JP2003089926A - Flameproof black-pigmented polytrimethylene terephthalate polyester fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flameproof black-pigmented polyester fiber suitable for blackout curtains or shading curtains. SOLUTION: This flameproof black-pigmented polytrimethylene terephthalate polyester fiber is obtained by blending an isophthalic acid-copolymerized polyethylene terephthalate polymer containing specific carbon black with a polytrimethylene terephthalate polymer substantially containing no carbon black followed by carrying out melt spinning.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black-dyed polyester fiber suitable for use in dark curtains, light-shielding curtains, and the like. More specifically, it mainly contains polytrimethylene terephthalate, which has a particularly soft texture and excellent physical properties. Regarding black-dyed polyester fiber.

[0002]

Polytrimethylene terephthalate is a polyester obtained by polycondensing terephthalic acid and / or terephthalic acid ester with trimethylene glycol (1,3-propanediol) and has a low elastic modulus (softness). Texture), excellent elastic recovery properties similar to polyamide, and light resistance, heat setting property, dimensional stability,
It is a material that also has properties unique to polyester, such as low water absorption. Taking advantage of these features, commercialization is progressing for BCF carpets, brushes, tennis guts, etc.
-3724, JP-A-8-173244, JP-A-5-262862).

On the other hand, since the polyester polymer alone is inferior in easy dyeing property and color forming property when formed into a fiber, a black polyester fiber by so-called dyeing in which a pigment is mixed and dispersed in the polymer (hereinafter, simply referred to as a black dyeing yarn) Is widely used not only for clothing, but also for industrial and construction applications. As the application development of polytrimethylene terephthalate progresses, a sown with excellent texture and sufficient physical properties. Since yarn can be obtained, there is an increasing need in the fields of blackout curtains, blackout curtains, and the like.

By the way, the black polyester fiber by the dyeing is usually produced by adding carbon black at the polyester polymerization reaction or at any stage after the polymerization until molding. Methylene terephthalate fibers have a higher melt viscosity than fibers that do not contain carbon black.Therefore, the drip effect when the fibers are ignited (the polymer around the ignition becomes less viscous due to heat and falls with the ignited parts). The effect of preventing the spread of fire) is insufficient, and the flameproof performance is insufficient for use as a dark curtain or a light-shielding curtain.

Conventionally, in polyester fibers typified by polyethylene terephthalate, various measures have been taken in order to solve such problems. For example,
Japanese Examined Patent Publication (Kokoku) No. 4-44029 proposes a black spun-dyed yarn in which the amount of carbon black blended is reduced and the decrease in the light-shielding property due to this is compensated for by the blending of titanium oxide. However, the black curtain obtained from this has satisfactory light-shielding properties, but has a reduced blackness and lacks sharpness.

On the other hand, JP-A-60-45689, JP-A-63-92719 and JP-A-63-1170.
No. 71, etc. propose a method of obtaining a black dyeing by adding and spinning a liquid colorant in which carbon black is mixed with a liquid polyester into a molten polyester. Since the black dyed yarn obtained by such a method contains a low-viscosity liquid polyester, an increase in the viscosity of the molten polyester due to the addition of carbon black is suppressed, and the flameproof performance due to the drip effect is improved.

However, according to the study by the present inventors, the viscosity of the liquid colorant in which the ordinary carbon black is mixed with the liquid polyester in a high concentration is extremely high, so that the measuring accuracy is lowered and the coloring unevenness is caused. It has been found that there are drawbacks in that it is easy to generate, and bubbles are easily introduced to break the yarn during the yarn making. In order to solve this problem, the liquid colorant in which the amount of carbon black is reduced must be increased in order to obtain sufficient blackness and light-shielding properties. There is a drawback that causes deterioration of yarn forming property.

[0008]

SUMMARY OF THE INVENTION The present invention has been made against the background of the above-mentioned prior art, and its object is to provide both excellent blackness and flameproof performance, and is particularly suitable for dark curtains and light-shielding curtains. An object of the present invention is to provide a black dyed polytrimethylene terephthalate-based polyester fiber having excellent spinnability.

[0009]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a copolyester in which a large amount of carbon black having a specific thermal conductivity is dispersed and a polytriene The inventors have found that black melt-dyed polyester fibers excellent in flameproofing performance and blackness can be obtained with extremely stable spinnability by melt-spinning with methylene terephthalate and then melt spinning.

That is, an object of the present invention is a black-stained polytrimethylene terephthalate-based polyester fiber containing carbon black, which comprises the following polymer (A):
And (B) are mixed and melt-spun, and the content of carbon black in the fiber is 0.5 to 5 based on the weight of the fiber.
2.0% by weight, the content of the following polymer (A) is 2 to 10% by weight based on the weight of the fiber,
It can be achieved by flame-retardant black-stained polytrimethylene terephthalate-based polyester fiber. (A) 5 to 20 mol% of isophthalic acid component is copolymerized based on the total acid component, the average particle size is in the range of 5 to 25 nm, and the thermal conductivity is 200 × 10 ^{6 to} 1000 × 10 ⁶ W /
Isophthalic acid-copolymerized polyethylene terephthalate containing 5 to 40 wt% of carbon black in the range of m · K based on the total weight. (B) Polytrimethylene terephthalate substantially free of carbon black.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of carbon black that can be used in the present invention include channel black and furnace black. When the particle diameter is too small, the particles are easily aggregated when compounded in an isophthalic acid-copolymerized polyethylene terephthalate polymer (hereinafter sometimes referred to as polymer (A)), and it becomes difficult to form a yarn. If too much, the blackness decreases. Therefore, it is necessary that the primary particle diameter of carbon black is within the range of 5 to 25 nm.

The carbon black used in the present invention has a thermal conductivity of 200 × 10 ^{6 to} 1000 × 10 ⁶ W / m.
・ It must be in the K range. When the thermal conductivity is small, the heat energy is insufficiently dissipated, that is, heat is accumulated inside, so that a sufficient flameproof effect cannot be obtained. The structure of carbon black having a thermal conductivity of more than 1000 × 10 ⁶ W / m · K is porous,
The light blocking effect tends to be insufficient.

The polymer (A) containing such carbon black needs to have 5 to 20 mol% of isophthalic acid copolymerized based on all the acid components constituting the polymer. When the copolymerization ratio of isophthalic acid is less than 5 mol%, it is not preferable for the following reason. First, the effect of reducing the melt viscosity due to the copolymerization of isophthalic acid is lowered, so that the drip effect is not sufficiently exhibited. Therefore, in order to obtain sufficient flameproof performance, it is necessary to increase the content of the polymer (A) in the fiber, but on the contrary, the physical properties of the obtained fiber are deteriorated, and yarn breakage during spinning is caused. There are problems such as increasing troubles. Secondly, when carbon black is contained in a polymer having an isophthalic acid copolymerization amount of less than 5%, the viscosity becomes higher than that of a polymer substantially containing no carbon black,
Even if the both polymers are mixed, the two kinds of polymers are not uniformly mixed, and the carbon black particles are not sufficiently dispersed. In order to reduce the viscosity of the carbon black-containing polymer to the same level as the viscosity of the polymer which does not substantially contain carbon black, at least 5% or more of isophthalic acid must be copolymerized.

On the other hand, when the copolymerization ratio of isophthalic acid exceeds 20 mol%, there is a problem that the physical properties of the obtained black-dyed yarn are deteriorated and colored spots are generated.

The polyethylene terephthalate-based copolyester may be further copolymerized with a small amount of a copolymerization component other than the isophthalic acid component (for example, 5 mol% or less based on the total acid component). Specifically,
Adipic acid, sebacic acid, naphthalene dicarboxylic acid, phthalic acid, propylene glycol, butylene glycol,
Diethylene glycol etc. can be mentioned as a component which may be copolymerized.

The polymer (A) in the present invention is a polyester composition prepared by previously mixing carbon black and isophthalic acid copolymerized polyethylene terephthalate as described above, and in the present invention, this is used as a so-called masterbatch. The mixing ratio of the carbon black and the isophthalic acid copolymerized polyethylene terephthalate needs to be in the range of 5:95 to 40:60.

Here, the mixing ratio of carbon black is 5
When the content is less than wt%, the mixing ratio of the polymer (A) into the fiber must be increased, and the physical properties of the obtained black-dyed fiber are deteriorated and the process stability during spinning is deteriorated. On the other hand, when the mixing ratio of carbon black exceeds 40% by weight, the viscosity of the polymer (A) is extremely increased, which makes it difficult to stably produce the polymer (A).
The dispersion of carbon black in it is also non-uniform. In addition,
The polymer (A) may contain other additives such as a matting agent, an antibacterial agent and an antistatic agent as long as the object of the present invention is not impaired, and it also contains another type of polymer. You may let me.

In the present invention, the above-mentioned polymer (A)
The polymer melt-mixed with is a polytrimethylene terephthalate (hereinafter, may be simply referred to as a polymer (B)) whose repeating unit is substantially composed of trimethylene terephthalate, but the third component is less than 5 mol%. It may be a copolymer. Among them, those copolymerized with a phosphorus compound having two ester-forming functional groups are more preferable because the flameproof performance is further improved. If the intrinsic viscosity of polytrimethylene terephthalate is too high, the drip effect is lowered and the flameproof performance is lowered.
A range of 1.0 is preferable.

Further, it is necessary that the polymer (B) of the present invention contains substantially no carbon black,
When carbon black is contained, the effect of improving flameproof performance cannot be obtained.

The term "substantially free from" as used herein means that a small amount of carbon black may be contained within a range that does not impair the object of the present invention. Although it varies depending on the type of polytrimethylene terephthalate used as () and the type of carbon black, it is usually 0.1 wt% or less.

Further, the polymer (B) may contain additives such as a matting agent, an antibacterial agent and an antistatic agent, as long as the object of the present invention is not impaired. A small amount of another polymer may be contained.

The black dyed polytrimethylene terephthalate type polyester fiber of the present invention is produced by mixing and melt spinning the polymer (A) and the polymer (B). Here, the mixing ratio of the polymer (A) and the polymer (B) is such that the carbon black content in the obtained black dyed polytrimethylene terephthalate-based polyester fiber is 0.5.
˜2.0% by weight, and the content of the polymer (A) needs to be set to 2 to 10% by weight.

Carbon black content is 0.5% by weight
When it is less than 2.0%, the blackness and light-shielding properties are insufficient, and when it exceeds 2.0% by weight, the flameproof performance is insufficient. On the other hand, when the content of the polymer (A) is less than 2% by weight, color spots are likely to occur and the blackness becomes insufficient. On the other hand, when it exceeds 10% by weight, the physical properties of the obtained fiber are deteriorated and the spinning stability is deteriorated.

There is no need to employ a special method for melt-mixing the polymer (A) and the polymer (B). For example, after the chips are blended before melt-mixing, they are melted. Alternatively, both may be melted separately and then statically mixed using a static mixer or the like immediately before spinning. After mixing, it is made into fibers by a known melt spinning method. The cross-sectional shape at that time is arbitrary and may be any of round cross-section fiber, irregular cross-section fiber, and hollow fiber.

The fiber of the present invention has an intrinsic viscosity of 0.7 to 1.0.
Range, the fiber cutting strength is 8.0 to 9.5 cN / dte
When x and the elastic recovery rate are in the range of 50 to 80%, it is possible to produce a woven fabric having sufficient strength and at the same time having an excellent texture of polytrimethylene terephthalate.

The black-primed polytrimethylene terephthalate polyester fiber of the present invention thus obtained is
Short fibers or filaments may be formed, which may be used alone or in combination with other fibers and knitted or woven according to a known method to prepare a raw material for a curtain.

For example, if a black moped yarn is used as a weft yarn and a normal white polyester drawn yarn is used as a warp yarn to make a satin weave or a double weave in which a black moped yarn is arranged on one surface, it is used for a dark curtain. Can be used as the original fabric. The original fabric thus obtained may be dyed, flameproofed, and then formed into a dark curtain, if necessary, and sewn to, for example, a curtain.

As the flameproofing agent used for the flameproofing treatment, for example, cyclic hydrocarbons such as hexabromcycloheptane, tetrabromcyclooctane and hexabromcyclododecane are substituted with 4 to 6 bromine atoms. Examples thereof include brominated cycloalkanes, and among them, 1,2,5,6,9,10-hexabromocyclododecane is preferable. The rate of adhesion of the flameproof agent is preferably 1 to 10% based on the weight of the fiber. Further, as a method for applying the flameproof agent, any method such as a dipping method, a putting method or a spray method may be adopted.
It is preferable to perform heat treatment at 30 ° C. or higher, preferably 155 ° C. or higher for 30 seconds or longer, preferably 10 minutes or longer.

[0029]

The reason why the present invention can improve the flameproof performance of the black primary dyed poly (trimethylene terephthalate) polyester fiber and maintain the excellent texture is presumed as follows.

That is, in the conventional polyester fiber containing carbon black, the polymer in the ignition portion does not melt and fall off because of the thickening effect caused by carbon black.
Since the fire point was not removed, fire spread occurred, that is, the drip effect was insufficient, and the flameproof performance was deteriorated.

On the other hand, the black primed poly (trimethylene terephthalate) polyester fiber of the present invention is a heteropolymer called poly (trimethylene terephthalate) prepared by preliminarily dispersing carbon black in isophthalic acid copolymerized polyethylene terephthalate as a master batch. After being mixed and melt-spun, carbon black has a structure mainly surrounded by isophthalic acid-copolymerized polyethylene terephthalate. as a result,
In polyethylene terephthalate, the thickening effect of carbon black does not work so much, while in isophthalic acid copolyester, the thickening effect of carbon black is reduced due to the thinning effect of the isophthalic acid component, improving the drip effect as a whole. It is considered that the flameproof performance is improved.

[0032]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereby. The characteristic values in the examples were measured by the following methods. (1) Intrinsic viscosity: Measured in orthochlorophenol at 35 ° C. (2) Strength / elongation: Measured at a sample length of 25 cm and a tensile speed of 30 cm / min using an Instron type tensile tester. (3) Cutting strength: Tensilon is used and gauge length is 20 m
m, elongation rate = 100% / min, initial load 2 cN / dtex
The sample was stretched under the conditions of, and the strength at break was calculated from the SS curve drawn at a recording speed of 200 mm / min. (4) Elastic recovery rate: The fiber was attached to a tensile tester with a distance between holders of 15 cm, stretched to an elongation rate of 20% at 15 cm / min, and left for 5 minutes. After this, return to the installation length (A) at the same speed again, read the holder movement distance (residual elongation: B) while stress is applied,
It was calculated by the following formula.

[0033]

[Equation 1] Elastic recovery rate (%) = (A−B) × 100 / A (5) Blackness: A knitted yarn is knitted in a sock knitted fabric, and a color measuring device “Macbeth COLOR-E” manufactured by Macbeth Co.
YE "was used for measurement at a wavelength of 360 to 740 nm using a D65 light source as a 2 degree visual field to obtain an L ^* value. Those having L ^* of 20 or less are acceptable. (6) Light-shielding property: The dark curtain sample after dyeing is JIS L1
It measured based on 055 and was represented by the shading rate. Those having a light blocking rate of 99.99% or more are acceptable.

[0034]

## EQU2 ## Light-shielding rate (%) = (1-i / i ₀ ) × 100, where i: illuminance (lux) when the sample is mounted,
i ₀ : Illuminance (lux) when the sample is not attached, and i ₀ = 100,000 lux. (7) Flameproofness: The woven fabric sample after dyeing is JIS L-
1091 A-1 method (45 ° micro burner method)
The afterflame time was measured. The measurement was carried out for each of the 4 samples and expressed as the average afterflame time. The practically allowable afterflame time is 3 seconds or less.

Example 1 An isophthalic acid component was copolymerized in an amount of 10 mol% based on the total acid component and an intrinsic viscosity was 0.6.
80% by weight of polyethylene terephthalate-based copolyester of 4, an average primary particle diameter of 20 nm, and a thermal conductivity of 3
20% by weight of carbon black of 00 × 10 ⁶ W / mK
5 parts by weight of chips (polyester (A)) of a polyester composition (masterbatch) consisting of
90 parts of polytrimethylene terephthalate chips (95 parts by weight) were mixed, and then melt-mixed at 290 ° C. using a ruder, and then discharged at a rate of 60 g / min from a die having 30 holes having a hole diameter of 0.3 mm for 1100 m. An undrawn yarn was obtained by taking it off at a speed of 1 / min. The obtained unstretched yarn was stretched 3.3 times according to a conventional method to give 165 dtex /
30 filaments of black polyester fiber were obtained.

Polyethylene terephthalate having an intrinsic viscosity of 0.64 and a titanium dioxide content of 0.3% by weight was spun and drawn in the same manner as above to obtain 165 dtex / 48 filaments of white polyester fiber.

Using these polyester fibers, a satin woven fabric having 142 polyester fibers / 25 mm of white polyester for the warp and 87 polyester fibers / 25 mm of black-dyed polyester for the weft was prepared, and the white polyester fibers of the obtained woven fabric were changed to red. Stain and at the same time 45% of hexabromocyclododecane
A water dispersion was added and flameproofing was performed at 20% owf. The results are shown in Tables 1 and 2.

[Examples 2 to 6, Comparative Examples 1 to 3] Example 1
In, the same operation was performed except that the amount of isophthalic acid copolymerized, the amount of carbon black compounded, and the amount of copolymerized polyester compounded were changed. The results are shown in Tables 1 and 2.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

EFFECTS OF THE INVENTION The black dyed polytrimethylene terephthalate fiber of the present invention is mainly composed of conventional polyethylene terephthalate because it has excellent texture, blackness and flameproof property. Since it has physical properties comparable to the original dyed yarn and is excellent in texture, it is possible to provide the original dyed yarn with high aesthetic utility value.

Claims (3)

[Claims] 1. A black dyed polytrimethylene terephthalate polyester fiber containing carbon black, which is obtained by mixing and melt-spinning the following polymers (A) and (B). Of 0.5 to 2.0% by weight based on the weight of the fiber and 2 to 10% by weight of the following polymer (A) based on the weight of the fiber. Adhesive Polytrimethylene terephthalate polyester fiber. (A) 5 to 20 mol% of isophthalic acid component is copolymerized based on the total acid component, the average particle size is in the range of 5 to 25 nm, and the thermal conductivity is 200 × 10 ^{6 to} 1000 × 10 ⁶ W /
Isophthalic acid-copolymerized polyethylene terephthalate containing 5 to 40 wt% of carbon black in the range of m · K based on the total weight. (B) Polytrimethylene terephthalate substantially free of carbon black. 2. The intrinsic viscosity is 0.7 to 1.0, the breaking strength is 8.0 to 9.5 cN / dtex, and the elastic recovery rate is 50 to 8.
The fiber of claim 1 which is 0%. 3. The fiber according to claim 1, which has a shading ratio of 99.99% or more and an afterflame time of less than 3 seconds.