JPH0682893B2 - Electrical component board - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a three-dimensionally molded electrical component board such as a so-called printed wiring board.

[Conventional technology and problems]

Conventionally, various polymer materials have been used for substrates such as printed wiring boards, power transformer boards, and thyristor module boards.
From the viewpoint of rigidity and the like, a thermosetting resin has been used as a resin, such as a phenol resin laminate, a glass-epoxy laminate, and the like. Therefore, it could not be molded afterwards and had to be used as a flat plate. Therefore, in order to incorporate such a board into an electric device, a supporting portion on the same plane is provided on the electric device side in order to attach a flat plate to the electric device having a complicated shape, or a supporting portion for a component mounted on the board is made of metal. It was necessary to assemble it on a substrate and attach parts to it, which required a lot of man-hours for assembly and was extremely complicated.

[Means for solving problems]

The present inventors have found that the liquid crystalline polyester has excellent physical properties such as rigidity and heat distortion resistance that can be used for electric component substrates even though it is a thermoplastic resin. Furthermore, the liquid crystalline polyester has a specific thermal conductivity. The present invention has been completed by finding that the heat conductivity can be imparted to the obtained electric component substrate by intimately mixing the filler having the above.

That is, the present invention is mainly composed of a thermotropic liquid crystalline polyester (hereinafter abbreviated as "liquid crystalline polyester") capable of being melt-processed which exhibits anisotropy when melted, and has a thermal conductivity of 300 ° K
It is a plate-shaped molded product of an intimate mixture with a filler of 10 w / mk or more, and is three-dimensionally formed by heating bending of a flat plate portion provided with an electric circuit and a flat plate portion having no electric circuit. The present invention provides an electric component board comprising a functional part.

The present invention will be described in detail below.

The liquid crystalline polyester used in the present invention is a melt processable polyester and has a property that polymer molecular chains take a regular parallel arrangement in a molten state. The state in which the molecules are arranged in this manner is often called a liquid crystal state or a nematic phase of a liquid crystal substance. Such polymers are generally elongate, flattened, fairly rigid along the long axis of the molecule, and are composed of monomers that have multiple chain extension bonds, usually in either coaxial or parallel relationship. Manufactured.

The properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using a crossed polarizer. More specifically, the confirmation of the anisotropic molten phase can be performed by using a Leitz polarization microscope and observing the sample placed on the Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times. The polymer is optically anisotropic. That is, it transmits light when inspected between crossed polarizers. If the sample is optically anisotropic, polarized light will be transmitted even if it is stationary.

As the constituent component of the polymer forming the anisotropic molten phase as described above, one or more of aromatic dicarboxylic acid and alicyclic dicarboxylic acid is used. 1 of aromatic diol, alicyclic diol and aliphatic diol One or more One or more aromatic hydroxycarboxylic acids One or more aromatic thiolcarboxylic acids One or more aromatic dithiols, aromatic thiolphenols Aromatic hydroxyamine, aromatic diamine, or one or more thereof, etc., and the olimer forming the anisotropic melt phase is polyester III) consisting only of polyester II) consisting of I) and Polythiol ester consisting only of IV) Polythiol ester consisting only of V) Polythiol ester consisting of And a polyester amide consisting of a polythiol ester VII) and a polyester amide consisting of VIII).

Furthermore, although not included in the range of the combination of the above components,
Aromatic polyazomethine is included in the polymer forming the anisotropic molten phase, and specific examples of such a polymer include poly (nitrilo-2-methyl-1,4-phenylene nitriloethylidyne-1,4-phenyleneethyl). Lysine); poly (nitrilo-2-methyl-1,4-phenylene nitrilomethylidine-1,4-phenylenemethylidine); and poly (nitrilo-2-chloro-1,4-phenylene nitrilomethylidine-1,4) -Phenylenemethylidine).

Furthermore, although not included in the range of the combination of the above components,
Polyester carbonate is included as a polymer forming the anisotropic molten phase. It consists essentially of 4-oxybenzoyl units, dioxyphenyl units, dioxycarbonyl units and terephthaloyl units.

The compounds constituting the above-mentioned I) to VIII) are listed below.

Aromatic dicarboxylic acids include terephthalic acid and 4,4'-
Diphenyldicarboxylic acid, 4,4'-triphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenoxyethane-
4,4'-dicarboxylic acid, diphenoxybutane-4,4'-dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid, isophthalic acid, diphenylether-3,3'-dicarboxylic acid, diphenoxyethane-3, Aromatic dicarboxylic acids such as 3'-dicarboxylic acid, diphenylethane-3,3'-dicarboxylic acid, naphthalene-1,6-dicarboxylic acid,
Or chloroterephthalic acid, dichloroterephthalic acid,
Examples thereof include alkyl, alkoxy or halogen substitution products of the above aromatic dicarboxylic acids such as bromoterephthalic acid, methyl terephthalic acid, dimethyl terephthalic acid, ethyl terephthalic acid, methoxy terephthalic acid and ethoxy terephthalic acid.

Examples of the alicyclic dicarboxylic acid include trans-1,4-cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids or trans-1,4- ( 1-methyl) cyclohexanedicarboxylic acid, trans-1,4-
Examples thereof include alkyl-, alkoxy- or halogen-substituted products of the above alicyclic dicarboxylic acids such as (1-chloro) cyclohexanedicarboxylic acid.

Aromatic diols include hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxytriphenyl, 2,6-naphthalenediol, 4,4'-
Dihydroxydiphenyl ether, bis (4-hydroxyphenoxy) ethane, 3,3′-dihydroxydiphenyl, 3,3′-dihydroxydiphenyl ether, 1,6-naphthalenediol, 2,2-bis (4-hydroxyphenyl) propane, 2, 2-bis (4-hydroxyphenyl)
Aromatic diols such as methane, chlorohydroquinone, methylhydroquinone, 1-butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone: 4-chlororesorcin,
Examples thereof include alkyl-, alkoxy- or halogen-substituted products of the above aromatic diols such as 4-methylresorcin.

As the alicyclic diol, trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol,
Trans-1,4-cyclohexanedimethanol, cis-
Alicyclic diols such as 1,4-cyclohexanedimethanol, trans-1,3-cyclohexanediol, cis-1,2-cyclohexanediol, trans-1,3-cyclohexanedimethanol, or trans-1,4- ( 1-
Methyl) cyclohexanediol, trans-1,4-
Examples thereof include alkyl-, alkoxy- or halogen-substituted compounds of the alicyclic diols such as (1-chloro) cyclohexanediol.

Aliphatic diols include ethylene glycol and 1,3-
Examples thereof include linear or branched aliphatic diols such as propanediol, 1,4-butanediol and neopentyl glycol.

As aromatic hydroxycarboxylic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-
Aromatic hydroxycarboxylic acids such as 2-naphthoic acid and 6-hydroxy-1-naphthoic acid, or 3-methyl-4-
Hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid,
3-methoxy-4-hydroxybenzoic acid, 3,5-dimethoxy-4-hydroxybenzoic acid, 6-hydroxy-5-
Methyl-2-naphthoic acid, 6-hydroxy-5-methoxy-2-naphthoic acid, 3-chloro-4-hydroxybenzoic acid, 2-chloro-4-hydroxybenzoic acid, 2,3-dichloro-4-hydroxybenzoic acid Acid, 3,5-dichloro-4
-Hydroxybenzoic acid, 2,5-dichloro-4-hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 6
Alkyl and alkoxy of aromatic hydroxycarboxylic acid such as -hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-7-chloro-2-naphthoic acid and 6-hydroxy-5,7-dichloro-2-naphthoic acid Another example is a halogen-substituted product.

As the aromatic mercaptocarboxylic acid, 4-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercapto-
Examples thereof include 2-naphthoic acid and 7-mercapto-2-naphthoic acid.

Examples of aromatic dithiols include benzene-1,4-dithiol, benzene-1,3-dithiol, 2,6-naphthalene-dithiol, and 2,7-naphthalene-dithiol.

Examples of the aromatic mercaptophenol include 4-mercaptophenol, 3-mercaptophenol, 6-mercaptophenol and 7-mercaptophenol.

4- as aromatic hydroxy amine and aromatic diamine
Aminophenol, N-methyl-4-aminophenol, 1,4-phenylenediamine, N-methyl-1,4-phenylenediamine, N, N'-dimethyl-1,4-phenylenediamine, 3-aminophenol, 3 -Methyl-4-aminophenol, 2-chloro-4-aminophenol, 4
-Amino-1-naphthol, 4-amino-4'-hydroxydiphenyl, 4-amino-4'-hydroxydiphenyl ether, 4-amino-4'-hydroxydiphenylmethane, 4-amino-4'-hydroxydiphenylsulfide, 4, 4'-diaminophenyl sulfide (thiodianiline), 4,4'-diaminodiphenyl sulfone,
2,5-diaminotoluene, 4,4′-ethylenedianiline,
4,4'-diaminodiphenoxyethane, 4,4'-diaminodiphenylmethane (methylenedianiline), 4,4'-diaminodiphenylether (oxydianiline) and the like can be mentioned.

The polymers I) to VIII) composed of the above components may or may not form an anisotropic melt phase depending on the composition ratio in the components, the polymer, and the sequence distribution, but they are used in the present invention. The polymers are limited to those forming an anisotropic melt phase among the above polymers.

Polyesters of I), II), III) and V which are polymers forming an anisotropic melt phase suitable for use in the present invention.
The polyesteramide of III) can be produced by various ester forming methods that allow organic monomer compounds having functional groups that form the required repeating units by condensation to react with each other. For example, the functional groups of these organic monomer compounds may be carboxylic acid groups, hydroxyl groups, ester groups, acyloxy groups, acid halides, amine groups and the like. The organic monomer compound can be reacted by a molten acidolysis method without the presence of a heat exchange fluid. In this method, the monomers are first heated together to form a molten solution of the reactants. As the reaction continues, solid polymer particles become suspended in the liquid.
Volatile by-products of the final stage of condensation (eg acetic acid or water)
A vacuum may be applied to facilitate removal of the.

Further, a slurry polymerization method can also be adopted to form a wholly aromatic polyester suitable for use in the present invention. In this way, the solid product is obtained in suspension in the heat exchange medium.

Whichever of the above melt acidolysis method and slurry polymerization method is adopted, the organic monomer reactant that induces a wholly aromatic polyester is in a modified form in which the hydroxyl group of such a monomer is esterified at room temperature (that is, a It can be subjected to the reaction (as an acyl ester). The lower acyl group preferably has about 2 to 4 carbon atoms. Preferably, the acetic acid ester of such an organic monomer reactant is subjected to the reaction.

Further, as typical examples of the catalyst which can be optionally used in either the molten acidolysis method or the slurry method, dialkyl tin oxide (eg, dibutyl tin oxide), diaryl tin oxide, titanium dioxide, antimony trioxide, alkoxy titanium silicate, titanium alkoxide. , Alkali and alkaline earth metal salts of carboxylic acids (eg zinc acetate), Lewis (eg BF ₃ ), hydrogen halides (eg HCl)
Gaseous acid catalysts such as The amount of catalyst used is generally about 0.001 to 1% by weight, especially about 0.01 to 0.2% by weight, based on the total weight of the monomers.

The wholly aromatic polymers suitable for use in the present invention tend to be substantially insoluble in common solvents and therefore unsuitable for solution processing. However, as already mentioned, these polymers can be easily processed by conventional melt processing methods. Particularly preferred wholly aromatic polymers are somewhat soluble in pentafluorophenol.

The wholly aromatic polyesters suitable for use in the present invention generally have a weight average molecular weight of about 2,000 to 200,000, preferably about
It is 10,000 to 50,000, particularly preferably about 20,000 to 25,000. On the other hand, suitable wholly aromatic polyesteramides generally have a molecular weight of about 5,000 to 50,000, preferably about 10,000 to 3
It is 000, for example, 15,000 to 17,000. The measurement of such a molecular weight can be carried out by a standard measurement method which does not involve solution formation of gel permeation chromatography and other polymers, for example, by quantifying an end group by infrared spectroscopy on a compression molded film. The molecular weight can also be measured by using a pentafluorophenol solution and using a light scattering method.

The above fully aromatic polyesters and polyesteramides also have an inherent viscosity (IV) of at least about 2.0 dl / g, for example about 2.0 to 10.0 dl / g, when dissolved in pentafluorophenol at a concentration of 0.1% by weight at 60 ° C. Is generally indicated.

The polymer exhibiting an anisotropic melt phase used in the present invention is preferably an aromatic polyester and an aromatic polyesteramide, and also preferably a polyester partially containing the aromatic polyester and the aromatic polyesteramide in the same molecular chain. Polyester partially contained in is also a preferred example.

Preferred examples of compounds constituting them are 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene and 1,4
-Naphthalene compounds such as dihydroxynaphthalene and 6-hydroxy-2-naphthoic acid, biphenyl compounds such as 4,4'-diphenyldicarboxylic acid and 4,4'-dihydroxybiphenyl, the following general formulas (I), (II) or ( III)
Compound represented by: (However, X: alkylene (C _{1 to} C ₄ ), alkylidene, -O
A group selected from —, —SO—, —SO ₂ —, —S—, and —CO— Y: — (CH ₂ ) _n — (n = 1 to 4), —O (CH ₂ ) _n O—
(Group selected from n = 1 to 4) Para-substituted benzene compounds such as p-hydroxybenzoic acid, delephthalic acid, hydroquinone, p-aminophenol and p-phenylenediamine and their nucleus-substituted benzene compounds (substituents) Are selected from chlorine, bromine, methyl, phenyl, 1-phenylethyl), isophthalic acid, resorcin, and the like, and meta-substituted benzene compounds.

A preferable example of the polyester partially containing the above-mentioned constituents in the same molecular chain is polyalkylene terephthalate, and the alkyl group has 2 to 4 carbon atoms.

Among the above-mentioned constituents, a compound containing one or more kinds of compounds selected from naphthalene compounds, biphenyl compounds and para-substituted benzene compounds as essential constituents is a further preferable example. Of the p-position-substituted benzene compounds, p-hydroxybenzoic acid, methylhydroquinone and 1-phenylethylhydroquinone are particularly preferable examples.

The following are exemplified as specific combinations of constituent components.

Wherein, Z is -Cl, -Br, a substituent selected from -CH _3, X is alkylene (C ₁ ~C _4), alkylidene, -O
It is a substituent selected from —, —SO—, —SO ₂ —, —S—, and —CO—.

Particularly preferred anisotropic melt phase forming polyesters for use in the present invention include repeating units containing naphthalene moieties such as 6-hydroxy-2-naphthoyl, 2,6-dihydroxynaphthalene and 2,6-dicarboxynaphthalene. It is contained in an amount of about 10 mol% or more. Preferred polyesteramides are those containing repeating units of the above-mentioned naphthalene moieties and moieties consisting of 4-aminophenol or 1,4-phenylenediamine. Specifically, it is as follows.

(1) A polyester essentially consisting of the following repeating units I and II.

This polyester contains about 10-90 mole% of Unit I and about 10-90.
It contains mol% of unit II. In one aspect unit I is about
It is present up to an amount of 65 to 85 mol%, preferably about 70 to 80 mol% (eg about 75 mol%). In another embodiment, the units II are present in much lower concentrations of about 15-35 mol%, preferably about 20-30 mol%. Further, at least some of the hydrogen atoms bonded to the ring are optionally selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and combinations thereof. It may be substituted with a selected substituent.

(2) A polyester consisting essentially of the following repeating units I, II and III.

This polyester contains about 30 to 70 mol% of Unit I. The polyester is preferably about 40-60 mol%
Unit I, about 20 to 30 mol% of unit II, and about 20 to 30 mol% of unit III. In addition, at least a part of the hydrogen atoms bonded to the ring may be an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen,
It may be substituted with a substituent selected from the group consisting of phenyl, substituted phenyl and combinations thereof.

(3) A polyester consisting essentially of the following repeating units I, II, III and IV: (In the formula, R means methyl, chloro, bromo or a combination thereof, and is a substituent for a hydrogen atom on the aromatic ring), and the unit I is about 20 to 60 mol%,
II in amounts of about 5 to 18 mol%, unit III in amounts of about 5 to 35 mol%, and unit IV in amounts of about 20 to 40 mol%. The polyester is preferably about 35-45 mole% of Unit I, about 10
Containing ~ 15 mol% Unit II, about 15-25 mol% Unit III, and about 25-35 mol% Unit IV. However, unit II
The total molarity of and III is substantially equal to the molarity of unit IV. In addition, at least a part of the hydrogen atoms bonded to the ring may be a group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and a combination thereof. It may be substituted with a substituent selected from This wholly aromatic polyester has 0.3w of pentafluorophenol at 60 ℃.
at least 2.0 dl / g when dissolved at a concentration of / v% eg
Logarithmic viscosities of 2.0 to 10.0 dl / g are generally indicated.

(4) A polyester consisting essentially of the following repeating units I, II, III and IV: III General formula O-Ar-O (wherein Ar is at least 1
A dioxyaryl unit represented by (meaning a divalent group containing one aromatic ring), (Wherein Ar ′ means a divalent group containing at least one aromatic ring), and the unit I is about 20 to 40 mol% and the unit II is 10 mol%. Above 50 mol%, unit III above 5 mol% and below about 30 mol% and unit IV above 5 mol%,
It is contained in an amount of about 30 mol% or less. This polyester is
Preferably, about 20-30 mol% (eg, about 25 mol%) of unit I, about 25-40 mol% (eg, about 35 mol%) of unit II, about 15
~ 25 mol% (eg, about 20 mol%) of unit III, and about 15
Contains ~ 25 mol% (eg, about 20 mol%) of unit IV. In addition, at least a part of the hydrogen atoms bonded to the ring may be a group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and a combination thereof. It may be substituted with a substituent selected from

Units III and IV have symmetrically arranged divalent bonds on one or more aromatic rings that connect these units to other units on either side within the polymer backbone (eg, on a naphthalene ring). When present, they are preferably symmetrical with respect to each other in the para position or arranged on a diagonal ring). However, asymmetric units such as those derived from resorcinol and isophthalic acid can also be used.

Preferred dioxyaryl units III are And a preferred dicarboxyaryl unit IV is Is.

(5) Polyester consisting essentially of the following repeating units I, II and III: II A dioxyaryl unit represented by the general formula O-Ar-O (wherein Ar represents a divalent group containing at least one aromatic ring), (Wherein Ar ′ means a divalent group containing at least one aromatic ring), and the unit I is about 10 to 90 mol% and the unit II is 5 to 5 mol%.
45 mol%, containing unit III in an amount of 5-45 mol%. The polyester preferably contains about 20-80 mol% Unit I, about 10-40 mol% Unit II, and about 10-40 mol% Unit III. More preferably, the polyester comprises about 60-80 mol% units I, about 10-20 mol% units.
II, and about 10-20 mol% of unit III. In addition, at least a part of the hydrogen atoms bonded to the ring may be a group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and a combination thereof. It may be substituted with a substituent selected from

Preferred dioxyaryl units II are And a preferred dicarboxyaryl unit III is Is.

(6) Polyesteramide consisting essentially of the following repeating units I, II, III and IV: (In the formula, A means a divalent group containing at least one aromatic ring or a divalent trans-cyclohexane group), III General formula Y-Ar-Z (wherein Ar is at least 1)
A divalent group containing one aromatic ring, Y means O, NH or NR, Z means NH or NR, respectively, and R means an alkyl group having 1 to 6 carbon atoms or an aryl group), IV general formula O-Ar'-O (wherein Ar 'means a divalent group containing at least one aromatic ring), and the unit I is about 10 to 90 mol% and the unit II is about 5%.
~ 45 mol%, about 5-45 mol% unit III, and unit IV
In an amount of about 0 to 40 mol%. In addition, at least a part of the hydrogen atoms bonded to the ring may be a group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and a combination thereof. It may be substituted with a substituent selected from

Preferred dicarboxyaryl units II are And the preferred unit III is And a preferred dioxyaryl unit IV is Is.

Further, the polymer forming the anisotropic molten phase of the present invention,
A part of one polymer chain is composed of the polymer segment forming the anisotropic melt phase described above, and the remaining part is composed of the thermoplastic resin segment not forming the anisotropic melt phase. Polymers are also included.

The above-mentioned liquid crystalline polyester is a high-strength material in combination with the self-reinforcing effect, and has a small linear expansion coefficient and a small molding shrinkage ratio, so that there is little dimensional deviation. It has low melt viscosity and good flowability, but it can withstand high temperatures of 200-240 ℃. It has good chemical resistance, weather resistance, and hot water resistance, is chemically extremely inert, and at the same time does not affect other substances.

The electric component substrate of the present invention is a plate-shaped molded product of an intimate mixture of the above-mentioned liquid crystalline polyester and a filler having a thermal conductivity of 300 ° k and 10 w / m · k or more, in which the filler is intimately mixed. As a result, the thermal conductivity is improved. The filler is one or more compounds selected from metal oxides, metal nitrides and metal carbides, specifically beryllium oxide,
Oxides and nitrides of elements up to the 7th column of each of Groups II, III, and IV of the Periodic Table, such as magnesium oxide, aluminum oxide, thulium oxide, zinc oxide, silicon nitride, boron nitride, aluminum nitride, and silicon carbide. Also, it is preferable to use one or more compounds selected from carbides.

The amount of the filler added varies depending on the particle size, specific surface area, surface activity, etc., but is 5 to 90% by volume, preferably 20 to 70% by volume, based on the total composition. The shape of the filler is not particularly limited, but is preferably fine. Such a filler improves the thermal conductivity of the substrate made of liquid crystalline polyester and assists in heat dissipation, and thus further improves the function of the substrate of the present invention.

The electric component substrate of the present invention is formed by extruding a close mixture of a liquid crystalline polyester and a filler having a thermal conductivity of 300 ° k and a heat conductivity of 10 w / m · k or more into a flat plate to form a flat plate, and then form a flat plate as usual. And a copper-clad laminated board, and after providing the necessary electrical circuits from this laminated board by the subtract method, which is generally used in the production of printed wiring boards, heat bending as normally used for molding plastics. It is formed into a desired shape by a processing method. The heating bending method includes not only simple bending but also drawing processing, for example, three-dimensional protrusion processing such as vacuum forming and press forming. The shape to be molded can be appropriately selected according to need, but it is good for bending, but if large deformation or extension is applied like deep drawing in vacuum molding, the electric circuit does not deform It needs to be shaped like this. In other words, it is necessary to provide an electric circuit in a portion that is not affected by the deformation. In the present invention, the functional portion provided by heating and bending means a component portion used for various purposes, and specifically, a mounting portion to a housing of an electric device, a board reinforcing portion, a component protecting portion, a component mounting portion, etc. Is. For example, to protect ICs, LSIs, and other parts mounted on the board, provide a convex part around the board at the height of those parts, or a part protection part that says that the mounting part of the part is recessed in a tray, a battery, It is possible to form a component mounting portion such as a recess in the insertion portion of the motor, or a substrate reinforcing portion such that a rib is provided at a peripheral portion or a central portion in the case of a large substrate.
In the past, the housing was provided with a convex portion and the substrate was screwed thereto. However, if the mounting portion is formed by bending the substrate, it is not necessary to provide the housing with the convex portion.

Bending should be done before mounting parts such as ICs.

Further, it is also possible to attach a functional body of another resin to the substrate by the outsert molding method at the same time as bending the substrate with the same molding machine.

The extruded plate of liquid crystal polyester has directionality, and the strength is relatively low in the direction perpendicular to the extruded direction, so that a plurality of extruded plates are stacked so that their extruded directions are orthogonal to each other like a veneer plate. It is better to use a laminate that cancels the directivity.

In order to further improve the performance of the electric component substrate of the present invention, the liquid crystal polyester and the thermal conductivity are 10 w / m.
In addition to the above-mentioned fillers, various inorganic fillers may be added to the intimate mixture with the filler having k or more, depending on the purpose. Examples of the inorganic substance include substances added to general thermoplastic resins and thermosetting resins, that is, general inorganic fibers such as glass fiber, carbon fiber, metal fiber, ceramic fiber, boron fiber, potassium titanate fiber, and asbestos. ,
Calcium carbonate, aluminum hydroxide, talc powder, mica, glass flakes, glass beads, quartz powder, silica sand,
Wollastonite, various metal powders, carbon black,
It includes powder substances such as barium sulfate and calcined gypsum, whiskers and metal whiskers. It is also preferable to use a conductive filler such as fibrous or powdery carbon because it has an effect of preventing electrostatic charge.

The larger the blending amount of these fillers, the better, but it is preferably 70% by weight or less based on the entire mixture with the resin from the viewpoint of moldability and the like.

Further, known substances added to general thermoplastic resins and thermosetting resins, that is, plasticizers, stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, coloring of dyes and pigments, etc. Agents, lubricants for improving fluidity and releasability, crystallization accelerators (nucleating agents) and the like can be appropriately used depending on the required performance.

Next, the shape of the substrate of the present invention is shown as a model in FIG.
Reference numeral 1 is a substrate of the present invention, 2 is a recess for inserting a dry battery, 3 is a motor insertion portion, 4 is an electronic component, 5 is an electric circuit, and 6 is a housing of an electric device.

〔The invention's effect〕

As is clear from the above description, the present invention utilizes the characteristics of liquid crystal polyester such as high strength, heat resistance, and low linear expansion coefficient, and at the same time, the liquid crystal polyester is provided with a filler having a specific thermal conductivity. By intimately mixing and imparting excellent thermal conductivity, it has become possible to provide an electric component board with an electric circuit having high dimensional accuracy and function and having excellent thermal conductivity.

Further, since the liquid crystalline polyester has a high elastic modulus, for example, if the dry battery insertion part is formed according to the present invention as shown in FIG. 1, its holding property is good, and if the motor insertion part is formed, the motor can be elastically held. There is also an advantage that the assembly process can be simplified. In addition, the electric component substrate of the present invention can be used in many ways, and it is considered that it will greatly contribute to the rationalization and simplification of the production of electric components and electronic components.

〔Example〕

 Examples of the present invention will be described below.

Example 1 A resin A described later having a weight average molecular weight of 20,000 has an average of 80
Micron α-alumina (Thermal conductivity is 36 W / m at 300 ° K.
K) was mixed at 35% by volume and extruded at 290 ° C to form pellets, which was then extruded with a vacuum bend and a gear pump at the mouthpiece to extrude a 0.4 mm thick plate at 50 cm / min. The sheet was molded by taking it up with a take-up roll heated to ℃. The thermal conductivity of this plate is 300 ° K
It was 1.5 w / m · K. The plate did not deform at all when heated to 200 ° C.

This extruded sheet is roughened by double-sided sandblasting, three ply boards are laminated so that the extruding directions are orthogonal to each other, laminated with an epoxy adhesive, and then cut into 15 cm squares.
A copper foil of μm was laminated with the same epoxy adhesive. Then, an unnecessary portion of the copper foil was removed by etching by a usual method, and a circuit was formed in a part of a 12-cm square in the central portion 1.5 cm away from each side. This was heated to about 200 ° C with a far-infrared rod-shaped heater provided in a quadrilateral shape so that the heating was concentrated especially in the peripheral part, and vacuum-molded to form a tray with a depth of 1 cm.

The circuit part did not extend, only the peripheral part extended and was molded into a tray shape.

ICs, connectors and other electrical parts were attached to the inner part of the tray in the usual way. The electric component substrate having the electric circuit thus obtained is not only easy to make,
The strength, dimensional accuracy, heat transfer, heat resistance, etc. were good, and as a result of a vibration test, it was confirmed that electrical parts could be sufficiently protected.

Examples 2 to 6 Instead of the resin A of Example 1, the resins B, C, D, E and F described later are used.
The same operation as in Example 1 was carried out except that was used to form a tray-shaped molded part having the same shape. An electric circuit was formed in the same manner as in Example 1, and after bending, an IC, a connector and other electric parts were attached to the inner side of the tray.

This electric component substrate also had good required performance as in Example 1.

The resins A, B, C, D, E and F used had the following constitutional units.

A specific method for producing the above resins A, B, C, D, E and F will be described below.

<Resin A> 1081 parts by weight of 4-acetoxybenzoic acid, 6-acetoxy-
2-naphthoic acid 460 parts by weight, isophthalic acid 166 parts by weight, 1,
194 parts by weight of 4-diacetoxybenzene was charged into a reactor equipped with a stirrer, a nitrogen introducing tube and a distilling tube, and the mixture was heated to 260 ° C under a nitrogen stream. While distilling acetic acid from the reactor, the mixture was vigorously stirred at 260 ° C. for 2.5 hours and then at 280 ° C. for 3 hours. Furthermore, after raising the temperature to 320 ° C. and stopping the introduction of nitrogen, the pressure inside the reactor was gradually reduced and after 15 minutes the pressure was lowered to 0.1 mmHg, and stirring was continued for 1 hour at this temperature and pressure.

The resulting polymer had an inherent viscosity of 5.0 as measured in pentafluorophenol at a concentration of 0.1% by weight at 60 ° C.

<Resin B> 1081 parts by weight of 4-acetoxybenzoic acid, 489 parts by weight of 2,6-diacetoxynaphthalene, and 332 parts by weight of terephthalic acid were charged into a reactor equipped with a stirrer, a nitrogen introducing tube and a distilling tube,
The mixture was heated to 250 ° C under a stream of nitrogen. While distilling acetic acid from the reactor, at 250 ° C for 2 hours, then at 280 ° C.
Stir vigorously for 2.5 hours. Furthermore, after raising the temperature to 320 ° C and stopping the introduction of nitrogen, the pressure inside the reactor was gradually reduced and after 30 minutes the pressure was lowered to 0.2 mmHg, and at this temperature and pressure 1.5
Stir for hours.

The polymer obtained had an inherent viscosity of 2.5, measured in pentafluorophenol at a concentration of 0.1% by weight and at 60 ° C.

<Resin C> 4-acetoxybenzoic acid 1261 parts by weight, 6-acetoxy-
691 parts by weight of 2-naphthoic acid was charged into a reactor equipped with a stirrer, a nitrogen introducing tube and a distilling tube, and the mixture was heated to 250 ° C under a nitrogen stream. While distilling acetic acid from the reactor, the mixture was vigorously stirred at 250 ° C. for 3 hours and then at 280 ° C. for 2 hours. Furthermore, after raising the temperature to 320 ° C and stopping the introduction of nitrogen, the pressure inside the reactor was gradually reduced and after 20 minutes the pressure was reduced to 0.1 m.
The pressure was lowered to mHg, and the mixture was stirred at this temperature and pressure for 1 hour.

The polymer obtained had an inherent viscosity of 5.4 measured in pentafluorophenol at a concentration of 0.1% by weight at 60 ° C.

<Resin D> 1612 parts by weight of 6-acetoxy-2-naphthoic acid, 290 parts by weight of 4-acetoxyacetanilide, 249 parts by weight of terephthalic acid, 0.4 parts by weight of sodium acetate, a reactor equipped with a stirrer, a nitrogen introducing pipe and a distilling pipe. Charged in and heated the mixture to 250 ° C. under a stream of nitrogen. While distilling acetic acid from the reactor, the mixture was vigorously stirred at 250 ° C. for 1 hour and then at 300 ° C. for 3 hours. Furthermore, after raising the temperature to 340 ° C. and stopping the introduction of nitrogen, the pressure in the reactor was gradually reduced and the pressure was reduced to 0 after 30 minutes.
It was lowered to 2 mmHg, and stirred at this temperature and pressure for 30 minutes.

The polymer obtained had an inherent viscosity of 3.9 as measured in pentafluorophenol at a concentration of 0.1% by weight at 60 ° C.

<Resin E> 4-acetoxybenzoic acid 1056 parts by weight, terephthalic acid 324
Parts by weight, 356 parts by weight of 4,4'-dihydroxybiphenyl were charged into a reactor equipped with a stirrer, a nitrogen inlet tube and a distillation tube, and the mixture was heated to 300 ° C under a nitrogen stream. Distill acetic acid from the reactor for 2 hours at 300 ° C, then 400
The mixture was vigorously stirred at ℃ for 3 hours. Furthermore, after raising the temperature to 430 ° C and stopping the introduction of nitrogen, the pressure inside the reactor was gradually reduced and after 30 minutes the pressure was lowered to 0.2 mmHg.
Stir for 1.5 hours.

The polymer obtained had an inherent viscosity of 7.2, measured in pentafluorophenol at a concentration of 0.1% by weight at 60 ° C.

<Resin F> 4-acetoxybenzoic acid 1056 parts by weight, terephthalic acid 259
Parts by weight, 65 parts by weight of isophthalic acid, and 356 parts by weight of 4,4′-dihydroxybiphenyl were charged into a reactor equipped with a stirrer, a nitrogen introducing tube and a distilling tube, and this mixture was mixed under a nitrogen stream.
Heated to 270 ° C. While distilling acetic acid from the reactor, 2
The mixture was vigorously stirred at 70 ° C for 2 hours and then at 300 ° C for 2.5 hours. Furthermore, after raising the temperature to 350 ° C and stopping the introduction of nitrogen, the pressure inside the reactor was gradually reduced and after 30 minutes the pressure was reduced to 0.2 mmHg.
And stirred at this temperature and pressure for 1.5 hours.

The resulting polymer had an inherent viscosity of 5.6 as measured in pentafluorophenol at a concentration of 0.1% by weight at 60 ° C.

[Brief description of drawings]

 FIG. 1 is an explanatory view of the substrate of the present invention. 1: Substrate 2: Battery insertion recess 3: Motor insertion part 4: Electronic component 5: Electric circuit 6: Housing

Claims (7)

[Claims] 1. A melt-moldable thermotropic liquid crystalline polyester which exhibits anisotropy when melted and has a thermal conductivity of 300 ° K.
It is a plate-shaped molded product of an intimate mixture with a filler of 10 w / m · k or more, and is three-dimensionally formed by heating and bending the flat plate portion with the electric circuit and the flat plate portion without the electric circuit. An electric component substrate, which comprises an integrated functional unit. 2. The electric component board according to claim 1, wherein the filler is one or more compounds selected from the group consisting of metal oxides, metal nitrides and metal carbides. 3. The filler is one or more compounds selected from the group consisting of oxides, nitrides and carbides of elements up to the seventh column of each of Groups II, III and IV of the periodic table. The electric component board according to claim 1. 4. The filler is one or more compounds selected from the group consisting of beryllium oxide, magnesium oxide, aluminum oxide, thulium oxide, zinc oxide, silicon nitride, boron nitride, aluminum nitride and silicon carbide. The electric component board according to claim 1. 5. The electric component board according to claim 1, wherein the functional portion is an attachment portion to an electric device housing, a board reinforcing portion, a component protection portion, and a component attachment portion. 6. The electric component substrate according to claim 1, wherein the heating bending process is a heating drawing process. 7. The electric component substrate according to claim 6, wherein the heat drawing is vacuum forming or press forming.