JPH0819572B2 - Method for producing flame-retardant polyester composite fiber - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a flame-retardant polyester conjugate fiber, and more particularly to a method for producing a polyester conjugate fiber having bulkiness and flame retardancy.

(Prior Art) Polyester is widely used industrially for fibers, films, and plastics, but it has a drawback that it is easily burned, and flame retardancy is strongly desired due to the recent movement of the flame-proof laws and regulations. ing.

Various studies have been made on the flame retardancy of polyesters, but a method that balances the flame retardant performance with manufacturing conditions and general quality has not been established yet.

As a durable flame retardant method, there are a method of copolymerizing a halogen compound, a phosphorus compound, and a phosphorus-containing halogen compound with polyester, and a method of adding and mixing them.

A method for copolymerizing a halogen compound is disclosed in JP-A-49
-54494. As a method of adding a phosphorus compound or the like for improving the thermal stability of the obtained copolymer, JP-A-50-82160, JP-A-50-78646, JP-A-50-67354, JP-A-50-67354, The improved techniques described in Japanese Patent Publication No. 50-34395 are known.

As a method of adding and mixing, there is known a method of blending a halogen-containing phosphorus compound as described in JP-B-52-24943.

(Problems to be Solved by the Invention) When a halogen compound is copolymerized in making the polyester flame-retardant, the thermal stability of the obtained flame-retardant polyester is remarkably lowered, and coloring and manufacturing problems due to heat during molding are caused. In addition, since it is merely kneading in the addition and mixing method, there is a drop in the solvent treatment such as dry cleaning and there is a difficulty in sustaining the effect, but the present inventors have no trouble such as thermal decomposition during production. The present invention has been completed as a result of earnestly studying an easy and simple method for producing a flame-retardant polyester and improving the durability of the effect of the flame-retardant polyester obtained by the method.

An object of the present invention is to provide a method for producing a durable flame-retardant polyester composite fiber. Another object is to provide a method for industrially producing the polyester uniformly, inexpensively and easily. Still another object is to provide a flame-retardant polyester that can be used for clothing as a fiber having bulkiness and flame retardancy.

(Means for Solving the Problems) In the method of the present invention, a polyester of polyethylene terephthalate (polyester A) and a polyester of polyethylene terephthalate (polyester A) are used in the general formula ( I) [X: methylene group, isopropylidene group, sulfonyl group, Y: H or methyl group, n: an integer of 1 to 3] 0.05 to 12% by weight of at least one halogenated diol compound represented by the general formula (II ) [R ₁ : H and / or CH ₃ group, R ₂ : H or C _{1 to} C ₄ alkyl group, X: methylene group, isopropylidene group, sulfonyl group, l: an integer of 1 or more] Glycidyl ether compound 0.05
˜12% by weight, and the total amount of the halogenated diol compound and the halogenated glycidyl ether compound is 0.1 to 1
A flame-retardant polyester composite fiber characterized by being eccentrically joined at a cross section of 2/8 to 8/2 (weight ratio) with a polyester composition (component B) in which 5% by weight is mixed and reacted with polyethylene terephthalate. Is a manufacturing method.

The polyalkylene terephthalate applied to the present invention preferably comprises at least 85% by weight of polyalkylene terephthalate, and as dicarboxylic acids other than terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, trimellitic acid, 5-sodium sulfoisophthalate. Aromatic carboxylic acids such as taric acid, adipic acid, sebacic acid,
Aliphatic dicarboxylic acids such as glutaric acid, or glycols other than ethylene glycol and butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, pentamethylene glycol, neopentyl glycol, hexamethylene glycol, etc. The glycols may be copolymerized with one kind or two or more kinds, and polyethylene terephthalate is particularly preferable.

The number average molecular weight of the polyester applied to the present invention is preferably 18,000 to 22,000.

The halogenated diol compound applied to the present invention is represented by the above general formula (I), wherein X is a methylene group,
Either an isopropylidene group or a sulfonyl group is possible, but an isopropylidene group is preferred. Further, in order to improve the heat resistance of the compound, it is possible to mix and use both of the isopropylidene group and the sulfonyl group. or,
In the formula, Y is H or a methyl group, but H is H from the viewpoint of heat resistance.
Is preferable, and n is 1 from the viewpoint of reactivity with polyester.
Is particularly preferable. Furthermore, the hydroxyl value of the halogen-containing compound is 20.
It is preferably 0 or less.

The halogenated glycidyl ether compound blended in the polyester together with the halogenated diol compound is represented by the general formula (II), and R ₁ is H and / or a methyl group, and H is particularly preferably heat resistant and versatile. It is suitable. R ₂ is H or a C ₁ -C ₄ alkyl group is applied,
Similar to R ₁ , a methyl group, an ethyl group, a propyl group, and a butyl group are preferable in terms of heat resistance and versatility, and an isobutyl group is particularly preferable. X may be a methylene group, an isopropylidene group, or a sulfonyl group, but an isopropylidene group is preferable. It is also possible to mix and use both an isopropylidene group and a sulfonyl group in order to improve the heat resistance of the compound. Further, as l, an integer of 1 or more is applied, but 1 to 8 is preferable, and 1 to 6 is particularly preferable.

The halogenated glycidyl ether compound is specifically prepared by ring-opening at least one halogenated aromatic bishydroxy derivative glycidyl ether with at least one monofunctional compound.

As the aromatic bishydroxy derivative, bisphenol A, bisphenol F, bisphenol S, brominated bisphenols, bisphenols added with ethylene oxide and / or propylene oxide, bis-
(Β-hydroxyethyl) terephthalate and bis-
Examples thereof include halogen compounds such as (β-hydroxyethyl) isophthalate.

Examples of the monofunctional compound include alcohols such as methyl alcohol, ethyl alcohol, amino alcohol and benzyl alcohol, or phenol, 2-methylphenol, 3-methylphenol, 4 and the like.
-Methylphenol, 2,3-Dimethylphenol, 2,4
-Dimethylphenol, 2,6-Dimethylphenol, 3,4
-Dimethylphenol, 3,5-dimethylphenol, 2
-Ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert
-Butylphenol, 2-sec-butylphenol, 4
-Sec-butylphenol, 2-n-butylphenol, 3-n-butylphenol, 4-n-butylphenol, 4-methyl-2-tert-butylphenol, 4-
tert-aminophenol, 6-n-amylphenol,
4-methyl-2-tert-amylphenol, 2,5-dimethyl-4-tert-butylphenol, 4-ethyl-2-
tert-butylphenol, 2,6-di-tert-butylphenol, 4-diisobutylphenol, 3-methyl-4,
6-di-tert-butylphenol, 3-methyl-4diisobutylphenol, 2,3-dimethyl-4,6-di-tert-
Alkyl phenols such as phenol, 3-ethyl-4,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-amylphenol and 2,4,6-tri-tert-butylphenol However, tert-butylphenol, sec-butylphenol and a-butylphenol are particularly preferable. Examples of other monofunctional compounds include phenyl glycidyl ether, meta-cresol glycidyl ether, tert-butylphenol glycidyl ether, and the like.

The halogenated diol compound is blended in an amount of 0.05 to 12% by weight, preferably 0.1 to 8% by weight, particularly 0.2 to 6% by weight, and the halogenated glycidyl ether is 0.05 to 12% by weight, preferably 0.1 to 8% by weight, particularly 0.2. The total amount of the halogenated diol compound and the halogenated glycidyl ether compound is 0.1 to 15% by weight, preferably 0.5 to 10% by weight, and particularly 1 to 8% by weight. If the total amount of the halogenated diol compound and the halogenated glycidyl ether in the component B is less than the above range, the flame retardant effect may be insufficient, and if it exceeds the above range, single yarn cutting during spinning may occur. It tends to cause manufacturing problems such as.

It is also possible to add commercially available dyes and pigments, fluorescent brightening agents, matting agents, gloss imparting agents, foaming agents, antistatic agents, heat and light stabilizers, etc. to the compounds applied to the present invention. .

As a method of adding the halogenated diol compound and the halogenated glycidyl ether compound to the polyester of the present invention, for example, mixing using a static mixer at the time of chip formation, or stirring and mixing in a chip state is also possible. Although it is possible, in such a case, the complexity of chip storage and process complexity due to many brands of products cannot be avoided, and in order to impair the features of the present invention, it is added to polyester on one side during spinning. As an addition position of the additive at the time of spinning, an association part is provided in the polyester having a normal polymerization degree at the outlet of the polymer introduction pipe, and the halogenated diol compound and the halogenated glycidyl ether compound measured by the plunger pump or the gear pump are injected from the injection nozzle. Added.

The polymer flow path after the association part is, for example, the first kneading part-gear pump-second kneading part-spin beam (third kneading part)-
Depending on the order of spinning bags, the allowable pressure loss in the kneading section can be increased as much as possible, and the number of known static kneading elements used can be increased to enhance the kneading effect.

Examples of the static kneading element include a static mixer (manufactured by Kenix Co., Ltd.), an R0SS-LSG mixer (manufactured by Tokushu Kika Co., Ltd.), an SM mixer (manufactured by Sulsar Co.) and a BKM mixer (manufactured by Zulsar Co.). The associating part, the first kneading part, and the gear pump can be incorporated into a wear plate for joining the gear pumps to improve the accuracy of measuring the additive and to make the apparatus compact. Before the meeting part, the flow path is branched in parallel into two sets, each of which is provided with a meeting part, a first kneading part, a gear pump and a second kneading part, and the second kneading part outlet is joined to a spinning bag having two inlets. Then, the polyol is added only to the single association part, and the polyester composite fiber is spun out.

At the time of spinning, the A component and the B component are eccentrically in the cross section and are 2/8 to 8/2 (weight ratio), preferably 3/7 to 7/3 (weight ratio), particularly preferably 4/6 to 6 Join at / 4 (weight ratio). The A component and the B component can be eccentrically or parallelly connected in a core-sheath shape, but the parallel connection is preferable in terms of crimpability. Bonding ratio is 2 /
If it is out of the range of 8 to 8/2 (weight ratio), sufficient crimp cannot be obtained, and uniform and good quality flame-retardant polyester conjugate fiber cannot be obtained.

The shape of the spinneret may be circular or irregular, or hollow fibers may be spun out, for example, slits may be arranged in parallel.

(Effects of the Invention) The flame-retardant polyester conjugate fiber obtained by the present invention has excellent bulkiness and is widely used not only for clothing but also for padded cotton and non-woven fabrics.

(Examples) Hereinafter, the present invention will be described with reference to examples.

The flame retardant performance is based on Fire Defense Project No. 69 (April 1, 1982) Attachment 2 "Performance test standards for flameproof products" (bedding), 45
Evaluation was made based on the carbonization length (mm) of the mesenamin basket method and the number of times of flame contact with the 45 degree coil method. For futon cotton bulkiness, we made a web of 200 g of polyester cotton with a sample card, cut the web into 200 mm × 200 mm square, and weighed 80
Webs were stacked so as to have g, and the height of the web was measured and evaluated.

Example 1 A polymer flow path was provided in the order of an association part branched into two sets, a first kneading part, a gear pump, and a second kneading part for polyethylene terephthalate having a number average molecular weight of 21,000 at the outlet of the polymer introducing pipe at 280 ° C. The two kneading parts were joined to a spinning bag having two inlets, and the EO2 mol adduct of tetrabromobisphenol A and tetrabromobisphenol A diglycidyl ether were opened at the association part on one side with p-sec butylphenol. Glycidyl ether compound (epoxy equivalent 2800, melting point 105 ° C, Br cont 47.8%)
Gear pump quantitatively in a mixed state of a certain ratio, and the total amount is 3.
5 wt% was added. The halogenated diol compound had a melting point of 118 ° C. and a hydroxyl value of 178.

In order to mix and disperse the B component polyester composition, the first and second kneading sections each have an inner diameter of 25 mm, a static mixer (made by Kenix) with L / D = 1.5, and 12 elements, and an inner diameter of 16.2 mm and a length. Two elements of a 23 mm BKM mixer (manufactured by Sulcer) were used, and further, a BKM mixer (manufactured by Sulsar) S element was used in the spin beam. The spinning back uses a 240H hollow side-by-side spinneret, the joining ratio of A component and B component is 1: 1 and winding speed is 780.
Spinned at m / min. The undrawn yarn thus obtained was drawn and heat-treated to obtain the results shown in Table 1. The single yarn denier of each drawn yarn was 7.3.

Futon batting was prepared from the above-mentioned cotton, and a flame-retardant test was carried out by the mesenamine 45 ° basket method, and the futon cotton bulkiness was measured.

Example 2 In the same manner as in Example 1, the ratio of the halogenated diol compound / halogenated glycidyl ether compound was set to 6/4, and the mixture was added in the range of 5 to 20% by weight with respect to the polyester.
I got a single yarn. The results are shown in Table 2.

Example 3 Polyethylene terephthalate flow rate of 390 g / min, core of sheath / core eccentric type 400H, bonding ratio of A component and B component
The results of Table 3 were obtained by changing the addition amount of the mixture in the same manner as in Example 2 except that the winding speed was 1: 1 and the winding speed was 850 m / min.

After spinning, stretch crimping was applied, each single yarn 3d was cut into 51 mm, and it was spun by ring spinning to 20'S with 100% polyester. After cylindrical knitting, the number of 45 ° coil flame contact was measured.

Example 4 Polyethylene terephthalate having a number average molecular weight of 21,000 polymerized by a direct continuous weight method was melted at a polymer tube temperature of 282 ° C., and 50 parts by weight of an EO adduct of a mixture of tetrabisphenol A and tetrabisphenol S (weight ratio 1: 1). And 50 parts by weight of a halogenated glycidyl ether compound (epoxy equivalent 3870, softening point 138 ° C, bromine content 53.6%) obtained by ring-opening tetrabromobisphenol A diglycidyl ether with t-butylphenol glycidyl ether were melt mixed and quantified with a gear pump. , 3.0% by weight relative to polyester. The melting point of these halogenated diol compounds was 145 ° C., and 93% of EO addition was a 2 mol addition product.

As in Example 1, a static mixer was used to measure the rapid reaction. The bonding ratio is A component: B component = 6: 4,
A 6d x 51mm polyester cotton with a hollow side by side was obtained.

When a futon batting was prepared from the above cotton and subjected to a flame retardant test by the mesenamine 45 ° basket method, excellent results were obtained with a maximum carbonization length of 105 mm and an average of 93 mm.

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Claims (3)

[Claims] Claims: When composite spinning of two types of polyester, a polyester mainly composed of polyethylene terephthalate (component A) and a polyester mainly composed of polyethylene terephthalate are added to the general formula (I). [X: methylene group, isopropylidene group, sulfonyl group, Y: H or methyl group, n: an integer of 1 to 3] 0.1 to 8 parts by weight of at least one halogenated diol compound represented by the general formula (II ) Halogenated glycidyl ether represented by [R ₁ : H and / or CH ₃ group R ₂ : H or C ₁ -C ₄ alkyl group X: methylene group, isopropylidene group, sulfonyl group, integer of 1: 1 or more] Compound 0.05
˜12% by weight, and the total amount of the halogenated diol compound and the halogenated glycidyl ether compound is 0.1 to 1
5% by weight of polyethylene terephthalate is mixed eccentrically in a cross section at 2/8 to 8/2 (weight ratio) with a polyester composition (component B) obtained by compounding reaction by rapid kneading using a static kneading element. A method for producing a flame-retardant polyester composite fiber, comprising: 2. A method according to claim 1 wherein at least 85% by weight of the polyester is polyethylene terephthalate. 3. The method according to claim 1, wherein X in the halogenated diol compound and the halogenated glycidyl ether compound is an isopropylidene group.