JP2015165056A - Water-repellent fabric and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-repellent fabric with a non-fluorine water repellent adhered thereto, which has excellent washing durability and antistatic property, and a method for manufacturing the fabric.SOLUTION: The water-repellent fabric comprises a fabric composed of organic fibers and a silicone-based water repellent adhered hereto, obtained by imparting a water repellent comprising a hydroxyl group-containing organopolysiloxane (a), a polymer (b) having an aliphatic hydrocarbon group having 16 or more carbon atoms in a side chain, and an antistatic (c) to a fabric composed of organic fibers. The fabric shows a water repellency degree of Class 3 or higher specified by JIS L 1092 (spray method) after washing 20 times (HL-20) in accordance with JIS L 0217-103, and has a triboelectric voltage of less than 1,000 V in accordance with JIS L 1094 5.2.

Description

  The present invention relates to a water-repellent fabric having a non-fluorine-based water repellent attached thereto, which has excellent washing durability and antistatic properties, and a method for producing the same.

  Fluorine-based water repellents have long been known for imparting water repellency to fabrics. Fluorine-based water repellents are generally (co) polymers of ethylenically unsaturated monomers having a perfluoroalkyl group and exhibit excellent water repellency, but are highly bioaccumulative and hardly degradable. Problems such as environmental pollution have been highlighted. Therefore, recently, a demand for a water repellent fabric using a non-fluorinated water repellent is increasing.

  Based on this situation, silicone-based chemicals are used in combination with organopolysiloxanes called H-silicones having hydrogen atoms bonded to silicon atoms and organic acid metal salts to make the fabric durable. The most commonly used method for imparting water repellency is to treat a fabric with an amino group-containing organoalkoxysilane or a hydrolyzate thereof, and a carboxyl group-containing organopolysiloxane (for example, Patent Document 1), a method of applying a copolymer of a silicone macromonomer and a (meth) acrylate monomer containing no fluorine element to a fabric (for example, see Patent Document 2), a fabric using an isocyanate compound in combination with aminosilicone There is a proposal such as a method of assigning to (for example, see Patent Document 3).

  On the other hand, in non-fluorine-based water repellents other than silicone chemicals, water repellents that utilize hydrocarbon compounds such as paraffin and wax, fatty acid metal salts, and long-chain alkylureas (see, for example, Non-Patent Document 1), Examples thereof include a method of applying a non-fluorinated polymer having a specific molecular weight obtained by copolymerizing 80% or more of a (meth) acrylic acid ester having 12 or more carbon atoms in the ester portion to a fabric (for example, see Patent Document 4).

  However, these have the problem that the water-repellent washing durability is inferior as compared with a water-repellent fabric made of a fluorine-based water repellent. The main reason is that the water repellent is removed by stagnation or washing. In addition, unpleasant static electricity is likely to be generated, or troubles such as unpleasant fish rot odor and yellowing of the treated fabric are likely to occur.

Japanese Patent Publication No. 61-9432 JP-A-7-97770 JP 2004-59609 A JP 2006-328624 A

“Super-water-repellent finish, new overview of processing agents and moisture-permeable and waterproof materials” published by Osaka Chemical Marketing Center, 1996

  The present invention has been made in view of the above-described background, and an object thereof is a water-repellent fabric formed by adhering a non-fluorine-based water repellent and having excellent washing durability and antistatic properties. It is providing the fabric and its manufacturing method.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventor has found that a hydrogen group-containing organopolysiloxane (a), a polymer (b) having an aliphatic hydrocarbon group having 16 or more carbon atoms as a side chain, When a water repellent containing the electrical agent (c) is applied to the fabric and heat treated, the hydrogen group-containing organopolysiloxane (a) is finely dispersed in close contact with each other with a particle size of 200 to 500 nm, and further contains hydrogen groups. A tough water-repellent film is formed by the dehydrogenative condensation reaction between the hydrogen group contained in the organopolysiloxane (a) and the hydroxyl group contained in the polymer (b), and has excellent washing durability and antistatic properties. The present inventors have found that a water-repellent fabric having water content can be obtained, and have further earnestly studied to complete the present invention.

  Thus, according to the present invention, “a water-repellent fabric in which a silicone-based water repellent is adhered to a fabric composed of organic fibers, and after 20 washings (HL-20) according to JIS L 0217 103, JIS L A water-repellent fabric characterized in that the water repellency specified in 1092 (spray method) is grade 3 or higher and the frictional voltage according to JIS L 1094 5.2 is less than 1000 V.

Moreover, according to this invention, the hydrogen group containing organopolysiloxane (a), the polymer (b) which has a C16 or more aliphatic hydrocarbon group as a side chain, and an antistatic agent (c) are included. The method for producing a water-repellent fabric is provided, wherein a water-repellent agent is applied to a fabric composed of organic fibers.
In that case, it is preferable that the said polymer (b) is a polymer containing the (meth) acrylate which has a C16 or more hydrocarbon group in a side chain. Moreover, it is preferable that the said polymer (b) has a methylol group or a hydroxyl group. The antistatic agent (c) is preferably guanidine hydrochloride. Moreover, it is preferable that the water repellent further contains a triazine ring-containing compound. Moreover, it is preferable that the water repellent agent further contains an isocyanate compound. Further, it is preferable that the hydrogen group-containing organopolysiloxane (a) is brought into close contact with each other with a particle size of 200 to 500 nm by further heat-treating the fabric.

  ADVANTAGE OF THE INVENTION According to this invention, it is a water-repellent cloth formed by adhering a non-fluorine-type water repellent, and has the water-repellent cloth which has the outstanding washing durability and antistatic property, and its manufacturing method.

The compounded liquid prepared in Example 1 was dropped on an aluminum foil, dried for 3 minutes with a 130 ° C. hot air circulating dryer, and further heat-set for 1 minute with a 170 ° C. hot air circulating dryer, and then scanned in an undeposited state. It was observed with a microscope. The compounded liquid prepared in Comparative Example 2 was dropped on an aluminum foil, dried for 3 minutes with a 130 ° C hot air circulating dryer, and further heat-set for 1 minute with a 170 ° C hot air circulating dryer, and then scanned in an undeposited state. It was observed with a microscope. The compounded liquid prepared in Comparative Example 4 was dropped on an aluminum foil, dried for 3 minutes with a 130 ° C. hot air circulating dryer, and further set with a 170 ° C. hot air circulating dryer for 1 minute, and then scanned in an undeposited state. It was observed with a microscope.

Hereinafter, embodiments of the present invention will be described in detail.
The water-repellent fabric of the present invention is a water-repellent fabric in which a silicone-based water repellent is attached to a fabric composed of organic fibers, and is JIS L after 20 washings (HL-20) according to JIS L 0217 103. The water repellency specified in 1092 (spray method) is 3 or more (preferably 4 or more), and the frictional voltage according to JIS L 1094 5.2 is less than 1000 V (preferably 5 to 500 V). It is a water-repellent fabric characterized.
Here, the organic fibers are not particularly limited, such as polyester fibers, nylon fibers, natural fibers such as cotton and wool, but are preferably polyester fibers.

  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 2004-2111268 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 60 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.

Such a water-repellent fabric includes, for example, a hydrogen group-containing organopolysiloxane (a), a polymer (b) having an aliphatic hydrocarbon group having 16 or more carbon atoms as a side chain, and an antistatic agent (c). It can be produced by applying a water repellent to a fabric composed of organic fibers.
Here, the hydrogen group-containing organopolysiloxane (a) is an organopolysiloxane having a hydrogen atom bonded to a silicon atom, and an aqueous dispersion thereof is preferred. The molecular structure is not particularly limited, and examples thereof include a straight chain, a partially branched chain, a branched chain, and a ring. For example, POLON MWS and POLON MK-206 (both manufactured by Shin-Etsu Chemical Co., Ltd.) can be cited as examples disclosed in JP 2002-114972 A and commercially available products, but are not limited thereto.

  Next, as the polymer (b) having an aliphatic hydrocarbon group having 16 or more carbon atoms (preferably 16 to 25) as a side chain, a (meth) acrylate having a hydrocarbon group having 16 or more carbon atoms in the side chain. A polymer containing an ethylenically unsaturated monomer such as (meth) acrylates of long-chain aliphatic alcohols such as octadecyl (meth) acrylate and hexadecyl (meth) acrylate, vinyl esters of long-chain fatty acids, and the like. A monomeric copolymer may be mentioned. In addition, the introduction of a functional group into the long-chain alkyl polymer (b) is performed by introducing an ethylenically unsaturated monomer having a functional group such as hydroxyethyl (meth) acrylate or N-methylol (meth) acrylic into the ethylenically unsaturated monomer. It is preferred to copolymerize saturated monomers.

In addition, the long-chain alkyl polymer (b) has at least one functional group of hydroxyl group or methylol group, and the functional group value (weight per function equivalent: g solid / eq.) Is 1000 to 10,000 g. Preferably, it is 3000-7000g.
The long-chain alkyl polymer (b) is prepared by preparing an emulsion of an ethylenically unsaturated monomer in advance using an appropriate anionic, cationic, or nonionic surfactant and ion-exchanged water. A method of emulsion polymerization of an emulsion using a radical initiator is preferred. As the radical initiator, persulfates, organic peroxides, and azo compounds are preferably used.
In addition, the antistatic agent (c) is not particularly limited, but water repellency and antistatic property are ensured by maintaining the dispersed state stably without aggregating the organopolysiloxane and the aliphatic hydrocarbon polymer. Since it can do, guanidine hydrochloride is preferable.

  Further, the water repellent preferably contains a cross-linking agent. As such a cross-linking agent, a melamine formaldehyde adduct is suitable as the lyazine ring-containing compound, and commercially available products are becamine M-3, PM. -N (both manufactured by DIC), UNIKA RESIN 380-K (manufactured by Union Kasei). As the isocyanate compound, an aliphatic or alicyclic isocyanate-based water dispersion type polyisocyanate compound is suitable.

The composition ratio (all by weight) of the water repellent will be described. The solid content ratio of the long-chain alkyl polymer (b) to the solid content of the hydrogen group-containing organopolysiloxane (a) is preferably in the range of 50 to 200% by weight, more preferably in the range of 100 to 150% by weight. The solid content ratio of the antistatic agent (c) to the solid content of the non-fluorinated water repellent (A) is preferably in the range of 10 to 100%, more preferably in the range of 20 to 60% by weight. Further, the solid content ratio of the crosslinking agent to the solid content of the non-fluorinated water repellent (A) is preferably in the range of 10 to 50% by weight, more preferably in the range of 20 to 30% by weight.
Application of the water repellent to the fabric is impregnated with a blended solution diluted to a predetermined concentration, squeezed the excess blended solution with a mangle roll or the like, dried at 100 to 130 ° C. with a hot air circulating dryer, 150 The usual fiber processing method of heat curing at ˜180 ° C. can be adopted.
Furthermore, normal dyeing processing, weight reduction processing, raising processing, calendar processing, embossing processing, heat storage processing, sweat absorption processing, negative ion processing, and the like may be appropriately performed.

By this method, the hydrogen group-containing organopolysiloxane (a) is finely dispersed in close contact with each other with a particle size of 200 to 500 nm, and the hydrogen group-containing organopolysiloxane (a) is contained in the polymer (b). A tough water-repellent film is formed by a dehydrogenative condensation reaction with the hydroxyl group contained, and as a result, a water-repellent fabric having excellent washing durability and antistatic properties is obtained.
Since the cloth is a water-repellent cloth having excellent washing durability and antistatic properties, shirts, uniforms, white coat uniforms for food factories, office uniforms, uniforms for cosmetic salespersons, apparel clothes, sports clothes, men's clothes It is suitably used as clothing such as women's clothing and school clothes, 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) 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 Surface with no moisture or water droplets Water repellency 4 Surface does not wet but shows small water droplets attached Water repellency 3 Surface with small individual water droplets water repellency 2 Surface One half shows wetness and a small individual wetness penetrates the cloth. Water repellency 1 One shows wetness on the entire surface (2) Friction withstand voltage The frictional band voltage is JIS L 0194 5.2 The frictional band voltage It was measured based on the measurement method. The sample cloth is 20 ° C. and humidity is 40% R.D. H. The humidity was adjusted for 24 hours under the environment, and the measurement was performed using a cotton white cloth specified in JIS L 0803 as a friction cloth.
(3) Laundry Laundry was carried out based on JIS L 0217 103, and drying was carried out by suspending and drying. L-20 shown in Table 1 and Table 2 refers to the 20 times of washing.
(4) Tear strength Measured based on the JIS L 1096 8.15.5 (Method D) pendulum method.

[Water repellent]
[Synthesis Example 1]
A mixture of 204 g of octadecyl methacrylate, 3.5 g of 60% N-methylol acrylamide and 1 g of dodecyl mercaptan, 208.5 g in total, is warmed to 35 to 40 ° C.
In a 1 L glass beaker, 208.5 g of the above ethylenically unsaturated monomer mixture, 24 g of 25% hexadecyltrimethylammonium, and 10 g of polyoxyethylene tridecyl ether (HLB: 12-13) were heated to 40 ° C. The ion-exchanged water 142.5g was put in, and it emulsified with the homogenizer, and the emulsion liquid 385g of ethylenically unsaturated monomer mixture was prepared.
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 20% with ion-exchanged water to obtain about 1000 g of an octadecyl methacrylate (carbon number 18) / N-methylolacrylamide copolymer emulsion having a methylol group as a functional group.

[Synthesis Example 2]
Replacing 3.5 g of 60% N-methylolacrylamide described in Synthesis Example 1 with 2.1 g of β-hydroxyethyl methacrylate, and then performing the same operation as in Synthesis Example 1, octadecyl methacrylate having a hydroxyl group as a functional group About 1000 g of (carbon number 18) / β-hydroxyethyl methacrylate copolymer emulsion was obtained.

[Synthesis Example 3]
Substituting 204 g of octadecyl methacrylate described in Synthesis Example 1 with 204 g of tridecyl methacrylate, tridecyl methacrylate (16 carbon atoms) / N having a methylol group as a functional group in the same manner as in Synthesis Example 1 -About 1000 g of a methylolacrylamide copolymer emulsion was obtained.
POLON MWS Shin-Etsu Chemical Co., Ltd. Hydrogen Group-Containing Silicone Oil Emulsion POLON MK-206 Shin-Etsu Chemical Co., Ltd. Hydrogen Group-Containing Silicone Oil Emulsion Silicolan CH Keihin Kasei Co., Ltd. Special Reactive Polysiloxane Petrox P200 Meisei Chemical Co., Ltd. Polymer Wax Emulsion NUVA N2114L Clariant Fluorine Water Repellent

[Adjuvant]
Becamine M-3 Product made by DIC Co., Ltd. Melamine formaldehyde adduct Barnock NDW-5000 Product made by DIC Co., Ltd. Water dispersible isocyanate compound Catalyst 376 Product made by DIC Co., Ltd. Catalyst for melamine cross-linking agent Catalyst CHB Product made by Keihin Kasei Co., Ltd. Salt-based catalyst Guanidine hydrochloride Kishida Chemical Co., Ltd. Reagent grade Nispol FE-26 Nikka Chemical Co., Ltd. Antistatic aqueous solution

[Example 1]
Polyethylene terephthalate filament taffeta (weighing 63 g / m ² , warp: polyethylene terephthalate filament total fineness 56 dtex / 72 fil, weft: polyethylene terephthalate filament total fineness 56 dtex / 72 fil, warp density: 140 / 2.54 cm, weft density: 140/2 .54 cm) of sample cloth (width: 28 cm, length: 80 cm) was immersed in 500 g of a water repellent compounding liquid having a mixing ratio shown in Table 1 Examples, then squeezed to 60% with a mangle roll and heated at 130 ° C. It dried for 3 minutes with the circulation dryer, and also heat-set for 1 minute with the 170 degreeC hot-air circulation dryer. Table 1 shows the results of evaluating the sample cloth obtained in this example by the evaluation method described later.

[Examples 2-6, Comparative Examples 1-8]
The water repellent composition liquid described in Example 1 was mixed with the water repellent composition liquid of the blending ratio shown in Examples 2 to 6 of Table 1 Example, and the water repellent composition of the blending ratio shown in Table 2 Comparative Examples 1 to 8 The procedure was the same as in Example 1 except that the formulation was replaced. Each evaluation result was similarly described in each table.
Also, the compounded liquid prepared in Example 1 was dropped on an aluminum foil, dried for 3 minutes with a 130 ° C hot air circulating dryer, and further heat set for 1 minute with a 170 ° C hot air circulating dryer, and then scanned in a non-deposited state. What was observed with the electron microscope is what processed the compounding liquid of FIG. 1, Comparative Example 2, and Comparative Example 4 similarly, and is FIG. 2, FIG. In Comparative Example 2, organopolysiloxanes are scattered inhomogeneously, whereas in Example 1, it is recognized that the particles are 200-500 nm in size and finely dispersed while being in close contact with each other.

  According to the present invention, there is provided a water-repellent fabric having a non-fluorinated water repellent attached thereto, which has excellent washing durability and antistatic properties, and a method for producing the same. It is a comfortable processed product with consideration for the environment and health, and its industrial value is extremely large.

Claims (8)

  A water-repellent fabric in which a silicone-based water repellent is adhered to a fabric composed of organic fibers, and is defined in JIS L 1092 (spray method) after 20 washes (HL-20) according to JIS L 0217 103. A water repellent fabric characterized by having a water repellency of 3 or more and a frictional voltage according to JIS L 1094 5.2 of less than 1000V.   A water repellent comprising a hydrogen group-containing organopolysiloxane (a), a polymer (b) having an aliphatic hydrocarbon group having 16 or more carbon atoms as a side chain, and an antistatic agent (c) is made of an organic fiber. The method for producing a water-repellent fabric according to claim 1, which is applied to the constructed fabric.   The method for producing a water-repellent fabric according to claim 2, wherein the polymer (b) is a polymer containing (meth) acrylate having a hydrocarbon group having 16 or more carbon atoms in the side chain.   The method for producing a water-repellent fabric according to claim 2 or 3, wherein the polymer (b) has a methylol group or a hydroxyl group.   The method for producing a water-repellent fabric according to any one of claims 2 to 4, wherein the antistatic agent (c) is guanidine hydrochloride.   The method for producing a water-repellent fabric according to any one of claims 2 to 5, wherein the water-repellent agent further contains a triazine ring-containing compound.   The method for producing a water-repellent fabric according to any one of claims 2 to 6, wherein the water-repellent agent further contains an isocyanate compound.   The method for producing a water-repellent fabric according to any one of claims 2 to 7, wherein the hydrogen group-containing organopolysiloxane (a) is brought into close contact with each other with a particle size of 200 to 500 nm by further heat-treating the fabric.