JP6206876B2 - Kneading equipment - Google Patents

Description

  The present invention relates to a kneading apparatus used for producing a resin composition.

An epoxy resin composition is used as a resin composition for sealing an optical semiconductor such as a light emitting diode or for a reflector. As a method for producing the epoxy resin composition, a production method for producing continuously with high production efficiency has been proposed (for example, see Patent Document 1). This production method uses a kneading apparatus shown in FIG. That is, in this kneading apparatus, the first kneader N ₁ provided with the heating means H ₁ and the second kneader N ₂ provided with the cooling means C ₁ are connected in series, and each kneader N ₁ , N _{2 is connected.} The supply ports 11 and 12 are formed in the upstream portion of the second, and the discharge port 13 is formed in the downstream portion of the second kneader N ₂ . Then, a mixture of a powdery epoxy resin and a liquid curing agent in advance, is supplied from the first kneader N ₁ of the supply port 11, while heating the mixture by heating means H _1, first kneader N ₁ The kneading screw S _{1 is} kneaded. The mixture is uniformly kneaded by this heat kneading. Then, feeding the kneaded product in the second kneader N _2. Subsequently, the powder kneading accelerator is supplied from the supply port 12 of the second kneader N ₂ , and the kneaded product and the curing accelerator are cooled by the cooling means C ₁ while kneading the second kneader N ₂ . kneaded by the use screw S _2. By this cooling and kneading, the curing accelerator is sufficiently and uniformly kneaded into the kneaded product while suppressing the reaction between the epoxy resin and the liquid curing agent. Subsequently, the kneaded product (epoxy resin composition) is discharged from the discharge port 13.

JP 2002-121261 A

In the conventional method for producing an epoxy resin composition, a powdery epoxy resin and a liquid curing agent are mixed in advance prior to supply to the supply port 11 of the first kneader N ₁ . The reason is that if the powdery material (epoxy resin) and the liquid material (curing agent) are simply kneaded with a kneader, they cannot be uniformly dispersed, resulting in uneven reaction and ash content shift, resulting in unstable quality. Because. Moreover, prior to supply to the first kneader N ₁ of the supply port 11, mixing of the powdery epoxy resin and liquid curing agent is a batch to be mixed with every predetermined amount by using the stirred tank, etc. Yes.

That is, in the conventional method for producing an epoxy resin composition, after a premixed mixture of a powdery epoxy resin and a liquid curing agent is supplied to the supply port 11 of the first kneader N ₁ , it can be continuously produced. However, if the process of mixing the powdery epoxy resin and the liquid curing agent before the supply is included, the production is not continuous. When continuously kneaded for continuous production, the quality of the produced epoxy resin composition cannot be stabilized as described above.

  The present invention has been made in view of such circumstances. Even if a resin composition can be produced by continuous kneading, a powder composition and a liquid material can be uniformly kneaded using a kneader. An object of the present invention is to provide a kneading apparatus capable of stabilizing the quality of the product.

In order to achieve the above object, a kneading apparatus of the present invention is a kneading apparatus for an epoxy resin composition, and includes a kneader having a first supply port and a second supply port downstream of the first supply port, A powder material supply means connected to one supply port for supplying powder material into the kneader, and a liquid connected to the second supply port for supplying the liquid material into the kneader at a pressure higher than the pressure in the kneader. A material supply means, a low temperature maintenance means provided between the first supply port and the second supply port, for maintaining the powdery material supplied from the first supply port at a temperature that does not melt, and the second A heating means provided between the supply port and a predetermined downstream portion, for heating to melt the powdered material fed to the second supply port, and provided downstream from the heating means; Cool the kneaded material heated by the heating means A configuration that includes a cooling means.

  In order to achieve the intended purpose, the present inventors use a kneader having a first supply port and a second supply port downstream of the first supply port, and a powdery material and a liquid necessary for the production of the resin composition. Research was repeated on how to supply materials to the kneader. As a result, it was found that the following first to third steps should be performed. That is, as the first step, the powdery material is supplied into the kneader from the first supply port, and the powdery material is moved to the second supply port side at a temperature at which the powdery material is not melted by the kneader. Send it in. After that, as a second step, the powdery material is melted by heating, and the liquid material is supplied from the second supply port at a pressure higher than the pressure in the kneader, The liquid material is kneaded. Subsequently, as a third step, the kneaded product is further kneaded while cooling. Through such first to third steps, it becomes possible to uniformly knead the powdery material and the liquid material with a kneader, and the quality of the resin composition to be produced even if continuously kneaded as described above Has been found to be stable, and the present invention has been achieved.

The kneading apparatus of the present invention is a kneading apparatus for an epoxy resin composition, and in a kneader having a first supply port and a second supply port on the downstream side thereof, a powdery material supply means is provided at the first supply port. And a low temperature maintaining means is provided between the first supply port and the second supply port, and the powdery material supplied from the first supply port is melted by the low temperature maintenance means between the first supply port and the second supply port. It is designed to maintain a temperature that will not be allowed to occur. Therefore, the powdery material can be uniformly dispersed, and the produced resin composition can be easily discharged quantitatively at the end of the kneader. Even when there are a plurality of powdery materials supplied from the first supply port, they can be mixed sufficiently uniformly before being fed to the second supply port side. Further, a heating means is provided between the second supply port and a predetermined downstream portion, and the heated material melts the powdery material fed to the second supply port. . At the same time, liquid material supply means is connected to the second supply port, and the liquid material supply means supplies the liquid material into the kneader at a pressure higher than the pressure in the kneader. For this reason, the melt of the powdery material becomes easily compatible with the liquid material supplied with high pressure, and both can be uniformly kneaded by a kneader. Further, the kneaded material is further kneaded on the downstream side from the heating means, but a cooling means is provided to knead while cooling by the cooling means. Therefore, the reaction of the kneaded product itself can be suppressed, and the target epoxy resin resin composition can be obtained in that state. Since the kneading apparatus of the present invention is configured as described above, the powdery material and the liquid material can be uniformly kneaded with a kneader, and the epoxy resin produced even if continuously kneaded as described above The quality of the resin composition can be stabilized.

In particular, the liquid material supply means is a means for supplying a curing agent that is a liquid material, and the powdery material supply means is a powdery material, an epoxy resin, a filler, an antioxidant, and a curing accelerator. If it is a means to supply , the epoxy resin composition whose quality was stable can be manufactured.

Furthermore, the low temperature maintenance means is a means in the range of 5 to 50 ° C. The set temperature, the heating means is a means in the range of 100 to 170 ° C. The set temperature is the cooling means, when the set temperature is a means in the range of 20 to 85 ° C. may be quality to obtain a more stable epoxy resin composition.

It is explanatory drawing which shows typically one Embodiment of the kneading apparatus of this invention. It is explanatory drawing which shows the conventional kneading apparatus typically.

  Next, embodiments of the present invention will be described in detail with reference to the drawings.

  FIG. 1 is an explanatory view schematically showing an embodiment of the kneading apparatus of the present invention. In the kneading apparatus of this embodiment, the first supply port 1 is formed in the upstream part (left part of FIG. 1), the second supply port 2 is formed in the midstream part (center part of FIG. 1), and the downstream part ( In the kneader N in which the discharge port 3 is formed in the right portion of FIG. 1, a powder supply means (powder material supply means) F is connected to the first supply port 1, and the second supply port 2 is connected to the kneader N. The pressure injection means (liquid material supply means) P is connected. Furthermore, a low temperature maintaining means L is provided between the first supply port 1 and the second supply port 2, and a heating means H is provided between the second supply port 2 and a predetermined downstream portion. The cooling means C is provided downstream from the heating means H.

  More specifically, as the kneader N, for example, one having parallel biaxial kneading screws S is used. In FIG. 1, since the biaxial kneading screw S overlaps, only the uniaxial kneading screw S is shown.

  As said powder supply means F, the powder supply machine generally used for the kneader etc. is used, for example.

  For example, a pressure injection pump or the like is used as the pressure injection means P.

  As the low temperature maintaining means L, for example, a water jacket type cooling circulation device or the like is used. The powdery material supplied from the first supply port 1 into the kneader N is not melted at a high temperature by the low temperature maintaining means L until it is fed to the second supply port 2 side. In the meantime, the powdery state can be maintained.

  As the heating means H, for example, an electric heater or the like is used. And the powdery material sent to the portion of the second supply port 2 is melted by the heating means H.

  As the cooling means C, for example, a water jacket type cooling circulation device or the like is used. The kneaded material heated and kneaded on the upstream side is cooled by the cooling means C.

Next, using the above kneading apparatus, a method for producing the d epoxy resin composition.

  First, an epoxy resin, a filler, an antioxidant, and a curing accelerator are prepared as powder materials and set in the powder supply means F. Moreover, a curing agent is prepared as a liquid material and set in the pressure injection means P.

  Next, a predetermined amount of powdery material is continuously supplied from the powder supply means F into the kneader N through the first supply port 1 and mixed by the kneading screw S of the kneader N. Then, it is fed to the second supply port 2 side. Since the low temperature maintaining means L is provided between the first supply port 1 and the second supply port 2, the powdery material does not melt and maintains a powdery state. Thereby, a plurality of powdery materials such as the epoxy resin and the filler are uniformly mixed and uniformly dispersed without becoming a lump. In addition, it is preferable that the supply amount accuracy of the powdery material from the powder supply means F is within 3% of the set value from the viewpoint of preventing the occurrence of a shift in composition ratio such as an ash shift. Moreover, it is preferable that the temperature set by the said low temperature maintenance means L exists in the range of 5-50 degreeC from a viewpoint which does not fuse the said powdery material.

  Next, the powdery material fed to the portion of the second supply port 2 is melted by the heating means H. At the same time, a predetermined amount of liquid material (curing agent) is continuously supplied from the pressure injection means P into the kneader N through the second supply port 2. The supply pressure at this time is set higher than the pressure in the kneader N. For example, it is 0.05 to 1.5 MPa, preferably 0.1 to 1.3 MPa, and more preferably 0.15 to 1.0 MPa. Then, the melt of the powdery material and the liquid material are kneaded by the kneading screw S of the kneader N. In this step, since the powdery material is melted, it becomes easy to blend in with the liquid material supplied with the high pressure, and both can be uniformly kneaded. In addition, it is preferable that the supply amount accuracy of the liquid material from the pressure injection means P is within 1.5% of the set value from the viewpoint of preventing occurrence of composition ratio deviation such as ash deviation. Moreover, it is preferable that the temperature set by the said heating means H exists in the range of 100-170 degreeC from a viewpoint of melting the said powdery material.

  Thereafter, the kneaded product of the powdered material melt and the liquid material is further kneaded by the kneading screw S of the kneader N while being cooled by the cooling means C to produce an epoxy resin composition. The gas is continuously discharged from the discharge port 3. The cooling by the cooling means C is to suppress the reaction of the kneaded product itself, and from this viewpoint, the set cooling temperature is preferably in the range of 20 to 85 ° C. Further, in the process from the first supply port 1 to the second supply port 2, the amount of the epoxy resin composition discharged from the discharge port 3 because the powdery material is uniformly dispersed without becoming a lump. Is substantially constant. By continuous kneading as described above, an epoxy resin composition with stable quality can be obtained.

  Here, the powdery material (epoxy resin, filler, antioxidant, curing accelerator) and liquid material (curing agent) will be described in detail.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin such as phenol novolak type epoxy resin and cresol novolak type epoxy resin, alicyclic epoxy resin, triglycidyl isocyanurate, hydantoin. Type epoxy resin, nitrogen-containing ring epoxy resin, water-added bisphenol A type epoxy resin, aliphatic epoxy resin, glycidyl ether type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy that is the mainstream of low water absorption rate cured type Examples thereof include a resin, a dicyclocyclic epoxy resin, and a naphthalene epoxy resin. These may be used alone or in combination of two or more. Among these epoxy resins, it is preferable to use an alicyclic epoxy resin and triglycidyl isocyanurate alone or in combination from the viewpoint of excellent transparency and discoloration resistance.

  The average epoxy equivalent of the epoxy resin is preferably 90 to 1000. If the epoxy equivalent is too small, the cured resin composition may become brittle, and if the epoxy equivalent is too large, the glass transition temperature (Tg) of the cured resin composition tends to be low.

  Examples of the filler include titanium oxide, zinc oxide, white lead, kaolin, calcium carbonate, zirconium oxide, quartz glass powder, talc, silica powder such as fused silica powder and crystalline silica powder, alumina powder, and aluminum nitride powder. And silicon nitride powder. These may be used alone or in combination of two or more. Among them, it is preferable to use titanium oxide from the viewpoint of excellent whiteness, high light reflectivity, hiding power and coloring power, high dispersibility, excellent weather resistance, extremely excellent chemical stability, etc. However, from the viewpoint of fluidity and light shielding properties, it is preferable to use those having an average particle size of 0.05 to 1.0 μm. Especially preferably, it is 0.08-0.5 micrometer from the point of light reflectivity. Moreover, it is preferable to use a silica powder from the viewpoint of reducing the linear expansion coefficient, and it is particularly preferable to use a spherical fused silica powder from the viewpoint of high filling property and high fluidity. Among them, it is preferable to use those having an average particle size in the range of 5 to 60 μm, particularly preferably in the range of an average particle size of 15 to 45 μm. The average particle diameter can be measured using, for example, a laser diffraction / scattering particle size distribution meter.

  Examples of the antioxidant include antioxidants such as phenol compounds, amine compounds, organic sulfur compounds, and phosphine compounds. In addition, you may use modifier | denaturants (for example, glycols, silicones, alcohols, etc.) and a defoaming agent (for example, silicone type etc.) as needed.

  Examples of the curing accelerator include tertiary amines such as 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, tri-2,4,6-dimethylaminomethylphenol, 2 -Imidazoles such as ethyl-4-methylimidazole and 2-methylimidazole, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium dimethylphosphate, tetra-n-butylphosphonium-o, o-diethylphosphorone dithioate And phosphorus compounds, quaternary ammonium salts, organometallic salts, and derivatives thereof. These may be used alone or in combination of two or more. Among these curing accelerators, it is preferable to use tertiary amines, imidazoles, and phosphorus compounds. Among them, it is particularly preferable to use a phosphorus compound in order to obtain a transparent and tough cured body with a low degree of coloring.

  It is preferable to set content of the said hardening accelerator to 0.01 to 8.0 weight% with respect to the said epoxy resin, More preferably, it is 0.1 to 3.0 weight%. That is, if the content of the curing accelerator is too small, a sufficient curing acceleration effect may not be obtained, and if the content of the curing accelerator is too large, the resulting cured product tends to be discolored. Because.

  As the curing agent, acid anhydride type liquid is used, for example, methyltetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, methylhexahydro And phthalic anhydride. These may be used alone or in combination of two or more. In addition, what is necessary is just liquid finally, and what dissolved the solid thing in the liquid thing may be used.

In the above embodiment, as the kneader N, a pair of kneading screws S as shown in FIG. 1 is used. However, if kneading can be performed continuously, two pairs as shown in FIG. A kneading screw S ₁ or S ₂ arranged in series may be used. In the above embodiment, the kneading screw S is biaxial, but it may be uniaxial or may be triaxial or more.

Moreover, in the said embodiment, although the epoxy resin composition was manufactured , another resin composition may be sufficient as a reference form .

  Next, examples will be described together with comparative examples. However, the present invention is not limited to the examples.

  As a powdery epoxy resin, 1000 g of triglycidyl isocyanurate and 50 g of (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate were prepared.

  As powder fillers, 4000 g of titanium oxide (rutile type, average particle size 0.21 μm) and 15000 g of silica (spherical melt, average particle size 23 μm) were prepared.

  As a powdery antioxidant, 15 g of butylhydroxytoluene was prepared.

  As a powdery accelerator, 10 g of tetra-n-butylphosphonium-o, o-diethylphosphorone dithioate was prepared.

  As a liquid curing agent, 1320 g of Rikacid MH-700 [70% (4-methylhexahydrophthalic anhydride) + 30% (hexahydrophthalic anhydride)] manufactured by Shin Nippon Chemical Co., Ltd. was prepared.

〔Example〕
Using the kneading apparatus shown in FIG. 1, an epoxy resin composition was produced from the powdery material and liquid material in the same manner as in the above embodiment. At this time, the set temperature by the low temperature maintaining means was 25 ° C., the set temperature by the heating means was 150 ° C., and the set temperature by the cooling means was 80 ° C. The supply amount of the powdery material from the powder supply means was set to 25 kg (accuracy ± 3.0%) per hour. Furthermore, the supply amount of the liquid material from the pressure injection means is 1678 g per hour (accuracy ± 1.5%), and the injection pressure (supply pressure) is 0.2 MPa (accuracy 0.1 to 0.5 MPa). Set to.

[Comparative Example 1]
In the above embodiment, the kneading apparatus used was a liquid material supply port moved to the same upstream position as the first supply port. Other than that, it was the same as the above-described example.

[Comparative Example 2]
In the above embodiment, as the kneading apparatus, the liquid material supply port moved to the upstream position between the first supply port and the second supply port was used. Other than that, it was the same as the above-described example.

[Comparative Example 3]
In the above embodiment, as the kneading apparatus, the liquid material supply port moved to the downstream position corresponding to the cooling means was used. Other than that, it was the same as the above-described example.

[Comparative Example 4]
In the above Examples, a kneading apparatus without a pressure injection means was used, and the liquid material was supplied from the second supply port without applying pressure. Other than that, it was the same as the above-described example.

[Comparative Example 5]
In Comparative Example 1, a kneading apparatus without a pressure injection means was used, and the liquid material was supplied without applying pressure. Other than that, it was the same as in Comparative Example 1 above.

[Inspection of state of epoxy resin composition]
The state of the epoxy resin compositions produced in the above Examples and Comparative Examples 1 to 5 was visually inspected. As a result, in the Example, the high quality thing without an ash content shift was obtained. On the other hand, in Comparative Example 1, since the liquid material supply port was at the same upstream position as the first supply port, the pressure of the liquid material supplied under pressure escaped from the first supply port and could not be sufficiently kneaded. In Comparative Example 2, since the liquid material was supplied in a state where the powdery material was not melted, it became a slurry. In Comparative Example 3, since the liquid material was supplied in a state where the melt of the powdery material was cooled, it could not be sufficiently uniformly mixed. In Comparative Example 4, since the liquid material was supplied without being pressurized, the liquid material was pushed back by the pressure in the kneader, and the melt of the powdery material and the liquid material could not be kneaded. In Comparative Example 5, the liquid material supply port was at the same upstream position as the first supply port, and the liquid material was not sufficiently mixed with the powdery material and accumulated in the kneader, resulting in ash shift.

  From the above results, it can be seen that when the powdery material and the liquid material are supplied into the kneader and continuously kneaded using the kneading apparatus of the example, the resulting epoxy resin composition has high quality.

The kneading apparatus of the present invention can be used when an epoxy resin composition is produced by continuously kneading a powdery material and a liquid material.

N Kneader F Powder supply means P Pressure injection means L Low temperature maintenance means H Heating means C Cooling means 1 First supply port 2 Second supply port

Claims (3)

A kneading apparatus for an epoxy resin composition, a kneader having a first supply port and a second supply port downstream of the first supply port, and connected to the first supply port to supply a powdery material in the kneader A powder material supply means, a liquid material supply means connected to the second supply port and supplying a liquid material into the kneader at a pressure higher than the pressure in the kneader, the first supply port, and the second supply. A low temperature maintaining means for maintaining the powdered material supplied from the first supply port at a temperature that does not melt, provided between the second supply port and a predetermined downstream portion, A heating means for heating to melt the powdery material fed to the second supply port, and a cooling means for cooling the kneaded material provided downstream from the heating means and heated by the heating means. A kneading device characterized by comprising . It said liquid material supply means is a means for supplying a curing agent is a liquid material, supplying said powdery material supply means is a powdery material, an epoxy resin, a filler, an antioxidant, and a curing accelerator The kneading apparatus according to claim 1, wherein the kneading apparatus is a means for performing the above. The low-temperature maintaining means is a means in the range of 5 to 50 ° C. The set temperature, the heating means is a means in the range of 100 to 170 ° C. The set temperature, the cooling means, the set temperature The kneading apparatus according to claim 2, wherein the kneading apparatus is a means for adjusting the temperature to 20 to 85 ° C.

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