JP2590913B2 - Curl cord - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention relates to telephones, OA equipment, household electric equipment, audio equipment,
And codes used for wiring and the like.

(Prior Art) Conventionally, in a curl cord, polyethylene is mainly used as an insulating material of a core wire, and a polyvinyl chloride resin, a polypropylene resin, or the like is generally used as a sheath layer.

(Problems to be solved by the invention) The curl durability of the conventional curl cords in the first half is not satisfactory, and the curl diameter is small, the curl length is short, the curl length is short, and the curl is more compact. Instead, a curl cord excellent in restoring force and durability is required.

The present invention seeks to provide a curl code that satisfies these requirements.

(Means for Solving the Problems) That is, the present invention relates to a curled cord having a core wire having a conductor covered with an insulating material and a sheath layer covering the core wire.
The insulating material is a polyester / polyester block copolymer comprising a crystalline aromatic polyester segment and a polylactone segment or / and a polyester / polyether block copolymer comprising a crystalline aromatic polyester segment and an aliphatic polyether segment. Wherein the sheath layer is a blend composition of a polyvinyl chloride resin and the polyester / polyester block copolymer or / and the polyester / polyether block copolymer, and wherein the blend composition of the polyvinyl chloride resin is Is a curl cord having a compounding ratio of 50% by weight or more.

The polyester / polyester block copolymer used in the present invention comprises a crystalline aromatic polyester segment and a polyester lactone segment, and is obtained, for example, by reacting a crystalline aromatic polyester with a lactone. In the present invention, the crystalline aromatic polyester is a polymer mainly composed of an ester bond or an ester bond and an ether bond, has at least one aromatic group in a main repeating unit, and has a marine group at a molecular terminal. is there. The crystalline aromatic polyester is preferably a polyester having a melting point of 150 ° C. or higher when a high polymer is formed. The molecular weight is preferably 3000 or more.

Preferable specific examples include polyethylene terephthalate, polytetramethylene terephthalate, poly-1,4-
Cyclohexylene dimethylene terephthalate, homopolyesters such as polyethylene-2,6-naphthalate, polyethylene oxybenzoate, polyester ethers such as poly-p-phenylenebisoxyethoxy terephthalate, mainly tetramethylene terephthalate units or ethylene terephthalate units, and Copolymerization components such as tetramethylene or ethylene isophthalate units, tetramethylene or ethylene adipate units, tetramethylene or ethylene sebacate units, 1,4-cyclohexylene dimethylene terephthalate units, tetramethylene or ethylene-p-oxybenzoate units; Copolymerized polyester or copolymerized polyester ether. In the case of a copolymer, the tetramethylene terephthalate or ethylene terephthalate unit has 60 units.
Desirably, the content is at least mol%.

As the lactones, ε-caprolactone is most preferred, but enantholactone, caprylolactone and the like are also used. Further, two or more lactones can be used.

The copolymerization ratio of the crystalline aromatic polyester and the lactone is such that the weight ratio of the aromatic polyester / lactone is
It can be appropriately selected within the range of 97/3 to 5/95. For applications requiring strength, the above ratio is preferably selected in the range of 95/5 to 70/30, and for applications requiring flexibility and flexibility, 80/20 to 60 / Preferably, a range of 40 is selected.

The polyester / polyester block copolymer can be obtained by heating and melting and reacting a crystalline polyester and a lactone. In this case, a catalyst may be used or a catalyst may be used.

The polyester-polyether block copolymer used in the present invention is a dicarboxylic acid mainly composed of an aromatic dicarboxylic acid having a molecular weight of less than 300 and 250
A crystalline aromatic polyester segment consisting of an ester unit with a glycol having a smaller molecular weight and 400 to 6
An aliphatic polyether segment consisting of a polyalkylene glycol having a molecular weight of 000.

Examples of the dicarboxylic acid constituting the crystalline aromatic polyester segment include terephthalic acid, isophthalic acid, phthalic acid, 2,6- and 1,5-naphthalenedicarboxylic acid, and the like.
In addition to aromatic dicarboxylic acids having a molecular weight of less than 300, aliphatic dicarboxylic acids such as alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, oxalic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dimer acid Acids and the like. These dicarboxylic acids may be of two or more kinds.

250 constituting the crystalline aromatic polyester segment
Glycols having a lower molecular weight include ethylene glycol, 1,2- or 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol,
Alkylene glycols such as 1,6-hexanediol,
And cycloalkylene glycols such as 1,4-cyclohexanedimethanol. These glycols may be two or more kinds.

Preferred examples of the crystalline aromatic polyester segment include polybutylene terephthalate, polybutylene terephthalate / polybutylene phthalate, polybutylene terephthalate / polybutylene isophthalate, polybutylene terephthalate / polybutylene sebacate, polybutylene terephthalate / polyhexamethylene isolate Examples include homopolyesters such as phthalate, polyethylene terephthalate / polyethylene isophthalate, and polyhexamethylene terephthalate, and copolyesters.

400-6000 that make up the aliphatic polyether segment
As a polyalkylene glycol having a molecular weight of
Examples include polyethylene glycol, poly (1,2- or 1,3 propylene oxide) glycol, poly (tetramethylene oxide) glycol, and a copolymer of ethylene oxide and propylene oxide. The molecular weight of the polyalkylene glycol is between 400 and 6000, preferably between 500 and 4500. These polyalkylene glycols may be of two or more kinds. Preferred examples of the aliphatic polyether segment include poly (tetramethylene oxide) glycol.

In the polyester / polyether block copolymer, the ratio of the crystalline aromatic polyester segment to the aliphatic polyether segment is 90/10 to 10/90 (weight ratio).
If the ratio exceeds 90/10, the low-temperature properties cannot be improved because the polyalkylene glycol unit, which is a low Tg component of the polymer, is small.If the ratio is less than 10/90, the properties of the polymer hard segment almost disappear. Would.

Although the method for producing the polyester / polyether copolymer is arbitrary, an example of a suitable polymerization method is to use dimethyl ester of dicarboxylic acid in an excess mole number, that is, about
In the presence of a conventional esterification catalyst together with 1.2 to 2.0 moles of low molecular weight glycol and poly (alkylene oxide) glycol, heat exchange reaction is carried out under normal pressure at a temperature of about 150 to 260 ° C to carry out transesterification to distill methanol, Then, it can be produced by heat polycondensation at a reduced pressure of 5 mmHg or more at 200 to 270 ° C. If necessary, a component that can be partially chemically cross-linked to the polyester / polyether copolymer is introduced and, for example, a tricarboxylic or more functional polycarboxylic acid, polyol, or polyoxyacid is copolymerized as a part of dicarboxylic acid or glycol to be elasticized. It is also possible to improve the mechanical properties.

The polyvinyl chloride resin of the present invention is a stabilizer, a lubricant, a pigment,
A commonly used compounding agent such as a plasticizer may be added, or a modifier such as polyurethane may be used in combination. Further, a modifier such as polyurethane may be used in combination. A small amount of vinyl acetate, vinylidene chloride,
A polyvinyl chloride resin obtained by copolymerizing propylene, acrylic acid, acrylate, chlorinated polyethylene, or the like may be used.

As the insulating material for the core wire, a polyester / polyester block copolymer or / and a polyester / polyether block copolymer is used, and both have excellent melt coatability. The above-mentioned copolymer enables the conductor to be uniformly and thinly coated, so that the core wire can be thinned, and the core wire can be given any elasticity and rigidity. This affects the characteristics of the later-described curled cord, and is effective in selecting the form, curling characteristics, spring characteristics, and the like of the curled cord by selecting the core wire. The use of polyester / polyester block copolymer makes it possible to make the core wire excellent in heat resistance and elasticity, and the heat resistance is high, so that the sheath layer can be easily coated and the obtained curl cord has excellent elasticity. It will be. When a polyester / polyether block copolymer is used, a core wire having excellent flexibility can be obtained, which is suitable for obtaining a curl cord having high flexibility.

The insulating material used for the sheath layer contains at least 50% by weight of a polyvinyl chloride resin, and is a blend composition of the polyvinyl chloride resin and a polyester / polyether block copolymer or / and a polyester / polyester block copolymer. However, the preferred blending ratio of the polyvinyl chloride resin and the polyester / polyether block copolymer or / and the polyester / polyester block copolymer is 97/3 to 70/30 (weight ratio), more preferably Is 9
It is 5/5 to 75/25 (weight ratio).

When the amount of the polyvinyl chloride resin exceeds 97% by weight, the improvement effect of the polyvinyl chloride resin is small, and the polyester / polyether block copolymer or / and the polyester /
When the polyester block copolymer exceeds 30% by weight,
It is not preferable from the viewpoints of an increase in extrusion temperature, a decrease in curl cord light-emitting properties, a decrease in flame retardancy, and an increase in cost.

Since the insulating material used for the sheath layer of the present invention has good core wire coverage, it is easy to create a thinner cord, and the curl cord can be made more compact.
A curl cord having excellent shape stability, curl characteristics, and restoring force can be obtained.

When a polyester / polyether block copolymer is used as a compounding partner with polyvinyl chloride resin,
Flexible and suitable for imparting excellent curl characteristics, and when using a polyester / polyester block copolymer, it is suitable for imparting rigidity and curl spring characteristics,
Less decrease in flame retardancy. There is an advantage of being excellent in heat aging resistance, weather resistance and the like.

In the present invention, since the insulating material of the sheath layer is different from the insulating material of the core wire, there is an advantage that when the cord is connected, the sheath and the core wire are easily separated and the operation is easy. In this sense, the polyester-based block copolymer is more preferably different between the sheath and the core. A preferred example of the combination is an example in which the insulating material of the core wire is a polyester / polyester block copolymer and the sheath layer is a polyester / polyether block copolymer.

The polyester-based block copolymer used in the present invention may be an epoxy compound, a carbodiimide compound, an isocyanate compound, an oxazoline compound, or an alkali metal of an aliphatic polycarboxylic acid, depending on the purpose, such as heat resistance, improvement in water resistance, and thickening. Salts and the like may be blended.

In addition, a heat stabilizer, an ultraviolet absorber, a pigment, a fluorescent whitening agent, carbon black, and the like can be added to the insulating material according to the use of the curl cord.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 Polyester / polyester block copolymer A obtained by reacting polybutylene terephthalate with ε-caprolactone (polycaprolactone component 15% by weight, polybutylene terephthalate component 85% by weight, melting point 225 ° C., reduced specific viscosity 1.95) Polyester / polyether block copolymer B consisting of polybutylene terephthalate and polytetramethylene oxide glycol (number average molecular weight 1100)
(Polytetramethylene oxide glycol component 60% by weight, polybutylene terephthalate component 40% by weight, melting point 17
Using 5 ° C. and a reduced specific viscosity of 1.90), an insulating coating was extruded around a stranded copper body having a conductor outer diameter of 0.3 mm to obtain a core having a diameter d = 0.6 mm. Next, four core wires obtained were twisted, and a sheath material shown in Table 1 was extruded thereon to obtain a cord having a diameter d = 2.5 mmφ. Then the code is
It was wound and fixed on a cylindrical column having a diameter of 1 mm, and heat-treated at 140 ° C. for 30 minutes to obtain a curl cord having a curl outer diameter D = 11 mmφ.
Similarly, polyethylene resin (PE) as the core insulating material
The test was performed when using polyvinyl chloride resin (PVC) and when using polyvinyl chloride resin as the sheath material.

Table 1 shows the results of comparing the characteristics of these curl codes.

Example 2 In the combination of each core material of Example 1 with a sheath material,
An attempt was made to produce a curl cord as compact as possible.

For No. 1 and No. 2 in Table 1, the diameter d = 2.0 mmφ
No. 3-5 was difficult to produce curl cords having a curl length of 180 mm or less.

(Effect of the Invention) In the curled cord of the present invention, the insulating material of the core wire is excellent in melt coatability and excellent in elasticity, and the insulating material of the sheath layer is also excellent in melt coatability and excellent in elasticity. Therefore, the diameter of the cord can be reduced, and the curl diameter and the curl length can be reduced, so that a compact and unobtrusive curl cord can be obtained. Further, the obtained curl cord is excellent in curl restoring force, durability, weather resistance, flame retardancy and the like, and can be used for various industrial uses.

[Brief description of the drawings]

FIG. 1 is a view showing the external shape of a curl cord, and FIG. 2 is a cross-sectional view of the curl cord. 1: conductor, 2: core material, 3: sheath layer

Claims (1)

(57) [Claims] 1. A curled cord comprising a core wire having a conductor covered with an insulating material and a sheath layer covering the core wire, wherein the insulating material comprises a polyester / polyester block comprising a crystalline aromatic polyester segment and a polylacto segment. A polyester / polyether block copolymer comprising a united or / and crystalline aromatic polyester segment and an aliphatic polyether segment,
The sheath layer is a blended composition of a polyvinyl chloride resin and the polyester / polyester block copolymer or / and the polyester / polyether block copolymer, and a blend of the polyvinyl chloride resin in the blended composition. A curl cord having a proportion of 50% by weight or more.