KR20000023539A - Method and apparatus of reactive polymerization formation - Google Patents

Abstract

PURPOSE: A molding method of reactivity polymerization and a molding device are provided to obtain a mold not to cause a greasy on a surface regardless of a season. CONSTITUTION: A molding device(20) has a single metal mold(22). The metal mold is formed a cavity to mold a molding body such as a upper tub or a lower tub of a purifying tub. And the device(20) has at least two tanks of a reactive undiluted solution(30,32). Each tank(30,32) is equipped with each sensor, inner temperature of each tank is sent to a control device, and the inner temperature of each tank is controlled according to the temperature data. To control the temperature of solution stored in each tank(30,32), a jacket for exchanging heat is installed in each tank(30,32). The inner temperature of each tank(30,32) is controlled to a regular temperature in the range of 15-25°C by controlling the temperature or the flow of a solution medium introduced in the jacket which heat exchanging with the control device.

Description

Reactive polymerization molding method and molding apparatus {Method and apparatus of reactive polymerization formation}

The present invention relates to a reactive polymerization molding method and a molding apparatus, and more particularly, to a reactive polymerization molding method and a molding apparatus capable of obtaining a molded article that does not cause stickiness on the surface regardless of the season.

In the present specification, the reactive polymerization molding method broadly means a method of reacting and polymerizing a reaction stock solution in a mold, and is a reaction injection molding (RIM) method as a form of the reactive polymerization molding method. This RIM method is a manufacturing method in which two or more reaction stock solutions are mixed in a mixing chamber, injected into a cavity of a mold apparatus, and injection molding while reacting in the mold apparatus. This RIM method is suitably used for molding a polymer (molded product) from a norbornene-based monomer.

In such RIM molding, it has long been a problem that the surface of the molded body is sticky in summer. Since the temperature is high in the summer, the temperature of the reaction stock solution when it is injected into the mold increases, and as a result, the activity of the reaction in the mold increases, so that the molding becomes difficult to control. It was compelled to lower the reaction activity by changing the chemical composition.

However, in such a conventional method, stickiness occurs on the surface of the molded body in summer, and this problem cannot be solved for a long time.

The present invention has been made in view of such a situation, and an object of the present invention is to provide a reactive polymerization molding method and a molding apparatus that can obtain a molded article having no stickiness or the like on the surface regardless of the season.

The present inventors have diligently studied the reactive polymerization molding method and the molding apparatus which can obtain a molded article which does not have stickiness on the surface, especially in summer, and as a result, at least immediately before supplying the reaction stock solution to the inside of the mold, By controlling, it has been found that a molded article having no stickiness or the like on the surface can be obtained, and the present invention has been completed based on this new aspect.

That is, the reactive polymerization molding method according to the present invention is a reactive polymerization molding method in which two or more reaction stock solutions are supplied into a mold, and the reaction stock solution is reacted and polymerized in the mold, at least immediately before the reaction stock solution is supplied into the mold. The temperature of the reaction stock solution is controlled.

The molding apparatus according to the present invention includes at least one mold, at least two reaction stock solution supplying means for supplying a reaction stock solution to the mold, and immediately before the reaction stock solution is supplied from the reaction stock supply means to the inside of the mold. It has a temperature control means for controlling the temperature of the stock solution.

In the present invention, the method for controlling the temperature of the reaction stock solution at least immediately before the reaction stock solution is supplied into the mold is not particularly limited. Temperature control of the pipe from the tank to the mixing means (or mold), ③ A method of controlling the internal temperature of the mixing means for mixing and supplying two or more reaction stock solutions into the mold, ④ The temperature of the mold itself is controlled by warm air, etc. The method of temperature control, the method of temperature control combining these, etc. are illustrated. Among these, the method of controlling the temperature of (1) tank itself is preferable, and the method of temperature control combining the method of (1) and (2) is especially preferable.

That is, the temperature of the tank of the reaction stock solution is controlled by a heat exchange jacket or the like, and the return pipe of the tank is connected to the middle of the pipe from the tank of the reaction stock solution to the mixing means of the mold (preferably near the mixing means). It is preferable to install a heat exchanger in the middle of the pipe, and to control the temperature of the reaction stock solution in the pipe at a constant temperature at all times by the heat exchanger before injection into the mixing means. In addition, the piping from the tank to the mixing means of the mold and the return piping are preferably pipes wound around the temperature control pipes through which the temperature control water flows, or pipes having high heat insulation (heat insulation).

At least immediately before the reaction stock solution is supplied into the mold, the temperature of the reaction stock solution whose temperature is controlled is preferably 10 to 30 ° C., more preferably 15 to 25 ° C., regardless of seasons such as summer and winter. It is preferable that it is constant temperature within a range. In addition, the control temperature of less than +/- 3 degreeC, preferably +/- 2 degreeC of fixed temperature shall be included in fixed temperature control.

Although it does not specifically limit as a means for controlling temperature, For example, what is necessary is just to attach a temperature sensor to the site | part which should control temperature, and to feedback control so that temperature may become constant in the said site | part. The heat exchange means for controlling the temperature is not particularly limited, but cooling elements such as heat exchange jackets (both heating and endotherm) circulating the heat medium, heat transfer heaters (heating only), planar heating elements (heating only), and Peltier elements ( Means such as cooling only), warm air (heating only), cold air (cooling only), or a combination thereof. Among these, Preferably it is an outer jacket, a heat exchanger, Especially preferably, they are a combination.

In the molding apparatus according to the present invention, the reaction stock solution supply means is not particularly limited, but includes a casting tank for storing the reaction stock solution, a piping system from the tank to the mold, a valve, a pump, and the like. It is preferable that each mold is equipped with mixing means for mixing the reaction stock solution before injection into the cavity of the mold. Although it does not specifically limit as a mixing means, A mixing head (also called a mixing chamber) etc. can be illustrated.

Moreover, as a temperature control means, the control apparatus etc. which control the quantity of heat which heat or endotherm by a heat exchange means can be illustrated. The control device may have a built-in or connected microcomputer or personal computer. The control device may be input with an output signal of a temperature sensor for detecting the temperature of the reaction stock solution immediately before being supplied into the cavity of the mold, or may control the temperature of the reaction stock solution immediately before being supplied to the mold in accordance with the output signal.

In the present invention, the term "reactive polymerization molding" broadly means a method of reacting and polymerizing a reaction stock solution inside a mold, and is a reaction injection molding (RIM) method as one form of a reactive polymerization molding method.

Reaction stock solution

Although it does not specifically limit as a reaction stock solution, Although urethane type, urea type, nylon type, epoxy type, unsaturated polyester type, phenol type, norbornene system, etc. are mentioned, norbornene system is especially preferable. The viscosity of the reaction stock solution before injection into the mold is, for example, 5 cps to 3000 cps, preferably about 100 cps to 1000 cps at 30 ° C.

In such molding, a reinforcing material is provided in a mold in advance, and a reinforcing polymer (molded product) can be produced by supplying and polymerizing the reaction stock solution therein.

Examples of the reinforcing material include glass fiber, aramid fiber, carbon fiber, ultra high molecular weight polyethylene fiber, metal fiber, polypropylene fiber, aluminum coated glass fiber, cotton, acrylic fiber, boron fiber, silicon carbide fiber, alumina fiber and the like. Can be. These reinforcing materials can be used in various shapes, such as those in which a fibrous or chopped strand is matified, a woven in a cloth, or a chopped shape. These reinforcing materials are those obtained by treating the surface with a coupling agent such as a silane coupling agent. However, these reinforcing materials are preferable for improving the adhesion to the resin. Although the compounding quantity of a reinforcing material does not have a restriction | limiting in particular, Usually, 10 weight% or more, Preferably it is 20-60 weight% per weight of a molded object.

Moreover, the characteristic of the polymer obtained by mix | blending various additives, such as antioxidant, a filler, a pigment, a coloring agent, a foaming agent, a flame retardant, a sliding imparting agent, an elastomer, a dicyclopentadiene type thermal polymerization resin, and its water additive, can be modified.

Antioxidants include antioxidants for various plastics and rubbers such as phenolic, phosphorus and amine based. Fillers include inorganic fillers such as milled glass, carbon black, talc, calcium carbonate, aluminum hydroxide, mica and the like. Elastomers include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), ethylene-propylene-diene -Terpolymer (EPDM), ethylene vinyl acetate copolymer (EVA), and hydrides thereof.

The additive is usually mixed in one side or both sides of the reaction stock solution beforehand. It is preferable to store in the inert gas in a metal mold | die and to use for the polymerization reaction, and to store and operate in inert gas atmosphere, such as nitrogen gas. The mold pressure is usually in the range of 0 to 100 kg / cm 2. The polymerization time may be appropriately selected, but is usually 30 seconds to 20 minutes after the completion of the injection of the reaction stock solution.

The activity regulator of the reaction stock solution that can be used in the present invention is determined depending on the type of the reaction stock solution, and is not particularly limited, but in the case of using a norbornene system as the reaction stock solution, for example, Japanese Patent Application Laid-Open No. 3-146516, It is a regulator disclosed in Unexamined-Japanese-Patent No. 4-337318. Japanese Patent Application Laid-Open No. 3-146516 discloses 5-vinylbicyclo [2.2.1] hepto-2-ene (vinylnorbornene), 5-isopropenylbicyclo [2.2.1] hepto-2-ene as a reaction regulator. A process for producing a norbornene-based polymer using 5-alkenyl-2-norbornene such as is disclosed. Japanese Patent Laid-Open No. 4-337318 discloses 5-ethynyl-2-norbornene as an activity regulator. The use of 5-alkenyl-2-norbornenes is disclosed.

Moreover, as an activity regulator, the compound etc. which have the effect | action which reduces the metathesis catalyst which are the main catalysts of the reaction stock liquid containing a norbornene-type monomer as a main component can also be used, In this case, as an activity regulator, alcohol, halo alcohol, ester , Ethers, nitriles and the like are exemplified. Among these, for example, specific examples of alcohols include n-propanol, n-butanol, n-hexanol, 2-butanol, isobutyl alcohol, isopropyl alcohol, t-butyl alcohol, and the like. Specific examples include 1,3-dichloro-2-propanol, 2-chloroethanol, 1-chlorobutanol, and the like.

In addition, in this invention, as a reaction activity control agent, it is not limited to reducing reaction activity as mentioned above, The main catalyst which can raise reaction activity, cocatalyst itself, etc. may be sufficient.

The supply amount of such a reaction activity regulator is determined depending on the size and shape of the cavity of the mold. In the case where the norbornene system is used as the reaction stock solution, the time from the start of the injection of the reaction stock solution into the cavity of the mold until the reaction proceeds rapidly, and a little white smoke is generated from the surface of the production resin (t '; SMT), The filling time t from the start of injection to the completion of filling is preferably determined according to the size of the molded body. The SMT time t 'is necessarily larger than the charging time t, preferably 10 to 300 seconds, and the charging time t at that time is preferably about 1 to 50 seconds. The SMT time t 'is more preferably 20 to 200 seconds, and the charging time t at that time is more preferably about 15 to 35 seconds. Although t '/ t also depends on temperature, Preferably it is about 1.5-20.

mold

The material of the metal mold | die used in this invention is not specifically limited, It is not limited to metals, such as cast iron, iron, stainless steel, aluminum, and nickel electroplating, It may be synthetic resin or other materials. Reaction injection molding as a form of reactive polymerization molding can be molded at a relatively low pressure, and it is not necessary to use a high rigid mold. In the present invention, even when molding a relatively large molded article, such as a septic tank, etc., it is not necessary to use a high rigid mold, so that the manufacture of the mold is relatively easy.

As the mold, a rotatable mold may be used. In such a case, the reaction stock solution may be placed in the mold, and then the structure may be applied to accelerate the reaction stock solution inside the mold.

[Action]

In the method and apparatus according to the present invention, the temperature of the reaction stock solution is controlled at least immediately before the reaction stock solution is supplied into the mold. For this reason, the temperature of the reaction stock solution immediately before being supplied into the mold can be made constant regardless of the season. As a result, the stickiness of the surface of the molded body, which occurs especially in the summer and whose improvement has been demanded for a long time, has been improved.

Moreover, the method and apparatus which concerns on this invention can be used suitably also for multi metal mold shaping | molding.

1 is a schematic configuration diagram of a molding apparatus according to an embodiment of the present invention.

FIG. 2 is a perspective view of a boot tank assembly showing an example of a molded body obtained by the molding apparatus shown in FIG.

3 is a schematic configuration diagram of a molding apparatus (multi-die molding apparatus) according to another embodiment of the present invention.

<Description of Symbols for Major Parts of Drawings>

6. Body 37, 39. First control valve

7. Premise 41, 43, 49, 51. Return piping

8 … Flanges 42, 44, 46... Pump

9. Hazo 45, 47... 2nd control valve

20, 20a... Molding apparatus 48, 50, 56, 58, 64, 66... Branch piping

22, 24... Molds 52, 54, 60, 62, 68, 70... Control valve

26, 28... Mixing head 53, 55. heat transmitter

30, 32... Reaction stock tanks 31, 33, 35, 72, 74... temperature Senser

34. Reaction activity regulator tank 80... Controller

36, 38, 40... Main relationship

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated according to embodiment shown in drawing.

1 is a schematic configuration diagram of a molding apparatus according to an embodiment of the present invention, FIG. 2 is a perspective view of a septic tank assembly showing an example of a molded body obtained by the molding apparatus shown in FIG. 1, and FIG. 3 is another embodiment of the present invention. It is a schematic block diagram of the shaping | molding apparatus (multi-die shaping | molding apparatus) which concerns on a form.

(First embodiment)

The molding apparatus 20 shown in FIG. 1 performs reaction injection molding using the method of the present invention, and forms the upper tank 7 or the lower tank 9 of the tank 6 of the septic tank as shown in FIG. It is an apparatus for doing so.

First, the septic tank 6 will be described with reference to FIG. The tank 6 of the septic tank which concerns on this embodiment has the upper tank 7 and the lower tank 9. The upper tank 7 and the lower tank 9 are joined by flanges 8 and 8.

An inlet 10 and a discharge port 11 are formed in the upper tank 7, and the sewage flowing in from the inlet 10 is formed in an anaerobic treatment chamber (or a tank; the same below) formed by a plurality of partition plates in the septic tank, It is processed in process chambers, such as an aerobic process chamber, a precipitation chamber, and a disinfection chamber, and is discharged | emitted from the discharge port 11.

Moreover, three manholes 15a, 15b, and 15c are formed in the upper part of the upper tank 7 along the longitudinal direction of the tank.

In the present embodiment, the upper tank 7 or the lower bath 9 of the septic tank is composed of polynorbornene-based resin obtained by reaction injection molding (RIM), and particularly obtained by reaction injection molding of norbornene-based monomers modified with an elastomer. It is preferable that it consists of a ring-opening polymer.

Next, with reference to FIG. 1, the reactive polymerization molding apparatus which concerns on this embodiment is demonstrated.

The molding apparatus 20 according to the present embodiment has a single mold 22. In this mold 22, for example, a cavity for forming a molded article such as the upper tank 7 or the lower tank 9 of the septic tank 6 shown in Fig. 2 is formed. The mold 22 is equipped with a mixing head 26 as a mixing means. A piping system is connected to the mixing head 26 from the first reaction stock solution tank 30 and the second reaction stock solution tank 32.

The apparatus 20 which concerns on this embodiment has at least two reaction stock solution tanks 30 and 32, The reaction stock solution A liquid mentioned later is stored in one 1st reaction stock solution tank 30, and the other agent 2 The reaction stock solution tank 32 stores the reaction stock solution B described later.

Each of these tanks 30 and 32 is provided with a temperature sensor, and the internal temperature data of each tank is sent to the control device, and the internal temperature of each tank is controlled in accordance with the temperature data. In this embodiment, in order to control the temperature of the liquid stored in each tank 30 and 32, each tank 30 and 32 is equipped with the heat exchange jacket. By controlling the temperature and flow rate of the heat medium flowing through the heat exchange jacket with the controller, the internal temperature of each of the tanks 30 and 32 is preferably controlled to a constant temperature within the range of 15 to 25 ° C.

A first main distribution system 36 is connected to the first reaction stock solution tank 30, and a second main distribution system 38 is connected to the second reaction stock solution tank 32. The pumps 42 and 44 as liquid feeding means are respectively attached to it, and the liquid in these tanks can be sent to the metal mold 22 direction.

First control valves 37 and 39 are connected to the downstream side of the pumps 42 and 44 attached to the piping systems 36 and 38. The first control valves 37 and 39 are three-way valves, respectively, to supply the reaction stock solution from each of the tanks 30 and 32 in the direction of the mixing head 26, and the return pipes 41 and 43, respectively. Direction and the state in which the liquid is fed in the direction of the mixing head 26 and also in the direction of the return pipes 41 and 43, respectively. In Fig. 1, each control valve 37 and 39 is in a state of feeding the reaction stock solution from each of the tanks 30 and 32 toward the respective return pipes 41 and 43.

Each return pipe 41 and 43 is a line for sending the reaction stock solution sent by the pumps 42 and 44 from the respective tanks 30 and 32 to the respective tanks 30 and 32, during which the heat exchangers 53 and 55 ) Is installed. The heat exchangers 53 and 55 exchange heat with the reaction stock solution flowing through the return pipes 41 and 43, and control the reaction stock solution at a constant temperature.

In each main distribution system 36 and 38, the second control valves 45 and 47 are connected to the near side of the mixing head 26, respectively. The second control valves 45 and 47 are also three-way valves, which feed the reaction stock solution from each of the tanks 30 and 32 toward the mixing head 26 and toward the return pipes 49 and 51. The state of the liquid feeding is switched to the state in which the liquid is fed in the direction of the mixing head 26 and also in the direction of the respective return pipes 49 and 51. In FIG. 1, the control valves 45 and 47 are in a state of feeding the reaction stock solution from each of the tanks 30 and 32 toward the respective return pipes 49 and 51. As shown in FIG.

Each return pipe 49 and 51 is connected to each return pipe 41 and 43, respectively, and it is possible to return the reaction stock solution to each tank 30 and 32 through the heat exchangers 53 and 55. have.

In the present embodiment, the main pipes 36 and 38 and the return pipes 41, 43, 49, and 51 are each formed of a pipe wound around a pipe through which a temperature control water flows, a pipe having high heat insulation (heat insulation), and the like. It is designed so that the temperature of the reaction stock solution flowing in the pipe is always at a constant temperature.

The second control valves 45 and 47 are preferably connected in the main pipes 36 and 38 as close to the mixing head 26 as possible, preferably within 5 m, more preferably within 2 m, Especially preferably, it is 1 m or less. The closer the distance between the mixing head 26 and the mold 22 is, the more preferable it is, preferably within 2 m, more preferably within 1 m, and particularly preferably within 0.5 m.

In the present embodiment, the mixing head 26 is equipped with a heat exchange jacket, and the temperature or flow rate of the heat medium flowing through the heat exchange jacket is controlled, and the internal temperature of the mixing head 26 can be controlled to a constant temperature. When the distance between the two control valves 45 and 47 and the mixing head 26 is close, temperature control of only the mixing head 26 is unnecessary.

The temperature control of the tanks 30 and 32 is performed by controlling the heat exchange jacket mounted on itself and the temperature of the reaction stock solution flowing through the return pipes 41 and 43 by controlling the first control valves 37 and 39. Do it. In the state before the reaction injection molding is started, the first control valves 37 and 39 pass through the return pipes 41 and 43 from the tanks 30 and 32 and through the return pipes 41 and 43, respectively. After the temperature control by the step, the tanks 30 and 32 return to the respective tanks. Then, for a predetermined time before the start of reaction injection molding, the first control valves 37 and 39 pass the reaction stock solution from each of the tanks 30 and 32 through the main pipes 36 and 38 to the second control valves 45 and 47. Send in the direction.

At this point, the second control valves 45 and 47 block the flow path to the mixing head 26, and send all the reaction stock to the heat exchangers 53 and 55 through the return pipes 49 and 51, Return to tanks 30 and 32. Therefore, the reaction stock solution flowing through the main pipes 36 and 38 positioned near the mixing head 26 until the start of the reaction injection molding is controlled at a constant temperature. In such a system, temperature control is carried out with respect to the reaction stock solution, preferably at least 80% by weight, more preferably at least 90% by weight, particularly preferably at least 95% by weight, of all the reaction stock solutions present in the system.

In order to start the reaction injection molding, the second control valves 45 and 47 are controlled, and the temperature-controlled reaction stock solution is introduced into the mixing head until immediately before entering the mixing head 26, and then, in the mixed state, Injection molding is performed by injecting into the cavity.

In this embodiment, what contains a norbornene-type monomer is used as a reaction stock solution for reaction injection molding.

Norbornene-based monomer

In the present invention, the reaction injection molding is a mass polymerization of norbornene-based monomers in a mold in the presence of a metathesis catalyst, and any monomer may be used as long as it has a norbornene ring, but a molded article having excellent heat resistance may be obtained. It is preferable to use a tricyclic or higher polycyclic norbornene-based monomer because of its loss.

As a specific example of a norbornene-type monomer, For example, bicyclic bodies, such as norbornene and norbornadiene; Tricyclic compounds such as dicyclopentadiene (cyclopentadiene dimer) and dihydrodicyclopentadiene; Tetracycles such as tetracyclododecene; Pentacyclic bodies such as cyclopentadiene trimer; Heterocyclic compounds such as cyclopentadiene tetramers; Substituents such as alkyl such as methyl, ethyl, propyl and butyl, alkenyl such as vinyl and alkylidene such as ethylidene, and aryl such as phenyl, tolyl and naphthyl; Moreover, the substituent etc. which have polar groups, such as these ester group, an ether group, a cyano group, and a halogen atom, are illustrated. These monomers may combine 1 or more types. The monomer of a tricyclic, tetracyclic or pentagon is preferable at the point which is easy to acquire, excellent in reactivity, and excellent in the heat resistance of the obtained resin molded object.

The ring-opening polymer to be produced is preferably a thermosetting type. For this purpose, at least a crosslinkable monomer having two or more reactive double bonds such as cyclopentadiene trimer is used among the norbornene-based monomers. As for the ratio of a crosslinkable monomer among all norbornene-type monomers, 2-30 weight% is preferable.

And monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, cyclododecene and the like which can be ring-opened copolymerized with norbornene-based monomers within the scope of not impairing the object of the present invention are used as a comonomer You may also

Metathesis catalyst

The metathesis catalyst which can be used for reaction injection molding using a norbornene-based monomer is not particularly limited as long as it can ring-open-polymerize the norbornene-based monomer by the RIM method. For example, halides such as tungsten or molybdenum, oxyhalides, oxides, ammonium salts, heteropolyacids (P ⁵⁺ , As ⁵⁺ , Si ⁴⁺ , Ge ⁴⁺ , Ce ⁴⁺ , Th ⁴⁺ , Mn ⁴⁺ , Ni Hetero atoms such as ⁴⁺ , Te ⁶⁺ , I ⁷⁺ , Co ³⁺ , Al ³⁺ , Cr ³⁺ , Cu ²⁺ , and compounds of tungsten or molybdenum). In the present invention, molybdenum-based metathesis catalysts such as organic molybdates such as tridodecyl ammonium molybdate and tri (tridecyl) ammonium molybdate, and organic ammonium salts of molybdate such as ammonium acid are preferably used.

The use amount of the metathesis catalyst is usually 0.01 mmol or more, preferably 0.1 mmol or more, and 50 mmol or less, and preferably 20 mmol or less with respect to 1 mol of the monomer used in the entire reaction solution. If the amount of metathesis catalyst is too small, the polymerization activity is too low and the reaction takes time, and thus the production efficiency is poor. If the amount of the metathesis catalyst is too high, the reaction is too severe, so that it is easy to cure before being sufficiently charged in the mold or to precipitate the catalyst. It becomes difficult to store it homogeneously. The metathesis catalyst is usually used after being dissolved in a monomer, but if it is in a range which does not substantially impair the properties of the molded product by the RIM method, it is suspended by dissolving in a small amount of solvent, and then mixed with the monomer to make it difficult to precipitate or solubility. You can also increase the use.

Active agent

The activator (cocatalyst) is not particularly limited as long as it is a known activator as disclosed in Japanese Patent Application Laid-Open Nos. 58-127,728, JP-A 4-226,124, JP-A 58-129,013, and JP-A 4-145,247. However, in the present invention, for example, organoaluminum compounds such as alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride and alkoxyalkylaluminum halides are preferably used.

Although the usage-amount of an active agent is not specifically limited, Usually, it is 0.1 mol or more, Preferably it is 1 mol or more, and 100 mol or less, Preferably it is 10 mol or less with respect to 1 mol of metathesis catalysts used for the whole reaction liquid. If the activator is not used or if the amount of the activator is too small, the polymerization activity is so low that the reaction takes time, resulting in poor production efficiency. On the contrary, if the amount is too large, the reaction is so severe that it may be cured before it is sufficiently filled in the mold. The active agent is dissolved in a monomer and used, but as long as the properties of the molded body by the RIM method are not inherently impaired, the active agent may be suspended in a small amount of solvent and then mixed with the monomer to make it difficult to precipitate or increase solubility.

Other optional ingredients

If necessary, additives such as antioxidants, fillers, elastomers, pigments, colorants, foaming agents, flame retardants, sliding imparting agents, elastomers, dicyclopentadiene-based thermal polymerization resins and their water additives may be blended into the reaction stock solution, The characteristics of the RIM product thus obtained can be modified.

In particular, in order to obtain a molded article having high mechanical strength, the reinforcing material may be filled in the mold in advance, and then the polymerization reaction liquid may be injected into the mold and cured. The filling amount of the reinforcing material is not particularly limited, but is usually 10% by weight or more, preferably 20 to 60% by weight of the monomer weight. If the filling amount is small, the ratio of the mechanical strength is small. If the filling amount is too large, it may not be able to charge uniformly, and there is a tendency for staining or filling inhibition to occur.

Examples of the reinforcing material include glass fiber, aramid fiber, carbon fiber, ultra high molecular weight polyethylene fiber, metal fiber, polypropylene fiber, aluminum coated glass fiber, cotton, acrylic fiber, boron fiber, silicon carbide fiber, alumina fiber and the like. have. These reinforcing materials can be used in various shapes such as mats of long fiber or chopped strands, woven into cloth, and chopped. These reinforcing materials are those obtained by treating the surface with a coupling agent such as a silane coupling agent. However, these reinforcing materials are preferable for improving the adhesion to the resin. Although the compounding quantity of a reinforcing material does not have a restriction | limiting in particular, It is 10 weight% or more normally, Preferably it is 20 to 60 weight%, making a monomer whole quantity 100 weight%. By mix | blending a reinforcement material in such a range, the mechanical strength of a molded object can be improved.

In addition, in order to further improve the mechanical strength of the molded body, a metal rod, a metal plate, or the like may be previously inserted into the mold for performing reaction injection molding, and then reaction injection molding may be performed (insert molding). By this insert molding, the molded object excellent in the mechanical strength by which the metal rod or the metal plate was integrally formed can be obtained.

Antioxidants include antioxidants for various plastics and rubbers such as phenolic, phosphorus and amine based. Fillers include inorganic fillers such as milled glass, carbon black, talc, calcium carbonate, aluminum hydroxide, mica, potassium titanate, calcium sulfate.

Elastomers include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), ethylene-propylene-diene -Terpolymer (EPDM), ethylene vinyl acetate copolymer (EVA), and hydrides thereof. The amount of the elastomer added is suitably selected such that the viscosity of the reaction stock solution is at least 5 cps, preferably at least 50 cps, and at most 1,000 cps, preferably at most 500 cps.

The additive is usually mixed in advance on either or both of the reaction stock solutions.

As preparation for reaction injection molding, a reaction injection molding material mainly composed of a norbornene-based monomer, a metathesis catalyst and an aluminum-based activator is composed of a B liquid comprising a norbornene-based monomer and a metathesis catalyst, and the norbornene-based Divided into stable two liquids of liquid A consisting of a monomer and an aluminum-based activator, each placed in a separate tank. In this embodiment, the liquid A is stored in the first reaction stock solution tank 30, and the liquid B is stored in the second reaction stock solution tank 32.

The viscosity of the reaction stock solution consisting of A liquid or B liquid is, for example, 5 cps to 3000 cps, preferably about 100 cps to 1000 cps at 30 ° C.

In the present embodiment, in the case where other optional components such as carbon black are included in the reaction stock solution, the first reaction stock solution tank 30 containing the A solution or the second reaction stock solution tank 32 containing the B solution are included. It is preferable to provide an auxiliary tank, to store a liquid containing an optional component therein, and to mix it with the reaction stock solution stored in these tanks to supply the mold to the mold if necessary. By making the composition of the reaction stock solution stored in these reaction stock tanks 30 and 32 constant, the reaction stored in the tanks 30 and 32 even when the mold 22 is replaced and a RIM molded body having a different composition is formed. There is no need to change the composition of the stock solution.

Molding method

In reaction injection molding, a reinforcing material may be provided in advance in the metal mold | die 22 as needed, and a reinforcement polymer (molded body) can also be manufactured by supplying and superposing | polymerizing by supplying a reaction liquid therein. Alternatively, a metal material or the like may be installed in the mold in advance to insert molding.

In order to start the reaction injection molding, the second control valves 45 and 47 are controlled, and the temperature-controlled reaction stock solution is introduced into the mixing head until immediately before entering the mixing head 26. Then, the mold is mixed with the mold. It is injected into a cavity and reaction injection molding is performed.

In each mixing head 26, A liquid and B liquid from the tanks 30 and 32 are mixed, and the mixed liquid mixed with the appropriate compounding ratio for every metal mold | die 22 is filled into the cavity of each metal mold | die 22 as a reaction stock solution. . The reaction stock filled in the cavity is passed into the cavity. The temperature of the reaction stock solution immediately before being filled into the cavity of the mold is controlled by the heat exchangers 53 and 55 through the return pipes 49 and 51, and at the same time by the heat exchange jacket mounted on the mixing head 26. The temperature is controlled. The temperature is constant temperature in the range of 15-25 degreeC regardless of a season.

The polymerization time may be appropriately selected depending on the size of the mold 22 and the like, but is usually about 20 seconds to 20 minutes after completion of injection of the reaction stock solution. The pressure clamping the mold is usually in the range of 0 to 100 x 10 ⁵ Pa. Moreover, it is preferable that the injection pressure of a reaction stock solution is 2 * 10 <^{5> -5} * 10 <^5> Pa. If the injection pressure is too low, the transfer of the transfer surface formed on the cavity inner circumferential surface of the mold tends not to be performed well. If the injection pressure is too high, it is not economical unless the rigidity of the mold is increased.

In the reaction injection molding, the reaction proceeds rapidly from the start of the injection of the reaction stock solution into the cavity of the mold, and the time (SMT: t ') from the start of the injection until the white smoke is generated from the surface of the resulting resin is filled. The filling time t to completion is preferably determined according to the size of the molded body. The SMT time t 'is necessarily larger than the charging time t, preferably 10 to 300 seconds, and the charging time t at that time is preferably about 1 to 50 seconds. The SMT time t 'is more preferably 20 to 200 seconds, and the charging time t at that time is more preferably about 15 to 35 seconds. Although t '/ t also depends on temperature, Preferably it is about 1.5-20.

In this embodiment, by maintaining the temperature of the reaction stock solution immediately before being filled in the cavity of the metal mold | die 22, the favorable molded object which is not sticky on a surface can be obtained irrespective of a season.

Therefore, it is unnecessary to prepare a reaction stock solution having different activities for each size or shape of the cavity of the mold 22 or to adjust the reaction activity in the reaction stock solutions tanks 30 and 32. In addition, even when the mold 22 is replaced with a mold for molding another molded body, the preparation of the reaction stock solution having different activities or the adjustment of the reaction activity in the reaction stock solutions tanks 30 and 32 becomes unnecessary. .

Since the purification tank 6 shown in FIG. 2 obtained by the method and apparatus which concerns on this embodiment is comprised from the polynorbornene system resin obtained by reaction injection molding method, a comparatively large molded object can be shape | molded easily. In addition, the polynorbornene-based resin can have a sufficient pressure drop required as a septic tank using a material characteristic of low specific rigidity but high specific strength.

(2nd embodiment)

The molding apparatus 20a shown in FIG. 3 performs reaction injection molding of a multi-die system using the method of the present invention, and the upper tank 7 and / or the lower tank of the septic tank assembly 6 as shown in FIG. (9) is an apparatus for molding.

Description of the septic tank 6 is omitted since it is overlapped with the first embodiment.

Next, with reference to FIG. 1, the reactive polymerization molding apparatus of the multi metal mold system which concerns on this embodiment is demonstrated.

Apparatus 20a according to the present embodiment has at least two molds 22 and 24. These molds 22 and 24 have different shapes for forming molded bodies of different shapes and sizes, for example, the upper tank 7 and the lower tank 9 of the septic tank 6 shown in FIG. The cavity is formed. These molds 22 and 24 are equipped with mixing heads 26 and 28 as mixing means, respectively. Piping systems from the first reaction stock solution tank 30, the second reaction stock solution tank 32, and the reaction activity regulator tank 34 are connected to the mixing heads 26 and 28.

The apparatus 20a which concerns on this embodiment has at least two reaction stock solution tanks 30 and 32, the reaction stock solution A liquid is stored in one 1st reaction stock solution tank 30, and the other 2nd reaction The reaction stock solution B liquid is stored in the stock solution tank 32. The reaction activity regulator tank 34 stores a liquid containing a reaction activity regulator for controlling the reaction activity of these reaction stock solutions.

Each of these tanks 30, 32, and 34 is provided with temperature sensors 31, 33, and 35, respectively, and the internal temperature data of each tank is sent to the controller 80, and according to the temperature data, Control the internal temperature. In this embodiment, in order to control the temperature of the liquid stored in each tank, each tank is equipped with the heat exchange jacket. By controlling the temperature and flow rate of the heat medium flowing through the heat exchange jacket with the controller 80, the internal temperature of each of the tanks 30, 32, and 34 is preferably controlled to a constant temperature within the range of 15 to 25 ° C.

A first main distribution system 36 is connected to the first reaction stock solution tank 30, a second main distribution system 38 is connected to the second reaction stock solution tank 32, and a reaction activity regulator tank 34. The third main distribution relationship 40 is connected. These main distribution systems 36, 38, and 40 are connected with pumps 42, 44, and 46 as liquid feeding means, respectively, and the liquids in these tanks can be directed to the molds 22 and 24, respectively.

Branch pipes 48, 50, 56, 58, 64, and 66 are connected to the pump downstream of these main pipes 36, 38, and 40. The branch pipes 48 and 50 are pipes for sending the reaction stock solution in the first main pipe 36 to the mixing heads 26 and 28, respectively. Branch pipes 56 and 58 are pipes for sending the reaction stock solution in the second main pipe to the mixing heads 26 and 28, respectively. The branch pipes 64 and 66 are pipes for sending the reaction-activating agent-containing liquid in the third main pipe 40 to the mixing heads 26 and 28, respectively. Each branch pipe 48, 50, 56, 58, 64, 66 is equipped with control valves 52, 54, 60, 62, 68, 70, respectively, to control the opening and closing of the flow path and / or the flow rate. have.

In this embodiment, these piping 36, 38, 40, 48, 50, 56, 58, 64, 66 is coat | covered with a heat insulating material, or the piping itself is comprised with a heat insulating material, and the temperature of the liquid which flows inside these piping is It is configured to be constant regardless of the outside temperature. And from such a viewpoint, it is preferable to coat the pumps 42, 44, 46 and control valves 52, 54, 60, 62, 68, 70 with a heat insulating material, or to constitute them with a high heat insulating material.

Each mixing head 26 and 28 is equipped with temperature sensors 72 and 74, respectively, and it is possible to detect the temperature of the reaction stock solution mixed in each mixing head and injected into the cavities of the respective molds 22 and 24. . The temperature output signal detected by each of the temperature sensors 72 and 74 is input to the control device 80 as a control means.

In the present embodiment, each of the mixing heads 26 and 28 is equipped with heat exchange jackets, respectively, and controls the temperature or flow rate of the heat medium flowing through the heat exchange jacket in accordance with a control signal from the controller 80, and mixes each of the mixing heads. The internal temperature of the head can be controlled to a constant temperature. The temperature of each mixing head 26 and 28 is fixed temperature in the range of 15-25 degreeC in this embodiment.

In addition, the control device 80 receives inputted information (type of reaction stock solution, type of reaction activity regulator, size and shape of cavity of each mold 22 and 24, outside temperature, etc.) and temperature sensors 72 and 74. The pumps 42, 44, 46 and the control valves 52, 54, 60, 62, 68, 70 are controlled in accordance with the temperature information.

Specifically, the control device 80 controls the pumps 42 and 44 and the control valves 52, 54, 60, and 62 to send the reaction stock solution to the mixing head through the control valves 52, 54, 60, and 62. Pressure and flow rate are controlled for each mold 22 and 24. In addition, the control device 80 controls the pump 46 and the control valves 68 and 70 so that the pressure, flow rate and / or temperature of the reaction-activating agent-containing liquid sent to the mixing head through the control valves 68 and 70. Is controlled for each mold 22 and 24.

In addition, the control device 80, in response to the output signals from the temperature sensors 72 and 74, when the temperature of the reaction stock solution is higher than a predetermined value, each mixing head 26 and 28 from the reaction activity regulator tank 34. The pump 46 and the control valves 68 and 70 are controlled so as to correct the flow rate of the liquid sent to the dies in comparison with the flow rates set for the respective molds 22 and 24. For example, in the case where the reactive activator stored in the reactive activator tank 34 is the reactive activator for enhancing the reaction activity, when the temperature of the semi-ungwoon solution is higher than the predetermined value, it is not sent to the mixing heads 26 and 28. Controls the flow rate of the liquid to be smaller than the set value. In addition, when the reaction activity regulator stored in the reaction activity regulator tank 34 is a reaction activity regulator for lowering the reaction activity, it is sent to the mixing heads 26 and 28 when the temperature of the reaction stock solution is higher than a predetermined value. The flow rate of the liquid is controlled to be larger than the set value. These flow rate control is performed for each mold 22 and 24. The control valves 52, 54, 60, 62, 68, and 70 are preferably driven by electric signals and capable of controlling the flow rate.

In this embodiment, what contains a norbornene-type monomer is used as a reaction stock solution for reaction injection molding. Examples of norbornene-based monomers, metathesis catalysts, activators, other optional components, and the like are the same as those in the first embodiment, and the description thereof is omitted. In this embodiment, the reaction activity regulator is stored in the reaction activity regulator tank 34 shown in FIG.

Reaction activity regulator

As a reaction activity regulator which can be used in this invention, there exists a regulator disclosed by Unexamined-Japanese-Patent No. 3-146, 516, 4-337, 318, for example. Japanese Patent Application Laid-Open No. 3-146, 516 discloses 5-vinylbicyclo [2.2.1] hepto-2-ene (vinylnorbornene) and 5-isopropenylbicyclo [2.2.1] hepto-2 as reaction control agents. A process for producing a norbornene-based polymer using 5-alkenyl-2-norbornene such as -ene is disclosed, and Japanese Patent Application Laid-Open No. 4-337, 318 discloses 5-ethynyl-2- as a reaction activity regulator. The use of 5-alkyl-2-norbornenes, such as norbornene, is disclosed.

Moreover, as a reaction activity regulator, the compound etc. which have the effect | action which reduces the metathesis catalyst which are the main catalysts of the reaction stock liquid containing a norbornene-type monomer as a main component can also be used, In this case, as an activity regulator, alcohol, halo alcohol, ester , Ethers, nitriles and the like are exemplified. For example, specific examples of alcohols include n-propanol, n-butanol, n-hexanol, 2-butanol, isobutyl alcohol, isopropyl alcohol, t-butyl alcohol, and the like. Examples include 1,3-dichloro-2-propanol, 2-chloroethanol, 1-chlorobutanol, and the like.

In addition, in this invention, as a reaction activity control agent, it is not limited to reducing reaction activity as mentioned above, The main catalyst which can raise reaction activity, co-solvent itself, etc. may be sufficient.

The supply amount of such a reaction activity regulator is determined depending on the size and shape of the cavity of the molds 22 and 24, and is supplied to each mold 22 and 24 in a predetermined amount separately from the reaction stock solution. In this embodiment, although there is only one tank 34 for supplying a reaction activity regulator, a plurality may be sufficient and the reaction activity regulator of a different kind may be contained in several tank.

In the reaction activity regulator tank 34, it is preferable that the viscosity of the liquid containing the reaction activity regulator is approximately equal to the viscosity of the reaction stock solutions in the reaction stock solutions tanks 30 and 32. The liquid containing the reaction activity regulator is mixed with the reaction stock solution before being injected into the cavities of the molds 22 and 24. The liquid containing the reaction activity regulator may also contain a monomer such as the monomer contained in the reaction stock solution.

In the present embodiment, even when the molds 22 and 24 are replaced with other molds, the composition of the reaction activity regulator-containing liquid stored in the reaction activity regulator tank 34 is preferably constant, and the tank 34 and It is preferable that the liquid is always stored in the piping system 40. This is because the control of the reaction activity can be realized by controlling the pump 46 and the control valves 68 and 70 by the controller 80 and changing the supply flow rate for each mold 22 and 24. In addition, since the liquid is always stored in the tank 34 and the piping system 40, it is possible to prevent clogging in the tank or piping system.

In the present embodiment, the reaction activity regulators described above may also be included in the reaction stock solutions stored in the reaction stock solutions tanks 30 and 32.

Molding method

In reaction injection molding, a reinforcing material can be prepared in advance in the molds 22 and 24 if necessary, and the reaction liquid can be supplied and polymerized therein to produce a reinforced polymer (molded product). Alternatively, a metal material or the like may be provided in the mold in advance to insert molding.

In order to start the reaction injection molding, in accordance with a control signal from the control device 80, the control valves 52, 54, 60 and 62 are opened and the pumps 42 and 44 are driven to react the reaction stock solution from the tanks 30 and 32. Is supplied to the mixing heads 26 and 28 at flow rates and / or injection times calculated for each mold 22 and 24. At the same time, in response to the control signal from the control device 80, the control valves 68 and 70 are opened and the pump 46 is driven to supply the reaction activity regulator-containing liquid from the tank 34 to the mixing heads 26 and 28. Each mold 22 and 24 are supplied at the calculated flow rate and / or injection time. The flow rate and / or injection time calculated for each mold 22 and 24 may be the same or different for each mold.

In each mixing head 26 and 28, the liquid A and the liquid B from the tanks 30 and 32, and the reaction activity regulator containing liquid from the tank 34 are mixed, and the mixed liquid mixed by the appropriate mixing ratio for each mold is mixed. The reaction stock solution is filled into the molds 22 and 24 in the cavities. Reaction stock solution filled in the cavity is passed into the cavity. The temperature of the reaction stock solution immediately before being filled in the cavity of the mold is controlled at a constant temperature by heat exchange jackets mounted on the mixing heads 26 and 28. The temperature is constant temperature in the range of 15-25 degreeC as mentioned above regardless of a season.

The polymerization time may be appropriately selected differently for each of the molds 22 and 24, but is usually about 20 seconds to 20 minutes after completion of injection of the reaction stock solution. The pressure clamping the mold is usually in the range of 0 to 100 x 10 ⁵ Pa. In addition, the injection pressure of the reaction stock solution and the reaction activity regulator-containing liquid is preferably 2 × 10 ^{5 to} 5 × 10 ⁵ Pa. If the injection pressure is too low, the transfer of the transfer surface formed on the inner circumferential surface of the mold tends not to be performed well. If the injection pressure is too high, it is not economical because the rigidity of the mold must be increased.

In the reaction injection molding, the reaction proceeds rapidly from the start of the injection of the reaction stock solution into the cavity of the mold, and the time (SMT: t ') from the start of the injection until a little white smoke is generated from the surface of the product resin is filled. The filling time t to completion is preferably determined according to the size of the molded body. The SMT time t 'is necessarily larger than the charging time t, preferably 10 to 300 seconds, and the charging time t at that time is preferably about 1 to 50 seconds. The SMT time t 'is more preferably 20 to 200 seconds, and the charging time t at that time is more preferably about 15 to 35 seconds. Although t '/ t also depends on temperature, Preferably it is about 1.5-20.

In this embodiment, the amount of supply of the reaction activity regulator supplied from the tank 34 to the mixing heads 26 and 28 for each mold 22 and 24 is controlled for each mold, and the reaction stock solution immediately before being filled into the cavity of the mold. By making temperature constant, the favorable molded object which is not sticky to a surface can be obtained irrespective of the size and shape of the cavity of each metal mold | die 22 and 24, and irrespective of a season.

Therefore, it is unnecessary to prepare a reaction stock solution having different activities for each size or shape of the cavity of each mold 22 and 24 or to adjust the reaction activity in the reaction stock tanks 30 and 32. In addition, even when the molds 22 and 24 are replaced to mount a mold for forming another molded body, there is no need to prepare a reaction stock solution having different activities or to adjust the reaction activity in the reaction stock tanks 30 and 32. Done. In addition, even when the mold is replaced, the pipe size of the main piping system 36, 38, 40 and the branch piping 48, 50, 56, 58, 64, 66, the nozzle diameter in the mixing heads 26 and 28, and the like. There is no need to change it.

Therefore, in the method and apparatus according to the present invention, the reaction stock solution can be used in a wide range without depending on the size and shape of the cavity of the mold. Moreover, the method and apparatus which concerns on this embodiment can be used suitably also for multi metal mold | die shaping | molding, as shown to the example to show in figure.

Since the purification tank 6 shown in FIG. 2 obtained by the method and apparatus which concerns on this embodiment is comprised from the polynorbornene system resin obtained by reaction injection molding, a comparatively large molded object can be shape | molded easily. In addition, the polynorbornene-based resin can have sufficient internal pressure required as a septic tank using a material characteristic of low specific rigidity but high specific strength.

In addition, this invention is not limited to embodiment mentioned above, It can variously change within the scope of this invention.

For example, in the above-described embodiment, as an example of the reactive polymerization molding method, RIM molding is illustrated and the tank of the septic tank is molded by RIM molding. However, the present invention is not limited to ordinary RIM molding, but using the reaction stock solution. It is also applicable to the case of forming the tank of a septic tank or another molded body by rotational molding (including centrifugal molding).

EXAMPLE

Hereinafter, the present invention will be described according to more detailed examples, but the present invention is not limited to these examples. In the examples shown below, parts or percentages are by weight unless otherwise specified.

Example 1

In order to mold the lower tank 9 of the tank (for 6 persons) of the septic tank shown in FIG. 2, in the mold 22 shown in FIG. 1, a mold for forming the lower tank of 6 persons is used for reaction injection molding. Done.

In reaction injection molding, norbornene-based monomers composed of 90% of dicyclopentadiene (DCP) and 10% of asymmetric cyclopentadiene trimer are placed in two tanks, and diethylaluminum chloride (DEAC) is used for one monomer. Was added so as to have a concentration of 40 mmol, 48 mmol of 1,3-dichloro-2-propanol (dcPrOH) (solution A). On the other side, tri (tridecyl) ammonium molybdate was added to the monomer so as to have a concentration of 10 mmol (B liquid). These A liquid and B liquid SMTs were 110 seconds.

The liquid A and liquid B thus prepared were stored in the first reaction stock solution tank 30 and the second reaction stock solution tank 32 shown in FIG. 1, respectively. The first control valves 37 and 39 are controlled before the start of the reaction injection molding, the second control valves 45 and 47 are controlled, and the reaction stock solution from each of the tanks 30 and 32 is returned to the pipes 41 and 43. , 49 and 51 were thermostated through heat exchangers 53 and 55 to each tank 30 and 32. Temperature control was performed for 2 hours.

Thereafter, the second control valves 45 and 47 are controlled, and the liquid A and the liquid B are transferred from the tanks 30 and 32 to the mold 22 at an injection pressure of 7 × 10 ⁶ Pa and an injection flow rate of 2650 Pa / sec, respectively. The flow rate was injected into the cavity of the mold through the mixing head 26. Their charging time t was 16.5 seconds. Moreover, it was 20 degreeC when the temperature of the mixed reaction stock solution just before filling in the cavity inside of the metal mold | die 22 was measured by the temperature sensor. The mixing head 26 was temperature-controlled by the heat exchange jacket. Incidentally, the outside air temperature was 34 ° C.

Although the molded object was taken out from the metal mold | die 22 and evaluated for a void defect, an unfilled defect, a needle defect, and a double layer defect in the molded object, none of these defects were found. Moreover, although stickiness of the molded object was evaluated, stickiness was not observed.

The void defect means that voids or the like exist in the molded body, the unfilled defect means that molding defects due to unfilling of the stock solution exist in the molded body, and the needle defect means that fine needle-like bubbles appear in the molded body. Is a state in which a two-layer surface such as one sheet of resin skin is covered on the core surface of the molded body.

Example 2

Except for the state where the outside air temperature was changed to 15 ° C., the molded product was removed from the mold 22 under the same conditions as in Example 1, and the voids, unfilled defects, needle failures, and double layer defects were evaluated for the molded bodies. No defects were found. Moreover, although stickiness of the molded object was evaluated, stickiness was not observed.

Example 3

In order to mold the lower tank 9 of the tanks having different capacities (for 6 and 10 pairs) in the septic tank shown in FIG. 2, the mold 22 for forming the lower tank of 6 pairs is used in the mold 22 shown in FIG. In the mold 24, reaction injection molding was performed by using a mold for forming a 10-join lower tank.

In reaction injection molding, norbornene-based monomers composed of 90% of dicyclopentadiene (DCP) and 10% of asymmetric cyclopentadiene trimers are placed in two tanks, and on one side, diethylaluminum chloride (DEAC) is used. ) Was added to make 40 mmol, 48 mmol of 1,3-dichloro-2-propanol (dcPrOH) (solution A). On the other side, tri (tridecyl) ammonium molybdate was added to the monomer so as to have a concentration of 10 mmol (B liquid). Moreover, SMT in these liquid A and liquid B alone was 110 seconds.

The liquid A and liquid B thus prepared were stored in the first reaction stock solution tank 30 and the second reaction stock solution tank 32 shown in FIG. 1, respectively.

Moreover, liquid C as a reaction activity regulator containing liquid stored in the reaction activity regulator tank 34 was adjusted separately from these A liquid and B liquid. As C liquid, what mix | blended 15 weight part vinyl norbornene (delay agent) and 1 weight part dcPrOH with respect to 100 weight part of monomers was prepared. This C liquid was stored in the reaction activity regulator tank 34 shown in FIG.

In the mold 22, the liquid A and the liquid B were injected from the tanks 30 and 32 into the cavity of the mold through the mixing head 26 at a flow rate of 7 × 10 ⁶ Pa and an injection flow rate of 2650 Pa / sec, respectively. . At the same time, C liquid was injected from the tank 34 into the cavity of the mold through the mixing head 26 at a flow rate of 4 × 10 ⁶ Pa and an injection flow rate of 30 Pa / sec. Their charging time t was 16.5 seconds. Moreover, it was 20 degreeC when the temperature of the mixed reaction stock liquid just before filling in the cavity inside of the metal mold | die 22 was measured by the temperature sensor 72. FIG. The mixing head 26 was temperature-controlled by the heat exchange jacket. Incidentally, the outside temperature was 34 ° C.

For the mold 24, the liquid A and the liquid B were injected from the tanks 30 and 32 into the cavity of the mold through the mixing head 28 at a flow rate of 6 × 10 ⁶ Pa and an injection flow rate of 2650 Pa / sec, respectively. . At the same time, the C liquid was injected from the tank 34 into the cavity of the mold through the mixing head 28 at a flow rate of 5.5 × 10 ⁶ Pa and an injection flow rate of 45 Pa / sec. Their charging time t was 28 seconds. Moreover, it was 21 degreeC when the temperature of the mixed reaction stock solution just before filling in the cavity inside of the metal mold 24 was measured by the temperature sensor 74. As shown in FIG. The mixing head 28 was temperature controlled with a heat exchange jacket.

The molded bodies were removed from the molds 22 and 24 and evaluated for void defects, unfilled defects, needle defects, and double layer defects in the molded bodies, but none of these defects were found. Moreover, although stickiness of the molded object was evaluated, stickiness was not observed.

In addition, the supply flow rate of the C liquid supplied to the molds 22 and 24 shown in FIG. 3 is changed to ± 5 kPa / sec, reaction injection molding is performed to obtain a molded product, and voids, unfilled defects, and needle defects are obtained. And two-layer defects were evaluated, but none of these defects were found. In addition, no stickiness of the molded body was observed.

Comparative Example 1

Reaction injection molding was carried out under the same conditions as in Example 1 except that SMT was adjusted to 160 seconds with an activity regulator to adjust activity without controlling the temperature of the tank at an outdoor temperature of 35 ° C. As a result of taking out the molded product from the mold 22 and observing it, stickiness was observed in the molded product.

Then, the temperature of the mixed reaction stock solution immediately before filling the inside of the cavity of the mold 22 was measured by a temperature sensor, which was 29 ° C. close to the outside air temperature.

As described above, according to the reactive polymerization method and the molding apparatus according to the present invention, the temperature of the reaction stock solution immediately before being fed into the mold can be made constant regardless of the season. As a result, the stickiness of the surface of the molded body, which occurs especially in summer and whose improvement has been demanded for a long time, has been improved.

Claims (2)

In a reactive polymerization molding method wherein at least two reaction stock solutions are supplied into a mold, and the reaction stock solution is reacted and polymerized in the mold. And controlling the temperature of the reaction stock solution at least immediately before the reaction stock solution is supplied into the mold. At least one mold, At least two reaction stock solution supplying means for supplying the reaction stock solution to the mold; And a temperature control means for controlling the temperature of the reaction stock solution immediately before supplying the reaction stock solution from the reaction stock solution supply means to the inside of the mold.