TW200944562A - Metal-coated resin molded article, and process for production thereof - Google Patents

Abstract

Disclosed is a metal-coated resin molded article comprising a base and a metal coating film formed on the surface of the base. The base is produced by molding a resin composition comprising the components A, B and C shown below, wherein the component C is contained in an amount of 0.1 to 25 parts by mass relative to the total amount (100 parts by mass) of the components A and B. A: a first liquid crystalline polyester having a heat deflection temperature of 200 DEG C or higher. B: a second liquid crystalline polyester having a lower heat deflection temperature than that of the first liquid crystalline polyester. C: an ethylene copolymer having an epoxy group (provided that the ethylene copolymer has an ethylene unit and an unsaturated carboxylic acid glycidyl ester unit and/or an unsaturated glycidyl ether unit in amounts of 50 to 99.9 mass% and 0.1 to 30 mass%, respectively, in the molecule.

Description

[Technical Field] The present invention relates to a metal-coated resin molded article and a method for producing the same, which are used in a substrate containing a resin composition containing a liquid crystalline polyester. Electronics industry. [Prior Art] In recent years, liquid crystalline polyester has been widely used as a material for electronic parts or mechanical parts. For example, a circuit board obtained by forming a metal film on the surface of a substrate on which a resin composition containing a liquid crystalline polyester is formed has good formability, dimensional stability, high modulus of elasticity, and strength, and thus functions as a three-dimensional circuit substrate (M丨D). The use of materials has attracted a lot of attention. However, since there is no strong chemical bond between the resin substrate and the metal film, it is generally difficult to obtain high adhesion between the resin substrate and the metal film. In particular, in the case of a circuit board, when the circuit board receives a heat load, the adhesion of the metal film is lowered, and there is a problem that peeling from the resin substrate occurs. The resin substrate obtained by molding the liquid crystalline polyester resin composition has a problem of adhesion to the metal film. In order to improve the problem, it is proposed to form a liquid crystal polyester resin composition and to form a resin substrate. The resin substrate is heated in a vacuum chamber to have a surface temperature of 60 ° C or higher, and the metal film is evaporated by sputtering, ion plating, or true 3 200944562 (refer to Japanese Patent Laid-Open No. Hei 3-8388) ). However, according to such a vapor deposition method of controlling only the metal film, it is not possible to sufficiently improve the material properties. Under such circumstances, the inventors of the present invention have found that a resin composition obtained from a liquid crystalline polyester resin, an epoxy group-containing ethylene polymer, and an inorganic filler is molded to form a substrate on the surface of the substrate. The metal coating film is formed by a physical vapor deposition method, and a metal-coated resin molded article having high adhesion between the surface of the substrate and the metal film can be obtained (refer to Japanese Laid-Open Patent Publication No. Hei 2 〇〇 5 2 9 7 307) . As described above, in the metal-coated resin molded article obtained by the invention of Patent Document 2, the metal film is formed with high adhesion, but the metal film is required to respond in recent years to form a finer electric (four) demand. From the viewpoint of further improving the production yield, etc., the current situation is to further improve the adhesion of the metal film. SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a metal-coated resin molded article which can form a metal film and which is more highly adhesive, and a method for producing the same. The metal-coated resin molded article of the present invention is a substrate obtained by molding a resin composition containing the following components A, B, and C, and a metal film formed on the surface of the substrate: 200944562: A: first liquid crystallinity The polyester 'has 2 〇〇. (3 or more load offset temperature; B: second liquid crystalline polyester, the load offset temperature is lower than the load shift temperature of the first liquid crystalline polyester; and C: epoxy group-containing ethylene copolymer,

(Only the epoxy group-containing ethylene copolymer system contains ethylene units of 50 to 9.9 mass percent, unsaturated carboxylic acid glycidyl ester units, and/or unsaturated propylene propylene monomer units 〇·1 to 3 〇 mass percentage), the total amount of the resin composition relative to the component A and the component B is 100 parts by mass 'component C is Q.; [to 2 5 f parts by weight range. Here, the definition of the load offset temperature refers to the load offset temperature obtained by A s τ M D 6 4 8 (1998). According to the present invention, by blending the epoxy group-containing ethylene copolymer of the liquid crystalline polyester, not only the (4) of the surface layer of the substrate but also the adhesion of the metal to the substrate can be improved. At the same time, as a liquid crystal polyphenolic system, the first liquid crystalline polyester has a load offset temperature of 2 generations or more; and the second liquid crystal property (4) has a load offset temperature higher than that of the first liquid crystalline polyester. The offset temperature is lower, whereby the heat resistance can be maintained by the first liquid crystal poly 5 200944562, and the adhesion of the metal bead to the substrate can be questioned by the second liquid crystalline polymer to be more highly The adhesion forms a metal film. Further, the present invention is characterized in that in the resin composition, the component 8 is a mass percentage of 5 parts by mass based on the total amount of the component A and the component b. According to the present invention, the heat resistance can be maintained by the component A (first liquid crystalline polyester), and the adhesion to the metal film of the substrate can be improved by the component B (second liquid crystalline polymer). Get it more efficiently. The present invention is characterized in that the component B of the component A and the component B is 30 mass% or less. According to the present invention, the resulting heat resistance is maintained to be usefully used. The component A (first liquid crystalline polyester) can be used in the application of heat resistance, and the second liquid crystalline polyacetate group is bonded by an ester bond. The aromatic group contains 1 '2-phenylene, 1,3-phenylene, 2,3 = at least one of the sowing stalks, stalks, stalks, stalks, and aromatics. 4 people, relative to the divalent aromatic brigade, soil s

The total amount of T w Fangxiang base is 1〇 to 45莫”. 4 J Guan J According to the present invention, i, 2 200944562: phenyl, 1 '3-phenylene, 2,3-naphthyl group having a structure of a flexible molecule, as a divalent aromatic group, and the second liquid crystal can be adjusted. The viscosity shift of the polyester is low. m Further, in the present invention, the epoxy group-containing ethylene copolymer is characterized in that it contains ethylene units in the molecule from 8 9 to 98% by mass, unsaturated carboxylic acid glycidyl ester units and/or unsaturated propylene glycol. The ether level is from 2 to 15 mass percent. According to the present invention, it is possible to suppress a decrease in heat resistance of a substrate due to blending of an epoxy group-containing ethylene copolymer, and to obtain a metal-coated product excellent in heat resistance. Further, the present invention is characterized in that the resin composition contains, in addition to the components A to C, a fibrous inorganic filler having a diameter of 6 to 15 and an aspect ratio of 5 to 50. According to the present invention, the adhesion to the metal film can be ensured, and the strength of the substrate can be improved by the fibrous inorganic filler. The method for producing a metal-coated resin molded article of the present invention comprises the steps of: forming a resin composition to obtain a matrix; and coating a metal film on the surface of the substrate. According to the present invention, in the resin composition, by forming an epoxy group-containing ethylene-containing ethylene copolymer which is blended in a liquid enthalpy, a substrate having improved surface toughness can be formed, and the metal film can be improved on the substrate. The adhesion is also used as a liquid crystal polyester: first liquid crystal 7 200944562 polyester, which has a load offset temperature of 2 ο 〇 °c or more; and second liquid crystalline polyester 'its load offset temperature It is lower than the first liquid crystalline polyester, and the heat resistance can be maintained by the first liquid crystalline polyester, and the adhesion to the metal film of the substrate can be improved by the second liquid crystalline polymer, and A high degree of adhesion forms a metal film. Further, the present invention is characterized in that a step of performing a plasma treatment on the surface of the substrate is included before the coating step. According to the present invention, the surface of the substrate can be activated by plasma treatment, and the adhesion to the metal film on the surface of the substrate can be further improved. Further, the present invention is characterized in that, before the coating step, one is contained in (Tml - 12 〇) °c to (Tml - 2 〇) c [eight, and m 1 represents the beginning of the first liquid crystalline polyester. The temperature of the flow temperature (C) is subjected to a step of heat treatment of the substrate. According to the present invention, in addition to the metal film, in addition to the metal film, the effect of reducing the dielectric loss of the substrate can be obtained, and a metal-coated resin molded article excellent in high-frequency characteristics and the like can be obtained. ^... The feature is that the child coating step is a step of forming a metal film on the surface of the substrate by the physical vapor deposition method. The physical vapor deposition method of the method is formed to be high. According to the present invention, the surface of the dry gas substrate can be made to adhere to the metal. By the metal film, the feature of the present invention contains the step of performing laser patterning on 200944562 to form a circuit pattern. According to the present invention, the patterning by laser irradiation does not reduce the adhesion to the metal film of the substrate, and the metal film other than the circuit portion can be removed to form a circuit, and the circuit of the fine pattern can be easily performed. form.

As described above, according to the metal-coated resin molded article of the present invention, the epoxy group-containing ethylene copolymer is blended, whereby the toughness of the surface layer of the substrate can be improved, and the adhesion to the metal film of the substrate can be improved. And as a liquid crystalline polyester, by using: a liquid crystal polyester having a load shift temperature of 2 〇〇h and a second liquid crystal property (IV), which has a specific liquid crystalline polyester The load shift temperature is lower than the load offset temperature, and the first liquid crystalline polyester can maintain the heat resistance, and the second liquid crystalline polymer can improve the adhesion to the metal film of the substrate, and the height can be increased. The adhesion forms a metal film. Then, in the metal-coated resin molded article, a fine circuit pattern can be formed by a metal film having high adhesion, and in the field of the electric and electronic industry, in particular, high-frequency characteristics are considered to be necessary. The aspect of the present invention is as follows. 9 200944562 The substrate used in the present invention is obtained by molding a resin composition containing the components A, B and C as essential components. First, the liquid crystalline polyester of the component A and the component B will be described. Here, the liquid crystalline polyester refers to a polyester which can form a molten phase having an optically anisotropic property, and is preferably a polymer main chain system derived from an aromatic group from the viewpoint of obtaining a substrate having high heat resistance. The aromatic group is a polyester bonded by an ester bond c (〇)〇 or - 0 C (〇)~). Further, the aromatic group means a group which further contains a monocyclic aromatic group or a condensed cyclic aromatic group to bond directly, in addition to a monocyclic aromatic group, a condensed ring aromatic group, or is selected from an oxygen atom. The concept of a sulfur atom, a group having a enthalpy of up to 6 stone anisotropy, a sulfhydryl group, and a bond group of several groups.

The first liquid crystalline polyester which is component A has 2 〇 〇 which is at a load offset temperature, and the second liquid crystalline polyester which is component B has a load offset temperature lower than that of the first liquid crystalline polyester. That is, the combination of the first liquid crystalline polyester and the second liquid crystalline polyester is selected such that the load offset temperature of the first liquid crystalline polyester is T b 1 (t ), and the load shift of the second liquid crystalline polyester When the temperature is τ b 2 (it), the subtype can be satisfied. Tb 12200 °CT b 1 > T b 2 In addition, the liquid crystal polyester load shift temperature can control the molecular weight of 200944562 liquid crystalline polyester; change the monomer unit combination method to attack the Japanese polyester The method of controlling the liquid crystal of the load shift temperature of the liquid crystal at the desired (four) load-shift temperature by these methods is described in detail. The second liquid crystal singer is as described above, and the load shift is 2 〇C or more, preferably 23 〇m, more preferably 240 ° C or more. The first liquid helium, the ground pick... The load temperature of the nighting polyester (L) 2 〇Μ, the thermal deformation of the matrix formed by the formation of the resin composition becomes large, and the desired size is obtained. Metal-coated resin molded articles have become difficult. In addition, the upper limit of the load offset temperature (T b 1 ) I* im and 1 b 1 of the first nature is not particularly limited. The upper limit is 3 〇 〇t:. Further, the load offset temperature (T b 2 ) of the second liquid crystalline polyester is lower than the load shift temperature (τ b 1 ) of the above-mentioned liquid crystal polyester, and the load shift temperature ( Tb 2 ) may be selected according to the load offset temperature (Tb i ) of the first liquid crystalline polyester. The load offset temperature (Tb2) is preferably not less than l9crc, and more preferably not more than 15 ◦ C. When the load shift temperature (Tb2) of the second liquid crystal polymer is more than 190 〇C, the effect of improving the adhesion of the metal film may not be sufficiently obtained. Further, the lower limit of the load deflection temperature (Tb 2) of .. ^ - crystal clear polyester is not particularly specified. However, the practical lower limit is about 1 〇 〇〇c. 11 200944562 A combination of the above: a liquid crystalline polyester having a load offset temperature (Tb 1) as a gate; and a first liquid crystalline polyester having a low load offset temperature (T b 2 ), which may be loaded biased The temperature (D) is the first liquid crystalline polyester to ensure heat resistance, and at the same time: the second liquid crystalline polyester with a low offset/tap (T b 2) is "close to the metal film." The base material is preferably 5 CTC or more, more preferably 〇8 (JC or more), in the shape of the mold, and the load offset temperature of the second liquid crystalline polyester is η 〇 1 Tb2)'. π' is referred to as the first liquid crystal (four) or the second liquid crystalline poly: it is described as suitable. For the liquid crystalline polyester, for example, 11) will be composed of aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid and aromatic The monomers obtained by combining the diols are combined and polymerized; (2) the different kinds of aromatics are obtained by polymerization; the hydroxycarboxylic acid is used as a monomer.

The monomer formed by the diol Q 3 ) is obtained by combining and polymerizing an aromatic dicarboxylic acid and an aromatic compound. In addition, by using these ester-forming derivatives = aromatic phthalic acid, aromatic dicarboxylic acid, aromatic diol, liquid crystalline polyester is also produced, and liquid crystal polymerization can be obtained by using such a derivative. The manufacture of esters is easier and better. 12 200944562 In the above (1) to (3), it is more preferable to use the crystallized vinegar. In the manufacture of such a liquid crystalline poly-father, it is wrong to cause the aromatic diol and the aromatic hydroxy group to be condensed with a fatty acid anhydride. The phenolicity of corpse/carboxy oxime is violent and the alkaloids are comparable. 1 and, the aromatic dicarboxylic acid and the aromatic sulfonium are vinegar exchanged to carry out the polymerization method == By vinegar exchange reaction and polycondensation between monomers

Jf, 'serving a relatively low molecular weight polyacetate (referred to as "the first stage 22, and the second stage: making the low molecular weight polyester into each other =,.". High molecular weight (referred to as "the second stage Polymerization:): a polymerization method of a segment. This polymerization method has an advantage that the molecular weight of the liquid crystalline polyester can be easily controlled. Here, the above-mentioned fatty acid can be used, for example, acetic anhydride, propionic acid, Butyric anhydride, isobutyric acid, valeric anhydride, trimethylacetic anhydride ethyl hexane anhydride, monogas acetic acid liver, di-glycolic anhydride, bis-acetic anhydride, mono-methanol anhydride, di-an acetic anhydride, tri-acetic acid :, early fluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, pentane: anhydride: maleic anhydride, succinic anhydride, s-bromopropionic acid. These may be used alone or in combination. In the above, in terms of price and handling, it is preferably acetic anhydride, propionic acid, butyric acid, isobutyric acid, more preferably acetic acid needle. Also, in liquid crystalline polyester In the polymerization reaction, it is preferred to use a non-imidazole compound of the following formula (C 1 ) as a catalyst. With Increases in these 200,944,562 of producing a liquid crystal polyester, the polyester obtained with no significant polymerization reaction of the imidazole compound to coexist laugh, an appropriate occasion, the polymerization time is shortened with the color, etc. advantages of [1]

(In the formula (C1), the ruler 1 to the ruler 4 represent a group independently selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a cyano group, a cyano group having 1 to 4 carbon atoms, and a carbon number of 1. a cyanoalkoxy group, a carboxyl group, an amine group, an amine alkyl group having 1 to 4 carbon atoms, an amine alkoxy group having 1 to 4 carbon atoms, a phenyl group, a benzyl group, a phenylpropyl group and a methyl group; . Specifically, the p-mistazole compound represented by the formula (C 1 ) is, for example, imidazole, 1-methylimidazole, 2-mercaptoimidazole, 4-mercaptoimidazole, 1-ethylimidazole, 2-ethylidene Imidazole, 4-ethylimidazole, 1,2 dinonyl imidazole, 1,4-dimethylimidazole, 2'4-methyl-methyl 11-seat, 1-mercapto- 2-ethyl 1-methyl-tetraethylimidazole, 1-ethyl-2-methylimidazole, 1-ethyl-2-ethylimidazole, 1-ethyl-2-phenylimidazole, 2-ethyl-4- - mercapto imidazole, 2-phenylimidazole, 2-undecyl imidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4-indolyl imidazole, 1-cyano Ethyl-2-mercaptoimidazole, 1-cyanoethyl-2-phenylimidazole, 200944562 aminoethyl 4-cyanoethyl-2-ethyl- 4, w~methylimidazole, etc. A single type may be used, and two or more types may be used in combination. Among them, preferred imidazole compounds, = is the latter number, and R2 and m4 are all hydrogen fields, and in particular, in terms of ease of availability, it is preferred to use methylimidazole and/or 2-methylimidazole.

In the above transesterification/polycondensation reaction, the molecular weight of the obtained liquid crystalline polyester can be controlled by the ratio of the carboxyl group to the aromatic dicarboxylic acid and/or the aromatic hydroxycarboxylic acid in the transesterification/polycondensation reaction. For the liquid crystalline polyester having a molecular weight of two, the number of thiol equivalents of the brewing base compound to be supplied to the polymerization reaction, and the number of carboxyl equivalents of the aromatic dicarboxylic acid and/or aromatic hydroxycarboxylic acid are determined. The number of equivalents / / [m base equivalent number] indicates that it is preferably from 0 8 to 12. Further, the polymerization reaction of the liquid crystalline polyester as described above is preferably carried out in two stages, and in the first stage of polymerization (mainly in the stage of carrying out the transesterification reaction), the polymerization temperature is preferably from 25 to 4 Torr. . Preferably, it is between 150 and 350. . The scope is carried out. Further, in the case where the thiolation reaction and the first-stage polymerization are carried out in the same reactor, it is preferred to raise the temperature from the reaction temperature of the thiolation reaction to the reaction temperature of the first-stage polymerization. The heating rate is preferably from $ to 50 ° C / min, more preferably from 1 to 丄 0 ^ 〆. As the starting material for the thiol compound, it is preferred to use a thiolated aromatic diol and/or an aromatic oxindole 200944562 acid in advance. Among them, from the viewpoint of availability of raw materials, etc., it is preferred to use a phenolic hydroxyl group of an aromatic diol and an aromatic hydroxycarboxylic acid to be thiolated with a fatty acid anhydride in a reactor similar to the polymerization reaction, and hunting The brewing base thus paid. In this case, the amount of the fatty acid anhydride is preferably from 1 〇 to 1. 2 equivalents (equ' iv) in the total amount of the phenolic hydroxyl group of the aromatic diol and the aromatic hydroxycarboxylic acid. Alent ^111168), more preferably 1. 〇 5 to 1. 1 million. In the case where the equivalent amount of the sulphuric acid base is less than 1.0, the balance deviation during the thiolation may cause sublimation of the raw material during the polymerization of the liquid crystalline polyester, and it is easy to make The reaction system is blocked (c 1 ogg i ng). On the other hand, in the case where the amount of the fatty acid anhydride exceeds 1.2 times the number of equivalents of the phenolic hydroxyl group, the coloring of the obtained liquid crystalline polyester causes problems. The conditions for obtaining the thiolation of the thiol compound are from 1 3 Q to 18 〇 ° C, from 30 minutes to 20 hours, more preferably from 1 4 〇 to 16 〇i to 5 hours.

Time. Further, in order to utilize the balance deviation and promote the transesterification reaction of the mercapto group with the carboxyl group, it is preferred to evaporate the by-produced fatty acid and the unreacted fatty acid anhydride and remove it from the reaction system. Moreover, if a part of the distilled fatty acid is returned to the 'OIL' in the reactor, the evaporated or sublimated raw material component can be returned to the refluxed fatty acid by condensation or g-sublimation. Reaction 16 200944562

The first stage polymerization is carried out, and the second stage polymerization is carried out. The relatively low molecular weight polymer (hereinafter referred to as "prepolymer") obtained by the first-stage polymerization is cooled, preferably after being cooled to about room temperature, and then solidified, and the obtained solid matter is pulverized, etc., and processed. Powdered, thin 4 (f lake) powder. Here, "powdered" means a powder having an average particle diameter of i mm or less, preferably a powder having an average particle diameter of 0.1 to 1 mm. Second order

The stage polymerization is such that the pre-temperature of 200 to 35 is processed into a powder (TC is polymerized. In addition, the stage I polymerization can be carried out while the temperature is raised stepwise, in particular, the polymerization temperature is higher than that of the first stage polymerization. At a low temperature, the temperature is raised in about 5 to 2 hours, and then until the final polymerization temperature (2 〇〇 to 3 5 0 C), after raising the temperature for 1 to 1 hour, the final polymerization temperature is maintained and polymerization is carried out. First, the prepolymer is polymerized to form a liquid crystalline polyester. The molecular weight of the obtained liquid crystalline polyester can be controlled by the polymerization conditions of the second-stage polymerization, and can be produced under the control of polymerization conditions. A liquid crystalline polyester having a desired molecular weight. As described above, the first-stage polymerization is carried out by melt polymerization, and the second-stage polymerization is carried out by solid phase polymerization. Generally, the higher the molecular weight of the liquid crystalline polyester, the load is shifted. The tendency of higher temperature is suitable for the production of the first liquid crystalline polyester and the second 17 200944562 liquid crystalline polyester of the present invention, by the solid phase polymerization σ < the second stage polymerization The polymerization condition can be obtained as a liquid crystalline polyester having a desired desired load offset temperature. In the case of adding a taste compound represented by the above formula (c) as a suitable catalyst, The addition amount 'the total mass of the aromatic dicaptanic acid, the musk diol and the aromatic hydroxycarboxylic acid to be supplied to the polymerization reaction is i 〇〇 part by mass, preferably 0.02 to 1 part by mass. In terms of the color tone and productivity of the polyester, the amount of addition is preferably from 5 to 5 parts by mass. When the amount is added in this range, in addition to making the polymerization of the liquid crystalline polyester easier, When the metal coating resin molded article described later is obtained, the compatibility between the base recording surface and the metal coating film can be further improved. The reason why the adhesion improving effect is exhibited is not clear, and it is based on the original insight of the present inventors. In addition, the timing of the addition of the '(IV) compound is not based on the presence of the sulfonate at the time of transesterification, but may be combined with the various monomers constituting the liquid crystal condensate. : The method of loading 'may also be a method of charging between the first-stage polymerization and the first-stage polymerization. As described above, in the polymerization reaction for obtaining liquid crystal polymerization, the taste-sit-mouth is used as a catalyst. It is particularly useful: however, other catalysts may be used as needed. Among other catalysts, ruthenium compounds such as ruthenium oxide, such as tin (II) oxalate (tin 0Xa 200944562 a V, yttrium acetate (" (tinacetat:), tin dialkyl oxide, tin compound of diaryl tin oxide, titanium compound such as titanium, titanium alkoxide, alkoxytitanate, ruthenium compound such as ruthenium dioxide, such as acetic acid Sodium, potassium acetate, acetic acid?, zinc acetate, iron(II) acetate, organic acid metal salt, such as boron trifluoride<; such as chlorinated Lewis acid, amines, amines, talc, etc. Inorganic acid. Among them, in the case of obtaining a liquid crystalline polyester

In the case of the catalyst of the polymerization T method, if the metal component is used, the electrical properties of the substrate are known, and in the case of using a catalyst containing a metal component, the characteristics of the obtained substrate should be determined to determine the type, Usage amount. In the method for producing a liquid crystalline polyester, the polymerization conditions are adjusted by adjusting the equivalent ratio of the thiol group of the hydrazide to the aromatic dicarboxylic acid and the aromatic carboxylic acid thiol group. The medium or the like can control the molecular weight of the obtained liquid crystalline polyester, and the load shift temperature of the obtained liquid crystalline polyester can be suitably adjusted. Further, in the case where the molecular weight of the liquid crystalline polyester is controlled to obtain a desired load offset temperature, the molecular weight is expressed by a reset average molecular weight from the viewpoint of heat resistance of the obtained substrate, and is preferably from 1 Torr to 5 Torr. Within the scope of 〇〇〇. In the liquid crystalline polyester of the present invention, in addition to adjusting the molecular weight as described above, in addition to adjusting the molecular weight as described above, it is controlled by optimizing various monomer units constituting the liquid crystalline polyester 19 200944562. It is also useful to have a partial planting of Jiang, Tian Xugu, and Ben (4) (4). The above-mentioned aromatic pens are tick-salted, aromatic-homo-cool, pen-yong + ί_ as follows. The monomer of the scented alcohol is exemplified as a scented diol, for example, a 4-block, a hydrogen roller, a stupid-base, a sputum-a lung gas, a gas hydrazine, an ethoxylated hydrazine. Bismuth, nitrohydroquinone, catechol, 1,4, 1, 1, 5-di-naphthalene, i, 6-di-naphthalene, 2, Qiaojing, di-naphthalene, 2,7-di-naphthalene , 2, = = (4-Hanji) propane, 2,2-bis (4__ thiol-' 5-nonylphenyl) propane, 2,2-bis (4-hydroxy-3,5- Diphenylphenyl)propane, 2,2-bis(4-based-3-ylphenyl)propane, 2,2-bis"-hydroxy'-3-phenylphenyl)propane, bis-(4 -Hydroxyphenyl)methane, bis-(4-hydroxy-3,5-diphenylene)methane, bis(4 fluorene, 3,5-dichlorophenyl)-methyl, bis-(4 hydroxy- 3 ,5-dibromophenyl)methane, bis(4-hydroxy-3-methylphenyl)methane, bis-(4-carbo-3-chlorophenyl)-methyl, 1,1-bis(4-benzoic acid) Cyclohexane, bis-(4-phenyl) ketone, bis-(4-carbyl-3,5-dimethylphenyl) fluorene, bis-(4-carbazhen-3,5-dichlorophenyl) Ketone, bis-(4-hydroxyphenyl) Sulfide, bis(4-hydroxyphenyl)sulfone. The aromatic diols selected from these may be used alone or in combination of two or more. Then in these, 4,4,-dihydroxybiphenyl, hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,2-bis(4 ❹ 20 200944562 monohydroxyphenyl)propane, The use of bis(4-hydroxyphenyl)sulfone is preferred in terms of ease of use. Further, the aromatic hydroxycarboxylic acid may, for example, be p-hydroxybenzoic acid, m-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-3-naphthoic acid or 1-hydroxy-4-naphthoquinone. Acid, 3-hydroxy-2-naphthoic acid, 4-hydroxy- 4, a rebel diphenyl scale, 2,6-dichloro-p-hydroxybenzoic acid, 2- gas-p-hydroxybenzoic acid, 2,6-difluoro A pair of hydroxybenzoic acid, 4-hydroxy-4,-biphenylcarboxylic acid. The aromatic hydroxycarboxylic acid selected from these may be used alone or in combination of two or more. Therefore, in these, it is preferred to use benzoic acid or 2-hydroxy-6-naphthoic acid for ease of availability. Further, in the first liquid crystalline polyester and the second liquid crystalline polyester, from the viewpoint of obtaining practical liquid crystallinity, it is preferable to be relatively =

The total number of monomer units constituting the liquid crystalline polyester contains at least an ear percentage of a monomer unit derived from p-hydroxyindole acid represented by the following formula (2).

Acid, isoacid, acid, 2 naphthalene to dioxin 2, 21 200944562 naphthalene dinonanoic acid, 1,5-naphthalene dicarboxylic acid, 4,4, biphenyl diterpene, terephthalic acid , isoammonic acid vinegar, diphenyl hydrazine - 4, 4 dicarboxylic acid, dipyl sulfone - 4, 4, dicarboxylic acid, diphenyl ketone - 4 ' 4 ' - dicarboxylic acid, 2, 2 '-Diphenylpropanone~Λ 9 Λ 9 — — Vjfe 3-i, ^ 4 A citric acid. The aromatic dicarboxylic acid selected from these may be used alone or in combination of two or more. In the case of the use of 'terephthalic acid, isoacid, and 2,6-tea bismuth acid', it is preferred to obtain easiness.

Next, in the present invention, it is applied to the monomer of the first liquid crystalline poly(s) of the component A, and is selected from the group consisting of 4, 4, - di-biphenyl, hydroquinone, resorcinol, 2' 6 - 2 Hydroxynaphthalene, 2,2-bis(4-(tetra)yl)propane H (4-sweetyl) milled aromatic monool' and aromatic hydroxy selected from p-hydroxybenzoic acid, 2-hydroxy-6-naphthoquinone The combination of a carboxylic acid and an aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isoacid, and 2,6:naphthalenedicarboxylic acid is preferred in terms of ease of obtaining the raw material.

In particular, in the case of the first liquid crystalline polyester, the total of the total monomer units is preferably from 30 to 80 mole percent of the monomer unit derived from the aromatic hydroxamic acid, from the aromatic diol. The unit weight is from 3 to 5 mole percent, and the monomer unit derived from aromatic di-oroxic acid is from 10 to 35 mole percent. The first crystal unit of the above-mentioned monomer unit, the load shift temperature is easy to be in the above range of 20 〇c or more, and the first liquid crystal concentration can be made by 22 200944562 The body is obtained by blending and polymerizing at the same ratio. Further, the first liquid crystalline polyester preferably has an initial flow temperature of 270 or more. By setting the initial flow temperature of the first liquid crystalline polyester to 270 ° C or higher, a substrate having good heat resistance can be obtained. The upper limit of the initial flow temperature is not particularly set, and the practical upper limit is about 350 °C.

This initial flow temperature can be obtained by the following method. In addition, the initial flow temperature measurement method described below is an index indicating the molecular weight of a liquid crystal polymer in the field (see, for example, "Small Liquid Crystal Polymer-Composite Forming Application", page 95 to 1-5 , CMC, issued June 5, 1987). (Initial flow temperature measurement method) Using a capillary rheometer having an inner diameter of 1 mm and a length of 1 nozzle, under the load of 980 N/cm 2 (1 〇〇 kgf / cm 2 ), the dew melt (me i " From the nozzle extrusion day, the melting viscosity is measured to show the temperature of 4800 berth, which is the initial flow temperature. In the relevant specification of IS, it is j ϊ s κ 6 7 1 9 ( 9 7". In order to reduce the load-shifting temperature of the liquid crystalline polyester, it is effective to introduce a monomer unit that lowers the rigidity of the liquid crystalline polyester. Here, the rigidity of the liquid crystalline polyester is lowered, and the product is taken over. Introduction 23 200944562 A monomer unit (hereinafter referred to as "flexible monomer unit") which imparts flexibility to the main chain of liquid crystal polyester, and imparts a main chain of flexibility (four) polyester. Further, the load offset temperature can be reduced. In terms of the flexible monomer, specifically, a single f unit having a frame of i, 2 -= = and a <RTIgt; 2 ' 3 - a monomer unit of a naphthyl skeleton. The monomer unit having a 1,3-phenylene skeleton is derived from meta-benzene: The monomer unit derived from the isoacid, preferably having a soil, 〇: a raw monomer unit, which is composed of a tea, and an acid having a 2,3-naphthyl skeleton: a body early position, which is 2, 3-di-naphthalene, acid hydrazine:; body: 2-naphthoquinone, preferably aromatic-alcoholic acid in the flexible monomer unit group acid, mono- or di-fragrant acid, aromatic In this case, in the monomer unit of the first compound, 20 〇 is obtained. (: The composition of the first liquid crystalline monomer unit is preferably not less than the percentage of work, particularly preferably - The content of the monomer unit is larger than the liquid crystal polyester in which the liquid crystal polypacing monomer unit is less, and the higher the load shift temperature is, the more the monomer unit of the vinegar is deflected. The percentage of 0% of the moles is more preferably 8 moles below 6 moles. The liquid crystalline polyester, by making the first liquid crystalline polyester more flexible, can make the 24th 200944562 liquid crystalline polyester The load offset temperature is lower than the load offset temperature of the first liquid crystalline polyester. Specifically, the second liquid crystalline polyester is formed. The total of the monomer units is preferably more than 1% by mole of the flexural monomer unit, more preferably more than 1.25 percent by mole, and particularly preferably more than 15 mole percent. From the viewpoint of practical heat resistance of the polyester, it is preferable that the total of the monomer units constituting the second liquid crystalline polyester is 45 mol% or less of the flexural monomer unit, and more preferably 4 mol%. The percentage of the ear is less than or equal to the above. The first liquid crystalline polyester suitable for the component A of the present invention and the second liquid crystalline polyester constituting the component B are controlled by the molecular weight of the liquid crystalline polyester or constitute a single liquid crystalline polyester. Various combinations can be obtained by changing the body unit. In the resin composition used in the present invention, the content ratio of the liquid crystalline polyester of the component A blended with the liquid crystalline polyester and the second liquid crystalline polymer of the component B is such that the component A and the component B are Total quality: When it is 100% by mass, the component B is preferably 丄 to 5 〇 by mass. Further, the base-coated resin article obtained from the resin composition of the present invention or the metal-coated resin molded article in which the metal coating film is coated on the substrate is more preferably a component... to 3 观点 from the viewpoint of maintaining a higher level of mechanical strength and heat resistance. The range of mass percentages. For example, in the case where the substrate which can withstand 25 Qt: reflow soldering is formed, it is preferable to set the component B in the range of 丄 to 〇 百 25 25 200944562. Next, the epoxy group-containing ethylene copolymer of the component c of the resin composition used in the present invention will be described. The epoxy group-containing ethylene copolymer of the component C has 5 to 99.9 mass% of ethylene units in the molecule, 〇1 to 3 〇 mass percent of unsaturated oxirane acrylate unit and/or unsaturated epoxy (4) Units. In particular, in order to obtain excellent heat resistance and stringability of the matrix obtained from the resin composition, and at the same time, in order to further improve the adhesion between the metal and the metal film, the epoxy group-containing ethylene copolymer preferably contains 80 to 98 in the molecule. Percentage by mass of women's units 2 to 15% by mass of unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units. In addition to these units, / can also contain ethylenically unsaturated ester units as needed. In this case, it should be the amount of ethylenically unsaturated ester units, which is less than 5 〇 mass percentage. a The compound represented by the following formula (3) or (4) can be used for each of the compounds of the above-mentioned unsaturated carboxylic acid glycidyl ester unit or unsaturated oxime oxime unit. [化3]

R*—~~C 0 CH2-CH (In the formula (3), R is a carbon having an ethylenically unsaturated bond. 26 (4) 200944562 Number 2 to 1qap#, hydrocarbon group of '丄3】 【Chemical 4】

Ο -CH, live under

In the formula (4), R species) is synonymous with the formula (3), and χ is 〇 [chemical CH2^-〇一 or

〇*-**- acrylate ring negative compound, oxypropyl acrylate =) dipropyl propyl acrylate propylene vinegar or ikon 4

Oxypropane di t i = : in terms of matter, propylcyclopropene. The methallyl & oxypropyl ether, the acetophenone to the epoxy, and the derivative compound of the above ethylenically unsaturated ester unit, for example, vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, Ethyl carboxylic acid ester such as butyl acrylate, methyl methacrylate, ethyl methacrylate or butyl methacrylate or α, cold monounsaturated carboxylic acid. In the case where the ethylenically unsaturated ester unit is introduced into the epoxy group-containing ethylene-based copolymer, even among these examples, vinyl acetate, methyl acrylate, and C are preferably used. Further, as the epoxy group-containing ethylene copolymer of the component C, a binary or ternary copolymer which is a mixture of ethylene, unsaturated, ortho-glycidyl acrylate and/or unsaturated propylene acrylate may be used, or A ternary system (te Γ nary sy st em) or a ternary system or more multicomponent copolymer obtained by copolymerizing an arbitrary monomeric ethylenically unsaturated ester. Next, the epoxy group-containing ethylene copolymer is usually ethylene which is a compound to be supplied with an ethylene unit, and a compound which supplies a unit of an unsaturated carboxylic acid glycidyl ester unit and/or an unsaturated glycidyl ether unit, and can be reacted thereto A compound to be supplied to an ethylenically unsaturated ester unit in the presence of a radical generator (generat 〇r) at 50.7 to 405.3]^3 (50 Torr to 4 Torr), 100 to 30,000 t Under the conditions of the copolymerization, the copolymerization reaction can also be carried out in the presence of a suitable solvent or a chain transfer agent. In terms of a preferred epoxy group-containing ethylene copolymer, for example, a unit derived from B, a unit derived from glycidyl methacrylate, and a substance 'from a woman's unit and a methacrylic acid propylene vinegar Derived LI position ί methyl: a unit derived from a unit derived from epoxidized acrylate, 1 unit of ethylene and a propylene acrylate derived from glycidyl methacrylate; or an acetonitrile/earth The copolymers derived from the units derived from ® 曰 are copolymerized with units derived from 200944562 units derived from glycidyl methacrylate and units derived from vinyl acetate. In particular, a copolymer of 7 units of a unit derived from a unit derived from glycidyl methacrylate is preferred as the epoxy group-containing ethylene copolymer of the component c. Further, the epoxy group-containing ethylene copolymer is preferably a melt index FR . JIS κ 7 2 1 〇, measurement conditions: 1 9 〇 ° c, 2 * 1 6 kg load) at 0.5 to l〇〇g/l , range, better 2 to 50g / l. A liquid crystal polyester of the component A and the component B and an epoxy group-containing ethylene copolymer can be obtained from a matrix obtained by melting a resin composition containing an epoxy group-containing ethylene copolymer in the range. The compatibility is highly available.

In the resin composition used in the present invention, the content of the epoxy group-containing vinyl filaments of the component c is preferably from 1 to 25 when the total mass of the liquid crystalline polyesters of the component VIII and the component 6 is 100 parts by mass. The range 'is more preferably in the range of 1 ◦ to 2 ◦ by mass. When the content of the oxy-ethylene copolymer is less than 0.1 part by mass, the adhesion to the metal of the formed substrate cannot be obtained and the effect is high. When the content is more than 25 parts by mass, the heat resistance of the substrate is deteriorated, and the formability of the resin composition is remarkably lowered. Further, in the resin composition to which the present invention is applied, it is possible to add a Z inorganic filler from the viewpoint of improving the rhythmic strength of the obtained substrate. For example, when a fibrous inorganic filler such as glass fiber or carbon fiber is added to a resin or a composition, the blending amount of the fibrous filler is a liquid crystalline polyester of the component A and the component 6. When the total mass is 1 part by mass, it is preferably set in the range of 5 to 500 parts by mass. When the blending amount of the fibrous inorganic filler is within this range, the adhesion between the matrix and the metal film is not lowered, and the mechanical strength of the south substrate can be raised, and the fuse is formed at the time of forming the matrix (we id) The 1 ine ) area can effectively prevent cracks from occurring. Regarding the shape of the fibrous inorganic filler, it is preferred that the fiber diameter is in the range of 6 to 15 // m, and the aspect ratio is in the range of 5 to 5 Å. When the fiber diameter is less than 6", when the inorganic filler is dispersed in the resin composition, or when the matrix is formed, the inorganic filler is easily damaged, and the inorganic filler is uniformly dispersed in the resin composition. On the one hand, when the fiber diameter exceeds 5 β m, the non-uniform distribution of the inorganic filler may cause problems in the measurement deviation of the mechanical properties of the substrate, and further damage the matrix. When the metal-coated resin molded article of the present invention is used as a circuit board or the like, the reliability of wire bonding (re 1 1 ab Η " y) is lowered. When the aspect ratio of the fibrous inorganic filler is less than 5, the effect of preventing cracking in the refining line is lowered. On the other hand, when the aspect ratio exceeds 5 Q, it is liable to occur in kneading of the resin composition. The damage of the inorganic filler is also detrimental to the processing property of the matrix. 30 200944562 In addition, in order to reduce the linear expansion coefficient of the substrate, as the inorganic filling, the whisker may be mixed with the resin composition. The substrate obtained from the resin composition containing whiskers is excellent in dimensional stability, and at the same time, a material having improved surface strength can be obtained. When the surface strength of the substrate is increased, the adhesion between the substrate and the metal film can be improved, and In the case where the metal-coated resin molded article of the present invention is used as a circuit board, it is extremely advantageous for improving the reliability of bump bonding. In this whisker, for example, tantalum carbide, tantalum nitride, zinc oxide, or the like can be used. A whisker formed by alumina, calcium titanate, potassium titanate, barium titanate, aluminum borate, calcium citrate, magnesium borate, calcium carbonate, magnesium sulphate, etc. in the use of titanate whiskers or borate whiskers In the case of the base line, the effect of reducing the % expansion coefficient of the base line is extremely high. Moreover, in the case of using the titanate 'I's clear shape, in addition to the adhesion between the base and the metal film, the medium of the substrate can be reduced. Loss factor. As an inorganic filler, in the case of using a short fibrous filler such as the above whisker, the fiber can be suppressed at the time of forming the matrix as compared with the case of using a long fibrous filler. (^ worker g nm ent ). Therefore, the obtained matrix has a small unidirectionality with respect to the linear expansion coefficient or the shrinkage ratio. As a result, the warpage or deformation of the substrate can be reduced, and a material having high dimensional accuracy can be obtained. The base is excellent in flatness (initial flatness) at the time of molding, and at the same time, it can reduce the advantage that the flatness of the substrate changes due to temperature, etc. Further, the dimensional stability of the substrate can be improved and the height is 31 200944562 talc, mica, Glass flakes, machine fillers. Plate-like inorganic filling 0//m, more preferably 1 to 50 (length/thickness), 2 to 6 in order to not reduce the heterogeneity of the metal film and increase the size of the substrate. From the viewpoint of the strength of the liquid plate-like inorganic filler of the component b and the strength of the plate, the plate-shaped agent-free system such as montmorillonite or bentonite may have an average length of 1 to 8 // m, and the average length is The width ratio 0' is preferably from 1 to 4 inches. The phase-crystalline polyester is preferably 10 to 40 parts by mass, and is preferably 10 to 40 parts by mass, from the viewpoint of the adhesion and the stability of the substrate. The fibrous inorganic filler, the whiskers, and the plate-like inorganic filler may be used alone or in combination of two or more. Further, a powdery or needle-shaped inorganic filler may be added to the resin composition. Further, carbon black or the like may be added to the coloring agent. The metal-coated resin molded article of the present invention is produced by molding a resin composition containing the above-mentioned A component and B component, a liquid crystalline polyester, an epoxy group-containing ethylene copolymer, and an inorganic filler which can be used as needed. The substrate is then obtained by forming a metal film on the surface of the resulting substrate. The metal material constituting the metal film is not limited, and for example, a metal selected from the group consisting of copper, nickel, gold, aluminum, titanium, turn, chromium, tungsten, tin, lead, and rhodium may be used, or two or more types may be used. An alloy formed from a metal selected from the group. Further, the metal material constituting the metal film can be partially oxidized by oxygen present in the environment. 32 200944562. The base body produced by the resin composition of the present invention is formed by, for example, limited, and in order to improve the adhesion improving effect by the heat treatment of the metal-coated resin forming material described later, it is preferable to use the liquid-hanging composition as Kneading is performed at a temperature higher than the initial flow temperature of the first liquid crystal polyester. In a typical matrix forming method, for example, a resin composition containing a first liquid crystalline polyester having an initial momentum of 3 2 0 C is kneaded by a biaxial extrusion machine at 3 4 to prepare a pellet. 'It is difficult to carry out injection molding into a desired shape, and the base body can be formed. In this way, the method of performing the granulation to obtain the granules is compared with the case of not granulating, and the heat treatment of the post a is preferred to further improve the adhesion. In the case where the matrix is formed by the shape, the melt viscosity of the resin binder = shearing speed 1...' is preferably 100 to 2 Torr. After the substrate is formed as described above, it is preferable to heat-treat the substrate as a pretreatment for forming a metal film. In this case, it is preferable that the temperature is lower than the temperature at which the flow temperature of the first liquid crystalline polyester contained in the resin composition is lower, and the initial flow temperature of the first liquid crystalline polyester is 'Tm; (c), it is better to heat treatment in the temperature range above (Tml - l2 〇 c), (d 2 or less. By adding this heat treatment, the surface sand metal can be further improved while being 'It can further reduce the thermal expansion coefficient of the matrix, and it is also effective to reduce the medium secret factor of the matrix itself. Implementation 33 200944562

The metal-coated resin molded article obtained by the heat treatment can be suitably used as a circuit board having excellent high-frequency characteristics and the like. In the above heat treatment, when the heat treatment temperature is lower than (Tm 1 - 1 2 0 ) t:, the effect of improving the adhesion cannot be sufficiently obtained, and when the heat treatment temperature exceeds (400 ml), the matrix is generated. Warp or deformation. Further, the heat treatment time is preferably between 1 and 4 hours. Further, in the case of performing such heat treatment, it is preferably carried out in an inert gas atmosphere such as nitrogen gas from the viewpoint of suppressing oxidative degradation of the substrate. Further, in an inert gas atmosphere, the residual oxygen concentration is preferably not more than i by volume, more preferably 5% by volume.

Further, in order to form a metal film on the surface of the substrate, it is preferable to prepare the plasma treatment on the surface of the substrate. Further, in the case of performing the above heat treatment, the plasma treatment may be performed before or after the heat treatment, and it is preferably carried out after the heat treatment. Since the resin composition contains an epoxy group-containing ethylene copolymer and has a highly reactive functional group, the surface of the substrate can be effectively activated by plasma treatment, and the adhesion to the metal film can be improved. The effect of plasma treatment is extremely high. The plasma treatment can be carried out using an existing plasma processing apparatus. For example, a plasma processing apparatus can be used, comprising: a pair of electrodes disposed to face each other in a chamber (chamb e); and a high frequency unit to which a high frequency electric field is applied Between the electrodes. 34 200944562 隋 open /, the substrate is placed on an electrode, the chamber is decompressed by about 4Pa. Next, a plasma forming gas such as nitrogen gas or ammonia gas is introduced into the chamber to pressurize the chamber to 8 to 5 p a. Then, using a high-frequency unit, a high-frequency power of 300 〇W is applied between the electrodes in 1 〇 to 1 〇〇 second (working 3.6 MHZ), and plasma is generated between the electrodes, thereby generating plasma in the plasma. The cation or free radical will collide (co 1 1 isi 〇n) on the surface of the substrate to activate the surface of the substrate. Here, the activation of the surface of the substrate is such that, in the plasma treatment, by the collision with the cation, a nitrogen polar group or an oxygen polar group which is easily bonded to the metal is formed on the surface of the substrate, as will be described later. When the metal film is formed, the adhesion can be further improved. 〃 The plasma treatment conditions can be arbitrarily set so that the surface of the resin substrate is not excessively roughened by the electropolymerization treatment. Further, the type of the plasma forming gas is not limited, and nitrogen is preferably used. In the case of using a nitrogen plasma, the detachment of the carbonic acid gas due to the cleavage of the ester bond of the liquid crystalline polyester constituting the matrix can be reduced as compared with the case of using the oxygen plasma treatment, whereby the strength of the surface of the substrate can be avoided. More specifically, the strength of the surface layer of the substrate is reduced. The method of forming a metal film on the surface of the substrate is explained. In the formation of the metal film, physical vapor deposition such as sputtering, vacuum evaporation, or ion plating is preferably used. In addition, the pretreatment aspect before the formation of the metal film 35 200944562 'as in the case where the plasma treatment is performed on the substrate as described above' is preferably such that the substrate is not in contact with the atmosphere, and it is preferable to continuously perform the plasma treatment and the formation of the metal film in the same chamber. ,. In the case of the DC plating method, for example, the substrate of the substrate device is decompressed to a temperature of 1 〇 to 4 p a or less, and then an inert gas such as argon is introduced into the chamber to make the internal pressure 〇1. P a or so. Then, a 5 〇〇v DC voltage is applied and a copper bump is bombarded to form a copper coating film having a film thickness of 2 〇 0 to 500 nm as a metal film on the surface of the substrate to obtain a metal-coated resin molded article. . In the case of using electron beam heating vacuum evaporation as the vacuum evaporation, for example, the chamber of the internal device has a substrate decompressed to i 〇 4 Pa, and the electron flow of 400 to 8 mA and the copper in the crucible The collision evaporates the copper. Thereby, a copper film having a film thickness of about 30 〇 nm is formed as a metal film on the surface of the substrate, whereby a metal-coated resin molded article can be obtained. Λ In the case of ion plating, for example, the chamber with the substrate in the internal device is decompressed to below 1 U Pa, and the copper is evaporated in the same manner as in vacuum evaporation. Further, an inert gas such as argon is introduced between the substrate and the crucible to set the internal pressure to 〇.〇5 to 〇.1Pa. Next, the desired bias voltage (biasv Q丄tage) is applied to the electrode holding the substrate, and a rain frequency power of (3·56 ΜΗΖ) is applied to the sensing antenna (in 36 200944562 duct ion antenna). In order to produce plasma in the chamber. Thereby, a metal-coated resin molded article having a copper film having a film thickness of 200 to 5 Å on the surface of the substrate can be obtained. ❹ As described above, the resin composition containing the components A to C is used to form the substrate, and heat treatment and plasma treatment are required as pretreatment, and physical metallization such as sputtering is used to form a metal film on the surface of the substrate. A series of methods can be used to obtain a metal-coated resin molded article having high adhesion between the surface of the substrate and the metal film. In particular, in the metal-coated resin molded article obtained by the present invention, it is not necessary to use an adhesive or a drug or the like between the metal film and the surface of the substrate to have high adhesion. Further, in the conventional metal-coated resin molded article described in Patent Document 1, when the mechanical strength or the resistance of the surface layer portion is deteriorated, there is a problem that the adhesion between the surface of the substrate and the metal film is lowered. Invention: A specific resin composition, that is, a liquid crystalline polyester having different load offset temperatures, is effective in reacting with an epoxy group-containing acetamethylene copolymer, thereby greatly improving the tear resistance of the surface layer portion of the substrate (te 3 Γ Γ 6 S 1 S t 3 n C e ), as a result, the strength or the deterioration of the surface layer portion of the substrate can be prevented. m body surface The metal-coated resin of the present invention can be formed into a metal film forming circuit 37 200944562 in particular as a circuit board. In the method of forming the circuit pattern, for example, it is recommended to use a laser pattern from the viewpoint of effectively removing the non-essential metal film other than the circuit pattern without lowering the adhesion of the metal film. In the metal-coated resin molded article of the present invention, in order to improve the adhesion to the metal film, it is not necessary to perform the roughening treatment of the surface of the substrate, so that the accuracy of the circuit pattern is not lowered as a result, and the laser pattern can be reduced by the laser pattern. Form a high-precision and fine circuit pattern. Therefore, the metal-coated resin molded article of the present invention can also be applied to a three-dimensional circuit substrate (Μ I D ). ' @ Further, after performing laser patterning on the metal film, a metal layer such as steel may be plated on the formed circuit pattern to form a circuit having a total thickness of, for example, 5 to 2 〇β m. After the circuit diagram i is also completed, the soft money engraving can be performed as needed, and the unnecessary metal film remaining on the substrate is surely removed. Further, it is also possible to provide a shovel nickel layer or a bond gold having a thickness of about a few (four) on the additional metal layer: the port can be obtained by using the metal-coated resin of the present invention to form a G> Forming a circuit board. EXAMPLES Next, the present invention will be specifically described by way of examples. Usage 1 Test piece In addition, the load offset temperature was measured by the following method. That is, the polymer of the test object was formed into a test piece having a length of 1 2 7 mm, a width of 2 · 7 mjn, and a thickness of 6.4 mm, and the "heat distortion tester 38 200944562 (heat distortion) manufactured by Nishida Seiki Co., Ltd. was used for this test. Teste r )"' was measured under the load of i. 8 2 Μ P a (1.86 kg / cm 2 ) in accordance with ASTM D 6 4 8 . (Ingredient A: Synthesis of the first liquid crystalline polyester) Weighed 9 1 1 g (6.6 mol) of p-hydroxybenzoic acid, 409 g (2.2 mol) of 4, 4'-dihydroxybiphenyl, and p-dicarboxylic acid 274 g (1.65 mol), 91 g of isoacid (〇. _ 55 mol) and 1235 g of acetic anhydride (12.1 mol), and then weigh 1 曱 imidazole 0.17 g, and put this into The reactor of the mixing device, the torque meter, the nitrogen introduction tube, the thermometer, and the reflux cooler are sufficiently replaced with nitrogen in the reactor. Subsequently, the temperature was raised to 150 Torr over 15 minutes under a nitrogen stream, and further refluxed at 150 ° C for 1 hour. Then, '1 曱 曱 咪唑 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 The time point is regarded as the completion of the reaction 'take out the contents. The solid component obtained from the content was cooled to room temperature, and pulverized by a coarse pulverizer, and the resulting powder was heated to room temperature from room temperature over 1 hour under a nitrogen atmosphere. (:, further heated from 2500 ° C to 2 8 5 ° C for 5 hours, and held at 2 8 5 ° C for 3 hours to carry out polymerization in a solid phase. Thus, the first liquid crystalline polyester was obtained. In this case, the first liquid crystal polyester was measured for the initial flow temperature by using a flow tester (f 1 〇wtpc , 39 200944562 r ) ("C F τ — 5 〇〇 type" manufactured by Shimadzu Corporation), and was 3 27 . Further, the portion of the first liquid crystal polymer is granulated into granules, and the test piece for injection biasing temperature measurement is injection-molded to measure the load deflection temperature using a known test piece. 1. (Ingredients Β: Synthesis of the second liquid crystalline polyester) 1 pair of benzoic acid 87 9 g (6.0 mol), 4, 4, dihydroxybiphenyl 5 5 9 g (3 . Moer), 98 g of isoammonium sulphate (3.0 mol) and 348 g of acetic anhydride 丄 (丄 3 2 mol)', and then weighed 9 gram of imidazolium hydrazine. 将该 9 g, the input was equipped with a stirring device, and Momentmeter, nitrogen inlet tube, temperature 4 and reflux-cooled H reactor, the reactor is fully replaced by nitrogen followed by 'heating under nitrogen gas for 15 minutes 1 5 〇C ' and then refluxed at 150 ° C for 1 hour. Then 'distilled by-produced acetic acid and unreacted acetic anhydride, while heating up to 3 2 2 for 2 hours and 5 minutes, confirming the torque The time point of the rise is regarded as the completion of the reaction. The contents are taken out. The obtained solid component is cooled to room temperature from the contents, and after being pulverized by a coarse pulverizer, the obtained powder is heated in a nitrogen atmosphere at room temperature for 1 hour. Up to 20 〇c, and then from 2 〇〇 °c to 5 8 C for 5 hours and at 2 9 8 ° C for 3 hours to carry out polymerization in a solid phase. 200944562 From here, the first liquid crystal polymerization was obtained. In this case, the second crystalline poly s is the same as the above, and the initial flow temperature is determined to be = 8 C. The second liquid crystalline polyester is the same as above, and the load-shift temperature is 1 3 3 〇C. y On the one hand, the epoxy group-containing ethylene copolymer as the component c is the product number "BF-E" of "b 〇ndfast" (registered trademark) manufactured by Sumitomo Chemical Co., Ltd. This rb 0 n"d °f ® ast BF — E”, a standard ethylene-glycidyl methacrylate copolymer (Glycidyl methacrylate content 丄 2 mass%, MFR = 3 g / 1 〇). In addition, MFR (melt flow rate) is the standard JIS - K 7 2 1 〇 ' at 1 9 〇 °c値 measured under the condition of 2 1 60 g load.

Further, as the inorganic filler, ground glass fiber (M: "EFH75 - 10 〇 1" (fiber diameter l〇/zm, aspect ratio 1 〇) manufactured by Centra 1 Glass Co., Ltd.) was used. (Examples 1 to 4, Comparative Examples 1 and 2) The first liquid crystalline polyester, the second liquid crystalline polyester, rb 〇nd fast BF — E”, and ground glass fiber (MG F) “EFH7 5 — 0 1" was mixed in the amounts shown in Table 1 to prepare a resin composition. Further, Examples 1 to 4 are those in which the ratio of the first liquid crystalline polyester to the second liquid crystalline polyester is changed to prepare a resin composition. 200944562 Next, a two-axis extruder ("p CM — 30" made by Chiba Iron Works Co., Ltd.) was used at 3 4 ◦. (: Particles of the resin composition were prepared. Then, the obtained pellets were injection molded into a molding machine "PS40E5ASE" manufactured by Nissei Resin Co., Ltd., and injection molding was carried out at a cylinder temperature of 35 ° C and a mold temperature of 130 ° C. Obtaining a substrate having a thickness of 1 mm of 4 Ommx 3 Ommx. Next, the substrate thus obtained is subjected to a heat treatment under a nitrogen atmosphere at a temperature of 2800 ° C for 3 hours, and a substance not subjected to the heat treatment. The surface of the two kinds of substrates is formed into a metal film in the following manner. First, after the plasma treatment on the surface of the substrate, a metal film is formed by using a D ◦ magnetron sputtering device, that is, the substrate is disposed in the cavity of the plasma processing device. In the room, the chamber is depressurized to about —Q—4p a. Then, nitrogen gas is introduced into the chamber to make the gas pressure in the chamber become 10 P a, by adding a high frequency of 3 〇〇w between the electrodes (3. 56 MHz) The power is applied for 30 seconds, and the substrate can be subjected to electric pulverization treatment. Below P a. After the plasma treatment, the chamber is depressurized until the working chamber is in this state, and argon gas is introduced into the chamber to become the pressure of 〇lpa. 'In addition to 5 Q QV DC Pressing and bombarding (4), a metal film formed by a copper film having a film thickness of 400 is formed on the plasma-treated surface of the substrate. Thereafter, a metal film is formed by a t-ray to form a pattern of a width of 5 mm and a pattern of 200944562. On the pattern of the metal film, copper plating was performed by electroplating, and a circuit-formed substrate in which a circuit pattern for a peel strength test of thickness 15 was formed on the surface of the substrate was obtained.

As described above, the substrate was formed by the circuit of Example 1, and the electric heat distortion temperature (measurement of DTUL peel strength, "EG Test" was used) was used, and the peel strength of the road pattern obtained in Comparative Examples 1 and 2 was measured. Base: load offset temperature). In addition, the universal testing machine (Shimadzu Corporation performs the 90-degree peel strength in the vertical direction with respect to the resin flow during molding. The results are shown in Table 1. The first liquid crystalline polyester and the second liquid crystalline polyester are also used. The relationship between the ratio of the second liquid crystalline polyester measured by σ and the peel strength is as shown in the first figure (a), and the relationship with the heat distortion temperature (d Τ ϋ L ) is as shown in the first figure (b). 43 200944562 [Table 1] (mixing amount is part by mass) Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Comparative Example 2 First liquid crystal poly S is 100 88.9 77.8 66.7 50 0 Second liquid crystal brewing 0 11 1 22.2 33.3 50 100 BOND FAST ΒΡΕ 11 • 1 11.1 11.1 11 .1 11 • 1 11 • 1 MGF 74 .1 74 .1 74 1 74.1 74.1 74.1 With or without heat treatment, with or without any peel strength (N/ Mm) 0.43 0.53 0.43 0.67 0.45 0.77 0.45 0.78 0.53 0.79 0.53 0.81 Heat distortion temperature (°C) 260 300 < 216 288 184 281 163 236 128 128 128 128 Observed from Table 1 or Figure 1 (a), as Liquid crystalline polyester with 2 The first liquid crystalline polyester having a load offset temperature of 0 0 ° C or higher and the second liquid crystalline polyester having a lower load offset temperature than the first liquid crystalline polyester can be used to confirm that the peel strength is improved. The metal film is formed with a higher degree of adhesion. In this case, when the content ratio of the second liquid crystalline polyester is increased, it can be observed from the first figure (b) that the heat distortion temperature is lowered and the heat resistance is lowered. The content of the second liquid crystalline polyester is 5 ◦ or less by mass. Especially when the content of the second liquid crystalline polyester exceeds 3 Q% by mass, it can be observed from the first figure (b) that the heat distortion temperature is large. In order to reduce 'and it can be observed from the first figure (a), even if the content rate of the second liquid 曰44 200944562 T ester exceeds 3 〇 mass percentage, the peeling strength 2 is not very effective. Therefore, the second liquid crystalline polycondensation The content of the ester is more preferably 30% by mass or less. Further, it can be observed from Table 1 or the first diagram (a) that by performing heat treatment of the substrate, the peel strength can be made higher, and it is confirmed that the height is excellent. Improve the effect. In Example 2 and Comparative Example (with heat treatment), the shrinkage ratio of the substrate was measured. The shrinkage ratio is the shrinkage ratio of the substrate size with respect to the mold size, and the above molding conditions were made flat = 'measurement MD (resin flow direction) The shrinkage rate of the size of the disk scale is calculated by the size of the base of the crucible (in the direction perpendicular to the flow direction of the resin). The results are shown in Table 2. ^, 45 200944562 [Table 2] (mixing amount is part by mass) - Comparative Example 1 Example 2 The first liquid crystal poly s is 100 77.8 The first liquid crystal poly S is 0 22.2 BOND FAST BF-E 11.1 11.1 MGF _ _ 74.1 74.1 With or without heat 1 ^ Treatment Γ - There is shrinkage MD% 0.36 0.54 Rate TD% 1.32 1.05 (TD-MD)% 0.96 0.51 Observed from Table 2 'In Example 2, by the first - liquid crystal The second liquid crystalline polyester is used in combination with the polyester, and the difference in the forming shrinkage coefficient (differentce 1 n molding shrinkage fact 〇r ) between the MD (resin flow direction)' and the TD (the direction perpendicular to the resin flow direction) is made smaller. By reducing the forming warpage and simultaneously making the base size high-precision, it is possible to suppress thermal deformation caused by reflow soldering or the like. (Examples 5 to 8, Comparative Examples 3 and 4) The first liquid crystalline polyester, the second liquid crystalline polyester, rb 0 ndfast BF - E", and ground glass fiber (mg 46 200944562 F) EFH75-01 The resin composition was prepared by mixing in the amounts shown in Table 3. Further, in Examples 5 to 8, the ratio of the liquid aa polyester to the second liquid crystalline polyester was changed, and the blending amount of "b〇ndiast BF-E" was further changed to prepare a resin composition. Example 6 and In the same manner as in the above-mentioned Example 2, the comparative example 3 was blended in the same manner as in the above Comparative Example 1. Therefore, in the same manner as described above, the base body is molded, the heat treatment is performed, the copper film is formed after the plasma treatment, and the circuit is formed by laser patterning. The substrate was formed in this circuit, and the peel strength of the circuit pattern was measured. The results are shown in Table 3. [Table 3] (mixing amount is part by mass) Comparative Example 3 Example 5 Example 6 Example 7 Example 8 Comparative Example 4 First liquid crystal polyacetate 100 88.9 77.8 66.7 50 0 Second liquid crystal poly 8 means 0 11.1 22.2 33.3 50 100 BOND FAST BF-E 11.1 5.4 11.1 17.2 23.7 30.7 MGF 74.1 74.1 74.1 74.1 74.1 74.1 With or without heat treatment, there are some peel strength (N/mm) 0.53 0.66 0.77 0.80 0.79 0.78 47 200944562 Observed from Table 3 In the first liquid crystal polyester and the second liquid crystalline polyester, the contents of the respective examples were compared with the comparative example 3 using the first liquid crystalline polyester alone, and the peel strength was further improved, and again, by making "bondfast" The BF - E" increment, while showing the peel strength tends to increase. The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and the equivalent technical changes of the present invention and the contents of the drawings are included in the scope of protection of the present invention. Within, combined with Chen Ming. Θ [Simple description of the drawing] In the first figure, (a) shows a graph of the relationship between the content ratio of the second liquid crystalline polyester and the peel strength. (b) shows the relationship between the content ratio of the second liquid crystalline polyester and the heat distortion temperature. Graphics. [Main component symbol description] 48

Claims (1)

200944562 VII. Patent application scope: AJ ί 属 包 包 树脂 树脂 树脂 树脂 树脂 A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A聚自自, with a load bias of 2 generations or more. The second liquid crystalline polyester, the load offset temperature is lower than the load shift temperature of the first liquid crystalline polyester; and C: epoxy-containing ethylene copolymer , ❹ Ο (only, the epoxy group-containing ethylene copolymer system contains: = 99.9 mass%, unsaturated (tetra) ring J, and/or unsaturated glycidyl ether unit 〇 J to 3 〇 mass ratio), In the resin composition, the component c and the component 〇◦ mass part 'component c are 0. u25 in the mass range of "1. 2 = The metal-coated resin described in the first item of the patent range is formed. π, wherein In the resin composition, the component β is in a total amount of 1 to 5 Å by mass with respect to the component a. The opening of the metal coating resin described in the second item of the patent range is "3=t". 30 mass% of the total amount of component A and component B the following. The varnished resin molded article of any one of the second to third aspects of the present invention, wherein the second liquid crystalline polyester is scented by a cool bond. The aromatic group contains 1, 2, phenyl, 1,3 -phenyl, 2,3 -naphthyl to two aromatic groups, and at the same time, relative to the total amount of the divalent aromatic group, the aromatic The total amount of the group base is from 1 45 to 45 mol%. The metal-coated resin molded article according to any one of claims 1 to 4, wherein the epoxy group-containing ethylene northern poly molecule contains an ethylene unit of 8 〇 to 98% by mass, not; 49 200944562 Acidic propylene glycol vinegar units and / or unsaturated epoxidized ether mono-mass percentage. The metal-coated resin molded article according to any one of claims 1 to 5, wherein the resin composition contains the component D in addition to the A to C. A fibrous inorganic filler having a U diameter of 6 to 1 and an aspect ratio of 5 to 50. The metal-coated resin molded article according to any one of claims 1 to 6, wherein the metal film is selected from the group consisting of copper, gold, aluminum, titanium, molybdenum, chromium, and tungsten. Or tin, lead, and zinc or two or more alloys selected from the metals. The metal-coated resin molded article according to any one of the preceding claims, wherein the metal is patterned by the metal. A method for producing a metal-coated resin molded article, a method for forming a resin composition obtained by molding a resin composition according to any one of items 1-4 to 8 of the patent application; and α The surface of the substrate forms a coating step of the metal being rubbed.形成 Forming the metal-coated resin described in item stmt®9 = 2, which is a step of performing a plasma treatment on the surface of the substrate before the coating step. μ 1 1. A method for producing a +-fat molded article as described in the θth item or the item ii of the patent application, which is in the coating step (Tml-120). . To (Tml - 2 〇) rr 1 represents a step of performing a substrate heat treatment at the initial flow temperature (°C) of the first liquid crystalline polyester. Correction, +, 1 2. The method for producing a metal-coated resin molded article according to any one of the items 9 to 1 of the patent application, which is formed by physical vapor deposition on the surface of the substrate ί中=50 200944562 * The method for producing a metal-coated resin molded article according to any one of the preceding claims, wherein the metal film is formed into a circuit pattern by performing laser patterning on the metal film. step. 51