JPS6350571A - Flameproof synthetic fiber and its production - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a flame-retardant synthetic fiber and a method for producing the same, and more particularly, to a flame-retardant synthetic fiber containing a halogenated cycloalkane compound and a specific phosphorus compound. It relates to fibers and their manufacturing methods.

(Prior Art) Various proposals have been made to provide flame retardant to synthetic fibers to produce flame retardant synthetic fibers. Among them, brominated cycloalkanes having 7 to 12 ring carbon atoms and 4 to 6 bromine atoms bonded to the ring carbon atoms, and dispersants such as lignin sulfonates are used. It is known that flame-retardant synthetic fibers obtained by treating with a flame-retardant agent containing a protective colloid and water, as the case may be, have excellent flame-retardant properties (Japanese Patent Publication No. 53-8840). ).

In addition, polybrominated organic compounds such as brominated cycloalkanes and dispersants are used to further enhance the flame retardant effect and prevent a decrease in color fastness, discoloration during high-temperature processing, and metal corrosion. A flame retardant agent dispersed in water is also known (Japanese Patent Publication No. 59-36032).

On the other hand, the general formula: [wherein R1, Rt, and R3 are an aryl group, an alkyl group, or a cycloalkyl group with or without a substituent, and may be the same or different. ] It is stated in Japanese Patent Publication No. 49-22958 that polyester containing a phosphoric acid ester represented by the formula % has flame retardant properties. , an open-chain or cyclic alkylene, arylene or aralkylene residue, and R2 means an alkyl, aryl or aralkyl group having up to 6 carbon atoms. ] Flame-retardant polyester containing a phosphorus compound shown in JP-A-50-56488 and JP-A-51-823
It is described in Publication No. 92.

Furthermore, the general formula, [wherein, R6 is a monovalent ester-forming functional group, and R
t and Rs are the same or different groups, each selected from a hydrocarbon group having 1 to 10 carbon atoms, R6, and A
represents a divalent or trivalent organic residue. Further, n represents 1 or 2, and nt % n 3 represents an integer of O to 4, respectively. ] A flame-resistant polyester containing a phosphorus compound represented by the following is also described in JP-A-52-47891.

(Problems to be Solved by the Invention) However, the halogenated cycloalkane compound (
Since HCA (hereinafter referred to as HCA) is a halogen compound,
(HCA imparting equipment in the synthetic fiber manufacturing process) () Post-processing equipment for the fibers imparted with CA, such as heat treatment machines, cutters,
It has the serious drawback of corroding metals in packaging machines, spinning machines, etc. Furthermore, when an aqueous dispersion of HCA is applied before crimping in the synthetic fiber manufacturing process, it has the effect of increasing the coefficient of friction between the fiber and metal, so that the passability of the crimping device, such as a push-in crimper, is reduced. The disadvantage is that it becomes extremely bad. The effect of increasing the coefficient of friction in this manner also causes troubles such as poor card passage and clogging of the coiler tube even in the spinning process when synthetic fibers are used as spun yarn.

Furthermore, there is also the problem that foaming in the HCAC diversion bath is significant, resulting in poor workability, and a large amount of white powder is generated during the spinning process.

On the other hand, when the various phosphorus compounds mentioned above are contained in polyester, although the flame retardant property is improved, the degree of improvement is insufficient, and it has been desired to improve the flame retardant performance of the layer.

The purpose of the present invention is to solve the problems of the prior art, improve workability and processability in the synthetic fiber manufacturing process, improve spinnability, reduce corrosion of equipment, and improve texture and flame resistance. To provide flame-retardant synthetic fibers with excellent properties.

(Means for Solving the Problems) As a result of intensive studies to achieve the above object, the present inventors have found that by combining the phosphorus compound and the HCA, flame retardancy is significantly improved. The present invention was achieved by discovering that sufficient flame retardant performance can be obtained by simply incorporating a small amount of HCA into synthetic fibers.

That is, the present invention provides a halogenated cycloalkane compound [A]
and at least one kind of phosphorus compound [B] represented by the following general formulas (1) to (3).

[In the formula, RI, R1, and R3 are an aryl group, an alkyl group, or a cycloalkyl group with or without a substituent, and may be the same or different.] HO-P-R, -COOH... ...(2) R3 [wherein Ra is a saturated, open-chain or cyclic alkylene, arylene or aralkylene residue, and R3 is an alkyl group, arylene or aralkyl group having up to 6 carbon atoms means. ] In formula C, R4 is a monovalent ester-forming functional group, and R
t and Ra are the same or different groups, each being a hydrocarbon group having 1 to 10 carbon atoms, avoided from R8, and A
represents a divalent or trivalent organic residue. Further, nl represents 1 or 2, and nt and R3 each represent an integer of O to 4. ] And a synthetic polymer prepared by mixing or copolymerizing at least one of the phosphorus compounds [B] represented by the following general formula is spun, and then a halogenated cycloalkane compound [A] is spun.
1. A method for producing flame-retardant synthetic fibers, which comprises treating with a treatment liquid containing.

[In the formula, RI, Rz, and Rs are an aryl group, an alkyl group, or a cycloalkyl group with or without a substituent, and may be the same or different. ]

HO-P-R, -COOH (wherein R4 is a saturated, open-chain or cyclic alkylene, arylene or aralkylene residue, and R3 is an alkyl, aryl or aralkyl group having up to 6 carbon atoms) [In the formula, R6 is a monovalent ester-forming functional group, and R
7 and R8 are the same or different groups, each selected from a hydrocarbon group having 1 to 10 carbon atoms and R6, and A represents a divalent or trivalent organic residue. Also, nl is 1
Alternatively, 2, R2, and R2 each represent an integer of 0 to 4. ] The synthetic fibers of the present invention include conventionally known synthetic fibers such as polyester fibers, polyamide fibers, polyacrylonitrile fibers, polyolefin fibers, and polyvinyl chloride fibers. Favorable results can be obtained in terms of durability, texture, etc.

Although the shape of the fibers may be either long fibers or short fibers, the effect is particularly remarkable in the case of short fibers. Further, the cross-sectional shape of the fiber is not limited to round, solid, and may be any shape such as round, hollow, irregularly shaped solid, or irregularly hollow.

Examples of HCA [A] contained in the synthetic fiber of the present invention include 1.2,3,4,5.6-hexabromocyclohebutane, 1,2.3.4-tetrabromocyclooctane,
1,2,4,6-tetrabromocyclooctane, l,2
, 5,6,9.10-hexapromocyclododecane and the like. In particular, in the case of polyester fibers, it is desirable to use 1,2°5,6,9.10-hexabromocyclododecane in terms of fastness to flame retardant adhesion, flame retardancy, texture, etc.

Since HCA is a water-insoluble solid, it is dissolved in a solvent such as perchloren or toluene, or used as an aqueous dispersion. When creating an aqueous dispersion of HCA, HCA is made into fine particles with an average particle size of less than 1 micron, and then water and a protective colloid are mixed and stirred in a ball mill for several hours to form water with good dispersion stability. A dispersion can be obtained. Note that the HCA particles are preferably fine particles of less than 1 micron in view of the dispersion stability of the aqueous dispersion, the efficiency of adhesion of the flame retardant to the fibers, and the fastness of adhesion.

Examples of protective colloids include, for example, polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose or hydroxypropylcellulose, gelatin, acid casein, starch paste, polymers of acrylic monomers such as polyacrylic acid, ethyl acrylate or methacrylate. It is a copolymer of methyl acid. Good results are especially obtained with polyvinyl alcohol, hydroxyethylcellulose and especially carboxymethylcellulose.

Further, the amount of protective colloid to be used is preferably as small as possible in terms of flame retardancy, texture, spinnability, etc., and is preferably 1% or less based on HCA.

Moreover, the phosphorus compound CB) contained in the synthetic fiber of the present invention is represented by the following general formulas (1) to (3).

[In the formula, R+, Rt, and R3 are an aryl group, an alkyl group, or a cycloalkyl group with or without a substituent, and may be the same or different.] HO-P-R, -COOH... ...(2)■ [wherein R4 is a saturated, open-chain or cyclic alkylene, arylene or aralkylene residue, and R2 is an alkyl group, arylene or aralkyl group having up to 6 carbon atoms means. [In the formula, R6 is a monovalent ester-forming functional group, and R
7 and R8 are the same or different groups, each selected from a hydrocarbon group having 1 to 10 carbon atoms and R8, and A represents a divalent or trivalent organic residue. Also, n is 1
Alternatively, 2, nt, and R3 each represent an integer of O to 4. ] In the phosphorus compound represented by the above general formula (1), R+, Rz, and R3 are phenyl, naphthyl,
Aryl groups such as biphenyl; substituent aryl groups such as nonylphenyl, ethoxyphenyl, and methoxyphenyl; alkyl groups such as methyl, ethyl, butyl, octyl, and nonyl; substituted alkyl groups such as ethoxyethyl and butoxyethyl; cyclohexyl, Examples include cycloalkyl groups such as decahydronaphthyl; substituted cycloalkyl groups such as methylcyclohexyl; and the like. These may be the same or different. Examples of such phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, trinonyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, butyl diphenyl phosphate, methyl diphenyl phosphate, octyldiphenyl phosphate, and cyclohexyl diphenyl phosphate. , naphthyl diethyl phosphate, methylcyclohexyl diethyl phosphate and the like.

Further, in the phosphorus compound represented by the above general formula (2), R4 is methylene, ethylene, propylene,
Chain alkylene groups such as isopropylene, butylene, and imbutylene; cyclic alkylene groups such as cyclohexylene;
Examples of R5 include arylene groups such as phenylene; aralkylene groups such as methylphenylene;
Examples include chain alkyl groups such as methyl, ethyl, butyl, and isobutyl, cyclic alkyl groups such as cyclohexyl, aryl groups such as phenyl, and aralkyl groups such as benzyl.

Furthermore, in the phosphorus compound represented by the above general formula (3), R6 specifically includes a carboxyl group, an alkyl ester of a carboxyl group having 2 to 7 carbon atoms, a cycloalkyl ester, an aryl ester, a hydroxyl group, Examples include a hydroxylalkoxycarbonyl group having 2 to 7 carbon atoms, and groups represented by .

Preferred examples of R1 and Rs include an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryol group, and the monovalent group of R6 described above.

On the other hand, preferred A is methylene, ethylene, 1,
Lower alkylene groups such as 2-propylene and 1,3-propylene, arylene groups such as 1.3-phenylene and 1゜4-phenylene, 1.3-xylylene, 1.4-xylylene, CHt C+CHzha (R9 is a hydrogen atom or a lower alkyl group such as methyl or ethyl, or a trivalent group represented by R4 represents O or 1). Even if these phosphorus compounds (B) are used alone,
Also, two or more types may be used in combination. The flame-retardant synthetic fiber of the present invention contains HCA [A] in an amount of 0.2 to 8% by weight based on the fiber weight, and phosphorus compound CB'J in an amount of 0.05 to 8% by weight based on the fiber weight.
It is desirable that the content is 5% by weight. HCA [A]
If the content is too low, the flame retardant properties will be insufficient, and if the content is too high, white powder will be generated, which tends to reduce spinnability. In addition, if the content of the phosphorus compound [B] is too low, the flame retardant properties will be insufficient, and if it is too high, the spinning condition of the synthetic fiber will worsen, and furthermore, the degree of polymerization during spinning will increase, resulting in There is a tendency for the mechanical properties to deteriorate.

The flame retardant synthetic fiber of the present invention is preferably a crimped fiber from the viewpoint of spinnability, and the crimping performance is 10 crimps.
-18 pieces/25 cranes, especially 12 to 15 pieces/25 dragons, and a crimp rate of 8 to 38%, especially 10 to 20% is preferable.

The crimp form is not limited to plane crimp, but may also be three-dimensional crimp obtained by composite spinning, asymmetric cooling spinning, or the like.

In order to obtain the flame-retardant synthetic fiber of the present invention, the phosphorus compound [
A synthetic polymer prepared by mixing or copolymerizing at least one of B] may be spun, and then treated with a treatment liquid containing HCA[A].

The phosphorus compound [B] can be added to the synthetic polymer at any stage. For example, in order to copolymerize a phosphorus compound CB) with polyester, the phosphorus compound (B) may be added during the transesterification reaction, or the phosphorus compound (B) may be added after the transesterification reaction, before the polycondensation reaction, or before the polycondensation reaction. It can also be added at an early stage. Furthermore, when the phosphorus compound (B) is mixed into the synthetic polymer, the phosphorus compound CB) may be added to the synthetic polymer at a stage after the polymerization reaction is completed and before melt spinning. The phosphorus compound (B) is added in an amount of 0.05 to 5% by weight based on the weight of the fiber.

Melt spinning of the phosphorus compound-containing polymer can be performed according to a conventional method.

A treatment liquid containing HCA [A] is applied to the fiber thus obtained. The HCA treatment liquid may be applied to the synthetic fibers before the crimping treatment, either at the unstretched stage immediately after melt spinning or at the stage after stretching, but it is preferably applied when the synthetic fibers are in the unstretched state. This is more advantageous because the HCA sufficiently penetrates into the fibers and does not fall off during the spinning, dyeing, and weaving processes.

The adhesion amount of HCA [A] is from 0°2 to the fiber weight.
It is desirable that the amount is 8% by weight, and for this purpose, it is preferable that the HCACA)'a degree of the treatment liquid is 1 to 30% by weight. In addition, when a phosphate compound represented by the general formula below is used in combination with this HCA treatment solution, foaming of the treatment bath is suppressed, the stability of the solution is improved, and rust prevention, push crimper passability, and spinnability are significantly improved. It has been improved and is suitable.

Rho (CHt CHz O) -0P OM0
M' [Here, R8° is an alkyl group having an average carbon number of 6 to 30,
M and M' each represent hydrogen or an alkali metal, and may be the same or different, and n is an integer of 0 to 30. ] However, since the phosphate has no action as a dispersant, it is desirable to use a known dispersant together.

Furthermore, ultraviolet absorbers such as benzotriapole-based ultraviolet absorbers may be used in combination as long as the object of the present invention is not impaired. In addition to HCA, it is also possible to use other types of flame retardants in combination to the extent that they do not impede spinnability, texture, etc. Furthermore, if the treatment bath is prone to foaming, a small amount of antifoaming agent may be used in combination without impairing the flame retardant properties. Furthermore, if necessary, HC
After applying the treatment solution A to the synthetic fibers, drying and fixing them with heat, if necessary, the synthetic fibers may be washed with water and other oils for improving spinnability may be applied by spraying, patting, etc.

Any conventionally known method may be used to apply the HCA treatment liquid to the synthetic fibers, but examples include a dipping method, a putting method, a spray method, and an oil roller type used for applying spinning oil in melt spinning. Can be used.

After applying a treatment solution containing HCA [A] to the surface of the synthetic fiber, heat treatment is performed at 130° C. or higher, preferably 155° C. or higher for 30 seconds or more, preferably 10 minutes or more, to form HCA [A].
penetrates into the fibers. This heat treatment can also be used as a heat treatment for fixing the crimp, which is performed after the crimp is applied.

(Function) According to the present invention, HCA [A] and the phosphorus compound (B
), the flame retardant properties are dramatically improved.

As a result, in the conventional method, it was necessary to treat synthetic fibers with a treatment solution containing a large amount of HCA to deposit a large amount of HCA on the synthetic fibers, but with the present invention, a very low concentration HCA solution is used. Treatment to reduce the amount of HCA deposited on synthetic fibers can still provide satisfactory flame retardancy.

Therefore, it is possible to significantly improve various problems caused by HCA, such as corrosion of equipment, passability through a push-in crimper, deterioration of spinning stack, and foaming in the HCA treatment bath. This improvement effect is greatly promoted by adding the specific phosphate compound to the HCA treatment bath.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.

In addition, the adhesion rate of the treatment agent, flame retardancy, adhesion fastness of HCA,
Spinnability, texture, treatment liquid stability, foaming during operation, push-in crimper passability, rust prevention, and crimp performance were evaluated by the following methods.

(1) Adhesion rate of treatment agent Adhesion rate of treatment agent = (treatment agent/fiber) X100 (,
(wt%) (2) After repeating water washing 5 times according to the flame retardant test method of the Fire Service Act (
Water hardness adjusted to 75 ppm with calcium chloride), JI
The number of times of flame contact (average value of 5 samples) was determined by the S L1091D method.

The greater the number of times of flame contact, the better the flame resistance, and the practically acceptable number of times of flame contact is two or more times, particularly preferably three or more times.

(3) Adhesion fastness of HCA Regarding the above values, 50% or more was considered good (O mark), and less than 50% was judged poor (x mark).

(4) Spinnability 10 kg of raw cotton was placed on a card and the spinnability was evaluated based on the presence or absence of clogging of the card coiler tube.

A case where there was no clogging was judged as good (◯ mark), a case where coiling was impossible due to clogging was judged as bad (x mark), and a case where spinning was barely possible between the two was judged as good (∆ mark).

(5) Texture Based on the tactile evaluation, it was determined whether the product was good (○ mark) or poor (x mark).

(6) Stability of processing solution When the solution is placed in a beaker No. 11 and left to stand for 15 minutes, if no layer separation occurs, it is good (○ mark), if it completely occurs, it is bad (x mark), and there is slight layer separation. Those showing this tendency were judged to be normal (Δ mark).

(7) If foaming was severe in the foaming circulation tank or immersion treatment bath during operation, it was rated as poor (x mark), if there was no problem, it was rated as good (○ mark), and in the middle between the two was rated fair (Δ mark).

(8) Push-in crimper - Passage Push-in crimper - If the push crimper rattles and cannot operate normally, it is defective (x mark), if there is a problem (it can be operated, it is good (○ mark), and in between the two is normal (∆ mark). mark).

(9) If an appropriate amount of rust-preventive treatment agent is put into a test tube and an iron nail is immersed in it and left for one day and night, rust will form on the surface of the nail (x mark), and if no rust occurs, it will be defective. The score was rated good (○ mark), and the middle mark was rated fair (Δ mark).

(10) Crimp performance The number of crimp and crimp rate of flame retardant synthetic fiber is JIS-L-101.
Measured by method 5.

Example 1 97 parts dimethyl terephthalate, 69 parts ethylene glycol, 0.09 parts calcium acetate and 0.03 parts
A mixture of parts of antimony trioxide was heated at 165-220°C until methanol distillation was completed. Next, 0.7 parts of trimethyl phosphate and 0.99 parts of p-diphenylcarboxylic acid were added, and as the reaction progressed at 275°C, the pressure was gradually reduced to 0.4 mHg and the reaction was continued for 200 minutes. continued.

The obtained polyester had an intrinsic viscosity of 0.64. This polyester was melt-spun by a conventional method to obtain a tow of 450,000 deniers, and further stretched 3.5 times in a hot water bath at 90° C. to obtain a drawn tow having a single fiber fineness of 2 deniers.

On the other hand, 1.2, 5, 6°9.10 with an average particle diameter of 0.5μ
- 45 parts of hexabromocyclododecane (hereinafter referred to as HBCD), average molecular weight 1400.00 as a protective colloid
0.5 parts of carboxymethylcellulose and 54 parts of water
．． H produced by grinding and mixing 5 parts in a ball mill for 5 hours
BCD water dispersion (active content 45% by weight, viscosity: 4.50
A treatment bath was prepared by adding water to 44 parts (0 centivoise, measured with a rotating B-type viscometer) to make a total of 100 parts.

After passing the stretched tow through the treatment bath, the treatment solution was squeezed using a push-in crimper so that the amount of HBCD attached was 1.0% by weight, and the number of crimps was 12/25 t.
The cotton was crimped to give a crimp rate of 12%, and then subjected to relaxation heat treatment at 170° C. for 15 minutes in a continuous dryer, and then cut into 51 pieces with a cutter to prepare raw cotton. The phosphorus content in the raw cotton was 0.13% by weight.

The obtained raw cotton was spun to create a 30/2 spun yarn, and the yarn was bundled using a package dyeing machine under the following dyeing conditions. A jacquard fabric with a basis weight of 400g1rd was made using a jacquard loom using the two types of dyed yarns obtained, and a nonionic activator (score roll 400 #) was added to the fabric to create a jacquard fabric with a fabric weight of 400 g/l.
After scouring in a bath at a temperature of 80°C, a treatment time of 10 minutes, and a bath ratio of 1:20, flame retardancy, fastness to HBCD adhesion, spinnability, and texture were evaluated. The various processing baths were also evaluated for their processing solution stability, rust prevention, foaming during operation, and permeability through an indentation crimper. The results obtained are shown in Table 1.

Dyeing conditions (a) Dye composition: Re5olin Blue FBL
O,5%owfDisper VG O,
2g/12 Vinegar MO, 2g/R Processing conditions: Bath ratio 1:20 Temperature
130℃ time
30 minutes (b) Dye composition: Dyanix Red BN-SEo
, 5% 0g f Disper VG O, 2g/1 vinegar
Acid 0.2 g/l Treatment conditions = Comparative Examples 1 to 5 Same as (a) The treatment was carried out in exactly the same manner as in Example 1 except that the treatment with the HB CD treatment bath was not performed (Comparative Example 1 ).

Further, in Example 1, the treatment was carried out in exactly the same manner as in Example 1 except that trimethyl phosphate was not added during the production of polyester (Comparative Example 2).

Furthermore, in Example 1, instead of using HBCD as a flame retardant, Anti-Blaze 19 (manufactured by Mobil Chemical Co., cyclic phosphate ester, active ingredient 1) was used as Comparative Example 3.
00%), Comparative Example 4 is an emulsion of tris 2.3 dichloropropyl phosphate (effective content 45%), and Comparative Example 5 is an emulsion of tetrabromobisphenol A (effective content 45%).
The process was carried out in exactly the same manner as in Example 1, except that 5%) was added.

The results are also shown in Table 1.

As is clear from Table 1, the synthetic fiber of the present invention containing HCA [A] and phosphorus compound CB (Example 1)
It has good flame retardancy, HBCD adhesion fastness, spinnability, and texture, excellent treatment liquid stability and rust prevention, little foaming of the treatment bath during operation, and good passage through the push crimper. Ta. On the other hand, when HCA [A] is not contained (Comparative Example 1) and when the phosphorus compound (B3 is not contained [Comparative Example 2]), the flame retardant property is significantly reduced. When other conventionally used flame retardants are used instead of HBCD (Comparative Examples 3 to 5), not only the flame retardant properties are inferior, but also the adhesion fastness, spinnability, and texture of the flame retardant are also deteriorated. .

Table 1 (this page, below margin) Example 2.3 In Example 1, 1°2.3.
4-tetrabromocyclooctane (Example 2) and 1
．． 2. 3. 4. 5. Using 6-hexabromocyclohebutane (Example 3), other conditions were as in Example 1.
The same treatment was performed. The results are shown in Table 2, and all showed good performance.

(This page, below margin) Table 2 Example 4 A mixture of 1000 parts of dimethyl terephthalate, 798 parts of ethylene glycol, and 0.23 parts of manganese acetate was heated at 170 to 220°C until methanol distillation was completed. Then, 8 parts of 2-carboxyethyl-methylphosphinic acid was added at 220° C. for esterification. Thereafter, 0.35 part of antimony trioxide was added, and as the reaction progressed at 275° C. under a nitrogen atmosphere, the pressure was gradually reduced to 0.2 wHg and the reaction was continued for 100 minutes.

The obtained polyester had an intrinsic viscosity of 0.63.

Using this polyester, spinning,
Raw cotton was prepared by stretching, treatment with an HBCD treatment liquid, crimping, and cutting. The phosphorus content of this raw cotton is 0.14% by weight
The amount of HBCD deposited was 1.0%.

This raw cotton was spun, dyed, and woven in the same manner as in Example 1, and evaluated on the same items as in Example 1. The results obtained are shown in Table 3.

Example 5 388 parts dimethyl terephthalate, 248 parts 0.
A mixture of 34 parts of zinc acetate and 0.34 parts of antimony trioxide was heated at 150 to 230°C until methanol distillation was completed. Next, as the reaction progresses at 275°C under a nitrogen atmosphere, the pressure is gradually reduced until it reaches 0.
The reaction was continued for 160 minutes at 2 mHg.

The resulting polyester had an intrinsic viscosity of 0.65, and was subjected to spinning, stretching, and spinning in the same manner as in Example 1.
Raw cotton was prepared by treatment with an HBCD treatment solution, crimping, and cutting. The amount of phosphorus compound copolymerized in this raw cotton is approximately 0.9%.
, the phosphorus content was 0.09% by weight, and the HBCD adhesion amount was 1.
It was 0% by weight.

This raw cotton was spun, dyed, and woven in the same manner as in Example 1, and evaluated on the same items as in Example 1. The results obtained are shown in Table 3.

Comparative Example 6.7 In Example 4.5, the same treatment as in Example 4.5 was performed except that the treatment with the HBCD treatment bath was not performed. The results are also shown in Table 3.

As is clear from Table 3, the synthetic fiber of the present invention (Example 4.
5) has good flame retardancy, HBCD adhesion fastness, spinnability, and texture, and has excellent treatment solution stability, prevention, and rust resistance, and has little foaming in the treatment bath during operation (and is easy to pass through the push-in crimper). On the other hand, when HCA [A] was not contained (Comparative Examples 6 and 7), the flame retardant properties were significantly lower.

, (This page, blank space below) Table 3 [- [“Example 121” Example [-・ (Wood page, blank space below)] Examples 6 to 8 In Example 1, as the HBCD treatment bath, the HBCD water dispersion A treatment bath was used in which aqueous solutions of various phosphate compounds as shown in Table 4 were added to 44 parts to make a total of 100 parts. The results are shown in Table 4. Foaming in the treatment bath was suppressed by the addition of the phosphate compound represented by the general formula %, and rust prevention, push-in crimper passability, and spinnability were also significantly improved. be done.

Table 4 (1) Stearyl phosphate potassium salt (2) Polyoxyethylene (7 mol) nonyl ether phosphate potassium salt (3) Polyoxyethylene (5 mol) hexadecyl phosphate potassium salt (effects of the invention) As explained above ( According to the present invention, by incorporating a halogenated cycloalkane compound and a specific phosphorus compound into synthetic fibers, flame retardancy is greatly improved, and as a result,
It becomes possible to reduce the amount of the halogenated cycloalkane compound used, and it is possible to provide a flame-retardant synthetic fiber with excellent texture and significantly improved spinnability and rust prevention properties.

Furthermore, in the process of producing the flame-retardant synthetic fiber of the present invention, the stability of the treatment liquid, the foaming during operation, and the ability to pass through the indentation crimper are also significantly improved.

The flame-retardant synthetic fiber of the present invention is extremely useful for use in various fields such as clothing, cotton padding, interior decoration, nonwoven fabrics, artificial leather, and artificial fur.

Claims (1)

[Scope of Claims] 1. A protective compound characterized by containing a halogenated cycloalkane compound [A] and at least one phosphorus compound [B] represented by the following general formulas (1) to (3). Flame-resistant synthetic fiber. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) [In the formula, R_1, R_2, and R_3 are aryl groups, alkyl groups, and cycloalkyl groups with or without substituents, and may be the same or different. good. [In the formula, R_4 is a saturated, open-chain or cyclic alkylene, arylene or aralkylene residue, and R_5 is 6
means an alkyl, aryl or aralkyl group having up to 5 carbon atoms. ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_6 is a monovalent ester-forming functional group,
R_7 and R_8 are the same or different groups, each selected from a hydrocarbon group having 1 to 10 carbon atoms and R_6, and A represents a divalent or trivalent organic residue. Also n
_1 is 1 or 2, n_2 and n_3 are each 0 to 4
represents an integer. 2. The flame-retardant synthetic fiber according to claim 1, wherein the content of the halogenated cycloalkane compound [A] is 0.2 to 8% by weight based on the weight of the fiber. 3. The content of phosphorus compound [B] is 0 relative to the fiber weight
．． The flame-retardant synthetic fiber according to claim 1, wherein the content of the flame-retardant synthetic fiber is 05 to 5% by weight. 4. Claims 1 to 3, wherein the halogenated cycloalkane compound [A] is hexapromocyclododecane
The flame-retardant synthetic fiber according to any one of the items. 5. Claim 1 in which the synthetic fiber is polyester
The flame-retardant synthetic fiber according to any one of items 1 to 4. 6. Any one of claims 1 to 5, wherein the synthetic fiber is a crimped fiber having a number of crimps of 10 to 18/25 mm and a crimp ratio of 8 to 38%. The flame retardant synthetic fibers listed. 7. Spinning a synthetic polymer prepared by mixing or copolymerizing at least one phosphorus compound [B] represented by the following general formula, and then treating it with a treatment liquid containing a halogenated cycloalkane compound [A]. A method for producing characteristic flame-retardant synthetic fibers. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, and R_3 are an aryl group, an alkyl group, or a cycloalkyl group with or without a substituent, and may be the same or different. ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_4 is a saturated, open-chain or cyclic alkylene, arylene or aralkylene residue, and R_5 is 6
means an alkyl, aryl or aralkyl group having up to 5 carbon atoms. ] [In the formula, R_6 is a monovalent ester-forming functional group,
R_7 and R_8 are the same or different groups, each selected from a hydrocarbon group having 1 to 10 carbon atoms and R_6, and A represents a divalent or trivalent organic residue. Also,
n_1 is 1 or 2, n_2, n_3 are each 0 to 2.
Represents an integer of 4. 8. The method for producing a flame-retardant synthetic fiber according to claim 7, wherein the halogenated cycloalkane compound [A] is contained in an amount of 0.2 to 8% by weight based on the weight of the fiber. 9. Phosphorus compound [B] from 0.05 to fiber weight
8. The method for producing a flame-retardant synthetic fiber according to claim 7, which comprises mixing or copolymerizing the flame-retardant synthetic fiber with a synthetic polymer to a concentration of 5% by weight. 10. The method for producing a flame-retardant synthetic fiber according to any one of claims 7 to 9, wherein the halogenated cycloalkane compound [A] is hexapromocyclododecane. 11. The method for producing a flame-retardant synthetic fiber according to any one of claims 7 to 10, wherein the synthetic polymer is polyester. 12. Production of flame-retardant synthetic fiber according to any one of claims 7 to 11, which is treated with a treatment solution containing a halogenated cycloalkane compound [A] and then subjected to a crimping treatment. Method.