JPS6037102A - 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 electrical resistor or conductor (referred to as a conductor, etc.) with a smooth surface in which a conductive part and an insulating part are on the same surface. Close and cover.

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 is used, for example, for resistors such as variable resistors, semi-fixed resistors, potentiometers, and encoders, as well as for electrocardiograms in rain sensors, snow sensors, and various sheet heating elements. There is. All of these conductors are constructed by combining a conductive resin composition and an insulator with an electrically insulating portion. In other words, an electrically resistive part or a conductive part (hereinafter referred to as the "conductive part") is formed on the surface of an insulating base material, and together they form the main part of a power grid, etc. .Sometimes also a membrane consisting of an insulator.

In some cases, the conductive layer 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 the long-term reliability of electronic components due to poor sliding properties due to the uneven surface, generation of noise, and deterioration of electrical properties under high temperature and high humidity. , and was unsuitable for forming electrical circuits.

The present inventors have considered the above-mentioned problems and have developed an ink for electrical resistors that has a small temperature coefficient of resistance value, excellent temperature and humidity characteristics, and good sliding properties, or has good conductivity and high temperature/humidity characteristics.
Highly heat resistant, moisture resistant, water resistant, and dimensionally stable, just like inks for conductive circuits that can withstand use in high humidity environments.

We have conducted extensive research into manufacturing methods that allow for mass production of electrical conductors, etc., which are composed of an electrically insulating base material that has excellent insulation performance under high temperature and high humidity conditions, 1 mechanical strength, and strong adhesion to the above-mentioned ink. As a result, the present invention has been completed. That is, the present invention applies predetermined printing on an electrically insulating base material with an ink made of a conductive diallyl phthalate resin composition, and when producing an electrical resistor or conductor by thermoforming, the overlay (Δ This is a method for producing an electrical resistor or conductor with a smooth surface, which is characterized by using a prepreg containing a diallyl phthalate resin composition and precuring the prepreg before hot-pressing molding.

According to the present invention, the above-mentioned characteristics are satisfied by using the sialylphthalate-1 resin as a vehicle for resistors or conductors and as a component of an insulating base material. It has become clear that a conductor that can be used as a conductor can be obtained.

Further, according to the present invention, it is possible to form a predetermined pattern on a base material with high precision, and it is possible to accurately and easily mold this pattern integrally with the base material, so that it has a completely smooth mirror-like surface. Conductors and the like 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 create an integrally molded product. It is also possible to do so. 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 selected from the above-mentioned reactive heptamers;
Furthermore, it is a general term for a mixture of two or more selected from the diallyl phthalate prepolymer, copolymerized prepolymer, and unsaturated polyesters, or a mixture of the mixture and at least one of the above reactive monomers.

Examples of the reactive polymer having an unsaturated group include styrene, styrene yarn polymers such as α-chlorostyrene, methyl (meth)acrylate, butyl (meth)acrylate, 1-octyl (meth)acrylate, 2- 1 Derhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (
meth)acrylate, 2-hydroxyethyl(meth)acrylate-1~, hydroxypropyl(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol Acrylic monomers such as tetra(meth)acrylate, vinyl acetate, vinyl ester monomers such as vinyl acetate, allyl acetate, allyl benzoate, allyl (meth)acrylate 1~, diallyl adipate, diallyl adipate, diethylene glycol bis(allyl) Examples include allyl ester yarn mercury such as diethylene glycol bis(allyl carbonate), diethylene glycol bis(allyl phthalate), polyethylene glycol bis(allyl phthalate), diallyl maleate, diallyl fumarate, diallyl zitrate, and diallyl phthalate. The blending amount is approximately 70% diallylphthalate resin width! Examples include amounts of 1% or less, preferably about 50% by weight or less.

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. A viscous liquid at room temperature with an acid value of 5 to 100 and a solid with a softening point of 150"Q or more manufactured by a conventional method are preferably used. The blending amount is approximately 70% by weight of the diallylphthalate resin width. % or less, preferably about 5%
An example of the amount is 0% by weight or less.

The conductor of the present invention has the following 4S components (I) to (
Produced from I[).

(I> The ink made of the brazingly conductive diallyl phthalate resin composition (hereinafter simply referred to as conductive ink) used in the present invention is mainly composed of the above-mentioned diallyl phthalate resin and a conductive substance, in addition to a curing agent. and a solvent-type or solvent-free paste or liquid composition containing Libery agent.

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 usually used, and depending on the purpose, silver etc. A good conductive substance 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.

They are selected and used in consideration of size, yj conductivity, oil absorption, slipperiness, etc. For example, when used as a resistor, the particle diameter of the conductive substance is o, oi~7 depending on its resistance value.
It is desirable to select the particle size distribution so that the packing density of the 5μ particles becomes geometrically large.

The conductive ink of the present invention may have a separate area between the conductive part and the lead wire or the connecting terminal part of the lead wire (hereinafter referred to as electrode part) depending on the purpose of the conductor etc. and manufacturing cost. Since it is often advantageous to use an ink having appropriate conductivity in order to reduce contact resistance, it is desirable to use two types of ink, one for conductive parts and one for electrode parts, depending on the purpose.

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 ink of the present invention includes:
Dialkyl peroxides and diaryl peroxides, such as di-tart-butyl peroxide and dicumyl peroxide;
peroxyketals such as -3,3,5-trimedelcyclohexane; hydroperoxides such as cumene hydroperoxide; sialoyl peroxides such as lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide; Diacyl peroxide: peroxycarbonate such as diisopropyl peroxydicarbonate; tert-butylperoxyacetate-1~
, tert-butyl peroxyvivalate, te'rt
Examples include peroxy esters such as -butylperoxyoctoate and tert-butylperoxybenzoate, and azo compounds such as azobisisobutyronitrile other than the above-mentioned organic peroxides can also be used.

In addition, as a slipping agent, boron nitrite 1-. Teflon powder, molybdenum sulfide, potassium ditanate, mica, colloidal silica, 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, at least to the prepreg that forms the surface layer of the insulating base material, and in some cases to the insulating group (Δ and -It) to the molding material used for molding. The coefficient of friction on the surface of the body, etc. can be made less sensitive, and the method of the present invention can be applied to a wider range of applications.For example, in slide switches, rotary switches, connectors, etc., the base material part also slides. Therefore, the addition of a slip agent is extremely effective.

The proportion of each component of the conductive ink in the present invention is as follows: 30 to 180 parts by weight, preferably 40 to 150 parts by weight of the conductive material per 10 parts by weight of the diallyl phthalate resin used in the conductive part; More preferably 40
~100fi (fi parts, curing agent 0.01 to 10 parts by weight,
Preferably o, 1-eafHB, t-heli agent o, 1-60
mff is 1 part, preferably 0.3 to 50 parts by weight, and is used as a solvent-free ink by uniformly dispersing them, or 400 parts by weight or less, preferably 20 parts by weight of an organic solvent.
It is used as a solvent-based ink dissolved in 0 parts by weight or less.

If the amount of the conductive substance is too large beyond the above range, it may be difficult to cross-wire uniformly, the leveling property of the pattern printed surface may be reduced, the formation of cracks, the mold releasability during molding may be deteriorated, and the conductivity may be reduced. Deterioration of sliding properties of parts, decrease in linearity,
There are disadvantages such as deterioration of heat resistance and moisture resistance, and a decrease in adhesive strength with the base material. Conversely, if the amount added 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. To adjust the resistance value,
It is possible to prepare two or more types of masterbatches 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 practically unnecessary, but also causes the resin to harden extremely quickly, causing distortion and reducing the accuracy of the desired pattern.
Cracks occur, the adhesive strength with III decreases, and the performance of the conductor etc. due to these decreases. 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 blend m of the slip agent is too large beyond the above range,
This results in a decrease in adhesion between the conductive part, electrode part, and base material part and with the terminal, and a decrease in the linearity and temperature characteristics of the resistor.

When conductive ink is used for the electrode part, the preparation is basically the same as the ink for the conductive part described above, but in consideration of resistance value, chemical stability, etc., silver or other ink is usually used for the electrode part. Good conductive substances are often used. A suitable ratio of each component is 200 to 1,000 parts of a highly conductive material such as silver to 100 parts of the diallyl phthalate resin, preferably 300 parts to 1,000 parts of the highly conductive material such as silver.
900 parts by weight, more preferably 300 to 700 mf
l parts, 0.01 to 10 parts of curing agent, preferably 0.1 parts.
The amount is 1 to 6 parts by weight, and 0.05 to 60 parts by weight of the slip agent, preferably 0.3 to 50 parts by weight, and used as a solvent type or non-solvent type ink similar to the above-mentioned ink for the conductive part.

The conductive substances used here are 50 to 70% by weight of particles with a particle size of 2-J3oμ and 50 to 70% by weight of particles with a particle size of 0.05 to 1μ.
It is preferable to use it in combination with 30% by weight.

Examples of solvents include acetone, aliphatic ketones such as methyl ethyl ketone, and methyl isobutyl ketone, aromatic 1N hydrocarbons such as benzene, toluene, xylene, and chlorobenzenes, and halogenated carbonates such as stanned methylene and chloroform. Examples include hydrogen, acetic acid ester of diethylene glycol monoalkyl ether, and one or more of these can be selected and used.

The conductive ink of the present invention may contain various additives as required. For example, as the filler, inorganic and/or organic fillers can be used, and one or more of these can be used. An example of the amount used is about 1 to about 300@ff1t% based on the weight of the diallylphthalate resin. 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 l! Strings, whiskers, etc.; Examples of organic fillers include natural LLI fibers such as cellulose, pulp, acrylic fibers, and polyester fibers such as polyethylene terephthalate.

Examples include cotton, rayon, and vinylon.

Examples of the polymerization accelerator include metal salts such as cobalt salts, vanadium salts, and manganese salts of naphthenic acid or octoic acid, and aromatic tertiary amines such as dimedylaniline 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.

Further, examples of polymerization inhibitors include quinones such as p-benzoquinone and naphthoginone, polyhydric phenols such as hydroquinone, p-jcrj-butylcatechol, hydroquinone monomethyl ether, and p-cresol, and trimethylammonium chloride. Examples include quaternary ammonium salts such as Its use (■) is approximately o based on the weight of the diallyl phthalate resin.
, ooi to about 0.1% by weight.

Examples of internal mold release agents include gold fi JM of stearic acid such as calcium stearate, zinc stearate, and magnesium stearate. The amount ω used can be exemplified in an amount of about 0.1 to about 5% by weight based on the weight of the diallylphthalate resin.

Furthermore, examples of silane coupling agents include Y-methacryloxypropyltrimethoxysilane,
Examples include vinyltriethoxysilane and allyl-rimethoxysilane. The amount used is
Approximately 0.01 based on the weight of the diallylphthalate resin
Examples of usage include 3% by weight to about 3% by weight.

Examples of pigments include carbon black, iron black, cadmium yellow, benzidine yellow, cadmium orange, cadmium red, cadmium red, cobalt blue, and anthraquinone blue, and the amount used is as follows: Based on the weight of the diallyl phthalate resin, the amount used may be from about 0.01 to about 10% by weight (1n%).

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

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

In preparing the conductive ink, the above-mentioned components can be uniformly dispersed by kneading them using, for example, a stirring tank, a ball mill, a vibrating mill, a three-roll mill, or the like. The curing agent may be added from the start of mixing, but it is preferably added at the end of kneading +'+1 to prevent gelation.

(I[) As the electrically insulating group Δ used in the present invention, a prepreg in which a reinforcing material is coated or impregnated with a diallyl phthalate resin composition is used.

As the reinforcing material, a woven fabric, a non-woven fabric, 1M 1. There are mats, etc., and the material for these is hill loin.

Examples include natural 1i 111 such as cotton and asbestos, inorganic fibers such as ceramics and glass fibers, and synthetic I11 such as polyamide, polyimide, polyimide amide, and polyester. In order to obtain the smoothness of the surface of the prepreg, mechanical bonding is performed without a binder using a filament with a minor diameter of 0.8 to 10 μm and a fiber length of 1 mm, preferably 3 mm or more, more preferably 6 nm or more. It is desirable to use legally manufactured nonwoven fabrics.

Diallylphtasy 1- supported on the prepreg of the present invention
The resin composition is composed of diallyl phthalate resin, a curing agent, and a slipping agent, excluding the conductive substance in the composition used in the conductive ink, and is mixed with 100 parts by weight of diallyl phthalate resin. , curing agent o, oi~
A solvent-free resin liquid containing 10 parts by weight, preferably 0.1 to 6 parts by weight, and 0.1 to 50 parts by weight, preferably 0.2 to 30 parts by weight of a slip agent, or as used in the conductive ink. It is used as a resin liquid dissolved in a solvent. The resin liquid contains, as necessary, a filler, a polymerization accelerator, a polymerization inhibitor, an internal mold release agent,
Various additives such as silane coupling agents, pigments, viscosity modifiers, and leveling agents can be added within a range that does not impair the resin properties.

Preparation of the resin liquid may be adjusted depending on the method of supporting the reinforcing material, ie, impregnation method or coating method, and the method by which the resin should be supported on the reinforcing material. When using a solvent, it is usually 300 parts per 1001 parts of resin.
The weight is less than 200 parts, preferably less than 200 parts.

There is no particular restriction on the support of the resin composition in the prepreg, and it may be possible to mold the conductive part and the insulating part during hot press molding so that the conductive part and the insulating part are in close contact with each other and have a smooth mirror-like surface on the same surface. However, usually, the weight of the 4DI fat silk composition (hereinafter referred to as resin content) excluding the weight of the solvent out of the total weight of the prepreg excluding the weight of the solvent is 0.20~
0.95, preferably 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 blurring of the pattern of the electrical part during hot press molding, large mold shrinkage or warping, etc., resulting in poor precision. Good molding will not be possible. Furthermore, if the resin content is too low, poor adhesion between the conductive part and the insulating part may occur, making it impossible to obtain a smooth mirror surface in the IC.

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 the resin composition, etc.

Coating method 1 using a comma coater, bar coater, gravure coater, flow coater, spray coater, etc. can be applied.

The prepreg coated or impregnated with the resin composition is dried to remove volatile components. When drying in batches,
For example, about 0.2 to about 1 hour at Muro Prayer, followed by 40 to 12 hours.
It may be dried at 0° C. for about 3 to about 30 minutes. It's lc,
For example, when using a curing agent with a low decomposition temperature such as benzoyl peroxide, the combination of high temperature and long drying conditions must be avoided. It is of course possible to perform the coating or impregnating process and drying process continuously.
It can be cut using a commercially available impregnation machine, coating machine, dryer, etc.

In carrying out the present invention, a predetermined pattern of 59 electric parts is printed on the prepreg, which is the electrically insulating base material obtained in (I), using the conductive ink prepared in (I) above, and The same 4-in-1 drying bed as in the prepreg drying process ('
Dry to the touch with I. If necessary, a predetermined pattern is then printed on a portion corresponding to the electrode portion using conductive ink 4 prepared separately so that at least a portion thereof overlaps with the conductive portion, and the printed prepreg is dried to the touch in the same manner as above. Create.

Although there are no particular restrictions on the printing method, screen printing is advantageous. The film thickness of the conductive portion and the electrode portion should be adjusted depending on the desired resistance value, but in the method of the present invention, it is preferably 5 to 100 μm, preferably 10 to 70 μm.

In variable resistors, it is often done to print ink for the conductive part with different resistance values two or more times depending on the characteristics of the resistor, and then print ink for the electrode part, and the printed prepreg obtained in this way When molded using the method of the present invention, the change in resistance value can be smoothed out due to the diffusion of the conductive substance between the inks having different resistance values during molding. Another important feature is that it is possible to obtain an excellent conductor with little noise, especially sliding noise and jump noise.

Next, the printed prepreg is precured to the extent that the diallylphthalate resin does not lose its reactivity and fluidity during hot press molding. This precure is the most important point in the present invention.

In the present invention, this precure process is carried out in two ways: after printing a predetermined pattern on the prepreg with conductive ink as described above, and after pre-curing the prepreg, pattern printing is carried out with conductive ink. There are two methods, and either method can be used.

By pre-curing the resin, it becomes possible to incorporate a predetermined pattern into a conductor or the like with extremely high precision.

When precure is not performed, the pattern of the conductive portion or electrode portion that has been stepped η1 is misaligned.

It becomes deformed due to distortion, bleeding, twitching, etc. Among them, the conductive parts and electrode parts seep into the insulating base material part.
On the other hand, it is absolutely necessary to avoid blurring the boundary line due to phenomena such as the insulating base material part entering the conductive part or electrode part, or these parts intermingling with each other. . 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 the boundary with the insulating part can be adjusted at the position set with the designed dimensions. It becomes possible to integrally mold a conductor having a conductive part and an electrode part with very clear characteristics. Another major advantage is that precure reduces shrinkage during molding.

Therefore, precure conditions are extremely important.

The degree of precure of the prepreg of the present invention can be selected within 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 heat generation m between the diallyl phthalate resin, the conductive ink containing the resin, and the prepreg using a differential scanning calorimeter (DSC) before and after a certain operation. can. In the present invention, the calorific value of the diallyl phthalate resin is based on L
1+; and this state is taken as a DSC reaction rate of 0%. Since the amount of heat generated is substantially due to the reaction of the diallylphthalate resin, if the amount of heat generated only by the resin is calculated in advance, the amount of heat generated by the conductive ink and prepreg of the present invention at a reaction rate of 0% can be estimated. can be determined theoretically since the content of the resin is known.

In other words, the DSC reaction rate is the calorific value when the reaction rate of the prepreg is 0%, which is calculated from the calorific value due to DSC after precure of printed or unprinted prepreg, and the calorific value m of the diallylphthalate-based EI fat itself. This difference is expressed by the following formula, and by setting the precure conditions using this DSC reaction rate, the degree of precure can be adjusted.

Q: Calculated from the measured value during heat generation of only the diallylphthalate resin used and the content m of the resin, calorific value (cai)/L when the DSC reaction rate of the prepreg is 0%) Q': After precure The calorific value (ca (110) of the pre-cured prepreg is measured by the following method. After pre-curing the prepreg printed with conductive ink or the unprinted prepreg, three test pieces are measured. was punched out, and the heat generation m was measured using DSC.
The average value is calculated as Q'. From the obtained value, D
Figure out the SC reaction rate.

Precure conditions for obtaining a 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 DS, C reaction rate is higher than the above range and the precure is performed excessively, the adhesion between the prepreg and the conductive ink and the adhesion to the lead wire enclosed in the conductor etc. will be weak or there will be no adhesion at all. I won't. Furthermore, adhesion with metal plates and ceramic plates used as necessary 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 printed conductive part will be damaged during hot press molding.
Misalignment, smudging.

It is deformed due to distortion, twitching, etc., and the precision of the conductor, etc. cannot be achieved as designed. As already explained, in drying one culm to remove volatile components, 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 less than 5%. Drying conditions should be adjusted so that

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

Furthermore, it is also possible to perform precure continuously following the prepreg manufacturing process.

There are various lamination modes when hot-pressing the precure printed prepreg.

for example, (a) A method of thermoforming printed prepreg as it is.

(b) A method in which a desired number of unprinted prepreg sheets are formed into a fa layer on the non-printing surface of the printed prepreg and then hot-press molded.

(c) A method in which the non-printing surface of the printed prepreg is separately prepared and hot-press molded by overlapping the molding sheets.

(d) A method in which a metal plate, such as an iron plate or an aluminum plate, or a ceramic plate is stacked on the non-printed surface of the printed prepreg, with or without the unprinted prepreg interposed therebetween, and hot-press-formed.

etc.

Examples of the preparation of the molding material (c) above include those listed below.

That is, the diallylphthalate resin of the present invention has the above (
This is a mixture of additives similar to those for conductive ink mentioned in I) at the following blending ratio.

About 1 to about 300 parts by weight of filler, preferably about 30 to about 100 parts by weight, per 100 parts by weight of diallylphthalate resin.
! ! ffi parts, about 0.01 to about 10M parts of curing agent,
Preferably about 0.1 to about 6 parts, internal mold release agent about 0.0
5 to about 51 parts ffi, preferably about 0.1 to about 3 parts (6
) part, silane coupling agent about o, oos to about 5 times fH
c, Qr J: L < C about 0.01 to about 3 parts by weight,
About 0.0005 to about 0.3 parts by weight (6) parts by weight of a polymerization inhibitor, preferably about 0.001 to about 0.1 parts by weight, and if desired, further blending a polymerization accelerator, a slip agent, a pigment, etc. After dissolving and mixing in a solvent, evaporating to dryness and pulverizing, or without adding a solvent again,
After mixing the rolls, it is cooled and pulverized to form a substrate compound. When rolls are mixed, the front roll should be heated at 50 to 130°C.
, preferably 80-iooC, rear roll 40-110C
, preferably at a temperature of 50 to 90° C. for 1 to 10 minutes, preferably 2 to 7 minutes, is both necessary and sufficient. If the temperature is too high or the crosstalk time is too long, gelation will occur, making molding difficult or impossible, so care must be taken.

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 5k (1/d to approximately 1000kg/d).
A pressure range such as aj can be exemplified. After molding, aging is further carried out at 100 to 200°C for 0.1 to 4 hours to improve the adhesion between the metal plate or ceramic plate and the prepreg in the case of the laminated form as described in (d) above. The particles of the conductive substance in the conductive ink and the diallyl phthalate resin move to an equilibrium position with each other, exhibiting a minimum resistance value and settling down, thereby improving the temperature characteristics.

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. Further, 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.

The method of the present invention has excellent linearity, excellent sliding properties,
Like conductive ink, which has a high retention rate of electrical properties under high temperature and high humidity conditions, it also has high heat resistance, moisture resistance, water resistance, legal stability, excellent insulation performance under high temperature and high humidity conditions, mechanical strength, It provides a conductor made of conductive ink and an electrically insulating base material with high adhesion and excellent workability, and is especially suitable for high-precision mass production! lI
It is a manufacturing method that 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/rain/snow sensors, sheet heating elements, etc. - The method of the present invention is of great value as it provides a high degree of performance and a method of mass production in the formation of conductive and insulating parts in these containers 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 the embodiments thereof, and it goes without saying that the present invention is not limited thereto.

However, 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. Instead, 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 overall shape of the conductor etc. is not only flat but also curved.
Alternatively, all other 1i crude shapes depending on the purpose are also included in the 81 electric body etc. according to the present invention.

The diallyl phthalate resins used on each side below are not shown in Table 1.

DAPP Diallyl A Rusophthalate Prepolymer "Daiso Sodatsubu" manufactured by Osaka Soda Co., Ltd. DAIP: Diallyl Isophthalate Prepolymer [Daiso Isodatsubu] manufactured by Osaka Soda Co., Ltd. DATP: Diallyl terephthalate prepolymer number average intermolecular distance 8000, iodine value 85 DAPM : diallyl orthophthale-1-monomer DATM
Nidialyl terephthalate monomer USP: An unsaturated polyester obtained by dehydration condensation of 0.5 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. Examples 1 to 2 Using diallyl phthalate resins shown in Table 1, diallyl phthalate resin compositions for electrically insulating substrates having the following formulations were prepared.

Compound Weight: Diaryl phthalate resin (I [> 100 boron nitride (1) 30 Potassium titanate whisker (2) 40 Colloidal silica (3) 20 (4) 10 Dicumyl peroxide (5) 2 Ditanate coupling agent ( 6) 1.5 Silane coupling agent (7) 1.5 Methyl edyl ketone 150 In the above formulation (1): Denki Kagaku Kogyo Co., Ltd. r G l) J (2): Ohita Chemical Co., Ltd. “Tismo” DJ (3) "Aerosil 0X-50J" manufactured by Japan 70 Kosil Co., Ltd. (4): "Ae" Gil 200" (5): "Bark Mill D" manufactured by Nippon Oil & Fats Co., Ltd. (6): Manufactured by Ajinomoto Co., Ltd. [Blen Act TTSJ ( 7): rKBM503J manufactured by Shin-Etsu Chemical Co., Ltd. was used.

In the above formulation, the diallyl phthalate resin was dissolved in methyl ethyl ketone, placed in a VFI pot, and the other components except dicumyl peroxide were added while stirring. 3 kq of steel balls with a diameter of 611 and 12 kjJ of steel balls with a diameter of 81 m were added to 12 kg of prepared material, and mixed and dispersed at 40 revolutions per minute (240 fRriil). After the dispersion was completed, 150 fflfffi parts 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 centibois.

A polyester nonwoven fabric (manufactured from filaments with a fiber diameter of 3 μm and a fiber length of 12 to 251 m) was impregnated with the above resin solution, and after drying to the touch at 60°C for 30 minutes, the resin content was 0.80 in terms of weight fraction. A prepreg for the base material was produced.

Next, a conductive ink for resistors having a sheet resistance of 100 Ω/d was prepared with the following formulation.

Compound 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 additive (5) 1.0 Aluminum-based coupling agent (6) 1.0 Carpitol acetate 67.5 Among the above formulations (1) Manufactured by Bifunctional Film Research Institute [300GF April (2): "Teismo BK" manufactured by Ohita Chemical Co., Ltd. -7J (3): "Perc Mill D" manufactured by Nippon Oil & Fats Co., Ltd. (4) "Duomin TDDJ" manufactured by Nilion Oil Co., Ltd. (5): "Aramide 0FJ" (6): "8L-MJ" manufactured by Ajinomoto Co., Ltd. were used.

The diallyl phthalate resin was dissolved in carpitol acetate, other components were added thereto, and the mixture was thoroughly mixed in advance and then passed through a triple roll four times to prepare a conductive ink.

Using the above conductive ink, a horseshoe shape was printed on the prepared prepreg using a #200 polyester screen with a total thickness of 120μ, which became a conductive part, and sufficient air was blown.
For 3 minutes (temperature 1
It was dried to the touch at 20° C.) to obtain a printed prepreg.

The printing prepreg was placed in a constant temperature bath at 150° C. and precured for 2 minutes to give a DSC reaction rate of 19%.

In Example 1, this precure printed prepreg was placed with the printed side facing up, and the six non-printed prepregs described above were stacked underneath, and heated at a temperature of 165°C and a pressure of 50 kg/ca.
Shape for 30 minutes. 185 after n-type. A resistor 4 was obtained by aging at ℃ for 2 hours.

In addition, in Example 2, below the pre-cured printed brief leg, a mold with a terminal set therein was filled with Funbound of the following C composition, molded for 10 minutes at a temperature of 180°C and a pressure of 100k (1/all), and further molded at 180°C and a pressure of 100k (1/all). After aging for 2 hours, 1 q of JS antibody as shown in FIG. 1 was obtained.

Compound formulation Part by weight Diallyl phthalate resin (I) 100 Dicumyl peroxide "Percyl DJ" 2 Short glass fiber (1) 60 Calcium carbonate (2) 40 Methacryloxysilane 0.6 1 Calcium stearate 2 Hydroquinone 0.01 Above In the formulation, (1) Asahi Fiberglass Co., Ltd. rcsO3FI8830AJ, and (2) Nitto Funka Kogyo Co., Ltd. equipment NS-100J were used.

The above formulation was thoroughly mixed in advance and then kneaded with a roll. Front (coal temperature 90-100℃, rear roll temperature 60-80℃
The mixture was kneaded at ℃ for 5 minutes, taken out from the room in a sheet form, allowed to cool, and then roughly crushed using a Henschel mixer.

Each of the obtained resistors has a conductive part on the same surface as the base material surface, a smooth mirror-like surface, and a clear resistance pattern without blurring at the boundary line with the conductive part. Right? It was a 1ffi gas resistor. In addition, the characteristics as a -1 resistor were measured according to JIS C6444, and Table 2
It was shown to.

Table 2 The resistance change characteristics were smooth and it was excellent as a potentiometer.

In the manufacturing process of the resistors of Examples 1 and 2 above, the prepreg was first pre-cured at 160°C for 1 minute to adjust the DSC reaction rate to 24%, and then a pattern of the conductive portion was printed with conductive ink. The resistors manufactured in the same manner as in Examples 1 and 2 except for the above characteristics had a temperature coefficient of +170 to +225p1) m/de(1, and a soldering heat resistance of -0.70 to -0.95. % range, and other characteristic values were similar to those in Table 2.

Example 3 1 used in Example 1 [electrical insulation 1'i j-:', 4Δ
A similar resin solution was prepared except that among the components of Kawa's diallyl phthalate resin composition, diallyl phthalate resin (■) was replaced with diallyl phthalate resin (IV), and this was mixed with an aromatic polyamide nonwoven fabric (fiber diameter 5μ, Fiber length 25-31
1, Thickness 0.13mm, Tsubo ff1looiJ/T11'
) A prepreg for substrates having a resin content of 0.60 in weight fraction was prepared by drying for 30 minutes at 80° C. for 30 minutes. Next, a J8 conductive ink to be used for a conductive part having a sheet resistance of 1 MΩ/d for a resistor was prepared in the same manner as in Example 1 with the formulation shown below.

Composition (y1 conductive content) Part by weight diallyl phthalate resin (l[) 100 Carbon graphite 1~<1) 40 Potassium titanate whisker<2) 25 Colloidal silica "Aerosil 200"
[Aerosil OX-50J 0 Mica 20 Dicumyl peroxide "Percyl" J 2.0 Diamine salt dispersant [Duomin TDDJ0.5 Amide additive "Aramide 0FJ 1.0 Aluminum coupling agent [8L-MJ1. 0 Titanate coupling agent "Plenact TTSJ 1.0 Silane coupling agent rKBM 503J1.0 Acetate power ruby 1~-ru 150 Among the above formulations (1): Functional coating research rupture "60CG J (2): Ohita Chemical Tismo BK40J manufactured by Yakuhin Co., Ltd. was used, and the other ingredients were the same as in Example 1.

In the formulation, instead of 4 parts of carbon graphite and 1 part, silver powder (60% by weight of flaky silver powder with a particle size of 1.2 to 5.7μ and 40% by weight of colloidal silver powder with a particle size of 0.05 to 0.8μ) was added. A conductive ink to be used for the electrode portion was prepared in the same manner except that the amount of the mixture was 660i parts.

A conductive part pattern was printed on the prepared base material prepreg using the conductive ink for the conductive part in the same manner as in Example 1, and after air drying, the electrode part was printed using the ink for the electrode part. , remove the solvent by air drying, then 1
Pre-cure at 45°C for 4.5 minutes, DSC reaction rate 18%
A pre-cured printed prepreg was obtained.

On the other hand, the thickness is 1:5. Prepare an alumite-processed aluminum plate of
One sheet of the above precure printing prepreg was stacked in order with the printed side facing up, and heated at a temperature of 170°C and a pressure of 20 kQ/cd for 15 minutes.
It was molded for a minute. Furthermore, a resistor with a smooth surface, good heat resistance, and thermal conductivity was obtained by aging at 190°C for 1.5 hours. Six rhodium-plated wire brushes (sliding pressure 15
0g) with the above resistor set at the above JISG
The results of measurement according to No. 444 were as shown in Table 3.

Table 3 Comparative Example Printed prepreg without pre-curing 7j
When press molding was carried out in the same manner as in Example 1 except for this, the conductive part and the electrode part oozed out radially onto the base material, and a pattern with clear boundary lines to the right could not be obtained. still,
m degree coefficient Lt of the obtained letter resistor > +5001111
m/deg, the solder heat resistance was about -5%.

[Brief explanation of the drawing]

The drawings show one embodiment of the present invention, so FIG. 1 shows embodiment 2.
FIG. 2 is a sectional view taken along line IA-A'. 1... Conductive part 2... Electrode part 3... Insulating base material 4... Terminal applicant Osaka Yotsutsuji Co., Ltd. Agent Patent attorney Toru Mayo / A 1 Mawari

Claims (1)

[Claims] When producing an electrical resistor or conductor by hot-pressing a predetermined printing process using an ink made of a conductive diallyl phthalate resin composition on an electrically insulating base material, the diallyl phthalate resin composition is used as the base material. 1. A method for producing an electrical resistor or conductor with a smooth surface, the method comprising using a prepreg containing the above and precuring the prepreg before hot-pressing molding.