WO2013011876A1 - Mold-cleaning resin composition - Google Patents
Mold-cleaning resin composition Download PDFInfo
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- WO2013011876A1 WO2013011876A1 PCT/JP2012/067619 JP2012067619W WO2013011876A1 WO 2013011876 A1 WO2013011876 A1 WO 2013011876A1 JP 2012067619 W JP2012067619 W JP 2012067619W WO 2013011876 A1 WO2013011876 A1 WO 2013011876A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/70—Maintenance
- B29C33/72—Cleaning
- B29C33/722—Compositions for cleaning moulds
Definitions
- the present invention relates to a mold cleaning resin composition.
- a thermosetting resin composition represented by epoxy resin, silicone resin, phenol resin, polyimide resin, etc.
- a mold cleaning resin composition containing an amino-based resin such as a melamine resin, and a mineral powder having a controlled maximum particle size and average particle size.
- an amino-based resin such as a melamine resin
- a mineral powder having a controlled maximum particle size and average particle size.
- the content of mineral powder having a maximum particle size of 180 ⁇ m or less and a particle size of 100 ⁇ m or more is set to the total amount of mineral powder. 1% by mass or less with respect to the total amount, and the content of mineral powder is 5 to 30% by mass with respect to the total amount of the resin composition for mold cleaning. Dirt is captured by spreading to every corner of the void inside the mold.
- the shape and structure of sealing molding of integrated circuits, LED elements, and the like are becoming diversified and refined. Therefore, the shape and structure of the molding die are required to be diversified and refined. In such a cleaning of the molding die, it is required to remove the dirt to every corner of the cavity of the molding die, including the corner part where the dirt tends to remain and the narrow gap part.
- conventional mold cleaning resin compositions including the mold cleaning resin composition disclosed in the above-mentioned JP-A-2003-62835 are molding molds that are being diversified and refined as described above. In terms of dealing with the shape and structure of the mold, the effect is not sufficient and there is room for improvement.
- the present invention has been made in view of the above circumstances, and can thoroughly clean every corner of the cavity of the molding die, and wear and scratches are generated on the inner surface of the molding die and the gate portion. It is an object of the present invention to provide a mold cleaning resin composition that is difficult to perform.
- the first aspect of the present invention includes at least a melamine-based resin, an average particle diameter of 4 to 12 ⁇ m, a standard deviation of particle diameter of 10 ⁇ m or less, and an average aspect ratio of particle diameter of 1 to 1.3. And an inorganic filler having a standard deviation of the particle diameter aspect ratio of 0.5 or less, and a mold cleaning resin composition.
- the mold cleaning resin composition preferably further contains a metal salt of a saturated fatty acid composed of a saturated fatty acid having 14 to 18 carbon atoms and a metal selected from calcium, zinc and magnesium.
- the inorganic filler is at least one selected from silicon carbide, silicon oxide, titanium carbide, titanium oxide, boron carbide, boron oxide, aluminum oxide, magnesium oxide, and calcium oxide.
- it is at least one selected from silicon oxide and aluminum oxide.
- the resin composition for mold cleaning is preferably used for transfer molding.
- the resin composition for mold cleaning of the present invention it is possible to sufficiently clean every corner of the cavity of the molding die, and wear and scratches are generated on the inner surface of the molding die and the gate portion. hard.
- the shapes and structures of sealing molds such as integrated circuits and LED elements have also been diversified and refined.
- the cleaning of the molding die it is required to remove the dirt to every corner of the cavity of the molding die, including corner portions and narrow gaps where dirt is likely to remain.
- the conventional mold cleaning resin composition cannot sufficiently cope with the diversification and refinement of the shape and structure of the mold, and in particular, is satisfied with dirt adhered to corners and narrow gaps. It was difficult to remove to the extent of.
- the filler contained in the conventional resin composition for mold cleaning has caused the internal surface of the mold to be worn or damaged.
- At least a melamine-based resin and an inorganic filler are selected as components, and the average particle diameter of the inorganic filler, the standard deviation of the particle diameter, the average aspect ratio of the particle diameter, and the aspect ratio of the particle diameter
- the resin composition for mold cleaning of the present invention includes at least a melamine resin, an average particle diameter of 4 to 12 ⁇ m, a standard deviation of particle diameter of 10 ⁇ m or less, and an average aspect ratio of particle diameter of 1 to 1 3 and an inorganic filler having a standard deviation of the particle diameter aspect ratio of 0.5 or less.
- the resin composition for mold cleaning of the present invention can be further constituted by using a saturated fatty acid or a metal salt thereof, an organic filler, other additives, and the like as necessary.
- the mold cleaning resin composition of the present invention is a sealing molding containing a thermosetting resin composition typified by an epoxy resin, a silicone resin, a phenol resin, a polyimide resin, etc. It is preferably used for removing dirt originating from the material.
- the mold cleaning resin composition of the present invention contains a melamine-based resin.
- the “melamine resin” refers to a melamine resin, a melamine-phenol cocondensate, and a melamine-urea cocondensate. More specifically, in the present invention, “melamine resin” refers to methylol melamine, which is a reaction product of melamine and formaldehyde, and a reaction product of melamine, phenol, or urea, and methylol melamine. In the present invention, one or more of these are selected and used.
- the resin composition for mold cleaning of the present invention contains a melamine-based resin, it exhibits excellent cleaning properties against dirt on the inner surface of the molding mold.
- Melamine resins have highly polar methylol groups.
- the highly polar methylol group possessed by the melamine resin acts on the dirt derived from the sealing molding material containing the thermosetting resin composition, so that an excellent cleaning effect is expected. It is done.
- the mold cleaning resin composition of the present invention is stable even in the vicinity of 160 to 190 ° C., which is a general temperature at the time of cleaning the molding die. It is considered that the cleaning performance is high.
- the melamine resin is a condensate of triazines and aldehydes.
- triazines include melamine, benzoguanamine, acetoguanamine and the like.
- aldehydes include formaldehyde, paraformaldehyde, acetaldehyde and the like.
- the melamine resin preferably has a molar ratio of a repeating unit derived from triazines and a repeating unit derived from aldehydes of 1: 1.2 to 1: 4.
- the melamine-phenol cocondensate is a cocondensate of triazines, phenols and aldehydes.
- the melamine-phenol cocondensate has a molar ratio of a repeating unit derived from triazines, a repeating unit derived from phenols, and a repeating unit derived from aldehydes from 1: 0.3: 1 to 1. It is preferably 1: 3.
- the melamine-urea cocondensate is a cocondensate of triazines, ureas, and aldehydes. Examples of ureas include urea, thiourea, and ethylene urea.
- the melamine resin in the present invention can be produced by a known method.
- the melamine resin is prepared by stirring melamine crystals and formaldehyde under the conditions of a molar ratio of 1: 1.2 to 1: 4, a reaction temperature of 80 to 90 ° C., and a pH of 7 to 7.5. It can be obtained by reacting for a time until an aqueous solution of 3% by mass becomes cloudy, adding NaOH and cooling.
- a melamine resin produced by a known method as described above may be used, or a commercially available melamine resin may be used.
- the content of the melamine-based resin in the present invention is preferably 60 to 80 parts by mass and more preferably 65 to 75 parts by mass with respect to 100 parts by mass of the total solid content of the mold cleaning resin composition. preferable.
- the content of the melamine resin is within the above range, the strength of the resin composition for mold cleaning is appropriately maintained when molded, and the curing during the cleaning also proceeds appropriately. Goods show excellent cleaning performance.
- the mold cleaning resin composition of the present invention includes an inorganic filler.
- the inorganic filler in the present invention include silicon carbide, silicon oxide, titanium carbide, titanium oxide, boron carbide, boron oxide, aluminum oxide, magnesium oxide, calcium oxide, and calcium carbonate. In the present invention, these inorganic fillers may be used alone or in combination.
- the inorganic filler in the present invention is preferably at least one selected from silicon carbide, silicon oxide, titanium carbide, titanium oxide, boron carbide, boron oxide, aluminum oxide, magnesium oxide, and calcium oxide. These inorganic fillers are preferable from the viewpoint of good mixing with the melamine-based resin when the resin composition for mold cleaning is produced.
- the more preferable inorganic filler is at least one selected from silicon oxide, titanium oxide, and aluminum oxide
- still more preferable inorganic filler is at least one selected from silicon oxide and aluminum oxide.
- a particularly preferred inorganic filler is a silicon oxide.
- silicon oxide, titanium oxide, and aluminum oxide have appropriate hardness and suppress the occurrence of wear and scratches on the inner surface of the mold and the gate part. This is preferable because it is possible.
- the temperature at which the mold is cleaned is usually 160 to 190 ° C., but silicon oxide, titanium oxide, and aluminum oxide are preferable because they are thermally stable near the above temperature.
- the hardness (new Mohs hardness) of the inorganic filler exemplified above is 13 for silicon carbide, 8 for silicon oxide, 9 for titanium carbide, 8 for titanium oxide, 14 for boron carbide, 3 for boron oxide, and oxidation.
- Aluminum is 12, magnesium oxide is 4, and calcium oxide is 3.
- the inorganic filler in the present invention has an average particle diameter of 4 to 12 ⁇ m, a standard deviation of the particle diameter of 10 ⁇ m or less, an average aspect ratio of the particle diameter of 1 to 1.3, and an aspect ratio of the particle diameter.
- the standard deviation of the ratio is 0.5 or less.
- the resin composition for mold cleaning of the present invention comprises an inorganic filler whose average particle diameter, standard deviation of particle diameter, average aspect ratio of particle diameter, and standard deviation of particle diameter aspect ratio are within a specific numerical range. Therefore, it is possible to sufficiently clean up to the corner portion of the cavity of the molding die, and it is difficult for the inner surface of the molding die and the gate portion to be worn or damaged.
- the average particle size of the inorganic filler in the present invention is in the range of 4 to 12 ⁇ m, and preferably in the range of 6 to 10 ⁇ m.
- An inorganic filler having a remarkably small average particle size has a small mass and surface area, and therefore it is considered difficult to exhibit cleaning performance in a cavity of a molding die.
- the average particle size of the inorganic filler is 4 ⁇ m or more, it exhibits a sufficient cleaning property against dirt on the inner surface of the molding die.
- the average particle size of the inorganic filler is 12 ⁇ m or less, it is possible to sufficiently clean up to the corner portion of the cavity of the molding die, and to the inner surface of the molding die and the gate portion. Abrasion and scratches are unlikely to occur.
- the standard deviation of the particle size of the inorganic filler in the present invention is 10 ⁇ m or less.
- the fluidity of the mold cleaning resin composition is deteriorated during cleaning, and the cleaning effect at the corner portion of the cavity of the molding die where dirt easily remains is reduced.
- the standard deviation of the particle size of the inorganic filler is 10 ⁇ m or less, the fluidity of the mold cleaning resin composition is maintained at the time of cleaning, and as a result, up to the corner of the cavity of the molding die. It becomes possible to clean thoroughly.
- the average aspect ratio of the particle size of the inorganic filler in the present invention is in the range of 1 to 1.3, preferably in the range of 1 to 1.25, and in the range of 1.10 to 1.23. It is more preferable that If the average aspect ratio of the particle size of the inorganic filler is large, the fluidity of the mold cleaning resin composition will deteriorate during cleaning, and the cleaning effect at the corners of the mold cavities where dirt tends to remain will be reduced. Also, wear and scratches are likely to occur on the inner surface of the molding die and the gate portion.
- the average aspect ratio of the particle size of the inorganic filler is 1.3 or less, the fluidity of the mold cleaning resin composition is maintained during cleaning, and as a result, the cavity of the mold It is possible to sufficiently clean up to the corner portion, and the inner surface of the molding die and the gate portion are less likely to be worn or damaged.
- the standard deviation of the aspect ratio of the particle size of the inorganic filler in the present invention is 0.5 or less, and preferably 0.45 or less. If the standard deviation of the aspect ratio of the particle size of the inorganic filler is large, the fluidity of the mold cleaning resin composition will deteriorate during cleaning, and the cleaning effect at the corners of the mold cavities where dirt tends to remain will be lost. In addition, the inner surface of the molding die and the gate portion are likely to be worn or damaged. In the present invention, the standard deviation of the aspect ratio of the particle size of the inorganic filler is 0.5 or less, and the inorganic filler has a substantially uniform shape. As a result, it is possible to sufficiently clean up to the corner portion of the cavity of the molding die, and it is difficult for the inner surface of the molding die and the gate portion to be worn or damaged.
- the “particle diameter” in the present invention is a value measured by the following method.
- the inorganic filler is photographed at a magnification of 1500 times using an electron microscope (JSM-5510, manufactured by JEOL Ltd.). Photographed so that about 30 inorganic fillers were included in one field of view, and measured the major axis (X) and minor axis (Y) five times each for a total of 150 inorganic fillers included in five different fields of view. To do.
- the minor axis (Y) is set to be orthogonal to the major axis (X).
- An average value of five measured values of the long diameter (X) and the short diameter (Y) is obtained and applied to the following formula 1, and the particle diameter of one inorganic filler is calculated.
- Particle size ((average value of 5 measured values of X) + (average value of 5 measured values of Y)) / 2 ... Formula 1
- the “average particle size” in the present invention is the average value of the particle sizes of 150 inorganic fillers measured by the above method. Further, the “standard deviation of particle diameter” in the present invention is a standard deviation of the particle diameters of 150 inorganic fillers measured by the above method.
- the “aspect ratio of particle diameter” in the present invention is a value measured by the following method.
- the inorganic filler is photographed at a magnification of 1500 times using an electron microscope (JSM-5510, manufactured by JEOL Ltd.). Photographed so that about 30 inorganic fillers were included in one field of view, and measured the major axis (X) and minor axis (Y) five times each for a total of 150 inorganic fillers included in five different fields of view. To do.
- the minor axis (Y) is taken to be orthogonal to the major axis (X).
- An average value of five measured values of the long diameter (X) and the short diameter (Y) is obtained and applied to the following formula 2 to calculate the particle diameter aspect ratio of one inorganic filler.
- the major axis (X) ⁇ the minor axis (Y).
- Aspect ratio of particle size (average value of five measured values of X) / (average value of five measured values of Y) Equation 2
- the aspect ratio of the particle size is 1. Further, according to the measurement method defined above, the aspect ratio of the particle diameter does not take a value less than 1.
- the shape of the inorganic filler in the present invention is substantially spherical (confirmation by an electron microscope). Therefore, the closer the aspect ratio of the particle size is to 1, the closer the shape of the inorganic filler is to a spherical shape.
- the inorganic filler used in the mold cleaning resin composition is crushed, that is, indeterminate. In the crushed inorganic filler, the particle diameter aspect ratio is, for example, 1.5 or more.
- the “average aspect ratio” in the present invention is an average value of the aspect ratios of the particle diameters of 150 inorganic fillers measured by the above method.
- the “standard deviation of aspect ratio” in the present invention is a standard deviation of the aspect ratio of the particle diameters of 150 inorganic fillers measured by the above method.
- the inorganic filler in the present invention satisfies the conditions of the above average particle diameter, standard deviation of particle diameter, average aspect ratio of particle diameter, and standard deviation of particle diameter aspect ratio.
- the maximum particle size is preferably 100 ⁇ m or less, and more preferably 75 ⁇ m or less. When the maximum particle size of the inorganic filler is 100 ⁇ m or less, the cleaning effect at the corner of the cavity of the molding die is further enhanced, which is preferable.
- suitable commercially available inorganic fillers that satisfy the above conditions of the average particle diameter, the standard deviation of the particle diameter, the average aspect ratio of the particle diameter, and the standard deviation of the particle diameter aspect ratio include, for example, HS203 ( NS And fused silica such as SE-15 (manufactured by Tokuyama Co., Ltd.), SE-8T (manufactured by Tokuyama Co., Ltd.), and alumina of CB-P10 (manufactured by Showa Denko KK).
- HS203 NS And fused silica such as SE-15 (manufactured by Tokuyama Co., Ltd.), SE-8T (manufactured by Tokuyama Co., Ltd.), and alumina of CB-P10 (manufactured by Showa Denko KK).
- the content of the inorganic filler in the present invention is preferably 10 to 30 parts by mass, and preferably 15 to 25 parts by mass with respect to 100 parts by mass of the total solid content of the mold cleaning resin composition. More preferred.
- the content of the inorganic filler is within the above range, the strength of the resin composition for mold cleaning is appropriately maintained when molded, so that workability when peeling from the mold after cleaning becomes good. Also, the cleaning performance of the inner surface of the molding die is improved.
- the mold cleaning resin composition of the present invention preferably contains an organic filler as an additive in order to appropriately maintain the strength of the mold cleaning resin composition.
- organic filler include pulp, wood powder, and synthetic fiber. Among these, pulp is particularly preferable.
- the pulp examples include wood pulp (conifer pulp, hardwood pulp), non-wood pulp (wood, bamboo, bagasse, cotton) and the like.
- wood pulp conifer pulp, hardwood pulp
- non-wood pulp wood, bamboo, bagasse, cotton
- the size of these pulps is not particularly limited, but is preferably 5 to 1000 ⁇ m, and more preferably 10 to 200 ⁇ m. If the size of the pulp is within the above range, the fluidity of the mold cleaning resin composition becomes good, which is preferable. Also, if the size of the pulp is within the above range, the strength of the mold cleaning resin composition is appropriately maintained when molded, so that the workability when peeling from the mold after cleaning is good. This is preferable.
- the content of the organic filler is preferably 3 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the mold cleaning resin composition.
- the content of the organic filler is within the above range, the fluidity of the mold cleaning resin composition becomes appropriate, which is preferable.
- the strength of the resin composition for mold cleaning is appropriately maintained when molded, so that workability when peeling from the mold after cleaning is improved. Since it becomes favorable, it is preferable.
- the resin composition for cleaning a mold according to the present invention has a good mold separation between the molded product after cleaning and the inner surface of the molding mold, and improves workability when the molded product is peeled from the mold.
- a metal salt of a saturated fatty acid composed of a saturated fatty acid having 12 to 20 carbon atoms and a metal selected from calcium, zinc, and magnesium as an additive is preferably included. It is more preferable to include a metal salt of a saturated fatty acid composed of a fatty acid and a metal selected from calcium, zinc, and magnesium.
- saturated fatty acid having 12 to 20 carbon atoms examples include lauric acid having 12 carbon atoms (IUPAC name: dodecanoic acid), myristic acid having 14 carbon atoms (IUPAC name: tetradecanoic acid), and palmitic acid having 16 carbon atoms (IUPAC name). : Hexadecanoic acid), stearic acid having 18 carbon atoms (IUPAC name: octadecanoic acid), arachidic acid having 20 carbon atoms (IUPAC name: eicosanoic acid), and the like.
- zinc myristate composed of a saturated fatty acid having 14 carbon atoms and zinc, zinc stearate composed of a saturated fatty acid having 18 carbon atoms and zinc, and a saturated fatty acid having 18 carbon atoms and calcium. More preferably, it comprises at least one of the constituted calcium stearate, and particularly preferably contains zinc myristate.
- Zinc myristate is preferable because it has a melting point of about 123 to 130 ° C., has sufficient fluidity at a temperature of 160 to 190 ° C. during mold cleaning, and easily acts on dirt.
- the content of the metal salt of the saturated fatty acid in the present invention is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total solid content of the mold cleaning resin composition, and 0.3 to 3 More preferably, it is part by mass.
- the content of the saturated fatty acid is within the above range, the mold separation between the molded product after cleaning and the inner surface of the molding die is good, and the workability when peeling the molded product from the mold is improved. Moreover, the cleaning performance of the inner surface of the molding die is improved.
- the resin composition for mold cleaning of the present invention further includes resins such as alkyd resin, polyester resin, acrylic resin, epoxy resin, and rubber as necessary, as long as the effects of the present invention are not impaired. But you can. Moreover, you may also contain additives, such as a well-known additive, for example, a curing catalyst, a lubricant, a coloring agent, an antioxidant.
- resins such as alkyd resin, polyester resin, acrylic resin, epoxy resin, and rubber as necessary, as long as the effects of the present invention are not impaired. But you can. Moreover, you may also contain additives, such as a well-known additive, for example, a curing catalyst, a lubricant, a coloring agent, an antioxidant.
- curing catalyst examples include phthalic anhydride, sulfamic acid, p-toluenesulfonic acid, benzoic acid, myristic acid, stearic acid, oxalic acid and other organic acids, hydrochloric acid, sulfuric acid and other inorganic acids.
- the lubricant examples include fatty acid amide type lubricants, specifically, saturated or unsaturated monoamide type lubricants such as lauric acid amide, myristic acid amide, erucic acid amide, oleic acid amide and stearic acid amide, Examples thereof include saturated or unsaturated bisamide type lubricants such as acid amide, ethylene bis stearic acid amide and ethylene bis oleic acid amide.
- the resin composition for mold cleaning of the present invention includes, for example, the melamine-based resin, the inorganic filler, and, if necessary, other components such as the organic filler, a metal salt of the saturated fatty acid, and an additive. Is prepared by almost uniformly mixing using a kneader, a ribbon blender, a Henschel mixer, a ball mill, a roll kneader, a raking machine, a tumbler, or the like.
- the mold cleaning resin composition of the present invention is suitable as a so-called transfer type mold cleaning resin composition for cleaning the inner surface of a molding mold by transfer molding.
- the resin composition for mold cleaning of the present invention is usually processed into a tablet shape and used for cleaning the inner surface of the molding mold. Specifically, after arranging the lead frame on the molding die, a tablet-like mold cleaning resin composition is inserted into the pot portion, clamped, and then washed away with a plunger. In this case, the mold cleaning resin composition in the pot portion flows through the runner portion, the gate portion, and into the cavity. After a predetermined molding time has elapsed, the mold is opened, and the molded product integrated with the lead frame, that is, the molded product of the mold cleaning resin composition containing dirt is removed.
- the resin composition for mold cleaning of the present invention removes dirt on the inner surface of a molding die that is produced during sealing molding operations for integrated circuits and the like by the method described above.
- the material of the molding die is, for example, iron or chromium, and the inner surface of the molding die is usually plated.
- the inner surface of the molding die is scratched and worn by micron size when the sealing molding operation and the cleaning operation are repeated. As a result, the plating surface applied to the inner surface of the molding die is lost or the surface state is roughened. Missing or roughened plating surface leads to deterioration of moldability and mold release during sealing molding operation, poor surface appearance, and loss of cleaning workability of the inner surface of the molding die.
- the resin composition for mold cleaning of the present invention has a specific range of the average particle diameter, the standard deviation of the particle diameter, the average aspect ratio of the particle diameter, and the standard deviation of the particle diameter aspect ratio of the inorganic filler as a constituent component. Therefore, it is possible to suppress the occurrence of scratches and wear on the inner surface of the molding die.
- die cleaning of this invention is shown.
- ⁇ 1> At least the melamine resin, the average particle diameter is 4 to 12 ⁇ m, the standard deviation of the particle diameter is 10 ⁇ m or less, the average aspect ratio of the particle diameter is 1 to 1.3, and the particle diameter And an inorganic filler having a standard deviation of the aspect ratio of 0.5 or less.
- ⁇ 2> Further for cleaning a mold according to the above ⁇ 1>, further comprising a saturated fatty acid metal salt composed of a saturated fatty acid having 14 to 18 carbon atoms and a metal selected from calcium, zinc, and magnesium. It is a resin composition.
- ⁇ 3> The above ⁇ 1> or wherein the inorganic filler is at least one selected from silicon carbide, silicon oxide, titanium carbide, titanium oxide, boron carbide, boron oxide, aluminum oxide, magnesium oxide, and calcium oxide.
- ⁇ 4> The mold cleaning resin composition according to ⁇ 3>, wherein the inorganic filler is at least one selected from silicon oxide and aluminum oxide.
- ⁇ 5> The mold cleaning resin composition according to any one of ⁇ 1> to ⁇ 4>, which is used for transfer molding.
- Example 1 As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd.) as an inorganic filler, and zinc stearate (zinc stearate GF200, as a metal salt of saturated fatty acid) 0.5 parts by mass (manufactured by NOF Corporation) and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized.
- silicon oxide fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd.
- zinc stearate zinc stearate
- GF200 zinc stearate GF200
- Example 1 0.35 parts by mass of stearamide as a lubricant was added using a Nauter mixer, and the mold cleaning resin composition of Example 1 was obtained.
- the mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
- the inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
- Example 2 As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, HS205, manufactured by Nippon Steel Materials Co., Ltd.) as an inorganic filler, and zinc stearate (zinc stearate GF200, 0.5 parts by mass (manufactured by NOF Corporation) and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized.
- silicon oxide fused silica, HS205, manufactured by Nippon Steel Materials Co., Ltd.
- zinc stearate zinc stearate
- benzoic acid as a curing catalyst
- Example 2 a mold cleaning resin composition of Example 2 was obtained.
- the mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
- the inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
- Example 3 As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, SE-40, manufactured by Tokuyama Co., Ltd.) as an inorganic filler, and zinc stearate (zinc stearate GF200, Japan) as a saturated fatty acid metal salt (Oil Co., Ltd.) 0.5 parts by mass and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized.
- silicon oxide fused silica, SE-40, manufactured by Tokuyama Co., Ltd.
- zinc stearate zinc stearate GF200, Japan
- benzoic acid as a curing catalyst
- Example 3 0.35 parts by mass of stearic acid amide was added as a lubricant by a Nauta mixer to obtain a mold cleaning resin composition of Example 3.
- the mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
- the inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
- Example 4 As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, SE-15, manufactured by Tokuyama Corporation) as an inorganic filler, and zinc stearate (zinc stearate GF200, NOF) as a metal salt of saturated fatty acid Co., Ltd.) 0.5 parts by mass and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized.
- silicon oxide fused silica, SE-15, manufactured by Tokuyama Corporation
- zinc stearate zinc stearate (zinc stearate GF200, NOF) as a metal salt of saturated fatty acid Co., Ltd.)
- Example 4 a mold cleaning resin composition of Example 4 was obtained.
- the mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
- the inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
- Example 5 As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of aluminum oxide (CB-P10, manufactured by Showa Denko KK) as an inorganic filler, and zinc stearate (Zinc stearate GF200, NOF Corporation) as a metal salt of saturated fatty acid (Product) 0.5 parts by mass and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized.
- CB-P10 aluminum oxide
- Zinc stearate GF200, NOF Corporation zinc stearate
- 0.5 parts by mass and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized.
- a lubricant 0.35 parts by mass of stearamide was added with a Nauta mixer to obtain a mold cleaning resin composition of Example 5.
- the mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
- the inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
- Example 6 As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by weight of melamine resin, 20 parts by weight of calcium carbonate (whiten SB blue, manufactured by Shiraishi Calcium Co., Ltd.) as an inorganic filler, and zinc stearate (zinc stearate GF200, NOF Corporation) as a metal salt of saturated fatty acid 0.5 parts by mass (made by company) and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized.
- calcium carbonate whiten SB blue, manufactured by Shiraishi Calcium Co., Ltd.
- zinc stearate zinc stearate GF200, NOF Corporation
- a lubricant 0.35 parts by mass of stearamide was added with a Nauta mixer to obtain a mold cleaning resin composition of Example 6.
- the mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
- the inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
- Example 7 As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, HS 203, manufactured by Nippon Steel Materials Co., Ltd.) as an inorganic filler, and calcium stearate (calcium allate GF200, Japan) as a metal salt of saturated fatty acid (Oil Co., Ltd.) 0.5 parts by mass and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized.
- silicon oxide fused silica, HS 203, manufactured by Nippon Steel Materials Co., Ltd.
- calcium stearate calcium stearate
- benzoic acid as a curing catalyst
- Example 7 As a lubricant, 0.35 parts by mass of stearamide was added with a Nauta mixer to obtain a mold cleaning resin composition of Example 7.
- the mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
- the inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
- Example 8 As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd.) as an inorganic filler, and zinc myristate (powder base M, Nikko) as a metal salt of saturated fatty acid (Oil Co., Ltd.) 0.5 parts by mass and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized.
- silicon oxide fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd.
- zinc myristate (powder base M, Nikko) as a metal salt of saturated fatty acid (Oil Co., Ltd.)
- Example 8 a mold cleaning resin composition of Example 8.
- the mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
- the inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
- Example 9 As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd.) as an inorganic filler, and zinc laurate (ZS-3, Nitto) as a metal salt of saturated fatty acid 0.5 parts by mass (made by Kasei Kogyo Co., Ltd.) and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized.
- silicon oxide fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd.
- ZS-3, Nitto zinc laurate
- Example 9 As a lubricant, 0.35 parts by mass of stearamide was added with a Nauta mixer to obtain a mold cleaning resin composition of Example 9.
- the mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
- the inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
- Example 10 As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd.) as an inorganic filler, and 0.5 parts by mass of zinc alkydate as a metal salt of saturated fatty acid As a curing catalyst, 0.05 part by mass of benzoic acid was charged into a ball mill and pulverized.
- silicon oxide fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd.
- Example 10 a mold cleaning resin composition of Example 10 was obtained.
- the mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
- the inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
- Example 11 As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd.) as an inorganic filler, and stearic acid (F-3, manufactured by Kawaken Fine Chemical Co., Ltd.) 5 parts by mass and 0.05 part by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized.
- silicon oxide fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd.
- stearic acid F-3, manufactured by Kawaken Fine Chemical Co., Ltd.
- Example 11 a mold cleaning resin composition of Example 11.
- the mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
- the inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
- a lubricant 0.35 parts by mass of stearamide was added with a Nauta mixer, and a mold cleaning resin composition of Comparative Example 2 was obtained.
- the mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
- the inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
- melamine resin As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of a melamine resin, and as an inorganic filler, silicon oxide (fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd. Micron) and silicon oxide (fused silica, HS302, manufactured by Nippon Steel Materials Co., Ltd.
- Micron 20 parts by mass of a mixture having a mass ratio of 1: 1, 0.5 parts by mass of zinc stearate (Zinc stearate GF200, manufactured by NOF Corporation) as a metal salt of a saturated fatty acid, and 0.05 ppm of benzoic acid as a curing catalyst Part by mass was charged into a ball mill and pulverized. Next, 0.35 parts by mass of stearamide as a lubricant was added using a Nauta mixer, and a mold cleaning resin composition of Comparative Example 3 was obtained. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
- the inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
- Comparative Example 7 As a melamine resin, 76.1 parts by mass of methylol melamine (Nicaridine S-176, manufactured by Nippon Carbide Industries Co., Ltd.), 23 parts by mass of hardwood pulp (LDPR, manufactured by Nippon Paper Industries Co., Ltd.), saturated fatty acid As a metal salt, 0.5 parts by mass of zinc stearate (Zinc stearate GF200, manufactured by NOF Corporation) and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized. Next, 0.35 parts by mass of stearamide as a lubricant was added using a Nauter mixer, and a mold cleaning resin composition of Comparative Example 7 was obtained. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
- methylol melamine Nicaridine S-176, manufactured by Nippon Carbide Industries Co., Ltd.
- LDPR manufactured by Nippon Paper Industries Co., Ltd.
- the inorganic filler was photographed at a magnification of 1500 times using an electron microscope (JSM-5510, manufactured by JEOL Ltd.). Photographed so that about 30 inorganic fillers were included in one field of view, and measured the major axis (X) and minor axis (Y) five times each for a total of 150 inorganic fillers included in five different fields of view. did.
- the minor axis (Y) was taken to be orthogonal to the major axis (X).
- the gate part of the mold used for this evaluation had a width of 800 ⁇ m and a height of 300 ⁇ m. The smaller the number of shots, the better the cleaning performance.
- a mold cleaning resin composition was molded using a mold having a width of 10 mm, a length of 100 mm, and a thickness of 4 mm, and used as an evaluation sample.
- a transfer automatic molding machine (mold temperature: 170 ° C., transfer pressure: 6.9 MPa, transfer time: 30 seconds, curing time: 90 seconds) was used.
- place # 1500 sandpaper on a rotating table of a Taber abrasion tester and then place a sample for evaluation of the resin composition for mold cleaning on the test machine so that the surface of 10 mm ⁇ 4 mm faces down.
- the sample was fixed using a tool, and the turntable was rotated 30 times at a speed of 60 rpm to obtain a flat surface of the sample for evaluation.
- a test piece is placed on a rotating table of a Taber abrasion tester, and an evaluation sample with a flat surface is fixed thereon with a testing machine jig, and the rotating table is rotated 30 times at a speed of 60 rpm while applying a load of 1000 g.
- a wear test was performed. After the abrasion test, the surface roughness (Ra: arithmetic average roughness, conforming to JIS B 0601-2001) was measured using a laser microscope (VK-9710, manufactured by Keyence Corporation).
- the value of the height was used as an index for evaluating the scratch resistance of the mold cleaning resin composition.
- FIG. 1 shows the relationship between the particle size and frequency of the inorganic filler used in the mold cleaning resin compositions of Example 8 and Comparative Example 6.
- the inorganic filler used in the mold cleaning resin composition of Example 8 contained 7% (11 out of 150) particles having a particle size of 2.5 ⁇ m or less.
- FIG. 2 shows the relationship between the particle diameter aspect ratio and the frequency of the inorganic filler used in the mold cleaning resin compositions of Example 8 and Comparative Example 6.
- the inorganic filler used in the mold cleaning resin composition of Example 8 contained 49% (74 out of 150 particles) whose particle diameter aspect ratio was in the range of 1.0 to 1.1. .
- die cleaning of Example 8 and Comparative Example 6 and frequency is shown in FIG.
- the volume of the inorganic filler was approximated by the following formula 3 with the average value of the major axis (X) and the minor axis (Y) as the particle size.
- the volume of approximation 4 ⁇ 3.14 ⁇ (particle diameter) 3/3 Equation 3
- the inorganic filler used in the mold cleaning resin composition of Example 8 contained 12% (18 out of 150) having an approximate volume value in the range of 10 to 100 ⁇ m 3 .
- At least the melamine-based resin composition and the inorganic filler are selected as constituent components, and the average particle size of the inorganic filler, the standard deviation of the particle size, the particle size
- the average aspect ratio and the standard deviation of the particle diameter aspect ratio within a specific range, it is possible to thoroughly clean all the cavities of the mold, and the inner surface of the mold.
- the mold cleaning resin composition of the present invention is a transfer-type mold cleaning resin composition for removing dirt on the mold surface derived from the thermosetting resin composition, and is a corner of the cavity of the molding mold. It can be thoroughly cleaned and suppresses wear and damage to the inner surface of the molding die and the gate portion.
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Abstract
Description
しかしながら、上記特開2003-62835号公報に開示された金型清掃用樹脂組成物をはじめとする、従来の金型清掃用樹脂組成物は、上記のような多様化、精密化しつつある成形金型の形状及び構造への対応という点では、効果が十分とはいえず、改善の余地がある。 In recent years, with the improvement in performance of electronic devices and the like, the shape and structure of sealing molding of integrated circuits, LED elements, and the like are becoming diversified and refined. Therefore, the shape and structure of the molding die are required to be diversified and refined. In such a cleaning of the molding die, it is required to remove the dirt to every corner of the cavity of the molding die, including the corner part where the dirt tends to remain and the narrow gap part.
However, conventional mold cleaning resin compositions including the mold cleaning resin composition disclosed in the above-mentioned JP-A-2003-62835 are molding molds that are being diversified and refined as described above. In terms of dealing with the shape and structure of the mold, the effect is not sufficient and there is room for improvement.
しかしながら、従来の金型清掃用樹脂組成物では、該金型清掃用樹脂組成物に含まれる充填材が、成形金型の内部表面を磨耗させたり、傷付けたりするため、めっき処理面の欠落や表面状態の荒れが発生していた。成形金型の内部表面に付いた傷の放置は、汚れを成形金型の内部表面に滞留させる原因となり、金型清掃の作業性を低下させることにもなる。さらに、成形金型のキャビティーのゲート部が磨耗すると、成形金型の修理や交換が必要となる。 By the way, dirt derived from the sealing molding material adhering to the inner surface of the molding die can be easily obtained by using the mold cleaning resin composition if the inner surface of the molding die is almost smooth. Can be removed. Usually, the inner surface of the molding die is plated.
However, in the conventional mold cleaning resin composition, the filler contained in the mold cleaning resin composition wears or damages the inner surface of the molding die. The surface condition was rough. Leaving scratches on the inner surface of the molding die causes dirt to stay on the inner surface of the molding die, and also reduces the workability of mold cleaning. Furthermore, when the gate portion of the mold cavity is worn, it is necessary to repair or replace the mold.
上記金型清掃用樹脂組成物は、更に、炭素数14~18の飽和脂肪酸と、カルシウム、亜鉛、及びマグネシウムから選択される金属と、から構成される飽和脂肪酸の金属塩を含むことが好ましい。 The first aspect of the present invention includes at least a melamine-based resin, an average particle diameter of 4 to 12 μm, a standard deviation of particle diameter of 10 μm or less, and an average aspect ratio of particle diameter of 1 to 1.3. And an inorganic filler having a standard deviation of the particle diameter aspect ratio of 0.5 or less, and a mold cleaning resin composition.
The mold cleaning resin composition preferably further contains a metal salt of a saturated fatty acid composed of a saturated fatty acid having 14 to 18 carbon atoms and a metal selected from calcium, zinc and magnesium.
本発明では、構成成分として、少なくとも、メラミン系樹脂と無機充填材とを選択し、該無機充填材の平均粒径、粒径の標準偏差、粒径の平均アスペクト比、及び粒径のアスペクト比の標準偏差を制御することにより、成形金型のキャビティーの隅々まで十分に清掃することができ、且つ、成形金型の内部表面及びゲート部に磨耗や傷が発生し難い、金型清掃用樹脂組成物の提供を実現可能とした点に意義がある。 In recent years, with the improvement in performance of electronic devices and the like, the shapes and structures of sealing molds such as integrated circuits and LED elements have also been diversified and refined. In the cleaning of the molding die, it is required to remove the dirt to every corner of the cavity of the molding die, including corner portions and narrow gaps where dirt is likely to remain. However, the conventional mold cleaning resin composition cannot sufficiently cope with the diversification and refinement of the shape and structure of the mold, and in particular, is satisfied with dirt adhered to corners and narrow gaps. It was difficult to remove to the extent of. Furthermore, the filler contained in the conventional resin composition for mold cleaning has caused the internal surface of the mold to be worn or damaged. If scratches on the inner surface of the molding die are left undisturbed, dirt stays on the inner surface of the molding die, and the workability of mold cleaning is reduced. Further, when the gate part of the cavity of the molding die is worn, it is necessary to repair or replace the molding die.
In the present invention, at least a melamine-based resin and an inorganic filler are selected as components, and the average particle diameter of the inorganic filler, the standard deviation of the particle diameter, the average aspect ratio of the particle diameter, and the aspect ratio of the particle diameter By controlling the standard deviation of the mold, it is possible to clean the mold cavity thoroughly, and the mold surface is hard to be worn and scratched on the inner surface of the mold and the gate part. It is significant that it is possible to provide a resin composition.
本発明の金型清掃用樹脂組成物は、少なくとも、メラミン系樹脂と、平均粒径が4~12μmであり、粒径の標準偏差が10μm以下であり、粒径の平均アスペクト比が1~1.3であり、且つ、粒径のアスペクト比の標準偏差が0.5以下である無機充填材とを用いて構成されている。本発明の金型清掃用樹脂組成物は、必要に応じて、更に、飽和脂肪酸又はその金属塩、有機充填材、その他添加剤等を用いて構成することができる。
本発明の金型清掃用樹脂組成物は、成形金型の内部表面の汚れ、特に、エポキシ樹脂、シリコーン樹脂、フェノール樹脂、ポリイミド樹脂等に代表される熱硬化性樹脂組成物を含む封止成形材料に由来する汚れを取り除くために、好適に用いられる。 [Resin composition for mold cleaning]
The resin composition for mold cleaning of the present invention includes at least a melamine resin, an average particle diameter of 4 to 12 μm, a standard deviation of particle diameter of 10 μm or less, and an average aspect ratio of particle diameter of 1 to 1 3 and an inorganic filler having a standard deviation of the particle diameter aspect ratio of 0.5 or less. The resin composition for mold cleaning of the present invention can be further constituted by using a saturated fatty acid or a metal salt thereof, an organic filler, other additives, and the like as necessary.
The mold cleaning resin composition of the present invention is a sealing molding containing a thermosetting resin composition typified by an epoxy resin, a silicone resin, a phenol resin, a polyimide resin, etc. It is preferably used for removing dirt originating from the material.
本発明の金型清掃用樹脂組成物は、メラミン系樹脂を含む。本発明において、「メラミン系樹脂」とは、メラミン樹脂、メラミン-フェノール共縮合物、及びメラミン-ユリア共縮合物をいう。より詳しくは、本発明において、「メラミン系樹脂」とは、メラミンとホルムアルデヒドとの反応物であるメチロールメラミン、及びメラミン、フェノール、又はユリアと、メチロールメラミンとの反応物をいう。本発明では、これらの中から1種以上を選択して用いる。
本発明の金型清掃用樹脂組成物は、メラミン系樹脂を含むので、成形金型の内部表面の汚れに対して優れたクリーニング性を示す。メラミン系樹脂は、極性の高いメチロール基を有している。本発明においては、メラミン系樹脂が有する極性の高いメチロール基が、熱硬化性樹脂組成物を含む封止成形材料に由来する汚れに作用することで、優れたクリーニング効果が奏されるものと考えられる。また、メラミン系樹脂は、熱に対して安定であるので、成形金型の清掃時の一般的な温度である160~190℃付近においても、本発明の金型清掃用樹脂組成物は、安定したクリーニング性を示すものと考えられる。 (Melamine resin)
The mold cleaning resin composition of the present invention contains a melamine-based resin. In the present invention, the “melamine resin” refers to a melamine resin, a melamine-phenol cocondensate, and a melamine-urea cocondensate. More specifically, in the present invention, “melamine resin” refers to methylol melamine, which is a reaction product of melamine and formaldehyde, and a reaction product of melamine, phenol, or urea, and methylol melamine. In the present invention, one or more of these are selected and used.
Since the resin composition for mold cleaning of the present invention contains a melamine-based resin, it exhibits excellent cleaning properties against dirt on the inner surface of the molding mold. Melamine resins have highly polar methylol groups. In the present invention, the highly polar methylol group possessed by the melamine resin acts on the dirt derived from the sealing molding material containing the thermosetting resin composition, so that an excellent cleaning effect is expected. It is done. In addition, since the melamine-based resin is stable against heat, the mold cleaning resin composition of the present invention is stable even in the vicinity of 160 to 190 ° C., which is a general temperature at the time of cleaning the molding die. It is considered that the cleaning performance is high.
本発明において、上記メラミン樹脂は、トリアジン類由来の繰り返し単位と、アルデヒド類由来の繰り返し単位とのモル比が、1:1.2~1:4であることが好ましい。
上記メラミン-フェノール共縮合物は、トリアジン類と、フェノール類と、アルデヒド類との共縮合物である。フェノール類としては、例えばフェノール、クレゾール、キシレノール、エチルフェノール、ブチルフェノール等が挙げられる。
本発明において、上記メラミン-フェノール共縮合物は、トリアジン類由来の繰り返し単位と、フェノール類由来の繰り返し単位と、アルデヒド類由来の繰り返し単位とのモル比が、1:0.3:1~1:1:3であることが好ましい。
上記メラミン-ユリア共縮合物は、トリアジン類と、ユリア類と、アルデヒド類との共縮合物である。ユリア類としては、例えば尿素、チオ尿素、エチレン尿素等が挙げられる。 The melamine resin is a condensate of triazines and aldehydes. Examples of triazines include melamine, benzoguanamine, acetoguanamine and the like. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde and the like.
In the present invention, the melamine resin preferably has a molar ratio of a repeating unit derived from triazines and a repeating unit derived from aldehydes of 1: 1.2 to 1: 4.
The melamine-phenol cocondensate is a cocondensate of triazines, phenols and aldehydes. Examples of phenols include phenol, cresol, xylenol, ethylphenol, butylphenol and the like.
In the present invention, the melamine-phenol cocondensate has a molar ratio of a repeating unit derived from triazines, a repeating unit derived from phenols, and a repeating unit derived from aldehydes from 1: 0.3: 1 to 1. It is preferably 1: 3.
The melamine-urea cocondensate is a cocondensate of triazines, ureas, and aldehydes. Examples of ureas include urea, thiourea, and ethylene urea.
本発明の金型清掃用樹脂組成物は、無機充填材を含む。本発明における無機充填材としては、例えば、炭化ケイ素、酸化ケイ素、炭化チタン、酸化チタン、炭化ホウ素、酸化ホウ素、酸化アルミニウム、酸化マグネシウム、酸化カルシウム、炭酸カルシウム等が挙げられる。本発明においては、これらの無機充填材を、単独で、或いは複数組み合わせて用いてもよい。 (Inorganic filler)
The mold cleaning resin composition of the present invention includes an inorganic filler. Examples of the inorganic filler in the present invention include silicon carbide, silicon oxide, titanium carbide, titanium oxide, boron carbide, boron oxide, aluminum oxide, magnesium oxide, calcium oxide, and calcium carbonate. In the present invention, these inorganic fillers may be used alone or in combination.
本発明において、より好ましい無機充填材は、酸化ケイ素、酸化チタン、及び酸化アルミニウムから選択される少なくとも1種であり、更により好ましい無機充填材は、酸化ケイ素、及び酸化アルミニウムから選択される少なくとも1種であり、特に好ましい無機充填材は、酸化ケイ素である。
金型の材質や状態にもよるため一概には言えないが、酸化ケイ素、酸化チタン、及び酸化アルミニウムは、硬度が適当であり、金型の内部表面及びゲート部の磨耗や傷の発生を抑制できるので、好ましい。また、金型を清掃する際の温度は、通常160~190℃であるが、酸化ケイ素、酸化チタン、及び酸化アルミニウムは、上記温度付近においても熱的に安定であるので、好ましい。 The inorganic filler in the present invention is preferably at least one selected from silicon carbide, silicon oxide, titanium carbide, titanium oxide, boron carbide, boron oxide, aluminum oxide, magnesium oxide, and calcium oxide. These inorganic fillers are preferable from the viewpoint of good mixing with the melamine-based resin when the resin composition for mold cleaning is produced.
In the present invention, the more preferable inorganic filler is at least one selected from silicon oxide, titanium oxide, and aluminum oxide, and still more preferable inorganic filler is at least one selected from silicon oxide and aluminum oxide. A particularly preferred inorganic filler is a silicon oxide.
Depending on the material and condition of the mold, it cannot be generally stated, but silicon oxide, titanium oxide, and aluminum oxide have appropriate hardness and suppress the occurrence of wear and scratches on the inner surface of the mold and the gate part. This is preferable because it is possible. The temperature at which the mold is cleaned is usually 160 to 190 ° C., but silicon oxide, titanium oxide, and aluminum oxide are preferable because they are thermally stable near the above temperature.
本発明の金型清掃用樹脂組成物は、平均粒径、粒径の標準偏差、粒径の平均アスペクト比、及び粒径のアスペクト比の標準偏差が特定の数値範囲内である無機充填材を含むので、成形金型のキャビティーのコーナー部まで十分に清掃することができ、且つ、成形金型の内部表面及びゲート部に磨耗や傷が発生し難い。 The inorganic filler in the present invention has an average particle diameter of 4 to 12 μm, a standard deviation of the particle diameter of 10 μm or less, an average aspect ratio of the particle diameter of 1 to 1.3, and an aspect ratio of the particle diameter. The standard deviation of the ratio is 0.5 or less.
The resin composition for mold cleaning of the present invention comprises an inorganic filler whose average particle diameter, standard deviation of particle diameter, average aspect ratio of particle diameter, and standard deviation of particle diameter aspect ratio are within a specific numerical range. Therefore, it is possible to sufficiently clean up to the corner portion of the cavity of the molding die, and it is difficult for the inner surface of the molding die and the gate portion to be worn or damaged.
本発明では、無機充填材の平均粒径が4μm以上であるので、成形金型の内部表面の汚れに対して十分なクリーニング性を示す。また、本発明では、無機充填材の平均粒径が12μm以下であるので、成形金型のキャビティーのコーナー部まで十分に清掃することができ、且つ、成形金型の内部表面及びゲート部に磨耗や傷が発生し難い。 The average particle size of the inorganic filler in the present invention is in the range of 4 to 12 μm, and preferably in the range of 6 to 10 μm. An inorganic filler having a remarkably small average particle size has a small mass and surface area, and therefore it is considered difficult to exhibit cleaning performance in a cavity of a molding die.
In the present invention, since the average particle size of the inorganic filler is 4 μm or more, it exhibits a sufficient cleaning property against dirt on the inner surface of the molding die. Further, in the present invention, since the average particle size of the inorganic filler is 12 μm or less, it is possible to sufficiently clean up to the corner portion of the cavity of the molding die, and to the inner surface of the molding die and the gate portion. Abrasion and scratches are unlikely to occur.
本発明では、無機充填材の粒径の標準偏差が10μm以下であるので、清掃時に、金型清掃用樹脂組成物の流動性が保たれ、その結果、成形金型のキャビティーのコーナー部まで十分に清掃することが可能となる。 The standard deviation of the particle size of the inorganic filler in the present invention is 10 μm or less. When the standard deviation of the particle size of the inorganic filler is large, the fluidity of the mold cleaning resin composition is deteriorated during cleaning, and the cleaning effect at the corner portion of the cavity of the molding die where dirt easily remains is reduced.
In the present invention, since the standard deviation of the particle size of the inorganic filler is 10 μm or less, the fluidity of the mold cleaning resin composition is maintained at the time of cleaning, and as a result, up to the corner of the cavity of the molding die. It becomes possible to clean thoroughly.
本発明では、無機充填材の粒径の平均アスペクト比が1.3以下であるので、清掃時に、金型清掃用樹脂組成物の流動性が保たれ、その結果、成形金型のキャビティーのコーナー部まで十分に清掃することが可能となり、また、成形金型の内部表面及びゲート部に磨耗や傷が発生し難い。 The average aspect ratio of the particle size of the inorganic filler in the present invention is in the range of 1 to 1.3, preferably in the range of 1 to 1.25, and in the range of 1.10 to 1.23. It is more preferable that If the average aspect ratio of the particle size of the inorganic filler is large, the fluidity of the mold cleaning resin composition will deteriorate during cleaning, and the cleaning effect at the corners of the mold cavities where dirt tends to remain will be reduced. Also, wear and scratches are likely to occur on the inner surface of the molding die and the gate portion.
In the present invention, since the average aspect ratio of the particle size of the inorganic filler is 1.3 or less, the fluidity of the mold cleaning resin composition is maintained during cleaning, and as a result, the cavity of the mold It is possible to sufficiently clean up to the corner portion, and the inner surface of the molding die and the gate portion are less likely to be worn or damaged.
本発明では、無機充填材の粒径のアスペクト比の標準偏差が0.5以下であり、無機充填材がほぼ均一な形状であるため、清掃時に、金型清掃用樹脂組成物の流動性が保たれ、その結果、成形金型のキャビティーのコーナー部まで十分に清掃することが可能となり、また、成形金型の内部表面及びゲート部に磨耗や傷が発生し難い。 The standard deviation of the aspect ratio of the particle size of the inorganic filler in the present invention is 0.5 or less, and preferably 0.45 or less. If the standard deviation of the aspect ratio of the particle size of the inorganic filler is large, the fluidity of the mold cleaning resin composition will deteriorate during cleaning, and the cleaning effect at the corners of the mold cavities where dirt tends to remain will be lost. In addition, the inner surface of the molding die and the gate portion are likely to be worn or damaged.
In the present invention, the standard deviation of the aspect ratio of the particle size of the inorganic filler is 0.5 or less, and the inorganic filler has a substantially uniform shape. As a result, it is possible to sufficiently clean up to the corner portion of the cavity of the molding die, and it is difficult for the inner surface of the molding die and the gate portion to be worn or damaged.
粒径 = ((Xの5回の計測値の平均値)+(Yの5回の計測値の平均値))/2
・・・式1 The “particle diameter” in the present invention is a value measured by the following method. The inorganic filler is photographed at a magnification of 1500 times using an electron microscope (JSM-5510, manufactured by JEOL Ltd.). Photographed so that about 30 inorganic fillers were included in one field of view, and measured the major axis (X) and minor axis (Y) five times each for a total of 150 inorganic fillers included in five different fields of view. To do. The minor axis (Y) is set to be orthogonal to the major axis (X). An average value of five measured values of the long diameter (X) and the short diameter (Y) is obtained and applied to the following formula 1, and the particle diameter of one inorganic filler is calculated.
Particle size = ((average value of 5 measured values of X) + (average value of 5 measured values of Y)) / 2
... Formula 1
粒径のアスペクト比 = (Xの5回の計測値の平均値)/(Yの5回の計測値の平均値) ・・・式2 The “aspect ratio of particle diameter” in the present invention is a value measured by the following method. The inorganic filler is photographed at a magnification of 1500 times using an electron microscope (JSM-5510, manufactured by JEOL Ltd.). Photographed so that about 30 inorganic fillers were included in one field of view, and measured the major axis (X) and minor axis (Y) five times each for a total of 150 inorganic fillers included in five different fields of view. To do. The minor axis (Y) is taken to be orthogonal to the major axis (X). An average value of five measured values of the long diameter (X) and the short diameter (Y) is obtained and applied to the following formula 2 to calculate the particle diameter aspect ratio of one inorganic filler. In the following formula 2, the major axis (X) ≧ the minor axis (Y).
Aspect ratio of particle size = (average value of five measured values of X) / (average value of five measured values of Y) Equation 2
本発明の金型清掃用樹脂組成物は、該金型清掃用樹脂組成物の強度を適切に保つために、添加剤として有機充填材を含むことが好ましい。有機充填材としては、例えば、パルプ、木粉、合成繊維等が挙げられる。これらの中でも、パルプが特に好ましい。 (Organic filler)
The mold cleaning resin composition of the present invention preferably contains an organic filler as an additive in order to appropriately maintain the strength of the mold cleaning resin composition. Examples of the organic filler include pulp, wood powder, and synthetic fiber. Among these, pulp is particularly preferable.
本発明の金型清掃用樹脂組成物は、清掃後における成形物と成形金型の内部表面との型離れを良好なものとし、成形物を金型から剥離する際の作業性を向上させるために、添加剤として炭素数12~20の飽和脂肪酸と、カルシウム、亜鉛、及びマグネシウムから選択される金属と、から構成される飽和脂肪酸の金属塩を含むことが好ましく、炭素数14~18の飽和脂肪酸と、カルシウム、亜鉛、及びマグネシウムから選択される金属と、から構成される飽和脂肪酸の金属塩を含むことがより好ましい。
炭素数12~20の飽和脂肪酸としては、例えば、炭素数12のラウリン酸(IUPAC名:ドデカン酸)、炭素数14のミリスチン酸(IUPAC名:テトラデカン酸)、炭素数16のパルミチン酸(IUPAC名:ヘキサデカン酸)、炭素数18のステアリン酸(IUPAC名:オクタデカン酸)、炭素数20のアラキジン酸(IUPAC名:エイコサン酸)等が挙げられる。
本発明においては、炭素数14の飽和脂肪酸と亜鉛とから構成されるミリスチン酸亜鉛、炭素数18の飽和脂肪酸と亜鉛とから構成されるステアリン酸亜鉛、及び炭素数18の飽和脂肪酸とカルシウムとから構成されるステアリン酸カルシウムの少なくとも1種を含むことが更に好ましく、ミリスチン酸亜鉛を含むことが特に好ましい。ミリスチン酸亜鉛は、融点が約123~130℃であり、金型清掃時の160~190℃の温度で十分な流動性があり、汚れに作用しやすいので好ましい。 (Metal salt of saturated fatty acid)
The resin composition for cleaning a mold according to the present invention has a good mold separation between the molded product after cleaning and the inner surface of the molding mold, and improves workability when the molded product is peeled from the mold. In addition, a metal salt of a saturated fatty acid composed of a saturated fatty acid having 12 to 20 carbon atoms and a metal selected from calcium, zinc, and magnesium as an additive is preferably included. It is more preferable to include a metal salt of a saturated fatty acid composed of a fatty acid and a metal selected from calcium, zinc, and magnesium.
Examples of the saturated fatty acid having 12 to 20 carbon atoms include lauric acid having 12 carbon atoms (IUPAC name: dodecanoic acid), myristic acid having 14 carbon atoms (IUPAC name: tetradecanoic acid), and palmitic acid having 16 carbon atoms (IUPAC name). : Hexadecanoic acid), stearic acid having 18 carbon atoms (IUPAC name: octadecanoic acid), arachidic acid having 20 carbon atoms (IUPAC name: eicosanoic acid), and the like.
In the present invention, zinc myristate composed of a saturated fatty acid having 14 carbon atoms and zinc, zinc stearate composed of a saturated fatty acid having 18 carbon atoms and zinc, and a saturated fatty acid having 18 carbon atoms and calcium. More preferably, it comprises at least one of the constituted calcium stearate, and particularly preferably contains zinc myristate. Zinc myristate is preferable because it has a melting point of about 123 to 130 ° C., has sufficient fluidity at a temperature of 160 to 190 ° C. during mold cleaning, and easily acts on dirt.
本発明の金型清掃用樹脂組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、更に、アルキッド樹脂、ポリエステル樹脂、アクリル系樹脂、エポキシ樹脂等の樹脂類、ゴム類を含んでもよい。また、公知の添加剤、例えば、硬化触媒、滑剤、着色剤、抗酸化剤等の添加剤を含んでもよい。 (Other ingredients)
The resin composition for mold cleaning of the present invention further includes resins such as alkyd resin, polyester resin, acrylic resin, epoxy resin, and rubber as necessary, as long as the effects of the present invention are not impaired. But you can. Moreover, you may also contain additives, such as a well-known additive, for example, a curing catalyst, a lubricant, a coloring agent, an antioxidant.
本発明の金型清掃用樹脂組成物は、例えば、上記メラミン系樹脂、上記無機充填材、さらに、必要に応じて、上記有機充填材、上記飽和脂肪酸の金属塩、添加物等のその他の成分を、ニーダー、リボンブレンダー、ヘンシェルミキサー、ボールミル、ロール練り、らいかい機、タンブラー等を用いて、ほぼ均一に混合することにより、調製する。 [Method for preparing resin composition for mold cleaning]
The resin composition for mold cleaning of the present invention includes, for example, the melamine-based resin, the inorganic filler, and, if necessary, other components such as the organic filler, a metal salt of the saturated fatty acid, and an additive. Is prepared by almost uniformly mixing using a kneader, a ribbon blender, a Henschel mixer, a ball mill, a roll kneader, a raking machine, a tumbler, or the like.
本発明の金型清掃用樹脂組成物は、トランスファー成形されることにより、成形金型の内部表面を清掃する、いわゆるトランスファータイプの金型清掃用樹脂組成物として好適である。
本発明の金型清掃用樹脂組成物は、通常、タブレット状に加工して、成形金型の内部表面の清掃作業に用いられる。具体的には、成形金型の上にリードフレームを配置した後、タブレット状の金型清掃用樹脂組成物をポット部に挿入し、型締めした後、プランジャーで押し流す。この際、ポット部の金型清掃用樹脂組成物は、ランナー部を経由し、ゲート部を通り、キャビティー内部に流れ込む。所定の成形時間が経過した後、金型を開き、リードフレームと一体となった成形物、すなわち、汚れを含む金型清掃用樹脂組成物の成形物を取り除く。 [Usage method of resin composition for mold cleaning]
The mold cleaning resin composition of the present invention is suitable as a so-called transfer type mold cleaning resin composition for cleaning the inner surface of a molding mold by transfer molding.
The resin composition for mold cleaning of the present invention is usually processed into a tablet shape and used for cleaning the inner surface of the molding mold. Specifically, after arranging the lead frame on the molding die, a tablet-like mold cleaning resin composition is inserted into the pot portion, clamped, and then washed away with a plunger. In this case, the mold cleaning resin composition in the pot portion flows through the runner portion, the gate portion, and into the cavity. After a predetermined molding time has elapsed, the mold is opened, and the molded product integrated with the lead frame, that is, the molded product of the mold cleaning resin composition containing dirt is removed.
本発明の金型清掃用樹脂組成物は、構成成分である無機充填材の平均粒径、粒径の標準偏差、粒径の平均アスペクト比、及び粒径のアスペクト比の標準偏差が特定の範囲内であるので、成形金型の内部表面等への傷や磨耗の発生を抑制することができる。 The resin composition for mold cleaning of the present invention removes dirt on the inner surface of a molding die that is produced during sealing molding operations for integrated circuits and the like by the method described above. The material of the molding die is, for example, iron or chromium, and the inner surface of the molding die is usually plated. The inner surface of the molding die is scratched and worn by micron size when the sealing molding operation and the cleaning operation are repeated. As a result, the plating surface applied to the inner surface of the molding die is lost or the surface state is roughened. Missing or roughened plating surface leads to deterioration of moldability and mold release during sealing molding operation, poor surface appearance, and loss of cleaning workability of the inner surface of the molding die.
The resin composition for mold cleaning of the present invention has a specific range of the average particle diameter, the standard deviation of the particle diameter, the average aspect ratio of the particle diameter, and the standard deviation of the particle diameter aspect ratio of the inorganic filler as a constituent component. Therefore, it is possible to suppress the occurrence of scratches and wear on the inner surface of the molding die.
<1> 少なくとも、メラミン系樹脂と、平均粒径が4~12μmであり、粒径の標準偏差が10μm以下であり、粒径の平均アスペクト比が1~1.3であり、且つ、粒径のアスペクト比の標準偏差が0.5以下である無機充填材と、を含む金型清掃用樹脂組成物である。
<2> 更に、炭素数14~18の飽和脂肪酸と、カルシウム、亜鉛、及びマグネシウムから選択される金属と、から構成される飽和脂肪酸の金属塩を含む上記<1>に記載の金型清掃用樹脂組成物である。
<3> 上記無機充填材が、炭化ケイ素、酸化ケイ素、炭化チタン、酸化チタン、炭化ホウ素、酸化ホウ素、酸化アルミニウム、酸化マグネシウム、及び酸化カルシウムから選択される少なくとも1種である上記<1>又は<2>に記載の金型清掃用樹脂組成物である。
<4> 上記無機充填材が、酸化ケイ素及び酸化アルミニウムから選択される少なくとも1種である上記<3>に記載の金型清掃用樹脂組成物である。
<5> トランスファー成形に用いられる上記<1>から<4>のいずれか1つに記載の金型清掃用樹脂組成物である。 Hereinafter, the preferable aspect of the resin composition for metal mold | die cleaning of this invention is shown.
<1> At least the melamine resin, the average particle diameter is 4 to 12 μm, the standard deviation of the particle diameter is 10 μm or less, the average aspect ratio of the particle diameter is 1 to 1.3, and the particle diameter And an inorganic filler having a standard deviation of the aspect ratio of 0.5 or less.
<2> Further for cleaning a mold according to the above <1>, further comprising a saturated fatty acid metal salt composed of a saturated fatty acid having 14 to 18 carbon atoms and a metal selected from calcium, zinc, and magnesium. It is a resin composition.
<3> The above <1> or wherein the inorganic filler is at least one selected from silicon carbide, silicon oxide, titanium carbide, titanium oxide, boron carbide, boron oxide, aluminum oxide, magnesium oxide, and calcium oxide. <2> A resin composition for cleaning a mold according to <2>.
<4> The mold cleaning resin composition according to <3>, wherein the inorganic filler is at least one selected from silicon oxide and aluminum oxide.
<5> The mold cleaning resin composition according to any one of <1> to <4>, which is used for transfer molding.
[メラミン-フェノール共縮合物の調製]
(製造例1)
メラミン346質量部と、フェノール131質量部と、ホルムアルデヒド(37%水溶液)522質量部と、有機充填材として、広葉樹パルプ(LDPR、日本製紙株式会社製)248質量部とを、80~90℃、pH7~7.5のアルカリ条件下で、60℃において反応物の3質量%水溶液が白濁するまでの時間、加熱反応させた後、減圧乾燥し、粉末化して、有機充填材を含むメラミン-フェノール共縮合物を得た。 -Preparation of mold cleaning resin composition-
[Preparation of melamine-phenol cocondensate]
(Production Example 1)
Melting 346 parts by weight of melamine, 131 parts by weight of phenol, 522 parts by weight of formaldehyde (37% aqueous solution) and 248 parts by weight of hardwood pulp (LDPR, manufactured by Nippon Paper Industries Co., Ltd.) as an organic filler, Under alkaline conditions of pH 7 to 7.5, the reaction product is heated and reacted at 60 ° C. until it becomes cloudy, then dried under reduced pressure, pulverized, and melamine-phenol containing an organic filler. A cocondensate was obtained.
(実施例1)
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化ケイ素(溶融シリカ、HS203、新日鉄マテリアルズ株式会社マイクロン社製)20質量部と、飽和脂肪酸の金属塩として、ステアリン酸亜鉛(ジンクステアレート GF200、日油株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、実施例1の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、略球状であった。 [Preparation of resin composition for mold cleaning]
Example 1
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd.) as an inorganic filler, and zinc stearate (zinc stearate GF200, as a metal salt of saturated fatty acid) 0.5 parts by mass (manufactured by NOF Corporation) and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized. Next, 0.35 parts by mass of stearamide as a lubricant was added using a Nauter mixer, and the mold cleaning resin composition of Example 1 was obtained. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
The inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化ケイ素(溶融シリカ、HS205、新日鉄マテリアルズ株式会社マイクロン社製)20質量部と、飽和脂肪酸の金属塩として、ステアリン酸亜鉛(ジンクステアレート GF200、日油株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、実施例2の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、略球状であった。 (Example 2)
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, HS205, manufactured by Nippon Steel Materials Co., Ltd.) as an inorganic filler, and zinc stearate (zinc stearate GF200, 0.5 parts by mass (manufactured by NOF Corporation) and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized. Next, 0.35 parts by mass of stearamide as a lubricant was added using a Nauter mixer, and a mold cleaning resin composition of Example 2 was obtained. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
The inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化ケイ素(溶融シリカ、SE-40、株式会社トクヤマ社製)20質量部と、飽和脂肪酸の金属塩として、ステアリン酸亜鉛(ジンクステアレート GF200、日油株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、実施例3の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、略球状であった。 (Example 3)
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, SE-40, manufactured by Tokuyama Co., Ltd.) as an inorganic filler, and zinc stearate (zinc stearate GF200, Japan) as a saturated fatty acid metal salt (Oil Co., Ltd.) 0.5 parts by mass and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized. Next, 0.35 parts by mass of stearic acid amide was added as a lubricant by a Nauta mixer to obtain a mold cleaning resin composition of Example 3. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
The inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化ケイ素(溶融シリカ、SE-15、株式会社トクヤマ製)20質量部と、飽和脂肪酸の金属塩として、ステアリン酸亜鉛(ジンクステアレート GF200、日油株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、実施例4の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、略球状であった。 (Example 4)
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, SE-15, manufactured by Tokuyama Corporation) as an inorganic filler, and zinc stearate (zinc stearate GF200, NOF) as a metal salt of saturated fatty acid Co., Ltd.) 0.5 parts by mass and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized. Next, 0.35 parts by mass of stearamide as a lubricant was added using a Nauter mixer, and a mold cleaning resin composition of Example 4 was obtained. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
The inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化アルミニウム(CB-P10、昭和電工株式会社製)20質量部と、飽和脂肪酸の金属塩として、ステアリン酸亜鉛(ジンクステアレート GF200、日油株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、実施例5の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、略球状であった。 (Example 5)
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of aluminum oxide (CB-P10, manufactured by Showa Denko KK) as an inorganic filler, and zinc stearate (Zinc stearate GF200, NOF Corporation) as a metal salt of saturated fatty acid (Product) 0.5 parts by mass and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized. Next, as a lubricant, 0.35 parts by mass of stearamide was added with a Nauta mixer to obtain a mold cleaning resin composition of Example 5. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
The inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、炭酸カルシウム(ホワイトンSB青、白石カルシウム株式会社製)20質量部と、飽和脂肪酸の金属塩として、ステアリン酸亜鉛(ジンクステアレート GF200、日油株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、実施例6の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、略球状であった。 (Example 6)
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by weight of melamine resin, 20 parts by weight of calcium carbonate (whiten SB blue, manufactured by Shiraishi Calcium Co., Ltd.) as an inorganic filler, and zinc stearate (zinc stearate GF200, NOF Corporation) as a metal salt of saturated fatty acid 0.5 parts by mass (made by company) and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized. Next, as a lubricant, 0.35 parts by mass of stearamide was added with a Nauta mixer to obtain a mold cleaning resin composition of Example 6. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
The inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化ケイ素(溶融シリカ、HS203、新日鉄マテリアルズ株式会社マイクロン社製)20質量部と、飽和脂肪酸の金属塩として、ステアリン酸カルシウム(カルシウムアレート GF200、日油株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、実施例7の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、略球状であった。 (Example 7)
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, HS 203, manufactured by Nippon Steel Materials Co., Ltd.) as an inorganic filler, and calcium stearate (calcium allate GF200, Japan) as a metal salt of saturated fatty acid (Oil Co., Ltd.) 0.5 parts by mass and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized. Next, as a lubricant, 0.35 parts by mass of stearamide was added with a Nauta mixer to obtain a mold cleaning resin composition of Example 7. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
The inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化ケイ素(溶融シリカ、HS203、新日鉄マテリアルズ株式会社マイクロン社製)20質量部と、飽和脂肪酸の金属塩として、ミリスチン酸亜鉛(パウダーベースM、日油株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、実施例8の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、略球状であった。 (Example 8)
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd.) as an inorganic filler, and zinc myristate (powder base M, Nikko) as a metal salt of saturated fatty acid (Oil Co., Ltd.) 0.5 parts by mass and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized. Next, 0.35 parts by mass of stearic acid amide was added as a lubricant by a Nauta mixer to obtain a mold cleaning resin composition of Example 8. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
The inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化ケイ素(溶融シリカ、HS203、新日鉄マテリアルズ株式会社マイクロン社製)20質量部と、飽和脂肪酸の金属塩として、ラウリン酸亜鉛(ZS-3、日東化成工業株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、実施例9の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、略球状であった。 Example 9
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd.) as an inorganic filler, and zinc laurate (ZS-3, Nitto) as a metal salt of saturated fatty acid 0.5 parts by mass (made by Kasei Kogyo Co., Ltd.) and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized. Next, as a lubricant, 0.35 parts by mass of stearamide was added with a Nauta mixer to obtain a mold cleaning resin composition of Example 9. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
The inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化ケイ素(溶融シリカ、HS203、新日鉄マテリアルズ株式会社マイクロン社製)20質量部と、飽和脂肪酸の金属塩として、アルキジン酸亜鉛0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、実施例10の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、略球状であった。 (Example 10)
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd.) as an inorganic filler, and 0.5 parts by mass of zinc alkydate as a metal salt of saturated fatty acid As a curing catalyst, 0.05 part by mass of benzoic acid was charged into a ball mill and pulverized. Next, 0.35 parts by mass of stearamide as a lubricant was added using a Nauter mixer, and a mold cleaning resin composition of Example 10 was obtained. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
The inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化ケイ素(溶融シリカ、HS203、新日鉄マテリアルズ株式会社マイクロン社製)20質量部と、ステアリン酸(F-3、川研ファインケミカル株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、実施例11の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、略球状であった。 (Example 11)
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd.) as an inorganic filler, and stearic acid (F-3, manufactured by Kawaken Fine Chemical Co., Ltd.) 5 parts by mass and 0.05 part by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized. Next, 0.35 parts by mass of stearic acid amide was added as a lubricant by a Nauta mixer to obtain a mold cleaning resin composition of Example 11. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
The inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化ケイ素(破砕シリカ、FS200、電気化学工業株式会社社製)20質量部と、飽和脂肪酸の金属塩として、ステアリン酸亜鉛(ジンクステアレート GF200、日油株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、比較例1の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、破砕状であった。 (Comparative Example 1)
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (crushed silica, FS200, manufactured by Denki Kagaku Kogyo Co., Ltd.) as an inorganic filler, and zinc stearate (zinc stearate GF200, Japan) as a metal salt of saturated fatty acid (Oil Co., Ltd.) 0.5 parts by mass and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized. Next, 0.35 parts by mass of stearamide as a lubricant was added using a Nauter mixer, and a mold cleaning resin composition of Comparative Example 1 was obtained. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
The inorganic filler was crushed when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化ケイ素(溶融シリカ、SO-C6、株式会社アドマテックス社製)20質量部と、飽和脂肪酸の金属塩として、ステアリン酸亜鉛(ジンクステアレート GF200、日油株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、比較例2の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、略球状であった。 (Comparative Example 2)
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (fused silica, SO-C6, manufactured by Admatechs Co., Ltd.) as an inorganic filler, and zinc stearate (zinc stearate GF200, 0.5 parts by mass (manufactured by NOF Corporation) and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized. Next, as a lubricant, 0.35 parts by mass of stearamide was added with a Nauta mixer, and a mold cleaning resin composition of Comparative Example 2 was obtained. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
The inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化ケイ素(溶融シリカ、HS203、新日鉄マテリアルズ株式会社マイクロン社製)と、酸化ケイ素(溶融シリカ、HS302、新日鉄マテリアルズ株式会社マイクロン社製)との質量比1:1の混合物20質量部と、飽和脂肪酸の金属塩として、ステアリン酸亜鉛(ジンクステアレート GF200、日油株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、比較例3の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、略球状であった。 (Comparative Example 3)
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of a melamine resin, and as an inorganic filler, silicon oxide (fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd. Micron) and silicon oxide (fused silica, HS302, manufactured by Nippon Steel Materials Co., Ltd. Micron) 20 parts by mass of a mixture having a mass ratio of 1: 1, 0.5 parts by mass of zinc stearate (Zinc stearate GF200, manufactured by NOF Corporation) as a metal salt of a saturated fatty acid, and 0.05 ppm of benzoic acid as a curing catalyst Part by mass was charged into a ball mill and pulverized. Next, 0.35 parts by mass of stearamide as a lubricant was added using a Nauta mixer, and a mold cleaning resin composition of Comparative Example 3 was obtained. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
The inorganic filler was substantially spherical when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化ケイ素(溶融シリカ、TS10-141、新日鉄マテリアルズ株式会社マイクロン社製)と、酸化ケイ素(破砕シリカ、F-CD10、キンセイマテックス社製)との質量比1:2の混合物20質量部と、飽和脂肪酸の金属塩として、ステアリン酸亜鉛(ジンクステアレート GF200、日油株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、比較例4の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、略球状と破砕状とが混在していた。 (Comparative Example 4)
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, silicon oxide (fused silica, TS10-141, manufactured by Nippon Steel Materials Co., Ltd., Micron) and silicon oxide (crushed silica, F-CD10, manufactured by Kinsei Matex Co., Ltd.) as
When the inorganic filler was observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.), a substantially spherical shape and a crushed shape were mixed.
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化ケイ素(溶融シリカ、HS203、新日鉄マテリアルズ株式会社マイクロン社製)と、酸化ケイ素(破砕シリカ、F-CD10、キンセイマテックス社製)との質量比1:3の混合物20質量部と、飽和脂肪酸の金属塩として、ステアリン酸亜鉛(ジンクステアレート GF200、日油株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、比較例5の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、略球状と破砕状とが混在していた。 (Comparative Example 5)
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and Mass ratio of 50 parts by mass of melamine resin and silicon oxide (fused silica, HS203, manufactured by Nippon Steel Materials Co., Ltd., Micron) and silicon oxide (crushed silica, F-CD10, manufactured by Kinsei Matex Co., Ltd.) as
When the inorganic filler was observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.), a substantially spherical shape and a crushed shape were mixed.
メラミン系樹脂として、上記有機充填材を含むメラミン-フェノール共縮合物29.1質量部(うち、メラミン-フェノール共縮合物として21.3質量部、有機充填材として7.8質量部)、及びメラミン樹脂50質量部と、無機充填材として、酸化ケイ素(純硅石粉、瀬戸窯業原料株式会社製)20質量部と、飽和脂肪酸の金属塩として、ミリスチン酸亜鉛(パウダーベースM、日油株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、比較例6の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。
なお、上記無機充填材を、電子顕微鏡(JSM-5510、日本電子株式会社製)で観察したところ、破砕状であった。 (Comparative Example 6)
As the melamine resin, 29.1 parts by mass of the melamine-phenol cocondensate containing the above organic filler (including 21.3 parts by mass as the melamine-phenol cocondensate, 7.8 parts by mass as the organic filler), and 50 parts by mass of melamine resin, 20 parts by mass of silicon oxide (pure meteorite powder, manufactured by Seto Ceramic Industry Co., Ltd.) as an inorganic filler, and zinc myristate (powder base M, NOF Corporation) as a metal salt of saturated fatty acid (Product) 0.5 parts by mass and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized. Next, 0.35 parts by mass of stearamide as a lubricant was added using a Nauter mixer, and a mold cleaning resin composition of Comparative Example 6 was obtained. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
The inorganic filler was crushed when observed with an electron microscope (JSM-5510, manufactured by JEOL Ltd.).
メラミン系樹脂として、メチロールメラミン(ニカレヂンS-176、日本カーバイド工業株式会社製)76.1質量部と、有機充填材として、広葉樹パルプ(LDPR、日本製紙株式会社製)23質量部と、飽和脂肪酸の金属塩として、ステアリン酸亜鉛(ジンクステアレート GF200、日油株式会社製)0.5質量部と、硬化触媒として、安息香酸0.05質量部と、をボールミルに仕込み、粉砕した。次いで、滑剤として、ステアリン酸アミド0.35質量部をナウターミキサーにて加え、比較例7の金型清掃用樹脂組成物を得た。このようにして得た金型清掃用樹脂組成物をタブレット成形して、金型清掃評価に用いた。 (Comparative Example 7)
As a melamine resin, 76.1 parts by mass of methylol melamine (Nicaridine S-176, manufactured by Nippon Carbide Industries Co., Ltd.), 23 parts by mass of hardwood pulp (LDPR, manufactured by Nippon Paper Industries Co., Ltd.), saturated fatty acid As a metal salt, 0.5 parts by mass of zinc stearate (Zinc stearate GF200, manufactured by NOF Corporation) and 0.05 parts by mass of benzoic acid as a curing catalyst were charged into a ball mill and pulverized. Next, 0.35 parts by mass of stearamide as a lubricant was added using a Nauter mixer, and a mold cleaning resin composition of Comparative Example 7 was obtained. The mold cleaning resin composition thus obtained was tablet-molded and used for mold cleaning evaluation.
実施例1~11、及び比較例1~7の金型清掃用樹脂組成物に用いた無機充填材の平均粒径、粒径の標準偏差、粒径の平均アスペクト比、及び粒径のアスペクト比の標準偏差は、以下の方法により求めた。測定結果を下記表1に示す。 -Measurement-
Average particle diameter, standard deviation of particle diameter, average aspect ratio of particle diameter, and aspect ratio of particle diameter of inorganic filler used in resin compositions for mold cleaning of Examples 1 to 11 and Comparative Examples 1 to 7 The standard deviation of was determined by the following method. The measurement results are shown in Table 1 below.
粒径 = ((Xの5回の計測値の平均値)+(Yの5回の計測値の平均値))/2
・・・式1 The inorganic filler was photographed at a magnification of 1500 times using an electron microscope (JSM-5510, manufactured by JEOL Ltd.). Photographed so that about 30 inorganic fillers were included in one field of view, and measured the major axis (X) and minor axis (Y) five times each for a total of 150 inorganic fillers included in five different fields of view. did. The minor axis (Y) was taken to be orthogonal to the major axis (X). And after calculating | requiring the average value of five measured values of major axis (X) and minor axis (Y), applying to the following formula 1, and calculating the particle size of one inorganic filler, 150 inorganic fillers The average value of the particle size of the material and the standard deviation of the particle size of 150 inorganic fillers were determined.
Particle size = ((average value of 5 measured values of X) + (average value of 5 measured values of Y)) / 2
... Formula 1
粒径のアスペクト比 = (Xの5回の計測値の平均値)/(Yの5回の計測値の平均値) ・・・式2 Moreover, after calculating the aspect ratio of the particle size of one inorganic filler by applying the average value of the measured values of the major axis (X) and the minor axis (Y) five times to the following formula 2, 150 The average value of the aspect ratio of the particle size of the inorganic filler and the standard deviation of the aspect ratio of the particle size of 150 inorganic fillers were determined.
Aspect ratio of particle size = (average value of five measured values of X) / (average value of five measured values of Y) Equation 2
実施例1~11、及び比較例1~7の金型清掃用樹脂組成物のクリーニング性、及び傷付き性について、以下に示す方法で評価した。評価結果を下記表1に示す。 -Evaluation-
The cleaning properties and scratch resistance of the mold cleaning resin compositions of Examples 1 to 11 and Comparative Examples 1 to 7 were evaluated by the following methods. The evaluation results are shown in Table 1 below.
市販のエポキシ樹脂成形材料(EME-G700L、住友ベークライト株式会社製)を用い、トランスファー自動成形機(金型温度:175℃、トランスファー圧:8.7MPa、トランスファー時間:6.5秒、硬化時間:90秒)で、QFP(Quad Flat Package)を400ショット成形し、金型の内部表面を汚れさせた。
この汚れた金型を用い、上記と同様の成形条件で、上記にて調製した金型清掃用樹脂組成物を繰り返し成形した。そして、金型の内部表面に付着した汚れが完全に除去できるまでに要したショット数を測定し、このショット数を、金型清掃用樹脂組成物のクリーニング性を評価するための指標とした。汚れが完全に除去できたか否かは、目視にて判断した。
評価に際しては、特に、金型のキャビティーのゲート部やコーナー部に付着した汚れが除去できているかに注目した。今回の評価に用いた金型のゲート部は、幅が800μmで、高さが300μmであった。
ショット数は、小さいほどクリーニング性が優れていることを示す。 (1) Cleanability Using a commercially available epoxy resin molding material (EME-G700L, manufactured by Sumitomo Bakelite Co., Ltd.), an automatic transfer molding machine (mold temperature: 175 ° C., transfer pressure: 8.7 MPa, transfer time: 6.5) Second, curing time: 90 seconds), 400 shots of QFP (Quad Flat Package) were molded to stain the inner surface of the mold.
Using this dirty mold, the mold cleaning resin composition prepared above was repeatedly molded under the same molding conditions as above. Then, the number of shots required to completely remove the dirt attached to the inner surface of the mold was measured, and this number of shots was used as an index for evaluating the cleaning property of the mold cleaning resin composition. Whether or not the dirt was completely removed was judged visually.
In the evaluation, we paid particular attention to whether or not dirt adhered to the gate and corner portions of the mold cavity could be removed. The gate part of the mold used for this evaluation had a width of 800 μm and a height of 300 μm.
The smaller the number of shots, the better the cleaning performance.
金型清掃用樹脂組成物の傷付き性の評価には、市販のテーバー摩耗試験機(MODEL 5155、TABER INDUSTRIES社製)を用いた。
SUS板(材質:ASP-23H)に硬質クロムメッキ処理を施した試験片(100mm×100mm、厚み:7mm)を準備した。レーザー顕微鏡(VK-9710、株式会社キーエンス社製)を用いて、この試験片の表面粗さ(Ra:算術平均粗さ、JIS B 0601-2001準拠)を測定したところ、0.099μmであった。
金型清掃用樹脂組成物を、幅10mm、長さ100mm、厚み4mmの形状となる金型を用いて成形し、評価用試料とした。装置には、トランスファー自動成形機(金型温度:170℃、トランスファー圧:6.9MPa、トランスファー時間:30秒、硬化時間:90秒)を用いた。
事前準備として、#1500サンドペーパーをテーバー摩耗試験機の回転台に置き、その上に、金型清掃用樹脂組成物の評価用試料を10mm×4mmの面が下になるように、試験機治具を用いて固定し、回転台を速度60rpmで30回転させて、評価用試料の平面を出した。
試験片をテーバー摩耗試験機の回転台に置き、その上に、平面を出した評価用試料を試験機治具にて固定し、1000gの荷重をかけながら、回転台を速度60rpmで30回転させる磨耗試験を実施した。
磨耗試験後、レーザー顕微鏡(VK-9710、株式会社キーエンス社製)を用いて、試験片表面の表面粗さ(Ra:算術平均粗さ、JIS B 0601-2001準拠)を測定し、この表面粗さの値を金型清掃用樹脂組成物の傷付き性を評価するための指標とした。
この試験片表面の表面粗さの値が小さいほど、評価用試料による傷付きが少ないことを示す。したがって、この試験片表面の表面粗さの値が小さいほど、成形金型の内部表面及びゲート部に磨耗や傷が発生し難い金型清掃用樹脂組成物であることを示す。 (2) Scratch property A commercially available Taber abrasion tester (MODEL 5155, manufactured by TABER INDUSTRIES) was used for evaluation of the scratch property of the resin composition for mold cleaning.
A test piece (100 mm × 100 mm, thickness: 7 mm) prepared by subjecting a SUS plate (material: ASP-23H) to hard chrome plating was prepared. Using a laser microscope (VK-9710, manufactured by Keyence Corporation), the surface roughness (Ra: arithmetic average roughness, conforming to JIS B 0601-2001) of this test piece was measured and found to be 0.099 μm. .
A mold cleaning resin composition was molded using a mold having a width of 10 mm, a length of 100 mm, and a thickness of 4 mm, and used as an evaluation sample. As an apparatus, a transfer automatic molding machine (mold temperature: 170 ° C., transfer pressure: 6.9 MPa, transfer time: 30 seconds, curing time: 90 seconds) was used.
As a preliminary preparation, place # 1500 sandpaper on a rotating table of a Taber abrasion tester, and then place a sample for evaluation of the resin composition for mold cleaning on the test machine so that the surface of 10 mm × 4 mm faces down. The sample was fixed using a tool, and the turntable was rotated 30 times at a speed of 60 rpm to obtain a flat surface of the sample for evaluation.
A test piece is placed on a rotating table of a Taber abrasion tester, and an evaluation sample with a flat surface is fixed thereon with a testing machine jig, and the rotating table is rotated 30 times at a speed of 60 rpm while applying a load of 1000 g. A wear test was performed.
After the abrasion test, the surface roughness (Ra: arithmetic average roughness, conforming to JIS B 0601-2001) was measured using a laser microscope (VK-9710, manufactured by Keyence Corporation). The value of the height was used as an index for evaluating the scratch resistance of the mold cleaning resin composition.
The smaller the surface roughness value of the surface of the test piece, the smaller the damage caused by the sample for evaluation. Therefore, the smaller the surface roughness value of the surface of the test piece, the lower the surface roughness of the molding die, and the lower the surface roughness of the test piece, the lower the surface roughness value.
体積の近似値=4×3.14×(粒径)3/3・・・式3
実施例8の金型清掃用樹脂組成物に用いた無機充填材は、体積の近似値が10~100μm3の範囲内のものを12%(150個中18個)含んでいた。 The relationship between the approximate value of the volume of the inorganic filler used for the resin composition for metal mold | die cleaning of Example 8 and Comparative Example 6 and frequency is shown in FIG. In addition, the volume of the inorganic filler was approximated by the following formula 3 with the average value of the major axis (X) and the minor axis (Y) as the particle size.
The volume of approximation = 4 × 3.14 × (particle diameter) 3/3 Equation 3
The inorganic filler used in the mold cleaning resin composition of Example 8 contained 12% (18 out of 150) having an approximate volume value in the range of 10 to 100 μm 3 .
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的に、且つ、個々に記された場合と同程度に本明細書中に参照により取り込まれる。 The disclosure of Japanese application 2011-156953 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described in this specification are specifically incorporated by reference as if individual documents, patent applications, and technical standards were incorporated by reference. To the extent incorporated herein by reference.
Claims (5)
- 少なくとも、メラミン系樹脂と、平均粒径が4~12μmであり、粒径の標準偏差が10μm以下であり、粒径の平均アスペクト比が1~1.3であり、且つ、粒径のアスペクト比の標準偏差が0.5以下である無機充填材と、を含む金型清掃用樹脂組成物。 At least the melamine resin, the average particle diameter is 4 to 12 μm, the standard deviation of the particle diameter is 10 μm or less, the average aspect ratio of the particle diameter is 1 to 1.3, and the aspect ratio of the particle diameter A mold cleaning resin composition comprising: an inorganic filler having a standard deviation of 0.5 or less.
- 更に、炭素数14~18の飽和脂肪酸と、カルシウム、亜鉛、及びマグネシウムから選択される金属と、から構成される飽和脂肪酸の金属塩を含む請求項1に記載の金型清掃用樹脂組成物。 2. The mold cleaning resin composition according to claim 1, further comprising a saturated fatty acid metal salt composed of a saturated fatty acid having 14 to 18 carbon atoms and a metal selected from calcium, zinc, and magnesium.
- 前記無機充填材が、炭化ケイ素、酸化ケイ素、炭化チタン、酸化チタン、炭化ホウ素、酸化ホウ素、酸化アルミニウム、酸化マグネシウム、及び酸化カルシウムから選択される少なくとも1種である請求項1又は請求項2に記載の金型清掃用樹脂組成物。 The inorganic filler is at least one selected from silicon carbide, silicon oxide, titanium carbide, titanium oxide, boron carbide, boron oxide, aluminum oxide, magnesium oxide, and calcium oxide. The resin composition for metal mold | die cleaning of description.
- 前記無機充填材が、酸化ケイ素及び酸化アルミニウムから選択される少なくとも1種である請求項3に記載の金型清掃用樹脂組成物。 The mold cleaning resin composition according to claim 3, wherein the inorganic filler is at least one selected from silicon oxide and aluminum oxide.
- トランスファー成形に用いられる請求項1から請求項4のいずれか1項に記載の金型清掃用樹脂組成物。 The resin composition for mold cleaning according to any one of claims 1 to 4, which is used for transfer molding.
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WO2013111709A1 (en) * | 2012-01-23 | 2013-08-01 | 日本カーバイド工業株式会社 | Resin composition for cleaning die |
JP2017170632A (en) * | 2016-03-18 | 2017-09-28 | 日本カーバイド工業株式会社 | Resin composition for cleaning mold |
WO2021145199A1 (en) * | 2020-01-17 | 2021-07-22 | 日本カーバイド工業株式会社 | Resin composition for die cleaning |
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KR102325676B1 (en) | 2019-12-18 | 2021-11-11 | 황진상 | Resin composition for mold cleaning and manufacturing method thereof |
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- 2012-07-10 CN CN201280034674.2A patent/CN103702813B/en active Active
- 2012-07-10 KR KR1020147000888A patent/KR101934065B1/en active IP Right Grant
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2013111709A1 (en) * | 2012-01-23 | 2013-08-01 | 日本カーバイド工業株式会社 | Resin composition for cleaning die |
JPWO2013111709A1 (en) * | 2012-01-23 | 2015-05-11 | 日本カーバイド工業株式会社 | Mold cleaning resin composition |
JP2017170632A (en) * | 2016-03-18 | 2017-09-28 | 日本カーバイド工業株式会社 | Resin composition for cleaning mold |
WO2021145199A1 (en) * | 2020-01-17 | 2021-07-22 | 日本カーバイド工業株式会社 | Resin composition for die cleaning |
JP2021112859A (en) * | 2020-01-17 | 2021-08-05 | 日本カーバイド工業株式会社 | Resin composition for die cleaning |
JP7265495B2 (en) | 2020-01-17 | 2023-04-26 | 日本カーバイド工業株式会社 | Mold cleaning resin composition |
Also Published As
Publication number | Publication date |
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KR101934065B1 (en) | 2019-01-02 |
TW201311423A (en) | 2013-03-16 |
JPWO2013011876A1 (en) | 2015-02-23 |
CN103702813B (en) | 2016-03-30 |
JP5972266B2 (en) | 2016-08-17 |
CN103702813A (en) | 2014-04-02 |
KR20140039047A (en) | 2014-03-31 |
TWI580547B (en) | 2017-05-01 |
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