Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/642—Compounds containing nitrogen
  • D06P1/6426—Heterocyclic compounds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/35—Heterocyclic compounds
  • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings

Definitions

• the present invention relates to a process for the photochemical and thermal stabilization of undyed and dyed or printed polyester fiber materials.
• Undyed and dyed or printed polyester fiber materials are damaged under the influence of light and especially when exposed to heat.
• effective protection of undyed and dyed or printed fiber materials from UV radiation is essential.
• the present invention accordingly relates to a process for the photochemical and thermal stabilization of undyed and dyed or printed polyester fiber materials, which is characterized in that the fiber material is treated with at least one compound of the formula treated in what R1 the rest of the formula R2 and R'2 are each independently hydrogen, C1-C12-alkyl, C5-C7-cycloalkyl, (C1-C8-alkyl) -phenyl, phenyl, C7-C9-phenylalkyl or C1-C4-alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or C1-C4 alkyl, and R5 C1-C12-alkyl, C1-C6-monohalalkyl, C1-C6-dihaloalkyl, C1-C1-alkenyl, C1-C1-monohalogenalkenyl, C5-C7-cycloalkyl, phenyl, by C1-C4-alkyl
• Halogen is e.g. for fluorine, bromine and preferably chlorine.
• C1-C12 alkyl is e.g. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. Butyl, tert. Butyl, n-pentyl, n-hexyl, n-octyl or n-decyl.
• C5-C7-cycloalkyl is e.g. Cyclopentyl, cyclohexyl or cycloheptyl.
• phenyl is e.g. Methylphenyl, ethylphenyl, tert. Butylphenyl or di-tert. Butylphenyl.
• C7-C9-phenylalkyl is e.g. Benzyl or phenethyl.
• C1-C4-alkoxy means methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec. Butoxy or tert. Butoxy.
• C1-C4-alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. Butyl or tert. Butyl.
• C1-C6 monohalalkyl is e.g. Chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloro-n-propyl or 4-chloro-n-butyl.
• C1-C6 dihaloalkyl is e.g. 1,2-dichloroethyl, 1,2-dibromoethyl or 2,3-dichloropropyl.
• C2-C4-alkenyl is, for example, vinyl, 2-propenyl or 2-butenyl.
• C2-C4 monohalogenalkenyl is e.g. 1-chloroethen-1-yl, or 1-bromoethen-1-yl.
• Phenyl-C1-C4-alkyl is e.g. Benzyl or phenethyl.
• R1, R2 and R3 have the meanings given under formula (1), in particular those compounds of the formula (4) are used in which R1 is the rest of the formula R2 is hydrogen, C1-C12-alkyl, C5-C7-cycloalkyl, (C1-C8-alkyl) -phenyl, phenyl, C7-C9-phenylalkyl or C1-C4-alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or C1-C4 alkyl, and R5 C1-C12 alkyl, C1-C6 monohalalkyl, C1-C6 dihaloalkyl, C1-C4 alkenyl, C1-C4 monohalogenalkenyl, C5-C7 cycloalkyl, phenyl or by C1-C4 alkyl, C1-C4- Alkoxy or halogen substituted pheny
• a method is particularly preferred which is characterized in that at least one compound of the formula (1) or (4) is used, in which R1 is a radical of the formula (2), R2 is hydrogen, C1-C4-alkyl, C5-C7-cycloalkyl, (C1-C4-alkyl) -phenyl, phenyl, benzyl or phenethyl, R'2 is hydrogen or C1-C4 alkyl, R3 is hydrogen, chlorine or bromine, R4 hydrogen, and R5 C1-C6-alkyl, C1-C4-chloroalkyl, C1-C4-dichloroalkyl, C1-C4-dibromoalkyl, C1-C4-alkenyl, C1-C4-chloroalkenyl, C1-C4-bromoalkenyl, C5-C7-cycloalkyl, phenyl , phenyl or benzyl substituted by C1
• a very particularly preferred process is characterized in that at least one compound of the formula used where R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec. Butyl, tert. Butyl, isobutyl or n-butyl, R3 is hydrogen or chlorine, and R8 methyl, ethyl, isopropyl, n-propyl, sec. Butyl, tert.
• Another very particularly preferred process is characterized in that at least one compound of the formula used where R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec. Butyl, tert. Butyl, isobutyl or n-butyl, R3 is hydrogen or chlorine, and R9 is a radical of formula (3a), (3b) or (3c), wherein n is the number 3, R6 is hydrogen or methyl, and R7 is hydrogen.
• Another particularly important process is characterized in that a mixture of at least one compound of the formula (1) and a compound of the formula used in which R2, R'2 and R3 have the meanings given under formula (1), in particular mixtures are suitable in which at least one compound of formula (1) is used together with a compound of formula (8), wherein R1, R2, R'2 and R3 have the meanings given above as preferred and particularly preferred to have.
• a very particularly important process is characterized in that a mixture of two compounds of the formula (1) is used.
• the compounds of formula (1) are partly New.
• the new compounds of formula (1a) represent a further subject of the invention.
• R1 the rest of the formula R2 and R'2 independently of one another are hydrogen, C1-C12-alkyl, C5-C7-cycloalkyl, (C1-C8-alkyl) -phenyl, phenyl, C7-C9-phenylalkyl or C1-C4-alkoxy
• R3 is hydrogen or halogen is is
• R4 is hydrogen or C1-C4 alkyl
• R5 C1-C12-alkyl, C2-C6-monohalalkyl, C1-C6-dihaloalkyl, C1-C4-alkenyl, C1-C1-monohalogenalkenyl, C5-C7-cycloalkyl, phenyl, by C1-C4-alkyl, C1-C4- Alkoxy or halogen substituted phenyl or phenyl-C1-C4-alkyl means or R4 and R5
• R1, R2 and R3 have the meanings given under formula (1a), in particular wherein R1 is the rest of the formula R2 is hydrogen, C1-C12-alkyl, C5-C7-cycloalkyl, (C1-C8-alkyl) -phenyl, phenyl, C7-C9-phenylalkyl or C1-C4-alkoxy, and R3 is hydrogen or halogen R4 is hydrogen or C1-C4 alkyl, and R5 C1-C12 alkyl, C1-C6 monohalalkyl, C1-C6 dihaloalkyl, C1-C4 alkenyl, C1-C4 monohalogenalkenyl, C5-C7 cycloalkyl, phenyl or by C1-C4 alkyl, C1-C4- Alkoxy or halogen substituted phenyl, or R4 and R5 together with the -N-CO radical connecting
• R1 is the rest of the formula (2a)
• R2 is hydrogen, C1-C4-alkyl, C5-C7-cycloalkyl, (C1-C4-alkyl) -phenyl, phenyl, benzyl or phenethyl
• R'2 is hydrogen or C1-C4 alkyl
• R3 is hydrogen, chlorine or bromine
• R4 hydrogen
• R5 C1-C6-alkyl
• R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec. Butyl, tert. Butyl, isobutyl or n-butyl
• R3 is hydrogen or chlorine
• R8 methyl, ethyl, isopropyl, n-propyl, sec. Butyl, tert. Butyl, isobutyl, n-butyl, phenyl, chlorophenyl, dichlorophenyl, 1,2-dichloroethyl, 1,2-dibromoethyl, cyclohexyl, 1-chlorovinyl or 1-bromovinyl.
• R2 is hydrogen, methyl, ethyl, isopropyl, n-propyl, sec. Butyl, tert. Butyl, isobutyl or n-butyl
• R3 is hydrogen or chlorine
• R9 is a radical of the formula (3a '), (3b') or (3c '), wherein n is the number 3
• R6 is hydrogen or methyl
• R7 is hydrogen.
• the compounds of formula (1) or (1a) are prepared by using a compound of formula wherein R2, R'2 and R3 have the meanings given under formula (1) or (1a), with one the rest of the formula introductory compound in which R4 and R5 have the meanings given under formula (2) or (2a).
• the reaction is carried out at a temperature between 0 and 100 ° C.
• the implementation takes place e.g. by homogenizing the compounds of formula (7) and the compound introducing the rest of formula (2) and adding them to concentrated sulfuric acid with stirring.
• the reaction mass is then discharged onto ice / water and isolated in a manner known per se.
• the present invention accordingly also relates to a process for the preparation of compounds of the formula (1a).
• Examples of compounds which introduce the rest of the formula (2) or (2a) are: N-hydroxymethylbenzamide, N-hydroxymethylacetamide, N-hydroxymethyl-4-chlorobenzamide, N-hydroxymethyl-2,4-dichlorobenzamide, N-hydroxymethylbutyric acid amide, N-hydroxymethyl-2,3-dichloropropionic acid amide, N-hydroxymethyl-2,3-dibromopropionic acid amide.
• the invention further relates to a process for the photochemical and thermal stabilization of undyed polyester fiber materials, which is characterized in that the fiber material is treated with a dyeing liquor which, in addition to a disperse dye, is a compound of the formula wherein R1 the rest of the formula R2 and R'2 are each independently hydrogen, C1-C12-alkyl, C5-C7-cycloalkyl, (C1-C8-alkyl) -phenyl, phenyl, C7-C9-phenylalkyl or C1-C4-alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or C1-C4 alkyl, and R5 C1-C12-alkyl, C1-C6-monohalalkyl, C1-C6-dihaloalkyl, C1-C1-alkenyl, C1-C1-monohalogenalkenyl, C5-C7-cycloalkyl, phenyl,
• the invention also relates to mixtures comprising at least one, in particular two or three, preferably two, compound (s) of the formula wherein R1 the rest of the formula R2 and R'2 are each independently hydrogen, C1-C12-alkyl, C5-C7-cycloalkyl, (C1-C8-alkyl) -phenyl, phenyl, C7-C9-phenylalkyl or C1-C4-alkoxy, and R3 is hydrogen or halogen, R4 is hydrogen or C1-C4 alkyl, and R5 C1-C12-alkyl, C1-C6-monohalalkyl, C1-C6-dihaloalkyl, C1-C1-alkenyl, C1-C1-monohalogenalkenyl, C5-C7-cycloalkyl, phenyl, by C1-C4-alkyl, C1-C4- Alkoxy or halogen substituted pheny
• the UV absorbers according to the invention are used in an amount of 0.01 to 5% by weight, preferably 0.1 to 3, and in particular 0.25 to 2% by weight of the weight of the fiber material.
• the ratio of the compounds of the formulas (1) or at least one compound of the formula (1) and one compound of the formula (8) can vary within wide limits; preferred is a ratio of two compounds of formula (1) or a compound of formula (1) and a compound of formula (8) from 1:10 to 10: 1; and the ratio of two compounds of formula (1) and one compound of formula (8) is preferably from 1:10:10, 10: 1: 10 to 10: 10: 1.
• the UV absorbers according to the invention are practically insoluble in water and are therefore applied in dispersed form. To do this, they are mixed with an appropriate dispersant e.g. ground to a fineness of ⁇ 1-2 ⁇ m using quartz balls and a high-speed mixer.
• an appropriate dispersant e.g. ground to a fineness of ⁇ 1-2 ⁇ m using quartz balls and a high-speed mixer.
• Dispersions which are only slightly soluble in water are suitable as dyes. They are therefore largely in the form of a fine dispersion in the dyeing liquor. They can belong to different classes of dyes, for example the acridone, azo, anthraquinone, coumarin, methine, perinone, naphthoquinone imine, quinophthalone, styryl or nitro dyes. Mixtures of disperse dyes can also be used according to the invention.
• polyester fiber material which can be dyed or printed and treated with the UV absorbers mentioned, there are e.g. Cellulose ester fibers, e.g. Cellulose-21 ⁇ 2-acetate fibers and triacetate fibers and especially linear polyester fibers, which may also be acid-modified, to be understood, e.g. can be obtained by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane, and also copolymers of terephthalic and isophthalic acid and ethylene glycol, or the incorporation of sulfoisophthalic acid.
• the linear polyester fiber material used almost exclusively in industry so far consists of terephthalic acid and ethylene glycol.
• the fiber materials can also be used as a blend with one another or with other fibers, e.g. Mixtures of polyacrylonitrile / polyester, polyamide / polyester, polyester / cotton, polyester / viscose and polyester / wool, and can be dyed or printed discontinuously or continuously by known methods.
• the textile material can be presented in various forms.
• Piece goods such as knitted or woven fabrics or yarn on cross-wound bobbins, warp beams, etc., are preferably used.
• the dyeings are carried out from an aqueous liquor using a continuous or batch process.
• the liquor ratio can be chosen in a wide range, e.g. 1: 4 to 1: 100, preferably 1: 6 to 1:50.
• the temperature at which dyeing is carried out is at least 50 ° C and usually it is not higher than 140 ° C. It is preferably in the range from 80 to 135 ° C.
• the dye liquors are used in addition to the dyes can optionally contain other auxiliaries, applied to the piece material by padding or slapping, for example, and developed by means of heat-setting or HT steaming processes.
• Linear polyester fibers and cellulose fibers are preferably dyed by the so-called high-temperature process in closed and pressure-resistant apparatus at temperatures> 100 ° C., preferably between 110 ° and 135 ° C. and, if appropriate, under pressure.
• Circulation devices such as cross-wound or tree dyeing machines, reel runners, nozzle or drum dyeing machines, muff dyeing machines, paddles or jiggers are suitable as closed vessels.
• foulards or paddles are used; the development is carried out by hot air in the stenter or in HT dampers.
• Cellulose-21 ⁇ 2-acetate fibers are preferably dyed at temperatures of 80-85 ° C.
• the UV absorbers according to the invention are used in the dyeing application, they are used in such a way that the fiber material is first treated with these compounds and then the dyeing is carried out, or preferably the fiber material is simultaneously treated with the UV absorber and the dye in the dye bath.
• the application of the UV absorber can also be applied subsequently to the finished color e.g. using pad application and heat setting in the stenter, e.g. at 190 to 230 ° C in a period of 30 seconds to 5 minutes.
• the dye liquors can also contain other additives, e.g. Dyeing aids, dispersants, diffusion accelerators, wool protection and wetting agents as well as defoamers.
• additives e.g. Dyeing aids, dispersants, diffusion accelerators, wool protection and wetting agents as well as defoamers.
• the dye baths can also contain mineral acids, e.g. Contain sulfuric acid or phosphoric acid, or expediently organic acids, for example aliphatic carboxylic acids such as formic acid, acetic acid, oxalic acid or citric acid and / or salts such as ammonium acetate, ammonium sulfate or sodium acetate.
• mineral acids e.g. Contain sulfuric acid or phosphoric acid
• organic acids for example aliphatic carboxylic acids such as formic acid, acetic acid, oxalic acid or citric acid and / or salts such as ammonium acetate, ammonium sulfate or sodium acetate.
• the acids are used primarily to adjust the pH of the liquors used according to the invention, which is between 4 and 5.
• the fiber material is preferably left in the bath at 40 to 80 ° C. for 5 minutes, that contains the dye, the UV absorber and optionally other additives and is adjusted to a pH of 4.5 to 5.5, increases the temperature within 10 to 20 minutes to 125 to 130 ° C. and treats for 15 to 90 minutes, preferably 30 minutes, further at this temperature.
• the dyeings are completed by cooling the dye liquor to 50 to 80 ° C., rinsing the dyeings with water and, if appropriate, cleaning in a conventional manner in an alkaline medium under reductive conditions. The dyeings are then rinsed again and dried.
• the UV absorbers according to the invention are added to the printing pastes in the form of their aqueous dispersions.
• the printing paste contains the corresponding UV absorber in amounts of 0.5 to 5%, preferably 1 to 2%, based on the weight of the fiber material to be printed.
• the amount of dyes added to the printing pastes depends on the desired shade; In general, amounts of 0.01 to 15, preferably 0.02 to 10 percent by weight, based on the textile material used, have proven successful.
• the printing pastes advantageously contain acid-stable thickeners, preferably of natural origin such as seed flour derivatives, in particular sodium alginate, alone or in a mixture with modified cellulose, in particular with preferably 20 to 25 percent by weight carboxymethyl cellulose.
• the print pastes can also contain acid donors such as butyrolactone or sodium hydrogen phosphate, preservatives, sequestering agents, emulsifiers, water-insoluble solvents, oxidizing agents or deaerating agents.
• Particularly suitable preservatives are formaldehyde-releasing agents, such as paraformaldehyde or trioxane, especially aqueous, approximately 30 to 40 percent by weight formaldehyde solutions, sequestering agents, for example sodium nitrilotriacetic acid, sodium ethylenediaminetetraacetic acid, especially sodium polymethaphosphate, especially sodium hexamethaphosphate, as Emulsifiers, especially adducts of an alkylene oxide and a fatty alcohol, in particular an adduct of oleyl alcohol and ethylene oxide, as water-insoluble solvents, high-boiling, saturated hydrocarbons, especially paraffins with a boiling range of about 160 to 210 ° C (so-called Lackbenzine), as an oxidizing agent, for example an aromatic nitro compound, especially an aromatic mono- or dinitrocarboxylic acid or sulfonic acid, which is optionally present as an alkylene oxide adduct, especially a nitrobenzen
• the printing paste is applied over the entire surface or in places directly to the fiber material, whereby printing machines of conventional design, e.g. Gravure printing, rotary screen printing and flat film printing machines are used.
• the fiber material is dried at temperatures up to 150 ° C., preferably 80 ° to 120 ° C.
• the fixation is then carried out by heat treating the material at temperatures of preferably 100 ° to 220 ° C.
• the heat treatment is generally carried out with superheated steam under atmospheric pressure.
• the fixation can take place for 20 seconds to 10 minutes, preferably 4 to 8 minutes.
• the prints are also finished in the usual way by rinsing with water and can, if appropriate, be carried out by additional cleaning in an alkaline medium under reductive conditions, e.g. be made with sodium dithionite. In the latter case, the printing stains are again rinsed, dewatered and dried.
• the printing paste is applied to paper and later transferred from the paper to the fiber material.
• the transfer print on the calender is preferably carried out at 210-240 ° C for 20 to 60 seconds.
• polyester fiber materials treated with the compounds of the formula (1) reduce the diffuse transmission of UV radiation through textiles made from polyester fibers and polyester fiber blended fabrics.
• the percentages relate to the weight.
• the amounts relate to pure substance in the case of dyes and UV absorbers.
• the temperatures are given in degrees Celsius.
• the fixed point of the connection is 198-200 ° C.
• Example 18 If, as in Example 18, 11.3 g of the compound of the formula (100) and 2.1 g of N-hydroxymethylbenzamide and 5.1 g of N-hydroxymethylchloroacetamide are homogenized and added to 55 ml of sulfuric acid (95-97%) within 25 minutes, the result is after drying 16.3 g of the mixture of the compounds of the formulas (102) and (103) in a ratio of 1: 3. The melting point of the mixture is 178 to 190 °.
• Example 18 5.6 g of the compound of formula (100) according to Example 1 are homogenized with 7.9 g of the compound of formula (105) and 6.8 g of N-hydroxymethylchloroacetamide and within 20 minutes to 55 ml of sulfuric acid (95 to 97%) admitted. Subsequently the procedure is as given in Example 18. After drying, 17.8 g of the mixture of the compounds of the formulas (103) and in a ratio of 1: 1. The melting point of the mixture is 168 to 176 °.
• 3 samples of 10 g each of a PES jersey are dyed in an HT dyeing machine, for example a ®Turbomat (company Mathis, Niederhasli) at a liquor ratio of 1:10.
• the liquors contain 2 g / l ammonium sulfate, 0.5 g / l of a dyeing aid, for example ®Univadin 3-flex and the dyes of the formulas (I) to (IV) in the following amounts: 0.035% of the dye of the formula 0.016% of the dye of the formula 0.02% of the dye of the formula and 0.016% of the dye of the formula
• fleet 1 contains no further additives
• fleet 2 additionally contains 0.75% of the compound of the formula
• fleet 3 additionally 0.75% of the compound of the formula added as 25% grinds.
• the liquors 1 to 3 are adjusted to pH 5 with dilute acetic acid and dispersed intensively.
• fleets and jersey pieces are placed in pressure bombs.
• the dyeing begins at 70 ° C., after 5 minutes the temperature is raised to 135 ° C. at a rate of 2 ° / minute, the mixture is left at 135 ° C. for 30 minutes and then allowed to cool to 60 ° C. the dyeing is then rinsed.
• This is followed by reductive post-cleaning at 70 ° C for 30 minutes with a solution containing 2 ml / liter of sodium hydroxide solution 36 ° Bè and 3g / liter of sodium dithionite. Then it is rinsed warm and cold and dried.
• Table 2 shows that the light fastness of the gray colorings is improved by the UV absorbers of the formulas (102) and (101).
• Table 3 shows that the lightfastness of the beige colorations is improved by the UV absorbers of the formulas (102) and (101).
• the trunk thickening corresponds to the following composition: 120 g of a starch ether thickener 480 g of a sodium alginate thickener 5 g sodium dihydrogen phosphate 5 g sodium chlorate 5 g of a printing aid (e.g. LYOPRINT AP®) 385 g of deionized water 1000 g trunk thickening
• the compounds of the formulas (102) and (101) are used as 25% finely dispersed grinding.
• the cleaned jersey pieces are printed on a printing table (company Zimmer, Klagenfurt, Austria).
• the swatches are then dried at 100 ° C for 10 minutes and then steamed with superheated steam at 180 ° C for 8 minutes. It is then rinsed with water and reductively cleaned at 70 ° C. for 30 minutes with a solution of 2 ml / liter sodium hydroxide solution 38 ° Bé and 3 g / liter sodium dithionite. Finally, it is rinsed well and dried at 80 ° C. The samples obtained are then checked for their light fastness.
• Table 5 shows that the lightfastness of the prints is improved by the UV absorbers of the formulas (102) and (101).

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Coloring (AREA)
• Plural Heterocyclic Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Citations (4)

• 1994
  • 1994-11-29 EP EP94810674A patent/EP0657577A1/fr not_active Withdrawn
  • 1994-12-02 CA CA 2137212 patent/CA2137212A1/fr not_active Abandoned
  • 1994-12-06 JP JP6302388A patent/JPH07196631A/ja active Pending

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