JP5235403B2 - Surface treatment method for cyclic olefin resin molded products - Google Patents

Description

  The present invention relates to a surface treatment method for a cyclic olefin resin molded product having excellent transparency, and more particularly to a surface treatment method for a cyclic olefin resin molded product having excellent plating adhesion.

  Conventionally, as a plating method on a resin molded product, a material obtained by kneading other components that are easily dissolved during etching into the resin is used, and the anchor effect by the holes in which other components are removed by dissolution or the like by etching is applied to the surface of the resin molded product. It is known to improve plating adhesion (Patent Document 1).

  On the other hand, cyclic olefin-based resins are known as materials having excellent electrical properties, particularly dielectric loss, and high transparency among thermoplastic resins. For this reason, the cyclic olefin-based resin has been conventionally used for a three-dimensional circuit board or the like in which a circuit is formed by plating taking advantage of the above-described characteristics.

  However, the conventional method uses a material obtained by kneading a cyclic olefin resin with a component that is easily soluble during etching, such as a rubber component, and removes the rubber component by etching in the same manner as the plating method on the surface of the resin molded product. The plating effect was improved by the anchor effect. For this reason, there is a problem that the three-dimensional substrate using the cyclic olefin-based resin is remarkably lowered in transparency by kneading the rubber component or the like (Patent Documents 2, 3, and 4).

Further, as a plating method for resin, dry plating methods such as sputtering and ion plating are also known, but these methods have a problem that it is difficult to plate through holes and vertical surfaces (Patent Document 5). ).
JP-A-5-287176 JP 2003-115645 A JP 2007-67260 A JP 2007-20122 A JP 9-193293 A

  Therefore, in order to take advantage of the high transparency of the cyclic olefin resin suitable for the material of the three-dimensional circuit board due to good electrical characteristics, the surface of the cyclic olefin resin molded product does not include a component that is easily dissolved during etching such as a rubber component. In addition, there is a need for a technique for making minute irregularities as obtained after the conventional etching process and improving the adhesion of the plating by the anchor effect.

  In addition, chemical plating treatment using cyclic olefin resin molded products starts with the process of adding rubber etc. to cyclic olefin resin, degreases and removes the resin surface, and then etching, neutralization, catalyst application, catalyst Since this is followed by chemical plating, many steps are involved. There is a need for a method for reducing the number of steps as much as possible and easily and efficiently chemically plating a cyclic olefin-based resin molded article.

  The present invention has been made in order to solve the above-mentioned problems. The purpose of the present invention is to make use of the transparency of the cyclic olefin resin, and the surface of the cyclic olefin resin molded article achieves high plating adhesion due to the anchor effect. A surface treatment method for a cyclic olefin resin molded product for performing a chemical plating treatment more easily than a chemical plating treatment for a conventional cyclic olefin resin molded product Is to provide.

In order to solve the above-mentioned problems, the present inventors have conducted extensive research. As a result, the surface of the cyclic olefin-based resin molded article is treated with an organic solvent having a solubility parameter of 12.0 J ^{l / 2} / cm ^{3/2 to} 20.1 J ^{l / 2} / cm ^3/2 , The present inventors have found that the problem can be solved and have completed the present invention. More specifically, the present invention provides the following.

(1) With respect to the surface of the cyclic olefin-based resin molded article, the surface is washed with an organic solvent having a solubility parameter of 12.0 J ^{l / 2} / cm ^3/2 to 20.1 J ^{l / 2} / cm ^3/2. A method for surface treatment of a cyclic olefin-based resin molded article, characterized by performing chemical plating after an etching step of etching.

According to the invention of (1), strong plating adhesion due to the anchor effect can be realized without using a material in which a cyclic olefin resin is kneaded with a component that is easily dissolved during etching, such as a rubber component. This is because the surface of the cyclic olefin-based resin molded product is formed using an organic solvent having a solubility parameter (SP value) of 12.0 J ^{l / 2} / cm ^{3/2 to} 20.1 J ^{l / 2} / cm ^3/2. This is because the microcracks generated by the treatment replace the irregularities that have been generated by melting the rubber component after the conventional etching process. Therefore, according to this invention, the high transparency of cyclic olefin resin can be utilized.

  In the present invention, the surface of a cyclic olefin-based resin molded article is treated with an organic solvent having a specific solubility parameter. This treatment generates microcracks on the surface of the cyclic olefin-based resin molded product. Although the transparency of the cyclic olefin-based resin molded product is slightly lowered due to the microcrack, it is possible to obtain a plated product having high transparency by selective etching by masking or the like.

  In addition, by adjusting the solubility parameter of the cyclic olefin resin and the solubility parameter of the organic solvent, the transparency and the plating adhesion due to the anchor effect can be adjusted.

  In the present invention, first, it is not necessary to add a filler such as rubber to the cyclic olefin-based resin, and the labor and cost of the filler can be reduced. Furthermore, since the surface of the cyclic olefin-based resin molded product is not originally contaminated and the etching solution used in the etching process of the present invention also serves as a degreasing process, the present invention relates to a conventional cyclic olefin-based resin molded product. The chemical plating treatment can be performed on the cyclic olefin-based resin molded product more easily than the chemical plating treatment.

  The solubility parameter is a numerical value that is a measure of the solubility and compatibility of the polymer, and it is known that the solubility and the compatibility increase as the difference in SP value between the polymer and the solvent decreases. Assuming that the interaction between the polymer and the solvent is only an intermolecular force, the cohesive energy of the solution is equivalent to the enthalpy of evaporation, so the SP value on the solvent side is calculated from the heat of molar evaporation ΔH and the molar volume V. (Δ) is defined by the following equation.

  On the other hand, as the SP value of the polymer, a value experimentally determined so as not to contradict the solubility in a solvent with a known SP value or a value estimated from the molecular structure of the polymer by the atomic group contribution method is used. It is done. For specific values of SP values of polymers and various solvents, see Polymer Handbook 4th Ed. The values described in (Page VII / 675 or less) and the like can be adopted.

  (2) After the etching step, a wetting step for imparting polarity to the surface of the cyclic olefin-based resin molded product, and a catalyst imparting step for imparting a catalyst to the cyclic olefin-based resin molded product that imparts polarity to the surface, An activation step of activating the applied catalyst, and the surface treatment method for a cyclic olefin-based resin molded article according to (1).

  According to the invention of (2), the microcracks generated on the surface of the cyclic olefin-based resin molded product are moistened, then provided with a catalyst, and the applied catalyst is activated, so that the anchor effect is transparent. A chemical plating process having excellent adhesion can be formed on the surface of the cyclic olefin-based resin molded product.

  (3) Furthermore, the surface treatment method of the cyclic olefin resin molded article according to (1) or (2), wherein electroplating is performed after the chemical plating.

  According to the invention of (3), a circuit can be formed on a transparent material by performing electroplating after chemical plating. In addition, a desired circuit can be formed after electroplating. Since the present invention does not use a filler such as rubber as in the prior art, the substrate of the cyclic olefin resin maintains high transparency, and a circuit can be formed on the transparent substrate.

  (4) The cyclic olefin according to any one of (1) to (3), wherein the organic solvent is one or more of n-hexane, cyclohexane, toluene, benzene, chloroform, dichloromethane, and dichloroethane. Surface treatment method for resin-based resin molded products.

  According to the invention of (4), desired microcracks can be easily generated on the surface of the cyclic olefin resin molded product by treating the surface of the cyclic olefin resin molded product with the nonpolar organic solvent. .

  (5) The surface treatment method for a cyclic olefin-based resin molded product according to any one of (1) to (4), wherein the boiling point of the organic solvent is 50 ° C to 100 ° C.

  According to the invention of (5), if the boiling point of the organic solvent is in the above range, the boiling point is not too low, so the management of the organic solvent becomes easy. In addition, since the boiling point is not too high, the organic solvent can be prevented from remaining in the microcracks, and overetching can be prevented. Therefore, the chemical plating treatment can be easily performed on the cyclic olefin resin molded article by treating the surface of the cyclic olefin resin molded article with an organic solvent having a boiling point in the above range.

  (6) The organic solvent according to any one of (1) to (5), wherein the organic solvent is a mixed solvent obtained by adding at least one of acetone, methanol, ethanol, isopropanol, n-butanol, ethyl acetate, and methyl ethyl ketone. A surface treatment method for a cyclic olefin-based resin molded product.

  According to the invention of (6), the etching rate of the etching of the surface of the cyclic olefin-based resin molded article can be controlled by adding any one or more of the above organic solvents to the organic solvent described in (4). . For this reason, microcracks having a desired size, depth, and the like can be easily generated on the surface of the cyclic olefin resin molded product. Therefore, according to the present invention, the chemical plating treatment can be easily performed on the cyclic olefin-based resin molded product.

  (7) Between the etching step and the chemical plating treatment, treatment with one or more solvents of acetone, methanol, ethanol, isopropanol, n-butanol, ethyl acetate, and methyl ethyl ketone, and further treatment with water ( The surface treatment method for a cyclic olefin-based resin molded product according to any one of 1) to (6).

  According to the invention of (7), the surface of the cyclic olefin resin molded product is treated with one or more organic solvents after the etching step and before the chemical plating treatment, and the surface of the cyclic olefin resin molded product is further treated with water. By performing the treatment, the chemical plating treatment can be easily performed on the cyclic olefin-based resin molded product. This is because the normal chemical plating process is carried out in a water-soluble solution, so that the etching treatment liquid remaining on the surface of the cyclic olefin resin molded product is removed and the water on the surface of the cyclic olefin resin molded product is removed using the above solvent. This is because the chemical plating treatment can be promoted by improving the wettability of the film.

According to the present invention, in the chemical plating treatment of a cyclic olefin-based resin molded product, the solubility parameter is 12.0 J ^{l / 2} / cm ^3/2 to 20.1 J ^{l / 2 with} respect to the surface of the cyclic olefin-based resin molded product. By providing an etching process that etches the surface using an organic solvent that is / cm ^3/2 , the transparency of the cyclic olefin-based resin can be utilized while having the same plating adhesion as that of the prior art. Furthermore, according to the present invention, the chemical plating treatment can be performed on the cyclic olefin resin molded product more easily than the chemical plating treatment of the conventional cyclic olefin resin molded product.

  Hereinafter, embodiments of the surface treatment method for a cyclic olefin-based resin molded article of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and is within the scope of the object of the present invention. It can be implemented with appropriate modifications. In addition, although description may be abbreviate | omitted suitably about the location where description overlaps, the summary of invention is not limited.

<Cyclic olefin resin>
Hereinafter, the cyclic olefin-based resin will be described. The cyclic olefin resin used in the present invention contains a cyclic olefin component as a copolymerization component, and is not particularly limited as long as it is a polyolefin resin containing a cyclic olefin component in the main chain. For example,
(A1) Cyclic olefin addition polymer or hydrogenated product thereof,
(A2) an addition copolymer of a cyclic olefin and an α-olefin or a hydrogenated product thereof,
(A3) A ring-opening (co) polymer of a cyclic olefin or a hydrogenated product thereof.

In addition, as a cyclic olefin resin containing a cyclic olefin component used in the present invention as a copolymerization component,
(A4) A resin obtained by grafting and / or copolymerizing an unsaturated compound having a polar group to the resins (a1) to (a3).

  Examples of the polar group include a carboxyl group, an acid anhydride group, an epoxy group, an amide group, an ester group, and a hydroxyl group. Examples of the unsaturated compound having a polar group include (meth) acrylic acid and maleic acid. Acid, maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (carbon number 1-10) ester, maleic acid alkyl (carbon number 1-10) ester, (meth) acrylamide, (meta ) 2-hydroxyethyl acrylate.

  In the present invention, the cyclic olefin-based resins (a1) to (a4) containing the cyclic olefin component as a copolymerization component may be used alone or in combination of two or more. In the present invention, (a2) an addition copolymer of cyclic olefin and α-olefin or a hydrogenated product thereof can be preferably used.

  Moreover, as the cyclic olefin-based resin containing the cyclic olefin component used in the present invention as a copolymerization component, a commercially available resin can be used. Examples of commercially available cyclic olefin resins include TOPAS (registered trademark) (manufactured by TOPAS ADVANCED POLYMER), Apel (registered trademark) (manufactured by Mitsui Chemicals), Zeonex (registered trademark) (manufactured by Nippon Zeon), Examples include ZEONOR (registered trademark) (manufactured by ZEON Corporation), ARTON (registered trademark) (manufactured by JSR Corporation), and the like.

（式中、Ｒ^１〜Ｒ^１２は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、炭化水素基からなる群より選ばれるものであり、Ｒ^９とＲ^１０、Ｒ^１１とＲ^１２は、一体化して２価の炭化水素基を形成してもよく、Ｒ^９又はＲ^１０と、Ｒ^１１又はＲ^１２とは、互いに環を形成していてもよい。また、ｎは、０又は正の整数を示し、ｎが２以上の場合には、Ｒ^５〜Ｒ^８は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。） The addition copolymer of (a2) cyclic olefin and α-olefin preferably used in the composition of the present invention is not particularly limited. Particularly preferred examples include a copolymer containing [1] an α-olefin component having 2 to 20 carbon atoms and [2] a cyclic olefin component represented by the following general formula (I).

(In the formula, R ^{1 to} R ¹² may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R ⁹ , R ¹⁰ , R ^11, and R ¹² may be integrated to form a divalent hydrocarbon group, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other, and n is When 0 or a positive integer is represented and n is 2 or more, R ^{5 to} R ⁸ may be the same or different in each repeating unit.

[[1] α-olefin component having 2 to 20 carbon atoms]
The C2-C20 alpha-olefin used as the copolymerization component of the addition polymer of the cyclic olefin component preferably used for this invention and other copolymerization components, such as ethylene, is not specifically limited. For example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-octene, Examples include decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene. These α-olefin components may be used alone or in combination of two or more. Of these, ethylene is most preferably used alone.

[[2] Cyclic olefin component represented by formula (I)]
In the addition polymer of the cyclic olefin component preferably used in the present invention and another copolymer component such as ethylene, the cyclic olefin component represented by the general formula (I) serving as the copolymer component will be described.

R ^{1 to} R ¹² in the general formula (I) may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.

Specific examples of R ^{1 to} R ⁸ include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; a lower alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group. May be different from each other, may be partially different, or all may be the same.

Specific examples of R ^{9 to} R ¹² include, for example, hydrogen atom; halogen atom such as fluorine, chlorine, bromine; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, stearyl. Alkyl group such as cyclohexyl group; cycloalkyl group such as cyclohexyl group; substituted or unsubstituted aromatic hydrocarbon group such as phenyl group, tolyl group, ethylphenyl group, isopropylphenyl group, naphthyl group, anthryl group; benzyl group, phenethyl And an aralkyl group in which an aryl group is substituted with an alkyl group, and the like. These may be different from each other, may be partially different, or all may be the same.

Specific examples of the case where R ⁹ and R ¹⁰ or R ¹¹ and R ¹² are integrated to form a divalent hydrocarbon group include, for example, alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group. Can be mentioned.

When R ⁹ or R ¹⁰ and R ¹¹ or R ¹² form a ring with each other, the formed ring may be monocyclic or polycyclic, or may be a polycyclic ring having a bridge. , A ring having a double bond, or a ring composed of a combination of these rings may be used. Moreover, these rings may have a substituent such as a methyl group.

  Specific examples of the cyclic olefin component represented by the general formula (I) include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-methyl-bicyclo [2.2.1] hepta. 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-ethylidene-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-methylidene-bicyclo [2.2.1] hept-2-ene 5-vinyl-bicyclo [2.2.1] hept-2-ene, - propenyl - bicyclo [2.2.1] of the two rings, such as hept-2-ene cyclic olefin;

Tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene), tricyclo [4.3.0.1 ^2,5 ] dec-3-ene; tricyclo [ 4.4.0.1 ^2,5 ] undeca-3,7-diene or tricyclo [4.4.0.1 ^2,5 ] undeca-3,8-diene or a partially hydrogenated product thereof (or cyclopentadiene) Tricyclo [4.4.0.1 ^2,5 ] undec-3-ene; 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene A cyclic olefin of the ring;

Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (also simply referred to as tetracyclododecene), 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyltetracyclo [4,4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] tetracyclic olefins such as dodec-3-ene;

8-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene; tetracyclo [7.4.1 ^3,6 . 0 ^1,9 . 0 ^2,7 ] tetradeca-4,9,11,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene), tetracyclo [8.4.1 ^4,7 . 0 ^1,10 . 0 ^3,8 ] pentadeca-5,10,12,14-tetraene (also called 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene); pentacyclo [6.6.1]. ^.1,3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene, pentacyclo [7.4.0.0 ^2,7. 1 ^3,6 . 1 ^10,13] -4-pentadecene; heptacyclo [8.7.0.1 ^2,9. 1 ^4,7 . 1 ^{11, 17} . 0 ^3,8 . 0 ^12,16 ] -5-eicosene, heptacyclo [8.7.0.1 ^2,9 . 0 ^3,8 . 1 ^4,7 . 0 ^12,17 . 1 ^13,16 ] ^-14-eicosene ; and polycyclic cyclic olefins such as cyclopentadiene tetramer.

  These cyclic olefin components may be used singly or in combination of two or more. Among these, bicyclo [2.2.1] hept-2-ene (common name: norbornene) and tetracyclododecene are preferably used.

  [1] A method for polymerizing an α-olefin component having 2 to 20 carbon atoms and a [2] cyclic olefin component represented by formula (I) and a method for hydrogenating the obtained polymer are particularly limited. Instead, it can be carried out according to known methods. Random copolymerization or block copolymerization may be used, but random copolymerization is preferred.

  The polymerization catalyst used is not particularly limited, and can be obtained by a known method using a conventionally known catalyst such as a Ziegler-Natta, metathesis, or metallocene catalyst. The addition copolymer of cyclic olefin and α-olefin or the hydrogenated product thereof preferably used in the present invention is preferably produced using a metallocene catalyst or a Ziegler-Natta catalyst.

  Examples of the metathesis catalyst include molybdenum or tungsten-based metathesis catalysts (for example, described in JP-A Nos. 58-127728 and 58-129003) as a catalyst for ring-opening polymerization of cycloolefin. In addition, the polymer obtained by the metathesis catalyst uses an inorganic carrier-supported transition metal catalyst or the like, and 90% or more of the main chain double bond and 98% or more of the carbon-carbon double bond in the side chain aromatic ring are hydrogenated. It is preferable to add.

[Other copolymer components]
The addition copolymer of (a2) cyclic olefin and α-olefin particularly preferably used in the composition of the present invention comprises [1] the α-olefin component having 2 to 20 carbon atoms and [2] the general formula (I In addition to the cyclic olefin component represented by (), other copolymerizable unsaturated monomer components may be contained as necessary within the range not impairing the object of the present invention.

  The unsaturated monomer that may be optionally copolymerized is not particularly limited, and examples thereof include hydrocarbon monomers containing two or more carbon-carbon double bonds in one molecule. Can be mentioned. Specific examples of hydrocarbon monomers containing two or more carbon-carbon double bonds in one molecule include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 4 A chain non-conjugated diene such as methyl-1,5-hexadiene, 5-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene; cyclohexadiene, di Cyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl- 2-norbornene, 4,9,5,8-dimethano-3a, 4,4a, 5,8,8a, 9,9a-octahydro-1H-benzoy Cyclic non-conjugated dienes such as Den; 2,3-isopropylidene-5-norbornene; 2-ethylidene-3-isopropylidene-5-norbornene; may be mentioned 2-propenyl-2,2-norbornadiene and the like. Among these, 1,4-hexadiene, 1,6-octadiene, and cyclic nonconjugated dienes, especially dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-methylene-2 -Norbornene, 1,4-hexadiene, 1,6-octadiene are preferred.

  The number average molecular weight of the cyclic olefin resin is preferably 20,000 to 100,000, more preferably 30,000 to 60,000. If the number average molecular weight of the cyclic olefin resin is too small, the solubility of the resin becomes high and it becomes difficult to obtain the desired microcracks, which is not preferable. If the number average molecular weight is too high, the solubility of the resin becomes too low and the micro Since it becomes difficult to produce a crack in a cyclic olefin resin molded product, it is not preferred. If the number average molecular weight of the cyclic olefin-based resin is in the above range, it is preferable because microcracks having a desired size and depth can be easily obtained.

The solubility parameter of the cyclic olefin-based resin is not particularly limited, but is preferably 12.0 J ^{l / 2} / cm ^{3/2 to} 19.0 J ^{l / 2} / cm ^3/2 , more preferably 15.0 J ^{l / 2} / cm ^{3/2 to} 17.0 J ^{l / 2} / cm ^3/2 . If the solubility parameter of the cyclic olefin resin is within the above range, it is preferable because the compatibility and solubility with the organic solvent used for the surface treatment are appropriate.

  The cyclic olefin-based resin molded article includes a sheet-like material such as a film, and the thickness thereof is not particularly limited, but is preferably 5 μm or more, more preferably 1 mm or more. If it is too thin, it becomes difficult to maintain the transparency of the cyclic olefin resin, which is not preferable.

  The shape of the cyclic olefin-based resin molded product used in the present invention is not particularly limited, and can be applied from a simple shape such as a plate shape to a complicated shape including irregularities.

<Organic solvent>
The organic solvent used for the surface treatment of the present invention is not particularly limited as long as the solubility parameter is in the range of 12.0 J ^{l / 2} / cm ^{3/2 to} 20.1 J ^{l / 2} / cm ^3/2 . The organic solvent may be any solvent that dissolves the cyclic olefin-based resin, and is particularly preferably an organic solvent that generates microcracks that are uniform on the surface of the cyclic olefin-based resin molded product and easily obtain an anchor effect after the plating treatment after dissolution. . Examples of the organic solvent that satisfies these conditions include n-hexane, cyclohexane, toluene, benzene, chloroform, dichloromethane, and dichloroethane.

Solubility parameter of the organic solvent is preferably from ^{12.0J l / 2 / cm 3/2 ~20.1J} l / 2 / cm 3/2, and more preferably ^18.0J l ^/ 2 / ^{cm 3/2} ~ 20.0 J ^{l / 2} / cm ^3/2 . If the solubility parameter of the organic solvent is within the above range, it is preferable because there is a certain solubility and compatibility between the organic solvent and the cyclic olefin-based resin molded product. Due to these solubility and compatibility, preferable microcracks are produced in the cyclic olefin resin molded product.

The difference in solubility parameter between the cyclic olefin-based resin and the organic solvent is preferably 0.0 J ^{l / 2} / cm ^{3/2 to} 4.0 J ^{l / 2} / cm ^3/2 , more preferably 2.0 J ^l. a ^{/ 2 / cm 3/2 ~4.0J l /} 2 / cm 3/2. The difference in solubility parameter between the cyclic olefin resin and the organic solvent is within the above range, so that microcracks that do not substantially impair the transparency of the cyclic olefin resin can be obtained in the cyclic olefin resin molded product, and further the anchor effect It is preferable because the effect of improving the plating adhesion can be obtained.

  The boiling point of the organic solvent is preferably 40 ° C to 120 ° C, more preferably 50 ° C to 100 ° C, and further preferably 60 ° C to 90 ° C. If the boiling point of the organic solvent is too low, vaporization at normal temperature is accelerated, and management of the solvent becomes difficult. On the other hand, if the boiling point of the organic solvent is too high, the organic solvent may remain attached to the surface of the cyclic olefin-based resin molded product after the etching, resulting in overetching. Therefore, in order to maintain the transparency of the cyclic olefin resin, in order to obtain microcracks having a certain size, depth, etc. on the surface of the cyclic olefin resin molded product, the boiling point of the organic solvent is within the above range. Preferably there is.

  When a high boiling point organic solvent is used as an etching solvent, the problem of overetching can be solved by providing a drying step after the etching process.

  Further, as the organic solvent used for etching, a mixed solvent obtained by mixing two or more organic solvents having the SP value can be used. Examples of such a mixed solvent include a mixed solvent obtained by mixing two or more solvents selected from n-hexane, cyclohexane, toluene, benzene, chloroform, dichloromethane, and dichloroethane. Among them, n-hexane, cyclohexane, toluene, A mixed solvent of two or more solvents selected from dichloromethane is preferred. By using the mixed solvent, an effect that the adjustment range of etching conditions is widened can be obtained.

<Etching process>
In the etching step of the present invention, the surface of the cyclic olefin resin molded product is treated with the organic solvent in order to cause micro cracks in the cyclic olefin resin molded product. It is preferable that the microcracks generated on the surface of the cyclic olefin-based resin molded product are uniform and the anchor effect can be easily obtained after plating.

The amount of the organic solvent used in the etching step is not particularly limited, and the amount of the organic solvent used is preferably changed as appropriate depending on the organic solvent used and the cyclic olefin resin. The solubility parameter of the organic solvent used is 12.0 J ^{l / 2} / cm ^{3/2 to} 20.1 J ^{l / 2} / cm ^3/2 , and 0.3 ml to 10 ml per 1 cm ² of the surface of the cyclic olefin resin. Is preferred. More preferably, it is 1 ml-3 ml. If the amount of the organic solvent used is within the above range, it is preferable because microcracks that are uniform on the surface of the cyclic olefin-based resin molded product and easily obtain an anchor effect after plating are easily generated.

  In order to adjust the size of the generated microcracks or the like, it is preferable to control the etching rate in order to prevent overetching or the like. The etching rate can be controlled by mixing the organic solvent with an organic solvent having a higher solubility parameter. Examples of the organic solvent higher than the value of the solubility parameter include one or more mixed solvents selected from acetone, methanol, ethanol, isopropanol, n-butanol, ethyl acetate, and methyl ethyl ketone. Among these, acetone, methanol, ethanol, and isopropanol are preferable.

  Etching with an organic solvent can be performed if it is not higher than the boiling point of the organic solvent, but it is preferably performed at room temperature from the viewpoint of handling.

Also, the etching time varies depending on the organic solvent, but if it is too long, the dissolution proceeds and the microcracks generated during etching dissolve, and conversely if it is too short, sufficient microcracks will not be generated, so the plating adhesion will decrease. Problems occur. Therefore, when using only an organic solvent having an SP value of 12.0 J ^{l / 2} / cm ^{3/2 to} 20.1 J ^{l / 2} / cm ^3/2 , the etching time is preferably 10 to 180 seconds, more preferably 15 seconds to 60 seconds. When a solvent having a large SP value is mixed as an etching solvent, for example, when an organic solvent having an SP value of 18.0 J ^{l / 2} / cm ^{3/2 to} 20.1 J ^{l / 2} / cm ^3/2 is used, 10 seconds to 30 seconds is preferred. More preferably, it is 15 to 20 seconds.

  The etching process using an organic solvent can be selectively etched not only by etching the entire surface of the molded product but also by performing masking or the like.

  The size and depth of the microcracks obtained by the etching process are not particularly limited. However, when the microcracks are large and deep, the transparency of the cyclic olefin-based resin is not preferable. In addition, it is preferable that the size of the microcracks and the like is such that an anchor effect can be easily obtained after the plating treatment. The size of the microcrack is preferably 0.1 μm to 30 μm, more preferably 1 μm to 10 μm. The depth of the microcrack is preferably 0.5 μm to 30 μm, more preferably 1 μm to 20 μm. The size of the microcrack means the length of cracks appearing on the surface of the cyclic olefin resin molded product.

In order to maintain sufficient plating adhesion and transparency, there are preferably 500 to 10000 microcracks per cm ² . More preferably, it is 600 to 5000. Here, the microcracks are formed in a direction perpendicular to the plating surface, and the size and depth of the microcracks are included in the preferable range.

  The preferable microcracks as described above can be obtained by setting some of the organic solvent to be used, the solubility parameter of the organic solvent, the etching conditions, and the like within the above preferable range.

  A cleaning step is preferably provided at the end of the etching step. Although it is a cleaning process after the etching process, since the plating process after the etching is performed with a water-soluble solution, the organic solvent used in the etching process is removed to improve the wettability with water. This cleaning process can be replaced with water itself, but in order to completely remove the organic solvent used for etching, it can be replaced by mixing with the organic solvent used for etching and after removal by evaporation. There is a method of washing with water or a method of washing with water after replacing the organic solvent using a solvent mixed with the organic solvent used for etching and water. Solvents that can be used in such a method include acetone, methanol, ethanol, isopropanol, n-butanol, ethyl acetate, and methyl ethyl ketone. Among these, acetone, methanol, ethanol, and isopropanol are preferred for ease of handling. Acetone and isopropanol are more preferable.

<Chemical plating treatment>
The chemical plating treatment step performed after treating the cyclic olefin-based resin molded product with an organic solvent is not particularly limited, and can be performed by a conventionally known method. For example, the cyclic olefin resin molded article is preferably treated in the order of wetting, catalyst application, catalyst activation, and chemical plating after treatment with an organic solvent.

  Wetting is a step of improving the wettability of the plastic surface in order to attach a plating catalyst, and can usually be performed by treating the plastic with an aqueous solution containing a surfactant.

  The catalyst application is a step of attaching the catalyst to the plastic surface. For example, in the case of a palladium catalyst, it can be usually performed by immersing the plastic in a hydrochloric acid aqueous solution of tin chloride and palladium chloride.

  Activation is a step of activating the plating catalyst attached to the plastic surface, and can usually be carried out by contacting an acid such as hydrochloric acid.

  Chemical plating is a process in which an activated catalyst is attached to the plastic surface and immersed in a chemical plating solution to deposit metal on the plastic surface. For example, chemical copper plating contains copper and formalin. This can be done by immersing the plastic in an alkaline aqueous solution of sodium hydroxide. Examples of the metal for plating include nickel, chromium, tin, lead, copper, silver, gold, and zinc, with copper and nickel being preferred. These may be used alone or in combination of two or more. Further, the plating layer may be a single layer or a multilayer of the same or different metals.

  After the chemical plating process, it is also possible to perform an electric circuit formation or an electroplating process by using a circuit forming method such as an additive method, a semi-additive method, a subtractive method or the like. Conventionally known methods can be used for circuit formation and electroplating.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

  A pellet of cyclic olefin-based resin Topas 6013 (manufactured by Polyplastics Co., Ltd.) was molded into a 70 □ × 2 mmt flat plate using an injection molding machine at a cylinder temperature of 280 ° C., a mold temperature of 120 ° C., an injection pressure of 100 MPa, and an injection speed of 30 mm / sec. Created. Etching is carried out under the conditions shown in Tables 1 and 2 using the flat plate molded article, immersed in a conditioner SP (Okuno Pharmaceutical Co., Ltd.) for 3 minutes as a wetting step, washed with water, and provided with a catalyst. As a process, it is immersed in an aqueous hydrochloric acid solution of Catalyst A-30 (Okuno Pharmaceutical Co., Ltd.) for 5 minutes at room temperature, washed with water, then immersed in a 5 wt% aqueous hydrochloric acid solution for 1 minute as an activation process, washed with water, and then chemically plated As a process, it was immersed in OPC-750 (Okuno Pharmaceutical Co., Ltd.) for 20 minutes at room temperature to form a chemical copper plating film of about 0.8 μm. After the formation of the chemical copper plating film, the presence or absence of swelling or peeling of the plating film was evaluated visually as an evaluation of the presence or absence of plating adhesion. The results are shown in Tables 1 and 2.

As can be seen from Examples 1 to 5, if the solubility parameter is in the range of 12.0 J ^{l / 2} / cm ^{3/2 to} 20.1 J ^{l / 2} / cm ^3/2 , etching is performed at room temperature for 10 seconds or 20 seconds. It was confirmed that high plating adhesion could be obtained. On the other hand, in Comparative Examples 1 to 3, although the etching time was as long as 30 seconds, the plating adhesion could not be confirmed. If the solubility parameter is in the range of 12.0 J ^{l / 2} / cm ^{3/2 to} 20.1 J ^{l / 2} / cm ^3/2 , the anchor effect is obtained after the plating process is uniform on the surface of the cyclic olefin resin molded product. This is considered to generate microcracks that are easily formed.

  As can be seen from Example 5 and Comparative Example 1, it was confirmed that when high boiling point toluene was used as an etching solvent, a plating process with excellent adhesion could not be performed unless a drying step was provided after etching.

Claims (7)

The surface of the thermoplastic cyclic olefin resin molded product is etched with an organic solvent having a solubility parameter of 12.0 J ^{l / 2} / cm ^3/2 to 20.1 J ^{l / 2} / cm ^3/2. A surface treatment method for a thermoplastic cyclic olefin-based resin molded article, wherein chemical plating treatment is performed after the etching step of forming micro cracks of 0.1 μm to 30 μm on the surface. After the etching process,
Furthermore, a wetting step for imparting polarity to the surface of the thermoplastic cyclic olefin resin molded article,
A catalyst application step for applying a catalyst to a thermoplastic cyclic olefin-based resin molded article having polarity on the surface;
A surface treatment method for a thermoplastic cyclic olefin-based resin molded article according to claim 1, comprising an activation step of activating the applied catalyst. Furthermore, the surface treatment method of the thermoplastic cyclic olefin resin molded product of Claim 1 or 2 which performs an electroplating process after the said chemical plating process. The thermoplastic cyclic olefin-based resin molding according to any one of claims 1 to 3, wherein the organic solvent is n-hexane, cyclohexane, toluene, benzene, chloroform, dichloromethane, or a mixed solvent of two or more of dichloroethane. Product surface treatment method. The surface treatment method for a thermoplastic cyclic olefin resin molded article according to any one of claims 1 to 4, wherein the organic solvent has a boiling point of 50 to 100 ° C. The thermoplastic cyclic olefin system according to any one of claims 1 to 5, wherein the organic solvent is a mixed solvent in which at least one of acetone, methanol, ethanol, isopropanol, n-butanol, ethyl acetate, and methyl ethyl ketone is added. Surface treatment method for resin molded products. From the etching step and the chemical plating treatment, after treating with any one or more solvents of acetone, methanol, ethanol, isopropanol, n-butanol, ethyl acetate and methyl ethyl ketone, further treating with water. 7. The surface treatment method for a thermoplastic cyclic olefin resin molded article according to any one of 6 above.