JP4275130B2 - Method for molding coal ash-containing resin composition - Google Patents

Description

The present invention relates to a resin composition, particularly a method for molding an energy ray curable coal ash-containing resin composition, and more particularly, coal ash (including fly ash and the like) that is an industrial waste of a thermal power plant by energy ray curing. This relates to a method for molding a coal ash-containing resin composition that enables reuse (recycling) of the resin .

  Coal ash recycling products include, for example, roof tiles, flower pots, building materials, and the like, and thermosetting resins such as phenol resins and room temperature curing resins are used as matrix resins. However, since the matrix resin of coal ash recycling products uses thermosetting resins such as phenol resin and room temperature curing resins, it takes time and money to manufacture, as with other filler-containing curable resin products. The product unit price was high. And the point that productivity was low was also a problem.

  On the other hand, in recent years, energy ray curable resins represented by UV curable resins have been used in various fields and applications, but such resins cure only portions irradiated with a certain amount or more of energy rays. And energy rays represented by UV are attenuated in the process of passing through the resin, so it is difficult to reach the deep part of the resin, or properties such as attenuation or large absorption due to substances that absorb the same wavelength as the energy rays. Have Therefore, the photo-curing resin cures only the surface layer of several μm to mm where the energy rays reach, and the deep portion is uncured, so that it is difficult or impossible to apply to a thick material, and the transmission of energy rays In the case of a resin containing an obstacle filler or the like, there is a problem that curing inhibition easily occurs and the resin cannot be cured. For these reasons, the range of use has also been limited to fields such as photoresists, coatings, paints, adhesives, and varnishes. Representative examples of solutions to such problems include high UV curable resins (Mitsubishi Rayon Co., Ltd., active energy ray curable composition, Patent Document 1) and UV / heat combination curable resins (Asahi Denka Kogyo Co., Ltd.). Company: Optmer KS series, Hitachi Chemical Co., Ltd .: Radicure, Toyobo: UE resin, Patent Document 2, etc.).

  However, the high UV curable resin still has a problem that it cannot be cured when the energy beam is blocked by a filler or the like. In addition, the UV / heat combination type resin that is heated after UV irradiation has the same level of curing ability with energy rays as the conventional photo-curing resin, and the problems of thick-wall curing and filler-containing curing are not solved at all. The point corresponds to the thermal curing by heating performed after photocuring (only the surface layer), and the present situation is that this problem cannot be solved. If a technology capable of rapidly curing a thick resin that contains the above-mentioned energy ray shielding substance or has a large attenuation or absorption of energy rays can be established, not only in the conventional application field, but also in such photo-curing resin. Although it can be applied to various other fields that have been impossible to apply due to problems, one of them is FRP, which is mainly composed of thermosetting or thermoplastic resin, and particularly a matrix resin for CFRP. Problems in molding FRP, especially CFRP, include that the temperature control is complicated and requires a long time for curing, so that the processing cost is high, a large heating furnace is required when curing large FRP, In the case of a resin that can be cured in a short period of time, it cannot be used for a large FRP that requires a long time for molding, the resin impregnation state changes due to a change in temperature of the resin viscosity, and molding is difficult, and the resin is cured by the residual solvent Occasionally, voids are generated and the quality of the formed crystal is lowered.

  Recently, the use of a photocurable resin as a matrix resin has attracted attention as a solution to this problem. As a typical example of such a matrix resin curing method, a filament winding molding method (Loctite Corporation, a fiber / resin composition and a method for preparing the same, Patent Document 3) that uses both UV curing and heat curing of Loctite Corporation in particular Can do. However, the FRP molding method using such a composition is that the uncured FRP impregnated with resin is irradiated with UV to cure the surface and extremely thicken the inside (gelation) to maintain the shape and impregnation state. Is made possible to some extent, and is then completely cured by heating. Therefore, the temperature change of the resin viscosity is extremely small compared with the conventional manufacturing method using plastic or thermosetting resin, and handling after impregnation is easy, but heat curing process is necessary for complete curing. Further, there are unsolved problems such as a problem of processing cost due to the light and heat cost required for heat curing, work time, and the like, a problem that a long time is required for completion of curing, and a large heating furnace is required for forming a large FRP.

Similarly, when the thermosetting resin is simply replaced with an energy ray curable polymer, the coal ash, ceramic, etc. to be mixed are ultraviolet (UV), electron beam (EB), infrared ray, heat ray, laser beam (excimer, argon, CO2). ₂ ) Since it does not pass energy rays represented by visible rays, sunlight rays, X-rays, etc., it cannot be cured and molded. And even if it uses the metal mold | die which has an optical fiber etc., since light does not permeate | transmit to the inside, the composition which did not harden | cure in liquid form and was highly filled with coal ash etc. could not be manufactured. In addition, when a conventional photo-curing resin is used, it is difficult to provide a product excellent in strength and the like because it is simply cured and pressure is not applied. That is, in order to apply pressure, it is necessary to use a metal mold. However, using the conventional method , light itself cannot be irradiated, and it is usually difficult to form.
JP-A-8-283388 Japanese Examined Patent Publication No. 61-38023 Japanese National Patent Publication No. 7-507836

In view of the above problems, the present inventors have been able to completely cure even a highly-filled composition such as coal ash that does not transmit light, and further to photocuring the composition. We have intensively studied to develop a method that can be used. As a result, the present inventors have found that this problem can be solved by preparing a coal ash-containing resin composition using a specific energy ray-curable resin mixture and using this . The present invention has been completed from such a viewpoint.

That is, in order to achieve the above object, the present invention provides a method for molding a coal ash-containing resin composition, which comprises an energy ray curable resin mixture containing a photopolymerizable resin and a photopolymerization initiator system, coal ash, And the energy ray curable resin mixture is selected from the group consisting of photopolymerizable epoxy polymers consisting of alicyclic epoxy, glycidyl ether type epoxy, epoxidized polyolefin, and vinyl ether compounds. A cationic photo / thermal polymerization initiator system component comprising 0.5 to 6.0 parts by weight of a photopolymerization initiator system component comprising at least two components with respect to 100 parts by weight, and constituting the photopolymerization initiator system component; The weight ratio with the cationic photopolymerization initiator is 1 to 4 as the cationic light / thermal polymerization initiator system component / cationic photopolymerization initiator, and depending on the injection mechanism, A serial-energy-ray-curable resin mixture, the coal ash containing resin composition containing the above coal ash, a mold of the light transmission type, fed into a mold through an optical fiber inside, light to mold The coal ash-containing resin composition is cured by introducing light from the introduction part.

According to the molding method of the present invention, the matrix resin of the recycled coal ash product can be cured with energy rays regardless of the presence or absence of an energy ray shielding substance in the resin composition, and can be cured even with a thick plate. Products can be used to cure such products with energy rays. Therefore, in the present invention, when coal ash is recycled, energy represented by ultraviolet rays (UV), electron beams (EB), infrared rays, heat rays, laser beams (excimer, argon, CO2, etc.), visible rays, solar rays, X-rays, etc. By using a resin composition that can be cured even with a thick plate as a matrix resin for coal ash products, regardless of the presence or absence of a shielding substance (energy ray shielding substance) that shields energy rays in the resin composition by using wires. Regardless of the type and thickness of the reinforcing fiber, it enables easy molding of coal ash-containing resin products, short-time molding, improved productivity, low processing costs, low equipment costs, and low running costs.

And as a resin composition used in the present invention for enabling these, a resin composition that self-generates energy effective for curing inside the resin when energy is applied or energy rays are irradiated. Further, a resin composition that continuously self-generates energy effective for curing inside the resin, a resin composition that self-generates or continuously self-generates heat energy inside the resin as energy effective for these curing, these thermal energy Resin composition that actively generates curing reaction heat or continuously reacts by chain reaction to generate self-generated resin, resin composition using cations, radicals, anions in the series of curing reactions, resin inside Examples thereof include a resin composition that positively generates cations and heat of curing reaction or continuously self-generates.

According to the molding method of the present invention, it is possible to cure regardless of the presence or absence of the energy ray shielding substance in the matrix resin of the coal ash recycled product, and even if the plate thickness is thick, the product is cured by the energy ray. Can be made. Moreover, this invention is applicable not only to this product but other filler high filling products. Thereby, if the shaping | molding method which concerns on this invention is used, it is possible to harden a resin composition in a short time (several minutes level) by energy ray hardening. For this reason, productivity improvement and cost reduction can be expected. In addition, energy efficiency is good and running costs are low. It has excellent advantages such as a small size of equipment such as a UV lamp and no need for cost and space.

A preferred embodiment of the present invention will be described with reference to the accompanying drawings.
Embodiment (Part 1)
The coal ash-containing resin composition used in the present invention is composed of an energy beam curable resin mixture (chain curable resin) containing a cationic photopolymerization initiator and a photopolymerizable polymer, and coal ash.
The composition ratio of the coal ash-containing resin composition used in the present invention is preferably such that the energy beam curable resin mixture is contained in a proportion of 15% by weight or more. Specifically, for example, 100 g (20 wt%) of the energy ray curable resin mixture with respect to 400 g (80 wt%) of fly ash, or energy rays with respect to 425 g (85 wt%) of fly ash. In a proportion of 75 g (15% by weight) of the curable resin mixture, it is easily cured by irradiation with energy rays.

  On the other hand, if the composition ratio is less than 15% by weight of the energy beam curable resin mixture and more than 85% by weight of coal ash, it is not preferable because rapid and reliable curing is difficult. Further, the curing itself is not performed when the energy ray curable resin mixture is about 5% by weight and the coal ash is about 95% by weight. On the other hand, the amount of the resin to be blended may vary greatly depending on the use of the cured molded product, and the composition ratio is not particularly limited. Therefore, if the energy ray curable resin mixture is 15% by weight or more, the amount ratio of the resin is determined on a case-by-case basis, and a preferable composition ratio is determined depending on the application. Generally, within the above composition ratio range, when a large amount of coal ash is blended, the resulting molded product is hard and high in strength, while when a large amount of resin is blended, it becomes soft. First, the energy beam curable resin mixture will be described.

  The energy beam curable resin mixture (chain curable resin) used in the present invention includes a cationic photopolymerization initiator system and a photopolymerizable resin. Here, although a photopolymerizable resin is also expressed as an oligomer, application of a cationic photopolymerizable polymer or a photopolymerizable epoxy polymer is particularly preferable. Specific examples of this type of photopolymerizable polymer include alicyclic epoxy, glycidyl ether type epoxy, epoxidized polyolefin, epoxy (meth) acrylate, polyester acrylate, vinyl ether compound and the like. The photopolymerizable resin may contain a cationic photopolymerizable monomer or a photopolymerizable epoxy monomer. Specific examples of such a photopolymerizable monomer include an epoxy monomer, an acrylic monomer, a vinyl ether, Examples include cyclic ethers. Of the above specific examples, the photopolymerizable resin preferably contains a photopolymerizable alicyclic epoxy polymer or a photopolymerizable alicyclic epoxy monomer. As the cyclic epoxy resin, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferred.

  The photopolymerization initiator system includes a photopolymerization initiator composed of at least two components, and the photopolymerization initiator includes a cationic photo / thermal polymerization initiator or a cationic photopolymerization initiator. Specifically, at least one of an aryl sulfonium salt type (photoinitiator such as triarylsulfonium salt) as a cationic photopolymerization initiator and at least one of a sulfonium salt as a cationic photo / thermal polymerization initiator , A photopolymerization initiator system comprising at least two components is preferably used.

  A preferable mixing ratio of the energy ray curable resin mixture that can be used in the present invention is a photopolymerization initiator system (reaction) comprising at least two components with respect to 100 parts by weight of the photopolymerizable resin (photopolymerizable oligomer or monomer). (Catalyst system) component of 0.5 to 6.0 parts by weight, more preferably 1.5 to 3.5 parts by weight, and a photo / thermal polymerization initiator / photopolymerization start constituting a photopolymerization initiator system component The weight ratio of the agent is 1 to 4, more preferably 1.3 to 3.5. When the ratio of the photopolymerization initiator composed of at least two components is less than 0.5 parts by weight, the photopolymerization initiation effect is hardly obtained, and the amount of the photopolymerization initiator is less likely to function because the amount is small relative to the whole. On the other hand, even if it exceeds 6.0 parts by weight, the photocuring function itself does not change, and from the viewpoint of cost, 6.0 parts by weight or less is preferable. Also, if the weight ratio of cationic photo / thermal polymerization initiator / cationic photopolymerization initiator is smaller than 1, heat generation at the initial stage of curing is difficult to obtain, and the curing function that is a feature of the present invention is difficult to exert. It is not preferable because it only cures. On the other hand, when the weight ratio exceeds 4, the curing characteristics, particularly the heat generation characteristics, are abnormally increased, which causes a problem that the resin foams due to rapid heat curing, which is not preferable.

  The mixing pattern of the energy beam curable resin mixture is not particularly limited as long as it is within the scope of the present invention. Specifically, the following energy beam curable resin mixture is mentioned as a preferred embodiment. (I to iii). These are all preferred embodiments that can be used in the present invention, have the property of being easily and rapidly cured, and are the basic form of the energy beam curable resin mixture used in the present invention.

i: Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd .: alicyclic epoxy resin; 3,4-cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate) 100 parts by weight of Sun-Aid SI-80L (Sanshin Chemical ( Co., Ltd .: Cationic light / thermal polymerization initiator) 1.75 parts by weight, DAICAT11 (Daicel Chemical Industries, Ltd .: Cationic photopolymerization initiator; aryl sulfonium salt) 0.75 parts by weight .
ii: Epicoat 828 (Oilized Shell Epoxy Co., Ltd.) with respect to 50 parts by weight of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd .: alicyclic epoxy resin; 3,4-cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate) ): Bisphenol A type epoxy) 50 parts by weight, Sun-Aid SI-80L (manufactured by Sanshin Chemical Co., Ltd .: cationic photo / thermal polymerization initiator) 1.75 parts by weight, DAICAT 11 (manufactured by Daicel Chemical Industries, Ltd.) (Cationic photopolymerization initiator; aryl sulfonium salt) mixed with 0.75 part by weight.

iii: Celamide 2021P (manufactured by Daicel Chemical Industries, Ltd .: cycloaliphatic epoxy resin; 3,4-cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate) with respect to 100 parts by weight, Sun Aid SI-80L (Sanshin Chemical ( Co., Ltd .: Cationic light / thermal polymerization initiator) 1.50 parts by weight, DAICAT11 (Daicel Chemical Industries, Ltd .: Cationic photopolymerization initiator; aryl sulfonium salt) 0.50 parts by weight, 4, 4 '-Bis [di (β-
Hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate 0.50 part by weight and 2-butynyltetramethylenesulfonium hexafluoroantimonate 0.50 part by weight.
The above can be mentioned as a suitable mixture.

  Additives that can be added to the above-mentioned energy ray curable resin mixture in a curable range include energy ray shielding substances (for example, carbon and carbon fibers (short fibers, long fibers, continuous fibers, carbon cloth, etc.), One or more commonly used additives such as inorganic fillers, blocking substances other than coal ash such as metal powders, and various fillers, organic components, photosensitizers, reactive diluents, sharpeners, and the like can be added. .

Next, the coal ash used in the present invention will be described. The resin composition used in the present invention is composed of an energy ray curable resin mixture (chain curable resin) containing a photopolymerization initiator system and a photopolymerizable resin, and coal ash. Coal ash widely includes what is called fly ash as an inorganic substance-containing material. Although various things can be considered as fly ash, it is usually applied to fly ash discharged from a thermal power plant or the like, and has a configuration including a glass (silica) particle ceramic. The amount ratio of the coal ash is large, and the coal ash-containing resin composition of the present invention is used in a wide range of 85% by weight or less according to the use of the molded product. For example, although it will not be limited if the ratio in which the said energy-beam curable resin mixture enters is 15 weight% or more with respect to 400g of fly ash, Preferably it is 80g-400g, More preferably, it is 100g-200g. From the viewpoint of fly ash recycling, a higher fly ash ratio is better, but these ratios must be determined according to the required specifications of the target product. If the physical properties such as heat resistance are high and the fly ash is small, it is considered easy moldability.

  Further, the resin composition used in the present invention may contain reinforcing fibers, pigments and the like in addition to the energy ray curable resin mixture and coal ash, and the amount ratio thereof is not particularly limited. However, for example, in the case of 400 g of coal ash and 100 g of energy ray curable resin mixture, it is preferable to mix about 0.5 to 5 g of reinforcing fibers and about 5 to 50 g of pigment.

  The coal ash-containing resin composition having the above-described composition is cured by heat or light, or is cured by both heat and light. In curing, it is a chain reaction type, and curing proceeds with other energy self-generated inside the resin composition along with external energy. Therefore, the curing method changes depending on the energy beam irradiation method, but the curing proceeds much faster than the conventional thermosetting composition. Further, if heat is applied during the energy ray irradiation (for example, about 120 ° C.), the curing can be controlled more easily.

Specifically, the light source, time, and the like change as the curing conditions. When irradiating the resin composition with energy rays, the heating conditions at the time of curing can be appropriately changed to optimum conditions. It is also possible to preheat the resin composition before curing, and then form it by irradiating energy rays. In the case of preheating, there is an advantage that it can be cured in a shorter time (usually about 1/2 to 2/3).
When irradiation is performed using ultraviolet light (UV) as an energy ray, curing by UV irradiation can be performed, for example, by satisfying the following requirements. Curing conditions: Lamp type: Metal halide lamp, Lamp strength: 120 W / cm Lamp length: 250 mm, Atmosphere / temperature / pressure: In-air / room temperature / atmospheric pressure Irradiation distance: 20 cm Irradiation time: 5 minutes [curing completed in 5 minutes]

  If the resin composition as described above is used, it is possible to provide a molded product that is highly filled with coal ash that does not transmit light and that is excellent in strength and the like. By using such a resin, a highly filled composition can be cured, and a good product can be produced with pressure applied. This is because, by applying pressure, the resin composition is sufficiently distributed to the details, and the composition becomes sufficiently dense and a product having strength can be obtained.

Embodiment (2)
In terms of apparatus, a curing method using light cannot be employed in a molding apparatus having a normal mold. In the method for molding a coal ash-containing resin composition according to the present invention, an apparatus that can load pressure and can be irradiated with light is required. Then, as a shaping | molding apparatus employ | adopted by this invention , the shaping | molding apparatus which has an optical fiber as shown in FIGS. 1-3, for example is mentioned. In these apparatuses shown in FIGS. 1 to 3, a method is adopted in which a hole is formed in a movable mold and irradiation is performed through an optical fiber. Hereinafter, the shaping | molding apparatus employ | adopted with the shaping | molding method of the coal ash containing resin composition which concerns on this invention is demonstrated .

Although several mechanisms can be employed as the injection mechanism in the molding apparatus employed in the present invention, FIG. 1 shows a screw type injection molding apparatus in which the injection mechanism is a screw system as an example. This device is provided with a hopper 20, a screw 18 and the like, and is not only extruded for injection molding, but also has a valve 11 at the tip of the screw 18. First, when the resin composition is stored in the hopper 20, it is extruded by applying pressure. In order to extrude, the cylinder 19 for that is prepared, and the motor 23 for rotating a screw is also prepared.

A rotating valve 11 is provided at the tip of the cylinder 19 because it is difficult for the resin composition to flow and solidify while storing the resin composition. When the resin is fed in with the rotary valve 11 closed, when a certain amount of resin is accumulated, the rotary valve 11 is turned to extrude the resin composition. On the extruded side, molds 1 and 2 having a shape to be molded are provided. Here, after the resin composition of the above embodiment (No. 1) is driven into the mold, light must be irradiated for curing. In the molding apparatus employed in the present invention , the right mold in FIG. 1 is a fixed mold 1 and the left mold is a movable mold 2. If the movable mold 2 moves forward, the molded product cavity 3 is completed, and if the movable mold 2 moves backward, the space is opened and the ejector is ejected.

In the molding apparatus employed in the present invention, the raw material supply process is important. In the raw material supply, the energy beam curable resin mixture and coal ash described above are mixed and charged by the hopper 20. While putting the coal ash into the hopper 20, the resin mixture containing the resin and the catalyst is put separately and stirred. Specifically, for example, a mixture or coal ash is charged into the hopper 20 at a constant ratio at a stretch, and the hopper 20 and the subsequent screw 18 are mixed well to obtain a coal ash-containing resin composition.

  On the other hand, at present, not only thermoplastic resins but also thermosetting resins (such as phenolic resins) are injection-molded using an injection molding machine (extruder). Therefore, a molding machine suitable for curing the resin composition of the present invention is particularly characterized in that irradiation with energy rays (UV light, visible light, etc.) is possible in the mold part. In the case where rapid curing is mainly considered, it is preferable that the energy ray is UV. The molding machine shown in FIG. 1 manufactures a molded product by guiding light from a UV light source into a mold using an optical fiber. Here, a hole is made in the movable mold 2 and the optical fiber 7 is passed through.

  When a molded product containing a resin is produced, a material to which pressure is applied exhibits very good performance, and it is an advantage of performing injection molding that such pressure can be applied. This is because the contents of the molded product are tightly packed and a high density can be produced, and the strength and other qualities are improved. If the molding apparatus of the present invention is used, a sufficient pressure can be applied during curing by the movable mold 2 and the fixed mold 1, and a product excellent in strength and the like can be obtained. The strength of the pressure in the mold is determined in consideration of the required strength of the product. When strength is required, it is necessary to load a high pressure. However, since energy is required, the cost tends to increase.

  Here, the relationship between the light source and the connector in FIG. 1 will be described. The connector 9 has a role of bundling a plurality of optical fibers 7 and is arranged in the vicinity of the light source 8. The optical fiber 7 may be a material that transmits UV light. Further, even a bundle of thin optical fibers 7 may be irradiated at once using a thicker optical fiber 7. However, in order to irradiate uniformly, it is more preferable to use the optical fiber 7 provided with a plurality of thin optical paths. By using the optical fiber 7, the light of the same light source having the same curing action can be arbitrarily changed in direction, the light path can be freely bent, and the light can be guided into the mold. In addition, the optical fiber 7 has low energy loss and high efficiency. However, glass or the like can also be used.

  As a method of securing the optical path in the mold, for example, a hole can be made in the mold itself, and the optical fiber 7 or glass can be filled therein, but it can be selected as appropriate depending on the shape of the mold. If the mold can make a hole (light path) straight, light may be moved to the entrance of the mold by an optical fiber, and the light path in the mold may be made of glass. That is, even if a material such as glass is used, since the optical path is straight and the surroundings are made of metal, it is possible to use glass or the like if less light is lost. Therefore, in the mold, an optical path can be secured without using an optical fiber, and there is no need to use an expensive optical fiber 7 up to the portion of the molded article cavite 3 having a resin composition. Therefore, for example, an optical fiber is used up to the entrance of the mold, and an optical path is provided inside the mold by a material such as glass that satisfies a certain reflection efficiency.

Embodiment (Part 3)
The molding apparatus employed in the present invention is a specific mold having an optical path of energy rays (for example, UV, visible light, etc.), an injection mechanism (preferably a pressurizing apparatus) such as a screw system, and the mold. And a light introducing portion. Here, in the apparatus employed in the present invention , the configuration as in the above-described embodiment (No. 2) is a preferred example, but the injection mechanism of the resin composition combined with the specific mold, preferably the pressurizing mechanism As such, several mechanisms can be applied. That is, the screw 18 and the fixed mold 1 can be replaced with other forms in the molding apparatus employed in the present invention. Here again, the movable mold 2 which is a light transmission mold that determines how to transmit light, and the feeding device such as the light introducing section such as the optical fiber 7 are the same as in the second embodiment.

  Examples of the injection mechanism include a device (pressurizing device) that can introduce the resin composition into the mold under pressure, for example, the screw device with a check valve shown in FIG. There is a check ring 16. And if this check ring 16 exists, since the resin composition does not flow, it is a structure in which the groove 12 is cut. On the other hand, a pressure at the time of injection (introduction) is not necessarily required, but a certain amount of pressure is usually required to inject a composition containing coal ash or the like. What is necessary is just to be able to inject so that it may spread in a mold.

  For this reason, not only the screw system, but generally a device that can add coal ash and mixed resin, stir (there is a stirring section), and inject into a mold (for example, a piston). For example, a plunger type injection mechanism as shown in FIG. Further, as a method similar to the blanker method of FIG. 2, an embodiment in which an apparatus for press molding as shown in FIG. 3 in which pressure is applied by pressing after pouring into a mold is also possible.

  When using any of these injection mechanisms, it is preferable to preheat the mold, cylinder, blanker, etc. to some extent in advance. For example, when using a screw method, the screw can be heated in advance, but by performing temperature control at a preheating level before curing in this way, efficient molding is possible. The preheating in the molding process may be performed by preheating a mold or the like, or by preheating the resin composition itself.

  Since the resin system used in the present invention is a chain reaction type, when heat is applied, the resin composition itself generates heat and tends to be gradually cured. First, when the energy beam is irradiated, the energy irradiation amount (joule) is integrated, so that it reacts (cures) and the temperature of the resin rises. When the temperature exceeds a certain temperature, the thermosetting (pattern) resin itself reacts, so that the curing speed changes. That is, firstly, preheating has an advantage that the time required for reaching a certain temperature and thermosetting can be shortened. Since the time before curing begins (before thermal reaction) can be shortened, the curing reaction can be started quickly. However, the curing of the resin composition itself must be performed in a mold. Second, if the ambient temperature of the molding is increased, the resin composition is cured, and immediately when the resin itself generates energy and generates heat, the ambient temperature is further increased to a constant temperature. The curing time itself becomes extremely short. And time after hardening starts (after thermosetting reaction start) can also be shortened, and hardening reaction can be advanced rapidly.

  Therefore, for example, in the case of a screw system (extruder), it is effective to preheat the part of the supply hopper 20, the part of the screw 18, or the parts of the molds 1 and 2. As the preheating temperature, the threshold value of the composition of the first embodiment (part 1) is about 100 ° C. (80 to 120 ° C.), and therefore the temperature needs to be lower than this. However, in a range close to this temperature, a certain amount of heat is generated due to friction in the screw and the like, and there is a possibility that curing will start in the apparatus. The degree is preferred.

FIG. 1 is a cross-sectional view of a screw type injection molding apparatus in which an injection mechanism is a screw system as an example of a molding apparatus employed in the present invention. FIG. 2 is a cross-sectional view of a plunger type injection mechanism as an example of the injection mechanism used in the molding apparatus employed in the present invention. FIG. 3 is a cross-sectional view showing an embodiment applied to a press molding apparatus as an example of a molding apparatus employed in the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Fixed metal mold | die 2 Movable metal mold | die 3 Molded product cavite 4 Die head 5 Platen 7 Optical fiber 8 UV light source 9 Connector 10 Sheet | seat 11 Rotary valve 12 Groove | channel 13 Gas passage | gas escape groove | channel 15 Gas reservoir 16 Cylinder 20 hopper 21 hydraulic cylinder 22 hydraulic piston 23 hydraulic motor 24 heating barrel 25 stirring screw groove 26 stirring screw 27 heater 29 blanker 30 space 31 nozzle 32 check valve 33 ram 34 inlay 35 bolt 36 groove 37 inlet 38 bed

Claims (1)

An energy ray curable resin mixture containing a photopolymerizable resin and a photopolymerization initiator system and coal ash are mixed, and the energy ray curable resin mixture is an alicyclic epoxy, a glycidyl ether type epoxy, an epoxidized polyolefin. The photopolymerization initiator system component consisting of at least two components with respect to 100 parts by weight of the photopolymerizable resin selected from the group of photopolymerizable epoxy polymers consisting of and the group consisting of vinyl ether compounds. The weight ratio of the cationic light / thermal polymerization initiator component and the cationic photopolymerization initiator constituting the photopolymerization initiator component is the cationic light / thermal polymerization initiator component / cationic system. As a photopolymerization initiator, it is 1-4, and the coal ash-containing resin composition containing the energy ray curable resin mixture and the coal ash is light-transmitted by an injection mechanism. Features of a mold, fed into a mold through an optical fiber therein, to make it curing the coal ash-containing resin composition by introducing the light from the introducing portion of light to the mold A method for forming a coal ash-containing resin composition.

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