TW200407483A - Brightening of textile materials - Google Patents

Abstract

A process for brightening textile materials by treatment with optical brighteners in an aqueous liquor, which comprises using from 20 to 80% by weight, each percentage being based on the sum total of all brightening compounds, of the compound I, of which up to 40 mol% can be present as cis isomer, and also from 80 to 20% by weight of at least one compound II selected from, and also from 0 to 30% by weight of at least one compound of the general formula III, where R is selected from C4-C10-alkyl, in the optional presence of one or more blue or violet shading dyes from the class of the anthraquinones, azo dyes or methine dyes.

Description

200407483 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for brightening fabric materials by using an optical brightener in an aqueous solution, which includes using 20 to 80% by weight Compounds with up to 40 mole% cis isomers,

And 20% to 80% by weight of at least one compound π selected from

And 0 to 30% by weight of at least one compound of the general formula III:

III 200407483

OMe QHe, where R is selected from C4-C1 (r); based on the total amount of all percentages of the base reversing agent mentioned above; and if possible, there are-or more blue or purple colors selected from even or methine dyes Dark-dyeing dye. Milk [Prior technology]-As an auxiliary for the textile industry and the plastics industry, it is of great economic importance to give female shellfish blood husks first. Numerous compounds ^ 〇 /, can be given to fabrics or plastics White Moon Dagger Force 0 However, most of them should be driven; p ... Hai Xun's known compounds also have disadvantages. For example, compounds of general formula 1:

Phenyl, trifluoromethyl wherein (for example) R 丨 and R2 may each be such as hydrogen, fluorine, chlorine, alkyl, or various other groups, and wherein v is selected from ...

0

-CH3 can be seen in EP 0023 026 ′ and it is used in low temperature, but its efficiency is limited by) The product needs to achieve the desired white effect. Square 9, which brightens fabrics by using a stupid vinyl benzene compound, is also known. This compound is also found in, for example, CH-A 360 5 1 2, A 3δ. 85036 200407483 709, CH-A 388 294, CH-A 389 585, CH-A 41 1 329, CH-A 416 078 and CH-A 465 548. The references cited in EP-A 0 023 027 and EP-B2 0 030 917 and EP-B2 0 030 917 demonstrate the use of mixtures of two or more dicyanobenzylbenzyl compounds for optical brightening of polyesters 0 EP 0 023 026 discloses a mixture of optical brighteners, which comprises from 0.05 to 0.95 parts by weight of one or more compounds of formula 2p: '2p where A is ortho- or para-cyano-substituted phenyl , And 0.95 to 0.05 parts by weight or more of 4 from other extremely diverse other compounds. Preferably 2 p, 0 ,:

NC- mixture with a compound of formula 1: R2

Among them, R1 and R2 can each be: 笱, tired, 翕

It is the main group of Liaoning lice, trifluoromethyl, Ci-CV fluorenyl, alkoxy, alkylamino, and several other groups described on lines 2 and 4-21 on page 2, and V is as defined above; or Mixture of compounds of formula 3b-4b: 85036 -10- 200407483

Among them, B is a functional group, and R ′ and R2 are each as defined above. 嘀 is an integer, ㈣ is selected from chlorine and Cl-c4-carboxy, R4 is selected from C ″ C4-carbonoxy, and r5 is selected from compounds such as CVC. , -Alkyl, and B is preferably a functional group; or a mixture with a compound of formula ⑼:

Among them, R6 to R10 are each selected from various radicals, and V is as defined above, and thus various examples are shown in Table 2. ^ ^ ^ No 1 is 2 P, o, or other isomers and 3 c

And a substantial mixture with 4 b.l and 4 b.2: 85036 -II-200407483

The brighteners thus defined can be applied by various methods and provide good CIE whiteness. -EP-A 〇 023 028 claims a mixture that can be used as an optical brightener, which comprises 0.05 to 0.95 parts by weight of a mixture consisting of 2 to 100% by weight 2 ρ, 〇 ':

2 PxO, and 0 to 80% by weight of each compound 2 p, p, and 2 0, 0 ,: NCO ^ CH = CH-2

2 〇, 〇, and the formula containing 0.05 to 0.95 parts by weight s < two, Bali I knife heart eight la and 3a to 6a one or more derivatives' la and 3a to 6a definition is basically the same as the eight. 〇23〇26 is similar. DE A 197 32 109 proves that polyamines or polyamino acids are intended to include 85036 -12-

V 200407483 Optical brightening of a mixture of ingredients: derivatives of la compounds: R1 la R2 wherein R1 and R2 are each independently H or CVC6-alkyl, A is selected from N and CH ′ and X is selected from:

~ iy and X is also selected from stilbenevinyl, styryl, or imidazolyl; one or more isomers of 2 or one of several 4 derivatives:

CH «CH ~ CB ^ CH R3

cn

0

In particular, several other derivatives are shown, such as 5b (see the figure above). By way of example (examples 19-21) a mixture of 1 a.l and 4b.l:

H3〇X ^ c h3c K C〇〇Ch 4 ba 85036 13-200407483 This mixture exhibits a multiplicative effect on CIE whiteness and excellent light resistance. EP-A 0 32 1 393 describes 1 class b compounds:

[Wherein '0 is CrC4_alkynyl]; and the use of a compound of formula 2 in a brightener dispersion. The compounds of class 1 b or 2 are disclosed as themselves or as specific mixtures, see the references cited as mixtures 1 to 6 (pages 6-8). In EP-A 0 32 1 393, on page 9, line 18, the essence of the invention is that the mixed- # compound contains a copolymer of 2-vinylpyrrolidone and ethylene propionic acid. In EP A 0 682 I45, the fabric is treated with a formula containing a fluorescent UV absorber to improve its light fastness. The absorption wavelength of the fluorescent 1 / ¥ absorber is 28.

Or 1 d (item 8 in the scope of patent application), 85036 -14-200407483

Where:-each R14 is independently hydrogen or C4-C4-alkyl or third butyl or -C (CH3) 2-phenyl or COO-crc4-alkyl, R15 and R16 are the same or different and are selected from Η , C "C4-alkyl and CH2-ch2-〇h, each R17 is the same or different, and is selected from the group consisting of Η and S03-X:

And X1 is selected from:

However, the improvement of light fastness is usually controlled by other factors rather than participating in the optical brightening of the fabric. 85036 -15-: Moon White has great experience for a wide range of products: for example, related to fabrics and molded plastic items. The above proofs, especially 19 ^ burley / t dipper combination, 疋 A 0 023 〇26 and EP-A 0 023 028 and EP-A 〇 68 5 The example demonstrated by the mixture shown in the example of the white guest Ancient from Φ ... times to Gu ^ Er again. In addition, there is room for improvement in its performance characteristics. For the economic reasons, it is more effective to do ancient farming, ancient farming, and farming, and you can use less farming clams to achieve the same or better results. [Summary of the Invention] An object of the present invention is to provide: a method for brightening a textile material, which provides a particularly bright and improved efficiency, and also the same improved performance characteristics;-a method for the brightening textile material Formula; and-the purpose of the new formula. Word of mouth has found that this can be achieved by the methods defined at the outset. The fabric materials used for the purpose of the present invention include: fibers, slivers, yarns, threads, 'fabrics', woven fabrics, and non-woven fabrics', as well as clothing composed of fabrics or polymers. The fabric material is preferably composed of a synthetic polymer or a blend comprising 45 to 90% by weight of polyester.

The brightening or optically brightening compound used for the purpose of the present invention is a fluorescent compound, which can absorb in a wavelength range from 280 to 400 nm and emit at a higher wavelength. Examples include species of stilbene, stilbene, stilbene #, and three. Qin, Benzene, Diphenyl hydrazone, Diphenyl hydrazone. Compounds of stilbene, phenanthrene, stilbene, succinic acid, coumarin, and succinylcycloimide. Brightening or optically brightening compounds should also specifically refer to Formula I 85036-16-200407483, [Increase 7C of I and III or optically brightening compounds. Unless expressly stated otherwise, the weight percentages in the following should be based on the total amount of the brightening compound. The term "aqueous solution" as used herein also includes liquids which contain up to 40% by volume of-or more other solvents, such as alcohols (such as ethanol) and water as their main ingredients. The pH of the solution used according to the invention It is preferably in the range of 3 to η, and more preferably in the range of 3 to 8. The method defined at the beginning is to carry you forcefully and treat the fabric material with the following ingredients • 20 to 80% by weight and better 2 〇 $ said compound of formula I from Hiramano to 70% summer and better 30 to 50%: 〇, 85036

Up to 40 mole% of the compound may be in the corresponding cis isomer form to 20 weight. /. Of Compound II and at least 80 nc

NC

! Work P, P, -17- 200407483 and 0 to 30% by weight of the compound of general formula in:

OMe OMe /, R ′ is from C 4 -C 1 〇- :): End group, such as n-butyl, iso-butyl, first butyl, second-butyl, n-pentyl, isopentyl Base, second pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, second-hexyl, n-heptyl, -isoheptyl, n-octyl, 2-ethylhexyl, n-nonyl and n-decyl; n-butyl and 2-ethylhexyl are preferred. Preferably 20 to 80% by weight of the compound is used! And at least one of 0 to 30% by weight of the compound of the general formula III and 20 to 70% by weight of each of the compounds π p, 0 '* m, p'. It is particularly preferred to use 20 to 70% by weight of compound II p, 0, and 10 to 50% by weight. /. Compounds m, p, and 20 to 70% by weight of compound I and 0 to 30% by weight of compound of formula III. Another particularly preferred example is the use of 30 to 50% by weight of compound I and 0 to 30% by weight of a compound of the general formula ⑴, and 30 to 60% by weight of a compound ιΐρ, 0 ', 10 to 30% by weight of a compound π 0; 0, and optionally 10 to 50% by weight of the compound m, p ,. Compound I is synthesized, for example, as described in U.S. Patent Nos. 2,842,545, 2,875,089 or 85036-18-200407483 3, M7,253. Included for the purposes of the present invention are mixtures of such isomers, which contain 0.2 to 40 mole% and preferably "cis isomers" to mole%. By light exaggeration known to those skilled in the art 5 iy〇 / 27 (2), pp. 413-22. The dicyanostyrene compound ΙΙρ, 〇 ,, Hm, p, its trans isomer form, 〇, 0 to (M to 5 ... often contains 0.01 to 10 mol% and better, the photochemical ancient 1 known to those skilled in the art having at least one cis double bond. The hunting is described by 4. It can be determined by -4. The fraction of the isomers of the formula is also heavy. Wlttlng reaction can easily obtain the methyl carbon B in the scale of the two caffeine. The purple dark-toned dye can be used during the implementation of the method of the present invention. Available The following types of blue or dyes. These categories are general ;: fixed = belong to disperse dyes and reducing dyes such as disperse blue or 1 color color cable 丨 list the material or sub-primary blue or Reduced Violet. Onion dyes are suitable for example: 4: blue dyes are particularly suitable. S5036 -19. 200407483

A 1

Where z is a C "C1G-alkyl group, which is inserted or not inserted into one or two of the ether functional groups and contains or contains no ci_C4-alkoxycarbonyl or cyano substituted or unsubstituted or alkoxy, benzene Or substituted phenyl, "", alkyl 'with or without insertion of 1 or 2 oxygen atoms in the ether functional group and with or without hydroxyl, phenyl or CrCs-alkoxycarbonyl substitution, Z3 is oxygen or NH , Z4 is hydrogen, crc1 (r alkyl group with or without an ether functional group oxygen 85036 -20- 200407483 atom, and containing or not containing crc4-alkoxycarbonyl or cyano G-Cr alkoxy substituted phenyl group, Substituted or unsubstituted or Z5 is hydrogen or halogen or CN, z6 is hydrogen or Yasyl, and Z7 is C2-C6-alkylene or phenylene.

The dyes mentioned above are generally known dyes. For example, the dye of formula 8 is described in A 2,628,963 ^ US-A 3,835,154 > DE-A 12 66 425 ^ DE-A 20 16 794. Dyes conforming to the formula ~, 8-3, and 8-4 can be found in, for example, K. Venkataraman, "Chemical Properties of Synthetic Dyes", Volume 3, pages 3 ^ to 423, 1970. A suitable azo dye is especially a monoazo dye having a diazo group component of the aniline or heterocyclic series and a coupling component of the aniline or heterocyclic fluorene. A suitable heterocyclic group from which he is a heavy I-based component is selected from, for example, amido, amido, amido, and amino. Sigma sits and faces ‘such as thiathiazolyl or aminobenzoisothiazolyl. The coupling plant fractions from which it is derived are known and the heterocyclic system is selected from, for example, a pyrazole or a diamine group. More specifically, these azo dyes conform to formula 85036

-2U 200407483

85036 -22- 200407483

z is a methyl group, a cyano group, a K ^ 79 ^ alkoxycarbonyl group or a sulfonyl sulfonyl group, dimethyl hydrogen, halogen, crc8-alkoxy group, ^ benzyl group, cvc6-alkylthio group, claw group , Cvc4-calcium-based fluorenyl, fluorene-based fluorenyl, fluorenyl, or unsubstituted or chlorinated-, fluorenyl-, ethoxylated-, field test ceremonial- or methyl-substituted benzene As the cyano group, one or two oxygen atoms with or without the fluorene functional group inserted in the alkynyl chain, 2CrC6 · alkoxycarbonyl, amino fluorenyl, or mono- or di-C "C4_ alkylamine Methylmethyl, z and Z 2 are independently crC8_alkyl, with or without the ether functional group] ^ to 3 oxygen atoms and with or without hydroxyl, cyano, chlorine, phenyl, C ^ C6_ Alkoxy, crc6-fluorenyloxycarbonyl, Cl_c6-alkoxycarbonyloxy, or mono- or di-C6-C6-alkylaminoamino-oxy-substituted or C3-C4-alkenyl, otherwise in the case of ζπ is hydrogen But it is not an example of Z12, y1 is hydrogen, cVc4-alkyl, C, C4-alkoxy, gas, bromine or formula 85036 -23- 200407483 -nh-co-r1 CrC4-alkoxy C2 " * C3-dilute F, where R " is C | fluorenyl, or does not contain murine, meridian, gas, or cvq-Uoxy Or Y is hydrogen, q-cv alkyl, or (^ < 4-alkoxy 'Z, unsubstituted or substituted with c, _c4-alkyloxy, alkyl, unsubstituted, or substituted with 4 oxygen Unsubstituted phenylmethyl, unsubstituted chloromethyl, methyl-, foxy- or ethoxy-substituted phenyl, 2-pyridyl or 3-yl, _z 14 is cyano, chloro or bromo, Is un, di-substituted or C rC4_alkoxy- or ethamino-substituted fluorenyl or sigmathio, and ζ16 is cyano, gas, or bromine. The azo dyes themselves are already The dyes of formulas B 丨 and B2 are described in, for example, US Patent Nos. 5,283,326 or 5,145,952. EP-A 0 087 616, £? -0087 677, £? -80 0 121 875, Ugly? -80 151 287 and U.S. Patent No. 4,960,873 discloses dyes of formula B3. U.S. Patent No. 5,216,139 discloses dyes of formula B4. U.S. Patent No. 5,132,412 discloses dyes of formula B5. The dyes of formulas B6 and B7 are described in For example, U.S. Patent No. 3,981,883, DE-A 31 12 427, EP-A 0 064 221, or Venkataraman, "Chemical Properties of Synthetic Dyes", Vol. 3, pages 444 to 447, or by And the method of obtaining.

Suitable secondary fluorene-based dyes conform to formulae C 85036 -24- 220200407483

C

Where Y3 is nitrogen or CH, z is CrC2G-alkyl, substituted or unsubstituted phenyl or hydroxyl group, with or without substitution and with or without insertion of one of the ether functional groups or an oxygen atom, Z is 5 -Member aromatic heterocyclic group, Z20 is hydrogen, cyano, aminofluorenyl, carboxyl or Crc4-alkoxycarbonyl, Z21 is oxygen or formula C (CN) 2, C (CN) COOZ23 or c (co. z23) 2, wherein in each case Z23 is a Crc8-alkyl group with or without an 1 or 2 oxygen atom of an ether functional group, and z2 is hydrogen or a crc4-alkyl group. Substituted alkyl groups in formula C may have the following substituents, unless stated otherwise, for example, benzyl, CrC4-alkylphenyl, CrCralkoxyphenyl, _phenylC1oxy, crc8-alkylamine Carbonyloxy, crC2Q-carboxycarbonyl, alkylcarbonyloxy (the alkyl chain in the last two groups mentioned may be optionally inserted with 1 to 4 oxygen atoms of the ether functional group and / or via phenyl or benzene Oxy substituted), halogen, hydroxy, or cyano. The number of substituted alkyl groups is generally one or two. The alkyl groups that differ from the oxygen atom of the ether functional group, unless otherwise stated, are preferably via the ether functional group to 4 oxygen atoms and particularly preferably 85036 -25-200407483 2 oxygen atoms. Inserted alkyl. The substituted benzyl or σpyridinyl group present in formula C may have a substituent such as a radical, a crCV alkoxy group, a halogen (especially gas or bromine), or a carboxyl group. The number of substituents in a substituted phenyl or pyridyl group is generally 1 to 3. The Z19 group can be derived from components such as the pyrrole, thiazole, thiophene, or indole series. Important Z19 radicals include those radicals of formulae C1 to c 4, for example:

c 4 where m is 0 or 1, and Z24 and Z25 are the same or different and each independently is hydrogen or a ci-Cf alkyl group, substituted or unsubstituted or substituted with one or more oxygen atoms of an ether functional group, or Unsubstituted phenyl or a nitrogen atom in the middle to form a 5- or 6-membered saturated heterocyclic ring with or without other heterocyclic atoms. Z26 is hydrogen, halogen, C, C8-alkyl, Substituted or substituted with alkynyl-alkoxy-substituted benzyl, unsubstituted or benzyl, cyclohexyl, thienyl or 6 < 4-alkynyl or C! -C4-alkoxy-substituted , Hydroxyl, or 85036 -26- 200407483 monoalkylamino, each Z "is the same or; ί; and each independently represents hydrogen, radical, unsubstituted or via phenyl- or C, -C4 · alkyl Phenyl-substituted Ci_c8 alkyl, unsubstituted or substituted by phenyl- or crc4-alkylphenyl-substituted Ci_c8_ ^ oxy, c′c8_alkylamino, CVCValkylamino Or monohexylaminomethylamino, P is cyano, aminomethylamino, mono. Or di-C "CJ aminoaminomethyl, crCs-alkoxycarbonyl or substituted or unsubstituted Phenyl, and -Z horse halogen, hydrogen, C | _C 4-Alkyl, .4-Alkoxy, thio, unsubstituted or phenyl or thienyl substituted with 4-Alkyl- or Ci_c4_Alkyloxy. These subfluorenyl dyes are described For example in the previous German patent application DE_A 44 033 083. Of particular importance is a method in which a polyester or polyester blend is treated in the presence of one or more blue or purple dark-tone dyes, which are selected Since anthraquinone, especially a dye of formula A. φ This method works well technically when operated in the presence of a dye of formula A 3 · 1

This dye is also called C.I. Disperse Violet 28 (61 102). The use amount of the brightening compounds according to the present invention is based on the texture to be brightened 85036 -27- 200407483 = material and = is from _ to G.7% by weight, and preferably-the white effect ^ is the same or better than the previous The amount of coloring or weaving dye provided by the technical optical brightening material is generally (based on the woven fabric to be brightened) in the range of 0.00005 to 0.02% by weight and preferably in the range of 0 to 0:% by weight. However, it is not necessary to use a darkening dye. The fabric material is usually brightened by a dip dye method or a hot melt method. The dip-dyeing method is performed from an aqueous solution, and most of them are 90 to 13 ^ when two: two right. In the case of the above applications, the heart must be placed on or pressed against the machine. The hot-melt method is performed under atmospheric pressure. ^ Using the fabric material to be brightened to guide people's aqueous solution often: Dip method, the aqueous solution contains optical brightening compounds, optionally: color or purple dark-dye dyes or mixtures thereof and additives as appropriate For example, = powder, carboxylic acid or basic donor, and the pH value of the solution is usually in the range of 3 to 2 and preferably in the range of 3 to 8 at 10 to 35. The weight ratio of the liquid two liquid to the fabric material) ranges from 3: 1 to 40: 1 and preferably from Η to 20.1. The dye bath was then heated to 90-13 (rc lasted 15-30 minutes, then heated to 95-10 ..., and kept at this temperature for ⑽ minutes .: :: Rinse and dry the brightened fabric material. In the hot-melt method, the fabric material to be brightened is usually pressure-sucked with an aqueous solution containing the optical brightener f, optionally ^ color $ purple dark-tuned fuel or a mixture thereof, and Additives (see above). The wet pick is generally in the range of 50 to 100%. Thereafter, at 150 to 2000; it is dried and held for 5 to 60 seconds. 85036 -28- 200407483 The dispersant used is preferably a dispersant with a yellow helmet. 'Stable at at least 2l0t is an example of an anionic or non-ionic dispersant, especially a B :, a secondary fatty acid or a benzene ring The anionic or non-ionic dispersant of the oxyethylene calcined propylene glycol adducts is an alkoxylated product (which is an aliphatic or alkyl aromatic radical, amine or amino radical compound) (Main), you can use the brand names synperonic⑯ and ukanil⑧, Dehypon® 'Neopoll® ethoxylates, Emullen ^, Lutensol®, Prurafac® (plurafac (g)) and Available from Pluronic® or Elfapur®. Particularly preferred is the oxidized benzene S fraction. Excellent dispersants are the oxidized benzenes of the general formula IV and V. Fan:

h3c IV

h3c of which 85036 -29-

V 200407483 3 and 6 are integers, so that the range of a is 0 to 180 and preferably 0 to 125. The younger brother is already 20 to 180 and especially 3m25, but the condition is: M is the metal test Preferably it is Na or K, and more preferably Na; d is 0 or 1; or a mixture thereof.

The preparation of these compounds _V is known, 1 is preferably made by making phenol VII: N

It is carried out by reacting with propylene oxide and then reacting the adduct with ethylene oxide, or by reacting VI and VII with ethylene oxide, respectively. Thereafter, the adduct may be completely or partially converted into acidic sulfate with chlorosulfonic acid or sulfur trioxide, and the resulting acid ester may be neutralized with a test. A phenol of formula VI or VII can be obtained by reacting bisphenol A (2,2- (p, p, bishydroxyphenyl) propane) or phenol with 4 or 2 moles of styrene in the presence of an acid as a catalyst, respectively. obtain. In the presence of acidic or basic catalysts (such as NaOCH3 or SbCb) by known methods, the phenol VI and V [[are converted separately using propylene oxide and then ethylene oxide, or only with ethylene oxide. For the corresponding alkoxylation products 85036-30 · 200407483 compounds IV and V, where d = 0. This alkoxylation can be performed by a method as described in U.S. Patent No. 2,979,528. The acidic sulfate is prepared by reacting an alkoxylated product with chlorosulfonic acid or sulfur trioxide, and the amount of gas sulfonic acid or sulfur trioxide is selected such that all free hydroxyl groups or only a specific percentage of free hydroxyl groups Sulfate. The latter case will produce a mixture of compounds of formula ... or v containing free hydroxyl groups and phosphatelated hydroxyl groups. As a surfactant, the acid ester of the newly synthesized sulfuric acid is converted into a water-soluble salt. The water-soluble salt preferably comprises an alkali metal salt, such as a sodium or potassium salt. Gas sulfonic acid needs to be two equivalents of the base compound, and sulfur trioxide is -equivalent. It is advantageous that the alkali compound used is an aqueous solution of an alkali metal hydroxide. The temperature during neutralization should not exceed 70. 〇. The resulting salt can be used as an aqueous solution, or it can be isolated therefrom and used as a solid. Dispersants IV and V are preferred, where 3 is 0 to an average of 2, 5, b is an average of 25 to 250 and d is 0 to an average of 0.5. Particularly preferred are dispersants ... and v, where & is 0 to an average of 2.5, b is an average of 50 to 100, and 4 is an average of 0.5. Compounds of formula IV and V are known, and several representative examples are described in, for example, U.S. Patent No. 4,218,218. "Depending on the conditions of the month" "Additives in the mouth * include biocides or water-holding aids commonly used in the textile industry, for example. Additives that can be added as appropriate also include ... ethyl ketone. Each ketone and 3-ethylene propionic acid The copolymer is described in Μρ-Α () 32ΐ 393. The method of the X method uses a formula, the formula includes (each percentage is based on the weight of the formula of the formula X, 17 „μ mainly) 1 to 40% by weight, and preferably 3 to 10% by weight of the above-mentioned brightener and dark-dye dye mixture, 3 to 12% by weight of anionic or non-ionic knife agent '1 to 15% by weight 2N • ethylene t Ketone and ethyl acetate 85036 -31-copolymers or mixtures of vinegar or ethyl propionate, and other additives (such as water-holding aids or biocides) and water. . It is also expected to give the fabric its fastness during the dazzling process. Self-color effect. The exempted fabric has excellent durability and light hunting. It is prepared by measuring the individual pre-dispersed optical brightening substances separately and each or each of the darkening dyes, dispersants and / or other tonics used as appropriate. The above aqueous solution. ， 2, and _ It is better to apply the A-brightening compound and optionally one or more kinds of k 3 withered wood, dispersant and other additives as a formula to implement the method of the present invention. The invention therefore further provides a formulation comprising 20 to 80% by weight of a compound, each percentage being based on the total amount of all brightening compounds, 20 to 80% by weight of at least one compound π, 0 to 30% by weight of formula m At least one compound, and a li-color or purple-dark shade dye that can be used in each case as appropriate, which is selected from the group consisting of anthracene, azo dye, -human methyl dye, purple onion g, or scattered anthracene Kun Kun, one or more dispersants, water and other additives. The formulation according to the invention generally comprises water and (each percentage is based on the weight of the formulation) 1 to 40% by weight, and preferably 3 to 25% by weight of the mixture of said brightening compounds, and optionally 0.001 to 1%. 0.1% by weight dark-dyeing dye, optionally 0.5 to 40% by weight dispersant, and 5 to 60% by weight and preferably 5 to 52% by weight of additives. The present invention further provides the use of the formula according to the present invention for the brightening of fabric materials 85036 -32- 200407483 ′ especially for the use of polyester or polyester blends for brightening. The following examples will illustrate the invention. The overall description of the isomer distribution is as follows: I trans-cis, 95: 5 mole%; Ηρ, 〇 ,, π mp ', Πο, 〇', each higher than 95 mole% trans, each borrowed 1hnmr spectroscopy. 1. Local temperature dip dyeing process 1000 liters of dyeing bath (which contains the total concentration of brightening compound poplars listed in Table 丨, the individual dispersion ("completed") added in water), at 25.0 and丨 0 kg of polyester fabric was fed into the autoclave together. Then the dyeing bath was heated to 130. (: 430 minutes, and maintained at 130 ° C for another 30 minutes. Thereafter, the fabric was removed from the dyeing bath, rinsed and dried The optical CIE whiteness was measured to analyze each case. The comparative (V) test each used a mixture of 50% by weight of η 0, p, and 50% by weight of 4 b. 1 85036

c 〇〇c It is found in Table 2 -33-200407483 of EP 0 023 026 Table 1 Poly v / rq J / J {^ 3 fluorinated compounds (: ts%) ) H concentration in solution CIE whiteness 1.1 ~ IIp'o 'II m, p, 4b.I .45 55 — 0.02 147 1.2 45 55-0.03 155 1.3 45 55 plug 0.057 166 1.4 45 55 _ 0.077 167 1.5 45 55-_ 0.095 167 1.6 40 40 20 0.02 150 1.7 40 40 20 series 0.03 158-1.8 40 40 20 0.057 164 1.9 40 40 20 _ 0.077 169 1.10 40 40 20 0.095 Π 169 V 1.11-50-50 0.02 145 V 1.12- 50-50 0.03 153 V 1.13-50-50 h 0.057 163 V 1.14-50-50 0.077 163 V 1.15-50 嶋 50 0.095 163 The method of the present invention provides an increase over previous methods in various situations ^ vVW 5 /? Ti ^ Gu y (bu Yeqiang effect, while using a smaller amount of brightening compound. Similarly, the method of the present invention achieves a peak brightening effect at a lower concentration of optical brightening substance. 2 · heat The melting process is performed by pressure-absorbing the polyester fabric with an aqueous solution at room temperature. 2.1 to 2 · 8, the aqueous solution contains a total of 0.8 g / L of optical brightening compounds with the ingredients listed below. The pH value is adjusted to 5 · 5 with acetic acid. The wet pick-up is 60%. Thereafter, the fabric was allowed to air dry for about 20 seconds at 11 (°), and thereafter, maintained at the temperature shown in Table 2 for 30 seconds. Comparative Examples V2.9 to V2.12 were implemented in a similar manner, but were used 〇8 g / L of liquid, which is 50% by weight Π 0, ρ, and 50% by weight of the following compound 85036 200407483

It is found in Table 2 of EP 0 023 026. Comparative Examples V 2.13 to V 2.16 were carried out in a similar manner to the Inventive Example, but using 70% by weight of IIg, p 'and 30% by weight at 1.5 g / l. /.丨 丨 〇, 〇, a mixture. -Table 2 Brightens the fabric with various mixtures of optical compounds through the hot-melt process; fixed at different temperatures

85036 -35-

Claims (1)

200407483 Patent application scope: i • -A method of brightening fabric materials with optical brightener treatment in aqueous solution, which includes the use, each percentage based on the total of all brightening compounds '20 to 80 weight % Up to 40 mole% of Compound I as a cis isomer: I ch3 •, and at least one compound π from 2 Q% to 80% by weight, which is selected from: XI ρ, ρ, and 0 to 30% by weight of at least one compound of the general formula IIII 85036 III OMe, where R is selected from C4_C 'hydrazone, depending on the condition, there are one or more ^ phoenix or ochre dark-tone dyes, which are selected from the group of graceful, azo dyes or methine dyes. 2. As in the method of claim 1 of the scope of patent application, jl φ #-which uses 20 to 70 weight of compound II p, 0, and 20 to 80 weight of compound I and 0 to 30 weight % Of compounds of general formula III. 3 · If the scope of patent application is the first one? The method of Gongbaixishi, + ^ 2A, which uses a compound Π m, p ′ of 20 to 70 t / o and a compound of 20 to 80% by weight and a compound of 0 to 30% by weight. Compound of formula III. (As in the method of applying for the scope of patent application (ii), wherein 20 to 70% by weight of the compound II ρ, 〇 ′ and 10 to 50% by weight of the compound 丨 m, 〆, and 20 to 70% of the reset compound are used I and 0 to 30% by weight of a compound of the general formula III. 5. The method as claimed in claim 1 of the patent scope, wherein 30 to 60% by weight of the compound II ρ, ο ′ and 10 to 30% by weight Compound η 〇, 〇, and 30 to 60% by weight of compound I and 0 to 30% by weight of compound of general formula m. 6. The method according to item 1 of the patent application, wherein 20 to 60 is used. Compound II ρ, ο ′ by weight, compound π m, p of 10 to 50% by weight, and compound 10 to 30 by weight 85036 200407483% compound II 〇, 〇, and 20 to 50% by weight of compound 丨 and ^ To 30% by weight of a compound of the general formula III. 7. The method according to item i or item 2 of the scope of patent application, wherein R in compound m is 2-ethylhexyl. 8. As the item in scope of patent application Or the method of item 2, wherein an additional weight of 0.5 to 2000 based on the total amount of all the brightening compounds is used - A ^ or dispersant wherein the fabric material. 9. If the method of the first or second item of the patent application scope is polyester. 10. The method according to item 1 or item 2 of the patent application range is a blend containing 45 to 90% by weight of polyester. 11 · A formulation comprising 20 to 80% by weight of a compound! Each percentage is based on the total amount of all brightening compounds, ° 20 to 70% by weight of at least one compound π, 0 to 30% by weight of at least one compound of formula hi, and in each case one or more blues are selected as appropriate Color or purple dark-tone dyes are selected from the group consisting of anthracene rolls, dioxins, hypofluorenyl dyes, violet anthrones, or indoanthraquinones, one or more dispersants, water, and other additives. 12. —The use of the formula such as item 丨 丨 in the scope of patent application is for brightening materials. ^ 85036 200407483 (1) Designated representative map: (1) The designated representative map in this case is: (). (2) A brief description of the component symbols in this representative map: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: h3c gh3 NC II P / P * OMe OMe 85036 III