JPH0633317A - Yarn having excellent durable water repellency and its production - Google Patents

Abstract

PURPOSE:To obtain yarn having excellent durable water repellency, showing water-repellent effects not simply reducing by washing, friction during wearing, etc. CONSTITUTION:Yarn comprises a sheath-core type structure having a ratio of a core component/a sheath component of 60/40-95/5wt.% wherein the sheath component contains 2-15wt.% modified silica fine particles which are made hydrophobic with methyl group, trimethyl group or octylsilane and have 50-150m<2>/g specific surface area and <=90wt.% SiO2 content.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber having excellent durable water repellency and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, various methods have been proposed as techniques for increasing the water repellency of textile products. For example, a method of treating a fiber cloth with a silicone-based or fluorine-based water-generating agent (JP-A-48-103900, JP-A-49-10169).
No. 7, etc.), a method in which ultrafine fibers are made into a high-density woven fabric and further treated with a silicone-based or fluorine-based water-generating agent (JP-A-52-
121571, JP-A-52-1552692, JP-A-53-38762, and JP-A-56-37.
No. 9, JP-A-59-130367, JP-A-Sho 6
0-239565).

However, the water-repellent effect obtained by these methods has been problematic in that the water-repellent agent gradually falls off due to friction during washing and wearing, and thus the durability of the water-repellent effect is difficult. .

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a fiber having a very excellent durable water-repellent property without easily deteriorating the water-repellent effect due to friction during washing or wearing, and a method for producing the same. To provide.

[0005]

The water-repellent fiber according to the present invention for achieving the above object is composed of at least one kind of fiber-forming polymer and has a core component / sheath component ratio of 60 /.
40 to 95/5% by weight of a fiber having a substantially core-sheath structure, and the sheath component is hydrophobized with a methyl group, a trimethyl group or octylsilane and has a specific surface area of 50 to
It is characterized by containing 2 to 15% by weight of modified silica fine particles having 150 m ² / g and a SiO ₂ content of 90% by weight or more.

Further, the method for producing this fiber is
Hydrophobized with trimethyl group or octylsilane, specific surface area 50-150 m ² / g, SiO ₂ content 9
While using a fiber-forming polymer containing 2 to 15% by weight of modified silica fine particles of 0% by weight or more as a sheath component, the content of the modified silica fine particles is smaller than that of the sheath component or contains the modified silica fine particles. A fiber-forming polymer that does not exist is used as a core component, and both components have a core component / sheath component ratio of 60.
It is characterized in that it is spun into a core-sheath type fiber of / 40 to 95/5% by weight.

In the production method of the present invention, it is preferable that the core-sheath type fiber after spinning is further subjected to dissolution reduction treatment on the surface of the sheath component. In order to make the dissolution weight loss treatment more effective, the core component and the sheath component of the core-sheath fiber are made of polymers having different solubility weight loss properties, and the sheath component has a higher solubility weight loss property than the core component. It is advisable to arrange a polymer. Alternatively, the sheath component of the core-sheath fiber may be composed of a mixed polymer of hot water-soluble polyester and non-hot water soluble polyester.

In another embodiment, the above-mentioned core-sheath type fiber is once formed into a sea-island type polymer mutual array fiber containing at least one or more as an island component, and this polymer mutual array fiber is subdivided. It is also possible to separate the core-sheath type fiber and subject the surface of the sheath component of the separated core-sheath type fiber to the dissolution weight loss treatment. Hereinafter, the present invention will be described in detail.

In the present invention, as the polymer forming the core component and the sheath component constituting the core-sheath fiber, polyester and its copolymers, polyamide and its copolymers, polyacrylonitrile and its copolymers are used. , Polyolefins and the like. Above all,
Polyesters and copolymers thereof, polyamides and copolymers thereof are particularly preferable. When the homopolymer polymer side is used as a core component and the copolymer polymer side is used as a sheath component, spinnability and processability are improved. In terms of both productivity such as and fiber characteristics such as strength, a fiber having an excellent aspect can be obtained.

In the present invention, the modified silica fine particles contained in the sheath component of the core-sheath fiber are very important. The modified silica fine particles are hydrophobized with a methyl group, a trimethyl group or octylsilane and have a specific surface area of 50 to 150.
m _² / g, SiO ² content is used as 90% by weight or more. Then, 2 to 15% by weight of at least one type of modified silica fine particles having such characteristics is contained.

The surface of the modified silica fine particles is chemically hydrophobized with a methyl group, a trimethyl group or octylsilane as described above, so that the water-repellency durability is longer than that of a physically hydrophobized one. Can be made even better. The modified silica fine particles having a specific surface area of 50 m ² / g or more can be uniformly and evenly dispersed in the coating thickness of the sheath component polymer, so that the water repellency of the fiber is higher. Can be This specific surface area is more preferably 80 m ² /
It is better to be g or more, and when the core-sheath type fiber is extra fine denier, it is desirable to have a specific surface area larger than that. However, if the specific surface area becomes so large as to exceed 150 m ² / g, the kneading processability deteriorates and secondary aggregation easily occurs, which is not preferable.

[0012] Further, SiO of hydrophobic silica fine particles
_{When the} content of ₂ is 90% by weight or more, the density of methyl group, trimethyl group or octylsilane can be made very high, and the improvement of hydrophobicity can be made advantageous. This SiO ₂ content is preferably 95% by weight
The above is better. Examples of the modified silica fine particles satisfying the conditions of the present invention as described above include, for example, Nippon Aerosil
Modified silica fine particles manufactured by Co., Ltd., product numbers R972 and R80
5, etc. can be mentioned.

The amount of the modified silica fine particles satisfying the above conditions added to the sheath component is 2 to 15% by weight, preferably 4 to
The range is 10% by weight. If the added amount is less than 2% by weight,
The desired water repellent property of the present invention cannot be obtained sufficiently. On the other hand, when the amount added exceeds 15% by weight, the polymer chip forming property tends to be deteriorated, and knotting yarn is generated during spinning, or the take-up property is deteriorated.

The sheath component containing these modified silica fine particles has a core component / sheath component ratio of 60/40 with respect to the core component.
~ 95/5 wt%, preferably 60/40 to 90/10
It is good to make it into the weight%, more preferably 70/30 to 80/20 weight%. If the ratio of the sheath component to the core component exceeds 40% by weight, the fiber strength will decrease. Also, 5
If it is less than wt%, the water repellency and water repellency are reduced. By setting the sheath component in the above range, a part of the modified silica fine particles can be exposed on the surface of the sheath component, and the water-repellency of the methyl group, trimethyl group or octylsilane and the fine irregularities formed by the ultrafine particles. By the synergistic action with, it becomes possible to obtain fibers having extremely high water repellency.

In order to further improve the water-releasing performance, it is preferable to increase the exposed area where the modified silica fine particles are exposed on the surface of the sheath component. To increase this exposed area,
It is desirable to reduce the surface of the sheath component of the core-sheath type fiber after spinning, as in the fiber production method of the present invention described later. Further, in order to prevent the modified silica fine particles from falling off and further improve the durability, it is desirable to strengthen the adhesiveness between the modified silica fine particles and the sheath component polymer. for that purpose,
For example, post-processing may be performed with a crosslinking agent such as a silane coupling agent.

The core-sheath type of the core-sheath type fiber is sufficient if the sheath component covers the core component, so that the sheath component and the core component do not necessarily have to be concentric and eccentric. It does not matter if you The cross-sectional shape of the core-sheath fiber is
There is no particular limitation such as a circular cross section, a triangular cross section, and a Y-shaped cross section. The fineness of these core-sheath fibers may be 10 denier in consideration of strength, abrasion resistance, sheet formability, etc., as long as they are used in the field of industrial materials. If it is used in the field of clothing, it should be 5 denier or less. Above all, in order to obtain a water-repellent fabric that is particularly soft and has a good feel, it is preferable to make the fineness of 1 to 0.05 denier.

In the method for producing fibers of the present invention described above, at least one of which is hydrophobized with a methyl group, a trimethyl group or octylsilane and has a specific surface area of 50 to 150 m ² / g and a SiO ₂ content of 90% by weight or more. A fiber-forming polymer containing 2 to 15% by weight of modified silica fine particles is used as a sheath component, and a fiber-forming polymer containing less or no content of the modified silica fine particles than the sheath component is used as a core component. Both components have a core component / sheath component ratio of 60 /
Spun into a core-sheath type fiber of 40 to 95/5% by weight,
It is obtained by subjecting this to a stretching treatment so as to give a predetermined fiber denier, and then removing the spinning oil agent and the stretching oil agent.

In the thus obtained core-sheath type fiber, the modified silica fine particles themselves exposed on the surface of the sheath component are hydrophobized with methyl group, trimethyl group or octylsilane,
Since the number of water-releasing groups on the surface of the fine particles is extremely large, it exhibits high water-repelling property and high water-releasing durability. In this case, if the surface of the sheath component of the core-sheath type fiber is appropriately dissolved and reduced by a solvent, finer micro-concavities and convexities are formed on the surface of the fiber, which is preferable for further enhancing the water repellency.

In order to further enhance the effect of such a dissolution weight loss treatment, a polymer having different solubility weight loss properties is combined as a core component and a sheath component forming polymer, and a polymer having a high solubility weight loss property is used for the sheath component. It should be set to. For example, using polyethylene terephthalate as the core component,
A combination using 5-sodium sulfoisophthalate copolyester as a sheath component can be mentioned. A low-concentration alkaline solution may be used as a solvent for the dissolution weight loss treatment. The low-concentration alkaline solution can slightly reduce the surface of the sheath component to increase the residual degree of the modified silica fine particles and prevent the influence on the core component-forming polymer. Further, if the core component is polyethylene terephthalate having a high degree of polymerization, the fiber strength can be increased, and the effect can be improved as the fiber becomes ultrafine.

The dissolution reduction treatment is preferably carried out to such an extent that the surface of the sheath component is slightly dissolved so that the modified silica fine particles remain on the surface of the sheath component as much as possible. Such treatment may be carried out by appropriately adjusting the treatment temperature, concentration and time. In order to effectively leave the modified silica fine particles on the surface of the sheath component, the sheath component may be a hot water-soluble polyester. It is preferable to use a mixed polymer of non-hot water soluble type polyester. By using such a mixed polymer, it is possible to improve processing stability during weight reduction treatment.

Further, the sheath component is a hot water-soluble polyester /
When a mixed polymer of non-hot water soluble type polyester is used, the modified silica fine particles are preliminarily contained in the non hot water soluble type polyester, and the hot water soluble type polyester is mixed and spun. Good to do. By such a mixing method, it is possible to increase the residual rate of the modified silica fine particles after the dissolution reduction treatment and to generate micro unevenness on the surface layer of the sheath component.

The hot water-soluble polyester referred to here is
It refers to a polymer having a low crystal orientation and further imparting hydrophilicity, and examples thereof include polymers described in JP-B-1-6286. These hot-water-soluble polyesters can be easily weight-reduced with an extremely low-concentration alkaline solution or hot water of 80 ° C. or higher, so that the hot-water-soluble polyester existing near the surface of the sheath component is prioritized. The amount of the non-hot water soluble polyester is effectively left while the amount of the non-hot water soluble polyester is effectively reduced. Therefore, the exposure of the modified silica fine particles contained in the non-hot water soluble type polyester and the micro unevenness caused by the dissolution weight loss of the hot water soluble type polyester can be remarkably revealed, and the water-generating effect is further enhanced. be able to.

Since the above-mentioned mixed polymer can be subjected to weight reduction treatment with hot water, use of this hot water weight reduction treatment makes it easier to control as compared with weight reduction treatment with an alkaline solution, and is economically and environmentally preferable. can do. In order to further improve the effect of the hot water reduction treatment, the mixing ratio of hot water soluble type polyester / non-hot water soluble type polyester is 30/70 to 5/95% by weight,
It is preferably 20/80 to 5/90% by weight.

The effect of the fiber of the present invention can be further improved by making the fiber extremely fine. As a method for making the fibers ultrafine, the sea-island type polymer mutual array fibers in which at least one core-sheath type fiber is arranged as an island component are once formed, and then the fibers are subdivided into It is advisable to separate the core-sheath fibers. In the case of the sea-island type polymer mutual array fiber, it is preferable to distribute the sea-island component so that the residual rate of the core-sheath type fiber after the subdivision treatment is 80% by weight or more. That is, even the same woven or knitted fabric can have higher density and higher water repellency.

In the above-mentioned polymer mutual array fiber, it is preferable to use a polymer having a solubility different from that of the core-sheath fiber as the sea component. For example, polystyrene, polyethylene and their copolymers can be preferably used. Using these polymers as a sea component, a polymer mutual array type spinner which can be spun so that at least one core-sheath type island component is arranged therein is spun into a polymer mutual array fiber, and then stretched. After that, the sea component may be removed with a solvent and finely divided.

Further, in the polymer inter-array fiber, the sea component is not necessarily combined with the core-sheath type fiber in different solubility, and the same polymer as the sheath component of the core-sheath type fiber is used. You can also For example, the sea component is hot water-soluble polyester, and the sheath component of the core-sheath fiber is a mixed polymer of hot water soluble polyester / non-hot water soluble polyester, or the sea component is 5-sodium. For example, sulfoisophthalate copolymerized polyester is used, and the core component of the core-sheath fiber is 5-sodium sulfoisophthalate copolymerized polyester. When the polymer inter-array fibers are subdivided using hot water or an alkaline solution, the resulting ultrafine core-sheath fibers can be made into fibers with extremely high water repellency. More preferably, after subdividing the polymer mutual array fibers in this manner, the surface of the sheath component of the ultrafine core-sheath fiber obtained is further subjected to a weight reduction treatment.

In the present invention, in order to further enhance the water retention of the core-sheath type fiber, a cross-linking agent such as a silane coupling agent is added to the core-sheath type fiber after the subdivision treatment and the weight reduction treatment to form a sheath component polymer. The modified silica fine particles may be firmly bonded to each other. By such treatment, the friction durability is improved and the water-releasing durability can be further enhanced. The water-repellent fiber of the present invention described above is intentionally impregnated with a conventional water-repellent resin,
Since there is no need for coating, it is possible to prevent the softness, breathability, and moisture permeability of the woven or knitted fabric or the raised fabric from being deteriorated. Also, taking advantage of these features,
Waterproof clothing, such as raincoats, windbreakers, sports clothing, or rain gear such as umbrellas, curtains, tablecloths, and even ropes that utilize water
It can be an industrial material such as a net or a brush. In addition, this fiber is used as a cut pile by making it extremely fine, and by making it a dense woven or knitted fabric, it is partially exposed to the adhesion preventing base material of seawater living organisms or the algae cultivation rope, and the rope with controlled breeding degree etc. Can be suitably used.

[0028]

【Example】

Example 1 Polyethylene terephthalate having an average particle size of 20 μm
Fine particles with an intrinsic viscosity of 0.68 and modified silica fine particles (manufactured by Nippon Aerosil Co., Ltd., product number R972, specific surface area 110)
m ² / g, SiO ₂ content 99.8%) with a mixing ratio of 92/8% by weight, stirring and mixing with a Henschel mixer, followed by vacuum drying and use in an extruder to form chips.
(Hereinafter referred to as chip A).

Next, using a sea-island type polymer mutual array core-sheath cap (island component is a core-sheath type and the number is 16), the sea component is polystyrene, and the island component has a high degree of polymerization polyethylene terephthalate. (Intrinsic viscosity 1.0), chip A is placed on the sheath component, and the island component / sea component ratio = 90 /
Polymer inter-array fibers with 10 wt% and core / sheath ratio = 70/30 wt% were spun. The obtained unstretched yarn was dry-heat stretched at a draw ratio of 3.2 to obtain a 54D-18F stretched yarn.

Then, this drawn yarn is woven density warp × weft = 15
Processed into a plain weave of 8 x 120 pieces / in, and scouring this weave.
After washing with hot and cold water, drying, desealing with trichlorethylene, and heat setting for a specified width with a pin tenter in the 150 ° C-160 ° C-180 ° C zone
(A) was created. Example 2 Chip A described in Example 1 and a hot water-soluble polyester chip (TPI / IPA / SI = 70/18/12 mol)
% And intrinsic viscosity 0.92) were mixed at a ratio of 93/7% by weight to prepare 56D-18F drawn yarn under the same conditions as in Example 1 except that the sheath component was used.

The drawn yarn was subjected to fabric processing and sea removal treatment under the same conditions as in Example 1. Then, it was put into a circular dyeing machine, treated at a hot water temperature of 90 ° C. for 30 minutes, washed with water and dried to a constant weight, and then heat set under the same conditions as in Example 1 to prepare an ultrafine fiber fabric (B). Comparative Example Using the chips used in Example 1 before atomizing the polyethylene terephthalate as the sheath component in the island component, spinning drawing was performed in the same manner as in Example 1 to produce 56D-18F drawn yarn. Next, this drawn yarn was treated under the fabric processing and post-processing conditions of Example 1 to obtain a fabric. A 5% water-diluted solution of Asahi Guard AG-710 (manufactured by Asahi Glass Co., Ltd., emulsion) was dipped on this woven fabric, lightly squeezed with a mangle to make a constant weight at 90 ° C. to prepare an ultrafine fiber material (C).

Three types of fabrics obtained as described above
The water discharge performance of (A), (B), and (C) is JIS L-10.
92 (Spray method) When measured under the prescribed conditions,
The results shown in Table 1 were obtained. From the measurement results, the measured value I immediately after processing shows good water repellency for each woven fabric, but the measured value II after forcibly rubbing the surface of these woven fabrics is While the water repellency is reduced, the woven fabrics of the present invention of Examples 1 and 2 (A)
(B) did not decrease and had excellent wear durability.

[0033] Water repellency measurement conditions Measurement value I: A value obtained by measuring the surface of the fabric after heat setting.

Measured value II: A cotton / polyester blended taffeta was wound around the surface of a metal roller having a diameter of 10 cm and rotated at 60 times / minute, and 25% of the taffeta surface was brought into contact with the fabric to be measured which had been heat-set. 5 at the bottom of the measured fabric
A value obtained by measuring the frictional surface after attaching a load of 00 g and rotating for 5 minutes.

[0035]

As described above, according to the present invention, a fiber is made into a core-sheath structure by at least one kind of fiber-forming polymer, and the sheath component has a predetermined specific surface area and S.
Since the modified silica fine particles having an iO ₂ content and hydrophobized with a methyl group, a trimethyl group or octylsilane are contained, a fiber having an excellent durable water-repellent property in which the water-repellent property is not easily deteriorated by friction or the like is provided. You can

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location D06M 11/38 // D01F 6/92 301 M 7199-3B Q 7199-3B D06M 101: 16

Claims (7)

[Claims] 1. A core / sheath ratio of 60/40 to 95 which is composed of at least one fiber-forming polymer.
/ 5% by weight of a substantially core-sheath type fiber, and the sheath component is hydrophobized with a methyl group, a trimethyl group or octylsilane and has a specific surface area of 50 to 150 m ^2.
/ G, ₂ to 15% by weight of modified silica fine particles having a SiO ₂ content of 90% by weight or more, and a fiber having excellent durable water repellency. 2. A hydrophobized with a methyl group, a trimethyl group or an octylsilane and having a specific surface area of 50 to 150 m.
² / g, a fiber-forming polymer containing 2 to 15% by weight of modified silica fine particles having a SiO ₂ content of 90% by weight or more is used as a sheath component, while the content of the modified silica fine particles is smaller than that of the sheath component. Alternatively, a fiber-forming polymer not containing the modified silica fine particles is used as a core component, and both components are spun into a core-sheath type fiber having a core component / sheath component ratio of 60/40 to 95/5% by weight. A method for producing a fiber having excellent durability and water repellency. 3. The method for producing a fiber having excellent durable water-repellent property according to claim 2, wherein the surface of the sheath component of the core-sheath fiber is subjected to dissolution weight loss treatment. 4. The durable water-repellent property according to claim 2, wherein the sheath component of the core-sheath type fiber is composed of a polymer having a higher dissolution weight loss property than the core component, and the surface of the sheath component is subjected to the dissolution weight loss treatment. Fiber manufacturing method. 5. The sheath component of the core-sheath type fiber is composed of a mixed polymer of hot water-soluble polyester and non-hot water soluble polyester, and the surface of the sheath component is subjected to dissolution weight loss treatment. A method for producing a fiber excellent in durable water repellency. 6. The core-sheath type fiber is produced by producing a sea-island type polymer mutual array fiber containing at least one core-sheath type fiber as an island component, and subjecting the polymer mutual array fiber to subdivision. The method for producing fibers excellent in durable water repellency according to claim 2, wherein the fibers are separated. 7. The fiber having excellent durable water-repellent property according to claim 6, wherein the core-sheath type fiber separated by subdividing the polymer mutual array fiber is further subjected to dissolution weight reduction treatment on the surface of the sheath component. Production method.