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
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
• • 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
  • D06P1/649—Compounds containing carbonamide, thiocarbonamide or guanyl groups
  • D06P1/6495—Compounds containing carbonamide -RCON= (R=H or hydrocarbons)
• • 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
  • D06P1/651—Compounds without nitrogen
  • D06P1/65106—Oxygen-containing compounds
• • 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
  • D06P1/673—Inorganic compounds
  • D06P1/67333—Salts or hydroxides
  • D06P1/67341—Salts or hydroxides of elements different from the alkaline or alkaline-earth metals or with anions containing those elements
• • 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
  • D06P1/673—Inorganic compounds
  • D06P1/67333—Salts or hydroxides
  • D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
• • 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
  • D06P1/90—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 dyes dissolved in organic solvents or aqueous emulsions thereof
• • 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
  • D06P1/90—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 dyes dissolved in organic solvents or aqueous emulsions thereof
  • D06P1/92—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 dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents
  • D06P1/922—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 dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents hydrocarbons
• • 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
  • D06P1/90—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 dyes dissolved in organic solvents or aqueous emulsions thereof
  • D06P1/92—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 dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents
  • D06P1/928—Solvents other than hydrocarbons
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/92—Synthetic fiber dyeing
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/92—Synthetic fiber dyeing
  • Y10S8/922—Polyester fiber
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/929—Carpet dyeing

Definitions

• This invention relates to a method for coloring fibers or fibrous structures prepared from phenolic resins. More specifically, this invention relates to a method for uniformly coloring phenolic fibers or their structures in deep colors with fastness characteristics.
• phenolic fibers As is well known, fibers composed of phenolic resins (to be referred to simply as phenolic fibers) have poor affinity with dyes and extremely low dyeability for a variety of reasons such as their compact fibrous structure, the lack of dye-affinitive groups, or their high negative surface potential. it is very difficult therefore to color phenolic fibers uniformly in deep fast colors.
• Fibers having a compact fibrous structure and no dye-affinitive groups such as polyester fibers or polypropylene fibers, are colored at a temperature as high as 1 10 to 130C. using dyes having a small molecular volume, or using a dye liquor containing a carrier material (swelling agent) such as ortho-phenylphenol, chlorobenzene, a salicylic acid ester or a benzoic acid ester in order to give satisfactory dyeings.
• a carrier material such as ortho-phenylphenol, chlorobenzene, a salicylic acid ester or a benzoic acid ester
• the phenolic fibers can scarcely be colored substantially even at 1 10 to 130C. using a carrier material such as those mentioned above, and it has been difficult to provide colored phenolic fibers which are useful for practical applications.
• Certain kinds for such difficultly-dyeable synthetic fibers have previously been colored, for example, by a method wherein a substance having dye-affinitive groups, such as a polymer having a free amino group, is incorporated in a spinning solution, and fibers obtained by spinning this solution are dyed by conventional methods, a method wherein a pigment is incorporated in a spinning solution beforehand, and the spinning solution is spun to form colored fibers, or a method wherein a pigment is fixed to the surface of the fibers by a binder to color the fibers.
• a substance having dye-affinitive groups such as a polymer having a free amino group
• a primary object of this invention is to provide an improved method for coloring fibers composed of phenolic resins and structures formed from these fibers (to be referred to generically as phenolic fibrous materials).
• a secondary object of this invention is to provide a method for uniformly coloring phenolic fibrous material in deep fast colors.
• Another object of this invention is to provide a method for coloring phenolic fibrous materials that can be utilized industrially.
• a method for coloring fibers or fibrous structures composed of phenolic resins which comprises dyeing the fibers or fibrous structures using a dye bath containing as a dyeing assistant at least one amide compound expressed by the following general formula wherein R, R and R" are the same or different and each represent a hydrogen atom, an alkyl group, a phenyl group, a benzyl group or a phenetyl group, but R, R and R" do not represent hydrogen atoms at the same time.
• coloring( or dyeing) denotes coloring in a broad sense, and therefore, includes (a) the dip dyeing whereby a fibrous material is dyed as dipped in a dye solution, (b) the pad dyeing whereby a dye solution is padded on a fibrous material, and then the fibrous material is heated, and (c) the printing whereby a printing paste is applied to a fibrous material, and the material is then heated to color the printed portions.
• the dye liquor used in accordance with the process of this invention may be in the form of a solution containing a dye (especially in the case of dip dyeing) or a paste containing a dye (pad dyeing and printing).
• a typical composition of such a dye liquor is illustrated as follows although the invention is not limited thereto.
• composition of the dye liquor for dip dyeing and pad dyeing Dye in an amount corresponding to about 0.0l to about 30% by weight of the material to be dyed Amide compound of formula (I) above in the amount to be indicated below Viscosity Absent or present in a small regulator amount Water the remainder Composition of the dye liquor for printing Dye in an amount corres nding to about 5 to about 5 of the total weight of the dye liiuor Paste in an amount correspond ng to about (H to about 10% of the total weight of the dye liquor Amide compound of formula (I) sbove in the amount to be indicated below Water remainder of: i J.
• I j tmbbflnflch I m,- t t My t mahyl stsreh, gelatin, death-it, British gum. polyviiyl alcohol, kerosene. and l,1,l-trlspinning, or wet spinning, etc.
• a prepolymer of the novolak or resol type prepared from a phenol (e.g., phenol, cresol, xylenol, ethylphenol, phenylphenol, amylphenol, bisphenol A, or resorcinol) and an aldehyde (Formaldehyde, acetaldehyde, para-formaldehyde, hexamethylene tetramine, furfural, glutaraldehyde, or glyoxal), or the cured products thereof obtained by curing such uncured fibers with a curing agent such as an aldehyde in the presence of an alkaline or acidic catalyst.
• a curing agent such as an aldehyde in the presence of an alkaline or acidic catalyst.
• the phenolic fibers can be produced by any known method, we will not describe it here.
• the phenolic fibers to be dyed by the method of this invention may be composed of a phenolic resin alone, or a blend of a major proportion of the phenolic resin with a minor proportion (generally, 140% by weight) of another fiber-forming polymer.
• the amount of the fiber-forming polymer should be as small as possible, preferably up to 30 by weight, when the blend is used, or the phenolic fibers should be composed solely of the phenolic resin.
• the fiber-forming polymer that can be used include polyamide resins such as nylon 6, nylon 11, nylon 12, nylon 66', nylon 610, nylon 6i i, nylon 6l2, and blends of two or more of these with each other; polyester resins such as polyethylene terephthalate, polyesters derived from the same constituent elements as polyethylene terephthalate with part of ethylene glycol replaced by other known glycols, polyesters derived from the same constituent elements as polyethylene terephthalate with the terephthalic acid replaced by orthoor metaphthalic acids, other known aliphatic dicarboxylic acids or blends of two or more of these with each other; polyester ethers such as polyeth' ylene hydroxybenzoate, and polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymer, or blends of two or more of these with each other.
• polyester resins such as polyethylene terephthalate, polyesters derived from the same constituent elements as polyethylene terephthalate with
• fibrous structures composed of phenolic resins denotes a fibrous product such as a web, yarn, woven fabric, knitted fabric, non-woven fabric, carpet, batt or laminated clothcomposed of the phenolic fibers alone or a composite of the phenolic fibers and other natural, semi-synthetic or synthetic fibers.
• the dyes that are usually used in the dyeing of natural, semi-synthetic or synthetic fibrous materials can be used in accordance with the method of this invention for dyeing the phenolic fibrous materials.
• vat dyes azoic dyes, cationic dyes, disperse dyes, metal-containing dyes, acid dyes, direct dyes, reactive dyes, and chrome dyes.
• the azoic dyes, cationic dyes, disperse dyes and vat dyes have good dyeability with regard to the phenolic fibers, and can be conveniently used in the present invention.
• Typical examples of these dyes are as follows:
• Cationic dyes Cationic dyes of the azo, diphenylmethane, triphenylmethane, xanthene, acridine, quinollne, methine, thiazole, azine, thiazine, and oxazine types. Specific ex amples are Sumiacryl Orange G (Cl. Basic Orange 21), Sumiacryl Brilliant Red BB, Sumiacryl Red 68 (Cl. Basic Violet 7), Sumiacryl Brown 30 (CJ, Basic Orange 30), Sumiacryl Blue GO (C. I. Basic Blue 22), Diacryl Brilliant Pink R (Ci. Basic Red 35), Diacryl Blue 2RL (Ci. Basic Blue 59), Diacryl Green 2.3L
• Disperse dyes Disperse dyes of the azo, anthraquinone, nitro, aminoquinone and methine types. Specific examples are Dianix Fast Orange R-FS, Dianix Fast Red B-FS, Dianix Red Brown R-FS, Kayalon Polyester Violet BNF (C.l. Disperse Violet 30), Kayalon Polyester Pink BSF (Cl. Disperse Red 55), Sumikalon Red FB (C.]. Disperse Red 60), Sumikalon Blue R (C.[. Disperse Blue 71 and Sumikalon Dark Blue RB (Cl. Disperse Blue 55).
• Azoic dyes As the azoic diazo component, there are C]. Azoic Diazo Component 4] C.l. Azoic Diazo Component 48, CI. Azoic Diazo Component ll8, C.l. Azoic Diazo Component I24, C.l. Azoic Diazo Component 125, etc. As the azoic coupling component, there are C.l. Azoic Coupling Component 8, C.[. Azoic Coupling Component ll, C.l. Azoic Coupling Component l7, C.[. Azoic Coupling Component 35, etc. C.l. Azoic Red 79, Cl. Azoic Red 81, C.[. Azoic Blue 30, C1. Azoic Green I, and Cl. Azoic Brown 15 are also used.
• Vat dyes Vat dyes of the antraquinone and indigozoyl types. Specific examples are Caledon Orange Brown 26 (Cl. Vat Orange 14), Caledon Red B (C.l. Vat Red 41 Mikethrene Violet FFBN (C.l. Vat Violet l3), Nihonthrene Dark Blue B0 (C1. Vat Blue 20), Caledon Olive OMW (C.l. Vat Green 26), and lndanthrene Black Brown RV (C.l. Vat Brown 56).
• the alkyl group represented by R, R and R" in the general formula (I) expressing the amide compound to be incorporated in the dye liquor may be a straightchain or branched chain alkyl group.
• it is a lower alkyl group, especially an alkyl group of l to 3 carbon atoms, that is a methyl, ethyl, n-propyl or i-propyl group.
• amide compound examples include acetamide, acetomethyl amide, acetoethyl amide, acetopropyl amide, form-methyl amide, fonnethyl amide, formpropyl amide, formanilide, acetanilide, N,N-dimethyl formamide, N,N'-diethyl fon'nanilide, N,N-dipropyl formamide, N,N-diphenyl formamide, N,N-dimethyl acetamide, N,N-diethyiacetamide, N,N-dipropyl acetamide, N,N-diphenyl acetamide, benzamide, methylbenzamide, ethylbenzamide, propionbenzamide, N,N- dimethylpropionylamide, N,N-diethylpropionyl amide, N,N-diphenylpropionyl amide, N,N-dimethylbenzamide, N,N-diethyl
• amide compounds may be used alone or in admixture of two or more.
• N,N'9 dimethylformamide, N,N'-dimethylacetamide, N,N- diethyl formamide, N,N-diethyiacetamide, N,N-diphenyl forrnamide, N,N-diphenyl acetamlde, methylbenzamide, benzamide, benzanilide, acetanilicle, ethylbenzamide, and propyl benzamide are preferred.
• Especially useful amide compounds are N,N-diethylformamide, N,N-dimethylacetamide and N,N-diethylacetamide.
• the suitable concentration of the amide compound is generally from 3.0 to 50.0% based on the total weight of the dye liquor although it may differ depending upon the type, form and amount of the phenolic fibrous material to be colored. Preferably, the concentration is 15.0 to 40.0% by weight. Within this concentration range, the amide compound does not cause a deterioration in the physical properties of the phenolic fibrous material, nor does it pose any difficulty in dyeing operation. 1f the concentration of the amide compound exceeds 50%, the diffusion of the compound into the inner structure of the fibers is prevented because of its extremely great ability to dissolve the dye, which in turn causes a reduction in dyeability.
• the amide compound has a strong action of swelling the phenolic fibers, and reduces the tenacity of the fibers. If, on the other hand, the concentration of the amide compound is less than 3 by weight, the addition of the amide compound does not produce an improved dyeing effeet.
• the procedure for dyeing the phenolic fibrous material in accordance with the method of this invention does not differ from the conventional methods.
• the fibrous material can be dyed by the conventional dyeing method using a dye liquor containing a dye in the concentration described above and if desired, using a size such as tragacanth rubber or dextrin and a conventional additive.
• the suitable dyeing temperature (temperature of the dye bath) is 80 to 140C, more preferably 100 to 130C. when dip dyeing from an aqueous solution of a dye. If the temperature is below 80C., the swelling action of the phenol fibers is not sufficiently exhibited, and it becomes difficult to dye them uniformly in deep colors. On the other hand, if the temperature is higher than 140C., swelling occurs excessively to cause a reduction in the tenacity of the phenolic fibers or result in the decomposition of the amide compound.
• a solution or paste-like matter (printing paste) containing a dye and the amide compound is padded on the material to be dyed or printed thereon, and then the material is treated with steam.
• the temperature of the steam is not critical, but preferably 110 to 140C., more preferably 120 to 130C.
• the steaming time is generally minutes to 60 minutes.
• the fibrous material so dyed is then washed, and dried.
• a disperse dye is used, the dyed material is washed by a conventional method with an aqueous solution held at 60-80C. containing hydrosulfite (0.5 to 2 g/l), soda ash (0.3-1 g/l) and a nonionic surfactant (0.5-2 g/l) for about to 30 minutes.
• the dyed material is desirably washed with an aqueous solution held at 60-80C. containing a nonionic surfactant (0.5 to 2g/l) for about 20 to 30 minutes.
• the amide compound Since the amide compound generally tends to remain on the dyed fibers as a result of adsorption to it, it is essential to wash the material sufficiently free of the amide compound.
• the amide compound is somewhat flammable, and toxic to the skin, which results in a reduction in the commercial value of the fibrous product.
• the action of the amide compound on the phenolic fibers is not a mere swelling action of a conventional carrier substance used in the dyeing of synthetic fibers such as phenol, dichlorobenzene, cresol or ethylene glycol, but also is an action of neutralizing negative charge on the surface of the fibers, causing the dye to be adsorbed to the fibers, and rendering it readily diffusible.
• this neutralizing action gives rise to an increased solubility of a dye or paste to give it an effect of dyeing the material in deep fast colors.
• a surface active agent is usually added in order to better the dispersibility of the carrier and cause it to be adsorbed uniformly to the fibers.
• a surfactant can be omitted, and even in the absence of the surfactant, it is possible to dissolve and disperse a dye or paste uniformly by the amide compound and promote the penetrability of the dye to provide a dyeing of uniform deep color.
• the adsorption and diffusion of the dye can be promoted by the neutralization of negative charge on the surfaces of the phenolic fibers which is caused by the action of the amide compound. These derivatives cannot be expected from the conventional technique of dyeing the phenolic fibers.
• the amide compound and the oxygen-containing compound is present in the dye liquor, a number of remarkable commercial advantages can be expected. For example, the diffusion of the dye into the phenolic fibrous material and its dyeability are remarkably improved by the synergistic effect of the amide compound and the oxygen-containing compound, even if the concentration of the amide compound is low. Also, there is a greatly reduced tendency of the amide compound to be adsorbed to the surfaces of the phenolic fibers. Therefore, by ordinary washing, the amide compound can be completely removed.
• a method for dyeing fibers composed of phenolic resins or their fibrous structures which comprises dyeing said fibers or fibrous structures using a dye liquor containing as a dyeing assistant (A) at least one amide compound expressed by the general formula wherein R, R and R" are the same or different and each represent a hydrogen atom, an alkyl group, a phenyl group, a benzyl group, or phenetyl group, but R, R and R" do not represent hydrogen atoms at the same time, and (B) (i) at least one watersoluble metal sulfate, or (ii) at least one oxygen-containing compound selected from the group consisting of alkanols having 3 to 5 carbon atoms, benzyl alcohol, tetrahydrofurfuryl alcohol, dioxane, dialkyl ketones having 3 to 5 carbon atoms, cyclohexanone and lower alkyl esters of formic acid and acetic
• any metal sulfates that are water-soluble can be used as component (B) (i) described above, and its selection will be obvious to those skilled in the art.
• the metal sulfates are sodium sulfate, potassium sulfate, beryllium sulfate, magnesium sulfate, aluminum sulfate, potassium alum (potassium aluminum sulfate), chromium sulfate, chlorium alum, ferrous sulfate, ferric sulfate, ferrous ammonium sulface, cobalt sulfate, and nickel sulfate.
• Sodium sulfate, potassium sulfate and potassium alum are especially preferred. These metal sulfates can be used either alone or in admixture of two or more.
• the metal sulfate can be incorporated in a concentration of 3.0 to 35.0 preferably l0.0 to 30.0%, based on the total weight of the dye bath. If the concentration of the metal sulfate is in excess of 30.0%, it becomes difficult to dissolve in the dry liquor. lf it is less than 3.0%, the addition of the sulfate cannot be expected to produce a dyeing effect, and moreover, the amide compound becomes easier to adsorb to the surface of the phenolic fibers, in which case the removal of the amide compound by washing is time-consuming.
• the alkanols having 3 to 5 carbon atoms to be used together with the amide compound may, for example, be n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-amyl alcohol, and sec.- amyl alcohol.
• Examples of the dialkyl ketones having 3 to 5 carbon atoms are acetone, methyl ethyl ketone, and diethyl ketone.
• Examples of the lower alkyl esters of formic acid and acetic acid are methyl forrnate, ethyl forrnate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, and butyl acetate.
• n-propanol, n-butanol, benzyl alcohol, dioxane and cyclohexanone are preferred.
• the oxygen-containing compounds may be used alone or in admixture of two or more.
• the oxygen-containing compound is miscible with the dye liquor.
• water-miscible oxygen containing compounds are conveniently used in the present invention.
• the oxygen-containing compound can be incorporated in the same concentration as the metal sulfate, that is, in a concentration of 3.0 to 35.0 by weight based on the total weight of the dye liquor. Preferably, it is used in a concentration of 5.0 to 35.0 by weight based on the total weight of the dye liquor. If the concentration of the oxygen-containing compound is lower than 3.0% by weight, sufficient effects obtainable by its addition cannot be expected. On the contrary, if it is higher than 30.0% by weight, the solubility of the dye becomes exceedingly high, and the diffusion of the dye into the fibers is prevented. This results in a reduction in dyeability, and even if the fibers can be temporarily dyed, the dye tends to bleed out. Furthermore, the concentration of the oxygen-containing compound is lower than 3.0% by weight, sufficient effects obtainable by its addition cannot be expected. On the contrary, if it is higher than 30.0% by weight, the solubility of the dye becomes exceedingly high, and the diffusion of the dye into the fibers is prevented. This results in a
• the metal sulfate and the oxygen-containing compound can be used separately or in combination. When both of them are used at the same time, the total amount of these compounds is 3.0 to 35.0% by weight.
• the greatest advantage of this embodiment is that the amount of the amide compound which is difficult to remove by washing from the phenolic fibrous material can be remarkably reduced.
• the concentration of the amide compound is 5.0 to 10.0% by weight.
• phenolic fibers can be colored in the same way as in the case of using the amide compound alone in the dye liquor, that is, by any of the dip dyeing, pad dyeing or printing process.
• the action of the metal sulfate or the oxygen-containing compound is not clear. But it is presumed that it is not a mere swelling action of a conventional carrier substance, but serves to increase the solubility of the dye and promote the diffusion of the dye. in conjunction with the action of neutralizing negative charge on the surfaces of the fibers which is exhibited by the amide compound, these additional compounds can produce an effect of uniformly coloring the phenolic fibers in deep fast colors.
• the invention is in no way restricted by this presumption.
• the amount of the amide compound can be markedly reduced by the addition of the metal sulfate and/or the oxygen-containing compound. Also, the adsorption of the amide compound to the fibers can be prevented by these additional compounds, to render it easy to remove the amide compound by washing.
• the phenolic fiberous materials heretofore considered difficult to dye can be colored uniformly in deep colors, and the dyeings have marked fastness characteristics. Furthermore, this method does not result in impairing the desirable incombustibility of the phenolic fibers.
• the method of this invention is very advantageous commercially, because no additional step of dyeing is required.
• A is the concentration in g/l of the dye in the dye solution before dyeing and B is the concentration in g/l of the dye after dyeing.
• the dyeability (K/S) was determined by the Kubelka- Munk equation shown below.
• the fastness to laundering was measured in accordance with JlS-L-l045, the fastness to rubbing in accordance with .llS-L-l048, and the fastness to light in accordance with JlS-L- l 044.
• the carbonized length was measured in accordance with the vertical method (JIS-L- 1004) whereby the test cloth was maintained perpendicular and flames were caused to come in contact with the test cloth using a Bunsen burner for 12 seconds, and then the length of the carbonized portion of the test cloth was measured.
• the fabric was dipped in the dye bath, and the dyeing was started at C., the temperature being raised to 130C. during a period of 30 minutes, where the dyeing was carried out for 60 minutes.
• the fabric was then washed with water and thereafter treated for 20 min utes at 80C. with a reducing wash liquid consisting of 1 gram per liter of hydrosulfate, 1 gram per liter of soda ash, 1 gram per liter of Noigen HC (a nonionic surfactant produced by Daiichi Kogyo Seiyaku Co., Japan) and water, followed by water-washing and drying.
• the so obtained dyed fabric was dyed to a deep shade of purple.
• the dye exhaustion was 69.8%.
• the top was dipped in the dye bath, and the dyeing was started at 30C., after which the temperature was raised to 120C. during a period of 30 minutes, where the dyeing was carried out for 90 minutes followed by water-washing.
• the top was then treated for 20 minutes at C. with a reducing wash liquid consisting of 1 gram per liter of hydrosulfite, 0.5 gram per liter of soda ash, 1 gram per liter of a nonionic surfactant and water, after which the top was water-washed and dried.
• the so obtained dyed product was dyed to a deep shade of blue, and the dye exhaustion was 90.5
• EXAMPLE 3 A knit fabric made up the phenolic filaments of Example l was dyed in a dye bath of the following composition.
• the fabric was dipped in the dye bath, and the dyeing was started at 40C., after which the temperature was raised up to 100C. during a period of 30 minutes, where the dyeing was continued for 60 minutes.
• the fabric was then water-washed and thereafter treated for 20 minutes at 80C. in a reducing wash bath consisting of 1 gram per liter of hydrosulfite, 1 gram per liter of soda ash, 1 gram per liter of a nonionic surfactant and water, followed by water-washing and drying.
• the so obtained dyed fabric was dyed to a red shade.
• EXAMPLE 4 A curtain material made up of the same phenolic yarn as that of Example 1 was dyed in a dye solution of the following composition.
• the temperature was raised up to lC. during a period of minutes, and then the dyeing was continued for 60 minutes at this temperature.
• the dyed material was then waterwashed and thereafter washed for 20 minutes at 80C. in a wash liquid consisting of an aqueous solution of 1 gram per liter of a nonionic surfactant. This was followed by water-washing and drying the material.
• the so obtained dyed fabric was dyed a blue shade.
• EXAMPLE 5 A 2-ply weaving yarn consisting of the phenolic filaments of Example 1 was dyed with a dye solution of the following composition.
• TD Black B25 (diazo component produced by Daito Chemical Co, Japan)
• TD 1200 2S (coupling component produced by Daito Chemical Co.)
• the temperature was raised to l l5C. during a period of 20 minutes, at which temperature the dyeing was continued for minutes and followed by washing the dyed yarn in water and then in hot water.
• the yarn was then developed by diazotizing for 30 minutes at C. in a diazotizing coupling bath consisting of 10 (based on weight of material dyed) of sulfuric acid and 9 (based on weight of material dyed) of sodium nitrite, after which the yarn was water-washed and dried.
• the so obtained dyed product was dyed to a deep shade of black.
• the yarn was dyed to a deep shade when either benzanilide, benzamide, methylbenzamide, ethylbenzamide, propylbenzamide, N,N-diethylbenzamide or N,N'-dipropylbenzamide was added.
• EXAMPLE 6 A tweed made up of Z-ply yarn of the phenolic filaments of Example 1 was dyed with a dye bath of the following composition.
• Foron Black S 2BL (disperse dye produced by Sandoz Company) Acetoethylamide 22 It (based on weight of dye bath) lSO-fold the weight of material dyed.
• the temperature was raised up to 100C. during a period of 60 minutes followed by washing the dyed material in water.
• the dyed fabric was then submitted to a reductive washing for 20 minutes at 80C. in a reduction wash bath consisting of 1 gram per liter of hydrosulfite, 0.5 gram per liter of soda ash, 1 gram per liter of Noigen HC (nonionic surfactant) and water followed by water-washing and drying.
• the so obtained dyed fabric was dyed to deep shade of black tinged with blue.
• the fabric was dyed to a deep shade as well as evenly when either acetoethylamide, acetopropylamide or acetoanilide was added.
• EXAMPLE 7 A twill fabric made up 2-ply yarn of the phenolic filaments of Example 1 was printed with a printing paste of the following composition and thereafter submitted to a steaming treatment.
• Dianix Black ZGSE (disperse dye 14 l gram per liter of a nonionic surfactant, after which it was washed with water and dried.
• EXAMPLE 8 Sumikalon Violet R (C.l. Disperse Violet 22) N,N-dimethylformamide 20 (o.w.f.) added in an amount as previously indicated. (based on weight of dye bath) Sodium sulfate added in amounts indicated in Table 8.
• Amount of dye solution -fold the weight of material dyed.
• the material to be dyed was dipped in the dye bath, and its dyeing was started at a temperature of 40C., after which the temperature was raised up to 130C. during a period of 30 minutes, at which temperature the dyeing was continued for minutes.
• the material was then waterwashed and thereafter submitted to a reductive washing for 20 minutes at 80C. in a reduction wash liquid consisting of 1 gram per liter of hydrosulfite, l gram per liter of said ash, l gram per liter of Noigen HC and water followed by water-washing and drying.
• Table 8 The results obtained are shown in Table 8.
• the fabric was immediately steamed for 30 minutes at 130C. and then water-washed. This was followed by washing the fabric for 20 minutes at 80C. in an aqueous solution of measurements shown in Table 8, the dye exhaustion is exceedingly small when sodium sulfate is not added to the dye solution containing 10 of N,N'-dimethylformarnide but becomes increasingly greater as the so dium sulfate is added in increasingly greater amounts of 3 72,10 7c and However, the addition of the sodium sulfate in an amount of is not to be desired, for difficulty is experienced in its dissolution and moreover the rate of dye exhaustion drops.
• dyeing effects equal utes at 80C. in a solution consisting of 1 gram per liter of hydrosulfite, 1 gram per liter of soda ash, 1 gram per liter of a nonionic surfactant and water followed by water-washing and drying.
• the dyeing and reductive washing were carried out in liquids amounting to 50- fold the weight of the material treated. The results of these dyeings are shown in Table 9,
• the fabric dyed in accordance with the invention method demonstrated a length of carbonization of the same degree as that of the undyed fabric. It is thus clear that the fabric dyed according to the invention method possesses fire resistance.
• EXAMPLE 9 A 2-ply yarn consisting of filaments obtained by meltspinning a novolak type phenolic resin and thereafter curing with formaldehyde was dyed with a dye solution of the following composition.
• the concentration (amount used) of the N,N- diethylformamide can be greatly reduced by about onehalf or more.
• the defect that the flame spreads during burning due to the adhesion of the amide compound is also improved.
• EXAMPLE 10 A tweed fabric made up of Z-ply yarn consisting of the phenolic filaments of Example 8 was dipped in a dye solution consisting of 20 (o.w.f,) of Sumikalon Blue GR (Cl: Disperse Blue 55 produced by Sumitomo Chemical Company), l0 (based on weight of dye solution) of methylbenzamide, and 20 (based on weight of dye solution) of a salt indicated in Table 10. The dyeing was started at 40C., and the temperature was raised up to l 10C. during a period of 30 minutes, at which temperature the dyeing was continued for a further 90 minutes. The so dyed fabric was then washed in water and thereafter submitted to a reductive washing for 20 minutes at C.
• a dye solution consisting of 20 (o.w.f,) of Sumikalon Blue GR (Cl: Disperse Blue 55 produced by Sumitomo Chemical Company), l0 (based on weight of dye solution) of methylbenzamide, and 20 (based on weight
• EXAMPLE 1 l A curtain material made up of single yarns consisting of the phenolic resin of Example 8 was dipped in a dye solution consisting of 30 of Diacryl Pink FG (cationic dye produced by Mitsubishi Chemical Company), 8 of N,N-dimethylformamide, of sodium sulfate, l of sodium cetyl sulfate (penetrant) and 36 of water and, after padding, was rolled up and immediately steamed for 60 minutes at 120C. This was followed by washing the material in water and thereafter washing it for 20 minutes in a wash liquid (80C.) consisting of an aqueous solution of 1 gram per liter of a nonionic surfactant followed by water-washing and drying. By way of comparison, the foregoing experiment was repeated. In one case the experiment was carried out without adding the N,N'-dimethylformamide;
• EXAMPLE 12 A knit fabric made up of single yarns of the phenolic filaments of Example 8 was printed by means of the screen printing technique with a printing paste consisting of 30 of Dianix Fast Dark Green B (disperse dye produced by Mitsubishi Chemical Co.), 10 of acetanilide, l0 of potassium sulfate, 5 of propyl alginate (thickener) and 45 of water and having a viscosity of 6000 centipoises, after which the fabric was immediately steamed for 40 minutes at 130C.
• a printing paste consisting of 30 of Dianix Fast Dark Green B (disperse dye produced by Mitsubishi Chemical Co.), 10 of acetanilide, l0 of potassium sulfate, 5 of propyl alginate (thickener) and 45 of water and having a viscosity of 6000 centipoises, after which the fabric was immediately steamed for 40 minutes at 130C.
• the fabric was then washed in water and thereafter washed for 20 minutes in a wash liquid consisting of an aqueous solution containing 1 gram per liter of hydrosulfite, 0.5 gram per liter of soda ash and 1 gram per liter of a nonionic surfactant followed by water-washing and drying.
• a wash liquid consisting of an aqueous solution containing 1 gram per liter of hydrosulfite, 0.5 gram per liter of soda ash and 1 gram per liter of a nonionic surfactant followed by water-washing and drying.
• EXAMPLE 13 A plain weave fabric made up of yarns obtained by melt-spinning a novolak type phenolic resin and thereafter curing with formaldehyde was dyed with a dye solution of the following composition.
• Dianix Brilliant Red BS-E 12 (disperse dye produced by Mitsubishi Chemical CO.) N.N'-dimethylformamide added in an amount indicated in Table 13 (based on weight of dye solution) added in an amount indicated in Table 13 (based on weight of dye solution) 50-fold the weight of material dyed.
• the material to be dyed was dipped in the dye bath, and the dyeing was started at 40C., after which the temperature was raised up to 130C. during a period of 30 minutes. The dyeing was continued for a further 60 minutes at this temperature. This was followed by washing the material in water and thereafter submitting the material to a reductive washing for 20 minutes at 80C. with a reduction wash liquid consisting of 1 gram per liter of hydrosulfate, 1 gram per liter of soda ash, 1 gram per liter of a nonionic surfactant and water followed by water-washing and drying. The results obtained are shown in Table 13.
• EXAMPLE 14 A 2-ply yarn consisting of filaments obtained by meltspinning a novolak type phenolic resin and thereafter curing with formaldehyde was dyed with a dye solution of the following composition.
• the yarn to be dyed was clipped in the dye solution, and the dyeing was started at 40C., after which the temperature was raised up to 130C. during a period of 30 minutes, and the dyeing was continued for a further 60 minutes at this temperature. This was followed by water-washing the yarn and thereafter washing it for 20 minutes at C. in a wash liquid containing 1 gram per liter of hydrosulfite, 0.5 gram per liter of soda ash and 21 l gram per liter of a nonionic surfactant followed by water-washing and drying.
• Table l4 The results obtained are shown in Table l4.
• the fabric was then water-washed 6 5 I: and thereafter washed for 20 minutes at 80C. in a wash Z; 8 12 ⁇ 5 liquid containing 1 gram per liter of hydrosulfite, 0.5 9 10 5 70.1 gram per liter of soda ash, 0.8 gram per liter of a non- ⁇ g 58 23-2 ionic surfactant and water followed by water-washing 12 10 50 10:0 and drying.
• Table 15 The results are shown in Table 15.
• dioxdye exhaustion is low when the N,N'-dimethylacetaane, cyclohexane or acetone the rate of dye exhaustion mide is not contained or when it exceeds even 50 is greatly improved. though conjoint addition is made of dioxane. ln addition, residual N,N-dimethylacetamide is noted.
• EXAMPLE l5 Sumiacryl Red 78 (cationic dye l8 '1: (o.w.f.) A knit fabrlc made up of 2 ply yarn of filaments ob Produced by Sumimmo Chemical tamed by melt-spinning a novolak type phenolic resin was dyed with a dye solution of the following composi- 7 weig 0 ye solution) Various compounds indicated in Table l6 8 (based on Terasil Brilliant Pink F0 is 7!
• the fabric was dipped in the dye bath and the dyeing was started at 40C., the temperature being raised to T bl 16 128C. during a period of 40 minutes, where the dyeing E was carried out for 80 minutes.
• the fabric was then NNudimehyt Consent, j i washed in water and thereafter treated for 20 minutes NU fUI'mumlLlC 71] Additive ration (M (9H 15 at 80C.
• R, R' and R" are the same or different and each represent a hydrogen atom, an alkyl group, a phenyl group, a benzyl group or a phenetyl group, but R, R' and R" do not represent hydrogen atoms at the same time.
• said amide compound is selected from compounds of formula (1) wherein R, R and R" are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group and a benzyl group and R, R and R" do not represent hydrogen atoms at the same time.
• said amide compound is selected from the group consisting of N,N- dimethyl formamide, N,N-dimethyl acetamide, N,N- diethyl formamide, N,N-diethyl acetamide, N,N-diphenyl forrnamide, N,N-diphenyl acetamide, methyl benzamide, benzanilide, benzamide, acetanilide, ethyl benzamide and propyl benzamide.
• said dye liquor contains at least one metal sulfate 6.
• the amount of said metal sulfate is 3 to 35% by weight based on the total weight of the dye liquor and the amount of amide compound is 3 to by weight based on the total amount of the dye liquor.
• said metal sulfate is selected from the group consisting of sodium sulfate, potassium sulfate, beryllium sulfate, magnesium sulfate, aluminum sulfate, potassium alum, chromium sulfate, chromium alum, ferrous sulfate, ferric sulfate, ferrous ammonium sulfate, cobalt sulfate and nickel sulfate.
• said dye is a disperse dye, azoic dye, cationic dye or vat dye.
• dyeing is carried out by printing method by applying said paste-like dye liquor to the phenolic fibers or fibrous structures, and then steaming them at 1 10 to l40C. for 10 to 50 minutes.
• said dye liquor further contains at least one oxygen-containing compound selected from the group consisting of alkanols having 3 to 5 carbon atoms, benzyl alcohol, tetrahydrofurfuryl alcohol, dioxane, dialkyl ketones having 3 to 5 carbon atoms, cyclohexane and lower alkyl esters of formic acid and acetic acid.
• at least one oxygen-containing compound selected from the group consisting of alkanols having 3 to 5 carbon atoms, benzyl alcohol, tetrahydrofurfuryl alcohol, dioxane, dialkyl ketones having 3 to 5 carbon atoms, cyclohexane and lower alkyl esters of formic acid and acetic acid.
• said dye liquor further contains both (i) at least one metal sulfate and (ii) at least one oxygen-containing compound selected from the group consisting of alkanols having 3 to 5 carbon atoms, benzyl alcohol, tetrahydrofurfuryl alcohol, dioxane, dialkyl ketones having 3 to 5 carbon atoms, cyclohexanone and lower alkyl esters of formic acid and acetic acid.
• the method for coloring fibers or fibrous structures composed of phenolic resins which comprises coloring said fibers of firbous structures using a dye liquor which contains, as a dye assistant, N,N-dimethyl formamide and benzyl alochol.

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• 1973
  • 1973-04-10 US US349771A patent/US3918901A/en not_active Expired - Lifetime
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