JPS63235573A - Flameproof black synthetic fiber - Google Patents

Abstract

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

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a black synthetic fiber with excellent flame retardancy, and a flame retardant black synthetic fiber containing carbon black and/or titanium black, which is particularly suitable for blackout curtains and curtains. It concerns fibers.

(Prior Art) Various attempts have been made to use synthetic fibers dyed black with carbon black in areas requiring light-shielding properties, such as blackout curtains and curtains.

On the other hand, instead of dyeing the yarn with carbon black, synthetic fibers dyed with black dye are also being used.

(Problems to be Solved by the Invention) However, synthetic fibers containing carbon blanks do not have sufficient flame retardancy even when treated with flame retardants.
Until now, it has hardly been used in fields such as blackout curtains and curtains.

In addition, synthetic fibers dyed with black dye tend to discolor when subjected to anti-dyeing or flame-retardant treatment, making it difficult to obtain high-quality products, having poor light resistance, and costing more. It had the disadvantage of being expensive.

An object of the present invention is to solve the problems of the prior art and to provide a synthetic fiber with good flame retardant properties suitable for blackout curtains, curtains, etc.

(Means for Solving the Problems) In order to achieve the above object, the present inventors have made intensive studies and found that a halogenated cycloalkane compound (hereinafter referred to as HC
The present invention was achieved by discovering that flame retardancy can be significantly improved by using carbon black and/or titanium black-containing synthetic fibers in combination with a specific phosphorus compound.

That is, the present invention provides a halogenated cycloalkane compound [A]
, phosphorus compound CB represented by the following general formulas (1) to (3)
), and carbon black and/or titanium black.

[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. [In the formula, R4 is a saturated, open-chain or cyclic alkylene, arylene or aralkylene residue, and R7 is up to 6 carbon atoms] [In the formula, R6 is a monovalent ester-forming functional group, and R
t and R11 are the same or different groups, each selected from a hydrocarbon group having 1 to 10 carbon atoms, R4, and A
represents a divalent or trivalent organic residue. Also, n is 1
Alternatively, 2, R2, and R2 each represent an integer of 0 to 4. ] 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, 1.2
．． Examples include 5,6,9.10-hexabromocyclododecane. 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.

In addition, the amount of protective colloid used is determined by flame retardancy, texture, spinnability, etc., and it is better to use as little as possible.
1% or less is desirable.

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

R3o/ [In the formula, R,, R, and R are a ring group, an alkyl group, or a cycloalkyl group with or without a substituent, and may be the same or different. [In the formula, R4 is a saturated, open-chain or cyclic alkylene, arylene or aralkylene residue, and R3 is up to 6 carbon atoms] It means an alkyl group, an aralkyl group, or an aralkyl group having an atom. [In the formula, R6 is a monovalent ester-forming functional group, and R
t and R1 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. Further, nl represents 1 or 2+nz + ns each represents an integer of O to 4. ] In the phosphorus compound represented by the above general formula (2), in the formula R
+, Rt, and Rz include aryl groups such as phenyl, naphthyl, and biphenyl; substituent ryl groups such as nonylphenyl, ethoxyphenyl, and methoxyphenyl; methyl,
Alkyl groups such as ethyl, butyl, octyl and nonyl; substituted alkyl groups such as ethoxyethyl and butoxyethyl; cycloalkyl groups such as cyclohexyl and decahydronaphthyl; substituted cycloalkyl groups such as methylcyclohexyl. 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, octyl diphenyl phosphate, cyclohexyl diphenyl phosphate,
Examples include naphthyl diethyl phosphate and methylcyclohexyl diethyl phosphate.

In addition, in the phosphorus compound represented by the above general formula (2), R4 includes a linear alkylene group such as methylene, ethylene, propylene, isopropylene, butylene, and isobutylene; a cyclic alkylene group such as cyclohexylene; phenylene, etc. arylene group; examples include aralkylene groups such as methylphenylene; R1 is a chain alkyl group such as methyl, ethyl, butyl, isobutyl, a cyclic alkyl group such as cyclohexyl, and a chain alkyl group such as phenyl; and aralkyl groups such as benzyl.

Furthermore, in the phosphorus compound represented by the above general formula (3), R specifically refers to a carboxyl group, an alkyl ester of a carboxyl group having 2 to 7 carbon atoms, a cycloalkyl ester, and a cycloalkyl ester. Examples include a hydroxyl ester, a hydroxyl group, a hydroxyalkoxycarbonyl group having 2 to 7 carbon atoms, and a group represented by -C-O-C-.

R again? , R11 is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, and the above-mentioned R8
Preferred examples include monovalent groups.

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, -cHz -c-yunCH2 A trivalent group represented by a fan R drop (R9 is a hydrogen atom or a lower alkyl group such as methyl or ethyl, and R4 is 0 or 1). These phosphorus compounds (B) can be used alone. too,
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 weight of the fiber, and phosphorus compound (B) in an amount of 0.05 to 5% by weight based on the weight of the fiber.
It is desirable that the content be % by weight. If the content of HCA (A) 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 property 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.

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, to copolymerize polyester with a phosphorus compound CB), the phosphorus compound CB) may be added during the transesterification reaction, or may be added before the polycondensation reaction after the transesterification reaction or at a relatively early stage of the polycondensation reaction. It can also be added in stages. Furthermore, when the phosphorus compound CB) is mixed into the synthetic polymer, the phosphorus compound (B) 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 0°2 to fiber weight.
It is desirable that the amount is 8% by weight, and for that purpose, it is suitable that the HCA(A)tW degree of the treatment liquid is 1 to 30% by weight. Additionally, when this HCA treatment liquid is combined with a phosphate compound represented by the general formula below, foaming of the treatment bath is controlled, liquid stability is improved, and rust prevention, push-in crimper passability, and spinnability are greatly improved. It has been improved and is suitable.

R1゜-(CHz CHz O), O-P OM
0M' [Here, R1° 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 benzotriazole-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, )(
After applying the CA treatment liquid 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 obtain HCA (A).
penetrates into the fibers.

Examples of 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. Among them, in the state of fibers containing blackening agents, flame retardants, etc.
When a polyester having a melt viscosity of 2,000 poise or less at 280° C. is used, the drip effect is greatly increased and the flame retardant effect is greatly improved. Examples of such polyesters include polyethylene terephthalate copolymerized with 10 mol% or more of isophthalic acid;
Examples include polytetramethylene terephthalate copolymerized by mole % or more.

Further, the black synthetic fiber of the present invention is colored with carbon black and/or titanium black using a stock solution, and the content of carbon black and/or titanium black is usually 0.3 to 5% by weight. If the content is too low, the black color becomes pale, and if the content is too high, the spinning condition tends to deteriorate.

(Function) According to the present invention, HCA (A) and the phosphorus compound CB
), the flame retardant properties of black synthetic fibers containing carbon black and/or titanium black are significantly improved.

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

The adhesion rate and flame retardance of the treatment agent were evaluated by the following methods.

(1) Adhesion rate of treatment agent Adhesion rate of treatment agent = (treatment agent/fiber) x 100 (weight, f%) (2) Flame retardancy After repeated washing with water 5 times according to the fire 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.

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. Then, 1.5 parts of carbon black, 0.7 parts of trimethyl bosphate, and 0.99 parts of p-diphenylcarboxylic acid were added,
As the reaction progresses at 5°C under a nitrogen atmosphere, the pressure gradually decreases.
Finally, Q was set to 4 mmHg and the reaction was continued for 200 minutes.

The obtained polyester had an intrinsic viscosity of 0.64 and a carbon blank content of 1.5% by weight. 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 400,0 as a protective colloid
0.00 carboxymethyl cellulose 0.5 part and water 5
An aqueous dispersion of HBCD (active content 45% by weight, viscosity: 4.5%) prepared by pulverizing and mixing 4.5 parts in a ball mill for 5 hours.
00 centipoise, measured with a rotating B-type viscometer) 44 parts,
A treatment bath was prepared by adding water to make a total of 100 parts.

After passing the stretched tow through immersion in this treatment bath, the treatment solution was squeezed using a push crimper so that the amount of HBCD attached was 1.0% by weight, and the number of crimps was 12/25mm.
The cotton was crimped to give a crimp rate of 12%, then subjected to relaxation heat treatment at 170'C for 15 minutes in a continuous dryer, and then cut at 51°C 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 a black fabric for blackout curtains with a jacquard structure having a warp density of 100 yarns/inch and a weft yarn density of 75 yarns/inch was woven using a jacquard loom. The flame retardancy of this fabric is as shown in Table 1.
It had a black appearance and good aesthetics, making it suitable for blackout curtains.

Comparative Examples 1 to 5 In Example 1, the treatment was carried out in exactly the same manner as in Example 1, except that the treatment with the HBCD 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).

Further, in Example 1, instead of using HBCD as a flame retardant, Comparative Example 3 used Anti-Blaze 19 (manufactured by Mobil Chemical Company, cyclic phosphate ester, active ingredient 100%), and Comparative Example 4 used Tris 2. Emulsion of 3-dichloropropyl phosphate (active content 45%), Comparative Example 5
The process was carried out in exactly the same manner as in Example 1, except that an emulsion of tetrabromobisphenol A (effective content: 45%) 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 (B) (Example 1)
had good flame retardant properties, but when it did not contain HCA (A) (Comparative Example 1), when it did not contain phosphorus compound (B) (Comparative Example 2), and when other conventionally used flame retardants When the agent was used (Comparative Examples 3 to 5), the flame retardant properties were poor.

Table 1 Example 2.3 In Example 1, 1°2.3.
4-tetrabromocyclooctane (Example 2) and 1
．． 2,3.4,5.6-hexabromocyclohebutane (
Example 3) was used, and the other conditions were the same as in Example 1. The results are shown in Table 2, and all showed good flame retardancy.

Table 2 Example 4 840 parts dimethyl terephthalate, 160 parts dimethyl isophthalate, 798 parts ethylene glycol, 0
．． A mixture of 23 parts of manganese acetate was heated at 170-220°C until methanol distillation was complete. Then 220
Esterification was carried out by adding 8 parts of 2-carboxyethyl-methylphosphinic acid at °C. Then carbon black 10
parts, titanium blank 15 parts, antimony trioxide 0.35 parts
As the reaction progressed at 275° C. under a nitrogen atmosphere, the pressure was gradually reduced to 0.2 mmHg and the reaction was continued for 150 minutes.

The obtained polyester has an intrinsic viscosity of 0.53, a carbon black content of 1.0% by weight, and contains titanium black!
1.5% by weight, melting point: 215°C, melt viscosity at 280°C: 1.900 Bois.

Using this polyester, spinning, stretching, treatment with an HBCD treatment liquid, crimping, and cutting were performed in the same manner as in Example 1 to prepare raw cotton. The amount of phosphorus compound copolymerized in this raw cotton is approximately 0.8
The phosphorus content was 0.16% by weight, and the amount of HBCD deposited was 2.0% by weight. This raw cotton was spun and woven in the same manner as in Example 1, and evaluated on the same items as in Example 1. The results were good as shown in Table 3. The appearance of this fabric was black and had good aesthetics, making it suitable for blackout curtains.

Example 5 A mixture of 349 parts of dimethyl terephthalate, 39 parts of dimethyl isophthalate, 360 parts of tetramethylene glycol, 3.5 parts of a phosphorous compound, 0.34 parts of zinc acetate, and 0.34 parts of antimony trioxide was prepared. The mixture was heated at 150 to 230°C until the distillation of methanol was completed. Next, carbon black5.
As the reaction progressed at 275° C. under a nitrogen atmosphere, the pressure was gradually reduced to 0.2 mHg and the reaction was continued for 160 minutes.

The obtained polyester had an intrinsic viscosity of 0.65, a carbon black content of 1.5% by weight, a melting point of 200°C, and a melt viscosity at 280°C of 1,300 poise.

Using this polyester, spinning,
Raw cotton was prepared by stretching, false twisting, treatment with an HBCD treatment liquid, crimping, and cutting. The amount of phosphorus compound copolymerized in this raw cotton is approximately 0.9% by weight, the phosphorus content is 0.09% by weight,
The amount of HBCD deposited was 2.0% by weight.

This raw cotton was spun and woven in the same manner as in Example 1, and Example 1
The same items were evaluated. 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 black synthetic fiber of the present invention (Example 4.5) containing HCA (A) and a phosphorus compound (B) had good flame retardancy, but HCA (A)
(Comparative Example 6.7), flame retardancy was significantly reduced.

Table 3 (Effects of the Invention) As explained above, according to the present invention, by incorporating a halogenated cycloalkane compound and a specific phosphorus compound into a black synthetic fiber containing carbon black and/or titanium black, , flame resistance is greatly improved.

The flame-retardant black synthetic fiber of the present invention is extremely useful for use in fields such as blackout curtains and curtains.

Claims (1)

[Scope of Claims] 1. A halogenated cycloalkane compound [A], at least one phosphorus compound [B] represented by the following general formulas (1) to (3), and carbon black and/or titanium black. A flame-retardant black synthetic fiber characterized by containing. ▲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 are the same. But it can be different. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(2) [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 and n_3 are each 0 to 4
represents an integer. 2. The flame-retardant black 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 black synthetic fiber according to claim 1, which has a content of 0.05 to 5% by weight. 4. Claims 1 to 3, wherein the halogenated cycloalkane compound [A] is hexabromocyclododecane
The flame-retardant black synthetic fiber according to any one of the items. 5. Claim 1 in which the synthetic fiber is polyester
The flame-retardant black synthetic fiber according to any one of items 1 to 4. 6. Polyester has a melt viscosity of 2.0 at 280°C
The flame-retardant black synthetic fiber according to claim 5, which is a polymer having a poise of 00 poise or less.