JPS59150111A - Flame-retardant acrylic synthetic fiber having high shrinkage - Google Patents

Abstract

PURPOSE:To obtain a high-shrinkage flame-retardant acrylic synthetic fiber having excellent dyeability, soft feeling, etc., and composed of specific amounts of flame-retardant acrylic polymer and a polyurethane, wherein said polyurethane is dispersed linearly along the fiber axis. CONSTITUTION:50-95pts.wt. of a flame-retardant acrylic polymer containing 30-60wt% of a halogen-containing monomer (e.g. vinylidene chloride) is mixed with 50-5pts.wt. of a polyurethane (e.g. polyester-type polyurethane), and the resultant spinning dope is spun and drawn to obtain the objective flame-retardant acrylic synthetic fiber having a shrinkage of >=30%, wherein the sum of the halogen-containing monomer and the polyurethane is >=38pts.wt., and the polyurethane is dispersed linearly along the fiber axis.

Description

[Detailed description of the invention] The present invention relates to highly shrinkable flame-retardant acrylic synthetic fibers.

Flame-retardant acrylic synthetic fibers have great performance advantages such as flame retardancy and self-extinguishing properties, so they are used in construction, interior decoration, clothing,
It is a fiber that is needed as an industrial material and in all fields, and can also meet the social needs of ensuring the safety of living spaces.

On the other hand, most of Hatanen's acrylic fibers are made from modacrylic fibers and are not as good as regular polyacrylonitrile fibers in terms of performance such as stiffness, bulkiness, and stiffness. However, in terms of quantity, it is still not being used sufficiently. I can't ignore these shortcomings, but I think it should be used in more fields.
Jff: I believe that it can fully contribute to society and the nation 0 Therefore, as a way to improve the above-mentioned drawbacks in flame retardant acrylic yarn fiber products, it is possible to use other fibers with poor physical properties, such as nylon, polyester, and polyacrylonitrile fibers. It is common practice to use a blend of awls, etc.;
Disadvantages such as a decrease in flame retardancy will inevitably arise.

Flame-retardant acrylic fiber products with bulkiness, waist feel,
In order to improve the flammability and fatigue, it is necessary to use shrink cotton that has the same flammability. Furthermore, in recent years, due to advances in processing methods and the need to develop new products, high shrinkage type fibers have been mixed with regular fibers to create special texture A yarns, ivory-based yarns, 6-layer pile products, artificial animal hair products, etc. There is a great need for flammable acrylic synthetic fibers with a high degree of shrinkage, as they are produced in large numbers.

However, high shrinkage polyacrylic synthetic fibers with a shrinkage rate of at least 30% and sufficient quality ('I Until now, there have been almost no proposals regarding highly shrinkable flame-retardant acrylic synthetic Pat fibers. However, in order to provide a higher degree of shrinkage, fibers with high heat resistance and morphological stability are required. Needless to say, there are manufacturing problems such as a decline in productivity and quality due to difficult conditions in the manufacturing process, increased troubles, etc., and problems such as dyeability, strength, and flexibility. This is probably due to the lack of practicality, such as the presence of LF with excellent product performance.
920% or more, preferably 60% by spinning a mixture of 60 to 40 parts Ui and 60 to 40 parts Ui
However, according to the present inventors' knowledge, when such a large ratio of mixed polymers is spun, the phase separation between the two is extremely significant. This resulted in the generation of thermal cracks and voids, resulting in an increase in the number of fibers, and poor quality in terms of workability, dyeability, and strength, making it impossible to obtain fibers that could be used for practical purposes.

! Mochiko 54-. No. 53291 public axis and bamboo public 4% 54
-41J655 Publication No. 11λ proposes a ternary or /i quaternary copolymer of acrylonitrile, vinyl chloride, vinyl chloride, vinyl bromide, or vinylidene bromide, and a halogen-containing monomer with high plasticity. There is no fiber available that combines shrinkability, flame retardancy, and good qualities such as gloss, dyeability, texture, and heat resistance.

As mentioned above, the flame-retardant acrylic synthetic gJ, j (Q's 47. No flame-retardant acrylic synthetic fibers have been obtained.

The present inventors have arrived at the present invention as a result of intensive studies.

The object of the present invention is to provide a highly shrinkable flame-retardant acrylic synthetic fiber that has a very large shrinkage rate and has the excellent characteristics inherent in flame-retardant acrylic synthetic fiber. is a combination of 50 to 95 parts by weight of a flame-retardant acrylic polymer containing 60 to 60% by weight of a halogen-containing monomer and 50 to 5 parts by weight of polyurethane, and 2-=4.
Synthesis of a flame-retardant acrylic system in which the total amount of the halogen-containing monomer and polyurethane is at least 38%, and the shrinkage rate is 30% or more, in which the polyurethane is dispersed in stripes in the fiber axis direction. The flame-retardant acrylic polymer used as fiber has good flame retardancy, strength and elongation, and flexibility, so it contains 30 to 60 percent by weight of the flame-retardant monomer.
The composition preferably contains 35 to 50% by weight, more preferably 65 to 50% by weight of the monomer containing nitrogen and 0.5 to 3.5% by weight of the dyeable group-containing monomer. ...If the rogen-containing monomer is less than 50% by weight, the flame retardancy of the fiber will be insufficient, and if it exceeds 60% by weight, the heat resistance of the fiber will be significantly reduced, resulting in a decrease in productivity in the fiber manufacturing process and coloring of the fiber.
Significant deterioration in quality, such as sticking and deterioration in dyeability, must be avoided.

Halogen-containing tops are vinyl chloride, vinylidene chloride,
Vinyl bromide, vinylidene bromide, etc. are common, but vinylidene chloride or vinylidene chloride-based monomers are preferred in consideration of handling properties, quality of the flame-retardant acrylic polymer, etc. Sodium allylsulfonate, sodium methallylsulfonate, sodium styrenesulfonate, sodium 2-acrylamido-2-methylpropylsulfone, etc. are used alone or in combination.The polyurethane used in the present invention is a common one. For example, polyurethanes include polyester type, polyether type, polyester ether type, polyester amide type, and polythioether type polyurethane. Specifically, ethylene glycol-propylene glycol, butylene glycol-hexamethylene glycol- 1-4-cyclohexyl glycol, p-=v silene glycol, or bisphenol-A and gammabin,
polyester amide made from superic acid, hetano(tinic acid, terephthalic acid, isophthalic acid or -lactone) - adipine-bleached - diethanolamide or terephthalic acid - bisupronochnolamide and the aforementioned dicarboxylic acids; Polyniskel ether made from ethylene glycol, 1,4-phenylene-bisoxyethyl ether tcid2-2'-diphenylpropane-4,4-bisoxyethyl ether, and the aforementioned dicarboxylic acids,
Polyethers made of ethylene oxide, propylene oxide-tetrahydrofuran, polythioethers such as thiodiglycol, etc. molecules jt200-500
A linear polymer having 0 terminal hydroxyl groups is converted into an organic diisocyanate such as 1-6-) diyne diinocyanate, 1-
4-phenylene diinone-1 nate-2-4-tolylene diisocyanate, 4,4'-diphenylmethane diisonoanate, hexamethine diyn 7anate, gycilediinone-1 nate or 1,5-naphthylene diyne Along with chain lengthening agents of cyanate and dihydric alcohol,
It is a polyurethane polymer reacted using a polymerization method.

The degree of combination of the polyurethane is preferably 111. Dimethylporumamide solution σ) with a combined concentration of 20% by weight has a viscosity of 20 poise or more at 20°C. Also, the elastic modulus of polyurethane is 100
The initial elastic modulus at % elongation is 40 M/ci, preferably 1 or more.

When the amount of polyurethane used increases, for example, 10 to 20 iL, the flame retardant properties of the fibers decrease. Phosphate ester type flame retardants such as sulfate, polybosphate, tris (2,5-chloropropyl) bosphate, tris (2-chloropropyl) phosphate, tris (chloroethyl) phosphate, etc. Fuel and oxidation
- A film containing an antimony chloride flame retardant and other brominated flame retardants, or a polyurethane film containing a flame retardant monomer of Miyarin and Nisuor as one of its components. By doing so, it is possible to prevent a decrease in flammability.The flame-retardant acrylic resin 5 combination and polyurethane must be miscible in a mixed solution, but must be incompatible. -If the compatibility between the acrylic polymer and polyurethane is high, they will form a sufficiently homogeneous solution even at a large mixing ratio, and a new molecular arrangement structure will be formed, which will affect the heat resistance of the fiber. This causes a decrease in strength, elasticity, stiffness, and dyeability. By mixing materials that are miscible but not compatible, it is possible to produce fibers with good quality over a wide range of mixing ratios without reducing operability or productivity. '6#, Compatibility means that when a flame-retardant acrylic polymer and polyurethane are mixed together (for example, when both solutions are mixed or when the other polymer is dissolved and mixed in one solution), one does not gel or aggregate. This indicates that one component is well dispersed and mixed in the other component.

In addition, if there is no compatibility, the flame-retardant acrylic resin (if polyurethane is mixed with the coalesce, the mixed solution will be inhomogeneous not only by visual observation but also by microscopic observation (approximately 600 to 100 times magnification). Or, when a film obtained by drying a mixed solution with a solvent is stretched, whitening or porosity is observed.

The fiber of the present invention is composed of 50 to 951 parts by weight of a flame-retardant acrylic polymer and 50 to 5 M'J (parts), preferably 60 to 95 parts by weight of a flame-retardant acrylic polymer and 40 parts by weight of polyurethane.
~5 parts by weight, more preferably flame-retardant acrylic polymer 65
~90 parts by weight and 65~10 parts by weight of polyurethane.

^W If the amount of smoked acrylic polymer exceeds 95 parts by weight and the amount of polyurethane exceeds 5 M parts, the shrinkage rate may not be sufficient - or the heat resistance and shape stability of the fibers may be poor. In addition, if the flame retardant acrylic polymer is less than 50 parts by weight and the polyurethane is more than 50 parts by weight, the strength of the fiber will suddenly decrease, and the dyeability and stiffness will decrease, and the shrinkage rate will reach saturation. Should.

In order for the fiber to have a sufficient shrinkage rate, that is, 30% or more, and good strength, elongation, and morphological stability, the halogen-containing monomer and polyurethane in the flame-retardant acrylic polymer in the fiber must be combined. A total amount of at least 38 parts by weight - preferably 40 parts by weight is required. If the total amount of the halogen-containing monomer and polyurethane is less than 58 parts by weight, the shrinkage rate is not sufficient or the shape stability is not sufficient. Although it is not clear whether the fibers of the present invention have the properties of stability, which were considered to be contradictory in the past, careful observation of the sitting state and structure of the fibers of the present invention reveals that the polyurethane phase separates in the flame-retardant acrylic polymer. Exist in scattered islands,
The island-like polyurethane is elongated in the fiber axis direction by spinning the acrylic fibers and stretching during the manufacturing process, usually with a ratio of short length to length of 1:5 or more, preferably 1:10 or more. This stretched polyurethane has an elasticity of 1
If the fibers in this state are unheated, j + l, θμ, which has a large amount of energy to shrink due to coalescence, will be repulsed in water, and the acrylic yarn will soften and contract. It is thought that the combination of the shrinkage force of the polyurethane and the shrinkage energy of the polyurethane results in a large fan-collecting ability that far exceeds that of ordinary flame-retardant acrylic synthetic fibers.

The fibers of the present invention are easily shrunk by heating in water, steam, or air, but the shrinkage ratio in boiling water must be at least 50%, preferably 65% or more. If the shrinkage rate is less than 60%, the performance as the above-mentioned high shrinkage cotton is not sufficient, and the product quality is also not sufficient.

As mentioned above, 11) uses a flame-retardant acrylic polymer as a base material and a predetermined amount of polyurethane, which is incompatible with it, is mixed and used. It is now possible to obtain a hammer-burning acrylic synthetic fiber cone with excellent heat resistance, morphological stability, and strength.

Next, the present invention will be explained in more detail by showing an example of a method for producing the fiber of the present invention.

The production of flame retardant acrylic polymer is acrylonitri #6.
Polymerize a halogen 6-containing monomer with a titt ratio of U to 60 and optionally a dyeable group-containing monomer with a weight of 05 to 6.5 by a known method called aqueous emulsion polymerization or bath liquid Togane, and remove the remaining monomer. -The process of dissolving it in a spinning bath agent or making it into a spinning dope as it is is generally possible, but since a large amount of flame-retardant acrylic polymers and rogen-containing hexamers are used, there are problems with the sealability and workability of the process. Therefore, solution polymerization is preferable. The logen-containing monomer is preferably vinylidene chloride or a monomer mainly composed of vinylidene chloride, from the viewpoints of ease of handling and heat resistance and weather resistance of the fiber.

The solvent for the spinning dope is usually an organic solvent such as dimethylpolamide, dimethylformamide, dimethylsulfoxide, or acetone. Ru. ) Dimethylformamide is particularly preferred in terms of ease of handling and recovery. The polymer concentration of the spinning stock solution is usually 15 to 35% by weight, preferably 20 to 60% by weight, and is determined depending on operability, productivity, cost, personnel, etc.

Polyurethane is also polymerized in dimethylformamide using the above-mentioned hexamer, and the polymer concentration is 20-40i4% by weight.
Obtain a polymer solution of The flame-retardant acrylic polymer spinning stock solution and the polyurethane polymer solution a were each mixed at a polymer ratio of 50 to 50.
95 parts and 50 to 5 parts, preferably 60 to 9 parts
5 parts by weight and 40-5 parts by weight, more preferably 65-9
0 parts by weight and 55 to 10 parts by weight are mixed to prepare a yarn stock solution.

Any known method can be used for polymerization. However, if the mixing ratio is high and the spinning dope is left for a long time, especially under heating, the dispersion form of polyurethane will coagulate.
This is undesirable as it becomes large and reduces operability and quality.

The mixed edge spinning stock solution is spun through a conventional spinneret into a coagulation bath. In order to reduce the cost of solvent recovery and simplify the recovery process, the coagulation bath is preferably an aqueous solution of the same organic solvent as that of the spinning dope, and the concentration of the organic solvent is 40 to 70% by weight, preferably 50 to 65% by weight. Weight% and temperature is 15~
The temperature is 65°C, preferably 18-28°C.

The spinning dope is spun into a coagulation bath, and the coagulated filament is usually subjected to spinning and drawing through several types of spinning baths in which the degree of solvent e is gradually decreased.

The spinning draw ratio is usually 6 times or more, preferably 4 to 10 times,
More preferably, it is 5 to 8 times. Spinning and drawing The product is washed once in a water washing tank at a temperature of 150° C. or higher, dried and crushed in an i-reoil adhesive hot roller type dryer or a dryer used in combination with a hot air dryer.

If the pre-oil has a low polyurethane content phase, e.g.
If the polyurethane content is higher than the oil agent and oil agent adhesion amount used for ordinary flame-retardant acrylic synthetic fibers at 0 to 60 parts by weight or less, it tends to stick to some extent during the drying process. It is also necessary to take into consideration the fact that the oil agent is easy to split and that the amount of oil adhered to it increases. In this drying process, a slight shrinkage of 10 ml of paper was performed during the constant length tension drying.
Heating is better for drying, crushing effect and prevention of mechanical strain.

For ordinary rekunow acrylic fibers, a method of primary stretching before drying is often used, but in the production of high shrinkage fibers, primary stretching after drying improves shrinkage performance.
It is very effective in terms of the gloss and dyeability of the fibers. The primary stretching is carried out using moist heat at 60-110°C, preferably 80-100°C.
The stretching ratio at 0°C will vary depending on the amount of halogen-containing monomer in the flame-retardant acrylic polymer and the content of polyurethane and tan in the fiber, but it will improve shrinkage performance, strength,
In terms of fiber performance such as gloss and dyeability, as well as operability and productivity, it is better to use a stretching ratio immediately before entering the overstretching region.

-Next Stretching Ratio and String Performance Looking at the relationship between shrinkage ratio, we can see that at low draw ratios, the shrinkage ratio increases as the draw ratio increases, but when the draw ratio exceeds a certain ratio, the shrinkage ratio decreases. Saturation has been reached. Or, conversely, the draw ratio may decrease.

The stretching ratio greater than or equal to this stretching ratio is called the overstretching region. In this over-stretching and stretching region, not only saturation and decrease in shrinkage rate but also various drawbacks occur such as low strong elongation IW of the fiber, decrease in dyeability, and single yarn breakage.

Since the highly shrinkable flame-retardant acrylic synthetic fiber of the present invention contains 5 to 50 parts by weight of polyurethane, this overstretched region is higher than that of the flame-retardant acrylic synthetic fiber that does not contain polyurethane. Therefore, high shrinkage can be easily achieved and productivity is high, and the quality deterioration due to single yarn breakage and fluffing is small.0 An example of large continuous shrinkage is 20 A process of shrinking up to 50% and then stretching is also possible, but it requires equipment for the continuous shrinking process and the energy cost required for shrinking, and it also has a particularly large effect on the shrinkage performance of the fiber braid. However, in the present invention, there is no particular care to be taken.

After the first stretching, the carpet is then oiled and mechanically crimped.
The product is dried and dried at a temperature of 100°C, preferably 80°C or lower, to prevent shrinkage.

The fibers of the present invention not only have a high degree of flammability, but also have a high quality cotton content, sufficient fiber strength, and excellent morphological stability. Even in terms of shrinkage ratio, there was no hardening or embrittlement of the fibers, and compared to conventional high-shrinkage fibers, it had excellent physical properties at -1. In terms of manufacturing the fiber M, the total stretching ratio in the manufacturing process can be made larger than that of conventional highly flammable acrylic polymers, resulting in a dramatic improvement in productivity. . Furthermore, the silky feel that was developed for the first time in fibers made of a mixture of polyurethane and flame-retardant acrylic polymers is similar to the feel of high-quality animal hair, which has never been achieved before. Therefore, the industrial significance of the present invention is extremely large.

The present invention will be explained in detail by showing two specific examples below.

Parts and % in the examples indicate parts by weight and % by weight unless otherwise specified. The fiber quality was measured according to JISL-1074.

The arbitrariness is expressed by the oxygen index (hereinafter referred to as iJ1).
? :,. To measure υ■, cut the fiber into 51 parts per piece by the foreman. Twist the sample 40 times in a machine, fold it in half, and attach it to the twisting rod. It is expressed as the oxygen gas concentration in the mixed gas when combusting.

LOL Example 1 Acrylonitrile (hereinafter referred to as AN); Vinyline chloride (hereinafter referred to as '7 DC); Allylsul□・Honmae Zutrium-, i7:50:13 (X) group・
4 (combined with dimethylformamide (hereinafter referred to as 'FD'))
It was made by polymerizing azobisdimethylvaleronitrile in IJ 1r and 111,11\). 10 parts of this polymer and 28 parts of this polymer
After dissolving in 22 parts of D0 and 50 parts of DMF, add a small amount of At and Sulfone, polymerize with azobisdimethylvaleronitrile as an initiator in an old autoclave for 9 hours, and add N2VVC. : Sodium furyl sulfonate = 57.2 : 40.0 : 2.8 '=
) A flame-retardant acrylic polymer gold having the composition was obtained. The polymerization solution was evaporated in vacuum using a rotary evaporator to remove unreacted monomers, and then water/Dh4F
Add the mixed solution to obtain a polymer concentration of 24.0% and a moisture content of 3.0.
% flame-retardant acrylic polymer solution was obtained. Next, the method for producing a polyurethane solution will be described. A urethane prepolymer having an isocyanate end was produced by reacting 100 parts of ethylene glycol with 40 parts of methylene-bis(4-phenylisocyanate) and 2 parts of tolylene diiso-anate.

After dissolving this prepolymer in DMF 100
M F 1 soo fig, 25 parts of methyl-iminopisglobylamine, 95 parts of ethylenediamine, and 1 part of jetanolamine were dropped into a solution, stirred, and then combined using a rotary evaporator to achieve a freshness of 20%.
Up to 7. A polyurethane M liquid with a rich texture was obtained.

Ingredients 1: A spinning JJA solution was obtained by mixing and stirring the acrylic ester coalescent solution and the polyurethane solution using a propeller-type stirrer so that the polymer ratios shown in Table 1 were achieved.

The mixed spinning stock solution of the two was cloudy and phase separation was observed by microscopic observation.

The spinning solution was spun through a spinneret with a hole diameter of 0.06 m and 4000 holes into a coagulation bath containing DMF:water = 57:43 (%) at 15°C. Is the spun yarn DMF? Solvent removal and 5.0x spinning and stretching were carried out in two baths in which the degree of A decreased sequentially to 60% and 15%, followed by washing with water at 70°C; thoroughly washing with water in a convex section, and placing it in a 11iJ oil bath. After applying the oil agent, it was dried and densified using a hot roller at 120°C and a dryer with hot air at 150°C. -Next stretching is wet heat 95-1
00 DEG C. as shown in Table 1. −
After drying, a product was obtained after drying 5N1 with oil and 6I-1 to 70' with 4 crimps.

The yield rate of the product is as follows: cut the fibers into 51 pieces, defibrate them well, put them in a Polyvarnish '1 mold, and soak them in He+ and 9 water for 30 minutes.
The treatment was carried out for 1 minute and the I# of the plate before treatment was determined.

The stretching ratio and shrinkage ratio in the table indicate the stretching ratio immediately before entering the overstretching region and the shrinkage ratio at that time.

Example 2 Similar to Example 1, -VDO-containing - 7t! I
An iI acrylic polymer solution was prepared. In addition, the content of allylsulfnone branch sodium was 2.8%.

Polyurethane tii is real M 4 rows 1σ) and polyurethane/combustible acrylic, 21 yarn polymer - 15
/85 (parts) to prepare a spinning stock solution f
C, O spinning and subsequent processing conditions were the same as in Example 1, resulting in a product with no defects.

Claims (1)

[Scope of Claims] 1) 30 to 60% by weight of the halogen-containing monomer, and the j5V Jti of the halogen-containing monomer and the polyurethane is at least 58 TA N parts, and the polyurethane is a fiber+i! A highly shrinkable flame-retardant acrylic synthetic fiber having a shrinkage rate of 50% or more and distributed in a striped manner in the j direction. h) The flame-retardant acrylic polymer absorbs halogen-containing monomers.
The fiber according to claim 1m containing 5 to 50% by weight. 3) Flame-retardant acrylic polymer absorbs halogen-containing monomers
5 to 50% by weight, dyeable group-containing monomer (i70.5 to
Patent containing 35% by weight,? H requirement range 1st term or 2nd term
4) The fiber according to any of claims 1 to 5, wherein the halogen-containing monomer is vinylidene chloride. 5) Claim 1 comprising 60 to 95 M parts of a flame-retardant acrylic polymer and 40 to 5 parts by weight of polyurethane.
The fiber according to any of item 4. 6) Claim 1 consisting of 65-90 parts by weight of a flame-retardant acrylic polymer and 65-90 parts by weight of polyurethane
The fiber according to any one of Items 1 to 5. 7) Claims 1 to 6 in which the total amount of the halogen-containing monomer and polyurethane is at least 40 parts by weight.
Fibers listed in Section Isuri and Crab 0