JPH0757839B2 - Method for producing colored polymer molding and combination of reactive solution - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention is a polymer molded product obtained by molding a metathesis polymerizable monomer at the same time as polymerization in the presence of a metathesis polymerization catalyst. It is about things.

More specifically, it relates to the above-mentioned colored polymer molded article in which a pigment such as carbon black, titanium oxide, iron oxide, cobalt oxide or ultramarine blue is dispersed.

b. Prior Art It is known that cyclic olefins give ring-opening polymers via metathesis polymerization catalyst systems. Therefore, a method has been proposed in which a metathesis-polymerizable cyclic olefin such as dicyclopentadiene (DCP), which is inexpensively obtained, is polymerized and molded in a single step in a mold with a metathesis polymerization catalyst to obtain a polymerized molded product. That is, by utilizing the fact that the metathesis polymerization catalyst system is composed of two components, that is, a catalyst component such as tungsten chloride and an activator component such as alkylaluminum, two types of liquids each containing two components and a monomer are used. Thus, a method has been proposed in which a polymer molding is obtained by rapid mixing during polymerization and then pouring into a mold (see, for example, JP-A-58-129013).

According to such a method, an inexpensive low-pressure mold can be used to obtain a large molded product having good mechanical performance, which can be said to be an industrially very attractive method, but as it is actually applied, some It has become clear that the one with the function of is needed.

The colored product of such a polymer molded product is one of the most important.

What is important is that the above-mentioned polymer molded product usually has a yellowish color, and it is used by being colored or surface-coated depending on the requirements from the application for weather resistance and cosmetics. Furthermore, the polymer molded product has many double bonds and is susceptible to oxidative deterioration or photooxidative deterioration. Therefore, usually, the polymer molded product can be made into a stable molded product having weather resistance and beauty by adding a pigment to the reactive liquid of the raw material or by surface coating.

US Pat. No. 4,598,102 describes glass, wolstonite, mica in metathesis-polymerizable cyclic olefin monomers,
The use of carbon black, talc or calcium carbide as a strengthening agent or filler is disclosed.
However, in this patent, the specific type of carbon black, or which side of the catalyst component or the activator component side of the metathesis catalyst system the carbon black should be dispersed to carry out the polymerization is described. Has not been done.

U.S. Pat. No. 4,080,491 discloses the addition of colorants to metathesis polymerizable monomers, but does not mention the specific type of colorant.

On the other hand, according to the conventional knowledge, activator components such as alkylaluminum and alkylaluminum halides in the metathesis polymerization catalyst system are more reactive and unstable than catalyst components such as tungsten salts and molybdenum salts. Was known. Therefore, conventionally, additives such as fillers and pigments have been added to the monomer liquid containing the catalyst component rather than the monomer liquid containing the activator component.

As a result of the present inventor's research on coloring of metathesis polymer moldings, surprisingly, among a number of pigments, a specific pigment, that is, carbon black, titanium oxide, iron oxide obtained by the incomplete combustion method, Cobalt oxide or ultramarine is usually an activator component that is considered to be more active than the catalyst component than dispersed in a reactive liquid (solution A) containing the catalyst component that is considered to be more stable than the activator component. It has been found that dispersion in a reactive liquid (Solution B) containing the above enables storage for a long period of time without deteriorating activity.

The catalyst component and the above-mentioned pigment do not interact very violently, but continuously react, that is, the reactive liquid (solution A) containing the catalyst component gradually becomes inactive in the presence of the above-mentioned pigment. It becomes impossible to regain the activity by simply adding a catalyst.

On the other hand, in the case of the above-mentioned pigment with the activator component, it reacts rapidly, but the reaction thereafter does not proceed, and by supplementing the activator lost by the reaction, a polymerizable and stable pigment dispersion reactive liquid is obtained. Is obtained. This finding is unexpected and can be effectively used for the production of colored molded articles from the reactive liquid. This phenomenon is not necessarily found in all metal oxides. For example, antimony trioxide gradually reacts not only with the catalyst component but also with the activator component,
These results in deterioration of activity. Fortunately, the above five types of pigments can be used in various colors such as black to white and red to purple by modifying the chemical structure or by mixing other components, or by mixing these as described below. Color can be provided.

Further, the present inventors have found that a colored polymer molded product produced by the combination of the reactive liquids containing the pigment in the solution B is a colored polymer produced by the combination of the reactive liquids containing the pigment in the solution A. We found that it has a brighter color than the molded product. This is especially noticeable for light pigments. Solution A is usually dark in color due to its catalytic components. Most of this dark-colored component is decolorized by the polymerization reaction, but it may remain on the surface of the pigment particles without disappearing even at the end of the polymerization reaction.

The present inventor, by dispersing a specific pigment in a reactive liquid containing an activator component that does not cause such a phenomenon, a reaction that does not adversely affect its reactivity even after long-term storage. It has been found that a beautiful colored polymer molded product can be obtained by obtaining a combination of the reactive liquids and polymerizing and molding the combination of the reactive liquids.

Therefore, the present invention is to provide a method for producing a colored polymer molded article which is excellent in cosmetic properties, oxidation resistance and light resistance deterioration. The present invention further provides a combination of reactive solutions used in the production of the colored polymer moldings.

c. Structure of Invention The present invention includes the following inventions.

(1) Mixing a reactive solution of a metathesis polymerizable monomer containing a catalyst component of a metathesis polymerization catalyst system (solution A) and a reactive solution of a metathesis polymerizable monomer containing an activator component of a metathesis polymerization catalyst system (solution B) In the production method of obtaining a polymer molded product by molding at the same time as polymerization,
(A) carbon black obtained by an incomplete combustion method of hydrocarbons, (b) a pigment based on titanium oxide,
At least one pigment selected from the group consisting of (C) iron oxide-based pigments, (D) cobalt oxide-based pigments, and (E) ultramarine-based pigments was dispersed in the solution B. A method for producing a colored polymer molded article, comprising:

(2) (a) Carbon black obtained by incomplete combustion method of hydrocarbons, (b) pigment based on titanium oxide, (c) pigment based on iron oxide, (d) based on cobalt oxide And (e) At least one pigment selected from the group consisting of (e) ultramarine-based pigments is dispersed in a proportion of 0.05 to 20% by weight based on the weight of the colored polymer molded product. Method.

(3) (a) The carbon black obtained by the incomplete combustion method of hydrocarbons is one kind selected from the group consisting of oil furnace carbon black and lamp black, and (b) a pigment based on titanium oxide is Titanium dioxide, nitrogen added titanium oxide and titanium yellow (TiO ₂ -NiO
-Sb ₂ O ₃ ) selected from the group consisting of (c) iron oxide-based pigments selected from the group consisting of iron black, red iron oxide and oak, and (d) cobalt oxide. (1) in which the pigment based on is cobalt blue
The manufacturing method described.

(4) The method according to (1) above, wherein the at least one metathesis polymerizable monomer is dicyclopentadiene or a mixture of dicyclopentadiene and another metathesis polymerizable monomer.

(5) (a) Reactive solution of metathesis polymerizable monomer containing catalyst component of metathesis polymerization catalyst system (solution A) and (b) Reactive solution of metathesis polymerizable monomer containing activator component of metathesis polymerization catalyst system And (b) carbon black obtained by the incomplete combustion method of hydrocarbons, (b) a pigment based on titanium oxide, (c) a pigment based on iron oxide, and (d) cobalt oxide. At least one pigment selected from the group consisting of a pigment based on (b) and a pigment based on (um) ultramarine blue is dispersed in the solution B, and a reactive solution for producing a colored polymer molded article. Combination of.

(6) (a) Carbon black obtained by incomplete combustion method of hydrocarbons, (b) pigment based on titanium oxide, (c) pigment based on iron oxide, (d) based on cobalt oxide And (e) at least one pigment selected from the group consisting of (e) ultramarine-based pigments in an amount of 0.05 to 20% by weight based on the total weight of the combination of the reactive solutions. ) A combination of the reactive solutions described.

(7) (a) The carbon black obtained by the incomplete combustion method of hydrocarbons is one kind selected from the group consisting of oil furnace carbon black and lamp black, and (b) a pigment based on titanium oxide is Titanium dioxide, nitrogen added titanium oxide and titanium yellow (TiO ₂ -NiO
-Sb ₂ O ₃ ) selected from the group consisting of (c) iron oxide-based pigments selected from the group consisting of iron black, red iron oxide and oak, and (d) cobalt oxide. (5) wherein the pigment based on is cobalt blue
A combination of the reactive solutions described.

(8) The combination of reactive solutions according to (5) above, wherein the at least one metathesis polymerizable monomer comprises dicyclopentadiene or a mixture of dicyclopentadiene and another metathesis polymerizable monomer.

According to the present invention, the above-mentioned inorganic pigments, which are found to be stably usable in a reactive solution for the first time, are inexpensive and widely used and easily available. It includes a wide range of shades from white, red to purple, and according to the present invention, the coloring matter of the metathesis polymer molding as described above is suitable for any of the shades required, whether alone or mixed. It can be said that it is possible to make it possible to contribute to the practicality of the molded product of the metathesis polymer. In particular, for white and black, which are often used for coloring, the most commonly used titanium dioxides and carbon black, which are 90% of the production amount, are inexpensive incompletely burned carbon such as oil fanis black. It has a great significance in that it can be used without any processing and without any special operation.

The carbon black used in the present invention is obtained by the incomplete combustion method of hydrocarbons.

Generally, carbon black is used as the black pigment. Such carbon blacks are roughly classified into those obtained by the thermal decomposition method of hydrocarbons and those obtained by the incomplete combustion method of hydrocarbons. As the former, there are acetylene black obtained from acetylene and thermal black obtained from hydrocarbons, which is more pure as carbon black, but its properties and costs are limited, so special It is used only for various purposes, and the number of manufacturers is limited.
It would be most desirable to use the incomplete combustion method in which a wide variety of properties are inexpensively produced in large quantities.

That is, the majority of commercially available carbon black is generally produced by the incomplete combustion method of natural gas or heavy oil (generally 90% or more of the total carbon black),
Depending on the details of the manufacturing method, it will be classified into channel black, oil furnace black, lamp black, etc. However, the carbon black produced by these incomplete combustion methods obtains a high temperature by burning a part of the raw material hydrocarbon in the presence of air, and the thermal decomposition of the hydrocarbon is also performed at that temperature to obtain carbon. That is, since it is obtained in an oxidizing atmosphere, it is inevitable that the obtained carbon black contains a large amount or a small amount of a polar compound containing oxygen. The presence of such a polar compound is effective in producing good mutual affinity when dispersed and used in a polymer having polarity such as a general coating resin, and in general, the polar compound is more easily mixed. Channel black is more luxurious than oil furnace black and lamp black.
Used for such applications.

Furthermore, in the oil furnace black, the carbon black obtained in order to bring the dispersibility closer to that of the channel black is heated or air-treated to increase the amount of polar compounds. The magnitude of the content of the polar compound is generally represented by two characteristic values of pH and volatile content among various characteristic values representing the characteristics of carbon black. That is, in general, the lower the pH and the higher the volatile content, the greater the content of such polar compound.

However, when it is attempted to use such a carbon black in the production of a metathesis polymerization molded product as described above, it is considered that it is due to the presence of such a polar compound, but it has a strong interaction with the components of the metathesis catalyst system, It was found to inhibit the activity. Therefore, in order to remove the polar compound, the carbon black may be heat-treated in an inert atmosphere at a high temperature of 500 ° C. or higher for a considerable time, but such a carbon black becomes very expensive. It is also conceivable to perform pretreatment with a very strong reducing agent, but this is also expensive, and it is desired and troublesome to completely remove the treated reducing agent.

Therefore, it is most preferable that the incompletely burned carbon black can be used for coloring without any such treatment.

However, as a result of detailed research on the interaction with the components of the metathesis catalyst system, the present inventor has a difference in the manner of action between the main catalyst component and the activator component among the components of the metathesis catalyst system. The present invention has been completed by finding that a stable carbon black dispersion system can be obtained by utilizing the difference without any pretreatment and practically no problem.

That is, the present inventors have found that even if carbon black containing a polar compound is added to and dispersed in a metathesis-polymerizable monomer reactive solution containing a main catalyst component, it becomes a metathesis-polymerizable monomer-reactive solution containing an activator component. Even if dispersed, they both react with the catalyst component and inhibit the polymerizability, but there are differences in the way of reaction, and in the case of the main catalyst component, the reaction seems to continue for a long time, and the polymerizability gradually decreases with time. However, the polymerizability does not recover even if the main catalyst component, which is considered to correspond to the reaction component, is added, but in the case of the activator component, it reacts rapidly, but the subsequent reaction does not proceed and is lost by the reaction. It has been found that a stable combination of carbon black dispersion and reactive solution can be obtained by supplementing the above-mentioned activator.

The carbon black obtained by the incomplete combustion of hydrocarbons used in the present invention includes oil fan black, channel black, lamp black and the like as described above.

On the other hand, various types of characteristic values are used as the characteristic values representing the properties of carbon black, and in particular, the following three characteristic values are generally recognized as basic characteristics.

(I) Particle size or specific surface area Measurement of average particle size by electron microscope, iodine adsorption method and BE
The specific surface area measurement method by the nitrogen adsorption method by the T method is used, but the most common one is the BET method specific surface area (m ² / g).

The larger the specific surface area, the finer the carbon black.

(Ii) Structure Generally, carbon black has a structure in which a number of spherical carbon black basic particles are fused together, and the way in which the structure develops differs depending on the structural conditions, and the extent of this is discussed depending on the size of the structure. , DBP oil absorption (ml / 100g) is used as a parameter expressing it. The larger the oil absorption, the larger the structure.

(Iii) Surface properties pH and volatile matter (%) are used as parameters that indicate the magnitude of polar compound content due to oxidation of the surface of carbon black. For the same type of carbon black, there is a correlation between the pH and the volatile content, and the larger the volatile content, the larger the polar compound content and generally the lower the pH.

The appropriate range of the above three characteristics of carbon black is generally determined depending on its application.

Generally, for coloring, the one with a larger specific surface area has a greater coloring property, and the one with a developed structure has the characteristic of giving a bluish black color, and in many cases the dispersion stability is also improved. The one with a large size and a well-developed structure is prized. In addition, when used with a resin or solvent that generally has polarity, such as for paints, the one with a larger polar compound content has better affinity, better dispersibility and dispersion stability, and the carbon black is oxidized as described above. The one with a high volatile content and a low pH is used as a prize.

In the present invention, as the metathesis-polymerizable monomer, a non-polar hydrocarbon-based monomer is generally used except for a special case, as described later. Therefore, it is considered unnecessary to increase the content of the polar compound in the carbon black in order to increase the dispersion in the reactive solution and the affinity. Furthermore, the presence of such a polar compound causes an interaction with the catalyst component and is added to the activator side to inhibit polymerization, and pre-react with the activator (probably a reduction reaction is performed), It is a feature of the present invention that the inhibition reaction does not occur during the polymerization reaction, and therefore, the greater the content of the polar compound, the greater the amount of the activator consumed to render it harmless, It is conceivable that not only it will be economically disadvantageous, but there may also be inconveniences such as an increase in the metal content as debris of the activator consumed by the reaction in the resin molded product. Therefore, it is preferable that the carbon black used in the present invention has a small volatile content and has a high pH when the alkali treatment or the like is not performed.

Also, in terms of specific surface area, generally, the larger the specific surface area, the more the portion to which the polar compound is attached tends to increase, and it takes time to complete the reaction with the activator. In terms of consumption,
The smaller the specific surface area is, the more preferable it is. However, since the coloring property having the larger specific surface area enables more efficient coloring, it is possible to determine the optimum material by the balance between the two.

As for the structure, there are few factors that are greatly related to the consumption of the activator, and an appropriate structure may be selected from the viewpoint of dispersibility and dispersion stability.

Further, the amount of such carbon black added to the polymer molded product largely varies depending on the purpose of black coloring. In other words, when trying to color the base color of the base of a coated product, it is sufficient that the resin is generally black, so a very small amount of addition is sufficient, but it is unpainted as a moped coating. In order to increase the blackness and the light stability, it is necessary to add a larger amount thereof. Furthermore, in order to have conductivity, a larger addition amount is required.

The amount of carbon black added is generally in the range of 0.05 to 20% by weight, preferably 0.1 to 5% by weight, and more preferably 0.1 to 3% by weight, based on the whole polymer molded product.

As described above, carbon requiring a large amount of activator consumed for deactivating polar compounds in carbon, that is, carbon having a large specific surface area and a large volatile content, is used only in a small amount. It is disadvantageous in that it does not exist.

From this point of view, as the carbon black that can be used corresponding to a wide range of addition amount, the volatile matter is 1.5% or less, the specific surface area is 200 m ² / g or less, more preferably the volatile matter is 1.0% or less, the specific surface area is 120 m ² The following can be mentioned: / g or less.

As the incomplete combustion method carbon black used in the present invention, channel black made from natural gas was the mainstream before, but this method has a large effect of soaring raw material because of low carbon yield to the raw material. Moreover, the pollution problem is serious, and the production of traditional channel black is currently discontinued, and it is produced by some manufacturers as a high-grade carbon black for coloring by the modified channel method with special ingenuity. Naturally, these are large in specific surface area, oil absorption amount, and volatile content, and therefore, in the present invention, use is limited to a very low concentration which is not preferable. On the other hand, similarly, the lamp black produced by the traditional method is inexpensive, has a very small specific surface area, and does not have a large amount of volatile matter. Granules are also included, and care must be taken in actual use in terms of the quality of the reactive solution during dispersion.

At present, most of oil furnish black is used as a carbon black manufacturing method, and a wide range of the above three characteristics is available, and it is most suitable for use in the present invention. The characteristics may be selected in consideration of the above-mentioned conditions, but it is not preferable to treat the acid value as described above or to subject it to alkali treatment to adjust the pH. In the oil furnish method, coal-based and / or petroleum-based heavy oil is used as a raw material,
It is generally preferred to use good quality raw materials that do not have too much sulfur or ash.

The (b) titanium oxide-based pigment used in the present invention includes a wide range of titanium oxide pigments currently available.

Titanium oxide pigments consist of only titanium and oxygen, or metal (for example, barium, antimony,
Some include nickel, chromium) and nitrogen.
As titanium oxide, titanium monoxide (TiO), titanium (II
I) Oxide (Ti ₂ O ₃ ), titanium dioxide (TiO ₂ ), titanium peroxide (TiO ₃ ), and intermediates thereof can be used. Titanium dioxide and titanium monoxide as pigments are usually used in pure form, salt form, modified form or doped form. Among these, titanium white (titanium dioxide), titanium black (nitrogen-added titanium oxide), titanium yellow (TiO ₂ -NiO-S)
b ₂ O ₂ ) and titanium oxide based on barium, nickel,
Pigments thermally treated with other metals such as chromium or antimony oxide are used. White titanium oxide is particularly preferable.

White titanium oxide is titanium dioxide represented by TiO ₂ , and has been praised as an excellent white pigment because of its high dispersibility due to its high refractive index. Other known white pigments are zinc white (zinc oxide), lead white (basic lead carbonate), and lithopone (zinc sulfide + barium sulfate), but not only whiteness, but also acid resistance, alkali resistance, etc. Titanium oxide is by far the best from the standpoint of chemical resistance and nontoxicity, which is why it is widely used.

Nitrogen-added black-titanium oxide is a fine black powder obtained by reducing titanium dioxide in a nitrogen atmosphere, and is commercially available under the name of Titanium Black. Although several grades of titanium black are commercially available, they can be used as black pigments as well as white titanium dioxide. Titanium yellow is white titanium oxide modified by dissolving oxides such as nickel and antimony, and is used as a stable and safe yellow pigment.

White titanium oxide is known to have three crystal forms, anatase type, rutile type, and brookite type, but two types of white pigments, anatase type and rutile type, are industrially produced. . The rutile type has a slightly higher density, a larger refractive index, and excellent weather resistance, but it is slightly yellow due to its large absorption in the ultraviolet region. On the other hand, the anatase form is inferior to the rutile form in terms of stability, but has an advantage that a clean whiteness can be exhibited. Both can be used in the present invention, each taking advantage of its properties.

On the other hand, in terms of manufacturing methods, the sulfuric acid method and the chlorine method have been put into practical use. The sulfuric acid method is a method in which ilmenite, which is a natural raw material, is digested with sulfuric acid, titanium content is extracted and separated as titanium sulfate, hydrolyzed with alkali, and then calcined. On the other hand, the chlorine method is a method of using rutile ore or synthetic rutile as a raw material, separating and purifying as titanium chloride with chlorine, and oxidizing it to separate as titanium oxide.The rutile type is both a sulfuric acid method and a chlorine method, The anatase form is manufactured by the sulfuric acid method. Although the chlorine method is more expensive, it is said that a high purity and high quality product can be obtained, and an appropriate one is selected and used in relation to the application. Furthermore, in order to improve the dispersibility with the medium, coating with hydrous aluminum oxide, coating with a mixture of hydrous aluminum oxide and hydrous silicon oxide, and when zinc oxide is added separately, it is further added with silicone oil or silane coupler. It is devised and selected for use depending on the partner to whom the various types of processed products and the products treated in 1 are dispersed.

As described above, the titanium oxide-based pigment has excellent stability as described above, but is a metal oxide and can react with a strongly acidic compound such as tungsten chloride, which is the main catalyst component of the metathesis polymerization catalyst system. In addition, it has the potential to be reduced to a strongly reducing compound such as alkylaluminum.

Therefore, the present inventor has studied in detail the interaction between the titanium oxide-based pigment and the component of the metathesis catalyst system, and as a result, of the components of the metathesis catalyst system, the main catalyst component and the activator component have different actions. It has been found that there is a difference, and by utilizing this difference, it is possible to obtain a stable titanium oxide pigment dispersion system that does not cause any practical problem, and the present invention has been accomplished.

That is, the present inventors, in a wide range of titanium oxide pigment,
It has been found that, in almost all cases, the metathesis polymerization reactivity is gradually inhibited when dispersed in a metathesis polymerization monomer reactive solution (solution A) containing a main catalyst component. When dispersed in a metathesis polymerizable monomer reactive solution (solution B) containing an activator of a metathesis polymerization catalyst system, which should have a higher reaction activity, almost no reaction occurs, or even if a reaction occurs, a rapid reaction occurs. However, the subsequent reaction did not proceed, and it was found that a combination of stable polymerizable titanium oxide-based pigment dispersion reactive solution can be obtained by supplementing the activator considered to be lost by the reaction. .

The titanium oxide pigments used in the present invention include the wide range of titanium oxides currently available as described above. That is, in the case of white titanium oxide, naturally, either anatase type or rutile type can be used. Also, in the manufacturing method, either the sulfuric acid method or the chlorine method can be used. Further, as described above, not only the inside of the pigment but also the one whose surface is coated with aluminum oxide, silicon oxide, a part of zinc oxide, or a silicone compound can be used. However, with respect to the reaction with the activator component, there is a difference depending on the type of the activator component, and therefore, the amount of the activator that needs to be added is different. Therefore, the titanium oxide used in the present invention has a coloring degree of the obtained colored molded article,
It may be determined in consideration of coloring stability, resin stability, dispersibility of titanium oxide in the liquid, dispersion stability, and economic efficiency due to the amount of extra activator component required.

From the standpoint of extra activator components, pigments with a large amount of adsorbed water generally tend to be large, so heating the titanium oxide pigment to be used to reduce the amount of adsorbed water is consumed. It is effective in reducing the amount of the activator component. Further, anatase tends to consume less activator than rutile when the coating amount of aluminum oxide, zinc oxide, silicon oxide or the like is smaller than that of rutile.

As the pigment, the average particle size and particle size distribution of titanium oxide also affect the dispersion stability in the coloring reactive liquid, and generally fine particles are preferable in that respect, but conversely the surface area becomes large and consumed. The amount of activator may be high. It should be selected according to the required performance.

Further, in the case of white titanium oxide, a chromatically colored molded product can be obtained by additionally using other coloring pigments. It goes without saying that it is necessary to select those coloring pigments that do not have an inhibitory effect on the metathesis polymerization catalyst. In particular, other coloring pigments included in the present invention can be preferably used for that purpose.

The titanium oxide pigment is used in an amount of 0.05 to 20% by weight, preferably 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, based on the polymer molding.

The (c) iron oxide-based pigment used in the present invention can be any pigment that is generally used as a pigment.

The iron oxide pigments of the present invention may include other materials such as manganese, silicon, chromium, zinc, aluminum. Examples of such pigments are iron black or ferric tetroxide (Fe ₃ O ₄ ), red iron or iron sesquioxide (Fe ₂ O ₃ ),
Amber (that is, brown iron sesquioxide containing MnO ₂ and / or Mn ₃ O ₄ ), oak (Fe ₂ O ₃ · SiO ₂ · Al ₂ O ₂ ), synthetic pigment containing iron oxide as a main component, etc. There is.

Of these, iron black (Fe ₃ O ₄ ) and red iron oxide (Fe ₂ O ₃ ) are preferable because they are widely used as pigments.

Compared to carbon black and titanium black, iron black (Fe ₃ O ₄ ) has a strong magnetizing property in a magnetic field, that is, magnetism, and can be a molded product having magnetism.

The amount of iron black added depends on the purpose. In other words, it is easy to understand that the optimum addition amount differs depending on whether it is used as a base color for coating, when used with other pigments, or when it is used without coating as a primary coating, and it is best determined by experiments. It is easy to determine the value. Generally, the range of 0.05 to 20% by weight, especially the range of 0.1 to 5% by weight, more preferably the range of 0.1 to 5% by weight,
A range of 0.2-3% by weight is used.

Since the dispersibility in the reactive solution B may differ depending on the type of iron black, an appropriate method may be selected for achieving sufficient dispersion.

Generally, a small amount of a monomer mixture, or a rubber-containing monomer solution in which an elastomer to be described later is dissolved, is prepared with a high-concentration, high shear-type dispersing device to prepare a sufficiently dispersed masterbatch, and this is given a predetermined concentration. A masterbatch method in which the reactive solution B is diluted so as to be used and used is preferable. For the dispersion when obtaining such a masterbatch, a method generally well known as a dispersion method for preparing a pigment masterbatch, that is, a ball mill, a roll mill, a Banbury mixer, an ultrasonic dispersion device, or the like can be used.

In addition, as a special case of masterbatch, an iron black dispersion rubber is prepared by previously kneading the elastomer and iron black used for adjusting the viscosity of the reactive solution and improving the impact resistance of the molded product. It is also possible to dissolve iron black as a masterbatch and disperse iron black.

If iron black that is easy to disperse is used and the mixing device is sufficient for dispersion, take the method of adding and dispersing iron black when preparing the reactive solution B without preparing a master batch in advance. Is also possible.

The (d) cobalt oxide-based pigment used in the present invention can be used in the same manner as the titanium oxide-based pigment and iron oxide-based pigment. As the pigment, pure cobalt oxide is rarely used alone, and usually cobalt oxide thermally treated with an oxide such as aluminum, zinc, chromium or nickel is used.

Of these, cobalt blue (CoO.Al ₂ O ₃ ) is widely used as a pigment for plastics, and is preferably used in the present invention. Addition amount is 0.05 to 20% by weight in polymer molding
Range, especially 0.1 to 5% by weight, more preferably
A range of 0.2-3% by weight is used.

As the blue pigment, an inorganic pigment is preferable in terms of cost and stability. Examples of such inorganic blue pigments include ultramarine blue and dark blue. However, dark blue has poor heat resistance and is difficult to use for the resin of the present invention, which has a high temperature of 150 ° C. or higher during polymerization.

On the other hand, ultramarine also has insufficient chemical resistance, especially acid resistance,
It is feared that the polymerization inhibitory property may appear in the metathesis polymerizability.

Therefore, as a result of a detailed examination of the metathesis polymerization inhibitory property of ultramarine, surprisingly, when it was added to the liquid side containing the activator, which is generally said to have high reactivity, the metathesis polymerization inhibitory property did not appear, and it was stable. It has been found that it can be used.

That is, the ultramarine used in the present invention is obtained by firing kaolin, diatomaceous earth, sulfur, soda ash, sulfate and carbon, and is commercially available as a pigment.

The amount of ultramarine blue added depends on the purpose. That is, it is easy to understand that the optimum addition amount differs depending on whether it is used with other pigments for bluing of white original dye, or when it is used as an original dye without coating, etc. It is easy to determine the value. Generally, the range of 0.05 to 20% by weight, especially the range of 0.1 to 5% by weight, more preferably the range of 0.1 to 5% by weight,
A range of 0.2-3% by weight is used.

The above-mentioned pigments can be used alone or in combination. For example, when a white pigment such as titanium oxide is used alone, a white metathesis polymer molded product can be obtained. A black molded product can be obtained by using a black pigment such as carbon black, titanium black, iron black (Fe ₃ O ₄ ) alone by the incomplete combustion method.

It is possible to obtain a mixed color of these colors by mixing and using two or more kinds of these pigments. The color of the molded product can be various colors depending on the type and amount of the pigment.

In the present invention, (a) carbon black by incomplete combustion method, (b) titanium oxide-based pigment, (c) iron oxide-based pigment, (d) cobalt oxide-based pigment and (e)
At least one pigment selected from ultramarine-based pigments is generally used in an amount in the range of 0.05 to 20% by weight, preferably 0.1 to 5% by weight, based on the total weight of the combination of metathesis polymerization reactive liquids. %, More preferably 0.2 to 3% by weight is used. The amount of pigment added depends on the type of pigment,
The surface condition of the pigment, the required color of the molded product, the usage conditions of the molded product, whether to further coat the molded product, etc.
It depends on various conditions.

Since the dispersibility in the reactive solution B may vary depending on the properties of the pigment, an appropriate method may be selected for achieving sufficient dispersion.

Generally, a small amount of a monomer mixture, or a rubber-containing monomer solution in which an elastomer to be described later is dissolved, is prepared with a high-concentration, high shear-type dispersing device to prepare a sufficiently dispersed masterbatch, and this is given a predetermined concentration. A masterbatch method in which the reactive solution B is diluted so as to be used and used is preferable. For the dispersion when obtaining such a masterbatch, a method that is generally well known as a dispersion method for preparing a pigment masterbatch, that is, a ball mill, a roll mill, a Banbury mixer ultrasonic dispersion device, or the like can be used.

Further, as a special case of a masterbatch, an elastomer and a pigment used for adjusting the viscosity of a reaction solution and improving the impact resistance of a molded product are kneaded in advance to prepare a pigment-dispersed rubber, which is used as a masterbatch. It is also possible that the pigment is dispersed while being dissolved in the monomer.

When using a pigment that is easily dispersed and having a sufficient mixing device for dispersion, a method of adding and dispersing titanium oxide when preparing the reactive solution B without preparing a master batch in advance may be used. It is possible.

As a concrete molding method of the method for producing a polymer molded product of the present invention, as described above, the reactive solution is mixed with a static mixer or the like, or a premix is prepared in advance and poured into a mold. , A resin injection method for obtaining a molded product or a molding method similar to that can be used, but since the reaction after mixing is generally fast, a reaction injection molding method (RIM) in which a mixed reaction liquid is injected into a mold immediately after collision mixing The molding method is the most suitable.

Generally, the metathesis polymerization catalyst system consists of two components, a main catalyst component and an activator component.

The metathesis polymerization reaction is an exothermic reaction and the reaction proceeds rapidly.
For this reason, a reaction occurs before introducing a mixed liquid of respective monomers containing a main catalyst component and an activator component into the mold, making it difficult to introduce the mixture into the mold, and producing a large molded product. It gets harder. Therefore, it is preferable that the catalyst component of the metathesis catalyst system and the activator component are separately added to the monomer liquid to form a combination of the reactive liquids. That is, solution A and solution B. A method of rapidly mixing these with impingement mixing (RIM method), a static mixer, a dynamic rotary mixer or the like and introducing them into the mold is adopted.

In this case, each monomer component of the reactive mixture combination need not have the same composition as each other. The composition of the monomer may be arbitrarily determined in consideration of the composition after mixing.

Suitable specific examples of the metathesis polymerizable monomer used in the present invention include dicyclopentadiene, tricyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-ethylidene norbornene, norbornene, norbornadiene, 5-cyclohexenyl norbornene. , 1,4,5,8-Dimethano-1,4,4a, 5,6,7,8,8,8a-octahydronaphthalene, 1,4-methano-1,4,4a, 5,6,7 , 8,8,8
a-Octahydronaphthalene, 6-ethylidene-1,4,5,8-
Dimethano-1,4,4a, 5,6,7,8,8a-heptahydro-naphthalene, 6-methyl-1,4,5,8-dimethano-1,4,4a, 5,6,7,8,
8a-heptahydronaphthalene, 1,4,5,8-dimethano-1,4,
One or a mixture of two or more cyclic olefins having 1 to 3 norbornene structures such as 4a, 5,8,8a-hexahydronaphthalene and ethylenebis (5-norbornene) may be mentioned, but dicyclopentadiene is particularly preferable. Alternatively, a monomer mixture mainly containing it is preferably used.

Further, if necessary, a metathesis-polymerizable cyclic compound having a different element such as oxygen or nitrogen can be used. Such polar monomers are often used in copolymerization with dicyclopentadiene and the like.

Such a polar monomer also preferably has a norbornene structural unit, and the polar group is preferably an ester group, an ether group, a cyano group, an N-substituted imide or the like.

Specific examples of the copolymerization monomer include 5-methoxycarbonylnorbornene, 5- (2-ethylhexyloxy) carbonyl-5-methylnorbornene, 5-phenyloxymethylnorbornene, 5-cyanonorbornene, 6-cyano-1, Examples include 4,5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, N-butyl nadic acid imide and the like.

As described above, the metathesis-polymerizable monomer is required to have as few impurities as possible that deactivate the metathesis polymerization catalyst.

As the main catalyst component in the metathesis polymerization catalyst system used in the present invention, salts such as halides of tungsten, rhenium, tantalum, molybdenum and the like are used, but compounds of tungsten and molybdenum are preferable, and tungsten compounds are particularly preferable. As such a tungsten compound, tungsten halide, tungsten oxyhalide and the like are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride and the like are preferable. Further, organic ammonium tungstate or the like can be used. Such a tungsten compound is
It is not preferable since it is known that when it is directly added to the monomer, cationic polymerization is immediately started. Therefore, the tungsten compound is preferably suspended in an inert solvent such as 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, as described above, it is preferable to add about 1 to 5 mol of a Lewis base or a chelating agent to 1 mol of the tungsten compound in order to prevent undesired polymerization. Examples of such additives include acetylacetone, acetoacetic acid alkyl esters, tetrahydrofuran, and benzonitrile.

Thus, the monomer solution containing the catalyst component (solution A) is
It has practically sufficient stability.

On the other hand, the activator component in the metathesis polymerization catalyst system is preferably an organometallic compound centered on an alkylated compound of a metal of Group I to Group III of the Periodic Table, particularly tetraalkyltin, an alkylaluminum compound, an alkylaluminum halide compound, Specific examples thereof include diethyl aluminum chloride, diethyl aluminum dichloride, trioctyl aluminum, dioctyl aluminum iodide, and tetrabutyl tin. The other solution (corresponding to solution B) is formed by dissolving the organometallic compound as the activator component in the raw material monomer.

The present invention is characterized in that the specific pigment as described above is dispersed on the side of the reactive solution B. The type of pigment, the addition amount, the dispersion method, and the addition method are as described above. It should be noted here that the polar compound in the pigment reacts with the activator,
Although the pigment is added to the reactive solution B in order to prevent the polymerization inhibiting reaction, the contact between the activator and the pigment may be performed at the time of preparing the reactive solution B. , Other masterbatch stages may be carried out. However, the activator is generally very active and decomposes even when contacted with air, water, etc., and therefore the handling of the liquid containing it may be determined in consideration of the fact. In addition, such contact may cause an initial reaction between the pigment and the activator, and the activator corresponding to that may be consumed. In that case, the activator is consumed in order to secure a necessary amount for polymerization. It means that it is necessary to add the activator in an amount added to the amount.

As a special measure in such a case, first, for the amount consumed by the reaction with the pigment, the cheapest activator is used, and the activator added after the reaction is used as a reactive solution for polymerization. The method of using the composition most suitable for use can be used. For example,
When using a mixture of trioctylaluminum and dioctylaluminum iodide for the polymerization, first use the cheapest triethylaluminum in an amount sufficient for the reaction with the pigment, and then add the above mixture after the reaction. Therefore, it is economical to use a pigment having a large initial consumption of an activator such as carbon having a relatively large content of polar compounds.

In the present invention, as described above, the activator reacts relatively quickly with the specific pigment that can be used in the present invention, even if it reacts at the initial stage of contact, and thereafter the reaction does not proceed. ,
Based on the knowledge that it does not have any adverse effect on the subsequent storage of the reactive solution and the execution of the polymerization reaction,
It is clear that the reaction due to the interaction between the activator and the pigment is completed within a relatively short time after mixing.

In the present invention, basically, a crosslinked polymer molded product can be obtained by mixing the solution A and the solution B, but with the above composition as it is, the polymerization reaction is started very quickly, Curing may occur before it sufficiently flows into the casting mold, which often causes a problem. As described above, it is preferable to use an activity modifier for that purpose.

As such a regulator, Lewis bases are generally used, 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 Lewis base group 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 catalyst component, the ratio of the tungsten compound to the raw material monomer is about 10 on a molar basis.
When the activator component is an alkylaluminum compound, the ratio of the aluminum compound to the raw material monomer is such that the interaction with carbon black is 00: 1 to 15000: 1, preferably 2000: 1. About 100 to 1 to about 2000 to 1, preferably about 200 to 1 to about 500 to 1, on a molar basis, excluding those lost in. Further, as described above, the masking agent and the adjusting agent can be appropriately adjusted and used depending on the amount of the catalyst system used by experiments.

The crosslinked polymer molded product according to the present invention may further contain various additives in order to improve or maintain its properties in practical use. Such additives include fillers, antioxidants, light stabilizers, flame retardants, polymer modifiers and the like. Even with such an additive, the cross-linked polymer cannot be added after the cross-linked polymer has been molded similarly to the pigment in the present invention, and therefore, when it is added, it is necessary to add it to the above-mentioned raw material solution in advance. .

The easiest method is the solution A and the solution B.
It is possible to cite a method of adding to either or both of them in advance, but in that case, the catalyst component or the activator component having strong reactivity in the liquid does not react to a certain extent with practical use, and It must not interfere with polymerization. Inevitably, if the reaction is unavoidable but coexists even if it does not substantially inhibit the polymerization, it is possible to mix with the monomer to prepare the third liquid, and to use the mixture immediately before assembling. . Further, in the case of a solid filler, when both components are mixed and the shape is such that the voids can be sufficiently filled immediately before starting the polymerization reaction or during the polymerization, It is also possible to fill it in advance.

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

Further, in the present invention, a pigment other than the target pigment may be mixed with the catalyst component and used.

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

Further, to the polymer molded product according to the present invention, another polymer may be added particularly in a monomer solution state. As described above, the addition of an elastomer as the polymer additive is effective in enhancing the impact resistance of the molded product and controlling the viscosity of the solution. Elastomers used for this purpose include styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene propylene-dienta-polymer,
A wide range of elastomers such as nitrile rubber can be mentioned.

Further, if a large amount of residual monomer remains in the molded product of the present invention, a peculiar odor may be emitted. Examples of the residual monomer reducing agent include α, α, α-trichlorotoluene, trichloroacetic acid ester, phthalic acid chloride, benzoic anhydride, phosphorus oxychloride, benzenesulfonic acid chloride and the like.

The polymer molded product of the present invention is produced by simultaneously performing polymerization and molding as described above.

As the molding method, as described above, the catalyst and the raw material monomers are mixed with a simple mixer such as a static mixer, or a resin injection method and a catalyst system in which a premix which is mixed in advance is allowed to flow into a mold. It is possible to adopt the RIM method in which the solution A and the solution B, which are divided into two parts, are collided and mixed at the head portion and directly poured into the mold. Especially R
The IM method is generally used.

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

In the present invention, as described above, the molded product of the present invention is colored and can be used as it is without coating as a moped-molded product, but it can be coated as necessary as described above. Since it has many heavy bonds, an oxide layer is formed on the surface, so that it has good adhesion to commonly used paints such as epoxy and polyurethane.

The molded product thus obtained can be used in a wide range of applications centered on large molded products such as members of various transportation equipment including automobiles, various leisure vehicles, housings of electric and electronic devices.

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

Examples 1 to 10 Commercially available DCP was purified by distillation in a nitrogen stream under reduced pressure to give a freezing point of 3
Purified dicyclopentadiene showing 3.4 ° C. was obtained. Purity measurement by gas chromatography showed a purity of 99% or higher.

The purity measured by gas chromatography using commercially available high-purity ethylidene norbornene (ENB) as a monomer was 99% or more.

[Preparation of concentrated liquid of main catalyst] 19.80 g (0.05 mol) of high-purity tungsten hexachloride was added to 90 ml of dry toluene under a nitrogen stream to give t-butanol 0.92.
A solution prepared by dissolving 5 g in 5 ml of toluene was added and stirred for 1 hour, and then a solution of 11.05 g (0.05 mol) of nonylphenol and 5 ml of toluene was added and stirred for 1 hour under a nitrogen purge. 10 g of acetylacetone was added to the mixture, and stirring was continued overnight under a nitrogen purge while expelling by-product hydrogen chloride gas, and then partially distilled toluene was supplemented.
A 0.5M tungsten-containing catalyst concentrate was prepared.

[Preparation of Activator Concentrated Liquid] Di-n-octylaluminum iodide 5.70 g, tri-n-octylaluminum 31.17 g, diglyme 13.42 g
Under a stream of nitrogen, then add DCP to bring the total volume to 100 ml.
To obtain a 1.0 M aluminum-containing activator concentrate.

[Monomer mixture] 96.25 wt% of DCP and 3.75 wt% of ENB were mixed to obtain a monomer mixture which remained liquid at room temperature.

[Preparation of Standard Reactive Solution A] After taking 197 g of the above-mentioned monomer mixture in a glass bottle with a serum cap and purging with nitrogen well, 2.96 ml of the main catalyst concentrate was injected with a syringe and well stirred to obtain standard reactivity. Solution A was prepared.

[Preparation of Standard Reactive Solution B] After taking 197 g of the above-mentioned monomer mixture in a glass bottle with a serum cap and thoroughly purging with nitrogen, 4.44 ml of activator concentrate was injected with a syringe and well stirred to prepare standard reactive solution B. Was prepared.

[Preparation of Reactive Solution A Containing Carbon] In a glass bottle, 197 g of the above-mentioned monomer mixture and 5 g of carbon black by a predetermined incomplete combustion method as shown in Table 1 were put,
After thoroughly stirring under a nitrogen purge to disperse carbon black well, 2.96 ml of the main catalyst concentrate was injected with a syringe and well stirred to prepare a carbon-containing reactive solution A.

[Preparation of Reactive Solution B Containing Carbon] In a glass bottle, 197 g of the above-mentioned monomer mixture and 5 g of the predetermined carbon black shown in Table 1 were put, stirred well under a nitrogen purge to disperse the carbon black well, and then activated. 4.44 ml of the agent concentrate was injected with a syringe and mixed well with stirring to prepare a carbon-containing reactive solution B.

[Polymerization activity test] Put 2 ml of the reactive solution B, which was heated to 30 ° C with a syringe under a nitrogen stream, into a test tube equipped with a serum cap and having the thermocouple detection end at the tip through the cap. Similarly, add 2 ml of Reactive Solution A adjusted to 30 ° C with a syringe in the same manner, mix both solutions with a vigorously stirring machine, and from the start of mixing, the polymerization proceeds and heat is generated, and the time until the internal temperature reaches 100 ° C is set. It is measured as the polymerization time. Further, by increasing or decreasing the addition amount of the reactive solutions A and B, the volume ratio of the reactive solution B to the reactive solution A and the polymerization time when the polymerization time becomes the shortest are used as the reactivity evaluation value of the combination of the reactive solutions. To do. In this case, based on the volume ratio of the standard reactive solutions A and B containing no carbon into both and the polymerization time, the combination of the standard solution A and the carbon-containing solution B, and the combination of both the carbon-containing solutions A and B were used. In this case, it was decided to evaluate the polymerizability by dispersing carbon by measuring and comparing the volume ratio and the polymerization time.

That is, immediately after the preparation, the influence of the change with time is observed by observing the reactivity after leaving the reactive solution. Even in the case of a standard reactive solution containing no carbon, in the case of an experiment with a small amount of liquid using a bottle like this experiment, the polymerization reactivity may deteriorate slightly, so this combination of standard solutions should be used as a control. Is it worse than that,
The effect of carbon black was evaluated based on whether or not it changed.

When used for RIM applications, etc., it has been found that the polymerization time can be used without any problem if it is within 70 seconds.

Incidentally, in this example, 2.5% of carbon black was added to one of the reactive solutions, but it was the most used for coloring, and the addition amount is enough to support the original wearing without coating. It is used even in about 1/10 of that, and it is a severe test to see the effect of carbon black.

The test results are summarized in Table 2.

In any case, the one in which carbon black was dispersed on the side of the reaction solution B showed a polymerization time which was almost the same as the case where the standard reaction solutions A and B containing no carbon were used. It can be seen that in both cases where carbon black was added to the reaction solution A and where carbon was added to both reaction solutions A and B, the polymerization time became longer and the deterioration became severe with time.

The volume ratio of the reaction solution that gives the shortest polymerization time is, in any case, compared to the case of the combination of the standard solutions A and B, and the combination of the carbon-containing solution B and the standard solution A has the side of the carbon-containing solution B side. However, this is because a part of the activator was lost by reacting due to the inactivation of the polymerization inhibition of carbon black. Is stable, indicating that once the reaction is complete, the activator is rarely consumed in the reaction with carbon black thereafter.

Furthermore, this increase rate differs depending on the type of carbon, and the carbon black of Example 3 having a large surface area, a large volatile content, and a low pH has a large volume ratio, and thus the polymerization inhibitory property is poor. It has been shown that many activators are required for activation.

The cross-linked polymer molded product obtained in the test tube for such a polymerization test was obtained by combining the reactive solution B containing carbon and the standard solution A, which was uniformly colored black.
Moreover, it was very strong like the one obtained by combining the standard solutions A and B, and had little odor.

Examples 11-25 DCPs prepared in the same manner as used in Examples 1-10
And ENB were also used in Examples 11-25.

The main catalyst concentrate, activator concentrate, monomer mixture, standard reactive solution A and standard reactive solution B were also prepared in the same manner as in Examples 1-10.

[Preparation of Reactive Solution A with Titanium Oxide] In a glass bottle, 197 g of the above-mentioned monomer mixture and 2 g of predetermined titanium oxide as shown in Table 3 were put, and well stirred under a nitrogen purge to sufficiently disperse the titanium oxide. Main catalyst concentrate 2.
96 ml was injected with a syringe and well stirred to prepare a titanium oxide-containing reactive solution A.

[Preparation of Reactive Solution B Containing Titanium Oxide] In a glass bottle, 197 g of the above-mentioned monomer mixture and 2 g of predetermined titanium oxide shown in Table 3 were put, and well stirred under a nitrogen purge.
Disperse titanium oxide well, then activate activator concentrate 4.44
ml was injected with a syringe and well mixed with stirring to prepare a titanium oxide-containing reactive solution B.

[Polymerization activity test] Put 2 ml of the reactive solution B, which was heated to 30 ° C with a syringe under a nitrogen stream, into a test tube equipped with a serum cap and having the thermocouple detection end at the tip through the cap. Similarly, add 2 ml of Reactive Solution A adjusted to 30 ° C with a syringe in the same manner, mix both solutions with a vigorously stirring machine, and from the start of mixing, the polymerization proceeds and heat is generated, and the time until the internal temperature reaches 100 ° C is set. It is measured as the polymerization time. Further, by increasing or decreasing the addition amount of the reactive solutions A and B, the volume ratio of the reactive solution B to the reactive solution A and the polymerization time when the polymerization time becomes the shortest are used as the reactivity evaluation value of the combination of the reactive solutions. To do. In this case, the standard reactive solutions A and B without titanium oxide in both
By comparing the volume ratio and the polymerization time in the case of the combination of the standard solution A and the solution B containing titanium oxide, and the combination of the solutions A and B containing titanium oxide, based on the volume ratio and the polymerization time of We decided to evaluate the polymerizability by dispersing titanium oxide.

That is, immediately after the preparation, the influence of the change with time is observed by observing the reactivity after leaving the reactive solution. Even in the case of the standard reactive solution containing no titanium oxide, in the case of a small volume experiment using a bottle like this experiment, the polymerization reactivity may deteriorate slightly, so control this combination of standard solutions to the last. As a result, the effect of titanium oxide was evaluated depending on whether it was worse or unchanged.

In the examples here, the amount of titanium oxide added was changed to
One of the reactive solutions was set at 1%, but this is generally
When titanium oxide is added to plastic for coloring purposes, it is generally about 0.5 PHR with respect to the resin, and the concentration is set to correspond to it.

The test results are summarized in Table 4.

In any case, in the case of the combination of the reaction solution A using the standard solution and the titanium oxide dispersed on the side of the reaction solution B, there is almost no difference from the case of using the standard reaction solutions A and B containing no titanium oxide. While the polymerization time is not shown, the combination of titanium oxide added to the reaction solution A and the standard solution B, and titanium oxide added to both the reaction solutions A and B in both cases show the lapse of time. It can be seen that the polymerization time is long and the deterioration is severe.

In addition, the volume ratio of the reaction solution that gives the shortest polymerization time is, in any case, compared with the case of the combination of the standard solutions A and B, and the combination of the titanium oxide-containing solution B and the standard solution A is the titanium oxide-containing solution B. The amount used on the side of is not at least small, but when it is large, it is because a part of the activator was lost due to reaction due to inactivation of polymerization inhibition of titanium oxide. Indicates that the activator is stable with time, and that once the reaction is completed, the activator is rarely consumed in the reaction with titanium oxide thereafter.

Furthermore, this rate of increase varies depending on the type of titanium oxide, suggesting that the amount of activator consumed may vary depending on the type of titanium oxide, that is, the crystal form, surface area, surface treatment, and other conditions. In any case, it is shown that a reactive solution having stable polymerization reactivity can be obtained by using an appropriate amount of the activator.

The crosslinked polymer molded product obtained by such a polymerization test,
The product obtained by combining the reactive solution B containing titanium oxide and the standard solution B has a slight yellowish brown color but is uniformly colored white, and is obtained by combining the standard solutions A and B. Was as sturdy as.

Examples 26-27 DCP and ENB prepared in a similar manner to Examples 1-10 were also used in Examples 26-27.

The main catalyst concentrate, activator concentrate, monomer mixture, standard reactive solution A and standard reactive solution B were also prepared in the same manner as in Examples 1-10.

[Preparation of Reactive Solution A with Titanium Black] In a glass bottle, 197 g of the above monomer mixture and 2 g of each of MITSUBISHI METAL CO., LTD.
After thoroughly stirring under a nitrogen purge to disperse titanium black well, 2.96 ml of the main catalyst concentrate was injected with a syringe and well stirred to prepare two types of reactive solutions A containing titanium black.

[Preparation of Reactive Solution B Containing Titanium Black] Into a glass bottle, 2 g each of 197 g of the above monomer mixture and 2 g of the same titanium black as above were separately charged, and well stirred under a nitrogen purge to thoroughly disperse the titanium black. Then, 4.44 ml of the activator concentrate was injected with a syringe and mixed well with stirring to prepare two types of titanium black-containing reactive solutions B.

[Polymerization activity test] Put 2 ml of the reactive solution B, which was heated to 30 ° C with a syringe under a nitrogen stream, into a test tube equipped with a serum cap and having the thermocouple detection end at the tip through the cap. Similarly, add 2 ml of Reactive Solution A adjusted to 30 ° C with a syringe in the same manner, mix both solutions with a vigorously stirring machine, and from the start of mixing, the polymerization proceeds and heat is generated, and the time until the internal temperature reaches 100 ° C is set. It is measured as the polymerization time. Further, by increasing or decreasing the addition amount of the reactive solutions A and B, the volume ratio of the reactive solution B to the reactive solution A and the polymerization time when the polymerization time becomes the shortest are used as the reactivity evaluation value of the combination of the reactive solutions. To do. In this case, the standard reactive solution A without titanium black in both
Based on the volume ratio of B and B and the polymerization time, the volume ratio and the polymerization time in the case of the combination of the standard solution A and the solution B containing titanium black, and the combination of the solutions A and B containing titanium black are measured and compared. By doing so, it was decided to evaluate the polymerizability by dispersing titanium black.

That is, immediately after the preparation, the influence of the change with time is observed by observing the reactivity after leaving the reactive solution. Even in the case of the standard reactive solution containing no titanium black, in the case of an experiment with a small amount of solution using a bottle like this experiment, the polymerization reactivity may deteriorate slightly, so control this combination of standard solutions to the last. As a result, the effect of titanium black was evaluated based on whether it was worse or unchanged.

The test results are summarized in Table 5.

In any case, in the case of the combination of the reaction solution A in which the standard solution is used and titanium black is dispersed on the side of the reaction solution B, there is almost no difference from the case where the standard reaction solutions A and B containing no titanium black are used. While the polymerization time and the volume ratio of the reaction solution are not shown, the combination of titanium black added to the reaction solution A and the standard solution B and the addition of titanium black to both the reaction solutions A and B are shown. In each case, the polymerization time was longer than that of the reaction solution B to which titanium black was added with the passage of time, and it can be seen that the degree of decrease in the polymerization reactivity is large.

Generally, the polymerization time is preferably about 70 seconds or less, and from this point of view, when titanium black is added to solution B, even when the disadvantage is that it is contained in a small bottle, Same liquid life as 1
Ketsu shows that it can be used enough.

In addition, the volume ratio of the reaction solution that gives the shortest polymerization time is, in any case, compared with the case of the combination of the standard solutions A and B, and the combination of the titanium black-containing solution B and the standard solution A is the titanium black-containing solution B. There is no case where the amount used on the side of is at least small, but this is because a part of the activator was lost due to reaction due to the polymerization inhibitory inactivation of titanium black. Is stable, and it seems that once the reaction is completed, the activator is rarely consumed in the reaction with titanium black thereafter.

Furthermore, this increase rate varies depending on the type of titanium black, suggesting that the consumption of the activator may differ depending on the type of titanium black, that is, the crystal form, surface area, surface treatment, etc. In any case, it is shown that a reactive solution having stable polymerization reactivity can be obtained by using an appropriate amount of the activator.

The crosslinked polymer molded product obtained by such a polymerization test,
It was uniformly colored black and was as strong as the one obtained by combining the standard solutions A and B.

Examples 28 to 30 DCP and DNB prepared in the same manner as in Examples 1 to 10 were also used in Examples 28 to 30.

The main catalyst concentrate, activator concentrate, monomer mixture, standard reactive solution A and standard reactive solution B were also prepared in the same manner as in Examples 1-10.

[Preparation of Reactive Solution A Containing Iron Oxide] 197 g of the above-mentioned monomer mixture and 2 g of predetermined iron oxide as shown in Table 6 were put in a glass bottle, stirred well under nitrogen purge to disperse iron oxide well, 2.96 ml of the main catalyst concentrate was injected with a syringe and stirred well to prepare a reactive solution A containing iron oxide.

[Preparation of Reactive Solution B Containing Iron Oxide] In a glass bottle, 2 g of iron oxide which is the same as 197 g of the above monomer mixture
Was thoroughly stirred under a nitrogen purge to disperse the iron oxide well, 4.44 ml of the activator concentrate was injected with a syringe, and well mixed with stirring to prepare an iron oxide-containing reactive solution B.

[Polymerization activity test] Put 2 ml of the reactive solution B, which was heated to 30 ° C with a syringe under a nitrogen stream, into a test tube equipped with a serum cap and having the thermocouple detection end at the tip through the cap. Similarly, add 2 ml of Reactive Solution A adjusted to 30 ° C with a syringe in the same manner, mix both solutions with a vigorously stirring machine, and from the start of mixing, the polymerization proceeds and heat is generated, and the time until the internal temperature reaches 100 ° C is set. It is measured as the polymerization time. Further, by increasing or decreasing the addition amount of the reactive solutions A and B, the volume ratio of the reactive solution B to the reactive solution A and the polymerization time when the polymerization time becomes the shortest are used as the reactivity evaluation value of the combination of the reactive solutions. To do. In this case, based on the volume ratio of the standard reactive solutions A and B containing no iron oxide and the polymerization time, the combination of the standard solution A and the iron oxide-containing solution B, both of the iron oxide-containing solutions A and B were used. It was decided to evaluate the polymerizability by dispersing iron oxide by measuring and comparing the volume ratio and the polymerization time in the case of the combination.

That is, immediately after the preparation, the influence of the change with time is observed by observing the reactivity after leaving the reactive solution. Even in the case of the standard reactive solution containing no iron oxide, in the case of a small amount solution experiment using a bottle like this experiment, the polymerization reactivity may deteriorate slightly, so control this combination of standard solutions. As a result, the effect of iron oxide was evaluated based on whether it was worse or unchanged.

The test results are summarized in Table 6.

When the reaction solution A is a standard solution and iron oxide is dispersed on the side of the reaction solution B, the polymerization time and the reaction solution are almost the same as those of the standard reaction solutions A and B containing no iron oxide. In contrast to the above, the combination of iron oxide added to the reaction solution A and the standard solution B and the addition of iron oxide to both the reaction solutions A and B show the volume ratio of It can be seen that the polymerization time is long and the deterioration is severe.

The crosslinked polymer molded product obtained by such a polymerization test,
The product obtained by the combination of the reactive solution B containing iron oxide and the standard solution B was uniformly colored, and was as strong as the product obtained by combining the standard solutions A and B.

Examples 31-32 DCP and ENB prepared in a similar manner to Examples 1-10 were also used in Examples 31-32.

The main catalyst concentrate, activator concentrate, monomer mixture, standard reactive solution A and standard reactive solution B were also prepared in the same manner as in Examples 1-10.

[Preparation of Reactive Solution A with Cobalt Oxide Base Pigment] In a glass bottle, 197 g of the above-mentioned monomer mixture and 2 g of each predetermined cobalt oxide base pigment as shown in Table 7 were put, and well stirred under a nitrogen purge to prepare a cobalt oxide base pigment. After dispersing the pigment well, inject 2.96 ml of the main catalyst concentrate with a syringe and stir well to make the cobalt oxide base pigment-containing reactive solution A 2
Seed prepared.

[Preparation of Cobalt Oxide Base Pigment-Containing Reactive Solution B] Into a glass bottle, 197 g of the above-mentioned monomer mixture and 2 g of the same cobalt oxide base pigment as above were separately charged, and 2 g were separately stirred and thoroughly stirred under a nitrogen purge to prepare a cobalt oxide base pigment After being well dispersed, 4.44 ml of the activator concentrate was injected with a syringe and mixed well with stirring to prepare two types of cobalt oxide-based pigment-containing reactive solutions B.

[Polymerization activity test] Put 2 ml of the reactive solution B, which was heated to 30 ° C with a syringe under a nitrogen stream, into a test tube equipped with a serum cap and having the thermocouple detection end at the tip through the cap. Similarly, add 2 ml of Reactive Solution A adjusted to 30 ° C with a syringe in the same manner, mix both solutions with a vigorously stirring machine, and from the start of mixing, the polymerization proceeds and heat is generated, and the time until the internal temperature reaches 100 ° C is set. It is measured as the polymerization time. Further, by increasing or decreasing the addition amount of the reactive solutions A and B, the volume ratio of the reactive solution B to the reactive solution A and the polymerization time when the polymerization time becomes the shortest are used as the reactivity evaluation value of the combination of the reactive solutions. To do. In this case, a combination of the standard solution A and the cobalt oxide-based pigment-containing solution B based on the volume ratio of the standard reactive solutions A and B containing no cobalt-oxide-based pigment and the polymerization time,
In both cases, it was decided to evaluate the polymerizability by dispersing the cobalt oxide base pigment by measuring and comparing the volume ratio and the polymerization time in the case of the combination of the solutions A and B containing the cobalt oxide base pigment.

That is, immediately after the preparation, the influence of the change with time is observed by observing the reactivity after leaving the reactive solution. Even in the case of a standard reactive solution containing no cobalt oxide-based pigment, in the case of an experiment with a small amount of liquid using a bottle like this experiment, the polymerization reactivity may deteriorate slightly, so this combination of standard solutions should be used. As a control, the effect of the cobalt oxide based pigment was evaluated based on whether it was worse or unchanged.

The test results are summarized in Table 7.

Table 7 shows that the solution A containing the main catalyst component to which cobalt oxide was added has a longer polymerization time due to aging, but the solution containing cobalt oxide to the solution A and B is oxidized. It indicates that the polymerization time is extended by the same time-dependent change as that without cobalt. In other words, the polymerization time becomes longer depending on the storage time, but when the cobalt oxide is added to the solution A, the polymerization time becomes longer to a greater extent than when the cobalt oxide is added to the solution B. This is because cobalt oxide gradually reacts with the catalyst component and reduces the catalytic activity. From this result, it is understood that the cobalt oxide should be added to the monomer solution containing the activator component, not the monomer solution containing the catalyst component. Furthermore, cobalt oxide is
It reacts with the activator component, but the reaction stops immediately,
It can be seen that the activator component-containing monomer liquid having high activity can be obtained by adding the activator in an amount corresponding to the consumed activator component.

The combination of solution A containing no cobalt oxide and solution B containing cobalt oxide has a polymerization time of about 1 month.
Since it is about 50 seconds, it can be used for the RIM method.
The metathesis polymer obtained from the combination of Examples 31 and 32 has a beautiful color. In particular, the color of the polymer molded product obtained by combining the cobalt oxide-containing solution A and the cobalt oxide-free solution B is brighter. Due to the combination of the solution A containing no cobalt oxide and the solution B containing cobalt oxide, the polymer molded product has a beautiful color such that surface coating is unnecessary.

Example 33 DCP and ENB prepared in a similar manner to Examples 1-10 were also used in this Example 33.

The main catalyst concentrate, activator concentrate, monomer mixture, standard reactive solution A and standard reactive solution B were also prepared in the same manner as in Examples 1-10.

[Preparation of Reactive Solution A Containing Ultramarine Blue Pigment] In a glass bottle, put 197 g of the above monomer mixture and 2 g of blue #A (ultraviolet) manufactured by Dainichi Seika, stir well under nitrogen purge, and disperse ultramarine blue well. After that, 2.96 ml of the main catalyst concentrate
Was injected with a syringe and well stirred to prepare an ultramarine reactive solution A.

[Preparation of ultramarine base pigment-containing reactive solution B] 2g of the same ultramarine blue as the monomer mixture 197g was put in a glass bottle and well stirred under a nitrogen purge to disperse ultramarine blue well. Ultraviolet reactive solution B was prepared by injecting with a syringe and thoroughly stirring and mixing.

[Polymerization activity test] Put 2 ml of the reactive solution B, which was heated to 30 ° C with a syringe under a nitrogen stream, into a test tube equipped with a serum cap and having the thermocouple detection end at the tip through the cap. Similarly, add 2 ml of Reactive Solution A adjusted to 30 ° C with a syringe in the same manner, mix both solutions with a vigorously stirring machine, and from the start of mixing, the polymerization proceeds and heat is generated, and the time until the internal temperature reaches 100 ° C is set. It is measured as the polymerization time. Further, by increasing or decreasing the addition amount of the reactive solutions A and B, the volume ratio of the reactive solution B to the reactive solution A and the polymerization time when the polymerization time becomes the shortest are used as the reactivity evaluation value of the combination of the reactive solutions. To do. In this case, based on the volume ratio of the standard reactive solutions A and B not containing ultramarine and the polymerization time, the combination of the standard solution A and the ultramarine solution B, and the combination of the ultramarine solutions A and B In this case, the volume ratio and the polymerization time were measured and compared to evaluate the polymerizability by dispersing the ultramarine.

That is, immediately after the preparation, the influence of the change with time is observed by observing the reactivity after leaving the reactive solution. Even in the case of the standard reactive solution that does not contain ultramarine, in the case of the experiment of a small amount solution using a bottle like this experiment, the polymerization reactivity may deteriorate slightly, so this combination of standard solutions should be used as a control. , And the effect of ultramarine was evaluated based on whether it was bad or unchanged.

The test results are summarized in Table 8.

In the case of a combination of reaction solution A in which standard solution is used and ultramarine is dispersed on the side of reaction solution B, standard reaction solution without ultramarine
The polymerization time and the volume ratio of the reaction solution which are almost the same as those of A and B are shown, whereas the combination of ultramarine blue added to the reaction solution A and the standard solution B and the reaction solution A, B
It can be seen that, in each of the cases where ultramarine was added to both of them, the polymerization time became longer with time and the deterioration became severe.

The crosslinked polymer molded product obtained by such a polymerization test,
The product obtained by combining the ultramarine blue reactive solution B and the standard solution B was uniformly colored in blue, and was as strong as the product obtained by combining the standard solutions A and B.

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Claims (8)

[Claims] 1. A reactive solution of a metathesis polymerizable monomer containing a catalyst component of a metathesis polymerization catalyst system (solution A) and a reactive solution of a metathesis polymerizable monomer containing an activator component of a metathesis polymerization catalyst system (solution B). (A) carbon black obtained by an incomplete combustion method of hydrocarbons, (b) a pigment based on titanium oxide, (C) At least one pigment selected from the group consisting of iron oxide-based pigments, (d) cobalt oxide-based pigments, and (e) ultramarine-based pigments is dispersed in the solution B. A method for producing a colored polymer molded article, comprising: 2. (a) Carbon black obtained by the incomplete combustion method of hydrocarbons, (b) a pigment based on titanium oxide, (c) a pigment based on iron oxide, (d)
0.05 to 20% by weight of at least one pigment selected from the group consisting of pigments based on cobalt oxide and (e) ultramarine blue pigment, based on the weight of the colored polymer molding.
The manufacturing method according to claim 1, wherein the dispersion is carried out at a ratio of. 3. (a) The carbon black obtained by the incomplete combustion method of hydrocarbons is one selected from the group consisting of oil furnace carbon black and lamp black, and is based on (b) titanium oxide. Pigments include titanium dioxide, nitrogen-added titanium oxide and titanium yellow (Ti
O ₂ -NiO-Sb ₂ O ₃ ), which is a kind selected from the group consisting of
The production method according to claim 1, wherein (c) the iron oxide-based pigment is one selected from the group consisting of iron black, red iron oxide and oak, and (d) the cobalt oxide-based pigment is cobalt blue. . 4. The method according to claim 1, wherein the at least one metathesis-polymerizable monomer comprises dicyclopentadiene or a mixture of dicyclopentadiene and another metathesis-polymerizable monomer. 5. A reactive solution (solution A) of (a) a metathesis polymerizable monomer containing a catalyst component of a metathesis polymerization catalyst system.
And (b) at least a reactive solution of a metathesis polymerizable monomer containing an activator component of a metathesis polymerization catalyst system, (a) carbon black obtained by an incomplete combustion method of hydrocarbons, and (b) oxidation At least one pigment selected from the group consisting of titanium-based pigments, (c) iron oxide-based pigments, (d) cobalt oxide-based pigments, and (e) ultramarine-based pigments. A combination of reactive solutions for producing a colored polymer molded article, which is dispersed in the solution B. 6. (a) Carbon black obtained by incomplete combustion method of hydrocarbons, (b) pigment based on titanium oxide, (c) pigment based on iron oxide, (d)
At least one pigment selected from the group consisting of a pigment based on cobalt oxide and (e) a pigment based on ultramarine blue is dispersed in a proportion of 0.05 to 20% by weight based on the total weight of the combination of the reactive solutions. 6. A combination of reactive solutions according to claim 5. 7. (a) The carbon black obtained by the incomplete combustion method of hydrocarbons is one selected from the group consisting of oil furnace carbon black and lamp black, and is based on (b) titanium oxide. Pigments include titanium dioxide, nitrogen-added titanium oxide and titanium yellow (Ti
O ₂ -NiO-Sb ₂ O ₃ ), which is a kind selected from the group consisting of
The reactivity according to claim 5, wherein (c) the iron oxide-based pigment is one selected from the group consisting of iron black, red iron oxide and oak, and (d) the cobalt oxide-based pigment is cobalt blue. Solution combination. 8. A combination of reactive solutions according to claim 5, wherein the at least one metathesis polymerizable monomer comprises dicyclopentadiene or a mixture of dicyclopentadiene and another metathesis polymerizable monomer.