WO2013123673A1 - Agent and method for refining and bleaching - Google Patents

Agent and method for refining and bleaching Download PDF

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Publication number
WO2013123673A1
WO2013123673A1 PCT/CN2012/071577 CN2012071577W WO2013123673A1 WO 2013123673 A1 WO2013123673 A1 WO 2013123673A1 CN 2012071577 W CN2012071577 W CN 2012071577W WO 2013123673 A1 WO2013123673 A1 WO 2013123673A1
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WIPO (PCT)
Prior art keywords
bleaching
scouring
mass
group
salt
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PCT/CN2012/071577
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French (fr)
Chinese (zh)
Inventor
梅村深雪
吴俊毅
杨伟
赵波
杨詹
Original Assignee
日华化学株式会社
日华化学研发（上海）有限公司
浙江日华化学有限公司
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Application filed by 日华化学株式会社, 日华化学研发（上海）有限公司, 浙江日华化学有限公司 filed Critical 日华化学株式会社
Priority to PCT/CN2012/071577 priority Critical patent/WO2013123673A1/en
Priority to JP2014543748A priority patent/JP5710847B2/en
Priority to CN201280003315.0A priority patent/CN103492632B/en
Publication of WO2013123673A1 publication Critical patent/WO2013123673A1/en

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    • 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
    • D06M13/10—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 oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • 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
    • D06M13/10—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 oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D06M13/148—Polyalcohols, e.g. glycerol or glucose
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers

Definitions

  • the present invention relates to batch scouring, bleaching or simultaneous scouring of fibers.
  • oils such as oils, pastes, and machine oils, such as oils, pastes, and machine oils, which are added at the stage of spinning or the like, adhere to the fibers as inclusions, and they often cause fuming or dyeing and unevenness in the drying process. Therefore, a scouring treatment for removing these inclusions from the fibers, and a bleaching treatment for chemically decomposing inclusions and pigments with hydrogen peroxide and an alkali agent to whiten the fibers can be carried out. For such scouring and bleaching, it is sometimes possible to carry out refining, bleaching, and sometimes simultaneously in the same bath.
  • a winding of a yarn, a blank, or the like wound around a cylindrical body, a fiber package called a so-called cheese or a cone, and a processing liquid are circulated.
  • the method of treatment, or a method of circulating the yarn or the billet along with the treatment liquid, and performing treatment are used as the former method, for example, there is a method in which a cheese dyeing machine is used, and a package yarn as a winding of the yarn is fixed to a spinning machine having a liquid jet and an absorption cylinder, and the treatment liquid is from the inside of the fixed cheese yarn.
  • the scouring is performed by circulating to the outside and/or from the outside to the inside.
  • a cheese dyeing machine is usually used for scouring bleaching.
  • a method using a liquid flow dyeing machine is utilized as the scouring bleaching method as described above or the treating agent used in the treatment.
  • Patent Document 1 discloses a bleaching method in which an aminoalkylphosphoric acid derivative or the like is used, and a sugar alcohol or an aldonic acid, etc., JP-A-62-32195 (Patent Document 2)
  • a bleaching improver which combines a polycarboxylic acid-based polymer composed of a specific carboxylic acid and a sugar alcohol and/or an aldonic acid is disclosed.
  • Japanese Laid-Open Patent Publication No. Hei 8-81696 discloses a multifunctional fiber auxiliary.
  • Patent Document 1 Japanese Special Open No. 61-41367
  • Patent Document 2 JP-A-62-32195
  • Patent Document 3 Japanese Laid-Open Patent Publication No. 8-81696 SUMMARY OF INVENTION
  • the present invention has been made in view of the problems of the prior art described above, and an object thereof is to provide a scouring bleaching aid and a scouring and bleaching method which can achieve excellent scouring bleaching property and carry out fiber winding such as cheese yarn or tapered wire
  • scouring bleaching the batch scouring bleaching of the scouring unevenness of the fiber package can be suppressed.
  • the present inventors have conducted intensive studies, and as a result, it has been found that by using a specific compound in combination at a predetermined ratio, it is possible to achieve excellent refining bleachability and to perform fiber wrapping such as cheese or tapered wire.
  • the present invention has been completed based on this finding in the case of scouring and bleaching in the case of scouring and bleaching, which suppresses the scouring unevenness of the fiber package.
  • the present invention provides a scouring bleaching aid comprising the following components (A) to (D), and the mass ratio of the component (A) to the component (B) is 80: 20 to 30: 70.
  • (A) one or more selected from the group consisting of aldonic acid represented by the following formula (1), a salt thereof, a lactone thereof, and a sugar alcohol represented by the following formula (2).
  • n represents an integer of 2 to 6.
  • n an integer of 2 to 6.
  • the alkylene oxide adduct of a primary or secondary amine having 2 to 4 carbon atoms and having an ethyleneoxy group in an amount of 55 to 70% by mass.
  • the scouring bleaching aid of the present invention can be used in batch scouring bleaching.
  • the scouring bleaching aid of the present invention can be used for scouring or bleaching, and can achieve scouring or bleaching.
  • the scouring or bleaching of the fiber package can be suppressed from being uneven or bleaching unevenness.
  • the scouring bleaching aid of the present invention is used for simultaneous scouring and bleaching treatment, it is possible to achieve scouring and bleaching properties, and to refine and bleach the object into a fiber package such as a cheese yarn or a tapered wire.
  • the scouring and bleaching of the fiber package can be suppressed and the bleaching unevenness can be suppressed.
  • the present invention also provides a scouring bleaching method which is a scouring bleaching method which is treated in a bath containing the following components (A) to (D), characterized in that (A) component and (B) component in the treatment bath are The mass ratio is 80: 20 ⁇ 30: 70.
  • n represents an integer of 2 to 6.
  • n an integer of 2 to 6.
  • the alkylene oxide adduct having a carbon number of 2 to 4 of a primary or secondary amine has an ethyleneoxy group in an amount of 55 to 70% by mass in the molecule.
  • the scouring bleaching process of the present invention can be applied to batch scouring bleaching.
  • the scouring bleaching method of the present invention can be used in the case of scouring or bleaching, and can achieve scouring property of the fiber package in the case where the scouring property or the bleaching property is excellent, and the scouring object is a fiber package such as a cheese yarn or a tapered wire. Uneven or uneven bleaching.
  • the scouring bleaching method of the present invention can be suppressed in the case where the scouring and bleaching treatment are simultaneously performed, and the scouring property and the bleaching property are excellent, and the scouring and bleaching object is a fiber package such as a cheese yarn or a tapered wire.
  • the scouring and bleaching of the fiber package is refined and bleached.
  • a scouring bleaching aid or a scouring bleaching method according to the present invention a so-called cheese yarn or a cone which is wound around a winding of a cylindrical body by a fiber which is applied to intermittent scouring of fibers, in particular, a yarn or a blank.
  • the scouring and bleaching of the fiber package such as the wire can be achieved by scouring and bleaching, which can suppress the scouring and uneven bleaching of the fiber package such as the cheese yarn or the tapered wire.
  • the scouring bleaching aid of the present invention is characterized by comprising the following components (A) to (D).
  • n represents an integer of 2 to 6.
  • n an integer of 2 to 6.
  • the alkylene oxide adduct having a carbon number of 2 to 4 of a primary or secondary amine has an ethyleneoxy group in an amount of 55 to 70% by mass in the molecule.
  • the acid sugar acid in the component (A) is a compound represented by the following formula (1).
  • m represents an integer of 2 to 6.
  • Examples of the tyrosic acid represented by the above formula (1) include erythroic acid, ribonic acid, arabinic acid, xylogonic acid, lysolic acid, aloponic acid, altrose acid, and gluconic acid. , mannonic acid, gulonic acid, iduronic acid, galactonic acid, teraloic acid, and the like.
  • the component (A) may be a salt obtained by neutralizing the above-mentioned tyrosic acid with an alkali compound or an amine compound.
  • a salt include an alkali metal salt such as a sodium salt, a potassium salt or a lithium salt, an alkaline earth metal salt such as a magnesium salt or a phosphonium salt, and an amine compound such as an ammonia salt, a monoethanolamine salt, a diethanolamine salt or a triethanolamine salt. salt.
  • component (A) may be a lactone produced by dehydration condensation of a hydroxy acid group and a carboxyl group in the same molecule.
  • the sugar alcohol in the component (A) is a compound represented by the following formula (2).
  • n an integer of 2 to 6.
  • sugar alcohol represented by the above formula (2) examples include erythritol, threitol, arabitol, xylitol, ribitol, iditol, galactitol, glucose alcohol, and mannose. Alcohol, sorbitol, heptagon, avocado, and the like.
  • the component (A) is preferably a tyrosonic acid wherein m of the formula (1) is 2 - 4 or a sodium salt thereof, a potassium salt thereof or a magnesium salt thereof, or n of the formula (2) 2 ⁇ 4 sugar alcohol.
  • the component (B) is a polymer obtained by polymerizing a carboxyl group-containing monomer as an essential monomer and/or a salt thereof.
  • the carboxyl group-containing monomer is a monomer having a carboxyl group and an unsaturated bond, and examples of such a monomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and 2-methylene.
  • C Alkenoic acid, methacrylic acid, maleic acid, a salt thereof, and an anhydride thereof.
  • the polymer of the component (B) may be a polymer obtained by polymerizing one type of the carboxyl group-containing monomer alone, or may be a copolymer obtained from two or more kinds of the above-mentioned carboxyl group-containing monomers.
  • the polymer of the component (B) may be a copolymer of one or more kinds of the above-mentioned carboxyl group-containing monomer and one or more kinds of monomers copolymerizable therewith.
  • the monomer which can be copolymerized is not particularly limited, and examples thereof include a vinyl monomer such as ethylene, vinyl chloride or vinyl acetate, an acrylamide, an acrylate or a methacrylate.
  • the acrylate or methacrylate to be used is not particularly limited, and is preferably an acrylate or methacrylate having a hydrocarbon group having 1 to 3 carbon atoms, and the hydrocarbon group may have a substituent such as a hydroxyl group.
  • acrylates or methacrylates examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxy methacrylate. Ester, propyl acrylate, propyl methacrylate, and the like.
  • the weight average molecular weight of the polymer is preferably from 1,000 to 20,000, more preferably from 3,000 to 15,000, particularly preferably from 4500 to 8,000. If the weight average molecular weight of the polymer is within the above range, the unevenness of the scouring bleaching property can be sufficiently suppressed. Among them, when the weight average molecular weight exceeds 20,000, there is a possibility that the unevenness of the scouring bleaching property or the excessive viscosity may not be sufficiently suppressed depending on the situation, which may cause problems in workability.
  • the polymer of the component (B) may be a salt obtained by neutralizing a carboxyl group and an alkali or an amine compound in the above polymer.
  • a salt include an alkali metal salt such as a sodium salt, a potassium salt or a lithium salt, an alkaline earth metal salt such as a magnesium salt or a phosphonium salt, and an amine such as an ammonia salt, a monoethanolamine salt, a diethanolamine salt or a triethanolamine salt.
  • an alkali metal salt such as a sodium salt, a potassium salt or a lithium salt
  • an alkaline earth metal salt such as a magnesium salt or a phosphonium salt
  • an amine such as an ammonia salt, a monoethanolamine salt, a diethanolamine salt or a triethanolamine salt.
  • the method for producing the polymer of the component (B) is not particularly limited, and examples thereof include a conventionally known radical polymerization reaction. Further, a commercially available product can also be used as the polymer of the component (B).
  • the radical polymerization reaction is not particularly limited, and for example, a radical polymerization initiator may be added to an aqueous solution of a carboxyl group-containing monomer and/or a salt thereof at 30 °. The method of heating the reaction at 150X for 2 to 5 hours, and the like.
  • an alcohol such as methanol, ethanol or isopropyl alcohol or a water-soluble solvent such as acetone may be added to the aqueous solution of the carboxyl group-containing monomer and/or its salt.
  • radical polymerization initiator to be used is not particularly limited, and examples thereof include redox formation of a combination of persulfate such as potassium persulfate, sodium persulfate or ammonium persulfate, persulfate and sodium hydrogen sulfite.
  • persulfate such as potassium persulfate, sodium persulfate or ammonium persulfate, persulfate and sodium hydrogen sulfite.
  • the polymerization initiator, the hydrogen peroxide, the water-soluble azo polymerization initiator, and the like may be used alone or in combination of two or more.
  • a chain transfer agent for example, octyl thioglycolate
  • octyl thioglycolate may be added in order to adjust the degree of polymerization.
  • the component 0 is an organic phosphonic acid and/or a salt thereof.
  • the organic phosphonic acid may, for example, be an amino poly(alkylenephosphonic acid), an alkylene diamine poly(alkylenephosphonic acid) or a dialkylene triamine poly(alkylenephosphonic acid). Hydroxyalkylene diphosphonic acid, polycarboxyalkanephosphonic acid, and the like.
  • the amino poly(alkylenephosphonic acid) may, for example, be an amino poly(alkylenephosphonic acid) having an alkylene group in the alkylene phosphonic acid structure of the molecule and having a carbon number of 1 to 3.
  • the amino poly(alkylenephosphonic acid) may, for example, be an amino group (methylene phosphonic acid), an amino group (methylene phosphonic acid), an amino group (methylene phosphonic acid), or an amino group ( Ethylene phosphonic acid), aminobis(ethylenephosphonic acid), aminotris(ethylenephosphonic acid), and the like.
  • the alkylene diamine poly(alkylene phosphonic acid) may, for example, be an alkylene group in the alkylene diamine structure having a carbon number of 2 to 6 and an alkylene phosphonic acid structure.
  • the alkylene diamine poly(alkylenephosphonic acid) having an alkyl group having 1 to 3 carbon atoms, and such an alkylene diamine poly(alkylenephosphonic acid) may, for example, be: Amine tetra (methylene phosphonic acid), ethylene diamine tetra (ethylene phosphonic acid), hexamethylene diamine tetra (methylene phosphonic acid), and the like.
  • the dialkylene triamine poly(alkylene phosphonic acid) may, for example, be an alkylene group having a carbon number of 2 to 6 in the dialkylene triamine structure in the molecule, and an alkylene phosphonic acid structure
  • the alkylene group has a dialkylene triamine poly(alkylenephosphonic acid) having a carbon number of 1 to 3, and as such a dialkylene triamine poly(alkylenephosphonic acid), for example, For example: diethylene triamine penta (methylene phosphonic acid), di 1,6-hexylenetriamine penta (methylene phosphonic acid) and the like.
  • the hydroxyalkylene diphosphonic acid may, for example, be a hydroxyalkylene group having 2 to 5 carbon atoms.
  • Phosphonic acid, such a hydroxyalkylene diphosphonic acid may, for example, be hydroxyethylidene diphosphonic acid or hydroxypropylene diphosphonic acid.
  • the polycarboxyalkanephosphonic acid may, for example, be a polycarboxyalkanephosphonic acid having a linear hydrocarbon group of 2 to 8 and a carboxyl group of 2 to 6.
  • a polycarboxyalkanephosphonic acid for example, for example, : 1, 2, 3-tricarboxybutane-2-phosphonic acid, 1, 2, 4-tricarboxyhexane- 1-phosphonic acid, and the like.
  • examples of the salt of the organic phosphonic acid include alkali metal salts such as sodium, potassium, and lithium; alkaline earth metal salts such as magnesium and barium; ammonium salts; methylamine, ethylamine, propylamine, butylamine, and octylamine.
  • An organic amine salt such as dodecylamine, hexadecylamine, octadecylamine, dimethylamine, diethylamine or triethylamine; an alkanolamine salt such as monoethanolamine, diethanolamine or triethanolamine.
  • ethylenediaminetetrakis methylenephosphonic acid
  • ethylenediaminetetrakis ethylenephosphonic acid
  • ethylenephosphonic acid ethylenediaminetetrakis
  • ethylenephosphonic acid ethylenediaminetetrakis
  • the like are preferably used from the viewpoint of further suppressing the unevenness of the scouring bleaching property.
  • Ethylene triamine penta methylene phosphonic acid
  • diethylene triamine penta ethylene phosphonic acid
  • hydroxyethylidene diphosphonic acid and salts thereof and more preferably diethylene trisole Amine penta (methylene phosphonic acid), hydroxyethylidene diphosphonic acid and salts thereof.
  • the ethylene oxide adduct of a monohydric alcohol, a diol or a phenol in the component (D) has an ethyleneoxy group in an amount of from 65 to 85% by mass.
  • the amount of the ethyleneoxy group in the molecule is less than 65% by mass, the scouring bleaching property may be insufficient or the scouring unevenness of the scouring may not be sufficiently suppressed.
  • the amount of ethyleneoxy groups in the molecule exceeds 85 mass % .
  • the amount of ethyleneoxy group in the molecule is preferably 65 to 80% by mass, and more preferably 65 to 70% by mass, from the viewpoint of further improving the refining bleaching property and further suppressing the unevenness of the polishing bleaching property.
  • the monohydric alcohol or the diol may be linear or branched, may be a saturated alcohol or an unsaturated alcohol, or may be substituted on an aliphatic hydrocarbon group like benzyl alcohol or the like. a phenyl alcohol. From the viewpoint of easier availability, as a monohydric alcohol or a diol, an aliphatic monohydric alcohol or a carbon number of 8 to 22 carbon atoms is preferred. 2 - 12 aliphatic diols.
  • aliphatic monohydric alcohol having 8 to 22 carbon atoms for example, octanol, decyl alcohol, decyl alcohol, dodecanol, tridecyl alcohol, tetradecanol, pentadecyl alcohol, and hexadecane may be mentioned.
  • Alkanol, heptadecyl alcohol, stearyl alcohol, nonadecanol, eicosyl alcohol, diundecyl alcohol, dodecanol and the like from the viewpoint of easier availability, an aliphatic monohydric alcohol having 10 to 16 carbon atoms is more preferable.
  • examples of the aliphatic diol having 2 to 12 carbon atoms include ethylene glycol, propylene glycol (1,2-propylene glycol), 1, 3-propanediol, butanediol, pentanediol, and hexanediol. 1, 10 - decanediol, dodecanediol, and the like.
  • the phenol is a phenol having one or more phenolic hydroxyl groups as a hydroxyl group
  • the aromatic ring having the phenolic hydroxyl group is a hydrocarbon group such as an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group having 8 to 30 carbon atoms.
  • a phenol is preferably a phenol, an alkylphenol, a phenylphenol or an aralkylphenol.
  • a phenol and a monostyrenated phenol obtained by adding phenol to styrene are preferable.
  • polystyrenated phenol more preferably monostyrenated phenol, distyrylated phenol or tristyrenated phenol.
  • the average addition mole number of ethylene oxide in the ethylene oxide adduct may be appropriately adjusted by using a type of monohydric alcohol, a diol or a phenol to achieve an ethylene oxide amount in the molecule, but it is easy to It is preferably from 5 to 50, more preferably from 5 to 35, from the viewpoint of being more excellent in the production and refining of the bleaching property and further suppressing the unevenness of the polishing bleaching property.
  • the copolymerized adduct of the alkylene oxide having 2 to 4 carbon atoms of the monohydric alcohol, the diol or the phenol in the component (D) has an ethyleneoxy group in an amount of 45 to 70% by mass.
  • the amount of the ethyleneoxy group in the molecule is less than 45% by mass, the scouring bleaching property may be insufficient or the scouring unevenness of the scouring may not be sufficiently suppressed.
  • the amount of the ethyleneoxy group in the molecule exceeds 70% by mass, the inclusions are not sufficiently acted on, and the fibers which are the object of scouring and bleaching are not sufficiently impregnated, and the scouring bleaching property may be insufficient or impossible.
  • the amount of ethyleneoxy group in the molecule is preferably from the viewpoint of further improving the bleaching property and further suppressing the unevenness of the scouring bleaching property. 50 to 70% by mass, more preferably 55 to 65% by mass.
  • the monohydric alcohol, the diol or the phenol is the same as described above.
  • the alkylene oxide having 3 or 4 carbon atoms may, for example, be propylene oxide or butylene oxide.
  • propylene oxide is more preferable from the viewpoint that the scouring bleaching property is more excellent and the scouring bleaching unevenness can be further suppressed.
  • the addition method of the alkylene oxide may be a block addition or a random addition.
  • the total average addition mole number of the alkylene oxide can be appropriately adjusted by the type of the monohydric alcohol, the diol or the phenol to achieve the target of the ethyleneoxy group in the molecule, and is easy to manufacture and more excellent in the bleaching property. Further, from the viewpoint of further suppressing the unevenness of the scouring bleaching property, it is preferably 5 to 40. Further, in the case of a copolymerized product of ethylene oxide and propylene oxide, the average number of moles of propylene oxide added is preferably from 1 to 4, more preferably from 1 to 3.
  • the amount of the ethyleneoxy group in the molecule of the alkylene oxide adduct having 2 to 4 carbon atoms of the primary or secondary amine in the component (D) is 55 to 70% by mass.
  • the amount of ethyleneoxy group in the molecule is less than 55 mass%, the scouring bleaching property may be insufficient or the scouring unevenness of bleaching may not be sufficiently suppressed.
  • the amount of the ethyleneoxy group in the molecule exceeds 70% by mass, the inclusions are not sufficiently acted on, and the fibers which are the objects of the scouring and bleaching are not sufficiently impregnated, and the scouring bleaching property may be insufficient or impossible. Sufficient bleaching unevenness is sufficiently suppressed.
  • the amount of ethyleneoxy group in the molecule is preferably from 60 to 65 mass% from the viewpoint that the refining bleaching property is more excellent and the refining bleaching property can be further suppressed.
  • the hydrocarbon group in the primary or secondary amine may be linear or branched, and may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.
  • the number of carbon atoms of the aliphatic hydrocarbon group is preferably from 8 to 22, more preferably from 12 to 20, from the viewpoint of availability.
  • a primary amine is preferable among the primary or secondary amines, and as such a primary amine, octylamine, dodecylamine, and ten are exemplified. Octaamine, stearylamine, and the like.
  • alkylene oxide having 3 or 4 carbon atoms examples include propylene oxide and butyl oxide. Alkene and the like.
  • the addition method of the alkylene oxide having 2 to 4 carbon atoms may be a single addition of ethylene oxide, or may be a block of ethylene oxide and an alkylene oxide having 3 carbon atoms and/or an alkylene oxide having 4 carbon atoms or Random bonus.
  • the addition mode is preferably a single addition of ethylene oxide or a random or block addition of ethylene oxide and propylene oxide, more preferably ethylene oxide, from the viewpoint of further improving the scouring bleaching property and further suppressing the scouring bleaching property. Addition separately.
  • the total average addition mole number of the alkylene oxide can be appropriately adjusted by the type of the primary or secondary amine so that the amount of ethyleneoxy group in the molecule can be achieved, and it is easy to manufacture and the bleaching property is more excellent, and the scouring bleaching property can be further suppressed. From the viewpoint of no-hook, it is preferably 4 - 35, more preferably 7 - 15.
  • the component (D) is preferably an ethylene oxide adduct of a monohydric alcohol or a carbon number of a monohydric alcohol in the above-mentioned adduct from the viewpoint of further improving the scouring bleaching property and further suppressing the scouring bleaching property.
  • the (A) - (D) component may be a scouring bleaching aid comprising a single agent in a single reagent, or may be a component of (A) to (D).
  • a scouring bleaching aid comprising a plurality of reagents and comprising a plurality of reagents. The number of constituents can be appropriately adjusted depending on the condition of the processing plant such as equipment.
  • the components (A) to (D) are separately contained in a plurality of reagents, they may be arbitrarily selected and combined, and one component may be contained in a reagent of 2 or more.
  • the number of the agents in the bleaching and scouring aid of the present invention is preferably 1 from the viewpoint of easily adjusting the concentration of the components (A) to (D) in the treatment bath and facilitating the easy transportation of the scouring and bleaching aid. ⁇ 4, more preferably 2 or 3.
  • the component (D) is not contained together with the components (A) to (C) from the viewpoint of higher stability of the reagent, or (A) When the (C) component is contained at the same time, it is contained only in combination with any one of the components (A) to (C).
  • the mass ratio of the component (A) to the component (B) in the scouring bleaching aid of the present invention is 80: 20 - 30: 70» When the mass ratio of the components (A) and (B) is outside the above range, Not enough scouring bleaching ability and insufficient suppression of scouring bleaching unevenness.
  • the ratio of the total amount of the components (A) and (B) to the component (C) or the component (D) in the scouring bleaching aid of the present invention is not particularly limited, and is easily adjusted to be suitable in a treatment bath to be described later
  • the ratio of the component (D) to the ratio of the total amount of the components (A) to (D) in the reagent is preferably:
  • the total amount of the components (A) and (B) is 10 to 60% by mass.
  • the component is 3 to 10% by mass, and the component (D) is 30 to 80% by mass.
  • the ratio of each component in the reagent to the total amount of the components (A) to (D) is preferably: (A) The total amount of the component (B) is 25 to 50% by mass, the component (C) is 3 to 8 mass%, and the component (D) is 40 to 70 mass%.
  • the amount of the components (A) to (D) in each reagent is not particularly limited, and the reagent may contain only the components (A) to (D), and other known components currently used for scouring the bleach may be added to the reagent.
  • Such an additive component examples include water, a solvent or a dispersing agent such as a monohydric alcohol or a diol other than the above component (A), an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the above (D).
  • Surfactants such as nonionic surfactants other than nonionic surfactants, antifoaming agents, and penetrating agent components.
  • the scouring bleaching aid of the present invention can be applied to batch scouring bleaching of fibers.
  • the scouring bleaching aid of the present invention is usually dissolved or dispersed in a treatment bath of the intended fiber.
  • the scouring bleaching aid of the present invention is added to the treatment bath so that the mass ratio of the components (A) and (B) is 80: 20 to 30: 70.
  • the mass ratio of the components (A) and (B) is outside the above range, sufficient scouring bleaching property may not be obtained and the scouring unevenness of the scouring may not be sufficiently suppressed.
  • the ratio of the total amount of the components (A) and (B) in the treatment bath to the component (C) or (D) is not particularly limited, and is excellent in refining bleaching property, and further suppresses scouring bleaching. From the viewpoint of unevenness, it is preferred to add the scouring bleaching aid of the present invention to the bath so that the total amount of the components (A) and (B) is 10 to 60 mass with respect to the total amount of the components (A) - (D). % and (C) components are 3 to 10% by mass, and (D) components are 30 to 80% by mass.
  • the ratio of each component in the treatment bath to the total amount of (A) to (D) components is preferably from the viewpoint of further improving the bleaching property and further suppressing the unevenness of the scouring bleaching property: the total amount of the components (A) and (B) It is 25 to 50% by mass, (C) is 3 to 8% by mass, and (D) is 40 to 70% by mass.
  • the amount of the scouring agent to be added to the treatment bath of the present invention is preferably such that the concentration of the total amount of the components (A) to (D) in the treatment bath is from 0.05 to 15 g/L.
  • concentration of the total amount of the components (A) to (D) in the treatment bath is less than 0.05 g/L, the scouring bleaching property may be insufficient.
  • concentration exceeds 15 g/L it may be used. No further improvement in effect will occur, and the cost is unfavorable.
  • the scouring bleaching aid is preferably added to the treatment bath in such a manner that the scouring bleaching agent is more excellent in the scouring bleaching property, further suppressing the scouring bleaching unevenness and being more advantageous in terms of cost, so that the total amount of (A) - (D) components in the treatment bath is The amount of the amount is 0.5 to 5 g / L.
  • the scouring bleaching aid of the present invention can be applied to batch scouring bleaching of natural fibers, chemical fibers, and blended woven fibers thereof.
  • natural fiber include cotton, hemp, and wool.
  • chemical fiber include regenerated cellulose fibers such as rayon or acetate, and synthetic fibers such as polyester fibers or polyamide fibers, acrylic fibers, and spandex.
  • blended woven fibers thereof include cotton or hemp and other fibers (such as wool, polyester, polyamide fiber, and acrylonitrile), wool and other fibers (polyester, polyamide, and acrylonitrile).
  • blended polyester fiber with other fibers (rayon, acetate, polyamide, acrylonitrile, spandex, etc.), polyamide fiber and other fibers (rayon, acetate, acrylonitrile, spandex, etc.) .
  • the scouring bleaching temperature can be appropriately adjusted depending on the scoured fibers, and is usually about 5 to about 30 minutes.
  • a machine for scouring bleaching a machine currently used for batch scouring bleaching can be used, and as such a machine, for example, a liquid dyeing machine or a warp beam dyeing machine, a cheese dyeing machine, an austenite dyeing machine, Rope dyeing machine Machine ), washing dyeing machine, etc.
  • the bath ratio of the treatment bath is not particularly limited and is usually 1:4 to 1:40, preferably 1:6 to 1:20.
  • the scouring bleaching method of the present invention is characterized in that it is treated in a bath containing the following components (A) to (D).
  • n represents an integer of 2 to 6.
  • n an integer of 2 to 6.
  • the alkylene oxide adduct having a carbon number of 2 to 4 of a primary or secondary amine has an ethyleneoxy group in an amount of 55 to 70% by mass in the molecule.
  • the components (A) to (D) in the scouring method of the present invention are those described above.
  • the mass ratio of the components (A) and (B) in the treatment bath is 80: 20 to 30: 70. As long as the mass ratio of the components (A) and (B) is within the above range, sufficient refining bleaching properties can be obtained, and scouring bleaching unevenness can be sufficiently suppressed.
  • the ratio of the total amount of the components (A) and (B) to the component (C) or the component (D) in the treatment bath is not particularly limited, but the scouring bleaching property is more excellent, and the scouring bleaching property is further suppressed.
  • the relative total amount of (A) ⁇ (D) components excellent
  • the total amount of the components (A) and (B) is preferably 10 to 60% by mass, the component (C) is 3 to 10% by mass, and the component (D) is 30 to 80% by mass.
  • the ratio of each component in the treatment bath to the total amount of (A) to (D) components is preferably from the viewpoint of further improving the bleaching property and further suppressing the unevenness of the scouring bleaching property: the total of the components (A) and (B)
  • the amount is 25 to 50% by mass, (0 is 3 to 8 mass%, and (D) is 40 to 70 mass%.
  • the concentration of the total amount of the components (A) to (D) in the treatment bath in the scouring method of the present invention is preferably 0.05 to 15 g/L.
  • concentration of the total amount of the components (A) to (D) in the treatment bath is less than 0.05 g/L, the scouring bleaching property may be insufficient.
  • concentration exceeds 15 g/L it may not be used. Further improvement in the effect will occur, and the cost is unfavorable.
  • the concentration of the total amount of the components (A) to (D) in the treatment bath is preferably 0.5 to 5 g/L from the viewpoint that the refining bleaching property is more excellent, the scouring bleaching property is further suppressed, and the cost is more favorable.
  • the scouring bleaching method of the present invention can be applied to the intermittent scouring bleaching which is currently prevalent, for example, using the above-described machine, and can be applied to the scouring bleaching of the above-mentioned fibers.
  • a cheese dyeing machine manufactured by Risaka Manufacturing Co., Ltd., LLC-1/25
  • the treatment bath was cycled at a bath ratio of 1:10, and the treatment liquid was circulated in the direction from the inner side to the outer side of the cheese yarn at a flow rate of 40 L/min, and scouring was carried out by the following procedure, followed by drying in a hot air for 30 minutes.
  • Treatment bath composition :
  • the treatment bath temperature was set to 40, and the treatment liquid was circulated for 10 minutes and then heated to 110 in 2/min. After the treatment liquid was circulated for 30 minutes in H O , it was cooled to drain. Then, hot water is washed at 80* € for 10 minutes to drain.
  • the normal temperature water was added, and 0. 2 g/L of a hydrogen peroxide neutralizer (manufactured by Nikko Chemical Co., Ltd., trade name: CROAKS E) was added, and the mixture was circulated for 5 minutes, neutralized with hydrogen peroxide, and added with acetic acid.
  • the mass % aqueous solution lg/L was circulated for 10 minutes, neutralized with NaOH, drained, and washed with water at normal temperature.
  • the web from the center to the outer circumference is divided into five equal parts in the radial direction, and is divided into the outermost layer, the outer layer, the middle layer, the inner layer and the innermost layer.
  • the treated yarns are taken from each layer.
  • the processed yarn was attached to a cylinder knitting machine (a cylinder diameter of 3.5 inches, a number of needles of 240, and an NE450W manufactured by Ins. Co., Ltd.), and a knitting yarn of 40 cm was knitted with one yarn.
  • the sample was obtained as a knitted fabric.
  • the sample knitted fabric in which the obtained circular knitted fabric was folded four times to have eight overlapping states was measured for whiteness and rewet by the following method.
  • the sample knit of all layers has a soaking time of less than 1 second.
  • B The permeation time of the sample knitted fabric of each layer was dispersed in the range of 1 to 180 seconds.
  • C The sample knit of all layers has a soaking time of 180 seconds or more.
  • the whiteness of the sample knitted fabric of each layer was measured using a MINOLTA colorimeter CM-3700d under the conditions of a light source D65 and a field of view of 10 degrees.
  • Tables 1 and 2 The higher the whiteness It shows that the scouring bleaching property is excellent.
  • the whiteness is determined by subtracting the minimum whiteness from the highest whiteness. The smaller the whiteness difference, the more the scouring unevenness of the cheese yarn is suppressed.
  • EO represents ethylene oxide
  • PO represents propylene oxide
  • the value in () immediately after E0 or P0 represents the average addition mole number of E0 or P0.
  • EO represents ethylene oxide
  • PO represents propylene oxide
  • the value in 0 immediately after E0 or P0 represents the average addition mole number of E0 or P0.
  • the scouring bleaching aid or the scouring method of the present invention By applying the scouring bleaching aid or the scouring method of the present invention, scouring bleaching which achieves excellent scouring bleaching can be carried out.
  • the scouring of the present invention When the white auxiliaries or the scouring bleaching method is applied to the scouring and bleaching of a fiber package such as a cheese yarn or a tapered wire, it is possible to carry out scouring bleaching which can suppress the scouring unevenness of the fiber package while achieving excellent refining bleaching properties. Thus, it can contribute to the stabilization of the fiber quality after scouring.

Abstract

Provided are an agent and a method for refining and bleaching. The agent comprises components A, B and D. The weight ratio of component A to B is 80:20 to 30:70. Component D is selected from one or more of the following adducts: adduct of monohydric alcohol, di-alcohol or phenol with ethylene oxide with 65-85 wt% of ethyleneoxy, copolymerized adducts of monohydric alcohol, di-alcohol or phenol with C2-4 oxyalkylene with 45-70 wt% of ethyleneoxy and adducts of primary amine or secondary amine with C2-4 oxyalkylene with 55-70 wt% of ethyleneoxy. The agent for refining and bleaching can be used in the batch refining and bleaching method of fiber, and for solving the problem of non-uniformity of refining and bleaching of fiber packages.

Description

精炼漂白助剂及精炼漂白方法  Refining bleaching aid and refining bleaching method
技术领域 Technical field
本发明涉及用于纤维的间歇式精练、 漂白或两者同时进行的 精练 ·漂白的精练漂白助剂及使用了该助剂的精练、 漂白或精 练 ·漂白方法。 背景技术  The present invention relates to batch scouring, bleaching or simultaneous scouring of fibers. Bleaching scouring bleaching auxiliaries and scouring, bleaching or scouring/bleaching methods using the auxiliaries. Background technique
在纺紗等阶段加入的油剂、 糊剂和机器油等工艺油剂、 锈、 灰尘或蜡等作为夹杂物附着于纤维， 它们常常引起在干燥工序的 发烟或染色、 整理不匀。 因此， 可实施用于将这些夹杂物从纤维 除去的精练处理、 用过氧化氢和碱剂等对夹杂物和色素等进行化 学分解而使纤维变白的漂白处理。 对于这样的精练及漂白而言， 有时可分别依次进行精练、 漂白， 有时也可同时在同浴中进行。 在本说明书中，将"精练、漂白或同时进行精练和漂白的精练 -漂 白" 统一记载为 "精练漂白" ， 另外， 将 "精练性、 漂白性或精 练 ·漂白性" 统一记载为 "精练漂白性" 。  Process oils such as oils, pastes, and machine oils, such as oils, pastes, and machine oils, which are added at the stage of spinning or the like, adhere to the fibers as inclusions, and they often cause fuming or dyeing and unevenness in the drying process. Therefore, a scouring treatment for removing these inclusions from the fibers, and a bleaching treatment for chemically decomposing inclusions and pigments with hydrogen peroxide and an alkali agent to whiten the fibers can be carried out. For such scouring and bleaching, it is sometimes possible to carry out refining, bleaching, and sometimes simultaneously in the same bath. In this manual, "refining, bleaching or scouring and bleaching at the same time and bleaching" is collectively described as "refined bleaching", and "sleeve, bleaching or scouring and bleaching" are collectively described as "sweet bleaching". Sex".
对于间歇式的精练漂白方法而言， 根据纤维的种类等有各种 方法。 例如有： 将纱线或坯料等卷绕于圆筒体的卷绕物、 被称为 所谓的筒子纱 （cheese )或雉形筒丝（cone)等纤维卷装固定并使 处理液循环来进行处理的方法， 或随处理液一起沿紗线或坯料流 动而使之循环来进行处理的方法等。 作为前一种方法， 例如有使 用了筒子紗染色机的方法， 作为纱线的卷绕物的筒子纱被固定于 具有液体喷射及吸收筒的纺缍， 处理液从固定好的筒子纱的内侧 向外侧和 /或从其外侧向内侧循环，从而进行精练漂白。在将纱线 精练漂白的情况下，通常用这样的筒子纱染色机来进行精练漂白。 另外， 作为后一种方法， 例如有使用了液流染色机的方法， 利用 作为如上所述的精练漂白方法或该处理中所使用的处理剂， 例如， 公开有如下所述的精练漂白方法和处理剂。 For the intermittent scouring method, various methods are available depending on the type of the fiber and the like. For example, a winding of a yarn, a blank, or the like wound around a cylindrical body, a fiber package called a so-called cheese or a cone, and a processing liquid are circulated. The method of treatment, or a method of circulating the yarn or the billet along with the treatment liquid, and performing treatment. As the former method, for example, there is a method in which a cheese dyeing machine is used, and a package yarn as a winding of the yarn is fixed to a spinning machine having a liquid jet and an absorption cylinder, and the treatment liquid is from the inside of the fixed cheese yarn. The scouring is performed by circulating to the outside and/or from the outside to the inside. In the case of scouring and bleaching of the yarn, such a cheese dyeing machine is usually used for scouring bleaching. Further, as the latter method, for example, a method using a liquid flow dyeing machine is utilized. As the scouring bleaching method as described above or the treating agent used in the treatment, for example, a scouring bleaching method and a treating agent as described below are disclosed.
日本特开昭 61- 41367号公报（专利文献 1)公开了漂白法， 其 中使用氨基烷基磷酸衍生物等与糖醇或醛糖酸等， 日本特开昭 62-32195号公报（专利文献 2)公开了将由特定羧酸构成的多羧酸 系聚合物与糖醇和 /或醛糖酸并用的漂白性改善剂， 日本特开平 8-81696号公报（专利文献 3)公开了多功能纤维助剂组合物，其中 以特定的比率使用特定的非离子表面活性剂、 特定的非离子表面 活性剂和烯键式不饱和磺酸或羧酸或其酸酐的反应产物、 水溶助 长性试剂等。  JP-A-61-41367 (Patent Document 1) discloses a bleaching method in which an aminoalkylphosphoric acid derivative or the like is used, and a sugar alcohol or an aldonic acid, etc., JP-A-62-32195 (Patent Document 2) A bleaching improver which combines a polycarboxylic acid-based polymer composed of a specific carboxylic acid and a sugar alcohol and/or an aldonic acid is disclosed. Japanese Laid-Open Patent Publication No. Hei 8-81696 (Patent Document 3) discloses a multifunctional fiber auxiliary. A composition in which a specific nonionic surfactant, a specific nonionic surfactant, and a reaction product of an ethylenically unsaturated sulfonic acid or a carboxylic acid or an anhydride thereof, a hydrotrope reagent, or the like is used in a specific ratio.
但是， 对这些精练漂白方法或处理剂而言， 在用筒子紗染色 机的纱线的精练漂白中， 存在产生精练漂白性不匀的情况， 即筒 子纱的内层、 中层和外层等不同层间的纱线中的再润湿性差和白 度差。 对于存在这样的精练漂白性不匀的纱线， 可能会产生后面 的加工工艺中试剂的调节繁杂或由该纱线得到的产品的品质不稳 定等问题。 另外， 所处理的紗线越细越容易产生这样的精练漂白 性不匀， 近年来， 用细纱线的加工在增加， 产生这样的精练漂白 性不匀的问题已日趋显著。  However, in these scouring bleaching methods or treating agents, in the scouring and bleaching of the yarn of the cheese dyeing machine, there is a case where the scouring unevenness is generated, that is, the inner layer, the middle layer and the outer layer of the cheese yarn are different. Poor rewet in the yarn between the layers and poor whiteness. In the case of such a yarn having a refining and unevenness in bleaching, there may be problems such as troublesome adjustment of the reagents in the subsequent processing process or unstable quality of the product obtained from the yarn. Further, the finer the yarn to be treated, the more likely it is to cause such scouring unevenness. In recent years, the processing of fine yarns has increased, and the problem of such scouring unevenness has become increasingly remarkable.
因此， 期望有实现精练漂白性优异、 且可抑制精练漂白性不 匀的精练漂白的方法或处理剂。  Therefore, it is desired to have a method or treatment agent which is excellent in scouring bleaching property and can suppress scouring bleaching of scouring bleaching unevenness.
专利文献 1: 日本特开昭 61- 41367号公 4艮  Patent Document 1: Japanese Special Open No. 61-41367
专利文献 2: 日本特开昭 62- 32195号公艮  Patent Document 2: JP-A-62-32195
专利文献 3: 日本特开平 8-81696号公报 发明内容  Patent Document 3: Japanese Laid-Open Patent Publication No. 8-81696 SUMMARY OF INVENTION
发明要解决的问题 本发明是鉴于上述现有技术具有的问题而完成的， 其目的在 于， 提供精练漂白助剂及精练漂白方法， 其可以实现精练漂白性 优异、 且在进行筒子纱或锥形筒丝等纤维卷装的精练漂白的情形 下可抑制纤维卷装的精练漂白性不匀的间歇式精练漂白。 Problems to be solved by the invention The present invention has been made in view of the problems of the prior art described above, and an object thereof is to provide a scouring bleaching aid and a scouring and bleaching method which can achieve excellent scouring bleaching property and carry out fiber winding such as cheese yarn or tapered wire In the case of scouring bleaching, the batch scouring bleaching of the scouring unevenness of the fiber package can be suppressed.
为了解决上述课题， 本发明人反复进行了深入研究， 结果发 现， 通过以规定的比率组合使用特定的化合物， 可以实现精练漂 白性优异、 且在进行筒子纱或锥形筒丝等纤维卷装的精练漂白情 形下可抑制纤维卷装的精练漂白性不匀的间歇式精练漂白， 基于 该见解完成了本发明。  In order to solve the problem, the present inventors have conducted intensive studies, and as a result, it has been found that by using a specific compound in combination at a predetermined ratio, it is possible to achieve excellent refining bleachability and to perform fiber wrapping such as cheese or tapered wire. The present invention has been completed based on this finding in the case of scouring and bleaching in the case of scouring and bleaching, which suppresses the scouring unevenness of the fiber package.
即， 本发明提供精练漂白助剂， 其特征在于， 含有下述 (A) ~ (D)成分, 且（A)成分和（B)成分的质量比为 80: 20 ~ 30: 70。  That is, the present invention provides a scouring bleaching aid comprising the following components (A) to (D), and the mass ratio of the component (A) to the component (B) is 80: 20 to 30: 70.
(A)选自由下述通式（1)所示的醛糖酸、 其盐、 其内酯和由下 述通式（2)所示的糖醇中的 1种以上，  (A) one or more selected from the group consisting of aldonic acid represented by the following formula (1), a salt thereof, a lactone thereof, and a sugar alcohol represented by the following formula (2).
CH20H (CHOH) X00H (1) CH 2 0H (CHOH) X00H (1)
(式（1)中， m表示 2 ~ 6的整数。 ）  (In the formula (1), m represents an integer of 2 to 6.)
CH20H (CHOH) nCH20H (2) CH 2 0H (CHOH) n CH 2 0H (2)
(式（2)中， n表示 2 ~ 6的整数。 ）  (In the formula (2), n represents an integer of 2 to 6.)
(B)以含羧基单体为必需单体的聚合物和 /或其盐  (B) a polymer having a carboxyl group-containing monomer as an essential monomer and/or a salt thereof
(C)有机膦酸和 /或其盐  (C) an organic phosphonic acid and/or a salt thereof
(D)选自如下所述的加成物中的 1种以上：  (D) One or more selected from the group consisting of the following additives:
一元醇、 二醇或酚类的氧化乙烯加成物， 其分子中具有量为 65 ~ 85质量％的亚乙基氧基；  An ethylene oxide adduct of a monohydric alcohol, a diol or a phenol having an ethyleneoxy group in an amount of from 65 to 85% by mass in the molecule;
一元醇、二醇或酚类的碳数 2 ~ 4的氧化烯的共聚加成物， 其 分子中具有量为 45 ~ 70质量％的亚乙基氧基，  a copolymerized product of an alkylene oxide having 2 to 4 carbon atoms of a monohydric alcohol, a diol or a phenol, and having an ethyleneoxy group in an amount of 45 to 70% by mass in the molecule,
伯胺或仲胺的碳数 2 ~ 4 的氧化烯加成物， 分子中具有量为 55 ~ 70质量％的亚乙基氧基。  The alkylene oxide adduct of a primary or secondary amine having 2 to 4 carbon atoms and having an ethyleneoxy group in an amount of 55 to 70% by mass.
本发明的精练漂白助剂可用于间歇式精练漂白。 本发明的精 练漂白助剂用于精练或漂白的情形下， 可以实现精练性或漂白性 优异、 且精练对象为筒子纱或锥形筒丝等纤维卷装的情形下可抑 制纤维卷装的精练性不匀或漂白性不匀的精练或漂白。 另外， 本 发明的精练漂白助剂用于同时进行精练和漂白的处理的情形下， 可以实现精练性及漂白性优异、 且精练及漂白对象为筒子纱或锥 形筒丝等纤维卷装的情形下可抑制纤维卷装的精练性及漂白性不 匀的精练及漂白。 The scouring bleaching aid of the present invention can be used in batch scouring bleaching. The scouring bleaching aid of the present invention can be used for scouring or bleaching, and can achieve scouring or bleaching. In the case of a fiber package such as a cheese yarn or a tapered wire which is excellent and refined, the scouring or bleaching of the fiber package can be suppressed from being uneven or bleaching unevenness. Further, in the case where the scouring bleaching aid of the present invention is used for simultaneous scouring and bleaching treatment, it is possible to achieve scouring and bleaching properties, and to refine and bleach the object into a fiber package such as a cheese yarn or a tapered wire. The scouring and bleaching of the fiber package can be suppressed and the bleaching unevenness can be suppressed.
本发明还提供精练漂白方法， 其是在含有下述 (A) ~ (D)成分 的浴中进行处理的精练漂白方法， 其特征在于， 处理浴中的（A) 成分和 (B)成分的质量比为 80: 20 ~ 30: 70。  The present invention also provides a scouring bleaching method which is a scouring bleaching method which is treated in a bath containing the following components (A) to (D), characterized in that (A) component and (B) component in the treatment bath are The mass ratio is 80: 20 ~ 30: 70.
(A)选自由下述通式（1)所示的醛糖酸、 其盐、 其内酯和由下 述通式（2)所示的糖醇中的 1种以上  (A) one or more selected from the group consisting of an aldonic acid represented by the following formula (1), a salt thereof, a lactone thereof, and a sugar alcohol represented by the following formula (2)
CH20H (CHOH) X00H (1) CH 2 0H (CHOH) X00H (1)
(式（1)中， m表示 2 ~ 6的整数。 ）  (In the formula (1), m represents an integer of 2 to 6.)
CH20H (CHOH) nCH20H (2) CH 2 0H (CHOH) n CH 2 0H (2)
(式（2)中， n表示 2 ~ 6的整数。 ）  (In the formula (2), n represents an integer of 2 to 6.)
(B)以含羧基单体为必需单体的聚合物和 /或其盐  (B) a polymer having a carboxyl group-containing monomer as an essential monomer and/or a salt thereof
(C)有机膦酸和 /或其盐  (C) an organic phosphonic acid and/or a salt thereof
(D)选自如下所述的加成物中的 1种以上：  (D) One or more selected from the group consisting of the following additives:
一元醇、 二醇或酚类的氧化乙烯加成物， 其分子中具有量为 65 ~ 85质量％的亚乙基氧基，  An ethylene oxide adduct of a monohydric alcohol, a diol or a phenol having an ethyleneoxy group in an amount of from 65 to 85% by mass in the molecule,
一元醇、二醇或酚类的碳数 2 ~ 4的氧化烯的共聚加成物， 其 分子中具有量为 45 ~ 70质量％的亚乙基氧基， 和  a copolymerized product of an alkylene oxide having 2 to 4 carbon atoms of a monohydric alcohol, a diol or a phenol, having an ethyleneoxy group in an amount of 45 to 70% by mass in the molecule, and
伯胺或仲胺的碳数 2 ~ 4的氧化烯加成物，其分子中具有量为 55 ~ 70质量％的亚乙基氧基。  The alkylene oxide adduct having a carbon number of 2 to 4 of a primary or secondary amine has an ethyleneoxy group in an amount of 55 to 70% by mass in the molecule.
本发明的精练漂白方法可以应用于间歇式的精练漂白。 本发 明的精练漂白方法应用于精练或漂白的情形下， 可以实现精练性 或漂白性优异、 且精练对象为筒子纱或锥形筒丝等纤维卷装的情 形下可抑制纤维卷装的精练性不匀或漂白性不匀的精练。 另外， 本发明的精练漂白方法应用于同时进行精练和漂白的处理的情形 下， 可以实现精练性及漂白性优异、 且精练及漂白对象为筒子紗 或锥形筒丝等纤维卷装的情形下可抑制纤维卷装的精练性及漂白 性不匀的精练及漂白。 The scouring bleaching process of the present invention can be applied to batch scouring bleaching. The scouring bleaching method of the present invention can be used in the case of scouring or bleaching, and can achieve scouring property of the fiber package in the case where the scouring property or the bleaching property is excellent, and the scouring object is a fiber package such as a cheese yarn or a tapered wire. Uneven or uneven bleaching. In addition, The scouring bleaching method of the present invention can be suppressed in the case where the scouring and bleaching treatment are simultaneously performed, and the scouring property and the bleaching property are excellent, and the scouring and bleaching object is a fiber package such as a cheese yarn or a tapered wire. The scouring and bleaching of the fiber package is refined and bleached.
发明效果  Effect of the invention
根据本发明的精练漂白助剂或精练漂白方法， 通过应用于纤 维的间歇式精练漂白、 特别是纱线或坯料等的纤维被卷绕于圆筒 体的卷绕物的所谓筒子纱或锥形筒丝等纤维卷装的精练漂白， 可 以实现精练漂白性优异、 可抑制筒子纱或锥形筒丝等纤维卷装的 精练漂白性不匀的精练漂白。 具体实施方式  A scouring bleaching aid or a scouring bleaching method according to the present invention, a so-called cheese yarn or a cone which is wound around a winding of a cylindrical body by a fiber which is applied to intermittent scouring of fibers, in particular, a yarn or a blank. The scouring and bleaching of the fiber package such as the wire can be achieved by scouring and bleaching, which can suppress the scouring and uneven bleaching of the fiber package such as the cheese yarn or the tapered wire. detailed description
本发明的精练漂白助剂的特征在于，含有下述 (A) ~ (D)成分。  The scouring bleaching aid of the present invention is characterized by comprising the following components (A) to (D).
(A)选自由下述通式（1)所示的醛糖酸、 其盐、 其内酯和由下 述通式（2)所示的糖醇中的 1种以上  (A) one or more selected from the group consisting of an aldonic acid represented by the following formula (1), a salt thereof, a lactone thereof, and a sugar alcohol represented by the following formula (2)
CH20H (CHOH) X00H (1) CH 2 0H (CHOH) X00H (1)
(式（1)中， m表示 2 ~ 6的整数。 ）  (In the formula (1), m represents an integer of 2 to 6.)
CH20H (CHOH) nCH20H (2) CH 2 0H (CHOH) n CH 2 0H (2)
(式（2)中， n表示 2 ~ 6的整数。 ）  (In the formula (2), n represents an integer of 2 to 6.)
(B)以含羧基单体为必需单体的聚合物和 /或其盐  (B) a polymer having a carboxyl group-containing monomer as an essential monomer and/or a salt thereof
(C)有机膦酸和 /或其盐  (C) an organic phosphonic acid and/or a salt thereof
(D)选自如下所述的加成物中的 1种以上：  (D) One or more selected from the group consisting of the following additives:
一元醇、 二醇或酚类的氧化乙烯加成物， 其分子中具有量为 65 ~ 85质量％的亚乙基氧基，  An ethylene oxide adduct of a monohydric alcohol, a diol or a phenol having an ethyleneoxy group in an amount of from 65 to 85% by mass in the molecule,
一元醇、二醇或酚类的碳数 2 ~ 4的氧化烯的共聚加成物， 其 分子中具有量为 45 ~ 70质量％的亚乙基氧基， 和  a copolymerized product of an alkylene oxide having 2 to 4 carbon atoms of a monohydric alcohol, a diol or a phenol, having an ethyleneoxy group in an amount of 45 to 70% by mass in the molecule, and
伯胺或仲胺的碳数 2 ~ 4的氧化烯加成物，其分子中具有量为 55 ~ 70质量％的亚乙基氧基。 (A)成分中的酸糖酸为由下述通式（1)所示的物质。 The alkylene oxide adduct having a carbon number of 2 to 4 of a primary or secondary amine has an ethyleneoxy group in an amount of 55 to 70% by mass in the molecule. The acid sugar acid in the component (A) is a compound represented by the following formula (1).
CH20H (CHOH) X00H (1) CH 2 0H (CHOH) X00H (1)
上述式（1)中， m表示 2 ~ 6的整数。  In the above formula (1), m represents an integer of 2 to 6.
作为由上述式（1)所示的酪糖酸， 可列举例如： 赤糖酸、 核糖 酸、 阿拉伯糖酸、 木糖酸、 来苏糖酸、 阿洛糖酸、 阿卓糖酸、 葡 萄糖酸、 甘露糖酸、 古洛糖酸、 艾杜糖酸、 半乳糖酸、 太罗糖酸 等。  Examples of the tyrosic acid represented by the above formula (1) include erythroic acid, ribonic acid, arabinic acid, xylogonic acid, lysolic acid, aloponic acid, altrose acid, and gluconic acid. , mannonic acid, gulonic acid, iduronic acid, galactonic acid, teraloic acid, and the like.
对于（A)成分而言，另外也可以是上述酪糖酸被碱系化合物或 胺系化合物中和而得到的盐。作为这样的盐， 可列举钠盐、钾盐、 锂盐等碱金属盐， 镁盐、 钡盐等碱土金属盐， 以及， 氨盐、 单乙 醇胺盐、 二乙醇胺盐、 三乙醇胺盐等胺系化合物盐。  Further, the component (A) may be a salt obtained by neutralizing the above-mentioned tyrosic acid with an alkali compound or an amine compound. Examples of such a salt include an alkali metal salt such as a sodium salt, a potassium salt or a lithium salt, an alkaline earth metal salt such as a magnesium salt or a phosphonium salt, and an amine compound such as an ammonia salt, a monoethanolamine salt, a diethanolamine salt or a triethanolamine salt. salt.
对于（A)成分而言，进而也可以是上述酪糖酸利用同一分子内 的羟基和羧基的脱水缩合而生成的内酯。  Further, the component (A) may be a lactone produced by dehydration condensation of a hydroxy acid group and a carboxyl group in the same molecule.
(A)成分中的糖醇为由下述通式（2)所示的物质。  The sugar alcohol in the component (A) is a compound represented by the following formula (2).
CH20H (CHOH) nCH20H (2) CH 2 0H (CHOH) n CH 2 0H (2)
式（2)中， n表示 2 ~ 6的整数。  In the formula (2), n represents an integer of 2 to 6.
作为由上述式（2)所示的糖醇， 可列举例如： 赤藓糖醇、 苏糖 醇、 阿拉伯糖醇、 木糖醇、 核醣醇、 艾杜糖醇、 半乳糖醇、 葡萄 糖醇、 甘露醇、 山梨糖醇、 庚七醇、 鳄梨糖醇等。  Examples of the sugar alcohol represented by the above formula (2) include erythritol, threitol, arabitol, xylitol, ribitol, iditol, galactitol, glucose alcohol, and mannose. Alcohol, sorbitol, heptagon, avocado, and the like.
从精练漂白性更优异的观点考虑， （A)成分优选式（1)的 m为 2 - 4的酪糖酸或者其钠盐、其钾盐或其镁盐、或者式（2)的 n为 2 ~ 4的糖醇。  From the viewpoint of more excellent scouring bleaching property, the component (A) is preferably a tyrosonic acid wherein m of the formula (1) is 2 - 4 or a sodium salt thereof, a potassium salt thereof or a magnesium salt thereof, or n of the formula (2) 2 ~ 4 sugar alcohol.
(B)成分为以含羧基单体为必需单体进行聚合而得到的聚合 物和 /或其盐。  The component (B) is a polymer obtained by polymerizing a carboxyl group-containing monomer as an essential monomer and/or a salt thereof.
含羧基单体为具有羧基和不饱和键的单体，作为这样的单体， 可列举例如： 丙烯酸、 甲基丙烯酸、 马来酸、 富马酸、 衣康酸、 巴豆酸、 2-亚甲基戊二酸、 它们的盐及它们的酸酐等。 在这些单 体中， 从进一步抑制精练漂白性的不匀的观点考虑， 优选使用丙 烯酸、 甲基丙烯酸、 马来酸、 其盐、 其酸酐。 The carboxyl group-containing monomer is a monomer having a carboxyl group and an unsaturated bond, and examples of such a monomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and 2-methylene. A glutaric acid, a salt thereof, an acid anhydride thereof, and the like. Among these monomers, from the viewpoint of further suppressing the unevenness of the scouring bleaching property, it is preferred to use C. Alkenoic acid, methacrylic acid, maleic acid, a salt thereof, and an anhydride thereof.
对（B)成分的聚合物而言，可以是使 1种上述含羧基单体单独 聚合而得到的聚合物， 也可以是由 2种以上上述含羧基单体得到 的共聚物。  The polymer of the component (B) may be a polymer obtained by polymerizing one type of the carboxyl group-containing monomer alone, or may be a copolymer obtained from two or more kinds of the above-mentioned carboxyl group-containing monomers.
对（B)成分的聚合物而言，进而也可以是 1种以上上述含羧基 单体和可与其共聚的 1种以上单体的共聚物。 作为这样的可共聚 的单体， 没有特别限制， 可例举乙烯、 氯乙烯、 乙酸乙烯酯等乙 烯基系单体、 丙烯酰胺、 丙烯酸酯类、 甲基丙烯酸酯类等。 所使 用的丙烯酸酯类或甲基丙烯酸酯类也没有特别限制， 优选为具有 碳数 1 ~ 3的烃基的丙烯酸酯类或甲基丙烯酸酯类，该烃基也可以 具有羟基等取代基。 作为这样的丙烯酸酯类或甲基丙烯酸酯类， 可例举丙烯酸甲酯、 甲基丙烯酸甲酯、 丙烯酸乙酯、 甲基丙烯酸 乙酯、丙烯酸 2-羟基乙酯、甲基丙烯酸 2-羟基乙酯、丙烯酸丙酯、 甲基丙烯酸丙酯等。  Further, the polymer of the component (B) may be a copolymer of one or more kinds of the above-mentioned carboxyl group-containing monomer and one or more kinds of monomers copolymerizable therewith. The monomer which can be copolymerized is not particularly limited, and examples thereof include a vinyl monomer such as ethylene, vinyl chloride or vinyl acetate, an acrylamide, an acrylate or a methacrylate. The acrylate or methacrylate to be used is not particularly limited, and is preferably an acrylate or methacrylate having a hydrocarbon group having 1 to 3 carbon atoms, and the hydrocarbon group may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxy methacrylate. Ester, propyl acrylate, propyl methacrylate, and the like.
聚合物的重均分子量优选为 1000 ~ 20000、 更优选为 3000 ~ 15000、 特别优选为 4500 ~ 8000。 如果聚合物的重均分子量为上 述范围内， 则可充分抑制精练漂白性的不匀。 其中， 当重均分子 量超过 20000时， 有可能会导致不能充分根据情况抑制精练漂白 性的不匀或粘度过高而使操作性上产生问题。  The weight average molecular weight of the polymer is preferably from 1,000 to 20,000, more preferably from 3,000 to 15,000, particularly preferably from 4500 to 8,000. If the weight average molecular weight of the polymer is within the above range, the unevenness of the scouring bleaching property can be sufficiently suppressed. Among them, when the weight average molecular weight exceeds 20,000, there is a possibility that the unevenness of the scouring bleaching property or the excessive viscosity may not be sufficiently suppressed depending on the situation, which may cause problems in workability.
(B)成分的聚合物另外也可以是利用上述聚合物中的羧基与 碱或胺系化合物的中和而得到的盐。 作为那样的盐， 可例举： 钠 盐、 钾盐、 锂盐等碱金属盐， 镁盐、 钡盐等碱土金属盐， 以及， 氨盐、 单乙醇胺盐、 二乙醇胺盐、 三乙醇胺盐等胺系化合物盐等。  The polymer of the component (B) may be a salt obtained by neutralizing a carboxyl group and an alkali or an amine compound in the above polymer. Examples of such a salt include an alkali metal salt such as a sodium salt, a potassium salt or a lithium salt, an alkaline earth metal salt such as a magnesium salt or a phosphonium salt, and an amine such as an ammonia salt, a monoethanolamine salt, a diethanolamine salt or a triethanolamine salt. A compound salt or the like.
作为（B)成分的聚合物的制造方法， 没有特别限制， 可例举例 如目前公知的自由基聚合反应。 另外， （B)成分的聚合物也可以使 用市售品。  The method for producing the polymer of the component (B) is not particularly limited, and examples thereof include a conventionally known radical polymerization reaction. Further, a commercially available product can also be used as the polymer of the component (B).
作为自由基聚合反应没有特别限制，可以例举例如：在含羧基 单体和 /或其盐的水溶液中添加自由基聚合引发剂， 使其在 30 ~ 150X下加热反应 2 ~ 5小时的方法等。 这时， 在含羧基单体和 /或 其盐的水溶液中， 可以添加甲醇、 乙醇、 异丙醇等醇类或丙酮等 水溶性溶剂。 另外， 所使用的自由基聚合引发剂也没有特别限制， 可例举： 过硫酸鉀、 过硫酸钠、 过硫酸铵等过硫酸盐、 过硫酸盐 和亚硫酸氢钠等的组合形成的氧化还原系聚合引发剂、 过氧化氢、 水溶性偶氮系聚合引发剂等， 这些自由基聚合引发剂可以单独使 用 1种， 或者也可以并用 2种以上。 进而， 在自由基聚合时， 为 了调节聚合度， 也可以添加链转移剂（例如巯基乙酸辛酯）。 The radical polymerization reaction is not particularly limited, and for example, a radical polymerization initiator may be added to an aqueous solution of a carboxyl group-containing monomer and/or a salt thereof at 30 °. The method of heating the reaction at 150X for 2 to 5 hours, and the like. In this case, an alcohol such as methanol, ethanol or isopropyl alcohol or a water-soluble solvent such as acetone may be added to the aqueous solution of the carboxyl group-containing monomer and/or its salt. Further, the radical polymerization initiator to be used is not particularly limited, and examples thereof include redox formation of a combination of persulfate such as potassium persulfate, sodium persulfate or ammonium persulfate, persulfate and sodium hydrogen sulfite. The polymerization initiator, the hydrogen peroxide, the water-soluble azo polymerization initiator, and the like may be used alone or in combination of two or more. Further, in the case of radical polymerization, a chain transfer agent (for example, octyl thioglycolate) may be added in order to adjust the degree of polymerization.
(0成分为有机膦酸和 /或其盐。  (The component 0 is an organic phosphonic acid and/or a salt thereof.
作为有机膦酸， 可例举氨基多聚（亚烷基膦酸）、 亚烷基二胺 多聚（亚烷基膦酸）、 二亚烷基三胺多聚（亚烷基膦酸）、 羟基亚烷 基二膦酸、 多羧基链烷膦酸等。  The organic phosphonic acid may, for example, be an amino poly(alkylenephosphonic acid), an alkylene diamine poly(alkylenephosphonic acid) or a dialkylene triamine poly(alkylenephosphonic acid). Hydroxyalkylene diphosphonic acid, polycarboxyalkanephosphonic acid, and the like.
作为氨基多聚（亚烷基膦酸）， 可例举分子中的亚烷基膦酸结 构中的亚烷基的碳数为 1 ~ 3的氨基多聚 (亚烷基膦酸），作为那样 的氨基多聚（亚烷基膦酸）， 可例举例如： 氨基单（亚甲基膦酸）、 氨基二（亚甲基膦酸）、 氨基三（亚甲基膦酸）、 氨基单（亚乙基膦 酸）、 氨基二（亚乙基膦酸）、 氨基三（亚乙基膦酸)等。  The amino poly(alkylenephosphonic acid) may, for example, be an amino poly(alkylenephosphonic acid) having an alkylene group in the alkylene phosphonic acid structure of the molecule and having a carbon number of 1 to 3. The amino poly(alkylenephosphonic acid) may, for example, be an amino group (methylene phosphonic acid), an amino group (methylene phosphonic acid), an amino group (methylene phosphonic acid), or an amino group ( Ethylene phosphonic acid), aminobis(ethylenephosphonic acid), aminotris(ethylenephosphonic acid), and the like.
作为亚烷基二胺多聚（亚烷基膦酸）， 可例举分子中的亚烷基 二胺结构中的亚烷基的碳数为 2 ~ 6、亚烷基膦酸结构中的亚烷基 的碳数为 1 ~ 3的亚烷基二胺多聚（亚烷基膦酸），作为那样的亚烷 基二胺多聚（亚烷基膦酸），可例举例如： 乙二胺四（亚甲基膦酸）、 乙二胺四（亚乙基膦酸）、 己二胺四（亚甲基膦酸）等。  The alkylene diamine poly(alkylene phosphonic acid) may, for example, be an alkylene group in the alkylene diamine structure having a carbon number of 2 to 6 and an alkylene phosphonic acid structure. The alkylene diamine poly(alkylenephosphonic acid) having an alkyl group having 1 to 3 carbon atoms, and such an alkylene diamine poly(alkylenephosphonic acid) may, for example, be: Amine tetra (methylene phosphonic acid), ethylene diamine tetra (ethylene phosphonic acid), hexamethylene diamine tetra (methylene phosphonic acid), and the like.
作为二亚烷基三胺多聚（亚烷基膦酸）， 可例举分子中的二亚 烷基三胺结构中的亚烷基的碳数为 2 ~ 6、亚烷基膦酸结构中的亚 烷基的碳数为 1 ~ 3的二亚烷基三胺多聚（亚烷基膦酸），作为那样 的二亚烷基三胺多聚（亚烷基膦酸）， 可例举例如： 二亚乙基三胺 五（亚甲基膦酸）、 二 1 , 6 -亚己基三胺五（亚甲基膦酸)等。  The dialkylene triamine poly(alkylene phosphonic acid) may, for example, be an alkylene group having a carbon number of 2 to 6 in the dialkylene triamine structure in the molecule, and an alkylene phosphonic acid structure The alkylene group has a dialkylene triamine poly(alkylenephosphonic acid) having a carbon number of 1 to 3, and as such a dialkylene triamine poly(alkylenephosphonic acid), for example, For example: diethylene triamine penta (methylene phosphonic acid), di 1,6-hexylenetriamine penta (methylene phosphonic acid) and the like.
作为羟基亚烷基二膦酸，可例举碳数为 2 - 5的羟基亚烷基二 膦酸， 作为那样的羟基亚烷基二膦酸， 可例举例如： 羟基亚乙基 二膦酸、 羟基亚丙基二膦酸等。 The hydroxyalkylene diphosphonic acid may, for example, be a hydroxyalkylene group having 2 to 5 carbon atoms. Phosphonic acid, such a hydroxyalkylene diphosphonic acid may, for example, be hydroxyethylidene diphosphonic acid or hydroxypropylene diphosphonic acid.
作为多羧基链烷膦酸， 可例举直链烃基的碳数为 2 ~ 8、 羧基 数为 2 ~ 6的多羧基链烷膦酸，作为那样的多羧基链烷膦酸，可例 举例如： 1， 2， 4-三羧基丁烷- 2-膦酸、 1, 2, 4-三羧基己烷- 1-膦酸 等。  The polycarboxyalkanephosphonic acid may, for example, be a polycarboxyalkanephosphonic acid having a linear hydrocarbon group of 2 to 8 and a carboxyl group of 2 to 6. As such a polycarboxyalkanephosphonic acid, for example, for example, : 1, 2, 3-tricarboxybutane-2-phosphonic acid, 1, 2, 4-tricarboxyhexane- 1-phosphonic acid, and the like.
另外， 作为有机膦酸的盐， 可例举： 钠、 钾、 锂等的碱金属 盐； 镁、 钡等的碱土金属盐； 铵盐； 甲胺、 乙胺、 丙胺、 丁胺、 辛胺、 十二烷胺、 十六烷胺、 十八烷胺、 二甲胺、 二乙胺、 三乙 胺等有机胺盐； 单乙醇胺、 二乙醇胺、 三乙醇胺等链烷醇胺盐等。  Further, examples of the salt of the organic phosphonic acid include alkali metal salts such as sodium, potassium, and lithium; alkaline earth metal salts such as magnesium and barium; ammonium salts; methylamine, ethylamine, propylamine, butylamine, and octylamine. An organic amine salt such as dodecylamine, hexadecylamine, octadecylamine, dimethylamine, diethylamine or triethylamine; an alkanolamine salt such as monoethanolamine, diethanolamine or triethanolamine.
在有机膦酸及其盐中， 从可进一步抑制精练漂白性的不匀的 观点考虑，优选使用乙二胺四（亚甲基膦酸）、 乙二胺四（亚乙基膦 酸）、 二亚乙基三胺五（亚甲基膦酸）、 二亚乙基三胺五（亚乙基膦 酸）、 羟基亚乙基二膦酸及它们的盐， 进而， 更优选二亚乙基三胺 五（亚甲基膦酸）、 羟基亚乙基二膦酸及其盐。  Among the organic phosphonic acids and salts thereof, ethylenediaminetetrakis (methylenephosphonic acid), ethylenediaminetetrakis (ethylenephosphonic acid), and the like are preferably used from the viewpoint of further suppressing the unevenness of the scouring bleaching property. Ethylene triamine penta (methylene phosphonic acid), diethylene triamine penta (ethylene phosphonic acid), hydroxyethylidene diphosphonic acid and salts thereof, and more preferably diethylene trisole Amine penta (methylene phosphonic acid), hydroxyethylidene diphosphonic acid and salts thereof.
(D)成分中的一元醇、二醇或酚类的氧化乙烯加成物的分子中 具有量为 65 ~ 85质量％的亚乙基氧基。 当分子中的亚乙基氧基量 低于 65质量％时， 可能会使精练漂白性不充分或不能充分抑制精 练漂白性不匀。另一方面，当分子中的亚乙基氧基量超过 85质量0 /。 时， 不能充分作用于夹杂物， 同时不能使作为精练漂白对象物的 纤维充分浸透， 可能使精练漂白性不充分或不能充分抑制精练漂 白性不匀。 从精练漂白性更优异、 进一步抑制精练漂白性不匀的 观点考虑， 分子中的亚乙基氧基量优选为 65 ~ 80质量％、 更优选 为 65 ~ 70质量％。 The ethylene oxide adduct of a monohydric alcohol, a diol or a phenol in the component (D) has an ethyleneoxy group in an amount of from 65 to 85% by mass. When the amount of the ethyleneoxy group in the molecule is less than 65% by mass, the scouring bleaching property may be insufficient or the scouring unevenness of the scouring may not be sufficiently suppressed. On the other hand, when the amount of ethyleneoxy groups in the molecule exceeds 85 mass % . At the same time, the inclusions are not sufficiently acted on, and at the same time, the fibers which are the objects of the scouring and bleaching are not sufficiently impregnated, and the scouring bleaching property may be insufficient or the scouring unevenness may not be sufficiently suppressed. The amount of ethyleneoxy group in the molecule is preferably 65 to 80% by mass, and more preferably 65 to 70% by mass, from the viewpoint of further improving the refining bleaching property and further suppressing the unevenness of the polishing bleaching property.
对于一元醇或二醇而言， 可以是直链状也可以是支链状， 可 以是饱和醇也可以是不饱和醇， 另外， 也可以是像苄醇等那样在 脂肪族烃基上有作为取代基的苯基的醇。 从更容易获得的观点考 虑， 作为一元醇或二醇， 优选碳数 8 ~ 22的脂肪族一元醇或碳数 2 - 12的脂肪族二醇。 The monohydric alcohol or the diol may be linear or branched, may be a saturated alcohol or an unsaturated alcohol, or may be substituted on an aliphatic hydrocarbon group like benzyl alcohol or the like. a phenyl alcohol. From the viewpoint of easier availability, as a monohydric alcohol or a diol, an aliphatic monohydric alcohol or a carbon number of 8 to 22 carbon atoms is preferred. 2 - 12 aliphatic diols.
作为所述碳数 8 ~ 22的脂肪族一元醇， 可例举例如： 辛醇、 壬醇、 癸醇、 十二烷醇、 十三烷醇、 十四烷醇、 十五烷醇、 十六 烷醇、 十七烷醇、 十八烷醇、 十九烷醇、 二十烷醇、 二十一烷醇、 二十二烷醇等。其中，从更容易得到的观点考虑，更优选碳数 10 - 16的脂肪族一元醇。  As the aliphatic monohydric alcohol having 8 to 22 carbon atoms, for example, octanol, decyl alcohol, decyl alcohol, dodecanol, tridecyl alcohol, tetradecanol, pentadecyl alcohol, and hexadecane may be mentioned. Alkanol, heptadecyl alcohol, stearyl alcohol, nonadecanol, eicosyl alcohol, diundecyl alcohol, dodecanol and the like. Among them, from the viewpoint of easier availability, an aliphatic monohydric alcohol having 10 to 16 carbon atoms is more preferable.
另外， 作为上述碳数 2 ~ 12的脂肪族二醇， 可例举例如： 乙 二醇、 丙二醇（1, 2-丙二醇）、 1, 3-丙二醇、 丁二醇、 戊二醇、 己 二醇、 1 , 10 -癸二醇、 十二烷二醇等。  Further, examples of the aliphatic diol having 2 to 12 carbon atoms include ethylene glycol, propylene glycol (1,2-propylene glycol), 1, 3-propanediol, butanediol, pentanediol, and hexanediol. 1, 10 - decanediol, dodecanediol, and the like.
酚类是具有 1个以上作为羟基的酚性羟基的酚类， 具有该酚 性羟基的芳香族环由碳数 1 ~ 4的烷基、苯基或碳数 8 - 30的芳烷 基等烃基取代。 从容易获得的观点考虑， 作为那样的酚类， 优选 为苯酚、 烷基苯酚、 苯基苯酚、 芳烷基苯酚， 其中， 优选为苯酚、 使苯酚加成苯乙烯而成的单苯乙烯化苯酚或多苯乙烯化苯酚， 进 而， 更优选单苯乙烯化苯酚、 二苯乙烯化苯酚、 三苯乙烯化苯酚。  The phenol is a phenol having one or more phenolic hydroxyl groups as a hydroxyl group, and the aromatic ring having the phenolic hydroxyl group is a hydrocarbon group such as an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group having 8 to 30 carbon atoms. Replace. From the viewpoint of easy availability, such a phenol is preferably a phenol, an alkylphenol, a phenylphenol or an aralkylphenol. Among them, a phenol and a monostyrenated phenol obtained by adding phenol to styrene are preferable. Further, polystyrenated phenol, more preferably monostyrenated phenol, distyrylated phenol or tristyrenated phenol.
另外，对于氧化乙烯加成物中的氧化乙烯的平均加成摩尔数， 可利用一元醇、 二醇或酚类的种类适当调节以使分子中的亚乙基 氧基量达到目标， 但从容易制造而且精练漂白性更优异、 进一步 抑制精练漂白性不匀的观点考虑，优选其为 5 ~ 50、更优选为 5 ~ 35。  Further, the average addition mole number of ethylene oxide in the ethylene oxide adduct may be appropriately adjusted by using a type of monohydric alcohol, a diol or a phenol to achieve an ethylene oxide amount in the molecule, but it is easy to It is preferably from 5 to 50, more preferably from 5 to 35, from the viewpoint of being more excellent in the production and refining of the bleaching property and further suppressing the unevenness of the polishing bleaching property.
(D)成分中的一元醇、 二醇或酚类的碳数 2 ~ 4的氧化烯的共 聚加成物的分子中具有量为 45 ~ 70质量％的亚乙基氧基。 当分子 中的亚乙基氧基量低于 45质量％时， 可能会使精练漂白性不充分 或不能充分抑制精练漂白性不匀。 另一方面， 当分子中的亚乙基 氧基量超过 70质量％时， 不会充分作用于夹杂物， 同时不能使作 为精练漂白对象物的纤维充分浸透， 可能使精练漂白性不充分或 不能充分抑制精练漂白性不匀。 从精练漂白性更优异、 进一步抑 制精练漂白性不匀的观点考虑， 分子中的亚乙基氧基量优选为 50 ~ 70质量％、 更优选为 55 ~ 65质量％。 The copolymerized adduct of the alkylene oxide having 2 to 4 carbon atoms of the monohydric alcohol, the diol or the phenol in the component (D) has an ethyleneoxy group in an amount of 45 to 70% by mass. When the amount of the ethyleneoxy group in the molecule is less than 45% by mass, the scouring bleaching property may be insufficient or the scouring unevenness of the scouring may not be sufficiently suppressed. On the other hand, when the amount of the ethyleneoxy group in the molecule exceeds 70% by mass, the inclusions are not sufficiently acted on, and the fibers which are the object of scouring and bleaching are not sufficiently impregnated, and the scouring bleaching property may be insufficient or impossible. Sufficient bleaching unevenness is sufficiently suppressed. The amount of ethyleneoxy group in the molecule is preferably from the viewpoint of further improving the bleaching property and further suppressing the unevenness of the scouring bleaching property. 50 to 70% by mass, more preferably 55 to 65% by mass.
一元醇、 二醇或酚类为与上述同样的物质。  The monohydric alcohol, the diol or the phenol is the same as described above.
作为碳数 3或 4的氧化烯， 可例举氧化丙烯、 氧化丁烯等。 其中， 从精练漂白性更优异、 可进一步抑制精练漂白性不匀的观 点考虑， 更优选氧化丙烯。  The alkylene oxide having 3 or 4 carbon atoms may, for example, be propylene oxide or butylene oxide. Among them, propylene oxide is more preferable from the viewpoint that the scouring bleaching property is more excellent and the scouring bleaching unevenness can be further suppressed.
对于氧化烯的加成方式， 可以是嵌段加成， 也可以是无规加 成。  The addition method of the alkylene oxide may be a block addition or a random addition.
另外， 对于氧化烯的总平均加成摩尔数， 可利用一元醇、 二 醇或酚类的种类适当调节以使分子中的亚乙基氧基量达到目标， 从容易制造而且精练漂白性更优异、 进一步抑制精练漂白性不匀 的观点考虑， 优选为 5 ~ 40。 进而， 在氧化乙烯和氧化丙烯的共 聚加成物的情况下， 氧化丙烯的平均加成摩尔数优选为 1 ~ 4、 更 优选为 1 ~ 3。  Further, the total average addition mole number of the alkylene oxide can be appropriately adjusted by the type of the monohydric alcohol, the diol or the phenol to achieve the target of the ethyleneoxy group in the molecule, and is easy to manufacture and more excellent in the bleaching property. Further, from the viewpoint of further suppressing the unevenness of the scouring bleaching property, it is preferably 5 to 40. Further, in the case of a copolymerized product of ethylene oxide and propylene oxide, the average number of moles of propylene oxide added is preferably from 1 to 4, more preferably from 1 to 3.
(D)成分中的伯胺或仲胺的碳数 2 ~ 4的氧化烯加成物的分子 中具有的亚乙基氧基量为 55 ~ 70质量％。 当分子中的亚乙基氧基 量低于 55质量％时， 可能会使精练漂白性不充分或不能充分抑制 精练漂白性不匀。 另一方面， 当分子中的亚乙基氧基量超过 70 质量％时，无法充分作用于夹杂物， 同时无法使作为精练漂白对象 物的纤维充分浸透， 可能会使精练漂白性不充分或不能充分抑制 精练漂白性不匀。 从精练漂白性更优异、 可进一步抑制精练漂白 性不勾的观点考虑，分子中的亚乙基氧基量优选为 60 ~ 65质量％。  The amount of the ethyleneoxy group in the molecule of the alkylene oxide adduct having 2 to 4 carbon atoms of the primary or secondary amine in the component (D) is 55 to 70% by mass. When the amount of ethyleneoxy group in the molecule is less than 55 mass%, the scouring bleaching property may be insufficient or the scouring unevenness of bleaching may not be sufficiently suppressed. On the other hand, when the amount of the ethyleneoxy group in the molecule exceeds 70% by mass, the inclusions are not sufficiently acted on, and the fibers which are the objects of the scouring and bleaching are not sufficiently impregnated, and the scouring bleaching property may be insufficient or impossible. Sufficient bleaching unevenness is sufficiently suppressed. The amount of ethyleneoxy group in the molecule is preferably from 60 to 65 mass% from the viewpoint that the refining bleaching property is more excellent and the refining bleaching property can be further suppressed.
对于伯胺或仲胺中的烃基而言， 可以是直链状也可以是支链 状， 可以是饱和脂肪族烃基也可以是不饱和脂肪族烃基。 从容易 获得的观点考虑，脂肪族烃基的碳数优选为 8 ~ 22、更优选为 12 ~ 20。 进而， 从精练漂白性更优异、 进一步抑制精练漂白性不匀的 观点考虑， 在伯胺或仲胺中， 优选伯胺， 作为那样的伯胺， 可例 举辛胺、 十二烷胺、 十八烷胺、 硬脂胺等。  The hydrocarbon group in the primary or secondary amine may be linear or branched, and may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably from 8 to 22, more preferably from 12 to 20, from the viewpoint of availability. Further, from the viewpoint of further improving the refining bleaching property and further suppressing the unevenness of the scouring bleaching property, a primary amine is preferable among the primary or secondary amines, and as such a primary amine, octylamine, dodecylamine, and ten are exemplified. Octaamine, stearylamine, and the like.
另外， 作为碳数 3或 4的氧化烯， 可例举氧化丙烯、 氧化丁 烯等。 Further, examples of the alkylene oxide having 3 or 4 carbon atoms include propylene oxide and butyl oxide. Alkene and the like.
对于碳数 2 ~ 4的氧化烯的加成方式，可以是氧化乙烯的单独 加成，也可以是氧化乙烯和碳数为 3的氧化烯和 /或碳数为 4的氧 化烯的嵌段或无规加成。 从精练漂白性更优异、 进一步抑制精练 漂白性不勾的观点考虑， 加成方式优选为氧化乙烯的单独加成或 氧化乙烯和氧化丙烯的无规或嵌段加成， 更优选为氧化乙烯的单 独加成。  The addition method of the alkylene oxide having 2 to 4 carbon atoms may be a single addition of ethylene oxide, or may be a block of ethylene oxide and an alkylene oxide having 3 carbon atoms and/or an alkylene oxide having 4 carbon atoms or Random bonus. The addition mode is preferably a single addition of ethylene oxide or a random or block addition of ethylene oxide and propylene oxide, more preferably ethylene oxide, from the viewpoint of further improving the scouring bleaching property and further suppressing the scouring bleaching property. Addition separately.
氧化烯的总平均加成摩尔数可利用伯胺或仲胺的种类适当调 节以使分子中的亚乙基氧基量达到目标， 从容易制造而且精练漂 白性更优异、 可进一步抑制精练漂白性不勾的观点考虑， 优选为 4 - 35, 更优选为 7 ~ 15。  The total average addition mole number of the alkylene oxide can be appropriately adjusted by the type of the primary or secondary amine so that the amount of ethyleneoxy group in the molecule can be achieved, and it is easy to manufacture and the bleaching property is more excellent, and the scouring bleaching property can be further suppressed. From the viewpoint of no-hook, it is preferably 4 - 35, more preferably 7 - 15.
作为（D)成分， 在上述加成物中， 从精练漂白性更优异、 可进 一步抑制精练漂白性不勾的观点考虑， 优选一元醇的氧化乙烯加 成物、 一元醇的碳数 2 ~ 4 的氧化烯的共聚加成物或伯胺的碳数 2 ~ 4的氧化烯加成物。  The component (D) is preferably an ethylene oxide adduct of a monohydric alcohol or a carbon number of a monohydric alcohol in the above-mentioned adduct from the viewpoint of further improving the scouring bleaching property and further suppressing the scouring bleaching property. A copolymerized adduct of an alkylene oxide or an alkylene oxide adduct having a carbon number of 2 to 4 of a primary amine.
在本发明的精练漂白助剂中， 可以是使（A) - (D)成分含有在 单一试剂中而由单一试剂构成的精练漂白助剂，也可以是使 (A) ~ (D)成分分开含有在多个试剂中而由这些多个试剂构成的精练漂 白助剂。 构成剂数可根据设备等处理工厂的情况等适当调节。 使 (A) ~ (D)成分分开含有在多个试剂中时可以任意选择组合，另外， 也可以使 1种成分分开含有在 2以上的试剂中。  In the scouring bleaching aid of the present invention, the (A) - (D) component may be a scouring bleaching aid comprising a single agent in a single reagent, or may be a component of (A) to (D). A scouring bleaching aid comprising a plurality of reagents and comprising a plurality of reagents. The number of constituents can be appropriately adjusted depending on the condition of the processing plant such as equipment. When the components (A) to (D) are separately contained in a plurality of reagents, they may be arbitrarily selected and combined, and one component may be contained in a reagent of 2 or more.
作为本发明的漂白精练助剂中的剂数， 从容易调节处理浴中 的（A) ~ (D)成分浓度且容易制造精练漂白助剂以及精练漂白助剂 容易输送的观点考虑， 优选为 1 ~ 4、 更优选为 2或 3。  The number of the agents in the bleaching and scouring aid of the present invention is preferably 1 from the viewpoint of easily adjusting the concentration of the components (A) to (D) in the treatment bath and facilitating the easy transportation of the scouring and bleaching aid. ~ 4, more preferably 2 or 3.
剂数为多个的情况下， 从试剂的稳定性更高的观点考虑， 对 于（D)成分而言， 优选不与（A) ~ (C)成分同时含有， 或者， 在其与 (A) ~ (C)成分同时含有的情况下， 仅与（A) ~ (C)成分的任意 1种 成分同时含有。 本发明的精练漂白助剂中的（A)成分和（B)成分的质量比为 80: 20 - 30: 70» 当（A)及（B)成分的质量比为上述范围外时， 可能 得不到充分的精练漂白性且不能充分抑制精练漂白性不匀。 When the number of the components is plural, it is preferable that the component (D) is not contained together with the components (A) to (C) from the viewpoint of higher stability of the reagent, or (A) When the (C) component is contained at the same time, it is contained only in combination with any one of the components (A) to (C). The mass ratio of the component (A) to the component (B) in the scouring bleaching aid of the present invention is 80: 20 - 30: 70» When the mass ratio of the components (A) and (B) is outside the above range, Not enough scouring bleaching ability and insufficient suppression of scouring bleaching unevenness.
本发明的精练漂白助剂中的（A)及（B)成分的总量与（C)成分 或（D)成分之比没有特别限制，从容易调节为后述的处理浴中的适 当的（A) ~ (D)成分之比的观点考虑，试剂中的各成分相对（A) - (D) 成分总量的比例优选： （A)及（B)成分的总量为 10 ~ 60质量％、 (C) 成分为 3 ~ 10质量％、 （D)成分为 30 ~ 80质量％。 进而， 从容易调 节为处理浴中的更适当的（A) - (D)成分之比的观点考虑， 试剂中 的各成分相对（A) ~ (D)成分总量的比例优选： （A)及 (B)成分的总 量为 25 ~ 50质量％、 （C)成分为 3 ~ 8质量％、 （D)成分为 40 ~ 70 质量％。  The ratio of the total amount of the components (A) and (B) to the component (C) or the component (D) in the scouring bleaching aid of the present invention is not particularly limited, and is easily adjusted to be suitable in a treatment bath to be described later ( A) The ratio of the component (D) to the ratio of the total amount of the components (A) to (D) in the reagent is preferably: The total amount of the components (A) and (B) is 10 to 60% by mass. (C) The component is 3 to 10% by mass, and the component (D) is 30 to 80% by mass. Further, from the viewpoint of easily adjusting the ratio of the more appropriate components (A) to (D) in the treatment bath, the ratio of each component in the reagent to the total amount of the components (A) to (D) is preferably: (A) The total amount of the component (B) is 25 to 50% by mass, the component (C) is 3 to 8 mass%, and the component (D) is 40 to 70 mass%.
各试剂中的（A) ~ (D)成分的配合量没有特别限制， 试剂可以 仅包含（A) ~ (D)成分， 也可以在试剂中添加目前用于精练漂白剂 的其他公知成分。  The amount of the components (A) to (D) in each reagent is not particularly limited, and the reagent may contain only the components (A) to (D), and other known components currently used for scouring the bleach may be added to the reagent.
作为那样的添加成分， 可例举例如： 水、 上述（A)成分以外的 一元醇、 二醇等溶剂或分散剂、 阴离子表面活性剂、 阳离子表面 活性剂、两性表面活性剂、上述 (D)以外的非离子表面活性剂等表 面活性剂、 消泡剂成分、 浸透剂成分等。  Examples of such an additive component include water, a solvent or a dispersing agent such as a monohydric alcohol or a diol other than the above component (A), an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the above (D). Surfactants such as nonionic surfactants other than nonionic surfactants, antifoaming agents, and penetrating agent components.
本发明的精练漂白助剂可应用于纤维的间歇式精练漂白。 在 将本发明的精练漂白助剂用于精练漂白时， 通常使本发明的精练 漂白助剂溶解或分散于设为对象的纤维的处理浴来使用。  The scouring bleaching aid of the present invention can be applied to batch scouring bleaching of fibers. When the scouring bleaching aid of the present invention is used for scouring bleaching, the scouring bleaching aid of the present invention is usually dissolved or dispersed in a treatment bath of the intended fiber.
本发明的精练漂白助剂添加在处理浴中， 以使（A)及（B)成分 的质量比为 80: 20 ~ 30: 70。 当（A)及（B)成分的质量比为上述范围 外时， 有可能得不到充分的精练漂白性且不能充分抑制精练漂白 性不匀。  The scouring bleaching aid of the present invention is added to the treatment bath so that the mass ratio of the components (A) and (B) is 80: 20 to 30: 70. When the mass ratio of the components (A) and (B) is outside the above range, sufficient scouring bleaching property may not be obtained and the scouring unevenness of the scouring may not be sufficiently suppressed.
另外， 处理浴中的（A)及 (B)成分的总量与（C)成分或（D)成分 之比没有特别限制， 从精练漂白性更优异、 进一步抑制精练漂白 性不匀的观点考虑， 优选在浴中添加本发明的精练漂白助剂以使 相对于（A) - (D)成分总量，（A)及（B)成分的总量为 10 ~ 60质量％、 (C)成分为 3 ~ 10质量％、 （D)成分为 30 ~ 80质量％。从精练漂白性 更优异、 进一步抑制精练漂白性不匀的观点考虑， 处理浴中的各 成分相对（A) ~ (D)成分总量的比例优选： （A)及 (B)成分的总量为 25 ~ 50质量％、 （C)成分为 3 ~ 8质量％、 （D)成分为 40 ~ 70质量％。 Further, the ratio of the total amount of the components (A) and (B) in the treatment bath to the component (C) or (D) is not particularly limited, and is excellent in refining bleaching property, and further suppresses scouring bleaching. From the viewpoint of unevenness, it is preferred to add the scouring bleaching aid of the present invention to the bath so that the total amount of the components (A) and (B) is 10 to 60 mass with respect to the total amount of the components (A) - (D). % and (C) components are 3 to 10% by mass, and (D) components are 30 to 80% by mass. The ratio of each component in the treatment bath to the total amount of (A) to (D) components is preferably from the viewpoint of further improving the bleaching property and further suppressing the unevenness of the scouring bleaching property: the total amount of the components (A) and (B) It is 25 to 50% by mass, (C) is 3 to 8% by mass, and (D) is 40 to 70% by mass.
对于本发明的精练漂白助剂向处理浴中的添加量， 优选使处 理浴中的（A) ~ (D)成分总量的浓度为 0. 05 ~ 15g/L的量。 处理浴 中的（A) ~ (D)成分总量的浓度低于 0. 05g/L时， 可能会使精练漂 白性不充分， 另一方面， 即使该浓度超过 15g/L来使用， 可能也 不会发生效果的进一步改善， 且成本方面不利。 从精练漂白性更 优异、进一步抑制精练漂白性不匀且成本方面更有利的观点考虑， 精练漂白助剂向处理浴中的添加量优选为使处理浴中的（A) - (D) 成分总量的浓度为 0. 5 ~ 5g/L的量。  The amount of the scouring agent to be added to the treatment bath of the present invention is preferably such that the concentration of the total amount of the components (A) to (D) in the treatment bath is from 0.05 to 15 g/L. When the concentration of the total amount of the components (A) to (D) in the treatment bath is less than 0.05 g/L, the scouring bleaching property may be insufficient. On the other hand, even if the concentration exceeds 15 g/L, it may be used. No further improvement in effect will occur, and the cost is unfavorable. The scouring bleaching aid is preferably added to the treatment bath in such a manner that the scouring bleaching agent is more excellent in the scouring bleaching property, further suppressing the scouring bleaching unevenness and being more advantageous in terms of cost, so that the total amount of (A) - (D) components in the treatment bath is The amount of the amount is 0.5 to 5 g / L.
本发明的精练漂白助剂可应用于天然纤维、 化纤纤维及它们 的混纺交编织纤维的间歇式精练漂白。作为天然纤维，可例举棉、 麻及羊毛等， 作为化纤纤维， 可例举： 人造丝或醋酸酯等再生纤 维素纤维、 及聚酯纤维或聚酰胺纤维、 丙烯腈系、 氨纶等合成纤 维。 作为它们的混纺交编织纤维， 可例举： 棉或麻与其他纤维（羊 毛、 聚酯、 聚酰胺纤维及丙烯腈系等）、 羊毛与其他纤维（聚酯、 聚酰胺及丙烯腈系等）、 聚酯纤维与其他纤维（人造丝、 醋酸酯、 聚酰胺、 丙烯腈系及氨纶等）、 聚酰胺纤维与其他纤维（人造丝、 醋酸酯、 丙烯腈系及氨纶等）的混纺交编织纤维。  The scouring bleaching aid of the present invention can be applied to batch scouring bleaching of natural fibers, chemical fibers, and blended woven fibers thereof. Examples of the natural fiber include cotton, hemp, and wool. Examples of the chemical fiber include regenerated cellulose fibers such as rayon or acetate, and synthetic fibers such as polyester fibers or polyamide fibers, acrylic fibers, and spandex. . Examples of the blended woven fibers thereof include cotton or hemp and other fibers (such as wool, polyester, polyamide fiber, and acrylonitrile), wool and other fibers (polyester, polyamide, and acrylonitrile). , blended polyester fiber with other fibers (rayon, acetate, polyamide, acrylonitrile, spandex, etc.), polyamide fiber and other fibers (rayon, acetate, acrylonitrile, spandex, etc.) .
精练漂白温度可根据被精练漂白的纤维适当调节，通常为 5 ~ 左右、 优选为 30 ~ 130 X左右。  The scouring bleaching temperature can be appropriately adjusted depending on the scoured fibers, and is usually about 5 to about 30 minutes.
作为用于精练漂白的机器， 可以使用目前用于间歇式精练漂 白的机器， 作为那样的机器， 可例举例如： 液流染色机或经轴染 色机、 筒子纱染色机、 奥氏染色机、 绳状染色机（wince dyeing machine ) 、 洗漆染色机等。 As a machine for scouring bleaching, a machine currently used for batch scouring bleaching can be used, and as such a machine, for example, a liquid dyeing machine or a warp beam dyeing machine, a cheese dyeing machine, an austenite dyeing machine, Rope dyeing machine Machine ), washing dyeing machine, etc.
处理浴的浴比没有特别限制， 通常为 1: 4 ~ 1: 40、 优选为 1: 6 - 1: 200 The bath ratio of the treatment bath is not particularly limited and is usually 1:4 to 1:40, preferably 1:6 to 1:20.
本发明的精练漂白方法的特征在于， 在含有下述（A) ~ (D)成 分的浴中进行处理。  The scouring bleaching method of the present invention is characterized in that it is treated in a bath containing the following components (A) to (D).
(Α)选自由下述通式（1)所示的醛糖酸、 其盐、 其内酯和由下 述通式（2)所示的糖醇中的 1种以上  (Α) one or more selected from the group consisting of aldonic acid represented by the following formula (1), a salt thereof, a lactone thereof, and a sugar alcohol represented by the following formula (2)
CH2OH (CHOH) XOOH (1) CH 2 OH (CHOH) XOOH (1)
(式（1)中， m表示 2 ~ 6的整数。 ）  (In the formula (1), m represents an integer of 2 to 6.)
CH2OH (CHOH) nCH20H (2) CH 2 OH (CHOH) n CH 2 0H (2)
(式（2)中， n表示 2 ~ 6的整数。 ）  (In the formula (2), n represents an integer of 2 to 6.)
(B)以含羧基单体为必需单体的聚合物和 /或其盐  (B) a polymer having a carboxyl group-containing monomer as an essential monomer and/or a salt thereof
(C)有机膦酸和 /或其盐  (C) an organic phosphonic acid and/or a salt thereof
(D)选自如下所述的加成物中的 1种以上：  (D) One or more selected from the group consisting of the following additives:
一元醇、 二醇或酚类的氧化乙烯加成物， 其分子中具有量为 65 ~ 85质量％的亚乙基氧基，  An ethylene oxide adduct of a monohydric alcohol, a diol or a phenol having an ethyleneoxy group in an amount of from 65 to 85% by mass in the molecule,
一元醇、二醇或酚类的碳数 2 ~ 4的氧化烯的共聚加成物， 其 分子中具有量为 45 ~ 70质量％的亚乙基氧基，  a copolymerized product of an alkylene oxide having 2 to 4 carbon atoms of a monohydric alcohol, a diol or a phenol, and having an ethyleneoxy group in an amount of 45 to 70% by mass in the molecule,
伯胺或仲胺的碳数 2 ~ 4的氧化烯加成物，其分子中具有量为 55 ~ 70质量％的亚乙基氧基。  The alkylene oxide adduct having a carbon number of 2 to 4 of a primary or secondary amine has an ethyleneoxy group in an amount of 55 to 70% by mass in the molecule.
本发明的精练漂白方法中的（A) ~ (D)成分为上述的物质。 在本发明的精练漂白方法中， 处理浴中的（A)及 (B)成分的质 量比为 80: 20 ~ 30: 70。 只要（A)及（B)成分的质量比在上述范围 内， 就可得到充分的精练漂白性， 而且可以充分抑制精练漂白性 不匀。  The components (A) to (D) in the scouring method of the present invention are those described above. In the scouring bleaching method of the present invention, the mass ratio of the components (A) and (B) in the treatment bath is 80: 20 to 30: 70. As long as the mass ratio of the components (A) and (B) is within the above range, sufficient refining bleaching properties can be obtained, and scouring bleaching unevenness can be sufficiently suppressed.
另外， 处理浴中的（A)及 (B)成分的总量与（C)成分或（D)成分 之比没有特别限制， 但从精练漂白性更优异、 进一步抑制精练漂 白性不匀的观点考虑， 在处理浴中， 相对（A) ~ (D)成分总量， 优 选含有（A)及（B)成分的总量为 10~60 质量％、 （C)成分为 3~10 质量％、 （D)成分为 30~80质量％。 从精练漂白性更优异、 可进一 步抑制精练漂白性不匀的观点考虑，处理浴中的各成分相对（A) ~ (D)成分总量的比例优选： （A)及（B)成分的总量为 25~50质量％、 (0成分为 3 ~ 8质量％、 (D)成分为 40 - 70质量％。 In addition, the ratio of the total amount of the components (A) and (B) to the component (C) or the component (D) in the treatment bath is not particularly limited, but the scouring bleaching property is more excellent, and the scouring bleaching property is further suppressed. Consider, in the treatment bath, the relative total amount of (A) ~ (D) components, excellent The total amount of the components (A) and (B) is preferably 10 to 60% by mass, the component (C) is 3 to 10% by mass, and the component (D) is 30 to 80% by mass. The ratio of each component in the treatment bath to the total amount of (A) to (D) components is preferably from the viewpoint of further improving the bleaching property and further suppressing the unevenness of the scouring bleaching property: the total of the components (A) and (B) The amount is 25 to 50% by mass, (0 is 3 to 8 mass%, and (D) is 40 to 70 mass%.
本发明的精练漂白方法中的处理浴中的（A) - (D)成分总量的 浓度优选为 0.05~15g/L。 处理浴中的（A) ~ (D)成分总量的浓度 低于 0.05g/L时， 可能会使精练漂白性不充分， 另一方面， 即使 该浓度超过 15g/L而使用 , 可能也不会发生效果的进一步改善， 且成本方面不利。 从精练漂白性更优异、 进一步抑制精练漂白性 不匀且成本方面更有利的观点考虑， 处理浴中的（A) ~ (D)成分总 量的浓度优选为 0.5~5g/L。  The concentration of the total amount of the components (A) to (D) in the treatment bath in the scouring method of the present invention is preferably 0.05 to 15 g/L. When the concentration of the total amount of the components (A) to (D) in the treatment bath is less than 0.05 g/L, the scouring bleaching property may be insufficient. On the other hand, even if the concentration exceeds 15 g/L, it may not be used. Further improvement in the effect will occur, and the cost is unfavorable. The concentration of the total amount of the components (A) to (D) in the treatment bath is preferably 0.5 to 5 g/L from the viewpoint that the refining bleaching property is more excellent, the scouring bleaching property is further suppressed, and the cost is more favorable.
本发明的精练漂白方法可应用于目前盛行的间歇式精练漂 白， 例如， 使用上述的机器， 可应用于上述的纤维的精练漂白。 实施例  The scouring bleaching method of the present invention can be applied to the intermittent scouring bleaching which is currently prevalent, for example, using the above-described machine, and can be applied to the scouring bleaching of the above-mentioned fibers. Example
以下， 利用实施例进一步说明本发明， 但本发明并不受这些 实施例的任何限制。  Hereinafter, the present invention will be further illustrated by the examples, but the present invention is not limited by these examples.
对于 70号棉单纱 1kg的筒子纱（卷绕密度 0.4g/cm3) ,使用筒 子纱染色机（ (林）日阪制作所社制、 LLC- 1/25), 用以下所示的组 成的处理浴， 以浴比为 1: 10,使处理液以流速 40L/分钟沿着从筒 子紗的内侧到外侧的方向循环， 通过如下工序进行精练漂白， 然 后， 在 ΙΟΟ 热风干燥 30分钟。 For the package yarn (winding density: 0.4 g/cm 3 ) of the No. 70 cotton single yarn, a cheese dyeing machine (manufactured by Risaka Manufacturing Co., Ltd., LLC-1/25) was used, and the composition shown below was used. The treatment bath was cycled at a bath ratio of 1:10, and the treatment liquid was circulated in the direction from the inner side to the outer side of the cheese yarn at a flow rate of 40 L/min, and scouring was carried out by the following procedure, followed by drying in a hot air for 30 minutes.
处理浴组成：  Treatment bath composition:
NaOH 1.6g/L  NaOH 1.6g/L
H2O2(30质量％水溶液） 4g/L H 2 O 2 (30% by mass aqueous solution) 4g/L
精练漂白助剂 lg/L  Refined bleaching aid lg/L
(将精练漂白助剂的组成示于表 1及 2) 工序： (The composition of the scouring bleaching aid is shown in Tables 1 and 2) Process:
使处理浴温度为 40 , 使处理液循环 10分钟后、 以 2 /分 钟升温至 110 。使处理液在 H O 循环 30分钟后，冷却至 进行排水。 然后， 在 80*€进行热水洗涤 10分钟， 进行排水。 添 加常温水， 加入 0. 2g/L过氧化氢中和剂（日华化学（株)社制、 商 品名： CROAKS E) , 使其循环 5分钟， 进行过氧化氢中和， 加入醋 酸的 80质量％水溶液 lg/L，使其循环 10分钟，进行 NaOH中和后， 进行排水， 在常温下进行水洗。  The treatment bath temperature was set to 40, and the treatment liquid was circulated for 10 minutes and then heated to 110 in 2/min. After the treatment liquid was circulated for 30 minutes in H O , it was cooled to drain. Then, hot water is washed at 80*€ for 10 minutes to drain. The normal temperature water was added, and 0. 2 g/L of a hydrogen peroxide neutralizer (manufactured by Nikko Chemical Co., Ltd., trade name: CROAKS E) was added, and the mixture was circulated for 5 minutes, neutralized with hydrogen peroxide, and added with acetic acid. The mass % aqueous solution lg/L was circulated for 10 minutes, neutralized with NaOH, drained, and washed with water at normal temperature.
精练漂白及干燥后， 在得到的处理好的筒子纱的上面， 将从 中心到外周的幅面沿半径方向分成 5等份， 分成最外层、 外层、 中层、 内层、 最内层， 从各层采取处理好的紗线。 将采取的处理 好的纱线安装在圆筒编织机 (针筒径 3. 5英寸、针根数 240根、英 光产业（株）社制、 NE450W)上以 1根给纱针织 40cm的筒针织物， 得到试样针织物。 对于将得到的圆筒针织物折叠 4次从而呈 8片 重叠状态的试样针织物， 通过以下方法测定白度和再湿润性， 进 行评价。  After scouring and drying, on the upper surface of the obtained treated cheese, the web from the center to the outer circumference is divided into five equal parts in the radial direction, and is divided into the outermost layer, the outer layer, the middle layer, the inner layer and the innermost layer. The treated yarns are taken from each layer. The processed yarn was attached to a cylinder knitting machine (a cylinder diameter of 3.5 inches, a number of needles of 240, and an NE450W manufactured by Ins. Co., Ltd.), and a knitting yarn of 40 cm was knitted with one yarn. The sample was obtained as a knitted fabric. The sample knitted fabric in which the obtained circular knitted fabric was folded four times to have eight overlapping states was measured for whiteness and rewet by the following method.
(再湿润性与再湿润性差）  (re-wetting and rewet)
在各层的试样针织物滴加水滴（0. 05mL) , 测定直至水滴浸透 的时间（浸透时间）， 比较各层的试样针织物的浸透时间。 将其结 果示于表 1及 2。 浸透时间越短、 离差越小表示再湿润性越好、 再湿润性差越小， 即精练漂白性良好、 可抑制精练漂白性不匀。  Water droplets (0.0 mL) were dropped on the sample knitted fabric of each layer, and the time until the water droplets permeated (the permeation time) was measured, and the permeation time of the sample knitted fabric of each layer was compared. The results are shown in Tables 1 and 2. The shorter the soaking time and the smaller the difference, the better the rewetting property and the smaller the rewetting property, that is, the refining bleaching property is good, and the scouring bleaching unevenness can be suppressed.
A: 所有层的试样针织物的浸透时间低于 1秒。  A: The sample knit of all layers has a soaking time of less than 1 second.
B:各层的试样针织物的浸透时间在 1 ~ 180秒的范围内分散。 C: 所有层的试样针织物的浸透时间为 180秒以上。  B: The permeation time of the sample knitted fabric of each layer was dispersed in the range of 1 to 180 seconds. C: The sample knit of all layers has a soaking time of 180 seconds or more.
(白度和白度差）  (whiteness and whiteness difference)
使用美能达（MINOLTA )测色仪 CM- 3700d, 在光源 D65、 视野 10度的条件下测定各层的试样针织物的白度。在各层的试样针织 物的白度中， 将最高白度及最低白度示于表 1及 2。 白度越高表 示精练漂白性越优异。 另外， 从最高白度中减去最低白度来定为 白度差。 白度差越小，表示筒子纱的精练漂白性不匀越得到抑制。 The whiteness of the sample knitted fabric of each layer was measured using a MINOLTA colorimeter CM-3700d under the conditions of a light source D65 and a field of view of 10 degrees. Among the whiteness of the sample knitted fabric of each layer, the highest whiteness and the lowest whiteness are shown in Tables 1 and 2. The higher the whiteness It shows that the scouring bleaching property is excellent. In addition, the whiteness is determined by subtracting the minimum whiteness from the highest whiteness. The smaller the whiteness difference, the more the scouring unevenness of the cheese yarn is suppressed.
[表 1] [Table 1]
Figure imgf000020_0001
Figure imgf000020_0001
EO表示氧化乙烯， PO表示氧化丙烯， 紧随 E0或 P0后面的（) 内的数值表示 E0或 P0的平均加成摩尔数。 EO represents ethylene oxide, PO represents propylene oxide, and the value in () immediately after E0 or P0 represents the average addition mole number of E0 or P0.
[表 2〗 [Table 2〗
精练漂白助剂的组成 (质量％)及评价结果  Composition of refined bleaching auxiliaries (% by mass) and evaluation results
Figure imgf000021_0001
Figure imgf000021_0001
表 2中， EO表示氧化乙烯， PO表示氧化丙烯， 紧随 E0或 P0 后面的 0内的数值表示 E0或 P0的平均加成摩尔数。  In Table 2, EO represents ethylene oxide, PO represents propylene oxide, and the value in 0 immediately after E0 or P0 represents the average addition mole number of E0 or P0.
如表 1及 2所示可知， 在使用实施例 1 ~ 9的本发明的精练 漂白助剂进行精练漂白的情况下， 与比较例 1 ~ 11相比， 精练漂 白性优异、 且可抑制筒子纱的精练漂白性不匀。 工业上的可利用性  As shown in Tables 1 and 2, in the case of the scouring bleaching using the scouring bleaching aid of the present invention of Examples 1 to 9, the scouring performance was excellent compared with Comparative Examples 1 to 11, and the cheese yarn was suppressed. The scouring and bleaching properties are uneven. Industrial availability
通过应用本发明的精练漂白助剂或精练漂白方法， 可以进行 可实现优异的精练漂白性的精练漂白。 另外， 将本发明的精练漂 白助剂或精练漂白方法应用于筒子纱或锥形筒丝等纤维卷装的精 练漂白时， 可以进行在实现优异精练漂白性的同时可抑制纤维卷 装的精练漂白性不匀的精练漂白。 因而， 可有助于精练漂白后的 纤维品质的稳定化。 By applying the scouring bleaching aid or the scouring method of the present invention, scouring bleaching which achieves excellent scouring bleaching can be carried out. In addition, the scouring of the present invention When the white auxiliaries or the scouring bleaching method is applied to the scouring and bleaching of a fiber package such as a cheese yarn or a tapered wire, it is possible to carry out scouring bleaching which can suppress the scouring unevenness of the fiber package while achieving excellent refining bleaching properties. Thus, it can contribute to the stabilization of the fiber quality after scouring.

Claims

权利要求 Rights request
1. 精练漂白助剂， 其特征在于， 含有下述 (A) ~ (D)成分， 且 (A)成分和 (B)成分的质量比为 80: 20 - 30: 70, 1. A scouring bleaching agent characterized by containing the following components (A) to (D), and the mass ratio of the component (A) to the component (B) is 80: 20 - 30: 70,
(A)选自由下述通式（1)所示的醛糖酸、 其盐、 其内酯和由下 述通式（2)所示的糖醇中的 1种以上，  (A) one or more selected from the group consisting of aldonic acid represented by the following formula (1), a salt thereof, a lactone thereof, and a sugar alcohol represented by the following formula (2).
CH20H (CHOH) mC00H (1) CH 2 0H (CHOH) m C00H (1)
式（1)中， m表示 2 ~ 6的整数，  In the formula (1), m represents an integer of 2 to 6,
CH20H (CHOH) nCH20H (2) CH 2 0H (CHOH) n CH 2 0H (2)
式（2)中， n表示 2 ~ 6的整数，  In the formula (2), n represents an integer of 2 to 6,
(B)以含羧基单体为必需单体的聚合物和 /或其盐，  (B) a polymer having a carboxyl group-containing monomer as an essential monomer and/or a salt thereof,
(C)有机膦酸和 /或其盐，  (C) an organic phosphonic acid and/or a salt thereof,
(D)选自如下所述的加成物中的 1种以上：  (D) One or more selected from the group consisting of the following additives:
一元醇、 二醇或酚类的氧化乙烯加成物， 其分子中具有量为 65 ~ 85质量％的亚乙基氧基；  An ethylene oxide adduct of a monohydric alcohol, a diol or a phenol having an ethyleneoxy group in an amount of from 65 to 85% by mass in the molecule;
一元醇、二醇或酚类的碳数 2 ~ 4的氧化烯的共聚加成物， 其 分子中具有量为 45 ~ 70质量％的亚乙基氧基， 以及  a copolymerized product of an alkylene oxide having 2 to 4 carbon atoms of a monohydric alcohol, a diol or a phenol, having an ethyleneoxy group in an amount of 45 to 70% by mass in the molecule, and
伯胺或仲胺的碳数 2 ~ 4的氧化烯加成物，其分子中具有量为 55 ~ 70质量％的亚乙基氧基。  The alkylene oxide adduct having a carbon number of 2 to 4 of a primary or secondary amine has an ethyleneoxy group in an amount of 55 to 70% by mass in the molecule.
2. 精练漂白方法， 其在含有下述 (A) ~ (D)成分的浴中进行处 理， 其特征在于， 处理浴中的（A)成分和（B)成分的质量比为 80: 20 - 30: 70, 2. A scouring bleaching method which is treated in a bath containing the following components (A) to (D), characterized in that the mass ratio of the component (A) to the component (B) in the treatment bath is 80: 20 - 30: 70,
(A)选自由下述通式（1)所示的醛糖酸、 其盐、 其内酯和由下 述通式（2)所示的糖醇中的 1种以上，  (A) one or more selected from the group consisting of aldonic acid represented by the following formula (1), a salt thereof, a lactone thereof, and a sugar alcohol represented by the following formula (2).
CH20H (CHOH) mC00H (1) CH 2 0H (CHOH) m C00H (1)
式（1)中， m表示 2 ~ 6的整数，  In the formula (1), m represents an integer of 2 to 6,
CH20H (CHOH) nCH20H (2) 式（2)中， n表示 2 ~ 6的整数， CH 2 0H (CHOH) n CH 2 0H (2) In the formula (2), n represents an integer of 2 to 6,
(B)以含羧基单体为必需单体的聚合物和 /或其盐，  (B) a polymer having a carboxyl group-containing monomer as an essential monomer and/or a salt thereof,
(C)有机膦酸和 /或其盐，  (C) an organic phosphonic acid and/or a salt thereof,
(D)选自如下所述的加成物中的 1种以上：  (D) One or more selected from the group consisting of the following additives:
一元醇、 二醇或酚类的氧化乙烯加成物， 其分子中具有量为 65 ~ 85质量％的亚乙基氧基，  An ethylene oxide adduct of a monohydric alcohol, a diol or a phenol having an ethyleneoxy group in an amount of from 65 to 85% by mass in the molecule,
一元醇、二醇或酚类的碳数 2 ~ 4的氧化烯的共聚加成物， 其 分子中具有量为 45 ~ 70质量％的亚乙基氧基，  a copolymerized product of an alkylene oxide having 2 to 4 carbon atoms of a monohydric alcohol, a diol or a phenol, and having an ethyleneoxy group in an amount of 45 to 70% by mass in the molecule,
伯胺或仲胺的碳数 2 ~ 4的氧化烯加成物，其分子中具有量为 55 ~ 70质量％的亚乙基氧基。  The alkylene oxide adduct having a carbon number of 2 to 4 of a primary or secondary amine has an ethyleneoxy group in an amount of 55 to 70% by mass in the molecule.
PCT/CN2012/071577 2012-02-24 2012-02-24 Agent and method for refining and bleaching WO2013123673A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86104895A (en) * 1985-08-05 1987-02-04 花王株式会社 Improved bleaching composition
US6200948B1 (en) * 1994-08-11 2001-03-13 Ciba Specialty Chemicals Corporation Multifunctional textile auxiliary formulations
CN101341241A (en) * 2005-12-28 2009-01-07 花王株式会社 Liquid detergent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86104895A (en) * 1985-08-05 1987-02-04 花王株式会社 Improved bleaching composition
US6200948B1 (en) * 1994-08-11 2001-03-13 Ciba Specialty Chemicals Corporation Multifunctional textile auxiliary formulations
CN101341241A (en) * 2005-12-28 2009-01-07 花王株式会社 Liquid detergent

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