WO2000065135A1

WO2000065135A1 - Polyparaphenylene terephthalamide fiber and method for producing the same

Info

Publication number: WO2000065135A1
Application number: PCT/JP1999/002195
Authority: WO
Inventors: Takeshi Hatano; Shiro Sakamoto; Kazuhiko Kosuge
Original assignee: Du Pont-Toray Co., Ltd.
Priority date: 1998-10-22
Filing date: 1999-04-26
Publication date: 2000-11-02
Also published as: CA2336245A1; ATE399890T1; BR9911583A; AU763815B2; EP1101843B1; EP1101843A1; CA2336245C; AU3536399A; CN1205365C; CN1314959A; EP1101843A4; EP1101843B2; BR9911583B1

Abstract

A dyeable polyparaphenylene terephthalamide fiber which has been wound once after spinning and has not be dyed yet, characterized in that it has a tensile strength of 15 g/denier or more and a crystal size (110 direction) of 30 to 55 angstroms and has been dried to have a water content of 8% or less, and in that it has no history of treatment, and a method for producing the same. A polyparaphenylene terephthalamide fiber which has capability of being dyed without detriment to excellent inherent properties of high strength and high modulus elasticity, and textile products made of the fiber which are dyed in a variety of colors can be provided.

Description

Specification

POLYBARAPHENE LENTIRE PHTHALAMIDE FIBER AND PROCESS FOR PRODUCING THE SAME

Technical field

TECHNICAL FIELD The present invention relates to a para-aramid woven fiber maintaining high strength and a high elastic modulus, and a method for producing the same.

Background technology

Polyparaphenylene terephthalamide fiber (hereinafter referred to as para-aramid fiber) has high functionality, such as high strength, high elastic modulus, high heat resistance, non-conductivity, and no cracks. It is a synthetic fiber that combines the flexibility and lightness of organic fibers. Due to these features, it is used as a reinforcing material for tires for automobiles, motorcycles and bicycles, toothed belts for automobiles, and conveyors. It is also used for reinforcing optical fiber cables and ropes. In addition, applications are being made to bulletproof vests, work gloves that use the property of being difficult to cut with blades, protective clothing such as work clothes, and fire clothes that use flame resistance.

In these applications, dyeing properties are required in addition to the above-mentioned properties.However, it is difficult to dye aramid textiles because of its high crystallinity, strong intermolecular bonding force and dense structure. there were.

The following means have been proposed as methods for dyeing aramide fibers.

Japanese Patent Application Laid-Open No. 50-123232 proposes a method in which additives such as a dye, an antioxidant, an ultraviolet ray blocking agent, and a flame retardant are diffused into fibers swollen with water. However, Japanese Patent Application Laid-Open No. 50-122322 does not describe the diffusion of all kinds of dyes into textiles, and does not specify the conditions. In particular, there is no description about staining at a water content of 50% or less.

Japanese Patent Application Laid-Open No. 54-594476 discloses a method of applying a crimp of 10 or more inches and dyeing from a buckled portion. Also, Japanese Patent Application Laid-Open No. 2-41414 discloses a method of adding an organic pigment to a spinning dope. In addition, Japanese Patent Application Laid-Open No. 63-145454 proposes a method of bringing a para-oriented type of amide into a process of reducing tension during coagulation immediately after spinning and bringing the same into contact with a dye solution. I have. Further, Japanese Patent Application Laid-Open No. 7-258890 discloses a method of contacting a para-aromatic polyimide having an intrinsic viscosity of 2.5 d 1 / g or less with a dye solution in a state of being swollen with water. Has been proposed. Japanese Patent Application Laid-Open No. 8-260362 discloses a method of dyeing at 130 ° C. or higher with a cationic dye using a textile swelling agent. Japanese Patent Application Laid-Open No. Hei 5-209372 discloses a method for dyeing a copolymerized para-aramid fiber at a temperature of 160 ° C. or more using a disperse dye having a molecular weight of 400 or less. . In addition, JP-A-9-87979 and JP-A-9-87979 have disclosed that para-aramid fibers are treated with a polar solution such as dimethyl sulfoxide after the treatment. A method for high-pressure staining at ° C has been proposed.

However, the method described in the above-mentioned Japanese Patent Application Laid-Open No. 54-59476 does not industrially crimp 10 crimp inches or more of high-strength, rigid para-aramid fibers. It is difficult and it is limited to stable. Japanese Unexamined Patent Publication No. Hei 2-414414 proposes a so-called spinning spinning method, and the method described in Japanese Unexamined Patent Publication No. Sho 63-145254 discloses a method of once winding immediately after spinning. This is a method of contacting the dyeing liquor without tension. All of them require quantitative production per color and have limited hues. The method described in Japanese Patent Application Laid-Open No. 7-258980 has extremely low fiber strength due to low polymer viscosity, and does not have the characteristics of aramide fiber, which is a high-strength fiber. The method described in Japanese Patent Application Laid-Open No. Hei 8-266032 is a proposal for a spun yarn inferior to filament yarn in tensile strength and tensile elastic modulus, and utilizes the inherent high strength and high elastic modulus functions of the aramide fiber. It is not a means of dyeing filaments that can be used. The methods described in JP-A-5-209732, JP-A-9-87979 and JP-A-9-87979 have a polar solution recovery facility and a high temperature. It requires special equipment such as dyeing and is not common.

Until now, a method of post-dyeing, in which various types of colors can be developed in the form of filaments, which maintains the characteristics of high strength and high elastic modulus, which are the characteristics of aramide fibers, that is, once wound into a tube after spinning No method has been realized in which the process is discontinued, for example, by picking, and then transferred to a dyeing process in which individual colors can be dyed and dyed in various hues.

In general, the yarn forming process for forming filament fibers and the dyeing process for dyeing fibers are The process is different and is carried out by dedicated equipment and specialized technicians. In order to satisfy the strict customer requirements for the color of dyed textile products, once the fibers are formed, the process is stopped once, the fibers are transported to a dyeing factory, and a specialized dyeing technician dyes the colors to the colors required by the customer. That has important implications.

Disclosure of the invention

Accordingly, an object of the present invention is to provide a para-aramid fiber that can be dyed while maintaining the features of high strength and a high elastic modulus, and a para-aramid fiber dyed in various hues.

To achieve the above object, the present invention takes the following measures.

(1) Polyparaphenylene terephthalamide fiber, which has been spun and unwound before dyeing, has a tensile strength of 15 g Z denier or more, and a crystal size (110 direction) of 30 A dyeable polyparaphenylene terephthalamide fiber, characterized in that it has a dry history of up to 55 angstrom pi-medium and a water content of 8% or less.

(2) The dyeable polyparaffin perylene terephthalamide fiber according to the above (1), wherein the fiber has no history of drying to a water content of 15% or less.

(3) A dyeable staple obtained by applying a crimp of 4 to 9 ridges Z 25 mm to the fiber according to (1) or (2) above and forcing it to a fiber length of 20 to 150 mm. Polyparaphenylene terephthalamide fiber.

(4) A floc-like polyparaphenylene terephthalamide fiber obtained by cutting the fiber according to (1) or (2) above to 0.1 to 3 mm.

(5) A dyed polyparaffin-ylene terephthalamide fiber obtained by dyeing the fiber according to (1) or (2).

(6) The dyed polyparaffin-dentalene phthalamide fiber according to (5), which has been dyed with a cationic dye.

(7) Stable-shaped dyed polyparaphenylene terephthalamide fibers obtained by dyeing the step-shaped polyparaphenylene terephthalamide fibers described in (3) above.

(8) The stable-stained polyparaphe-dentalenephthalamide fiber of (7), which has been dyed with a cationic dye. (9) A floc-dyed polyparaphenylene terephthalamide fiber obtained by dyeing the floc-like polyparaphenylene terephthalamide fiber according to the above (4).

(10) The floc-dyed polyparaphenylene lenterephthalamide fiber according to the above (9), which is dyed with a cationic dye.

(11) A dope for spinning is prepared from polyparaphenylene terephthalamide having an intrinsic viscosity (inh) of 5 or more and concentrated sulfuric acid, and the dope is once spun into the air through the pores of a spinneret, and immediately in water. In the method of forming a high-strength, high-modulus filament in a step where the fiber is dyed, and a step of dyeing the filament in a separate step without being continuous, the fiber has a tensile strength of 1%. Dyeable polyparaffin water, characterized by having a denier of 5 gZ or more, a crystal size (110 direction) of 30 to 55 angstroms, and a water content of the fiber of always 8% or more. Evening luminide fiber manufacturing method.

(1 2) The dyeable polyparaphenylene terephthalamide fiber produced by the method described in (10) above is cheese-dyed with a cationic dye at a twist number of 0.2 or less represented by the following formula. how to.

K = (T ^ D) / 2 8 7 0

K: Combustion coefficient

T _: Number of twists (times m)

D: Fineness at absolute dryness (denier)

Forms for carrying out the invention

The polyparaphenylene terephthalamide (hereinafter sometimes abbreviated as “PPTA”) in the present invention is a polymer obtained by polycondensation of terephthalic acid and paraphenylenediamine. Also, those obtained by copolymerizing a small amount of dicarboxylic acid and diamine can be used. The polybarrazine perylene phthalamide fiber (hereinafter referred to as para-based aramide fiber) of the present invention is an optically anisotropic glass obtained from PPTA and concentrated sulfuric acid having an intrinsic viscosity of 5 or more (7 to inh). The dope is once spun into the air through the pores of the spinneret, immediately introduced into water and solidified, guided to a Nelson roller, neutralized with an aqueous solution of sodium hydroxide, and subjected to a water washing process. It is dried slightly by trawl and passes seamlessly through the process of winding it into a tube as filament. Obtained. The wound para-aramid fiber is wrapped in polyethylene film or the like so that it does not dry before the dyeing process. At this time, the crystallinity of the para-based amide fiber is 50% or less. At this stage, the tensile modulus of the fiber exceeds 400 g Z denier, and it has the performance as a high modulus yarn. The crystallinity usually exceeds 50% when heat-treated at 0 to 5 to 10 seconds.

The intrinsic viscosity (7? Inh) of PPTA used in the present invention is desirably 5 or more. If the intrinsic viscosity (V in) is less than 5, it is difficult to obtain a fiber material having high strength and high elastic modulus.

The para-aramid fiber of the present invention needs to have a crystal size (110 direction) force of 30 to 55 angstroms and always have a water content of 8% or more. If the crystal size is less than 30 angstroms, the densification of the fibers is insufficient, and high-strength, high-modulus fiber properties cannot be obtained. If it exceeds 55 angstroms, dyeing becomes difficult.

Here, that the water content is always 8% or more means that there is no history of drying below 8%. If the water content is dried to 8% or less, the structure becomes dense and dyeing becomes difficult. Even if water is added again, the dyeability does not recover. Preferably, the para-aramid fiber has a water content of 15 to 49%. If the water content is 50% or more, the frictional resistance to the guides becomes large, and winding becomes difficult. In order to achieve such a water content, it is desirable to dry the spun para-aramid fiber at a hot filter temperature of 100 to 150 for 5 to 20 seconds. If the drying temperature is lower than 100 ° C, it is difficult to remove water, and there is a problem in handling after winding the tube. When it exceeds 150, crystallization proceeds, and dyeing becomes difficult.

In the present invention, para-aramid fibers having such physical properties are stained. The dyeing method does not require special equipment or special methods, and existing synthetic fiber dyeing equipment can be used. This can be achieved by adjusting the pH by adding appropriate amounts of dyes, auxiliaries and acids, for example, starting the dyeing at 60 ° C., raising the temperature to 130 in 60 minutes and dyeing for 30 minutes. When the water content is less than 50%, the dye is most preferably a cationic dye which easily penetrates even into a dense structure.

The para-based amide fiber of the present invention is useful for various uses. Dyed para system Mid fiber filaments can be sewing threads, cords, ropes, and fabrics of each color. The para-aramid fiber woven fabric having a rich hue obtained according to the present invention can be used for sport clothing, satin, work clothes, firefighting clothing, various protective clothing, tent fabric, and the like. The bulletproof vest fabric dyed in an inconspicuous hue is inconspicuous even if the outer skin is torn and the outer skin is torn, exposing the para-aramid fiber fabric as the bulletproof fabric.

Further, applied products of the dyed para-aramid fiber of the present invention include automobile seat belts, protective clothing for boat racers, Japanese bow strings, tennis guts, fishing lines and the like. When the dyed para-aramid fiber of the present invention is used as a fiber reinforcing material of a transparent or translucent resin, a colored reinforcing material can be seen through the transparent or translucent resin, so that a colorful resin product can be obtained. It becomes possible. For example, plastic glasses frames, tennis rackets, table tennis rackets, hockey sticks, fishing rods, golf shafts, etc. When the resin is an elastomer, it is useful for resin transmission belts, resin hoses, bicycle tires, etc. The para-based aramide fiber of the present invention can also be applied to □ oop® electric wires, in which the production year is indicated by color. When multiple wires are collected and converged into a single wire, they can be used as reinforcing materials of different colors to both reinforce individual wires and identify terminals. It can be used as a so-called rip cord, which is located under the covering of the electric wire and is used to cut the covering and expose the terminal.

The dyed para-aramid fiber filaments are crimped to give 4 to 9 ridges / 25 mm crimp (for example, 6 crimps / inch) similar to commercially available para-aramid fibers, making it suitable for spinning. It is possible to obtain a para-aramid fiber stable that has been cut to a length of 20 to 150 mm and colored. By cutting the dyed para-aramid fiber into 0.1 to 3 mm without crimping, it can be used as a floc for electric flocking. The para-aramid fiber before dyeing according to the present invention may be cut with a clamp, cut into a step, and then dyed. Similarly, it can be cut and dyed to make flocks for electric flocking.

(Example)

Hereinafter, the present invention will be described by way of examples. The physical properties in the examples were based on the following measurements. (1) Crystal size

Wide angle X-ray analysis was used. • X-ray analyzer: Rigaku Denki Co., Ltd. Model 4036 A2

• X-ray source: Cu K line

Curved crystal monochromator (using graphite)

(2) Intrinsic viscosity

The intrinsic viscosity (inh) is measured by a conventional method at 30 using a solution prepared by dissolving a polymer in 98.5% by weight of concentrated sulfuric acid at a concentration (C) of 0.5 g / dl.

7? I n h = l n * 7? R e l ZC

(3) Strong elongation characteristics of fiber

The tensile strength and tensile modulus (initial tensile resistance) of the yarn were determined according to JIS-L-113.

(4) Moisture percentage

The moisture content was measured according to JIS-L-101.

Moisture content (%) = (W-W *) X 100 / W

Where: W: mass at the time of sampling

W: Mass of the sample when dry

(5) Nao

The measurement of the L value was in accordance with JIS—Z—8729. As a measuring instrument, MacbethhCholorEyes300, manufactured by Sumika Chemical Analysis Service, Ltd. was used.

Example 1, Comparative Example 1

PPTA (inh = 6.5) obtained by the usual method was dissolved in 99.9% concentrated sulfuric acid to give a spin dope with a polymer concentration of 19.0% and a temperature of 80 ° C, and a pore diameter of 0.0 After spinning out into the air for a short time from a die with 6 mm pores of 1000, it is introduced into water at 4 ° C to solidify it, guided to a Nelson roller, and treated with an 8% aqueous sodium hydroxide solution. After washing with water, drying with a hot roller at 110 ° C for 15 seconds and winding it into a plastic tube without interruption, the number of filaments is 100 A para-aramid fiber A (filament yarn) having a total fineness of 150 denier (equivalent to absolute dryness) was obtained.

Without winding the para-aramid fiber A into the tube, it was led to the installed hot-roller for a further 350. C, after heat treatment for 10 seconds, wind up, A dried para-aramid fiber B (filament yarn) was obtained.

Table 11 shows the physical properties of these para-aramid fibers.

Table 1

These para-aramid woven filament yarns were dyed dark blue under the following conditions. "owf" indicates the weight percent of dye based on dry fiber weight. gZl indicates the weight ratio of the auxiliaries to 1 liter of the prepared dyeing bath.

• Dye (cationic dye)

"ASTRAZON GOLDEN YELLOW G

(C I YE L LOW 28, DYSTER): 0. l% owf

"KAYACRYL RED G

(C I RED 29, manufactured by Nippon Kayaku): 2.0% owf

"A I Z E N C ATH I L ON B LUE T B L H"

(Hodogaya Chemical Co., Ltd.) 8.0% 0 wf

"NEODESPON AC" (Molin Chemical) 2 g / 1

Folic acid 1/1

Sodium nitrate 20 g / 1

Teryl Carrier A 1 1 1 "(Meisei Chemical): 20 gZl Take 10 g of para-aramid fiber yarn in terms of absolute dry weight, start dyeing at a bath ratio of 1:15, 60 ° C, and raise the temperature to 130 ° C in 60 minutes. Stained for minutes. After staining, the substrate was subjected to reduction washing at 80 ° C. for 20 minutes in a bath containing a nonionic activator and a reducing agent, and after dehydration and drying, the L value was measured. The smaller the L value, the lower the light reflection and the darker the color. In the case of the same hue, smaller values indicate better dyeing. In the dyeing method using the dyeing bath prepared as described above, a level of L value of 50 or less was determined to be dyed.

The para-aramid fiber A adsorbed the dye well, but the para-aramid fiber B was hardly dyed.

Examples 2 to 4, Comparative Example 2

Para-aramid fiber A was allowed to stand at room temperature to evaporate water, and the water content before dyeing was changed. Except for Comparative Example 2 with a moisture content of 5%, dye was well dyed _c Comparative Example 3

Para-aramid fiber A was dried with a circulating hot air dryer at 100 ° C. for 60 minutes, and dyed under the above conditions with a water content of 0%. It hardly dyed.

Table 12 shows these results.

Table 1 2

Example 5

Para-aramid weave A Without twisting the yarn, many holes with a diameter of 8 mm were drilled at the part where the yarn was wound.The inner diameter was 51 mm, the outer diameter was 57 mm, and the length was 250 mm. The plastic tube was wound up with a tension of 0.04 gZ denier. The winding amount was lkg in terms of absolute dry weight. This was dyed under the above-mentioned dyeing conditions using a cheese dyeing machine in which a dyeing solution was circulated from the hole formed in the plastic tube through the yarn to the outside of the cheese. The water content of the para-aramid fiber before dyeing was 48%. As the temperature during dyeing increased, the para-aramid fiber A released a small amount of water and decreased in volume, so gaps were formed between the fibers and the dye liquor circulated well. The L value of the para-aramid fiber A after staining was 45.5, indicating that the dye was well stained. Of dyed para-aramid Tensile strength 2 3. 0 g Z denier, tensile modulus, 5 6 High strength 5 denier, _c Comparative Example properties was achieved fully satisfactory as para-§ la Mi de O維high modulus Four

The para-aramid fiber A yarn was burned 74 times Zm, which corresponds to a twist coefficient of 1 shown in the following equation, with a ring twisting machine. This twisted yarn was dyed with cheese in the same manner as in Example 5. The filament yarn has a round cross-sectional shape due to the burning, and a space is formed between the fibers while being wound up by the plastic tube. It was good. However, inadequately stained areas with a low concentration partially occurred.

Filament water was released due to ballooning during twisting and centrifugal force applied to the rotating bobbin, and water droplets were observed to scatter around the twisting machine. As a result, a portion with low moisture was formed in the length direction of the para-aramid fiber, and the dyeing became insufficient.

K = (T v ^ D) / 2 8 7 0

K: Twist coefficient

：: Burning number (times m)

D: Fineness at absolute dryness (denier)

As described above, according to the present invention, polyparaphenylene terephthalamide fibers capable of maintaining characteristics of high strength and high elasticity and capable of being dyed, and polyparaphenylene terephthalamide fibers which are dyed in various hues are provided. Can be provided.

Industrial availability

In the present invention, dyeable polyparaphenylene terephthalamide fibers and polyparaphenylene terephthalamide fibers dyeable in various colors are provided while maintaining the features of high strength and high elastic modulus. The para-aramid fiber of the present invention is useful for various applications, and the dyed para-aramid fiber filament can be used as a sewing thread, cord, rope, or woven fabric of each hue. The color-rich para-aramid woven fabric obtained by the present invention can be used for sports clothing, satin, work clothing, firefighting clothing, various protective clothing, tent fabric, and the like.

Claims

Scope of demand

1. After spinning, it is a non-dyed polybaraphthalene terephthalamide fiber that has once been wound and has a tensile strength of 15 denier or more and a crystal size (110 direction) of 30 to 55 angstroms. Dyeable polyparaphenylene terephthalamide fiber _c characterized by having no history of drying to a moisture content of 8% or less

2. The dyeable polyparaphenylene terephthalamide fiber according to claim 1, wherein the fiber has no history of drying to a water content of 15% or less.

3. The dyeable staple-shaped polyparaffin obtained by applying a crimp of 4 to 9 ridges to the fiber according to claim 1 or 2 and forcing it to a fiber length of 20 to 150 mm. Nylene terephthalamide fiber.

4. A floc-like polyparaphenylene terephthalamide woven fiber obtained by cutting the woven fiber according to claim 1 to 0.1 to 3 mm.

5. A dyed polyparaphenylene terephthalamide fiber dyed with the fiber according to claim 1 or 2.

6. The dyed polyparaphenylene terephthalamide fiber according to claim 5, dyed with a cationic dye.

7. A step-like stained polyparaphenylene terephthalamide fiber obtained by dyeing the stable polyparaphenylene terephthalamide fiber according to claim 3.

8. The stable dyed polyparaphenylene terephthalamide fiber according to claim 7, dyed with a cationic dye.

9. Dyeing the floc-like polyparaphenylene terephthalamide fiber according to claim 4. Colored floc dyed polyparaphenylene terephthalamide fiber.

10. The hook-dyed polyparaphenylene terephthalamide fiber according to claim 9, which is dyed with a cationic dye.

1 A dope for spinning is prepared from polyparaphenylene terephthalamide having an intrinsic viscosity of 5 or more (7? Inh) and concentrated sulfuric acid, and the dope is once spun into the air through the pores of a spinneret. Immediately in water, solidified to form a high-strength, high-modulus filament, and a method of dyeing the filament in a separate, non-continuous process, the fiber has a tensile strength of 1 A dyeable polyparaphenyleneteref characterized by having a denier of 5 g_Z or more, a crystal size (110 direction) of 30 to 55 angstroms, and constantly maintaining the water content of the fiber at 8% or more. Talamide fiber manufacturing method.

1 2. Dyeable polyparaffin perylene phthalamide fiber produced by the method according to claim 11 is dyed with cheese using a cationic dye at a burn number of 0.2 or less as shown by the following equation. how to.

K = (T> TD) / 2 8 7 0

K _: Combustion coefficient

T _: Burn number (times Zm)

D: Degree of dryness (denier)