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    Simultaneous dyeing and resin finishing of polypropylene textile materials
    36.
    发明专利
    Simultaneous dyeing and resin finishing of polypropylene textile materials 未知

    公开(公告)号：GB952147A

    公开(公告)日：1964-03-11

    申请号：GB1898662

    申请日：1962-05-17

    Applicant: BASF AG

    Inventor： MAHLING DIETER ,  LEUBE HERBERT ,  LANGE GUENTER ,  WEIDINGER HANS ,  LOUIS GERD ,  WILHELM HANS

    IPC: D06P1/00 ,  D06P3/79

    Abstract: Coloured solution or aqueous dispersion polymers are obtained by copolymerization of dyes which contain a polymerizable olefinic group (chromophoric monomers), non-coloured polymerizable compounds which contain groups accessible to condensation or addition reactions as well as olefinic groups (reactive monomers) and, optionally, other known polymerizable compounds (inert monomers). The chromophoric monomers may be derived from dyes of the azo, anthraquinone, triarylmethane, phthalocyanine, phenazine and oxazine series and may contain a group of the formula: wherein R is a hydrogen or halogen atom, a lower alkyl, hydroxyalkyl, cyano, carboxy or carboxylic acid ester group, X is a hydrogen or halogen atom, an alkyl, substituted or unsubstituted aromatic radical and Y a hydrogen or halogen atom or an alkyl group. The polymerizable group may be attached to the dye molecule by way of a phenylene, -C(O)-, -SO2- or -NR1- radical, R1 being a hydrogen atom or an alkyl radical. Numerous suitable inert and reactive monomers are listed. Polymerization may be carried out by bulk, precipitation, emulsion, suspension or solution polymerization. Usual polymerization initiators may be used as well as the usual emulsifiers and protective colloids. The coloured polymers may be applied to textile materials of polypropylene in combination with number of other substances (see Division D2). In the examples copolymers are prepared from (1) butyl acrylate, butanediol monoacrylate, and 2, 4-dichloroaniline-->N-b -acryloylhydroxyethyl-N-ethylaniline in emulsion, (3) butyl acrylate, acrylonitrile, butanediol monoacrylate and 2-amino anisole-4-sulpho-n-butylamide--> N-ethyl-N-b -acryloyloxyethylaniline in emulsion, (4) butyl acrylate ethyl acrylate, N-methylol-methacrylamide and the dye from (1) in emulsion, (6) butyl acrylate, methyl methacrylate, N-methylolmethacryl-amide and N-acryloyl-p-phenylenediamine--> 1-(2-chloro-5-sulphophenyl)-3-methyl-5-pyrazolone in emulsion, (7) butyl acrylate, acrylonitrile, methyl methacrylate, N-methylolmethacrylamide and the dye from (6) in emulsion, (8) butyl acrylate, acrylamide, methyl methacrylate, butanediol monoacrylate and 2, 4-dichloroaniline--> N-ethyl-N-vinyloxy-ethylaniline in ethanol solution and (9) methyl methacrylate, butyl acrylate, acrolein, the dye from (1) in ethanol/toluene solution. Specifications 830,876, 858,183, 875,946 and 877,402 are referred to.ALSO:Textile materials of polypropylene are coated with solutions or aqueous dispersions of a coloured polymer obtainable by copolymerization of chromophoric monomers (i.e. dyes which contain a polymerizable olefinic group) with uncoloured polymerizable compounds at least some of which also contain groups capable of entering into cross-linking reactions (reactive monomers), and cross-linking the copolymers after application either alone or with the aid of suitable bi- or poly-functional compounds. The chromophoric monomers may be based on dyes of the azo, anthraquinone, triarylmethane, phthalocyamine, phenazine and oxazine series which contain a polymerizable group of the formula in which R is a hydrogen or halogen atom, a lower alkyl, hydroxyalkyl, cyano, carboxy or carboxylic acid ester group, X is a hydrogen or halogen atom, an alkyl or a substituted or unsubstituted aromatic radical and Y is a hydrogen or halogen atom or an alkyl group and in which the polymerizable group is attached to the dyestuff molecule by way of a phenylene, -C(O)-, -SO2- or -NR1-radical where R1 is a hydrogen atom or an alkyl group. Numerous reactive and inert monomers are specified as are suitable cross-linking agents which include hexamethylenediisocyanate and its bisulphite compound, N,N1-dimethylol - butanediol - 1,4 - diurethane, tetramethylolacetylene - tetramethylolacetyleneurea and its tetrabutyl ether. Cross-linking without a cross-linking agent may be accomplished by raising the temperature or changing the pH. Numerous suitable catalysts are specified. The cross-linking agents and/or catalysts may be applied before, after or with the coloured copolymer. The coated fabric may be dried and heated to 110-200 DEG C. to effect the cross-linking. The coloured copolymers may also be used together with other resins, e.g. aminoplasts and water-soluble natural, synthetic and semi-synthetic substances such as starches, cellulose ethers, vegetable gums and polymers of carboxylic acids or their salts or amides. Non-woven fabrics of polypropylene may be prepared with the present copolymers which then act as binding agent and dye. With the aid of embossing rollers or graining presses artificial leathers may be prepared. Specifications 830,876, 858,183, 875,946 and 877,402 are referred to.ALSO:Textile materials of polypropylene are simultaneously dyed and finished by treatment with solutions or aqueous dispersions of a coloured polymer obtainable by copolymerization of chromophoric monomers (i.e. dyes which contain a polymerizable olefinic group) with uncoloured polymerizable compounds at least some of which also contain groups capable of entering into cross-linking reactions (reactive monomers), and cross-linking the copolymers after application either alone or with the aid of suitable bi- or poly-functional compounds. The chromophoric monomers may be based on dyes of the azo, anthraquinone, triarylmethane, pthalocyamine, phenazine and oxazine series which contain a polymerizable group of the formula in which R is a hydrogen or halogen atom, a lower alkyl, hydroxyalkyl, cyano, carboxy or carboxylic acid ester group, X is a hydrogen or halogen atom, an alkyl or a substituted or unsubstituted aromatic radical and Y is a hydrogen or halogen atom or an alkyl group and in which the polymerizable group is attached to the dye-stuff molecule by way of a phenylene, -C(0)-, -SO2- or -NR1- radical where R1 is a hydrogen atom or an alkyl group. Numerous reactive and inert monomers are specified as are suitable cross-linking agents which include hexamethylenediisocyanate and its bisulphite compound, N, N1 -dimethylol-butanediol-1, 4-diurethane, tetramethylolacetyleneurea and its tetrabutyl ether. Cross-linking without a cross-linking agent may be accomplished by raising the temperature or changing the pH. Numerous suitable catalysts are specified. The cross-linking agents and/or catalysts may be applied before, after or with the coloured copolymer. The impregnated fabric may be dried and heated to 110-200 DEG C. to effect the cross-linking. The coloured copolymers may also be used together with other textile finishes, e.g. aminoplasts and water-soluble natural, synthetic and semi-synthetic substances such as starches, cellulose ethers, vegetable gums and polymers of carboxylic acids or their salts or amids. Examples are given. Non-woven fabrics of polypropylene may be prepared with the present copolymers which act as binding agent and dye. With the aid of embossing rollers or graining presses artificial leathers may be prepared. Specifications 830,876, 858,183, 875,946 and 877,402 are referred to.

    38.
    发明专利
    未知

    公开(公告)号：DE1154629B

    公开(公告)日：1963-09-19

    申请号：DEB0062495

    申请日：1961-05-16

    Applicant: BASF AG

    Inventor： WILHELM HANS ,  PENNING ERNST ,  LOUIS GERD ,  LANGE GUENTER ,  WEIDINGER HANS ,  MAHLING DIETER

    IPC: C08F2/04 ,  C08F2/22 ,  C08F2/44 ,  C08F16/12 ,  C08F20/62 ,  C08F28/00 ,  C09B69/10 ,  D06L3/12 ,  D06L4/60 ,  D06M15/39 ,  D06P1/00

    Abstract: Coloured cross-linked or cross-linkable copolymers are obtained by copolymerizing at least one olefinic monomer dyestuff, containing, in addition to the unsaturated at least one olefinic monomer polymerizable group, a group capable of condensation or addition, and, if desired, at least one further copolymerizable monomer, and then, if desired, cross-linking the resulting copolymers by way of the groups capable of condensation or addition. The dyestuff monomers may be of the azo, anthraquinone, phthalocyanine, triarylmethane, phenazine, or oxazine type, such dyestuffs being described in Specifications 779,781, 830,876, 858,183, 875,946 and 879,071. The examples describe the following processes: (1) emulsion copolymerizing butyl acrylate, N-methylol methacrylamide and an unsaturated azo dyestuff to yield a copolymer which cross-links on drying; (2) emulsion copolymerizing acrylonitrile, butyl acrylate, N-methyldimethacrylamide and an unsaturated azo dyestuff; (3) as in (2) but using an unsaturated anthraquinone dyestuff; (4) emulsion copolymerizing styrene, methylolacrylamide, butyl acrylate, N-methylolacryloylurea and acryloylaminobenzene, and cross-linking the resulting polymer by heating in the presence of ammonium nitrate; (5) emulsion polymerizing ethyl acrylate, vinyl propionate, N-methylolmethacrylamide, N-methylol maleimide and an unsaturated azo dyestuff and cross-linking the resulting copolymer by heating; (6) emulsion copolymerizing butyl acrylate, acrylonitrile, butane-diol monoacrylate and an unsaturated azo dyestuff, and cross-linking the resulting copolymer with hexamethylene diisocyanate; (7) emulsion copolymerizing butyl acrylate, methacrylamide and an unsaturated azo dyestuff and cross-linking the product by heating with dimethylol urea; (8) cross-linking the copolymer of (7) by heating with N,N1-dimethylolbutane-(1,4)-diurethane; (9) emulsion copolymerizing butyl acrylate, acrylonitrile, acrylic acid and an unsaturated azo dyestuff, neutralising the carboxyl groups in the product with ammonia, and heating it with a polyepoxide derived from pentaerythritol and epichlorohydrin; (10) emulsion copolymerizing butyl acrylate, N-methylolacrylamide and an unsaturated azo dyestuff, mixing the resulting dispersion with an acrylamide/methacrylamide copolymer, sawdust and a mixture of N,-N1 dimethylolurea monomethyl and dimethyl ethers, drying the composition and moulding at 150 DEG C.; (11) emulsion copolymerizing butyl and ethyl acrylates, methyl methacrylate methacrylamide and an azo dyestuff containing vinyl ether groups, adding a mixture of N,N1-dimethylol urea monomethyl and dimethyl ethers and heating in the presence of ammonium nitrate; (12) emulsion copolymerizing butyl acrylate, N-methylol methacrylamide, a triazine derivative of acrylamide and an unsaturated azo dyestuff, mixing the dispersion with N,N1-dimethylolbutane-(1, 4)-diurethane and ammonium nitrate and subjecting the mixture to heat; (13) emulsion copolymerizing butyl acrylate, acrylamide, vinyl chloride and an unsaturated azo dyestuff, mixing the dispersion with N,N1-dimethylol urea and cross-linking at 130 DEG C.; (14) solution copolymerizing butyl acrylate, acrylamide, methyl methacrylate, butanediol monoacrylate and an azo dyestuff containing vinyl ether groups and cross-linking the product with hexamethylene diisocyanate; (15) solution copolymerizing methyl methacrylate butyl acrylate, acrolein and an unsaturated azo dyestuff, and cross-linking the product with the glycol ester of bisacetoacetic acid; (16) solution copolymerizing butyl acrylate, vinyl propionate, methacrylamide, N-methylol methacrylamide and an unsaturated anthraquinone dyestuff, and heating the product after the addition thereto of phosphoric acid; (17) as in (3) but with the use of tetramethylolacetylene diurea tetrabutyl ether at the cross-linking stage and with the addition of wood pulp to the curable mixture; (18) bulk copolymerizing methyl methacrylate, butanediol monoacrylate and an unsaturated azo dyestuff in the presence of dibutylphthalate until the product is syrupy, discontinuing polymerization and then heating the product with hexamethylene diisocyanate; (19) solution copolymerizing vinyl pyrrolidone, methyl methacrylate, butyl acrylate, N-methylol methacrylamide and a copper phthalocyanine dyestuff containing sulphonic groups which have been reacted with N-acryloyl - p - phenylene diamene, and heating the product with tetramethylolacetylenediure tetrabutyl ether; and (20) solution copolymerizing acrylamide ethyl acrylate, N-methylol methacrylamide and an unsaturated azo dyestuff, and heating the product with tetramethylolacetylene diurea.ALSO:Surfaces of paper, wood and metal are coated with coloured copolymers obtained from olefinic monomer dyestuffs, monomers containing cross-linkable groups, and, if desired, other copolymerizable monomers. In examples: (2) wood and paper are coated with an aqueous dispersion of a copolymer of butyl acrylate, N-methylol methacrylamide and an unsaturated azo dyestuff, and the coating is dried at 180 DEG C.; (13) paper and a metal plate are coated with an aqueous dispersion containing a copolymer of butyl acrylate, vinyl chloride, acrylamide and an unsaturated azo dyestuff, N,N1-dimethylolurea and ammonium nitrate, the coating is dried at room temperature and cross-linked at 130 DEG C.; (15) a toluene-ethanol solution containing a copolymer of methyl methacrylate, acrolein and an unsaturated azo dyestuff, the glycol ester of bisacetoacetic acid, phosphoric acid and piperidine is brushed or sprayed on to bleached wood, and the coating is dried at 80-90 DEG C.; and (19) a tolueneethanol solution containing a copolymer of vinyl pyrrolidone, methyl methacrylate, butyl acrylate, N-methylol methacrylamide and a copper phthalocyanine dyestuff containing sulphonic groups which have been reacted with N-acryloyl-p-phenylene diamine, tetramethylolacetylenediurea tetrabutyl ether and glacial acetic acid is brushed on to wood or paper and dried at 140 DEG C. Specifications 779,781, 830,876, 858,183, 875,946 and 879,071 are referred to.

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