JP2020180391A - Water repellent fabric, and its manufacturing method - Google Patents

Abstract

To provide a water-repellent fabric that contains water repellent reproduced cellulose fibers on a surface of which the water-repellent is bound, free from dyeing unevenness, having high color fastness, and having durable water repellency, and its manufacturing method.SOLUTION: The present invention relates to a water repellent fabric that is a water repellent fabric containing water repellent regenerated cellulose fiber, in which the water repellent regenerated cellulose fiber contains a compound containing one or more acidic groups selected from a carboxylic group and a sulfonate group, on a fiber surface of the fiber, a crosslinking agent and a non-fluorine type water repellent is bonded, the water repellent fabric is dyed with a reactive dye, and a contact angle with water is 90° or larger. The water repellent fabric can be manufactured by dying and drying, after hydrophilizing a water repellent fabric containing a water-repellent regenerated cellulose fiber containing a compound containing one or more acidic groups selected from the group consisting of the carboxylic group and a sulfonate group, and containing the water repellent regenerated cellulose fiber on a surface of which the crosslinking agent and non-fluorine type water repellent are bonded.SELECTED DRAWING: None

Description

The present invention relates to a water repellent fabric and a method for producing the same. Specifically, the present invention relates to a water-repellent fabric containing water-repellent regenerated cellulose fibers and dyed with a reactive dye, and a method for producing the same.

Regenerated cellulose fibers such as rayon fibers have excellent texture and biodegradability, and are therefore used in various textile products such as clothing. Since regenerated cellulose fibers such as rayon fibers have high hydrophilicity, when they are used for applications requiring water repellency, the regenerated cellulose fibers are used with water repellency. For example, in Patent Document 1, water and cellulose fibers are put into a container, isocyanate and a fluorine-based resin are put in, and the mixture is heated to 100 to 180 ° C. to crosslink the fluorine-based resin to the cellulose fibers to form cellulose fibers. It has been proposed to impart water repellency. Patent Document 2 proposes to impart water repellency to a cellulosic fiber material by treating the cellulosic fiber material with a compound that reacts with a hydroxyl group and then treating the cellulosic fiber material with a fluorine-based water repellent.
Further, there is disclosed a water-repellent dyed fabric in which cellulosic fibers are previously hydrophobized or water-repellent and then dyed. Patent Document 3 discloses a technique for transferring and dyeing a hydrophobically modified cellulosic fiber with a disperse dye. Patent Document 4 discloses a technique for dyeing a water-repellent cellulosic fiber cloth by a naphthol dyeing method, a vinyl sulfone cold fix method, or a slene dyeing method. Patent Document 5 discloses a technique for dyeing only cellulose fibers by combining cellulose water-repellent fibers processed with a fluorine-based water repellent and cellulose fibers.

JP-A-2002-266241 Japanese Unexamined Patent Publication No. 2003-20570 JP-A-57-128282 Japanese Unexamined Patent Publication No. 60-34687 JP-A-2018-197406

However, when a fabric using water-repellent cellulose fibers cross-linked with a fluorine-based water repellent is dyed by immersing it in a dyeing bath, the dyeing property is not good, resulting in uneven dyeing or poor dyeing fastness. There was a problem of lowering. In addition, when the water repellent is removed during dyeing or the dyeing treatment is performed by hydrophobization to the extent that the hydrophilicity of cellulose is suppressed, there is a problem that the water repellent performance is lowered and a predetermined water repellency cannot be obtained. It was.

In order to solve the above-mentioned conventional problems, the present invention contains a water-repellent regenerated cellulose fiber in which a water-repellent agent is bonded to the fiber surface, a water-repellent fabric having no uneven dyeing, high dyeing fastness, and durable water repellency. And a method for producing the same.

The present invention is a water-repellent fabric containing water-repellent regenerated cellulose fibers, wherein the water-repellent regenerated cellulose fibers contain a compound containing one or more acidic groups selected from the group consisting of carboxyl groups and sulfonic acid groups. A cross-linking agent and a non-fluorinated water-repellent agent are bonded to the fiber surface, the water-repellent fabric is dyed with a reactive dye, and the water-repellent fabric has a contact angle with water of 90 ° or more. The present invention relates to a water-repellent fabric.

The present invention is also a method for producing a water-repellent fabric containing a water-repellent regenerated cellulose fiber, which comprises a compound containing one or more acidic groups selected from the group consisting of a carboxyl group and a sulfonic acid group. A step of binding a non-fluorinated water-repellent agent to the fiber surface with a cross-linking agent to obtain a water-repellent regenerated cellulose fiber, a step of obtaining a water-repellent cloth containing the water-repellent regenerated cellulose fiber, water and / or an interface on the water-repellent cloth. The present invention relates to a method for producing a water-repellent fabric, which comprises a step of applying an aqueous solution containing an activator and hydrophilizing the fabric, a step of dyeing the hydrophilized fabric with a reactive dye, and a step of drying the dyed fabric.

According to the present invention, it is possible to provide a water-repellent fabric which contains a water-repellent regenerated cellulose fiber in which a water-repellent agent is bound to the fiber surface, has no uneven dyeing, has high dyeing fastness, and has durable water repellency.
Further, according to the production method of the present invention, a water-repellent fabric having a water-repellent regenerated cellulose fiber in which a water-repellent agent is bonded to the fiber surface, having no uneven dyeing, high dyeing fastness, and durable water repellency can be obtained. be able to.

The present inventor is keen to eliminate dyeing unevenness during dyeing, improve dyeing fastness, and impart durable water repellency to a water-repellent fabric containing water-repellent regenerated cellulose fibers in which a water-repellent agent is bound to the fiber surface. investigated. As a result, the regenerated cellulose fiber such as rayon fiber contains a compound containing one or more acidic groups selected from the group consisting of a carboxyl group and a sulfonic acid group, and a cross-linking agent and a non-fluorine-based water repellent agent are applied to the fiber surface. It has been found that by binding, the fixability of the non-fluorine-based water repellent on the fiber surface is enhanced, and by including the water-repellent regenerated cellulose fiber in the cloth, durable water repellency can be imparted to the cloth. Further, before dyeing, by applying water or an aqueous solution containing a surfactant to the fabric containing the water-repellent regenerated cellulose fiber to which the non-fluorine-based water repellent is bound, the non-fluorine-based water repellent on the fiber surface can be obtained. It was found that by disturbing the orientation of the water-repellent group and temporarily making it hydrophilic, when dyed with a reactive dye, dyeing can be performed evenly and the dyeing fastness is also improved. In addition, since the fabric contains water-repellent regenerated cellulose fibers having high fixability of the non-fluorine-based water repellent on the fiber surface, the non-fluorine-based water repellent does not fall off in the hydrophilic treatment and the dyeing step before dyeing. , It was found that the highly durable water repellency is restored by drying after dyeing.

The water-repellent regenerated cellulose fiber contains a compound containing one or more acidic groups selected from the group consisting of a carboxyl group and a sulfonic acid group. In the following, unless otherwise specified, the "compound containing an acidic group" means a compound containing one or more acidic groups selected from the group consisting of a carboxyl group and a sulfonic acid group. At the time of producing regenerated cellulose fiber, a compound containing an acidic group is kneaded into the fiber by spinning a viscous solution for spinning prepared by mixing a compound containing an acidic group with a stock solution of viscose. Immerse the regenerated cellulose fiber in an aqueous solution containing a compound containing an acidic group to impregnate the fiber with a compound containing an acidic group, or spray or apply an aqueous solution containing a compound containing an acidic group to the regenerated cellulose fiber. By attaching a compound containing an acidic group to the regenerated cellulose fiber or the like, the compound containing an acidic group can be contained in the regenerated cellulose fiber. Among them, kneading is preferable because the compound containing an acidic group is uniformly mixed and dispersed on the surface and the entire inside of the fiber.

The compound containing a carboxyl group is not particularly limited, but for example, a (meth) acrylic acid-based polymer is preferable from the viewpoint of easily imparting a carboxyl group to the regenerated cellulose fiber. In the present invention, (meth) acrylic acid means to include acrylic acid and methacrylic acid. The (meth) acrylic acid-based polymer may be a homopolymer of a (meth) acrylic acid-based monomer, or a copolymer of a (meth) acrylic acid-based monomer and another monomer. You may. The carboxyl group-containing compound is more preferably one or more selected from the group consisting of polyacrylic acid and acrylic acid-maleic acid copolymers.

As the polyacrylic acid, for example, it is preferable to use an unneutralized product of polyacrylic acid, that is, H-type polyacrylic acid in which the carboxyl group of polyacrylic acid is H-type. The H site of the carboxyl group of polyacrylic acid may be partially replaced with a metal ion such as Na or an ionic compound. In the following, unless otherwise specified, polyacrylic acid means an unneutralized product of polyacrylic acid. The polyacrylic acid has a structure in which a carboxyl group is attached to the main chain as a main component, and a compound having the largest contribution of the carboxyl group to the molecular weight of the polymer can be used. For example, the theoretical amount of the carboxyl group is 72 g / mol. It is preferable to use the above polyacrylic acid.

The acrylic acid-maleic acid copolymer is an ethylenically unsaturated monomer containing at least one selected from the group consisting of acrylic acid and acrylate (hereinafter, also referred to as acrylic acid-based monomer). , A polymer of an ethylenically unsaturated monomer containing at least one selected from the group consisting of maleic acid, maleate and maleic anhydride (hereinafter, also referred to as a maleic acid-based monomer). A polymer of ethylenically unsaturated monomers containing at least one selected from the group consisting of acrylic acid and acrylate and at least one selected from the group consisting of maleic acid, maleate and maleic anhydride. It may be. Further, from the viewpoint of easily imparting a carboxyl group to the fiber, the acrylic acid-maleic acid copolymer includes an ethylenically unsaturated monomer containing at least one selected from the group consisting of acrylic acid and acrylate, and malein. A polymer of an ethylenically unsaturated monomer containing at least one selected from the group consisting of acid and maleate, and / or at least one selected from the group consisting of acrylic acid and acrylate, and maleic acid. It is preferably a polymer of an ethylenically unsaturated monomer containing at least one selected from the group consisting of and maleate. Further, if necessary, the acrylic acid-maleic acid polymer copolymerizes an acrylic acid-based monomer and a monomer other than the maleic acid-based monomer, as long as the effects of the present invention are not impaired. It may be the one that has been used. The other monomer may be, for example, an unsaturated monocarboxylic acid-based monomer.

The acrylic acid-maleic acid copolymer preferably has a weight average molecular weight of 5,000 or more and 500,000 or less, more preferably 6,000 or more and 250,000 or less, further preferably 10,000 or more and 100,000 or less, and 30,000 or more and 80,000. The following is particularly preferable. When the weight average molecular weight is within the above-mentioned range, it is easy to knead into the regenerated cellulose, and the compound containing a carboxyl group is less likely to come off or be modified even when washed or dyed / washed.

The acrylic acid-maleic acid copolymer preferably contains maleic acid in an amount of 5% by mass or more and 95% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and contains 30% by mass or more and 70% by mass or less. It is more preferable, and it is particularly preferable to contain 40% by mass or more and 60% by mass or less. When the content of maleic acid in the acrylic acid-maleic acid copolymer is within the above range, it is easy to impart a carboxyl group to the regenerated cellulose fiber. When the regenerated cellulose fiber contains the same amount of acrylic acid-maleic acid copolymer, the amount of H-type carboxyl group increases when the acrylic acid-maleic acid copolymer having a high maleic acid ratio is contained. Therefore, it is preferable.

In the present invention, the maleic acid ratio in the acrylic acid-maleic acid copolymer is measured and calculated as follows, assuming that the organic components in the acrylic acid-maleic acid copolymer are only acrylic acid and maleic acid. can do.
(1) About 4 to 5 mL of a sample (an aqueous solution containing an acrylic acid-maleic acid copolymer salt) is placed in a glass vial and heated at 110 ° C. for 20 hours to dry.
(2) Dissolve about 50 mg of a dry sample in about 0.7 mL of heavy water.
(3) 1H-NMR analysis was performed on the heavy aqueous solution of the sample using an FT-NMR apparatus (JMTC-300 / 54 / SS manufactured by JEOL Ltd.), and methylene group carbon and methine in the polymer main chain. From the abundance ratio of the base carbon, the composition ratio of the acrylic acid component (A) and the maleic acid component (M) is obtained. The number of measurements is 16 and the average value is calculated.

The compound containing a sulfonic acid group is not particularly limited, and for example, naphthaline sulfonate, polystyrene sulfonate, phenol sulfonate, dihydroxydiphenyl sulfone, formalin condensate of hydroxyphenyl sulfone, and the like can be used.

The content of the compound containing one or more acidic groups selected from the group consisting of the carboxyl group and the sulfonic acid group in the water-repellent regenerated cellulose fiber is, for example, 1% by mass or more and 35% by mass with respect to 100% by mass of cellulose. % Or less, more preferably 3% by mass or more and 30% by mass or less, and further preferably 4% by mass or more and 25% by mass or less. When the content of the compound containing one or more acidic groups selected from the group consisting of the carboxyl group and the sulfonic acid group in the water-repellent regenerated cellulose fiber is less than 1% by mass with respect to 100% by mass of the cellulose, it depends on the acidic group. The effect tends to be difficult to exert, and if it exceeds 35% by mass, the fiber strength decreases and there is a possibility that fine fineness cannot be achieved.

In the water-repellent regenerated cellulose fiber, the total amount of one or more acidic groups selected from the group consisting of a carboxyl group and a sulfonic acid group is preferably 0.30 mmol / g or more and 1.60 mmol / g or less, more preferably 0. It is .35 mmol / g or more and 1.50 mmol / g or less, and more preferably 0.40 mmol / g or more and 1.40 mmol / g or less. When the total amount of one or more acidic groups selected from the group consisting of a carboxyl group and a sulfonic acid group is within the above range, the effect of the acidic group is likely to be exhibited. In the water-repellent regenerated cellulose fiber, as described above, the acidic group is a non-fluorine-based water-repellent fiber even in a heat treatment in which an isocyanate-based compound is bonded to the fiber surface to a low temperature of 40 ° C. or higher and 110 ° C. or lower. It has the effect of improving the fixability of the surface and imparting ammonia deodorant property and pH buffer property to the regenerated cellulose fiber. In the present invention, the total amount of one or more acidic groups selected from the group consisting of a carboxyl group and a sulfonic acid group is measured and calculated as described later.

The non-fluorine-based water repellent is not particularly limited, but for example, a hydrocarbon-based water repellent is preferable. As the hydrocarbon-based water repellent, for example, a hydrocarbon-based water repellent composed of a polymer containing a (meth) acrylic acid ester having 12 or more carbon atoms as a hydrocarbon group existing via an ester bond as a basic unit of a monomer. It is preferable to use a liquid agent. The number of carbon atoms of the hydrocarbon group is more preferably 24 or less, and further preferably 21 or less. The hydrocarbon group may be linear or branched, may be a saturated hydrocarbon or an unsaturated hydrocarbon, and may have an alicyclic or aromatic ring. You may be doing it. Among these, those having a linear shape are preferable, and those having a linear alkyl group are more preferable. As used herein, the (meth) acrylic acid ester means an acrylic acid ester and / or a methacrylic acid ester.

The (meth) acrylic acid ester monomer is preferably 80% by mass or more and 100% by mass or less with respect to the total amount of the monomer units constituting the polymer. The weight average molecular weight of the hydrocarbon-based water repellent is preferably 100,000 or more, and more preferably 500,000 or more. The hydrocarbon-based water repellent may be a copolymer of an acrylic acid ester and a methacrylic acid ester.

As the hydrocarbon-based water repellent, a water-repellent composition in which hydrocarbon-based water repellent particles are dispersed in water can be used. The water repellent composition may contain a surfactant and an organic solvent. As such a water repellent composition, for example, a commercially available product such as Neoseed NR series (manufactured by NICCA CHEMICAL CO., LTD.) May be used.

In the water-repellent regenerated cellulose fiber, the amount of the non-fluorinated water-repellent agent attached is preferably 0.1% by mass or more and 10% by mass or less, preferably 0.2% by mass, based on 100% by mass of cellulose. It is more preferably 8% by mass or less, more preferably 0.3% by mass or more and 6% by mass or less, and further preferably 0.5% by mass or more and 2% by mass or less. When the amount of the non-fluorine-based water repellent adhered is within the above range, the water repellency is improved and the fibers are less likely to become rigid.

The non-fluorine-based water repellent may be used alone or in combination of two or more as appropriate.

The cross-linking agent is not particularly limited, but for example, an isocyanate-based compound is preferably used from the viewpoint of easily fixing the non-fluorine-based water repellent to the fiber surface. As the isocyanate-based compound, for example, a cross-linking agent such as a compound having an isocyanate group and a compound having a blocked isocyanate group can be used.

Examples of the compound having an isocyanate group include monoisocyanates such as butyl isocyanate, phenylisocyanate, tolylisocyanate, and naphthalene isocyanate, diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate, and isocyanurate rings thereof. Examples thereof include a trimeric body and a trimethylol propan adduct body.

Examples of the compound having a blocked isocyanate group include the above-mentioned compound having an isocyanate group whose isocyanate group is protected by a blocking agent. Examples of the blocking agent used at this time include organic blocking agents such as secondary or tertiary alcohols, active methylene compounds, phenols, oximes and lactams, and sodium bisulfite such as sodium bisulfite and potassium bisulfite. Examples include salt. The blocked isocyanate group is masked with a highly reactive isocyanate group, and the block is usually dissociated by heat treatment at 120 to 180 ° C. However, in the present invention, the blocked isocyanate group consists of a group consisting of a carboxyl group and a sulfonic acid group. Since it has one or more acidic groups of choice, it is presumed that the block dissociates at a low temperature of 40 ° C. or higher and 110 ° C. or lower on the fiber surface. Therefore, the blocked isocyanate group exists in a dissociated state on the surface of the water-repellent regenerated cellulose fiber.

In the water-repellent regenerated cellulose fiber, the adhesion amount of the isocyanate-based compound is preferably 0.010% by mass or more and 5.0% by mass or less, and 0.020% by mass or more, with respect to 100% by mass of cellulose. It is more preferably 3.0% by mass or less, further preferably 0.03% by mass or more and 2.0% by mass or less, and further preferably 0.05% by mass or more and 1.0% by mass or less. preferable. When the amount of the non-fluorine-based water repellent adhered is within the above range, the durability of water repellency (hereinafter, also referred to as durable water repellency) is improved, and the fibers are less likely to become rigid.

As the cross-linking agent such as the isocyanate compound, one kind may be used alone, or two or more kinds may be used in an appropriate combination.

The mass ratio of the non-fluorinated water repellent to the isocyanate compound (non-fluorinated water repellent: isocyanate compound) is not particularly limited, but for example, from the viewpoint of improving water repellency and its durability, 3: It is preferably 1 or more and 7: 1 or less, and more preferably 4: 1 or more and 6: 1 or less.

The water-repellent fabric of the present invention has highly durable water repellency by containing the water-repellent regenerated cellulose fiber. The water-repellent fabric may be a woven fabric or a knitted fabric. The structure of the woven fabric or knitted fabric is not particularly limited. For example, in knitting, circular knitting, weft knitting, warp knitting (tricot) and the like are preferable, and in woven fabrics, plain weave, twill weave, satin weave and the like are preferable because they tend to exert the soft texture effect of cellulose fibers.

The water-repellent fabric may be composed of only the water-repellent regenerated cellulose fibers, or may contain other fibers. Examples of other fibers include regenerated cellulose fibers other than the water-repellent regenerated cellulose fibers, natural fibers, synthetic fibers and the like. Examples of other regenerated cellulose fibers include rayon, cupra, solvent-spun cellulose, polynosic and the like. Examples of natural fibers include cotton, linen, wool, silk and the like. Examples of the synthetic fiber include acrylic fiber, polyester fiber, polyamide fiber, polyolefin fiber, polyurethane fiber and the like. The synthetic fiber may be a single fiber or a composite fiber.

The water-repellent fabric preferably contains the water-repellent regenerated cellulose fiber in an amount of 10% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more. If the content of the water-repellent regenerated cellulose fiber is low, the performance such as water repellency of the fiber may be difficult to be exhibited. The upper limit of the content of the water-repellent regenerated cellulose fiber is not particularly limited, and can be appropriately determined depending on the use of the fabric and the like. When a soft texture or the like is required, it may be composed of 100% by mass of water-repellent regenerated cellulose fiber, or other regenerated cellulose fiber and / or natural fiber may be used as another fiber. In the case of mixed cotton with other hydrophilic regenerated cellulose fibers and / or natural fibers, water-repellent regenerated cellulose fibers 50% by mass or more and 90% by mass or less, and other regenerated cellulose fibers and / or natural fibers 50% by mass or more and 10% by mass. The following may be contained, and 60% by mass or more and 90% by mass or less of the water-repellent regenerated cellulose fiber, and 40% by mass or more and 10% by mass or less of other regenerated cellulose fibers and / or natural fibers may be contained. It may contain 70% by mass or more and 90% by mass or less, and 30% by mass or more and 10% by mass or less of other regenerated cellulose fibers and / or natural fibers. When firmness or the like is required, water-repellent regenerated cellulose fiber may contain 10% by mass or more and 50% by mass or less, synthetic fiber may be contained in an amount of 50% by mass or more and 90% by mass or less, and water-repellent regenerated cellulose fiber may contain 20% by mass or more and 45% by mass or less. , Synthetic fiber may be contained in an amount of 55% by mass or more and 80% by mass or less, water-repellent recycled cellulose fiber may be contained in an amount of 25% by mass or more and 40% by mass or less, and synthetic fiber may be contained in an amount of 60% by mass or more and 75% by mass or less.

The water-repellent fabric is dyed with a reactive dye. By using the reactive dye, the dyeing fastness of the water-repellent fabric, particularly the sweat fastness, is enhanced. The reactive dye will be described in detail later.

The water-repellent fabric has a contact angle with water of 90 ° or more, preferably 100 ° or more, and more preferably 110 ° or more. When the contact angle with water is within the above range, the durability and water repellency are excellent.

From the viewpoint of enhancing water repellency, the water-repellent fabric preferably has a surface tension of 72.75 mN / m or less, more preferably 58.85 mN / m or less, and further preferably 38.50 mN / m or less. is there. The lower limit of the surface tension of the water-repellent fabric is not particularly limited, but for example, from the viewpoint of hydrophilic treatment, it is preferably 20 mN / m or more, and more preferably 25 mN / m or more.

The basis weight of the water-repellent fabric is not particularly limited, and can be appropriately determined depending on the intended use and the like. For example, in the case of knitted fabrics, from the viewpoint of wearability such as light weight, for example, the basis weight is preferably 450 g / m ² or less, more preferably 400 g / m ² or less, and 300 g / m ² or less. It is more preferable, and it is particularly preferable that it is 200 g / m ² or less. The water-repellent fabric is not particularly limited, but the basis weight is preferably 50 g / m ² or more from the viewpoint of heat retention and the like.

The water-repellent fabric is not particularly limited, but is, for example, non-fluorine-based repellent by a cross-linking agent on the fiber surface of a regenerated cellulose fiber containing a compound containing one or more acidic groups selected from the group consisting of a carboxyl group and a sulfonic acid group. A step of binding a water agent to obtain a water-repellent regenerated cellulose fiber, a step of obtaining a water-repellent cloth containing the water-repellent regenerated cellulose fiber, and a hydrophilization treatment by applying water or an aqueous solution containing a surfactant to the water-repellent cloth. It is preferable to prepare the fabric by a step of dyeing the hydrophilized cloth with a reactive dye, a step of drying the dyed cloth, or the like. It is possible to obtain a water-repellent fabric having no uneven dyeing, high dyeing fastness, and excellent durability and water repellency.

The water-repellent regenerated cellulose fiber is not particularly limited, but for example, a compound containing one or more acidic groups selected from the group consisting of a carboxyl group and a sulfonic acid group in a viscose stock solution (raw material viscose) containing cellulose is added. A viscose solution for spinning is prepared by mixing, and the viscose solution for spinning is extruded from a nozzle and coagulated and regenerated to form a viscose rayon thread, and the viscose rayon thread is made into an isocyanate-based compound and a non-cellulose-based water repellent. It can be produced by treating with a water-repellent treatment liquid containing an agent and then heat-treating.

The raw material viscose may contain, for example, 7% by mass or more and 10% by mass or less of cellulose, 5% by mass or more and 8% by mass or less of sodium hydroxide, and 2% by mass or more and 3.5% by mass or less of carbon disulfide. At this time, if necessary, additives such as ethylenediaminetetraacetic acid (EDTA) and titanium dioxide can be used. The temperature of the raw material viscose is preferably maintained at 18 ° C. or higher and 23 ° C. or lower.

The amount of the compound containing one or more acidic groups selected from the group consisting of a carboxyl group and a sulfonic acid group may be 1% by mass or more and 35% by mass or less with respect to 100% by mass of cellulose in the raw material biscous. It is preferable that it is 3% by mass or more and 30% by mass or less, and further preferably 5% by mass or more and 25% by mass or less. Within the above range, a compound containing one or more acidic groups selected from the group consisting of a carboxyl group and a sulfonic acid group can be effectively kneaded into the fiber while increasing the fiber strength.

The viscose rayon yarn can be manufactured using, for example, a normal circular nozzle. As the spinning nozzle, although it depends on the target production amount, it is preferable to use a circular nozzle having a diameter of 0.05 mm or more and 0.12 mm or less and a number of holes of 1000 or more and 20000 or less. Further, a nozzle having a modified cross section may be used. Using the spinning nozzle, the spinning viscose solution is extruded into a spinning bath for spinning and solidification and regeneration. The spinning speed is preferably in the range of 30 m / min or more and 80 m / min or less. The draw ratio is preferably 39% or more and 55% or less. Here, the stretching ratio indicates how much the sliver speed after stretching is increased when the sliver speed before stretching is 100. In terms of magnification, it is 1 before stretching and 1.39 times or more and 1.55 times or less after stretching.

As a spinning bath (Muller bath), for example, a strong acid containing 95 g / L or more and 130 g / L or less of sulfuric acid, 10 g / L or more and 17 g / L or less of zinc sulfate, and 290 g / L or more and 370 g / L or less of sodium sulfate (Glauber's salt). It is preferable to use a sex bath. A more preferable sulfuric acid concentration is 95 g / L or more and 120 g / L or less.

The viscose rayon yarn (regenerated cellulose fiber) obtained as described above is cut to a predetermined length and usually subjected to a refining treatment. The scouring step can generally be performed in the order of hot water treatment, water washing, hydrosulfide treatment (desulfurization), bleaching, pickling, and water washing. Bleaching and pickling may be omitted.

If necessary, the rayon fiber yarn after the refining step may be subjected to pH adjustment treatment to adjust the pH of the fiber to 8.0 or less. The pH adjustment treatment can be performed by immersing the fibers in a buffer solution having a pH of 6.0 or less. The bath ratio at the time of immersion is not particularly limited, but is preferably 1:10 or more and 1:30 or less, and more preferably 1:15 or more and 1:25 or less. The immersion time is not particularly limited, but is preferably 0.5 minutes or more and 50 minutes or less, and more preferably 1 minute or more and 20 minutes or less. The pH adjusting buffer solution is not particularly limited, and for example, a general buffer solution such as an acetic acid-sodium acetate buffer solution can be used, but it is desirable that the buffer solution contains sodium. .. After immersing in a pH adjusting buffer solution, it may be washed with water and dried.

In the regenerated cellulose fiber (before water repellent treatment), the amount of H-type carboxyl group and / or H-type sulfonic acid group is preferably 0.20 mmol or more and 1.60 mmol / g or less, and more preferably 0.30 mmol. It is / g or more and 1.50 mmol / g or less, and more preferably 0.35 mmol / g or more and 1.40 mmol / g or less. Further, in the regenerated cellulose fiber, the amount of the salt-type carboxyl group and / or the salt-type sulfonic acid group is preferably 1.0 mmol / g or less, more preferably 0.35 mmol / g or less, still more preferably. It is 0.015 mmol / g or more and 0.20 mmol / g or less.

In the regenerated cellulose fiber (before water repellent treatment), the ratio of the amount of H-type carboxyl group and / or H-type sulfonic acid group to the total amount of carboxyl group and / or sulfonic acid group is 45% or more and 100% or less. It is preferable, more preferably 80% or more and 98% or less, and further preferably 90% or more and 95% or less. When the ratio of the amount of the H-type carboxyl group and / or the H-type sulfonic acid group is within the above range, the carboxyl group and / or the sulfonic acid group and the isocyanate group are likely to be bonded in the water-repellent processing step described later, and the isocyanate group is easily bonded. The carboxyl group and / or the sulfonic acid group act as an acid catalyst, and the amine produced by the efficient reaction between the isocyanate group and water easily causes various side reactions, and the durable water repellency can be enhanced.

After the refining process, a water repellent finish is performed. First, the viscose rayon yarn is treated with a water-repellent treatment liquid containing a cross-linking agent such as an isocyanate-based compound and a non-fluorine-based water-repellent agent to attach the isocyanate-based compound and the non-fluorine-based water repellent. The treatment method using the water-repellent treatment liquid is not particularly limited, and examples thereof include processing methods such as dipping, spraying, and shower coating. The treatment with the water-repellent treatment liquid is performed under the condition that the water content of the viscose rayon yarn is 100% by mass or more and 180% by mass or less from the viewpoint of easily adhering the isocyanate compound and the non-fluorine-based water repellent to the fibers. , And more preferably under the condition that the water content is 120% by mass or more and 150% by mass or less.

In the water-repellent treatment liquid, the non-fluorine-based water-repellent agent and the isocyanate-based compound are dispersed in a solvent such as water. The concentration of the non-fluorine-based water repellent in the treatment liquid is not particularly limited, but is preferably 0.15% by mass or more and 40% by mass or less. More preferably, it is 0.35% by mass or more and 35% by mass or less. When the concentration of the treatment liquid is within the above range, the amount of adhesion between the non-fluorinated water repellent and the isocyanate compound can be easily adjusted, and the temperature of the fiber surface is adjusted to a low temperature when the solvent such as water is evaporated during the heat treatment. Easy to use and preferable.

The amount of the non-fluorinated water repellent used can be appropriately adjusted according to the required degree of water repellency, but the amount of the non-fluorinated water repellent (as a water repellent) is based on 100% by mass of the regenerated cellulose fiber. , Even when a water repellent composition is used, it is preferable to adjust the content (only for non-fluorinated water repellent) to be 0.1% by mass or more and 10% by mass or less, and 0.2% by mass or more and 8.0. It is more preferable to adjust the mass% or less. When the amount of the non-fluorine-based water repellent adhered is within the above range, water repellency can be easily imparted and the softness of the regenerated cellulose fiber can be maintained.

The amount of the isocyanate-based compound (for example, a cross-linking agent such as a compound having an isocyanate group and a compound having a blocked isocyanate group) is not particularly limited, but the regenerated cellulose is easily maintained from the viewpoint of maintaining the softness of the regenerated cellulose fiber. It is preferably 0.010% by mass or more and 5.0% by mass or less, and more preferably 0.02% by mass or more and 3.0% by mass or less with respect to 100% by mass of the fiber.

The water-repellent treatment liquid is not particularly limited, but from the viewpoint of enhancing durable water repellency and maintaining the softness of the regenerated cellulose fiber, the mass ratio (non-fluorescent) of the non-fluorine-based water repellent and the isocyanate-based compound. The fluorine-based water repellent (isocyanate compound) is, for example, preferably 3: 1 or more and 7: 1 or less, and more preferably 4: 1 or more and 6: 1 or less.

Next, by heat-treating the fiber, a non-fluorinated water repellent is bonded to the fiber surface of the regenerated cellulose fiber by a cross-linking agent. The heat treatment is preferably performed under conditions such that the fiber surface has a temperature of 40 ° C. or higher and 110 ° C. or lower. A more preferable lower limit of the actual temperature in the heat treatment temperature (actual temperature) is 50 ° C. or higher on the fiber surface, and a more preferable lower limit of the actual temperature is 60 ° C. or higher on the fiber surface. A more preferable upper limit of the actual temperature is that the fiber surface is less than 100 ° C., more preferably 95 ° C. or lower, and even more preferably 90 ° C. or lower. When the heat treatment temperature is within the above range, the isocyanate compound and the non-fluorine water repellent are firmly bonded to the fiber, and the deterioration of the fiber due to heat such as yellowing of the fiber is suppressed. When the water-repellent treatment liquid contains water, the drying treatment performed to remove the water can be heat treatment.

After the water-repellent treatment, an oil agent may be added as needed to the extent that the water repellency is not impaired.

The water-repellent treatment of the present invention has been described above by taking as an example that it is performed during the manufacturing process of rayon yarn, but the water-repellent treatment is performed after making a spun yarn containing rayon fiber, a rayon filament yarn, and a fabric containing rayon fiber. You may go.

The water-repellent regenerated cellulose fiber is not particularly limited, but for example, the single fiber fineness is preferably 0.3 dtex or more and 8.0 dtex or less. It is more preferably 0.6 dtex or more and 6.0 dtex or less, and further preferably 0.7 dtex or more and 3.6 dtex or less. If the single fiber fineness is less than 0.3 dtex, single fiber breakage tends to occur during drawing. If the single fiber fineness exceeds 8.0 dtex, the regenerated state of the fiber tends to be poor, and the hue or the like of the fiber may be poor.

The water-repellent regenerated cellulose fiber has a whiteness of Hw80 or more, and is preferably Hw80 or more and Hw90 or less from the viewpoint of maintaining the texture of cellulose. In the case of general regenerated cellulose fibers, it is necessary to react the cross-linking agent under the conditions of 120 ° C. or higher when performing water-repellent treatment and 170 ° C. or higher to improve the water-repellent durability, and it becomes white when exposed to high temperature. The degree is significantly reduced (less than Hw80). In the present invention, since regenerated cellulose containing a specific acidic group is used, deterioration of cellulose can be suppressed, and as a result, the whiteness tends not to be substantially lowered.

The water-repellent regenerated cellulose fiber preferably has a standard tensile strength (hereinafter, also referred to as dry strength) measured according to JIS L 1015 of 1.5 cN / dtex or more and 3.0 cN / dtex or less. More preferably, it is 1.7 cN / dtex or more and 2.7 cN / dtex or less. The tensile strength at the time of wetting (hereinafter, also referred to as wet strength) is preferably 0.6 cN / dtex or more and 2.0 cN / dtex or less. More preferably, it is 0.8 cN / dtex or more and 1.8 cN / dtex or less.

The water-repellent regenerated cellulose fiber preferably has a standard elongation rate (hereinafter, also referred to as dry elongation) measured according to JIS L 1015 of 15% or more and 25% or less. More preferably, it is 16% or more and 24% or less. The elongation rate when wet (hereinafter, also referred to as wet elongation) is preferably 15% or more and 40% or less. More preferably, it is 18% or more and 35% or less.

When the tensile strength and the elongation rate are within the above ranges, the spinnability is good and the product strength tends to be good.

Normally, when water-repellent treatment is applied to regenerated cellulose fibers, it is necessary to react the cross-linking agent under the conditions of 120 ° C. or higher, and 170 ° C. or higher to improve the water-repellent durability. Since film formation and cross-linking of the liquid agent occur strongly, the rigidity and strength of the entire fiber increase in the standard state (dry state), but the strength of the cellulose itself decreases due to deterioration of the amorphous part of the cellulose due to heat. There is. Therefore, as in the case of wetness, the strength of cellulose itself tends to decrease due to swelling due to water, breakage of hydrogen bonds in amorphous portions, and the like, and the wet strength tends to decrease significantly due to the influence of deterioration due to heat. In the present invention, cellulose has one or more acidic groups selected from the group consisting of a carboxyl group and a sulfonic acid group, and can be subjected to a predetermined water repellent treatment at a low temperature of 100 ° C. or lower. While the rigidity and strength of the cellulose are increased, the damage caused by heat to the cellulose itself is small, and the decrease in wet strength tends to be small.

The water-repellent regenerated cellulose fiber preferably has an apparent Young's modulus (hereinafter, also referred to as dry Young's modulus (DY)) at standard time measured according to JIS L 1015, which is 3500 MPa or more and 8500 MPa or less. More preferably, it is 4000 MPa or more and 8000 MPa or less. The apparent Young's modulus when wet (hereinafter, also referred to as wet Young's modulus (WY)) is preferably 800 MPa or more and 1300 MPa or less. More preferably, it is 900 MPa or more and 1200 MPa or less. When the apparent Young's modulus is within the above range, it is possible to impart an appropriate elasticity to the fiber while maintaining the softness of the fiber itself.

The ratio of wet / standard time (wet and dry) to the apparent Young's modulus is expressed as a factor that firmly binds the water repellent while suppressing deterioration of the cellulose itself, and is represented by the following formula.
Wet-dry Young's modulus ratio = (WY / DY) x 100 (1)
The apparent Young's modulus indicates the rigidity of the fiber to the initial tension, and the dry Young's modulus (DY) tends to increase due to the strength of the cellulose itself and the water repellent due to the cross-linking, but the wetness Young's modulus (WY) tends to decrease due to the swelling of cellulose by water and the breaking of hydrogen bonds in the amorphous part, which reduces the rigidity to the initial tension and the effect of deterioration of the amorphous portion due to heat. It is in. Therefore, as in the present invention, by suppressing the deterioration of cellulose, the decrease in WY is suppressed, and as a result, the WY / DY tends to increase. WY / DY is preferably 12.0 or more. More preferably, it is 12.5 or more.

Next, a water-repellent fabric containing the water-repellent regenerated cellulose fiber is obtained. For example, a knitted fabric or a woven fabric is produced by a known method. For example, a spun yarn containing a water-repellent regenerated cellulose fiber can be produced by a conventional method, and a knitted fabric or a woven fabric can be produced by a conventional method using the spun yarn. The count of the spun yarn is not particularly limited, but the English cotton count may be in the range of 5 to 100S, preferably 10 to 90S, more preferably 15 to 85S, and further preferably 20 to 20 to 90S. It is 80S.

Next, the water-repellent fabric is hydrophilized by adding water or an aqueous solution containing a surfactant. Normally, when a fabric containing water-repellent cellulose fibers in which a water-repellent agent is crosslinked is dyed by immersing it in a dyeing bath, uneven dyeing occurs, dyeing fastness is lowered, and water-repellent performance is lowered. .. In the present invention, since the non-fluorine-based water repellent is used, the orientation of the water-repellent groups of the non-fluorine-based water repellent on the surface of the fiber is disturbed when an aqueous solution containing water or a surfactant is applied to the water-repellent fabric. The water-repellent fabric can be temporarily made hydrophilic. Further, as described above, a non-fluorine-based water repellent is used, and the water-repellent regenerated cellulose fiber contains a compound containing one or more acidic groups selected from the group consisting of a carboxyl group and a sulfonic acid group, whereby the fiber surface is formed. The fixability of the non-fluorinated water-repellent agent bound to is increased, and the dyeing fastness and water-repellent performance are not deteriorated.

When the hydrophilization treatment is carried out with water, it is not particularly limited, but for example, from the viewpoint of enhancing the hydrophilic effect, it is preferable to immerse in water at 20 ° C. or higher and 70 ° C. or lower, and more preferably water at 30 ° C. or higher and 60 ° C. or lower. Immerse in. The immersion time is preferably 5 minutes or longer, more preferably 10 minutes or longer, and even more preferably 20 minutes or longer, for example, from the viewpoint of enhancing the hydrophilicity effect. Further, from the viewpoint of productivity, it is preferable to soak for 40 minutes or less, and more preferably for 30 minutes or less. If desired, high pressure water may be used or the water may be agitated during immersion. The bath ratio is preferably 1:10 to 1: 100 (water-repellent fabric: water), more preferably 1:15 to 1:80, and further preferably 1:20 to 1:70. preferable. The water may be purified water, tap water, industrial water, or a mixture thereof.

When the hydrophilic treatment is carried out with an aqueous solution containing a surfactant, the hydrophilization treatment is not particularly limited, but for example, from the viewpoint of enhancing the hydrophilic effect, it is preferable to immerse in an aqueous solution containing a surfactant at 30 ° C. or higher and 70 ° C. or lower. It is more preferable to immerse in an aqueous solution containing a surfactant at ° C. or higher and 65 ° C. or lower. The immersion time is preferably 5 minutes or more, and more preferably 10 minutes or more, for example, from the viewpoint of enhancing the hydrophilic effect. Further, from the viewpoint of productivity, it is preferable to soak for 30 minutes or less, and more preferably for 20 minutes or less. Further, if necessary, an aqueous solution containing a high-pressure surfactant may be used, or the aqueous solution containing the surfactant may be agitated during immersion. The bath ratio is preferably 1:10 to 1: 100 (water-repellent fabric: aqueous solution containing a surfactant), more preferably 1:15 to 1:80, and 1:20 to 1:70. Is more preferable. After treating the aqueous solution containing the surfactant, it may be dehydrated and then further treated with water. The water used in the aqueous solution containing the surfactant may be purified water, tap water, industrial water, or a mixture thereof.

The surfactant is not particularly limited as long as it can make the fabric hydrophilic. For example, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and the like can be used. In the subsequent dyeing step, from the viewpoint of enhancing the permeability of the reactive dye, the surfactant preferably contains at least one selected from the group consisting of nonionic surfactants and anionic surfactants, and has nonionic properties. It is more preferable to include a surfactant.

Examples of the nonionic surfactant include glycerin fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, alkyl diethanolamine, hydroxyalkyl monoethanolamine, polyoxyethylene alkyl amine, polyoxyethylene alkyl amine fatty acid ester, and poly. Examples thereof include oxyethylene sorbitan fatty acid esters and alkyldiethanol amide. Of these, polyoxyethylene alkyl ethers are preferable from the viewpoint of enhancing the hydrophilicity effect and the permeability of the reactive dye.

The polyoxyethylene alkyl ether is not particularly limited, but for example, the number of carbon atoms of the alkyl group is preferably 6 or more and 22 or less, more preferably 8 or more and 20 or less, and 10 or more and 18 or less. Is even more preferable. The average number of moles of ethylene oxide added is preferably 1 mol or more and 60 mol or less, more preferably 3 mol or more and 40 mol or less, and further preferably 5 mol or more and 20 mol or less.

The anionic surfactant is not particularly limited, and for example, α-sulfo fatty acid ester salt, α-olefin sulfonate, alkyl ether sulfate ester salt, higher fatty acid salt, straight chain or branched alkyl sulfate ester salt. , Alcan sulfonate having an alkyl group, alkyl ether carboxylate, polyoxyalkylene ether carboxylate, alkylamide ether carboxylate or alkenylamide ether carboxylate, acylaminocarboxylate, etc. Surfactants, alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate ester salts, polyoxyalkylene alkylphenyl phosphate ester salts, glycerin fatty acid ester monophosphate ester salts and other phosphoric acid ester type anionic surfactants and the like can be mentioned. Be done. Among them, one or more selected from the group consisting of α-sulfo fatty acid ester salt, α-olefin sulfonate salt and alkyl ether sulfate ester salt is preferable from the viewpoint of enhancing the hydrophilic effect and the permeability of the reactive dye.

Examples of the salt form of the anionic surfactant include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; monoethanolamine salt (monoethanolammonium) and diethanolamine salt (monoethanolammonium). Diethanolammonium), alkanolamine salts such as triethanolamine salt (triethanolammonium); ammonium salts and the like, and alkali metal salts are preferable.

The cationic surfactant is not particularly limited, and is, for example, an aliphatic amine or a quaternary ammonium salt thereof, a fatty acid amidamine salt, an alkyltrialkylene glycol ammonium salt, an acylguanidine derivative, or a mono-N-long-chain acyl basicity. Examples thereof include amino acid-based cationic surfactants such as lower amino acid alkyl ester salts, alkylbenzalconium salts, alkylpyridinium salts, and imidazolinium salts.

The amphoteric surfactant is not particularly limited, and is, for example, an alkyl betaine type, an alkylamide betaine type, an imidazoline type, an alkylaminosulfone type, an alkylaminocarboxylic acid type, an alkylamide carboxylic acid type, an amide amino acid type, or a phosphoric acid. Examples include molds.

The above-mentioned surfactants may be used alone or in combination of two or more.

The aqueous solution containing the surfactant is not particularly limited, but the concentration of the surfactant is preferably 0.1 g / L or more and 1.0 g / L or less, and more preferably 0.15 g / L or more and 0.8 g. It is less than / L. When the concentration of the surfactant is 0.1 g / L or more, the hydrophilic effect is likely to be exhibited. When the concentration of the surfactant is 1.0 g / L or less, the water repellency is not inhibited.

It is preferable to adjust the water content of the hydrophilized fabric to be 100% by mass or more and 250% by mass or less by dehydrating or the like after the hydrophilic treatment, and to 150% by mass or more and 200% by mass or less. It is preferable to adjust so as to be. When the water content is within the above-mentioned range, the temporary hydrophilicity of the hydrophilized fabric is well expressed, and uneven dyeing can be more effectively eliminated in the subsequent dyeing step.

Next, the hydrophilized fabric is dyed with a reactive dye. The dyeing method is not particularly limited, and a known method can be used. For example, dyeing can be performed by dipping the hydrophilized fabric with a dyeing solution containing a reactive dye and a dyeing aid. The bath ratio can be, for example, in the range of 1:10 to 1:50. The immersion time can be appropriately determined according to the type of reactive dye used, and may be, for example, 50 minutes or more and 100 minutes or less.

The reactive dye is not particularly limited, but for example, a reactive dye having a high direct level and a medium to high level of reactivity, for example, Sumifix (manufactured by Sumitomo Chemical Co., Ltd.), Remazole (Distar Co., Ltd.) (Company), Capizol (Kiwa Chemical Industry Co., Ltd.) Sumifix Supra (Sumitomo Chemical Co., Ltd.), Levafix (Distar Co., Ltd.), Procion (Mitsui BASF Dye Co., Ltd.), Shibacron (Ciba Specialty Chemicals Co., Ltd.) ), Bacillen (manufactured by Mitsui BASF Dye Co., Ltd.), Kayashion (manufactured by Nippon Kayaku Co., Ltd.) and other reactive dyes can be used. These reactive dyes may be used alone or in combination of two or more. The amount of the reactive dye used may be appropriately determined according to the desired hue.

As the dyeing aid, an alkaline compound can be used alone, or a neutral salt and an alkaline compound can be used in combination. Examples of the alkaline compound include caustic soda, sodium carbonate, baking soda and the like. Examples of the neutral salt include salt, Glauber's salt and the like. The amount used can be used according to the standard method of the dyeing method using a reactive dye.

After the dipping treatment is completed, it can be washed with water or hot water in the same manner as in the known dyeing. In addition, soaping may be performed as needed.

After the dyeing is completed, a drying process is performed. The hydrophilization treatment disturbs the water-repellent groups of the non-fluorine-based water-repellent agent on the fiber surface of the water-repellent cellulose fibers in the water-repellent fabric, so that the fibers are temporarily hydrophilized and become uniform with a reactive dye in the dyeing step. On the other hand, when the dye is dried after the dyeing is completed, the water-repellent groups of the non-fluorophilic water repellent are oriented outward and the water repellency is restored. The drying is not particularly limited, and can be carried out under the same conditions as the drying after normal dyeing. For example, from the viewpoint of improving water repellency such as washing durability, drying is preferably performed at a temperature of 60 ° C. or higher and 180 ° C. or lower, more preferably 80 ° C. or higher and 170 ° C. or lower, and 90 ° C. or higher. It is more preferably performed at a temperature of 160 ° C. or lower, and may be performed at a temperature of 100 ° C. or lower. The drying time is not particularly limited as long as the water repellency is restored, but may be, for example, 5 seconds or more and 15 minutes or less, 5 seconds or more and 10 minutes or less, or 5 seconds or more and 5 minutes or less. You may go.

The water-repellent fabric may be refined and bleached before dyeing. In this case, the hydrophilic treatment may be performed at the same time as the refining and bleaching treatments, or the hydrophilic treatment may be performed after the refining and bleaching treatments. From the viewpoint of further reducing dyeing unevenness, it is preferable to perform hydrophilization treatment after refining and bleaching treatment.

The water-repellent fabric can be used for clothing, industrial base materials, and the like. Examples of clothing include underwear, underwear, shirts, jumpers, sweaters, pants, training wear, tights, abdominal wraps, mufflers, hats, gloves, socks, earmuffs, and the like. Examples of the industrial base material include carpets, bedding, furniture and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to the following examples.

First, the measurement methods used in Examples and Comparative Examples will be described.

(Measurement of weight average molecular weight)
The weight average molecular weight (Mw) was determined by measurement under the following conditions by GPC (gel permeation chromatography). When calculating the weight average molecular weight, a portion having a molecular weight of 300 or more on the chart obtained by GPC was defined as a polymer.
Column: GF-7MHQ (manufactured by Showa Denko KK).
Mobile phase: Pure water was added to 34.5 g of disodium hydrogen phosphate dodecahydrate and 46.2 g of sodium dihydrogen phosphate dihydrate (both are special grade reagents) to make the total amount 5,000 g, and then An aqueous solution filtered through a 0.45 micron membrane filter.
Detector: UV 214nm (manufactured by Japan Waters Corp. 30, model 481).
Pump: L-7110 (manufactured by Hitachi, Ltd.).
Flow rate: 0.5 mL / min.
Temperature: 35 ° C.
Calibration curve: Sodium polyacrylate standard sample (manufactured by Sowa Kagaku Co., Ltd.).

(Measurement of total amount of carboxyl groups)
(1) 1.2 g of the sample was immersed in 50 mL of a 1 mol / L hydrochloric acid aqueous solution (pH 0.1), stirred, and left for 5 minutes. Then, the mixture was stirred again to adjust the pH of the aqueous solution to 2.5. As a result, all the carboxyl groups in the sample (fiber) exist as H type. Next, the sample was washed with water and dried at 105 ° C. for 2 hours in a constant temperature blower dryer to make it absolutely dry. By washing the sample with water, all excess hydrochloric acid adhering to the fibers will be removed.
(2) 100 mL of ion-exchanged water, 0.4 g of sodium chloride, and 20 mL of a 0.1 mol / L sodium hydroxide aqueous solution were placed in a beaker.
(3) 1 g of the sample prepared in (1) is precisely weighed [W1 (g)], cut into small pieces so as not to be wrapped around the stirrer, placed in the beaker prepared in (2), and stirred with a stirrer for 15 minutes. did. As a result, all the carboxyl groups in the sample (fiber) are converted into the salt type. The stirred sample was suction filtered. 60 mL of the filtrate was taken and titrated with a 0.1 mol / L hydrochloric acid aqueous solution using phenolphthalein as an indicator, and the titration amount was X1 (mL).
(4) The total amount Y (mmol / g) of carboxyl groups was calculated based on the following formula. As described above, the amount of sodium hydroxide obtained by subtracting the amount of residual sodium hydroxide from the total amount of sodium hydroxide corresponds to the total amount of carboxyl groups in the sample (fiber).
Total amount of carboxyl groups Y (mmol / g) = [[(0.1 × 20)-(0.1 × X1)] × (120/60)] / W1

(Measurement of amount of H-type carboxyl group and amount of salt-type carboxyl group)
(1) The sample was washed with water and dried at 105 ° C. for 2 hours in a constant temperature blower dryer to make it absolutely dry.
(2) 100 mL of ion-exchanged water, 0.4 g of sodium chloride, and 20 mL of a 0.1 mol / L sodium hydroxide aqueous solution were placed in a beaker.
(3) 1 g of the sample was precisely weighed [W2 (g)], cut into small pieces so as not to be wrapped around the stirrer, placed in the beaker prepared in (2), and stirred with a stirrer for 15 minutes. The stirred sample was suction filtered. 60 mL of the filtrate was taken and titrated with a 0.1 mol / L hydrochloric acid aqueous solution using phenolphthalein as an indicator, and the titration amount was X2 (mL).
(4) Based on the following formula, the amount of H-type carboxyl group Z (mmol / g), the amount of salt-type carboxyl group U (mmol / g), the ratio (%) of the amount of H-type carboxyl group, and the salt-type carboxyl group. The proportion (%) of the amount of was calculated.
Amount of H-type carboxyl group Z (mmol / g) = [{(0.1 × 20)-(0.1 × X2)] × (120/60)] / W2
Amount of salt-type carboxyl groups U (mmol / g) = total amount of carboxyl groups Y (mmol / g) -amount of H-type carboxyl groups Z (mmol / g)
Percentage of amount of H-type carboxyl group (%) = {Amount of H-type carboxyl group Z (mmol / g)}
/ {Total amount of carboxyl groups Y (mmol / g)} x 100
Percentage of amount of salt-type carboxyl groups (%) = {Amount of salt-type carboxyl groups U (mmol / g)}
/ {Total amount of carboxyl groups Y (mmol / g)] x 100

(Contact angle of fabric with water)
(1) Ion-exchanged water was put into a 25 mL burette (manufactured by AS ONE) and set on a burette stand.
(2) The distance between the tip of the burette and the cloth was set to be 1 cm.
(3) One drop (0.049 mL) of ion-exchanged water was dropped, and 10 seconds after landing, the contact angle of the cloth with the water drop was measured. The measurement was performed at n = 2, and the contact angles of both the left and right water droplets were measured and averaged.

(Surface tension of fabric)
(1) As shown in Table 1 below, ethanol and distilled water were mixed to prepare reagents having different ethanol concentrations, which were used as a standard for surface tension.
(2) Reagents were added dropwise onto the measurement sample in ascending order of concentration.
(3) The surface tension of the reagent when the contact angle was maintained at 90 ° or more after standing for 30 seconds was used as the reference value of the surface tension of the measurement sample. That is, the surface tension of the measurement sample is smaller than the reference value.

(Washing fastness)
Measurements were taken at the Kaken Test Center, a general incorporated foundation, in accordance with JIS L 0844 A-2.

(Sweat fastness)
It was measured at the Kaken Test Center, a general incorporated foundation, according to JIS L 0848.

(Washing process)
The washing treatment was performed 10 times by the method specified in JIS L 0217 103 method.

(Example 1)
[Preparation of water-repellent regenerated cellulose fiber]
<< Preparation of viscose solution for spinning >>
Acrylic acid-maleic acid copolymer salt aqueous solution ("Aqualic TL400" manufactured by Nippon Catalyst Co., Ltd., an aqueous solution containing 40% by mass of acrylic acid-maleic acid copolymer sodium having a weight average molecular weight of 50,000, viscosity: 1990 mPa. s, The content of maleic acid in the acrylic acid-maleic acid copolymer sodium is 45% by mass) so that the acrylic acid-maleic acid copolymer salt is 5% by mass with respect to 100% by mass of cellulose. It was added to the raw material biscous and mixed by stirring with a mixer to prepare a biscous solution for spinning. The temperature was kept at 20 ° C. The raw material viscose contained 8.5% by mass of cellulose, 5.7% by mass of sodium hydroxide, and 2.8% by mass of carbon disulfide. In Examples and Comparative Examples, the viscosity was measured at 20 ° C. using a B-type viscometer manufactured by Tokyo Keiki Co., Ltd. The weight average molecular weight of the compound containing a carboxyl group was measured and calculated as described later.
<< Spinning process >>
The obtained viscose liquid for spinning was spun by a two-bath tension spinning method at a spinning speed of 50 m / min and a draw ratio of 50% to obtain a viscose rayon yarn having a fineness of 1.4 dtex. As the first bath (spinning bath), a Mueller bath (50 ° C.) containing 100 g / L of sulfuric acid, 15 g / L of zinc sulfate, and 350 g / L of sodium sulfate was used. A circular nozzle (hole diameter 0.06 mm, number of holes 4000) was used for the spinneret for discharging viscose.
《Refining process》
The viscose rayon yarn obtained above was cut to a fiber length of 38 mm, treated with hot water, washed with water, and sodium hydrosulfide was showered for desulfurization. The obtained treated cotton was washed with water again, bleached with sodium hypochlorite, pickled and then washed with water. After that, the fibers were squeezed with a compression roller so that the water content became 130%. In the regenerated cellulose fiber (before the water repellent treatment), the ratio of the H-type carboxyl group to the total amount of the carboxyl group was 94%, and the amount of the H-type carboxyl group was 0.53 mmol / g.
《Water repellent finish》
First, a hydrocarbon-based water repellent composition ("Neoseed NR-158" manufactured by NICCA CHEMICAL CO., LTD.) Is used as a non-fluorine-based water repellent agent, and a blocked isocyanate-based cross-linking agent (manufactured by NICCA CHEMICAL CO., LTD. Using "NK Assist NY-30", solid content concentration 40% by mass), mix so that the mass ratio of water repellent (water repellent particles): cross-linking agent (solid content) is 5: 1 to make water repellent. A processing liquid for processing was obtained. Next, the fibers having a water content of 130% obtained above were immersed in a water-repellent treatment liquid (50 ° C.) for 30 seconds. The bath ratio of the fiber: water-repellent treatment liquid was set to 1:10. Then, the fibers are squeezed with a compression roller so that the adhesion rate of the water repellent (solid content) to the fibers is 1% by mass, and then dried in a dryer set at 100 ° C. for 10 minutes to obtain the fibers A. Obtained. The actual temperature at this time was 85 ° C. The total amount of carboxyl groups in the obtained water-repellent regenerated cellulose fiber was 0.52 mmol / g.

[Preparation of fabric]
A 30-count (30S) spun yarn was produced by using 100% by mass of the fiber A. Using 100% by mass of the spun yarn, a tubular knitting (mesh 130 g / m ² ) was produced by a conventional method.
The unrefined and unbleached fabric (cylinder knitting) obtained above is immersed in an aqueous solution containing 0.1 g / L of JAFET standard-blended detergent (blended with polyoxyethylene alkyl ether and sodium alphaolefin sulfonate) (bath). Ratio 1:30) Stirring for 5 minutes, then dehydrating and washing twice with a bath ratio of 1:30 to adjust the water content to about 100%. After the hydrophilized fabric was air-dried at room temperature (about 23 ° C), the contact angle with water was measured and found to be smaller than the contact angle of the hydrophilized fabric with water (contact angle is 77 °). It was confirmed that it was hydrophilic.
The hydrolyzed cloth (moisture content of about 100%) obtained above is subjected to a reaction dyeing bath (Glauber's salt 42 g / L, sodium carbonate 5 g / L, reaction dye: Sumifix Supra) BLUE BRF (blue). After immersing in (2.1% owf composition) at 25 ° C. for 40 minutes, dyeing was performed at a temperature of 50 ° C. and a time of 60 minutes. The bath ratio was 1:50. Then, it was soaped at 0.5 g / L of Sencanol C-100 (bath ratio 1:30) at a temperature of 60 ° C. for 10 minutes, and then washed with hot water at 70 ° C. for 10 minutes.
Next, the dyed fabric was treated at 150 ° C. for 10 seconds and dried.

(Comparative Example 1)
A fabric was produced in the same manner as in Example 1 except that the unrefined and bleached fabric (cylinder knitting) was used as it was in the dyeing step without being hydrophilized.

The washing fastness, sweat fastness, contact angle (also referred to as water repellent angle) and surface tension of the fabrics of Examples and Comparative Examples were measured as described above, and the results are shown in Table 2 below. In addition, the presence or absence of uneven dyeing of the fabrics of Examples and Comparative Examples was visually observed, and the results are shown in Table 2 below.

As can be seen from the results in Table 2, in the examples, it was possible to obtain a fabric having no uneven dyeing and high washing fastness and sweat fastness. In addition, the water repellency of the fabric was also good, and the washing durability of the water repellency was also good. On the other hand, in Comparative Example 1, since the hydrophilic treatment was not performed before dyeing, uneven dyeing occurred.

The fabric of the present invention can be used for clothing, industrial materials and the like.

Claims (9)

A water-repellent fabric containing regenerated cellulose fibers.
The water-repellent regenerated cellulose fiber contains a compound containing one or more acidic groups selected from the group consisting of a carboxyl group and a sulfonic acid group, and a cross-linking agent and a non-fluorine-based water-repellent agent are bonded to the fiber surface. ,
The water-repellent fabric is dyed with a reactive dye and
The water-repellent fabric is a water-repellent fabric having a contact angle with water of 90 ° or more. The water-repellent fabric according to claim 1, wherein the non-fluorine-based water repellent is a hydrocarbon-based water repellent. The water-repellent fabric according to claim 1 or 2, wherein the compound containing a carboxyl group is one or more selected from the group consisting of polyacrylic acid and acrylic acid-maleic acid copolymers. The water-repellent regenerated cellulose fiber according to any one of claims 1 to 3, wherein the water-repellent fabric contains the water-repellent regenerated cellulose fiber in an amount of 50% by mass or more and 100% by mass or less. A method for producing a water-repellent fabric containing water-repellent regenerated cellulose fibers.
A non-fluorinated water repellent is bonded to the fiber surface of a regenerated cellulose fiber containing a compound containing one or more acidic groups selected from the group consisting of a carboxyl group and a sulfonic acid group with a cross-linking agent to obtain a water-repellent regenerated cellulose fiber. Process,
The step of obtaining a water-repellent fabric containing the water-repellent regenerated cellulose fiber,
A step of adding an aqueous solution containing water and / or a surfactant to the water-repellent fabric to hydrophilize the fabric, and
The step of dyeing the hydrophilized water-repellent fabric with a reactive dye,
A method for producing a water-repellent fabric, which comprises a step of drying the dyed fabric. The method for producing a water-repellent fabric according to claim 5, wherein the hydrophilic treatment is performed immediately before the step of dyeing. The method for producing a water-repellent fabric according to claim 5 or 6, wherein the drying is performed at a temperature of 60 ° C. or higher. The method for producing a water-repellent fabric according to any one of claims 5 to 7, wherein the cross-linking agent is an isocyanate compound. The method for producing a water-repellent fabric according to any one of claims 5 to 8, wherein the surfactant contains at least one selected from the group consisting of a nonionic surfactant and an anionic surfactant.