JP2886946B2 - Insulation material composed of melt anisotropic aromatic polyester fiber - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an insulating material comprising a melt-anisotropic aromatic polyester fiber.

2. Description of the Related Art It is known from JP-A-54-77691 and JP-A-1-92408 that spinning a polymer exhibiting melt anisotropy to obtain a fiber having a high strength and a high elastic modulus. The use of organopolysiloxane as an oil agent for organic fibers is disclosed in
It is known in US Pat.

[Problems to be solved by the invention]

When high-strength, high-modulus aramid fiber or aromatic polyester fiber is used as the core material of the wire material, the relative humidity is 60%.
%, The conventional product can provide an electric resistance of only 10 ¹³ (Ω / cm) or less, and a high-strength and high-modulus fiber having excellent electric resistance is desired.

Further, the melt-anisotropic aromatic polyester fiber is sometimes used as a rope or the like, and its characteristics are required for abrasion resistance as well as electric resistance.

[Means for solving the problem]

The present invention is an insulating material composed of a melt-anisotropic aromatic polyester fiber having a polysiloxane composed of a repeating unit represented by the following general formula (A) adhered to the fiber in an amount of 0.1% by weight or more based on the fiber.

(Wherein, R ₁ and R ₂ represent a hydrogen atom, an alkyl group or an aryl group.) A preferred example of the melt anisotropic aromatic polyester according to the present invention comprises a combination of the following repeating units. Things.

Japanese Patent Application Laid-Open No. 54-77 discloses that aromatic polyester fibers having higher strength and lower elongation than conventional polyester fibers for clothing can be obtained from the aromatic polyester compound by a melt spinning method.
No. 691, JP-A-50-43223 and JP-A-58-191219.

Furthermore, a technique for producing a high-strength, high-modulus fiber by spinning an aromatic polyester polymer capable of forming an anisotropic melt under appropriate conditions (heat treatment and / or stretching if necessary) is disclosed in No. 20008, JP-A-60-239600 and the like.

The effect of the present invention is most remarkably exhibited when the polymer comprising the repeating unit of the following [I] and [II] is at least 80 mol%, particularly 5 to 45 mol% of the component [II]. Is an aromatic polyester compound.

As the third component, for example, one or more of the following structural units may be contained in an amount of 20 mol% or less.

A method of spinning a fiber from this compound is disclosed in
This is described in detail in Japanese Patent Publication No. 410.

The polysiloxane in the present invention comprises a repeating unit represented by the general formula (A), wherein R ₁ ,
R ₂ represents a hydrogen atom, an alkyl group such as —CH ₃ or —CH ₂ CH ₃ or an aryl group such as —C ₆ H ₅ . Preferably, those in which R ₁ and R ₂ are each a methyl group have a high electric resistance and are good.

The polysiloxane used in the present invention is a surface treatment agent that imparts lubricity, water repellency, oil repellency, and the like to fibers and fabrics, and can impart considerable smoothness to fibers. The polysiloxane used in the present invention has a viscosity at 25 ° C of 1 to 100,000.
Centistokes (cst) are preferred.

As an oil agent used as an insulating material, a vegetable insulating oil (for example, coconut oil,
It is possible to improve the adhesion of oils of tung oil, linseed oil, castor oil, soybean oil) and mineral insulating oils (mainly paraffinic hydrocarbons and naphthenic hydrocarbons). Even if you attach electrical resistance,
Insufficient wear resistance.

Polysiloxane diluted with low-viscosity mineral oil may be used to uniformly adhere the polysiloxane to the fiber surface.

However, a commonly used emulsion type deposition method, that is, a method of using a nonionic, anionic or cationic emulsifier, emulsifying the composition according to the present invention in water, and attaching the composition to the fiber, a surfactant is contained in the fiber. Since it remains, the electrical resistance of the dried fiber becomes low, deviating from the gist of the present invention. A specific method of adhering to fibers is to discharge a solution of a certain concentration (a stock solution or a diluted solution) onto a traveling yarn at a certain speed from a crow's mouth or the like, or on a rotating roller partially immersed in a polysiloxane solution. There are a method of running the yarn, a method of running the yarn in a polysiloxane solution, and squeezing by an angle or the like, and any method may be used as long as a desired amount of adhesion can be obtained. Next, it can be achieved by drying and winding the polysiloxane solution.

The amount of polysiloxane adhering to the fiber may be any value as long as the fiber surface can be evenly and uniformly covered.
% By weight or more, preferably 0.5 to 20% by weight
It is.

By attaching a polysiloxane to the high-strength and high-modulus melt-anisotropic aromatic polyester fiber having a strength of 15 g / d or more and an elastic modulus of 400 g / d or more according to the present invention, at least 0.1% by weight of the fiber, It has become possible to significantly develop the electrical resistance of these fibers.

Specific applications of the insulating material of the present invention include the following 1. Filament, spun yarn, those used in a yarn shape,
Examples include optical fibers, tension members for optical fibers under high voltage, electric cables, insulating materials such as core materials, and the like.
It may be used in the form of a rope, a hose, a cord, a cable, a sewing thread, or the like.

2. Cut fiber, used in the form of chopped yarn, paper (insulating paper), reinforcing material for bases such as IC, resin reinforcing material for electric parts such as TV, video, audio, and general resin reinforcing material.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

The fineness (DB) ｛denier (d
r)｝, strength DT (g / d), elongation DE (%), and elasticity YM (g / d)
The measured value of d) is based on JIS L1013 using a sample in which the yarn is twisted at 80 turns / m.
It was obtained by measuring at room temperature at a tensile speed of min. The fineness was determined by a gravimetric method.

The electrical resistance R (Ω / cm) of the fiber is test length 1cm, applied voltage 1000
The measurement was performed by changing the measurement environment humidity at V. The inter-fiber abrasion means that a yarn test yarn with a twist of 80 turns / m (for example, 1500 denier / 300 filament) is twisted three times between the reversing pulley and the free roller at the other end and attached as a figure-eight. A 2 kg load was applied to the free roller, and the test yarn was reciprocally twisted and worn at a speed of 35 times / min.

 The logarithmic viscosity was determined as follows.

A sample is dissolved in pentafluorophenol at 0.1% by weight (60-80 ° C), and an Ubbelohde capillary viscometer (for example, “Polymer Science Experimental Method” edited by The Society of Polymer Science, Tokyo Chemical Dojin P179 (1986)) in a thermostat at 60 ° C. Tokyo).

[Ηrel; relative viscosity, C; measured solution concentration (g / dl)] Tm is a melting point and an endothermic peak temperature measured by DSC.

Example 1 An aromatic polyester polymer in which the structural units [I] and [II] had a 70/30 mol% ratio was used for melt spinning.

 Physical properties of this polymer were ηinh = 5.9 dl / g Tm = 281 ° C.

The polymer was extruded from a single-screw vent type extruder, passed through a sand (stainless powder) layer, and a filter made of a fine metal wire, and then spun at 320 ° C. The nozzle is
It is 0.12mmφ × 300H. Discharge rate 125g / min, spinning speed 800m / min
It was wound up.

This spun yarn is wound around a bobbin with a winding density of 0.57 g / CC, at 260 ° C for 1 hour, from 270 ° C to 280 ° C for 3 hours, at 280 ° C.
To 285 ° C. for 5 hours. The mechanical properties of the obtained heat-treated yarn were as follows: yarn denier (DR): 1510dr strength (DT): 26.8 g / d elongation (DE): 3.8% elastic modulus (YM): 587 g / d.

A 0.34 g / min to 6.8 g / min polydimethylsiloxane (10) of the following structural formula (B) is discharged from the crow mouth to the heat-treated yarn and adheres to the running yarn at a speed of 200 m / min (1, 2, 4, 10 ,
20% by weight) and guided to a heating roller maintained at 200 ° C. for dry heat treatment.

[Where n represents a natural number] Table 1 shows the mechanical properties and the electrical resistance of the obtained processed yarns at a relative humidity of 60% and room temperature.

Example 2 In the same manner as in Example 1, the polysiloxane represented by the following structural formula (C) was added to the heat-treated yarn obtained in Example 1 in the same manner as in Examples 1 and 4.
Wt% deposited, resulting mechanical properties and relative humidity 60
Table 1 also shows the results of% and the electrical resistance at room temperature.

[In the formula, n represents a natural number] Comparative Example 1 A fiber obtained by adhering 1% by weight of an aqueous solution obtained by emulsifying a polysiloxane represented by the following structural formula (D) to the heat-treated yarn obtained in Example 1 Table 1 also shows the results of the mechanical properties and the electrical resistance at a relative humidity of 60% and room temperature.

(Where m and n represent natural numbers) Example 3 To the heat-treated yarn obtained in Example 1, 9 mineral oil (liquid paraffin) was added to 1 part by weight of the polysiloxane represented by the structural formula (C) to form a 10% by weight solution.
4 g / min to 13.6 g / min was discharged and adhered to the running yarn at a speed of 200 m / min (1, 2, 4% by weight), and dried and heat-treated in the same manner as in Example 1. Table 2 shows the obtained measurement results.

Comparative Example 2 Palm oil was added to the heat-treated yarn obtained in Example 1 through a crow mouth.
1.36 g / min was discharged and adhered to a running yarn at a speed of 200 nm / min at 4% by weight, and dried and heat-treated in the same manner as in Example 1. Table 2 shows the obtained measurement results.

Comparative Example 3 Mineral oil (liquid paraffin) was discharged at 1.36 g / min from the crow mouth to the heat-treated yarn obtained in Example 1 and adhered to the running yarn at a speed of 200 m / min at a standard of 4% by weight. It was led to a heated heating roller and subjected to a dry heat treatment. Table 2 shows the obtained results.

Comparative Example 4 Using a para-aramid having the following mechanical properties as a sample, n was used to remove oil and dirt attached to the surface.
-Washed with stirring in a hexane solution for 10 minutes and then in water for 10 minutes and dried.

(After washing) Yarn denier (DR): 1531dr Strength (DT): 22.6 g / d Elongation (DE): 3.7% Elastic modulus (YM): 558 g / d The yarn of the above structural formula (B) Siloxane was discharged from the crow mouth at 0.34 g / min to 3.4 g / min and adhered (4% by weight) to the running yarn at a speed of 200 m / min, and dried and heat-treated in the same manner as in Example 1. Table 2 shows the results of the mechanical properties and electric resistance of each of the obtained processed yarns.

[Effects of the Invention] According to the present invention, an insulating material having excellent electric resistance and abrasion resistance can be obtained by attaching polysiloxane to a melt anisotropic aromatic polyester fiber.

────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yukio Sugita 1621 Sazu, Kurashiki-shi, Okayama Pref. −77691 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) D06M 15/00-15/72 D01F 11/08

Claims (1)

(57) [Claims] 1. An insulating material comprising a melt-anisotropic aromatic polyester fiber having a polysiloxane comprising a repeating unit represented by the following general formula (A) adhered to the fiber in an amount of 0.1% by weight or more based on the fiber. (Wherein, R ₁ and R ₂ represent a hydrogen atom, an alkyl group or an aryl group.)