DE3447391A1 - ELECTRICALLY CONDUCTIVE ALKALINE METAL TITANATE COMPOSITION AND MOLDED PARTS THEREOF - Google Patents

Description

The invention relates to a composition containing an electrically conductive alkali metal titanate (hereinafter marked with EAT) and products made from it.

There is a great need for electrically conductive materials for a wide variety of purposes and therefore, conductive compositions are desired which have very good properties in terms of heat resistance , chemical resistance and processability, especially those made from them molded products. There are various conductive compositions that are a filler material and a Binder included, known. Because binders are accessible with a high resistance to heat or chemicals common non-reinforcing materials such as carbon

fabric powder, metal or metal oxide powder and powder of Copper iodide and similar copper salts are used as conductive fillers. When the composition has an increased amount Contains conductive filler, so that increased conductivity occurs, the composition has greatly reduced strength. Setting the mechanical Properties and conductivity of the composition makes great experience in selecting the components and required for production monitoring. These common conductive powders are generally unstable and some become less conductive when subjected to a chemical change such as oxidation and others change their conductivity when, for example, they absorb water. It is therefore with the known powders difficult to maintain stable conductivity over an extended period To maintain period. It is therefore desirable to have conductive fillers with very good compatibility with binders and reinforcing properties and are stable. Although it has been tried through However, the use of carbon fibers or metal fibers to improve the stiffening properties is difficult to produce fibers of uniform length because these materials cause problems with respect to surface smoothness, malleability, manufacturability and the processability of molded articles made therefrom. Conductive fillers made of precious metal, e.g. Gold or platinum are stable in terms of conductivity, but they are expensive. It can thus be stated that the usual fillers do not have the desired properties. The object of the invention is therefore to to provide an electrically conductive composition containing a conductive filler that is stable is, has reinforcing properties and is compatible is with the binders.

The invention is also based on the object, shaped

to provide te articles from the conductive composition which have good surface smoothness, malleability, Exhibit productivity and machinability after molding.

The object is achieved by a composition containing EAT and a binder and products formed therefrom.

The composition according to the invention is suitable for materials which must be electrically conductive, e.g. conductive materials, resistance materials, antistatic materials, electrostatic charge protection materials, electromagnetic wave shielding materials, etc. When molded from the composition of the present invention Products or parts are manufactured, these materials are electrically conductive and extremely heat-resistant, chemically resistant and have a smooth surface.

The alkali metal titanate (EAT) used according to the invention includes the following compounds:

(1) EAT (I) of the general formula 25

aTiOx · bH 0,

where M is an alkali metal, e.g. Li, Na or K, CKa: £ 8, 0 ^ b64 and 0 <x <2 and a, b and χ are each an integer Number is. EAT (I) is generally referred to as reduced alkali metal titanate or alkali metal bronze titanate. (2) EAT (II) made by coating an alkali metal titanate the general formula

MO aTiOy bH ₂ O,

where M, a and b have the same meaning as given above and 0 <ya2 with at least one of the conductive ones

Metals and conductive metal compounds such as conductive metal oxides and conductive metal halides.

(3) EAT (III) prepared in a reducing atmosphere 5 or in an oxidizing atmosphere and a subsequent one Reduction treatment or doping treatment (if desired) when an alkali metal titanate of the following formula

ATiOy bH ₂ O,

where M, a, b and y have the meanings given above, is produced under such a condition that a conductive metal and / or a conductive metal compound, e.g. a conductive metal oxide or conductive metal halide that forms a eutectic with the titanate or is crystallized or precipitated on the surface of the titanate, i.e. when the titanate is the general Formula is made in the presence of materials for it and one of the conductive metals and the conductive Metal compounds (oxides, hydroxides, halides, carbonates, nitrates and sulfates of such metals) or mixtures from at least two of these compounds. The titanate of the invention also includes mixtures of at least two of the EAT connections listed above.

The EAT compounds of the invention differ of the alkali metal titanate (IV) (hereinafter referred to as AT (IV)) represented by the following formula 30th

M ₂ O aTiO ₂ bH ₂ O,

wherein a and b have the meanings given above.

In general, the titanate AT (IV) is obtained as a fibrous one Single crystal, which is used as a heat-resistant reinforce-

the filler is used, but an electrical insulation material is. When used alone, AT (IV) does not form a conductive composition. A conductive one Composition with the reinforcing and heat-resistant properties of AT (IV) is obtained by using a EAT of the invention or a conductive filler, conductive resin or similar material commonly used used in combination with AT (IV). The conductivity can only give the composition by using a material different from AT (IV).

There is already a process for making EAT (I) from AT (IV) and a process for making EAT (II) from AT (IV) and a process for the production of AT (IV) in connection with a process for the production developed by EAT (III). It has also been developed a method to the electrically insulating AT (IV) to impart a conductivity by a chemical coating of the titanate with a conductive one Metal and / or a conductive metal compound or through the formation of a eutectic of such substances. Of Furthermore, a process has been developed for the production of EAT by precipitation or crystallization such substances on AT (IV). A technical process for economical coating has also been found of AT (IV) with a conductive material by a chemical or physical treatment e.g. by chemical vapor deposition (CVD) or physical vapor deposition (PVD). There are therefore a number of methods for making it developed by EAT in which the physical properties of the alkali metal titanates are effective have been received.

Suitable EAT compounds are described, for example, in Japanese Patent applications 119481/1981, 14146/1982, 16742/1982, 114890/1982, 133943/1982, 21230/1982 and

JP-OS (o.P.) 20722/1983. Those which can be used according to the invention However, EAT connections are not limited to the connections according to the above documents.

The EAT compounds that are used according to the invention are conductive materials that have very good reinforcement properties and have a very good resistance to chemical attack. The connections will e.g. manufactured as follows:

(i) EAT (I) can be produced by heat treatment of AT (IV) at a temperature of at least 300 ^° C., preferably of at least 500 ^° C. in a reducing atmosphere containing a reducing gas, for example hydrogen or carbon monoxide or in a non-oxidizing one Atmosphere in the presence of a reducing agent such as carbon etc. Alternatively, EAT (I) can also be produced directly from a system for the production of AT (IV) by treating the system in a reducing atmosphere or in a non-oxidizing atmosphere Atmosphere in the presence of a reducing agent. If the metal M in the formula

M_0 aTiOx bH ₂ O,

wherein M, a, b and χ have the meanings given above, is potassium, then the EAT (I) is a reduced potassium titanate. Reduced potassium titanate, which comes in by changing χ color changes in the following order: light red, red, black, blackish-red, gold and silver-white.

With regard to the conductivity, according to the invention in particular the EAT (I) is used which is reduced to an extent up to x £ 1.99, in particular x <1.95 with a pale red to black color.
EAT (II) is produced by coating EAT (I) and / or AT (IV) with a conductive connection. Suitable coating methods are electroless piatation,

the wet neutralization, CVD and PVD, which are used to impart conductivity to the surfaces. In contrast, according to the invention, a process has been developed for the production of EAT (II) by depositing a conductive compound of tin, indium, antimony, copper or nickel on the surface of AT (IV) by a wet reaction. Furthermore, a process for the preparation of EAT (II) has been developed containing an alkali metal titanate of the general formula
10

M ₂ O aTiOy bH ₂ O,

(in which M, a, b and y have the meanings given) and in which titanate is coated with at least one metal selected from the group consisting of Ni, Cu, Pt, Ag, Au, Cr and Pd. It has been found that the the compounds of the above general formula, the reduced titanate compounds according to the formula

MO aTiOx bH ₂ O,

(in which M, a, b and χ have the meanings given) are conductive per se and that these by coating with a conductive metal connection can easily be coated by electroless piatation and so the conductivity is improved.

EAT (II) according to the invention has a higher conductivity as EAT (I) and can therefore be used to advantage. Also advantageous is the white EAT (II) that is produced is achieved by coating the insulating AT (IV) with a transparent conductive metal compound, e.g. Tin oxide, antimony oxide, indium or copper iodide.

(iii) EAT (III) is made using an alkali metal titanate the general formula

MO aTiOy bH ₂ O,

(where M, a, b and y have the meanings given) is prepared from a titanium starting material, for example titanium oxide or titanium hydroxide and an alkali, for example alkali carbonate or halide by heating these materials at 500 to 1200 ⁰ C or by treatment with microwaves in the presence an oxide, halide, carbonate, sulfate or nitrate of tin, copper or silver. A typical compound of EAT (III) is the white EAT, which is formed when titanium oxide, potassium carbonate and tin chloride react in the molten state and tin oxide is precipitated on the surface of potassium titanate needle crystals.

Typical examples of the EAT connections are described above but the EAT compounds which can be used according to the invention also include mixtures of at least two of the compounds EAT (I) to (III) and other reinforcing or non-reinforcing EAT compounds. Preferred from the standpoint of use are EAT compounds in the form of fine fibers with a Diameter from 0.1 to 100 μm and a height / width ratio from 1 to 1000, giving the molded article a reinforcing effect and a smooth surface to lend. The shape and conductivity of the EAT connections is not limited, but determined according to the respective area of application.

Various binders can be used according to the invention.

Suitable examples of such binders are selected from curable resins having at least one active reaction group from the group consisting of hydroxyl, alkoxyl, carboxyl, amino, cyano, epoxy, vinyl and acetyl. Typical examples

for curable resins are amino resin, phenolic resin, Alkyd resin, epoxy resin, urethane resin, polyamide resin, polyester resin, Vinyl resin, polyimide resin, polymercapto resin, Silicone resin, fluorocarbon resin, boron resin, organotitanium resin, inorganically curable substances such as silicate, phosphate and Borate, mixtures of at least two of these materials and prepolymers thereof. These materials are vulcanizable into insoluble and non-meltable binders through heat, light, electron beams or catalysts. 10

While the suitable curable binders are generally the organic curable resins, there are also inorganic ones curable binders can be used, provided that they are suitable for processing and binding.

Due to the processability, vulcanizable binders are used generally offered in the form of prepolymers, which are then vulcanized or crosslinked to form insoluble ones non-melting binders. The binder is therefore in the form of a powder, containing a liquid or a solution a solvent, a dispersion or an emulsion containing a dispersant or an emulsifier or in special cases as a gas. Binders in these forms also include those that are not stable are, but react immediately or harden under ambient conditions at room temperature and those that crosslink, when brought into a mixture of at least two types of binders and those which are crosslinked by Addition of a catalyst without the binder of any external energy, e.g. the effect of heat or light get abandoned. These reactive binders must be kept in an environment that prevents them from reacting, e.g. in an inert gas atmosphere or in cool and dark rooms and these binders make the addition a reaction inhibitor necessary or must be stored separately from the other binder component or separated from the catalyst. All of these binders are inven-

can be used as intended, provided they bind EAT.

Other suitable examples of the binders which can be used according to the invention are soft binders for the formation of a soft coating layer and hard binder for forming a hard coating layer.

Examples of the preferred soft binders are

1) amorphous or low-melting hydrocarbon compounds or derivatives thereof, e.g. petrolatum, lanolin, petrolatum and bituminous compounds,

2) oils and fats, e.g. glycerol esters of fatty acids,

3) Polyalkylene oxides in the form of homopolymers or copolymers the alkylene oxides, e.g. ethylene oxide and propylene oxide,

4) Alky! Polyalkylene oxides, which are adducts of fatty acid glycerol oxides and alkylene oxides and derivatives thereof and

5) Compounds that are liquid or plastic at room temperature, e.g. liquid polyethylene, liquid Polypropylene and liquid acrylic acid resin.

These binders are used alone or at least in mixtures of two of the binders.

Binder generally used for coating compositions, inks, adhesives, sealants, etc. are suitable as hard binders. Preferred examples of hard binders are higher fatty acid derivatives, polyolefin compounds, Rubbers, acrylic acid resin, vinyl ether resin, vinyl formal resin, vinyl acetal resin, cellulose resin, polyacetal, Polysulfone, polyimidazole, Pc.yoxazoline, polyoxazole, mixtures or copolymers of at least two of these compounds etc.

The EET compounds and the binder can be mixed with conventional devices, e.g. a dispersing device

direction, a mixer or kneader in the appropriate atmosphere, for example at room temperature, with heating, in a cooled atmosphere, in a vacuum or under a special gas atmosphere.
5

The binder which can be used according to the invention can be used are in the form of a solution or an emulsion, a colloid or a dispersion using a Solvent or dispersant. In order to easily prepare or use the composition of the invention, For example, additives conventionally used in such compositions can be added during or after the process of incorporating the EAT compound into the binder or before or after the Composition has been used. Suitable additives are solutions, solvents, auxiliary dispersants and auxiliaries for viscosity, disinfectants, fungicides, dyes, plasticizers, agents that prevent precipitation, Flame retardants, catalysts, accelerators, crosslinking agents, auxiliaries for crosslinking, Antioxidants, anti-aging agents and agents for adjusting hardness, adhesion and flexibility.

The proportions of EAT and Binder depend on the desired area of application and the type of EAT connection and the binder. If too small amounts of EAT are used, sufficient conductive properties cannot be achieved can be obtained, so that not only the conductivity, but rather also the antistatic properties and the effect for preventing the charging could be influenced. If too small an amount of binder is used, the bond strength is low, so that the Products molded from the material do not have sufficient strength. The proportions are therefore preferred at 0.1 to 1000 parts by weight, in particular

1 to 500 parts by weight of EAT per 100 parts by weight of binder. Since the EAT compounds according to the invention are different Own paints and very good reinforcement fillers represent, the compositions containing EAT are also suitable for the application where the reinforcing property and / or the color is useful, but where there is essentially no use of the electrical properties is made. Such a composition can be made conductive by other conductive substances that are incorporated will. The compositions according to the invention also encompass these compositions.

In the event that an unstable binder is used, there is a possibility that the binder will be vulcanized or vulcanized in a normal atmosphere at room temperature if it is mixed with other binders or if the binders are further mixed with EAT and other additives, catalysts, etc. in such a In this case, the tie should be stored separately until it is used and only with the other connections be mixed just before use.

The composition according to the invention is curable or crosslinkable under the action of heat, if the binder is thermosetting. or curable with UV rays or electron beams, when the binder is a photo-curable binder. If the binder is curable in the presence of moisture or is an anaerobic binder, the composition must be solidified in an appropriate atmosphere. In this time In this case, the composition can be solidified or hardened, for example, in a vacuum or with the application of pressure. Electric Conductive compositions according to the invention are alone or in the form of mixtures of at least two of the compositions can be used. In addition, the composition according to the invention is applicable to a substrate or an electrically conductive or electrically

insulating material in order to produce corresponding layer materials. For the production of these materials, all customary processes including coating can be used
and printing.
5

The electrically conductive composition according to the invention has a high resistance to heat and chemicals and enables the manufacture of shaped products that have a very smooth surface, high strength and Have durability. The composition can be used e.g. for covers, sheets and other shaped articles, various layer materials and as a replacement product for those products in which metals are used as conductive materials can be used, e.g. for electromagnetic wave shielding, electrical circuits and electrical Contacts. The electrically conductive according to the invention Compositions are characterized by the content of EAT. The EAT compounds are generally fibrous have a reinforcing effect, as well as elec-

Trically conductive properties and therefore they are of particular importance as reinforcing filler materials for industry. Depending on the application, the composition furthermore contains additives or materials for adjusting the properties, for example coloring pigments, extender pigments, reinforcing or non-reinforcing filler materials and reinforcing or non-reinforcing conductive ones
Filler materials including platinum, gold, silver, copper, nickel, aluminum, and carbon. The composition then shows in addition to the very good conductivity

strength and reinforcement properties good heat resistance caused by the EAT compound, a corresponding metallic color according to the EAT used and an orientation with regard to conductivity, if fibrous EAT in a particular orientation is arranged. For this reason the compositions according to the invention are of great industrial importance.

The invention also relates to conductive tracks or films, which are referred to below in a summarized manner as tracks are referred to, these webs are made from the composition of the invention from EAT and a binder.

The webs according to the invention are suitable as hard copy materials, Resistance materials, conductive materials, antistatic materials, prevention materials of charging, shielding materials for electromagnetic waves, etc. These conductive paths close such one that contain only one conductive portion, those that have at least one conductive layer and at least one Contain insulating layer, those that have at least two conductive layers of different conductivity and those that the at least two conductive layers of different conductivity and at least one insulating layer and those that contain a conductive layer and / or an insulating layer that are partially cut out is in the form of the pattern you want. At least one of the conductive layers includes each of these traces EAT. The conductive tracks are produced in the usual way, for example by applying or brushing on the materials according to the invention Composition on a strippable surface, by applying or spraying the composition to a web-shaped substrate layer, e.g. made of paper, fabric made of organic or inorganic fibers or a plastic film or by forming a multilayer material in the same way. The composition can be made in the form of a sheet directly by a suitable technique such as blow molding. In the conductive tracks according to the invention, customary modifying agents can be incorporated as well EAT and the binder. The conductive tracks of the present invention include those equipped with a substrate layer are.

The conductive sheets of the present invention have high strength due to the EAT, which acts as a reinforcing agent. The orientation of the path can be adjusted in their conductivity as the EAT can be oriented in a particular direction if so desired. the Orbit is stable due to the fact that the EAT is stable and is not affected by physical or physical effects chemical changes, e.g. due to oxidation in a normal atmosphere, the web also has a high level of heat resistance so that the railways are of great industrial importance.

The invention also provides pressure sensitive conductive ones Sheets or films (hereinafter collectively referred to as sheets) containing EAT and an elastic Binder. These webs have the characteristics that they are essentially sensitive to an external Pressure that changes the conductivity of the web.

The elastic ties that are made for the pressure sensitive Conductive tracks according to the invention are not limited as long as they are pressure sensitive or are elastic. Suitable binders of this type are, for example, those that are elastic or linear or ladder-like Have structure. Natural rubber, synthetic rubber, silicone rubber, urethane resin, Vinyl chloride resin and acrylic acid resin. Preferred elastic binders are those that have elastic deformability from about 40 to 65%, measured according to JISK6301 (Physical Test Method for Vulcanized Rubbers) .

The pressure-sensitive conductive sheets according to the invention can be made in the same way as the conductive tracks, except that an elastic tie is used as the tie.

The invention is explained in more detail below with reference to the following examples, in which the volume resistivity was determined using the following method, unless otherwise stated.
5

A mold was placed on a Teflon sheet, and then the composition was placed in the mold to a thickness of 6 mm to make a sheet 2.0 cm wide and 10.0 cm long. The thickness of the sample was measured with a micrometer with an accuracy of 0.01 mm. A silver foil is attached to each end face of the '■ sample pressed and two silver electrodes with a length of 2 cm are brought into contact with the a foil-coated end faces, the electrodes being separated from one another by 10.0 cm. The electric one Resistance between the two electrodes is measured with a digital multimeter TR-8641 (Takeda Riken Co., Ltd.).

The volume resistivity is calculated according to the

following equation: layer thickness of the web χ

Length of the electrodes χ volume resistivity = electrical resistance

Distance between electrodes 25

The surface resistivity is measured under Using a square sheet with a side length of 10 cm each made from a Teflon sheet as indicated above or using a smooth-faced, square sample of the same size as stated above and of a layer thickness of at least 1.0 mm. Using a sample chamber model TR-42 and a TR-6841 digital multimeter (Takeda Riken Co., Ltd.), the resistance between the electrodes was measured. The surface resistivity is calculated according to JIS K 6911 according to the following equation.

specific surface resistance = - χ electrical

resistance

In the above measurement condition, D = 7.0 cm and d = 5.0 cm.
5

Table 1
• Types of conductive potassium titanates

# 1 Reduced Potassium Titanate

TISMO BK (Otsuka Kagaku Kabushiki Kaisha), black. No. 2 Cu-reduced type

Titanate # 1 chemically plated with copper; Cu / Nr.1 = 2/1 (weight ratios); Titanate No. 1 was treated in a chemical copper plating bath (Ueno Seiyaku Co., Ltd.) at 40 ^° C. for 15 min

Stir. Color: metallic copper. No. 3 Ni-reduced type

Titanate # 1 chemically plated with nickel; Ni / No.1 = 2.5 / 1 (weight ratios). It was prepared in the same manner as described for No. 2, however except that an electroless nickel plating bath was used; Color: silver white. No. 4 Cu-TISMO Typ

Potassium titanate (TISMO D * from Otsuka Kagaku) was pretreated with a palladium activating agent, then treated in the same way as described in No. 2; Cu / TISMO D = 3.5 / 1 (weight ratios); Color: metallic copper-colored. No. 5 antimony type

TISMO D was treated with antimony oxide containing tin oxide, SnO ₂ / TISMO D = 2.5 / 1 (weight ratios). Methanol solution of antimony chloride and tin chloride (3/97 mole ratio) was applied to the TISMO D, and then heated to dry in the air and then for 10 min at 700 ⁰ C and 300 ⁰ C for 3 h. Color white.

No. 6 CuJ-TISMO Typ

Potassium titanate (TISMO L * from Otsuka Kagaku) was treated with copper iodide; CuJ / TISMO L = 2/1 (weight ratios); TISMO L was dispersed in an aqueous sulfuric acid solution containing 6.6% copper sulfate, and then 8.7% potassium iodide was added dropwise in uniform amounts with stirring. The reaction product was filtered, washed with water, dried at 50 ⁰ C. Color: pale yellow.

* TISMO D and TISMO L are electrical insulators.

example 1
15th

An electrically conductive curable composition was prepared from 85 parts of a conductive alkali metal titanate No. 1 and 100 parts of an epoxy resin (DER 324, Dow Chemical Corp.) - The composition was ^{heated to 50 °} C. and then 21.5 parts of N- (2nd The mixture was applied to a steel plate (SPCC-B) in accordance with JIS G 3141 until the layer thickness was 5 mm and then the composition was ^{cured at 50 °} C. for 30 min to form a 5 mm thick one conductive coating layer on the steel plate, the volume resistivity was 1.01 Ω ~-cm, and the surface resistivity was 170.il.

The sample thus prepared was examined for the electrodeposition using a Elektroablagerungsalkydharzes and then the coating 30 was heated at 15O ⁰ C min. The resin was sufficiently deposited on the surface of the conductive composition as well as on the intermediate layer between the composition and the steel plate, that is, the composition

composition showed good properties for use as a conductive carrier composition.

Example 2
5

Thermosetting conductive compositions were prepared from a conductive alkali metal titanate No. 3 according to FIG Table 1, the same binder as given in Example 1 and N- (2-aminoethyl) piperazine. In the same

As indicated in Example 1, each composition was used in terms of volume resistivity
and the specific surface resistance are checked.
The results are summarized in Table 2. Before measuring the resistances, the samples were ^{heated at 50 °} C. for 30 min and then cured ^{at 150 ° C. for 30 min.}

Table 2

2C No. elec
trisch
conduct
of the Al-
kaliti-
tanat Am
the specific volume-specific upper
resistance sheet resistance elec
tri speci
fi
shear
Volu
men-
contrary
was standing
(Λ-cm) electr
shear
Contrary
was standing
(Λ) specific
shear
Surface
chenwi
the state
U) 2-1 25th 100 layer
thickness shear
Contrary
was standing
(Λ) 1500 1.03x10 ⁵ 1.94x10 ⁶ 25th 2-2 50 100 (mm) 1.50x10 ⁴ 81, 4 1.23x10 ³ 2.31x10 ⁴ 2-3 75 100 5.0 798 1.53 54.14 1020 2-4 100 100 5.1 14.4 0.75 44.05 830 2-5 125 100 5.3 7.81 0.13 5.47 103 30th 2-6 150 100 4.8 1.3 0.02 0.63 11.9 5.0 0.196 5.1

Example 3

Conductive curable compositions 3-1 to 3-11 were prepared as shown in Table 3 based on different conductive alkali metal titanates and binders in different weight ratios. The samples were examined and the results of the volume resistivities and the surface resistivities are summarized in Table 4. 10

Table 3

15th No. Electric
senior
Alkaline
tanat Weight
share binder Weight
share other accessories Weight
share Art 100 Art 100 Art 21, 5 3-1 2 100 Epoxy resin
(Example 1) 100 Harder 2 20th 3-2 3 80 Silicone resin 100 Catal
gate 3-3 3 30th Acrylic acid
resin 100 30th 25th 3-4 3 70 Aminoalkyd
resin 100 Xylene 3-5 4th 50 phenolic
resin 100 2 3-6 4th 50 Polyester resin 100 Harder 0.2 30th 3-7 5 5 Alkyd resin 15th Harder 70
30th 3-8 6th 50 Polyamide resin
Torayzin F-30) 100 Methanol
Isopropyl
nol 2 35 3-9 1 70 Silicone resin 100 Catal
gate 3-1C 1 130 Urethane resin 100 3-1 ' 1 Fluorine contained
ting resin Catal
gate

Tabel

No. layer
thickness
(well) specific volume
resistance specific
shear Vo
lumenwi
the state
(JL- cm) specific waiter
surface resistance specific
shear
Surface
chenwi
the state
(Λ) 3-1 3.00 electr
shear
Contrary
was standing
(A) 0.95 electr
shear
Contrary
was standing
CftJ 103 3-2 3.01 15.8 1 .83 5.47 451 3-3 2.98 30.4 6.29 23.9 1080 3-4 4.99 106 121 57.3 1072x10 ⁴ 3-5 3.00 2020 187 9.13x10 ² 5.61x10 ⁴ 3-6 3.01 3120 1070 2.98x10 ³ 2.21x10 ⁵ 3-7 3.05 1.78x10 ⁴ 2350 1.17x10 ⁴ 5.61x10 ⁵ 3-8 3.00 3.85x10 ⁴ 8100 2.98x10 ⁴ 1.09x10 ⁶ 3-9 3.03 1.35x10 ⁵ 1900 5.79x10 ⁴ 3.83x10 ⁵ 3-10 3.00 3.14x10 ⁴ 251 2.03x10 ⁴ 4.29x10 ⁴ 3-11 3.00 4180 0.21 2.28x10 ³ 97 3.50 5.15

Example 4

Coating compositions No. 1 to No. were prepared from titanate No. 1 shown in Table 1 and the materials as listed in Table 5 using a three roll kneader. The values for The volume resistivity of these compositions are summarized in Table 5.

- 24 Table 5

Coating
grant
together-
settlement
No. Tismo
BK acrylic
acid-
resin* methyl
cello
so lve Chic!
thickness
(μπι) it- elec
tri specific
shear Vo
lume η wi
the state
(Λ-. Cm) 1 25th 100 - 41 shear
Contrary
was standing
Ul) 4500 2 50 100 25th 35 5.49x10 ⁶ 173 3 100 100 100 30th 2.47x10 ⁵ 3.85 4th 125 100 150 25th 6.42x10 ³ 1, 00 5 1.50 100 200 25th 2.00x10 ³ 0.83 1.66x10 ³

* Elecond PQ-50B (non-volatile content = 50%)

Example 5

Coating compositions 21 to 24 were prepared in the same manner as in Example 4, with the exception that reduced potassium titanate (TISMO BK), which had been chemically copper-plated, was used as the EAT with the materials as in Table 6 given. The volume resistivity of the samples was measured. The results are in the table 6 registered.

The reduced potassium titanate was chemically plated with copper by treatment of TISMO BK in a chemical Kupferplatierungsbad (üeno Seiyaku Co., Ltd.) at 40 ⁰ C for 15 min with stirring. In this treatment, a conductive potassium titanate containing TISMO BK coated with copper was obtained in a weight ratio of 3/1 and a metallic copper color.

- 25 Table 6

Coating Elec Epoxy Methy1- layer Electri 2.14x10 specific grant trisch resin* cello- thickness shear 2.10x10 ² shear Vo together- conduct solve (μπι) Contrary lumenwi settlement of the Al- was standing the state No. kaliti- (Λ) (A "cm) tanat 21 30th 100 - 45 2.22x10 ⁶ 2000 22nd 130 100 50 37 1.38x10 ⁴ 10.2 IC 2 23 170 100 100 28 0.12 - 24 220 100 150 19th 0.08

* Äraldite AT-15 with 7 parts by weight of N- (2-aminoethyl) piperazine per 100 parts by weight of epoxy resin

Example 6

Coating compositions No. 31 to No. 33 were prepared in the same manner as in Example 4, except that potassium titanate (TISMO D from Otsuka Kagaku KK) was coated with a white deposit of tin oxide containing antimony oxide as EAT and together with the materials as listed in Table 7 are d. In Table 7, the volume resistivity results of the compositions were also excluded, and they were measured as shown in Example 4. The EAT used was prepared by coating a methanol solution of antimony chloride and tin chloride (3/97 molar ratio) to TISMO B, drying the coating in air, and heating the coating for 60 min at 700 ⁰ C and then h at 300 ⁰ C for 3 hours. The EAT had a tin oxide / TISMO D ratio of 2.5 / 1 parts by weight.

- 26 Table 7

5 Coating
grant
together-
settlement
No. Elec
trisch
conduct
of the Al-
kaliti-
tanat acrylic
emul-
sion * water layer
thickness
(μπι) Electri
shear
Contrary
was standing
(Jl) specific
shear Vo
lumenwi
the state
(n.-cm) 10 31 25th 100 - 45 4.17x10 ⁸ 3.75x10 ⁵ 32 50 100 20th 30th 1.92x10 ³ 1.15x10 ³ 33 100 100 50 30th 3.42x10 ¹ 205

* Mowinyl 70 9, non-volatile content = 50%)

15th

Example 7

There were coating compositions 41 to 48 and as Comparative coating composition No. 1 shown in Table 8 prepared in the same manner as in Example 4 indicated, but with the exception that the EAT compounds shown in Table 1 and the other materials in different Proportions were used. The compositions were examined for the specific Volume resistivity indicated in the same way as in Example 4. The results are given in Table 4.

Experimental example 1

Some of the coating compositions made according to Example 7 were tested for the surface resistivity according to the method given above. The results are shown in Table 9.

35

Experimental example 2

Samples were made of some of the coating compositions of Example 7 in the same manner as the test samples for the measurement of the specific Volume resistance. The samples were immersed in 0.5 η hydrochloric acid or 0.5 η sodium hydroxide at room temperature for 24 hours and then the volume resistivity and the external appearance were checked. In table 10 the results are summarized.

Table 8

15th Coating
grant
together-
settlement
No. Eleki
leiti
Alka
tanai Aryan
= ndes
Lit- binder Weight
share Other accessories Weight
share 41 Art Weight
share Art 100 Art 150 42 1 120 Epoxy resin2
(Example 2) 100 Methylcello
solve 100
20th 20th 43 3 100 Epoxy resin
(Example 2) 100 Methylcello
solve
Silver powder 100 44 2 120 Acrylic resin
(Example 1) -100 Methylcello
solve 70
30th 25th 45 5 100 Aminoalkyl
resin (without
Oil) ) 30 Methylcello
solve
Butanol 40
60 46 6 - 40 polyamide
resin (to-
rayzinF-3C 15th Methanol
Propanol 60
40 30th 47 1 20th Butyral
resin 100 Propanol
Butanol 50 48 1 100 silicone
resin 100 Xylene 170
30th 35 Comp.-
example 1 120 Acrylic resin
(Example 1) 100 Methylcello
solve
Ketjenblack 100 1* 120 Acrylic resin
(Example 1) Methylcello
solve

* Electrolytic copper powder (EC-1110)

- 28 Table 9

No. Specific volume resistance
was standing Electri
shear Wi
the state Specifi
shear
volume
contrary
was standing
(Λ, -ciri) More specific
resistance Surfaces- 5 41 layer
thickness
(mm) 6.50x10 ³ 3.25 Electric
resistance
W. surfaces
resistance 42 25th 1.54x10 ³ 0.83 5.47 103 10 43 27 2.02x10 ³ 1, 09 8.65 163 44 30th 2.71x10 ⁴ 15.7 10.83 204 45 29 9.59x10 ⁴ 51, 8 55.73 1050 46 27 18.39x10 ⁴ 103 168.3 3170 15th 47 28 4.50x10 ³ 2.88 30.78 58000 48 32 3.27x10 ³ 1, 96 16.19 305 See
E.g 30th 2.26x10 ³ 1.13 21, 76 410 20th 25th 7.27 137

Table 10

No. 0.5 η • HCl 0.5 η · NaOH Appearance 25th 41 Specific volume
men resistance
(Λ-cm) Appearance Specific volume
men resistance
(Tl'cm) A. 42 3.10 A. 3.33 B. 43 1.09 B. 1, 22 B. 30th 44 1, 24 B. 1.13 B. 45 17.1 B. 30.9 B. 46 75.9 B. 107 A. 35 47 101 A. 98 A. 48 2.44 A. 2.79 A. Vg:
bsi 1, 83 A. 1, 93 C. . 6700
• C. 8900

A: without change

B: slightly bleached
C: faded

Example 8

Conductive compositions 8-1 to 8-5 were prepared of titanate no. 1 according to Table 1 and the materials as listed in Table 11 under use a three-roll kneader. Conductive tracks No. 8-1 to No. 8-5 were made from these compositions, then these compositions were based on the volume resistivity and the specific Surface resistance measured. The results are summarized in Table 11.

Table 11

20th No. Elec
trisch
conduct
of the Al-
kaliti-
tanat Epoxy
resin* Spec. ^
Squint
thickness
(mm) /O
It 1. Contradicts
-Electr
Contrary
was standing
(A) was standing
Spec.
VoI.-
contrary
was standing
Ui.'cm Spec. Above:
Electr.
Contrary-
■ stood
(A) : 1.resist
Spec.
Surface
contrary-
was standing
(Λ) 8-1 15th 100 5.21 1.93x10 ⁴ 2010 2.86x10 ⁴ 5.39x10 ⁵ 25th 8-2 50 100 5.77 8.75x10 ² 101 9.40x10 ² 1.77x10 ⁴ 8-3 75 100 5.91 48.3 5.71 26.1 492 8-4 100 100 5.49 9.56 1, 05 9.71 183 8-5 120 100 5.83 7.98 0.93 5.36 101

* DER 324 (Dow Chemical Co., Ltd.) with 21.5 parts of N- (2-aminoethyl) piperazine per 100 parts of epoxy resin

Example 9

A conductive composition was prepared from 100 parts of titanate no. 5 according to Table 1, 20 parts of vinyl chloride resin with a particle size of 0.01 to 1 μm, 25 parts of dioctyl phthalate, 0.3 parts of dibutyltin maleate and 15 parts of 4,4'-isopropylidenediphenol ( chromogenic material for dyes). The composition was applied to a paper web by means of a bar coater, and then heated for 2 min at 16O ⁰ C, so that a conductive trace of 5 g / m ² and a specific surface resistance was obtained from 40 KSL.

Then, a mixture of 1.5 parts of crystal violet lactone, 1.5 parts of polyvinyl alcohol and 50 parts of water was applied to the conductive sheet by means of a bar coater, and the mixture was ^{dried at 80 °} C. for 5 minutes to prepare a conductive recording paper having a coating layer containing a acidic color-forming dye, the coating layer being formed on the conductive layer in an amount of 0.8 g / m ² .

The recording paper was used in a facsimile system for discharging a carbon copy recording paper. Hard copies were obtained with a clear blue image reproduction at a recording speed of 1m / s and an a.c. Voltage of 100 V.

Example 10

Conductive tracks 51 to 59 according to Table 12 were produced in the same manner as indicated in Example 8, but with the exception that different EATs and different binders in different proportions were applied. The webs obtained were

investigated in terms of volume resistivity and surface resistivity. The results are summarized in Table 13.

Table 12

Coating
tungsZu
together
settlement Electric
senior
Alkaliti
tan at Weight
share binder Weight: -
share Other accessories Weight
share 10 51 Art 150 Art 100 Art 50 52 1 120 Urethane resin 100 Ethylcello
solve 50 53 1 40 Silicone resin 20th Xylene 150 15th 54 1 60 Butyral resin 30th Butanol 100 55 2 85 Polyamide resin
(TorayzinF-30 100 Isopropanol 20th 56 3 100 Epoxy resin
(Example 1) 100 57 4th 120 Epoxy resin
(Example 1) 20th 25th
0.3
20th 25th 58 5 100 Vinyl chlo-
ridharz
(Ex. 2) 20th A.
B.
C. 25th
0.3
15th 59 5 85 Vinyl chlo-
ridharz
(Ex. 2) 25th A.
B.
C. 30th
0.5
15th 30th VgI.-
E.g. 6th 120 Vinyl chlo-
ridharz
(Ex. 2) 100 A.
B.
C. 20th 1* Epoxyhar ζ
(Ex. 8) Ethylcello
solve

* Electrolytic copper powder (EL-1110)

A: dioctyl phthalate

B: dibutyl tin maleate

C: 4,4'-isopropylidenediphenol

- 32 Table 13

No. Specific volume resistance Electri
shear
Contrary
was standing
(Jl) Spec.
VoI.-
contrary-
was standing
(Jl.-cm) Specific surface resistance Spec.
Surface
chenwi
the state
(Λ) 5 51 layer
thickness
(mm) 12.5 1, 05 Electri
shear
Contrary
was standing 83.1 52 4.21 42.7 3.29 4.41 107 53 3.85 1.84x10 ² 10.1 5.68 385 10 54 2.75 3.69 0.23 20.4 10.2 55 3.12 89.3 1.93 5.41x10 ~ ¹ 75.1 56 1, 08 2.96x10 ³ 119 3.99 1120 57 2.01 1, 29x10 ⁴ 307 59.4 2650 15th 58 1.19 1.42x10 ⁴ 1030 141 1.71x10 ⁵ 59 3.62 4.64x10 ⁴ 2040 9.08x10 ³ 3.95x10 ⁵ See
E.g 2.20 17.9 1 .08 2.10x10 ⁴ 78.3 20th .3.01 4.16

Example 11

50 parts by weight of titanate No. 1 shown in Table 1, 50 parts by weight of dimethylpolysiloxane of the terminal hydroxyl block type (Toshiba Silicone Co., Ltd., 20000 mm ² / s) and 12.5 parts of propoxyphosphonitrile (SR 200, Otsuka Kagaku Kabushiki Kaisha) were carefully using a A three roll kneader was mixed to prepare a conductive composition, and then 3 parts of methyltrimethoxysilane and 0.3 part of dibutyltin laurate were added. The mixture was poured into the above-mentioned mold for the production of samples which can be subjected to the measurement of the volume resistivity, specifically for the production of an elastic pressure-sensitive line.

tend sheet with a thickness of 6.0 mm, a width of 2.0 cm and a length of 10.0 cm. The one made in this way Web had a volume resistivity of 1050 / i-cm (875JL electrical resistance). The electric Resistance of the web was 1780 when measured with square electrodes (1.0 cm x 1.0 cm) when the electrodes were brought into contact opposite to one another with the opposite ones Surfaces of the web in the middle part. The resistance was reduced to 3.2JL when the resistance measurements were made with the same electrodes in the same arrangement, but with the application of pressure, in which the web was compressed to a thickness of 1.0 mm. The volume resistivity in this case was 32 / U'cm, that is, the conductivity was increased by about 33 times with the application of pressure.

Example 12

Pressure-sensitive conductive tracks 121 to 125 became prepared in accordance with Table 14 in the same manner as indicated in Example 11, with the exception that the amount of titanate above the amount given in Example 11 was varied. The orbits were made in terms of Modification of the specific volume resistance examined. The results are summarized in Table 14.

- 34 Table 14

sample
SIr. Elec
trisch
lei Initial volume resist. Electr
Contrary Spec.
VoI.-
contrary-
was standing
(Λ. Cm) Volume resistance
after the together
to press Electr.
Contrary
was standing
(Sl) Spec.
VoI.-
contrary-
was standing
(Il.-cm) b 121 tendes
Alkali-
titanate layer
thickness was standing
(Λ.) 6.02x10 ⁶ layer
thickness
(mm) 261 2610 122 5 (well) 5.06x10 ⁷ 1.70x10 ⁴ 1.0 10.7 107 123 20th 6.0 8.91x10 ⁴ 3850 1.0 5.95 59.5 10 124 40 6.0 3.21x10 ⁴ 215 1.0 0.08 0, 8 125 80 6.0 1792 1.51 1.0 0.01 0.1 100 6.0 12.6 1.0 6.0

Example 13

Pressure sensitive conductive sheets were made in the same manner as in Example 11, except that different EATs were used and 100 parts by weight of silicone rubber (TSE 200) were used as a binder to prepare test samples 131-136. In the same manner as indicated in Example 11, the samples thus prepared were examined for the change in volume resistance. The results are summarized in Table 15.

- 35 table

sample Elec
trisch
lei Weight
share Initially. "* t- / o lumen resistance Spec.
VoI.-
contrary- Volume resistance
after the together
to press -Elek
tr.
Contrary ■ Spec.
VoI.-
-contrary- 5 No. tendes
Alkali-
titanate 30th Schich
thickness
(mm) Electr.
Contrary
was standing was standing
(JL? Cm) layer
thickness
(mm) was standing was standing
(a.-cm) Art 30th 8th (Λ) 1, 03x10 ⁴ 7.10 71, 0 131 1 30th 6.0 7th _r 58x10 ⁴ 8.81x10 ³ 1.0 5.33 53.3 10 132 2 40 6.0 7th _r 34x10 ⁴ 9.02x10 ³ 1, 0 4.29 42.9 133 3 50 6.0 2 _p 52x10 ⁴ 2.65x10 ⁴ 1.0 9.01 90.1 134 4th 50 6.0 • _r 21x10 ⁵ 1.92x10 ⁴ 1.0 6.33 63.3 135 5 6.0 _r 60x10 ⁵ 1.66x10 ⁴ 1.0 7.68 76.8 15th 136 6th 6.0 _r 38x10 ⁵ 1.0

example

Pressure sensitive conductive sheets were made in the same way as in Example 11, but with the exception that different ETAs and binders in different Quantities were used to prepare test samples 141-150 according to Table 16. In the same As indicated in Example 11, the samples were examined for the change in volume resistivity. The results are summarized in Table 17.

- 36 table

5 sample
No. Electric
senior
Alkali-
titanate Weight -
share binder Weight
share 141 Art 50 Art 100 142 1 45 SBR 100 143 1 35 Neoprene rubber 100 10 144 2 30th Silicone rubber (same
Connection as for example 11) 100 145 2 40 SBR 100 146 3 25th NBR 100 15th 147 3 50 Chlorosulfonated chew
schuk 100 148 4th 60 SBR 100 149 4th 50 NBR 100 20th 150 5 45 Chloroprene rubber 100 6th NBR

- 37 table

sample Initially .Vo luxnenwi the stand Special volume Volume resistance according to Electr. Spec. No. resistance pressing together Contrary VoI.- layer -Electr (-0 - CIIl) layer was standing contrary- 5 thickness shear thickness (A) was standing (mm) Contrary (mm) (Jl. * Cm) . · 141 was standing 1.92x10 ³ 2.33 23.3 142 (Λ.) 2.51x10 ³ 3.65 36.5 143 6.0 1, 61x10 ⁴ 5.17x10 ³ 1.0 8.09 80.9 144 6.0 2.09x10 ⁴ 7.93x10 ³ 1.0 6.81 68.1 IU 145 6.0 4.31x10 ⁴ 2.09x10 ³ 1.0 1, 86 18.6 146 6.0 6.61x10 ⁴ 2.01x10 ⁴ 1.0 7.01 70.1 147 6.0 1.74X10 ⁴ 9.93x10 ³ 1.0 6.53 65.3 15th 148 6.0 1.67x10 ⁵ 1.08x10 ³ 1.0 7.91 79.1 149 6.0 8.27x10 ⁴ 2.05x10 ⁴ 1.0 5.77 57.7 150 6.0 9.01x10 ⁴ 1, 19x10 ⁴ 1.0 8.02 80.2 6.0 1.71x10 ⁵ 1.0 20th 6.0 9.92x10 ⁴ 1.0

Claims (9)

Claims 1. Composition containing an electrically conductive Alkali metal txtanate and a binder. 2. Composition according to claim 1, characterized in that that the binder is at least one curable resin selected from the group consisting of amino resin, phenolic resins, alkyd resin, epoxy resin, urethane resin, Polyamide resin, polyester resin, vinyl resin, polyimide resin, Polymercaptoharζ, silicone resin, fluorocarbon resin, boron resin, Organotitanium resin, inorganic hardenable substances, in particular silicates, phosphates and borates, mixtures at least two of these materials and prepolymers thereof. 3. Composition according to claim 1, characterized in that that the binder is at least one compound selected from the group consisting of vaseline, lanolin, Petrolatum, bituminous compounds, glycerine esters of fatty acids, polyalkylene oxides in the form of homopolymers and copolyraers of alkylene oxides, alkyl polyalkylene oxides as adducts of fatty acid glycerol oxides and alkylene oxides and derivatives thereof, liquid polyethylene, liquid Polypropylene and liquid acrylic acid resin. 4. Composition according to claim 1, characterized in that the binder is at least one compound selected from the group consisting of higher fatty acid derivatives, polyolefin compounds, rubbers, acrylic acid resins, Vinyl ether resin, vinyl formal resin, vinyl acetate resin, Cellulose resin, polyacetal, polysulfone, polyimidazole, Polyoxazoline, polyoxazole, mixtures or copolymers of at least two of the above compounds. 5. The composition according to claim 1, characterized in that it contains 0.1 to 100 parts by weight of the electrical conductive alkali metal titanate / 100 parts by weight of binder contains. 6. Electrically conductive molded part produced from the composition according to any one of claims 1 to 5. 7. Molding according to claim 6, characterized in that it is in the form of a web or in the form of a film. 8. Molding according to claim 7, characterized in that the binder consists of an elastic binder and the web or film is pressure sensitive. 9. Molding according to claim 8, characterized in that the elastic binder is at least one connection, selected from the group consisting of natural rubber, synthetic rubber, silicone rubber, polyurethane resin, vinyl chloride resin and acrylic acid resin.