WO2011111658A1 - Procédé de traitement de fibre cellulosique ou de produit en fibre cellulosique - Google Patents

Procédé de traitement de fibre cellulosique ou de produit en fibre cellulosique Download PDF

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Publication number
WO2011111658A1
WO2011111658A1 PCT/JP2011/055255 JP2011055255W WO2011111658A1 WO 2011111658 A1 WO2011111658 A1 WO 2011111658A1 JP 2011055255 W JP2011055255 W JP 2011055255W WO 2011111658 A1 WO2011111658 A1 WO 2011111658A1
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WIPO (PCT)
Prior art keywords
cellulosic fiber
cellulosic
fiber product
cellulose
group
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PCT/JP2011/055255
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English (en)
Japanese (ja)
Inventor
美也 由井
千晶 田中
恭資 丸山
忍 田畑
文明 山下
俊明 梅田
祥弘 笹田
Original Assignee
グンゼ株式会社
日華化学株式会社
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Application filed by グンゼ株式会社, 日華化学株式会社 filed Critical グンゼ株式会社
Priority to CN201180012950.0A priority Critical patent/CN102791922B/zh
Publication of WO2011111658A1 publication Critical patent/WO2011111658A1/fr

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Classifications

    • 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
    • D06M15/507—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • 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
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
    • D06M14/04—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives 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
    • D06M15/21—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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • 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
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

Definitions

  • the present invention relates to a method for treating cellulosic fibers or cellulosic fiber products capable of realizing high flexibility and washing durability, and cellulosic fibers or cellulosic fiber products.
  • Patent Document 1 discloses a washing method in which clothes are passed at high speed through a mixture of water and air having a cleaning effect without adding a detergent containing hydronium ions, hydroxyl ions, or the like.
  • this method requires a special washing machine, and there has been a report that the cleaning effect on dirt due to oily components such as sebum dirt is insufficient.
  • the inventors of the present application disclose a method of imparting a detergent-free washing function to a fiber or fiber product by applying a hydrophilic treatment to the fiber or fiber product in Patent Document 2.
  • the textile product obtained by such a method can obtain a cleaning effect almost the same as that using a detergent even when washing is performed without using a detergent, but the flexibility is reduced by the hydrophilic treatment. There was something to do.
  • the treated fiber product also has problems such as a decrease in flexibility due to washing.
  • the present invention has a function of obtaining a cleaning effect substantially equivalent to that obtained when a detergent is used even when a cellulosic fiber or a cellulosic fiber product is washed without using a detergent. It is an object of the present invention to provide a method for treating cellulosic fibers or cellulosic fiber products, and cellulosic fibers or cellulosic fiber products that can impart high flexibility and washing durability.
  • the present invention includes a step of subjecting a cellulose fiber or a cellulose fiber product to a hydrophilic treatment, and a cellulose fiber or a cellulose fiber product that has been subjected to a hydrophilic treatment, an ester finishing agent, and a carbodiimide crosslinking agent.
  • the ester finishing agent is produced by an esterification reaction of an oxidatively or acid-modified polyethylene with an ethylene oxide and / or propylene oxide adduct of an aliphatic alcohol or an aliphatic amine. It is the processing method of the cellulosic fiber or cellulosic fiber product containing an ester compound.
  • the present invention is described in detail below.
  • Examples of methods for improving the flexibility of cellulose fibers or cellulose fiber products that have been subjected to a hydrophilic treatment include silicone softeners, polyester softeners, polyamide softeners, polyurethane softeners, and polyethylene softeners.
  • silicone softeners polyester softeners, polyamide softeners, polyurethane softeners, and polyethylene softeners.
  • the present inventors have used a predetermined ester-based finish and a carbodiimide-based crosslinking agent in combination, and a step of crosslinking the cellulose-based fiber or the cellulose-based fiber product subjected to the hydrophilic treatment. It is found that a cellulosic fiber or a cellulosic fiber product is obtained, which has an excellent detergent-free washing function, is imparted with high flexibility, and is less likely to lose flexibility even after repeated washing, The present invention has been completed.
  • a step of subjecting the cellulosic fiber or cellulosic fiber product to a hydrophilic treatment is performed.
  • a detergent-free washing function can be imparted.
  • most of the stains that are a problem with cellulosic fibers or cellulosic fiber products are oily components including sebum stains, and by making the cellulosic fibers or cellulosic fiber products hydrophilic, the soil components and fibers This is considered to be due to the fact that the binding force of the ink becomes weak and the soil components can be peeled off only with water without using a surfactant.
  • contamination other than an oil-based component if washing was originally performed using a lot of water, it can peel, without using surfactant.
  • the detergent-free washing function means that even when washing is performed without using a detergent, it is possible to obtain substantially the same cleaning effect as when washing with a detergent. Is obtained when the cellulosic fiber or cellulosic fiber product that has been subjected to hydrophilic treatment by the method for treating cellulosic fiber or cellulosic fiber product of the present invention is washed without using a detergent. This means that the cellulosic fiber or cellulosic fiber product of the treatment is equivalent to the cleaning effect when the detergent is used for washing.
  • the cellulosic fiber or cellulosic fiber product to be processed is white
  • the cellulosic fiber or the cellulosic fiber that has been subjected to a hydrophilic treatment by the method for treating cellulosic fiber or cellulosic fiber product of the present invention or After the cellulosic fiber product is soiled and washed without using a detergent the amount of change in whiteness with the cellulosic fiber or the cellulosic fiber product before soiling stains the untreated cellulosic fiber or cellulosic fiber product. It means that it is within 110% of the amount of change in whiteness with the cellulosic fiber or cellulosic fiber product before washing after washing with a detergent.
  • the cellulosic fiber or cellulosic fiber product to be used is a colored product containing white, for example, the cellulosic fiber subjected to a hydrophilic treatment by the method for treating the cellulosic fiber or cellulosic fiber product of the present invention.
  • 10% oleic acid on fiber or cellulosic fiber product o. w. f. Gelatin 2.5% o. w. f.
  • the residual percentage of oleic acid after laundering and without washing without detergent was 10% oleic acid in the untreated textile.
  • w. f. Gelatin 2.5% o. w. f. It means that it is within 110% of the residual ratio (%) of oleic acid after laundering and washing with a detergent.
  • the cellulose-based fiber or the cellulose-based fiber product includes single fibers and products using single fibers.
  • the products using the single fibers include yarns such as cotton yarn and cotton blended yarn, and cotton fabric, for example. And products manufactured from yarn such as cotton sliver (bundle).
  • fibers other than the cellulose fiber mentioned above can also be used.
  • fibers other than the above cellulose fibers include natural fibers such as hemp, silk, wool, etc .; polyethylene terephthalate, rayon, polynosic, cupra, acetate, nylon, vinylon, vinylidene, polyvinyl chloride, acrylic, acrylic And synthetic fibers such as polyethylene, polypropylene, and polyurethane, and mixed fibers thereof.
  • the cellulosic fiber product includes clothes such as underwear, outerwear, socks, gloves, hats, hair bands, handkerchiefs, towels, face masks, mufflers, sheets, pillowcases, futons, cushions, All the things using cellulosic fibers, such as a diaper and a diaper cover, are included.
  • the hydrophilization treatment is not particularly limited.
  • a method for introducing a hydrophilic group a method for introducing a hydrophilic molecule, a method for physically modifying a surface, and a coating with a coating agent containing a hydrophilic substance.
  • the method is carried out by at least one selected from the group consisting of methods.
  • the method for introducing the hydrophilic group is not particularly limited.
  • a carboxyl group, an amino group, a sulfone group, a hydroxyl group, a phosphate group, an epoxy group, an ether residue may be added to the cellulose fiber or the molecule constituting the cellulose fiber product.
  • Examples thereof include a method of directly bonding a polar group such as a group or a hydrophilic group such as a group having these groups.
  • the method of introducing the hydrophilic molecule is not particularly limited.
  • polar groups such as a carboxyl group, an amino group, and a sulfone group or a group having these groups may be added to a molecule constituting a cellulose fiber or a cellulose fiber product.
  • a method of bonding molecules having a hydrophilic group such as methacrylamide, hydroxyethyl acrylate, acrylic acid, methacrylic acid or the like to bond a highly hydrophilic side chain.
  • the method for physically modifying the surface is not particularly limited.
  • the surface of a cellulosic fiber or cellulosic fiber product is subjected to plasma treatment, corona treatment; ionizing actinic ray treatment such as ultraviolet ray, electron beam, radiation, and laser. , Flame treatment, ozone treatment, enzyme microorganism treatment, and the like.
  • the method of coating with the coating agent containing the hydrophilic substance is not particularly limited.
  • the moisture absorption rate of the cellulosic fiber is set to 7.1% or more by hydrophilic treatment. If it is less than 7.1%, the binding force between the oily soil component and the cellulosic fiber or cellulosic fiber product is strong, and the soil component may not be sufficiently removed with water alone. More preferably, it is 7.5% or more.
  • the upper limit of the moisture absorption rate is not particularly limited, the preferable upper limit is usually 20%, and the more preferable upper limit is 15%.
  • the said moisture absorption rate can be calculated
  • Moisture absorption rate (%) ([official weight] ⁇ [absolute dry weight] ⁇ 1) ⁇ 100 (1)
  • the absolute dry weight is measured, for example, after the cellulosic fiber or cellulosic fiber product to be measured is placed in a weighing bottle and dried at 105 ° C. for 2 hours, and weighed in advance. It can be calculated by subtracting the weight of the weighing bottle.
  • the official weight is determined by, for example, weighing a cellulosic fiber or a cellulosic fiber product that has been measured for absolute dry weight in a weighing bottle after leaving it in an atmosphere at a temperature of 20 ° C. and a humidity of 65% RH for 24 hours. It can be calculated by subtracting the weight.
  • a piece of dough having a size of about 10 ⁇ 20 cm can be used. Weighing is repeated until the weight is constant.
  • the hydrophilic treatment method is not particularly limited, but a method of introducing a carboxyl group is preferable because a high moisture absorption rate can be imparted relatively easily.
  • the carboxyl group includes salts such as sodium salt and potassium salt.
  • the carboxyl group can be easily converted into the cellulosic fiber in the form of carboxymethyl group by contacting the cellulosic fiber with a treatment liquid containing monochloroacetic acid or an alkali metal salt of monochloroacetic acid (for example, sodium salt or potassium salt). Can be introduced.
  • a treatment liquid containing monochloroacetic acid or an alkali metal salt of monochloroacetic acid for example, sodium salt or potassium salt.
  • the introduction of a carboxymethyl group in this way is hereinafter also referred to as carboxymethylation.
  • the concentration of monochloroacetic acid or the alkali metal salt of monochloroacetic acid in the treatment liquid in the case of performing carboxymethylation may be determined appropriately so that the desired degree of processing can be obtained.
  • / L more preferably 50 to 300 g / L, still more preferably 100 to 200 g / L.
  • blend alkali metal hydroxide for example, sodium hydroxide
  • blend alkali metal hydroxide for example, sodium hydroxide
  • the degree of carboxymethylation of the resulting treated fiber can be improved.
  • the reactivity tends to increase as the concentration of sodium hydroxide in the treatment liquid is increased, and it is usually preferably 20 g / L or more.
  • a large amount of sodium hydroxide is blended, the texture of the resulting fiber tends to deteriorate, so care must be taken.
  • Examples of the method of bringing the cellulosic fiber into contact with the treatment liquid include a liquid flow method in which the fiber is rotated in the treatment liquid; a method of padding (squeezing) after immersing the fiber in the treatment liquid, and the like. In terms of use efficiency, it is effective to lower the bath ratio (use ratio of the treatment liquid), and a method of padding after dipping in this respect is effective.
  • the temperature condition for bringing the cellulosic fiber into contact with the treatment liquid is not particularly limited, and can be in the range of 5 to 50 ° C., for example.
  • the time for contacting the cellulosic fiber with the treatment liquid may be appropriately selected from various conditions such as the desired degree of carboxymethylation, the concentration of monochloroacetic acid during treatment, the concentration of sodium hydroxide, and the like. It may be contacted at room temperature for several hours to several days, and the time required can be shortened by heat treatment.
  • the concentration of monochloroacetic acid or alkali metal salt of monochloroacetic acid in the treatment liquid, the concentration of alkali metal hydroxide in the treatment liquid, the treatment temperature, and the treatment It is preferable to adjust the time.
  • the concentration of the alkali metal hydroxide in the treatment liquid be as low as possible and the treatment temperature be lowered to suppress the influence of the alkali metal hydroxide.
  • the concentration of monochloroacetic acid or the alkali metal salt of monochloroacetic acid in the treatment liquid is set to be relatively high, It is necessary to lengthen the processing time.
  • the cellulosic fiber is treated with a treatment solution having an alkali metal hydroxide concentration of 20 to 100 g / L and monochloroacetic acid or an alkali metal salt of monochloroacetic acid of 100 to 400 g / L and 10 to 40 ° C.
  • a treatment solution having an alkali metal hydroxide concentration of 20 to 100 g / L and monochloroacetic acid or an alkali metal salt of monochloroacetic acid of 100 to 400 g / L and 10 to 40 ° C.
  • a preferable lower limit of the carboxymethylation degree is 0.1 mol%. If it is less than 0.1 mol%, sufficient moisture absorption may not be obtained. A more preferred lower limit is 1 mol%.
  • the upper limit of the degree of carboxymethylation is not particularly limited, but the preferable upper limit is 10 mol%, and the more preferable upper limit is 5 mol%.
  • the degree of carboxymethylation means the ratio (%) of hydroxyl groups of cellulose subjected to carboxymethylation reaction, that is, the ratio of the number of COO groups after carboxymethylation to the number of hydroxyl groups of untreated cellulose ( %).
  • the number of COO groups in the cellulosic fiber is determined by quantifying the amount of Na used for the substitution after immersing it in a sodium hydroxide aqueous solution (0.1N) with all the COO groups of the cellulosic fiber as COOH groups. It can ask for.
  • the amount of Na used for substitution can be quantified by titrating an aqueous sodium hydroxide solution in which treated cellulose fibers or cellulose fiber products are immersed using, for example, hydrochloric acid (0.1N). it can. Specifically, the following measurement methods can be employed.
  • the treated cellulosic fibers are immersed in 0.3N hydrochloric acid for 1 hour under conditions of a bath ratio of 1:50 and a liquid temperature of 20 ° C. to make all COO groups COOH groups, and dehydrated. And dry to remove residual HCl, sample approximately 4 g and weigh the absolute dry weight (W (g)).
  • the cellulose fibers and the like weighed in absolute dry weight are immersed in 50 mL (B (mL)) of 0.1 N sodium hydroxide aqueous solution that has been precisely weighed and left overnight at a liquid temperature of 20 ° C. Is replaced with COONa.
  • the liquid is titrated using 0.1N hydrochloric acid, and the titration value is set to X (mL). Phenolphthalein can be used as an indicator.
  • the degree of carboxymethylation was determined from the absolute dry weight (W (g)) of the cellulose fiber, the volume of sodium hydroxide aqueous solution (B (mL)), and the volume of hydrochloric acid required for titration (X (mL)) as follows. It can be calculated according to equation (2).
  • Carboxymethylation degree (mol%) 162.14 ⁇ (BX) ⁇ [10000W-59.04 ⁇ (BX)] ⁇ 3 ⁇ 100
  • a method in which at least one monomer selected from the group consisting of methacrylamide, hydroxyethyl acrylate, acrylic acid, and methacrylic acid is graft-polymerized on the cellulose fiber is also suitable.
  • Examples of the grafting method include a method of polymerizing the monomer in a state where the monomer is brought into contact with the cellulosic fiber. Specifically, for example, a cellulose-based fiber is immersed and squeezed in a liquid containing the monomer and a polymerization initiator (for example, ammonium peroxodisulfate), and then the hydrophilic molecule is grafted by heating. Cellulosic fibers can be obtained.
  • a polymerization initiator for example, ammonium peroxodisulfate
  • the amount of the hydrophilic molecule to be introduced by the grafting can be appropriately selected in consideration of the kind of the hydrophilic molecule, the moisture absorption rate required for the cellulosic fiber, etc.
  • the preferred lower limit of the graft rate is 1%. It is. If it is less than 1%, sufficient moisture absorption may not be obtained. A more preferred lower limit is 2%.
  • the upper limit of the graft ratio is not particularly limited, but a preferable upper limit is 30%, a more preferable upper limit is 25%, and a further preferable upper limit is 20%. In the present specification, the graft ratio is calculated from the following formula (absolute dry weight before treatment) and the absolute dry weight after treatment (absolute dry weight after treatment): 3).
  • Graft rate (%) ([absolute dry weight after treatment] ⁇ [absolute dry weight before treatment] ⁇ 1) ⁇ 100 (3)
  • the absolute dry weight is the weight of a weighing bottle that has been weighed in advance by weighing a dough piece of about 10 ⁇ 20 cm in a weighing bottle, drying it at 105 ° C. for 2 hours, weighing it, and so on. Can be calculated by subtracting.
  • the cellulose fiber or cellulosic fiber product that has been subjected to a hydrophilic treatment is then treated with a predetermined ester finish and a carbodiimide crosslinker.
  • a cross-linking step is performed.
  • this process is also referred to as a crosslinking process.
  • the crosslinking step for example, a cellulose fiber or a cellulose fiber product obtained by subjecting a crosslinking treatment liquid containing the ester finish, a carbodiimide crosslinking agent, and a catalyst to a hydrophilic treatment.
  • a crosslinking treatment liquid containing the ester finish, a carbodiimide crosslinking agent, and a catalyst to a hydrophilic treatment.
  • the method include padding (squeezing) after drying, drying, and a liquid flow method in which cellulosic fibers or cellulosic fiber products are rotated in a crosslinking treatment liquid. Of these, the padding method after immersion is effective.
  • the ester-based finish contains an ester-based compound produced by an esterification reaction between an oxidatively-modified or acid-modified polyethylene and an aliphatic alcohol or an ethylene amine and / or propylene oxide adduct of an aliphatic amine.
  • an ester-based compound produced by an esterification reaction between an oxidatively-modified or acid-modified polyethylene and an aliphatic alcohol or an ethylene amine and / or propylene oxide adduct of an aliphatic amine.
  • Examples of the oxidation-modified or acid-modified polyethylene include those obtained by introducing a carboxyl group by subjecting polyethylene to air oxidation or thermal decomposition, and those obtained by copolymerizing polyethylene and vinyl carboxylic acid such as acrylic acid or methacrylic acid. It is done.
  • Commercially available products include, for example, AC-629, AC-580, AC-540 (all manufactured by Honeywell International), Mitsui High Wax 4202E, 1105A (all manufactured by Mitsui Chemicals), Sun Wax E-310 (SANYO) Kasei Kogyo Co., Ltd.).
  • the ethylene oxide and / or propylene oxide adduct of the aliphatic alcohol or aliphatic amine is an ethylene oxide and / or propylene oxide adduct obtained by blocking or randomly adding ethylene oxide and / or propylene oxide to an aliphatic alcohol or aliphatic amine.
  • aliphatic alcohol ethylene oxide and / or propylene oxide adducts are more preferable because the decrease in whiteness during processing into cellulose fibers or cellulose fiber products is reduced.
  • the ethylene oxide and / or propylene oxide adduct preferably has an HLB of 10 to 19, more preferably 12 to 17. Further, when the HLB is within the above range, a more stable emulsion can be obtained as an ester finish.
  • HLB in this specification is a value according to the Griffin equation.
  • the reaction between the oxidatively modified or acid-modified polyethylene and the ethylene oxide and / or propylene oxide adduct is carried out by adding, for example, an oxidation equivalent of the oxidatively modified or acid-modified polyethylene and an equimolar amount of the ethylene oxide and / or propylene oxide to a reaction vessel. It is possible to carry out the dehydration reaction at 180 to 220 ° C. for 3 to 5 hours in a nitrogen stream by adding the product and further adding paratoluenesulfonic acid as a catalyst. The reaction rate can be monitored by oxidation measurement using a mixed solvent of xylene / dimethyl sulfoxide (2/1 to 9/1).
  • the reaction rate of the reactant is preferably 70 to 95%. More preferably, it is 80 to 90%. If the esterification reaction rate is less than the lower limit, a stable emulsion may not be obtained, and further, when the cellulose fiber or cellulose fiber product is processed, water absorption may be inhibited. When the upper limit is exceeded, the crosslinking reaction between the ester-based finish and the carbodiimide-based crosslinking agent does not proceed sufficiently, and the washing durability may be impaired when the cellulose-based fiber or the cellulose-based fiber product is processed.
  • the aliphatic alcohol or aliphatic amine may be saturated or unsaturated, and is preferably saturated.
  • the carbon number is preferably 4 to 22, more preferably 8 to 20. If the carbon number is smaller than the lower limit, the flexibility may be inferior when processed into cellulosic fiber or cellulosic fiber product. If the carbon number exceeds the upper limit, the cellulosic fiber or cellulosic fiber product may be used. It may have poor water absorption when treated.
  • the ester-based finish preferably further contains a water-soluble polyester resin represented by the following general formula [1].
  • the water-soluble polyester resin is also referred to as B component.
  • R 1 represents a HO— group or a HO (R 2 O) a — group
  • R 2 represents an alkylene group having 2 to 4 carbon atoms
  • a represents an integer of 1 to 200
  • R 4 may be the same or different and each represents a hydrogen atom or a —SO 3 X group (X represents a hydrogen atom, an alkali metal or an amine), and R 3 represents a hydrogen atom or the following general formula [2].
  • R 4 represents the same as R 4 in the formula [1].
  • R 1 represents a HO— group or a HO (R 2 O) a — group
  • R 2 represents an alkylene group having 2 to 4 carbon atoms.
  • the alkylene group having 2 to 4 carbon atoms include ethylene, trimethylene, propylene, tetramethylene, and butylene, and an ethylene group is particularly preferable from the viewpoint of solubility in water and dispersibility.
  • A represents an integer of 1 to 200, more preferably 1 to 150.
  • a exceeds the said upper limit, the viscosity of a polyester resin will become high too much and handling may become difficult.
  • R 2 O may be the same or different, and when R 2 O is 2 or more, random addition or block addition may be used.
  • the above b represents an integer of 1 to 100, but 1 to 50 is more preferable.
  • the upper limit is exceeded, the viscosity of the polyester resin becomes too high and handling becomes difficult.
  • R 4 may be the same or different, each represents a hydrogen atom or an -SO 3 X group, among -SO 3 X group, X represents a hydrogen atom, an alkali metal or an amine.
  • alkali metal include lithium, sodium and potassium.
  • amine include primary amines such as ammonia, methylamine, ethylamine, propylamine, butylamine and allylamine; dimethylamine, diethylamine and dipropyl.
  • Secondary amines such as amine, dibutylamine and diallylamine; tertiary amines such as trimethylamine, triethylamine, tripropylamine and tributylamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.
  • R 3 represents a hydrogen atom or a group represented by the above general formula [2]. Then, in the general formula [2], R 4 represents the same as R 4 in the formula [1].
  • the water-soluble polyester resin can be produced by a known method from aromatic dicarboxylic acid or a derivative thereof and alkylene glycol and / or polyalkylene glycol.
  • aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, and sulfoisophthalic acid
  • the derivatives thereof include dimethyl ester, diethyl ester, dipropyl ester of these dicarboxylic acids
  • Examples thereof include lower alkyl esters such as dibutyl ester, chlorides of these dicarboxylic acids, and phthalic anhydride.
  • These aromatic dicarboxylic acids or derivatives thereof may be used alone or in combination of two or more.
  • the polymerization ratio of the aromatic dicarboxylic acid or derivative thereof is not particularly limited, but when an aromatic dicarboxylic acid having a —SO 3 X group or derivative thereof is used, the polymerization ratio is 50 mol% or less. It is preferable. When the polymerization ratio of the aromatic dicarboxylic acid derivative having a —SO 3 X group exceeds the above upper limit, the polycondensation reaction of the water-soluble polyester resin becomes difficult, the falling off by washing becomes severe, and the detergent-free washing property is further improved. The improvement effect may not be obtained.
  • the water-soluble polyester resin has a weight average molecular weight of preferably 3000 to 60000, and more preferably 5000 to 30000.
  • the weight average molecular weight of the water-soluble polyester resin can be determined by gel permeation chromatography using monodispersed polyethylene glycol having a known molecular weight as a measurement standard substance.
  • the mass ratio of the A component to the B component is preferably 1: 0.01 to 1: 1.
  • the A component and the B component may be used in combination and emulsified in water.
  • glycerides, polyhydric alcohol fatty acid esters, polyamine higher fatty acid amides, paraffin, water soluble By blending a functional acrylic resin, amino-modified silicone, etc., an even better and more stable emulsion can be obtained.
  • the treatment amount of the ester finish is such that the adhesion amount of the component A to the fiber product is 0.1 to 5% o. w. f. Preferably, 0.5 to 2% o. w. f. More preferably.
  • the adhesion amount of the component A is less than the lower limit, the washing durability of the cellulose fiber or cellulose fiber product after treatment becomes insufficient, and when the upper limit is exceeded, the cellulose fiber or cellulose fiber after treatment.
  • the product cannot be further improved in flexibility and is uneconomical or the detergent-free washing function may be impaired.
  • the non-volatile content indicates the residue after drying at 105 ° C. for 3 hours.
  • w. f. Indicates the ratio to the weight of the fiber.
  • a carbodiimide-based crosslinking agent is used as a crosslinking agent simultaneously with the ester-based finishing agent.
  • the carbodiimide-based crosslinking agent causes a crosslinking reaction, it becomes possible to impart washing durability to the cellulosic fiber or the cellulosic fiber product and prevent a decrease in flexibility.
  • the carbodiimide-based crosslinking agent refers to a crosslinking agent containing a carbodiimide group represented by (—N ⁇ C ⁇ N—).
  • a carbodiimide type crosslinking agent what contains two or more carbodiimide groups in 1 molecule is preferable. Furthermore, from the viewpoint of workability and hygroscopicity, those having water solubility are more suitable.
  • the carbodiimide-based crosslinking agent include compounds having at least two carbodiimide groups in the molecule such as a polycarbodiimide compound obtained by decarboxylation condensation reaction of diisocyanate in the presence of a catalyst.
  • Examples of commercially available products include “Carbodilite SV-02”, “Carbodilite V-02”, “Carbodilite V-02-L1”, “Carbodilite V-04”, “Carbodilite E-01”, “Carbodilite E-02” ( All of them are manufactured by Nisshinbo Chemical Co., Ltd.). Among these, “Carbodilite E-01” and “Carbodilite E-02” are more preferable from the viewpoint of stability in the treatment bath.
  • the treatment amount of the carbodiimide-based crosslinking agent is such that the adhesion amount to the cellulosic fiber or cellulosic fiber product is 0.01 to 0.5% o. w. f. It is preferable that When the adhesion amount of the carbodiimide crosslinking agent is less than the lower limit, the washing durability of the cellulose fiber or cellulose fiber product after treatment becomes insufficient, and when the upper limit is exceeded, the cellulose fiber or cellulose after treatment. The fiber-based textile product may not be able to obtain further washing durability, which may be uneconomical and may lose flexibility.
  • a catalyst may be contained in order to promote the crosslinking reaction.
  • additives such as an antifungal agent, an antioxidant, a light stabilizer, an antistatic agent, a electrically conductive agent, a flame retardant, and a pigment, in the said crosslinking process liquid as needed.
  • the dipping time in the cross-linking treatment liquid in the cross-linking step and the drawing ratio when drawing the cellulosic fiber or cellulosic fiber product after dipping can be appropriately selected according to the desired performance.
  • the preferable lower limit of the temperature for drying is 80 ° C.
  • the preferable upper limit is 150 ° C.
  • the temperature is less than 80 ° C., the crosslinking agent is not sufficiently crosslinked, and the washing durability may be lowered.
  • the temperature exceeds 150 ° C. deterioration of the drug may occur.
  • the method for treating a cellulosic fiber or cellulosic fiber product of the present invention even if the cellulosic fiber or cellulosic fiber product is washed without using a detergent, it is almost the same as when the detergent is used. A function of obtaining an equivalent effect can be provided.
  • an operation (rinsing operation) for removing the detergent can be omitted, so that the washing can be performed in a shorter time. By shortening the washing time, resources such as water and electricity can be saved greatly.
  • the fiber product to which the processing method of the cellulosic fiber or the cellulosic fiber product of the present invention is applied is extremely excellent in moisture absorption and desorption and has a secondary effect that it is excellent in comfort in clothing.
  • the present invention by performing a crosslinking step in combination with a predetermined ester finish and a carbodiimide crosslinking agent, while having an excellent detergent-free washing function, high flexibility and washing durability Cellulosic fibers or cellulosic fiber products having both of the above are obtained.
  • the cellulosic fiber or cellulosic fiber product obtained using the method for treating cellulosic fiber or cellulosic fiber product of the present invention is also one aspect of the present invention.
  • the cellulosic fiber or cellulosic fiber product of the present invention may further contain a deodorant.
  • a deodorant When a carboxyl group is introduced as a hydrophilic treatment, there is a high deodorizing effect, but a higher deodorizing effect can be obtained by adding a deodorant.
  • the deodorizer is not particularly limited, and conventionally known deodorizers such as zinc oxide, titanium oxide, silver, zeolite, and plant extract can be used. Among them, it is preferable to use a zinc oxide-based deodorant because it can be easily processed into fibers.
  • the cellulose fiber or the cellulosic fiber product is provided with a function that even when washing is performed without using a detergent, almost the same cleaning effect as that obtained when using the detergent can be obtained.
  • Example 1 Cotton knit (100% cotton 40/1 (40th single yarn) milling knit) is used as the base fabric, and 1 in a treatment liquid containing sodium monochloroacetate (200 g / L) and sodium hydroxide (70 g / L). : It was immersed in a bath ratio of 20, and after squeezing with a padder, it was left to react at 25 ° C. for 24 hours. Unreacted substances were removed by washing with water and dried to obtain a hydrophilized cotton knit. It was 2.67 when the degree of carboxymethylation was measured about the obtained hydrophilic cotton knit, and it was 8.9% when the moisture absorption rate was measured.
  • the nitrogen stream was stopped, and after reacting at 250 to 260 ° C. under a reduced pressure of about 5 mmHg for 2 hours, further 30 ° C under a reduced pressure of 260 ° C. and about 2 mmHg. Reaction was performed for minutes, and 400 g of water-soluble polyester resin (II) was obtained.
  • the weight average molecular weight of the water-soluble polyester resin (II) was about 14,000 as a result of measurement by gel permeation chromatography [High-speed GPC manufactured by Tosoh Corporation, HLC-8120 type, measurement standard substance: polyethylene glycol].
  • ester-based finish 100 g of product (I) was melted at 85 to 90 ° C. together with 20 g of water-soluble polyester resin (II), and 280 g of hot water at 85 to 90 ° C. was added and emulsified to obtain a total of 400 g of ester-based finish. .
  • the component A contained in the ester finish is 25% by mass as a nonvolatile content.
  • Example 2 After obtaining a hydrophilized cotton knit by the same method as in Example 1, 5% by mass of the ester-based finish obtained in Example 1 and a polycarbodiimide-based crosslinking agent (carbodilite E-01, Nisshinbo Co., Ltd.) as a carbodiimide-based crosslinking agent.
  • a polycarbodiimide-based crosslinking agent carbodilite E-01, Nisshinbo Co., Ltd.
  • the obtained hydrophilized cotton knit was immersed in a treatment solution containing 0.4% by mass of Chemical), and then squeezed with a padder at a squeezing rate of 100%. Then, it dried at 120 degreeC for 3 minute (s), and obtained the process cloth.
  • Example 3 After obtaining a hydrophilized cotton knit by the same method as in Example 1, 7% by mass of the ester finish obtained in Example 1, and a polycarbodiimide crosslinker (carbodilite E-01, Nisshinbo Co., Ltd.) as a carbodiimide crosslinker.
  • Example 4 A hydrophilized cotton knit obtained by the same method as in Example 1 was used as a treated fabric.
  • Example 5 After obtaining a hydrophilized cotton knit in the same manner as in Example 1, the hydrophilized cotton knit obtained in a treatment liquid containing 2% by mass of a silicone softener (Softex A-1500, manufactured by Kitahiro Chemical Co., Ltd.) was immersed and then squeezed with a padder at a squeezing rate of 100%. Then, the process cloth was obtained by drying at 120 degreeC for 3 minute (s).
  • a silicone softener Softex A-1500, manufactured by Kitahiro Chemical Co., Ltd.
  • Example 6 After obtaining a hydrophilized cotton knit in the same manner as in Example 1, 3% by mass of a durable silicone softener (TK Silicon EP-301E, manufactured by Takamatsu Yushi Co., Ltd.) and a polycarbodiimide crosslinker as a carbodiimide crosslinker (The obtained hydrophilized cotton knit was immersed in a treatment liquid containing 0.4% by mass of Carbodilite E-01 (manufactured by Nisshinbo Chemical Co., Ltd.) and then squeezed with a padder at a squeezing rate of 100%. Then, the process cloth was obtained by drying at 120 degreeC for 3 minute (s).
  • TK Silicon EP-301E manufactured by Takamatsu Yushi Co., Ltd.
  • a polycarbodiimide crosslinker as a carbodiimide crosslinker
  • Example 7 After obtaining a hydrophilized cotton knit by the same method as in Example 1, the obtained hydrophilized cotton knit was immersed in a treatment solution containing 3% by mass of a durable cationic softener (Solussoft 1200, manufactured by Clariant). After that, it was squeezed with a padder at a squeezing rate of 100%. Then, the process cloth was obtained by drying at 120 degreeC for 3 minute (s).
  • a durable cationic softener Solussoft 1200, manufactured by Clariant
  • Bending softness Bending softness was measured by a method based on JIS L 1018. First, with respect to the obtained treated cloth, three sample pieces having a sample width of 200 mm and a sample length of 200 mm were prepared, and a sample piece was placed on a 10 mm wide slit using a texture meter (manufactured by Daiei Scientific Instruments). Then, when the arm pushed the sample between the slits, the maximum cN force required was measured at four points in the vertical and horizontal directions on the front and back of the sample, and the total value was obtained. The average value of three sample pieces was defined as the bending resistance. The bending resistance was measured for the state immediately after the treatment (L0), after washing 30 times (L30), after washing 50 times (L50), and after washing 100 times (L100). . Further, the obtained bending resistance was evaluated according to the following criteria.
  • Bending softness is less than 40 cN ⁇ Bending softness is 40-60 cN ⁇ The bending resistance exceeds 60 cN
  • Decreasing whiteness is less than 10 points ⁇ Decreasing whiteness is 10 to 12.5 points ⁇ Decreasing whiteness is 12.5 to 15.0 points x Decreasing whiteness is more than 15.0
  • the Erlenmeyer flask was quickly sealed with a silicon stopper covered with a double wrap, and further sealed with a rubber band made of triple wrap. Then, it was left to stand at 20 ° C. for 120 minutes while stirring with a magnetic stir bar. After leaving for 120 minutes, the silicon stopper is pulled out so that the wrap is not peeled off, and a measuring tube with a silicon stopper for measurement (Gastech, No.3La / ammonia: Gastech, No.81 / Acetic acid) was used to measure the gas concentration in the Erlenmeyer flask. A similar test was performed without suspending the test cloth in the Erlenmeyer flask, and this was used as a blank measurement value. The deodorization rate (%) was calculated
  • ⁇ Deodorization rate is 90-100% ⁇ Deodorization rate is 80-90% ⁇ Deodorization rate is 70-80% ⁇ Deodorization rate is less than 70%
  • Deodorization rate (%) ⁇ (blank measurement value ⁇ test cloth measurement value) / blank measurement value ⁇ ⁇ 100
  • Comparative Example 5 As shown in Table 1, in Comparative Example 5, the washing durability (the bending resistance of L100) was poor, but there was a phenomenon that the whiteness decrease after repeated washing tests was small and the detergent-free washing function was maintained. It is done. This is because non-durable softeners do not have a high affinity with oily soils that are a problem in cellulosic fibers or cellulosic fiber products. Therefore, it is considered that the same state as that of the softener untreated in Comparative Example 4 was obtained with a small number of washings. In Comparative Example 6, Comparative Example 7, and Comparative Example 9, although washing durability (L100 bending resistance) is good, a phenomenon in which the whiteness decrease after repeated washing tests is large and the detergent-free washing function is inferior is observed.
  • the cellulose fiber or the cellulosic fiber product is provided with a function that even when washing is performed without using a detergent, almost the same cleaning effect as that obtained when using the detergent can be obtained. It is possible to provide a cellulosic fiber or a cellulosic fiber product treatment method and a cellulosic fiber or cellulosic fiber product that can achieve high flexibility and washing durability.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un procédé de traitement de fibre cellulosique ou de produit en fibre cellulosique qui donne à une fibre cellulosique ou à un produit en fibre cellulosique une capacité d'atteindre sensiblement le même effet de nettoyage que lorsqu'un produit de nettoyage est utilisé, même après avoir été lavé sans utiliser de produit de nettoyage, et qui possède une haute flexibilité et durabilité au lavage, et une fibre cellulosique ou un produit en fibre cellulosique. Le procédé de traitement de fibre cellulosique ou de produit en fibre cellulosique comporte un traitement qui traite de façon hydrophile la fibre cellulosique ou le produit en fibre cellulosique, et un traitement qui réticule de façon hydrophile une fibre cellulosique traitée ou un produit en fibre cellulosique traité en utilisant un agent de finition à l'ester et un agent de réticulation au carbodiimide. La fibre cellulosique ou le produit en fibre cellulosique contient un composé ester généré par estérification de l'agent de finition à l'ester et de l'oxyde de polyéthylène modifié ou un polyéthylène modifié à l'acide, et des composés d'oxyde d'éthylène et/ou d'oxyde de propylène à alcool aliphatique ou à amine aliphatique.
PCT/JP2011/055255 2010-03-08 2011-03-07 Procédé de traitement de fibre cellulosique ou de produit en fibre cellulosique WO2011111658A1 (fr)

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JP6073151B2 (ja) * 2013-02-20 2017-02-01 日華化学株式会社 機能性繊維製品の製造方法及びそれに用いる繊維用紫外線吸収剤
JP6450237B2 (ja) * 2014-05-02 2019-01-09 出光興産株式会社 架橋体、架橋剤組成物、繊維状架橋体、繊維状架橋体の製造方法、細胞培養床、細胞培養床による細胞の培養方法、および細胞培養床による移植用細胞シートの製造方法
KR101837373B1 (ko) * 2017-08-04 2018-03-13 박명복 기능성 패션 가발
KR102085297B1 (ko) * 2017-08-25 2020-03-05 (주)에너지플래닛 납-카본 복합전지용 전극코팅조성물, 상기 코팅조성물로 형성된 코팅층을 포함하는 납-카본 복합전지용 전극 및 상기 전극을 포함하는 납-카본 복합전지
WO2019119296A1 (fr) * 2017-12-20 2019-06-27 日华化学株式会社 Procédé de fabrication d'un produit fonctionnel à base de fibres, et agent de traitement hydro-absorbant à séchage rapide
TWI798567B (zh) * 2020-07-13 2023-04-11 財團法人紡織產業綜合研究所 機能性樹脂材料、其製造方法及感濕收縮織物

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