JPH0347562B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an electrical resistor or conductor with excellent surface sliding properties and impact resistance, and a method for manufacturing the same. Using various resins as vehicles or binders,
2. Description of the Related Art Electrical resistors or conductors (hereinafter both referred to as conductors) manufactured from a conductive resin composition in which a conductive substance is dispersed are known. Examples include variable resistors, semi-fixed resistors, potentiometers, encoders, rain sensors, snow sensors, and sheet heating elements for various uses. In all of these, the conductive resin composition is naturally combined with an insulator that forms an electrically insulating part. That is, the resistive portion or the conductive portion (hereinafter both simply referred to as the conductive portion) is formed on the surface of the insulating base material, and the two together form the main part of the conductor or the like. Sometimes, the conductive portion is further covered with a membrane, film, sheet, etc. made of an insulator. Therefore, in a conductor or the like, it is desirable that the conductive part and the insulating part be completely integrated in order to obtain high mechanical strength, durability, and electrical properties. Conventionally, in most cases, conductive parts were formed by printing conductive ink on a laminate or ceramic plate made of phenol resin, epoxy resin, or other thermoset resin, and then baking it. However, these materials have poor sliding properties because their surfaces are not smooth, generate noise, and deteriorate electrical characteristics under high temperature and high humidity conditions, so they do not fully satisfy the long-term reliability of electronic components. It was unsuitable for circuit applications. The present applicant has previously filed an application for a method for producing a conductor, etc., in which a layer of a conductive resin composition containing a resin of the same type is provided on a base material made of a diallyl phthalate resin composition. However, although diallyl phthalate resin has excellent electrical properties, heat resistance, and moisture resistance, it lacks toughness, so products tend to crack, chip, and crack. It has become clear that because of its low solubility, it is difficult to modify with various modifiers, and it is also not very easy to prepare inks or impregnating liquids when used as conductors, etc., and its printability is not sufficient. In view of the above-mentioned problems, the present inventors have conducted intensive research on conductors with improved properties and methods for producing the same, and as a result, the present inventors have found that they can be used as conductive resin compositions and as resins for electrically insulating base materials. , using a terephthalic acid diallyl ester copolymer newly developed by the applicant (Patent Application No. 189981/1981),
The copolymer resin itself has good adhesion and compatibility, so it has excellent printability and processability, and the resulting conductor has the electrical, temperature, and humidity characteristics of conventional diallylphthalate resins. In addition, it has been discovered that it is a conductor that has a small temperature coefficient of resistance value, has further improved heat resistance characteristics and bending strength, and has no cracks, chips, or cracks, and also has impact resistance. Furthermore, we have completed a method for mass-producing such conductors and the like with good yield. That is, the present invention provides a conductor, etc. according to the following invention, and a method for manufacturing the same. () A layer of a conductive resin composition containing the terephthalic acid diallyl ester copolymer is provided on at least a part of the surface of an electrically insulating base material made of a resin composition containing the terephthalic acid diallyl ester copolymer described below. , an electrical resistor or conductor with excellent surface sliding properties, characterized by being integrally cured by heat and pressure. () A prepreg coated or impregnated with a conductive resin composition containing a terephthalic acid diallyl ester copolymer is cut out into a predetermined shape, and the cut-out prepreg is made of an electrically insulating resin composition containing a terephthalic acid diallyl ester copolymer. A method for producing an electrical resistor or conductor with excellent surface sliding properties, which comprises placing it on a base material and curing it under heat and pressure. () A predetermined printing is performed on a release sheet using an ink made of a conductive resin composition containing a diallyl terephthalate copolymer, and the printed surface of the printed release sheet is coated with a resin containing a diallyl terephthalate copolymer. 1. A method for producing an electrical resistor or conductor with excellent surface sliding properties, which comprises stacking the composition on an electrically insulating base material and curing and integrating the composition simultaneously with transfer by hot-press molding. () At least a portion of the surface of an electrically insulating base material made of a resin composition containing a terephthalic acid diallyl ester copolymer is coated with a predetermined ink made of a conductive resin composition containing the terephthalic acid diallyl ester copolymer. A method for producing an electrical resistor or conductor with excellent surface sliding properties, which comprises printing and then heat-pressure-curing the printed substrate. According to the present invention, the terephthalic acid diallyl ester copolymer is used as a resin component or as a component of a resin, and as a component in a composition or ink for an electrical resistor or conductor, or as a component in an electrically insulating base material. It has become clear that by using this material, it is possible to obtain a conductor etc. that satisfies various characteristics required for the above-mentioned conductor etc. Furthermore, the terephthalic acid diallyl ester copolymer used in the present invention can disperse carbon, silver, gold, and other conductive substances well, and can form a conductive part on a base material with good adhesion. It suppresses cracks, etc., and provides stable resistance or conductivity. Further according to the invention,
A predetermined pattern of conductive parts is formed on the base material with high precision, and this can be accurately and easily integrated with the base material, making it easy to create conductors with perfectly smooth mirror-like surfaces. It became possible to mass-produce it. In addition, if desired, it is possible to design and mold the shape at the same time to make it convenient for connecting lead wires, assembling and mounting conductors, etc., or it is also possible to directly encapsulate lead wires and mold them in one piece. It is. The conductor of the present invention and its manufacturing method will be explained in detail below. In the present invention, the terephthalic acid diallyl ester copolymer (hereinafter simply referred to as diallyl ester copolymer) used as the resin component of the electrically insulating base material and the conductive resin composition is a new product developed by the applicant. It refers to a copolymer obtained by polymerizing terephthalic acid diallyl ester and an aromatic hydrocarbon represented by the following formula (i) in the presence of an organic peroxide and an azo compound. In the present invention, a terephthalic acid diallyl ester copolymer as described below is particularly preferred as a modifier that imparts a high impact value to the composition. That is, the following formula (i) However, in the above formula (i), R ¹ and R ² each represent a group selected from the group consisting of a hydrogen atom and a lower alkyl group, and n = an integer of 1 to 3. An aromatic hydrocarbon having at least one hydrogen atom at the benzyl position represented by and the following formula (ii) A terephthalic acid diallyl ester copolymer represented by (a) one monomer unit of formula (i) at the terminal of the monomer unit of formula (ii), and an allyl group of the monomer unit of formula (ii) at the benzyl position. It has a carbon-carbon bonded structure with *C and/or *C. Furthermore, (b) the formula (ii) of the carbon-carbon bond molecular chain portion formed by the allyl group of the monomer unit of the formula (ii) of the copolymer;
The number of monomer units is 3 to 11, preferably 3 to 11
It is a copolymer with a structural feature of 10 molecules. The structure of the copolymer, for example, when toluene (R ¹ =R ² =H, n=1) is used as the compound of formula (i), is represented by the following formula (iii). In the above formula (iii), R is an unreacted allyl group and/or a chain derived from an allyl group constituting another molecular chain portion of the copolymer. represents. As an example of such an embodiment, for example, the following formula (iv) The structural part represented by can be mentioned.
Furthermore, in the structural part of formula (iii) above, the number of monomer units of formula (ii) in the carbon-carbon bond molecular chain part formed by the allyl group of the formula (ii) monomer unit is as shown in formula (iii). 3 to 11, this carbon-carbon bond molecular chain portion is the head-to-tail bond shown in formula (iii), that is, the following formula (v) In addition to this, it can also have a head-to-head bonding moiety as shown in formula (vi) below. The monomer unit of formula (ii) in structural sub-formula (iv) above constitutes a branching point that connects two structural moieties of formulas (v) and (vi) via two ester bonds. In addition, when R is an unreacted allyl group, the following formula (vii)
It can be expressed as The structural moiety of formula (vii) above is a moiety that becomes a crosslinking point during curing of the terephthalic acid diallyl ester copolymer. The terephthalic acid diallyl ester copolymer used in the present invention is preferably a copolymer having the following properties. (c) Iodine value measured by Wijs method: 40~
85. (d) True specific gravity at 25°C is 1.20 to 1.25 (e) Softening range is about 50 to about 120°C. (f) 50% methyl ethyl ketone solution viscosity 80-300 centipoise (30°C). (g) The polystyrene equivalent number average molecular weight (n) measured by GPC (gel permeation chromatography) method is 4,000 to 10,000, the weight average molecular weight (w) is 70,000 to 200,000, and the relationship between n and Mw is The molecular weight distribution expressed as the ratio w/n is
10-40. (h) Brabender melt viscosity measured with a Brabender plastograph is 250 to 2600 m/g, and processing time is 5 to 65 minutes. In producing the terephthalic acid diallyl ester copolymer of the present invention, the aromatic hydrocarbon of formula (i), which is a raw material monomer, and the terephthalic acid diallyl ester of formula (ii) are combined with organic peroxide or azo In the presence of a compound catalyst, preferably structures (a), (b) and
It is produced by conducting a copolymerization reaction under set reaction conditions to obtain a copolymer having the properties (c) to (h). R ¹ and R ² of the aromatic hydrocarbon in the above formula (i) are each selected from the group consisting of a hydrogen atom and a lower alkyl group, and the lower alkyl group is
Examples include _C1 to _C5 alkyl groups. Examples of such compounds of formula (i) include, for example, toluene,
Ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, sec-butylbenzene, n-amylbenzene, sec-amylbenzene, isoamylbenzene, (2-methylbutyl)-benzene, o-xylene, m- Xylene, p-xylene, xylene isomer mixture, pseudocumene, 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4
-diethylbenzene, 1,2-dipropylbenzene, 1,3-dipropylbenzene, 1,4-dipropylbenzene, diisopropylbenzenes, p
-cymene, 1,2-dibutylbenzene, 1,3-
Dibutylbenzene, 1,4-dibutylbenzene,
Examples include 1,2-diisoamylbenzene, 1,3-diisoamylbenzene, 1,4-diisoamylbenzene, and 1,2,3-trimethylbenzene. Further, as examples of organic peroxide catalysts and azo compound catalysts, the following compounds can be exemplified. Dialkyl peroxides and diaryl peroxides such as di-tert-butyl peroxide, di-sec-butyl peroxide, tert-butyl-sec-butyl peroxide, and dicumyl peroxide. Diaroyl peroxides and diacyl peroxides such as benzoyl peroxide. Di-tert-butyl peroxalate, tert-perbenzoate
- alkyl esters of percarboxylic acids such as butyl; 2,2'-azobisisobutyronitrile;
2,2'-azobis-(2-methylbutyronitrile), 2,2'-azobis-(2-methylheptanitrile), 1,1'-azobis-(1-cyclohexylcarbonitrile), 2,2' -Azo compounds such as methyl azobisisobutyrate, 4,4'-azobis-(4-cyanopentanoic acid), azidobenzene, etc.; tert
-butyl hydroperoxide, sec-butyl hydroperoxide, tetralyl hydroperoxide, cumyl hydroperoxide, benzyl hydroperoxide, benzhydryl hydroperoxide, decalyl hydroperoxide, acetyl peroxide, cyclohexyl hydroperoxide,
Hydroperoxides such as n-decyl hydroperoxide; Furthermore, compounds that are easily oxidized by molecular oxygen, in the present invention, terephthalic acid diallyl ester, at least one compound at the benzyl position represented by formula (i) The aromatic hydrocarbon having a hydrogen atom or the copolymer of the present invention is in charge, but if these are oxidized with air or oxygen in advance or during the copolymerization reaction to produce a peroxide, the copolymerization reaction of the present invention can be carried out. Can be used satisfactorily as a catalyst. Regarding the above terephthalic acid diallyl ester copolymer,
It is described in detail in Japanese Patent Application No. 189981/1989 filed by the present applicant. As the resin used in the present invention, in addition to the above-mentioned diallyl ester copolymer used alone, one or more types selected from diallyl phthalate resin, unsaturated polyester, and reactive monomer having an unsaturated group are added to the diallyl ester copolymer. A suitably mixed resin mixture may also be used. The above-mentioned diallyl phthalate resin is a homopolymer, a copolymer, or a mixture of a homopolymer and a copolymer obtained by polymerizing at least one type of monomer selected from ortho, iso, and tele. A curable diallyl phthalate prepolymer, or a post-curable copolymer obtained by polymerizing at least one selected from diallyl phthalate isomer monomers and at least one selected from the above-mentioned reactive monomers having an unsaturated group. It is a general term for a polymerized prepolymer or a mixture of the diallyl phthalate prepolymer and the copolymerized prepolymer. Unsaturated polyesters include polybasic unsaturated acids such as maleic acid and fumaric acid, phthalic anhydride,
From a viscous liquid at room temperature with an acid value of 5 to 100 manufactured by a conventional method using a polybasic saturated acid such as isophthalic acid or terephthalic acid and a polyhydric alcohol such as diethylene glycol or propylene glycol, to a softening point of 150°C or higher. A solid one is preferably used. In addition, examples of the reactive monomer having an unsaturated group include styrene monomers such as styrene and α-chlorostyrene, methyl (meth)acrylate,
Butyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)
Acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate Acrylic monomers such as acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate, vinyl ester monomers such as vinyl acetate and vinyl benzoate, allyl acetate,
Allyl benzoate, allyl (meth)acrylate, diallyl oxalate, diallyl adipate, diethylene glycol bis(allyl carbonate), diethylene glycol bis(allyl phthalate), polyethylene glycol bis(allyl phthalate), diallyl maleate, diallyl fumarate, diallyl citrate , allyl ester monomers such as diallyl phthalate and the like. In the present invention, when a resin mixture is used, the proportion of other components other than the diallyl ester copolymer in the mixture is suitably 70% by weight or less, preferably 50% by weight or less. In this case, the diallyl ester copolymer needs to be contained in the mixture at least 5% by weight, preferably 20% by weight or more. The conductor etc. of the present invention consists of the following constituent elements (A) and (B). (A) The conductive resin composition containing a diallyl ester copolymer in the present invention refers to a diallyl ester copolymer alone or a mixture of the above resins (hereinafter both are collectively referred to as a diallyl ester copolymer resin) and a conductive resin composition containing a diallyl ester copolymer. It refers to a solvent-type or solvent-free paste-like or liquid-like composition that contains a hardening agent and a slipping agent as a main component. As the conductive substance, powdered or fibrous substances such as carbon, graphite, silver, gold, nickel, palladium, platinum, etc. are used, and carbon, graphite, etc. are commonly used, and depending on the purpose, A highly conductive substance such as silver is used in combination. Examples of the carbon and graphite mentioned above include channel black, furnace black, thermal black, acetylene black, and electric arc black. Used selectively. For example, when used as a resistor, it is desirable to select a particle size distribution of conductive material having a particle diameter of 0.01 to 75 μm depending on the resistance value so that the packing density is geometrically large. For conductors, etc., a resin composition with appropriate conductivity separate from the conductive part is used between the conductive part and the lead wire or the connection terminal part of the lead wire (hereinafter referred to as the electrode part). Since it is often advantageous to reduce contact resistance, it is desirable to use two types of resin compositions, one for the conductive part and one for the electrode part, 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 these conductive material particles, the flake-like particle size is 2 to 2.
Particles with particle diameters in the range of 30μ and colloidal structures with a distribution in the range of 0.05 to 1μ are combined in such a way that the ratio of the former is 50 to 70% by weight, and the ratio of the latter is 50 to 30% by weight. It is better to use it. The curing agent used in the conductive resin composition of the present invention includes di-tert-butyl peroxide,
Dialkyl peroxides and diaryl peroxides such as dicumyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; peroxyketals such as 1,1-bis(tert-butyl peroxide)-3,3,5-trimethylcyclohexane; Hydroperoxides such as cumene hydroperoxide; diaroyl peroxides and diacyl peroxides such as lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide; peroxycarbonates such as diisopropyl peroxydicarbonate; tert-butyl peroxyacetate , tert-butyl peroxypivalate, tert
Examples include peroxy esters such as -butylperoxyoctoate and tert-butylperoxybenzoate, and azo compounds such as azobisisobutyronitrile other than organic peroxides can also be used. In addition, as slipping agents, boron nitrite, Teflon powder, molybdenum sulfide, potassium titanate, calcium metasilicate, mica, colloidal silica, colloidal alumina,
50% of the particle size or fiber diameter of colloidal titanium, etc.
Materials with a median value of 10μ or less, silicone oil, etc. can be used, and at least one type of these can 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 at least to the part that forms the surface layer of the conductor, etc., the coefficient of friction on the surface can be reduced, and the method of the present invention can be applied to a wider range of applications. It becomes like this. For example, a slide switch,
In rotary switches, connectors, etc., the base material also slides, so adding a slipping agent is extremely effective. The proportions of each component of the conductive resin composition of the present invention are:
The conductive material used in the conductive parts such as conductors is 30 to 180 parts by weight, preferably 40 to 150 parts by weight, more preferably 40 to 100 parts by weight, per 100 parts by weight of the diallyl ester copolymer resin. parts by weight, curing agent 0.01-10 parts by weight, preferably 0.1
~6 parts by weight, 0.1 to 60 parts by weight, preferably 0.3 to 50 parts by weight of a slip agent, and these can be uniformly dispersed and used as a solvent-free composition, or up to 400 parts by weight, preferably an organic solvent. is used as a solvent-based composition dissolved in 200 parts by weight or less. The resistance value of the composition is determined by the type of conductive substance, processing method, shape and size of particles, etc., and the amount of the conductive substance blended. It is better to select other types. If the amount of the conductive substance blended is too large beyond the above range, uniform kneading may become difficult, or
There are disadvantages such as deterioration of the sliding properties of the conductive part, deterioration of linearity, deterioration of heat resistance and moisture resistance, and deterioration of adhesive strength with the base material. On the other hand, if the blending amount is less than the above range, it may become difficult to adjust the resistance value or it may not be possible to obtain the desired resistance value. As a method for adjusting the resistance value, it is possible to prepare two or more types of masterbatches in advance and mix them to obtain a desired value. If the amount of the curing agent exceeds the above range, it is not only practically unnecessary, but also causes distortion because the resin hardens extremely quickly.
This results in a decrease in the precision of the pattern of the desired conductive portion, the occurrence of cracks, a decrease in adhesive strength with the base material, and a decrease in the performance of the conductor. On the other hand, if the amount is too small, the performance of the product will deteriorate due to delayed curing and incomplete curing. If the blending amount of the slipping agent is too large beyond the above range, the kneading properties of the conductive resin composition will be reduced, the printability will be deteriorated when the composition is used as an ink, and the composition will not adhere to the base material of the pattern that will become the conductive part. The adhesiveness of the composition decreases, and the adjustment range of the resistance value of the composition becomes narrow. When a conductive resin composition is used for the electrode part, the preparation is basically the same as the preparation of the composition for the conductive part above, but the electrode part is usually prepared in consideration of resistance value, chemical stability, etc. Highly conductive substances such as silver are often used. A suitable proportion of each component is 200 to 1000 parts by weight, preferably 200 to 1000 parts by weight of a highly conductive substance such as silver, to 100 parts by weight of the diallyl ester copolymer resin.
300 to 900 parts by weight, more preferably 300 to 700 parts by weight, curing agent 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight
6 parts by weight of the slip agent, 0.05 to 60 parts by weight, preferably 0.3 to 50 parts by weight, and used as a solvent type or non-solvent type similarly to the composition of the conductive part described above. The conductive material used here is 50 to 70% by weight of particles with a particle size of 2 to 30μ.
It is preferable to use it in combination with 30 to 50% by weight of 0.05 to 1μ. Examples of solvents include aliphatic ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzenes, and halogenated hydrocarbons such as methylene chloride and chloroform. , diethylene glycol monoalkyl ether acetate, etc.
One or more kinds can be selected and used from these. Various additives can be added to the conductive resin 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. Examples of the amount used include about 1 to about 300% by weight based on the weight of the diallyl ester copolymer resin. Specific examples of these fillers include mica, asbestos, glass powder, silica, titanium oxide,
Magnesium oxide, asbestos fibers, silica fibers, glass fibers, silicate glass fibers, boron fibers, whiskers, etc.; Examples of organic fillers include natural fibers such as cellulose, pulp, acrylic fibers, polyester fibers such as polyethylene terephthalate, Examples include cotton, rayon, and vinylon. Examples of the polymerization accelerator include metal soaps such as cobalt salts, vanadium salts, and manganese salts of naphthenic acid or octoic acid, and aromatic tertiary amines such as dimethylaniline and diethylaniline. An example of the amount used is about 0.005 to about 6% by weight based on the weight of the diallyl ester copolymer resin. Furthermore, examples of polymerization inhibitors include quinones such as p-benzoquinone and naphthoquinone, polyhydric phenols such as hydroquinone, p-tert-butylcatechol, hydroquinone monomethyl ether, and p-cresol;
Examples include quaternary ammonium salts such as trimethylammonium chloride. An example of the amount used is about 0.001 to about 0.1% by weight based on the weight of the diallyl ester copolymer resin. Examples of internal mold release agents include metal salts of stearic acid such as calcium stearate, zinc stearate, and magnesium stearate. The amount used is, for example, about 0.1 to about 5% by weight based on the weight of the diallyl ester copolymer resin. Furthermore, examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane. The amount used is approximately 0.01 to
An example usage amount is about 3% by weight. Examples of the pigment include pigments such as carbon black, iron black, cadmi yellow, benzidine yellow, cadmi orange, red red iron, cadmium red, cobalt blue, and anthraquinone blue. Based on polymerized resin weight,
Examples include amounts of about 0.01 to about 10% by weight. In addition, silica powder, titanate coupling agents, aluminum coupling agents, phosphate ester surfactants, and the like can be added as viscosity modifiers and leveling agents. In preparing the conductive resin composition, the above-mentioned components can be uniformly dispersed by kneading them using, for example, a stirring tank, a ball mill, a vibration mill, a three-roll mill, or the like. The curing agent may be added from the beginning of kneading, but it is preferably added before the end of kneading to prevent gelation. (B) The electrically insulating base material made of a resin composition containing a diallyl ester copolymer used in the present invention is a component obtained by removing the conductive substance from the conductive resin composition, that is, a diallyl ester copolymer resin. A molding material made of a resin composition containing components such as a curing agent, a curing agent, and a slipping agent is used. Such a molding material may be a prepreg prepared by coating or impregnating a suitable reinforcing material with the resin composition, or a prepreg in which the resin composition is coated with various additives such as those listed in (A) above, such as fillers. It may be a compound containing a pigment, an internal mold release agent, a silane coupling agent, a polymerization inhibitor, a polymerization accelerator, and the like. In the case of a compound, it may be a molded article that can be cured after being molded into a specific shape. In the case of the above prepreg, the supported resin composition includes 100 parts by weight of diallyl ester copolymer resin, 0.01 to 10 parts by weight, preferably 0.1 to 6 parts by weight, of a curing agent, 0.1 to 50 parts by weight of a slipping agent,
Preferably, there is a solvent-free type containing 0.2 to 30 parts by weight, or a solvent type dissolved in an organic solvent such as that used in the conductive composition of (A) above, which further includes, if necessary, a conductive composition. Additives such as those used in the polyester resin composition can be added within a range that does not impair the properties of the diallyl ester copolymer resin. In the case of solvent type, the amount of solvent is
A method for supporting a resin composition on a reinforcing material, that is,
The appropriate amount can be determined depending on whether it is a coating method or an impregnation method, but usually diallylphthalate resin is used.
The amount may be 300 parts by weight or less, preferably 200 parts by weight or less per 100 parts by weight. Reinforcing materials include woven fabrics, non-woven fabrics, paper, matte, etc. made of natural fibers, synthetic fibers, synthetic resins, etc. These materials include cellulose,
Natural fibers such as cotton and asbestos, inorganic fibers such as ceramics and glass fibers, polyamide, polyimide,
Examples include synthetic fibers such as polyimide amide and polyester. In order to obtain the smoothness of the surface of the prepreg, the fiber diameter is particularly 0.8 to 10μ, the fiber length is 1 mm or more, preferably 3 mm or more, and more preferably 6 mm.
It is desirable to use a nonwoven fabric produced by a mechanical bonding method using the above filament without a binder. There is no particular limit to the amount of the resin composition supported on the prepreg, and it is the amount that can be molded so that the conductive part and the insulating part are in sufficient contact with each other during hot press molding and have a smooth mirror-like surface on the same surface. That's fine. Usually, the supported amount is 0.20 to 0.95, preferably 0.4 to 0.85, of the weight fraction of the resin composition excluding the weight of the solvent (hereinafter referred to as resin content) out of the total weight of the prepreg excluding the weight of the solvent. A range of is good. If the resin content is too high beyond the above range, accurate molding may not be possible due to misalignment or bleeding of the pattern of the conductive portion, large mold shrinkage or warping during hot press molding. If the resin content is too low than the above range, poor adhesion will occur between the conductive part and the insulating part, making it difficult to obtain a smooth mirror surface. The method of supporting the resin composition on the reinforcing material depends on the type of reinforcing material, the viscosity of the resin composition, etc., and can be carried out using an impregnation method, an applicator, a comma coater,
A coating method using a bar coater, gravure coater, flow coater, spray coater, etc. can be applied. The prepreg coated or impregnated with the resin composition is subjected to a drying process to remove volatile components. When drying in batches, for example, about 0.2 to about 1
time, followed by drying at 40 to 120°C for about 3 to about 30 minutes. However, when using a curing agent with a low decomposition temperature, such as benzoyl peroxide, it is of course necessary to avoid combinations of drying conditions that require high temperatures and long periods of time. It is of course possible to perform the coating or impregnating step and the drying step continuously, and commercially available impregnators, coaters, dryers, etc. can be used. When using a compound as an electrically insulating base material, 0.01 to 10 parts by weight of a curing agent, preferably 0.1 to 6 parts by weight, and 0.1 to 50 parts by weight of a slipping agent, per 100 parts by weight of diallyl ester copolymer resin.
Preferably 0.3 to 30 parts by weight, additionally 1 to 300 parts by weight of filler, preferably 30 to 100 parts by weight, and 0.05 to 5 parts by weight of internal mold release agent, preferably
0.1~3 parts by weight, silane coupling agent 0.005~
5 parts by weight, preferably 0.01-3 parts by weight, polymerization inhibitor 0.0005-0.3 parts by weight, preferably 0.001-0.1
Parts by weight, if desired, a polymerization accelerator, pigment, etc. are added to the composition, which is dissolved in a solvent and mixed, and then evaporated to dryness and pulverized under the same drying conditions as the prepreg drying process, or a solvent is added. The mixture is thoroughly mixed beforehand, kneaded with rolls, cooled, and pulverized. In the above roll kneading, the front roll should be heated at 50 to 130℃, preferably 80 to 100℃.
℃, after roll 40~110℃, preferably 50~90℃
The base material of the present invention is preferably kneaded at a temperature of 1 to 10 minutes, preferably 2 to 7 minutes. Under the above kneading conditions, if the roll temperature is too high or the kneading 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 a material obtained by further molding the above compound into a sheet shape or the like. In this case as well, it is necessary to perform the molding under conditions that do not cause gelation, as described above. For example, it is appropriate to mold at room temperature to 50°C. The conductor of the present invention is produced by providing a layer of the conductive resin composition of the component (A) on the entire surface or part of the surface of the electrically insulating base material of the component (B), and then heat-pressure-curing the layer. The manufacturing method is, for example, the above-mentioned (), (),
It is very preferably produced by the three methods in parentheses. () Apply or impregnate a reinforcing material with the conductive resin composition of component (A) to produce a prepreg, cut out a predetermined shape that will become a conductive part from this prepreg, and use the cut prepreg as component (B).
A method of placing the product on an electrically insulating base material and curing it under heat and pressure. () Prepare an ink from the conductive resin composition of component (A), use this ink to print a predetermined pattern that will become a conductive part on a release sheet, and use the printed surface of the printed release sheet as a component. A method in which it is layered with the electrically insulating base material of (B) and cured and integrated at the same time as transfer by hot pressure molding. () Prepare an ink from the conductive resin composition of component (A), and use this ink to form a predetermined pattern that is to become a conductive portion on at least a portion of the surface of the electrically insulating base material of component (B). A method in which printing is performed and the printing base material is integrated by heat and pressure curing. The manufacturing method will be explained step by step below. Method () As a method for producing a cutout prepreg that will become the conductive part of the conductor of the present invention, a reinforcing material such as that used in producing the prepreg of the component (B) is added to the conductive part of the component (A). It is produced by coating or impregnating a resin composition to produce a prepreg, and cutting it out into a predetermined shape. The amount of the conductive resin composition supported on the reinforcing material depends on the electrical properties of the composition,
It should be adjusted appropriately by taking into account physical strength, desired resistance value, etc., and whether the conductive part and the insulating part can be formed in sufficient contact with each other and have a smooth mirror-like surface on the same surface. Usually, the resin content as described above is expressed as a weight fraction of 0.20 to 0.95, preferably
A range of 0.40 to 0.85 is good. If the resin content is too high beyond the above range, it is not only practically unnecessary, but also causes misalignment or bleeding of the pattern of the conductive portion during hot press molding, making it impossible to perform accurate molding. If the resin content is too low than the above range, poor adhesion between the conductive part and the insulating part may occur, or a smooth mirror-like surface may not be obtained. The method and apparatus for supporting the conductive resin composition on the reinforcing material, the drying method, etc. are the same as those for producing the prepreg of component (B). When providing an electrode part on a cutout prepreg that will become a conductive part, after drying the prepreg to the touch before cutting out, place a separately prepared conductive resin composition for the electrode part at a predetermined position according to the pattern of the conductive part to be cut out. The electrode portion is formed using a printing method or a transfer method. To cut out the prepreg thus obtained into a predetermined shape, there are methods such as punching with a press. Next, the cutout prepreg is
placed on the electrically insulating base material which is the component (B),
Subjected to hot pressure molding. The cutout prepreg to be placed may be placed on the entire surface of the electrically insulating base material or placed on a part of the base material, and these are selected as appropriate depending on the purpose of the conductor etc. Ru. During molding, the heating temperature for curing can be exemplified in a temperature range of about 120°C to about 190°C. In addition, the pressurization conditions are approximately 5
Pressure ranges such as Kg/cm ² to about 1000 Kg/cm ² may be exemplified. After molding, further 0.1 at 100-200℃
By aging for ~4 hours, for example, if a metal plate, ceramic plate, etc. is further laminated on the back side of the electrically insulating base material, the adhesion between these and the base material can be improved, and furthermore, The particles of the conductive substance and the diallyl ester copolymer resin in the conductive resin composition mutually move to an equilibrium position, exhibiting the minimum resistance value and settling down, thereby improving the temperature characteristics. The conductor etc. obtained by thermoforming may be further cut out into a predetermined shape and used. Further, during hot press molding, compression molding may be performed into a predetermined shape using a mold. Furthermore, it is also possible to simultaneously mold terminals and the like onto the electrode portions using a mold. For example, it is also possible to use a lead frame to encapsulate the lead wires at the same time as molding. Method () In this method, a conductive part such as a conductor is formed by uniformly dispersing the conductive resin composition of component (A) using a ball mill or triple roll to prepare an ink. It is formed by printing a predetermined pattern that will become a conductive part on a release sheet using this ink and transferring this to the base material of component (B). At this time, predetermined printing may be performed on the positions that will become the electrode portions using ink made from a separately prepared conductive resin composition. The release sheet to be used may be any material that is normally used for transfer molding, but polyester films or sheets such as polyethylene terephthalate have particularly good heat resistance, and they also have good release properties against diallyl ester copolymer resins. It is preferable because it has good moldability. The thickness of the release sheet is usually preferably 100 μm or more in order to improve the dimensional accuracy of the printed pattern and workability. Furthermore, as the mold release sheet of the present invention, a chrome-plated steel plate treated with silicone oil or a fluorine-based mold release agent can also be used; in this case, if it is given a mirror finish, it can also serve as a mirror plate during molding. I can do it. Although there are no particular restrictions on the method of printing on the release sheet, screen printing is usually preferably used.
The film thickness of the conductive part and electrode part should be adjusted depending on the desired resistance value, but in the present invention, the film thickness is 30
~200μ, preferably 50~150μ. In variable resistors, depending on their characteristics, two types of conductive ink are added to conductive parts with different resistance values.
After printing several times, conductive ink is often printed on the electrode part, and if the printing release sheet for transfer obtained in this way is used to hot-press mold the base material, different resistances will be applied during molding. Due to the diffusion of the conductive substance in the conductive ink, the change in resistance becomes smooth, which, together with the smoothness of the surface, results in an excellent sliding life and low noise, especially sliding noise and jump noise. One of the features of the present invention is that conductors and the like can be obtained. When the pattern-printed release sheet is hot-press molded with its printed surface overlapped with the base material, the base material and the transferred portions (conductive portions and electrode portions) are cured and integrated at the same time as the transfer. When transferring to a base material, there are cases where the transferred portion is laminated on the entire surface of the base material, and cases where it is transferred onto a part of the surface of the base material, but in the present invention, it is selected as appropriate depending on the use of the conductor etc. be done. Heating temperature and pressure conditions during molding, as well as
Heat treatment, processing treatment, etc. after molding can be performed in the same manner as in () above. Method () In this method, a pattern that will become a conductive part is printed on an electrically insulating base material (B) using an ink made of a conductive resin composition (A), and then the pattern is thermoformed. It is a method of obtaining conductors etc. by
Therefore, the base material for component (B) is mainly prepreg. Printing is done by printing a predetermined pattern on the base material with ink on the parts that will become conductive parts and letting it dry to the touch.If necessary, then at least a part of the parts corresponding to the electrode parts is printed with ink prepared separately. This is done by printing a predetermined pattern so as to overlap the conductive portion. Printing may be applied to the entire surface of the base material or to a portion thereof, but the printing may be appropriately selected depending on the intended use of the resulting product. 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 present invention, it is preferably 5 to 100 μm, preferably 10 to 70 μm. For variable resistors, as mentioned in () above, the resistance value changes smoothly by printing multiple times with ink with different resistance values, and conductive materials with excellent other properties are used. It can be done. Conditions for heating and pressurization during molding, post-treatment, etc. are the same as in () above. By the method mentioned above, the conductor etc. of the present invention having very excellent surface sliding properties and impact resistance can be manufactured. In the present invention, in the above manufacturing process,
When the diallyl ester copolymer resin used is precured to a carefully selected stage before final thermoforming, the pattern of the conductive part may shift, bleed, twitch, or otherwise deform. It has become clear that a conductor with very clear boundaries between the conductive part and the insulating part can be obtained.
Furthermore, it has been found that shrinkage during final hot press molding can be reduced by pre-curing. It has been found that the above effects can be achieved by performing this precure treatment on at least one of the components (A) and (B) of the present invention before the final hot press molding. Hereinafter, the precure treatment will be explained according to the above-mentioned manufacturing methods () to (). The precure processing in the method () above is as follows:
When performing this on a prepreg coated or impregnated with the conductive resin composition of the component (A) of the present invention before or after cutting it into a predetermined shape, or when performing on the base material of the component (B), or There are three methods when performing precuring on both the former two, ie, the prepreg and the base material. In any case, the degree of precure is selected within the range of 5 to 40%, preferably 10 to 30%, expressed as a DSC reaction rate. The DSC reaction rate is determined by measuring the difference in calorific value of the diallyl ester copolymer resin, the conductive composition containing the resin, the prepreg, or the base material before and after a certain operation using a differential scanning calorimeter (DSC). It can be determined by calculation. In the present invention, this state is defined as a DSC reaction rate of 0% based on the calorific value of the diallyl ester copolymer resin. Since the calorific value is substantially caused by the reaction of the diallyl ester copolymer resin, if the calorific value of only the resin is determined in advance, the prepreg containing the conductive composition of the present invention or the resin The calorific value of the base material made of the composition at a reaction rate of 0% can be determined theoretically since the content of the resin is known. In other words, the DSC reaction rate is calculated from the calorific value determined by DSC after precuring of the prepreg or electrically insulating substrate coated or impregnated with the conductive resin composition and the calorific value of the diallyl ester copolymer resin itself. Calculate the difference between the calorific value when the reaction rate is 0% for each of the above, and express this using the formula below. can be adjusted. DSC reaction rate (%) = Q-Q'/Q x 100 Q: DSC of the prepreg or base material calculated from the measured value of the calorific value of only the diallyl ester copolymer resin used and the content of the resin Calorific value when the reaction rate is 0% (cal/g) Q': Calorific value after precuring (cal/g) The calorific value of the precured prepreg or base material is measured by the following method. After precuring the prepreg or electrically insulating base material containing the conductive composition, three test pieces were punched out and DSC
Measure the calorific value for each, calculate the average value, and define it as Q'. DSC using the above formula from the obtained value
Calculate the reaction rate. When the base material is an amorphous material such as a powder, it can be pre-cured and then accurately weighed and subjected to a test. The precuring conditions for obtaining the DSC reaction rate in the above range are usually a heating temperature of 100 to 180°C, preferably 130 to 160°C, and a heating time of 0.5 to 10 minutes, preferably 1 to 5 minutes. desirable.
Of course, as long as the DSC reaction rate is within the above range, the precure conditions may be performed outside the above range. When the DSC reaction rate is less than 5%, the effect of precure is not good. If it exceeds 40%, the pre-cure becomes excessive, resulting in insufficient adhesion between the conductive part and the insulating part, poor adhesion with the lead wires enclosed in the conductor, etc. as required, and other base materials used arbitrarily, e.g. Adhesion with metal plates and ceramic plates deteriorates. The precuring method may be performed by placing the material in a heating drying oven or by using a hot press. When pre-curing the prepreg, it is also possible to perform the pre-curing continuously following the prepreg manufacturing process. The precure processing in the method () above is as follows:
A printed release sheet printed with a pattern using an ink made of a conductive resin composition as component (A), or a base material as component (B), or the former two, that is, a printed release sheet and a base material. There are three ways to do both. In either case, the degree of precure, precure conditions, etc. are the same as in the method () above. Q of the DSC reaction rate calculation formula in this method
is as follows. Q: The calorific value (cal/g) when the DSC reaction rate of the conductive ink or base material is 0%, calculated from the measured calorific value of only the diallyl ester copolymer resin used and the content of the resin. ) The DSC reaction rate is measured by the following method. In the case of a printed release sheet, after pre-curing, the printed conductive ink is scraped off and used as a sample, and the amount of heat generated is measured. Measure at 3 points and find the average value. In the case of a base material, three test pieces are punched out after pre-curing, the calorific value of each is measured, and the average value is determined. The DSC reaction rate is calculated from the obtained value using the above formula. When the base material is an amorphous material such as a powder, it is precisely weighed and tested in the same manner as in () above after pre-curing. The precure processing in the method () above is as follows:
There are two methods: when printing is carried out only on the base material of component (B), and when it is performed after pattern printing is performed on the base material with the ink of component (A). In either case, the degree of precure, precure conditions, etc. are the same as in the case of the method () above. Q of the DSC reaction rate calculation formula in this method
is as follows. Q: The calorific value (cal) when the DSC reaction rate of the base material or the printed base material is 0%, calculated from the measured value of the calorific value of only the diallyl ester copolymer resin used and the content of the resin. /g) DSC reaction rate is measured by the following method. Before printing with conductive ink or after precuring the substrate after printing, punch out three test pieces, measure the calorific value of each using DSC, calculate the average value, and use DSC from the above calculation. Calculate the reaction rate. In any of the above methods, when an electrode portion is formed on a conductor or the like, the electrode portion may or may not be precured in the same manner as the conductive portion. In the drying process for removing volatile components and the roll kneading process already explained, the above-defined
The DSC reaction rate is usually less than 5%, but especially when a curing agent with a low decomposition temperature is used, drying conditions and roll kneading conditions should be adjusted so that the DSC reaction rate is less than 5%. By performing the precure process as described above, it becomes possible to incorporate a predetermined pattern into a conductor or the like with extremely high precision. The conductor of the present invention may be formed in various laminated forms depending on its use. For example, if the base material is further laminated on the opposite side of the base material on which a conductive part such as a conductor is formed, or if a metal plate such as an iron plate or an aluminum plate or a ceramic plate is laminated, the base material There are various embodiments, such as laminating metal plates and ceramic plates via. In either case, after molding, it may be cut into a predetermined shape to form a conductor or the like, or it may be molded into a predetermined shape using a mold. Furthermore, if desired, terminals and the like can be molded at the same time using a mold, and lead wires can be sealed at the same time as molding using a lead frame. The present invention provides a conductive resin composition that has excellent linearity, slidability, and high retention rate of electrical properties under high temperature and high humidity conditions, as well as high heat resistance, moisture resistance, water resistance, dimensional stability, and high temperature and high humidity conditions. The present invention provides a conductor, etc. composed of an electrically insulating base material having excellent insulating performance, mechanical strength, high adhesiveness with the above-mentioned conductive resin composition, and excellent processability. Furthermore, the present invention provides a manufacturing method particularly suitable for high-precision mass production of the conductor and the like, and can be applied to an extremely wide range of uses. For example, it can be used in variable resistors, fixed resistors, potentiometers, linear encoders, rotary encoders, electrical circuits as printed circuit boards, rain sensors, snow sensors, planar heating elements, and the like. Furthermore, the present invention is extremely significant in that it can provide a high level of performance and mass production method for forming conductive parts and insulating parts in such devices and parts. The following examples will explain the conductor etc. and the manufacturing method thereof according to the present invention in more detail, but these are for illustrating one embodiment thereof, and it goes without saying that the present invention is not limited thereto. In other words, one of the important features of the present invention is that at least the conductive part, the electrode part, and the insulating base material part have no step at the boundary line, and the overall shape of the conductor etc. is not a problem. , can take any desired shape. In other words, the conductive part and the electrode part need only be completely buried in the insulating base material part. Therefore, the conductor according to the present invention includes not only a flat shape but also a curved shape or other complicated shapes depending on the purpose. Production examples of diallyl ester copolymers 1-2 Inner diameter equipped with a turbine blade type variable stirrer, double pipe type supply nozzle for monomer and catalyst supply, nitrogen purge port, leak valve, sampling port, thermometer and pressure gauge 600mm, with jacket with internal volume of 120mm
A polymerization tank made of SUS304 was used. The double-tube supply nozzle for monomer and catalyst supply is installed below the liquid level in the body of the polymerization layer, and the inner diameter of the outer tube is set to 1.5 mm before entering the polymerization tank to minimize the residence time in the supply piping. I made it shorter. Three such nozzles were installed in preparation for nozzle blockage. A sampling port was also installed in the body of the polymerization tank, making it possible to take samples of the liquid phase using the internal pressure during the polymerization reaction. An oil rotary vacuum pump and a nitrogen cylinder were connected to the nitrogen purge port so that they could be switched as needed. The above polymerization tank was charged with 60 kg of aromatic hydrocarbon (HC) of the formula (i) shown in Table 1 below, and the operation of reducing the pressure with a vacuum pump at room temperature and returning to normal pressure with nitrogen gas was repeated three times. After replacing the air in the tank with nitrogen, the pressure was reduced again and the polymerization tank was sealed. The stirrer was started and while stirring at 240 RPM, steam was passed through the jacket to raise the temperature to 140°C. The stirring speed was increased to 720 RPM, and terephthalic acid diallyl ester was added from the outer tube of the double tube nozzle at a specified rate, and at the same time, di-tert-butyl peroxide (DTBPO) and aromatic hydrocarbons of formula (i) ) were mixed in advance at a molar ratio of 0.5:1 and supplied to the polymerization tank at a predetermined rate using a pump with a discharge pressure of 70 kg/cm ² . During this time, the steam was adjusted so that the temperature of the polymerization tank was maintained at 140°C. The formula (ii) diallyl terephthalate (DAT) to be supplied is
The mixture of di-tert-butyl peroxide and aromatic hydrocarbon was cooled to 15°C, and the mixture was cooled to 5°C, and the piping leading to the polymerization tank was kept cool. Polymerization tank pressure is 0.3~
It was 2Kg/cm ² G. Once the specified amount of diallyl terephthalate, aromatic hydrocarbon, and di-tert-butyl peroxide has been supplied, the steam is turned off and the stirring speed is lowered.
It was set to 240 RPM and cooled by passing cooling water through the jacket. After cooling to around room temperature, the leak valve was opened to return to normal pressure, and the polymerization reaction was completed. During the polymerization reaction, samples were appropriately taken from the sampling port, and the reaction was monitored using refractive index and GPC. The feed rates and amounts of diallyl terephthalate, aromatic hydrocarbon, and di-tert-butyl peroxide are shown in Table 1 below. The volatile components of the polymerization reaction solution obtained above were distilled off using a thin film evaporator, and the total of unreacted aromatic hydrocarbons, copolymer and unreacted terephthalic acid diallyl ester in the evaporation residue was removed. the ratio by weight to
0.3:1, and then the evaporation residue was stirred while being dropped into a stirring tank containing methanol in an amount 5 times the weight of the supplied diallyl terephthalate.
A copolymer was precipitated. The precipitated copolymer was thoroughly washed with the same amount of methanol, filtered, dried, and pulverized to obtain a powdery copolymer. Table 1 shows the yield and physical properties of the copolymer.

【table】

[Table] In Table 1 above, (1) is the polystyrene equivalent value measured by gel permeation chromatography using a Waters "150CGPC" device. For (2), a light transmission type automatic melting point measuring device "PF61" manufactured by Mettler was used. (3) is the value measured by Brabender Plastograph manufactured by Brabender (Germany). Kneading chamber capacity 50c.c., rotor model W50H, sample 50g
+ Zinc stearate 0.5g, kneading chamber temperature 130℃, rotor rotation speed 22RPM until kneading resistance reaches 5000m・g. From the torque curve on the recording paper, the lowest torque value is taken as the Brabender melt viscosity, and at the end of sample addition. The processing time was defined as the time from Composition of Diallyl Ester Copolymer Resin Table 2 shows the composition of the diallyl ester copolymer resin used in each of the following examples.

[Table] Examples 1 to 2 Using the diallyl ester copolymer resin (d) in Table 2, an impregnating liquid for a resistor was prepared from a conductive resin composition having the formulation shown below. The sheet resistance of the composition made of this formulation was 250KΩ/cm ² . <Preparation of conductive impregnating liquid> Part by weight diallyl phthalate copolymer resin (d) 100 Conductive substance Acetylene black 80 Mica 15 Aerosil SiC200 5 Sliding agent Boron nitrite GP 5 Teflon powder 0.5 Hardening agent Parkmil D 2 Other additives Duomin TDD 1 Aramide OF 2 AL-M 2 Solvent Carbitol acetate 150 The components used in the above conductive impregnating liquid are as follows. Acetylene black: "electrified acetylene black"
Mica made by Denki Kagaku Co., Ltd.: "Suzolite 325-S" Aerosil SiC200 made by Kuraray Co., Ltd.: Boron Nitrite GP made by Nippon Aerosil Co., Ltd. Teflon powder made by Denki Kagaku Kogyo Co., Ltd.: 90% passing 13μ Percmill D: (Dicumyl peroxide) Japan Duomin TDD manufactured by Yushisha Co., Ltd.: (diamine salt dispersant) Aamide OF manufactured by Lion Yushisha Co., Ltd.: (amide based ink additive) AL-M manufactured by Lion Yushisha Co., Ltd.: (aluminum based coupling agent) manufactured by Ajinomoto Co., Ltd. Diallyl ester copolymerization The resin was dissolved in carbitol acetate, other components were added thereto, and the mixture was thoroughly mixed beforehand, and the mixture was passed through a three-roll system four times to obtain a conductive impregnating liquid. <Preparation of cutout prepreg> The above conductive impregnation liquid was applied to an aromatic polyamide nonwoven fabric with a fiber diameter of 5 μm and a fiber length of 25 to 31 mm, and prepreg was prepared by drying at room temperature for 1 hour and at 80° C. for 15 minutes to the touch. . The resin content of the prepreg is expressed as a weight fraction.
It was 0.60. Further, using the diallyl ester copolymer resin (a) shown in Table 2, an ink (area resistance 0.1 Ω/cm ² ) for the electrode part was prepared with the following formulation. (Preparation of ink for electrode part) Part by weight Diallyl ester copolymer resin (a) 100 Conductive material silver powder 600 Sliding agent Teismo BK7 45 Hardening agent Percmill D 2 Other additives Duomin TDD 1 Aramide OF 2 AL-M 2 Solvent Carbitol acetate 150 The components used in the ink for the electrode part are as follows. Silver powder: A mixture of 400 parts by weight of particles of which 90% or more has a particle size of 2 to 30 μm and 260 parts by weight of particles of which 90% or more has a particle size of 0.1 to 1 μm Teismo BK7: (Potassium titanate whisker) Manufactured by Otsuka Chemical Co., Ltd. Others The ingredients were the same as those used in the conductive impregnation solution above. Diallyl ester copolymer resin was dissolved in carbitol acetate, placed in a porcelain pot, and other ingredients were added while stirring. For the amount of 2 kg, 3 kg of steel balls with a diameter of 6 mm and 12 kg of steel balls with a diameter of 8 mm are required.
Kg pot and dispersed for 240 hours at 40 revolutions per minute. Using the ink for the electrode part on the prepreg prepared above, print the electrode part on the part corresponding to the terminal of the conductive part when cutting out with a #200 polyester screen with a total thickness of 120μ, and after air drying at room temperature,
It was dried at 80°C for 15 minutes. The prepreg on which the electrode portions were printed was cut into a predetermined pattern of conductive portions, that is, a horseshoe shape with a width of 4 mm and an inner diameter of 30 mm having electrode portions at both ends (Example 1). In addition, a prepreg printed with the above electrode part and dried in the same manner was precured at 150°C for 2 minutes.
A precured prepreg with a DSC reaction rate of 21% was cut out into a horseshoe shape in the same manner as above (Example 2). <Preparation of electrically insulating base material> A base material compound having the following formulation was prepared using the diallyl ester copolymer resin (c) shown in Table 2. Part by weight Diallyl ester copolymer resin (c) 100 Permil D 2 Short glass fiber 60 Calcium carbonate 35 Wollastonite NYAD400 5 Silane coupling agent A174 0.6 Calcium stearate 2 Hydroquinone 0.01 In the above formulation, short glass fiber: Asahi Fiber Glass Co., Ltd. Manufactured by “CSO”
Calcium carbonate: "NS-100" manufactured by Nitto Funka Kogyo Co., Ltd. Wollastonite NYAD400: (calcium metasilicate) Silane coupling agent A174 manufactured by Nagase Sangyo Co., Ltd.: manufactured by Nippon Unicar Co., Ltd. were used. After pre-mixing the above formulation well, pre-roll 90
Roll kneading was carried out for 5 minutes at ~100°C and a rear roll at 60-80°C. A sheet was taken out from the roll, left to cool, and then roughly crushed using a feather mill. This was compression molded at room temperature to produce a tablet with a diameter of 90 mmφ and a thickness of 6 mm. <Thermoforming> Cutout prepreg without precure (Example 1) is placed on a tablet which is an electrically insulating base material.
and precured cutout prepreg (Example 2) were placed separately, molded at a temperature of 180℃ and a pressure of 1000Kg/ ^cm2 for 10 minutes, and then decompressed.
After aging at 180° C. for 2 hours, each electrical resistor with a thickness of about 2 mm was obtained. In all cases, the conductive portion, the electrode portion, and the base material portion were on the same plane and had a smooth mirror-like surface, so that the boundary line of the conductive portion did not bleed. Especially in Example 2, the boundary line was very clear. FIG. 1 shows a plan view of the electrical resistor obtained in Example 2, which was punched out to about 50 mm. Examples 3 to 4 Using the diallyl ester copolymer resin (a) shown in Table 2, an ink for a resistor comprising a conductive resin composition having the formulation shown below was prepared. The sheet resistance of this composition was 100Ω/cm ² . <Preparation of conductive ink> Part by weight Diallyl ester copolymer resin (a) 100 Conductive substance Acetylene black 8 Kettien black EC 15 Scaly graphite 50 Artificial graphite 5 Sliding agent Teismo BK7 45 Hardening agent Parkmil D 2 Other Additives Duomin TDD 1 Aramide OF 2 AL-M 2 Solvent Carbitol acetate 150 The components used in the above formulation are as follows. Ketsuen Black EC: Made by Akzohemi Scaly graphite: 90% passing 15μ Artificial graphite: Diallyl ester copolymer resin is dissolved in carbitol acetate, other ingredients are added to it and mixed well in advance. This was passed through a three-roll roll four times to obtain a conductive ink. <Preparation of printed release sheet for transfer> A horseshoe-shaped pattern with an inner diameter of 30 mm and electrode parts at both ends of a conductive part with a width of 4 mm was used to create a #200 total thickness.
A 120μ polyester screen was made and the thickness
On a 100 μm polyethylene terephthalate film, first, a portion corresponding to the horseshoe-shaped electrode portion was printed with the ink for the electrode portion used in Examples 1 and 2, and then a conductive portion was printed with the conductive ink described above. After drying at room temperature, it was dried at 80° C. for 20 minutes to produce a printed release sheet for transfer with a printing thickness of 50 μm. <Preparation of electrically insulating base material> Using the diallyl ester copolymer resin (b) shown in Table 2, an impregnating solution for prepreg for a base material having the following formulation was prepared. Part by weight Diallyl ester copolymer resin (b) 100 Sliding agent Boron nitrite GP 30 Teismo D 40 Aerosil OX-50 20 Aerosil 200 10 Hardening agent Percmil D 2 Other additives PreneAct TTS 1.5 KBM503 1.5 Solvent Methyl ethyl ketone 300 The above compound Each component inside is as follows. Teismo D: (Potassium titanate whisker) Aerosil OX-50 manufactured by Otsuka Chemical Co., Ltd.: (Highly dispersed fine silica) Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.: ( 〃 ) 〃
PrenAct TTS: (Titanate coupling agent) manufactured by Ajinomoto Co., Ltd. KBM503: (Silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd. Dissolve diallyl ester copolymer resin in methyl ethyl ketone, add other ingredients to this, and disperse in a ball mill for 240 hours. After that, 100 parts by weight of methyl ethyl ketone and 100 parts by weight of acetone were added to make the viscosity at room temperature about 100 centipoise. The impregnation solution prepared above was applied to a polyester nonwoven fabric (fiber diameter
3μ, fiber length 12 to 25 mm) and dried at 80°C for 30 minutes to obtain a prepreg for base material.The resin content of the prepreg was 0.80 in weight fraction. One sheet of the above prepreg was taken and precured at 150°C for 2 minutes to obtain a precured prepreg with a DSC reaction rate of 21%. <Transfer molding> Six sheets of the above prepreg stacked (Example 3)
And on top of five sheets of prepreg and one sheet of pre-cured prepreg (Example 4), overlap so that the printed surface of the printed release sheet for transfer made above is in contact with the base material surface, At 160℃, 50Kg/ ^cm2
It was molded for 30 minutes, and then aged at 185° C. for 2 hours after molding to obtain a mirror-like electrical resistor in which the conductive portion was on the same plane as the base material surface and the boundary line of the conductive portion was clear and smooth. Examples 5 to 6 Using the diallyl ester copolymer resin (b) shown in Table 2, an ink for a resistor comprising a conductive resin composition having the formulation shown below was prepared. The sheet resistance of this composition was 1 MΩ/cm ² . <Preparation of conductive ink> Part by weight diallyl ester copolymer resin 100 Conductive substance Acetylene black 15 Kettien black 15 Sliding agent Aerosil 200 10 Aerosil OX-50 15 Mica 20 Teismo BK40 25 Hardening agent Parkmil D 2 Other additives Duomin TDD 0.5 Aramide OF 1 AL-M 1 Preact TTS 1 KBM503 1 Solvent Carbitol acetate 150 Among the components of the above formulation Teismo BK40: (Potassium titanate whisker)
It was manufactured by Otsuka Chemical Co., Ltd., and the other parts were the same as in the previous example. The diallyl ester copolymer resin was dissolved in carbitol acetate, and the solution was placed in a porcelain pot and the other components were added while stirring. For the amount of 2 kg, 3 kg of steel balls with a diameter of 6 mm and 12 with a diameter of 8 mm.
Kg was placed in a pot and dispersed at 40 revolutions per minute for 240 hours. <Preparation of electrically insulating base material> Using the impregnating solution of the prepreg for electrically insulating base materials prepared in Examples 3 to 4, fiber diameter was 3μ and fiber length was 12.
A ~25 mm polyester nonwoven fabric was impregnated with the impregnating solution and dried to the touch at room temperature for 1 hour and at 80° C. for 15 minutes to produce a prepreg for a printing base material. The resin content of the prepreg was 0.82 in weight fraction. On the other hand, using the same prepreg impregnating solution as above, a glass woven fabric treated with methacryloxysilane (Arisawa Seisakusho "S502" 202 g/m ² ) was impregnated with the above impregnating solution, and then heated at room temperature for 2 hours, then It was dried at ℃ for 15 minutes to produce a prepreg for a glass woven fabric substrate having a resin content of 0.47 in weight fraction. <Printing of conductive parts> Using the conductive ink prepared above on the prepreg for the printed base material prepared above, a pattern for a horseshoe-shaped variable resistor with a width of 4 mm and an inner diameter of 30 mm was printed using a #200 polyester screen with a total thickness of 120 μm. After printing and drying at room temperature, electrode parts were printed on both ends of the horseshoe shape using the ink for the electrode parts prepared in Examples 1 and 2, and after drying at room temperature, the printed film thickness was determined by drying at 80°C for 15 minutes. It was made into a 50μ printed prepreg. <Thermoforming> The above printed prepreg was precured in a constant temperature bath at 150°C for 2 minutes to give a DSC reaction rate of 21.7% (Example 6), and the above printed prepreg was used as is without precuring (Example 6). 5) were stacked on a 1.5 mm thick alumite-processed aluminum plate with one sheet of the prepreg for glass woven fabric substrate interposed therebetween, and molded at 170° C. and 30 kg/cm ² for 15 minutes. After further aging at 190°C for 1.5 hours, an electrical resistor with a smooth surface and good heat resistance and thermal conductivity was obtained. Table 3 shows the measurement results of the characteristic values of each of the electrical resistors obtained in Examples 1 to 6 above as a resistor.

[Table] Comparative Example In the blending composition of the conductive impregnating liquid of Examples 1 to 2, 75 parts by weight of DAP, 5 parts by weight of DATM, and
A conductive impregnation liquid was prepared in the same manner except that 20 parts by weight of USP resin was used, and a precured horseshoe-shaped prepreg (DSC reaction rate of 24) was produced. On the other hand, as an electrically insulating base material, DAP95
A tablet with a thickness of 6 mm was prepared in the same manner as in Examples 1 and 2 except that 5 parts by weight of the resin and 5 parts by weight of DAPM were used. The pre-cured cut-out prepreg was placed on this tab bullet and hot-press molded in the same manner as in Examples 1 and 2 to obtain an electrical resistor with a thickness of 2 mm. (Shock resistance test) 10 electrical resistors above and 10 electrical resistors of Example 2
When the sheet was subjected to a falling weight impact test according to JISK-7211 (Dupont type falling ball tester, load 500g, flat support, striking core 1/2 inch R), the 50% fracture height was determined by the Dickson mode method. was 570 mm in Example 2, while it was 470 mm in Comparative Example.

[Brief explanation of drawings]

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

Claims (1)

[Scope of Claims] 1. A conductive resin composition containing the following terephthalic acid diallyl ester copolymer on at least a portion of the surface of an electrically insulating substrate made of a resin composition containing the terephthalic acid diallyl ester copolymer. 1. An electrical resistor or conductor with excellent surface sliding properties, characterized by being formed by providing a layer of material and integrating the material by heat-pressure curing. The terephthalic acid diallyl ester copolymer refers to a copolymer of terephthalic acid diallyl ester and an aromatic hydrocarbon having at least one hydrogen atom at the benzyl position represented by the following formula. However, in the above formula, R ¹ and R ² each represent a group selected from the group consisting of a hydrogen atom and a lower alkyl group, and n = an integer of 1 to 3. 2 A prepreg coated with or impregnated with a conductive resin composition containing the terephthalic acid diallyl ester copolymer described below is cut out into a predetermined shape, and the cut-out prepreg is then coated with an electrically conductive resin composition containing the terephthalic acid diallyl ester copolymer. A method for producing an electrical resistor or conductor with excellent surface sliding properties, which comprises placing the electrical resistor or conductor on an insulating base material and curing it under heat and pressure. The terephthalic acid diallyl ester copolymer refers to a copolymer of terephthalic acid diallyl ester and an aromatic hydrocarbon having at least one hydrogen atom at the benzyl position represented by the following formula. However, in the above formula, R ¹ and R ² each represent a group selected from the group consisting of a hydrogen atom and a lower alkyl group, and n = an integer of 1 to 3. 3. In the method described in claim 2,
A method characterized in that at least one of the prepreg or the electrically insulating substrate is precured prior to heat curing integration. 4 Perform predetermined printing on a release sheet with an ink made of a conductive resin composition containing the following terephthalic acid diallyl ester copolymer, and print the printed surface of the printed release sheet containing the terephthalic acid diallyl ester copolymer. A method for producing an electrical resistor or conductor with excellent surface sliding properties, which comprises stacking it on an electrically insulating base material made of a resin composition, and curing and integrating it simultaneously with transfer by hot-press molding. The terephthalic acid diallyl ester copolymer refers to a copolymer of terephthalic acid diallyl ester and an aromatic hydrocarbon having at least one hydrogen atom at the benzyl position represented by the following formula. However, in the above formula, R ¹ and R ² each represent a group selected from the group consisting of a hydrogen atom and a lower alkyl group, and n = an integer of 1 to 3. 5. In the method described in claim 4,
A method characterized by pre-curing at least one of a printed release sheet and an electrically insulating substrate before thermoforming. 6 At least a portion of the surface of an electrically insulating base material made of a resin composition containing the following terephthalic acid diallyl ester copolymer is coated with an ink made of a conductive resin composition containing the terephthalic acid diallyl ester copolymer. 1. A method for producing an electrical resistor or conductor with excellent surface sliding properties, which comprises printing and then heat-pressure curing the printed substrate. The terephthalic acid diallyl ester copolymer refers to a copolymer of terephthalic acid diallyl ester and an aromatic hydrocarbon having at least one hydrogen atom at the benzyl position represented by the following formula. However, in the above formula, R ¹ and R ² each represent a group selected from the group consisting of a hydrogen atom and a lower alkyl group, and n = an integer of 1 to 3. 7 In the method described in claim 6,
A method characterized by pre-curing a printed substrate either before or after a predetermined printing is applied to the substrate, before the substrate is integrated by heat-pressure curing.