JPS6037103A - Method of producing electric resistor or conductor - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing an electrically resistive unit or conductor (hereinafter both referred to as "conductor") having a smooth surface in which a conductive part and an insulating part are on the same plane.

U-S conductive resin compositions are known in which conductive substances are dispersed in various resins as vehicles or binders. This product is used, for example, as a resistor in variable resistors, semi-fixed resistors, bodensimeters, encoders, etc., and as a conductor in rain sensors, snow sensors, and various sheet heating elements. has been done. Each of these conductors is composed of a combination of a conductive resin composition and an insulator serving as an electrically insulating part. That is, an electrically resistive part or a conductive part (hereinafter both referred to as "conductive part") is formed on the surface of an insulating base material, and the two together form the main part of a conductor, etc. A membrane made of an insulator.

In some cases, the conductive part is covered with a film, sheet, etc.

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 methods have been to form conductive parts by printing conductive ink on a laminate or ceramic plate made of, for example, phenol resin, epoxy resin, or other thermoset resin, and then baking it.

However, these methods have not been able to fully satisfy long-term reliability as an electronic component due to poor sliding properties due to the uneven surface, generation of noise, and deterioration of electrical properties under high temperature and high humidity. It was also unsuitable for forming electrical circuits.

The present inventors took the above problems into consideration and created a resin composition for electrical resistors that has a small temperature coefficient of resistance, excellent temperature and humidity characteristics, and good sliding properties, or a resin composition for electrical resistors that has good conductivity and high temperature/humidity characteristics. High heat resistance, moisture resistance, water resistance, 9 dimensional stability,
Excellent insulation performance under high temperature and high humidity conditions.

The present invention was completed as a result of intensive research into a manufacturing method capable of mass production of conductors, etc., which are made of an electrically insulating base material with strong adhesion to the above-mentioned resin composition on the inside of the machine. That is, the present invention provides a method for producing an electrical resistor or a 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 thermoforming. A prepreg coated with or impregnated with a diallyl phthalate resin composition is pre-cured, cut into a predetermined shape, and then the cut prepreg is placed on the base material and heat-pressure cured to form an integral surface. This is a method for manufacturing smooth electrical resistors or conductors.

According to the present invention, by using a diallylphthalate resin as a component of a composition for a resistor or an S conductor, and as a component of an insulating base material, a conductive resin that satisfies the above-mentioned properties can be obtained. It became clear that the body etc. could be obtained. In general, 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 this pattern onto the base material, resulting in a perfectly smooth mirror-like surface. It is possible to easily mass-produce conductors having such a surface.

If desired, connect lead wires, assemble conductors, etc.
It is possible to design the shape and mold it at the same time to make it convenient for mounting, or it is also possible to directly encapsulate the lead wire and make it an integrally molded product. The features of the method for manufacturing conductors and the like according to the present invention will be explained in detail below.

The diallyl phthalate resin referred to in the present invention refers to ortho,
A homopolymer or copolymer obtained by polymerizing at least one selected from iso and tele diallyl phthalate monomers,
or a post-curable diallyl phthalate prepolymer which is a mixture of homopolymers, or a mixture of the diallyl phthalate prepolymer and at least one reactive monomer having an unsaturated group such as an allyl group or a vinyl group; 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 type of 1-cyamyl phthalate monomer. Furthermore, it is a general term for a mixture of two or more selected from the above-mentioned diallylphthalate prepolymers, copolymerized prepolymers, and unsaturated polyesters, or mixtures of the above-mentioned mixtures with at least one of the above-mentioned reactive monomers.

Examples of the reactive monomers having an unsaturated group include styrene, styrene thread binders such as α-chlorostyrene, methyl (meth)acrylate, butyl (meth)acrylate-1
~, 1-octyl (meth)acrylate, 2-edylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-and droxyethyl (meth)acrylate
Acrylic monomers such as acrylate, human oxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimedylolpropane 1-(meth)acrylate, pentaerythritol tetra(meth)acrylate , vinyl ester yarns such as vinyl acetate and vinyl benzoate, allyl acetate, allyl benzoate, allyl (meth)acrylate, diallyl adipate, diallyl adipate, diethylene glycol bis(allyl carbonate), diethylene glycol bis(allyl phthalate), polyethylene glycol Examples include allyl ester monomers such as bis(allyl phthalate), diallyl maleate, diallyl fumarate, diallyl zitrate, and diallyl phthalate. An example of its blending amount is about 10% by weight or less, preferably about 50% by weight or less of the diallylphthalate resin width.

In addition, the proportion of the reactive upper additive in the copolymerized prepolymer is usually 50% by weight or less. It is also possible to select and add them as appropriate.

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. The blending amount is about 70% by weight or less, preferably about 50% by weight of the diallylphthalate resin.
Examples include stones with a weight percent or less.

The conductor etc. of the present invention includes the following constituent elements (I) to (
I).

■) The prepreg coated with or impregnated with the conductive diallyl phthalate resin composition used in the present invention is mainly composed of the aforementioned diallyl phthalate resin and a conductive substance, and a solvent containing a curing agent and a slipping agent. It refers to reinforcing materials coated or impregnated with molded or solvent-free paste or liquid resin compositions.

As the above-mentioned conductive substance, powdered or fibrous materials such as carbon, graphite, silver, gold, nickel, palladium, platinum, etc. are used, and carbon, graphite, etc. are often used, and depending on the purpose, silver A good conductive substance such as is used in combination.

Examples of the above-mentioned carbon and graphite include channel black, furnace black, thermal black, acetylene black, and electric arc black.

Materials are selected based on size, conductivity, oil absorption, slipperiness, etc. For example, when used as a resistor, the particle size of the conductive material is 0.01 to 15, depending on its resistance value.
It is desirable to select the particle size distribution so that the packing density of μ particles is geometrically large.

The conductive diallyl phthalate resin composition of the present invention (hereinafter simply referred to as conductive composition) can be used as a conductor, etc.
Depending on the manufacturing cost, there may be a
In many cases, it is advantageous to use an ink with appropriate conductivity that is separate from that for the conductive part, in order to reduce contact resistance. It is preferable to use

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 particles of these conductive substances, flaky particles with a diameter of 2 to 30μ and colloidal particles are used.
It is preferable to use particles with struts having a particle size distribution in the range of 0.05 to 1μ in combination such that the ratio of the former is 50 to 10% by weight and the ratio of the latter is 50 to 30% by weight. .

The curing agent used for curing the conductive composition of the present invention includes:
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: 1,1-bis(tert-butylperoxy) -3,3,5- peroxyketals such as trimethylcyclohexane; hydroperoxides such as cumene hydroperoxide; sialoyl peroxides such as lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and peroxylic acids such as diacyl peroxide: diisopropyl peroxydicarbonate. Carbonate; tert-butyl peroxyacetate, te
Examples include peroxy esters such as rt-butylperoxybivalate, tert-butylperoxyoctoate, tert-butylperoxybenzoate,
Furthermore, azo compounds such as azobisisobutyronitrile other than the above-mentioned organic peroxides can be used similarly.

In addition, as slipping agents, boron nitride, Deflon powder, molybdenum sulfide, potassium titanate, mica,
Colloidal silicone, colloidal alumina, colloidal titanium, etc. having a particle size of 5 μm or less, silicone oil, etc. can be used, and at least one of these may be selected and used. The slip agent is a conductive part.

It is important to add it to the electrode part, and by adding it to the insulating base material, it is possible to reduce the coefficient of friction on the surface of the conductor, etc., so that the method of the present invention can be applied to a wider range of applications. become. For example, a slide switch,
In rotary switches, connectors, etc., the base material also slides, so adding a lubricating 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 S-type part. parts, more preferably 40 parts
~100 parts by weight, curing agent 0.01-10 parts by weight, preferably 0.1-6 parts by weight, slip agent 0.1-60 parts by weight,
The amount is preferably 0.3 to 50 parts by weight, and these can be uniformly dispersed and used as a solvent-free composition, or dissolved in an organic solvent of 400 parts by weight or less, preferably 200 parts by weight or less, for a solvent-based composition. used as

If the amount of the conductive substance is too large beyond the above range, it may be difficult to form a uniform mixture, cause cracks when cutting into a predetermined shape, worsen mold releasability during molding, or cause damage to the conductive parts. There are disadvantages such as deterioration of sliding properties, deterioration of linearity, deterioration of heat resistance and moisture resistance, and deterioration of adhesive strength with the base material. Conversely, 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 a desired resistor. As a method for adjusting the resistance value, it is possible to prepare two or more types of master badges in advance and mix them to obtain a desired value.

If the amount of the curing agent exceeds the above range, it is not only unnecessary in practice, but also causes the resin to harden extremely quickly, causing distortion and reducing the precision of the desired conductive part.
This results in the occurrence of cracks, a decrease in adhesive strength with the base material, and a decrease in the performance of the conductor and the like. 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 amount of slip agent blended is too large beyond the above range,
This results in a decrease in adhesiveness between the conductive part, the Ti pole part, and the base material part and with the terminal, and a decrease in the linearity and temperature characteristics of the resistor.

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 the electrode part is usually made of silver in consideration of resistance 1+lf, chemical stability, etc. Highly conductive substances such as are often used. The preferred ratio of each component is 200 to 1000 parts of a highly conductive substance such as silver to 100 parts of the diallyl phthalate resin! m parts, preferably 300 to 900 parts by weight, more preferably 300 to 7 parts by weight
00 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. It is used as a solvent type or a solvent-free type like the other compositions. The conductive materials used here are 50 to 70% by weight with particle diameters of 2 to 30μ and 50% by weight of particles with particle diameters of 0.05 to 1μ.
It is preferable to use it in combination with ~30ffl1%.

Examples of solvents include acetone, aliphatic ketones such as methyl I-methyl ketone, and methyl isobutyl ketone, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzenes, and halogen carbons such as methylene chloride and chloroform. Examples include hydrogen and acetic acid ester of diethylene glycol monoalkyl ether, and one or more of them can be selected and used.

Various additives can be added to the conductive composition of the present invention, if necessary. For example, as fillers, inorganic and/or organic fillers can be used, 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 m fiber, and whiskers. etc.: Examples of organic fillers include natural fibers such as cellulose, pulp, acrylic fibers, and polyester fibers such as polyethylene terephthalate.

Examples include cotton, rayon, and vinylon.

Examples of polymerization accelerators include metal stones such as cobalt salts, vanadium salts, and manganese salts of naphthenic acid or octoic acid, and aromatic tertiary amines such as dimethylaniline and diethylaniline. I can give an example. The amount to be used may be, for example, about 0.00, 5 to about 6% by weight, based on the weight of the diallylphthalate resin.

Furthermore, examples of polymerization inhibitors include quinones such as p-benzoquinone and naphthoquinone, polyhydric phenols such as hydroquinone, D-tert-butylcatechol, hydroquinone monomethyl ether, and p-cresol.

Examples include quaternary ammonium salts such as trimethylammonium chloride. Its usability ranges from about o, ooi to about 0 based on the weight of the diallyl phthalate resin.
．． An example usage amount is 1% by weight.

Examples of internal mold release agents include metal salts of stearic acid such as calcium stearate, zinc stearate, and magnesium stearate. An example of the amount used is about 0.1 to about 5% by weight based on 14ffi of the diallylphthalate resin.

Furthermore, examples of the silane coupling agent include γ-methacryloxypropyl kII-Jk+S noguno, +1-I1. LIITLJ-Nno s1 run,
Examples include allyltrimethoxysilane. An example of the amount used is about 0.01 to about 3% by weight based on the diallylphthalate resin weight.

Examples of pigments include pigments such as carbon black, iron black, cadmi yellow, benzidine yellow, cadmi orange, red iron black, cadmi red, cobalt blue, and anthraquinone blue, and the amount used is based on the diallylphthalate resin. Based on type (6), usage amounts such as from about 0.01 to about 10% by weight can be exemplified.

In addition, silica powder, titanate coupling agents,
Aluminum coupling agent.

A phosphoric acid ester surfactant or the like can be added as a viscosity modifier or leveling agent.

In preparing the conductive composition, the above 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. Although the curing agent may be added from the beginning of mixing, it is preferable to add it before the end of mixing to prevent gelation.

The reinforcing material for prepreg in the present invention includes woven fabrics made of natural fibers, 1 synthetic fiber, 9 synthetic resins, non-woven paper, etc.
There are mats, etc., and these materials include cellulose,
Examples include natural fibers such as cotton, asbestos, ceramics, inorganic materials such as glass and miscellaneous materials, and synthetic materials such as polyamide, polyimide, polyimide amide, and polyester.

In order to obtain the smoothness of the prepreg surface, especially the fiber diameter of 0
．． Using a filament of 8 to 10μ and a fiber length of 1111 or more, preferably 3 dragons or more, more preferably 6n or more,
It is desirable to use nonwoven fabrics produced by mechanical bonding methods without binders.

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 supported on the reinforcing material depends on the electrical properties of the composition,
It should be adjusted as appropriate, taking into consideration the physical strength, desired resistance value, etc., and whether the conductive part and insulating part can be formed in sufficient contact with each other and have a smooth mirror-like surface on the same surface. Usually, the T1 fraction (hereinafter referred to as resin content) of the conductive composition excluding the weight of the solvent out of the total weight of the prepreg excluding the ff1fi7 of the solvent is 0.20 to 0.95, preferably 0.40 to 0. It is best to set it to .85. If the resin content exceeds the above range and is too high, it is not only practically unnecessary, but also causes misalignment and bleeding of the pattern of the conductive part during hot press molding, and further deformation of the cut out pattern. Precision molding becomes impossible. Also,
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.

The method for supporting the prepreg resin composition on the reinforcing material is as follows:
Impregnation method or applicator depending on the type of reinforcing material, viscosity of #I fat composition, etc.

A coating method using a comma coater, bar coater, gravure coater, flow coater, spray coater, etc. 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 in batches, for example, drying at room temperature for about 0.2 to about 1 hour, followed by drying at room temperature for about 40 to 12 hours.
It may be dried at 0° 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. Of course, it is possible to perform the coating or impregnating process and the drying process continuously,
Commercially available impregnation machines, coating machines, etc. can be used.

When providing an electrode part on a prepreg coated or impregnated with a conductive composition, after drying the prepreg to the touch, separately prepare a conductive composition for the electrode part in accordance with the pattern of the conductive part to be cut out. The printing method or the formation of rolls at predetermined positions may be performed after pre-curing the prepreg, which will be described later, but it is preferably performed before pre-curing.

(I) The electrically insulating base material used in the present invention is a resin composition containing the components of the conductive composition except for the conductive substance, that is, diallylphthalate resin, curing agent, and slipping agent. A prepreg coated with or impregnated with the same reinforcing material as the prepreg (I) above may be used, or a prepreg coated with or impregnated with the same reinforcing material as the prepreg (I) above may be used, or 5rit+l
It may also be a compound containing various additives such as fillers, pigments, internal mold release agents, silane coupling agents, polymerization inhibitors, polymerization accelerators, etc. as used in Composition A.

In the case of a compound, it may be formed into a bed-like or tablet-like molded product that can be cured after being molded into a specific shape.

In the case of the above prepreg, the resin composition to be supported includes 0.1 to 6 parts by weight of a diallyl phthalate resin, 0.1 to 50 parts by weight of a slip agent, preferably t, l1
=o, 2 to 30 parts by weight, or a solvent type dissolved in an organic solvent such as that used in the conductive composition (I>), which further includes, if necessary,
Additives such as those used in the conductive composition can be added within a range that does not impair the properties of the diallyl phthalate resin. In the case of a solvent type, the appropriate amount of solvent can be determined depending on the method of supporting the resin composition on the reinforcing material, that is, the coating method, the impregnation method, etc. , 300 parts by weight or less, preferably 200 parts by weight or less.

There are no particular restrictions on the diallyl phthalate resin composition supported on the prepreg, and it is necessary to ensure that the conductive part and the insulating part are in close contact with each other during hot press molding and have a smooth mirror-like surface on the same surface. Any M that can be molded is sufficient. Usually, the weight fraction of the resin content of the carrier is 0.20 to 0.95.
, preferably in the range of 0.40-0.85. If the resin content exceeds the above range and the -C is too high, 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 warpage, etc. . Furthermore, if the resin content is too low than the above range, poor adhesion will occur between the conductive portion and the insulating portion, resulting in a smooth, mirror-like surface, which may result in curvature.

The method for supporting the diallyl phthalate resin composition on the reinforcing material can be carried out using the same method and apparatus as for the prepreg in (I) above. ' When using a compound as a base material containing a diallyl phthalate resin composition, diallyl phthalate resin 1
0 parts by weight, 0.01 to 10 parts by weight of curing agent, preferably 0.1 to 6 parts by weight, 0.1 to 50 parts by weight, preferably 0.2 to 30 parts by weight of slipping agent, and 1 part by weight of filler. ~300
@ parts by weight, preferably 30 to 100 parts, internal mold release agent 0
．． 05 to 5 parts by weight, preferably 1 to 3 parts by weight, silane coupling agent 0.005 to 5 parts by weight, preferably 0.01 to 3 parts by weight, polymerization inhibitor 0.0005 to 0.3
Part by weight, preferably 0.001 to 0.1 part by weight, if desired, of a composition containing a polymerization accelerator, pigment, etc., is dissolved in a solvent and mixed, then evaporated to dryness, pulverized, or a solvent is added. The mixture is thoroughly mixed beforehand, kneaded with rolls, cooled, and pulverized. In case of the above roll confusion,
Front roll 50-130°C, preferably 80-100°C,
The substrate temperature of the present invention is preferably carried out under cross-circuit conditions at a temperature of 40 to 90°C, preferably 50 to 90°C, for 1 to 10 minutes, preferably 2 to 7 minutes. If J5 is under the above-mentioned cross-contact condition and the roll temperature is too high or the cross-contact time is too long, gelation of the compound will occur, which will be an obstacle during hot-press molding, so care must be taken.

As the base material of the present invention, it is also possible to use the above-mentioned compound further molded into a tablet shape, sheet shape, etc. at room temperature.

The conductor of the present invention is produced by cutting out a predetermined shape of a conductive portion from the prepreg of item nU (I>) and integrally molding it with the insulating base material of (I) above.
Prior to cutting out the pre-preg into a predetermined shape, pre-curing the conductive composition supported in advance to the extent that the conductive composition supported in advance does not lose its reactivity and fluidity during hot press molding provides the excellent performance aimed at by the present invention. It is most important in manufacturing conductors and the like. In other words, after pre-curing to a carefully selected stage, the material is cut into a predetermined shape, and then laminated with an insulating base material and molded to form a predetermined pattern into a conductor etc. with extreme precision. There are many things that are possible. If you don't do precure, IUT? I
The pattern of the conductive part or electrode part may be misaligned,
distorted.

It becomes deformed due to bleeding, cracking, etc.

Among them, the conductive parts and electrode parts are #I! ! The boundary line may be unclear due to phenomena such as the insulating base material part entering the conductive part or electrode part, or these parts intermingling with each other. You must absolutely avoid becoming By pre-curing the prepreg by the method of the present invention, the curing reaction rate and fluidity of these parts can be adjusted, so that
It becomes possible to integrally mold a conductor having a conductive part and an electrode part with a very clear boundary with the insulating part.

Another major advantage of precure is that shrinkage during molding can be reduced. Therefore, precure conditions are extremely important.

The degree of precure of the prepreg of the present invention can be selected in the range of 5 to 40%, preferably 10 to 30% in terms of DSC reaction rate. The DSC reaction rate can be calculated by measuring the difference in calorific value between the diallyl phthalate resin, the conductive composition containing the resin, and the prepreg before and after a certain operation using a differential scanning calorimeter (DSG). I can do it. In the present invention, this state is defined as a DSC reaction rate of 0% based on the heat generation M of the diallylphthalate resin. Since the calorific value is substantially due to the reaction of the diallylphthalate resin, if the calorific value of the resin alone is calculated in advance, the conductive composition and prepreg of the present invention, etc.
The amount of heat generated at a reaction rate of 0% can be determined theoretically since the content of the resin is known.

In other words, the DSG reaction rate is calculated from the calorific value determined by DSC after precure of the prepreg coated or impregnated with the composition and the calorific value of the diallyl phthalate resin itself when the reaction rate of the prepreg is 0%. The difference between the calorific value and the calorific value is expressed by the following formula, and this DSG
The degree of precure can be adjusted by setting the precure conditions at a rate of b °C.

Q: Calorific value (caR/Q) when the DSC reaction rate of the prepreg is 0%, calculated from the measured value of the calorific value of only the diallyl phthalate resin used and the content of the resin.Q': After pre-curing Calorific value (can/g) The calorific value of the breech-cored prepreg is measured by the following method. After pre-curing the prepreg coated or impregnated with the conductive composition, three test pieces were punched out and DSC
The calorific value is measured respectively, and the average value is calculated as Q'. The DSC reaction rate is calculated from the obtained value using the above formula.

The brake core conditions for obtaining the DSC reaction rate in the above range are usually at a temperature of 100 to 180°C, preferably at 13°C.
0-160°C, time 0.5-10 minutes, preferably 1-10 minutes
It is desirable to do this for 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 precure is performed excessively, the adhesion between the cut prepreg and the insulating base material and the adhesion between the cut prepreg and the encapsulating lead wire during hot press molding will be weakened, or 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 precure is insufficient, the pattern of the conductive part formed by the prepreg cut out during hot press molding will be deformed by misalignment, bleeding, distortion, twitching, etc., and it will not work as designed. The accuracy of conductors, etc. cannot be obtained. In the drying step 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 becomes less than 5. As such, dry tea should be prepared.

In the precure method, it may be placed in a heating drying oven,
This may also be done by hot pressing.

It is also possible to perform prekinia continuously following the prepreg manufacturing process.

Following the precure of the prepreg, the prepreg is cut out to become a conductive portion.

As a cutting method, for example, a predetermined moon shape may be used and punched out using a press.

The cut prepreg that will become the S-shaped portion is placed on the insulating base material obtained in (I) 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 prepregs of (I) and molded.

(0) Molding the cut prepreg with the compound of (I) above.

(c) The cut prepreg is molded into a base material using a combination of the prepreg and compound of (I).

(d) On the back side of the substrates in (a) to (c) above, another type of substrate, such as a metal plate such as an iron plate or an aluminum plate, or a ceramic plate, is superimposed and formed.

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. Furthermore, as described above, terminals and the like can be simultaneously molded onto the electrode portion using a mold, or, for example, lead wires can be enclosed at the same time as molding using a lead frame.

During molding, the heating temperature for curing is approximately 2
Temperature ranges such as 0°C to about 190°C can be exemplified. In addition, the pressurization conditions are approximately 5kQ/clj to approximately 1000kQ
/ crj pressure [1111 can be exemplified. After forming, the noodles are aged for 100 to 200 minutes for 1 to 4 hours to improve the adhesion between the metal plate or ceramic plate and the insulating base material in the case of a laminated form such as (d) above. The particles of the conductive substance in the conductive composition and the diallyl phthalate resin move to an equilibrium position with each other, exhibiting the minimum resistance value and settling down, thereby improving the temperature characteristics. .

The method of the present invention has excellent linearity, excellent sliding properties,
High heat resistance, moisture resistance, water resistance, dimensional stability, excellent insulation performance under high temperature and high humidity, and mechanical strength as well as conductive compositions that have high retention of electrical properties under high temperature and high humidity. This method provides a conductor made of an electrically insulating base material that has a high degree of adhesion with a conductive composition and excellent workability, and is a manufacturing method particularly suitable for high-precision mass production. Therefore, it 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, U-tally encoders, electrical circuits as printed circuit boards, rain sensors, snow sensors, sheet heating elements, etc. The method of the present invention is extremely valuable 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 are for illustrating aspects thereof, and it goes without saying that the present invention is not limited thereto.

That is, one of the important features of the present invention is that at least the conductive portion and the electrode portion are #! ! Since there is no difference in level between the border line and the boundary line, the shape of the rest of the conductor, etc. is not a problem, and a desired shape can be taken.

In other words, the conductive part and the electrode part should be completely buried in the insulating filling part. Therefore, the conductor according to the present invention includes not only a flat shape but also a curved shape, a shape of a curved surface, or a complex shape depending on the application.

Table 1 shows the diallyl phthalate resins used in each case below.

Table 1 D A P P' Nidialyl orthophthalate prepolymer "Daiso Isodatsubu" manufactured by Osaka Soda Co., Ltd. DAIP Nidialyl isophthalate prepolymer "Daiso Isodap" manufactured by Osaka Soda Co., Ltd. DATP Nidialyl terephthalate prepolymer number average molecule @ 8000, iodine Value: 85 DAPM Diallyl orthophthalate monomer DATM Diallyl terephthalate monomer USP: An unsaturated polyester obtained by dehydration condensation of 10.5 mol of phthalic anhydride, 0.5 mol of maleic anhydride, and 1 mol of propylene glycol by a melting method.

Acid value: 28, softening temperature: 80° C. Example 1 A conductive composition for impregnation having a sheet resistance of 100Ω/a11 for resistors was prepared using the diallyl phthalate resin shown in Table 1 according to the formulation not shown below.

Blend Part by weight Diaryl phthalate resin (I>' 45 carbon graphite (1) 35 Potassium titanate whisker (2> 20 dicumyl peroxide (3) 1.0 Diamine salt dispersant (4) 0.5 Amide addition Agent (5)' 1.0 Aluminum coupling agent 6) 1.0 Carpitol acetate 67.5 In the above formulation (1) Bifunctional coating?-F Kyusho R 30CG F 40
J (2) Ni-Otsuka Chemical Co., Ltd. [Teismo BK-, 7J (3): Nippon Oil & Fats Co., Ltd. "Percmil D" (4) Nilion Oil Co., Ltd. [Duomin TDDJ (5): rAramide 0FJ (6): Ajinomoto rA L-MJ manufactured by Co., Ltd. was used.

In the above formulation, the diallyl phthalate resin is dissolved in carpitol acetate, the other ingredients except dicumyl peroxide are added thereto, mixed well, passed through a triple roll four times, and then for the above formulation, 1 part of carpitol acetate in which dicumyl peroxide was dissolved was further added to adjust the viscosity at room temperature to about 110 centipoise.

In addition, in the formulation of the above conductive composition, silver powder (particle size 1.2 to 5 parts) is used instead of 35 parts carbon graphite.
．． 60% by weight of 7μ flaky silver powder and particle size 0.05~
An ink made of a conductive composition to be used for electrode portions was prepared in the same manner except that the amount was 290 parts by weight (mixed with 40% by weight of 0.8μ co1]oidal silver powder).

The conductive composition for impregnation was impregnated into a polyester nonwoven fabric (made from filaments with a fiber diameter of 2 μm and a fiber length of 25 to 31 mm), and after air-drying with 1 fA,
Next, ink made of the conductive composition used for the electrode part is applied to the part corresponding to the terminal of the resistor with #2.
00.1 A polyester screen with a thickness of 120 μm was used to print on the portions that would become the electrode portions when cut out. This was air-dried at room temperature and then dried at 80° C. for 30 minutes to obtain a prepreg for cutting out conductive parts.

The prepreg No. 1 was precured for 2.5 minutes in a constant temperature bath at 150° C., and the [)SC reaction rate was adjusted to 23%.

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 (I [> 100 Borosinirite (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): rGPJ manufactured by Denki Kagaku Kogyo Co., Ltd. (2): UTismo DJ manufactured by Battalion Chemical Co., Ltd. (3): Japan U Aerosil 0X-50J manufactured by Aerosil Co., Ltd. (4): r Aerosil 200J (5) ``Park Mill DJ'' manufactured by Nippon Oil & Fats Co., Ltd. (6) ``Plenact TTS'' manufactured by Ajinosaku Co., Ltd. (7): rKBM503J manufactured by Shin-Etsu Chemical Co., Ltd. there was.

In the above formulation, the diallylphtasy 1-based resin was dissolved in methyl ethyl ketone, placed in an LTL pot, and the other components except dicumyl peroxide were added while stirring.

Pour 3kll of steel balls with a diameter of 6n and 12kg of steel balls with a diameter of 81m for 2kg of preparation fi, and feed at 4 kll per minute.
Time dispersion I was completed for 240 hours at 0 rotation. After the dispersion was completed, 150 parts by weight of methyl ethyl ketone in which dicumyl peroxide had been dissolved was further added to the above formulation to adjust the viscosity at room temperature to about 120 centipoise.

The above resin composition was treated with methacryloxysilane-treated glass woven fabric (manufactured by Mizawa Seisakusho, plain weave, basis weight 202 (J/II).
I') and dried at room temperature for 2 hours and then in a constant temperature bath at 80°C for 30 minutes until the resin content was 0.5% by weight.
65 prepregs for base materials were produced.

The pre-cured prepreg for cutting out is cut out into a predetermined shape, that is, a horseshoe shape with a width of 4n and an inner diameter of 30n having electrode parts at both ends, and this cutout prepreg is placed on the six sheets of the prepreg for the base material, and the temperature is 165℃,
Molding was carried out for 30 minutes at a pressure of 50 kM d. 185℃ after molding
An electric resistor was obtained by aging for two pupils.

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 electrical resistor with a typical resistance pattern.

In addition, the characteristics as a resistor are determined according to JIS c64. It was measured according to i4 and shown in Table 2.

Example 2 A conductive composition for coating having a sheet resistance of 1 MΩ/cj 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 (II) 100 Carbon graphite (1) 40 Potassium titanate whisker (2) 25 Colloidal silica "Aerosil 200""Aerosil OX-50J 0 Mica 20 Dicumyl peroxide [ Bark Mill [)J 2.0 Diamine salt dispersant “DuAmin TDDJO,5 Amide additive “Aramide 0FJ-1,0 Aluminum coupling agent rAL-MJl, 0 Titanate coupling agent “Plenact 1-C” 3J 1.0 Silane force springing agent rKBM503J1.0 Carpitol acetate In the above formulation (1) Manufactured by Bifunctional Coating Research Institute [60C The same material as in Example 1 was 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-mentioned conductive composition was applied to an aromatic polyamide nonwoven fabric (fiber diameter 5μ, IIIf length 25-31n, thickness 0.13n, tsubo Wk 100M?Il') with an applicator, dried at room temperature for 2 hours, and prepared as a prepreg. did.

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 ℃.

The above prepreg was heated at a temperature of 150℃ and a pressure of 10kg/cJ.
Pre-cure by pressing for 2 minutes with DSC reaction rate of 24%.
Got pre-city near prepreg.

The above-mentioned precure prepreg was cut out into a horseshoe shape with electric parts similar to those in Example 1 covered at both ends to produce a cutout prepreg.

On the other hand, a diallyl phthalate resin composition used as an electrically insulating base material was prepared with the following formulation.

Blend Part by weight Diallyl phthalate resin (I) 100 Dicumyl peroxide [Percyl DJ 2 Glass short m fiber (1) 60 Calcium carbonate (2) 40 Methacryloxysilane 0.6 Calcium stearate 2 Hydroquinone 0.01 In the above formulation ( 1) rcsO31-IB 830AJ manufactured by Asahi Fiberglass Co., Ltd. (2) IN5-100J 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 60~80℃
The mixture was kneaded for 5 minutes, taken out from the roll into a sheet, left to cool, and coarsely crushed using a Henschel mixer.

The base material composition was filled into a mold with terminals set therein, the cutout prepreg was placed thereon, and the temperature was set at 180°C.
Pressure 100k (1/a7 molding for 10 minutes, then 180k
After aging at ℃ for 3 hours, an electric resistor as shown in FIG. 1 was obtained. The nominal resistance value of this material was 5.0 MΩ.

Further, the characteristics as a resistor were measured according to JIS C6444, and the results are shown in Table 2.

Table 2 Test Items Measurement Conditions Example 1 Song Guo Example 2 Each of the electrical resistors obtained had particularly low jump noise and smooth resistance change characteristics, and was excellent as a potentiometer.

Example 3 Pre-cured horseshoe-shaped cutout prepreg with a DSC reaction rate of 24% produced in Example 2 and resin gold l produced in Example 1
Two prepregs for electrically insulating base materials of O.65 were prepared.

Thickness 1.5. The two sheets of prepreg for the base material and the cut-out prepreg were stacked in order on an alumite-processed aluminum plate of
After molding for 5 minutes, it was further aged at 190° C. for 1.5 hours to obtain an electrical resistor with a smooth surface and excellent heat resistance and thermal conductivity.

6 rhodium-plated Wy V-brushes] (sliding pressure 1
50i11), the above resistor was set and press molding was performed in the same manner as in Example 1 except that the cut out prepreg in Example 1 was not pre-cured. An electrical resistor with the designed pattern could not be obtained. The temperature coefficient of the obtained resistor is > + 500 ppm/de
g, solder heat resistance was approximately -3%.

[Brief explanation of the drawing]

The drawings show one embodiment of the present invention, and FIG. 1 shows embodiment 2.
FIG. 2 is a sectional view taken along the line IA-A'. 1... Conductive part 2... Electrode part 3... Insulating base material 4... Terminal applicant Osaka Kaidatatsu Co., Ltd. Agent Patent attorney Masayo Toru I'l ゝ\, - 1・1'l 2 ni′ 22cho4 ----- / )2 \4 3 \3

Claims (1)

[Claims] When producing 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-pressing molding, the above-mentioned conductive diallyl phthalate resin composition is used. An electrical resistor or conductor with a smooth surface, characterized in that the prepreg coated or impregnated with is pre-cured and cut into a predetermined shape, and then the cut prepreg is placed on the base material and integrated by thermo-pressure curing. How the body is manufactured.