WO2019119296A1 - 功能性纤维制品的制造方法及吸水速干加工剂 - Google Patents

功能性纤维制品的制造方法及吸水速干加工剂 Download PDF

Info

Publication number
WO2019119296A1
WO2019119296A1 PCT/CN2017/117485 CN2017117485W WO2019119296A1 WO 2019119296 A1 WO2019119296 A1 WO 2019119296A1 CN 2017117485 W CN2017117485 W CN 2017117485W WO 2019119296 A1 WO2019119296 A1 WO 2019119296A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
water
fiber product
quick
Prior art date
Application number
PCT/CN2017/117485
Other languages
English (en)
French (fr)
Inventor
加藤忠彦
王大中
曹香红
邹文平
笹田祥弘
吴征
吴幼泉
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 CN201780096822.6A priority Critical patent/CN111886375B/zh
Priority to PCT/CN2017/117485 priority patent/WO2019119296A1/zh
Publication of WO2019119296A1 publication Critical patent/WO2019119296A1/zh

Links

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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process

Definitions

  • the present invention relates to a method for producing a functional fibrous product having water wicking and quick drying properties, and a water wicking quick-drying processing agent used in the method.
  • the cellulose-based fiber is a material having good skin feel and is excellent in water absorbability and moisture retention, but has a drawback that it is difficult to dry once (weak fast-drying property) once wet.
  • Patent Document 1 describes a composition for imparting quick-drying water absorption to a fiber, which comprises a copolymer obtained by copolymerizing a specific monomer and an organic solvent.
  • Patent Document 2 describes a method for processing a fabric containing a cellulose-based fiber, which is a fabric containing a cellulose-based fiber, and is provided with a treatment liquid containing a crosslinking agent and a crosslinking catalyst. The water content is adjusted to a certain level, followed by a contact type heat treatment, and a crosslinking reaction is carried out under a moist heat high pressure.
  • Patent Document 3 discloses a moisture-absorbing and heat-generating cellulose-based fiber obtained by applying an aqueous solution to a cellulose fiber and containing a polyalkylene glycol or an N-methylol-based resin processing agent.
  • the reaction catalyst and a water-soluble polymer having a hydroxyl group and a sulfonic acid group in the molecule are examples of a water-soluble polymer having a hydroxyl group and a sulfonic acid group in the molecule.
  • Patent Document 4 describes a method for processing a cellulose-based fabric, which is a method in which a cellulose-based fabric is treated with a mixed aqueous solution and is subjected to heat treatment, and the mixed aqueous solution is an N-methylol-based resin processing agent and a reaction thereof.
  • a mixed aqueous solution in which a catalyst is mixed with a water-soluble substance having a hydroxyl group and an amino group and/or a carboxyl group in a molecule, or a cellulose-based cloth is treated with a mixed aqueous solution, and then heated, and the mixed aqueous solution is N.
  • Patent Document 5 describes a method for processing a cellulose-based fiber using a fiber treatment agent and a treatment bath containing the fiber treatment agent and an acidic catalyst, wherein the fiber treatment agent contains 1.4 to 1 mol of an ethylene urea ring.
  • the fiber treatment agent contains 1.4 to 1 mol of an ethylene urea ring.
  • the diol is formed in an amount of 5 parts by weight or more, and the treatment bath is applied to a cellulose-based fiber at a temperature of 25 ° C and a pH of 2.5 to 5.
  • the present invention has been made in view of the above problems in the prior art, and an object thereof is to provide a cellulose-based fiber product which is excellent in skin feel and has water absorbability, moisture retention, and quick-drying properties.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, found that The cellulose-based fiber product is treated with a water-absorbent and quick-drying agent containing a specific compound, and then treated with a finishing agent containing a specific compound to provide a good skin feel, water absorption, moisture retention, and quick-drying property.
  • the cellulose-based fiber product is based on this finding to complete the present invention.
  • the present invention provides a method for producing a functional fiber product, comprising: a cellulosic fiber product comprising a group selected from the group consisting of an N-methylol compound, a glyoxal, an acrylamide compound, and an organic acid. a first step of treating a water-absorbent and quick-drying processing agent of at least one hydroxy-reactive compound; and subsequently, a group comprising a urethane resin selected from the group consisting of polyether-modified silicone oil, acid value-containing wax, and polyalkylene oxide-containing resin A second step of treating the finishing agent of at least one of the compounds.
  • the above-mentioned hydroxy-reactive compound is preferably an N-methylol-based compound.
  • the N-methylol compound is preferably a compound represented by the following formula (1).
  • R 1 is each independently hydrogen, an alkyl group having 1 to 3 carbon atoms, a methylol group, an alkyl-oxymethyl group having 1 to 3 carbon atoms, or -CH 2 -O-(R). 3 O) n -H, n is 1 to 5, R 3 is an alkylene group having 2 to 4 carbon atoms, and R 2 is independently hydrogen, an OH group, an alkyl group having 1 to 3 carbon atoms, and p is 0 or 1.
  • the finishing agent preferably contains an aminosilicone oil cationically modified silicone oil, A finishing agent for waxes with acid numbers.
  • the present invention also provides a water-absorbent and quick-drying processing agent used in the first step.
  • a cellulose-based fiber product which is excellent in skin feel and has the advantages of so-called cellulose-based fibers excellent in water absorbability and moisture retention, and which has quick-drying properties.
  • the method for producing a functional fiber product according to the present invention includes a first step of treating a cellulose-based fibrous product with a water-absorbent and quick-drying processing agent, wherein the water-absorbing and quick-drying processing agent contains a compound selected from the group consisting of N-methylol compounds, At least one hydroxy-reactive compound in the group consisting of glyoxal, an acrylamide-based compound, and an organic acid; and then, in a second step of treating with a finishing agent, the finishing agent contains a polysiloxane-modified silicone oil or an amino silicone oil. At least one finishing compound of the group consisting of a cationically modified silicone oil, a wax having an acid value, and a polyurethane resin containing a polyalkylene oxide.
  • cellulose-based fiber product examples include natural cellulose fiber products such as cotton, hemp, flax, pulp, and bacterial cellulose fibers; and cellulose fiber products such as regenerated cellulose fiber products such as rayon.
  • Cellulose fiber products which may also include synthetic fibers such as polyester, nylon, vinylon, acrylonitrile fiber, polyurethane, polyamide, polyethylene, polypropylene, etc.; animal fibers such as wool and enamel; inorganic fibers such as glass fiber and carbon fiber. Etc., can be used in the form of cotton, silk, fabric, knitted fabric, non-woven fabric, sewing products, and the like.
  • the cellulose fiber in the cellulose-based fiber product is contained in an amount of 35 mass% or more, and more preferably 50% by mass or more, more preferably from the viewpoint of skin touch property, water absorbability, and quick-drying property. More than 80% by mass is especially good Selected, 100% is most preferred.
  • the water-absorbent and quick-drying processing agent in the present invention is a water-absorbent and quick-drying processing agent used in the method for producing a functional fiber product according to the present invention, which comprises a compound selected from the group consisting of N-methylol compounds, glyoxal, and acrylamide compounds. And at least one hydroxy-reactive compound in the group consisting of an organic acid.
  • N-methylol-based compound examples include dimethylol urea, methylol melamine, and a compound represented by the formula (1).
  • acrylamide-based compound examples include N-(hydroxymethyl)acrylamide and N,N'-methylenebisacrylamide.
  • organic acid examples include glycolic acid, lactic acid, citric acid, and polycarboxylic acid.
  • hydroxy-reactive compounds from the viewpoints of skin touch, water absorbability, quick-drying property, and moisture retention, it is preferred to use an N-methylol-based resin, and a compound represented by the following formula (1) is used. More preferred.
  • R 1 is each independently hydrogen, an alkyl group having 1 to 3 carbon atoms, a methylol group, an alkyl-oxymethyl group having 1 to 3 carbon atoms, or -CH 2 -O-(R 3 O) n -H, n is 1 to 5, R 3 is an alkylene group having 2 to 4 carbon atoms, and R 2 is independently hydrogen, an OH group, an alkyl group having 1 to 3 carbon atoms, and p is 0 or 1.
  • p is 0 and two R 1 are -CH 2 -O-(R 3 O).
  • the hydroxy-reactive compound is preferably used in an amount of from 0.5 to 30% by mass based on 100% by mass of the cellulose-based fiber product, from the viewpoint of the balance of the skin sensation, the water absorbing property, the quick-drying property, and the moisture retention property. 20% by mass is more preferred.
  • the amount is less than 0.5% by mass, the quick-drying effect tends to be difficult to be exhibited.
  • the amount is more than 30% by mass, the quick-drying effect in accordance with the amount of use is not obtained, and the feeling of curing and strength of the skin is lowered. .
  • a catalyst may be contained in order to improve the reactivity of the hydroxy-reactive compound.
  • a catalyst include AlCl 3 , Al 2 (SO 4 ) 3 , MgCl 2 , Mg(H 2 PO 4 ) 2 , magnesium sulfate, Zn(BF 4 ) 2 , Zn(NO 3 ) 2 , and ZnCl 2 .
  • various metal salts such as Mg(BF 4 ) 2 , Mg(ClO 4 ) 2 , sodium hydrogen phosphate, Al 2 (OH) 4 Cl 2 ; acid salts of alkanolamines; strong acids such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, etc. Ammonium salt; organic acids such as glycolic acid, maleic acid, lactic acid, citric acid, tartaric acid and oxalic acid.
  • the amount of use of these catalysts is preferably 0.1 to 5% by mass based on 100% by mass of the cellulose-based fiber product. When it is less than 0.1% by mass, the quick-drying effect tends to be difficult to be exhibited, and when it exceeds 5% by mass, the raw material tends to yellow or the strength of the blank tends to decrease.
  • a penetrating agent in order to smoothly carry out the reaction in which the cellulose-based fiber product is uniformly treated with the hydroxyl-reactive compound, a penetrating agent may be contained as needed.
  • the penetrating agent include polyhydric alcohols such as glycerin, ethylene glycol, polyethylene glycol, and polypropylene glycol; ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, and diethylene glycol.
  • Ether alcohols such as alcohol monomethyl ether and diethylene glycol monobutyl ether; polyoxyalkylene alkyl ethers; dimethylformamide, morpholine, 2-pyrrolidone, dimethylacetamide, N-methyl Nitrogen-containing solvents such as pyrrolidone; ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ⁇ - Ester such as butyrolactone.
  • a penetrating agent is preferably used in an amount of 0.1 to 5% by mass based on 100% by mass of the cellulose-based fiber product.
  • the other compound 1 in addition to the hydroxy-reactive compound, the catalyst, and the above-mentioned penetrating agent, the other compound 1 may be contained to the extent that the effects of the present invention are not impaired.
  • the other compound 1 include a hydroxy-reactive compound other than the hydroxy-reactive compound of the present invention, a softening agent, an antibacterial agent, an antistatic agent, a deodorant, and the like.
  • the hydroxy-reactive compound of the present invention is preferably a total of 80% by mass or more of the hydroxy-reactive compound of the present invention, and contains 90% by mass of the hydroxy-reactive compound of the present invention and the other compound 1 (active ingredient). More than % is more preferred, and 100% by mass is most preferred.
  • the method of treating the cellulose-based fibrous product with a water-absorbent and quick-drying processing agent is not particularly limited.
  • a conventionally known method such as immersion treatment or dipping-pressure surface (dip) can be suitably used.
  • a method of padding, a spray treatment, a bubble processing, a method of performing immersion while coating a coater, and the like can be suitably used.
  • a method of performing immersion by a padding treatment, a spray treatment, a foaming treatment, or a coating which is constituted by a dip-nip method is preferable.
  • the first step it is preferred to carry out a drying treatment after the cellulose-based fibrous product is treated with a water-absorbent and quick-drying processing agent.
  • the drying treatment method is not particularly limited, and for example, air drying, dry drying with hot air, wet drying using a high temperature chamber (H.T.S.), a high pressure chamber (H.P.S.), microwave irradiation drying, or the like can be employed. These drying methods may be used alone or in combination of two or more.
  • Drying is preferably carried out at 100 to 180 ° C for 1 to 30 minutes as drying conditions, more preferably 100 to 170 ° C for drying, and particularly preferably 100 to 140 ° C.
  • the temperature is lower than 100 ° C, the drying effect tends to be weaker, in addition to the tendency to lengthen the drying time.
  • it exceeds 180 ° C the strength of the billet tends to decrease.
  • the method for producing a functional fiber product according to the present invention from the viewpoints of skin touch, water absorption, quick-drying property, and moisture retention, in particular, from the viewpoint of improving skin feel and quick-drying properties, in the cellulose system It is preferable to carry out a washing step between the first step of treating the fibrous product with the water-absorbent and quick-drying processing agent and the second step of treating with the finishing agent.
  • the washing step is not particularly limited, and for example, continuous washing, intermittent washing, washing with running water, or the like can be used. Among them, from the viewpoint of washing efficiency, batch washing is preferred, and washing at 5 to 90 ° C for 5 to 60 minutes is preferred, and washing at 20 to 90 ° C for 20 to 50 minutes is more preferred. Washing at -90 ° C for 20 to 30 minutes is especially preferred.
  • a group comprising a polyether-modified silicone oil, an aminosilicone cation-modified silicone oil, a wax having an acid value, and a polyalkylene oxide-containing urethane resin is used.
  • a step of treating at least one of the finishing agents of the finishing compound is used.
  • polyether-modified silicone oil a polyether-modified silicone oil having a polyalkylene oxide (particularly polyethylene oxide) introduced into at least one of a terminal, a side chain and a main chain of a siloxane skeleton can be used. .
  • a functional group other than a polyalkylene oxide such as an amino group, an imino group, an amide group, an epoxy group, a carboxyl group, a methanol group or an alkyl group may be introduced into the terminal or side chain of the siloxane skeleton. And at least one of the main chains.
  • KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640 can be cited.
  • the polyether-modified silicone oil is preferably from 4 or more in terms of water absorption, and more preferably has an HLB of 6 or more.
  • a plant wax such as carnauba wax, candelilla wax, palm wax or lacquer wax; an animal wax such as beeswax or cetyl wax; an acid wax having an acid value such as an oxidized wax, wherein Wax is preferred.
  • oxidized wax examples include a wax obtained by introducing polyethylene into a carboxyl group by air oxidation or thermal decomposition, and a wax obtained by copolymerizing polyethylene with a vinyl carboxylic acid such as acrylic acid or methacrylic acid.
  • the melting point of the oxidized wax is preferably 30 to 200 ° C as measured by the DSC method, and more preferably 50 to 150 ° C. Further, the acid value measured by the method described in 3.
  • the acid value of JIS K 0070-1992 is preferably 5 to 250 mgKOH/g, more preferably 5 to 100 mgKOH/g, and particularly preferably 10 to 80 mgKOH/g. . Further, a dropping point of 50 to 150 ° C as measured according to ASTM D-3954 is preferable, and 90 to 120 ° C is more preferable.
  • Such a wax having an acid value is preferred because the wax is dispersed (including emulsified, dissolved) in an aqueous medium from the viewpoint of ease of use.
  • a method of dispersing a wax in an aqueous medium for example, a method in which a wax is mixed with an aqueous medium and a dispersing agent as needed may be mentioned.
  • emulsifier disperser MILDER high speed mixer, homogenizer, ultrasonic homogenizer, high speed mixer, beads Mill, ball mill, sand mill (DYNO-MILL), ASPEC mill (ASPEC MILL), cage mill (BASKET MILL), ball mill, nano mixer (NANOMIZER), ARTI mixer (ARTI MISER), star An emulsion dispersing machine known hitherto such as STAR-BURST.
  • emulsification dispersers may be used alone or in combination of two or more.
  • aqueous medium water or a mixed medium of water and a hydrophilic solvent mixed in water is preferable.
  • hydrophilic solvent include methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, hexanediol, glycerin, butyl glycol, butyl diethylene glycol, and 3 -Methoxy-3-methylbutanol (SOLFIT), N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, and the like.
  • the dispersion liquid is preferably a dispersant or a surfactant from the viewpoint of dispersion stability.
  • the dispersing agent or the surfactant is not particularly limited as long as it can improve the emulsion dispersion stability, and examples thereof include a known nonionic surfactant, an anionic surfactant, and a cationic surface. Active agent, amphoteric surfactant, and the like. These may be used alone or in combination of two or more.
  • a urethane prepolymer having an isocyanate group at the terminal obtained by reacting (a) an organic polyisocyanate with (b) a polyol is optionally used in the presence of an emulsifier
  • An aqueous polyurethane resin obtained by emulsification and dispersion in water and carrying out a chain extension reaction using (c) a polyamine compound having two or more amino groups and/or imino groups is preferred.
  • the (a) organic polyisocyanate is not particularly limited, and examples thereof include an aliphatic polyisocyanate compound such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; isophorone diisocyanate and hydrogenation.
  • An alicyclic polyisocyanate compound such as benzene dimethylene diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate or 1,3-bis(isocyanatomethyl)cyclohexane; toluene diisocyanate, Aromatic such as phenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, benzene dimethylene diisocyanate, tetramethyl benzene dimethylene diisocyanate A polyisocyanate compound or the like. These polyisocyanate compounds may be used alone or in combination of two or more.
  • the (b) polyhydric alcohol is not particularly limited as long as it has two or more hydroxyl groups, and an ether bond and an ester may be used in addition to the polyester polyol, the polycarbonate polyol, the polyether polyol, and the like. Key polyether ester polyol.
  • polyester polyol examples include polyethylene adipate, polybutylene adipate, polyethylene butylene adipate, and polyhexamethylene isophthalate.
  • polycarbonate polyol examples include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, and poly-1,4-cyclohexane dimethylene carbonate diol. 1,6-hexanediol polycarbonate polyol, and the like.
  • polyether polyol examples include a homopolymer of polyethylene glycol, polypropylene glycol, and polybutylene glycol, a block copolymer, a random copolymer, ethylene oxide and propylene oxide, and epoxy B.
  • polyols may be used alone or in combination of two or more.
  • polyhydric alcohol for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid or the like may be used in combination (d) a compound having a carboxyl group and two or more active hydrogens. .
  • the compound having a carboxyl group and two or more active hydrogens may be used singly or in combination of two or more kinds.
  • Such a (b) polyol is more preferably contained in an amount of 30% or more of ethylene oxide based on the total mass of the (b) polyol, and more preferably 40% or more from the viewpoint of water absorption.
  • a specific method for producing a urethane prepolymer having an isocyanate group at the terminal is not particularly limited, and for example, a conventionally known one-stage type may be employed. It is produced by a one-step foaming method, a multistage isocyanate addition polymerization method, or the like.
  • the reaction temperature at this time is preferably 40 to 150 °C.
  • dibutyltin dilaurate, stannous octoate, dibutyltin 2-ethylhexanoate, triethylamine, triethylenediamine, N-methylmorpholine or the like may be added as needed.
  • catalyst an organic solvent which does not react with the isocyanate group may be added during the reaction or after the reaction is terminated.
  • an organic solvent for example, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone or the like can be used.
  • the carboxyl group can be neutralized by a known and known method before, during or after the production of the isocyanate group-terminated prepolymer.
  • the compound to be neutralized is not particularly limited, and examples thereof include trimethylamine, triethylamine, tri-n-propylamine, tributylamine, N-methyl-diethanolamine, N,N-dimethylmonoethanolamine, and N. , amines such as N-diethylmonoethanolamine and triethanolamine; potassium hydroxide, sodium hydroxide, ammonia, and the like.
  • tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine and tributylamine are particularly preferred.
  • the isocyanate group-terminated prepolymer is emulsified and dispersed in water
  • an emulsifier such as a high-speed mixer, a homogenizer or a disperser can be used.
  • the isocyanate-based terminal prepolymer is emulsified and dispersed in water
  • the isocyanate-based terminal prepolymer is emulsified and dispersed in water at a temperature ranging from room temperature to 40 ° C without using an emulsifier, and the isocyanate group and water can be suppressed as much as possible. The reaction is therefore preferred.
  • reaction inhibitor such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, p-toluenesulfonic acid, adipic acid or benzoyl chloride may be added as needed.
  • polyalkylene oxide-containing polyurethane resin in the polyalkylene oxide-containing polyurethane resin according to the present invention, after the isocyanate-based terminal prepolymer is emulsified and dispersed in water, (c) a polyamine compound having two or more amino groups and/or an imino group is used for chain growth. Reaction, which can be used as a target Polyalkylene oxide resin.
  • Such a (c) polyamine compound having two or more amino groups and/or imino groups may, for example, be ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine or diaminocyclohexane.
  • a diamine such as hexylmethane, piperazine, anthracene, 2-methylpiperazine, isophoronediamine, norbornanediamine, diaminodiphenylmethane, toluenediamine or benzodiamethylenediamine
  • Polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminodipropylamine, tris(2-aminoethyl)amine
  • Diacid dihydrazide maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydra
  • the chain extension reaction of the isocyanate group-terminated prepolymer can be carried out by adding (c) a polyamine compound having two or more amino groups and/or imino groups to the emulsified dispersion of the above isocyanate group-terminated prepolymer. get on. Further, it is also carried out by adding an emulsified dispersion of the above isocyanate group-terminated prepolymer to (c) a polyamine compound having two or more amino groups and/or imino groups.
  • the chain extension reaction is preferably carried out at a reaction temperature of from 20 to 40 ° C, usually between 30 and 120 minutes. In the case where an organic solvent is used in the production of the isocyanate group-terminated prepolymer, for example, after the chain extension reaction is terminated, it is preferred to remove the organic solvent by distillation under reduced pressure or the like.
  • A is a polysiloxane containing a reactive group at both ends
  • B is a fatty chain tertiary amine
  • C is a polyether primary amine
  • E is an organic ammonium blocking agent, n>1.
  • the substance A is a polysiloxane containing a reactive group at both ends, and the reactive group is generally an epoxy group, an amino group and a hydrogen group, and the structural formula is:
  • R is H, an epoxy group, an amino group or the like, and n is 0-260.
  • the substance A can be subjected to a ring-opening reaction by adding a base to octamethylcyclotetrasiloxane, and a silicone blocking agent containing hydrogen, an epoxy group and an amino group is added, and the molecular weight can be controlled by adjusting the amount of the terminal group. Size, control the value of n.
  • the silicone end group is generally tetramethyldihydrodisiloxane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 1,3-bis(3-glycidron C) -1,1,3,3-tetramethyldisiloxane, (3-aminopropyl)tetramethyldisiloxane, 1,3-bis(aminopropyl)tetramethyldisiloxane Alkane, etc.
  • the substance B is an aliphatic chain tertiary amine, and the terminal group is a tertiary amine, and the structure thereof is:
  • p 0-20.
  • the substance B may be tetramethylpentanediamine, tetramethyloctanediamine, tetramethylguanidinium diamine or the like.
  • the substance C is a polyether primary amine, and the end group is a primary amine ethylene oxide polymer, a propylene oxide polymer or an ethylene oxide/propylene oxide copolymer, and the structural formula is:
  • the substance C currently has two production methods, one is a catalytic reductive amination method: the polyether polyol, ammonia, hydrogen and a catalyst are subjected to a hydrogen-catalyzed reductive amination reaction at a certain temperature and pressure, which is a hydroxyl conversion.
  • the terminal amino group which is also the main method of industrial production; the other is the leaving group method: the first step is to firstly combine the polyether polyol with the easy leaving group (methanesulfonyl chloride, benzoic acid, p-toluene) The acid chloride or the like is reacted to introduce a corresponding leaving group at both ends of the polyether, followed by amination to form the corresponding polyetheramine.
  • the substance E is an organic ammonium type blocking agent, and the structure is an aliphatic hydrocarbon quaternary ammonium salt, and the structure thereof is:
  • R 1 and R 2 are an aliphatic hydrocarbon group having the formula CH 3 (CH 2 ) t , and X is Cl, Br, I, CH 3 COO wherein t is 0-50.
  • the preparation method of the above composite functional silicone softener has the following steps:
  • the organic solvent is an alcohol, an aromatic hydrocarbon or an alcohol ether.
  • the alcohol solvent is methanol, ethanol, isopropanol, butanol or n-propanol
  • the aromatic hydrocarbon solvent is benzene, toluene or xylene
  • the alcohol ether solvent is propylene glycol methyl ether or dipropylene glycol methyl ether.
  • the emulsifier is a mixed emulsifier which is compounded from two to four fatty alcohol polyoxyethylene ethers having different HLB values, and has an HLB value of 5-19.
  • Fatty alcohol polyoxyethylene ether also known as polyethoxylated fatty alcohol.
  • This type of surfactant is prepared by an addition reaction of a fatty alcohol with ethylene oxide and is represented by the following formula: RO-(CH 2 CH 2 O)nH.
  • R is generally a saturated or unsaturated hydrocarbon group having 12 to 18 carbon atoms, and may be a linear hydrocarbon group or a branched hydrocarbon group.
  • n is the number of additions of ethylene oxide, that is, the number of oxyethylene groups in the surfactant molecule.
  • the acid is glacial acetic acid, sulfuric acid, hydrochloric acid, formic acid, citric acid, succinic acid, and glycolic acid.
  • the desired water absorbability, quick-drying property, and moisture retention property are not impaired, and the skin feel is improved (in particular, it is not necessary to say that it can be imparted to softness and cotton even after water absorption).
  • a wax having an acid value is preferable from the viewpoint of balance of performance of the original smooth feeling. Further, from the viewpoint of very good touch and very softness of the skin, an aminosilicone cation-modified silicone oil is preferred.
  • the finishing compound is preferably 0.05 to 5% by mass based on 100% by mass of the cellulose-based fiber product, and is attached to 0.2 to 3% by mass, from the viewpoint of balance between skin sensation, water absorption, quick-drying property, and moisture retention. It is more preferable.
  • other compound 2 other than the finishing compound according to the present invention may be contained to the extent that the effects of the present invention are not impaired.
  • the other compound 2 include a softening agent, an antibacterial agent, an antistatic agent, a deodorant, and the like other than the finishing compound according to the present invention.
  • the finishing compound according to the present invention is preferably a total of the finishing compound of the present invention and the other compound 2 (active ingredient), and the content of the finishing compound according to the present invention is preferably 80% by mass or more, and more preferably 90% by mass or more. 100% by mass is most preferred.
  • the method of treating the finishing agent is not particularly limited.
  • the immersion treatment, the immersion treatment by the dip-nip method, the spray treatment, the bubble processing, and the coater are carried out.
  • a conventionally known method such as a method of performing immersion at the same time as coating can be suitably used.
  • the immersion treatment is excellent from the viewpoint of shortening the treatment process.
  • the treatment temperature is preferably 20 to 80 ° C, and more preferably 30 to 50 ° C.
  • a treatment time of 5 to 60 minutes is preferred, and 10 to 30 minutes is more preferred.
  • the third step is preferably subjected to a drying treatment after the treatment of the finishing agent.
  • the drying treatment method is not particularly limited, and for example, air drying, dry drying using hot air, wet drying using a high temperature chamber (H.T.S.), a high pressure chamber (H.P.S.), microwave irradiation drying, or the like can be employed. These drying methods may be used alone or in combination of two or more.
  • drying conditions 100 to 180 ° C is preferable, 100 to 170 ° C is more preferable, and 100 to 140 ° C is particularly preferable.
  • the temperature is lower than 100 ° C, the drying time tends to be lengthened, and the quick-drying effect tends to be weak.
  • the temperature exceeds 180 ° C, the billet becomes yellow and the strength of the billet tends to decrease.
  • the functional fiber product thus obtained is preferably 30% or less in quick-drying property (water residual ratio (%) in quick-drying evaluation).
  • the moisture retention rate is preferably from 5 to 15% by mass from the viewpoint of skin touch.
  • hydroxy-reactive compound K As the hydroxy-reactive compound K, the following compounds were used.
  • K1 to K6 hydroxyl-reactive compounds related to the present invention
  • K7 to K8 hydroxyl-reactive compounds other than the hydroxyl-reactive compound of the present invention
  • finishing agent the following compounds were used.
  • J1 an emulsion of oxidized polyethylene
  • KF-8002 amino silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.
  • acetic acid 0.5 parts by mass of acetic acid
  • SOFTANOL 50 5 parts by mass of SOFTANOL 50
  • J4 an emulsion of paraffin (an emulsion of a wax without an acid value)
  • paraffin wax 115°F, manufactured by Nippon Seiko Co., Ltd.
  • ARQUAD T-28 manufactured by Lion King Co., Ltd., active ingredient 28%, stearyl trimethyl chloride
  • a water-absorbent and quick-drying process agent wherein, as a compound represented by the formula (1), 10% by mass of the above K1, 1% by mass of S1 as a catalyst, and 0.5% by mass of an alkylene oxide of a higher alcohol as a penetrating agent are used.
  • the adduct was subjected to padding treatment with respect to a 100% bleached circular rib unit (weight per unit area: 130 g/m 2 ) to obtain a liquid pick-up ratio (PickUp) of 70% by mass. Then, it was dried at 120 ° C for 2 minutes to obtain a functional fibrous product (treated cloth 1).
  • the functional fiber product (treated cloth 1) was washed with water at 20 to 30 ° C for 20 minutes and at 120 ° C for 2 minutes to obtain a functional fiber product (treated cloth 2).
  • treatment cloth 2 The functional fiber product (treatment cloth 2) was treated with a finishing agent containing 2 g/l of finishing agent J1 at a bath ratio of 1:10 at 40 ° C for 20 minutes to prepare a liquid-liquid ratio of 120% by mass. Then, It was dried at 80 ° C for 1 hour using a tumble dryer to obtain a functional fiber product (treated cloth 3).
  • the obtained functional fiber product was measured for quick-drying property, skin touch property, water absorbability, and moisture retention by the following method. The results are shown in Table 1.
  • the billet mass of the 20 cm square treated cloth 1 was brought to a constant weight under the conditions of a temperature of 20 ° C and a relative humidity of 65% RH. 0.6 ml of water was added to the above-mentioned treated cloth 1 and allowed to stand under the conditions of 20 ° C and 65% RH for 60 minutes, and the mass change of the billet was observed.
  • the water residual ratio was calculated by the following formula, and the quick-drying property was evaluated. The smaller the water residual ratio (%), the better the quick-drying property was judged. In particular, when the water residual ratio (%) is 30% or less, it is judged that the quick-drying property is good.
  • Water residual ratio (%) (bone quality after 0.6 ml of water dripping - billet mass after 60 minutes) ⁇ 100 / 0.6
  • the touch sensitivity test was used to evaluate the skin sensation according to the following criteria.
  • ⁇ A soft touch is felt while being smooth. Compared with the skin feel of cotton 100% bleached round rib fabric, it is soft and has good skin feel.
  • ⁇ The same skin feel as cotton 100% bleached round rib fabric.
  • the test was carried out by the JIS L 1907:2010 7.1.1 dropping method.
  • the test cloth was allowed to stand at 20 ° C and a relative humidity of 80% for 2 hours, and the mass change was measured according to the following.
  • the formula calculates the moisturizing rate.
  • Moisture retention rate (%) (mass after 2 hours of standing at 20 ° C relative humidity of 80% - mass after drying for 3 hours at 105 ° C) ⁇ 100 / mass after drying at 105 ° C for 3 hours
  • the moisture retention rate of the treated cloth 1 obtained in Comparative Example 1 was used as a standard, and the following classification was performed.
  • the moisture retention rate of the test cloth is 70% or more to 100% or less with respect to the standard.
  • the moisture retention rate of the test cloth is 40% or more to less than 70% with respect to the standard.
  • the moisture retention rate of the test cloth is less than 40% with respect to the standard.
  • Example 2 to 6 and Comparative Examples 3 to 4 were obtained in the same manner as in Example 1 except that the type and amount of the hydroxyl-reactive compound and the catalyst were changed as shown in Tables 1 and 2. Dispose of cloth 3). The quick-drying property, the skin touch property, the water absorption property, and the moisture retention property of the obtained functional fiber product were measured similarly to Example 1. The results are shown in Tables 1 and 2.
  • the functional fiber product (treated cloth 2) obtained in Example 1 was subjected to padding treatment using a finishing agent containing 2% by mass of the finishing agent J2 to obtain a liquid-liquid ratio of 70% by mass. Then, it was dried at 120 ° C for 2 minutes and then dried at 160 ° C for 2 minutes to obtain a functional fibrous product (treated cloth 3).
  • the quick-drying property, the skin touch property, the water absorption property, and the moisture retention property of the obtained functional fiber product were measured similarly to Example 1. The results are shown in Table 1.
  • Example 8 A functional fiber product (treatment cloth 3) of Example 8 was obtained in the same manner as in Example 1 except that the functional fiber product (treated cloth 1) obtained in Example 1 was used.
  • the quick-drying was measured in the same manner as in Example 1. Sexuality, skin touch, water absorption, moisture retention. The results are shown in Table 1.
  • the functional fiber product (treatment cloth 2) obtained in Example 1 was treated with a finishing agent containing 2 g/l of finishing agent J5 at a bath ratio of 1:10 at 40 ° C for 20 minutes to prepare a liquid-liquid ratio of 120% by mass. Then, it was dried at 80 ° C for 1 hour in a tumble dryer to obtain a functional fiber product.
  • the quick-drying property, the skin touch property, the water absorption property, and the moisture retention property of the obtained functional fiber product were measured similarly to Example 1. The results are shown in Table 1.
  • the cotton 100% bleached circular rib unit (weight per unit area: 130 g/m 2 ) was subjected to padding treatment with water to prepare a liquid-liquid ratio of 70% by mass. Then, it was dried at 120 ° C for 2 minutes to obtain a functional fibrous product (treated cloth 1). The quick-drying property, the skin touch property, the water absorption property, and the moisture retention property of the obtained functional fiber product were measured similarly to Example 1. The results are shown in Table 2.
  • the treated cloth 2 obtained in the middle of Example 1 was used as the functional fiber product (treated cloth 2) of Comparative Example 2.
  • the quick-drying property, the skin touch property, the water absorption property, and the moisture retention property of the obtained functional fiber product were measured similarly to Example 1. The results are shown in Table 2.
  • the functional fiber products (treated cloth 3) of Comparative Examples 5 to 6 were obtained in the same manner as in Example 2 except that the finishing agent was changed as shown in Table 2.
  • the quick-drying property, the skin touch property, the water absorption property, and the moisture retention property of the obtained functional fiber product were measured similarly to Example 2. The results are shown in Table 2.
  • the functional fiber product (treatment cloth 1) obtained in Comparative Example 1 was treated with a finishing agent containing 2 g/l of finishing agent J1 at a bath ratio of 1:10 at 40 ° C for 20 minutes to prepare a liquid-liquid ratio of 120% by mass. . Then, it was dried at 80 ° C for 1 hour using a tumble dryer to obtain a functional fibrous product (treated cloth 3) of Comparative Example 7.
  • a functional fibrous product treated cloth 3 of Comparative Example 7.
  • the quick-drying property, the skin touch property, the water absorbability, and the moisture retention property were measured in the same manner. The results are shown in Table 2.
  • the oxidized alkane adduct of a higher alcohol as a penetrating agent was subjected to padding treatment on a cotton 100% bleached circular rib fabric (weight per unit area: 130 g/m 2 ) to obtain a liquid-liquid ratio of 60% by mass. Then, it was dried at 110 ° C for 1 minute to obtain a treated cloth 1.
  • the water content of the treated cloth 1 was adjusted so as to be 20% by mass. Specifically, the treated cloth 1 was dried at 105 ° C for 3 hours, and subjected to padding treatment with water to have a water content of 60% by mass, and air-dried at 20 ° C and a relative humidity of 65% to obtain a water content. 20% by mass.
  • the treated cloth 1 having a water content adjusted by a flat plate press (manufactured by Nippon Press Co., Ltd., model PMC3E) was pressure-treated at 160 ° C for 20 seconds under a pressure of 1 kgf/cm 2 .
  • the treated cloth 1 after the pressure treatment was washed with water at 25 to 30 ° C for 20 minutes, and then, as a softening agent, 3% by mass containing Nicca Silicone AMC800E (manufactured by Rihua Chemical Co., Ltd.) and 3 containing Finetex PE140.
  • the mass% of the treatment liquid was subjected to a padding treatment to obtain a liquid-liquid ratio of 60% by mass.
  • the treated cloth 2 after the padding treatment was dried at 25 ° C for 1 day to obtain a treated cloth 3.
  • the quick-drying property was 48%, and the skin touch property was ⁇ , water absorption: >60 s, moisture retention: ⁇ .
  • a cellulose-based fiber product having excellent skin feel, excellent water absorbability and moisture retention, and cellulose-based fibers, and a quick-drying property.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

纤维素系纤维制品的制造方法、由该制造方法得到的纤维素系制品以及在该制造方法中使用的吸水速干加工剂。该功能性纤维制品的制造方法包括：将纤维素系纤维制品用含有选自由N-羟甲基系化合物、乙二醛、丙烯酰胺系化合物及有机酸构成的组的至少1种羟基反应性化合物的吸水速干剂进行处理的第1工序；用含有选自由聚醚改性硅油、具有酸值的蜡及含聚环氧烷烃的聚氨酯树脂构成的组的至少1种整理剂进行处理的第2工序。该方法所得纤维素系制品具有肌肤触感性良好，吸水性、保湿性以及速干性较好的特点。

Description

功能性纤维制品的制造方法及吸水速干加工剂 技术领域
本发明涉及具有吸水速干性的功能性纤维制品的制造方法及该制造方法中使用的吸水速干加工剂。
背景技术
纤维素系纤维是肌肤触感性良好的原材料,吸水性与保湿性优异,但具有一旦湿润,难以干燥(速干性差)的缺点。
为了改良这样的纤维素系纤维的缺点,已进行了各种研讨。
例如,专利文献1中记载了赋予纤维用吸水速干性的组合物,其特征在于,含有特定的单体共聚而得到的共聚体与有机溶剂。
专利文献2中记载了含有纤维素系纤维的布帛的加工方法,其特征在于,其是对含有纤维素系纤维的布帛,赋予含有交联剂及交联催化剂的处理液后,将该布帛的含水率调至一定,接着进行接触型热处理,在湿热高压下进行交联反应。
专利文献3中记载了吸湿发热性纤维素系纤维,其是对纤维素纤维赋予水溶液,进行加热处理而得到的,该水溶液含有聚亚烷基二醇、N-羟甲基系树脂加工剂及其反应催化剂以及在分子中具有羟基与磺酸基的水溶性聚合物。
专利文献4中记载了纤维素系布帛的加工方法,其是将纤维素系布帛以混合水溶液进行处理,再进行加热处理的方法,该混合水溶液是N-羟甲基系树脂加工剂及其反应催化剂与在分子中具有羟基和氨基及/或羧基的水溶性物质混合溶解在水中的混合水溶液,或者,将纤维素系布帛以混合水溶液进行处理,再进行加热处理的方法,该混合水溶液是N-羟甲基系树脂加工剂及其反应催化剂与在分子中具有2个以上羟基的水溶性物质及在分子中具有 2个以上氨基及/或羧基的水溶性物质混合溶解于水的混合水溶液。
专利文献5中记载了纤维素系纤维的加工方法,该加工方法采用纤维处理剂及含该纤维处理剂及酸性催化剂的处理浴,该纤维处理剂是由1摩尔亚乙基脲环含1.4～2摩尔范围的羟甲基化的羟甲基二羟基亚乙基脲系化合物,以及该羟甲基二羟基亚乙基脲系化合物100重量份,含平均分子量处于400～1,000之间的聚乙二醇5重量份以上而成,该处理浴在25℃、pH处于2.5～5范围适用于纤维素系纤维。
但是,实情是,专利文献1～5中都没有得到肌肤触感性良好、具有吸水性与保湿性优异的所谓纤维素系纤维的长处,同时具有速干性的纤维素系纤维制品。
现有技术文献
专利文献
【专利文献1】特开2005-89882号公报
【专利文献2】特开2006-052480号公报
【专利文献3】特开2002-348780号公报
【专利文献4】特开2000-178881号公报
【专利文献5】特开2001-181968号公报
发明内容
发明所要解决的课题
本发明是鉴于上述现有技术中具有的课题而提出的,目的是提供肌肤触感性良好,具有吸水性、保湿性、速干性的纤维素系纤维制品。
用于解决课题的手段
本发明人等,为了解决上述的课题进行悉心研究，结果发现, 对纤维素系纤维制品,采用含特定的化合物的吸水速干加工剂进行处理,接着用含特定的化合物的整理剂进行处理,可提供肌肤触感性良好,具有吸水性、保湿性、速干性的纤维素系纤维制品,基于此见解完成本发明。
本发明提供功能性纤维制品的制造方法,该制造方法包含:将纤维素系纤维制品用含有选自由N-羟甲基系化合物、乙二醛、丙烯酰胺系化合物、及有机酸构成的组中的至少一种羟基反应性化合物的吸水速干加工剂进行处理的第1工序；接着,用含有选自由聚醚改性硅油、具有酸值的蜡及含聚环氧烷烃的聚氨酯树脂构成的组中的至少一种化合物的整理剂进行处理的第2工序。在本发明中,上述羟基反应性化合物优选N-羟甲基系化合物。另外,N-羟甲基系化合物优选由下述通式(1)表示的化合物。
【化1】
Figure PCTCN2017117485-appb-000001
通式(1)中,R1分别独立地为氢、碳数1～3的烷基、羟甲基、碳数1～3的烷基-氧基甲基、-CH2-O-(R3O)n-H，n为1～5,R3为碳数2～4的亚烷基,R2分别独立地为氢、OH基、碳数1～3的烷基,p为0或者1。
在本发明中,整理剂优选为含有氨基硅油阳离子改性硅油、 具有酸值的蜡的整理剂。
另外,优选的为，由通式(1)表示的化合物中,2个R1为-CH2-O-(R3O)n-H(R3为亚乙基,n＝2),并且2个R2为OH基。
本发明还提供在上述第1工序使用的吸水速干加工剂。
发明的效果
按照本发明,提供：肌肤触感性良好,具有吸水性、保湿性优良的所谓纤维素系纤维的长处,同时具有速干性的纤维素系纤维制品。
具体实施方式
本发明涉及的功能性纤维制品的制造方法包含:将纤维素系纤维制品用吸水速干加工剂进行处理的第1工序,所述吸水速干加工剂含有选自由N-羟甲基系化合物、乙二醛、丙烯酰胺系化合物及有机酸构成的组中的至少一种羟基反应性化合物；接着,用整理剂处理的第2工序,所述整理剂含有选自由聚醚改性硅油、氨基硅油阳离子改性硅油、具有酸值的蜡及含聚环氧烷烃的聚氨酯树脂构成的组的至少一种整理化合物。
作为纤维素系纤维制品,可以举出棉、麻、亚麻、纸浆、细菌纤维素纤维等天然纤维素纤维制品；人造丝等再生纤维素纤维制品等纤维素纤维制品。纤维素系纤维制品,还可以包含聚酯、尼龙、维尼龙、丙烯腈纤维、聚氨酯、聚酰胺、聚乙烯、聚丙烯等合成纤维；羊毛、绢等动物性纤维；玻璃纤维、碳纤维等无机纤维等,可在棉花、丝、织物、针织物、无纺布、缝制品等形态进行使用。
这样的纤维素系纤维制品,从肌肤触感性、吸水性、速干性的观点考虑,纤维素系纤维制品中的纤维素纤维含35质量％以上是优选的,含50质量％以上是更优选的,含80质量％以上是尤其优 选的,含100％是最优选的。
本发明中的吸水速干加工剂,是本发明涉及的功能性纤维制品的制造方法中使用的吸水速干加工剂,含有选自N-羟甲基系化合物、乙二醛、丙烯酰胺系化合物及有机酸构成的组中的至少1种羟基反应性化合物。
作为N-羟甲基系化合物,可以举出二羟甲基脲、羟甲基密胺、由通式(1)表示的化合物等。
作为丙烯酰胺系化合物,可以举出N-(羟甲基)丙烯酰胺、N,N′-亚甲基双丙烯酰胺等。
作为有机酸,可以举出乙醇酸、乳酸、柠檬酸、多元羧酸等。
这些的羟基反应性化合物中,从肌肤触感性、吸水性、速干性、保湿性的观点考虑,使用N-羟甲基系树脂是优选的,使用下述通式(1)表示的化合物是更优选的。
【化2】
Figure PCTCN2017117485-appb-000002
(式中,R1分别独立地为氢、碳数1～3的烷基、羟甲基、碳数1～3的烷基-氧基甲基、-CH2-O-(R3O)n-H,n为1～5,R3为碳数2～4的亚烷基,R2分别独立地为氢、OH基、碳数1～3的烷基,p为0或者1。)
其中,从可以得到肌肤触感性良好、吸水性、速干性、保湿 性达到高度平衡的观点考虑,优选的是，p为0，2个R1为-CH2-O-(R3O)n-H(R3为亚乙基,n＝2),并且，2个R2为OH基的化合物。
这样的羟基反应性化合物,从肌肤触感性、吸水性、速干性、保湿性的平衡的观点考虑,相对100质量％的纤维素系纤维制品使用0.5～30质量％是优选的,使用1～20质量％是更优选的。如低于0.5质量％时,则有难以呈现速干效果的倾向,如大于30质量％时,则得不到与使用量相符合的速干效果,肌肤触感性的固化及强度有降低的倾向。
本发明涉及的吸水速干加工剂中,为了提高羟基反应性化合物的反应性,可以含有催化剂。作为这样的催化剂,可以举出AlCl3、Al2(SO4)3、MgCl2、Mg(H2PO4)2、硫酸镁、Zn(BF4)2、Zn(NO3)2、ZnCl2、Mg(BF4)2、Mg(ClO4)2、磷酸氢钠、Al2(OH)4Cl2等各种金属盐；烷醇胺的酸式盐；醋酸、盐酸、硫酸、磷酸等强酸的铵盐；乙醇酸、马来酸、乳酸、柠檬酸、酒石酸及草酸等有机酸类。这些催化剂的使用量,相对100质量％的纤维素系纤维制品为0.1～5质量％是优选的。当不足0.1质量％时,有难呈现速干效果的倾向,当超过5质量％时,有坯料的变黄或坯料强度降低的倾向。
另外,本发明涉及的吸水速干加工剂中,为了使纤维素系纤维制品用羟基反应性化合物进行均匀地处理的反应顺利进行,可根据需要,含有浸透剂。作为浸透剂,例如,可以举出甘油、乙二醇、聚乙二醇、聚丙二醇等多元醇类；乙二醇单乙醚、二乙二醇单乙醚、乙二醇单甲醚、二乙二醇单甲醚、二乙二醇单丁醚等醚醇类；聚氧化亚烷基烷基醚类；二甲基甲酰胺、吗啉、2-吡咯烷酮、二甲基乙酰胺、N-甲基吡咯烷酮等含氮溶剂类；醋酸乙酯、醋酸异丙酯、醋酸丁酯、醋酸戊酯、醋酸乙二醇单甲醚、醋酸乙二醇单乙醚、γ- 丁内酯等酯类等。这样的浸透剂,相对100质量％的纤维素系纤维制品,使用0.1～5质量％是优选的。
另外,本发明涉及的吸水速干加工剂中,在不损害本发明效果的程度,除本发明涉及的羟基反应性化合物、上述催化剂及上述浸透剂以外,还可以含有其他的化合物1。作为其他的化合物1,可以举出本发明涉及的羟基反应性化合物以外的羟基反应性化合物、柔软剂、抗菌剂、抗静电剂,消臭剂等。
本发明涉及的羟基反应性化合物,相对本发明涉及的羟基反应性化合物与其他的化合物1的合计(有效成分),含80质量％以上本发明涉及的羟基反应性化合物是优选的,含90质量％以上是更优选的,含100质量％是最优选的。
在第1工序中,作为将纤维素系纤维制品用吸水速干加工剂进行处理的方法,未作特别限定,例如,可适当使用此前公知的方法如通过浸渍处理、由浸渍-压面(dip-nip)方式构成的浸轧(padding)处理、喷雾处理、泡加工、涂料器进行涂覆的同时进行浸入的方法等。其中,从易于处理的观点考虑,通过由浸渍-压面(dip-nip)方式构成的浸轧处理、喷雾处理、压泡加工、涂料进行涂覆的同时进行浸入的方法是优选的。
就第1工序而言,在纤维素系纤维制品用吸水速干加工剂加以处理后,进行干燥处理是优选的。作为干燥处理的方法,未作特别限定,例如,可以采用风干、用热风的干式干燥；使用高温室(H.T.S.)、高压室(H.P.S.)的湿式干燥；微波照射式干燥等。这些干燥方法,可以1种单独使用,或者,2种以上组合使用。
作为干燥条件,于100～180℃干燥1～30分钟是优选的,对于干燥温度，100～170℃是更优选的,100～140℃是尤其优选的。当低于100℃时,除干燥时间有加长的倾向外,速干效果也有变弱的倾向。当超过180℃时,坯料强度有降低的倾向。
本发明涉及的功能性纤维制品的制造方法中,从肌肤触感性、吸水性、速干性、保湿性的观点考虑,特别是从提高肌肤触感性与速干性的观点考虑,在纤维素系纤维制品用吸水速干加工剂进行处理的第1工序与用整理剂进行处理的第2工序之间,进行洗涤工序是优选的。
作为这样的洗涤工序,未作特别限定,例如,可以使用连续式洗涤、间歇式洗涤、利用流水的洗涤等。其中,从洗涤效率的观点考虑,进行间歇式洗涤是优选的,于5～90℃进行5～60分钟洗涤是优选的,于20～90℃进行20～50分钟洗涤是更优选的,于70～90℃进行20～30分钟洗涤是尤其优选的。
本发明涉及的第2工序为：在上述第1工序后,采用含有选自聚醚改性硅油、氨基硅油阳离子改性硅油、具有酸值的蜡及含聚环氧烷烃的聚氨酯树脂构成的组中的至少1种整理化合物的整理剂进行处理的工序。
作为聚醚改性硅油,可以使用在硅氧烷骨架的末端、侧链及主链之中的至少任何一处导入有聚环氧烷烃(特别是聚环氧乙烷)的聚醚改性硅油。
就该聚醚改性硅油而言,氨基、亚氨基、酰胺基、环氧基、羧基、甲醇基、烷基等聚环氧烷烃以外的官能团也可被导入硅氧烷骨架的末端、侧链及主链之中的至少任何一处。
作为这样的聚醚改性硅油的市场销售的商品,例如,可以举出KF-351A,KF-352A,KF-353,KF-354L,KF-355A,KF-615A,KF-945,KF-640,KF-642,KF-643,KF-644,KF-6020,KF-6204,X-22-4515,KF-6011,KF-6012,KF-6015,KF-6017,X-22-2516,KF-6004,X-22-2516(任何一种均为信越化学工业(株)制),SH8700,SF8410,SH8400,L-7002,FZ-2104,FZ-77,L-7604,FZ -2203,FZ-2208,BY16-891,FZ-3789,BY16-876,FZ-3736,SF8421,SF8419(任何一种均为东丽道康宁(株)制)等。聚醚改性硅油,从吸水性的观点考虑,HLB为4以上是优选的,HLB为6以上是更优选的。
作为具有酸值的蜡,可以使用巴西棕榈蜡、小烛树蜡、棕榈蜡、漆树蜡等植物系蜡；蜜蜡、鲸蜡等动物系蜡；氧化蜡等具有酸值的蜡,其中,氧化蜡是优选的。
作为氧化蜡,例如,可以举出将聚乙烯通过空气氧化或者热分解导入有羧基的蜡,聚乙烯与丙烯酸、甲基丙烯酸等乙烯基羧酸进行共聚而成的蜡等。作为市售品,例如,可以举出A-C673P,A-C680,A-C655,A-C629,A-C629A,A-C656,A-C307,A-C307A,A-C316,A-C316A,A-C325,A-C329,A-C330,A-C395,A-C395A,A-C540,A-C540A,A-C580,A-C5120,A-C5180(任何一种均为Honeywell International社制),三井Haiwatsukusu 4051E,4052E,4202E,4252E,1105A,2203A,3202A(任何一种均为三井化学社制),Sanwatsukusu E-310(三洋化成工业社制)等。氧化蜡的熔点,用DSC法测定的熔点为30～200℃是优选的,50～150℃是更优选的。另外,采用JIS K 0070～1992的3.酸值中记载的方法测定的酸值为5～250mgKOH/g是优选的,5～100mgKOH/g是更优选的,10～80mgKOH/g是尤其优选的。另外,按照ASTM D-3954测定的滴点为50～150℃是优选的,90～120℃是更优选的。
这样的具有酸值的蜡,从易于使用的观点考虑,蜡于水性介质中分散(包括乳化、溶解)而成的产物是优选的。作为蜡于水性介质中分散的方法,例如,可以举出蜡与水性介质、根据需要的分散剂进行混合搅拌的方法。混合搅拌时,可以使用乳化分散机MILDER、高速搅拌机、均质器、超声波均质器、高速混合机、珠 磨机、珠球磨机、砂磨机(DYNO-MILL)、ASPEC磨机(ASPEC MILL)、笼式磨机(BASKET MILL)、球磨机、纳米混合机(NANOMIZER)、ARTI混合机(ARTI MISER)、星暴(STAR-BURST)等迄今公知的乳化分散机。这些乳化分散机,可以单独使用1种,或者,2种以上组合使用。
作为水性介质,水、或者水与在水中混和的亲水性溶剂的混合介质是优选的。作为亲水性溶剂,例如,可以举出甲醇、乙醇、异丙醇、乙二醇、二乙二醇、己二醇、丙三醇、丁基乙二醇、丁基二乙二醇、3-甲氧基-3-甲基丁醇(SOLFIT)、N-甲基吡咯烷酮、二甲基甲酰胺、二甲基亚砜等。
上述分散液,从分散稳定性的观点考虑,还含有分散剂或者表面活性剂是优选的。作为这样的分散剂或者表面活性剂,只要可以提高乳化分散稳定性的即可，而未作特别限定,例如,可以举出公知的非离子性表面活性剂、阴离子性表面活性剂、阳离子性表面活性剂、两性表面活性剂等。这些可以单独使用1种,或者,2种以上组合使用。
作为含聚环氧烷烃的聚氨酯树脂,使(a)有机多异氰酸酯与(b)多元醇反应所得到的在末端具有异氰酸酯基的氨基甲酸酯预聚物视场合而定在乳化剂的存在下、在水中乳化分散,并采用(c)具有2个以上氨基及/或亚氨基的多胺化合物进行链增长反应所得到的水性聚氨酯树脂是优选的。
作为(a)有机多异氰酸酯,未作特别限定,例如,可以举出六亚甲基二异氰酸酯、三甲基六亚甲基二异氰酸酯等脂肪族多异氰酸酯化合物；异佛尔酮二异氰酸酯、加氢苯二亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、降冰片烷二异氰酸酯、1,3-双(异氰酸根合甲基)环己烷等脂环式多异氰酸酯化合物；甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、萘二异氰酸酯、联甲苯胺二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯等芳香族 多异氰酸酯化合物等。这些多异氰酸酯化合物可1种单独使用,或者,2种以上组合使用。
另外,作为(b)多元醇,只要具有2个以上羟基的即可，不作特别限定,除聚酯多元醇、聚碳酸酯多元醇、聚醚多元醇等以外,也可以使用具有醚键与酯键的聚醚酯多元醇。
作为这样的聚酯多元醇,例如,可以举出聚己二酸乙二醇酯、聚己二酸丁二醇酯、聚己二酸亚乙基亚丁基酯、聚六亚甲基间苯二甲酸己二酸酯、聚丁二酸乙二醇酯、聚丁二酸丁二醇酯、聚癸二酸乙二醇酯、聚癸二酸丁二醇酯、聚-ε-己内酯二醇、聚(3-甲基-1,5-亚戊基)己二酸酯、1,6-己二醇与二聚酸的缩聚物、1,6-己二醇与己二酸与二聚酸的共缩聚物、壬二醇与二聚酸的缩聚物、乙二醇与己二酸与二聚酸的共缩聚物等。
作为聚碳酸酯多元醇,例如,可以举出聚四亚甲基碳酸酯二醇、聚六亚甲基碳酸酯二醇、聚-1,4-环己烷二亚甲基碳酸酯二醇、1,6-己二醇聚碳酸酯多元醇等。
作为聚醚多元醇,例如,可以举出聚乙二醇、聚丙二醇、聚丁二醇的均聚物、嵌段共聚物、无规共聚物,环氧乙烷与环氧丙烷、环氧乙烷与环氧丁烷的无规共聚物及嵌段共聚物等。
这样的(b)多元醇,可单独使用1种,或者,也可2种以上组合使用。
另外,(b)多元醇中,例如,也可并用2,2-二羟甲基丙酸、2,2-二羟甲基丁酸等(d)具有羧基与2个以上的活性氢的化合物。这样的(d)具有羧基与2个以上的活性氢的化合物,可单独使用1种,或者,也可2种以上组合使用。
这样的(b)多元醇,从吸水性的观点考虑,相对(b)多元醇的总质量,含30％以上的环氧乙烷成分是优选的,含40％以上是更优选的。
本发明中,作为制造在末端具有异氰酸酯基的氨基甲酸酯预聚物(以下,又称异氰酸酯基末端预聚物)的具体的方法,没有特别限定,例如,可以采用此前公知的一段式的所谓一步发泡法、多段式的异氰酸酯加成聚合反应法等来制造。此时的反应温度,40～150℃是优选的。另外,这样的反应之际,可根据需要,添加二月桂酸二丁基锡、辛酸亚锡、2-乙基己酸二丁基锡、三乙胺、三亚乙基二胺、N-甲基吗啉等反应催化剂。另外,在反应中或者反应终止后,可添加与异氰酸酯基不反应的有机溶剂。作为这样的有机溶剂,例如,可以使用丙酮、甲乙酮、甲苯、四氢呋喃、二噁烷、二甲基甲酰胺、N-甲基吡咯烷酮等。
使用(d)具有羧基与2个以上的活性氢的化合物时,对于羧基,可在制造异氰酸酯基末端预聚物前、制造中或制造后,采用适宜的公知的方法进行中和。用于中和的化合物,没有特别限定,例如,可以举出三甲胺、三乙胺、三正丙胺、三丁胺、N-甲基-二乙醇胺、N,N-二甲基单乙醇胺、N,N-二乙基单乙醇胺、三乙醇胺等胺类；氢氧化钾、氢氧化钠、氨等。这样的上述化合物之中,三甲胺、三乙胺、三正丙胺、三丁胺等叔胺类是特别优选的。
在使异氰酸酯基末端预聚物于水中乳化分散时,例如,可以使用高速搅拌机、均质器、分散机等乳化机。另外,使异氰酸酯基末端预聚物于水中乳化分散时,使异氰酸酯基末端预聚物特别地在不用乳化剂下在室温～40℃的温度范围乳化分散于水中,可以尽可能抑制异氰酸酯基与水的反应,因此是优选的。另外,在这样的乳化分散时,可根据需要添加磷酸、磷酸二氢钠、磷酸氢二钠、对甲苯磺酸、己二酸、氯化苯甲酰等反应抑制剂。
就本发明涉及的含聚环氧烷烃的聚氨酯树脂而言,使异氰酸酯基末端预聚物于水中乳化分散后,采用(c)具有2个以上氨基及/或亚氨基的多胺化合物进行链增长反应,可得到作为目标的含聚 环氧烷烃的聚氨酯树脂。
这样的(c)具有2个以上氨基及/或亚氨基的多胺化合物,例如,可以举出乙二胺、丙二胺、四亚甲基二胺、六亚甲基二胺、二氨基环己基甲烷、哌嗪、肼、2-甲基哌嗪、异佛尔酮二胺、降冰片烷二胺、二氨基二苯基甲烷、甲苯二胺、苯二亚甲基二胺等二胺；二乙撑三胺、三乙撑四胺、四乙撑五胺、亚氨基双丙胺、三(2-氨基乙基)胺等多胺；从二伯胺及单羧酸衍生的酰胺胺(amideamine)；二伯胺的单酮亚胺等水溶性胺衍生体；草酸二酰肼、丙二酸二酰肼、琥珀酸二酰肼、戊二酸二酰肼、己二酸二酰肼、癸二酸二酰肼、马来酸二酰肼、富马酸二酰肼、衣康酸二酰肼、1,1’-亚乙基肼、1,1’-三亚甲基肼、1,1’-(1,4-亚丁基)二肼等肼衍生体。这些具有2个以上氨基及/或亚氨基的多胺化合物,可单独使用1种,或者,也可2种以上组合使用。
另外,本发明中,异氰酸酯基末端预聚物的链增长反应可通过向上述异氰酸酯基末端预聚物的乳化分散物中添加(c)具有2个以上氨基及/或亚氨基的多胺化合物来进行。另外,也通过可在(c)具有2个以上氨基及/或亚氨基的多胺化合物中添加上述异氰酸酯基末端预聚物的乳化分散物来进行。链增长反应优选在反应温度20～40℃进行,通常,在30～120分钟之间完成。在制造异氰酸酯基末端预聚物时使用有机溶剂的情形下,例如,在链增长反应终止后,通过用减压蒸馏等除去有机溶剂是优选的。
作为一种复合功能有机硅柔软剂，其通式为E-B[ABC]n-E、E-C[ABC]n-E、E-B[ACB]n-E、[AB]n、[AC]n、EAE、E-C[ACB]n-E、E-B[AB]n-E和E-C[AC]n-E。其中A为两端含活性基团的聚硅氧烷，B为脂肪链叔胺类物质，C为聚醚伯胺类物质，E为有机铵类封锁剂，n>1。
所述物质A为两端含活性基团的聚硅氧烷，活性基团一般为环氧基、氨基和氢基，其结构通式为：
Figure PCTCN2017117485-appb-000003
R为H、环氧基、氨基等，n为0-260。
所述物质A可以通过在八甲基环四硅氧烷中加碱进行开环反应，加入含氢、环氧基和氨基的有机硅封端剂，通过调节封端基的用量可以控制分子量的大小，控制n的数值。
所述有机硅封端基一般为四甲基二氢基二硅氧烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷、1,3-双(3-缩水甘油丙基)-1,1,3,3-四甲基二硅氧烷、(3-氨基丙基)四甲基二硅氧烷，1,3-二(氨基丙基)四甲基二硅氧烷等。
所述物质B为脂肪链叔胺，并且端基为叔胺，其结构为：
Figure PCTCN2017117485-appb-000004
p为0-20。
所述物质B可以为四甲基戊二胺、四甲基辛二胺、四甲基壬二胺等。
所述物质C为聚醚伯胺，并且端基为伯胺的环氧乙烷聚合物、环氧丙烷聚合物或环氧乙烷/环氧丙烷共聚物，其结构通式为：
Figure PCTCN2017117485-appb-000005
q为0-50，l为0-50.
所述物质C目前有两种生产方法，一种为催化还原胺化法：将聚醚多元醇、氨、氢气和催化剂在一定的温度、压力下进行临氢催化还原胺化反应，是羟基转化成端氨基，这也是目前工业化生产的主要方法；另一种为离去基团法：其步骤是首先将聚醚多元醇与易离去基团(甲磺酰氯、苯甲酸基、对甲苯甲酰氯等)反应，在聚醚两端引入相应离去基团，然后进行胺化反应生成相应的聚醚胺。
所述物质E为有机铵类封锁剂，该结构为脂肪烃季铵盐类，其结构为：
Figure PCTCN2017117485-appb-000006
R1、R2为脂肪烃基，通式为CH3(CH2)t，X为Cl、Br、I、CH3COO其中t为0-50。
上述复合功能有机硅柔软剂的制备方法，其步骤如下：
1)将聚醚伯胺、脂肪链叔胺、有机铵类封锁剂和端环氧硅油直接加入反应釜或借助有机溶剂进行，加热到60-150℃，在此温度下反应4-40小时生成无色至黄色透明粘稠液体；
2)将上述得到的产物加入乳化剂和酸，缓慢滴加去离子水，乳化至无色至黄色透明液体，即为复合功能有机硅柔软剂。
所述有机溶剂为醇类、芳香烃类或醇醚类。醇类溶剂为甲醇、乙醇、异丙醇、丁醇或正丙醇，所述芳香烃类溶剂为苯、甲苯或二甲苯，所述的醇醚类溶剂为丙二醇甲醚、二丙二醇甲醚、丙二醇正丁醚、丙二醇正丙醚或乙二醇单丁醚。
所述乳化剂为混合乳化剂，其由两种至四种HLB值不同的脂肪醇聚氧乙烯醚复配而成，其HLB值在5-19之间。脂肪醇聚氧乙烯醚，又称为聚乙氧基化脂肪醇。这种类型表面活性剂是用脂肪醇与环氧 乙烷通过加成反应而制得的，用以下通式表示：R-O-(CH2CH2O)n-H。R一般为饱和的或不饱和的碳原子数为12～18的烃基，可以是直链烃基，也可以是带支链的烃基。n是环氧乙烷的加成数，也就是表面活性剂分子中氧乙烯基的数目。
所述酸采用冰醋酸、硫酸、盐酸、甲酸、柠檬酸、琥珀酸和羟基乙酸等。
在这样的整理化合物之中,从实质上不损害所期望的吸水性、速干性、保湿性,提高肌肤触感性(特别是吸水前不用说、即使在吸水后,也可以赋予柔软、且棉本来顺滑的手感)的性能平衡的观点考虑,具有酸值的蜡是优选的。另外，从肌肤触感非常好并且非常柔软等的观点来看，优选氨基硅油阳离子改性硅油。
这样的整理化合物,从肌肤触感性、吸水性、速干性、保湿性的平衡的观点考虑,相对纤维素系纤维制品100质量％附着0.05～5质量％是优选的,附着0.2～3质量％是更优选的。
本发明涉及的整理剂中,在不损害本发明效果的程度内,也可包含本发明涉及的整理化合物以外的其他的化合物2。作为其他的化合物2,可以举出本发明涉及的整理化合物以外的柔软剂、抗菌剂、抗静电剂、消臭剂等。
本发明涉及的整理化合物,相对本发明涉及的整理化合物与其他的化合物2的合计(有效成分),本发明涉及的整理化合物含量为80质量％以上是优选的,含90质量％以上是更优选的,含100质量％是最优选的。
在第2工序中,作为处理整理剂的方法,未作特别限定,例如,通过浸渍处理、由浸渍-压面(dip-nip)方式构成的浸轧处理、喷雾处理、泡加工、涂料器进行涂覆的同时进行浸入的方法等此前公知的方法,均可适当使用。
第2工序中,从缩短处理工序的观点考虑,进行浸渍处理是优 选的。在该场合,处理温度为20～80℃是优选的,30～50℃是更优选的。处理时间为5～60分钟是优选的,10～30分钟是更优选的。
第3工序优选在整理剂处理后进行干燥处理。作为干燥处理的方法,未作特别限定,例如,可以采用风干、利用热风的干式干燥；使用高温室(H.T.S.)、高压室(H.P.S.)的湿式干燥；微波照射式干燥等。这些干燥方法,可以单独使用1种,或者,2种以上组合使用。
作为干燥条件,100～180℃是优选的,100～170℃是更优选的,100～140℃是尤其优选的。当低于100℃时,干燥时间有加长的倾向,速干效果也有变弱的倾向,当超过180℃时,有坯料变黄及坯料强度降低的倾向。
这样得到的功能性纤维制品,速干性(速干性评价中的水分残留率(％))为30％以下是优选的。
另外,本发明涉及的功能性纤维制品,从肌肤触感性的观点考虑,保湿率为5～15质量％是优选的。
【实施例】
以下,举出实施例更详细地说明本发明,但本发明不受这些实施例的限定。
作为羟基反应性化合物K,使用以下的化合物。
K1～K6:本发明涉及的羟基反应性化合物
K1:〔4,5-二羟基-1,3-双(羟基甲基)-2-咪唑啉二酮的二甘醇反应物＝通式(1)中,2个R1为-CH2-O-(R3O)nH(R3为亚乙基,n＝2),并且,2个R2为OH基的化合物〕
K2:N,N′-亚甲基双丙烯酰胺
K3:N-(羟基甲基)丙烯酰胺
K4:乙二醛
K5:二羟甲基二羟基亚乙基脲
K6:乙醇酸
K7～K8:本发明涉及的羟基反应性化合物以外的羟基反应性化合物
K7:1,4-丁二醇二缩水甘油醚
K8:二甘醇二缩水甘油醚
作为催化剂S,使用以下的化合物。
S1:MgCl2
S2:过硫酸钠
S3:次磷酸钠
作为整理剂,使用以下的化合物。
J1:氧化聚乙烯的乳化物
往高压反应釜中加入20质量份的A-C 629(氧化聚乙烯,HONEYWELL INTERNATIONAL公司制)、5质量份的SOFTANOL 50、75质量份的水,在120℃搅拌1小时,得到氧化聚乙烯的乳化物。
J2:TORAY SILICONE SF-8410(聚醚改性硅油,HLB＝6)
J3:氨基硅油的乳化物(不含聚醚的硅油的乳化物)
往烧瓶中添加20质量份的KF-8002(氨基硅油,信越化学工业株式会社制)、0.5质量份的醋酸、5质量份的SOFTANOL 50,搅拌均匀,一边搅拌一边在25～35℃加74.5质量份的水,得到氨基硅油的乳化物。
J4:石蜡的乳化物(不具有酸值的蜡的乳化物)
往烧瓶中添加20质量份的石蜡(115°F,日本精蜡株式会社制),5质量份的ARQUAD T-28(狮王(株)制,有效成分28％,硬脂基三甲基氯化铵),2质量份的SOFTANOL 50,3质量份的SOFTANOL70,加热熔融均匀,一边搅拌一边添加85～95℃热水70质量份,得到石蜡的乳化物。
J5：氨基硅油阳离子改性硅油乳液
在具有加热、降温、氮气保护、搅拌、温度、压力指示(记录)以及真空进料条件的不锈钢反应釜中，加入300质量份的式(4)结构的端环氧基硅油，10质量份的
Figure PCTCN2017117485-appb-000007
1质量份的十二烷基二甲基季铵盐和400质量份的甲苯，缓慢加热至110-130℃，保温15-25个小时，在140℃真空抽滤2-3小时，脱除低沸物，得到黄色粘稠液体。
Figure PCTCN2017117485-appb-000008
往烧瓶中添加20质量份上述的合成原料、3质量份的ノイゲンXL-70(日本第一工业制药株式会社制造)，搅拌均匀，升温至70-80℃，边搅拌边加入77质量份的水，冷却到常温即得氨基硅油阳离子改性硅油乳液。
实施例1
采用吸水速干加工剂,其中,作为通式(1)表示的化合物、采用10质量％的上述K1,1质量％的作为催化剂的S1,0.5质量％的作为浸透剂的高级醇的环氧烷烃加成物,相对含100％漂白圆形罗纹单元(单位面积重量:130g/m2)进行浸轧处理,制成带液率(PickUp)70质量％。然后,于120℃干燥2分钟,得到功能性纤维制品(处理布1)。
上述功能性纤维制品(处理布1),于20～30℃水洗20分钟,于120℃干燥2分钟,得到功能性纤维制品(处理布2)。
功能性纤维制品(处理布2),采用含2g/l整理剂J1的整理剂,在浴比1﹕10,于40℃处理20分钟,制成带液率120质量％。然后, 用滚筒式干燥机,于80℃干燥1小时,得到功能性纤维制品(处理布3)。
对于得到的功能性纤维制品,采用下述的方法,测定速干性、肌肤触感性、吸水性、保湿性。其结果示于表1。
速干性评价:
在温度20℃、相对湿度65％RH的条件下,使20cm四方形的处理布1的坯料质量达到恒重。往上述处理布1滴水0.6ml,在20℃、65％RH的条件下,放置60分钟,观察坯料的质量变化,用下述式算出水分残留率,评价速干性。水分残留率(％)越小,判断为速干性越良好。特别是,水分残留率(％)为30％以下时,判断为速干性良好。
水分残留率(％)＝(刚滴下水0.6ml后的坯料质量-60分钟后的坯料质量)×100/0.6
肌肤触感性:
用指触试验,按以下的基准评价肌肤触感性。
◎:感到顺滑的同时,非常柔软的手感。与棉100％漂白圆形罗纹织物的肌肤触感性相比,非常柔软,肌肤触感性非常良好。
○:感到顺滑的同时,柔软的手感。与棉100％漂白圆形罗纹织物的肌肤触感性相比,柔软,肌肤触感性良好。
△:与棉100％漂白圆形罗纹织物同等的肌肤触感性。
×:与棉100％漂白圆形罗纹织物的肌肤触感性相比,粗硬,肌肤触感性不良。
吸水性:
采用JIS L 1907:2010 7.1.1滴下法进行试验。
时间越少,判断为吸水性越好。
保湿性:
20cm四方形的试验布于105℃干透3小时后,该试验布于20℃、相对湿度80％的条件下放置2小时,测定质量变化,依下述 式算出保湿率。
保湿率(％)＝(20℃相对湿度80％的条件下放置2小时后的质量-105℃干透3小时后的质量)×100/于105℃干透3小时后的质量
比较例1中得到的处理布1的保湿率作为基准,进行下述的等级划分。
○:试验布的保湿率相对于基准为70％以上～100％以下的情况
△:试验布的保湿率相对于基准为40％以上～不足70％的情况
×:试验布的保湿率相对于基准为不足40％的情况
实施例2～6、比较例3～4
除羟基反应性化合物、催化剂的种类与使用量变为如表1、表2所示的以外,与实施例1同样进行操作,得到实施例2～6、比较例3～4的功能性纤维制品(处理布3)。对于得到的功能性纤维制品,与实施例1同样测定速干性、肌肤触感性、吸水性、保湿性。其结果示于表1、表2。
实施例7
实施例1中得到的功能性纤维制品(处理布2),采用含2质量％整理剂J2的整理剂进行浸轧处理,制成带液率70质量％。然后,于120℃干燥2分钟,再于160℃干燥2分钟,得到功能性纤维制品(处理布3)。对于得到的功能性纤维制品,与实施例1同样测定速干性、肌肤触感性、吸水性、保湿性。其结果示于表1。
实施例8
除使用实施例1中得到的功能性纤维制品(处理布1)以外,与实施例1同样地进行操作,得到实施例8的功能性纤维制品(处理布3)。对于得到的功能性纤维制品,与实施例1同样测定速干 性、肌肤触感性、吸水性、保湿性。其结果示于表1。
实施例9
实施例1中得到的功能性纤维制品(处理布2)，用含2g/l整理剂J5的整理剂,在浴比1:10，于40℃处理20分钟，制成带液率120质量％，然后在滚筒式干燥机中80℃干燥1小时，得到功能性纤维制品。对于得到的功能性纤维制品，与实施例1同样测定速干性、肌肤触感性、吸水性、保湿性。其结果于表1。
比较例1
用水,对棉100％漂白圆形罗纹单元(单位面积重量:130g/m2)进行浸轧处理,制成带液率70质量％。然后,于120℃干燥2分钟,得到功能性纤维制品(处理布1)。对于得到的功能性纤维制品,与实施例1同样测定速干性、肌肤触感性、吸水性、保湿性。其结果示于表2。
比较例2
实施例1中途得到的处理布2,作为比较例2的功能性纤维制品(处理布2)。对于得到的功能性纤维制品,与实施例1同样测定速干性、肌肤触感性、吸水性、保湿性。其结果示于表2。
比较例5～6
除整理剂按如表2所示进行改变以外,与实施例2同样地进行操作,得到比较例5～6的功能性纤维制品(处理布3)。对于得到的功能性纤维制品,与实施例2同样测定速干性、肌肤触感性、吸水性、保湿性。其结果示于表2。
比较例7
比较例1中得到的功能性纤维制品(处理布1),用含2g/l整理剂J1的整理剂,在浴比1﹕10,于40℃处理20分钟,制成带液率120质量％。然后,用滚筒式干燥机于80℃干燥1小时,得到比较例7的功能性纤维制品(处理布3)。对于得到的功能性纤维制品,与 比较例1同样测定速干性、肌肤触感性、吸水性、保湿性。其结果示于表2。
【表1】
Figure PCTCN2017117485-appb-000009
【表2】
Figure PCTCN2017117485-appb-000010
比较例8
采用含下述物质的处理液:30质量％的作为乙二醛系交联剂的UNIKA RESIN GS-20E(UNION化学工业株式会社制),7.5质量％的作为催化剂的UNIKA CATALYST MC-109(Union化学工业株式会社制),3质量％的作为柔软剂的EVAFANOL N-7(日华化学株式会社制)，3质量％的FINE TEX PE140(DIC株式会社制,聚乙烯系),以及0.5质量％的作为浸透剂的高级醇的氧化烷烃加成物,对棉100％漂白圆形罗纹织物(单位面积重量:130g/m2)进行浸轧处理,制成带液率60质量％。然后,于110℃干燥1分钟,得到处理布1。
然后,调整处理布1的含水率使成为20质量％。具体地说,相对处理布1于105℃干透3小时的质量,用水进行浸轧处理,使含水率成为60质量％,于20℃、相对湿度65％的条件下进行风干,使含水率成为20质量％。
含水率调整后的处理布1,采用平板压力机(株式会社日本压力机制造所制,型号PMC3E),用1kgf/cm2的压力,于160℃,加压处理20秒钟。加压处理后的处理布1,于25～30℃水洗20分钟,然后,作为柔软剂,用含Nicca Silicone AMC800E(日华化学株式会社制,硅酮系)3质量％与含Finetex PE140的3质量％的处理液,进行浸轧处理,制成带液率60质量％。浸轧处理后的处理布2,于25℃干燥1日,得到处理布3。
对于该处理布3,与实施例1同样测定速干性、肌肤触感性、吸水性、保湿性,结果是速干性:48％,肌肤触感性:◎,吸水性:>60s,保湿性:○。
【产业上的利用可能性】
按照本发明,由于能够提供肌肤触感性良好,以及具有优异的吸水性和保湿性及纤维素系纤维的长处,以及具有速干性的纤维素系纤维制品，所以是有用的。

Claims (6)

  1. 功能性纤维制品的制造方法,该制造方法包含:将纤维素系纤维制品用含有选自由N-羟甲基系化合物、乙二醛、丙烯酰胺系化合物及有机酸构成的组的至少1种羟基反应性化合物的吸水速干加工剂进行处理的第1工序；接着,用含有选自由聚醚改性硅油、氨基硅油阳离子改性硅油、具有酸值的蜡及含聚环氧烷烃的聚氨酯树脂构成的组的至少1种整理化合物的整理剂进行处理的第2工序。
  2. 按照权利要求1所述的功能性纤维制品的制造方法,其中,上述羟基反应性化合物为N-羟甲基系化合物。
  3. 按照权利要求2所述的功能性纤维制品的制造方法,其中,N-羟甲基系化合物为用通式(1)表示的化合物:
    Figure PCTCN2017117485-appb-100001
    式中,R1分别独立地为氢、碳数1～3的烷基、羟甲基、碳数1～3的烷基-氧基甲基、-CH2-O-(R3O)n-H,n为1～5,R3为碳数2～4的亚烷基,R2分别独立地为氢、OH基、碳数1～3的烷基,p为0或者1。
  4. 按照权利要求1～3的任一项所述的功能性纤维制品的制造方法,其中,上述整理化合物为具有酸值的蜡。
  5. 按照权利要求1～4的任一项所述的功能性纤维制品的制造方法,在通式(1)表示的化合物中,2个R1为-CH2-O-(R3O)nH，R3为亚乙基,n＝2,并且,2个R2为OH基。
  6. 吸水速干剂,其在权利要求1～5的任一项所述的功能性纤维制品的制造方法中使用。
PCT/CN2017/117485 2017-12-20 2017-12-20 功能性纤维制品的制造方法及吸水速干加工剂 WO2019119296A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201780096822.6A CN111886375B (zh) 2017-12-20 2017-12-20 功能性纤维制品的制造方法及吸水速干加工剂
PCT/CN2017/117485 WO2019119296A1 (zh) 2017-12-20 2017-12-20 功能性纤维制品的制造方法及吸水速干加工剂

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2017/117485 WO2019119296A1 (zh) 2017-12-20 2017-12-20 功能性纤维制品的制造方法及吸水速干加工剂

Publications (1)

Publication Number Publication Date
WO2019119296A1 true WO2019119296A1 (zh) 2019-06-27

Family

ID=66992890

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/117485 WO2019119296A1 (zh) 2017-12-20 2017-12-20 功能性纤维制品的制造方法及吸水速干加工剂

Country Status (2)

Country Link
CN (1) CN111886375B (zh)
WO (1) WO2019119296A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112609456A (zh) * 2020-11-28 2021-04-06 无锡市丹怡纺织品有限公司 一种防毡缩呢子大衣的制备方法
CN115287907A (zh) * 2022-08-23 2022-11-04 江苏陆亿纺织科技有限公司 一种耐磨抗黄变面料及其加工工艺

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5540952A (en) * 1993-12-27 1996-07-30 Rhone-Poulenc Chimie Non-yellowing textile softening process in which a composition comprising a polyorganosiloxane is used
JP2001181968A (ja) * 1999-12-24 2001-07-03 Sumitomo Chem Co Ltd 繊維処理剤及びセルロース系繊維の加工方法
JP2002348780A (ja) * 2001-05-24 2002-12-04 Kurabo Ind Ltd 吸湿発熱性セルロース系繊維
JP2005089882A (ja) * 2003-09-12 2005-04-07 Lion Corp 繊維用吸水速乾性付与組成物及びエアゾール型繊維用吸水速乾性付与剤
CN1734012A (zh) * 2004-08-10 2006-02-15 日清纺织株式会社 含纤维素系纤维的布帛的加工方法及含纤维素系纤维的布帛
CN101608403A (zh) * 2009-07-06 2009-12-23 江苏百花实业集团股份有限公司 一种吸水速干军用毛巾布及其生产工艺
CN102791922A (zh) * 2010-03-08 2012-11-21 郡是株式会社 纤维素类纤维或纤维素类纤维制品的处理方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5540952A (en) * 1993-12-27 1996-07-30 Rhone-Poulenc Chimie Non-yellowing textile softening process in which a composition comprising a polyorganosiloxane is used
JP2001181968A (ja) * 1999-12-24 2001-07-03 Sumitomo Chem Co Ltd 繊維処理剤及びセルロース系繊維の加工方法
JP2002348780A (ja) * 2001-05-24 2002-12-04 Kurabo Ind Ltd 吸湿発熱性セルロース系繊維
JP2005089882A (ja) * 2003-09-12 2005-04-07 Lion Corp 繊維用吸水速乾性付与組成物及びエアゾール型繊維用吸水速乾性付与剤
CN1734012A (zh) * 2004-08-10 2006-02-15 日清纺织株式会社 含纤维素系纤维的布帛的加工方法及含纤维素系纤维的布帛
CN101608403A (zh) * 2009-07-06 2009-12-23 江苏百花实业集团股份有限公司 一种吸水速干军用毛巾布及其生产工艺
CN102791922A (zh) * 2010-03-08 2012-11-21 郡是株式会社 纤维素类纤维或纤维素类纤维制品的处理方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112609456A (zh) * 2020-11-28 2021-04-06 无锡市丹怡纺织品有限公司 一种防毡缩呢子大衣的制备方法
CN115287907A (zh) * 2022-08-23 2022-11-04 江苏陆亿纺织科技有限公司 一种耐磨抗黄变面料及其加工工艺

Also Published As

Publication number Publication date
CN111886375A (zh) 2020-11-03
CN111886375B (zh) 2022-06-07

Similar Documents

Publication Publication Date Title
JP6272588B1 (ja) 撥水処理剤及びその製造方法
CN106029976B (zh) 片状物及其制造方法
CN108291000B (zh) 水分散型聚碳酸酯类聚氨基甲酸酯树脂组合物及其制造方法、以及由其处理的纤维制品
US6794446B1 (en) Water-borne urethane resin composition for forming microporous layer, method of producing fibrous sheet-like composite, and artificial leather
US20120015574A1 (en) Method for formulating a reactive polyurethane emulsion
TW201835240A (zh) 撥水劑組合物、撥水性纖維製品及撥水性纖維製品之製造方法
JPH0723585B2 (ja) ウール処理剤
TW201120275A (en) Method for producing leather material and leather material.
WO2019119296A1 (zh) 功能性纤维制品的制造方法及吸水速干加工剂
CN107075793A (zh) 片状物的制造方法
TW502073B (en) Treatment composition which provides anti-wrinkling properties to textiles
CN111350079A (zh) 皮革用材料的制造方法
CN107429478B (zh) 无氟疏水化处理
TWI665237B (zh) 聚胺甲酸酯有機聚矽氧烷
KR101368825B1 (ko) 면섬유 편성물용 섬유 가공제 및 이 가공제로 처리된 면섬유 편성물
JPH11158779A (ja) 繊維処理剤
JP2016125155A (ja) 皮革用材の製造方法及び皮革用材
JP2020007657A (ja) 繊維処理組成物、繊維処理キット、繊維製品、および撥水性繊維製品の製造方法
JP4810692B2 (ja) 制電性繊維布帛およびその製造方法
TWI823985B (zh) 積層體
JPH1096173A (ja) 繊維用処理剤
JPS5951632B2 (ja) 緻密かつしなやかな複合シ−ト状物
CN116744795A (zh) 抗病毒剂组合物以及用其处理过的抗病毒性布帛、抗病毒性聚氨酯片及抗病毒性聚氯乙烯片
CN117306263B (zh) 一种远红外负离子抗菌多功能健康被及其制备方法
KR20220163486A (ko) 발수제 조성물, 키트, 발수성 섬유 제품 및 그 제조 방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17935745

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17935745

Country of ref document: EP

Kind code of ref document: A1