of —R, wherein n is 1, 2 or 3 and R is hydrogen, lower alkyl, dialkalamino alkoxyalkyl or alkylthioalkoxyalkyl, alkyl group of the dialkylamino alkoxyalkyl group together is piperidino, pyrrolidino, Optionally form a hexamethyleneimino, morpholino or piperazino ring, or R ⁴ is of the formula-(CH ₂ ) m-CH = CH-R wherein m is an integer from 0 to 5; group

Wherein R ⁵ and R ⁶ are the same or different and are selected from hydrogen, chlorine or fluorine atom, phenyl, lower alkyl, lower alkoxy, acylamino group having 1 to 4 carbon atoms or optionally modified carboxy or sulfo group, two adjacent R ⁵ And R ⁶ together optionally form a lower alkylene, a fused benzo ring or 1, 3-dioxapropylene and B is a group of the general formula:

Wherein R ⁷ and R ⁸ are each hydrogen, fluorine, chlorine or alkyl having 1 to 4 carbons.

The invention was modified to find that the optical brightener of the above-described quality was obtained by mixing the fluorescent brightener of the general formula (I) and the fluorescent brightener of the general formula (IV) described later.

Accordingly, the present invention relates to a fluorescent brightener consisting of a mixture of 0.05 to 0.95 parts by weight of the compound of general formula (I) and 0.95 to 0.05 parts by weight of compound of the general formula (IV).

In the above general formula, B is a polycyclic aromatic group having at least three condensed rings optionally carrying a non-chromophore substituent, C is an amino group substituted with one or two alkyl, alkylhydroxyalkyl, acyl, or phenyl, and a phenyl group Optionally contains one or several non-chromophores and the two alkyl groups optionally form a pyrrolidino, piperidino ring with the nitrogen atom of the amino group or a piperazino or morpholino ring with another nitrogen or oxygen atom, or Or C is an alkoxy, hydroxyalkyl, acyloxy, alkylthio or carbalkyl mercapto group, D is independent of C, as defined in C and may further comprise a chlorine atom.

Suitable polycyclic aromatic groups are pyrene, anthracene, acenaphthene and saxene groups, with pyrene groups being preferred. Examples of alkyl, alkoxy and acyl groups are groups having 1 to 4 carbon atoms. Non-chromophore groups include halogen, alkyl, alkoxy, mono- and di-alkylamino, acylamino, cyano, sulfo, sulfonic acid alkyl esters, carboxy, carboalkoxy, sulfonamido, carbonamido and mono-derived therein. And di-alkylamides and alkyl, acyl or alkoxy having 1 to 4 carbon atoms.

Particularly preferred in the general formula (IV) compounds is when B is pyrene and C and D are each independently alkoxy having 1 to 4 carbon atoms.

In compounds of formula (I), X, A, R ¹ and R ² are as defined above and R ⁴ is the next group, i.e., alkyl of 1 to 6 carbon atoms, chloroalkyl of 1 to 6 carbon atoms, dimethyl- or diethyl Amino-C1-4 alkyl, morpholinoethyl, N-β-piperidinoethyl, N-β- (N'-methylpiperazino) -ethyl, benzyl, phenoxy-C1-4 alkyl , Chlorphenoxy-alkyl having 1 to 4 carbons, alkyl having 1 to 4 carbon mercapto-alkyl having 1 to 4 carbons, phenyl-mercapto-alkyl having 1 to 4 carbons, phenyl, alkyl having 1 to 6 carbon atoms- Phenyl, di-C1-C6 alkyl phenyl, chlorphenyl, dichlorophenyl, C1-C4 alkoxyphenyl or β-naphthyl or-(CH ₂ CH ₂ O) n-R groups, where n is 1 Is 2 or 3 and R is hydrogen, alkyl of 1 to 7 carbon atoms, alkyl mercapto to 1 to 4 carbon atoms, dimethyl- or diethyl Particularly amino-amino alkyl having 1 to 4 carbons and morpholino-alkyl having 1 to 4 carbon atoms.

Particularly preferred as compounds of formula (I) are those in which X is oxygen or sulfur, and R ¹ and R ² in positions 6 or 7 each form hydrogen or a chlorine atom, alkyl of 1 to 4 carbon atoms, phenyl or a benzo ring fused together; , R ⁴ in group A is C1-6 alkyl, C1-6 chloroalkyl, C1-4 alkoxy-C1-4 alkyl, hydroxy-C1-4 alkyl or n is 2 or 3, and R ¹ has a group of the general formula-(CH ₂ CH ₂ O) n-R ¹ wherein hydrogen or alkyl having 1 to 4 carbons.

Particularly advantageous as a subgroup of the compound of general formula (I) is that X is oxygen, R ^{1 in} position 5 is hydrogen, chlorine, methyl or phenyl and R ² is hydrogen or R ¹ and R ² are 5, 6 or 5, respectively. Is a methyl group at the 7-position, and R ⁴ in the A group is methyl, ethyl, n- or iso-propyl, n- or isobutyl, pentyl, chloromethyl, β-chloroethyl, β-hydroxyethyl and β-methoxy It is a compound which is ethyl, (beta) -ethoxyethyl, benzyl, phenyl, o-tolyl, 2, 3- dimethylphenyl, o-chlorophenyl, p-chlorophenyl, 2, 4- dichlorophenyl, or p-methoxyphenyl.

"Functionally modified carboxy group" broadly means carboxylic acid derivatives. That is, it refers to a compound bonded to three carbon atoms, in particular oxygen, nitrogen, and sulfur, in one carbon atom. In consultation these compounds include salts with colorless cations, of which alkali metal or ammonium ions are preferred, and further include cyano groups, carboxylic acid ester groups or carbonamides. The carboxylic ester group is in particular a general formula COOQ ¹ group wherein Q ¹ is a phenyl group or any C 1-4 branched alkyl. The carbonamide group is in particular a general formula CONQ ² Q ³ group wherein Q ² and Q ³ are hydrogen atoms or optionally substituted alkyl groups of 1 to 4 carbon atoms, together with the nitrogen atoms to form a hydroaromatic ring.

A "functionally modified sulfo group" is as described above, for example salts with colorless cations, preferably alkali metal or ammonium ions, sulfonic acid ester groups and sulfonamides having sulfo groups bound to heteroatoms. Groups are included. The sulfonic acid ester group is a group having the general formula SO ₂ OQ ¹ , wherein Q ¹ is as defined above, and the sulfonamide group is a group having the general formula SO ₂ NQ ² Q ³ . (Q ² and Q ^{3 are} also as defined above).

Suitable acyl groups are in particular groups having the general formula COQ ⁴ , wherein Q ⁴ is preferably an optionally substituted loweralkyl or phenyl, particularly preferably an unsubstituted alkanoyl or bezoyl. Preferred substituents on R ³ are alkyl, halogenalkyl or alkoxy having 1 to 6 carbon atoms.

In addition to the subgroups above, all other subgroups may be formed in the definitions of X, R ¹ , R ² , A, B, C and D. The formation of such new subgroups is not intended to introduce new materials in accordance with 35 USC 132.

Unless stated otherwise, derived alkyl groups and other groups each have 1 to 4 carbon atoms.

The groups in R ¹ and R ² are as follows. That is, methyl, ethyl, n- or isopropyl, n- or isobutyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, dimethylamino, diethylamino, trimethylammonium, Groups corresponding to triethylammonium, acetylamino, cyano, -SO ₃ H, carboxyl, carbomethoxy, -ethoxy, -propoxy, -butoxy and sulfonic acid alkylester derivatives, methyl-, ethyl-, propyl -, Butyl-carbonamide and corresponding dialkylcarbonamide groups or -sulfonamide groups Two adjacent R ¹ and R ² groups can form a fused benzo or cyclohexyl ring together. Such a compound preferably contains a benzoxazolyl group (X = 0).

R ⁴ is methyl, ethyl, n- or isopropyl, n- or isobutyl, pentyl, hexyl, chloroalkyl, hydroxyalkyl, dimethylaminoalkyl, diethylaminoalkyl, methoxyalkyl, ethoxyalkyl, propoxyalkyl Butoxyalkyl, methylene mercaptoalkyl, ethyl mercaptoalkyl, chloro-phenoxyalkyl, phenoxyalkyl, phenylmercaptoalkyl, phenylalkyl and naphthylalkyl groups and derivatives thereof; R ⁴ also represents a general formula (CH ₂ CH ₂ O) nR group wherein n is 1, 2 or 3 and R is hydrogen, methyl, ethyl, propyl, or carbon number at the butyl, alkyl or butyl, alkyl or alkoxy site Alkylthioalkoxyalkyl having 1 to 4 carbon atoms at 1 to 4 dimethyl or diethyl aminoalkoxyalkyl, alkyl or alkoxy moieties. Examples of such groups have the following general formula:

-CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ OC ₂ H ₅ , -CH ₂ CH ₂ OC ₃ H ₇ , -CH ₂ CH ₂ OC ₄ H ₉ , -CH ₂ CH ₂ OC ₆ H ₁₃ ,

, －CH₂CH₂OC₆H₁₁, －(CH₂CH₂O)₂CH₃, －(CH₂CH₂O)₂C₂H₅, －(CH₂CH₂O)₂C₄H₉,

, -CH ₂ CH ₂ OC ₆ H ₁₁ ,-(CH ₂ CH ₂ O) ₂ CH ₃ ,-(CH ₂ CH ₂ O) ₂ C ₂ H ₅ ,-(CH ₂ CH ₂ O) ₂ C ₄ H ₉ ,

-(CH ₂ CH ₂ O) ₃ C ₂ H ₅ , -CH ₂ CH ₂ OCH ₂ CH ₂ SC ₂ H ₅ , -CH ₂ CH ₂ OCH ₂ CH ₂ -N (CH ₂ ) ₂ ,

CH ₂ CH ₂ OCH ₂ CH ₂ —N (C ₂ H ₅ ) ₂ , or

R ^4, in contrast, is unsubstituted phenyl or phenyl substituted one or two times with alkyl, alkoxy, acyl, carboalkoxy, alkylcarbonamido, alkyl sulfonamido and sulfonic acid alkylester groups having 1 to 4 carbon atoms. Two substituents R ⁶ and R ⁵ may together form a fused benzo ring.

Compounds which do not contain an oxadiazole ring in the general formula (I) compounds are known from the following Japanese patent applications, namely, Digestion 43-7045, Digestion 44-6980, Digestion 44-6981, Digestion 44-6982, Digestion 42-21013. . The compound of formula (I) wherein A is an oladiazole ring may be prepared by reacting the following compound of formula (V) with the compound of formula (VI) according to German patent application p2709 924.7.

Wherein R ¹ , R ² , X and R ⁴ are as defined above and Y is a group of the formula

Z is a group of the following general formula

－COCI (Ⅷ)

Y is a group of general formula and Z is a group of general formula.

In the former case, the compound of general formula (I) containing 1, 2, 4-oxadiazolyl-3 groups is obtained, and in the latter case, a compound containing 1, 2, 4-oxadiazolyl-5 groups is obtained. The reaction preferably takes place at a temperature of 20 to 200 ° C. in the presence of an acid binder in an inert solvent.

Starting compounds of general formula (VI) wherein Z is a general formula (VII) can be prepared according to the methods described in the literature [Chem. Rev, 62 (1962), p 155], where Z is a compound of formula (VIII), starting compounds of formula (V) can be prepared in a similar manner according to the above process.

Formula (IV) compounds are known from German Patent Publication No. 1,273,479 and can be prepared according to the methods described in this publication.

The reaction product obtained according to the above process can be converted into branch methods. That is, functionally modifying the sulfo or carboxyl group, or by switching the sulfo or carboxyl group, other groups or free acids of this type are obtained. Moreover, chloromethyl groups can be bound according to known methods or the methyl groups can be oxidized. In addition, halogenated atoms are bonded or further reaction proceeds. That is, chlorine or bromine can be substituted with an amine functional group.

The mixing ratio of each component is in the range of 0.05 to 0.95 parts by weight of compound (I) and the corresponding amount (0.95 to 0.05 weight ratio) of compound (IV) mixture. The optimum mixing ratio depends on the properties of the compounds of general formulas (I) and (IV) and can be easily determined as a preliminary test.

Usually, the fluorescent brightener is a commercially available form in which each component is dispersed in a solvent by dispersing the components and mixing the dispersion. Alternatively, each component is mixed with the material and dispersed together. Dispersion is carried out in a conventional manner in ball mills, colloid mills, bead mills or dispersion mixers.

The mixtures according to the invention are particularly effective for the fluorescence of linear polyesters, polyamides and acetylcellulose. However, good results can also be obtained with linear polyesters and synthetic or natural fibers, in particular with fibers containing hydroxyl groups, especially textiles mixed with cotton. This mixture can be treated to the fibers according to the exhaust process or the heat treatment process with or without the addition of an accelerator (tobacco) at the usual conditions used for fluorescent brighteners, i.

Alternatively, the brighteners insoluble in water and the mixtures according to the invention can be dissolved in an organic solvent such as perchloroethylene before use. In this operation, the fabric can be treated with a solvent solution containing a fluorescent brightener in the dissolved state according to the exhaust process. Another method is a method of impregnating, padding, or spraying a fabric into a solution medium containing a fluorescent brightener and then drying the fabric at a temperature of 120 to 220 ° C. to fix all of the fluorescent brightener to the fiber.

An advantage of using the mixtures described above is that a synergistic effect can be obtained that is greater than expected in whiteness. That is, the mixture of the compounds of the general formulas (I) and (IV) shows a higher whiteness than the whiteness when the compounds of the general formula (I) or (IV) are used, respectively. The same effect is obtained also in fluorescent surface. In addition, the fabric fluoresced with the mixture according to the present invention exhibits a bluish violet color, which is red when the compound of Formula (I) is used alone or green when the compound of Formula (IV) is used alone. It is usually a good color for vision.

The following examples illustrate the invention. Unless otherwise indicated, parts and percentages are by weight. Whiteness was measured according to the method of Stansby (Soap and Chemicals Specialities, April 1967, p. 41 et seq) and Burger method (Die Farbe, 8 (2959), p.187 et seq). Temperature is Celsius.

Example 1

Woven fabrics of polyester state fibers were mixed at the mixing ratios of the following table, and then padded on a padding mangle with an aqueous dispersion containing 0.5 g / l of a mixture of fluorescent brighteners of formula (I) and formula (II). Before impregnation, it is washed and dried in a usual manner in advance.

The fabric was pressed and dehydrated in padded mungles between the rolls to obtain a liquid absorption of 80%, corresponding to 0.04% of the fluorescent brightener absorbed on the fabric. The whiteness obtained by drying the padded fabric in a tenter dryer for 30 seconds at 120 ° C. and heat treatment at 190 ° C. for 30 seconds is described in the table below.

It is evident that the compound is given a higher white color than when used individually.

Example 2

Polyester curtains with raschelle tulle bonds were washed in a continuous washer according to a conventional method, dried in a tenter drying stand at 120 ° C., and the fluorescent brighteners of formulas (I) and (II) were The mixture mixed in the ratio as shown in the table is impregnated on a padding mangle with an aqueous dispersion containing 0.5 g / L.

The fabric was pressed and dehydrated to obtain a liquid absorption of 80%, corresponding to 0.04% of the fluorescent brightener absorbed on the fabric. The swollen fabric is dried in a tenter dryer for 20 seconds at 120 ° C. and further heat treated at 190 ° C. for 20 seconds.

The fabric is bleached with 2 g / l sodium chlorite (50%), 1 g / l ammonium sulfate and 1 ml / l hydrogen peroxide (35% by weight) to achieve the desired whiteness. The pH of this solution is adjusted to 3.5 using formic acid. Bleaching is carried out at 95 ° C. for 60 minutes with a fabric to liquid ratio of 1:20.

The whiteness below is obtained after rinsing and drying at 120 ° C. for 30 seconds. It is clear that the whiteness obtained using the mixture is much higher than the whiteness obtained using each compound.

Claims (1)

A mixture of 0.05 to 0.95 parts by weight of the following general formula (I) compound and 0.95 to 0.05 parts by weight of the following general formula (IV) compound.

In the above general formula, X is oxygen or sulfur, R ¹ and R ² are the same or different, hydrogen, fluorine or chlorine atom, phenyl, alkyl of 1 to 9 carbon atoms, alkoxy of 1 to 4 carbon atoms, dialkyl of 1 to 4 carbon atoms A group selected from an amino, acyl amino group or optionally functionally modified carboxy or sulfo group or adjacent R ¹ and R ² together represent a benzo ring or lower alkylene or 1,3-dioxapropylene melted together and A is cyano, General formula-COOR ³ or

Where R ³ is hydrogen, alkyl having 1 to 18 carbon atoms, cycloalkyl, aryl, alkylaryl, halogenaryl, aralkyl, alkoxyalkyl, halogenalkyl, hydroxyalkyl, alkylamino-alkyl, carboxyalkyl or carbo Alkoxyalkyl, two alkyl or alkylene groups in R ³ or together with the nitrogen atom form a morpholino, piperidino, piperazino ring or A is a group of the general formula

Wherein R ⁴ is a straight or branched chain alkyl group having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, and is hydroxy, hydrogen, lower alkoxy, dialkylamino, lower alkyl mercapto, chloroaryloxy, aryloxy, aryl mer Optionally substituted with a capto or aryl group, the two alkyl groups contained in the dialkylamino alkyl group together optionally represent a morpholino, piperidino or piperazino ring, or R ⁴ is represented by the formula-(CH ₂ CH ₂ O) | _{A 3-} R group, where n is 1, 2 or 3, R is hydrogen, lower alkyl, dialkylaminoalkoxy-alkyl or alkylthio alkoxyalkyl, and the alkyl groups in the dialkyl aminoalkoxyalkyl together are piperidino, pipe Optionally form a lollidino, hexamethyleneimino, morpholino or piperazino ring, or R ⁴ is a group of the formula-(CH ₂ ) _m -CH = CH-R, wherein m is an integer of 0 to 5 Or R ⁴ is a general formula

Wherein R ⁵ and R ⁶ are the same or different and are selected from hydrogen, fluorine or chlorine atom, phenyl, lower alkyl, lower alkoxy, acylamino group of 1 to 4 carbon atoms or optionally modified carboxy or sulfo group R ¹ and R ² groups together represent an optionally lower alkylene, fused benzo ring or 1,3-dioxapropylene, B is a polycyclic aromatic group having at least three condensed rings optionally carrying a non-chromic substituent C is an amino group substituted with one or two alkyl, hydroxyalkyl, acyl or phenyl groups, wherein the phenyl group optionally contains one or several non-chromophores and the two alkyl groups optionally together with the nitrogen atoms in the amino group optionally pyrrolidino Or forms a piperidino ring or optionally forms a piperazino or morpholino ring with another nitrogen or oxygen atom, or C is Is a cocci, hydroxyalkyl, acyloxy, alkylthio or carbalkyl mercapto group, and D is independent of C, as defined for C and may represent a chlorine atom.