TW200415001A - Method for compounding metal onto surface of molded article of cyclic olefin based resin, and molded article of cyclic olefin based resin compounded with metal - Google Patents

Abstract

The present invention relates to a method for bonding metal on the surface of the molded article of a cyclic olefinic resin. More particularly, for bonding a metal to an cyclic olefinic resin molded article having very low dielectric constant, dielectric loss and moisture absorptivity and being very suitable as the constituting element of a device for treating high frequency signal at GHz zone, a metal whose surface is treated by a triazinedithiol compound represented by formula (1) wherein R represents -OR', -SR', -NHR' or -N(R')2, R' represents hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a phenylalkyl group, an alkylphenyl group or a cycloalkyl group having 1 to 10 carbon atom, M represents any one of H, Na, Li, K, 1/2Ca, 1/2Ba, aliphatic primary, secondary and tertiary amines, and quaternary ammonium salts is heated and pressed adhered to the surface of the molded article of a cyclic olefinic resin or its composition. A molded article of the cyclic olefinic resin or its composition has at least one part of the surface thereof being roughened to a ten-point average roughness Rz of 5 μm or more and then coated with a metal film by a wet plating method.

Description

200415001 (1) Description of the invention: (1) The technical field to which the invention belongs The present invention relates to a metal compounding method, which applies heat and pressure to the surface of a molded article of a cyclic olefin resin or a composition thereof through a triple well disulfide A metal body surface-treated with an alcohol compound; the present invention also relates to a metal composite cyclic olefin-based resin molded product obtained by this method. Metal composite cyclic olefin-based resin molded products are component parts of devices suitable for processing high-frequency electrical signals in the high-frequency band, especially in the GHz band. (II) Prior art ^ In recent years, the requirements for broadband communication in mobile phones, the Internet, and wireless LAN have become higher and higher. In order to transmit information at a high speed and in large quantities, the frequency of electrical signals is significantly increasing. In the substrate (insulator) of a device that processes higher frequency signals, materials with low dielectric constant and dielectric loss (dielectric tangent (t a η δ)) are required. This is because if the dielectric constant and dielectric loss are large, the delay or loss of the electrical signal becomes large, making signal processing difficult. In particular, in a device for processing a high-frequency signal in the GHz band, a low dielectric constant and a low loss of a substrate are clearly required. It is known that cyclic olefin resin is a material with very low dielectric constant and dielectric loss among plastic materials, and is comparable to the lowest dielectric constant fluororesin (polytetrafluoroethylene (PTFE)). For example, it is known that the dielectric constant of a cyclic olefin-based resin at 10 GHz is 2.17 ′ and the dielectric tangent is 0.000, and the dielectric constant of prpFE is 2.1 ′ under the same conditions, and the dielectric tangent is 0.000. 〇2 (refer to Racecourse Civilization, "Plastics" Vol. 45, No. 9 (1994), p. HM5 (Table 4)). Such a fluororesin has ideal dielectric properties of -6-200415001 as a substrate material for a high-frequency electronic device. However, since it is not a thermoplastic resin, its workability is significantly poor, and it is limited to use in very special applications. In contrast, cyclic olefin resins are thermoplastic and have excellent processability, and are expected to be applicable to a wide range of applications. For example, as a kind of cyclic olefin-based resin, it is proposed to use an original norbornene-based resin in the insulator of the connector to transmit a high frequency of 1.4 GHz or higher (see Japanese Patent Application Laid-Open No. 8-2131 No. 13 (Scope of Invention Application Patent) ). This invention is limited to connector insulators, and does not take into account the necessity of compounding with metals in the formation of circuits. Since the cyclic olefin-based resin is composed of only carbon and hydrogen, it has low polarity, and it is difficult to compound strongly with metals. In addition, there has been proposed a composition composed of a thermoplastic orbornene resin and a soft polymer, which is a kind of a cyclic olefin resin, and it is described that the molded product can be used in a printed wiring board, an antenna, and a connector for a high frequency range. Parts such as insulators (see Japanese Patent Application Laid-Open No. 8-3 25 440 (patent scope of invention application, paragraph 0019)). However, the invention is also essentially limited to the insulator of the connector, and there is no specific teaching at all that it must be compounded with metal in circuit formation. Further, there is proposed a printed circuit board in which a metal thin film is laminated on a thin film of a cyclic olefin resin having a polar group in a side chain. Since the cyclic olefin-based resin of the present invention has a polar group, its adhesion to a metal is high. However, its water absorption rate is 0.2%, which is very higher than that of cyclic olefin resins without polar groups. The water absorption rate is 0.01%. Due to the water absorption factor, the dielectric constant and dielectric loss in use increase, which is not suitable. (Refer to Japanese Patent Application Laid-Open No. 2000-30 1 088 (the solution means item on page 1, paragraph 03, table 1 on page 10)). On the other hand, there is a proposal to make gold-7-200415001 a surface treatment of three dithiol compounds in advance when compounding thermoplastic resins with metals, but the compounding system with cyclic olefin resins is unknown ( Refer to Japanese Patent Publication No. 1_6005 1 (Scope of Patent Application for Invention), Japanese Patent Publication No. U8604 (Scope of Patent Application for Invention) and Japanese Patent Publication No. 2000-2 1 8935 (Page 2-5)). The object of the present invention is a method for composite metal on the surface of a molded body of a cyclic olefin resin, and to provide a very low dielectric constant and dielectric loss, and a very small water absorption, which is most suitable for processing GHz high-frequency electrical signals. A composite molded body of a cyclic olefin resin molded product and a metal constituting the device. (3) Summary of the invention The inventor of the present case conducted a review and found that the surface of the molded article of the cyclic olefin resin 'heated and pressurized and adhered to the metal body surface-treated with the specific trioxane dithiol compound'. The adhesion force adhered to the surface of the molded article, and the present invention was finally completed. That is, the first aspect of the present invention is to provide a method for metal compounding the surface of a cyclic olefin resin molded article, characterized in that the surface of the cyclic olefin resin or a molded article thereof is heated and pressurized to adhere to the surface. A metal body surface-treated with a triple well dithiol compound represented by the following general formula (1),

MS

SM

Among them, R is -〇R ', -SR', -NHR ,, -N (R,) 2, R, is hydrogen, alkyl group having 1 to 10 carbon atoms, alkenyl group, phenyl group, phenyl alkyl group, and alkyl group. Phenyl or cycloalkyl; M-series fluorene, -8 ~ 200415001

Na, U, K, 1 / 2Ca, 1 / 2Ba, β is any one of aliphatic primary, secondary and tertiary amines, and quaternary salts. The second aspect of the present invention is to provide the metal composite method according to the first aspect of the present invention, wherein at least a part of the cyclic olefin resin is a modified cyclic olefin grafted with an unsaturated compound having a polar group. Department of resin. The third aspect of the present invention is to provide the metal composite method according to the second aspect of the present invention, wherein the concentration of the polar group contained in the cyclic olefin resin or the composition thereof is 1 mol / kg or less. The fourth aspect of the present invention is to provide the metal composite method according to any one of the first to third aspects of the present invention, wherein the cyclic olefin-based resin-based olefin and the cyclic olefin are addition copolymers. The fifth aspect of the present invention is to provide a metal composite method according to the fourth aspect of the present invention, in which the cyclic olefin is orthobornene or tetracyclododecan. The sixth aspect of the present invention is to provide the metal composite method according to any one of the first to fifth aspects of the present invention, wherein the cyclic olefin-based resin composition is composed of a cyclic olefin-based resin and a hollow inorganic aggregate. . The seventh aspect of the present invention is to provide a metal composite method according to the sixth aspect of the present invention, wherein the hollow inorganic material is a glass balloon or a Shirasu balloon. The eighth aspect of the present invention is to provide a metal composite cyclic olefin-based resin obtained by the metal composite method for the surface of a cyclic olefin-based resin molded article as described in any one of the first to seventh aspects of the present invention. Molded products. The ninth aspect of the present invention is to provide the metal composite cyclic olefin-based resin molded product according to the eighth aspect of the present invention, wherein the peel strength between the metal and the resin or its composition-9-200415001 is 0.2 kg. / cm or more. 1% Item 10 of the present invention is to provide a metal composite cyclic olefin-based resin molded article as described in item 8 or 9 of the present invention, wherein the water absorption of the cyclic olefin-based resin or its composition is 0.1% the following. The eleventh aspect of the present invention is to provide a metal composite cyclic olefin-based resin molded product according to any one of the eighth to tenth aspects of the present invention, which is used for processing high-frequency electrical signals in the GHz band. Component parts of the device. (4) Embodiments The best form for carrying out the invention The best mode for carrying out the invention will be described below. Cyclic olefin-based resin molded product The cyclic olefin-based resin (a) refers to a polymer compound having a main chain composed of carbon-carbon double bonds and having a cyclic hydrocarbon structure in at least a part of the main chain. Representatives of this cyclic hydrocarbon structure, such as orbornene or tetracyclododecene, can be introduced into the cyclic hydrocarbon structure using a compound (cyclic olefin) having at least one olefinic double bond as a monomer. Resin U) can be classified as cyclic olefin addition (co) polymers or their hydrogenated products (al), cyclic olefin and α-olefin addition copolymers or their hydrogenated products U2), cyclic Ring-opening (co) polymers of olefins or their hydrogenates U3). Furthermore, the cyclic olefin resin (a) may contain an unsaturated compound (u) having a polar group (for example, a carboxyl group, an acid anhydride group, an epoxy group, an amido group, an ester group, a hydroxyl group, and the like) and the aforementioned compound. Cyclic olefin-based resins (a 1) to (a 3) are grafted and / or copolymerized (a4). Two or more of the cyclic olefin resins (al) to (a4) may be mixed and used. 〇-10-200415001 The unsaturated compound (u) is, for example, (meth) acrylic acid, maleic acid, fumaric acid, or horse Maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) propionate (carbon number 1 to 10), (meth) acrylamide, (meth) acrylic acid-2 -Hydroxyethyl etc. Specific examples of cyclic olefins are cyclopentene, cyclohexene, cyclooctene; one-ring cyclic olefins such as cyclopentadiene, 1,3-cyclohexadiene; bicyclic [2.2.1] hept-2 -Ene (common name: probenbornene), 5-methyl-bicyclo [2.2.1] hept-2-ene, 5,5-dimethyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl -Bicyclo [2.2.1] hept-2-ene '5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylene-bicyclo [2.2.1] hept-2-ene, 5 -Hexyl-bicyclo [2.2.1] hept-2-ene, 5-octyl-bicyclo [2.2.1] hept-2-ene, 5-octadecyl-bicyclo [2.2.1] hept-2-ene, 5-methylene-bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, 5-propenyl-bicyclo [2.2.1] hept-2- 2-ring cyclic olefins such as alkenes; bicyclic [4.3.0.I2'5] dec-3,7-monoene (common name: dicyclopentadiene), tricyclic [4.3.0.12,5] dec- 3-ene; tricyclic [4.3.0.12'5] dec-3,7-diene or tricyclic [4.4.0.12'5] undec-3,8-diene or a partial hydrogenation thereof (or Addition of cyclopentadienyl and cyclohexene) tricyclo [4.4.0. I2'5] undec-3-ene; 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene , 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5 • cyclohexenyl-bicyclo [2. 2.1] 3-ring cyclic olefins such as hept-2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene; tetracyclic [4 · 4 · 0 · 12'5 · Γ'1 ( )] Dodeca-3-ene (also referred to as tetracyclododecyl), 8-methyltetracycline [4.4.0.12'5.17'1 °] dodeca-3-ene, 8-ethyltetracycline [ 4.4.0.12'5.17'1 °] Dodec-3-ene, 8-methylenetetracycline [4.4.0.0.12, 5.17,10] Dodecane-3-ene, 8-ethylenetetracycline [4.4.0.I2'5.I7'1. ] Dodecyl-3-dilute, 8-200415001 vinyl tetracyclo [4.4.0.1. 2'5.i7, 1Q] dodecyl-3-ene, 8-propenyl tetracyclic μ.4.0.12, 5. Γ, 1. ] Dodecane 1ene and other 4-ring cyclic olefins; 8-cyclopentyl-tetracyclo [4.4.0.12,5.17'1 ()] dodec-3-ene, 8-cyclohexyl-tetracyclic [ 4 · 4 · 0 · Γ, 5.17'I ()] dodecyl, 8-cyclohexenyl-tetracyclo [4.4.0.12,5 "7,1. ] Dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.0.12,5 "7,1. ] Dodecane-3-ene, tetracyclic [7.4.13'6.〇1'9.〇2'7] tetradecane-4,9,11,13-tetraene (also known as 1,4- Methylene-1,4,4 &, 93-tetrahydrofluorene), tetracyclic [8.4. L4,7 ^ 1,1. ^ 3,8] Heptadeca-5,10,12,14-tetraene (also known as M-methylene_1,4,4a, 5,10,10a-hexahydroanthracene), heptacyclic [6.6.1.13'6 · 〇2,7 · 09,14] -4-Sixteen burning, seven rings [6.5.1.1 · 〇 '· 〇9'13] -4- ~ [—b thin, five kings [7.4.0.02'7 · 13'6 · ι1 () '13] Heptadecene, Heptacyclic [8.7.〇.12'9.14,7.111, 丨 7.03,8.〇12'16] -5 -Pinene, heptacyclic [8.7.0.12'9 · 03 · 8 · 14'7 · 12 · 17 · 113'16] -14-pinene. Polycyclic cyclic olefins such as 4-mers of cyclopentadiene. These cyclic olefins may be used singly or in combination of two or more kinds. Specific examples of α-olefins copolymerizable with cyclic olefins are ethylene, propylene, butylene, pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene Ene, 3-ethyl-1-pentene, 4-methyl-fluorene-pentene, 4-methyl-1-hexene, 4,4-dimethyl-buhexene, 4,4-dimethyl 1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Hexadecene, octadecylbenzene, 1- 廿;) ¾ and the like having 2 to 20 carbon atoms, preferably 2 or 8 carbon olefins or the like. These ou olefins may be used singly or in combination of two or more kinds. The method for polymerizing the cyclic olefin or the cyclic olefin with the α-olefin and the method for hydrogenating the obtained polymer are not particularly limited, and can be carried out in accordance with the known method of -12-200415001. In the cyclic olefin-based resin (a) exemplified above, from the viewpoint of the zp balance of characteristics and cost, particularly preferred is an addition copolymer of a cyclic olefin and an α-olefin or a hydrogenated product U2 thereof. Cyclic olefin resins are industrially marketed under the trade names of TOPAS (German T1C0na), Aberu (Mitsui Chemicals), Leonix (Japan Leon), Leonjoya (Ben Leon), etc. For sale. The use of a modified cyclic dilute hydrocarbon resin (a 4) obtained by grafting and / or copolymerizing with an unsaturated compound (u) having a polar group can increase the adhesion to the metal, and is suitable for a higher demand. Case of metal tight contact. However, the presence of polar groups has the disadvantage of increasing the water absorption of the cyclic olefin-based resin. Therefore, the content of polar groups (for example, carboxyl group, acid anhydride group, epoxy group, amido group, ester group, hydroxyl group, etc.) is 0 to 1 mole per 1 kg of cyclic olefin resin. In the case of a molded product of a cyclic olefin resin alone, it is preferable to add a hollow inorganic filler because of insufficient rigidity or surface hardness. Generally speaking, the dielectric constant and dielectric tangent of inorganic fillers are large. However, hollow inorganic fillers contain a large amount of air with a dielectric constant of 1 inside. Therefore, even when added to a cyclic olefin resin, the dielectric constant is hardly improved. The constant of the dielectric constant and the dielectric tangent are preferable because they can improve the rigidity of the molded product. A typical hollow inorganic material is, for example, a glass balloon Shirasu balloon. The addition ratio of the hollow inorganic aggregate is 5 to 100 parts by weight, and preferably 15 to 60 parts by weight, with respect to 100 parts by weight of the cyclic olefin-based resin. To the cyclic olefin-based resin, other thermoplastic resins, thermoplastic elastomers, various compounding agents, etc. may be added, as long as the characteristics are not impaired. 200415001 ^ Thermoplastic 丨 green tree β is, for example, polyphenylene sulfide, polybenzoic acid, polyether maple, polyfluorene, polycarbonate, polyacetal, etc., as well as liquid crystal polymers, aromatic polyesters, polyaromatics Polyester polymers such as esters, polyethylene terephthalate, polybutylene terephthalate, and polyolefin polymers such as polyethylene, polypropylene, and poly 4-methylpentane-1; nylon 6 , Nylon 66, aromatic nylon and other polyamide polymers; polymethyl methacrylate, polyacrylonitrile styrene (AS resin), polystyrene, etc. The thermoplastic elastomer is, for example, an olefin-based, styrene-based, ester-based, ammonium-based, or urethane-based thermoplastic elastomer. Among them, olefin-based elastomers and styrene-based elastomers are highly compatible with smoldering smoke-like resins, and are more suitable. Specific examples of the hydrocarbon-based elastomer include an ethylene-propylene copolymer, an ethylene-propylene-diene composition, an ethylene-butene copolymer, and an ethylene-octene copolymer. Specific examples of the styrene-based elastomer are a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, or a hydrogenated product thereof. The above-mentioned various compounding agents are not particularly limited, and those commonly used in thermoplastic resin materials can be used, such as antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, slip agents, antistatic agents, flame retardants, dyes, or Coloring agents such as pigments, compounding agents such as near-infrared absorbers and fluorescent brighteners. The above-mentioned cyclic olefin-based resin or its composition is thermoplastic, and is soluble in a hydrocarbon-based solvent such as toluene, xylene, or cyclohexane. Therefore, it can be easily formed by a conventionally known method. For example, injection molding, extrusion molding, compression molding, injection compression molding, and blow molding can be used to shape a heated and molten resin. For example, solution casting molding can be temporarily dissolved in a solvent, and the solution can flow into a mold to evaporate the solvent. While shaping. The shape of the molded product is not particularly limited, and may be, for example, a plate shape or a film shape used in printed wiring boards 1 4 to 200415001, a plate shape or a three-dimensional shape used in antennas, or a circle used in cables. Cylindrical shape, three-dimensional shape used in connectors, etc. The material of the metal body with the surface-treated metal body compounded on the surface of the ring-shaped tobacco resin component is not particularly limited, and may be, for example, copper, aluminum, gold, silver, tin, nickel, iron, or an alloy thereof . In addition, in order to protect the metal surface from oxidation or corrosion, a known metal plating treatment such as nickel, tin, or gold is also applied. The shape of the metal body is not particularly limited, and may be a flat shape such as a foil or a sheet, or a rod shape or a linear shape such as a reed line, depending on the application. The metal body must be surface-treated with the triple well dithiol compound represented by the general formula (1) in advance. The surface treatment of the metal body of the triple well dithiol compound can be performed, for example, by immersing the metal body in a water or organic solvent solution of the triple well dithiol compound. Examples of the processing method are those described in Japanese Patent Publication No. 1_6005 or Japanese Patent Publication No. 8-8856. The surface treatment may be performed by electrochemical treatment. For example, an aqueous solution or organic solvent solution of trioxane dithiol compound is used as the electrodeposition solution, the metal of the metal body is used as the anode, and the cathode uses an appropriate conductor, such as a platinum plate or a titanium plate, for example, a voltage below 20V, A current density of 0.1 lmA / dm2 or more was passed, and a direct current was passed for 0.1 seconds or more. The processing method is, for example, the method described in JP 5-5 1671. Combination and method of resin molded body and metal body In the present invention, a resin molded product ~ 15-200415001 can be simply compounded with metal by a so-called hot stamping method. That is, when the metal body is carried on the surface of the cyclic olefin, and the pressure is applied while heating, the temperature at the time of heating and pressing which can have high adhesion must be a temperature equal to or higher than the glass transition temperature (Tg) of the E used. Select within the range of + 100 ° C. If the temperature is too low, it will not be obtained. If the temperature is too high, the formed body will be deformed, which is not suitable. The pressure during heating and pressurization is 0.1 MPa or more, particularly preferably 0.3 to 0.6 MPa. When the pressure is lower than the above range. In the present invention, an all-metal body can be composited on the surface of a resin molded body. In addition, on the surface of the cyclic olefin resin molded product, a metal foil previously cut into a circuit pattern shape can be multiplexed using a mold provided with a cutter having a predetermined circuit pattern shape. 'Either patterning and etching to remove the metal portion not carrying the photoresist may be any of the above. In the composite molded product obtained by forming the cyclic olefin resin obtained in this way into a composite molded product, the 'cyclic alkane-based dendritic system is easy, especially in the high frequency range of the GHz band and low dielectric tangent. The excellent dielectric properties are also the surface recombination of the resin molded body. The cyclic olefin resin has a sufficient adhesion force above Tg + 40 ° C, and preferably 0.2 to 1 MPa. When the composite system is inadequate or part of it, the method of hot stamping when forming a circuit pattern can be used. A method of forming an electric photoresist to form a circuit at the same time as the S-print, etc., the composition of the composite gold moon or its composition on the surface of the multi-product of the present invention has a low dielectric constant and often forms an electrical signal flow. 200415001 Metal_resin or resin The peel strength between the components (that is, between the metal and the resin molded product) is 0.2 kg / cm or more, preferably 0.4 kg / cm or more. The upper limit is t and there are other restrictions, but usually it is About 2 kg / cm. The water absorption of the cyclic olefin-based resin or its composition (that is, a molded product of the resin) is 0.1% or less, and preferably 0.5% or less. The dielectric constant of the cyclic olefin-based resin or its composition (that is, a molded product of the resin) in iGh is 2.0 to 3.0, preferably 2.0 to 2.5. _ Dielectric tangent system 1 > < 10 ~ 1 \ 1〇2, preferably 1 > < 1〇-4 ~ 5 > < 1〇-3. The elastic modulus of bending is 1,000 to 10,000 MPa, preferably 2,000 to 6,000 MPa °. Therefore, the composite molded product of the present invention can be applied to component parts of a device for processing high-frequency electrical signals in the GHz band, such as printed wiring boards, Antennas, connectors, cables, etc. Examples Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. The physical properties of the compositions of the examples and comparative examples were evaluated as follows. Peeling strength (adhesion evaluation of the metal film): The metal part of the test piece was cut to a width of 0 mm with a knife, and one end of the metal film was pulled and pulled about 20 mm. The peeled metal film was clamped by a clamp of a tensile testing machine, and was stretched at a speed of 50 mm / min while maintaining a right angle to the test piece. The average load at this time was taken as the peel strength (kg / cm) . Dielectric constant and dielectric tangent: A 15 mm square cut from a flat plate having a thickness of 1 mm -17- 200415001 obtained by injection molding was used as a test piece, and an impedance analyzer 42 87 manufactured by Aguiret Kurossi was used. A, Measure the dielectric constant and dielectric tangent at 1 GHz. Flexural modulus of elasticity (assessment of stiffness): Based on: IIS K7 1 7 1 Water absorption rate: 10 test pieces (70mmx50mmx3mm) were placed under the conditions of 2 ° C and 50% RH, and the weight change of the weight gain D amount when saturated was taken as the water absorption rate (shortly after forming Weight). As the cyclic olefin-based resin, the following commercially available resins are used. COP1 · TOPAS6015 (manufactured by Ticona, an addition copolymer of original norbornene and ethylene, glass transition temperature of 160 ° C, without polar groups) COP2: Abbe APL6015T (manufactured by Mitsui Chemicals, tetracyclododecene and ethylene Addition copolymer, glass transition temperature of 1 45 ° C, without polar groups) C0P3: Leonjoa 1 600R (made by Japan Leon, hydrogenated ring-opening polymer of original norbornene cyclic olefin , Glass transition temperature 16 3 ° C, does not contain polar groups) COP4: Adam G (made by Japan Synthetic Rubber, 8-methyl-8-methoxycarbonyl tetracyclo [4.4.0. 1. .1] ten_ • Chloride of carbon-3-fine ring-opening polymer, glass transition temperature 171 ° C, per kg of resin containing 4.27 mole ester group as polar group) Hollow inorganic materials are made of glass balloons (made by Sumitomo 3M) , 86 glass balloons, true density 0.60, 90% particle size 450111, hereinafter referred to as 08). Preparation Example 1 (Preparation of acrylic modified cyclic olefin resin COP1) 98 parts by weight of cyclic olefin resin TOPAS 60 1 3 (manufactured by Ticona, an addition copolymer of original norbornene and ethylene, and Addition copolymer, glass transition temperature 1 36 ° C, does not contain polar groups), 2 parts by weight of -18-200415001 acrylic acid, and 0.2 parts by weight of Bach machine Xin 2 5 B (Japanese oils and fats) Production), in a biaxial extruder, melt-kneading at a barrel temperature of 200 ° C to synthesize a cyclic olefin resin modified by acrylic grafting. This COPF1 system contains 0.2 8 mole carboxyl groups as polar groups per kg of resin. Preparation Example 2 (Preparation of maleic anhydride modified cyclic olefin resin COP2) 97.3 parts by weight of cyclic olefin resin TOP AS 6013 (manufactured by Tic Ona), 2.7 parts by weight of maleic anhydride, and 0.2 parts by weight of As a peroxide, the Baga machine Xin 25B (made by Japan Grease) was melt-kneaded in a biaxial extruder at a barrel temperature of 200 ° C to synthesize cyclic olefins modified by maleic anhydride grafting. Resin. This COPF2 contains 0.28 mole acid anhydride groups as polar groups per kg of resin. Preparation Example 3 (Production of copper foil Cu 1 with surface treatment) The following copper foil was subjected to surface treatment in accordance with the method shown in Experimental Example of Japanese Patent Publication No. 5-51671. An electrolytic copper foil (CF-T9-18 (made by Fukuda metal foil powder) with a thickness of 18 μm was used as an anode in an electrodeposition tank. A platinum electrode was placed 5 cm away from the copper foil and used as a cathode. The electrodeposition tank is filled with 1,3,5-tritrap-2,4,6-trithiol • monosodium (trade name: Shajilu N -1 (manufactured by Sankyo Chemical Co., Ltd.)) as the treated water liquid. After a 5% aqueous solution was applied at a current density of ImA / cm2 for five minutes, a copper foil (Cul) having an electrodeposition surface treated with triple well trithiol was obtained. Preparation Example 4 (Preparation of Surface-treated Copper Foil Cu2) The treatment solution was changed to a 6-dibutylamino-1, 3,5-tritrap-2,4-dithiol (trade name Tysnett DB (manufactured by Sankyo Chemical Co., Ltd.) 0.5% methanol solution. Example 3 was performed in the same manner to obtain a copper foil (cu 2) with a surface treated. -19- 200415001 [贝 施 例 1] At a cylinder temperature of 30 ° C and a mold temperature of 11 ° C, the cyclic olefin tree was intended Copi is injection-molded to produce a flat-shaped molded product (50mmx70mmx3mm). On the resin molded product, copper foil Cii 1 is superimposed so that the rough side of the copper foil contacts the resin molded product, and a commercially available one is used. Printing equipment (manufactured by Taiping Industrial, VD6 type) 'was heated and pressed at 220 ° C and pressure of 0.4 MPa for 5 seconds to adhere. The peel strength of the resin molded product and the copper foil was measured, and the result was 0.68 kg / cm. The cyclic olefin resin CoP1 has a dielectric constant of 2.31 at 1 GHz, a dielectric tangent of 0.0005, a flexural modulus of elasticity of 2900 MPa, and a water absorption of 0.01%. [Examples 2 to 6] Change to Table 1 Except for the hot stamping conditions shown below, the same procedure as in Example 1 was performed to produce a cyclic olefin-based resin molded article with copper foil adhered under heating and pressure. 200415001 Table 1 (In the following tables, @ 系 is "于”Meaning) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Composition COP1 (% by weight) 100 Hot stamping conditions Copper foil Cul Cu2 Temperature (° c) 220 230 220 220 230 220 Pressure (MPa ) 0.4 0.4 0.5 0.4 0.4 0.5 Time (seconds) 5 5 8 5 5 8 Physical peel strength (kg / cm) 0.67 0.68 0.72 0.70 0.69 0.74 Dielectric constant @lGHz 2.31 Dielectric tangent @lGHz 0.0005 Flexural modulus of elasticity (MPa) 2900 Water absorption (%) 0.01 [Examples 7 to 12] Ring The olefin resin COP1 and glass balloon GB have the composition shown in Table 2. Using a biaxial extruder, melt-kneading at a barrel temperature of 300 ° C, to obtain nine pellets of a cyclic olefin resin composition. It was formed by the same method as in Example 2 or 5, and was subjected to hot stamping and evaluation. The results are shown in Table 2. -2 1 200415001 By adding a glass balloon, the high frequency dielectric properties (low dielectric constant and low dielectric tangent) of the cyclic olefin resin can be maintained as before, the rigidity can be improved, and a higher value can be obtained. Peel strength. Table 2 Examples Example Example Example Example 7 8 9 10 11 12 Composition 丨 π II 1 U- COP1 (wt%) 80 90 70 GB (wt%) _ 20 10 30 Hot stamping conditions copper foil Cul Cu2 Cul Cu2 Cul Cu2 Temperature fc) 230 230 230 230 230 230 Pressure (MPa) 0.4 0.4 0.4 0.4 0.4 0.4 Time (seconds) 5 5 5 5 5 5 Physical peel strength (kg / cm) 0.89 0.90 0.82 0.81 0.91 0.93 Dielectric Constant @lGHz 2.26 2.31 2.26 Dielectric tangent @lGHz 0.0007 0.0002 0.0010 Flexural modulus of elasticity 3600 3300 4400 (MPa) Water absorption (%) 0.01 0.01 0.01 [Example 1 3 ~ 1 8] Change the cyclic olefin resin to COP2 Or COP3, the copper foil was hot stamped on the resin molded article under the conditions shown in Table 3. Both showed high peel strength. Results-22- 200415001 The results are shown in Table 3. Table 3 Examples Implementation Example Implementation ---------- Implementation 13 Example 14 Example 15 16 Example 17 Example 18 Composition: -ω-== «== COP2 (wt%) 100 80 COP3 ( % By weight) 100 80 GB (% by weight) 20 20 Hot stamping conditions Copper foil Cul Cul Cu2 Cul Cul Cu2 Temperature CC) 215 215 215 230 230 230 Pressure (MPa) 0.4 0.4 0.4 0.4 0.4 0.4 Time (seconds) __ 5 5 5 5 5 5 Physical peel strength (kg / cm) 0.65 0.85 0.88 0.59 0.79 0.80 Dielectric constant @lGHz 2.31 2.26 2.35 2.27 Dielectric tangent @lGHz 0.0006 0.0008 0.0004 0.0008 Flexural modulus of elasticity (MPa) 3200 3800 2600 3200 Water absorption (%) ) 0.01 0.01 0.01 0.01 [Examples 19 to 24] As shown in Table 4, a composition obtained by adding a modified cyclic olefin resin COPF1 or COPF2 grafted with a polar group to a cyclic olefin resin or A separate modified cyclic olefin-based resin was evaluated. By adding a modified ring-shaped soot-burning resin, although the dielectric constant, dielectric tangent, and water absorption are slightly increased, 200415001 can greatly increase the peel strength, so it is good. Table 4 Examples Examples Examples Examples Examples 19 20 21 22 23 24 Composition COP1 (wt%) 80 50 80 60 60 COP1 (wt%) 20 50 100 20 COPF2 (wt%) 20 20 GB (Wt%) 20 20 Extremes in resin composition 0.06 0.14 0.28 0.06 0.06 0.06 Sexual basis (mol / kg) Stamping conditions Copper foil Cul temperature CC) 230 Pressure (MPa) 0.4 Time (second) ζ Physical peel strength (Kg / cm) 1.30 1.61 1.70 1.35 1.80 1.88 Dielectric constant @lGHz 2.33 2.35 2.4 2.34 2.28 2.28 Dielectric tangent @ 1GHz 0.0008 0.0015 0.0025 0.0008 0.0009 0.0010 Flexural modulus of elasticity (MPa) 2900 2800 2800 2900 3600 3600 Water absorption (% ) 0.01 0.02 0.02 0.02 0.02 0.02

[Comparative Examples 1 to 4] As shown in Table 5, for the molded product of the composition of the cyclic olefin resin COP 1 or COP 2 and 24-200415001 glass balloon GB, the copper foil was not treated on the hot stamping surface, but The copper foil is easily peeled, and the peel strength cannot be measured. [Comparative Examples 5 and 6] As shown in Table 5, for a molded article having a composition containing a cyclic olefin resin CoP2, the copper foil was not easily peeled on the hot stamped surface, although Peel strength can be measured, but its 値 is very small. Table 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Composition COP1 (% by weight) 100 90 80 70 80 60 COPF2 (% by weight) 20 20 GB (% by weight) 10 20 30 20 Hot stamping conditions copper foil untreated copper temperature (° C) 230 pressure (MPa) 0.4 time (seconds) ί physical peel strength (kg / cm) copper foil is easy to peel, and cannot be measured 0.12 0.19 [Comparative Examples 7 and 8] As shown in Table 6, a cyclic olefin resin COP4 having an ester group in the side chain or a molded product of a composition of COP4 and glass balloon GB was stamped on the surface of 200415001 with copper foil treated. For example, COP4 contains a large number of polar groups. Although the peel strength is high, the system of dielectric constant and dielectric tangent is greatly increased, and the water absorption rate is increased by more than 10 times, which is not suitable for parts of high-frequency devices. Table 6 Comparative Example 7 Comparative Example 8 Composition CoP4 (% by weight) 100 80 GB (% by weight) 20 Amount of polar group (mol / kg) in the resin composition 4.27 3.42 Roughening conditions Copper range Cul temperature ΓΟ 240 Pressure (MPa) 0.4 Time (seconds) 5 Physical peel strength (kg / cm) 1.72 1.93 Dielectric constant @lGHz 2.71 2.66 Dielectric tangent @lGHz 0.021 0.022 Flexural modulus (MPa) 3000 3600 Water absorption (%) 0.2 0.16 Industry Availability

According to the present invention, it is possible to obtain a method for compounding metal on the surface of a cyclic olefin-based resin formed into a 26-200415001 shaped article suitable as a component of a device for processing high-frequency electrical signals in the high-frequency band, especially in the GHz band, and compounding the metal Cyclic olefin resin molded product.

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Claims (1)

200415001 The scope of patent application: 1. A metal compounding method for the surface of a cyclic olefin resin molded product, characterized in that the surface of the cyclic olefin resin or a molded product thereof is heated and pressed by the following methods: A metal body surface-treated with a triple well dithiol compound represented by the general formula (1), Where R is -OR ', -SR ,, -NHR ,, -N (R,) 2, R, is hydrogen, alkyl, alkenyl, phenyl, phenalkyl, alkylbenzene Or cycloalkyl; M is any of Η, Na, Li, K, 1/2 C a, 1/2 B a, aliphatic primary, secondary, and tertiary amines, and quaternary ammonium salts . 2. The metal composite method according to item 1 of the application, wherein at least a part of the cyclic olefin-based resin is a modified cyclic olefin-based resin grafted with an unsaturated compound having a polar group. 3. The metal composite method according to item 2 of the patent application, wherein the concentration of the polar group contained in the cyclic olefin resin or the composition thereof is 1 mole / kg or less. 4. The metal composite method according to any one of claims 1 to 3, wherein the cyclic olefin-based resin-based α-olefin and the cyclic olefin are addition copolymers. 5. The metal composite method according to item 4 of the patent application, wherein the cyclic olefin is orthobornene or tetracyclododecene. -28 200415001 6. The metal composite method according to any one of claims 1 to 5, wherein the cyclic olefin-based resin composition is composed of a cyclic olefin-based resin and a hollow inorganic material. 7. The metal composite method according to item 6 of the patent application, wherein the hollow inorganic material is a glass balloon or a Stnrasu balloon. 8 · A metal composite cyclic olefin-based resin molded product obtained by a metal composite method for the surface of a cyclic olefin-based resin molded product as described in any one of claims 1 to 7 of the application. 9. The metal composite cyclic olefin-based resin molded product according to item 9 of the application, wherein the peel strength between the metal and the resin or its composition is 0.2 kg / cm or more. 10. If the metal composite cyclic olefin-based resin molded product according to item 8 or 9 of the patent application is applied, the water absorption of the cyclic hydrocarbon-based resin or its composition is as follows. n. A metal composite cyclic diluent hydrocarbon-based resin molded product according to any one of items 8 to 1G in the scope of patent application, which is a component part of a device for processing high-frequency electrical signals in the GHz band. -29- 200415001 (1) Designated representative map: (1) The designated representative map in this case is: (). (2) Brief description of the representative symbols of the components in this representative drawing: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: SM (1)