JPH02186503A - Thermosetting resin sheet material having fine electricity-removability - Google Patents

Abstract

PURPOSE:To have the fine electricity-removability and eliminate the lower of its performance as it is repeatedly bent by arranging the organic conductive fiber, as it is long, in the surface or the inside of a sheet material. CONSTITUTION:The organic continuous fiber made of filament more than one and having the conductivity or the fiber bundle (organic conductive fiber) is included in the thermosetting resin sheet material less than 1 capacity %. This organic conductive fiber is arranged in one direction, and is presented under the continued condition form one end of a sheet to the other end. The unsaturated polyester resin, the vinylester resin, the epoxy resin and these modified resin are desirably used as the thermosetting resin from the point of the formability. Thereby, the thermosetting sheet material having the fine electricity- removability and the high degree of freedom of coloring without the danger of the electric shock and the lower of the performance by the repeated bending.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a thermosetting resin sheet having excellent static elimination performance. In more detail, walls in the building materials field, electricity, electronics field, automobile field, machinery field, food field, etc., where various problems have recently occurred due to static electricity accumulation,
Useful for bulkheads, partitions, housings, etc. A thermosetting resin sheet that is inexpensive and imparts non-static properties without damaging the properties of the sheet by arranging several conductive fibers as long fibers on the surface or inside of the sheet. It is about things.

[Prior art] Thermosetting resin sheet materials have traditionally been used to accumulate static electricity due to their non-conductivity, prevent sand, dust, and other dark objects from adhering to the sheet surface, and prevent charged charges from being discharged all at once. When doing so, the human body may receive an electric shock or damage to surrounding electronic components may occur frequently.

In order to prevent static electricity on these sheet-like materials, methods such as adding an antistatic agent or a conductive filler to a thermosetting resin, and applying a conductive paint to the surface of the sheet-like material have been generally used. The method of using an antistatic agent has the problem that the antistatic agent bleeds out during long-term use, reducing the antistatic performance and increasing the tackiness of the surface of the sheet-like material, making it resistant to adhesion of surrounding dust. When a conductive filler is added, it is expensive and requires a large amount of conductive filler in order to achieve antistatic performance, resulting in poor economic efficiency and a decrease in mechanical properties, especially when using fibrous conductive materials, due to bending. There are problems such as a decrease in antistatic performance, difficulty in coloring, and a lack of transparency, and the method of applying conductive paint can cause damage to surrounding electrical and electronic equipment due to paint falling off due to long-term use, wear, bending, etc. In addition to being the cause of the problem, there are also problems such as lack of freedom in coloring due to the hue of the conductive material in the conductive paint, and a lack of transparency.The current situation is that the methods used in the past have their own problems. There is.

[Problems to be Solved by the Invention] The objects of the present invention are to provide an economically advantageous, excellent static elimination effect,
To provide a thermosetting sheet-like material that is free from electric shock, has a high degree of freedom in coloring, and has no deterioration in performance due to repeated bending.

[Means for Solving the Problems] The above object is to produce a thermosetting fiber containing 1% or less by volume of organic continuous fibers or fiber bundles (hereinafter simply referred to as organic conductive fibers) consisting of at least one conductive filament. This is achieved by a sheet-like resin sheet material characterized by organic conductive fibers arranged in at least one direction and present in a continuous state from one end of the sheet to the other. .

The sheet-like material of the present invention is characterized by excellent static elimination properties, and because the organic conductive fibers exist in a continuous state, static elimination performance does not deteriorate even when repeatedly bent, and the filling rate is unprecedentedly low. It has the advantage of being able to achieve these performances.

The thermosetting resin used in the present invention is not particularly limited as long as it can be molded into a sheet, such as unsaturated polyester resin, vinyl ester resin, epoxy resin,
Examples include phenol resins, urea resins, melamine resins, and mixtures and modified resins thereof, but from the viewpoint of moldability, unsaturated polyester resins, vinyl ester resins,
Epoxy resins or modified resins thereof are preferably used.

It can be changed depending on the purpose.

In addition, in the present invention, within the scope that does not impair the purpose,
Various fillers such as mica, talc, glass flakes, glass fibers, calcium carbonate, aluminum hydroxide, and clay can be added to the resin; inorganic fiber mats such as glass chopped strand mats, glass long fiber mats, and glass woven fabrics; polyester; Organic fiber knits such as vinylon, nylon, acrylic fiber, cotton, wool, silk, etc., fiber absorbers for woven fabrics,
Additives such as air drying agents, thickeners, colorants, etc. can be included.

In the present invention, the organic continuous fiber or fiber bundle (organic conductive fiber) consisting of at least one conductive filament has, for example, a conventionally known organic composite conductive fiber having a core-sheath structure and whose core is conductive. It is possible to use synthetic fibers, organic fibers plated with metal, etc., and those having an electrical resistance value of 10 8 Ω·cm or less are preferably used. In particular, in the present invention, a multicore-to-sheath composite fiber is preferably used, and the fiber has a fiber-forming polymer (Δ) as a sheath component and a polymer (B) containing 15 to 50% by weight of conductive carbon black as a core component. A multicore-to-sheath composite fiber having a composite weight fraction of (B) and (A) of (B)/(A
) = 5/95-30/70, the diameter (D) of the composite fiber is 40 μm or less, - the number of cores per composite fiber is 2 to 8, especially 4 to 6, the diameter of the core is 5 μm or more and 110l7 or less,
However, the shortest distance (L) between the outer periphery of the composite fiber and the six cores is 1 μm or more and 5 μm or less, and the discharge current when 1 OKV is applied is 10-7 to 10. -3A multicore-to-sheath composite fiber.

More preferably, the above-mentioned multi-core core-sheath fiber is characterized in that the core components in the cross section of the fiber are arranged substantially in a row in the circumferential direction at substantially equal intervals. / (A) -10/90 to 20/8+H, - A composite fiber characterized in that the number of cores per composite fiber is 4, and in the above, the fiber-forming polymer (A) is a polyester polymer. It is a multi-core core-sheath composite fiber characterized in that the polymer (B) containing conductive carbon black is a polyamide-based polymer. Currently, such multi-core core-sheath composite fibers are sold under the trade name of Cracaho ■.

Although the static elimination mechanism of a thermosetting resin sheet containing organic conductive fibers as in the present invention is not yet clear, the charges on the sheet surface cause corona discharge to the organic conductive fibers, and
Furthermore, it is presumed that static electricity is removed by discharging from the tip of the organic conductive fiber.

If discharge static electricity is removed by discharging at the tip, the smaller the diameter of the organic conductive fiber, the easier the charge density at the tip will increase, and the discharge will occur even with a lower amount of charge.

In the present invention, the organic conductive fibers may be embedded at the same time as the sheet-like product is manufactured, or may be adhered to the surface of the thermosetting resin sheet by adhesive or other methods. It is necessary for the particles to be arranged in at least one direction at a concentration of 1% by volume or less, and to exist continuously from one end of the sheet to the other. The amount of the organic conductive fiber in the sheet-like article of the present invention is 1% by volume or less, preferably 0.1% by volume.
It shows excellent static elimination performance even at 0.02 to 0.5% by volume, and is extremely efficient compared to conventional conductive fillers that require a large amount of filling of this number % to several 10%. The organic conductive fibers are arranged in at least one direction in the sheet-like article of the present invention, and the direction is not particularly limited, and they may be arranged in any direction, vertically, horizontally, or diagonally. It is preferable to arrange them in only one direction for ease of preparation. Since the sheet-like material of the present invention is presumed to exhibit excellent static elimination effects due to so-called tip discharge, it is necessary that the organic conductive fibers are always exposed at the edge of the sheet and exist in a continuous state all the way to the other edge. If it is cut in the middle or is not continuous all the way to the end, the static elimination effect will be extremely reduced. In particular, since the organic conductive fiber used in the present invention is mainly organic and has high elongation, there is no deterioration in static elimination performance due to repeated bending.

Furthermore, in the present invention, the distance between adjacent organic conductive fibers arranged is 50 mm because the narrower the distance between adjacent organic conductive fibers, the higher the static elimination performance.
It is preferably 30 mm or less, and more preferably 30 mm or less. However, if it is less than 2mm, it is economically disadvantageous, so 2-3
A spacing of 0 mm is particularly preferably used.

Next, the distance between the sheet surface and the organic conductive fibers, that is, the depth of embedding the organic conductive fibers, is preferably 1 mm or less, more preferably 0.7 mm or less, because the shallower the static elimination effect becomes. .

The method for manufacturing the sheet-like product of the present invention is not particularly limited as long as the organic conductive fibers and the thermosetting resin can be integrated, but as an example of the manufacturing method, for example, A method of bonding arranged organic conductive fibers with an adhesive or embedding arranged organic conductive fibers between thermosetting resin layers, and continuously coating a thermosetting resin on a release film or a release belt. Examples include, but are not limited to, a method of manufacturing the sheet-like product of the present invention by continuously supplying organic conductive fibers arranged in one direction from above and curing at room temperature or by heating. Furthermore, a thermoplastic resin film can be adhered or welded to the surface of the sheet-like article of the present invention within a range that does not impair the object of the present invention. For example, organic conductive fibers arranged in one direction are continuously supplied onto an adhesive thermoplastic resin film, a thermosetting resin is continuously coated on top of the organic conductive fibers, and then a thermoplastic resin film is applied on top of that. After continuously feeding,
Examples include a method of curing a thermosetting resin to obtain the sheet-like article of the present invention, but the method is not limited to this method.

The organic conductive fibers are mixed or knitted between non-conductive fibers within the scope of the present invention, and it is easier to handle the organic conductive fibers when used in the form of a woven fabric. , is preferably used because there is no disorder in the arrangement. The non-conductive knitted or woven fabric is not particularly limited, but includes, for example, cotton,
Examples include knitted and woven fabrics of natural fibers such as silk and wool, synthetic fibers such as polyester, hinilon, acrylic, aramid, and arylate, artificial fibers such as rayon and cupro, and inorganic fibers such as glass.

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way.

Examples 1 to 4, Comparative Example 1 A vinylon film for mold release was pasted on a glass plate, and on top of that, Rivolac 158BQT (trade name, Showa Kobunshi Co., Ltd.) containing 1% by weight of Parmets 7N (trade name, Nippon Oil & Fats Co., Ltd.) was applied. Saturated polyester resin) was cast to a thickness of 0.1 mm after curing to a semi-cured state (hereinafter abbreviated as first stage casting)
Table 1 shows a fiber bundle consisting of eight 20-denier filaments. The fiber bundle is placed in a continuous state from one end to the other with the fiber spacing shown in , and then the Permec N is placed on top of it.
After casting and curing Rivolac 1.58BQT containing 1% by weight, the vinylon film was peeled off to obtain a sheet-like product with a thickness of 1 mm.

Next, a comparative sheet with a thickness of 1 mm was obtained using the same formulation and method except that the multicore-to-sheath Lacarbo ■ fiber bundle was not used. (Comparative Example 1) Regarding the rcosheet-like material obtained here, the rt 1S-TR-
78-1, the charge density was measured to examine the static elimination effect. Furthermore, after holding both ends of these seams and bending them at 60° 20 times, the charge density was adjusted to R.
r T 5-TR-78-1 was measured to examine the static elimination effect. The results are shown in Table 1.

It was confirmed that the static elimination effect of the sheet inserted with the organic conductive fiber Cracarpo ■ was reduced to about 1710 of the sample without the insertion of Kracarbo ■ (Comparative Example 1), and the static elimination effect did not decrease even after repeated bending. was confirmed.

Examples 5 to 7 In order to investigate the influence of the embedding depth of Kurakabo O, which is an organic conductive fiber, in the sheet-like material, the first stage casting was performed to a thickness of 0.5 mm after curing (Example 5), The same formulation and method as in Example 2 were used to obtain a thickness of 1 mm (
Example 5), 1.6 mm (Example 6) and 2.4 mm (
A sheet-like product of the present invention in Example 7) was obtained. The static elimination effect of the sheet-like material obtained here was examined in the same manner as in Example 1, and the results are shown in Table 1.

From this, it can be confirmed that satisfactorily static elimination performance can be achieved with an embedding depth of 1 mm or less, and this fact is actually industrially compatible with 1. This shows that there is no need to take any special consideration or ingenuity to control the embedding depth when manufacturing a sheet-like product with a thickness of about 2 mm.

Example 8 On a commercially available 0.05 mm thick polyester film, the same Cracapo ■ used in Example 1 was placed in a continuous state from one end to the other with fiber spacing of 3 mm in both the vertical and horizontal directions, and then Epitan E-303/Ratsukamite 03
6S (trade name, manufactured by Dainippon Ink and Chemicals) at 75/2
A 5% by weight mixed Evokin resin was coated and cured to obtain a 1 mm thick sheet containing 0.85% by volume of Cracapo. The static elimination effect of the sheet-like material obtained here was examined in the same manner as in Example 1, and the results are shown in Table 1.

Example 9 Instead of the multi-core sheath Lacarbo [F] fiber bundle, Example 1 was applied between polyester fibers in one direction with a fiber spacing of 10 mm.
100, which is a mixture of the same multi-core core-to-sheath La Capo 0 fiber bundles.
The same formulation as in Example 5 except that a plain weave fabric of g/m' was used,
A sheet-like product according to the present invention having a thickness of 1 mm was obtained in the same manner. The static elimination effect of the sheet-like material obtained here was examined in the same manner as in Example 1, and the results are shown in Table 1.

This will show that the static elimination effect does not change even if a woven fabric in which multi-core core-sheath Lacarbo ■ is used with non-conductive fibers arranged at regular intervals. It was confirmed that by using the woven fabric, the workability is very good when producing a sheet-like article according to the present invention.

Comparative Example 2.3 Same composition as Example 1 except that N1 plated glass fiber bundle (volume resistivity 10 Ω cm, diameter 24μ x 80 filaments) was used as the conductive fiber, and the spacing was the same as in Example 2.3. A sheet-like product according to the present invention having a thickness of 1 mm was obtained in the same manner. The static elimination effect of the sheet-like material obtained here was examined in the same manner as in Example 1, and the results are shown in Table I.

As a result, a clear decrease in static elimination performance was observed after repeated bending. This is thought to be due to deterioration of the static elimination performance due to peeling of the plating layer due to bending or cutting of the inorganic glass fiber that is the base material due to bending.

Comparative Examples 4 to 6 A vinylon film was pasted on a glass plate, and a conductive carbon black, Ketchen Black EC (trade name, manufactured by Ketchen Black International Co., Ltd.) was blended thereon with the content shown in Table 2. After casting and curing Rivolac 158B QT containing 1% by weight of N,
The vinylon film was peeled off to obtain a sheet with a thickness of 1 mm. The static elimination effect of the sheet-like material obtained here was examined in the same manner as in Example 1, and the results are shown in Table 2.

As is clear from this result, in order to obtain the static elimination effect in the sheet material of the present invention, it is necessary to mix Ketchen Black at 2 to 3% by volume or more;
The performance was lower than that in the case of embedding, and the sheet-like material obtained was pitch black.

Margins below [Effects of the Invention] The thermosetting sheet material of the present invention exhibits excellent static eliminating performance by using a small amount of organic conductive fibers, and does not deteriorate in performance due to repeated bending.

Patent applicant RiRashi Co., Ltd.

Claims (6)

[Claims] (1) A thermosetting resin sheet containing 1% by volume or less of organic continuous fibers or fiber bundles consisting of at least one conductive filament, the fibers or fiber bundles being arranged in at least one direction. , and exists in a continuous state from one end of the sheet to the other end. (2) The sheet-like article according to claim 1, wherein the fibers or fiber bundles are arranged in parallel in one direction on the surface or inside the sheet-like article, and the intervals between the fibers or fiber bundles are 50 mm or less. (3) The fiber or fiber bundle is a multi-core core-sheath composite fiber with conductivity in the core, and the electrical resistance of the fiber or fiber bundle is 10^
The sheet-like article according to claim 1 or 2, which has a resistance of 6 Ω·cm or less. (4) The sheet-like article according to any one of claims 1 to 3, wherein the thermosetting resin is an unsaturated polyester resin, a vinyl ester resin, or an epoxy resin. (5) The sheet-like article according to any one of claims 1 to 4, wherein the embedded depth of the fibers or fiber bundles from the surface of the sheet-like article is 1 mm or less. (6) The sheet-like article according to claim 1, comprising a woven or knitted fabric containing organic continuous fibers or fiber bundles made of at least one conductive filament.