JP2509084B2 - Plated cross-linked polymer molding - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is a crosslinked polymer molding obtained by molding a metathesis-polymerizable monomer in the presence of a metathesis polymerization catalyst system simultaneously with molding, the surface of which is metal-plated. The present invention relates to a plated crosslinked polymer molding.

[0002]

BACKGROUND OF THE INVENTION It is known that strained cyclic olefins undergo ring-opening polymerization with a metathesis polymerization catalyst system. Utilizing this, a metathesis polymerizable monomer such as dicyclopentadiene that can be obtained at a low cost is used, and the metathesis polymerization catalyst system is composed of two components, a main catalyst component and an activator component, and each of these two components is contained. A method has been proposed in which a reactive solution of monomers is poured into a molding mold immediately after mixing, and bulk polymerization is carried out therein to carry out polymerization and molding in one step (see, for example, JP-A-58-129013).

According to such a method, a large-sized crosslinked polymer molded product can be obtained by using an inexpensive molding mold, and therefore, it has a possibility of being used in a wide range of applications.

However, such molded products are often required to be metallized on the whole or part of the surface depending on the application.

As the metallizing method, there are two methods, that is, metal deposition under vacuum or a similar method and plating.

A plating method is commonly used as a metallizing method having a metallic feeling and durability. In order to electroplate plastics which are non-conductive conductors, a method of forming a conductive layer on the plastic surface by electroless plating is used.

[0007] Such electroless plating is usually carried out according to the following three steps, if detailed steps such as cleaning are omitted. That is, (1) pretreatment, (2) catalyst application / activation treatment, and (3) electroless plating treatment. (1) In the pretreatment, the surface of the plastic is treated with a chemical agent to introduce hydrophilic groups into the surface by oxidation or the like, and in some cases, the surface may be slightly etched to cause subsequent adhesion of the catalyst to the surface or electrolessness. This is a process for improving the adhesion of the plating layer. (2) The catalyst application / activation treatment is carried out by exposing colloidal metallic palladium to the plastic surface by the reducing action of, for example, palladium tin chloride (3). In the electroless plating treatment, for example, the treatment is carried out with a solution containing a combination of nickel chloride and a reducing agent, and in this case the nickel electroless plating layer is formed using the colloidal metal palladium formed above as a nucleus.

Generally, the electroless plating layer thus obtained is used as a conductor for electrolytic plating in the order of copper, nickel and the like.

In the above three steps, general methods have been established for (2) and (3) regardless of the type of plastic. Regarding (1), of course, the optimum method may differ depending on the type of plastic, but the most commonly used method is the method of treating with an aqueous solution of chromic acid-sulfuric acid, including the ABS resin that is most plated and used. is there.

Also in the case of a crosslinked polymer molded product by metathesis polymerization, it is chemically similar to an ABS resin containing a rubber component having many unsaturated bonds, and the same treatment method can be used as it is. Was expected.

However, it has been found that, due to the fact that it contains more unsaturated bonds than the ABS resin, it may not be possible to obtain a glossy and strong electroless plating layer by applying the same method. .

[0012]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of intensive research conducted by the present inventors in order to obtain an excellent plated product of such a metathesis crosslinked polymer molded product, the crosslinked polymer molded product contains a certain proportion of an olefin elastomer. It was found that a product having an excellent gloss and a strong plating layer can be obtained by virtue of this.

[0013]

Means for Solving the Problems That is, the present invention comprises a monomer solution (solution A) composed of a metathesis-polymerizable cyclic olefin containing a main catalyst component of a metathesis polymerization catalyst system and an activator component of the metathesis polymerization catalyst system. Monothesis liquid consisting of metathesis-polymerizable cyclic olefin (solution B)
And a cross-linked polymer molded product obtained by cross-linking polymerization in a mold, wherein the molded product contains 1 to 10% by weight of an olefinic elastomer, and the surface is metal-plated. And a plated cross-linked polymer molded article, characterized in that

As described above, the crosslinked polymer molding of the present invention uses at least one metathesis-polymerizable cyclic olefin as at least a part of the monomer component, and simultaneously performs polymerization and molding in the presence of a metathesis polymerization catalyst system. A crosslinked polymer molded product obtained by specifically using a metathesis-polymerizable cyclic olefin as a main monomer, and using at least a part of the cyclic olefin having two or more metathesis-polymerizable cyclic olefins, Separate the main catalyst component and activator component of the metathesis polymerization catalyst system into two solutions A and B together with the monomer, mix the two solutions by rapid mixing such as collision mixing, and then mix them in a molding mold. It is a cross-linked polymer molded product obtained by injecting into a polymer and simultaneously performing polymerization and molding.

As the metathesis-polymerizable cyclic olefin group, one having a large strain is preferable because of its high polymerizability. In particular, those having a norbornene structure are preferable in terms of ease of production and polymerizability.

Preferred examples of the cyclic olefins having two or more metathesis-polymerizable cyclic olefins and capable of forming a crosslinked polymer include dicyclopentadiene, tricyclopentadiene, 1,4,5,8-dimethano. -1, 4, 4
a, 5,8,8a-hexahydronaphthalene, 1,4
5,8,9,10-trimethano-1,4,4a, 5
Examples thereof include 8,8a, 9,9a, 10,10a-decahydroanthracene, 1,2-adducts of 1,5-cyclooctadiene and cyclopentadiene, ethylenebisnorbornene, phenylenebisnorbornene and the like.

On the other hand, as cyclic olefins that act as bifunctional for metathesis polymerization, norbornene, 5
-Methyl norbornene, 5-ethylidene norbornene,
5-phenylnorbornene, vinylnorbornene, dihydrodicyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a- Octahydronaphthalene, 6-methyl-1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4,5,8- Examples thereof include dimethano-1,4,4a, 5,7,8,8a-octahydronaphthalene.

In addition to the cyclic olefins composed of only hydrocarbons as described above, cyclic olefins containing different elements, that is, cyclic olefins having a polar group can be used as part of the monomer. The polar group is preferably an ester group, an ether group, a cyano group, an N-substituted imide group, a halogen or the like.

Specific examples of such a copolymerizable monomer include:
5-methoxycarbonylnorbornene, 5- (2-ethylhexyloxy) carbonyl-5-methylnorbornene, 5-phenyloxymethylnorbornene, 5-cyanonorbornene, 6-cyano-1,4,5,8-dimethano-1, 4,4a, 5,6,7,8,8a-octahydronaphthalene, N-butyl nadic acid imide, 5,6-
Dichloro norbornene etc. can be mentioned.

The metathesis-polymerizable cyclic olefin as described above is required to have as few impurities as possible that deactivate the metathesis polymerization catalyst system.

A particularly preferred monomer composition of the crosslinked polymer molding used in the present invention is a combination of 100 to 50 mol% of dicyclopentadiene, and the balance of metathesis polymerizable cyclic olefins having norbornene structural units as described above. Can be raised.

Salts such as halides of tungsten, rhenium, tantalum, molybdenum, etc. are used as the main catalyst component in the metathesis polymerization catalyst system used for obtaining the crosslinked polymer molded product used in the present invention, but especially the tungsten compound is used. preferable. As such a tungsten compound, tungsten halide, tungsten oxyhalide and the like are preferable, and more specifically, tungsten hexachloride, tung steoxy chloride and the like are preferable. Further, organic ammonium tungstate or the like can also be used. It has been found that such a tungsten salt compound starts cationic polymerization immediately when added directly to the monomer, which is not preferable. Therefore, such a tungsten salt compound is preferably suspended in an inert solvent, for example, benzene, toluene, chlorobenzene or the like in advance, and solubilized by adding a small amount of an alcohol compound or a phenol compound before use.

Further, in order to prevent the above-mentioned unfavorable polymerization, about 1 mol is added to 1 mol of the tungsten compound.
It is preferred to add ~ 5 moles of Lewis base or chelating agent as a masking agent. Examples of such additives include acetylacetone, acetoacetic acid alkyl esters, tetrahydrofuran and benzonitrile.

Thus, the monomer liquid containing the main catalyst component (Solution A) has practically sufficient stability.

On the other hand, the activator component in the metathesis polymerization catalyst system is an organometallic compound centered on an alkylated metal of Group I to Group III of the Periodic Table, especially tetraalkyltin,
Alkyl aluminum compounds, alkyl aluminum halide compounds are preferable, specifically, diethyl aluminum chloride, diethyl aluminum chloride, trioctyl aluminum, dioctyl aluminum iodide,
Examples thereof include tetrabutyl tin and tributyl tin hydride. By dissolving the organometallic compound as the activator component in the monomer component, a monomer solution (solution B) containing the activator is formed.

The crosslinked polymer molding of the present invention can be basically obtained by mixing the solution A and the solution B and polymerizing them in a molding mold. Since it starts quickly, curing may occur before it sufficiently flows into the molding mold, which often causes problems. Therefore, it is preferable to use an activity modifier.

Lewis bases are generally used as the regulator, and ethers, esters, nitriles and the like are used. Specific examples thereof include ethyl benzoate, butyl ether, diglyme and the like.
Such a regulator is generally used by adding it to the solution side of the component of the activator of the organometallic compound. When a monomer having a polar group that is a Lewis base is used as described above, it can also serve as a regulator.

The amount of the metathesis polymerization catalyst system used is, for example, when a tungsten compound is used as the main catalyst component, the ratio of the tungsten compound to the raw material monomer component is about 1000: 1 to 15000: 1 on a molar basis.
It is preferably around 2000: 1, and when the activator component is an alkylaluminum, the ratio of the aluminum compound to the raw material monomer component is about 100: 1 to about 2000: 1, preferably about 200 on a molar basis.
Around 1 to about 500 to 1 is used. Further, the masking agent and the regulator as described above can be appropriately adjusted and used according to the amount of the catalyst system used by experiments.

In the production of the crosslinked polymer molding of the present invention, a small amount of an active halogen compound such as trichloromethyltoluene, trichloroethyl acetate, isophthalic acid chloride or an acid anhydride such as benzoic acid anhydride is added to reduce residual monomers. Can be used.

The plated crosslinked polymer molding of the present invention can be obtained by incorporating 1 to 10% by weight or 2 to 7% by weight of an olefinic elastomer in the crosslinked polymer. By plating the crosslinked polymer molded product containing the olefinic elastomer in the above range, a metal film excellent in surface gloss and firmly fixed is formed. When the diene elastomer is contained or the elastomer is not contained, the surface of the crosslinked polymer molded article has unsatisfactory gloss or only a metal film having a weak fixing strength is formed.

The olefin elastomer used is an elastomer obtained by using a monoolefin as a main monomer, and includes, for example, butyl rubber, ethylene-propylene rubber,
Ethylene-propylene-diene rubber, for example ethylene-
Examples of the rubber include propylene-ethylidene norbornene rubber, and these rubbers preferably have a diene content of 10 mol% or less. A particularly desirable olefinic elastomer is ethylene-propylene rubber or ethylene-propylene-diene rubber.

The olefin elastomer is the solution A described above.
It is necessary to preliminarily mix one or both of the solution B and the solution B.

The crosslinked polymer molded product used in the present invention may further contain various additives in order to improve or maintain its properties in practical use. Such additives include fillers, pigments, antioxidants, light stabilizers, flame retardants,
There are combustible agents and polymer modifiers. Even with such additives, it is impossible to add them after the crosslinked polymer of the present invention has been molded. Therefore, when they are added, it is necessary to add them to the above-mentioned raw material solution in advance.

The easiest method is the solution A described above.
And a solution B may be added in advance to either or both of them. In that case, it may be practically used with the highly reactive main catalyst component, activator component or acid anhydride in the liquid. It should not react to some extent and should not hinder the polymerization. If the reaction is unavoidable, but coexistence does not substantially hinder the polymerization, mix with the monomer component to prepare the third liquid,
It is also possible to use a mixture immediately before the polymerization. Further, in the case of a solid filler, if both components are mixed and the shape is such that the voids can be sufficiently filled just before starting the polymerization reaction or during the polymerization, it is filled in the molding mold in advance. It is also possible to keep it.

The reinforcing material or filler as an additive is effective in improving the bending modulus. Examples thereof include glass fiber, mica, carbon black, wollastonite and the like. Those obtained by subjecting these to a surface treatment using a so-called silane coupler or the like can also be suitably used.

Further, it is preferable to add an antioxidant to the crosslinked polymer molded product used in the present invention. Therefore, it is desirable to add a phenol type or amine type antioxidant to the solution in advance. Specific examples of these antioxidants include 2,6-t-butyl-P-cresol,
Examples thereof include N, N'-diphenyl-P-phenylenediamine, tetrakis [methylene (3,5-di-t-butyl-4-hydroxycinnamate)] methane and the like.

The crosslinked polymer molded article of the present invention is produced by simultaneously performing polymerization and molding as described above. As the molding method, as described above, a resin injection method in which a premix in which a catalyst and raw material monomer components are mixed by a static mixer or the like is poured into a molding mold, and a solution A and a solution B in which the catalyst system is divided into two parts are used. It is possible to employ the RIM method in which the head is collided and mixed in the head portion and then directly poured into the molding mold. In particular, the RIM method is generally used.

In either case, the injection pressure into the molding mold can be set to a relatively low pressure, so that an inexpensive molding mold can be used. Further, when the polymerization reaction in the molding mold is started, the temperature in the molding mold rapidly rises due to the reaction heat, and the polymerization reaction ends in a short time. Unlike the case of polyurethane-RIM, the release from the molding mold is easy and a special release agent is often unnecessary.

The crosslinked polymer molded product thus obtained is subjected to electroless plating through the steps (1), (2) and (3) as described above.

In addition to the steps described above, it is recommended to carry out a washing step. In other words, if the surface to be plated is contaminated with oils and fats, etc., it is necessary to wash it well and remove it since the subsequent steps are difficult. In general plastic molded products, a releasing agent for releasing from the molding mold is often attached to the surface, which is a problem, but the crosslinked polymer molded product targeted by the present invention is Immediately after molding, the surface energy is generally small and the mold releasability is good, and since it can be molded without using a special mold release agent as described above, the surface is generally less contaminated and it is sufficient to wash it well with a neutral detergent. is there.

The washing step may be carried out after completion of the hydrophilic treatment described below. However, if the surface is dirty, contact with oxygen molecules is hindered. Therefore, depending on the degree of stain, the hydrophilic treatment of the present invention is performed. It is preferable to do it earlier.

In carrying out electroless plating of the metathesis crosslinked polymer molding of the present invention, the molding is brought into contact with oxygen molecules to make the surface hydrophilic at least and the surface energy is set to 38 dyne / cm or more. desirable. .

Further, such a hydrophilization treatment can also be achieved by leaving the molded product in the air at room temperature. this is,
By such contact with air, that is, contact with oxygen molecules, the metathesis crosslinked polymer containing a large amount of unsaturated bonds and allyl-type tertiary hydrogen is oxidized, and a polar group is introduced to make the polymer hydrophilic appropriately. This is because
The degree of such hydrophilization can be traced by the degree of increase in characteristic absorption of carbonyl which was not initially present in the crosslinked polymer in the measurement of the infrared absorption spectrum of the surface, but as a simpler and more direct method, various surfaces can be used. A method of estimating the surface energy by preparing a liquid of energy and then wetting the surface with the liquid can be given. According to such a method, in the case of a metathesis cross-linked polymer obtained by using dicyclopentadiene as a monomer, the wetting energy of the surface immediately after molding is about 34 dyne / cm, but it increases to 38 dyne / cm when left at room temperature for about 8 hours. However, if it is more than that, the adhesion of plating becomes good as described later.

That is, the wetting of the surface of the metathesis crosslinked polymer molded article was controlled to 38 dyne / c by contact with oxygen molecules.
By making it m or more, hydrophilic treatment can be achieved.

As described above, such a value can be generally achieved by leaving it in the air at room temperature for 8 hours or more, but such an oxidation reaction can be accelerated by raising the temperature, as is well known. Further, the surface oxidation can be similarly accelerated by means of UV irradiation or corona discharge in the presence of oxygen such as air. As the oxygen molecule-containing substance, it is most economical and preferable to use air, but if necessary, air having a higher oxygen concentration can also be used.

As described above, the molded product which has been washed and if necessary subjected to the above treatment is then subjected to a conventional plating treatment step. At this time, it is possible to omit the method used for general pretreatment for electroless plating of plastics, such as treatment of chromic acid, sulfuric acid, and other solvents, which is difficult to handle.

As the catalyst application / activation treatment of (2), the surface of the molded product is first treated with an acidic solution containing reducing ions such as stannous chloride-hydrochloric acid or titanium trioxide-hydrochloric acid, Then, a method of forming reduced colloidal particles of palladium, gold, or platinum on the surface by treating with palladium chloride-hydrochloric acid or a similar salt-acidic solution of gold or platinum can be given. Further, a method has been devised, in which stannous chloride and palladium chloride are mixed in hydrochloric acid to form a palladium colloid in the liquid, and a solution obtained by stabilizing this is used, and this method is now more commonly used. ing. In this case, to activate the surface of the palladium colloid, an acid treatment for dissolving the stabilizing ions is subsequently required.

Thus, the step of bringing the electroless plating solution into contact with the state where the colloidal nuclei adhere to the surface of the molded product to form the electroless plating layer is subsequently applied. As the electroless plating solution, nickel-based ones and copper-based ones are often used, but nickel-based ones are particularly often used. In principle, such electroless plating solution basically consists of a corresponding metal ion and a reducing agent capable of reducing the metal ion to a metal under appropriate PH conditions. In the case of nickel, hypophosphite salt or borane is used. What is used as a reducing agent is used. Generally, the ionic liquid and the reducing agent liquid are prepared separately, and they are mixed and used immediately before use. The life after mixing depends on the composition and use conditions.

In such electroless plating treatment, appropriate temperature and treatment time differ depending on the liquid composition, and in many cases, a high temperature of about 90 ° C. was used at first, but it was generally improved to 2
Many things are performed at a relatively low temperature of 5 to 40 ° C.

By subjecting the crosslinked polymer molded product of the present invention to such electroless plating, the advantage that a thin but glossy electroless plated layer can be attached very uniformly can be obtained.

After such electroless plating, copper
By sequentially plating nickel-chromium or the like, it is possible to obtain a molded product having a metal plating surface,
It can be used in a wide range of applications such as various types of transportation equipment, electric equipment, housings, and building members.

As described above, according to the present invention, there is provided a crosslinked polymer molded product having a plated layer which has a smooth surface and is firmly and firmly fixed.

[0053]

The present invention will be described in detail below with reference to examples.
It should be noted that the embodiment is for the purpose of explanation and is not limited thereto.

[Reference Example] a. Preparation of Solution A 20 parts by weight of tungsten hexachloride was added to 70 parts by volume of dry toluene under a nitrogen stream, and then nonylphenol 2 was added.
A 0.5 M tungsten-containing catalyst solution was prepared by adding a solution consisting of 1 part by weight and 16 parts by volume of toluene. The solution was purged with nitrogen gas overnight, and then reacted with tungsten hexachloride and nonylphenol. The produced hydrogen chloride gas was removed, and 1 part by volume of acetylacetone was further added to 10 parts by volume of the solution to obtain a main catalyst solution for polymerization.

Ethylene content 70 mol%, propylene content 27.7 mol% and ethylidene norbornene content 2. based on a monomer mixture consisting of 95 parts by weight of purified dicyclopentadiene and 5 parts by weight of purified ethylidene norbornene.
To a solution containing 3 parts by weight of 3 mol% of ethylene-propylene-ethylidene norbornene copolymer rubber and 2 parts by weight of Etanox 702 as an oxidation stabilizer, the main catalyst solution for polymerization was added so that the tungsten content was 0.001M. In addition, solution A was prepared.

B. Preparation of Solution B Triactyl aluminum 85, dioctyl aluminum iodide 15, and diglyme 100 were mixed and prepared to prepare a polymerization activator mixed solution in an amount of 95 parts by weight of purified dicyclopentadiene, 5 parts by weight of purified ethylidene norbornene, the same as above. A solution B was prepared by mixing 3 parts by weight of ethylene-propylene-ethylidene norbornene copolymer rubber in a mixture such that the aluminum content was 0.003 M.

Example 1 Using the solutions A and B prepared as in the above reference example, a molded plate made of a metathesis crosslinked polymer having a thickness of 3 mm was prepared by a reaction injection molding machine. Liquid temperature during injection is 30 ℃, mold temperature is 80 ℃
It was done in.

The flat plate thus obtained was allowed to stand at room temperature for 8, 24 and 48 hours. In the meantime, after washing at 50-60 ° C. for 5 minutes in an aqueous solution of 50 g / l of Okuno Seiyaku Co., Ltd. A-screen detergent, the surface was degreased and washed by washing with water.

After the lapse of the above time, the wettability of the surface was measured by a method of observing the wettability of liquids having various surface energies prepared in advance, and the respective plates showing the values of 38, 38 and 38 dyne / cm were used. Catalyst A manufactured by Co., Ltd.
-30 80 ml of concentrated hydrochloric acid and 150 ml of concentrated hydrochloric acid were immersed in a catalyst-imparting liquid having a concentration of 1 liter for 2 minutes at 25 ° C., washed with water, and then 100 ml of concentrated hydrochloric acid was added with water to activate the catalyst.
It was immersed in a solution diluted to 1 ° C. for 2 minutes at 35 ° C. and then washed with water.

After that, 160 ml of TMP chemical nickel A and 160 ml of B manufactured by Okuno Chemical Industries Co., Ltd. were immersed in an electroless plating solution diluted to 1 liter with water at 35 ° C. for 7 minutes. After washing with water, it was dried with a drier to obtain an electroless plated plate. Observation of the adhesion state of the plating revealed that after 8 hours to 48 hours (38 dyne / cm), the entire surface was covered with glossy plating and the adhesion was very good.

[Comparative Examples 1 and 2] For comparison, 1,4-cis butadiene was used in the same amount in Example 1 instead of the ethylene-propylene-ethylidene norbornene copolymer rubber (Comparative Example 1) or rubber. No plating was used at all (Comparative Example 2), and the plating treatment was performed in the same manner as in Example 1. The results are shown in Table 1 below together with Example 1 (which was left for 8 hours).

[0062]

[Table 1]

In the above table, the external appearance was determined by visually observing the external appearance of the plated molding. Further, the peeling strength was measured by making a notch in a strip shape with a width of 10 mm on the plated surface with a knife, peeling off one end of the strip of the plating layer, picking this and peeling the plating layer.

From the above table, when the elastomer component was not contained, plating was not applied and a plated product was not obtained. 1,
It is understood that in the case of 4-cis butadiene, the appearance of gloss and smoothness is inferior to that of the ethylene-propylene-ethylidene norbornene copolymer rubber, and the peeling strength is also low.

[0065]

EFFECTS OF THE INVENTION A plated product having excellent surface gloss and having a metal film firmly adhered thereto is provided.

Claims (3)

(57) [Claims] 1. A monomer solution comprising a metathesis polymerizable cyclic olefin containing a main catalyst component of a metathesis polymerization catalyst system (solution A) and a monomer solution comprising a metathesis polymerizable cyclic olefin containing an activator component of a metathesis polymerization catalyst system. A crosslinked polymer molded product obtained by mixing (Solution B) and crosslinking polymerization in a mold, wherein the molded product contains 1 to 10% by weight of an olefin elastomer and has a surface of A plated cross-linked polymer molded article characterized by being metal-plated. 2. The molded product according to claim 1, wherein the surface of the plated crosslinked polymer molded product is further coated. 3. The molded product according to claim 1, wherein the olefin-based elastomer is an ethylene-propylene elastomer containing a diene component in an amount of 10 mol% or less.