JP2014062348A - Water repellent fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water repellent fabric that hardly gums up to a roll while being processed, and has excellent washing durability.SOLUTION: A water repellent fabric comprises that a water repellent finishing agent is adhered to a fabric, wherein the water repellent finishing agent includes: an at least C8 perfluoroalkane acid and an at least C8 perfluoroalkene acid; and a fluorine-based water repellent agent (A) not including a precursor thereof, and a water repellent degree of a fabric by JIS L 1092 (spray test) is at least a third class by after 20 times (HL-20) of cleaning according to JIS L 0217 103.

Description

  The present invention relates to a water-repellent fabric having a water-repellent agent attached to the fabric, which is difficult to gum up on a roll during processing and has excellent washing durability.

  As the fluorine-based water repellent, those containing perfluoroalkanoic acid having 8 or more carbon atoms or perfluoroalkenoic acid having 8 or more carbon atoms (hereinafter referred to as PFOA water repellent) have been conventionally used. However, in recent years, in consideration of safety and environmental load, fluorine-based water repellents having less than 8 carbon atoms (hereinafter referred to as non-PFOA water-repellents) have come to be desired (for example, Patent Literature 1, Patent Literature 2, Patent Literature 3, and Patent Literature 4).

However, from the viewpoint of maintaining water repellency, the non-PFOA water repellent agent needs to copolymerize a hydrophobic ethylenic fluorine monomer that is difficult to emulsify and disperse at a high rate. The problem of gumming up on the mangle roll tended to become prominent.
In addition, since it is a non-PFOA fluorine-based water repellent with a high introduction of a monomer having a perfluoroalkyl group having 6 or less carbon atoms, the film of the fluorine-based water repellent formed on the fabric surface is coarse and brittle There was a problem that it was easy to fall off by washing, and as a result, the washing durability such as water repellency, water pressure resistance and breathability was poor.

JP 2007-247090 A JP 2007-247091 A JP 2007-270374 A JP 2010-150693 A

  The present invention has been made in view of the above background, and an object of the present invention is to provide a water-repellent fabric that is difficult to gum up on a roll during processing and has excellent washing durability.

  As a result of diligent studies to achieve the above-mentioned problems, the present inventors have used a mixture of a fluorine-based water repellent and a specific alcohol compound, which makes it difficult to gum up a roll during processing and has excellent washing durability. The present inventors have found that a water-repellent fabric having a property can be obtained, and have further intensively studied to complete the present invention.

  Thus, according to the present invention, “a water-repellent fabric formed by attaching a water-repellent agent to a fabric, wherein the water-repellent agent is a perfluoroalkanoic acid having 8 or more carbon atoms and a perfluoroalkene having 8 or more carbon atoms. The water repellency of the fabric according to JIS L 1092 (spray test) is 20 times after washing according to JIS L 0217 103 (HL-20), which contains an acid and a fluorine-based water repellent (A) not containing these precursors. And a water repellent fabric characterized by being a grade 3 or higher. "

At that time, the fluorine-based water repellent (A) is a heavy polymer comprising a fluorine element-containing ethylenically unsaturated monomer having a perfluoroalkyl group having less than 8 carbon atoms or a perfluoroalkenyl group having less than 8 carbon atoms. It is preferably a coalescence. Moreover, it is preferable that the said water-repellent processing agent contains the alcohol compound (B) which is represented by following formula (1) and whose boiling point in the atmospheric pressure of 1013 hPa exists in the range of 150-250 degreeC.
Formula (1)
X-R-Y
However, X is either selected from the group consisting of —H, —OH, —O (CH ₂ CZ ₂ O) _a —H, and —OC _m Z _{2m + 1} . Y is any selected from the group consisting of —H, —OH, —O (CH ₂ CZ ₂ O) _a —H, and —OC _m Z _{2m + 1} . In addition, R is _-C n _{Z 2n} -, and / or _-C n _{Z 2n-2} -, and / or _-C n _{Z 2n-4} - a. In that case, Z is H or _{CH 3, n = 2~12, a} = 0~3, an m = 1 to 3.

Moreover, it is preferable that solid content mass ratio of the said fluorine-type water repellent (A) and the said alcohol body compound (B) exists in the range of 1: 0.1-1: 20 (the former: latter).
In addition, after 20 washings (HL-20) and 0 washings (HL-0) according to JIS L 0217 103, the reduction rate of water resistance by JIS L 1092 (hydrostatic pressure method) = [(HL− 0 water resistance)-(HL-20 water resistance)] × 100 / (HL-0 water resistance) is preferably less than 30%. Further, the rate of increase in air permeability according to JIS L 1096 A method (fragile type) is compared between 20 times after washing (HL-20) and 0 times (HL-0) in accordance with JIS L 0217 103 = [(HL −20 breathability) − (HL-0 breathability)] × 100 / (HL-0 breathability) is preferably less than 30%. In addition, a decrease in the fluorescent X-ray intensity peculiar to the fluorine element by the wavelength dispersive X-ray fluorescence analyzer by comparing 20 times after washing (HL-20) and 0 times after washing (HL-0) according to JIS L 0217 103 It is preferable that the ratio = [(HL-0 the fluorescent X-ray intensity) − (HL-20 the fluorescent X-ray intensity)] × 100 / (HL-0 the fluorescent X-ray intensity) is less than 30%.

  According to the present invention, it is possible to obtain a water-repellent fabric that does not easily gum up on a roll during processing and has excellent washing durability.

It is a figure which shows a mangle apparatus typically.

Hereinafter, embodiments of the present invention will be described in detail.
First, the type of the fluorine-based water repellent (A) is perfluorooctanoic acid, perfluorooctane sulfonic acid, perfluoroalkanoic acid having 8 or more carbon atoms, carbon number in consideration of safety to the living body and environmental load. 8 or more perfluoroalkenoic acids (hereinafter referred to as PFOA analogues) and water repellents (non-PFOA water repellents) that do not contain precursors (hereinafter referred to as PFOA precursors) that change to these upon decomposition. ). “Not contained” means that the substance is below the detection limit when analyzed by a high performance liquid chromatograph mass spectrometer (LC-MS) or a pyrolysis gas chromatograph mass spectrometer (PyGC-MS). It is.

  Here, the fluorine-based water repellent (A) is a heavy polymer comprising a fluorine element-containing ethylenically unsaturated monomer having a perfluoroalkyl group having less than 8 carbon atoms or a perfluoroalkenyl group having less than 8 carbon atoms. It is preferably a coalescence. In particular, the fluorine-based water repellent (A) is more preferably a copolymer aqueous dispersion of the fluorine element-containing ethylenically unsaturated monomer and the ethylenically unsaturated monomer not containing fluorine element. .

  As the ethylenically unsaturated monomer to be composed, alkyl (meth) acrylate is preferred. Perfluorohexylethyl (meth) acrylate is preferred as the fluorine-containing ethylenic monomer. On the other hand, in the ethylenic monomer which does not contain a fluorine element, methyl (meth) acrylate, ethyl (meth) acrylate, (n, i, t) butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octadecyl (meth) Multifunctional such as N-methylol (meth) acrylamide, glycidyl (meth) acrylate, hydroxyalkyl (meth) acrylate, chlorohydroxyalkyl (meth) acrylate, etc. for crosslinkable ethylenic monomers such as acrylate and benzyl (meth) acrylate Examples of the ethylenic monomer include ethylene di (meth) acrylate, glycerol tri (meth) acrylate, and trimethylol tri (meth) acrylate. Examples of the cationic ethylenic monomer include N, N, N-trimethyl-N- (2 -Hydroxy-3-meta Such Leroy oxy propyl) ammonium chloride.

  In many cases, these ethylene monomer copolymer aqueous dispersions are prepared by adding a volatile organic solvent such as methyl isobutyl ketone and cellosolve acetate to an ethylenic monomer mixture in advance, and then adding an alkyl quaternary ammonium salt, Cationic surfactants such as alkylbenzyl quaternary ammonium salts, alkylimidazolinium salts, and alkylamine acetates, and in some cases, the aforementioned cationic group-containing ethylenically unsaturated monomers, polyoxyethylene alkyl ethers, polyoxy Non-ionic such as ethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan ester, polyoxyethylene alkylamide ether, polyoxyethylene polyoxypropylene block copolymer, etc. It is preferred that after the emulsified aqueous dispersion with surfactants to emulsion copolymerization using a water-soluble radical polymerization initiator.

In addition, as a water-soluble radical polymerization initiator source, for example, a water-soluble azo compound such as 2,2-azobis-2-amidinopropane dihydrochloride is used for emulsion polymerization to obtain a 20 to 30% solid dispersion in water. It is preferable.
As commercially available non-PFOA water repellents, Asahi Guard AG-E082, AG-E092 (manufactured by Meisei Chemical Co., Ltd.), NK Guard S-07, S-09, S-11, S-22 (manufactured by Nikka Chemical), Nuba N2114L, 2116 (manufactured by Clariant) and the like are exemplified. On the other hand, examples of conventional PFOA water repellents include Asahi Guard LS-317, GS-10 (manufactured by Meisei Chemical Co., Ltd.), NDN-7E, NDN-9E (Nikka Chemical), and the like.

The water-repellent fabric of the present invention has a water-repellent finishing agent containing the fluorine-based water repellent (A) attached thereto, and the water repellency of the fabric according to JIS L 1092 (spray test) is JIS L 0217 103. It is grade 3 or more after 20 washings (HL-20).
At that time, the water repellency of the fabric according to JIS L 1092 (spray test) is preferably grade 5 before washing (HL-0). Further, the rate of decrease in water resistance according to JIS L 1092 (hydrostatic pressure method) = [(HL-0 water resistance) − (HL-20 water resistance)] × 100 / (HL-0 water resistance) is less than 30%. It is preferable. Further, the increase rate of air permeability according to JIS L 1096 A method (fragile type) = [(HL-20 air permeability) − (HL-0 air permeability)] × 100 / (HL-0 air permeability) is less than 30%. Preferably there is. Further, the decrease rate of the fluorescent X-ray intensity peculiar to the fluorine element by the wavelength dispersive X-ray fluorescence analyzer = [(HL-0 fluorescent X-ray intensity) − (HL-20 fluorescent X-ray intensity)] × 100 / ( HL-0 (fluorescent X-ray intensity) is preferably less than 30%.

The water-repellent fabric having such washing durability has the following alcohol compound (B) together with the fluorine-based water repellent (A) when the water-repellent finish is adhered to the fabric. It is obtained by including.
Here, alcohol body compound (B) is represented by following formula (1), and the boiling point in the atmospheric | air pressure of 1013 hPa exists in the range of 150-250 degreeC.
Formula (1)
X-R-Y
However, X is either selected from the group consisting of —H, —OH, —O (CH ₂ CZ ₂ O) _a —H, and —OC _m Z _{2m + 1} . Y is any selected from the group consisting of —H, —OH, —O (CH ₂ CZ ₂ O) _a —H, and —OC _m Z _{2m + 1} . In addition, R is _-C n _{Z 2n} -, and / or _-C n _{Z 2n-2} -, and / or _-C n _{Z 2n-4} - a. In that case, Z is H or _{CH 3, n = 2~12, a} = 0~3, an m = 1 to 3.

In the alcohol compound (B), R shown in the chemical formula is a lipophilic group, X and Y are hydrophilic groups, and is an amphiphile capable of obtaining an aggregation-suppressing effect of water-dispersed particles. By including the amphiphile related to the water repellent finish, a water repellent finish that is difficult to gum up on the roll during processing can be obtained.
When the boiling point is lower than 150 ° C., it is not preferable because it is easily volatilized in the mangle roll squeezing step and the surface active effect is difficult to be sustained. On the other hand, if the boiling point is higher than 250 ° C., it tends to remain in the processed product due to difficulty of volatilization, which is not preferable.
In the alcohol compound (B), the solubility in water at 20 ° C. is preferably 5% by weight or more (more preferably 10% by weight or more) relative to the weight of water.

  Specific examples of the alcohol compound (B) include, for example, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 4,7 -Acetylene diols such as dimethyl-5-decyne-4,7-diol, and methyl diglycol, ethyl diglycol, propyl diglycol, butyl diglycol, isobutyl diglycol, allyl glycol, methylpropylene triglycol, butylpropylene And glycols such as glycol.

  Among these, acetylene diol such as 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, isopropyl diglycol, butyl diglycol, Glycols such as isobutyl diglycol stabilize fluorine polymer particles under the severe mechanical share that the fluorine-based water repellent (A) receives in the water-repellent processing step, and heat drying during the processing step This is particularly preferable in view of the balance of volatility.

  On the other hand, in the present invention, as an undesirable alcohol compound which is excluded, for example, polyoxyethylene polyoxypropylene block copolymer, polyoxypropylene polyoxyethylene polyoxypropylene triblock copolymer, polyoxyethylene alkyl ether, Non-volatile to non-volatile alcohol compounds having a boiling point of over 250 ° C, such as polyoxyethylene alkanolamine ether, polyoxyethylene polyoxypropylene alkanolamine ether, methanol, ethanol, propanol, butanol, isobutanol, methyl glycol , Ethyl glycol, etc., readily volatile alcohol compounds having a boiling point of less than 150 ° C., and water-soluble, easily volatile cellosolve acetate represented by ethylene glycol acetate And the like.

Moreover, as solid content mass ratio of the said fluorine-type water repellent (A) and the said alcohol compound (B), (the former: the latter) 1: 0.1-1: 20 (more preferably 1: 1-1). 1:10, particularly preferably within the range of 1: 2 to 1: 5).
Here, it is known that in the fiber processing, for the adsorption of the water-dispersed particles of the processing agent, the charge of the dispersed particles and the fiber surface is important. Generally, since the fiber surface is negatively charged, if the non-PFOA fluorine-based water repellent, which is a water-dispersed copolymer, is positively charged, it is basically adsorbed on the fiber surface, but the charge is too high. When the cationic surfactant is floating, dispersed particles with low water repellency that are adsorbed excessively by the cationic surfactant or the cationic polymerization initiator derivative are unevenly distributed, and the unevenly distributed particles have priority. In particular, it is adsorbed on the fiber, resulting in a decrease in water repellency and uneven processing, resulting in failure to obtain stable processing performance. On the other hand, if the potential is too low, the adsorption to the fiber is naturally too low and processing performance may not be obtained.

In addition, for the optimal adsorption of the fluorinated water repellent to the fiber, an appropriate amount of a suitable cationic surfactant or cationic polymerization initiator is used, and the positive charge strength ζ-potential of the fluorinated copolymer particles. Is preferably controlled in the range of +5 to +80 mV, more preferably +20 to +50 mV.
In addition, the water-repellent finishing agent preferably contains a triazine ring-containing compound or an isocyanate compound in order to improve the durability of water repellency and oil repellency. More specifically, it is preferable to use a crosslinking agent such as alkoxymethylmelamine, methylolurea, alkoxymethylurea, urea glyoxal adduct, isocyanate compounds such as blocked isocyanate and non-block type water-dispersible isocyanate, and polyglycidyl compounds. Commercially available products include becamine M-3, PM (manufactured by DIC), 380-K (manufactured by Union Kasei) for melamine and urea-based materials, Meikanate WEB (manufactured by Meisei Chemical), and Bernock DNW-5000 (manufactured by DIC) for isocyanate compounds. Examples of polyglycidyl compound-based compounds include Denacol EX-313 (manufactured by Nagase Kasei) and Epolite 40-E (manufactured by Kyoeisha Chemical).

  Furthermore, low boiling alcohols such as ethanol, propanol and cellosolves which are conventionally used as antistatic agents, antifoaming agents and penetrants may be used in the water repellent finishing agent. In that case, examples of the antifoaming agent include Adecanate B (manufactured by Asahi Denka), Nopco NXZ (manufactured by Nopco), FS anti-form (manufactured by Dow Corning), and the like.

The water-repellent finishing agent of the present invention contains the above-mentioned fluorine-based water repellent (A) and alcohol compound (B), so that it is excellent in water repellency (and / or oil repellency) and repellent. There is no risk of agglomeration or gum-up on the mangle roll even if it receives a severe share with the mangle roll squeeze in the water processing step.
In the present invention, the processing method may be coating or spraying, but if necessary, blended with various auxiliary agents such as a crosslinking agent and antistatic agent, impregnated with a liquid water-repellent processing agent, wet pick-up squeezing with a mangle roll, heat A heat setting method for drying and curing is preferred.
At that time, more preferably, the drawing with a mangle roll is 50 to 80% wet pick-up, and the heat drying is hot air drying at 120 to 140 ° C. at which the alcohol compound (B) of the present invention is volatilized, and heat setting for curing. Is a hot air set at a temperature of 170-200 ° C.

As the water repellent fabric of the present invention, a fabric containing polyester fibers is particularly preferable.
Here, the polyester fiber is produced from a dicarboxylic acid component and a diglycol component. It is preferable that terephthalic acid is mainly used as the dicarboxylic acid component, and it is preferable to use one or more alkylene glycols selected from ethylene glycol, trimethylene glycol and tetramethylene glycol as the glycol component. Moreover, the polyester resin may contain a third component in addition to the dicarboxylic acid component and the glycol component. Examples of the third component include cationic dye dyeable anion components such as sodium sulfoisophthalic acid; dicarboxylic acids other than terephthalic acid such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid; and glycol compounds other than alkylene glycol. For example, one or more of diethylene glycol, polyethylene glycol, bisphenol A, and bisphenol sulfone can be used. Such polyester may be material recycled or chemically recycled polyester, or polyethylene terephthalate, polylactic acid, or stereocomplex polylactic acid using a monomer component obtained using biomass, that is, a biological material as a raw material. Furthermore, the polyester obtained using the catalyst containing the specific phosphorus compound and titanium compound which are described in Unexamined-Japanese-Patent No. 2004-270097 and 2004-21268 may be sufficient.

The polyester fiber may be a short fiber or a long fiber (multifilament), but is preferably a long fiber in order to improve water absorption. Furthermore, a false twisted crimped yarn subjected to a normal false twist crimping process or a composite yarn obtained by subjecting two or more kinds of constituent yarns to air-mixing or composite false twisting may be used.
At that time, the single filament fineness, the total fineness, and the number of single yarns of the multifilament are as follows: single fiber fineness 0.1 to 10.0 dtex, total fineness 20 to 300 dtex (more preferably 20 to 50 dtex), single yarn number 10 to 200 (more The range is preferably 110 to 200). In particular, in order to obtain excellent water repellency, the single yarn fiber fineness is particularly preferably 2.0 dtex or less (more preferably 0.0001 to 0.5 dtex).

Further, in the polyester fiber, the cross-sectional shape of the single yarn fiber is not limited, and in addition to a normal circular cross section, a triangular shape, a flat shape, a constricted flat shape described in JP-A-2004-52167, a cross shape, and a hexagonal shape Alternatively, it may have an irregular cross-sectional shape such as a hollow shape.
In the above-mentioned fabric, as the fabric structure, for example, the weft knitting structure includes flat knitting, rubber knitting, double-sided knitting, pearl knitting, tuck knitting, floating knitting, one-sided knitting, lace knitting, splicing knitting, etc. Examples of the warp knitting structure include single denby knitting, single atlas knitting, double cord knitting, half knitting, half base knitting, satin knitting, half tricot knitting, fleece knitting, jacquard knitting, etc. Examples of the structure include a three-layer structure such as plain weave, twill weave, and satin weave, a change structure, a single double structure such as a vertical double weave and a horizontal double weave, and a vertical velvet. The number of layers may be a single layer or a multilayer of two or more layers. In addition, these woven fabrics and knitted fabrics can be manufactured by a conventional method.

In addition, the fabric may be appropriately subjected to normal dyeing processing, weight reduction processing, raising processing, calendering processing, embossing processing, heat storage processing, sweat absorption processing, negative ion processing, and the like.
Since the fabric is durable and excellent in water and oil repellency, shirts, uniforms, white coat uniforms for food factories, office uniforms, uniforms for cosmetic salespersons, apparel clothing, sports clothing, men's clothing, women's clothing, school clothes, etc. It is suitably used as clothing, curtains, pillow covers, car seats and the like.

Hereinafter, although this invention is demonstrated using a synthesis example, an Example, and a comparative example, this invention is not limited to this synthesis example, an Example, and a comparative example.
Tests, physical properties, and analyzes in Examples and Comparative Examples were performed by the following methods.

(1) Evaluation of water repellent finishing agent The test cloth which passed the mechanical stability test of the following (2) was squeezed to 60% with a mangle roll, dried for 2 minutes in a 130 ° C hot air circulating dryer, and then heated to 170 ° C hot air. Various characteristics were evaluated by heat setting for 1 minute in a circulating dryer.

(2) Mechanical stability test of water repellent finishing agent 2 L of the water repellent finishing agent mixture liquid shown in Table 1 was put in a polypad (35 × 22 × 5 cm), and the mangle device (diameter 12 cm, Installed on 44 cm wide, two narrow rubber rolls, test cloth (polyester filament taffeta fabric, warp: polyethylene terephthalate multifilament total fineness 44 dtex / 144 fil, warp density: 211 yarns / 2.54 cm, weft: polyethylene terephthalate multi A filament total fineness of 22 dtex / 72 fil, a weft density of 149 pieces / 2.54 cm, a sample cloth width of 28 cm, and a length of 80 cm was hung in a ring shape, and then a mangle roll pressure of 24.5 N / cm ² (2.5 kgf / cm ^2), a cloth speed of 10 m / min, impregnation of water-repellent agent formulation fluid, after performed the diaphragm 5 consecutive hours, water repellent Aggregation amount and mangle roll on gum-up amount of engineering blending solution was visually evaluated. The determination was performed as follows. (Judgment of fluorinated water and oil repellent compound liquid aggregates) Many: XX, Medium: x, Small amount: △, None: ○ (Determination of gum up on mangle roll) Many: xx, Medium: x, Small amount: △, None: ○

(3) Water repellency Water repellency was measured based on JIS L 1092 5.2 water repellency test (spray test). The determination was performed as follows.
Water repellency 5 No wetness or water droplets on the surface Water repellency 4 Water does not wet on the surface but shows small water droplets water repellency 3 Water repellency which shows small individual water droplets on the surface 2 Wetting on half of the surface, indicating that a small individual wetting penetrates the fabric Water repellency 1 Showing wetting on the entire surface

(4) Laundry Laundry was performed based on JIS L 0217 103 method.

(5) Water pressure resistance The water pressure resistance was measured based on the JIS L 1092 method (low water pressure method).

(6) Confirmation analysis of PFOA related substance and / or PFOA precursor substance It implemented with the high performance liquid chromatograph-mass spectrometer (LC-MS) and the pyrolysis gas chromatograph-mass spectrometer (PyGC-MS). Each analysis condition is as follows.
(LC-MS conditions)
LC-MS-2020 (Shimadzu Corporation)
Column: Shimadzu Shim / puck FC-ODS (2.0mmI.D. × 150mmL.)
Mobile phase A: 5 mmol / L Ammonium Acetate-water
Mobile phase B: acetonitrile
Time program: 35% B (0 min) → 50% B (7.5-12min) → 90% B (20min) →
35% B (20.01min) → stop (30min)
Flow rate: 0.2ml / min.
Injection volume: 10μL
Column Temp .: 40 ℃
Prove voltage: -3.5kV (ESI-Negative mode)
CDL Temp .: 250 ℃
Block heater temp .: 200 ℃
Nebulizing gas flow: 1.5L / min.
CDL voltage: using defnult value
Q-arry DC & RF voltage: using defnult values
Drying gas pressure: 0.1Mpa
Scan range: m / z 100-600
SIM: m / z 413 for PFOA (Segment 1; 0-12min.)
(PyGC-MS conditions)
GC-MS-QP2010 (Shimadzu Corporation)
Column: FS Capirally Column CBPI-M-50-025 50m × 0.2mmID
Column Temp: 60-250 ° C 10 ° C / min.
Injection Temp: 280 ℃
Pyrolysis Temp: 600 ℃
Ion Source Temp: 250 ℃
Erectron Energy: 70eV
Scanning Interval: 1 sec.
Mass Range: m / z 35-350

(7) Breathability Implemented according to JIS L 1096 A method (Fragile type method).

(8) Intensity of X-ray fluorescence (secondary X-ray) peculiar to fluorine element Using RZAK Co., Ltd. wavelength dispersion type fluorescent X-ray analyzer ZSX100e, zero washing (HL-0) and 20 washings (HL-) 20) Intensity (count / second, c / s) of fluorescent X-ray (secondary X-ray) 2θ angle (deg) 90.7 to 90.8 specific to fluorine element per 7 cm ² of sample cloth area for each sample ) Was measured. Since the fluorescence X-ray intensity peculiar to the fluorine element changes depending on the amount of the fluorine element, the degree of decrease in the fluorine adhesion amount becomes clear.

(9) Measurement of ζ-potential of water-dispersed fluorine-based water repellent agent Measured by using a zeta potential measuring device system ELSZ-1000Z manufactured by Otsuka Electronics Co., Ltd., adjusted to 0.1% solid content, ionic strength 10 ⁻³ , pH 7. did.

[Synthesis example]
(Synthesis Examples -1 to 3) are non-PFOA fluorine-based water repellents, and (Synthesis Example-4) is a PFOA fluorine-based water repellent. The ethylenically unsaturated monomer mixture solution used in each synthesis example is shown below.
[A] (Synthesis Examples -1 to 3) Ethylenically unsaturated monomer mixture solution perfluorohexyl ethyl acrylate 162 g used for non-PFOA fluorine-based water repellent
Octadecyl acrylate 40g
3-chloro-2-hydroxypropyl methacrylate 2g
60% N-methylolacrylamide 3.5g
Dodecyl mercaptan 1g
Methyl isobutyl ketone 25g
Total 233.5g
[B] (Synthesis Example 4) Ethylenically unsaturated monomer mixture solution perfluorooctylethyl acrylate 100 g used for PFOA fluorine-based water repellent
Octadecyl acrylate 50g
Butyl methacrylate 52g
3-chloro-2-hydroxypropyl methacrylate 2g
60% N-methylolacrylamide 3.5g
Dodecyl mercaptan 1g
Methyl isobutyl ketone 25g
Total 233.5g

(Synthesis Example-1)
In a 1 L glass beaker, 233.5 g of the ethylenically unsaturated monomer mixture solution of [i] above, 24 g of 25% hexadecyltrimethylammonium, and 10 g of polyoxyethylene tridecyl ether (HIB: 12-13) at 40 ° C. The mixture was heated, and 118.5 g of ion-exchanged water was put therein and emulsified with a homogenizer to prepare 385 g of an emulsion of an ethylenically unsaturated monomer mixture.
Next, 436 g of ion-exchanged water was placed in a 1.5 L glass separable four-necked flask, heated to 78 ° C. while blowing nitrogen gas, and 77 g of an emulsion of the ethylenically unsaturated monomer mixture was added. Subsequently, 20 g of 5% 2.2-azobis-2-amidinopropane dihydrochloride aqueous solution was added to initiate polymerization, and then 308 g of an emulsion of the ethylenically unsaturated monomer mixture and 5% 2.2. 20 g of an aqueous solution of azobis-2-amidinopropane dihydrochloride was dripped in parallel at 78 ° C. for 90 minutes. After completion of the polymerization, the solid content was adjusted to 22% with ion-exchanged water to obtain about 1000 g of a non-PFOA fluorine-based water repellent. The fluorine-based water repellent obtained in Synthesis Example-1 had a ζ-potential of +32 mV.

(Synthesis Example-2)
In a 1 L glass beaker, 233.5 g of the above-mentioned [I] ethylenically unsaturated monomer mixture solution, 84 g of 25% hexadecyltrimethylammonium chloride, and 5 g of polyoxyethylene tridecyl ether (HLB: 12 to 13) were added. The mixture was heated to 0 ° C., 63.5 g of ion-exchanged water was put therein, and emulsified with a homogenizer to prepare 385 g of an emulsion of an ethylenically unsaturated monomer mixture.
Next, 436 g of ion-exchanged water was placed in a 1.5 L glass separable four-necked flask, heated to 78 ° C. while blowing nitrogen gas, and 77 g of an emulsion of the ethylenically unsaturated monomer mixture was added. Subsequently, 20 g of 5% 2.2-azobis-2-amidinopropane dihydrochloride aqueous solution was added to initiate polymerization, and then 308 g of an emulsion of the ethylenically unsaturated monomer mixture and 5% 2.2. 20 g of an aqueous solution of azobis-2-amidinopropane dihydrochloride was dripped in parallel at 78 ° C. for 90 minutes. After completion of the polymerization, the solid content was adjusted to 23% with ion-exchanged water to obtain about 1000 g of a non-PFOA fluorine-based water repellent. The ζ-potential of the fluorine-based water repellent obtained in Synthesis Example-2 was +90 mV.

(Synthesis Example-3)
In a 1 L glass beaker, 233.5 g of the ethylenically unsaturated monomer mixture solution of [i] above, 0.2 g of 25% hexadecyltrimethylammonium chloride, 5 g of polyoxyethylene oleyl ether (HLB: 10), polyoxyethylene hexa 25 g of decyl ether (HLB: 15) was added and heated to 40 ° C., 122 g of ion-exchanged water was put therein, and emulsified with a homogenizer to prepare 385 g of an emulsion of an ethylenically unsaturated monomer mixture.
Next, 436 g of ion-exchanged water and 0.14 g of ascorbic acid are placed in a 1.5 L glass separable four-necked flask, and the temperature is raised to 78 ° C. while blowing nitrogen gas, and an emulsion of the ethylenically unsaturated monomer mixture is obtained. 77 g was added. Subsequently, 20 g of 3.5% tertiary butyl hydroperoxide aqueous solution was added to initiate polymerization, and then 308 g of an emulsion of the ethylenically unsaturated monomer mixture, 20 g of 3.5% tertiary butyl hydroperoxide aqueous solution. , And 20 g of a 0.7% ascorbic acid aqueous solution were dropped in parallel at 78 ° C. for 90 minutes. After completion of the polymerization, the solid content was adjusted to 24% with ion-exchanged water to obtain about 1000 g of a non-PFOA fluorine-based water repellent. The ζ-potential of the fluorine water repellent obtained in Synthesis Example-3 was +1 mV.

(Synthesis Example-4)
In a 1 L glass beaker, 233.5 g of the above-mentioned [b] ethylenically unsaturated monomer mixture solution, 16 g of 25% hexadecyltrimethylammonium, and 10 g of polyoxyethylene tridecyl ether (HLB: 12-13) at 40 ° C. The mixture was heated, and 125.5 g of ion-exchanged water was put therein, and emulsified with a homogenizer to prepare 385 g of an emulsion of an ethylenically unsaturated monomer mixture.
Next, 436 g of ion-exchanged water was placed in a 1.5 L glass separable four-necked flask, heated to 78 ° C. while blowing nitrogen gas, and 77 g of an emulsion of the ethylenically unsaturated monomer mixture was added. Subsequently, 20 g of 5% 2.2-azobis-2-amidinopropane dihydrochloride aqueous solution was added to initiate polymerization, and then 308 g of the ethylenically unsaturated monomer emulsion and 5% 2.2-azobis 20 g of 2-amidinopropane dihydrochloride aqueous solution was dropped in parallel at 78 ° C. for 90 minutes. After completion of the polymerization, the solid content was adjusted to 22% with ion-exchanged water to obtain about 1000 g of a PFOA fluorine-based water repellent. The fluorine-based water repellent obtained in Synthesis Example-4 had a ζ-potential of +25 mV.

[Example 1]
Polyester filament taffeta (238 g / m ² , warp: polyethylene terephthalate multifilament 167 dtex / 48 fil, weft: polyethylene terephthalate multifilament 167 dtex / 48 fil, warp density: 123 / 2.54 cm, weft density: 97 / 2.54 cm) A piece of cloth (width: 28 cm, length: 80 cm) is impregnated with the blended liquid shown in Table 3, squeezed to 60% wet pick-up with a mangle roll, dried for 4 minutes in a 130 ° C hot air circulating dryer, and then 180 ° C hot air circulated. After heat setting for 1 minute with a dryer, water repellency, oil repellency, water resistance, air permeability, and fluorescent X-ray intensity specific to the fluorine element were evaluated.
Furthermore, the mechanical stability test of the water-repellent finishing agent was carried out by putting the compounded liquid 2L shown in Table 1 into a polypad (35 × 22 × 5 cm) and a mangle device (diameter 12 cm, width 44 cm, schematically shown in FIG. After installing the polyester filament taffeta sample cloth piece in a ring shape, the mangle roll pressure is 24.5 N / cm ² (2.5 kgf / cm ² ), and the cloth speed is 10 m / min. Then, after the impregnation and squeezing of the blended liquid were continuously performed for 5 hours, the amount of aggregates in the blended liquid and the amount of gum up on the mangle roll were visually evaluated. The determination was performed as follows.
There are many aggregates in the mixed solution: XX, Medium: X, Low: △, None: ○
Gum up on mangle is high: XX, medium: X, low: △, nothing: ○

[Example 2, Comparative Example 1-5]
It carried out according to Example 1 using the liquid mixture of each Example described in Table 1, and each comparative example. The results are shown in Table 1.
In addition, when a shirt was obtained and worn using the water-repellent fabric (processed product) obtained in both Examples 1 and 2, it was durable and excellent in water repellency. It was excellent. Furthermore, there was no detection of a PFOA precursor, and it was excellent in environment and health.

  ADVANTAGE OF THE INVENTION According to this invention, the water repellent fabric which is hard to gum up to a roll at the time of a process, and has the outstanding washing durability is provided, The industrial value is very large.

1-1, 1-2: Mangle Roll 2: Test cloth (width 28 cm x circumference 80 cm)
3: 25 mm diameter PVC pipe 4: 5 L polypad 5: Water repellent finish

Claims (7)

  A water-repellent fabric in which a water-repellent agent is adhered to a fabric, the water-repellent agent comprising a perfluoroalkanoic acid having 8 or more carbon atoms, a perfluoroalkenoic acid having 8 or more carbon atoms, and a precursor thereof. It contains a fluorine-based water repellent (A) not contained, and the water repellency of the fabric according to JIS L 1092 (spray test) is grade 3 or higher after 20 washings (HL-20) according to JIS L 0217 103 A water-repellent fabric characterized by   The fluorine-based water repellent (A) is a polymer using a fluorine element-containing ethylenically unsaturated monomer having a perfluoroalkyl group having less than 8 carbon atoms or a perfluoroalkenyl group having less than 8 carbon atoms. The water-repellent fabric according to claim 1. The said water-repellent processing agent is represented by following formula (1), The boiling point in the atmospheric pressure of 1013 hPa contains the alcohol body compound (B) in the range of 150-250 degreeC, The Claim 1 or Claim 2 containing Water repellent fabric.
Formula (1)
X-R-Y
However, X is either selected from the group consisting of —H, —OH, —O (CH ₂ CZ ₂ O) _a —H, and —OC _m Z _{2m + 1} . Y is any selected from the group consisting of —H, —OH, —O (CH ₂ CZ ₂ O) _a —H, and —OC _m Z _{2m + 1} . In addition, R is _-C n _{Z 2n} -, and / or _-C n _{Z 2n-2} -, and / or _-C n _{Z 2n-4} - a. In that case, Z is H or _{CH 3, n = 2~12, a} = 0~3, an m = 1 to 3.   The solid content mass ratio of the fluorine-based water repellent (A) and the alcohol compound (B) is in the range of (the former: the latter) 1: 0.1 to 1:20. Water repellent fabric.   Compared with 20 times of washing (HL-20) and 0 times of washing (HL-0) according to JIS L 0217 103, the reduction rate of water resistance by JIS L 1092 (hydrostatic pressure method) = [(HL-0 water resistance The water-repellent fabric according to claim 1, wherein (degree) − (HL-20 water resistance)] × 100 / (HL-0 water resistance) is less than 30%.   Compared with 20 times after washing (HL-20) and 0 times (HL-0) according to JIS L 0217 103, the rate of increase in air permeability by the JIS L 1096 A method (fragile type) = [(HL-20 The water repellent fabric according to claim 1, wherein (breathability) − (HL-0 breathability)] × 100 / (HL-0 breathability) is less than 30%.   Compared with 20 washings (HL-20) and 0 washings (HL-0) according to JIS L 0217 103, the decrease rate of the fluorescent X-ray intensity peculiar to the fluorine element by the wavelength dispersive X-ray fluorescence analyzer = [(HL-0 the fluorescent X-ray intensity)-(HL-20 the fluorescent X-ray intensity)] × 100 / (HL-0 the fluorescent X-ray intensity) is less than 30%. The water repellent fabric according to any one of the above.

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