JPS6255133A - Conductive composite body - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention The present invention relates to an electrically conductive composite that exhibits an excellent balance between transparency or colorability and electrical conductivity.

In recent years, with the development of electrical and electronic equipment, there has been a strong demand for the development of materials that have conductivity, in addition to the properties of plastics such as moldability and strength.

In response to this demand, plastic materials are being put into practical use in which electrical conductivity is imparted by kneading carzen black, metal fibers, graphite, etc. into plastic.

However, these cannot be applied to applications that require transparency, such as those that are colored jet black, or applications that are colored other than black.

On the other hand, the demand for transparent or colored conductive plastic materials has become increasingly strong as the development of electrical and electronic equipment and systems that utilize phenomena involving both light and electricity progresses. Ru. There are also requests for the development of packaging materials that have antistatic properties and allow the contents to be seen through, as well as plastic molding materials that can express colorful colors and have antistatic properties. There is something to strengthen it.

Conventionally, materials such as tin oxide, indium oxide, etc. that are vacuum-deposited on a glass substrate have been used as transparent and conductive materials. However, since the substrate is glass, it is difficult to make the film thinner or larger in area, and it is not flexible and has low mechanical strength, so it has been limited to only a few applications such as displays.

To solve these problems, films have been developed in which tin oxide, indium oxide, gold, palladium, etc. are vacuum-deposited on polyester films. These have a good balance between transparency and conductivity, as well as thinning and
It is a material that can be made into a large area, has good flexibility, and has excellent mechanical strength.

However, when tin oxide, indium oxide, gold, indium, etc. are used as evaporation materials, the temperature of the surface of the polymer film being evaporated increases due to the high evaporation temperature or the heat of condensation of the metal vapor or inorganic semiconductor vapor. Therefore, the polymer film used as the base material is limited to a polymer film with excellent heat resistance.

Furthermore, since gold, palladium, and the like are extremely expensive materials, the cost of the resulting vapor-deposited film was extremely high.

In recent years, research on conductive polymers such as polyacetylene, polypyrrole, and polythiophene has been active, but 71
? Some of these conductive polymers are black and have poor transparency and colorability, such as Liacetylene, and these conductive polymers require doping with an electron donor or electron acceptor called a donor. The stability of the composite of the 0-band and the conductive polymer is poor, making it difficult to use it in air for long periods of time.
The deterioration in conductive performance due to this was unavoidable.

(2) Outline of the invention In view of the current situation, the present inventors have developed
We are working hard to develop conductive composite materials that do not require the use of radium, have a relatively wide selection of polymer materials for the base material, and have a good balance between stable conductive performance Q and transparency or colorability. As a result of my efforts, I am happy to have arrived at the present invention.

That is, the present invention uses a polar organic polymer compound as a base material,
On the substrate, the number average molecular jIk300 to 500, O
The object of the present invention is to provide a conductive composite which is formed by forming an aromatic vinylene sulfide polymer layer having the following formula (1) tS repeat unit of OO.

(1) R4-R8 in the formula hydrogen, halodane, carbon number 1-
Hail a group selected from 12 alkyl groups.

R1 to R8 are preferably hydrogen, an alkyl group having 1 to 5 carbon atoms, or helogne.

(3) Detailed Description of the Invention The number average molecular weight of the aromatic vinylene sulfide polymer having the above formula (1) as a repeating unit (hereinafter abbreviated as aromatic vinylene sulfide polymer) is determined by the ethynyl group or thiol group at the terminal of the molecule. It can be determined by complexing a group with a metal and quantifying the metal, or by vapor pressure osmosis (VPO). The number average molecular weight of the aromatic vinylene sulfide polymer used in the present invention is 300, which is 500.0.
00, preferably from 700 to 300,000. More preferably 1.000 to 100,000. Particularly preferred is 2,000 s o, o oo o.

The aromatic vinylene sulfide polymer may be a crystalline aromatic vinylene sulfide polymer in which crystals are observed when measured by an X-ray method, or may be a non-quality aromatic vinylene sulfide polymer. .

In the case of a crystalline aromatic vinylene sulfide polymer, for example, R1 to R and 6R5 to R8 in the above formula (1) are all H.
When an aromatic vinylene sulfide polymer layer is formed on a polyester base material, the conductivity is 10-5 s/crI
It becomes L.

Furthermore, even when a polar organic polymer compound is used as a base material and a non-quality aromatic vinylene sulfide polymer is grown on this base material, the conductivity of the aromatic vinylene sulfide polymer layer without doping is can be expressed at a sufficiently high level compared to conventionally known organic conductive polymers. On the other hand, the base material is glass, amorphous ST,
When using ht crystal etc., the conductivity of the aromatic vinylene sulfide polymer layer composited on the base material is
Regardless of whether it is amorphous or not, it is much lower than when a polar organic polymer compound is used as the base material.

The present invention improves the electrical conductivity of the aromatic vinylene sulfide polymer layer composited on the base material by using a polar organic polymer compound as the base material, compared to when glass, amorphous silicon, etc. are used as the base material. It is intended to be improved.

Polar organic polymer compounds used as base materials include polyester, polyether, polyamide, polyimide,
Polycarzenate, polymethyl methacrylate, polynoseraphenylene sulfide, polyvinyl alcohol,
Organic polymer compounds having a polar group such as acrylonitrile resin, poly(vinylidene-heronide), and poly(-hynylidene rhodanide) are used.

Alternatively, a non-polar organic polymer compound may be polarized, and the polar organic polymer compound may be used as long as it is used on the surface of the base material that is in contact with the aromatic vinylene sulfide. Therefore, it is possible to use a molded body formed from a nonpolar organic polymer compound and whose surface is polarized using a polar compound, oxygen, or the like.

In addition, in order to maintain sufficient adhesive strength between the base material and the aromatic vinylene sulfide polymer, the surface freeness of the base material (20°C energy r is 28 dyne/m or more, preferably 30 dyne/(y or more, more preferably 35d
It is preferable to select a base material having a hardness of yne/cm or more.

Particularly preferred are polyethylene terephthalate and polyacrylonitrile.

The shape of the base material may be arbitrarily selected depending on the intended use, such as film, sheet, filler, or fiber.

The aromatic vinylene sulfide polymer used in the present invention can be obtained by addition polymerization of both monomers having structures shown in the following structural formulas (2) and (3).

3R4 7R8 (2), (3) In the formula, R4 to R8 are hydrogen, /N
O) f is an alkyl group having 1 to 12 carbon atoms. Preferred are hydrogen, an alkyl group having 1 to 5 carbon atoms, and 710rn.

Examples of the compound represented by the above-mentioned structural formula (2) include p-jethynylbenzene, m-jethynylbenzene, and jetynyltoluene.

Compounds represented by structural formula (3) include P-benzenedithiol, m-benzenedithiol, 4-chloro-m
- Benzenedithiol, etc.

The reaction is carried out by irradiating a mixture of both monomers represented by structural formulas (2) and (3) with active light (visible light, ultraviolet rays, γ-rays, electromagnetic waves such as X-rays, electron beams, etc.), or An aromatic vinylene sulfide polymer can be obtained by adding a radical generator such as monooxide or monooxide, or in the presence of a trace amount of oxygen.

The reaction is carried out at -80°C to 200°C, preferably -50°C to
It is carried out at 150°C, more preferably at -20°C to 100°C. In particular, in order to obtain crystals of the aromatic vinylene sulfide polymer, a temperature below the melting point and sublimation temperature of the mixed vapor-deposited monomer crystals is selected.

The base material and the aromatic vinylene sulfide polymer are combined by the following method.

First, a method suitable for forming a crystalline aromatic vinylene sulfide polymer layer on a substrate will be described.

Monomers having the structural formulas shown by the above formulas (2) and (3).

At the same time, the mixed monomer is sublimated to form a mixed monomer vapor deposited film on the substrate. This mixed monomer vapor deposited film can form high quality crystals. Moreover, the crystal structure may differ depending on the type of base material. Solid-phase addition polymerization is performed by irradiating the mixed monomer vapor-deposited film on this substrate with actinic rays to form a crystalline layer of aromatic vinylene sulfide polymer on the substrate.

The X-ray diagram of the crystals of the aromatic vinylene sulfide polymer composited on the substrate shows an X-ray diagram very similar to that of the crystals of the mixed monomer deposited film.

From this, it is thought that the crystal structure of the aromatic vinylene sulfide polymer is formed differently depending on the type of substrate, but that the organic polymer compound has the effect of making the crystal structure advantageous for conductivity. It will be done.

Furthermore, a non-quality aromatic vinylene sulfide polymer can be composited onto a base material in the same manner as described above. That is, solid-phase addition polymerization is performed at a temperature higher than the melting point of the mixed vapor-deposited monomer crystal, or the above-mentioned composite is performed using a specific organic polymer base material, or aromatic vinylene sulfide formed on the base material. In this method, a polymer crystal is heated to a temperature higher than that at which it is formed, and then irradiated with light of a specific wavelength to effect a phase transition into a non-quality aromatic vinylene sulfide polymer.

In addition, a solution of a mixture of heptamines of structural formulas (2) and (3) is applied onto the substrate by a method such as a spin cord method, a blade coating method, a dipping method, a casting method, or a spray method, and then dried. Both monomer mixtures can be composited onto the substrate. Solid-phase addition polymerization is performed by irradiating this with actinic rays, etc., and a non-quality aromatic vinylene sulfide polymer can also be composited onto the base material.

INDUSTRIAL APPLICABILITY The present invention is suitable for obtaining an electrically conductive composite having excellent transparency because it can use an organic polymer compound with excellent transparency such as polyester as a base material. In addition, by using a polar organic polymer compound as a base material, it is possible to obtain a composite aromatic vinylene sulfide polymer with high electrical conductivity, as well as flexibility, mechanical strength, formability, and transparency. Therefore, the conductive composite of the present invention having excellent properties can be obtained.

Furthermore, despite its high conductivity, the aromatic vinylene sulfide polymer layer of the present invention has relatively good transparency, so even when used as a packaging material, the contents can be seen through. It can also be used as a colorful molding material.

Further, the above-mentioned conductivity is achieved without using any treatment such as doping, does not change even after long-term use, and has excellent transparency and quality stability.

The present invention will be specifically described below with reference to Examples.

[Example 1] A polyethylene terephthalate sheet (density 1, 45511/
cc, lattice constant 3.44. Surface energy (20℃)
43.8 dyneA1rL2) was set up as a substrate, and 0.134 & of an equimolar mixture of powdered crystals of P-jethynylbenzene and P-benzenedithiol was added.

The vapor deposition chamber was brought to a degree of vacuum of 0.5 mmHH by evacuation operation.

Further, the evaporation source was heated to 60° C. and sublimated for 30 seconds to form a vapor-deposited crystal thin film (thickness: 10.4 μm) of a mixed monomer of P-jethynylbenzene and P-benzenedithiol on the polyethylene terephthalate substrate. The crystal of this mixed monomer vapor deposited film has a maximum diffraction peak at d=7.73X in X-ray diffraction, and a=7. Near sl, further 3.90X, 2 pieces from 3.6 to 3.8X, 2.60X,
It has a diffraction peak at 1.95X. Figure 1 shows the relative intensity based on the height of the maximum diffraction peak.

The mixed monomer crystal thin film of p-jethynylbenzene and p-benzenedithiol obtained on a polyethylene terephthalate substrate was maintained at 60° C. and irradiated with ultraviolet rays for 12 minutes using a high-pressure mercury lamp (300 W). After irradiation with ultraviolet rays, the crystal thin film was washed with methanol to remove residual monomers, and N1 was polymerized with a yield of 91 yen.

The X-ray diffraction pattern of the addition M crystal of P-jethynylbenzene and P-benzenedithiol obtained on the PET substrate was very similar to the X-ray diffraction pattern of the mixed monomer vapor-deposited crystal. Ta.

The molecular weight of the above polymer was found to be 4000 by the copper acetylide method. In addition, the composition of the above polymer was determined using the flask combustion method [Organic Trace Quantitative Analysis 383-! ! The sulfur content was determined by analysis using the method (1969, Nankodo), and it was found to be 22.3 wt4. Furthermore, the conductivity of the polymer on the PET substrate is higher than that of the platinum electrode 2.
When measured by the terminal method, it was 4.5 x 10 8 hours.

In addition, the polymer on the PET substrate has a thickness of 200 to 500 nm.
Although the color was yellowish, it was transparent enough to be seen through. In the diffuse reflection spectrum of the above polymer, the absorbance at a wavelength of 500 nm is 0.
It was about 2 to 0.3.

In addition, the adhesive strength between the PET substrate and the above polymer was so strong that it easily peeled off.

Example 2 Everything was the same as Example 1 except that a polyacrylonitrile sheet (lattice constant 5.27X, surface free energy (2.0°C) = 52.3 dyneA-WL2) was used instead of the PET sheet as the substrate. P-jethynylbenzene and P
- A mixed monomer vapor-deposited crystalline thin film (thickness 10.6 μm) of benzenedithiol was formed. FIG. 2 shows an X-ray diffraction diagram of the crystal of this mixed monomer vapor-deposited film in terms of relative intensity based on the height of the maximum diffraction peak. This is significantly different from that obtained when a PET sheet is used as the substrate (FIG. 1), indicating strong dependence on the substrate.

The mixed monomer crystal thin film of P-jethynylbenzene and P-benzenedithiol thus obtained on the polyacrylonitrile substrate was polymerized in the same manner as in Example 1 to obtain an addition polymer with a yield of 904.

The X-ray diffraction pattern of the addition polymer crystal thus obtained on the polyacrylonitrile substrate was also very similar to the X-ray diffraction pattern of the mixed monomer vapor-deposited crystal.

The molecular weight of the above polymer was determined to be 3000 by the copper acetylide method. Moreover, the sulfur content in the above polymer was 23.81. The conductivity of the above polymer on the polyacrylonitrile substrate was measured in the same manner as in Example 1 and was 1.4 x 10
-'s/crIL.

,j? The color tone and transparency of the above polymer on the IJ acrylonitrile substrate were similar to the Example 10 polymer.

Furthermore, the adhesive strength between the polyacrylonitrile substrate and the above polymer was very strong.

Example 3 The substrate has a density of 1.491 dea, a lattice constant of 3.84X,
Surface free energy γ'520'c) = 44.6 d
P-jethynylbenzene and P
- An addition polymer of benzenedithiol was composited.

Figure 3 shows the X-ray diffraction pattern of the crystal of a mixed monomer film of P-jethynylbenzene and P-benzenedithiol deposited on a polyoxymethylene substrate, showing the relative intensity based on the height of the maximum diffraction peak. Ta.

Further, when the mixed monomer vapor-deposited film was polymerized in the same manner as in Example 1, an addition polymer was obtained with a yield of 92 mm, but the addition polymer thus obtained on the polyoxymethylene substrate was completely It was character.

The molecular weight of the above polymer was determined to be 5000 by the copper acetylide method. Moreover, the sulfur content in the above polymer was 23.74. The conductivity of the above polymer on the polyoxymethylene substrate was measured in the same manner as in Example 1 and was 3.2/cm0! l
It was /-.

Moreover, the polymer on the polyoxymethylene substrate is 20
It exhibited absorption in the range of 0 to 500 nm, and although the color tone was yellowish, it was transparent enough to be seen through. In the diffuse reflection spectrum of the above polymer, the absorbance at a wavelength of 500 nm was about 0.1 to 0.2.

The adhesion between the polyquine methylene substrate and the above addition polymer was very strong.

Comparative Example 1 Glass substrate (amorphous, surface free energy 7'
An addition polymer of P-jethinylbenzene and P-benzenedithiol was composited in the same manner as in Example 1 except that 20" = 300 dyne/cFrL) was used.

P-jethynylbenzene and P- deposited on a glass substrate
FIG. 4 shows the X-ray diffraction pattern of the crystal of the mixed monomer vapor-deposited film of benzenedithiol in terms of relative intensity based on the height of the maximum diffraction peak.

Further, the mixed monomer vapor-deposited film was polymerized in the same manner as in Example 1 to obtain an addition polymer with a yield of 90=1.

The X-ray diffraction pattern of the crystal of the addition polymer thus obtained on the glass substrate was very similar to the X-ray diffraction pattern of the Zummer-deposited crystal on the mixed substrate. The molecular weight of the above polymer was determined to be 3000 by the copper acetylide method. Further, the sulfur content in the polymer was 24.0. The conductivity of the above polymer on the glass substrate was measured in the same manner as in Example 1 and was found to be as low as 1.5 x 10-10 s/m. Further, the color tone and transparency of the above polymer were similar to those of the polymer of Example 1.

The adhesion between the glass substrate and the addition polymer was strong.

Comparative Example 2 On the glass substrate obtained in Comparative Example 1, seven crystals of the complexed jetynylbenzene and benzene dithiol tono addition polymer were placed.
Heat treatment was performed at 0°C for 1 hour.

Thus, the polymer crystals on the glass substrate turned out to be completely inferior polymers as seen from the X-ray diffraction pattern.

The electrical conductivity of the above-mentioned non-grade polymer on the glass substrate was determined in Example 1.
When measured in the same manner as 1.4×10-” s/
It was as low as lyn.

Further, the color tone and transparency of the non-quality polymer were similar to those of the polymer of Example 4.

Comparative Example 3 All examples were the same as Example 1 except that amorphous St was used for the substrate. ! : In the same manner, an addition polymer of P-jethinylbenzene and P-benzenedithiol was composited.

Figure 5 shows the X-ray diffraction pattern of the crystal of the mixed monomer film of P-jethynylbenzene and P-benzenedithiol deposited on the amorphous 81 substrate, showing the relative intensity based on the height of the maximum diffraction peak. .

Further, the mixed monomer vapor-deposited film was polymerized in the same manner as in Example 1 to obtain an addition polymer with a yield of 934.

The X-ray diffraction pattern of the crystals of the addition polymer obtained on the 81 substrate was very similar to the X-ray diffraction pattern of the mixed Zummer-deposited crystals. The molecular weight of the above polymer was determined to be 1000 by the copper acetylide method.

Further, the sulfur content in the above polymer was 17.01.

The conductivity of the above polymer on the St substrate was measured in the same manner as in Example 1 and was found to be as low as 3.2/cm0 g7-. Further, the color tone and transparency of the above polymer were similar to those of the heavy polymer of Example 1.

[Brief explanation of the drawing]

Figures 1 to 5 show the relative intensities of the Xa1 diffraction peaks of polar organic compound films formed on substrates in Example 1, Example 2, Example 3, Comparative Example 1, and Comparative Example 3, respectively. FIG.

Claims (1)

[Scope of Claims] 1) A polar organic polymer compound is used as a base material, and an aromatic vinylene sulfide polymer layer having a number average molecular weight of 300 to 500,000 and having the following formula (1) as a repeating unit is formed on the base material. A conductive composite characterized by being made into a composite by forming the conductive composite. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R＿! ~R_4, R_5 to R_8 are hydrogen, halogen, or an alkyl group having 1 to 12 carbon atoms 2) A polar organic polymer whose surface free energy γ^(^2^0^℃^)_s is 30 dyne/cm^2 or more The conductive composite according to claim 1, which uses a compound as a base material.