JP2003268089A - Liquid crystalline polyester resin for molded product and molded circuit board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystalline polyester resin highly adhesive to metal and intended for thin-walled precision molded products with high dimensional stability through making the best use of its high fluidity, heat resistance and mechanical properties, and to provide molded circuit boards having circuit adhesiveness, fine patterning effect, heat resistance and dimensional stability suitable to small-sized precision electronic circuit equipment. <P>SOLUTION: The liquid crystalline polyester resin for molded products is composed of specific structural units including those derived from ethylene glycol. The molded product is such one that the surface thereof is provided with a metallic film by either one of means i.e., sputtering, vacuum deposition or ion plating after subjected to plasma treatment. The three-dimensional molded circuit board is made by forming a metallic film by the above method on the surface of a molded product injection-molded using the resin and then carrying out a circuit patterning or the like by laser beam irradiation. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystalline polyester resin for molded products which has improved metal film adhesion and is excellent in fluidity, heat resistance and mechanical properties, and a molded circuit board using the same. .

[0002]

2. Description of the Related Art Thermoplastic resins take advantage of their excellent characteristics and are used as injection molding materials for mechanical and mechanical parts, electrical and electronic parts,
It is used in a wide range of fields such as automobile parts. In recent years, there has been an increasing demand for higher performance of the thermoplastic resins used in this way, and many polymers having various new properties have been developed. Among them, a liquid crystalline resin having an optical anisotropy when melted, which is characterized by parallel arrangement of molecular chains, has been drawing attention because it has excellent fluidity, dimensional stability, and mechanical properties.

Liquid crystal resins are excellent in heat resistance, chemical resistance, low linear expansion coefficient, flame retardancy, mechanical strength and elastic modulus, and electrical characteristics. It is used in a wide range of fields such as machine parts.

Further, the liquid crystalline resin has contributed to miniaturization of electric and electronic parts due to its excellent thin-wall fluidity. However, for these electric / electronic parts, it was necessary to directly adhere a metal film to the surface of the molded product in order to impart conductivity such as a circuit pattern or an electromagnetic wave shield, or to impart light reflectivity. However, the liquid crystalline resin has a low adhesion to the metal film and cannot secure sufficient quality.

Regarding the solder heat resistance, which is closely related to the electronics field, the liquid crystalline resin is in the highest class among plastics. Its characteristics are that unlike polyethylene terephthalate and polybutylene terephthalate, the orientation of the molecules is observed even in the molten state, there is little entanglement of the oriented molecules, it is oriented in one direction only by receiving a slight shear, and it is crystallized even in a liquid state. It has a liquid crystallinity, and even if the temperature is lowered, the orientation of the molecules in the molten state is fixed as it is, so that, for example, moldability such as thin fluidity and mechanical properties such as strength and elastic modulus. Alternatively, various excellent properties such as dimensional stability and heat resistance are exhibited. In addition, due to excellent moldability, it has been attempted to use a molded product obtained by molding a liquid crystalline resin as a resin molded circuit board such as MID (Molded Interconnect Device).

However, as can be seen from the fact that the liquid crystalline resin is excellent in heat resistance and chemical resistance, the molecular chain is extremely rigid and linear, so it is chemically extremely inactive, and it is Surface modification is difficult. Therefore, after performing the plasma treatment, a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method (P
When the metal film was formed by the VD method), only a low adhesion strength of 0.20 N / mm or less was obtained, and the quality was not suitable for practical use.

For example, in Japanese Unexamined Patent Publication No. 2000-216534, a metal film is formed on a surface of a molded article of a liquid crystalline resin composed of a p-hydroxybenzoic acid residue and a 2,6-hydroxynaphthoic acid residue by a sputtering method. Although it is described that it is formed, even if such a liquid crystalline resin is used, the adhesiveness to a metal is still insufficient, and there is a problem that it is easily peeled off even if a metal film is formed by plating or vapor deposition. .

When a molded product produced by molding a liquid crystalline resin is used as a circuit board, the surface of the molded product is chemically or physically treated in order to increase the adhesion strength with the metal film forming the circuit. Roughening is performed. For example, Japanese Patent Publication No. 7-24328 discloses a technique in which a molded body formed of a liquid crystalline polyester resin is subjected to an etching treatment, and then a surface metal coating treatment is performed by any one of sputtering, ion plating and vacuum deposition. Is disclosed. Further, Japanese Patent No. 2714440 discloses that
A technique in which a molded body formed by molding a liquid crystalline polyester resin is subjected to surface metal coating treatment by any one of sputtering, ion plating, and vacuum deposition while heating in a vacuum chamber to a surface temperature of 60 ° C or higher. Is disclosed.

In the former Japanese Patent Publication No. 7-24328, the surface of the molded body is roughened by performing an etching treatment, and the adhesion force is increased based on the mechanical anchoring effect of the metal film against the irregularities of the rough surface. It's about to get. However, if the surface of the molded body is roughened, it becomes difficult to form a fine line of a circuit formed on the surface of the molded body. For example, the line width of the circuit is 0.25 mm, the space width between adjacent circuits is 0.25 mm.
Since there is a limit of about mm, there is a problem that it is not possible to form a circuit of a fine fine line having a line width of 0.1 mm or less and a space width of 0.1 mm or less.

Further, in the latter Japanese Patent No. 2714440, even if the surface metal coating treatment is performed while heating the molded body to a surface temperature of 60 ° C. or more, a chemical bond is formed between the liquid crystalline polyester resin and the metal film. Since it does not intervene, it is difficult to obtain high adhesiveness of the metal film, and there is a problem in adhesiveness especially after receiving a heat load.

JP-A-1-252657 discloses a resin composition composed of a liquid crystal polyester and a thermoplastic resin, which is excellent in heat resistance, fluidity and mechanical properties, a molded product thereof, and the like. In addition, JP-A-1-292
Japanese Patent No. 058 discloses a thermoplastic resin composition comprising liquid crystal polyester and polyphenylene sulfide, which is excellent in heat resistance, moldability, fluidity, hydrolysis resistance, and mechanical properties. There is no disclosure of performing a film forming process.

[0012]

SUMMARY OF THE INVENTION The present invention solves the above problems and provides excellent adhesion between a liquid crystalline polyester resin and a metal. Further, the liquid crystalline polyester resin has excellent fluidity, heat resistance and mechanical properties. To obtain a thin liquid crystal polyester resin for molded products that is excellent in precise dimensional stability, and has circuit adhesion and fine patterning properties that are particularly suitable for small precision electronic circuit devices, heat resistance, and dimension. An object is to obtain a molded circuit board having excellent stability.

[0013]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems. That is, the present invention provides (1) a liquid crystalline polyester resin for a molded article comprising the following structural units (I), (II), (III) and (IV), wherein the molded article has a plasma on the surface of the molded article. The present invention provides a liquid crystalline polyester resin for a molded article, which comprises a metal film formed by any one of sputtering, vacuum deposition, and ion plating after the treatment.

[0014]

[Chemical 5] (However, R1 in the formula is

[0015]

[Chemical 6] R2 represents one or more groups selected from

[0016]

[Chemical 7] R3 represents one or more groups selected from

[0017]

[Chemical 8] And one or more groups selected from However, in the formula, X represents a hydrogen atom or a chlorine atom. Further, the present invention provides the following liquid crystalline polyester resin for molded products, liquid crystalline polyester resin composition for molded products and molded circuit boards. (2) The liquid crystalline polyester resin comprises the structural units (I), (II), (III) and (IV), and the total of the structural units (I) and (II) is a structural unit.
30 to 95 mol% based on the total of (I), (II) and (III), 70 to 5 mol% of the structural unit (III) based on the total of structural units (I), (II) and (III) % Of the structural unit (I) (I
The molar ratio [(I) / (II)] to I) is 75/25 to 95 /
5 is a liquid crystalline polyester resin for molded articles according to (1), and (3) 100 parts by weight of the liquid crystalline polyester resin according to (2) or (10) a filler 10
To 400 parts by weight of the liquid crystalline polyester resin composition for molded articles, (4) the filler has a fiber diameter of 3 to 15 μm and a weight average fiber length of 0.01 to 0.6 m.
m is a glass fiber, and the content thereof is 10 to 150 parts by weight relative to 100 parts by weight of the liquid crystalline polyester resin, (3) The liquid crystalline polyester resin composition for molded articles, ( 5) Filler has a fiber diameter of 0.05
Is 5 μm and the weight average fiber length is 1 to 100 μm, and the content thereof is the liquid crystalline polyester resin 100.
10 to 150 parts by weight based on parts by weight, (3) The liquid crystalline polyester resin composition for molded articles, and (6) (1) to (5) A molded circuit board, characterized in that a metal film is formed on the surface of a molded product molded using the liquid crystalline polyester resin composition for use in the molding, and a circuit is formed on the metal film, (7) Surface of the molded product The molded circuit board according to (6), characterized in that the metal film formed on the substrate is subjected to circuit patterning by laser light irradiation to form a circuit.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid crystalline polyester resin used in the present invention has the following structural units (I), (II), (III) and (IV)
Is a polyester composed of the structural unit of.

[0019]

[Chemical 9] (However, R1 in the formula is

[0020]

[Chemical 10] R2 represents one or more groups selected from

[0021]

[Chemical 11] R3 represents one or more groups selected from

[0022]

[Chemical 12] And one or more groups selected from However, in the formula, X represents a hydrogen atom or a chlorine atom. ) The total of structural units (II) and (III) and structural unit (IV)
Are preferably substantially equimolar.

The structural unit (I) is a structural unit formed from p-hydroxybenzoic acid and / or 2-hydroxy-6-naphthoic acid, and the structural unit (II) is 4,4'-dihydroxybiphenyl, 3, 3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-
Bis (4-hydroxyphenyl) propane and 4,4
A structural unit formed from one or more aromatic dihydroxy compounds selected from ′ -dihydroxydiphenyl ether, a structural unit (III) is a structural unit formed from ethylene glycol, and a structural unit (IV) is terephthalic acid, isophthalic acid, , 4'-Diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4 Each of one or more structural units formed from an aromatic dicarboxylic acid selected from ′ -dicarboxylic acid and 4,4′-diphenyl ether dicarboxylic acid is shown. Of these, R2

[0024]

[Chemical 13] And R3 is

[0025]

[Chemical 14] Are particularly preferred. The structural unit (I), (II),
The copolymerization amount of (III) and (IV) is arbitrary. However, in order to exert the characteristics of the present invention, the following copolymerization amount is preferable.

That is, the above structural units (I), (II), (III)
In the case of a copolymer consisting of and (IV), the above structural unit
The total of (I) and (II) is structural units (I), (II) and (III)
30 to 95 mol% is preferable relative to the total of 40 to 9
3 mol% is more preferable. Further, the structural unit (III) is preferably 70 to 5 mol%, and more preferably 60 to 7 mol% based on the total of the structural units (I), (II) and (III). Also,
The molar ratio [(I) / (II)] of the structural unit (I) to (II) is preferably 75/25 to 95/5, more preferably 7
It is 8/22 to 93/7. Further, the structural unit (IV) is preferably substantially equimolar to the total of the structural units (II) and (III).

The liquid crystalline polyester resin contains 3,3'-, in addition to the components constituting the structural units (I) to (IV).
Aromatic dicarboxylic acids such as diphenyldicarboxylic acid and 2,2′-diphenyldicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, Chlorhydroquinone, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone, 3,4 '
-Aromatic diol such as dihydroxybiphenyl, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, aliphatic such as 1,4-cyclohexanedimethanol, fat Aromatic hydroxycarboxylic acids such as cyclic diols and m-hydroxybenzoic acid and p
-Aminophenol, p-aminobenzoic acid and the like can be further copolymerized to the extent that the liquid crystallinity is not impaired.

The liquid crystalline polyester resin used in the present invention can have an inherent viscosity measured in pentafluorophenol. At that time, at a concentration of 0.1 g / dl, 60 ° C
It is preferably 0.5 to 15.0 dl / g as measured by
1.0 to 3.0 dl / g is particularly preferable.

The melt viscosity of the liquid crystalline polyester resin used in the present invention is preferably 0.5 to 500 Pa · s, more preferably 1 to 250 Pa · s. Further, when it is desired to obtain a composition having excellent fluidity, the melt viscosity is 5
It is preferably 0 Pa · s or less.

The melt viscosity is the melting point (Tm) +10.
It is a value measured by a Koka type flow tester under conditions of a shear rate of 1,000 (1 / sec) under conditions of ° C.

Here, the melting point (Tm) is the endothermic peak temperature (T) observed in the differential calorimetric measurement when the polymerized polymer is measured at a temperature rising condition from room temperature to 20 ° C./min.
After the observation of m1), the temperature was maintained at Tm1 + 20 ° C for 5 minutes, then once cooled to room temperature under the temperature lowering condition of 20 ° C / min, and then measured again under the temperature rising condition of 20 ° C / min. Refers to the endothermic peak temperature (Tm2).

The liquid crystalline polyester resin preferably has a melting point of 180 to 380 ° C., more preferably 210 to 36 in order to further develop the characteristics of the present invention.
It is 0 ° C.

The method for producing the above-mentioned liquid crystalline polyester resin used in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method.

For example, in the production of the above liquid crystalline polyester resin, the following production method is preferably mentioned. (1) aromatic acetoxycarboxylic acid such as p-acetoxybenzoic acid and 4,4′-diacetoxybiphenyl,
Diacylated aromatic dihydroxy compounds such as diacetoxybenzene and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid,
Polyester polymers such as polyethylene terephthalate, oligomers or bis (β-hydroxyethyl)
A method for producing a liquid crystalline polyester from a bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as terephthalate by a deacetic acid condensation polymerization reaction. (2) aromatic hydroxycarboxylic acid such as p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl,
Aromatic dihydroxy compounds such as hydroquinone and 2,
Aromatic dicarboxylic acids such as 6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid, polyester polymers such as polyethylene terephthalate, oligomers or bis (β-hydroxyethyl) esters of aromatic dicarboxylic acids such as bis (β-hydroxyethyl) terephthalate A method for producing a liquid crystalline polyester by reacting acetic anhydride with and acylating a phenolic hydroxyl group, followed by deacetic acid polycondensation reaction.

Although the polycondensation reaction of the liquid crystalline polyester resin proceeds without a catalyst, it is necessary to use a metal compound such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, or magnesium metal as a catalyst. You can also

In the present invention, it is preferable to use a filler for the liquid crystalline polyester resin for molded articles, which is not particularly limited, but may be fibrous, plate-like, powder-like,
Non-fibrous fillers such as granules can be used. Specifically, for example, glass fibers, PAN-based or pitch-based carbon fibers, stainless fibers, metal fibers such as aluminum fibers and brass fibers, aromatic polyamide fibers, organic fibers such as liquid crystal polyester fibers, gypsum fibers, ceramic fibers,
Asbestos fibers, zirconia fibers, alumina fibers, silica fibers, titanium oxide fibers, silicon carbide fibers, rock wool, potassium titanate whiskers, barium titanate whiskers, aluminum borate whiskers, silicon nitride whiskers, and other fibrous and whisker-like fillers. , Mica, talc,
Powders of kaolin, silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, titanium oxide, zinc oxide, calcium polyphosphate, graphite, etc.,
Granular or plate-shaped fillers can be mentioned. The surface of the above-mentioned filler used in the present invention may be treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.) or another surface treatment agent for use.

The amount of the above-mentioned filler added is usually preferably 10 to 400 parts by weight, more preferably 30 to 200 parts by weight, particularly preferably 30 to 100 parts by weight, based on 100 parts by weight of the liquid crystalline polyester resin. is there.

In the present invention, glass fiber is particularly preferably used in the above filler. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and for example, long fiber type or short fiber type chopped strands, milled fiber or the like can be selected and used. Also, two or more of these may be used in combination. As the glass fiber used in the present invention,
A weakly alkaline one is excellent in mechanical strength and can be preferably used. Further, the glass fiber is preferably treated with a coating or sizing agent such as an epoxy type, urethane type or acrylic type, and an epoxy type is particularly preferable. Further, it is preferably treated with a silane-based or titanate-based coupling agent or other surface treatment agent, and an epoxysilane- or aminosilane-based coupling agent is particularly preferable.

The fiber diameter of the glass fiber used for producing the liquid crystalline polyester resin composition for molded articles of the present invention has a reinforcing effect,
From the viewpoint of fluidity during molding and metal film adhesion, 3 to 15 μ
It is preferably m, and more preferably 5 to 15 μm.

In the liquid crystalline polyester resin composition for molded articles of the present invention, the fiber length distribution of glass fibers may affect the effect of the present invention. That is, the weight average fiber length of the glass fibers in the liquid crystalline polyester resin composition for molded articles is from 0.01 to 0.6 mm from the viewpoint of the reinforcing effect, the fluidity at the time of molding, and the metal film adhesion. Preferably, 0.1-0.4 mm is more preferable.

The method for measuring the fiber length distribution of the glass fiber was as follows: After about 5 g of pellets of the liquid crystalline polyester resin composition for molded articles was ashed in a crucible, about 100 mg of the remaining glass fiber was sampled, Disperse in 100 cc of soap water. Then, the dispersion is used for 1-2 with a spoid.
Place the drops on a glass slide, observe under a microscope and take a picture. The fiber length of the glass fiber photographed is measured. The measurement is performed 500 times, and a fiber length distribution chart is prepared at intervals of 0.010 mm. The weight average fiber length can be calculated from the following formula based on this distribution chart.

Lw = (ΣLi2Ni) / (ΣLiNi) (Lw: weight average fiber length, Li: fiber length at intervals of 0.10 mm, number of Ni: Li) Glass in the liquid crystalline polyester resin composition for molded articles of the present invention The content of fibers is 10
It is 10 to 150 parts by weight, more preferably 25 to 100 parts by weight, and particularly preferably 35 to 0 parts by weight.
~ 80 parts by weight. When it is at least the above lower limit, excellent reinforcing effect and heat resistance will be obtained, and when it is at most the above upper limit, more excellent fluidity and metal film adhesion will be obtained.

The above glass fiber is particularly suitable as a filler for a molded substrate intended for miniaturization and precision, such as a precision electronic circuit substrate for a compact precision electronic circuit device described later.

In the present invention, whiskers can be particularly preferably used as the filler. As the whiskers, there are whiskers such as zinc oxide, alumina, calcium titanate, aluminum silicate, calcium silicate, magnesium borate, calcium carbonate, magnesium oxalphate, etc., in addition to the potassium titanate whiskers mentioned above, and particularly aluminum borate whiskers. Are excellent in moldability, affinity with the liquid crystalline polyester resin composition, reinforcing effect and surface smoothness, and are preferable. Further, two or more kinds of these materials may be mixed and used, and an effect combining affinity with a liquid crystalline polyester resin composition characterized by each material, reinforcing effect, or surface smoothness can be expected.

From the viewpoint of fluidity at the time of molding, adhesion to a metal film, and surface smoothness of a molded product, the diameter of these whiskers is preferably 0.05 to 5 μm, more preferably 0.1 to 3 μm. And the weight average fiber length of the whiskers is 1
˜100 μm is preferable, and 5-70 μm is more preferable.

The content of whiskers is preferably 10 to 150 parts by weight, more preferably 25 to 100 parts by weight, and particularly preferably 35 to 80 parts by weight, based on 100 parts by weight of the liquid crystalline polyester resin. When it is at least the above lower limit, excellent reinforcing effect and heat resistance will be obtained, and when it is at most the above upper limit, more excellent fluidity, metal film adhesion and surface smoothness of the molded article will be obtained.

The above whisker is not only a miniaturized precision electronic circuit board for a small precision electronic circuit device described later, but also a circuit is further miniaturized to have a line width of 0.1 mm or less and a space width of 0.1 mm or less. Therefore, it is suitable as a filling material for a molded substrate for achieving ultra-compact and ultra-precision.

Further, the liquid crystalline polyester resin for molded articles of the present invention includes an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and their substitution products), an ultraviolet absorber (for example, resorcinol). , Salicylates, benzotriazole, benzophenone, etc.), phosphite, hypophosphite, etc., colorants, lubricants, dyes (eg, nigrosine) and pigments (eg, cadmium sulfide, phthalocyanine, etc.), colorants, release agents Molding agent (Montanic acid and its salts,
Its ester, its half ester, stearyl alcohol, stearamide, polyethylene wax, etc.), carbon black as a conductive agent or colorant,
Crystal nucleating agent, plasticizer, flame retardant (eg, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, magnesium hydroxide, melamine and cyanuric acid or its salt, red phosphorus, etc.), flame retardant aid, sliding property improvement Agents (graphite, fluororesin), usual additives such as antistatic agents, and other polymers can be added to further impart predetermined characteristics.

The liquid crystalline polyester resin composition for molded articles of the present invention is usually produced by a known method. For example, it is prepared by premixing the liquid crystal polyester resin with necessary additives and fillers, supplying the mixture to an extruder or the like, and sufficiently melting and kneading the mixture. In addition, when a filler is added, in order to control the fiber length of the filler, preferably, the liquid crystalline polyester resin and the additive are charged from the source of the extruder, and the filler is supplied to the extruder using a side feeder. It is adjusted by doing.

The thus obtained liquid crystalline polyester resin composition for molded articles is excellent in fluidity, heat resistance and mechanical properties, and after the surface of the molded article is subjected to plasma treatment, it is subjected to sputtering, vacuum deposition, ion plating. It has excellent metal film adhesion when a metal film is formed by any one of the coating methods, and thus is particularly suitable for a molded product subjected to such a treatment.

The molding method for molding a molded article can be processed into a three-dimensional molded article by a usual molding method (injection molding, extrusion molding, blow molding, press molding, injection press molding, etc.), and particularly Taking advantage of its excellent fluidity, it can be preferably applied to a molded product having a thin portion of 1.0 mm or less. Among them, it is particularly suitable for use in injection molding, and is suitable for various machine / mechanical parts, automobile parts, particularly electric / electronic parts.

Next, FIG. 1 shows a method for producing a molded circuit board using the molded product of the present invention thus obtained.

FIG. 1A shows a molded article 1 in which a liquid crystalline polyester resin composition filled with glass fibers or whiskers is injection molded into various three-dimensional shapes.

From the viewpoint of the reinforcing effect of the molded product 1, the fluidity at the time of molding, and the adhesion of the metal film, the line width of 0.25 on this surface.
In the case of forming a circuit having a space of 0.25 mm or less and a space width of 0.25 mm or less, the fiber diameter of the glass fiber is preferably 3 to 15 μm, more preferably 3 to 10 μm, and the weight average fiber length is 0.01 to 0. 6 mm is preferable, and 0.1 to
0.4 mm is more preferable, and the content of the glass fiber is 10 to 15 with respect to 100 parts by weight of the liquid crystalline polyester resin.
0 parts by weight is preferable, and 25 to 100 parts by weight is more preferable.

In the case of whiskers, the whisker diameter is preferably 0.05 to 5 μm, and the average fiber length is 1 to 100.
μm is preferable, and the content of whiskers is preferably 10 to 150 parts by weight, and more preferably 25 to 100 parts by weight, based on 100 parts by weight of the liquid crystalline polyester resin.

In particular, when forming a fine circuit having a line width of 0.1 mm or less and a space width of 0.1 mm or less,
Whiskers are preferable because they are superior in surface smoothness to glass fibers, have good removability of the metal film at the edge portion of the circuit pattern due to laser light irradiation, which will be described later, and improve the circuit pattern dimensional accuracy. At this time, the whisker diameter is preferably 0.1 to 3 μm, the average fiber length is preferably 5 to 70 μm, and the whisker content is preferably 25 to 100 parts by weight with respect to 100 parts by weight of the liquid crystalline polyester resin, and 35-8
0 weight part is more preferable.

When forming a fine circuit having a line width of 0.05 mm or less and a space width of 0.05 mm or less,
The whisker diameter is preferably 0.05 to 2 μm, the average fiber length is preferably 3 to 50 μm, and the whisker content is 25 to 10 parts by weight with respect to 100 parts by weight of the liquid crystalline polyester resin.
0 parts by weight is preferable, and 35 to 80 parts by weight is more preferable.

In forming a metal film on the surface of the thus obtained molded article of the present invention, the surface of the molded article is first plasma-treated to activate the surface of the molded article. FIG. 1B shows a molded product 2 whose surface is plasma-treated and activated (not visible). The plasma processing can be performed using a plasma processing apparatus in which a pair of electrodes are arranged to face each other in a chamber, a high frequency power source is connected to one electrode, and the other electrode is grounded. And when plasma-treating the surface of the molded product,
The molded product is set on one of the electrodes between the electrodes, the chamber is evacuated to reduce the pressure to about 10 ^-4 Pa,
A chemically active gas such as N ₂ or O ₂ is introduced and circulated in the chamber, and the gas pressure in the chamber is set to 8 to 15 P.
After controlling to a, a high frequency power source applies a high frequency voltage (RF: 13.56 MHz) between the electrodes for about 10 to 100 seconds.

At this time, the active gas in the chamber is excited by the gas discharge phenomenon due to the high-frequency glow discharge between the electrodes, plasma such as cations and radicals is generated, and cations and radicals are formed in the chamber. . The surface of the molded product can be activated by collision of these cations and radicals with the surface of the molded product. In particular, when cations are attracted and collided with the molded product, a nitrogen polar group or an oxygen polar group, which easily binds to a metal, is introduced into the surface of the molded product, so that the adhesion to the metal film is further improved. The plasma treatment conditions are not limited to the above, and may be arbitrarily set within the range in which the surface of the molded product is not excessively roughened by the plasma treatment. Further, since the plasma treatment is an intermediate treatment, a surface treatment method which replaces the plasma treatment may be used as long as the same surface activation as the plasma treatment can be performed.

After the plasma treatment as described above, a metal film is formed on the surface of the circuit-forming substrate by a physical vapor deposition method (PVD method) selected from sputtering, vacuum vapor deposition, ion plating and the like. FIG. 1C shows a molded product 3 on which the metal film is formed in this way.

Here, after the molded article 1 is plasma-treated in the chamber, the plasma-treated molded article 2 is subjected to the above-mentioned physical vapor deposition method without exposing the inside of the chamber to the atmosphere to form a continuous process. Is good. The metal forming the metal film is copper, nickel, gold, aluminum, titanium, molybdenum, chromium, tungsten, tin, lead,
A simple substance such as brass and nichrome, or an alloy can be used.

Here, as the sputtering, for example, a DC sputtering method can be applied. First, after the molded product is placed in the chamber, a vacuum pump is evacuated until the pressure in the chamber becomes 10 ⁻⁴ Pa or less, and in this state, an inert gas such as argon is evacuated to 0.1
It is introduced so that the gas pressure is Pa. By further applying a DC voltage of 500 V, a target such as copper can be bombarded, and a metal film such as copper having a thickness of 0.3 to 0.5 μm can be formed on the surface of the molded product.

As the vacuum vapor deposition, an electron beam heating type vacuum vapor deposition system can be applied. First, the chamber was evacuated by a vacuum pump until the pressure in the chamber became 10 ^-3 Pa or less, then an electron flow of 400 to 800 mA was generated, and the electron flow was made to collide with a vapor deposition material such as copper in the crucible and heated. Then, the vapor deposition material evaporates, usually 0.3 to 0.5 μm
A metal film such as copper having a thickness can be formed on the surface of the molded product.

When forming a metal film by ion plating, first, a vacuum pump is evacuated until the pressure in the chamber becomes 10 ^-4 Pa or less, and then 4
When an electron flow of 00 to 800 mA is generated, and the electron flow is made to collide with the vapor deposition material such as copper in the crucible and heated, the vapor deposition material evaporates, and the induction antenna portion between the molded article and the crucible is filled with argon or the like. Inert gas is introduced and the gas pressure is adjusted to 0.
The plasma is generated at a pressure of 05 to 0.1 Pa, and a power of 500 W is applied to the inductive antenna at a high frequency of 13.56 MHz, and a bias voltage of a DC voltage of 100 to 500 V is applied. ~
A metal film such as copper having a thickness of 0.5 μm can be formed on the surface of the molded product.

When the metal film is formed on the surface of the molded product by the physical vapor deposition method as described above, the surface of the molded product is chemically activated by the plasma treatment as described above. It is possible to obtain high adhesion of the metal film to the surface of.

The formation of a circuit such as MID will be described below. Normally, 0.3 to 0.3 is formed on the surface of the molded article 1 having various three-dimensional shapes to be the substrate of the molded circuit board as described above.
Molded product 3 having a 0.5 μm thick metal film such as copper
By forming a circuit on the metal film of, it can be finished as a molded circuit board of MID or the like.

Next, the circuit pattern can be formed by, for example, a laser method. In FIG. 1D, laser light is irradiated along the boundary between the circuit forming portion 4 and the circuit non-forming portion 5, and the metal film adhesiveness of the circuit forming portion 4 is not lowered, and the metal of the boundary portion 6 is not deteriorated. The state where the metal film of the circuit formation portion 4 is separated as a circuit pattern by removing the film is shown. Here, in general, the removal of the metal film by laser light irradiation is affected by the unevenness of the surface of the molded product, and the excess or deficiency of the removal of the metal film at the pattern edge portion easily occurs, and the unevenness occurs at the pattern edge line to cause the unevenness of the pattern edge portion. Although there is a problem that the dimensions vary, in the present invention, since the surface smoothness of the molded product is excellent, it is difficult to cause excess or deficiency in removing the metal film at the pattern edge portion, the dimensional accuracy of the pattern edge portion is good, and the precision of the circuit pattern is high. It is easy to achieve high density by thinning wires and minimizing circuit pattern gaps. In particular, when the above specified whiskers are used as the filler, the surface smoothness is further excellent, and the pattern width and pattern gap are 0.1 mm.
Hereafter, it becomes easier to form a film having a thickness of 0.05 mm or less.

Next, only the metal film of the circuit forming portion 4 is electrolytically plated with copper or the like to form a conductive layer usually having a thickness of 5 to 20 μm. FIG. 1E shows the circuit forming portion 7 thus electrolytically plated.

Next, a soft etching process is applied to the entire metal film of FIG. 1 (e) to remove the metal film remaining in the circuit non-formation portion having a thickness of 0.3 to 0.5 μm and electrolytic plating. By leaving most of the formed circuit formation portion, a molded circuit board 9 having a circuit pattern 8 having a desired shape as shown in FIG. 1F can be obtained. The surface of the circuit pattern 8 may be further subjected to nickel plating, gold plating, or the like, and another conductive layer may be formed to a thickness of several μm, if necessary.

In this circuit formation, the liquid crystalline polyester resin composition for molded products of the present invention was used to prepare molded products with a composition preferable as a circuit board, and the surface of the molded products was activated by the above plasma treatment. Combining various processes such as metal film formation by physical vapor deposition method, circuit pattern formation by metal film removal by laser light irradiation, electrolytic plating treatment, soft etching treatment, etc. is very compatible, without degrading desired characteristics. The processing quality of each process is improved.
As a result, it is possible to obtain a miniaturized or ultra-miniaturized molded circuit board that has excellent circuit pattern adhesion, mechanical strength, heat resistance, and dimensional stability as compared with conventional ones and has various three-dimensional shapes. Moreover, this molded circuit board can be suitably used particularly for small precision electronic circuit devices and the like.

Of course, the metal film-formed molded product thus obtained can be used for any purpose other than a molded circuit board such as MID, as long as it has a metal film forming treatment on its surface. Sensor, LED lamp, connector, socket, resistor, relay case, switch, coil bobbin, condenser, variable capacitor case, DVD,
Optical pickup parts such as CDs (lens holders, slide bases, etc.), crystal oscillators, various terminal boards, transformers,
Plug, printed wiring board, tuner, small motor,
Magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FDD carriage, FD
Electric / electronic parts such as D chassis, HDD parts, motor brush holder, built-in antenna, parabolic antenna, computer related parts, parts for portable information terminal equipment such as mobile phones; VTR parts, TV parts, irons, hair dryers , Rice cooker parts, microwave oven parts, microphones, headphones, speakers, audio / laser disk (registered trademark) / compact disks / mini disks, audio / audio equipment parts, lighting parts, refrigerator parts, air conditioner parts, photosensitive drums, paper Household parts such as copy parts such as separating claws, printer parts, typewriter parts, and word processor parts, office electrical product parts, fax related parts, copier related parts, office computer related parts, telephone related parts, cleaning tools Ingredient, Iruresu bearings, stern bearings, underwater bearings, various bearings such as various gears, such as motor parts and the like. In addition, it is also useful for machine parts, optical devices, precision machine parts, automobile / vehicle related parts, and other various applications for forming metal film-formed molded products.

[0072]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. Reference Example 1 LCP1: p-hydroxybenzoic acid 11.05 kg,
1.40 kg of 4,4'-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, and acetic anhydride 1
As a result of charging 0.67 kg into a pressure vessel and conducting a deacetic acid polycondensation reaction by heating, 8 units of aromatic oxycarbonyl units were obtained.
Melting point 314 ° C., melt viscosity 2 consisting of 0 molar equivalent, aromatic dioxy unit 7.5 molar equivalent, ethylenedioxy unit 12.5 molar equivalent, and aromatic dicarboxylic acid unit 20 molar equivalent.
5Pa ・ s (324 ℃, orifice 0.5mm diameter × 10m
Pellets having m and a shear rate of 1,000 (1 / sec) were obtained. Reference Example 2 LCP2: p-hydroxybenzoic acid 9.01 kg, 4,
1.26 kg of 4'-dihydroxybiphenyl, 1.12 kg of terephthalic acid, 3.46 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 8.8 acetic anhydride.
As a result of charging 4 kg into a pressure vessel and performing a deacetic acid polycondensation reaction by heating, an aromatic oxycarbonyl unit of 72.5
A melting point of 265 ° C. and a melt viscosity of 20 each consisting of a molar equivalent, an aromatic dioxy unit of 7.5 molar equivalent, an ethylenedioxy unit of 20 molar equivalent, and an aromatic dicarboxylic acid unit of 27.5 molar equivalent.
Pa ・ s (275 ℃, orifice 0.5mm diameter × 10mm,
Pellets with a shear rate of 1,000 (1 / sec) were obtained. Reference Example 3 LCP3: p-hydroxybenzoic acid 9.94 kg, 4,
1.84 kg of 4'-dihydroxybiphenyl, 1.64 kg of terephthalic acid, 1.56 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and acetic anhydride 10.
As a result of charging 11 kg into a pressure vessel and carrying out a deacetic acid polycondensation reaction by heating, aromatic oxycarbonyl unit 80 molar equivalent, aromatic dioxy unit 11 molar equivalent, ethylenedioxy unit 9 molar equivalent, aromatic dicarboxylic acid unit 20 Melting point consisting of molar equivalents 335 ° C, melt viscosity 20 Pa · s (3
Pellets having an orifice diameter of 0.5 mm × 10 mm and a shear rate of 1,000 (1 / sec) were obtained at 45 ° C. Reference Example 4 LCP4: p-hydroxybenzoic acid 11.05 kg, 6
As a result of charging 3.76 kg of dihydroxy-2-naphthoic acid and 9.70 kg of acetic anhydride into a pressure vessel and conducting a deacetic acid polycondensation reaction by heating, 8 oxybenzoyl units were obtained.
A melting point of 315 ° C. consisting of 0 molar equivalent and 20 molar equivalents of oxynaphthoyl unit, melt viscosity of 60 Pa · s (325 ° C., orifice 0.5 mm diameter × 10 mm, shear rate 1,000 (1
/ Sec)) pellets were obtained.

Each evaluation was measured according to the method described below.

(1) Flowability: Using the following molding machine, the flow length (bar flow length) of a 0.5 mm thick × 12.7 mm wide test piece was measured under the conditions of an injection speed of 99% and an injection pressure of 500 kgf / cm 2. It was measured.

(2) Heat resistance: Using the following molding machine, 3.
A test piece having a thickness of 2 mm, a width of 12.7 mm, and a length of 127 mm was molded, measured according to ASTM D648, and the deflection temperature under load (DTUL) was determined (1.82 MPa).

(3) Bending characteristics: Using the following molding machine,
A test piece of 3.2 mm thickness x 12.7 mm width x 127 mm length was molded and measured according to ASTM D790,
Flexural strength and flexural modulus were determined.

(4) Adhesion of metal film: A test piece of 1 mm thickness × 40 mm width × 30 mm length was molded using the following molding machine.

The surface of this resin molded body is plasma treated,
Further, a metal layer was formed using a DC magnetron sputtering device. That is, first, the resin molded body is set in the chamber of the plasma processing apparatus, the chamber is evacuated to reduce the pressure to about 10 ⁻⁴ Pa, and then N ₂ is introduced as an active gas into the chamber to be circulated. The gas pressure in the chamber was controlled to 10 Pa, and then a high frequency voltage with a power of 300 W (RF: 13.56 M) was applied between the electrodes.
The plasma treatment was performed by applying (Hz) for 30 seconds.

Next, the chamber was evacuated to a pressure of 10 ^-4 Pa or less, and then argon gas was introduced into the chamber so as to have a gas pressure of 0.1 Pa. By applying a voltage,
Bombard a copper target and apply 40 to the surface of the resin molding.
A copper metal layer having a film thickness of 0 nm was formed. Next, after applying a peel strength test pattern (width: 5 mm) with a laser,
The surface of the copper metal layer was electrolytically plated with copper to form a metal film having a thickness of 15 μm. Then, a peel strength test pattern (width: 5 mm) was applied by laser, and a film having a thickness of 15 μm was formed by copper plating.

A universal testing machine (EG manufactured by Shimadzu Corporation)
TEST) was used to determine the copper film peeling strength (90-degree peel strength) per unit width.

(5) Surface roughness: A test piece prepared in the same manner as the test piece for evaluating the adhesion of the metal film (1 mm thickness x
The surface roughness of 40 mm width × 30 mm length) was measured by a surface roughness meter (Surftest 500 manufactured by Mitutoyo), and the surface roughness was compared by the ten-point average roughness Rz.

Examples 1 to 6 and Comparative Example 1 A liquid crystal polyester resin was originally supplied using a TEX30 type twin screw extruder manufactured by Japan Steel Works at a ratio shown in Table 1, and glass fiber (6 μm diameter, 3 mm length) was supplied. , ECS made by Nippon Electric Glass
03T-790DE or 9 μm diameter, 3 mm length, ECS03T-790G manufactured by Nippon Electric Glass Co., Ltd. was supplied from the side feeder in an amount shown in Table 1 to 100 parts by weight of the resin component, and the cylinder temperature was set to the melting point of the liquid crystalline polyester resin +
The mixture was melt-kneaded at a setting of 5 ° C. to give pellets. The weight average fiber length of the glass fibers in this pellet was measured. The pellets were subjected to a Roboshot 30α-C injection molding machine (manufactured by Fanuc Co., Ltd.), and the cylinder temperature was set to the melting point of the liquid crystalline polyester resin + 5 ° C, and the mold temperature was set to 90 ° C according to each evaluation item. A test piece was molded.

[0083]

[Table 1]

Comparative Example 2 Commercially available liquid crystalline polyester resin (Vectra C130, manufactured by Polyplastics Co., liquid crystalline polyester resin consisting of 80 molar equivalents of oxybenzoyl units and 20 molar equivalents of oxynaphthoyl units, glass fiber (13 μm, weight average) A test piece was molded by injection molding in the same manner as in Example 1 (fiber length 0.4 mm) containing 30%), and the metal film adhesion was evaluated. As a result, the copper film peeling strength was 0.14 N / mm. It was

Example 7, Comparative Example 3 The liquid crystalline polyester resin was originally supplied using a TEX30 type twin screw extruder manufactured by Japan Steel Works at the ratio shown in Table 2, and aluminum borate whiskers (0.5 to 1) were used. 0.0 μm diameter, 10
~ 30μm long, Shikoku Chemicals Arborex YS3
The amount shown in Table 2 was supplied from the side feeder to 100 parts by weight of the resin component A) and the cylinder temperature was adjusted to 315
The mixture was melt-kneaded at a setting of ° C to obtain pellets. The weight average fiber length of the aluminum borate whiskers in this pellet was measured. The pellets were subjected to a Roboshot 30α-C injection molding machine (manufactured by FANUC Co., Ltd.) and a cylinder temperature of 32
Test pieces were molded by the method for each evaluation item under the conditions of 0 ° C. and mold temperature of 90 ° C.

[0086]

[Table 2]

As is clear from Tables 1 and 2, the composition of the present invention is superior in metal film adhesion, fluidity, heat resistance and mechanical properties as compared with Comparative Examples. Further, since the surface smoothness is enhanced by using whiskers as the filler, when the fine circuit having a line width of 0.1 mm or less and a space width of 0.1 mm or less is formed on a molded circuit board, laser light irradiation is performed. It is preferable since the metal film can be removed easily at the edge portion of the circuit pattern and the dimensional accuracy of the circuit pattern is improved.

[0088]

INDUSTRIAL APPLICABILITY The liquid crystalline polyester resin for molded articles of the present invention is excellent in metal adhesion, fluidity, heat resistance and mechanical properties, and is therefore a material suitable for use in coating a surface with a metal film. is there. Further, it can be suitably used for applications such as a molded circuit board that requires a fine and highly adhesive metal film. The molded circuit board of the present invention has a variety of three-dimensional shapes that are miniaturized or further miniaturized by combining the liquid crystalline polyester resin composition for molded articles with the above-described circuit forming process of MID, It is possible to realize a precision electronic circuit board having adhesion of a circuit pattern and fine patterning property, and having excellent mechanical strength, heat resistance, and dimensional stability.

[Brief description of drawings]

FIG. 1 illustrates an example of a process of manufacturing a molded circuit board of the present invention, and FIGS. 1A to 1F are perspective views, respectively.

[Explanation of symbols]

1. Molded product before the surface is plasma treated 2. Molded product whose surface is activated by plasma treatment 3. Molded product with metal film 4. Circuit formation part 5. Circuit non-formation part 6. Boundary between circuit formation part and circuit non-formation part 7. Circuit forming part with electrolytic plating 8. Circuit pattern 9. Molded circuit board

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 67/00 C08L 67/00 (72) Inventor Naoto Ikegawa 1048 Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Works, Ltd. (72) Inventor Masahiro Sato 1048, Kadoma, Kadoma-shi, Osaka Matsushita Electric Works Co., Ltd. F-term (reference) 4F073 AA01 BA24 BA25 BA47 BB02 CA01 4F100 AB01B AG00A AG00H AK41A AK41K BA02 BA10A BA10B CA23A DG03B66 GB43B66B11H EDG JK01 JK06 JL01 JM02B YY00A YY00H 4J002 CF041 CF051 CF081 CF091 CF101 CF181 DA016 DA086 DA096 DC006 DE107 DE136 DE146 DE147 DE187 DE237 DG056 DJ006 DJ007 DJ016 DJ0BA0BA05AQB BB07A08A05A08A05AQA 4A05AQA 4A0AJA02 BF09 BF11 BF14 BF17 BH02 CA00 CA06 CB01 CB05A CB06A CB10A CC06A CF0 8 CG05Y DB13 EB03 EB05A EC06A JA013 JA023 JA093 JA293 JA303 JD01

Claims (7)

[Claims] 1. The following structural units (I), (II), (III) and (IV)
A liquid crystalline polyester resin for a molded article, wherein the molded article has a surface of the molded article after plasma treatment,
A liquid crystalline polyester resin for molded articles, which is formed by forming a metal film by any one of sputtering, vacuum deposition, and ion plating. [Chemical 1] (However, R1 in the formula is R1 represents one or more groups selected from It represents one or more groups selected from, R ₃ is embedded image And one or more groups selected from However, in the formula, X represents a hydrogen atom or a chlorine atom. ) 2. A liquid crystalline polyester resin is the above structural unit.
(I), (II), (III) and (IV), the above structural unit
The total of (I) and (II) is structural units (I), (II) and (III)
30 to 95 mol% with respect to the total of the structural units (III), and 70 to 5 mol% with respect to the total of the structural units (I), (II) and (III). Molar ratio to (II) [(I) /
(II)] is 75/25 to 95/5, The liquid crystalline polyester resin for molded articles according to claim 1, which is characterized in that 3. A liquid crystalline polyester resin composition for molded articles, which comprises 10 to 400 parts by weight of a filler with respect to 100 parts by weight of the liquid crystalline polyester resin according to claim 1. 4. The filler is glass fiber having a fiber diameter of 3 to 15 μm and a weight average fiber length of 0.01 to 0.6 mm,
The liquid crystalline polyester resin composition for molded articles according to claim 3, wherein the content is 10 to 150 parts by weight with respect to 100 parts by weight of the liquid crystalline polyester resin. 5. The filler is a whisker having a fiber diameter of 0.05 to 5 μm and a weight average fiber length of 1 to 100 μm, and its content is 10 to 150 parts by weight with respect to 100 parts by weight of the liquid crystalline polyester resin. The liquid crystalline polyester resin composition for molded articles according to claim 3, wherein 6. A metal film is formed on the surface of a molded product molded using the liquid crystalline polyester resin composition for molded products according to claim 1, and a circuit is formed on the metal film. Molded circuit board characterized by. 7. A metal film formed on the surface of the molded article,
The molded circuit board according to claim 6, wherein the circuit patterning is performed by laser light irradiation to form a circuit.