JP2017137379A - Resin composition, and compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which prevents occurrence of a problem in a feed portion in production of a compound of the resin composition having a large content of a filler, and to provide a compound of the resin composition and a method for producing the same.SOLUTION: There is provided a resin composition which contains 50 pts.mass or more and 250 pts.mass or less of a filler with respect to 100 pts.mass of a polyolefin resin, where the filler is a powder shape and has a ratio (D/D) between an average particle ratio (D) obtained when volume distribution of the filler is measured at a crushing pressure of 0.3 MPa by a dry method using a laser diffraction type particle distribution measuring instrument and an average particle ratio (D) obtained when volume distribution of the filler is measured without the crushing pressure by the dry method is 1.5 or less.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a compound of the resin composition, and a method for producing the compound.

  Resin compositions such as plastics are widely used in packaging materials and machine product housings, and it is common to use polymers in which various additives are dispersed (for example, see Patent Document 1). ).

  For example, in resin compositions used for coating materials for electric wires and cables, for example, fillers such as flame retardants, antioxidants, colorants and the like are often used as additives (see, for example, Patent Document 2).

  Among these, coating materials that require flame retardancy include metal hydroxides such as magnesium hydroxide, phosphorus flame retardants, nitrogen compounds such as melamine cyanurate, halogen-containing compounds such as bromine and chlorine, antimony trioxide, and the like. Many are highly filled with flame retardant fillers (see, for example, Patent Document 3).

  When producing a compound of these resin compositions, a molding machine such as an internal mixer or a twin screw extruder is used, and the productivity of the twin screw extruder is particularly excellent.

JP 2013-87133 A JP 2007-103247 A JP 2006-286529 A

  However, in the production of a resin composition compound containing a large amount of filler, when the filler is added, the powder aggregates in the hopper and clogs at the outlet of the hopper, or the powder near the inner wall. In some cases, problems such as the rathole phenomenon (hereinafter referred to as the problem of the feed portion) that cannot be crushed and discharged.

  Although the above-mentioned problem of the feed portion has been dealt with by installing a vibrator in the hopper and preventing aggregation due to vibration, it is not always effective, and the cost of equipment is also increased.

  From such a background, a resin composition capable of efficiently producing a compound is expected.

  Accordingly, an object of the present invention is to provide a resin composition in which the problem of the feed portion does not occur even in the production of a resin composition compound having a high filler content, a compound of the resin composition, and a method for producing the same. There is.

  In order to achieve the above object, the present invention provides the following resin composition and compound and a method for producing the same.

[1] 50 parts by mass or more and 250 parts by mass or less of a filler with respect to 100 parts by mass of a polyolefin-based resin, and the filler is in a powder form and is made of the filler using a laser diffraction particle size distribution analyzer. The average particle size _{(D50 (P0.3)} ) when dry measuring the volume distribution at a crushing pressure of 0.3 MPa and the average particle size _{(D50 (P0)} ) when dry measuring without a crushing pressure The resin composition whose ratio ( _{D50 (P0)} / _{D50 (P0.3)} ) is 1.5 or less.
[2] The resin composition according to [1], wherein the filler has a mean particle diameter _{(D50 (P0.3)} ) of 5 μm or less when dry-measured at a crushing pressure of 0.3 MPa.
[3] The resin composition according to [1] or [2], wherein the filler is a metal hydroxide.
[4] A compound of the resin composition according to any one of [1] to [3].
[5] A method for producing a compound comprising a step of kneading the resin composition according to any one of [1] to [3].

  According to the present invention, it is possible to provide a resin composition in which the problem of the feed portion does not occur even in the production of a resin composition compound having a high filler content, the compound of the resin composition, and a method for producing the same. it can.

(Resin composition)
The resin composition according to the embodiment of the present invention contains 50 parts by mass or more and 250 parts by mass or less of a filler with respect to 100 parts by mass of the polyolefin-based resin, and the filler is powdery and has a laser diffraction particle size. The average particle diameter _{(D50 (P0.3)} ) when dry measuring the volume distribution of the filler with a crushing pressure of 0.3 MPa using a distribution measuring instrument and the average particle when dry measuring without crushing pressure diameter _{(D 50 (P0))} ratio of _{(D 50 (P0) / D} 50 (P0.3)) is 1.5 or less.

(Polyolefin resin)
The resin composition according to the embodiment of the present invention contains a polyolefin resin as a base polymer.

  Examples of the polyolefin resin used in the embodiment of the present invention include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), linear very low density polyethylene (VLDPE), high density polyethylene (HDPE), polypropylene ( PP), ethylene-ethyl acrylate copolymer (EEA), ethylene-vinyl acetate copolymer (EVA), ethylene-styrene copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-butene-hexene terpolymer Polymer, ethylene-propylene-diene terpolymer (EPDM), ethylene copolymer polypropylene, ethylene-propylene copolymer (EPR), poly-4-methyl-pentene-1, maleic acid grafted low density polyethylene, hydrogenated Styrene-butadiene copolymer (H-SBR), maleic acid grafted linear low density polyethylene, ethylene Copolymers of ethylene and α-olefins having 4 to 20 carbon atoms such as ten-1 copolymer and ethylene-octene copolymer (EOR), maleic acid grafted ethylene-methyl acrylate copolymer, maleic acid grafted ethylene -Vinyl acetate copolymer, ethylene-maleic anhydride copolymer, ethylene-ethyl acrylate-maleic anhydride terpolymer, ethylene-propylene-butene-1 terpolymer having butene-1 as the main component More preferred is ethylene-vinyl acetate copolymer (EVA). These can be used alone or in combination of two or more.

(filler)
The resin composition according to the embodiment of the present invention contains 50 to 250 parts by mass of a filler with respect to 100 parts by mass of the polyolefin resin.

The filler used in the embodiment of the present invention has an average particle diameter _{(D50 (P0.3} ) when the volume distribution of the filler is dry measured at a crushing pressure of 0.3 MPa using a laser diffraction particle size distribution analyzer. ₎₎ the ratio between the average particle diameter at the time of dry measured without solution砕圧force _{(D 50 (P0)) (} D 50 (P0) / D 50 (P0.3)) is 1.5 or less. Here, D _{50 (P0)} is a value of 50% volume distribution at a crushing pressure of 0 MPa, and D _{50 (P0.3)} is a value of 50% volume distribution at a crushing pressure of 0.3 MPa.
That is, the filler used in the embodiment of the present invention satisfies the following formula (1).
D _{50 (P0)} / D _{50 (P0.3)} ≦ 1.5 (1)

  As the laser diffraction particle size distribution analyzer, for example, a Microtrac MT3300ExII particle size analyzer manufactured by Microtrac Bell Co., Ltd. can be used, and a dry measurement unit manufactured by the same company can be used for dry measurement.

The filler used in the embodiment of the present invention must satisfy the above formula (1). The above formula (1) is an index representing the ease of aggregation of the filler. In the dry particle size distribution measurement, when the crushing pressure is increased to about 0.3 MPa, many powders are agglomerated and have an average particle size reflecting primary particles. On the other hand, when the crushing pressure is 0 MPa, the powder that easily aggregates has a larger average particle diameter than the primary particles. Therefore, the average particle diameter _{D 50} at the time of the solution砕圧force 0.3 MPa _(P0.3), the solution砕圧force average particle diameter _{D 50} ratio _{D 50} of _(P0) during 0 MPa _(P0) / _{D 50 (P0 .3)} indicates the ease of agglomeration of the powder, and a value close to 1 indicates that the powder is difficult to agglomerate without applying crushing pressure. When this numerical value is large, it indicates that the powder tends to aggregate. Specifically, when D _{50 (P0)} / D _{50 (P0.3)} is larger than 1.5, the twin screw extruder Aggregation at the hopper during molding causes feed abnormalities such as bridges and rat holes, and deterioration of molding processability such as clogging of the screen mesh.

The filler used in the embodiment of the present invention preferably has an average particle diameter _{(D50 (P0.3)} ) of 5 μm or less when dry-measured at a crushing pressure of 0.3 MPa, preferably 3 μm or less. Is more preferably 2 μm or less, and most preferably 1.6 μm or less.

  The filler used in the embodiment of the present invention is not particularly limited as long as it is powdery and satisfies the above formula (1). For example, magnesium hydroxide, aluminum hydroxide, hydroxide Metal hydroxides such as calcium, metal oxides such as aluminum oxide, silica, talc, clay, zinc stannate, zinc hydroxystannate, zinc borate, zinc oxide, etc., calcium borate, barium borate Boric acid compounds such as barium metaborate, phosphorus flame retardants, nitrogen flame retardants such as melamine cyanurate, halogen flame retardants such as bromine flame retardants, antimony trioxide, components that foam and solidify An intumescent flame retardant composed of a mixture is exemplified. More preferred are metal hydroxides, especially magnesium hydroxide. These can be used alone or in combination of two or more. As these fillers, silane coupling agents, titanate coupling agents, fatty acids such as stearic acid and calcium stearate, fatty acid metal salts and the like may be used.

  The addition amount of the filler is 250 parts by mass or less with respect to 100 parts by mass of the polyolefin-based resin, and the properties such as tensile strength and elongation of the resin composition tend to decrease with the addition. Part or less, more preferably 190 parts by weight or less. Although the minimum of the addition amount of a filler is 50 mass parts with respect to 100 mass parts of polyolefin resin, it is preferable that it is 60 mass parts, and it is more preferable that it is 65 mass parts.

(Other additives)
In addition to the filler, the resin composition according to the embodiment of the present invention, if necessary, a flame retardant other than the above, an inorganic filler other than the above, an antioxidant, a metal deactivator, a crosslinking agent, It is possible to add additives such as a crosslinking aid, a lubricant, a compatibilizer, a stabilizer, carbon black, and a colorant.

  Although it does not specifically limit as antioxidant, For example, a phenol type, sulfur type, amine type, and phosphorus antioxidant are mentioned. The type of phenolic antioxidant is not particularly limited. For example, dibutylhydroxytoluene (BHT), pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-t-butyl-4-hydroxy-benzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like, more preferably pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] ]. The type of sulfur-based antioxidant is not particularly limited, but didodecyl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate , Tetrakis [methylene-3- (dodecylthio) propionate] methane, and the like, more preferably tetrakis [methylene-3- (dodecylthio) propionate] methane. These antioxidants can be used alone or in combination of two or more.

  The metal deactivator is not particularly limited as long as it has an effect of stabilizing metal ions by chelate formation and suppressing oxidative degradation, and its structure is not particularly limited, but N- (2H-1,2,4-triazole- 5-yl) salicylamide, dodecanedioic acid bis [N2- (2-hydroxybenzoyl) hydrazide], 2 ', 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl ]] Propionohydrazide and the like, and 2 ′, 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide is more preferable. These can be used alone or in a blend of two or more.

  The crosslinking aid is not particularly limited, but for example, use of trimethylolpropane trimethacrylate (TMPT) or triallyl isocyanurate (TAIC) is desirable.

  Examples of the lubricant include, but are not limited to, fatty acids, fatty acid metal salts, fatty acid amides, and the like, specifically, use of zinc stearate. These can be used alone or in a blend of two or more.

  Carbon black is not particularly limited, but carbon black for rubber (N900-N100: ASTM D 1765-01) is generally used.

  Although it does not specifically limit as a coloring agent, The color masterbatch for non-halogens etc. can be used.

  The resin composition according to the embodiment of the present invention may be crosslinked by an organic peroxide or by radiation such as an electron beam. A known method can be used as the crosslinking method, and there is no particular limitation.

〔compound〕
The compound according to the embodiment of the present invention is a compound (kneaded material) of the resin composition according to the embodiment of the present invention, and undergoes a step of kneading the resin composition according to the embodiment of the present invention. Manufactured. For example, it can be manufactured by putting the raw material of the resin composition into a feeder of a twin screw extruder and kneading, and kneading conditions at that time are appropriately set.

[Effect of the embodiment of the present invention]
According to an embodiment of the present invention, there is provided a resin composition in which a problem of a feed portion does not occur even in the production of a resin composition compound having a high filler content, and a method for producing the compound of the resin composition can do. Therefore, it is possible to provide a resin composition excellent in molding processability and a method for producing a compound of the resin composition.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

[Production method of compound]
50 kg of the mixed raw material set to the blending ratio shown in Table 1 was put into a 200 L super mixer (manufactured by Kawata) and mixed at 500 rpm for 3 minutes. This mixed raw material was put into a feeder of a twin screw extruder having a screw diameter of 46 mm (L / D48) and kneaded to produce a compound. The kneading conditions at that time were all set to 160 ° C., the screw rotation speed was 260 rpm, the feeder rotation speed was 56 rpm, and 40 mesh and 60 mesh metal nets were installed on the discharge side as screen meshes one by one.

  Table 2 shows the filler used (in powder form). As a laser diffraction particle size distribution analyzer, a Microtrac MT3300ExII particle size analyzer manufactured by Microtrac Bell Co., Ltd. was used, and a dry measurement unit manufactured by the same company was used for dry measurement. The measurement results are shown in Table 2.

〔Evaluation method〕
(1) Quantitative supply ability It was confirmed whether feed abnormalities such as a bridge phenomenon and a rathole phenomenon occurred in the feeder portion. Those in which the feed abnormality occurred within 2 hours after the start of feeding the raw material into the feeder were rejected (x), and those in which the feed abnormality did not occur even after 2 hours passed were judged as acceptable (◯). The evaluation results are shown in Table 1.

(2) Cohesiveness Clogging of the screen mesh occurred within 2 hours after starting the feeding of the raw material into the feeder, and those that required replacement of the screen mesh failed (×), and replacement was required even after 2 hours. What did not do was set as the pass ((circle)). The evaluation results are shown in Table 1.

  In Examples 1 to 7, which are within the range defined by the present invention, feed abnormalities and screen mesh clogging did not occur, and the moldability was good.

On the other hand, in Comparative Examples 1 and 2 using a filler having a D _{50 (P0)} / D _{50 (P0.3)} value larger than 1.5, a feed abnormality occurred, and D _{50 (P0)} / In Comparative Example 3 using a filler having a D _{50 (P0.3)} value larger than those of Comparative Examples 1 and 2, clogging of the screen mesh occurred in addition to feed abnormality.

  In addition, this invention is not limited to the said embodiment and Example, A various deformation | transformation implementation is possible.

Claims (5)

Contains 50 to 250 parts by weight of filler with respect to 100 parts by weight of polyolefin resin,
The filler is powdery and has an average particle diameter _{(D50 (P0.3)} when dry measuring the volume distribution of the filler at a crushing pressure of 0.3 MPa using a laser diffraction particle size distribution analyzer. ) and the ratio of the average particle diameter at the time of dry measured without solution砕圧force _{(D 50 (P0)) (} D 50 (P0) / D 50 (P0.3)) is a resin composition is 1.5 or less . The resin composition according to claim 1, wherein the filler has a mean particle diameter _{(D50 (P0.3)} ) of 5 µm or less when dry-measured at a crushing pressure of 0.3 MPa.   The resin composition according to claim 1, wherein the filler is a metal hydroxide.   The compound of the resin composition of any one of Claims 1-3. The manufacturing method of a compound provided with the process of knead | mixing the resin composition of any one of Claims 1-3.