JPH0522363B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing an electrical resistor or conductor (hereinafter referred to as a conductor) having a smooth surface in which a conductive part and an insulating part are on the same plane. 2. Description of the Related Art Conductive resin compositions in which a conductive substance is dispersed in various resins as a vehicle or binder are known. This product can be used, for example, for resistors such as variable resistors, semi-fixed resistors, potentiometers, and encoders, as well as for rain sensors, etc.
It is used as a conductor in snowfall sensors and various sheet heating elements. All of these conductors are constructed by combining a conductive resin composition and an insulator serving as an electrically insulating portion. That is,
An electrically resistive part or a conductive part (hereinafter both referred to as a conductive part) is formed on the surface of the insulating base material, and the two together form the main part of a conductor or the like. Sometimes, the conductive portion is further covered with a membrane, film, sheet, etc. made of an insulator. Therefore, in a conductor or the like, it is desirable that the conductive part and the insulating part be completely integrated in order to obtain high mechanical strength, durability, and electrical properties. Conventionally, most of the methods have been to form conductive parts by printing conductive ink on a laminate or ceramic plate of phenolic resin, epoxy resin, or other thermoset resin, and then baking it. However, these methods have poor sliding properties because the surface is not smooth, noise generation, and deterioration of electrical characteristics under high temperature and high humidity, so long-term reliability as an electronic component cannot be fully satisfied. It was also unsuitable for forming electrical circuits. The present inventors took the above-mentioned problems into consideration, and developed a resin composition for electrical resistance that has a close temperature relationship between resistance values, excellent temperature and humidity characteristics, and good sliding properties, or a resin composition for electrical resistance that has good conductivity and high temperature and high temperature The above resins have the same high heat resistance, moisture resistance, water resistance, dimensional stability, excellent insulation performance under high temperature and high humidity conditions, and mechanical strength as the resin compositions for conductors for circuits that can withstand use in humid environments. The present invention was completed as a result of intensive research into a manufacturing method that can be mass-produced of a conductor made of a composition and an electrically insulating base material that has strong adhesive properties.
That is, the present invention provides, when manufacturing an electrical resistor or conductor in which a conductive diallyl phthalate resin composition is embedded in an electrically insulating base material made of a diallyl phthalate resin composition by hot-press molding,
The prepreg coated or impregnated with the above conductive diallyl phthalate resin composition is precured so that the reaction rate as measured by a differential scanning calorimeter is 5 to 40%, and then cut into a predetermined shape. This is a method for producing an electrical resistor or conductor with a smooth surface, which is characterized by placing the electrical resistor or conductor on the base material and curing it under heat and pressure. According to the present invention, by using a diallylphthalate resin as a component of a composition for a resistor or a conductor, and as a component of an insulating base material, a conductor etc. that can satisfy the above-mentioned properties can be obtained. It became clear that it was possible to obtain Furthermore, according to the present invention, it is possible to form a predetermined pattern on an insulating base material with high precision, and to precisely and easily mold it integrally with the base material, resulting in a perfectly smooth mirror-like surface. Conductors having surfaces can be easily mass-produced. If desired, it is also possible to design and mold the shape at the same time so that it is convenient for connecting lead wires, assembling and mounting conductors, etc., or it is possible to directly encapsulate lead wires and make an integrally molded product. is also possible. The features of the method for manufacturing conductors and the like according to the present invention will be explained in detail below. The dialphthalate resin referred to in the present invention is a homopolymer, a copolymer, or a mixture of homopolymers obtained by polymerizing at least one type of dialphthalate monomer selected from ortho, iso, and tele dialphthalate monomers, and is post-cured. possible diallyl phthalate prepolymers or mixtures of said diallyl phthalate prepolymers with at least one selected from reactive monomers having unsaturated groups such as allyl groups or vinyl groups;
Alternatively, a post-curable copolymerized prepolymer obtained by polymerizing at least one diallyl phthalate monomer selected from the above-mentioned isomeric monomers and at least one selected from the above-mentioned reactive monomers, furthermore, the above-mentioned diallyl phthalate prepolymer. , a mixture of two or more selected from copolymer prepolymers and unsaturated polyesters, or mixtures of at least one of the above-mentioned reactive monomers. Examples of the reactive monomers having an unsaturated group include styrene monomers such as styrene and α-chlorostyrene, methyl (meth)acrylate, butyl (meth)acrylate, n-octyl (meth)acrylate, etc.
Acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate
Acrylic monomers such as acrylate, ethylene glycolyl (meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate,
Vinyl ester monomers such as vinyl acetate and vinyl benzoate, acryl acetate, allyl benzoate, allyl (meth)acrylate,
Diallyl oxalate, diallyl adipate, diethylene glycol bis(allyl carbonate),
diethylene glycol bis(allyl phthalate),
Polyethylene glycol bis(allyl phthalate), diallyl maleate, diallyl fumarate,
Examples include allyl ester monomers such as diallylcitrate and diallylphthalate. Its blending amount is approximately 70% by weight or less, preferably approximately 50% by weight in the diallylphthalate resin.
The following blending amounts can be exemplified. In addition, the proportion of the reactive monomer in the copolymerized prepolymer is usually 50% by weight or less, and the reactive monomer is appropriately selected from the blending amount range in this copolymerized prepolymer. It can also be added. In addition, as the unsaturated polyester, polybasic unsaturated acids such as maleic acid and fumaric acid, polybasic saturated acids such as phthalic anhydride, isophthalic acid, and terephthalic acid, and polyhydric alcohols such as diethylene glycol and propylene glycol are used. Those in the form of a viscous liquid at normal temperature with an acid value of 5 to 100 and those in the solid state with a softening point of 150° C. or more are preferably used, manufactured by a conventional method. An example of the amount of the compound added is about 70% by weight or less, preferably about 50% by weight or less in the diallylphthalate resin. The conductor and the like of the present invention are manufactured using the following constituent elements () to (). () The prepreg coated with or impregnated with the conductive diallyl phthalate resin composition used in the present invention is a prepreg that is mainly composed of the above diallyl phthalate resin and a conductive substance, and a solvent containing a curing agent and a slipping agent. A reinforcing material is coated with a mold or solvent-free paste or liquid resin composition and is impregnated with the reinforcing material. As the conductive substance, powdered or fibrous substances such as carbon, graphite, silver, gold, nickel, palladium, platinum, etc. are used, and carbon, graphite, etc. are commonly used, and depending on the purpose, A highly conductive substance such as silver is used in combination. Examples of the carbon and graphite mentioned above include channel black, furnace black, thermal black, acetylene black, and electric arc black. Used selectively. For example, when used as a low antibody, it is desirable to select a particle size distribution of conductive material having a particle size of 0.01 to 75 μm depending on its resistance value so that the packing density is geometrically large. The conductive diallyl phthalate resin composition of the present invention (hereinafter simply referred to as a conductive composition) may be used depending on the use of the conductor, etc., and manufacturing cost. In many cases, it is advantageous to use an ink with a suitable conductivity that is different from that of the conductive part between the conductive part and the conductive part, in order to reduce contact resistance. It is desirable to use two types, one for the electrode part and one for the electrode part. Conductive materials such as silver and gold are often used for the electrode portion, but other metals may be used if desired. In order to improve the filling effect of these conductive material particles, the flake-like particle size is 2.
~30μ range and colloidal, structured particles with a distribution in the particle size range of 0.05~1μ, with the former proportion being 50~70% by weight,
They are preferably used in combination so that the ratio of the latter is 50 to 30% by weight. Curing agents used for curing the conductive composition of the present invention include dialkyl peroxides and diaryl peroxides such as di-tert-butyl peroxide and dicumyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; , 1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane; hydroperoxides such as cumene hydroperoxide; lauroyl peroxide, benzoyl peroxide, 2,4 peroxide
- diaroyl and diacyl peroxides such as dichlorobenzoyl; peroxycarbonates such as diisopropyl peroxycarbonate;
Examples include peroxy esters such as tert-butylperoxyacetate, tert-butylperoxypivalate, tert-butylperoxyoctoate, and tert-butylberoxybenzoate, and also peroxyesters such as azobisisobutyronitrile other than the above organic peroxides. Azo compounds can be used as well. In addition, as a slip agent, boron nitrite, Teflon powder, molybdenum sulfide, potassium titanate, mica, colloidal silica, colloidal alumina, colloidal titanium, etc. with a particle size of 5 μm are used.
The following materials, silicone oil, etc. can be used, and at least one of them may be selected and used. It is important to add a slip agent to the conductive parts and electrode parts, and by adding it to the insulating base material, the coefficient of friction on the surface of the conductor etc. can be reduced. It can be applied to a wider range of applications. for example,
In slide switches, rotary switches, connectors, etc., the base material also slides, so adding a slip agent is extremely effective. The proportion of each component in the conductive composition in the present invention is 30 to 180 parts by weight, preferably 40 to 150 parts by weight of the conductive material to 100 parts by weight of the diallyl phthalate resin used in the conductive part. , more preferably 40 to 100 parts by weight, curing agent
0.01 to 10 parts by weight, preferably 0.1 to 6 parts by weight,
The amount of the slip agent is 0.1 to 60 parts by weight, preferably 0.3 to 50 parts by weight, and these can be uniformly dispersed and used as a solvent-free composition, or an organic solvent can be used.
It is used as a solvent-based composition dissolved in 400 parts by weight or less, preferably 200 parts by weight or less. If the amount of the conductive substance blended is too large beyond the above range, uniform kneading may become difficult, or
Causes of cracks when cutting into a predetermined shape, deterioration of mold release properties during molding, deterioration of sliding properties of conductive parts,
There are disadvantages such as a decrease in linearity, deterioration in heat resistance and moisture resistance, and a decrease in adhesive strength with the base material. On the other hand, if the amount is less than the above range, it may become difficult to adjust the resistance value or it may not be possible to obtain the desired low antibody. As a method for adjusting the resistance value, it is possible to prepare two or more types of masterbatches in advance and mix them to obtain the desired value. If the amount of the curing agent exceeds the above range, it is not only practically unnecessary, but also causes the resin to harden extremely quickly, causing distortion, reducing the precision of the desired conductive part, causing cracks, and This leads to a decrease in the performance of the conductor, such as a decrease in adhesive strength with the base material. On the other hand, if the amount is too small, the performance of the product will deteriorate due to delayed curing and incomplete curing. If the blending amount of the slipping agent is too large beyond the above range, the adhesion between the conductive part, the electrode part and the base material part and with the terminals will be reduced, and the linearity and temperature characteristics of the resistor will be deteriorated. When a conductive composition is used for the electrode part, the preparation is basically the same as the composition for the conductive part described above, but silver is usually used for the electrode part in consideration of resistance value, chemical stability, etc. Good conductive substances such as are often used. The preferred ratio of each component is 200 to 1000 parts by weight of a highly conductive substance such as silver to 100 parts by weight of diallyl phthalate resin;
Preferably 300 to 900 parts by weight, more preferably
300 to 700 parts by weight, curing agent 0.01 to 10 parts by weight, preferably 0.1 to 6 parts by weight, and slipping agent 0.05 to 60 parts by weight, preferably 0.3 to 50 parts by weight, which are the same as the composition of the conductive part above. It is used as a solvent type or a solvent-free type. It is preferable to use a combination of 50 to 70% by weight of a highly conductive material having a particle size of 2 to 30 .mu.m and 50 to 30% by weight of a material having a particle size of 0.05 to 1 .mu.m. Examples of solvents include acetone, methyl ethyl ketone, aliphatic ketones such as methyl isobutyl ketone, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzenes, halogen hydrocarbons such as methylene chloride, chloroform, etc. Examples include acetate ester of diethylene glycol monoalkyl ether, and one or more of these can be selected and used. Various additives can be added to the conductive composition of the present invention, if necessary. for example,
Examples of fillers that can be used include inorganic and/or organic fillers, and these can be used alone or in combination. The amount used is
Based on the weight of the diallyl phthalate resin,
Examples include amounts of about 1 to about 300% by weight. Specific examples of these fillers include mica, asbestos, glass powder, silica, titanium oxide, magnesium oxide, asbestos fiber, silica fiber, glass fiber, silicate glass fiber, boron fiber, whiskers, etc. Examples of organic fillers include natural fibers such as cellulose, pulp, acrylic fibers, polyester fibers such as polyethylene terephthalate, cotton, rayon, and vinylon. Examples of the polymerization accelerator include metal soaps such as cobalt salts, vanadium salts, and manganese salts of naphthenic acid or octoic acid, and aromatic tertiary amines such as dimethylaniline and diethylaniline. An example of the amount used is about 0.005 to about 6% by weight based on the weight of the diallylphthalate resin. Furthermore, examples of polymerization inhibitors include, for example,
Quinones such as p-benzoquinone and naphthoquinone, hydroquinone, p-tert-butylcatechol, hydroquinone monomethyl ether, p-
Examples include polyhydric phenols such as -cresol and quaternary ammonium salts such as trimethylammonium chloride. An example of the amount used is about 0.001 to 0.1% by weight based on the weight of the diallylphthalate resin. Examples of internal mold release agents include metal salts of stearic acid such as calcium stearate, zinc stearate, and magnesium stearate. The amount used is, for example, about 0.1 to about 5% by weight based on the weight of the diallylphthalate resin. Furthermore, examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane. The amount used is, for example, about 0.01 to about 3% by weight based on the weight of the diallylphthalate resin. Examples of the pigment include pigments such as carbon black, iron black, cadmium yellow, benzidine yellow, cadmium orange, red iron black, cadmium red, cobalt blue, and anthraquinone blue, and the amount used is based on the diallylphthalate resin. Based on weight, approx.
Examples include amounts of 0.01 to about 10% by weight. In addition, silica powder, titanate coupling agents, aluminum coupling agents, phosphate ester surfactants, and the like can be added as viscosity modifiers and leveling agents. In preparing the conductive composition, the above-mentioned components can be uniformly dispersed by kneading them using, for example, a stirring tank, a ball mill, a vibration mill, a three-roll mill, or the like. The curing agent may be added from the beginning of kneading, but it is preferably added before the end of kneading to prevent gelation. Reinforcing materials for prepreg in the present invention include woven fabrics, non-woven fabrics, paper, matte, etc. made of natural fibers, synthetic fibers, synthetic resins, etc. These materials include natural fibers such as cellulose, cotton, and asbestos, and ceramics. , inorganic fibers such as glass fibers, and synthetic fibers such as polyamide, polyimide, polyimide amide, and polyester.
In order to obtain the smoothness of the surface of the prepreg, it is produced by a mechanical bonding method without a binder, using filaments with a fiber diameter of 0.8 to 10μ and a fiber length of 1 mm or more, preferably 3 mm or more, and more preferably 6 mm or more. It is desirable to use non-woven fabric. The prepreg of the present invention is produced by coating or impregnating the reinforcing material with a conductive composition. The amount of the conductive composition to be supported on the reinforcing material is determined based on the electrical properties, physical strength, desired resistance value, etc. of the composition, as well as ensuring that the conductive part and the insulating part are in close contact with each other and that a smooth mirror-like surface is formed on the same surface. The weight fraction of the conductive composition excluding the weight of the solvent (hereinafter referred to as (referred to as resin content) is 0.20~
It is best to set it to 0.95, preferably 0.40 to 0.85. If the resin content is too high beyond the above range, it is not only unnecessary in practice, but also may cause misalignment or bleeding of the pattern of the conductive part during hot press molding, as well as deformation of the cut out pattern, resulting in poor precision. Good molding will not be possible. Furthermore, if the resin content is too low, the conductive portion and the insulating portion may become unintentionally adhered to each other, or a smooth mirror-like surface may not be obtained. Depending on the type of reinforcing material, the viscosity of the resin composition, etc., the method for supporting the prepreg resin composition on the reinforcing material may include an impregnation method, an applicator, a comma coater, a bar coater, a gravure coater, a flow coater, a spray coater, etc. A coating method may be applied. A prepreg coated with or impregnated with a conductive composition is subjected to a drying process to remove volatile components. When drying is performed in batches, for example, drying may be performed at room temperature for about 0.2 to about 1 hour, and then at 40 to 120°C for about 3 to about 30 minutes. However, when using a curing agent with a low decomposition temperature, such as benzoyl peroxide, it is of course necessary to avoid combinations of drying conditions that require high temperatures and long periods of time. It is of course possible to perform the coating or impregnating step and the drying step continuously, and a commercially available impregnation machine, coating machine, etc. can be used. When providing an electrode part on a prepreg coated or impregnated with a conductive composition, after the prepreg is dry to the touch, a separately prepared conductive composition for the electrode part is applied in a predetermined manner according to the pattern of the conductive part to be cut out. An electrode portion is formed at the position by a printing method or a transfer method. Although the formation of the electrode portion may be performed after pre-curing the prepreg, which will be described later, it is preferable to form the electrode portion before pre-curing. () The electrically insulating base material used in the present invention is a component obtained by removing the conductive substance from the conductive composition, that is, diallylphthalate resin,
A prepreg may be used in which a reinforcing material similar to the prepreg in () above is coated with or soaked in a resin composition containing each component of a curing agent and a slipping agent, or the resin composition may be coated with or soaked in a reinforcing material similar to the prepreg in () above. various additives as used in the composition,
For example, a compound containing a filler, a pigment, an internal mold release agent, a silane coupling agent, a polymerization inhibitor, a polymerization accelerator, etc. may be used. In the case of a compound, it may be molded into a pellet or tablet shape that can be cured after being molded into a specific shape. In the case of the above prepreg, the supported resin composition is diallyl phthalate resin.
100 parts by weight, curing agent 0.01 to 10 parts by weight, preferably 0.1 to 6 parts by weight, slip agent 0.1 to 50 parts by weight,
Preferably, there is a solvent-free type containing 0.2 to 30 parts by weight of the conductive composition or a solvent type dissolved in an organic solvent such as that used in the above-mentioned conductive composition. Additives such as those used in products can be added within a range that does not impair the properties of the diallyl phthalate resin. In the case of a dissolving type, the appropriate amount of solvent can be determined depending on the method of supporting the resin composition on the reinforcing agent, that is, whether it is a coating method or an impregnation method. The amount may be 300 parts by weight or less, preferably 200 parts by weight or less. There is no particular limit to the amount of the diallyl phthalate resin composition supported on the prepreg, and the conductive part and the insulating part can be molded so that they are in close contact with each other and have a smooth mirror surface on the same surface during hot press molding. Any quantity is fine. Usually, the supported amount is in the range of 0.20 to 0.95, preferably 0.40 to 0.85 as a weight fraction of the resin content. If the resin content is too high beyond the above range, accurate molding may not be possible due to misalignment or bleeding of the pattern of the cut-out prepreg that becomes the conductive part during hot-press molding, large mold shrinkage or warping. Moreover, if the resin content is too low than the above range, poor adhesion will occur between the conductive part and the insulating part, making it difficult to obtain a smooth mirror-like surface. The reinforcing material can be supported with the dial rifthalate resin composition using the same method and apparatus as used for the prepreg described in () above. When using a compound as a base material containing a diallyl phthalate resin composition, add a curing agent to 100 parts by weight of the diallyl phthalate resin.
0.01 to 10 parts by weight, preferably 0.1 to 6 parts by weight,
0.1 to 50 parts by weight of a slip agent, preferably 0.2 to 30 parts by weight, and 1 to 300 parts by weight of a filler, preferably 30 to 30 parts by weight.
100 parts by weight, internal mold release agent 0.05-5 parts by weight, preferably 0.1-3 parts by weight, silane coupling agent
0.005 to 5 parts by weight, preferably 0.01 to 3 parts by weight,
Polymerization inhibitor 0.005-0.3 parts by weight, preferably 0.001
A composition containing ~0.1 part by weight, if desired, a polymerization accelerator, pigment, etc., is dissolved in a solvent and mixed, then evaporated to dryness, ground, or without adding a solvent, after being thoroughly mixed beforehand, rolled. The mixture is kneaded, cooled, and then ground. When kneading the above rolls, the front roll should be 50 to 130°C, preferably 80°C.
~100℃, after roll 40~110℃, preferably 50℃
at a temperature of ~90°C for 1-10 minutes, preferably 2-7
The base material of the present invention is preferably kneaded for 1 minute. Under the above-mentioned kneading conditions, if the roll temperature is too high or the kneading time is too long, the compound will gel, which will cause problems during hot-press molding, so care must be taken. As the base material of the present invention, the above-mentioned compound may be further molded into a tablet shape, sheet shape, etc. at room temperature. The conductor, etc. of the present invention is produced by cutting out a predetermined shape of a conductive part from the prepreg described in () above, and molding and integrating it with the insulating base material described in () above. It is important to pre-cure the conductive composition supported in advance to the extent that it does not lose its reactivity and fluidity during hot press molding, in order to produce a conductor etc. with excellent performance, which is the object of the present invention. is the most important. That is, after pre-curing to a carefully selected stage, cutting it into a predetermined shape and laminating it with an insulating base material and molding it, a predetermined pattern can be incorporated into a conductor etc. with extremely high precision. is possible. If pre-curing is not performed, the designed pattern of the conductive portion or electrode portion will be deformed due to misalignment, distortion, smearing, twitching, etc. Among these, phenomena in which conductive parts or electrode parts seep into insulating base material parts, conversely, insulating base material parts intrude into conductive parts or electrode parts, or these parts intermingle with each other. It is absolutely necessary to avoid blurring the boundaries due to By pre-curing the prepreg using the method of the present invention, the curing reaction rate and fluidity of these parts can be adjusted, so the insulating parts and It becomes possible to integrally mold a conductor having a conductive part and an electrode part with extremely clear boundaries. Another major advantage of precuring is that shrinkage during molding can be reduced. Therefore, pre-purchase conditions are extremely important. The degree of precuring of the prepreg of the present invention is:
The DSC reaction rate can be selected within the range of 5 to 40%, preferably 10 to 30%. The DSC reaction rate is determined by differential scanning calorimetry (DSC) before and after a certain operation.
It can be calculated by measuring the difference in calorific value between the diallylphthalate resin, the conductive composition containing the resin, and the prepreg. In the present invention, this state is defined as a DSC reaction rate of 0% based on the calorific value of the diallyl phthalate resin. Since the calorific value is substantially due to the reaction of the diallylphthalate resin, if the calorific value of the resin alone is determined in advance, it is possible to calculate the calorific value of the conductive composition of the present invention, prepreg, etc. at a reaction rate of 0%. Since the content of the resin is known, the calorific value can be determined theoretically. In other words, the DSC reaction rate refers to the rate of reaction after precuring of the prepreg coated or impregnated with the composition.
The difference between the calorific value and the calorific value calculated from the calorific value of the dial rifthalate resin itself when the reaction rate of the prepreg is 0% is determined by DSC, and this is expressed by the following formula: Even with this DSC reaction rate, the degree of pre-curing can be adjusted by setting the pre-curing conditions. DSC reaction rate (%) = Q-Q'/Q x 100 Q: DSC reaction rate of prepreg of 0%, calculated from the measured calorific value of only the diallylphthalate resin used and the content of this resin. Calorific value (cal/g) Q': Calorific value after pre-curing (cal/g) The calorific value of the pre-cured prepreg is measured by the following method. After precuring the prepreg coated or impregnated with the conductive composition, three test pieces are punched out and the calorific value of each is measured by DSC, and the average value is determined as Q'.
From the obtained value, calculate the DSC reaction rate using the above formula. The precure conditions for obtaining the DSC reaction rate of the above reaction are usually at a temperature of 100 to 180°C, preferably 130 to 160°C, and a time of 0.5 to 10 minutes, preferably 1 to 5 minutes. Of course,
As long as the DSC reaction rate is within the above range, there is no problem even if the precure conditions are performed outside the above range. If the DSC reaction rate is higher than the above range and pre-curing is performed excessively, the adhesion between the cut prepreg and the insulating base material during hot press molding and the adhesion between the cut prepreg and the lead wire for encapsulation will be weak or not at all. It will no longer adhere. In addition, adhesion with metal plates and ceramic plates used as needed also deteriorates. On the other hand, if the DSC reaction rate is lower than the above range and the precure is insufficient, the pattern of the conductive part formed by the prepreg cut out during hot press molding will be deformed due to misalignment, smearing, distortion, strain, etc., and the conductivity will not be as designed. The accuracy of the body etc. cannot be obtained. In the drying process for removing volatile components, which has already been explained, the DSC reaction rate defined above is usually less than 5%, but especially when a curing agent with a low decomposition temperature is used, it can be reduced to less than 5%. Drying conditions should be adjusted accordingly. The precuring method may be performed by placing the material in a heating drying oven or by using a hot press. Further, it is also possible to perform precuring continuously following the prepreg manufacturing process. Following the pre-curing of prepreg,
The prepreg that will become the conductive part is cut out. The cutting method may be, for example, by using a blade of a predetermined shape and punching it out with a press. The cut-out prepreg that will become the conductive portion is placed on the insulating base material obtained in () above and subjected to hot pressure molding. There are various lamination modes for the above-mentioned hot-press molding. For example, (a) a cut prepreg is placed on one or more of the prepregs in () and molded. (b) Molding the cut prepreg with the compound from () above. (c) Molding the cut-out prepreg with a base material made of a combination of the prepreg and compound described in () above. (d) On the back side of the base materials in (a) to (c) above, another type of base material, such as a steel plate or an aluminum plate, is formed by overlapping a metal plate or a ceramic plate. etc. The conductor etc. obtained by hot-press molding may be used by cutting it into a predetermined shape, or may be compression-molded into a predetermined shape using a mold during hot-press molding. In addition, as mentioned above, terminals etc. can be simultaneously molded on the electrode part using a mold,
For example, it is also possible to use a lead frame and encapsulate the lead wires at the same time as molding. During molding, the heating temperature for curing may range from about 120°C to about 190°C. In addition, the pressurization conditions are approximately 5Kg/cm ² to approx.
A pressure range such as 1000 Kg/cm ² can be exemplified. After molding, aging is further performed at 100 to 200°C for 0.1 to 4 hours to improve the adhesion between the metal plate or ceramic plate and the insulating base material in the case of the laminated form as in (d) above. Since the particles of the conductive substance and the diallyl phthalate resin in the conductive composition mutually move to an equilibrium position and exhibit a minimum resistance value, the temperature characteristics can be improved. The present invention includes a conductive composition having excellent linearity, excellent sliding properties, and high retention of electrical properties under high temperature and high humidity conditions, as well as high heat resistance, humidity resistance, water resistance, dimensional stability, It provides a conductor, etc. composed of an electrically insulating base material that has excellent insulating performance under high temperature and high humidity, mechanical strength, high adhesiveness with a conductive composition, and excellent processability. This manufacturing method is especially suitable for high-precision mass production, and can be applied to an extremely wide range of applications. For example, it is possible to manufacture variable resistors, semi-fixed resistors, potentiometers, linear encoders, rotary encoders, electrical circuits as printed circuit boards, rain sensors, snow sensors, sheet heating elements, etc. The method of the present invention is extremely useful in providing high performance and mass production methods for forming conductive and insulating parts in devices and components. The method of manufacturing a conductor, etc. according to the present invention will be explained in more detail with reference to the following examples, but these examples are intended to illustrate one embodiment thereof, and it goes without saying that the invention is not limited thereto. That is, one of the important features of the present invention is that at least the conductive part and the electrode part have no step between them and the insulating base material part, and the overall shape of the conductor etc. does not matter. It can take any desired shape. In other words, the conductive part and the electrode part need only be completely buried in the insulating base material part. Therefore, the conductor according to the present invention includes not only a flat shape but also a curved shape or other complicated shape depending on the purpose. Table 1 shows diallylphthalate resins used in each example below.

[Table] DAPP: Diallyl orthophthalate prepolymer "Daiso Isodap" manufactured by Osaka Soda Co., Ltd. DAIP: Diallyl isophthalate prepolymer "Daiso Isodap" manufactured by Osaka Soda Co., Ltd. DATP: Diallyl terephthalate prepolymer Number average molecular weight 8000, iodine value 85 DAPM: Diallyl orthophthalate monomer DATM: Diallyl terephthalate monomer USP: 0.5 mole of phthalic anhydride and 0.5 mole of maleic anhydride
An unsaturated polyester obtained by dehydration condensation of 1 mole of propylene glycol and 1 mole of propylene glycol using a melting method. Acid value: 28, softening temperature: 80° C. Example 1 A conductive composition for impregnating a resistor with a sheet resistance of 100 Ω/cm ² was prepared using the diallyl phthalate resin shown in Table 1 according to the formulation shown below. Blend Part by weight Diaryl phthalate resin () 45 Carbon black fluorite (1) 35 Potassium titanate whisker (2) 20 Dicumyl peroxide (3) 1.0 Diamine salt dispersant (4) 0.5 Amide additive (5) 1.0 Aluminum coupling agent (6) 1.0 Carbitol acetate 67.5 In the above formulation (1): “30CGF40” manufactured by Functional Coatings Research Institute (2): “Teismo BK-7” manufactured by Otsuka Chemical Co., Ltd. (3): Nippon Oil & Fats Co., Ltd. ``Percmill D'' manufactured by Lion Oil Co., Ltd. (4): ``Duomin TDD'' manufactured by Lion Oil Co., Ltd. (5): ``Aramide OF'' manufactured by Lion Oil Co., Ltd. (6): ``AL-M'' manufactured by Ajinomoto Co., Ltd. were used, respectively. In the above formulation, the diallylphthalate resin is dissolved in carbitol acetate, and other components except dicumyl peroxide are added thereto and mixed well;
After passing through the triple roll four times, for the above formulation,
Carbitol acetate with dicumyl peroxide dissolved in it
An additional 135 parts by weight was added to adjust the viscosity at room temperature to approximately 110 centipoise. In addition, in the formulation of the above conductive composition, instead of 35 parts by weight of carbon graphite, silver powder (60% by weight of flaky silver powder with a particle size of 1.2 to 5.7μ and colloidal silver powder with a particle size of 0.05 to 0.8μ) is used.
An ink was prepared using the conductive composition used for the electrode portion in the same manner except that the amount was 290 parts by weight (40% by weight). The conductive composition for impregnation was impregnated into a polyester nonwoven fabric (made from filament with a fiber diameter of 2 μm and a fiber length of 25 to 31 mm), and after air-drying at room temperature, Using an ink made of the conductive composition used for the electrode parts, printing was applied to the parts that would become the electrode parts when cut out using a #200 polyester screen with a total thickness of 120 μm. After air drying this at room temperature,
It was dried at ℃ for 30 minutes to prepare a prepreg for cutting out the conductive part. The above prepreg was precured for 2.5 minutes in a constant temperature bath at 150°C, and the DSC reaction rate was adjusted to 23%. next,
A diallyl phthalate resin composition used as an electrically insulating base material was prepared according to the formulation shown below. Composition Part by weight Diallyl phthalate resin () 100 Boron nitrite (1) 30 Potassium titanate whisker (2) 40 Colloidal silica (3) 20 〃 (4) 10 Dicumyl peroxide (5) 2 Titanate coupling agent (6) ) 1.5 Silane coupling agent (7) 1.5 Methyl ethyl ketone 150 In the above formulation (1): "GP" manufactured by Denki Kagaku Kogyo Co., Ltd. (2): "Teismo D" manufactured by Otsuka Chemical Co., Ltd. (3): ""AerosilOX-50" (4): "Aerosil 200" (5) "Percmil D" manufactured by Nippon Oil & Fats Co., Ltd. (6) "Plenact TTS" manufactured by Ajinomoto Co., Ltd. (7): "KBM503" manufactured by Shin-Etsu Chemical Co., Ltd. there was. In the above formulation, the diallyl phthalate resin was dissolved in methyl ethyl ketone, placed in a porcelain pot, and the other components except dicumyl peroxide were added while stirring. For a charged amount of 2 kg, 3 kg of steel balls with a diameter of 6 mm and 12 kg of steel balls with a diameter of 8 mm were added, and the mixture was mixed and dispersed at 40 revolutions per minute for 240 hours. After the dispersion was completed, 150 parts by weight of methyl ethyl ketone in which dicumyl peroxide had been dissolved was added to the above formulation to adjust the viscosity at room temperature to about 120 centipoise. Glass woven fabric treated with methacryloxysilane (manufactured by Arisawa Seisakusho, plain weave, basis weight)
202g/m ² ) for 2 hours at room temperature, then
It was dried in a constant temperature bath at 80°C for 30 minutes to produce a base material prepreg with a resin content of 0.65 in weight fraction. The above precured prepreg for cutting out was cut out into a predetermined shape, that is, a horseshoe shape with a width of 4 mm and an inner diameter of 30 mm having electrode portions at both ends. Molding was carried out at 165° C. and a pressure of 50 kg/cm ² for 30 minutes. After molding, it was aged at 185°C for 2 hours to obtain an electrical resistor. The obtained electrical resistor has a conductive part and an electrode part on the same plane as the base material surface, a smooth mirror-like surface, and a clear boundary line between the conductive part and the electrode part without blurring. It was an electrically low antibody with a typical resistance pattern. Further, the characteristics as a resistor were measured according to JIS C6444 and are shown in Table 2. Example 2 A conductive composition for coating having a sheet resistance of 1 MΩ/cm ² for resistors was prepared in the same manner as in Example 1 using the formulation shown below. Compound (conductive part) Part by weight Diallyl phthalate resin () 100 Carbon graphite (1) 40 Potassium titanate whisker (2) 25 Colloidal silica "Aerosil 200" 5 "Aerosil OX-50" 10 Mica 20 Dicumyl peroxide Percmil D” 2.0 Diamine salt-based dispersant “Dyuomin TDD” 0.5 Amide-based additive “Aamide OF” 1.0 Aluminum-based coupling agent “AL-M” 1.0 Titanate-based coupling agent “Plenact”
TTS" 1.0 Silane coupling agent "KBM 503" 1.0 Carbitol acetate 150 In the above formulation (1): "60CG" made by Functional Coatings Research Institute (2): "Teismo BK40" made by Otsuka Chemical Co., Ltd., etc. The same components as in Example 1 were used. In the preparation of the above formulation, dicumyl peroxide was dissolved in 10 parts by weight of methyl ethyl ketone and added to the above formulation during the fourth treatment using the three rolls, mixed and dispersed to form a conductive composition for coating. And so. The above conductive composition was applied to an aromatic polyamide nonwoven fabric (fiber diameter 5 μ, fiber length 25 to 31 mm, thickness 0.13 mm, basis weight
100 g/m ² ) with an applicator and dried at room temperature for 2 hours to obtain a prepreg. Next, with ink made of the same conductive composition for the electrode part as that used in Example 1, the part that will become the electrode part when cutting out is printed in the same manner as in Example 1, and after air-drying at room temperature. It was dried for 30 minutes in a constant temperature bath at 80°C. The above prepreg was precured by pressing at a temperature of 150℃ and a pressure of 10Kg/ ^cm2 for 2 minutes, and the DSC reaction rate was 24.
% of Prekyu Prepreg obtained. The above precured prepreg was cut out into a horseshoe shape having electrical parts similar to those in Example 1 at both ends. On the other hand, a diallylphthallate resin composition used as an electrically insulating base material was prepared with the following formulation. Blend Part by weight Diallyl phthalate resin () 100 Dicumyl peroxide "Percumil D" 2 Short glass fiber (1) 60 Calcium carbonate (2) 40 Methacryloxysilane 0.6 Calcium stearate 2 Hydroquinone 0.01 In the above formulation (1) Asahi Fiber "CSO3HB 830A" manufactured by Glass Co., Ltd. (2) and "NS-100" manufactured by Nitto Funka Kogyo Co., Ltd. were used, respectively. The above formulation was thoroughly mixed in advance and then kneaded with a roll. Front roll temperature 90~100℃, rear roll temperature 60℃
The mixture was kneaded at ~80°C for 5 minutes, taken out from the roll into a sheet, cooled down, and coarsely crushed using a Henschel mixer. The base material composition is filled into a mold in which terminals are set, and the cutout prepreg is placed on it.
Molded for 10 minutes at a temperature of 180℃ and a pressure of 100Kg/ ^cm2 , and then
After aging at 180° C. for 3 hours, an electrical resistor as shown in FIG. 1 was obtained. The nominal resistance value of this thing is
It was 5.0MΩ. In addition, identification as low antibody
It was measured according to JIS C6444 and shown in Table 2.

[Table] The obtained electrical low-voltage antibodies had particularly low jump noise and smooth resistance change characteristics, and were excellent as potentiometers. Example 3 The precured horseshoe-shaped prepreg prepared in Example 2 with a DSC reaction rate of 24% and the two sheets of electrically insulating base material prepreg prepared in Example 1 with a resin content of 0.65 were prepared. The above two sheets of prepreg for the base material and the cutout prepreg were stacked in order on a 1.5 mm thick anodized aluminum plate at a temperature of 170°C and a pressure of 20 kg/kg.
cm ² for 15 minutes, and then further aged at 190° C. for 1.5 hours to obtain an electrically low antibody with a smooth surface and excellent heat resistance and thermal conductivity. The low antibody was set using six rhodium-plated wire brushes (sliding pressure 150 g), and the results were as shown in Table 3.

【table】

[Table] Comparative Example When the cut prepreg in Example 1 was press-molded in the same manner as in Example 1 except that it was not precured, the pattern of the conductive part and electrode part was distorted, and an electrical low antibody with the designed pattern was not obtained. I couldn't help it. The temperature coefficient of the obtained low antibody is >+500ppm/deg, and the soldering heat resistance is approximately -3
It was %.

[Brief explanation of the drawing]

The drawings show one embodiment of the present invention; FIG. 1 is a plan view of an electric hypobody obtained in Example 2, and FIG. 2 is a sectional view taken along the line A-A' of FIG. 1... Conductive part, 2... Electrode part, 3... Insulating base material, 4... Terminal.

Claims (1)

[Claims] 1. When manufacturing an electrical resistor or conductor in which a conductive diallyl phthalate resin composition is embedded in an electrically insulating base material made of a diallyl phthalate resin composition by hot pressure molding, the above conductive diallyl phthalate resin composition is used. The prepreg coated or impregnated with the substance is precured so that the reaction rate measured with a differential scanning calorimeter is 5 to 40%, cut into a predetermined shape, and the cut prepreg is placed on the base material. A method for manufacturing an electrical resistor or conductor with a smooth surface, which is characterized by integrating heat-pressure curing.