JPH0976444A - Tape wire end reinforcing sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tape wire end reinforcing sheet having the excellent adhesive properties with a tape wire even in a low temperature environment at about 0 deg.C or lower. SOLUTION: The tape wire end reinforcing sheet is constituted by providing an adhesive layer containing polyester having weight-average molecular weight of 30,000 or more and synthesized by diol ingredient having indispensable liquid- like polycarbonate diol at the ambient temperature and dicarboxylic acid ingredient having indispensable dicarboxylic acid having 2-20C aliphatic or alicyclic hydrocarbon group as molecular skeleton on one side surface of an insulating base material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reinforcing sheet composed of an insulating base material and an adhesive layer used for reinforcing the end portion of a tape electric wire.

[0002]

2. Description of the Related Art In recent years, multi-core cables called "tape electric wires" (or "flat cables") have come into wide use with the spread of OA equipment and the development of LANs. This type of tape electric wire has a structure in which a predetermined number (two or more) of conducting wires are arranged in parallel in an insulating layer.

When connecting the end of this tape electric wire,
The insulating layer is removed at the terminal to expose the conductive wire, and a reinforcing sheet is bonded to the exposed portion. Examples of the reinforcing sheet include, for example, Japanese Utility Model Laid-Open No. 61-93936, Japanese Patent Laid-Open No. 3-2833312, and Japanese Patent Laid-Open No. 4-29.
Those described in Japanese Patent Application Laid-Open No. 8980, Japanese Patent Application Laid-Open No. 6-260249, Japanese Patent Application Laid-Open No. 6-260250 and the like are known.

In these reinforcing sheets, an insulating layer (polyester film) at a terminal portion of a tape electric wire and an adhesive layer for adhering to a conductor are provided on one surface of an insulating base material serving as a reinforcing layer. It has a different structure. Further, since this adhesive layer is firmly adhered to each of the insulating layer and the conductive wire, an adhesive suitable for each adherend is selected and has a structure such as streaking or double coating.

Further, components of this adhesive include thermoplastic copolymer polyester resin, epoxy group-containing ethylene copolymer, vinyl aromatic hydrocarbon polymer, acrylate ester polymer, rubber-like substance, ethylene polymer. Coalescence is recommended. However, in most cases, the adhesiveness between the insulating layer (polyester film) of the tape wire and the conductor,
A thermoplastic copolyester resin is widely used in consideration of balance characteristics such as adhesiveness with an insulating base material (reinforcing layer).

[0006]

However, the conventional reinforcing sheet having this thermoplastic copolyester resin as the adhesive layer is not suitable for insulation of the tape electric wire under a low temperature environment of about 0 ° C or less. There was a problem that the adhesive strength with layers and conductors) was extremely reduced.

In view of the above circumstances, the present invention provides a reinforcing sheet composed of an insulating base material and an adhesive layer for reinforcing the end portion of a tape electric wire, even under a low temperature environment. It is intended to provide a material having excellent adhesiveness with an electric wire.

[0008]

In order to achieve the above object, the inventors of the present invention have made various studies on the material constitution of the adhesive layer provided on one surface of the insulating base material, and as a result, have
By using a specific polyester with a diol component having a pearl structure as a base polymer, and by appropriately crosslinking this base polymer, a tape electric wire in an environment from normal temperature to low temperature It was found that a reinforcing sheet having excellent adhesiveness with can be obtained, and the present invention has been completed.

That is, the present invention relates to a sheet for reinforcing the terminal portion of a tape electric wire having a structure in which conductive wires are arranged at intervals in an insulating layer. And a diol component in which liquid polycarbonate diol is essential and a dicarboxylic acid component in which a dicarboxylic acid having an aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms as a molecular skeleton is essential. The present invention relates to a tape electric wire terminal reinforcing sheet comprising an adhesive layer containing a polyester having a weight average molecular weight of 30,000 or more, which is particularly synthesized by further crosslinking the above polyester, The reinforcing sheet can be provided in which the solvent insoluble content of the adhesive layer is 15% by weight or more.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the reinforcing sheet of the present invention,
The insulating base material may be one that effectively functions as a reinforcing layer at the end portion of the tape electric wire, and for example, a plastic film having a thickness of about 50 to 350 μm or the like, or paper, A porous material such as a non-woven fabric is used.

In the reinforcing sheet of the present invention, the thickness of the adhesive layer provided on one surface of the insulating base material is usually 10 to 1
It has a thickness of about 50 μm.
A specific polyester described below is used as a base polymer to exhibit good adhesiveness to an insulating layer and a conductor forming a wire, and particularly to exhibit good adhesiveness even in a low temperature environment of about 0 ° C or less. The adhesive composition described above is used.

The diol component constituting the polyester is
Polycarbonate diol that is liquid at room temperature is essential, and the above-mentioned definition of "liquid at room temperature" means that, for example, in the case of wax, the synthesized polyester is crystallized at room temperature. This is because it becomes too hard, for example, to become difficult to exhibit the above-mentioned adhesiveness.

This room temperature liquid polycarbonate carbon dioxide
The formula is: (In the formula, R is a straight-chain or branched hydrocarbon group having 2 to 20 carbon atoms) and has a repeating unit represented by a number average molecular weight of 500 or more, preferably 900. The above is preferable (usually up to 10,000). If the molecular weight is too low, the synthesized polyester will
As an adhesive, it becomes too hard and the adhesive strength is insufficient, making it difficult to balance the adhesive properties.

Examples of such polycarbonate include hexamethylene carbonate and diol.
, 3-methylpentenecarbonate diol, propylenecarbonate diol and the like, their mixtures or their copolymers. Commercially available product, product name: PLACCEL CD208 manufactured by Daicel Chemical Industries, Ltd.
PL, the same CD220PL, etc.

As the diol component, the above-mentioned liquid polycarbonate at room temperature is indispensable, and if necessary, ethylene glycol, propylene glycol, butanediol, hexanediol, Octanediol,
Linear diols such as decane diol and octadecane diol, or various branched diols may be appropriately mixed and used. The amount of these other diols used is 50% by weight or less, preferably 30% by weight or less based on the total amount of the diol components. In order to increase the molecular weight of the synthesized polyester, a small amount of a trifunctional or higher polyol component can be added.

The dicarboxylic acid component constituting the polyester essentially comprises a dicarboxylic acid having a molecular skeleton of an aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms, and the above hydrocarbon group is It may be linear or branched. Specifically, succinic acid, methylsuccinic acid, adipic acid, pimelicic acid, azelaic acid, sebacic acid,
Examples thereof include 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, an-hexyladipic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid and the like, and acid anhydrides or lower alkyl esters thereof.

As the dicarboxylic acid component, it is desirable to use the dicarboxylic acid having the above-mentioned aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms as a molecular skeleton alone, but in some cases, the dicarboxylic acid may be used. A dicarboxylic acid having an aromatic hydrocarbon group as a branched skeleton may be appropriately mixed and used together with the acid. The amount of the dicarboxylic acid having an aromatic hydrocarbon group as a branched skeleton is preferably 50% by weight or less, more preferably 30% by weight or less based on the entire dicarboxylic acid component. Further, for the purpose of increasing the molecular weight of the synthesized polyester, a trifunctional or higher polycarboxylic acid component may be added in a small amount.

The polyester can be obtained by subjecting the above-mentioned diol component and dicarboxylic acid component to an esterification reaction using an appropriate catalyst and the like according to a conventional method. At that time, it is desirable that the diol component and the dicarboxylic acid component are equimolar reactions, but in order to accelerate the esterification reaction,
Either may be used in excess for the reaction.

The polyester has a weight average molecular weight of 30,000 or more, preferably 50,000 or more (usually up to 300,000). If the weight average molecular weight is lower than 30,000, the cross-linked molecular weight is small when the polyester is cross-linked,
It has a high elastic modulus and very hard properties,
It tends to adversely affect the adhesive properties.

In the present invention, this polyester can be subjected to a crosslinking treatment by an appropriate means to obtain an adhesive composition having excellent adhesiveness under normal temperature and low temperature environments. The cross-linking treatment may be performed before or after applying the adhesive composition onto the insulating base material. As a cross-linking means, polyfunctional compounds such as polyisocyanate compounds, epoxy compounds, and aziridine compounds are used as a cross-linking agent, and a method of reacting this with a polyester (a hydroxyl group or a carboxyl group contained therein) is generally used. Is. The polyfunctional compound is particularly preferably a polyisocyanate compound.

Examples of the polyisocyanate compound include lower aliphatic polyisocyanates such as ethylene diisocyanate, butylene diisocyanate and hexamethylene diisocyanate, and cyclopentylene diisocyanate. , Cyclohexylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate , Aromatic diisocyanates such as xylylene diisocyanate, tolylene diisocyanate trimer adduct of trimethylol propane [Coronate L manufactured by Nippon Polyurethane Co., Ltd.], hexamethyl trimethyl propane Methylene diisocyanate 3
Additives of monomers [Coronate H manufactured by Nippon Polyurethane Co., Ltd.
L] and other isocyanate adducts.

These polyfunctional compounds can be used alone or in a mixture of two or more kinds. The amount used is appropriately selected depending on the balance with the polyester to be crosslinked.
Generally, about 0.5 per 100 parts by weight of polyester
It is preferable to add more than 1 part by weight, preferably 1 to 4 parts by weight, and to carry out crosslinking treatment. As a result, the solvent insoluble content is 15% by weight or more, preferably 20% by weight or more (usually 70% by weight).
Up to) is obtained. When the solvent-insoluble content of the adhesive composition is less than 15% by weight, the cohesive force is insufficient,
Sufficient adhesion cannot be obtained.

As another cross-linking means, there is a method in which a polyfunctional monomer is blended with polyester as a cross-linking agent, and this is cross-linked with an electron beam or the like. Examples of polyfunctional monomers include ethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, tetramethyl methane tetra (meth) acrylate, trimethylol propane tri (meth) acrylate. Etc.
The polyfunctional monomer is used in an amount of about 1 part by weight or more, preferably about 1 part by weight or more, per 100 parts by weight of the polyester, so that the solvent-insoluble content of the adhesive composition after crosslinking with an electron beam or the like becomes the above value. It is preferable that the amount is about 2 to 4 parts by weight.

As described above, the adhesive composition used in the present invention uses a specific polyester as the base polymer, and a crosslinking agent is usually added thereto to form a crosslinked structure. Further, various conventionally known tackifiers may be added to the composition to facilitate the balance between adhesiveness and cold resistance. In addition, the adhesive composition of the present invention may optionally contain various conventionally known additives such as inorganic or organic fillers, metal powders, powders such as pigments, particles and foils. You can

The reinforcing sheet of the present invention configured as described above
In order to reinforce the end portion of the tape electric wire with the use of a cord, it may be carried out according to a conventional method. For example, in a terminal portion of a tape electric wire having a structure in which two or more conducting wires are arranged at intervals in an insulating layer, the insulating layer is removed to expose the conducting wire, and the exposed portion is used for the reinforcement described above. The terminal portion may be reinforced by adhering the sheet using the adhesive force of the adhesive layer.

[0026]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited by the following examples.

Example 1 A four-necked separable flask equipped with a stirrer, a thermometer and a water separation tube was placed in a polycarbonate liquid liquefied at room temperature [PLACELCD22 manufactured by Daicel Chemical Industries Ltd.].
0 PL, hydroxyl value 56.1 KOH mg / g] 250 g (hydroxyl group: 0.25 equivalent), sebacic acid 25.28 g (acid group: 0.25 equivalent), dibutyltin oxide (hereinafter referred to as DBTO) 62 mg (0 as a catalyst) 1 equivalent%)
The mixture was heated to 180 ° C. while stirring was started in the presence of a small amount of toluene as a solvent for discharging reaction water, and kept at this temperature. After a while, effluent separation of water was observed, and the reaction began to proceed. The reaction was continued for about 25 hours to obtain a polyester having a weight average molecular weight of 72,000.

After diluting this polyester with toluene to a solid content concentration of 50% by weight, a trimer adduct of hexamethylene diisocyanate of trimethylolpropane as a crosslinking agent per 100 parts (solid content) of polyester [Japan An adhesive composition was prepared by adding 1 part (solid content) of Polyurethane Co., Ltd., Coronate HL. This is applied to one side of a polyethylene terephthalate film (hereinafter referred to as PET film) having a thickness of 38 μm as an insulating base material by an applicator and dried at 130 ° C. for 5 minutes,
An adhesive layer having a thickness of 50 μm was formed and used as a reinforcing sheet.

Example 2 Example 1 was repeated except that the thickness of the adhesive layer was changed to 20 μm.
A reinforcing sheet was produced in the same manner as in.

Example 3 The amount of hexamethylene diisocyanate trimer adduct of trimethylolpropane used as a cross-linking agent [Coronate HL manufactured by Nippon Polyurethane Co., Ltd.] was changed to 1.5 parts. An adhesive composition was prepared in the same manner as in Example 1 except for the above, and a reinforcing sheet having an adhesive layer with a thickness of 50 μm was prepared therefrom.

Example 4 Example 3 was repeated except that the thickness of the adhesive layer was changed to 20 μm.
A reinforcing sheet was produced in the same manner as in.

Comparative Example 1 A thermoplastic copolyester resin [Vylon # 300 manufactured by Toyobo Co., Ltd.] was added to toluene to give a solid content of 40% by weight.
After diluting to 100 parts of polyester (solid content), 2 parts of a trimer adduct of hexamethylene diisocyanate of trimethylolpropane as a cross-linking agent [Coronate HL manufactured by Nippon Polyurethane Co., Ltd.] ( (Solid content) was added to prepare an adhesive composition. Using this composition, a reinforcing sheet having an adhesive layer with a thickness of 50 μm was produced in the same manner as in Example 1.

COMPARATIVE EXAMPLE 2 Comparative Example 1 except that the thickness of the adhesive layer was changed to 20 μm.
A reinforcing sheet was produced in the same manner as in.

For each of the reinforcing sheets of Examples 1 to 4 and Comparative Examples 1 and 2 described above, the solvent insoluble matter in the adhesive layer was measured and the temperature was adjusted to room temperature (23 ° C.) and low temperature (0) by the following procedure.
The adhesive strength (adhesive strength with respect to the insulating layer (polyester film) constituting the tape electric wire and adhesive strength with respect to the tin-plated conductive wire) at the temperature (° C) was measured. The results are shown in Table 1 below.

<Measurement of Solvent Insoluble Content> About 0.1 g of the adhesive layer was sampled from the reinforcing sheet and precisely weighed. This was immersed in about 50 milliliters of toluene at room temperature for 5 days, the solvent-insoluble matter was taken out, dried at 130 ° C. for about 1 hour, and then weighed. The solvent-insoluble content [X] (% by weight) of the adhesive layer was calculated by the following formula.

<Measurement of Adhesive Strength> A reinforcing sheet was attached to a polyester film (insulating layer) and a tin-plated lead wire as adherends under the conditions of 150 ° C., 1 Kg / cm ² , and 2 seconds, respectively. At room temperature (23 ° C) and low temperature (0 ° C) at a peeling speed of 100 mm / min.
The 80 ° peel adhesion was measured.

[0037]

[Table 1]

As is clear from the results shown in Table 1 above, all the reinforcing sheets of Examples 1 to 4 of the present invention were made of the tape.
It can be seen that the adhesive layer has excellent adhesiveness to the insulating layer (polyester film) and the conductor wire (tin-plated conductor wire) that compose the electric wire both at room temperature and at low temperature. .

[0039]

As described above, according to the present invention, a specific polyester having a carbonate structure is used as a base polymer as an adhesive layer provided on one surface of an insulating base material. It is possible to provide a reinforcing sheet having excellent adhesiveness to the tape electric wire (insulating layer and conducting wire) even in a low temperature environment of ℃ or less.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location // H01B 3/00 H01B 3/00 G H01R 9/07 6901-5B H01R 9/07 Z (72 ) Inventor Yasuyuki Tokunaga, 1-2, Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Denko Corporation

Claims (3)

[Claims] 1. A sheet for reinforcing a terminal portion of a tape electric wire having a structure in which conducting wires are arranged at intervals in an insulating layer, the sheet being formed on one side of an insulating base material, and being a liquid polycarbonate at room temperature. -Bone-
Diole component with essential todiol and carbon number of 2 to 20
And an adhesive layer containing a polyester having a weight average molecular weight of 30,000 or more synthesized from a dicarboxylic acid component essentially including a dicarboxylic acid having an aliphatic or alicyclic hydrocarbon group as a molecular skeleton. Sheet for reinforcing the end of the electric wire. 2. The sheet for reinforcing the end portion of the tape electric wire according to claim 1, wherein the polyester is cross-linked and the solvent insoluble content of the adhesive layer is 15% by weight or more. 3. Polycarbonate diol which is liquid at room temperature has the following formula: A diol having a number average molecular weight of 500 or more having a repeating unit represented by the formula (wherein R is a linear or branched hydrocarbon group having 2 to 20 carbon atoms). A sheet for reinforcing the end portion of the tape electric wire described in 2.