JPH0482914A - Flame-retardant polyester conjugate fiber - Google Patents

Abstract

PURPOSE:To obtain the title conjugate fiber useful for carpets, curtain cloth, seat cloth, etc., having excellent stain resistance and light resistance, containing phosphorus atom, organic fluorescent brightening pigment and white-based inorganic pigment in a specific ratio. CONSTITUTION:The whole conjugate fiber which comprises (A) a polyester copolymerized or blended with a phosphorus compound or a polyester containing the phosphorus compound as a core component and (B) (i) a polyalkylene terephthalate or a polyester consisting essentially of the polyalkylene terephthalate as a sheath component mixed with (ii) 0.02-2wt.% organic fluorescent brightening pigment and (iii) 0.3-5wt.% white-based inorganic pigment having <=0.4mum average particle diameter of primary particles and contains (C) >=2,000ppm phosphorus atom to give the objective conjugate fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a flame-retardant polyester composite fiber with excellent stain resistance and light resistance, particularly for carpets.

The present invention relates to flame-retardant polyester composite fibers suitable for industrial material applications such as curtain fabrics and seat fabrics.

(Prior Art) Generally, polyester has excellent mechanical properties and chemical properties, and is widely used as a fiber for clothing, industrial materials, etc. In particular, polyester fibers used for industrial material applications have different performance requirements for each field.
Polyester fibers used for curtains, carpets, seats, etc. have flame retardancy and resistance to sagging, in addition to conventional properties.

Stain resistance, light resistance, etc. are required. Among these, flame retardancy and stain resistance are particularly required performances, with the former being more required from the viewpoint of fire prevention, and the latter from the viewpoint of aesthetics and cost.

Various attempts have been made to impart flame retardancy to polyester fibers, including adding halogen compounds and phosphorus compounds to the surface of polyester fibers, kneading them into the fibers, and copolymerizing them in one polymerization step. . When flame retardance is imparted using a halogen compound, there are problems such as generation of toxic gas during combustion and poor flame retardant performance.

Currently it is not widely implemented. Many polyester fibers using phosphorus compounds, especially fibers using polyesters copolymerized or blended with phosphorus compounds, have a satisfactory level of flame retardancy.

There has not been a polyester fiber that takes stain resistance as mentioned above into consideration at the same time.

The technology to impart stain resistance to polyester fibers is as follows:
These include those copolymerized with polyalkylene glycol, etc., those in which the surface of polyester fiber is coated with a hydrophilic agent8, and those in which the surface of polyester fiber is etched by plasma treatment and a compound having a hydrophilic functional group is grafted onto it. However, although polyester fibers copolymerized with polyalkylene gelylcol or the like do make the polyester fibers hydrophilic, they impair the light resistance of the polyester fibers and impair processability. Furthermore, polyester fibers whose surfaces are coated with hydrophilic agents have poor washing durability. Plasma processing has disadvantages in that the cost of installing equipment for plasma processing is high and the processing speed is slow.

Furthermore, when a flame-retardant polyester fiber copolymerized or blended with a phosphorus compound is subjected to the above-described hydrophilic treatment, there is a problem in that mechanical properties and processability are deteriorated.

On the other hand, recently, attempts have been made to improve stain resistance by kneading organic fluorescent whitening pigments into fibers (Japanese Unexamined Patent Publication No. 1-306673). However, when an organic fluorescent whitening pigment is added, although the stain resistance is improved, there is a problem in that the organic fluorescent whitening pigment itself has poor light resistance.

(Problems to be Solved by the Invention) In view of the shortcomings of the prior art, the present inventors developed a flame-retardant composite fiber made of polyester copolymerized or blended with a phosphorus compound, which is stain resistant without impairing the performance of polyester fiber. The object of the present invention is to economically provide polyester fibers with added properties such as durability and light resistance.

(Means for Solving the Problems) In order to solve the above problems, as a result of intensive studies, the present invention has a polyester copolymerized or blended with a phosphorus compound as a core component, an organic fluorescent whitening pigment, and absorbs ultraviolet rays. The inventors have discovered that the object can be achieved by forming a core-sheath type composite fiber whose sheath component is polyester blended with a white inorganic pigment, and have thus arrived at the present invention.

That is, the gist of the present invention is as follows.

The core component is a polyester copolymerized or blended with a phosphorus compound, or a polyester containing this.

A core-sheath type composite fiber whose sheath component is polyalkylene terephthalate or polyester mainly composed of polyalkylene terephthalate, which contains phosphorus atoms in an amount of 2,000 ppm or more based on the entire composite fiber, and in the sheath component, with respect to the sheath component. The organic fluorescent whitening pigment is 0.02 to 2% by weight and the average primary particle size is 0.02 to 2% by weight.
A flame-retardant polyester composite fiber containing 0.3 to 5% by weight of a white inorganic pigment with a size of 4μ or less.

In the present invention, the polyester copolymerized or blended with a phosphorus compound used as a core component can be obtained by adding a phosphorus compound when producing a polyester from a dicarboxylic acid component, a diol component, and/or a hydroxycarboxylic acid component. .

The dicarboxylic acid component is terephthalic acid.

Diol components include ethylene glycol and 1゜4-
Butanediol, hydroxycarboxylic acid component: 4
-Hydroxybenzoic acid (including ester-forming derivatives thereof) is preferably used. Isophthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, trimellitic acid, diethylene glycol, and 1,4-cyclohexane dimetatool are used as copolymerization components together with these as necessary.

A small amount of pentaerythritol or the like may be used in combination.

Furthermore, examples of phosphorus compounds include phosphoric acid esters and their derivatives, phosphonic acids and their derivatives, and phosphinic acids and their derivatives, and these can be used alone or in combination of two or more. Specific examples of phosphoric acid esters and derivatives thereof include trimethyl phosphate and triethyl phosphate.

Examples of phosphonic acid and its derivatives include phenylphosphonic acid, dimethylphosphonic acid, diethylphosphonic acid, etc. Specific examples of phosphinic acid and its derivatives include phosphorane,
Examples include maleic acid adducts and itaconic acid adducts of 9.10-dihydro-9oxa-10-phosphaphenanthrene-10-oxide. There are also compounds in which ethylene carbonate is added to a reaction product of diphenylphosphine oxide and p-benzoquinone.

The amount of the phosphorus compound added needs to be 2000 ppm or more in terms of phosphorus atoms based on the entire composite fiber. More preferably, the amount of phosphorus atoms is 4000 to 2
0000ppm, optimally 5000-12000ppm
It is better to make it so that If the amount of the phosphorus compound added is small, the flame retardance will be insufficient, and if it is too much, the polymer price will become high and the physical properties of the polyester fiber may be adversely affected.

Note that polyester copolymerized or blended with a phosphorus compound may be used alone as the core component, but it may also be used in combination with polyethylene terephthalate, polybutylene terephthalate, polynystyl, etc. mainly composed of these.

Moreover, as the polyalkylene terephthalate used for the sheath component, polyethylene terephthalate and polybutylene terephthalate are preferable.

These may contain about 15 mol% or less of a copolymer component.

Next, organic fluorescent whitening pigments added to impart stain resistance include pyrene-based, oxazole-based, coumarin-based, thiazole-based, and imidazole-based pigments.

Examples include imidasilone-based, pyrazole-based, benzidine-based, diaminocarbazole-based, naphthal-based, and diaminostilbendisulfonic acid-based fluorescent whitening pigments, and oxazole-based fluorescent whitening pigments, which have excellent heat resistance, are particularly preferred.

The amount of organic fluorescent whitening pigment added is 0.02 to the sheath component.
It is necessary to set it to 2% by weight. If the amount added is less than 0.02% by weight, the stain prevention effect after washing will be poor, and if it exceeds 2% by weight.

The color tone of the organic fluorescent whitening pigment itself is reflected on the fibers, causing problems such as yellowing, which is undesirable.

The organic fluorescent whitening pigment can be blended with polyester by adding it to the polyester chips as a powder prior to the process of melting them, or by kneading them with the polyester in a kneader in advance to form a high-concentration master chip. There are methods such as mixing with a specific ratio.

Next, the white inorganic pigment compensates for the fact that the light resistance of polyester copolymerized or blended with a phosphorus compound is slightly inferior to that of ordinary polyester.

It is added to maintain the effectiveness of organic fluorescent whitening pigments that do not have good light resistance over a long period of time.

As for the white inorganic pigment, the average primary particle size is 0.
A material having a diameter of 4μ or less, preferably 0.2μ or less is used. If the average primary particle diameter exceeds 0.4μ, the effect of improving light resistance will be poor, and if the particles are coarse, the spinning property will naturally deteriorate.

Specific examples of white inorganic pigments include TlO2゜Z n
O, AI! 203. S j02. Examples include those made of oxide ceramics such as Zr○2 and having the above particle diameter.

The amount of white inorganic pigment added is based on the sheath component.

It is necessary to set it as 0.3-5 weight%. The amount added is
If the amount is 0.3% by weight, the barrier effect against ultraviolet rays will be poor and the light resistance will not be sufficiently improved, and if it exceeds 5% by weight, there will be problems in spinning (early rise in vacuum).

This is undesirable because it causes an increase in the number of thread breakages, etc.).

White inorganic pigments can be blended into polyester by dispersing them in polyester monomers, oligomers, or polymerization raw materials and blending them during polymerization, or by kneading them with polyester in a kneader in the same way as organic fluorescent whitening pigments. There are methods such as using a highly concentrated master chip and mixing it with a pace chip in a specific ratio.

In the composite fiber of the present invention, the composite form is preferably a concentric core-sheath type, but an eccentric core-sheath type may be used as long as the ultraviolet barrier effect on the core component is not impaired.

In addition, the composite ratio of core and sheath is 20/80 to 80/2 at 1 weight ratio.
0, preferably 30/70 to 70/30.

=9 In addition, since the intrinsic viscosity of the fiber affects flame retardant performance and fiber strength, the intrinsic viscosity of the fiber is 0.4 to 1 as measured at 20°C in a mixed solvent of equal weights of tetrachloroethane and phenol.
．． 2. More preferably, it is 0.5 to 1.1. If the intrinsic viscosity of the fiber is less than 0.4, the strength will be low, post-processability will be impaired, and workability may deteriorate. Furthermore, if the intrinsic viscosity of the fiber exceeds 1.2, the viscosity when melted becomes high, so that melting and falling properties may deteriorate during combustion.

In addition, the shape of the fibers may be not only round, but also triangular, hexagonal, flat, and other special cross-sectional shapes, depending on the purpose and ease of use, such as long fibers.

You can choose either short fiber.

(Example) Next, the present invention will be explained by giving examples.

In addition, in the examples, the characteristic values of the polyester fibers were measured as follows.

Measurements were made at a temperature of 20.0°C as a medium.

Phosphorus atom content Quantification was done by fluorescent X-ray method.

Flame retardancy ■Number of flame contacts Melt-spun and drawn long fibers or short fibers are made into a spun yarn into a tubular knitted fabric, and 1g of it is rolled into a length of 10cm and inserted into a wire coil with a diameter of 10cm. death.

Hold it at a 45 degree angle, ignite it from the bottom end with a micro burner with a diameter of 0.64 cm, and if the fire is extinguished by moving the fire source away, repeat the ignition, and calculate the number of ignitions required until the entire sample is completely burnt out. Expressed as the average number of ignitions for 5 samples.

■Limiting Oxygen Index (LOI) Measured in accordance with JIS K 7201.

A contaminant solution is prepared by dissolving 0.3 g of stain-resistant sodium tripolyphosphate, 0.3 g of sodium laurylbenzenesulfonate, 0.5 g of used engine oil, and 0.5 g of clay in distilled water 11.

Using 4 pieces of 10cm x 10cm tube knitted fabric as samples,
Contamination treatment was carried out while stirring the contaminated liquid for 60 minutes at 50°C in a 200°C container. After rinsing this sample with running water and air-drying it, use a household automatic washing machine (manufactured by Toshiba Corporation, 1 liter-40 SL) and wash it with a washing liquid containing monogen manufactured by Daiichi Kogyo Seiyaku Co., Ltd. at a concentration of 3 g/l. , washed at 40°C for 10 minutes,
After repeating rinsing-dehydration twice and air drying.

Using a C light source with a Σ80 type color difference meter made by Nippon Juishikisha.

The hue value L++a++k)+ of the sample was measured.

In addition, a blank sample that was washed under the same conditions without any contamination treatment was measured under the same measurement conditions.

Hue value. + a Or b Q was determined.

Then, the degree of contamination was calculated using a linear equation.

HO=100 [(loo Lo)2+ao'+b
o”]”2Hl= 100-[(10(]-L+)2
+al'+bl']"2 contamination degree=Ho H! Note that the higher the contamination degree number, the poorer the contamination resistance.

Five pieces of tube-knitted fabric with light resistance of 10 cm x 10 cm were treated with a disperse dye solution (Disper TL manufactured by Meisei Kagaku Co., Ltd. 1 g/fl).
, ammonium sulfate 2g/fl.

Formic acid 0.01g/C Bayer disperse dye Re5oli
nRed GR3,0%owf), bath ratio 1:5
The dyeing process was carried out at 130° C. for 60 minutes.

Four of these were Pyrex glass plates with a UV transmittance of 98% (manufactured by Ikki Glass Co., Ltd., 50cm x 50cm,
The specimens were fixed to the bottom of an exposure container (a box made to prevent water from entering inside) with a cover (2 mm thick) so as not to wrinkle, and exposed to the sun for 100 days. The other one was stored in a cool, dark place for 100 days. A sample stored in a cool, dark place was used as a control, and the gray scale difference between it and a sample exposed to sunlight was determined.

When the average gray scale difference was within 1.5 grade, the light resistance was good, and when it exceeded 1.5 grade, the light resistance was poor.

Examples 1-2. Comparative Example 1 Copolymerized polyester chips A, B, and C made by copolymerizing polyethylene terephthalate with triethyl phosphate and having a phosphorus atom content of 10,000, 5,000, and 2,000 ppm and an intrinsic viscosity of 0.61, 0.62, and 0.61 were used as cores. prepared as an ingredient.

On the other hand, polyethylene terephthalate chip D with a one-sided viscosity of 0.67, 1% by weight of Eastman Kodak's organic fluorescent whitening pigment: East Bright ○ B1, and zinc oxide powder with an average primary particle size of 0.13μ A sheath component was prepared by blending chips with master chip E in which 10.0% by weight of (Zn○) was kneaded at a weight ratio of 4/1.

The weight ratio of the core component to the sheath component was set to 1/1, a spinning die with 265 holes was used, the discharge amount was 174 g/min, and the spinning temperature was 9.
Composite spinning was performed at 3° C. and a spinning speed of 1000 m/min.

The obtained undrawn yarn was drawn as a 100,000 denier tow at a draw ratio of 3 to 4 times, heat treated with a heat drum at 150°C, and then crimped with a push-in crimper to give a length of 5
The fibers were cut into 1 mm pieces to obtain composite short fibers having a single fiber fineness of 2 denyl.

In addition, these short fibers are mixed and batted according to the conventional method.

The yarn was passed through the carding, filament, roving, and spinning processes to obtain a 20-count spun yarn. These tube knitted fabrics are flame retardant.

Stain resistance and light resistance were measured.

As a result, the composite fiber of the present invention had good flame retardancy, and was also excellent in stain resistance and light resistance.

Table 1 shows the characteristic values of short fibers and spun yarn.

Note: The amounts of 013-1 and ZnO are antipodal components.

Examples 3-4. Comparative Examples 2 to 3 A phosphorus compound (see JP-A-2-1730) in which 2 moles of ethylene carbonate was added to 1 mole of a reaction product of diphenylphosphine oxide and p-benzoquinone was copolymerized. Using a polyethylene terephthalate copolyester with a phosphorus atom content of 110,000 pp and an intrinsic viscosity of 0.62 as a core component, the amount of 0B-1 and the amount of ZnO shown in Table 2 were obtained by changing the mixing ratio of Chip D and Chip E. Composite short fibers were obtained in the same manner as in Example 1, except that the sheath component was made of the following. Also.

A spun yarn was obtained from these short fibers in the same manner as in Example 1.

As a result, in Comparative Example 2, in which the amount of white inorganic pigment added was small, the light resistance was poor, and in Comparative Example 3, in which the amount of white inorganic pigment added was large, the spinnability was poor.

Table 2 shows the characteristic values of short fibers and spun yarn.

Table 2 Comparative Example 4 Same as Example 1 except that the core component was the copolymerized polyester used in Example 3, and the sheath component was a mixture of Chip D with 0.05% by weight of Yeast Bright ○B-1. Composite short fibers were obtained in the same manner. Also.

A spun yarn was obtained from these short fibers in the same manner as in Example 1.

The flame retardancy, stain resistance, and light resistance were evaluated in the same manner as in Example 1, and the flame retardance was good with a number of times of flame contact of 4.8 times and an average grade of 31.5, and a contamination degree of 4.03. The stain resistance was also good, but the light resistance was poor.

Comparative Examples 5 to 6 Yeast Bright 0B-1 was added to a core component of the copolymerized polyester used in Example 3, and 0.5% by weight of Zn○ with an average primary particle size of 0.13μ was kneaded into chip D. 0.
Composite staple fibers were obtained in the same manner as in Example 1, except that the sheath component was a mixture of 0.005% by weight and 4.0% by weight. Further, spun yarn was obtained from these short fibers in the same manner as in Example 1.

Table 3 shows the results of evaluating flame retardancy, stain resistance, and light resistance in the same manner as in Example 1.

Table 3 Comparative Example 5, in which a small amount of organic fluorescent whitening pigment was added, had significantly poor stain resistance, and Comparative Example 6, in which a large amount of organic fluorescent whitening pigment was added, had a significantly yellowed color tone.

Comparative Example 7 Using ZnO with an average primary particle size of 0.45μ,
Example 3 except that the amount of 0B-1 is 0.05% by weight
Composite staple fibers were obtained in the same manner as above. Further, a spun yarn of No. 20 was obtained from the short fibers in the same manner as in Example 1.

The flame retardancy, stain resistance, and light resistance were evaluated in the same manner as in Example 1, and the flame retardance was good with an LOI value of 31.9 when exposed to flames 4 and 6 times. The stain resistance was also good, but the light resistance was poor.

Example 5 The core component was the copolymerized polyester used in Example 3, the sheath component was a chip blend of chips D and E at a weight ratio of 4/1, a spinneret with 36 holes was used, and the discharge amount was 35g/min, spinning temperature 293°C.

Composite spinning was carried out at a spinning speed of 1400 m/min, and the drawing ratio was 3.
0x, stretched at a heater plate temperature of 160°C, 75d
/36f composite long fiber yarn was obtained.

This long fiber yarn was made into a tubular knitted fabric, and as in Example 1, flame retardant and
When the stain resistance and light resistance were evaluated, the flame retardance was good, with the number of flame contacts being 4.7 times and the LOI value being 31.3.

It had good stain resistance, with a stain degree of 3.33, and good light resistance, making it a material suitable for flame-retardant curtain fabrics, etc.

(Effect of the invention) According to the present invention, a flame-retardant polyester composite fiber whose core component is polyester copolymerized or blended with a phosphorus compound has stain resistance and light resistance without impairing the performance of polyester fiber. It becomes possible to economically obtain polyester composite fibers with added .

The fibers of the present invention can be widely used in industrial materials such as carpets, curtains, and seat fabrics.

Patent applicant: Nihon Ester Co., Ltd.

Claims (1)

[Claims] (1) A core-sheath type composite fiber whose core component is a polyester copolymerized or blended with a phosphorus compound or a polyester containing it, and whose sheath component is polyalkylene terephthalate or a polyester mainly composed of this, and which has phosphorus atoms in the composite fiber. A white inorganic pigment containing 2,000 ppm or more based on the entire fiber, and 0.02 to 2% by weight of an organic fluorescent whitening pigment based on the sheath component and an average primary particle size of 0.4 μ or less in the sheath component. A flame-retardant polyester composite fiber containing 0.3 to 5% by weight of