JP2003268241A - Liquid crystalline resin composition for molding and molded circuit board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystalline resin composition for molding which is improved in the adhesiveness of the liquid crystalline resin to a metal and is excellent in thin-wall moldability, precision moldability and dimensional stability based on the excellent fluidity, heat resistance and mechanical properties of the liquid crystalline resin; and a molded circuit board which has circuit adhesiveness, heat resistance and dimensional stability suitable for a small precision electronic circuit instrument. <P>SOLUTION: The liquid crystalline resin composition for molding comprises 10 parts by weight of (A) a liquid crystalline resin and 0.5-30 parts by weight of (B) an amorphous resin having a repeating unit having at least one aromatic ring, wherein the moldings will be treated to have a formed metal film on the surface. The steric molded circuit board is produced by injection molding the composition to get a molding, which is treated with plasma on the surface followed by spattering or the like to form a metal film and then irradiating laser ray to carry out circuit patterning. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid crystalline resin composition for molded articles having improved fluidity, heat resistance, and mechanical properties with improved metal film adhesion, and a molded circuit board using the same. is there.

[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, electric 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.

The liquid crystalline resin, which is excellent in thin-wall fluidity, has contributed to miniaturization of electric and electronic parts.

Especially, regarding the soldering heat resistance, which is closely related to the electronics field, the liquid crystalline resin is 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, a molded product obtained by molding a liquid crystalline resin is used 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 the plasma treatment, a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method (P
When a metal film is formed by the VD method), 0.2 to 0.25 N /
Only a low adhesion strength of about mm was obtained, which was not practical.

Therefore, 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, in Japanese Examined Patent Publication No. 7-24328, after a molded body molded of a liquid crystalline resin is subjected to an etching treatment, a surface metal coating treatment is carried out by any one of sputtering, ion plating and vacuum deposition. This technology is disclosed.

Further, in Japanese Patent No. 2714440, a molded body obtained by molding a liquid crystalline resin is used, and the surface temperature is 60 in a vacuum chamber.
A technique is disclosed in which the surface metal coating treatment is performed by any one of sputtering, ion plating, and vacuum deposition while heating to a temperature of not less than 0 ° C.

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 regarding the film forming treatment.

[0011]

[Problems to be Solved by the Invention] 7-
According to Japanese Patent No. 24328, the surface of a molded body is roughened by performing an etching treatment, and an adhesive force is obtained based on the mechanical anchoring effect of the metal film with respect to the unevenness of the roughened surface. However, if the surface of the molded body is roughened, it will be difficult to make fine lines in the circuit formed on the surface of the molded body.
For example, the line width of a circuit is 0.25 mm, the space width between adjacent circuits is about 0.25 mm, and a fine line circuit with a line width of 0.1 mm or less and a space width of 0.1 mm or less is formed. There was a problem that I could not.

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 higher, a chemical bond is formed between the liquid crystalline resin and the metal film. Since there is no interposition, it is difficult to obtain high adhesiveness of the metal film, and there is a problem in adhesiveness especially after receiving a heat load.

The present invention solves the problems described above, improves the adhesion of liquid crystalline resin to metal, and utilizes the excellent liquidity, heat resistance, and mechanical properties of liquid crystalline resin for thin and precise Excellent in dimensional stability, to obtain a liquid crystalline resin composition for a molded product used by forming a metal film on the surface thereof,
Another object is to obtain a molded circuit board having excellent circuit adhesion, heat resistance, and dimensional stability, which is particularly suitable for small precision electronic circuit devices.

[0014]

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 comprises (1) 0.5 to 30 parts by weight of a non-liquid crystalline resin (B) containing a repeating unit having at least one aromatic ring with respect to 100 parts by weight of a liquid crystalline resin (A). A liquid crystalline resin composition for a molded article, which comprises the step of forming a metal film on the surface of the molded article.

Furthermore, the present invention provides the following liquid crystalline resin composition for molded articles and molded circuit boards. (2) The molded product according to (1), wherein the non-liquid crystal resin (B) is one or more non-liquid crystal resin selected from polyphenylene sulfide, aromatic polyether ether ketone and polystyrene. (3) Liquid crystalline resin composition for molded articles according to (1), characterized in that the non-liquid crystalline resin (B) is polyphenylene sulfide, (4) Liquid crystalline resin ( A) is the following structural unit (I), (I
A liquid crystalline resin composition for molded articles according to any one of (1) to (3), which is a liquid crystalline polyester comprising I), (III) and (IV).

[0016]

[Chemical 5] (However, R ₁ is

[0017]

[Chemical 6] R ₂ represents one or more groups selected from

[0018]

[Chemical 7] R ₃ represents one or more groups selected from

[0019]

[Chemical 8] And one or more groups selected from However, in the formula, X represents a hydrogen atom or a chlorine atom. (5) The liquid crystalline resin (A) has the structural units (I) and (I
A liquid crystalline polyester comprising I), (III) and (IV), wherein the total of the structural units (I) and (II) is based on the total of the structural units (I), (II) and (III). 30 ~
95 mol%, structural unit (III) is structural unit (I), (I
70 to 5 mol% based on the total of I) and (III), and the molar ratio of the structural unit (I) to (II) [(I) /
(II)] is 75/25 to 95/5, (4) The liquid crystalline resin composition for molded articles according to (4), (6) the filler for 100 parts by weight of the liquid crystalline resin (A). (C) 5 to 200 parts by weight of the liquid crystal resin composition for molded articles according to any one of (1) to (5), (7) the filler (C) has a fiber diameter Glass fibers having a weight average fiber length of 3 to 15 μm and a weight average fiber length of 0.01 to 0.6 mm,
The content is 1 with respect to 100 parts by weight of the liquid crystalline resin (A).
The liquid crystalline resin composition for molded articles according to (6), which is from 0 to 150 parts by weight. (8) The filler (C) 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 100 parts by weight of the liquid crystalline resin (A).
150 parts by weight of the liquid crystalline resin composition for molded articles according to (6). (9) The molded product is subjected to a plasma treatment on the surface of the molded product, and then a metal film is formed on the surface of the molded product by any one of sputtering, vacuum deposition, and ion plating, and a circuit is formed on this metal film. (1) to (8) The liquid crystalline resin composition for a molded article according to any one of (1) to (8), wherein the molded article is a metal film formed on the surface of the molded article,
A liquid crystal resin composition for molded articles according to any one of (1) to (9), characterized in that a circuit is formed by circuit patterning by laser light irradiation, (11) (1) to ( (10) A molded circuit board, wherein a metal film is formed on the surface of a molded product molded using the liquid crystalline resin composition for molded products according to any one of (10) and a circuit is formed on the metal film. 12) Sputtering, vacuum evaporation,
(11) A molded circuit board according to (11), characterized in that a metal film is formed by any one of ion plating methods, and (13) a surface of the molded product is subjected to plasma treatment, followed by sputtering and vacuum deposition. A molded circuit board according to (12), characterized in that a metal film is formed by any one of the following methods: ion plating, and (14) the metal film formed on the surface of the molded product is irradiated with laser light. The molded circuit board according to any one of (11) to (13), which is formed by performing circuit patterning to form a circuit.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid crystalline resin (A) of the present invention is
Polymers that can form an anisotropic molten phase when melted, and include liquid crystalline polyesters, liquid crystalline polyester amides, liquid crystalline polycarbonates, liquid crystalline polyester elastomers, etc. Among them, those having an ester bond in the molecular chain are preferred. In particular, liquid crystalline polyester and liquid crystalline polyesteramide are preferably used.

The liquid crystalline resin (A) which can be preferably used in the present invention is a liquid crystalline polyester containing a structural unit composed of p-hydroxybenzoic acid as an aromatic oxycarbonyl unit, and has an ethylenedioxy unit as an essential component. Liquid crystalline polyester can also be preferably used. More preferably, a polyester comprising the following structural units (I), (III) and (IV) or (I), (II), (III)
And a polyester composed of structural units (IV),
Most preferred are (I), (II), (III) and (I
V) is a polyester composed of structural units.

[0022]

[Chemical 9] (However, R ₁ in the formula is

[0023]

[Chemical 10] R ₂ represents one or more groups selected from

[0024]

[Chemical 11] R ₃ represents one or more groups selected from

[0025]

[Chemical 12] And one or more groups selected from However, in the formula, X represents a hydrogen atom or a chlorine atom. It is desirable that the total of the structural units (II) and (III) and the structural unit (IV) be 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-dihydroxy Naphthalene, 2,
Structural units produced from one or more aromatic dihydroxy compounds selected from 2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether, structural units (III) are structural units produced from ethylene glycol. , Structural unit (IV) is terephthalic acid,
Isophthalic acid, 4,4'-diphenyldicarboxylic acid,
2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,4 Each of one or more structural units formed from an aromatic dicarboxylic acid selected from'-diphenyl ether dicarboxylic acid. Of these, R ₂

[0027]

[Chemical 13] And R ₃ is

[0028]

[Chemical 14] Are particularly preferred.

The copolymerization amount of the above structural units (I), (II), (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 structural units (I), (II),
In the case of the copolymer composed of (III) and (IV), the total of the structural units (I) and (II) is the structural unit (I),
30 to 95 mol% relative to the sum of (II) and (III)
Is preferred, and 40 to 93 mol% is more preferred. Also,
Structural unit (III) includes structural units (I), (II) and (II
70 to 5 mol% relative to the total of I) is preferred, 60 to
7 mol% is more preferable. In addition, the structural unit (I) (I
The molar ratio [(I) / (II)] to I) is preferably 7
5/25 to 95/5, more preferably 78/22
~ 93/7. Further, the structural unit (IV) is preferably substantially equimolar to the total of the structural units (II) and (III).

On the other hand, when the structural unit (II) is not contained, the structural unit (I) is the structural unit (I) in view of fluidity.
It is preferably 40 to 90 mol%, particularly preferably 60 to 88 mol%, with respect to the total of (III), and the structural unit (IV) is substantially equimolar to the structural unit (III). Preferably there is.

As the liquid crystalline polyesteramide, a polyesteramide forming an anisotropic melt phase containing a p-iminophenoxy unit produced from p-aminophenol in addition to the above structural units (I) to (IV) is used. preferable.

The liquid crystalline polyester and the liquid crystalline polyesteramide which can be preferably used are 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, and alicyclic dicarboxylic acids such as hexahydroterephthalic acid , Chlorohydroquinone, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone, 3,4
Aromatic diols such as'-dihydroxybiphenyl, propylene glycol, 1,4-butanediol, 1,6-
Hexanediol, neopentyl glycol, 1,4-
Aliphatic and alicyclic diols such as cyclohexanediol and 1,4-cyclohexanedimethanol, and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and p-aminobenzoic acid are further added to the extent that liquid crystallinity is not impaired. It can be copolymerized.

Some of the liquid crystalline resins (A) used in the present invention can be measured for logarithmic viscosity in pentafluorophenol. At that time, 6 at a concentration of 0.1 g / dl
The value measured at 0 ° C. is preferably 0.5 to 15.0 dl / g, and particularly preferably 1.0 to 3.0 dl / g.

The melt viscosity of the liquid crystalline resin (A) in the present invention is preferably 0.5 to 500 Pa · s, and particularly 1 to
250 Pa · s is more preferable. Further, when it is desired to obtain a composition excellent in fluidity, the melt viscosity is 50 Pa.
It is preferably s or less. The melt viscosity was 1,000 se under the condition of melting point (Tm) + 10 ° C.
It is a value measured by a Koka type flow tester under the condition of c ^-1 .

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 resin (A) has a melting point of preferably 180 to 380 ° C., more preferably 210 to 360 ° C., although it is not particularly limited in order to further develop the characteristics of the present invention.

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

For example, in the production of the above liquid crystalline polyester, the following production method is preferably mentioned. (1) Diacylated products of aromatic dihydroxy compounds such as p-acetoxybenzoic acid and 4,4′-diacetoxybiphenyl and diacetoxybenzene, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester by a deacetic acid condensation polymerization reaction. (2) Aromatic dihydroxy compounds such as p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl and hydroquinone, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid are reacted with acetic anhydride. Then, after acylating the phenolic hydroxyl groups, a liquid crystalline polyester is produced by a deacetic acid polycondensation reaction. (3) Phenyl ester of p-hydroxybenzoic acid and aromatic dihydroxy compound such as 4,4′-dihydroxybiphenyl and hydroquinone, and diphenyl ester of aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester by a dephenol polycondensation reaction. (4) p-Hydroxybenzoic acid and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid are reacted with a predetermined amount of diphenyl carbonate to form diphenyl esters, respectively,
A method of producing a liquid crystalline polyester by adding an aromatic dihydroxy compound such as 4,4′-dihydroxybiphenyl or hydroquinone and performing a dephenol polycondensation reaction. (5) Polyester polymers such as polyethylene terephthalate, oligomers or bis (β of aromatic dicarboxylic acids such as bis (β-hydroxyethyl) terephthalate
-A method for producing a liquid crystalline polyester by the method (1) or (2) in the presence of a hydroxyethyl) ester.

Although the polycondensation reaction of the liquid crystalline polyester proceeds without a catalyst, stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, metal compounds such as magnesium metal may be used as a catalyst. it can.

The non-liquid crystalline resin (B) used in the present invention contains a repeating unit having at least one aromatic ring, and may be a thermoplastic resin or a thermosetting resin. At least one aromatic ring contained in the repeating unit may be contained in the main chain of the polymer constituting the non-liquid crystalline resin or in the side chain. In the case of a thermoplastic resin or thermosetting resin produced from two or more raw materials, at least one repeating unit produced from at least one or more raw materials is used.
Any block copolymer may be used as long as it has at least one aromatic ring in the repeating unit of at least one of the blocks. The repeating unit having at least one aromatic ring is preferably contained in an amount of 10 mol% or more, and more preferably 30 mol% or more, in all the repeating units constituting the non-liquid crystalline resin. The aromatic ring has a benzene nucleus, but specifically, it may be a benzene ring or a condensed ring in which two or more benzene rings, preferably 2 to 4 are condensed. Preferable examples of the condensed ring include naphthalene and anthracene. The aromatic ring may have a substituent.

Specific examples of the non-liquid crystalline resin (B) containing a repeating unit having at least one aromatic ring include styrene resins such as polystyrene and syndiotactic polystyrene, 9T, 6T / 66, 6T / 6. , 6T / 12, 6
T / 610, 6I / 66, 6T / 6I, 6T / 6I / 6
Aromatic nylon resins such as 6T or 6I copolymers (6T is hexamethylene terephthalate unit, 6I is hexamethylene isophthalate unit, / is copolymer), polyethylene terephthalate, polybutylene terephthalate Representative of non-liquid crystal aromatic polyester resins such as polyethylene, 2,6-naphthalate, polybutylene-2,6-naphthalate, polyethylene isophthalate, polybutylene isophthalate and their copolymers, polyphenylene ether resins, polyphenylene sulfide Polyarylene sulfide,
Aromatic polycarbonate, aromatic polysulfone, aromatic polyether sulfone, aromatic polyether imide, aromatic polyamide imide, aromatic polyether ketone, aromatic polyether ether ketone, phenol resin, unsaturated polyester resin and the like. it can. Among them, polyphenylene sulfide, aromatic polyether ether ketone, and polystyrene are preferable because they have a high modification effect by plasma treatment and exhibit higher adhesion, and polyphenylene sulfide is particularly preferable.

The polyphenylene sulfide resin (PPS resin) (B) used in the present invention is a polymer having a repeating unit represented by the following structural formula,

[0044]

[Chemical 15] From the viewpoint of heat resistance, a polymer containing 70 mol% or more, further 90 mol% or more, of a polymer containing the repeating unit represented by the above structural formula is preferable. Further, 30 mol% or less of the repeating unit of the PPS resin may be composed of a repeating unit having the following structure.

[0045]

[Chemical 16] Such PPS resin is generally known in the art, that is, Japanese Patent Publication No.
A method for obtaining a polymer having a relatively small molecular weight described in JP-A-3368, a method for obtaining a polymer having a relatively large molecular weight described in JP-B-52-12240 and JP-A-61-7332, and the like. Can be manufactured by.

In the present invention, the PPS obtained as described above
Crosslinking / polymerization by heating the resin in air, heat treatment in an atmosphere of inert gas such as nitrogen or under reduced pressure, washing with organic solvent, hot water, acid aqueous solution, acid anhydride, amine, isocyanate, functional group-containing It is of course possible to use it after various treatments such as activation with a functional group-containing compound such as a disulfide compound.

A specific method for crosslinking / polymerizing the PPS resin by heating is as follows: in an atmosphere of an oxidizing gas such as air or oxygen, or a mixed gas of the oxidizing gas and an inert gas such as nitrogen or argon. An example is a method of heating in a heating container at a predetermined temperature in an atmosphere until a desired melt viscosity is obtained.

The heat treatment temperature is usually selected to be 170 to 280 ° C, preferably 200 to 270 ° C. Also,
The heat treatment time is usually selected from 0.5 to 100 hours, preferably 2 to 50 hours, but by controlling both of them, the target viscosity level can be obtained. The heat treatment apparatus may be a normal hot air dryer or a rotary type or a heating apparatus with a stirring blade, but for efficient and more uniform treatment, a heating type with a rotation type or a stirring blade is used. Is more preferable.

As a specific method for heat-treating the PPS resin in an atmosphere of an inert gas such as nitrogen or under a reduced pressure, an atmosphere of an inert gas such as nitrogen or a reduced pressure is used.
Heat treatment temperature 150 to 280 ° C., preferably 200 to 2
70 ° C., heating time 0.5 to 100 hours, preferably 2
A method of heat treatment for up to 50 hours can be exemplified.

The apparatus for the heat treatment may be an ordinary hot air dryer or a heating apparatus with a rotary blade or a stirring blade, but for efficient and more uniform treatment, heating with a rotary blade or a stirring blade is necessary. More preferably, a device is used.

The PPS resin used in the present invention is preferably a deionized PPS resin. As a specific method of such deionization treatment, an acid aqueous solution washing treatment,
Examples include hot water washing treatment and organic solvent washing treatment,
These treatments may be used in combination of two or more methods.

The following method can be exemplified as a specific method for washing the PPS resin with an organic solvent. The organic solvent used for washing is not particularly limited as long as it does not have a function of decomposing the PPS resin, but for example, a nitrogen-containing polar solvent such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dimethyl sulfone. Such as sulfoxides, sulfone solvents,
Acetone, methyl ethyl ketone, diethyl ketone, acetophenone and other ketone solvents, dimethyl ether, dipropyl ether, tetrahydrofuran and other ether solvents, chloroform, methylene chloride, trichloroethylene, dichloroethylene, dichloroethane, tetrachloroethane, chlorobenzene and other halogen solvents Solvent, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol,
Examples thereof include alcohols such as phenol, cresol and polyethylene glycol, phenol solvents, aromatic hydrocarbon solvents such as benzene, toluene and xylene. Among these organic solvents, N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like are preferable. Further, these organic solvents are used alone or in combination of two or more. As a method of washing with an organic solvent, there is a method of immersing a PPS resin in an organic solvent, and if necessary, it is possible to appropriately stir or heat. The washing temperature when washing the PPS resin with an organic solvent is not particularly limited, and any temperature from normal temperature to 300 ° C. can be selected. The higher the cleaning temperature is, the higher the cleaning efficiency tends to be, but usually the room temperature to 150 ° C.
A sufficient effect can be obtained at the washing temperature. The PPS resin that has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

The following method can be exemplified as a specific method for washing the PPS resin with hot water. The water to be used is preferably distilled water or deionized water in order to exert the preferable effect of chemically modifying the PPS resin by washing with hot water. The operation of hot water treatment is usually carried out by adding a predetermined amount of PPS resin to a predetermined amount of water and heating and stirring at normal pressure or in a pressure vessel. The ratio of the PPS resin to water is preferably such that the amount of water is large, but normally, a bath ratio of 200 g or less of PPS resin to 1 liter of water is selected.

The following method can be exemplified as a specific method for treating the PPS resin with an acid. As an acid treatment method, there is a method of immersing a PPS resin in an acid or an aqueous solution of an acid, and if necessary, it is possible to appropriately stir or heat. The acid used is not particularly limited as long as it has no action of decomposing the PPS resin, and aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halo-substituted aliphatic compounds such as chloroacetic acid and dichloroacetic acid. Saturated carboxylic acids, aliphatic unsaturated monocarboxylic acids such as acrylic acid and crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid and fumaric acid, and sulfuric acid. , Phosphoric acid, hydrochloric acid, carbonic acid,
Examples thereof include inorganic acidic compounds such as silicic acid. Of these, acetic acid and hydrochloric acid are more preferably used. The acid-treated PPS resin is preferably washed several times with water or warm water in order to remove residual acid or salt. Further, the water used for washing is preferably distilled water or deionized water in the sense that the effect of preferable chemical modification of the PPS resin by acid treatment is not impaired.

The melt viscosity of the PPS resin used in the present invention is not particularly limited, but usually 5 to 1000 Pa · s (300
C. and shear rate 1000 sec.sup.- ¹ ) are preferably used, and the range of 10 to 600 Pa.s is more preferable.

Examples of the aromatic polyether ether ketone resin (PEEK resin) (B) used in the present invention include polymers having a repeating unit represented by the following structural formula.

[0057]

[Chemical 17] The polystyrene resin (B) used in the present invention contains a unit produced from styrene and / or its derivative. Specific examples of units formed from styrene and its derivatives (these may be collectively referred to as aromatic vinyl-based monomers) include styrene, α-methylstyrene,
Examples thereof include vinyltoluene, p-methylstyrene, and pt-butylstyrene, but styrene and α-methylstyrene are particularly preferable. Moreover, these can also be used together.

Preferred polystyrene resins in the present invention include styrene polymers such as PS (polystyrene), rubber-reinforced styrene polymers such as HIPS (high impact polystyrene), and styrene such as AS (acrylonitrile / styrene copolymer). Type copolymers such as AES (acrylonitrile / ethylene / propylene / non-conjugated diene rubber / styrene copolymer), ABS (acrylonitrile / butadiene / styrene copolymer), MBS (methyl methacrylate / butadiene / styrene copolymer) Examples thereof include rubber-reinforced (co) polymers, of which polystyrene is preferred.

The blending amount of the non-liquid crystalline resin (B) used in the present invention is an effect of improving the metal film adhesiveness without impairing the characteristics of the liquid crystalline resin (A) such as fluidity, heat resistance and mechanical properties. From the viewpoint of simultaneously exhibiting 0.5 to 30 parts by weight, preferably 3 to 25 parts by weight with respect to 100 parts by weight of the liquid crystalline resin (A).
Parts by weight, more preferably 5 to 15 parts by weight.

In the present invention, the liquid crystalline resin composition for molded products, which is characterized in that the surface is subjected to a metal film forming treatment, can use the filler (C), and is not particularly limited. Non-fibrous fillers such as fibrous, plate-like, powdery and granular can be used. Specifically, for example, glass fiber, PAN-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber or brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber,
Ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker,
Fibrous materials such as silicon nitride whiskers, whisker-like fillers,
Mica, talc, kaolin, silica, calcium carbonate,
Examples thereof include powdery, granular or plate-like fillers such as glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, titanium oxide, zinc oxide, calcium polyphosphate and graphite.

The surface of the above-mentioned filler used in the present invention is treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.) or another surface treatment agent before use. You can also

The content of the above-mentioned filler (C) is usually preferably 5 to 200 parts by weight, more preferably 30 to 100 parts by weight, and particularly preferably 35 to 100 parts by weight of the liquid crystalline resin (A). 80 parts by weight.

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 in the production of the liquid crystalline resin composition for molded articles of the present invention is preferably 3 to 15 μm, more preferably from the viewpoint of the reinforcing effect, the fluidity at the time of molding, and the adhesion to the metal film. It is 5 to 15 μm.

In the liquid crystalline 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 resin composition for molded products is 0.01 to 0.6 in terms of the reinforcing effect, the fluidity at the time of molding, and the metal film adhesion.
mm is preferable, and 0.1-0.4 mm is more preferable.

The method of measuring the fiber length distribution of the glass fibers was as follows: after about 5 g of pellets of the liquid crystalline resin composition for moldings was ashed in a crucible, about 10 of the remaining glass fibers were used.
Take 0 mg and disperse in 100 cc of soap water.
Then, 1 to 2 drops of the dispersion liquid is placed on a slide glass using a spoid, observed under a microscope, and photographed. 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.

L _w = (ΣL _i ² N _i ) / (ΣL _i N _i ) (L _w : weight average fiber length, L _i : fiber length at 0.10 mm intervals, N _i : number of L _i ) The content of the glass fiber in the liquid crystalline resin composition for molded articles of 1 is 1 with respect to 100 parts by weight of the liquid crystalline resin (A).
0 to 150 parts by weight is preferred, more preferably 25 to 1
00 parts by weight, particularly preferably 35 to 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-mentioned glass fiber is particularly suitable as a filler (C) 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 also be particularly preferably used as the filler (C). 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 preferable in terms of moldability, affinity with the liquid crystalline resin composition, reinforcing effect and surface smoothness. Also, from these 2
They may be used as a mixture of two or more kinds, and it is expected that the effect of combining each material with the affinity with the liquid crystalline resin composition, the reinforcing effect, and the 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 whisker content 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 resin (A). . 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 used for miniaturizing precision electronic circuit boards for small precision electronic circuit devices described later, but also for further miniaturizing the circuit 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 filler (C) for a molded substrate for achieving ultra-compact and ultra-precision.

Further, in the liquid crystalline resin composition for molded articles, which is characterized in that the surface of the present invention is subjected to a metal film forming treatment, an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphite and Substitutes thereof, UV absorbers (eg resorcinol, salicylate, benzotriazole, benzophenone, etc.), phosphite, hypophosphite and other anti-coloring agents, lubricants, dyes (eg nigrosine) and pigments (eg. For example, colorants containing cadmium sulfide, phthalocyanine, etc., mold release agents (montanic acid and its salts, its esters,
Half ester, stearyl alcohol, stearamide, polyethylene wax, etc.), carbon black as a conductive agent or a coloring agent, a crystal nucleating agent, a plasticizer,
Flame retardants (eg brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, magnesium hydroxide, melamine and cyanuric acid or salts thereof,
Red phosphorus, etc., flame retardant aids, slidability improvers (graphite,
Fluorine resin), ordinary additives such as antistatic agents, and other polymers (polyamide, polyester such as polylactic acid, polyether sulfone, acrylic resin, polyethylene, polypropylene, ionomer resin, etc.) are added to obtain the desired characteristics. Can be further added.

The liquid crystalline resin composition for molded articles of the present invention is usually produced by a known method.

For example, the liquid crystal resin (A) component and the non-liquid crystal resin (B) component are premixed with the necessary additives and the filler (C), and then supplied to an extruder or the like and sufficiently melt-kneaded. Is prepared by. When the filler (C) is added, the liquid crystalline resin (A), the non-liquid crystalline resin (B) and the additive are preferably charged from the extruder in order to control the fiber length of the filler. , The filler (C) is supplied to the extruder by using a side feeder.

The liquid crystalline resin composition for molded articles thus obtained is excellent in fluidity, heat resistance and mechanical properties and is excellent in metal film adhesion. It is especially suitable for molded products.

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.). 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 article of the present invention thus obtained.

FIG. 1 (a) shows a molded product 1 in which a liquid crystalline 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 is formed 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 glass fiber content is preferably 10 to 150 parts by weight, and more preferably 25 to 100 parts by weight, relative to 100 parts by weight of the liquid crystalline resin (A).

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 resin (A).

Further, particularly 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. The diameter of the whiskers at this time is 0.05 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, and more preferably 35 to 80 parts by weight, based on 100 parts by weight of the liquid crystalline resin (A).

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 diameter of the whiskers is preferably 0.05 to 2 μm, the average fiber length is preferably 3 to 50 μm, and the content of the whiskers is preferably 25 to 100 parts by weight, and 35 to 100 parts by weight of the liquid crystalline resin (A). ˜80 parts by weight is more preferred.

In forming a metal film on the surface of the thus obtained molded product of the present invention, the surface of the molded product is first plasma-treated to activate the surface of the molded product. 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 the chamber, a high frequency power source is connected to one electrode, and the other electrode is grounded.
When the surface of the molded product is subjected to plasma treatment, the molded product is set on one electrode between the electrodes, the chamber is evacuated to reduce the pressure to about 10 ⁻⁴ Pa, and then N ₂ is introduced into the chamber. While introducing and circulating a chemically active gas such as O ₂ and O ₂ , control the gas pressure in the chamber to 8 to 15 Pa, and then apply a high frequency voltage (RF: 13.56 MHz) between the electrodes by a high frequency power source. 10-1
Apply for about 00 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 thus formed. Here, after the molded product 1 is plasma-treated in the chamber, the plasma-processed molded product 2 is preferably subjected to the above physical vapor deposition method without opening the chamber to the atmosphere, so that a continuous process is preferable. . As the metal forming the metal film, a simple substance such as copper, nickel, gold, aluminum, titanium, molybdenum, chromium, tungsten, tin, lead, brass, or nichrome, or an alloy can be used.

Here, as the sputtering, for example, D
A C sputtering method can be applied. First, a molded product is placed in the chamber, and then a vacuum pump is evacuated until the pressure in the chamber becomes 10 ⁻⁴ Pa or less. In this state, an inert gas such as argon is evacuated to a pressure of 0.
It is introduced so that the gas pressure is 1 Pa. Further 500V
A target such as copper can be bombarded by applying a DC voltage of (3) to form a metal film such as copper having a thickness of usually 0.3 to 0.5 μm 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, a vacuum pump was used to evacuate the chamber to a pressure of 10 ^-3 Pa or less, and then an electron flow of 400 to 800 mA was generated.
When this electron stream is made to collide with a vapor deposition material such as copper in a crucible and heated, the vapor deposition material evaporates, and usually 0.3 to 0.5 μm.
A metal film such as copper having a thickness of m can be formed on the surface of the molded product.

When forming a metal film by ion plating, first, a vacuum pump is used to evacuate the chamber until the pressure in the chamber becomes 10 ⁻⁴ Pa or less.
When an electron flow of 400 to 800 mA is generated and the electron flow is made to collide with a 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. An inert gas was introduced, the gas pressure was adjusted to 0.05 to 0.1 Pa to generate plasma, and the induction antenna was operated at a high frequency of 13.56 MHz to 500.
By applying a power of W and a bias voltage of a DC voltage of 100 to 500 V, normally,
A metal film such as copper having a thickness of 3 to 0.5 μm can be formed on the surface of the molded product.

In forming the metal film 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 an 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 as 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 adhesion of the circuit forming portion 4 is not deteriorated, and the boundary portion is formed. By removing the metal film of 6, the circuit forming portion 4
2 shows a state in which the metal film of is separated as a circuit pattern.
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 for excess and deficiency of metal film removal at the pattern edge to occur,
The dimensional accuracy of the pattern edge portion is good, and it is easy to achieve high density by making the circuit pattern fine lines and minimizing the circuit pattern gap. 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 or less, further 0.0
It becomes easy to form it to 5 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 5 having a thickness of 0.3 to 0.5 μm and electrolytic plating. By leaving most of the applied circuit forming portion 7, a molded circuit board 9 having a circuit pattern 8 having a desired shape as shown in FIG. 1F can be obtained. In addition, on the surface of this circuit pattern 8,
Furthermore, nickel plating, gold plating, or the like may be performed, and another conductive layer may be provided to a thickness of several μm, if necessary.

In this circuit formation, the liquid crystalline 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 product was activated by the plasma treatment described above, and the above physical properties were used. Combining various processes such as metal film formation by vapor deposition method, circuit pattern formation by metal film removal by laser light irradiation, electrolytic plating treatment, soft etching treatment, etc. is very compatible, and various characteristics can be achieved without degrading desired characteristics. The processing quality of the 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 molded product on which the metal film is formed can be used for any purpose, in addition to a molded circuit board such as MID, as long as a metal film is formed on the surface of the molded product. Sensor, LED lamp, connector, socket, resistor, relay case, switch, coil bobbin, capacitor, variable capacitor case, DVD, CD
Optical pickup parts (lens holders, slide bases, etc.), crystal oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystals Electric / electronic parts such as display parts, FDD carriage, FDD chassis, HDD parts, motor brush holders, built-in antennas, parabolic antennas, computer-related parts, parts for portable information terminal devices such as mobile phones; VTR parts, TVs Parts, irons, hair dryers, rice cooker parts, microwave oven parts, microphones, headphones, speakers, audio / laser disk (registered trademark) / compact disks / mini disks, and other audio / audio equipment parts, lighting parts, refrigerator parts,
Air-conditioner parts, photosensitive drums, copy parts such as paper separating claws, printer parts, typewriter parts, word processor parts, and other household, office electrical product parts, fax-related parts, copier-related parts, office computer-related parts, Various bearings such as telephone-related parts, cleaning jigs, oilless bearings, stern bearings, underwater bearings, various gears, motor parts, etc. can be mentioned. 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.

[0099]

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
Charge 0.67 kg into a pressure vessel and run under a nitrogen atmosphere.
After reacting at ~ 150 ° C for 4 hours, 2 hours over 2.5 hours
Deacetic acid polycondensation reaction by raising the temperature to 50 ° C., reacting at 250 ° C. for 2.5 hours, further raising the temperature to 320 ° C. over 2 hours, and then depressurizing the system to 1 mmHg in 1.5 hours. As a result, a melting point of 314 ° C. composed of 80 molar equivalents of aromatic oxycarbonyl units, 7.5 molar equivalents of aromatic dioxy units, 12.5 molar equivalents of ethylenedioxy units and 20 molar equivalents of aromatic dicarboxylic acid units, melt viscosity 25Pa ・ s (324 ℃, orifice 0.5mm diameter x 1
Pellets of 0 mm and a shear rate of 1,000 (1 / sec) were obtained. Reference Example 2 PPS (linear type): M2588 (manufactured by Toray) was used. Reference Example 3 PEEK: 450PF (manufactured by Victorex) was used. Reference Example 4 PS: G690K (manufactured by Nippon Polystyrene Co., Ltd.) was used.

Each evaluation was measured according to the method described below. (1) Flowability: Using the following molding machine, injection speed 99%,
0.5 mm thickness under injection pressure of 500 kgf / cm ²
A test piece with a width of 12.7 mm was molded and the flow length (bar flow length)
Was measured. (2) Heat resistance: 3.2 mm thickness x 1 using the following molding machine
Mold a test piece of 2.7mm width x 127mm length,
The deflection temperature under load (DTUL) was measured according to ASTM D648 (1.82 MPa). (3) Bending property: 3.2 mm thick × using the following molding machine
A test piece having a width of 12.7 mm and a length of 127 mm was molded and measured according to ASTM D790 to obtain bending strength and bending elastic modulus. (4) Adhesion of metal film: 1 mm thickness x using the following molding machine
A 40 mm wide x 30 mm long test piece was molded.

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 argon gas was introduced into the chamber to a gas pressure of 0.1 Pa in this state. 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.

A universal testing machine (EG manufactured by Shimadzu Corporation)
TEST) was used to determine the peel strength (90 degree peel strength) of the copper film per unit width. Examples 1 to 5 and Comparative Example 1 Using a TEX30 twin-screw extruder manufactured by Japan Steel Works at a ratio shown in Table 1, LCP1 was used as the liquid crystalline resin (A) and non-liquid crystalline resin (B) was dry blended. Glass fiber (6 μm diameter, 3 mm length, ECS manufactured by Nippon Electric Glass Co., Ltd.)
03T-790DE) was supplied from the side feeder in an amount shown in Table 1 to 100 parts by weight of the liquid crystalline resin (A), and melt-kneaded at a cylinder temperature of 315 ° C. to form pellets. The weight average fiber length of the glass fibers in this pellet was measured. Injection molding machine for this pellet (FANUC CORPORATION)
Manufactured by Roboshot 30α-C), cylinder temperature 32
Test pieces were molded by the method for each evaluation item under the conditions of 0 ° C. and mold temperature of 90 ° C. Comparative Example 2 Nylon 6 instead of PPS (Amylan CM10 manufactured by Toray)
Evaluation was performed in the same manner as in Example 1 except that 10) was used.

As is clear from Table 1, the composition of the present invention is superior in adhesiveness to the metal film as compared with the composition of Comparative Example,
It is also found that the fluidity, heat resistance, and mechanical properties are excellent.

[0105]

[Table 1]

Examples 6 and 7 and Comparative Example 3 Using the TEX30 twin-screw extruder manufactured by Japan Steel Works at a ratio shown in Table 2, LCP1 was used as the liquid crystalline resin (A) and the non-liquid crystalline resin (B) was used. Are dry-blended and supplied from the beginning, and aluminum borate whiskers (0.5 to 1 μm diameter, 10 to
30 μm long, Arbolex YS3A manufactured by Shikoku Chemicals)
The amount shown in Table 2 was supplied from 100 parts by weight of the liquid crystalline resin (A) from the side feeder, and melt-kneaded at a cylinder temperature of 315 ° C. to form pellets. The weight average fiber length of the aluminum borate whiskers in this pellet was measured. The pellets were subjected to an injection molding machine (Roboshot 30α-C manufactured by FANUC CORPORATION), and a cylinder temperature of 320
Test pieces were molded by the method for each evaluation item under the conditions of ℃ and mold temperature of 90 ℃.

As is clear from Table 2, the composition of the present invention is superior in adhesiveness to the metal film and excellent in fluidity, heat resistance and mechanical properties as compared with the compositions of Comparative Examples. I understand.

[0108]

[Table 2]

[0109]

The liquid crystalline resin composition for molded articles of the present invention is
Since it is excellent in metal film adhesion, fluidity, heat resistance, and mechanical properties, it is a material suitable for a molded product for forming a metal film such as a molded circuit board. In addition, the molded circuit board of the present invention has a variety of three-dimensional shapes that are miniaturized and further miniaturized by combining the liquid crystal 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 excellent circuit pattern adhesion, mechanical strength, heat resistance, and dimensional stability.

The liquid crystalline resin composition for molded products according to any one of claims 1 to 8 of the present invention is a non-liquid crystalline resin containing a repeating unit having at least one aromatic ring with respect to 100 parts by weight of the liquid crystalline resin (A). A liquid crystalline resin composition for a molded product, which comprises 0.5 to 30 parts by weight of a resin (B), wherein the molded product has a metal film formed on the surface of the molded product and adheres to the metal film. A molded article having excellent properties, fluidity, heat resistance, and mechanical properties can be obtained.

The liquid crystalline resin composition for molded articles according to claims 2 to 3 of the present invention can be further adhered to a metal film by selecting a specific non-liquid crystalline resin (B) in the constitution of claim 1. A molded product having excellent properties can be obtained.

The liquid crystalline resin composition for molded articles according to any one of claims 4 to 5 of the present invention can be prepared by selecting a specific liquid crystalline resin (A) among the constitutions according to any one of claims 1 to 3. Further, a molded product excellent in metal film adhesiveness can be obtained.

The liquid crystal resin composition for molded articles according to claim 6 of the present invention is the same as the composition according to any one of claims 1 to 5, in addition to 100 parts by weight of the liquid crystalline resin (A), a filler ( C) By containing 5 to 200 parts by weight,
Further, a molded product excellent in metal film adhesion, heat resistance and mechanical properties can be obtained.

The liquid crystalline resin composition for molded articles according to claim 7 of the present invention has a further metal content by selecting a specific amount of a specific glass fiber as the filler (C) in the constitution of claim 6. A molded article having excellent film adhesion, fluidity, heat resistance and mechanical properties can be obtained.

The liquid crystalline resin composition for molded articles according to claim 8 of the present invention has the same composition as in claim 6 by selecting a specific amount of a specific whisker as the filler (C).
In addition to being excellent not only in metal film adhesion, fluidity, heat resistance, and mechanical properties, but also in terms of surface smoothness, a molded product can be obtained. A molded substrate is obtained.

The liquid crystalline resin composition for molded articles according to claim 9 of the present invention is the same as the composition according to any one of claims 1 to 8,
After the plasma treatment is applied to the surface of the molded product, a metal film is formed by any of the methods of sputtering, vacuum deposition, and ion plating, so that a molded product with even better metal film adhesion can be obtained. is there.

The liquid crystalline resin composition for a molded product according to a tenth aspect of the present invention is the same as that according to any one of the first through ninth aspects, in which the metal film formed on the surface of the molded product is irradiated with laser light. By carrying out circuit patterning, a molded product in which a circuit having further excellent metal film adhesion is formed can be obtained.

A molded circuit board according to an eleventh aspect of the present invention has a metal film formed on the surface of a molded article molded using the liquid crystalline resin composition for a molded article according to any one of the first to tenth aspects. A molded circuit board characterized in that a circuit is formed in the film, compared to the conventional, it is possible to obtain a molded circuit board excellent in circuit pattern adhesion and mechanical strength, heat resistance and dimensional stability, In particular, it is possible to obtain a high-quality precision electronic circuit board which is suitable for small-sized precision electronic circuit equipment and which is miniaturized and ultra-miniaturized by various three-dimensional shapes.

In the molded circuit board according to claim 12 of the present invention, in addition to the structure of claim 11, a metal film is formed on the surface of the molded product by any one of sputtering, vacuum deposition and ion plating. As a result, a molded circuit board having further excellent metal film adhesion can be obtained.

According to the thirteenth aspect of the present invention, in addition to the configuration of the twelfth aspect, the surface of the molded article is subjected to plasma treatment, and then any one of sputtering, vacuum deposition and ion plating is performed. By forming the metal film by the method, a molded product having further excellent adhesion to the metal film can be obtained.

The liquid crystal resin composition for a molded product according to a fourteenth aspect of the present invention is the structure of any one of the eleventh to thirteenth aspects, wherein the metal film formed on the surface of the molded product is irradiated with laser light. When circuit patterning is performed, the metal film of the laser irradiation part is removed without lowering the metal film adhesion of the circuit part, and the surface smoothness of the molded product is excellent, so a circuit with excellent dimensional accuracy for precision fine line Thus, a molded circuit board on which is formed is obtained.

[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) H05K 3/08 H05K 3/08 D 3/14 3/14 A 3/16 3/16 3/38 3 / 38 A // (C08L 101/00 C08L 81:02 81:02) 71:10 (C08L 101/00 C08L 25:06 71:10) (C08L 101/00 25:06) (72) Inventor Masaru Okamoto Osaka 1-6-20 Dojima, Kita-ku, Osaka City, Toray Co., Ltd. Osaka Main Office (72) Inventor Naoto Ikegawa 1048 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works Co., Ltd. (72) Masahiro Sato Kadoma City, Osaka Prefecture Daiji Kadoma 1048 Matsushita Electric Works Co., Ltd. F-term (reference) 4J002 BC032 BC062 BN072 BN142 BN152 BN162 CC032 CF031 CF041 CF051 CF062 CF072 CF081 CF091 CF101 CF181 CF212 CG012 CH072 CH092 CL032 CM042 CN012 DE107 DE090 DA032 DA032 DA016 DE237 DJ006 DJ007 DJ016 DK007 DL006 FA046 FA067 5E339 AB02 AD01 BD11 BE05 DD03 5E343 AA16 AA36 BB23 BB24 BB34 BB35 BB39 BB40 BB55 DD23 DD24 DD25 DD43 EE36 GG02 GG08 GG16

Claims (14)

[Claims] 1. A molded product comprising 0.5 to 30 parts by weight of a non-liquid crystalline resin (B) containing a repeating unit having at least one aromatic ring with respect to 100 parts by weight of the liquid crystalline resin (A). A liquid crystalline resin composition for a molded product, wherein the molded product has a metal film formed on the surface of the molded product. 2. The molding according to claim 1, wherein the non-liquid crystalline resin (B) is at least one non-liquid crystalline resin selected from polyphenylene sulfide, aromatic polyether ether ketone and polystyrene. Liquid crystalline resin composition for products. 3. The liquid crystalline resin composition for molded articles according to claim 1, wherein the non-liquid crystalline resin (B) is polyphenylene sulfide. 4. The liquid crystalline resin (A) is a liquid crystalline polyester comprising the following structural units (I), (II), (III) and (IV), wherein The liquid crystalline resin composition for molded articles as described above. [Chemical 1] (However, R ₁ in the formula is It represents one or more groups selected from, R ₂ is ## STR3 ## 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. ) 5. The liquid crystalline resin (A) is the structural unit (I),
A liquid crystalline polyester comprising (II), (III) and (IV), wherein the total of the structural units (I) and (II) is based on the total of the structural units (I), (II) and (III). 30 to 95 mol%, the structural unit (III) is 70 to 5 with respect to the total of the structural units (I), (II) and (III).
The liquid crystal for a molded article according to claim 4, wherein the molar ratio is [(I) / (II)] of the structural unit (I) to (II) is 75/25 to 95/5. Resin composition. 6. A liquid crystal for a molded article according to claim 1, which contains 5 to 200 parts by weight of the filler (C) with respect to 100 parts by weight of the liquid crystalline resin (A). Resin composition. 7. The filler (C) is a glass fiber having a fiber diameter of 3 to 15 μm and a weight average fiber length of 0.01 to 0.6 mm, and the content thereof is 100 parts by weight of the liquid crystalline resin (A). The liquid crystalline resin composition for molded articles according to claim 6, wherein the amount is 10 to 150 parts by weight. 8. The filler (C) has a fiber diameter of 0.05 to 5 μm.
m is a whisker having a weight average fiber length of 1 to 100 μm, and the content thereof is 10 to 150 parts by weight with respect to 100 parts by weight of the liquid crystalline resin (A).
The liquid crystalline resin composition for molded articles as described above. 9. A metal film is formed on the molded product by subjecting the surface of the molded product to plasma treatment and then performing any one of sputtering, vacuum deposition, and ion plating. 8. The liquid crystalline resin composition for molded articles according to any one of 8 to 8. 10. The liquid crystal for molded product according to claim 1, wherein the metal film formed on the surface of the molded product is subjected to circuit patterning by laser light irradiation to form a circuit. Resin composition. 11. A metal film is formed on the surface of a molded product molded using the liquid crystalline resin composition for a molded product according to claim 1, and a circuit is formed on the metal film. Characterized molded circuit board. 12. The surface of the molded article is sputtered,
The metal film is formed by any one of vacuum deposition and ion plating.
The molded circuit board described. 13. The metal film is formed on the surface of the molded product by a plasma treatment and then by any one of sputtering, vacuum deposition, and ion plating. Molded circuit board. 14. The molding according to claim 11, wherein the metal film formed on the surface of the molded product is subjected to circuit patterning by laser light irradiation to form a circuit. Circuit board.