JP2601775B2 - Flame retardant acrylic composite fiber - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a flame-retardant acrylic composite fiber having excellent flame retardancy and latent crimp development.

(Prior Art) Conventionally, general acrylic fibers have a noble feel similar to wool, excellent physical properties, solid dyeing properties and dyeing clarity, and have been used in a wide range of applications. However, acrylic fibers are as flammable as most natural and synthetic fibers, and their demand is limited, for example, in the use of clothing, interior products, and industrial and construction applications, such as to help spread fires. Had been narrowed. Flame-retardant acrylic fibers, on the other hand, have the properties of flame retardancy and self-extinguishing properties, but they are still inferior to ordinary acrylic fibers in terms of product stiffness, bulkiness, and settling properties. Not in use. Therefore, in flame-retardant acrylic fiber products,
As a method of improving the above drawbacks, it is common practice to use a blend of other fibers having excellent physical properties, such as nylon, polyester, and polyacrylonitrile fibers, but the blending increases the number of processing steps and the dyeability. Inconveniences such as a reduction in the texture, a change in the texture, and a decrease in the flame retardancy arise.

In order to improve the bulkiness, waistness, settling, etc. of products made of flame-retardant acrylic fibers alone, shrinkable cotton with the same flame retardancy and fibers with latent crimpability, especially the latter, are necessary. Yes, this product has flame retardancy by mixed use of flame-retardant acrylic fiber with latent crimping property and ordinary flame-retardant acrylic fiber, and has good waist feeling, bulkiness, texture, dyeability, etc. Can be manufactured. However, flame-retardant acrylic composite fibers having both good crimpability and flame retardancy have not been obtained, and their studies have not been carried out much. JP-A-49-68014 discloses a composite fiber of a polyacrylonitrile-based polymer containing at least 85% by weight of acrylonitrile, a flame-retardant acrylic polymer, and an antimony halide compound. Cannot use a polyacrylonitrile-based polymer as one component to sufficiently enhance flame retardancy. If the vinyl chloride content or the content of antimony halide contained in other components is increased to increase the flame retardancy, gelation in the spinneret due to differences in miscibility and compatibility between the two components, clogging of the spinneret, It is difficult to set coagulation bath conditions that allow both components to coagulate densely, because threading occurs and the coagulation properties of both components are greatly different. Further, even after spinning, due to insufficient adhesion between the two components, a large decrease in operability and a large decrease in quality, such as occurrence of trouble due to peeling of the two components due to stretching and shrinkage, are expected. Further, it is expected that the consumption performance of the product, such as dyeability, heat resistance and gloss, will be reduced, and that the processing performance will also be reduced, such as yarn breakage and fluffing during spinning and weaving. JP-A-59-82410 is a composite fiber obtained by adding a polyurethane polymer to a flame-retardant acrylic polymer and spinning the fiber. However, the fiber obtained here only increases the cost of the fiber due to the added polyurethane polymer. However, the coloring properties and light resistance after dyeing were not yet satisfactory.

(Problems to be Solved by the Invention) As described above, a flame-retardant acrylic composite fiber using a flame-retardant acrylic polymer for both components and having sufficiently good flame retardancy and latent crimpability has not yet been developed. It has not been. The present inventors have made intensive studies to overcome the above-mentioned drawbacks, and as a result, completed the present invention.

The object of the present invention is good texture, bulkiness,
An object of the present invention is to provide a flame-retardant acrylic composite fiber having an excellent latent crimping property with a feeling of stiffness.

(Means for Solving the Problems) The present invention is characterized in that both components A and B are joined together. (A) A component is acrylonitrile 40% by weight or more, halogen-containing monomer and sulfonic acid-containing monomer 20 to 60% by weight Wherein (B) the component (B) is composed of 95 to 60 parts by weight of the polymer (I) of the component A and 30 to 75 parts of acrylonitrile.
Flame-retardant acrylic composite comprising a polymer composition in which 5 to 40 parts by weight of a polymer (II) consisting of 70 to 25% by weight of a vinyl monomer and optionally 0 to 10% by weight of a sulfonic acid-containing monomer is mixed. Fiber.

Examples of the halogen-containing monomer in the polymer (I) of the present invention include, but are not limited to, vinyl chloride, vinylidene chloride, vinyl bromide, and vinylidene bromide. Particularly, vinyl chloride and / or vinylidene chloride are preferred. If the content of the halogen-containing monomer is less than 20% by weight, excellent flame retardancy cannot be obtained. On the other hand, if the content exceeds 60% by weight, not only the quality of the obtained fiber such as heat resistance and strength decreases, but also the flame retardancy becomes saturated. Reached and not economical. Therefore, the amount of the halogen-containing monomer is preferably in the range of 20 to 60% by weight in view of operability, quality and cost.

In the present invention, examples of the sulfonic acid-containing monomer include sodium allyl sulfonate, sodium methallyl sulfonate, sodium styrene sulfonate, sodium 2-acrylamido-2-methylpropane sulfonate, but are not limited thereto. . When the sulfonic acid-containing monomer is contained in the polymer (I) in an amount of from 0.5 to 5% by weight, preferably from 1 to 4% by weight, the dyeing property can be improved, the coagulation property during spinning can be greatly improved, and the dry densification can be improved. Extensive improvement and acceleration are possible and fibers with good gloss and dyeability are obtained.

In the present invention, the vinyl monomer in the polymer (II) includes, for example, acrylic acid, methacrylic acid or alkyl esters thereof, vinyl acetate, acrylamide, methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate , Glycidyl methacrylate, vinyl chloride, vinylidene chloride, vinyl bromide, and vinylidene bromide.

In the present invention, the content of acrylonitrile and vinyl monomer in the polymer (II) is 30 to 75 acrylonitrile.
% By weight and 70 to 25% by weight of a vinyl monomer. Less than 30% by weight of acrylonitrile or 70
When the amount exceeds the weight percentage, the heat resistance of the obtained polymer becomes poor. On the other hand, if the amount of acrylonitrile exceeds 75% by weight or less than 25% by weight of the vinyl monomer, the crimping property of the blended and composite-spun fiber becomes poor. The number of crimping ridges after the boiling water treatment is preferably 5 to 50 / inch, particularly preferably 10 to 35 / inch.

In the present invention, when a sulfonic acid-containing monomer is also contained in the polymer (II), it is more preferable in terms of coagulation during spinning, and gloss and dyeability of the obtained composite fiber. In the present invention, the sulfonic acid-containing monomer in the polymer (II) is the same as the sulfonic acid-containing monomer in the polymer (I), and the sulfonic acid-containing monomers in the polymer (I) and the polymer (II) are The same or two or more kinds can be used in combination. The content of the sulfonic acid-containing monomer in the polymer (II) is preferably from 0 to 10% by weight.
If it exceeds 10% by weight, the amount of the polymer eluted in the coagulation bath when blended and composite-spun is increased, and the dyeability of the A component and the B component of the obtained fiber is greatly different, which causes flicker.

In the present invention, the mixing ratio of the polymer (II) to the polymer (I) of the component B is 5 to 40 parts by weight, preferably 7 to 30 parts by weight, more preferably 10 to 25 parts by weight. Polymer (I
If I) is less than 5 parts by weight, the number of crimps of the fiber obtained by compounding the two components A and B is insufficient. If it exceeds 40 parts by weight, A,
B The bicomponent composite spun fiber has a large amount of agglutination and an excessively large number of crimps, resulting in poor texture when mixed and used.

In the present invention, the joining form of the A and B components is not particularly limited, such as a side-by-side form or a seascore form. In the case of spinning with a sea core, there is no particular limitation on which of the AB components is used as the sheath portion or the core portion. preferable. The bonding ratio of the two components A and B is not particularly limited as long as a good crimp is developed.
The bonding ratio of the component B to 1 part of the component is preferably 1/5 to 5 parts.

In the present invention, the components A and B contain antimony trioxide,
Flame retardant aids such as antimony pentoxide, zinc borate, and metastannic acid, heat stabilizers, weather stabilizers, antibacterial agents, dyes and pigments, antistatic agents,
A conductive agent, an antifouling agent, and the like may be included.

Next, the present invention will be described in more detail with reference to an example of a method for producing the fiber of the present invention.

The polymer (I) is composed of 20 to 60% by weight of a halogen-containing monomer composed of vinyl chloride, vinylidene chloride or vinyl bromide or a mixture thereof, acrylonitrile, a small amount (for example, 0.5 to 5% by weight) of sodium allyl sulfonate, styrene sulfone Sodium acid or 2-acrylamide-
Polymerization of a dye-improving monomer such as sodium 2-methylpropanesulfonate with a polymerization initiator such as azobisisobutyronitrile and azobisdimethylvaleronitrile in an organic solvent such as dimethylformamide, dimethylsulfoxide or dimethylacetamide. Let it. Particularly preferably, sodium allyl sulfonate 5 to 40% by weight, acrylonitrile 10 to 85% by weight, halogen-containing monomer 10 to 50%
% By weight of a polymer having a composition of 20% to 60% by weight in a dimethylformamide solution containing the polymer, and 20 to 60% by weight of a halogen-containing monomer and acrylonitrile and, if necessary, allyl. The sodium sulfonate is polymerized in the presence of other additives, such as color inhibitors. The unreacted monomer in the obtained polymerization dope is removed by a rotary evaporator or a rotating thin film evaporator at a temperature as low as possible, and thereafter, the polymer concentration is adjusted to 20 to 30% by weight, and additives are added. A spinning dope of the polymer (I) is obtained.

On the other hand, the polymer (II) contains 30 to 75% by weight of acrylonitrile.
And 70 to 25% by weight of methyl acrylate and 0 to 10% by weight of sulfonic acid-containing monomer are polymerized in dimethylformamide by the above polymerization method, and the unreacted monomer in the obtained polymerization dope is removed. (II) concentration of 20-30
Adjust to weight%.

Next, the stock solution of the polymer (I) is used as the component A, and the solution of the polymer (II) having a polymer concentration of 20 to 30% by weight is added to the stock solution of the polymer (I) and mixed. Obtain a stock solution.
Each spinning dope is kept at 40 to 60 ° C. in order to adjust spinning viscosity and improve spinnability, and is led through separate inlets to a conjugate fiber die. The hole diameter and the number of holes of the nozzle of the base are determined by single yarn denier. For the coagulation bath, an aqueous solution of an organic solvent used for the spinning solution, an organic solvent such as isopropyl alcohol, ethylene glycol, or polyethylene glycol or an aqueous solution thereof is usually used. The composition, temperature and the like may be the same conditions as in the case of producing the flame-retardant acrylic fiber, or may be conditions under which the solidification is slightly accelerated. When dimethylformamide is used as the solvent of the spinning solution, the coagulation bath conditions are preferably an aqueous solution having a dimethylformamide concentration of 45 to 65% by weight and a temperature of 30 ° C. or less.

The spun fibers are subjected to a primary stretching of usually about 4 to 8 times in several baths in which the concentration of the organic solvent gradually decreases, followed by washing with water and pre-oil treatment. Next, drying and densification are performed using hot air of 100 to 180 ° C., a hot roller, or a combination of hot air and a hot roller. After drying or after primary stretching, secondary drying is performed before drying to adjust fiber properties. 2
The next stretching is performed about 1.05 to 2 times in hot water or steaming. After the secondary stretching, shrinkage, stretching, post-oil, mechanical crimping, crimp setting, etc. may be performed for the purpose of improving film shrinkage development, adjusting fiber physical properties, adjusting texture, and improving spinnability.

(Effect of the Invention) The flame-retardant acrylic composite fiber according to the present invention thus obtained is a fiber having both good flame retardancy and latent crimpability, and has high flame retardancy bulkiness and good wind. Bedding, sheets, bedspreads, carpets, curtains, etc. for bedding interior and safety,
It is capable of exerting its performance sufficiently in clothes for children and elderly people who require comfort, especially in pajamas and the like.

(Example) Next, the present invention will be specifically described with reference to examples. still,
Parts and% in Examples are parts by weight and% by weight unless otherwise specified.
Is shown.

 The crimping characteristics were performed according to JIS L-1074.

Flame retardancy was represented by the limiting oxygen index (hereinafter abbreviated as LOI). This is done by cutting the fiber to 51mm, defibrating with a hand card, collecting about 0.5g of cotton, stretching it evenly to a length of about 25cm, twisting it 70 times with a twisting machine, and then folding it in half. To make a twist rod. Next, a flame is brought into contact with the upper end of the twisting rod in a mixed gas of nitrogen gas and oxygen gas, and the oxygen gas concentration (volume) in the mixed gas when the sample burns by 5 cm is represented by the following formula.

Example 1 A polymer having a composition of acrylonitrile (hereinafter abbreviated as AN): vinylidene chloride (hereinafter abbreviated as VDC): sodium allyl sulfonate (hereinafter abbreviated as SAS) = 55: 43: 2 (%) was converted to dimethylformamide (hereinafter abbreviated as dimethylformamide). DMF) was used as a solvent in an autoclave. The polymerization dope was evaporated by vacuum using a rotary evaporator to remove and recover unreacted monomers. After the monomer recovery, the polymer solution was transparent, pale yellow and viscous. Polymer concentration 2
A spinning dope of the polymer (I) having a water content of 3.5% and a water content of 4.5% was obtained.

Next, AN, methyl methacrylate (hereinafter abbreviated as MMA), and sodium 2-acrylamido-2-methylpropanesulfonate (hereinafter abbreviated as SAM) were dissolved in DMF and polymerized in an autoclave.

Next, the clear light yellow viscous polymerization dope obtained by removing and recovering the unreacted monomer was diluted with DMF to obtain a polymer concentration of 2.
A 3.5% stock solution of polymer (II) was obtained. The stock solution of the polymer (II) was mixed with the stock solution of the polymer (I) such that the weight ratio of each polymer was as shown in Table 1 to obtain a stock solution of the component B.

With the polymer (I) as the component A, the spinning solution of the components A and B is a side-by-side type composite spinneret (nozzle hole diameter 0.06).
mm, 4000 holes), each introduced from a separate inlet, DMF:
Water = 53:47 (%) spun into a coagulation bath at 18 ° C. The discharge ratio of the A and B components was 1: 1. The spun fibers have a DMF concentration
Debathing agent and 4.5 in two baths which decrease sequentially to 30% and 15%
After performing primary stretching twice, it was sufficiently washed in a water washing tank at 70 ° C., adhered to an oil agent in an oil tank before drying, and then dried and densified with a hot roller at 135 ° C. After drying, it undergoes 1.4 times secondary stretching with 100 ° C steaming and 0.95 times tension shrinkage under 100 ° C steaming, after adhering oil and crimping, and then dried, 3 denier various flame-retardant acrylic composite fibers I got

The fibers obtained in the examples of the present invention had good texture, bulkiness and flame retardancy.

Example 2 The polymer (II) having the composition shown in Table 2 was polymerized in an autoclave. Next, the unreacted monomer was removed and recovered to obtain a spinning solution of the polymer (II) having a polymer concentration of 23.5%. 20% of the stock solution of the polymer (II) was added to and mixed with the stock solution of the polymer (I) obtained in Example 1 to obtain a stock solution of the B component.

Using a core-sheath composite die, the polymer (I) was used as the A component, and the B component was introduced into the sheath portion into the core portion, and DMF: water = 60: 40% 2
The wet spinning was performed in a coagulation bath at 5 ° C. The discharge ratio of the A and B components is
It was 1: 1. The spun fibers are firstly drawn 4.5 times with a debathing agent in two baths in which the DMF concentration gradually decreases to 30% and 15%, and then thoroughly washed in a 70 ° C water washing tank. The oil agent adhered in the previous oil tank, and then dried and densified with a 135 ° C. hot roller. After drying, it is 1.4 times 2 with 100 ℃ steaming.
Under tension and shrinkage of 0.95 times under the next stretching and steaming at 100 ° C,
After adhering oil and applying crimp, the mixture was dried to obtain 3 denier various flame-retardant acrylic composite fibers.

The fibers obtained in the examples of the present invention had good texture, bulkiness and flame retardancy.

Claims (1)

(57) [Claims] 1. A polymer (I) wherein both components A and B are joined, and (A) the component A is a polymer (I) comprising 40% by weight or more of acrylonitrile and 20 to 60% by weight of a halogen-containing monomer and a sulfonic acid-containing monomer. (B) The B component is composed of 95 to 60 parts by weight of the A component polymer (I), 30 to 75% by weight of acrylonitrile, 70 to 25% by weight of a vinyl monomer and, if necessary, 0 to 10% by weight of a sulfonic acid-containing monomer. Flame-retardant acrylic composite fiber which is a polymer composition obtained by mixing 5 to 40 parts by weight of the polymer (II).