JPH0228214A - Production of colored polymer moldings and combination with reactive solution - Google Patents

Abstract

PURPOSE:To obtain the title moldings having excellent beautifying properties, oxidation resistance, resistance to deterioration by light by dispersing a specific pigment into a reactive liquid containing an activating agent component, blending the dispersion with a catalyst component-containing reactive liquid and then molding the blend while carrying out polymerization. CONSTITUTION:A pigment selected from (A) a carbon black obtained by imperfect combustion of hydrocarbons, (B) a pigment consisting of titanium oxide, (C) a pigment consisting of iron oxide and (D) a pigment consisting of a cobalt oxide is dispersed into a reactive solution of polymerizable monomer containing an activating agent component of metathesis polymerization (hereinafter referred to as polymerization) catalyst system. Then the reactive solution of the polymerizable monomer containing catalyst component of the polymer catalyst system is blended with the reactive solution containing the dispersed and above- mentioned pigment and the blend is molded while carrying out polymerization to provide the aimed moldings.

Description

Detailed Description of the Invention a. Industrial Application Field The present invention is a polymer molded product obtained by simultaneously polymerizing and molding a metathesis polymerizable monomer in the presence of a metathesis polymerization catalyst. This relates to molded products.

More specifically, the present invention relates to the colored polymer molded product in which pigments such as carbon black, titanium monide, iron oxide, cobalt oxide, or ultramarine blue are dispersed.

b. Prior Art It is known that cyclic olefins can be subjected to metathesis polymerization catalyst systems to give ring-opened polymers. Therefore, a method has been proposed in which a metathesis-polymerizable cyclic olefin, which can be obtained at low cost, such as dicyclopentadiene (DCP), is polymerized and molded in a mold in one step using a metathesis polymerization catalyst to obtain a polymerized molded product. In other words, the metathesis polymerization catalyst system is
Taking advantage of the fact that it consists of two components: a catalyst component such as tungsten chloride and an activator component such as an alkyl aluminum, two types of liquids consisting of each component and a monomer are used during polymerization after rapid mixing. A method of obtaining a polymer molded product by pouring it into a mold was proposed (for example, Japanese Patent Laid-Open No. 58-12
See Publication No. 9013>.

According to this method, large-sized molded products with good mechanical performance can be produced using inexpensive low-pressure molds14, so it can be said to be a very attractive method from an industrial perspective. It has become clear that there is a need for something with additional functions.

Colored polymer molded products are one of these, and are particularly important.

The above-mentioned polymer molded products are usually yellowish in color, and are used after being colored or surface-coated depending on the requirements for applications that emphasize weather resistance and cosmetic properties. Furthermore, the above-mentioned polymer molded product has many double bonds and is susceptible to oxidative deterioration or photo-oxidative deterioration. Therefore, the above-mentioned polymer moldings are usually made weather resistant by incorporating pigments into the reactive liquid of the raw material or by coating the surface.

A stable molded product with cosmetic properties can be obtained.

US Patent No. 4.598.102 discloses the use of glass, wolstonite, mica, carbon black, talc or calcium carbide as reinforcing agents or fillers in metathesis-polymerizable cyclic olefin monomers. However, the patent does not mention the specific type of carbon black or whether the carbon black should be dispersed in the catalyst component side or the activator component side of the metathesis catalyst system for polymerization. It has not been done.

US Patent No. 4.080.491 discloses the addition of a coloring agent to a metathesis polymerizable material, but does not specifically state the type of coloring agent.

On the other hand, conventional knowledge suggests that activator components such as alkyl aluminum and alkyl aluminum halides in metathesis catalyst systems are more reactive and unstable than catalyst components such as tungsten salts and molybdenum salts. was known. Therefore, traditionally, additives such as fillers and pigments have been added to the monomer solution containing the catalyst component rather than to the monomer solution containing the activator component.

As a result of research on the coloring of metathesis polymer molded products by the present inventors, it was surprisingly found that among the many pigments, certain pigments, namely carbon black and titanium oxide obtained by an incomplete combustion method.

Iron oxide, cobalt oxide or ultramarine are usually used in reactive liquids containing catalyst components that are considered to be more stable than the activator components.
A reactive liquid containing an activator component considered to be more active than the catalyst component (solution B) is dispersed in solution A).
) was found to enable long-term storage without deterioration of activity.

Although the catalytic component and the above-mentioned pigment do not cause a very strong interaction, they do continue to react, and the reactive liquid (solution A) containing the catalytic component gradually reacts in the presence of the above-mentioned pigment. It becomes inactivated, and it is impossible to restore activity by adding a catalyst inside.

On the other hand, in the case of the activator component and the above-mentioned pigment, the reaction occurs rapidly, but the subsequent reaction does not proceed, and by supplementing the activator lost through the reaction, a pigment-dispersed reactive liquid with stable polymerizability is created. is reduced to 1q. This finding is unexpected and can be effectively utilized in the production of colored molded products from the reactive liquid. This phenomenon is not necessarily observed in all metal oxides. For example, antimony trioxide gradually reacts not only with catalyst components but also with activator components, resulting in deterioration of their activity. Fortunately, the above five types of pigments can vary from black to white, red to purple, by modifying their chemical structure, by mixing other components, or by mixing these as described below. It is important to provide a variety of colors.

In general, the present inventors believe that the colored polymer molded product produced by the combination of reactive liquids containing pigment in solution B is different from the colored polymer molded product produced by the combination of reactive liquids containing pigment in solution A. It was found that the color was more vivid than that of the composite molded product. This is particularly noticeable in the case of light colored pigments. Solution A has a dark brown color due to its catalytic components.

Most of this dark-colored component is decolored by the polymerization reaction, but it may remain on the surface of the pigment particles without disappearing even after the polymerization reaction is completed.

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

Therefore, an object of the present invention is to provide a method for producing a colored polymer molded article that is excellent in cosmetic properties, oxidation resistance, and light deterioration resistance. A further object of the present invention is to provide a combination of reactive solutions for use in the production of colored polymer moldings.

Structure of C1 invention The present invention includes the following inventions.

(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). Mix and mold at the same time as polymerization to obtain a polymer molded product! ! ! In the manufacturing method, (a) carbon black obtained by the incomplete combustion method of IrjA hydrogen hydride, (pigment based on titanium oxide).

The solution B is characterized in that at least one pigment selected from the group consisting of a pigment based on iron oxide, a pigment based on cobalt tetroxide, and (e) a pigment based on ultramarine blue is dispersed in the solution B. A method for producing a colored polymer molded article.

(2) (a) Carbon black obtained by incomplete combustion of hydrocarbons, (b) Pigments based on butane oxide, pigments based on iron oxide, (pigments based on cobalt tetroxide) The manufacturing method described above, wherein at least one pigment selected from the group consisting of pigments based on ultramarine blue and ultramarine blue is dispersed in a proportion of 0.05 to 20% by weight based on the weight of the colored polymer molded product.

(3) (A) The carbon black obtained by the incomplete combustion method of hydrocarbons is a type selected from the group consisting of oil furnace carbon black and lamp black, and (0) GFI based on retified titanium. Titanium dioxide, nitrogen-doped titanium oxide and titanium oxide
(TiOz-NiO-4bz 03) is a type selected from the group consisting of (TiOz-NiO-4bz 03), and the pigment based on iron oxide is a type selected from the group consisting of iron black, red iron oxide, and orca. The manufacturing method according to (1) above, wherein the cobalt-based pigment is cobalt blue.

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

(5) Reaction of (a) a reactive solution (solution A) of a metathesis polymerizable monomer containing a catalyst component of a metathesis polymerization catalyst system and (b) a metathesis polymerizable monomer containing an activator component of a metathesis polymerization catalyst system (a) Carbon black obtained by incomplete combustion of hydrocarbons.

(0) Pigment based on titanium oxide, (/\)r! !
gi'Fl based on iron i-oxide; and at least one pigment selected from AT consisting of a pigment based on cobalt oxide and a pigment based on ultramarine blue.
A combination of reactive solutions for producing colored polymer molded articles, characterized in that the reactive solutions are dispersed in:

(6) (a) Carbon black obtained by incomplete combustion of hydrocarbons, (0) Pigments based on titanium oxide, pigments based on iron oxide, (pigments based on cobalt tetroxide) and (e) at least one pigment selected from the group consisting of pigments based on ultramarine blue is dispersed at a ratio C' of 0.05 to 20 ω% relative to the total weight of the combination of the reactive solutions ( 5) Combination of reactive solutions as described.

(7) (a) The carbon black obtained by the incomplete combustion method of hydrocarbons is a type selected from the group consisting of oil furnace carbon black and lamp black, and (0) a pigment based on titane monoxide. is titanium dioxide, nitrogen-doped titanium oxide, titanium oxide, yellow (Ti0
It is a type selected from the group consisting of z-NiO-3bz O:l), and the pigment based on iron oxide is a type selected from the group consisting of iron black, red iron oxide, and orca, and (
d) The combination of reactive solutions described in (5) above, wherein the pigment based on cobalt oxide is cobalt blue.

(8) The combination of reactive solutions described in (5) above, wherein at least one meta-cis-polymerizable monomer is dicyclopentadiene or a mixture of dicyclopentadiene and another metathesis-polymerizable monomer.

The present invention enables stable use in reactive solutions for the first time (■
The above-mentioned inorganic pigments that have been discovered are all inexpensive, widely used, and easily available, and as mentioned above, they have a wide range of colors from black to white and red to purple. According to the present invention, the colored material of the metathesis polymer molded product as described above can be matched with any required color tone by itself or by mixing, and the coloring of the metathesis polymer molded product as described above can be adjusted to match any required color tone. It can be said that the contribution to practicality is extremely large. In particular, for white and black, which are often used for coloring, we use incomplete combustion methods such as titanium dioxide, which is the most commonly used, and cheap oil fluorine black, which accounts for 90% of the production volume. The discovery of the possibility of using carbon without any treatment or special operations is of great significance.

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

Carbon black is generally used as the black pigment. Such carbon blacks are broadly classified into those obtained by thermal decomposition of hydrocarbons and those obtained by incomplete combustion of hydrocarbons. The former includes acetylene black, which is obtained from acetylene, and thermal black, which is obtained from hydrocarbons.
However, it is only used for special purposes because its properties and cost make it difficult to obtain a product with a limited range of properties and costs.
Manufacturers are also limited, and for use in coloring applications, it is most desirable to use products manufactured by the incomplete combustion method, where products with a wide variety of properties are manufactured inexpensively and hung from the ceiling.

In other words, commercially available carbon black is generally produced using natural gas or heavy
The majority of carbon blacks are produced by the incomplete combustion method of I1 oil (generally more than 90% of all carbon blacks), and depending on the details of the manufacturing process, channel black and oil furnace black are produced.

Therefore, it will be classified as lamp black, etc.

However, carbon black produced by these incomplete combustion methods burns a part of the raw material hydrocarbon in the presence of air to generate high temperatures19, and depending on the temperature, the thermal decomposition of the hydrocarbons is also performed and carbon is obtained. In other words, since 1q is produced in an oxidizing atmosphere, it is inevitable that the obtained carbon black contains more or less M element-containing polar compounds. The presence of such polar compounds is effective in creating good mutual affinity when used dispersed in polar polymers such as general paint resins, and generally, the polar compounds are more miscible. Channel black, which is easy to use, is used for such purposes as a higher quality product than oil furnace black or lamp black.

Furthermore, in oil furnace black, in order to bring the dispersibility closer to that of channel black, the carbon black obtained is heated and treated with air to increase the amount of polar compounds. The content of such polar compounds is generally expressed by two characteristic values, DH and volatile content, among various characteristic values representing the characteristics of carbon black.

That is, in general, the lower the pN and the higher the volatile content, the greater the content of such polar compounds.

However, when such carbon black is used in the production of metathesis polymerization type products as described above, it is thought that due to the presence of such polar compounds, it has a strong interaction with the components of the metathesis catalyst system, and the catalyst It was found to inhibit the activity. Therefore, in order to remove such polar compounds, such carbon black may be heat-treated at a high temperature of 500° C. or higher for a considerable period of time in an inert atmosphere, but this makes such carbon black extremely expensive. It is also possible to pre-treat with a very strong reducing agent, but this is also expensive and troublesome as it is desirable to completely remove the treated reducing agent.

Therefore, it is most preferable that incomplete combustion 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 found that among the components of the metathesis catalyst system, there is a difference in the way the main catalyst component and the activator component act. The present invention was achieved based on the discovery that by utilizing this difference, a stable carbon black dispersion system with no practical problems can be obtained without any pretreatment.

In other words, the present inventors believe that carbon black containing a polar compound can be added and dispersed in a metathesis-polymerizable monomer-reactive solution containing a main catalyst component, but cannot be added to a metathesis-polymerizable monomer-reactive solution containing an activator component. Even if dispersed in the catalyst, they all react with the catalyst component and inhibit polymerization, but there are differences in the way the reaction occurs.In the case of the main catalyst component, the reaction seems to continue for a long time, and the polymerization gradually decreases over time. Even if the main catalyst component, which is thought to correspond to the reactive component, is added, the polymerizability does not recover.However, in the case of the activated subcomponent, it reacts rapidly, but subsequent reactions do not slow down, and the reaction causes It has been discovered that by supplementing the lost activator, a combination of a carbon black dispersion and a reactive solution with stable polymerizability can be obtained.

1 due to incomplete combustion of the hydrocarbons used in the present invention.
Examples of the carbon black that can be used include, as mentioned above, Oil Fun 7 Ness Black, Channel 1 Lac, Lamp Black, and the like.

On the other hand, various characteristic values are used to express the properties of carbon black, but the following three characteristic values are generally recognized as basic characteristics.

(i) Particle size or specific surface area S1 measurement of the average particle size using an electron microscope and specific surface area measurement methods using iodine adsorption method or nitrogen adsorption method using BET method are used, but the most common method is BET method. surface area y
d/g).

The larger the specific surface area, the more fine particles the carbon black consists of.

(ii) Structural carbon black generally has a structure in which a number of basic carbon black particles (one sphere) are fused together, and the way the structure develops differs depending on the structural conditions. The parameters representing curl are U and DBP oil absorption (KAI/100 (J)).The larger the oil absorption, the greater the hair structure.

(iii) Surface texture pH and volatile content (%) are used as parameters to express the polar compound content due to oxidation on the surface of carbon black.For the same type of carbon black, pH
There is a correlation between the volatile content and the volatile content, and those with a large volatile content have a large polar compound content and generally have a low pH.

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

In general, for coloring, those with a larger specific surface area have greater coloring properties, and those with developed stractures have the characteristic of giving a bluish tinge to black, and often have better dispersion stability. Those with a large Strucge V- and a certain degree of development are prized. In addition, when used with resins and solvents that are generally polar, such as for paints, carbon black with a larger content of polar compounds has better affinity, and has better dispersibility and dispersion stability.As mentioned above, carbon black can be oxidized It is prized when the pH is lowered by volatile separation.

In the present invention, nonpolar hydrocarbon-based monomers are generally used as metathesis-polymerizable monomers, as will be described later, except in special cases.

Therefore, it is considered that a large content of polar compounds in carbon black is not necessary to increase dispersion and affinity in reactive solutions. Furthermore, the presence of such polar compounds
In order to interact with the catalyst components and inhibit polymerization, it is added to the activated exfoliant to inhibit the reaction with the activator (possibly,
A feature of the present invention is to prevent inhibiting reactions from occurring during the polymerization reaction (reduction reaction is carried out), and therefore, the greater the content of polar compounds, the lower the amount of activator consumed to render them harmless. This will not only be economically disadvantageous, but it is also thought that there may be disadvantages such as an increase in the metal content as the remains of the activator consumed by the reaction in the resin molded product. . Therefore, the carphone black used in the present invention preferably has a low volatile content and a high pH when no alkali treatment or the like is performed.

In addition, regarding the specific surface area, generally speaking, the larger the specific surface area, the more areas the polar compound is likely to adhere to, and the more time it takes for the reaction with the activator to occur completely. From the standpoint of consumption, a smaller specific surface area is preferable, but in terms of colorability, a larger specific surface area can be colored more efficiently, so it is possible to decide on the optimal product based on the balance between the two. be.

Regarding the struture, there are few factors that greatly affect the consumption of the active agent, and it is sufficient to select an appropriate one from the viewpoints of dispersibility and dispersion stability.

Further, the amount of carbon black added to the polymer molded product varies greatly depending on the purpose of black coloring. In other words, when trying to color the base color of a painted product, it is sufficient that the resin is mostly black, so a very small amount of addition is sufficient. If it is intended to be used without coating, it is necessary to add a larger amount in 1F to increase blackness and photostability. Furthermore, in order to have conductivity,
A larger amount is required.

The amount of carbon black added is generally 0.05 to 20% by weight, preferably 0.1 to 5% by weight, based on the entire polymer molded product.
A range of weight percent is used, more preferably a range of 0.1 to triple star percent.

As mentioned above, carbon that requires a large amount of activating agent to inactivate polar compounds in carbon, that is, carbon that has a large specific surface area and a large volatile content, is used only when added in small amounts. It is disadvantageous in that it is not available.

From this point of view, 1q of carbon black used in a wide range of addition amounts should have a volatile content of 1.5% or less, a specific surface area of 200 TIt/g or less, more preferably a volatile content of 1.0% or less, and a specific surface area of 200 TIt/g or less. Examples include those having a surface area of 120 rIt10 or less.

Previously, the incomplete combustion method carbon black used in the present invention was mainly channel black made from natural gas, but since water droplet has a low carbon yield relative to the raw material, it has been greatly affected by the rising cost of raw materials. , and pollution problems are also serious, and production of traditional channel black has now been discontinued.However, it is produced in some parts of the country as high-grade carbon black for coloring using a specially devised modified channel method. . Naturally, these have large specific surface area, oil absorbency, and volatile content, and therefore, in the present invention, they are undesirable and their use is limited to extremely limited low a degrees. On the other hand, lamp black made using the same traditional method is
It is inexpensive, has a very small specific surface area, and does not have much volatile content, so it is suitable for use in the present invention.
It has a large particle size distribution and includes coarse particles, so care must be taken when actually using it in terms of the quality of the reactive solution during dispersion.

Currently, oil furnace black is the most popular method for producing carbon black, and a wide range of carbon blacks with the above three properties are available and are most suitable for use in the present invention. As for the characteristics, it may be selected in consideration of the above-mentioned item A1, but it is not preferable to use acid value treatment as described above or further alkali treatment to adjust the pH. In addition, in the oil furnace method, coal-based and/or petroleum-based heavy oil is used as a raw material, but it is generally preferable to use a high-quality raw material that does not contain too much sulfur or ash.

The (0) titanium oxide-based pigment used in the present invention encompasses a wide range of currently available titanium oxide pigments.

Titanium oxide pigments are those consisting only of titanium and oxygen, or those containing metals (for example, barium).

Some contain elements such as ambumon, nickel, chromium) and nitrogen. As titanium oxide, -titanium oxide
>, titanium (I[I) oxide (Ti203), titanium dioxide (TiOz>, butane peroxide (Ti0
x> and their intermediates can be used. Titanium dioxide and titanium oxide as pigments are usually used in pure, salt, modified or impure form.

Among these is titanium white (titanium dioxide).

Titanium black (nitrogen-added titanium oxide), titanium yellow (TiOz-NiO-3bzOz>) and pigments based on titanium oxide and thermally treated with other metals such as barium, nickel, chromium or antimony oxide are used. Particularly preferred is white titanium oxide.

White titanium oxide is titanium dioxide represented by TiOz, and is prized as an excellent white pigment because of its high dispersibility resulting from its high refractive index. Other known white pigments include zinc white (zinc oxide), lead white (basic lead carbonate), and lithopone (zinc sulfide/barium sulfate), but they are not only white, but also have chemical resistance such as acid resistance and alkali resistance. Titanium oxide is by far superior in terms of properties, non-toxicity, etc.
This is also the reason why it is widely used.

Nitrogen-doped black titanium oxide is a fine black powder produced by reducing titanium dioxide in a nitrogen atmosphere and is commercially available under the name titanium black. Several types of braided butane black are commercially available and can be used as black pigments in the same way as white titanium dioxide. Butane yellow is modified by dissolving oxides such as nickel and antimony in white titanium oxide, and is used as a stable and safe yellow pigment.

The crystalline form of white titanium oxide is anatase.

Three types of refined products are known: rutile and brookite, but there are two types of white pigment: anatari and rutile.
types are industrially produced. The rutile type has a slightly higher density, a higher refractive index, and better weather resistance, but it absorbs more ultraviolet light, giving it a slightly yellowish tinge.

On the other hand, the anatase type is inferior to the rutile type in terms of stability, but has the advantage of being able to express a clear white color.

Both can be used in the present invention by taking advantage of their respective characteristics.

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 the natural raw material ilmenai 1- is digested with sulfuric acid, the titanium component is extracted and separated as titanium sulfate, hydrolyzed with an alkali, and then calcined. On the other hand, the chlorine method uses rutile ore or synthetic rutile as a raw material, and uses chlorine to separate and refine it into butane chloride, which is then oxidized and separated as titanium oxide. The anatase form is produced by the sulfuric acid method.

Although the chlorine method is more expensive, it is said that 1q of high-purity, high-quality products can be used, and an appropriate product is selected and used in relation to the intended use. Furthermore, in order to improve dispersibility with the medium, coating with hydrous aluminum oxide, coating with a mixture of hydrous aluminum oxide and hydrous silicon oxide, coating with zinc oxide separately, and coating with silicone oil or silane coupler. The processed materials and various processed materials are devised and selected depending on the recipients and used.

Although the titanium oxide-based pigments described above have excellent stability as described above, they are metal oxides and can react with strong acidic compounds such as tungsten chloride, which is the main catalyst component of the metathesis polymerization catalyst system. J5, and has the possibility of being reduced to strongly reducing compounds such as alkylaluminium.

Therefore, as a result of detailed research on the interaction between the titanium oxide-based pigment and the components of the metathesis catalyst system, the present inventors found that among the components of the metathesis catalyst system, the main catalyst component and the activator component interact in different ways. The present invention was achieved by discovering that by utilizing this difference, a stable titanium oxide pigment dispersion system with no problem in practical use can be produced.

That is, the present inventor has discovered that in a wide range of titanium oxide pigments,
It has been found that when dispersed in a metathesis-polymerizable monomer-reactive solution (solution A) containing the main catalyst component, metalhesis polymerization reactivity is gradually inhibited in most cases. However, when dispersed in a metathesis small monomer reactive solution (solution B) containing an activator for a metathesis polymerization catalyst system, which should have higher reaction activity, there is almost no reaction, or even if it does react, it occurs rapidly. It was discovered that by supplementing the activator thought to have been lost during the reaction, a combination of titanium oxide-based pigment-dispersed reactive solutions with stable polymerizability could be obtained. be.

The titanium oxide pigment used in the present invention includes a wide range of currently available butane oxides, as described above. That is, in the case of white titanium oxide, both anatase form and rutile form can be used. In addition, in the manufacturing method -C, either the sulfuric acid method or the chlorine method can be used. Furthermore, as described above, in addition to the internal modification of the pigment, it is also possible to use coatings on the surface with aluminum oxide, gooey oxide, some zinc oxide, and even silicone-based compounds. However, the reaction with the activator component varies depending on its type, and therefore the amount of activator that needs to be added will vary.

Therefore, the butane oxide used in the present invention improves the coloring degree 2 of the colored molded product obtained, the color stability, the stability of the resin, the dispersibility of titanium oxide in the liquid, the dispersion stability, and the additional activator required. This can be determined by taking into consideration the economical efficiency of removing components.

In terms of the extra activator component required, pigments with a large amount of adsorbed water generally tend to have a large amount. This is effective in reducing the amount of activating agent component consumed.

Furthermore, in the case of ajturbi, the amount of activator consumed tends to be less when the coating ω of aluminum oxide, zinc oxide, silicon oxide, etc. is less than that of rutile.

As a pigment, the average particle size of titanium oxide is 1 particle size (I also has an effect on the dispersion stability in the coloring reactive liquid, etc., and in general, fine particles -b are preferable in that respect, but conversely, the surface area This means that there is a possibility that the amount of activator consumed will increase as the amount of activator increases.The selection should be made according to the required performance.

In addition, in the case of white titanium oxide, a chromatic colored molded product can also be obtained by using one piece of Haku's colored pigment. It goes without saying that these color pigments must be selected so that they do not inhibit the metathesis polymerization catalyst. In particular, other colored pigments included in the present invention can be suitably used for that purpose.

The amount of titanium oxide pigment added is 0.05 to 2 in the polymer molded product.
A range of 0% by weight, particularly a range of 0.1 to 5% by weight, more preferably a range of 0.2 to 3% by weight is used.

The iron oxide-based pigment used in the present invention can be any pigment that is normally used as a pigment.

The iron oxide pigments of the present invention may also contain other substances such as manganese, silicon, chromium, zinc, aluminum. Examples of such pigments include iron black or triferric tetroxide (FC, +04), red iron or iron sesquioxide (Fe203), and amber (i.e., brown iron sesquioxide containing HnQ2 and/or fn304). , Orca (Fe203 ・SiO+ ・AJ!z Oz >
.

There are synthetic pigments that contain iron oxide as a main component.

Among these, Tetsukuro (r (!304)) and Red Gara ([e
203) is preferred because it is widely used as a pigment.

Compared to carbon black and butane black, iron black (
re: l 04 > becomes (4↑(1
The quality is strong and magnetic, and it is the material that controls magnetism! It becomes a thing and vines.

The amount of iron black added varies depending on the purpose. In other words, it is easy to understand that the optimum amount to be added differs depending on whether it is used as a base color for painting, when used with white pigments, or when used without painting as a base dye. It is easy to determine the optimal value by

Generally, the range of 0.05 to 20% by weight in the polymer molded product, particularly the range of 0.1 to 5% by weight, more preferably 0.05% by weight.
A range of 2 to 3 times ω% is used.

Since there may be differences in the dispersibility in the reactive solution B depending on the type of iron black, an appropriate method may be selected to achieve sufficient dispersion.

Generally, first, a masterbatch is prepared by sufficiently dispersing a small amount of [Zummer mixture, or a rubber-containing E-Zummer solution in which an elastomer described later is dissolved therein, using a high-concentration, high-shear type dispersion device. However, it is preferable to use a master pap method in which this is diluted as a reactive solution B to obtain a predetermined concentration. When dispersing 1 q of such a masterbatch, a well-known dispersion method for preparing a pigment masterbatch is generally used, ie, a ball mill.

A roll mill, a panbari milli-1 ultrasonic dispersion device, etc. can be used.

In addition, as a special case of masterbatch, iron black dispersion rubber is prepared by kneading iron black with elastomer, which is used as a reactive solution to adjust the viscosity and improve the impact resistance of molded products. It is also possible to dissolve iron black in a monomer and disperse it as a masterbatch.

If you use iron black that is easy to disperse and have a mixing device sufficient for dispersion, use a method of adding and dispersing iron black when preparing reactive solution B without creating a master hatch in advance. It is also possible.

The gradient cobalt oxide-based pigment used in the present invention can be used in the same way as the butane oxide-based pigment and the iron oxide-based pigment. Pure cobalt oxide is rarely used alone as a pigment; Ordinary aluminum, 1.Chromium.

Cobalt oxide that has been thermally treated with an oxide such as nickel is used.

Among these, cobalt blue (Co0-AJ!203
) are widely used as pigments for plastics, and are preferably used in the present invention. The amount added is 0 in the hand-combined molded product.
．． A range of 0.05 to 20% by weight is used, particularly a range of 0.1 to 5% by weight, more preferably a range of 0.2 to 3000% by weight.

As the blue pigment, inorganic pigments are preferable in terms of cost and stability. Such inorganic blue pigments include ultramarine blue and deep blue.

However, dark blue has poor heat resistance, reaching temperatures of 150°C during polymerization.
It is difficult to use the resin in the present invention, which is heated to such a high temperature.

On the other hand, ultramarine blue also does not have sufficient chemical resistance, especially acid resistance.
There is a concern that polymerization inhibition may appear in metathesis polymerization.

As a result of a detailed study of ultramarine's ability to inhibit metathesis polymerization, we were surprised to find that it did not inhibit metathesis polymerization when added to a solution containing an activator, which is generally said to have high reactivity. It has been found that it can be used stably.

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

The amount of ultramarine added varies depending on the purpose. In other words, it is easy to understand that the optimum amount to be added differs depending on whether it is used together with other pigments for one ruing of a white base dye, or when it is to be used as a base dye without coating. It is easy to determine the value.

In general, the range of 0.05 to 20,000% by weight in the polymer molded product, particularly the range of 0.1 to 5% by width, and more preferably 0.1 to 5% by width.
A range of 2-3% by volume is used.

The pigments mentioned above can be used alone or in combination. For example, when a white pigment such as titanium oxide is used alone, a white metathesis polymer molding is produced. By using a black pigment such as carbon black, titanium black, or iron black (RE304) alone by the incomplete combustion method, it is possible to produce a black molded product of 1 q.

It is possible to obtain a mixture of these colors by using a mixture of two or more of these pigments. The color of the molded product can vary depending on the type and color of the pigment.

In the present invention, (a) a power pump rack using an incomplete combustion method; The pigment is used in a general amount of 0.05 to 20% by weight, preferably 0.1 to 5% by weight, with respect to the model m of combination V of the metathesis polymerization reactive liquid. preferably 0.2 to 3
Weight percent suspension is used.

The amount of pigment added depends on the type of pigment and the surface condition of the pigment.

It depends on various conditions such as the desired color of the molded product, the usage conditions of the molded product, and whether or not the molded product is further coated.

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

In general, first, a masterbatch is prepared which is sufficiently dispersed in a small amount of a monomer mixture or a monomer solution containing a rubber containing an elastomer as described above, using a high a degree, high silage type dispersion device, and then the masterbatch is dispersed in a predetermined manner. It is preferable to use a masterbatch method in which the reactive solution B is diluted to a concentration of . Dispersion for obtaining such a masterbatch is generally carried out by a well-known dispersion method for preparing a pigment masterbatch, that is, a ball mill.

A roll mill, Pan Bali mixer, ultrasonic dispersion device, etc. can be used.

In addition, as a special case of a masterbatch, a pigment-dispersed rubber is prepared by mixing an elastomer and a pigment, which are used as a reaction solution to adjust the viscosity and improve the impact resistance of objects, in advance. It is also possible to dissolve the pigment in the monomer as a masterpup and disperse the pigment therein.

If you use a pigment that is easy to disperse and you have a mixing device sufficient for dispersion, use a method of adding butane oxide to the preparation section of reactive solution B and dispersing it without creating a masterbatch in advance. is also possible.

As for the specific molding method of the method for manufacturing the polymer molded product of the present invention, as mentioned above, the reactive solution is mixed with a static mixer or the like, or a premix is prepared in advance and then poured into the mold. Resin injection molding and similar molding methods can be used to obtain molded products, but since the reaction after mixing is generally quick, reaction injection molding (reaction injection molding), in which the mixed reaction liquid is injected into the mold immediately after impact mixing, is used. RIM molding method)
is the most suitable.

Generally, metathesis polymerization catalyst systems consist of two components: a main catalyst component and an activator component.

Metathesis polymerization reactions are exothermic and proceed rapidly.

For this reason, a reaction occurs before the mixture of the respective monomers containing the main catalyst component and the activator component is introduced into the mold, making it difficult to introduce the mixture into the mold, and resulting in large-sized moldings. becomes difficult to manufacture. Therefore, it is preferred that the catalyst and activator components of the metathesis catalyst system are each added separately to the monomer liquid to form a combination of reactive liquids. That is, solution A and solution B.

These are impingement mixing (RIM method)
, a static mixer, a dynamic rotary mixer, etc., and the mixture is rapidly mixed and then introduced into the mold.

In this case, it is not necessary that each monomer component of the reactive mixture combination be of the same composition. The composition of the monomers may be arbitrarily determined in consideration of the composition after mixing.

A preferred example of the metathesis-polymerizable monomer used in the present invention is dicyclopentadiene.

Tricyclopentadiene, cyclopentadiene-methylcyclopentadiene codimer, 5-ethylidenenorbornene, norbornene, norbornadiene, 5-cyclohexenylnornene, 1,4゜5.8-dimethano-
1,4,4a, 5.6.7.8.8.8a-octahydrotaphthalene, 1,4-methane-1,4,4a,5,
8゜7, 8.8.8a-octahyde-buththalene, 6-
Nylidene-1,4,5,8-dimethano-1,4,4a
, 5, 6, 7, 8.8a to Butahytronaphthalene, 6
-Methyl-1,4゜5.8-dimethano-1,4,4a,
5.6.7.8.8a-heptahydronaphthalene,
1,4,5.8-dimethano-1,4,4a5.8.8a
-One type or a mixture of two or more types of cyclic olefins having 1 to 3 norbornene structures such as hekylihydronaphthalene and ethylenebis(5-norbornene) can be mentioned, but in particular dicyclopentadiene or a mixture thereof can be mentioned. A monomer mixture of the following is preferably used.

Further, if necessary, a metathesis-polymerizable cyclic compound containing a different element such as oxygen or nitrogen may be used.

Such polar polymers are often used in copolymerization with dicyclopentadiene and the like.

Preferably, such polar monomers have a nornene structural unit, and as the polar group, ester groups, ether groups, cyano u, N-substituted imides, etc. are preferable.

Specific examples of such copolymerizable polymers include 5-methoxycarbonylnorbornene (brunhexyloxy)carbonyl-5-methylnorbornene and 5-phenylenenorbornene.

5-cyanonorbornene, 6-diatu 1.4, 5.8
Dimethano-1. 4. 4a, 5, 6, 7, 8
．． Examples include 8a-octahydronophthalene, N-butylnadic acid imide, and the like.

As mentioned above, the small metathesis polymerizable monomer is required to contain as few impurities as possible that would inactivate the metathesis polymerization catalyst.

As the main catalyst component in the metathesis polymerization catalyst system used in the present invention, salts such as halides such as tungsten, rhenium, tantalum, and molybdenum are used, but compounds of tungsten and molybdenum are preferred, and tungsten compounds are particularly preferred.

As such a tungsten compound, tungsten halide, tungsten oxyhalide, etc. are preferable, and more specifically, tungsten=F dichloride, tungsten oxychloride, etc. are preferable. In addition, organic an[nium tungsten r! It depends on whether salt or the like is used. It is known that when such a tungsten compound is directly added to the T-summer, cabon polymerization starts sluggishly, which is not preferable. Therefore, the tungsten compound is in an inert solvent such as bempine. It is preferable to use it by suspending it in advance in toluene, chlorobenbin, etc., and solubilizing it by adding a small amount of an alcoholic compound or a phenolic compound.

Furthermore, in order to prevent undesirable polymerization as described above, it is preferred to add about 1 to 5 moles of Lewis base or chelating agent per mole of tungsten compound. Such additives include acetylacetone and acetoacetic acid alkyl esters.

Examples include tetrahydrofuran and benzonitrile.

Thus, the tsummer solution (solution A) containing the catalyst component is
It has sufficient stability for practical use.

On the other hand, the activator component in the metathesis catalyst system is an organometallic compound mainly containing alkylated products of metals from Groups 1 to 2 of the periodic table, especially tetraalkyltin, alkylaluminum compounds, and alkylaluminum halide compounds. is preferable, and specific examples include diethylaluminum chloride, ethylaluminum dichloride, trioctylaluminum, dioctylaluminum iodide, and tetrabutyltin. The other solution (corresponding to solution B) is formed by dissolving these organometallic compounds as activator components in the raw material monomer.

The present invention is characterized in that the above-mentioned specific pigment is dispersed on the side of the reactive solution B. The type of pigment, the amount added, the dispersion method, and the addition method are as described above. What must be kept in mind here is that the pigment is added to the reactive solution B in order to prevent the polar compound in the pigment from causing a polymerization inhibition reaction by reaction with the activator. Contacting the pigment with such an activator may be carried out during the preparation of reactive solution B, or at any other masterbatch stage.However, in general the activator is very active. , and decomposes on contact with air, water, etc., so care should be taken when handling liquids containing it.In addition, such contact may cause the town's 1st charge and its activity to deteriorate. In some cases, the initial reaction with the activating agent occurs and the activating agent () is consumed. It will be necessary to add a curing agent.

As a special technique in such cases, first, the least expensive activator is used for the amount consumed by the reaction with the pigment, and then the activator added after the reaction is added as a reactive solution to the polymerization. A method can be used such as using the most suitable composition for the use. for example,
When a mixture of I-helioctylaluminum and dioctylaluminum iodide is used for the polymerization,
Initially, triethylaluminum, which is the cheapest material used for reaction with pigments, is used, and after the reaction, the mixture described above is added. If a pigment that requires a large initial consumption of activator is used in the process, curvature will occur.

In the present invention, as mentioned above, the activator is a pigment that can be used in the present invention, and even if it reacts with the specific pigment at the initial stage of contact, the reaction proceeds relatively quickly, and thereafter the reaction does not proceed. ,
This is based on the knowledge that it does not have any adverse effect on the subsequent storage of the reactive solution or the implementation of the polymerization reaction.
It is clear that the reaction between the activator and the pigment due to the phase η action is completed within a relatively short period of time.

In the present invention, a cross-linked composite molded product can basically be obtained by mixing the solution B with the above solution, but if the composition remains as it is, the polymerization reaction will start uncontrollably quickly. Hardening may occur before it flows sufficiently into the mold, which often poses a problem, and as mentioned above, it is preferable to use an activity regulator for this purpose.

As such regulators, Lewis bases are generally used, and among them, ethers, esters, di-lyl, etc. are used. Specific examples include ethyl benzoate, bubble ether, and diglyme. Such regulators are generally added to the solution of the organometallic compound activator component. When mono-7- having a Lewis space group is used as described above, it can also serve as a regulator.

The amount of the metathesis polymerization catalyst system to be used is, for example, when a tungsten compound is used as a catalyst component, the ratio of the tungsten compound to the raw material monomer is about i on a molar basis.
ooo to 1 to 15,000 to 1, preferably around 2,000 to 1, and when an alkyl aluminum is used as the activator component, the ratio of the aluminum compound to the raw material alone should be adjusted depending on the interaction with carbon black. about 100:1 to about 2 on a molar basis, excluding what is lost in
000:1, preferably around 200:1 to about 500:1. Furthermore, as described above, the masking agent and the regulating agent can be appropriately adjusted and used depending on the product to be used in the catalyst system through experiments.

In practical use, various additives may be added to the crosslinked polymer molded product of the present invention in order to improve or maintain its properties. Such additives include fillers, antioxidants, light stabilizers.

There are flame inhibitors, polymer modifiers, etc. As with the pigments in the present invention, it is impossible to add such additives after the crosslinked polymer is molded, so if they are added, they must be added to the raw material solution described above in advance. .

The easiest method is to use the solution A and solution B.
One method is to add it to either or both of the above in advance, but in that case, it does not react with the highly reactive catalyst component or activator component in the liquid to a practical extent, and It must not inhibit polymerization. If the reaction cannot be avoided, but coexistence does not substantially inhibit the process, it is also possible to mix it with the monomer to prepare a third liquid and use it immediately before assembly. . In addition, in the case of a solid filler, if the two components are mixed and have a shape that can sufficiently fill the voids immediately before starting the hand-kneading reaction or while doing the hand-kneading reaction, the mold specifications should be Prefilling is also possible.

Reinforcing materials or fillers as additives are effective in improving the flexural modulus, such as glass fibers, mica, wollastonite, etc. Those surface-treated with a so-called silane coupler can also be suitably used.

Further, in the present invention, an inert pigment other than the target pigment may be mixed with the catalyst component.

Further, 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[meblen (3,
Examples include 5-dibutyl-4-hydroxycinnamate)]methane.

Furthermore, other polymers, especially in the form of monomer solutions, can be added to the polymer molded article according to the present invention. As described above, addition of an elastomer as such a polymer additive is effective in increasing the impact resistance of the molded product and controlling the viscosity of the solution. A wide variety of elastomers are used for this purpose, including styrene-butadiene-styrene triblock rubber, styrene-isobrene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene-propylene-dient polymer, and nitrile rubber. elastomers can be used.

In addition, if a large amount of residual slag remains in the molded product of the present invention, a characteristic odor may be emitted. Examples of such residual monomer reducing agents include α, -α, α-trichlorotoluene, trichlorothiolate, notaric acid chloride, benzoic anhydride, and A-oxyphosphorus chloride.

Examples include pembin sulfoyl chloride.

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

As mentioned above, such a molding method involves mixing the catalyst and the raw material monomer with a simple mixer such as a static mixer, or
It is possible to adopt the resin injection method in which a premix that has been mixed in advance is flowed into the mold, and the RIM method in which the catalyst system is divided into two parts, solution A and solution B, which are collided and mixed in the head and poured directly into the mold. can. Especially R
The IM method is commonly used.

In either case, the injection pressure into the mold can be relatively low, making it possible to use inexpensive molds. Further, when the polymerization reaction inside the mold is started, the temperature inside the mold rapidly rises due to the reaction heat, and the chassis reaction ends in a short time.

Unlike polyurethane-RIMs, they are easy to release from the mold and often do not require special mold release agents.

As described in (e) above, the molded product of the present invention is colored and can be used as it is as a doped molded product without painting, but as described above, it can be painted if necessary. , Since many diagonal bonds are eliminated, an oxidized layer is formed on the surface, which results in good adhesion to commonly used paints such as poxy and polyurethane.

The molded products thus obtained are used as parts for various transportation equipment, including automobiles, and for various cash registers!・-Vehicles.

It can be used in a wide range of applications, including large molded items such as housings for electrical and electronic equipment.

The present invention will be described in detail below with reference to Examples and Comparative Examples. Note that the embodiments are provided for illustrative purposes and are not limited thereto.

Examples 1 to 10 Commercially available DCP was purified by distillation under reduced pressure in a nitrogen stream (1tdJ dicyclopentadiene was purified by distillation and had a freezing point of 33.4°C. The purity was 99% when measured by gas chromatography.
The purity was above.

Commercially available? Purity measurement using Gask [1 Madograph, using 3-purity ethylidene norbornene (ENB) as a monomer, showed 99% or more.

[Preparation of main catalyst concentrate] High purity tungsten hexachloride 19.80 (] (00,0
5 mol was added to dry toluene 907 under a nitrogen stream, and 1
A solution of 0.925q of butanol dissolved in 5 volumes of toluene was added and stirred for 1 hour, and then 11.5q of nonylphenol was added.
A solution consisting of 0.05 U (0.05 El) and 5 ml of toluene is added and stirred for 1 hour under nitrogen purge. 10(]
of acylacetone was added to the mixture, stirring was continued overnight under a nitrogen purge while purging by-product hydrogen chloride gas, and then some of the toluene distilled out was supplemented to prepare a catalyst concentrate containing 0.58 tungsten. .

[Preparation of activator'a condensate] Yigo)-ocble aluminum iodide 5.70
CI, Tory')-octylaluminum 31.
17g.

Diglyme 13.42 () was mixed under a stream of nitrogen, then DCP was added to dilute it to a total of 1007.
．． 0) 1 An aluminum-containing activator concentrate was obtained.

[[Zuma mixture] D CP 96.25wt%, E N B 3.75w
t% was mixed to obtain a monomer mixture that remained liquid at room temperature.

[Preparation of Standard Reactive Solution A] 197 g of the above monomer mixture was placed in a glass bottle with a serum cap, and after thorough purging with nitrogen, 2.96 nf of the main catalyst concentrate was injected with a syringe, and stirred well to give It? A reactive solution was prepared.

[Preparation of standard reaction solution B] Place 197 g of the above monomer mixture in a glass bottle with a ram cap, and after thoroughly purging with nitrogen, pour 4.417 g of active agent concentrate into a syringe and stir well to perform the standard reaction. A solution B was prepared.

[Preparation of carbon-reactive solution A] 197 g of the above-mentioned -tsumer mixture in a glass bottle and Table 1
5g of carbon black produced by a prescribed incomplete combustion method such as
After stirring well under nitrogen purge to disperse the carbon black well, 2.96 d of the main catalyst concentrate was injected with a syringe and stirring well to prepare carbon reaction ↑1 solution A.

[Preparation of Carbon Reactive Solution B 1 197 g of the above monomer mixture and 5 g of the specified carbon black listed in Table 1 were placed in a glass bottle and stirred well under a nitrogen purge to disperse the carbon black well. Carbon reactivity solution B was prepared by injecting 4.44 ml of the agent concentrate using a syringe and thoroughly stirring and mixing.

[Polymerization activity test] Add reactive) H solution 82d heated to 30°C with a syringe under a nitrogen stream into a test tube fitted with a serum cap and through the cap so that the detection end of the thermocouple is at the tip. , then 2r11 to the reactive solution similarly brought to 30'C.
Add 1 using a syringe in the same way, mix both solutions vigorously using a shaker, and measure the time from the start of mixing to the time when polymerization progresses and heat is generated until the internal temperature reaches 100°C as the polymerization time.

Furthermore, when the amounts of reactive solutions △ and B are increased or decreased, and the polymerization time R is shortened, the volume ratio of the reactive solution B to the reactive solution and the polymerization time are the reaction P [reactivity evaluation value of the combination of solutions] Use as. In this case, based on the volume ratio and polymerization time of standard reactive solutions A and B, both of which do not contain carbon, the combination of standard solution A and carbon solution B, and the combination of solutions A and B both containing carbon. By measuring and comparing the volume ratio and polymerization time in each case, we decided to evaluate the polymerizability of dispersing carbon.

The effect of changes over time can be observed by observing the reactivity immediately after preparation and after leaving the reactive solution. Even in the case of a standard reactive solution that does not contain carbon, the polymerization reactivity may decrease or deteriorate in a small volume experiment using a bottle like this experiment, so this combination of standard solutions should only be used as a control. , is it worse than that?
The influence of carbon black was evaluated based on whether there was any change.

It has been found that when used for RIM purposes, etc., it can be used without any problem if the polymerization time is 70 seconds or less.

In addition, in this example, 2.5% carbon black was added to the reactive solution of -, 7-1, which is the most commonly used for coloring, and the amount added is enough to support original application without painting as is. 1710 is enough to be used as a paint base, etc., and it is a severe test to see the influence of carbon black.

The test results are summarized in Table 2.

In either case, the reaction solution B with carbon black dispersed in it showed almost the same polymerization time as the case using the standard reaction solutions A and B without carbon. It can be seen that in both the cases where carbon black was added to the reaction solution and the case where carbon was added to both reaction solutions A and B, the polymerization time became longer with time and the deterioration became more severe.

In addition, regarding the volume ratio of the reaction solution that gives the shortest polymerization time, in all cases, compared to the case of the combination of standard solutions A and B,
In the combination of carbon-containing liquid B and standard solution A, the amount of carbon-containing liquid B used is larger, or this is because part of the activator reacts to inhibit the polymerization of carbon black and inactivate it. - Once the reaction is completed, the activator is consumed by the reaction with carbon black. It shows that there are not many.

Furthermore, this rate of increase differs depending on the type of carbon, and carbon black with a large surface area, large volatile content, and low pH, such as the carbon black in Example 3, has a large volume ratio, and the polymerization inhibiting effect is correspondingly large. This indicates that a large amount of activating agent is required for the inactivation of .

The cross-linked polymer moldings obtained in a test tube for such polymerization tests using the combination of carbon-containing reactive solution B and standard solution A were uniformly colored black;
Also, like the one obtained by combining R quasi-solutions A and B, it was very durable and had little odor.

Examples 11-25 D prepared in the same manner as used in Examples 1-10
CP and ENB were also used in Examples 11-25.

The main catalyst concentrate, the active agent concentrate, the monomer mixture, the standard reactive solution, and the standard reactive solution B were also prepared in the same manner as in Examples 1 to 10 and used.

[Preparation of titanium oxide human-reactive solution A] 197 g of the above T-summer mixture and 2 g of the specified titanium oxide as shown in Table 3 were placed in a glass bottle and stirred well under nitrogen purge to disperse the titanium oxide well. Thereafter, 2.96 d of the main catalyst/concentrate solution was injected with a syringe and stirred thoroughly to prepare a titanium oxide reactive solution A.

[Titanium oxide reactive solution B made by η] 197 g of the above monomer mixture and 2 g of the specified titanium oxide listed in Table 3 were placed in a glass bottle and stirred well under nitrogen purge to disperse the titanium oxide well. 4.44 d of the active inhibitor concentrate was injected with a syringe, and the mixture was thoroughly stirred and mixed to prepare a titanium oxide human-reactive solution B.

[Polymerization activity test] A reactive solution 82d heated to 30°C was placed in a test tube with a syringe at 30°C under a nitrogen stream into a test tube fitted with a Zelum cap and the detection end of the thermocouple was placed at the tip of the test tube through the cap. Then, the reactive solution A2rnl, which had been heated to 30°C, was added using a syringe and stirred vigorously. Both solutions were mixed using a shaker, and from the start of mixing, polymerization progressed and generated heat, and the internal temperature reached 10°C.
The time until the temperature reaches 0°C is measured as the polymerization time. Furthermore, the amount of reactive solutions A and B added is increased or decreased, and the volume ratio of reactive solution B and reactive solution A and the polymerization time are used as the reactivity evaluation value of the combination of reactive solutions when the polymerization time becomes the shortest. do. In this case, based on the volume ratio and polymerization time of standard reactive solutions A and B, both of which do not contain titanium oxide, the combination of standard solution A and titanium oxide solution B, and solutions A and B both containing titanium oxide. By measuring and comparing the volume ratio and polymerization time in the case of the combination, we decided to evaluate the polymerizability of dispersing titanium oxide.

That is, the influence of changes over time can be observed by observing the reactivity of a reactive solution immediately after preparation and after it has been left to stand. Even in the case of a standard reactive solution that does not contain titanium oxide, the polymerization reactivity may be low and deteriorate when conducting a small volume experiment using a bottle like this experiment, so it is important to control the combination of this standard solution. The effect of titanium oxide was evaluated based on whether it was worse or the same as that.

Table Tested titanium oxide - List In this example, the addition m of titanium oxide was
1% in each reactive solution, which is generally
When titanium oxide is added to plastic for s-color use, it is generally said that the amount of titanium oxide is about 0.5 PHR to the resin, and the concentration is set accordingly.

The test results are summarized in Table 4.

In any case, when the reaction solution A is a standard solution and titanium oxide is dispersed on the side of the reaction solution B, the combination is almost the same as when standard reaction solutions A and B without titanium oxide are used. whereas it shows no polymerization time.
In both cases, the combination of titanium oxide added to reaction solution A and standard solution B, and the combination of titanium oxide added to both reaction solutions A and B, the polymerization time becomes longer over time and deterioration becomes more severe. I can see that it is.

In addition, the volume ratio of the reaction solution that gives the shortest polymerization time is, in all cases, compared to the case of the combination of standard solutions A and B.
In the combination of titanium oxide solution B and standard solution A, the amount of titanium oxide solution B used is not too small, but if it is large, part of the activator will not inhibit the polymerization of titanium oxide. This is because it was lost in the reaction due to activation, −
The increased ratio is stable for oral administration, indicating that once the reaction is completed, the activator is not consumed much in the reaction with titanium oxide.

Furthermore, this rate of increase differs depending on the type of titanium oxide, suggesting that the consumption amount of the activator varies depending on the type of titanium oxide, that is, the crystal form, 9 surface area, 1 surface treatment, etc. In either case, it is shown that by using an appropriate amount of activator, a reactive solution having stable polymerization reactivity can be obtained.

The crosslinked polymer molded product obtained by such polymerization test is
The product obtained by combining titanium oxide-containing reactive solution B and standard solution B has a slightly yellowish brown color, but is uniformly colored white and is d3, and the product obtained by combining standard solutions A and B. It was as durable as anything else.

Examples 26-27 DCP and EN prepared in the same manner as Examples 1-10
B was also used in Examples 26-27.

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 to 10.

[Preparation of titanium black human-reactive solution A] Put 197 g of the above monomer mixture and 2 g each of titanium black 13R and 105 manufactured by Mitsubishi Metals Co., Ltd. into a glass bottle, stir well under nitrogen purge, and disperse titanium black well. After cooling, 2.96 d of the main catalyst concentrate was injected with a syringe and stirred well to prepare two kinds of titanium black reactive solutions A.

[Preparation of titanium black human-reactive solution B] Put 197 g of the above-E-Tsumer mixture and 2 g of each of the same two types of titanium black as above into a glass bottle, stir well under nitrogen purge, and disperse the titanium black well. After cooling, 4.44 m of active inhibitor concentrate was injected with a syringe, and the mixture was thoroughly stirred and mixed to prepare two kinds of titanium black human-reactive solutions B.

[Polymerization activity test] Reactive solution B2InI was heated to 30°C with a syringe under a nitrogen stream into a test tube equipped with a serum cap and passed through the cap so that the detection end of the thermocouple was at the tip.
! and then the reactive solution A2r, which was also heated to 30°C.
Similarly, add nl using a syringe, mix the two solutions vigorously using a shaker, and measure the time from the start of mixing until the mixture progresses, generates heat, and reaches an internal temperature of 100'C as the polymerization time. The volume ratio of reactive solution B and reactive solution A and the polymerization time when the added amounts of reactive solutions A and B are roughly increased or decreased and the polymerization time R is shortened, and the reactivity evaluation value of the combination of reactive solutions Use as. In this case, based on the volume ratio and preparation time of standard reactive solutions A and B, both of which do not contain titanium black, standard solution A and titanium black solution B are roughly combined, and solutions A and B, both of which contain titanium black, are combined. It was decided to evaluate the polymerizability of dispersing titanium black by measuring and comparing the volume ratio and handling time for combination B.

That is, the influence of changes over time can be observed by observing the reactivity of the reactive solution immediately after preparation and after it has been left to stand. Even in the case of a standard reactive solution without titanium black, in the case of a small four-liquid experiment using a bottle like this experiment, the polymerization reactivity may be low and deteriorate, so it is important to control the combination of this standard solution. The effect of titanium black was evaluated based on whether it was worse or the same as that.

The test results are summarized in Table 5.

In either case, the combination U is obtained by using reaction solution A as a standard solution and dispersing titanium black on the side of reaction solution B.
In the case of standard reaction solutions A and B without titanium black
The polymerization time and the volume ratio of the reaction solution are almost the same as those obtained when titanium black is added to the reaction solution A, and the combination of the standard solution B and the reaction solution A and B. It can be seen that in both cases, the polymerization time becomes longer over time in the case where titanium black is added to both, compared to the case where titanium black is added to reaction solution B, indicating that the polymerization reactivity decreases significantly.

In general, it is preferable that the polymerization time is about 70 seconds or less, and from this point of view, even if the disadvantageous condition of putting it in a small bottle is taken into account, when titanium black is added to solution B, it is not possible to put it in. This shows that the liquid can be used for the same lifespan as , that is, one month.

In addition, regarding the volume ratio of the reaction solution that gives the shortest polymerization time, in any case, compared to the case of the combination U of standard solutions A and B,
Titanium Black Solution B This is because the activator is lost in the reaction due to activation, and the increased proportion is stable for oral administration. This seems to indicate that it is not often consumed.

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

The crosslinked polymer molded product obtained by such combination test is
It was uniformly colored black and was as durable as that obtained by combining standard solutions A and B.

Examples 28-30 DCP and DN prepared in the same manner as Examples 1-10
B was also used in Examples 28 to 3.0.

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

[Preparation of iron oxide human-reactive solution A] 197 g of the above monomer mixture in a glass bottle and Table 6
2. Add 2g of the specified iron oxide, stir well under nitrogen purge, and mix well to disperse the iron oxide.2.
Iron oxide reactive solution A was prepared by injecting 96d into a syringe and stirring well.

[Preparation of Iron Oxide Reactive Solution B] Put 2 g of the same iron oxide as 197 g of the above monomer mixture into a glass bottle, stir well under nitrogen purge to disperse the iron oxide well, and prepare 4.44 g of the activated inhibitor concentrate. - was injected with a syringe and stirred and mixed well to prepare iron oxide reactive solution B.

[Polymerization activity test] Into a test tube fitted with a serum cap and passed through a cap so that the detection end of the thermocouple is at the tip, 82 ml of the reactive solution heated to 30°C was poured with a syringe under a nitrogen stream, and then Similarly, reactive solution A2d heated to 30°C was added using a syringe, and both liquids were mixed vigorously. From the beginning of mixing, polymerization progressed and heat was generated, and the internal temperature reached 100°C.
The time required for this to occur is measured as the polymerization time. Furthermore, the reactivity evaluation value of the volume ratio of reactive solution B and reactive solution A and the polymerization time of the combination μ of reactive solutions when the addition amount of reactive solutions A and B is increased or decreased and the polymerization time R is shortened. Use as. In this case, based on the volume ratio and polymerization time of standard reactive solutions A and 8, both of which do not contain iron oxide,
,! : Evaluate the polymerizability of dispersing iron oxide by measuring and comparing the volume ratio and polymerization time of the combination with iron oxide solution B and the combination of solutions A and B both containing iron oxide. It was to be.

That is, the influence of changes over time can be observed by observing the reactivity of a reactive solution immediately after preparation and after it has been left to stand. Even with standard reactive solutions that do not contain iron oxide, polymerization reactivity may be low and deteriorate in experiments with small volumes of liquids using bottles, such as in this experiment, so it is important to control the combination of these standard solutions. The effect of iron oxide was evaluated based on whether it was worse or the same as that.

The test results are summarized in Table 6.

In the case of a combination in which reaction solution A is a standard solution and iron oxide is dispersed on the side of reaction solution B, the polymerization time 2 reaction solution is almost the same as when using standard reaction solutions A and B that do not contain iron oxide. On the other hand, the combination of iron oxide added to the reaction solution and standard solution B, and the combination of iron oxide added to both reaction solutions A and B are oral 4 It can be seen that the polymerization time became longer and the deterioration became more severe.

The crosslinked polymer molded product obtained by such polymerization test is
The product obtained with combination U of iron oxide-containing reactive solution B and standard solution B was uniformly colored and as durable as that obtained by combining standard solutions A and B.

Examples 31-32 DCP and EN prepared in the same manner as Examples 1-10
B was also used in Examples 31-32.

Main catalyst concentrate, activator concentrate, monomer mixture, standard reactive solution A and standard reactive solution B=b Examples 1-1
A sample prepared in the same manner as 0 was used.

[Preparation of F cobalt oxide-based pigment human-reactive solution A] Put 197 g of the above monomer mixture and 2 g each of the prescribed cobalt oxide-based pigments shown in Table 7 into a glass bottle,
After thorough stirring under nitrogen purge to disperse the cobalt oxide-based pigment well, 2.96 d of the main catalyst concentrate was injected with a syringe and stirred thoroughly to prepare two kinds of cobalt oxide-based pigment human-reactive solutions.

[Preparation of cobalt oxide-based pigment human-reactive solution B] 197 g of the above monomer mixture and 2 g of each of the same two cobalt oxide-based pigments as above were placed in a glass bottle and stirred well under a nitrogen purge, and the oxidized "balt base" was added. After the pigment was well dispersed, 4.44 d of the activated inhibitor concentrate was injected with a syringe, and the mixture was thoroughly stirred and mixed to prepare two kinds of cobalt oxide-based pigment type reactive solutions B.

[Polymerization activity test] Reactive solution B27 was heated to 30°C with a syringe under a nitrogen stream in a test tube equipped with a serum kill tube and passed through the kill tube so that the detection end of a thermocouple was at the tip. and then the reactive solution A2IIJl, which was also heated to 30°C.
was added with a syringe in the same way, and both solutions were mixed vigorously using a shaker. From the beginning of mixing, polymerization progressed and generated heat, and the internal temperature reached 1.
The time until the temperature reaches 00°C is measured as the polymerization time. Reactivity evaluation of the combination of reactive solutions between the volume ratio of reactive solution B and reactive solution A and Φ14 when the addition amount of reactive solutions A and B is roughly increased or decreased, and the polymerization time is the shortest. Use as value. In this case, based on the volume ratio and polymerization time of standard reactive solutions A and B, both containing no cobalt oxide-based pigment, the combination of standard solution A and cobalt oxide-based pigmented solution B, both containing cobalt oxide-based pigment By measuring and comparing the volume ratio and polymerization time for the combination of solutions A and B, we decided to evaluate the polymerizability of dispersing the cobalt oxide-based pigment.

That is, the influence of changes over time can be observed by observing the reactivity of a reactive solution immediately after preparation and after it has been left to stand. Even in the case of a standard reactivity solution that does not contain cobalt oxide-based pigments, in the case of a small mother liquor experiment using a bottle like this experiment, the polymerization reactivity may be low and deteriorate, so this combination of standard jtl liquids is recommended. was used as a control, and the effect of the cobalt oxide-based pigment was evaluated based on whether it was worse or remained the same.

The test results are summarized in Table 7.

Table 7 shows that when cobalt oxide is added to solution A containing the main catalyst component, the polymerization time becomes longer due to changes over time, but when cobalt oxide is added to solution B, solutions A and B are oxidized. This shows that the polymerization time is extended due to changes over time to the same extent as in the case where no cobalt is added. In other words, the polymerization time becomes longer depending on the storage time, but when cobalt oxide is added to solution A, the polymerization time becomes longer to a greater extent than when it is added to solution B. This is because cobalt oxide gradually reacts with catalyst components and reduces catalyst activity. This result shows that cobalt oxide should be added to the monomer solution containing the activator component rather than to the monomer solution containing the catalyst component. In general, cobalt oxide is
Although it reacts with the activator component, the reaction stops immediately,
It can be seen that by adding an amount of activator corresponding to the consumed activator component, a monomer liquid containing an activator component having high activity can be obtained.

The combination of solution A not containing cobalt oxide and solution B containing cobalt oxide can be used in the RIM method because the polymerization time is about 50 seconds even after about one month. The metathesis polymer obtained from the combination of Examples 31 and 32 has a beautiful color. In particular, the color is more vivid than that of the polymer molded product obtained by the combination of cobalt oxide solution A and solution B that does not contain cobalt oxide. The combination of cobalt oxide-free solution A and cobalt oxide-containing solution B gives the polymer molded product such a beautiful color that surface painting is unnecessary.

Example 33 DCP and EN prepared in a similar manner to Examples 1-10
B was also used in this Example 33.

Main catalyst concentrate, activator concentrate, monomer mixture, standard reactive solution and standard reactive solution B also Examples 1 to 10
I used Shino, which was adjusted in the same way.

[Preparation of a blue-based pigment human-reactive solution] Put 19'i'g of the above monomer mixture and 2g of Blue #A (ulmarine blue) manufactured by Dainichiseika into a glass bottle, and stir well under nitrogen purge. , After the ultramarine was well dispersed, the main catalyst concentrate 2.9
Ultramarine type reactive solution A was prepared by injecting f17 with a syringe and stirring well.

[Preparation of ultramarine blue-based pigment human-reactive solution B] Add 197 g of the above monomer mixture and 2 g of the same 1Y blue into a glass bottle and stir well under nitrogen purge to disperse the ultramarine blue well. Inject 441dl with a syringe,
The mixture was thoroughly stirred and mixed to prepare ultramarine-type reactive solution B.

[Hand activation test] Salem Kii? Reactive solution B 2l 1l was heated to 30°C with a syringe under a nitrogen stream into a test tube fitted with a knob and passed through a cap so that the detection end of the thermocouple was at the tip.
I! and then reactive solution A, which was also made to 30'Q.
2d was similarly added using a syringe, the two solutions were mixed vigorously using a shaker, and the polymerization time was measured as the time from the start of mixing to the time when polymerization progressed to generate heat and the internal temperature reached 100°C. Furthermore, the reactivity evaluation value and the amount of B added are increased or decreased, and the volume ratio of reactive solution B and 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 reactive solutions. do. In this case, based on the volume ratio and polymerization time of standard reactive solutions A and B, both of which do not contain ultramarine, the combination of standard solution A and solution B containing ultramarine, and the combination of solutions A and B, both of which contain ultramarine. We decided to evaluate the polymerizability of dispersing ultramarine blue by measuring and comparing the volume ratio and polymerization time.

That is, the influence of changes over time can be observed by observing the reactivity of the reactive solution immediately after preparation and after it has been left to stand. Even in the case of a standard reactive solution that does not contain ultramarine, polymerization reactivity may be low and deteriorate when conducting a small volume experiment using a bottle like this experiment, so this combination of standard solutions should only be used as a control. , the influence of ultramarine was evaluated based on whether it was worse or the same as that.

The test results are summarized in Table 8.

In the case of the -5 combination in which reaction solution A is a standard solution and ultramarine is dispersed on the side of reaction solution B, the polymerization n5 difference is almost the same as when standard reaction solutions A and B without ultramarine are used. While the volume ratio of the reaction solution is shown, the combination of ultramarine blue added to reaction solution A and standard solution B, and the combination of ultramarine blue added to both reaction solutions A and B, change over time in both cases. It can be seen that the polymerization time is longer and the deterioration is more severe.

The crosslinked polymer molded product obtained by such polymerization test is
The combination of ultramarine-containing reactive solution B and standard solution B is uniformly colored blue, and standard solution A,
It was as durable as the one obtained by combining B.

Claims (8)

[Claims] (1) Mix 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 incomplete combustion of hydrocarbons; (b) pigment based on titanium oxide; c) At least one pigment selected from the group consisting of a pigment based on iron oxide, (d) a pigment based on cobalt oxide, and (e) a pigment based on ultramarine blue is dispersed in the solution B. A method for producing a colored polymer molded article, characterized by: (2) (a) Carbon black obtained by incomplete combustion of hydrocarbons, (b) Pigment based on titanium oxide, (c) Pigment based on iron oxide, (d) Cobalt oxide and (e) at least one pigment selected from the group consisting of pigments based on ultramarine blue is dispersed in a proportion of 0.05 to 20% by weight based on the weight of the colored polymer molded product. The manufacturing method according to claim 1. (3) (a) The carbon black obtained by the incomplete combustion method of hydrocarbons is a type selected from the group consisting of oil furnace carbon black and lamp black, and (b) the pigment based on titanium oxide is titanium dioxide,
Nitrogen-doped titanium oxide and titanium yellow (TiO_2-
NiO-Sb_2O_3); (c) the pigment based on iron oxide is a type selected from the group consisting of iron black, red iron oxide, and orca; (d) the pigment is based on cobalt oxide. 2. The method according to claim 1, wherein the 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) A reactive solution of a metathesis polymerizable monomer containing a catalyst component of a metathesis polymerization catalyst system (solution A) and (b) a reactive solution of a metathesis polymerizable monomer containing an activator component of a metathesis polymerization catalyst system. (a) Carbon black obtained by incomplete combustion of hydrocarbons. (b) a pigment based on titanium oxide; (c) a pigment based on iron oxide; (d) a pigment based on cobalt oxide; and (e) a pigment based on ultramarine blue. A combination of reactive solutions for producing colored polymer molded articles, characterized in that one type of pigment is dispersed in the solution B. (6) (a) Carbon black obtained by incomplete combustion of hydrocarbons, (b) Pigments based on titanium oxide, pigments based on iron oxide, (d) Cobalt oxide as a base. Claim 5: At least one pigment selected from the group consisting of pigments and (e) ultramarine-based pigments is dispersed in a proportion of 0.05 to 20% by weight based on the total weight of the combination of reactive solutions. Combination of reactive solutions as described. (7) (a) The carbon black obtained by the incomplete combustion method of hydrocarbons is a type selected from the group consisting of oil furnace carbon black and lamp black, and (b) the pigment based on titanium oxide is titanium dioxide,
Nitrogen-doped titanium oxide and titanium yellow (TiO_2-
NiO-Sb_2O_3); (c) the pigment based on iron oxide is a type selected from the group consisting of iron black, red iron oxide, and orca; (d) the pigment is based on cobalt oxide. 6. A reactive solution combination according to claim 5, wherein the pigment is cobalt blue. (8) The reactive solution combination of claim 5, wherein the at least one metathesis-polymerizable monomer comprises dicyclopentadiene or a mixture of dicyclopentadiene and another metathesis-polymerizable monomer.