CN107435245A - The manufacture method of water proofing property fibre - Google Patents

The manufacture method of water proofing property fibre Download PDF

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Publication number
CN107435245A
CN107435245A CN201710370852.3A CN201710370852A CN107435245A CN 107435245 A CN107435245 A CN 107435245A CN 201710370852 A CN201710370852 A CN 201710370852A CN 107435245 A CN107435245 A CN 107435245A
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Prior art keywords
waterproofing agent
represent
water proofing
proofing property
acrylic acid
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Granted
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CN201710370852.3A
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CN107435245B (en
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山田美由纪
柘植好挥
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Nicca Chemical Co Ltd
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Nicca Chemical Co Ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • 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
    • D06M13/244—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 sulfur or phosphorus
    • D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41—Phenol-aldehyde or phenol-ketone resins
    • 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
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • 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
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • 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
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
    • 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
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Abstract

The manufacture method of water proofing property fibre of the present invention has following processes：Make at least one kind of non-fluorine system waterproofing agent and fiber contacts in acrylic acid series waterproofing agent, silicon-type waterproofing agent and dendritic macromole system waterproofing agent, the fiber contains selected from by SO3M1(in formula, M1Represent monovalence cation) shown in 1 valency group, by COOM2(in formula, M2Represent monovalence cation) shown in 1 valency group and by O P (O) (OX1)(OX2) (in formula, X1And X2Represent the alkyl of hydrogen atom or carbon number 1~22 independently of one another) shown in 1 valency group at least one kind of functional group.

Description

The manufacture method of water proofing property fibre
Technical field
The present invention relates to the manufacture method of water proofing property fibre, in more detail, is directed to use with non-fluorine system waterproofing agent The manufacture method of water proofing property fibre.
Background technology
In the past, it is known that there is the fluorine system waterproofing agent of fluoro-containing group, fibre etc. is carried out by using the fluorine system waterproofing agent Processing, it can obtain imparting its surface the fibre of water proofing property.Such fluorine system waterproofing agent will be typically by that will have fluorine The monomer polymerization of alkyl is copolymerized and manufactured.In order that water proofing property fully shows, it is necessary to make the orientation of fluoroalkyl neat, Generally, after fluorine system waterproofing agent is attached to fibre, heat treatment is implemented at a temperature of more than 130 DEG C.However, it is desirable to high energy It is worthless under the trend of the energy-saving of heat treatment in the world at a high temperature of amount.In addition, the monomer with fluoroalkyl is not Only price is high, and is hard-decomposed therefore big to the load of environment.
From such actual conditions, in recent years, studied for not fluorine-containing non-fluorine system waterproofing agent.For example, Being disclosed in non-patent literature 1 forms paraffin, hydrocarbon compound, fatty acid metal salts or ureine emulsion dispersion as wax Waterproofing agent.In addition, in patent document 1, in order to give water proofing property in no way inferior compared with conventional fluorine system waterproofing agent, it is proposed that make The waterproofing agent that specific non-fluorine based polymer emulsion dispersion forms.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2006-328624 publications
Non-patent literature
Non-patent literature 1：《The new trend of super waterproof processing, the overall picture of processing agent and moisture-permeability waterproof raw material》(《Super Dial water Processing, processing drug hold entirely the new Move of と moisture-permeability waterproof materials to》), (strain) Osaka ケ ミ カ ル マ ー ケ テ ィ Application グ セ Application タ ー is issued, 1996, page 7~9
The content of the invention
But even above-mentioned conventional non-fluorine system waterproofing agent, the performance that water proofing property is assigned to fibre are not also filled still Point.In addition, also require that water proofing property is not easy the durability because being reduced in outdoor use, washing etc. for water proofing property fibre (durable waterproof), in this respect, above-mentioned conventional non-fluorine system waterproofing agent are also still insufficient.
The present invention in view of above-mentioned actual conditions and complete, and it is an object of the present invention to provide can use non-fluorine system waterproofing agent be had The manufacture method of the water proofing property fibre of the water proofing property fibre of sufficient water proofing property and sufficient durable waterproof.
In order to solve above-mentioned problem, present inventor has performed further investigation, as a result finds：By using containing specific non-fluorine It is that the treatment fluid of waterproofing agent is handled the fiber with specific functional group, so as to obtain having sufficient water proofing property With the water proofing property fibre of sufficient durable waterproof, the present invention is completed based on the experience.
That is, the manufacture method of water proofing property fibre of the invention have make selected from acrylic acid series waterproofing agent, silicon-type The process of at least one kind of non-fluorine system waterproofing agent contact fiber in waterproofing agent and dendritic macromole system waterproofing agent, the fiber bag Containing selected from-SO3M1(in formula, M1Represent monovalence cation) shown in 1 valency group ,-COOM2(in formula, M2Represent monovalence sun from Son) shown in 1 valency group and-O-P (O) (OX1)(OX2) (in formula, X1And X2Hydrogen atom or carbon number 1~22 are represented independently of one another Alkyl) shown in 1 valency group at least one kind of functional group.
Sufficient water proofing property can be had by adopting the water proofing property fibre being obtained by the present invention, and can be had Sufficient durable waterproof.The water proofing property fibre even in outdoor long-term use of situation, wash repeatedly in the case of, Sufficient water proofing property can chronically be maintained.
Above-mentioned non-fluorine system waterproofing agent preferably comprises acrylic acid series waterproofing agent, and the acrylic acid series waterproofing agent is included to contain and come from down State the polymer of the construction unit of (methyl) acrylate monomer (A) shown in formula (A-1).
[in formula (A-1), R1Represent hydrogen or methyl, R2Represent there can be the alkyl of 1 valency of the carbon number more than 12 of substituent.]
Additionally, it is preferred that above-mentioned non-fluorine system waterproofing agent includes acrylic acid series waterproofing agent, the acrylic acid series waterproofing agent contains Construction unit from (methyl) acrylate monomer (A) shown in above-mentioned formula (A-1) and from vinyl chloride and inclined two chloroethene The polymer of the construction unit of at least any of monomer (E) in alkene.
Above-mentioned fiber can be the fiber of compound attachment, and the compound, which has, is selected from-SO3M1(in formula, M1Represent monovalence Cation) shown in 1 valency group ,-COOM2(in formula, M2Represent monovalence cation) shown in 1 valency group and-O-P (O) (OX1)(OX2) (in formula, X1And X2Represent the alkyl of hydrogen atom or carbon number 1~22 independently of one another) shown in 1 valency group in At least one kind of functional group.
And then preferably above-claimed cpd include there is-SO3M1(in formula, M1Represent monovalence cation) shown in 1 valency base The phenol system high-molecular compound of group.
In the manufacture method of the water proofing property fibre of the present invention, the zeta potential on the surface of preferably above-mentioned fiber for -100~- 0.1mV。
Use the manufacture of non-fluorine system waterproofing agent that there is sufficient water proofing property to prevent with sufficiently durable in accordance with the invention it is possible to provide The method of water-based water proofing property fibre.
In addition, although the method for the present invention is using the non-fluorine system waterproofing agent for being free of the compound with fluoroalkyl or fluorine, The water proofing property fibre with sufficient water proofing property can be obtained, the worry of fluorine supply source, the load to environment can be reduced.
Make in the case that fluorine system waterproofing agent is attached to fibre, generally to implement the heat treatment under high temperature, but according to this hair Bright method, it in the case of being heat-treated under conditions of less than 130 DEG C gentle, also can show sufficient water proofing property It is existing, in addition, in the case of being heat-treated at a high temperature of more than 130 DEG C, heat treatment time can be made than the situation of fluorine system waterproofing agent It is short.Therefore, method of the invention is due to suppressing being gone bad by thermally-induced for treated object, therefore sense of touch becomes soft, and energy Enough heats cut down involved by heat treatment etc., it is also excellent in terms of cost.
Embodiment
The manufacture method of the water proofing property fibre of present embodiment has will be selected from acrylic acid series waterproofing agent, silicon-type The process that at least one kind of non-fluorine system waterproofing agent in waterproofing agent and dendritic macromole system waterproofing agent assigns fiber, the fiber bag Containing selected from-SO3M1(in formula, M1Represent monovalence cation) shown in 1 valency group ,-COOM2(in formula, M2Represent monovalence sun from Son) shown in 1 valency group and-O-P (O) (OX1)(OX2) (in formula, X1And X2Hydrogen atom or carbon number 1~22 are represented independently of one another Alkyl) shown in 1 valency group at least one kind of functional group's (being also sometimes referred to as below " particular functional group ").
As M1, H, K, Na can be included or can have the ammonium ion of substituent.As M2, H, K, Na can be included or can Ammonium ion with substituent.X1Or X2In the case of for alkyl, the preferably alkyl of carbon number 1~22, more preferably carbon number 4~ 12 alkyl.
Fiber (being also sometimes referred to as below " fiber containing functional group ") comprising above-mentioned particular functional group can for example be adopted Prepared with following method.
(i) make that there is the compound of above-mentioned particular functional group to be attached to fibrous material.It should illustrate, the attachment of compound can To be a part of chemistry of the part and fiber that make compound in the range of above-mentioned particular functional group is with enough amount residuals The state that ground combines.
(ii) above-mentioned particular functional group has been introduced directly into the fiber for the material for forming fiber by preparation.
(i) in the case of, for example, by using more than one the preceding place comprising the compound with above-mentioned particular functional group The functional group that reason liquid is handled fibrous material imports process, can obtain the fiber containing functional group.
As the raw material of fibrous material, there is no particular restriction, can include the natural fibers such as cotton, fiber crops, silk, wool, people Make the synthetic fibers such as the semisynthetic fibres such as silk, acetate, polyamide (nylon etc.), polyester, polyurethane, polypropylene and they Composite fibre, blend fibre etc..The form of fibrous material can be fiber (tow, sliver etc.), silk thread, braid (comprising friendship Fork braiding), weaven goods (comprising interweave), non-woven fabrics, any form such as paper.
In present embodiment, from the viewpoint of the water proofing property of obtained fibre becomes good, preferably use comprising The fibrous material of polyamide and polyester as raw material, particularly preferably using nylon 6, the grade nylon of nylon 6,6, poly terephthalic acid second The polyester such as diol ester (PET), PTT, PLA and include their composite fibre.
As with above-mentioned-SO3M1Compound, phenol system macromolecule can be used.As such phenol system macromolecule, example The phenol system macromolecule for including at least one compound represented by following formulas (2) can such as be included.
[in formula (2), X2Expression-SO3M3(in formula, M3Represent the cation of 1 valency) or by following formulas (3) represent base Group, n are 20~3000 integer.]
[in formula (3), M4Represent the cation of 1 valency.]
As above-mentioned M3, H, K, Na can be included or can have the ammonium ion of substituent.
As above-mentioned M4, H, K, Na can be included or can have the ammonium ion of substituent.
The compound represented by above-mentioned formula (2) for example can be the formaline condensates of phenolsulfonic acid, sulfonated bis phenol S Formaline condensates, the product synthesized using the method described in embodiment described later can be used.
As with above-mentioned-COOM2Compound, polycarboxylic acid polymer can be included.
As polycarboxylic acid polymer, such as it can use and be adopted by the use of acrylic acid, methacrylic acid, maleic acid etc. as monomer The polymer or commercially available product synthesized with known radical polymerization.
As the manufacture method of polycarboxylic acid polymer, such as the aqueous solution in above-mentioned monomer and/or its salt can be included Middle addition radical polymerization initiator, make its heating response method of 2~5 hours at 30~150 DEG C.Now, can be above-mentioned The aqueous solvents such as alcohols, the acetone such as methanol, ethanol, isopropanol are added in the aqueous solution of monomer and/or its salt.As radical polymerization Initiator is closed, such as the persulfates such as potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate can be included, using persulfate and sulfurous The redox system polymerization initiator of the combination of sour hydrogen sodium etc., hydrogen peroxide, water-soluble azo system polymerization initiator etc..These are certainly It can be used alone a kind by base polymerization initiator, or two or more may be used.And then during radical polymerization, it is poly- in order to adjust It is right, chain-transferring agent (such as TGA monooctyl ester) can be added.
In radical polymerization, in addition to above-mentioned monomer, copolymerizable monomer can be used.As copolymerizable list Body, the vinyl monomers such as ethene, vinyl chloride, vinylacetate, acrylamide, esters of acrylic acid, metering system can be included Esters of gallic acid etc..Esters of acrylic acid and methyl acrylic ester are preferably with can the hydrocarbon with the carbon number 1~3 of the substituents such as hydroxyl Base.As such esters of acrylic acid or methyl acrylic ester, methyl acrylate, methyl methacrylate, third can be included Olefin(e) acid ethyl ester, EMA, acrylic acid 2- hydroxy methacrylates, 2-hydroxyethyl methacrylate, propyl acrylate, methyl Propyl acrylate etc..These copolymerizable monomers can be used alone a kind, or two or more may be used.
Carboxyl in polycarboxylic acid polymer can be free, can also be neutralized by alkali metal, amine compound etc..Make For alkali metal, sodium, potassium, lithium etc. can be included, as amine compound, ammonia, monoethanolamine, diethanol amine, three second can be included Hydramine etc..
The weight average molecular weight of polycarboxylic acid polymer, become good viewpoint from the water proofing property of obtained fibre and go out Hair, preferably 1,000~20,000, more preferably 3,000~15,000.
For polycarboxylic acid polymer, can use " ネ オ Network リ ス タ Le 770 " (Nicca Chemical Co., Ltd's manufacture, Trade name), " commercially available product such as セ ロ ポ ー Le PC-300 " (Sanyo Chemical Industries, Ltd. manufacture, trade name).
As with above-mentioned-O-P (O) (OX1)(OX2) compound, such as can include by following formulas (4) represent Phosphate compound.
[in formula (4), X1Or X2With above-mentioned synonymous, X3Represent the alkyl of carbon number 1~22.]
As above-mentioned phosphate compound, phosphate monoester, phosphorus of the alkylester moieties for the alkyl of carbon number 1~22 can be used Acid diesters and phosphotriester and their mixture.
In present embodiment, from the viewpoint of the water proofing property of obtained fibre becomes good, preferably using phosphoric acid Lauryl, phosphoric acid last of the ten Heavenly stems ester.
For phosphate compound, such as " Off ォ ス Off ァ ノ ー Le ML-200 " (eastern nation's chemical industry can be used Co., Ltd. manufacture, trade name) etc. commercially available product.
More than one pretreatment liquid containing the compound with above-mentioned particular functional group can for example be made above-mentioned The aqueous solution of compound.In addition, it can make in pretreatment liquid containing acid, alkali, surfactant, chelating agent etc..
As the method handled with above-mentioned pretreatment liquid fibrous material, such as tie dyeing processing, dipping can be included Processing, spraying treatment, coating process.Handled as tie dyeing, such as stock-dye processing dictionary (Showa 38 year, day can be included Print the distribution of industrial newspaper office) page 396~397, color contaminate chemical III (1975, real religion publish Co., Ltd.'s distribution) 256~ The method for having used tie dyeing device described in page 260.As coating process, such as machine overview on dyeing bodyguard can be included The method using coating machine described in page 473~477 of (Showa 56 years, fiber society distribution).As impregnation, such as can Include the use batch dying machines of the record of page 196~247 of machine overview (Showa 56 years, fiber society distribution) on dyeing bodyguard Method, can use liquid-flow dyeing machine, air flow dyeing machine, Revolving drum dyeing machine, rope dyeing machine, washing overflow dyeing machine, bobbin contaminate Color machine etc..As spraying treatment, such as the air for having used and having made treatment fluid be sprayed as vaporific with squeezing air can be included Sprayer, hydraulic atomizing mode air atomizer method.The concentration for the treatment of fluid now, assign after heat treatment etc. place Manage bar part it can be considered that each condition such as its purpose, performance and suitably adjust.In addition, in the case that pretreatment liquid contains water, it is excellent It is selected in and is attached to after fibrous material in order to which water is removed and makes its drying.As drying means, there is no particular restriction, can be dry Hot method, wet heating it is any.Drying temperature is also not particularly limited, such as 10 seconds~number can be dried at room temperature~200 DEG C Day.As needed, can heat after the drying at a temperature of 100~180 DEG C 10 seconds~5 minutes or so.
Further, in the case that fibrous material is fibrous material to be dyed, just use the processing of pretreatment liquid for, can be with Carry out before dyeing, can also be carried out with dyeing with bath, but carry out in the case that reduction soaps, it is upper in having for this process absorption The compound (such as phenol system high-molecular compound etc.) for stating particular functional group is possible to come off, therefore reduction preferably after dyeing Carried out after soaping.
Treatment temperature in impregnation can be set to 60~130 DEG C.Processing time can be set to 5~60 minutes.
For importing process using the functional group of pretreatment liquid, preferably with the compound with above-mentioned particular functional group The amount that adhesion amount turns into 1.0~7.0 mass parts relative to the mass parts of fibrous material 100 is handled.If in the range of, then can It is enough that durable waterproof and sense of touch are had concurrently with high level.
For pretreatment liquid, preferably pH is adjusted to 3~5.For pH regulations, acetic acid, malic acid etc. can be used PH adjusting agent.
In pretreatment liquid, in order to make there is the compound of above-mentioned particular functional group to be effectively adsorbed in using salting-out effect Fibrous material, salt can be also used in combination.As the salt that can be used, such as sodium chloride, sodium carbonate, ammonium sulfate, sulphur can be included Sour sodium.
Imported using the functional group of pretreatment liquid in process, preferably there is above-mentioned particular functional group by what is excessively handled Compound remove.As the method for removing, the method using washing can be included.By sufficiently being removed, can suppress In the waterproof processing of back segment water proofing property show it is hindered, in addition, the sense of touch of obtained fibre becomes good.Separately Outside, for the obtained fiber containing functional group, preferably its drying is fully made before non-fluorine system waterproofing agent is contacted.
(ii) fiber as the material that above-mentioned particular functional group has been introduced directly into composition fiber, such as sun can be included Ion dyeable polyester (CD-PET).
Fiber of the present embodiment containing functional group, become good sight from the water proofing property of obtained fibre Point sets out, and the preferably zeta potential on surface is -100~-0.1mV, more preferably -50~-1mV.The zeta potential on the surface of fiber is for example Zeta potential particle size determination system ELSZ-1000ZS (Otsuka Electronics Co., Ltd. can be used to manufacture) measure.
Next, carried out for the non-fluorine system waterproofing agent assigned to the fiber of the present embodiment containing functional group Explanation.Non- fluorine system waterproofing agent can include to be prevented selected from acrylic acid series waterproofing agent, silicon-type waterproofing agent and dendritic macromole system It is at least one kind of in aqua.
As acrylic acid series waterproofing agent, can include comprising containing from (methyl) propylene shown in following formulas (A-1) Acid ester monomer (A) (hereinafter also referred to " (A) composition ".) the polymer of construction unit (be also sometimes referred to as " non-fluorine system propylene below Sour based polymer ") acrylic acid series waterproofing agent.
[in formula (A-1), R1Represent hydrogen or methyl, R2Represent there can be the alkyl of 1 valency of the carbon number more than 12 of substituent.]
Wherein, " (methyl) acrylate " means " acrylate " or corresponding " methacrylate ", " (first Base) acrylic acid ", implication is also identical in " (methyl) acrylamide " etc..
(methyl) acrylate monomer (A) shown in above-mentioned formula (A-1) used in present embodiment has and can had The carbon number of substituted base is the alkyl of more than 12 1 valency.The alkyl can be straight-chain, or branch-like, can be full And alkyl, or unsaturated alkyl, and then can have ester ring type or aromatic ring-type.In these, preferably straight-chain, The more preferably alkyl of straight-chain.In this case, water proofing property becomes more excellent.The alkyl of 1 valency of carbon number more than 12 has In the case of substituent, as its substituent, hydroxyl, amino, carboxyl, epoxy radicals, NCO, end-blocking isocyanide can be included More than a kind in perester radical and (methyl) acryloxy etc..In present embodiment, in above-mentioned formula (A-1), R2Preferably Unsubstituted alkyl.
The carbon number of above-mentioned alkyl is preferably 12~24.If carbon number is more than 12, make non-fluorine system acrylic acid series polymeric compounds attached And in the case of fibre etc., be readily available excellent water proofing property.On the other hand, if carbon number is less than 24, with carbon number Situation outside for above range is compared, and is made in the case that non-fluorine system acrylic acid series polymeric compounds are attached to fibre etc., fiber system The sense of touch of product is tended to be difficult to become thick and stiff.
The carbon number of above-mentioned alkyl is more preferably 12~21.In the case that carbon number is the scope, water proofing property and sense of touch become special It is unexcellent.Alkyl as alkyl, the particularly preferably straight-chain of carbon number 12~18.
As above-mentioned (A) composition, such as (methyl) stearyl acrylate ester, (methyl) acrylic acid cetyl, (first can be included Base) lauryl acrylate, (methyl) dodecylacrylate, (methyl) myristyl ester, (methyl) acrylic acid 15 Arrcostab, (methyl) acrylic acid heptadecane base ester, (methyl) acrylic acid nonadecane base ester, (methyl) acrylic acid eicosane base ester, (methyl) acrylic acid heneicosane base ester, (methyl) behenyl base ester, (methyl) acrylic acid hexacosane base ester, (methyl) acrylic acid melissane base ester.
Above-mentioned (A) composition can have and can be selected from hydroxyl, amino, carboxyl, epoxy radicals and isocyanic acid with what crosslinking agent reacted At least one kind of functional group in ester group.In this case, the obtained durable waterproof of fibre can further be improved. NCO can form the blocked isocyanate base protected with end-capping reagent.In addition, above-mentioned (A) composition has a case that amino Under, it can further improve the obtained sense of touch of fibre.
Above-mentioned (A) composition is preferably (methyl) acrylic acid for the simple function for having 1 polymerism unsaturated group in 1 intramolecular Ester monomer.
Above-mentioned (A) composition can be used alone a kind, and also two or more can be applied in combination.
For above-mentioned (A) composition, in terms of the durable waterproof of obtained fibre, preferably by acrylate list Body (a1) and methacrylate monomers (a2) are used in combination.The quality of (a1) composition coordinated and the mass ratio of (a2) composition (a1)/(a2) is preferably 30/70~90/10, more preferably 40/60~85/15, more preferably 50/50~80/20. (a1)/(a2) be above range in the case of, the durable waterproof of obtained fibre becomes more good.
Non- fluorine system acrylic acid series polymeric compounds of the present embodiment preferably comprise the construction unit from above-mentioned (A) composition With the construction unit of monomer (E) (hereinafter also referred to " (E) composition ") at least any of in vinyl chloride and vinylidene chloride.
It regard monomer (E) at least any of in the vinyl chloride and vinylidene chloride used in present embodiment as this reality Apply the copolymer composition of the non-fluorine system acrylic acid series polymeric compounds of mode and comprising in the water proofing property of obtained fibre and for applying The aspect of the peel strength of layer, preferably vinyl chloride.
Construction unit from (A) composition in the non-fluorine system acrylic acid series polymeric compounds of present embodiment with from (E) into Point construction unit content ratio, emulsion stability and obtained fibre in the non-fluorine based polymer of present embodiment The peel strength for coating aspect, the quality of (A) composition preferably coordinated and mass ratio (A)/(E) of (E) composition For 40/60~90/10, more preferably 50/50~85/15, more preferably 60/40~80/20.(if A)/(E) is 90/ Less than 10, then the peel strength for coating of the fibre obtained is tended to be difficult to reduce.(if A)/(E) is 40/60 More than, then the emulsion stability of the non-fluorine system acrylic acid series polymeric compounds of present embodiment is tended to be difficult to reduce.
In addition, total quality of the quality of (A) composition coordinated and the quality of (E) composition, relative to the non-fluorine system third of composition The total amount of the monomer component of olefin(e) acid based polymer, preferably 80~100 mass %, more preferably 85~99 mass %, further preferably 90~98 mass %.
The weight average molecular weight of the non-fluorine system acrylic acid series polymeric compounds of present embodiment is preferably more than 100,000.If divide equally again For son amount less than 100,000, then the water proofing property that obtained fibre be present becomes insufficient tendency.And then non-fluorine system acrylic acid series The weight average molecular weight of polymer is more preferably more than 500,000.In this case, the fibre obtained can substantially more be sent out Wave water proofing property.The upper limit preferably 5,000,000 or so of the weight average molecular weight of non-fluorine system acrylic acid series polymeric compounds.
In present embodiment, the melt viscosity at 105 DEG C of non-fluorine system acrylic acid series polymeric compounds be preferably 1000Pas with Under.If the melt viscosity at 105 DEG C is below 1000Pas, the sense of touch of obtained fibre is tended to be difficult to become thick Firmly.Further, the melt viscosity at 105 DEG C is more preferably below 500Pas.In this case, fibre obtained etc. is abundant Ground plays water proofing property, while sense of touch also becomes more excellent.
" melt viscosity at 105 DEG C " refer to using overhead system flow tester (such as Shimadzu Seisakusho Ltd. CFT-500), 1g non-fluorine based polymer is loaded and is provided with the barrel of mouth mold (long 10mm, diameter 1mm), is kept for 6 minutes, adopted at 105 DEG C Apply 100kgf/cm with plunger2Load measure when viscosity.
In the case where the weight average molecular weight of the non-fluorine system acrylic acid series polymeric compounds of present embodiment is equal, non-fluorine system (first Base) acrylate monomer mixing ratio it is higher, the water proofing property for the fibre being attached to more is tended to raise.In addition, pass through Make copolymerizable non-fluorine system monomer copolymerization, it is possible to increase the performance such as the durable waterproof of the fibre being attached to, sense of touch.
The non-fluorine system acrylic acid series polymeric compounds of present embodiment, water proofing property in the fibre that can improve to obtain, with And the non-fluorine system acrylic acid series polymeric compounds of present embodiment emulsion polymerization or dispersin polymerization when and polymerization after composition in The aspect of emulsion stability, also containing being selected from (B1) HLB preferably beyond (A) composition or (A) composition and (E) composition Compound, (B2) HLB shown in 7~18 following formulas (I-1) be compound shown in 7~18 following formulas (II-1), (B3) HLB be 7~18, the oxyalkylene addition that makes carbon number 2~4 is in the change of the grease with hydroxyl and polymerism unsaturated group At least one kind of reactive emulsifier (B) (hereinafter also referred to " (B) composition ") in compound is used as monomer component.
[in formula (I-1), R3Hydrogen or methyl are represented, X represents the straight chain of carbon number 1~6 or the alkylidene of branch, Y1Expression includes The group of the divalent of the alkylene oxide group of carbon number 2~4.]
[in formula (II-1), R4Represent the unsaturated alkyl of 1 valency of the carbon number 13~17 with polymerism unsaturated group, Y2Table Show the group of the divalent of the alkylene oxide group comprising carbon number 2~4.]
" reactive emulsifier " is the emulsifying dispersant for having free-radical reactive, i.e., in intramolecular there is more than 1 to be gathered The surfactant of conjunction property unsaturated group, can be with monomer copolymerization as (methyl) acrylate.
In addition, " HLB " is by inferior ethoxyl is considered as hydrophilic group, all being considered as lipophilic group uses Griffin method in addition by it The HLB value calculated.
The HLB of the compound of above-mentioned (B1)~(B3) used in present embodiment is 7~18, in present embodiment Emulsion stability in composition when the emulsion polymerization of non-fluorine system acrylic acid series polymeric compounds or dispersin polymerization and after polymerization is (following Referred to as emulsion stability) aspect, preferably 9~15.And then in terms of the bin stability of waterproofing agent composite, it is more excellent Reactive emulsifier of more than two kinds (B) with the different HLB in above range is used in combination by choosing.
In the reactive emulsifier (B1) shown in above-mentioned formula (I-1) used in present embodiment, R3For hydrogen or first Base, in terms of with the copolymerizable of (A) composition, more preferably methyl.X be carbon number 1~6 straight chain or branch alkylidene, The straight-chain alkyl-sub of the aspect, more preferably carbon number 2~3 of the emulsion stability of the non-fluorine based polymer of present embodiment.Y1For bag The group of the divalent of alkylene oxide group containing carbon number 2~4.For Y1In alkylene oxide group species, combination and adduct number, Neng Goushi Locality selection is so that as in the range of above-mentioned HLB.In addition, in the case of alkylene oxide group is of more than two kinds, they can have embedding Duan Jiacheng structures or random addition structure.
As the compound shown in above-mentioned formula (I-1), the compound shown in preferably following formulas (I-2).
[in formula (I-2), R3Hydrogen or methyl are represented, X represents the straight chain of carbon number 1~6 or the alkylidene of branch, A1O represents carbon The alkylene oxide group of number 2~4, m can be properly selected so that as in the range of above-mentioned HLB, and specifically, it is preferable to 1~80 it is whole Number, m A when m is more than 21O can be with identical, also can be different.]
In compound shown in above-mentioned formula (I-2), R3For hydrogen or methyl, in terms of with the copolymerizable of (A) composition, more Preferably methyl.X is the straight chain of carbon number 1~6 or the alkylidene of branch, in the non-fluorine system acrylic acid series polymeric compounds of present embodiment Emulsion stability aspect, more preferably carbon number 2~3 straight-chain alkyl-sub.A1O is the alkylene oxide group of carbon number 2~4.For A1O Species and combination and m number, can properly select so that as in the range of above-mentioned HLB.In the non-of present embodiment The aspect of the emulsion stability of fluorine system acrylic acid series polymeric compounds, m preferably 1~80 integer, more preferably 1~60 integer.M is M A when more than 21O can be with identical, also can be different.In addition, A1In the case of O is of more than two kinds, they can have block addition Structure or random addition structure.
Reactive emulsifier (B1) shown in above-mentioned formula (I-2) can be obtained using known method, have no spy Do not limit.In addition, can be readily available by commercially available product, such as " the ラ テ system Le of Kao Corp's manufacture can be included PD-420 ", " ラ テ system Le PD-430 ", " ラ テ system Le PD-450 " etc..
In the reactive emulsifier (B2) shown in above-mentioned formula (II-1) used in present embodiment, R4For with poly- The unsaturated alkyl of 1 valency of the carbon number 13~17 of conjunction property unsaturated group, can include tridecylene base, oleatridecadiene base, ten Four carbene bases, 14 carbon dialkylenes, 15 carbene bases, 15 carbon dialkylenes, 15 carbon trialkenyls, heptadecene base, 17 carbon Dialkylene, 17 carbon trialkenyls etc..In terms of the emulsion stability of the non-fluorine system acrylic acid series polymeric compounds of present embodiment, R4 The more preferably unsaturated alkyl of 1 valency of carbon number 14~16.
Y2For the group of the divalent of the alkylene oxide group comprising carbon number 2~4.For Y2In alkylene oxide group species, combination and Adduct number, it can properly select so that as in the range of above-mentioned HLB.In addition, in the case of alkylene oxide group is of more than two kinds, They can have block addition structure or random addition structure.In the breast of the non-fluorine system acrylic acid series polymeric compounds of present embodiment Change the aspect of stability, alkylene oxide group more preferably inferior ethoxyl.
As the compound represented by above-mentioned formula (II-1), the compound preferably represented by following formulas (II-2).
[in formula (II-2), R4Represent the unsaturated alkyl of 1 valency of the carbon number 13~17 with polymerism unsaturated group, A2O The alkylene oxide group of expression carbon number 2~4, in the range of n can be properly selected so that turning into above-mentioned HLB, and specifically, it is preferable to 1~ 50 integer, n A when n is more than 22O can be with identical, also can be different.]
R in the compound represented by above-mentioned formula (II-2)4It can include and the R in above-mentioned formula (II-1)4Equally Group.
A2O is the alkylene oxide group of carbon number 2~4.In the stable emulsifying of the non-fluorine system acrylic acid series polymeric compounds of present embodiment The aspect of property, for A2O species and combination and n number, it can properly select so that as in the range of above-mentioned HLB. In terms of the emulsion stability of the non-fluorine system acrylic acid series polymeric compounds of present embodiment, A2O more preferably inferior ethoxyls, n preferably 1 ~50 integer, more preferably 5~20 integer, further preferred 8~14 integer.N A when n is more than 22O can with identical, Also can be different.In addition, A2In the case of O is of more than two kinds, they can have block addition structure or random addition structure.
The reactive emulsifier (B2) represented by above-mentioned formula (II-2) used in present embodiment can be by adopting Oxyalkylene addition is synthesized in the corresponding phenol with unsaturated alkyl with known method, be not particularly limited.Example Such as, the oxyalkylene of ormal weight can by using base catalysts such as caustic soda, caustic potash, be made under elevated pressure, at 120~170 DEG C Addition and synthesize.
In the above-mentioned corresponding phenol with unsaturated alkyl, in addition to the sterling or mixture that industrially manufacture, Comprising as the phenol existing for the sterling from Hydrolysis kinetics such as plants or mixture with unsaturated alkyl.Such as it can include Shell from cashew nut etc. extraction, collectively referred to as anacardol, 3- [8 (Z), 11 (Z), 14- 15 carbon trialkenyl] phenol, 3- [8 (Z), 11 (Z)-ten five carbon dialkylene] phenol, 3- [8 (Z)-ten five carbene base] phenol, 3- [11 (Z)-ten five carbene base] phenol etc..
Reactive emulsifier (B3) used in present embodiment is HLB for 7~18, with hydroxyl and polymerism not The addition compound of the oxyalkylene of carbon number 2~4 in the grease of saturation base.As the oil with hydroxyl and polymerism unsaturated group Fat, can include can include hydroxyl unrighted acid (palmitoleic acid, oleic acid, linoleic acid, alpha-linolenic acid, arachidonic acid, Eicosapentaenoic acid, clupanodonic acid etc.) aliphatic acid monoglyceride or diglyceride, comprising at least one kind of hydroxyl not The triglycerides of the aliphatic acid of saturated fatty acid (castor oil acid, ricinelaidic acid, 2- hydroxyl tetracosenoic acids etc.).In this reality The aspect of the emulsion stability of the non-fluorine system acrylic acid series polymeric compounds of mode is applied, preferably comprises at least a kind of hydroxyl unsaturated fat The alkylen oxide adducts of the triglycerides of the aliphatic acid of acid, more preferably the castor oil (glycerine three of the aliphatic acid comprising castor oil acid Ester) carbon number 2~4 alkylen oxide adducts, the ethylene oxide adduct of further preferred castor oil.And then can be to oxidation In the range of the addition molal quantity of alkene is properly selected so that turning into above-mentioned HLB, in the non-fluorine system acrylic acid series of present embodiment The aspect of the emulsion stability of polymer, more preferably 20~50 moles, further preferred 25~45 moles.In addition, oxyalkylene is 2 In the case of more than kind, they can have block addition structure or random addition structure.
Reactive emulsifier (B3) used in present embodiment can make oxidation by using known method Alkene addition synthesizes in the grease with hydroxyl and polymerism unsaturated group, is not particularly limited.Such as can be by using severe Base catalysts such as property sodium, caustic potash, under elevated pressure, at 120~170 DEG C make the oxyalkylene addition of ormal weight in comprising castor oil acid The triglycerides of aliphatic acid be castor oil and synthesize.
The composition of the monomer of above-mentioned (B) composition in the non-fluorine system acrylic acid series polymeric compounds of present embodiment, from energy Enough improve the water proofing property of obtained fibre and the non-fluorine system acrylic acid series polymeric compounds of present embodiment emulsion polymerization or From the viewpoint of the emulsion stability in composition during dispersin polymerization and after polymerization, gather relative to non-fluorine system acrylic acid series is formed The whole amount of the monomer component of compound, preferably 0.5~20 mass %, more preferably 1~15 mass %, more preferably 3 ~10 mass %.
On in terms of the durable waterproof for the fibre that can improve to obtain, the non-fluorine system acrylic acid of present embodiment Based polymer preferably also contains in addition to (A) composition and (E) composition to be selected from following (C1), (C2), (C3) and (C4) extremely Few a kind the 2nd (methyl) acrylate monomer (C) (hereinafter also referred to " C compositions ") is used as monomer component.
(C1) (methyl) acrylate monomer represented by following formulas (C-1)
[in formula (C-1), R5Represent hydrogen or methyl, R6Represent have selected from hydroxyl, amino, carboxyl, epoxy radicals, isocyanates The chain alkyl of 1 valency of the carbon number 1~11 of at least one kind of functional group in base and (methyl) acryloxy.Wherein, intramolecular The number of (methyl) acryloxy is less than 2.]
(C2) (methyl) acrylate monomer represented by following formulas (C-2)
[in formula (C-2), R7Represent hydrogen or methyl, R8Represent there can be the cyclic hydrocarbon of 1 valency of the carbon number 1~11 of substituent Base.]
(C3) methacrylate monomers represented by following formulas (C-3)
[in formula (C-3), R9Represent the chain alkyl of 1 valency of unsubstituted carbon number 1~4.]
(C4) (methyl) acrylate monomer represented by following formulas (C-4)
[in formula (C-4), R10Hydrogen or methyl are represented, p represents more than 2 integer, and S represents the organic group of (p+1) valency, T tables Show the organic group of 1 valency with polymerism unsaturated group.]
The monomer of above-mentioned (C1) is (methyl) acrylate for having in ester moiety the chain alkyl of 1 valency of carbon number 1~11 Monomer, the chain alkyl of 1 valency of the carbon number 1~11, which has, is selected from hydroxyl, amino, carboxyl, epoxy radicals, NCO and (first Base) at least one kind of functional group in acryloxy.From can with crosslinking agent react aspect, the 1 of above-mentioned carbon number 1~11 The chain alkyl of valency preferably has at least one kind of functional group in hydroxyl, amino, carboxyl, epoxy radicals and NCO. Non- fluorine system acrylic acid series polymeric compounds and crosslinking using the monomer of (C1) containing the group that can be reacted with these with crosslinking agent In the case that agent is handled fibre together, it can be improved in the case of the sense of touch for the fibre for maintaining to obtain resistance to Long water proofing property.NCO can be the blocked isocyanate base protected with end-capping reagent.
Above-mentioned chain alkyl can be straight-chain, or branch-like, can be saturated hydrocarbyl, or unsaturated Alkyl.In addition, chain alkyl in addition to above-mentioned functional group, can further have substituent.Wherein it can improve what is obtained The aspect of the durable waterproof of fibre, preferably straight-chain and/or be saturated hydrocarbyl.
As the monomer of specific (C1), (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid diformazan can be included Double (acryloyloxymethyl) ethyl isocyanates of base amino ethyl ester, (methyl) glycidyl acrylate, 1,1- etc..These lists Body can be used alone a kind, and also two or more can be applied in combination.Wherein in the durable waterproof for the fibre that can improve to obtain Property aspect, preferably (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) glycidyl acrylate, 1, the double (acryloxies of 1- Methyl) ethyl isocyanate.In terms of the sense of touch of obtained fibre is further improved, preferred (methyl) acrylic acid diformazan Base amino ethyl ester.
The composition of the monomer of above-mentioned (C1) in the non-fluorine system acrylic acid series polymeric compounds of present embodiment, from what is obtained From the viewpoint of the water proofing property and sense of touch of fibre, relative to the complete of the monomer component for forming non-fluorine system acrylic acid series polymeric compounds Portion is measured, preferably 1~30 mass %, more preferably 3~25 mass %, more preferably 5~20 mass %.
The monomer of above-mentioned (C2) is (methyl) acrylate for having in ester moiety the cyclic hydrocarbon group of 1 valency of carbon number 1~11 Monomer, as cyclic hydrocarbon group, isobornyl, cyclohexyl, Bicvclopentyl etc. can be included.These cyclic hydrocarbon groups can have alkyl etc. Substituent.But, in the case that substituent is alkyl, substituent and the total of the carbon number of cyclic hydrocarbon group is selected to turn into less than 11 Alkyl.In addition, from the viewpoint of durable waterproof raising, preferably these cyclic hydrocarbon groups and ester bond directly in conjunction with.Cyclic hydrocarbon group Can be ester ring type, or aromatic series, can be saturated hydrocarbyl, or unsaturated alkyl in the case of ester ring type. As specific monomer, it is double that (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid can be included Ring pentyl ester etc..These monomers can be used alone a kind, and also two or more can be applied in combination.Wherein in the fiber that can improve to obtain The aspect of the durable waterproof of product, preferably (methyl) isobornyl acrylate, more preferably cyclohexyl methacrylate, methyl-prop Olefin(e) acid isobornyl thiocyanoacetate.
The composition of the monomer of above-mentioned (C2) in the non-fluorine system acrylic acid series polymeric compounds of present embodiment, from what is obtained It is excellent relative to the whole amount for the monomer component for forming non-fluorine based polymer from the viewpoint of the water proofing property and sense of touch of fibre Elect 1~30 mass %, more preferably 3~25 mass %, more preferably 5~20 mass % as.
The monomer of above-mentioned (C3) for unsubstituted carbon number 1~4 the chain alkyl of 1 valency and the ester bond of ester moiety directly in conjunction with Methacrylate monomers.As the chain alkyl of carbon number 1~4, the preferably straight-chain alkyl of carbon number 1~2 and carbon number 3~4 Branched alkyl groups.As the chain alkyl of carbon number 1~4, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, uncle can be included Butyl etc..As specific compound, methyl methacrylate, EMA, methacrylic acid positive third can be included Ester, isopropyl methacrylate, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate.These lists Body can be used alone a kind, and also two or more can be applied in combination.Wherein in the durable waterproof for the fibre that can improve to obtain The aspect of property, preferably methyl methacrylate, isopropyl methacrylate, Tert-butyl Methacrylate, more preferably metering system Sour methyl esters.
The composition of the monomer of above-mentioned (C3) in the non-fluorine system acrylic acid series polymeric compounds of present embodiment, from what is obtained From the viewpoint of the water proofing property and sense of touch of fibre, relative to the complete of the monomer component for forming non-fluorine system acrylic acid series polymeric compounds Portion is measured, preferably 1~30 mass %, more preferably 3~25 mass %, more preferably 5~20 mass %.
The monomer of above-mentioned (C4) is (methyl) the acrylate list for having more than 3 polymerism unsaturated groups in 1 intramolecular Body.In present embodiment, the T in preferably above-mentioned formula (C-4) has more than 3 for (methyl) acryloxy, in 1 intramolecular (methyl) acryloxy polyfunctional (methyl) acrylate monomer.In formula (C-4), p T can may not be used with identical yet Together.As specific compound, such as ethoxylation isocyanuric acid triacrylate, tetramethylol methane tetrapropylene can be included Acid esters, tetramethylol methane tetramethyl acrylate, trimethylolpropane trimethacrylate, trimethylol propane trimethyl propylene Acid esters, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, dipentaerythritol acrylate, two seasons penta 4 Alcohol hexamethacrylate etc..These monomers can be used alone a kind, and also two or more can be applied in combination.It can wherein improve The aspect of the durable waterproof of obtained fibre, more preferably tetramethylol methane tetraacrylate and ethoxylation isocyanide urea Sour triacrylate.
The composition of the monomer of above-mentioned (C4) in the non-fluorine system acrylic acid series polymeric compounds of present embodiment, from what is obtained It is excellent relative to the whole amount for the monomer component for forming non-fluorine based polymer from the viewpoint of the water proofing property and sense of touch of fibre Elect 1~30 mass %, more preferably 3~25 mass %, more preferably 5~20 mass % as.
Total composition ratio of the monomer of above-mentioned (C) composition in the non-fluorine system acrylic acid series polymeric compounds of present embodiment Example, from the viewpoint of the water proofing property and sense of touch of obtained fibre, relative to the monomer component for forming non-fluorine based polymer Whole amount, preferably 1~30 mass %, more preferably 3~25 mass %, more preferably 5~20 mass %.
The non-fluorine system acrylic acid series polymeric compounds of present embodiment are except (A) composition, (E) composition, (B) composition and (C) composition In addition, the monomer (D) for the simple function that can be copolymerized with them can be contained in the range of the effect of the present invention is not damaged.
As the monomer of above-mentioned (D), such as can include beyond (methyl) acryloyl morpholine, (A) composition and (C) composition (methyl) acrylate with alkyl, (methyl) acrylic acid, fumarate, maleate, fumaric acid, maleic acid, (first Base) not fluorine-containing (E) such as acrylamide, N hydroxymethyl acrylamide, vinyl ethers, vinyl ester, ethene, styrene into Vinyl monomer beyond point etc..Further, (methyl) acrylate with alkyl beyond (A) composition and (C) composition exists There can be the substituents such as vinyl, hydroxyl, amino, epoxy radicals and NCO, blocked isocyanate base in alkyl, can have Substituent beyond the group that quaternary ammonium group etc. can react with crosslinking agent, can have ehter bond, ester bond, amido link or ammonia ester bond etc..Make For (methyl) acrylate beyond (A) composition and (C) composition, such as methyl acrylate, (methyl) acrylic acid 2- can be included Ethylhexyl, (methyl) benzyl acrylate, ethylene glycol two (methyl) acrylate etc..Wherein in the fiber system that can improve to obtain The aspect of the peel strength for coating of product, more preferably (methyl) acryloyl morpholine.
The composition of the monomer of above-mentioned (D) in the non-fluorine system acrylic acid series polymeric compounds of present embodiment, from what is obtained From the viewpoint of the water proofing property and sense of touch of fibre, relative to the complete of the monomer component for forming non-fluorine system acrylic acid series polymeric compounds Portion is measured, preferably below 10 mass %.
From the durable waterproof for improving obtained fibre, the non-fluorine system acrylic acid series of preferably present embodiment gathers Compound has at least one kind of function in hydroxyl, amino, carboxyl, epoxy radicals and NCO that can be reacted with crosslinking agent Group.NCO can form the blocked isocyanate base protected with end-capping reagent.In addition, from the fibre for also improving to obtain Sense of touch is set out, and preferably non-fluorine based polymer has amino.
The non-fluorine system acrylic acid series polymeric compounds of present embodiment can use radical polymerization to manufacture.In addition, at this certainly By in base polymerization, from the performance and environment aspect of obtained waterproofing agent, it is preferred to use emulsion polymerization or dispersin polymerization Method is polymerize.
For example, can be by making (the first shown in above-mentioned formula (A-1) in media as well, in the presence of above-mentioned (E) composition Base) acrylate monomer (A) carries out emulsion polymerization or dispersin polymerization and obtains non-fluorine system acrylic acid series polymeric compounds.More specifically, For example, add in media as well (A) composition, (E) composition and above-mentioned (B) composition added as needed, above-mentioned (C) composition and Above-mentioned (D) composition and emulsion adjuncts or disperse additive, the mixed liquor is emulsified or disperseed, and obtains emulsion or scattered Thing.By adding polymerization initiator in obtained emulsion or dispersion, so as to initiated polymerization, monomer and anti-can be made Answering property emulsifying agent polymerize.Further, as the means that above-mentioned mixed liquor is emulsified or disperseed, homomixer, height can be included Press mulser or ultrasonic wave etc..
As above-mentioned emulsion adjuncts or disperse additive etc. (hereinafter also referred to " emulsion adjuncts etc. "), choosing can be used Nonionic surfactant, cationic surfactant, anion surfactant from beyond above-mentioned reactive emulsifier (B) With more than a kind in amphoteric surfactant.The content of emulsion adjuncts etc., relative to whole mass parts of monomer 100, it is preferably 0.5~30 mass parts, more preferably 1~20 mass parts, more preferably 1~10 mass parts.If above-mentioned emulsion adjuncts Deng content to be more than 0.5 mass parts, compared with situation of the content of emulsion adjuncts etc. outside above range, point of mixed liquor Scattered stability is tended to be difficult to reduce, if the content of emulsion adjuncts etc. is below 30 mass parts, with emulsion adjuncts etc. Situation of the content outside above range is compared, and the water proofing property of obtained non-fluorine system acrylic acid series polymeric compounds is tended to be difficult to reduce.
As emulsion polymerization or the medium of dispersin polymerization, preferably water, water can be mixed with organic solvent as needed.As Organic solvent now, there is no particular restriction, such as can include the esters such as the alcohols such as methanol, ethanol, ethyl acetate, acetone, The glycols such as ethers such as the ketones such as MEK, Anaesthetie Ether etc., propane diols, DPG, tripropylene glycol.Further, to water with having The ratio of solvent is not particularly limited.
As above-mentioned polymerization initiator, can be suitably used known in azo system, peroxide system or redox system etc. Polymerization initiator.For the content of polymerization initiator, relative to whole mass parts of monomer 100, preferred polymeric initiator is 0.01~2 mass parts.If the content of polymerization initiator is above range, weight average molecular weight can be expeditiously manufactured as 10 More than ten thousand non-fluorine system acrylic acid series polymeric compounds.
In addition, in the polymerization, for the purpose of molecular-weight adjusting, the chains such as lauryl mercaptan, the tert-butyl alcohol can be used to turn Move agent.For the content of chain-transferring agent, relative to whole mass parts of monomer 100, preferably below 0.3 mass parts, more preferably Below 0.1 mass parts.If the content of chain-transferring agent is below 0.3 mass parts, molecular weight becomes to be difficult to reduce, high efficiency The non-fluorine system acrylic acid series polymeric compounds that ground manufacture weight average molecular weight is more than 100,000 tend to become easy.
Further, for molecular-weight adjusting, polymerization inhibitor can be used.By the addition of polymerization inhibitor, can be readily derived has The non-fluorine system acrylic acid series polymeric compounds of desired weight average molecular weight.
Preferably 20 DEG C~150 DEG C of the temperature of polymerisation.If temperature is more than 20 DEG C, with temperature outside above range Situation is compared, and polymerization is tended to become abundant, if temperature is less than 150 DEG C, the control of reaction heat is tended to become easy.
In polymerisation, the weight average molecular weight of obtained non-fluorine system acrylic acid series polymeric compounds can be drawn by above-mentioned polymerization Hair agent, the increase and decrease of content of chain-transferring agent, polymerization inhibitor are adjusted, and the melt viscosity at 105 DEG C can pass through multifunctional list The increase and decrease of the content of body and the content of polymerization initiator is adjusted.Further, to make the feelings that the melt viscosity at 105 DEG C reduces Under condition, the content of the monomer with more than 2 polymerizable functional groups can be reduced, or the content of increase polymerization initiator is Can.
Non- fluorine system acrylic acid series in the polymer emulsified liquid or dispersion liquid that are obtained by emulsion polymerization or dispersin polymerization gathers The content of compound, from the viewpoint of the bin stability of composition and treatability, relative to the whole of emulsion or dispersion liquid Amount, is preferably set to 10~50 mass %, is more preferably set to 20~40 mass %.
As silicon-type waterproofing agent, for example, can include hydrogen organosilicon, amino-modified silicone, dimethyl organosilicon, Epoxy modified silicone, carbinol-modified organosilicon etc..It is excellent from the viewpoint of the water proofing property of obtained fibre becomes good Select hydrogen organosilicon, amino-modified silicone.
Hydrogen organosilicon can use such as " city such as De ラ イ Port Application 600E " (Nicca Chemical Co., Ltd manufactures, trade name) Sell product.
Amino-modified silicone can use such as " ネ オ シ ー De SF-200 " (Nicca Chemical Co., Ltd's manufacture, business The name of an article) etc. commercially available product.
As dendritic macromole system waterproofing agent, can enumerate comprising with radial and from the structure of center regularly branch Dendrimer, dendritic polymer compound waterproofing agent.In order to obtain water proofing property, dendrimer, dendritic polymer compound can use the branch in end Part has the dendrimer, dendritic polymer compound of the alkyl of the carbon number more than 1 of straight-chain or branch-like.
As dendrimer, dendritic polymer compound, such as can use disclosed in International Publication WO2014/160906 pamphlets " a polymer extender (extender) ".Such as it can use selected from isocyanates, diisocyanate, polyisocyanates Or the compound containing NCO in its mixture is at least one kind of with being selected from following formula (Ia), (Ib) or (Ic) Compound obtained from least one kind of reaction of isocyanate-reactive compound.
In above-mentioned formula, R20Expression-H, R independently of one another21、-C(O)R21、-(CH2CH2O)n(CH(CH3)CH2O)mR22Or- (CH2CH2O)n(CH(CH3)CH2O)mC(O)R21, n is each independently 0~20, m and is each independently 0~20, m+n more than 0. In addition, R21The alkyl of the carbon number 5~29 containing more than 1 unsaturated bond, straight chain or branched chain is represented independently of one another, R22The alkane of expression-H or the carbon number 6~30 containing more than 1 unsaturated bond, straight chain or branched chain independently of one another Base.
Further, in formula (Ia), R20Or R22It is at least one be-H.
In above-mentioned formula, R23Expression-H ,-R independently of one another21、-C(O)R21、-(CH2CH2O(CH(CH3)CH2O)mR22Or- (CH2CH2O(CH(CH3)CH2OC(O)R21, R24Expression-H or unsaturated bond, straight containing more than 1 independently of one another The alkyl of chain or the carbon number of branched chain 6~30 ,-(CH2CH2O)n’(CH(CH3)CH2O)m’R22Or-(CH2CH2O(CH(CH3) CH2OC(O)R21, n ' is each independently 0~20, m ' and is each independently 0~20, m+n more than 0.
Further, in formula (Ib), R22、R23Or R24It is at least one be-H.
In above-mentioned formula, R25Expression-H ,-C (O) R21Or-CH2C[CH2OR20]3.Further, in formula (Ib), R25Or R20At least One is-H.
As the compound containing NCO, there is no particular restriction, for example, can include aliphatic polyisocyante, The modified polyisocyanate such as ester ring type polyisocyanates, aromatic polyisocyanate and their dimer, tripolymer.Energy It is enough to use " DESMODUR N-100 " (Bayer companies manufacture, trade name), " デ ュ ラ ネ ー ト THA-100 " (Asahi Chemical Industry's strain formulas Commercial firm's manufacture, trade name), " commercially available product such as デ ュ ラ ネ ー ト 24A-100 " (Asahi Kasei Corporation manufacture, trade name).Separately Outside, reaction can for example be carried out more than 1 hour at 80 DEG C.
For the process of non-fluorine system waterproofing agent is assigned to the fiber containing functional group, such as following side can be included Method：With comprising in above-mentioned, acrylic acid series waterproofing agent, silicon-type waterproofing agent and dendritic macromole system waterproofing agent extremely Few a kind treatment fluid is handled the fiber containing functional group.
As the method handled with above-mentioned treatment fluid the fiber containing functional group, such as dipping, spray can be included The processing methods such as mist, coating.In addition, in the case that treatment fluid contains water, preferably after the fiber containing functional group is attached to, it is Water is removed and is dried.
Also additive etc. can be added in treatment fluid as needed.As additive, other waterproofing agents, friendship can be included Join agent, Antibiotic-odor Resistant Agent, fire retardant, antistatic additive, softening agent, anti-creasing agent etc..
Non- fluorine system waterproofing agent can be appropriate according to the degree of required water proofing property to the adhesion amount of the fiber containing functional group Ground adjusts, relative to the fiber 100g containing functional group, preferably with non-fluorine system waterproofing agent contained in treatment fluid (for example, non-fluorine Be acrylic acid series polymeric compounds) adhesion amount be adjusted as 0.01~10g mode, more preferably with the side as 0.05~5g Formula is adjusted.If the adhesion amount of non-fluorine system waterproofing agent is more than 0.01g, the adhesion amount with non-fluorine system waterproofing agent is in above-mentioned model Enclose outer situation to compare, fibre tends to easily play sufficient water proofing property, if below 10g, with non-fluorine system waterproof Situation of the adhesion amount of agent outside above range is compared, and the sense of touch of fibre is tended to be difficult to become thick and stiff.
After the non-fluorine system waterproofing agent of present embodiment is imparted into the fiber containing functional group, hot place is preferably properly carried out Reason.To temperature conditionss, there is no particular restriction, but fibre can be made to show foot using 100~130 DEG C of gentle condition Enough good water proofing properties.Can be temperature conditionss be more than 130 DEG C (being preferably up to 200 DEG C) high-temperature process, such case Under, compared with the conventional situation for having used fluorine system waterproofing agent, processing time can be shortened.Therefore, using present embodiment The manufacture method of water proofing property fibre, suppresses the rotten of thermally-induced fibre, and fibre during water-proofing treatment touches Sense becomes soft, and fibre can be assigned under gentle heat treatment condition, i.e. low temperature curing conditions and sufficiently prevented It is water-based.
Especially, in the case of improving durable waterproof, it is preferred to use following method carries out waterproof to fibre and added Work, this method include：The above-mentioned work handled with the treatment fluid containing non-fluorine system waterproofing agent the fiber containing functional group Sequence；With make using melamine methylol, there is the compound of more than 1 NCO or blocked isocyanate base as representative Crosslinking agent is attached to the fiber containing functional group and the process being heated.And then further to improve the feelings of durable waterproof Under condition, preferred process liquid includes the non-fluorine system for forming the monomer copolymerization with the functional group that can be reacted with above-mentioned crosslinking agent and gathered Compound.
As the compound with more than 1 NCO, can include butyl isocyanate, phenyl isocyanate, The monoisocyanates such as tolyl isocyanate, naphthalene isocyanates, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, four The diisocyanate such as xylene diisocyanate, hydrogenated diphenyl methane diisocyanate and these isocyanuric acid Ring is tripolymer, trimethylolpropane addition body.In addition, as the compound with more than 1 blocked isocyanate base, can arrange Enumerate the compound for NCO being protected for the above-mentioned compound end-capping reagent with NCO.As now making End-capping reagent, the organic systems such as secondary or tertiary alcohols, activity methene compound, phenols, oximes, lactams end-blocking can be included The bisulfites such as agent, sodium hydrogensulfite, potassium bisulfite.Above-mentioned crosslinking agent can be used alone a kind, also can be by a variety of groups Close.
For crosslinking agent, such as following method can be used it is attached to treated object：Dissolved by crosslinking agent In organic solvent or make to impregnate treated object (fibre) in the treatment fluid of its emulsion dispersion in water, will attach to be located The treatment fluid for managing thing is dried.Then, heated by will attach to the crosslinking agent of treated object, so as to make crosslinking agent with being located The reaction for managing thing and non-fluorine system waterproofing agent (particularly non-fluorine system acrylic acid series polymeric compounds) is carried out.In order that the reaction of crosslinking agent is filled Ground is divided to carry out and more effectively improve washing resistance, heating now can be carried out 1~5 minute at 110~180 DEG C.Crosslinking The attachment of agent and the process of heating can simultaneously be carried out with the process handled with above-mentioned treatment fluid.Situation about carrying out simultaneously Under, for example, the treatment fluid containing non-fluorine system waterproofing agent and crosslinking agent is attached to treated object, after water is removed, and then will be attached The crosslinking agent heating in treated object.In the case of considering the simplification of waterproof processing process, the reduction of heat, economy, It is preferred that with simultaneously being carried out using the treatment process for the treatment of fluid.
In addition, if exceedingly use crosslinking agent, it is likely that infringement sense of touch.Relative to treated object (fibre), It is preferred that using above-mentioned crosslinking agent with 0.1~50 mass % amount, particularly preferably used with 0.1~10 mass % amount.
The water proofing property fibre of the present embodiment so obtained also can in the case of outdoor long-term use Water proofing property is fully played, further, since above-mentioned water proofing property fibre does not use the compound of fluorine system, therefore it can be made As environment amenable water proofing property fibre.
For the water proofing property fibre of present embodiment, processing can be coated to defined part.As painting Cloth process, can include in Sport Utility, outdoor applications moisture-permeability waterproof processing, it is windproof processing etc..As processing method, example Such as, can be by the way that the coating of polyurethane resin, acrylic resin etc. and medium will be included in the case where moisture-permeability waterproof is processed Liquid is coated on the one side for the fibre for having carried out water-proofing treatment, is dried and is processed.
The preferred embodiment of the present invention is illustrated above, but the present invention is not limited to above-mentioned embodiment party Formula.
For example, in the case of manufacturing non-fluorine system acrylic acid series polymeric compounds, in the above-described embodiment, using radical polymerization Carry out polymerisation, but also can be by irradiating the photopolymerization of ultraviolet, electron beam, ionization property radioactive ray as gamma-rays etc. To carry out polymerisation.
Embodiment
The present invention is further illustrated by the following examples, but the present invention is not by any limit of these embodiments System.
The preparation ＞ of ＜ polymer dispersion liquids
Using program as shown below to the mixed liquor with the composition (in table, numerical value represents (g)) shown in table 1 and 2 It is polymerize, has obtained polymer dispersion liquid.
(synthesis example 1)
Load stearyl acrylate ester 40g, vinyl chloride 20g, ラ テ system Le PD-430 (flower king's strain formula meetings in 500mL flasks Society's manufacture, polyoxyalkylene alkenyl ether, HLB=14.4) (Kao Corp manufactures, polyoxyalkylene alkene by 2g, ラ テ system Le PD-420 Base ether, HLB=12.6) 2g, stearyl dimethyl amine hydrochlorate 3g, tripropylene glycol 25g and water 207.70g, mixed at 45 DEG C Stirring, is made mixed liquor.Ultrasonic wave is irradiated to the mixed liquor, makes whole monomer emulsion dispersions.Next, by the (isobutyl of azo two Base amidine) dihydrochloride 0.3g is added in mixed liquor, make its radical polymerization 6 hours at 60 DEG C under nitrogen atmosphere, as non-fluorine It is the non-fluorine system acrylic acid series polymeric compounds dispersion liquid that waterproofing agent has obtained the mass % of polymer concentration 21.
(synthesis example 2~10)
In addition to having used the material described in table 1 and 2, it is polymerize similarly to Example 1, is prevented as non-fluorine system Aqua, the non-fluorine system acrylic acid series polymeric compounds dispersion liquid of the polymer concentration shown in table 1 and 2 is respectively obtained.
(synthesis example 11 and 12)
In addition to having used the material described in table 2, it is polymerize similarly to Example 1, as fluorine system waterproofing agent, The fluorine system acrylic acid series polymeric compounds dispersion liquid of the polymer concentration shown in table 2 is respectively obtained.
Further, for each polymer in the polymer dispersion liquid obtained in synthesis example 1~12, pass through gas-chromatography (GC-15APTF, the manufacture of (strain) Shimadzu Seisakusho Ltd.) confirms to be that more than the 98% of whole monomers is polymerized.
The details of material shown in table 1 and 2 is as described below.
ラテムルPD-420：" ラ テ system Le PD-420 " (Kao Corp's manufacture, trade name, polyoxyalkylene alkenyl Ether, HLB=12.6)
ラテムルPD-430：" ラ テ system Le PD-430 " (Kao Corp's manufacture, trade name, polyoxyalkylene alkenyl Ether, HLB=14.4)
Anacardol 12.5EO：12.5 moles of addition products (HLB=12.9) of oxirane of anacardol
Anacardol 8.3EO：8.3 moles of addition products (HLB=11.0) of oxirane of anacardol
ノイゲンXL-100：" ノ イ ゲ Application XL-100 " (Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture, trade name, polyoxy Hua Xi branches decyl ethers, HLB=14.7)
ノイゲンXL-60：" ノ イ ゲ Application XL-60 " (Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture, trade name, polyoxygenated Alkene branch decyl ethers, HLB=12.5)
" containing the fluorine-based acrylate of C8 " in table is by following logical formula (III)s：
CnF2n+1CH2CH2OCOCH=CH2(III) represent, n average value as 8 mixture (further, in the mixture It is mixed with the compound that n is 6,8,10,12,14).
The polymer obtained for polymer dispersion liquid obtained above and using method as shown below is evaluated.
(evaluation of physical property of polymer)
By adding acetone 500mL in the polymer dispersion liquid 50g that is obtained in synthesis example 1~10, so that polymer Separate, leaching polymer, the polymer is dried under reduced pressure 24 hours at 25 DEG C with emulsifying agent.It is poly- to what is obtained as described below Compound is evaluated.Show the result in table 1 and 2.
(1) assay method of melt viscosity
For embodiment obtained above and the polymer of comparative example, overhead system flow tester CFT-500 ((strain) is used Shimadzu Seisakusho Ltd. manufactures), 1g polymer is loaded and is provided with mouth mold (long 10mm, diameter 1mm) barrel, is protected at 105 DEG C Hold 6 minutes, 100kgf/cm is applied using plunger2Load, determine the melt viscosity at 105 DEG C.
(2) assay method of weight average molecular weight
For embodiment obtained above and the polymer of comparative example, using GPC devices (eastern Cao's (strain) GPC " HLC- processed 8020 "), in 40 DEG C of column temperature, under conditions of flow 1.0ml/ minutes, tetrahydrofuran is measured as eluent, passed through Polystyrene standard conversion determines weight average molecular weight.It should illustrate, for post, by the trade name of eastern Cao (strain) manufacture TSK-GEL G5000HHR, G4000HHR, G3000HHR 3 connection installations.
(preparation of fibrous material)
As fibrous material, the cloth of nylon 100% (being represented in table with Ny) for having prepared to be dyed, dyeing has been carried out Polyester 100% (polyethylene terephthalate system) cloth (being represented in table with Pet) and cation dyeable polyester (Co., Ltd.'s color dye Society's manufacture, dye test are with fiber " cation-dyeable type polyester Knit Smooth (processing silk thread) ") (being represented in table with CD-PET).
(preparation of pretreating reagent)
Following pretreating reagents 1~4 is prepared.
Pretreating reagent 1：The aqueous solution of the formaline condensates comprising phenolsulfonic acid synthesized using following methods.
Phenol 70g, phosphatase 11 .5g and formaldehyde 20g are put into reaction vessel, reacts 3 hours, connects down at 95~100 DEG C Come, last 30 minutes and be cooled to 70 DEG C after instillation acetic anhydride 45g.90% sulfuric acid 25g is instilled next, lasting 30 minutes, 100 Reacted at DEG C 1 hour.After reaction, water 138.5g is added, the content for having obtained the formaline condensates of phenolsulfonic acid is 38 Quality % pretreating reagent 1.
Pretreating reagent 2：The aqueous solution of the formaline condensates comprising sulfonated bis phenol S synthesized using following methods.
Bisphenol S 100g and acetic anhydride 45g are put into reaction vessel, is warming up to 80 DEG C.Dripped next, lasting 30 minutes After entering 90% sulfuric acid 14.5g, reacted 6 hours at 120 DEG C.Next, after being cooled to 50 DEG C, formaldehyde 10.5g is added, 100 Reacted at DEG C 6 hours.Then, 70 DEG C are cooled to, water 147g is added, has obtained sulfonated bis phenol S formaline condensates Content is 40 mass % pretreating reagent 2.
Pretreating reagent 3：The aqueous solution (Nicca Chemical Co., Ltd's manufacture, the business of Sodium Polyacrylate comprising molecular weight 7000 The name of an article " ネ オ Network リ ス タ Le 770 ", the mass % of content 43)
Pretreating reagent 4：Lauryl phosphate (mixture of monoesters and diester) (Toho Chemical Industry Co., Ltd.'s manufacture, business The name of an article " Off ォ ス Off ァ ノ ー Le ML-200 ", content 100%)
The manufacture ＞ of ＜ water proofing property fibres
(embodiment 1)
By the cloth of nylon 100% dyed be impregnated in comprising pretreating reagent 1 processing bath (imparting amount to fiber with Compound concentration conversion meter, is 2%o.w.f.), in bath raio 1：10th, 80 DEG C, handled under conditions of 20 minutes.Processing Afterwards, dried 2 minutes at 130 DEG C, obtained the fiber containing functional group.
Fiber obtained above containing functional group is being diluted the non-fluorine system waterproofing agent of synthesis example 1 so that polymerization with water After the content of thing is as impregnation (the mass % of pick-up rate 60) in 3 mass % treatment fluid, dries 2 minutes, obtain at 130 DEG C Water proofing property fibre is arrived.
(embodiment 2~12,14~35, comparative example 3~6)
Using the fibrous material shown in table 3~8, pretreating reagent, compound concentration and waterproofing agent, similarly to Example 1 Ground has obtained water proofing property fibre.Further, the waterproofing agent in embodiment 32~35 has used following waterproofing agents.
Silicon-type waterproofing agent 1：" De ラ イ Port Application 600E " (Nicca Chemical Co., Ltd's manufacture, trade name, hydrogen organosilicon The mass % of content 53)
Silicon-type waterproofing agent 2：" (Nicca Chemical Co., Ltd's manufacture, trade name, amino change ネ オ シ ー De SF-200 " Property silicone content 30 mass %)
(embodiment 13)
In addition to having used CD-PET as the fiber containing functional group, water proofing property has been obtained similarly to Example 1 Fibre.
(comparative example 1)
In addition to the pre-treatment of no progress fibrous material, water proofing property fibre has been obtained similarly to Example 1.
(comparative example 2)
Except used as fibrous material polyester 100% (polyethylene terephthalate system) cloth dyed with Outside, water proofing property fibre has been obtained in the same manner as comparative example 1.
The various evaluation ＞ of ＜
Manufacture for embodiment and the water proofing property fibre of comparative example, following various evaluations are carried out.
[the zeta potential measure of fiber surface]
Manufactured using zeta potential particle size determination system ELSZ-1000ZS (Otsuka Electronics Co., Ltd.) determine containing official The zeta potential on the surface for the fiber that can be rolled into a ball.
[waterproofing property evaluation of fibre]
According to JIS L 1092 (2009) spray-on process, spray water temperature is set to be tested for 20 DEG C.For water proofing property As a result, evaluated by visual observation with following grades.It should illustrate, in the case that characteristic is somewhat good, be marked at grade Remember "+", in the case that characteristic is somewhat poor, "-" is marked at grade.
Water proofing property：State
5：Moistened on surface without attachment
4：Attachment moistening is slightly shown on surface
3：The moistening of part is shown on surface
2：Moistening is shown on surface
1：Moistening is integrally shown on surface
0：Two sides fully shows moistening in table
[the sense of touch evaluation of fibre]
Using the product that obtained fibre is further heat-treated to 30 seconds at 170 DEG C, sense of touch is evaluated. As a result evaluated by handling with following 5 shown grades.
1：Firmly~5：It is soft
[experiment of processing bath stability]
The stability that processing for carrying out waterproof processing is bathed, is evaluated according to following program.After pre-treatment Fibrous material (embodiment 13 is CD-PET, and comparative example 1 and 2 is the fibrous material for not carrying out pre-treatment) 5g, waterproofing agent 12g, NK ア シ ス ト FU (crosslinking agent, Nicca Chemical Co., Ltd's manufacture) 1g is diluted so that turning into 200mL, by this with ion exchange water Dilution placed 12 hours at 40 DEG C.Then, fibrous material is removed, homogeneously mixed using TK in the state of maintaining 40 DEG C After conjunction machine has stirred 10 minutes with 5000 revs/min of revolution, filtered, visually confirmed in cotton with the cotton that dye is black The condensation product remained on surface.
5；Without condensation product
4：There is a little condensation product
3：Albefaction on the whole lightly
2：White condensation product residual on the whole
1：It can not filter
[durable waterproof evaluation]
According to JIS L 1092 (2009) spray-on process, spray water temperature is set to be tested for 20 DEG C.In this experiment, it will contain The fiber for having functional group is turning into 3 mass %, UNIKA RESIN 380-K (crosslinking agent, ユ ニ オ Application with the content of polymer Learn Industrial Co., Ltd manufacture, trimethylol melamine resin) content turn into 0.3 mass % and UNIKA CATALYST 3-P (surfactant, the manufacture of ユ ニ オ Application chemical industry Co., Ltd., amino alcohol hydrochloride salt) content turns into 0.2 mass % The mode water treatment fluid that forms waterproofing agent and the dilution of above-mentioned each medicament in after impregnation (the mass % of pick-up rate 60), At 130 DEG C dry 2 minutes, for and then fibrous material be Pet and CD-PET in the case of be heat-treated at 170 DEG C 60 seconds, Cloth (L-0) obtained from 60 seconds is heat-treated at 160 DEG C in the case of for Ny and has carried out 10 times (L-10) and is based on JIS L The water proofing property of cloth after the washing of 103 methods of 0217 (1995), evaluated in the same manner as above-mentioned waterproofing property evaluation method.
The fiber of the present invention containing functional group is carried out with specific non-fluorine system waterproofing agent of the present invention In the embodiment 1~35 of waterproof processing, and not using the comparative example 1 and 2 of the fiber of the present invention containing functional group Compare, it is thus identified that obtain the fibre with excellent water proofing property and durable waterproof.
In addition, with the acrylic acid series waterproof for including the non-fluorine system acrylic acid series polymeric compounds obtained using reactive emulsifier Agent has been carried out to the fiber of the present invention containing functional group in the embodiment 1~25,28~31 of waterproof processing, it is thus identified that energy Enough water proofing properties and durable waterproof and processing bath stability for meeting fibre with high level.
Further, using the fluorine system waterproofing agent comprising the fluorine system acrylic acid series polymeric compounds that use reactive emulsifier to obtain Comparative example 3 and 4 in, compared with Examples 1 and 2, the result for handling bath stability is poor.Think that this becomes due to fluorine system waterproofing agent Obtain and easily condense.
In accordance with the invention it is possible to there is sufficient water proofing property and sufficient durable waterproof using the manufacture of non-fluorine system waterproofing agent Water proofing property fibre.

Claims (6)

1. the manufacture method of water proofing property fibre, it has following processes：Make to prevent selected from acrylic acid series waterproofing agent, silicon-type At least one kind of non-fluorine system waterproofing agent and fiber contacts in aqua and dendritic macromole system waterproofing agent, the fiber contain selected from by- SO3M1Represent 1 valency group, by-COOM2Represent 1 valency group and by-O-P (O) (OX1) (OX2) represent 1 valency group in At least one kind of functional group, in formula, M1Represent the cation of monovalence, M2Represent the cation of monovalence, X1And X2Independently of one another Represent the alkyl of hydrogen atom or carbon number 1~22.
2. the manufacture method of water proofing property fibre according to claim 1, wherein, the non-fluorine system waterproofing agent includes third Olefin(e) acid system waterproofing agent, the acrylic acid series waterproofing agent are included containing (methyl) acrylate come shown in free following formulas (A-1) The polymer of the construction unit of monomer (A)：
In formula (A-1), R1Represent hydrogen or methyl, R2Represent there can be the alkyl of 1 valency of the carbon number more than 12 of substituent.
3. the manufacture method of water proofing property fibre according to claim 1 or 2, wherein, the non-fluorine system waterproofing agent bag Waterproofing agent containing acrylic acid series, the acrylic acid series waterproofing agent are included containing (methyl) propylene come shown in free following formulas (A-1) The construction unit of acid ester monomer (A) and the construction unit of at least any of monomer in vinyl chloride and vinylidene chloride (E) Polymer,
In formula (A-1), R1Represent hydrogen or methyl, R2Represent there can be the alkyl of 1 valency of the carbon number more than 12 of substituent.
4. the manufacture method of the water proofing property fibre according to any one of claims 1 to 3, wherein, the fiber is With selected from by-SO3M1Shown 1 valency group, by-COOM2Shown 1 valency group and by-O-P (O) (OX1) (OX2) shown in 1 valency group at least one kind of functional group compound attachment fiber, in formula, M1Represent the cation of monovalence, M2Represent one The cation of valency, X1And X2The alkyl of hydrogen atom or carbon number 1~22 is represented independently of one another.
5. the manufacture method of water proofing property fibre according to claim 4, wherein, the compound include have by- SO3M1The phenol system high-molecular compound of the 1 valency group represented, in formula, M1Represent the cation of monovalence.
6. the manufacture method of the water proofing property fibre according to any one of Claims 1 to 5, wherein, the fiber The zeta potential on surface is -100~-0.1mV.
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