JP2022084248A - Granular filler composition - Google Patents

Abstract

To provide a granular filler composition which is excellent in productivity, versatility of an application filler, and dispersibility of a filler in a thermoplastic resin composition.SOLUTION: A granular filler composition contains a filler, an expansive clay mineral, and a dispersant, in which the expansive clay mineral is at least one selected from the group consisting of a smectite group and a vermiculite group, and the dispersant is at least one selected from the group consisting of polyhydric alcohol fatty acid ester, fatty acid amide, polyglyceryl fatty acid ester, condensed hydroxy fatty acid, and alcohol esters of condensed hydroxy fatty acid.SELECTED DRAWING: None

Description

The present invention relates to a granular filler composition.

In recent years, thermoplastic resin compositions are required to have high functionality and high performance, and for that purpose, they are often provided by mixing fillers. A thermoplastic resin composition containing a filler (hereinafter, also referred to as a filler-containing resin composition) is usually produced by melt-kneading a powdery filler and a thermoplastic resin, but in recent years, a predetermined concentration (for example, for example) is produced. It has been proposed to use filler granules (containing 50-80% by weight of filler) (eg, Patent Documents 1-4). In the production of the filler-containing resin composition, the use of the filler granules is expected to be advantageous from the viewpoints of cost, safety and health, work environment, material management and the like. However, the filler granules are not yet sufficient in terms of increasing the concentration of the filler, the productivity of the filler granules, the versatility of the applicable filler, the dispersibility of the filler in the thermoplastic resin composition, and the like. Is required to be improved.

On the other hand, in the conventional structure of filler granules, as a binder for fillers, polyethylene, polypropylene, polystyrene, thermoplastic elastomer, etc., which are softened at low temperature, have low molecular weight and high fluidity, are used. Thermoplastic resins are often used, but their use is limited when the heat resistance of the thermoplastic resin used as a binder and the compatibility with the matrix resin of the final filler-containing resin composition are inferior. There is a problem. In particular, when a filler granulated product is used for a thermoplastic resin having a high melt processing temperature represented by engineering plastics, there often arises a problem that the thermoplastic resin component as a binder becomes an extra component.

Japanese Unexamined Patent Publication No. 2018-70856 International Publication No. 2017/147465 Patent No. 6482755 Japanese Unexamined Patent Publication No. 2014-101423

The present invention has been made to solve the above problems, and the object thereof is the productivity of the granular filler composition, the versatility of the applicable filler, and the dispersibility of the filler in the filler-containing resin composition. It is an object of the present invention to provide a granular filler composition having excellent versatility and the like of a usable thermoplastic resin (thermoplastic resin contained in a filler-containing resin composition).

The granular filler composition of the present invention contains a filler, a swellable clay mineral, and a dispersant, and the swellable clay mineral is at least one selected from the group consisting of a smectite group and a vermiculite group, and the dispersant. Is a granular filler composition which is at least one selected from the group consisting of polyhydric alcohol fatty acid esters, fatty acid amides, polyglycerin fatty acid esters, condensed hydroxy fatty acids and alcohol esters of condensed hydroxy fatty acids.
In one embodiment, the content ratio of the swellable clay mineral is 0.1 part by weight to 10 parts by weight with respect to 100 parts by weight of the granular filler composition.
In one embodiment, the content ratio of the dispersant is 0.1 part by weight to 10 parts by weight with respect to 100 parts by weight of the granular filler composition.
In one embodiment, the dispersant is at least one selected from the group consisting of polyglycerin fatty acid esters, condensed hydroxy fatty acids and alcohol esters of condensed hydroxy fatty acids.
According to another aspect of the present invention, there is provided a method for producing a granular filler granulated product. The method for producing this granular filler composition is a mixing step of mixing a filler, a swelling clay mineral, and a dispersant, and granulation of the mixture obtained through the mixing step to obtain a granulated precursor. It comprises a step and a drying step of drying the granulated precursor.
In one embodiment, the granulation step includes granulation by a semi-wet granulation method.
In one embodiment, the granulation step includes granulation by a disc peretter method.

According to the present invention, the productivity of the granular filler composition, the versatility of the applicable filler, the dispersibility of the filler in the thermoplastic resin composition, and the usable thermoplastic resin (heat contained in the filler-containing resin composition). It is possible to provide a granular filler composition having excellent versatility and the like (plastic resin).

A. Outline of Granular Filler Composition The granular filler composition of the present invention contains a filler, a swellable clay mineral, and a dispersant. The swellable clay mineral is at least one selected from the group consisting of the smectite group and the vermiculite group. The dispersant is at least one selected from the group consisting of polyhydric alcohol fatty acid esters, fatty acid amides, polyglycerin fatty acid esters, condensed hydroxy fatty acids and alcohol esters of condensed hydroxy fatty acids.

Typically, the granular filler composition of the present invention has a granular form. The granular filler composition may be a so-called granulated product.

The granular filler composition of the present invention is used in the production of a filler-containing resin composition, and can be added and used during melt-kneading of the filler-containing resin composition.

In one embodiment, the granular filler composition can be obtained by processing a mixture containing the filler, a swelling clay mineral and a dispersant by any suitable method.

In the present invention, the granular filler composition can be made into a granular form by containing the above-mentioned swellable clay mineral. The granular filler composition can be produced with excellent production efficiency, and is excellent in quality stability (shape stability, uniformity of pellet hardness). Further, if a filler-containing resin composition is prepared using the above-mentioned granular filler composition, the productivity of the resin composition can be improved. Specifically, since the granular filler composition is remarkably excellent in stability when it is put into an apparatus such as an extruder, the productivity of the filler-containing resin composition (compound processing per hour) can be obtained by using the granular filler composition. Speed) can be dramatically improved. In addition, the pollution of the work environment due to dust can be remarkably improved, the occupational safety and health environment of the worker can be improved, and the time for switching and cleaning the equipment can be significantly shortened. Further, the filler-containing resin composition obtained by using the granular filler composition of the present invention can have a high concentration of filler content and has excellent filler dispersibility. Further, if the granular filler composition of the present invention is used, it has an effect of enhancing the molding processability (high fluidity) of the filler-containing resin composition, so that the load on the extruder is reduced even though the filler is contained in a high concentration. It is possible to suppress excessive heat generation of the resin, enable melt-kneading while suppressing thermal deterioration of the resin, and can impart excellent mechanical performance and moldability to the obtained filler-containing resin composition. .. By using the granular filler composition of the present invention having such an effect, not only the cost of producing the filler-containing resin composition can be reduced, but also the performance can be improved.

In one embodiment, the granular filler composition is produced by a semi-wet granulation method. According to the semi-wet granulation method, the above effect becomes remarkable.

The granular filler composition can be of any suitable shape. Typically, the granular filler composition is cylindrical (pellet-shaped).

When the granular filler composition is cylindrical, the diameter of the granular filler composition is, for example, 2 mm to 5 mm. The length (height) of the granular filler composition is, for example, 1 mm to 5 mm. With such a shape, a granular filler composition that can be preferably used in combination with a resin (particularly a thermoplastic resin) can be obtained. The diameter of the granular filler composition can be adjusted by the diameter of the die hole of the disc plate during granulation, and the length can be adjusted by the distance between the disc plate and the cutter. By matching the granular filler composition to the pellet size of the resin (particularly the thermoplastic resin) used in combination, the handleability is improved and the dispersibility of the filler in the molten compound is improved.

The fracture stress of the granular filler composition in the Kiya-type hardness tester is preferably 0.05 kg to 5 kg, more preferably 0.1 kg to 3 kg, and further preferably 0.2 kg to 2 kg. Within such a range, the handleability and the filler dispersibility are excellent. Here, the fracture stress indicates the average decay stress measured for 20 or more grains.

The water content of the granular filler composition can be any suitable water content. The water content of the granular filler composition is preferably 10% by weight or less, more preferably 5% by weight or less, still more preferably 3% by weight or less, and particularly preferably 1% by weight or less. It is preferably 0.5% by weight or less.

The bulk density of the granular filler composition may be any suitable bulk density depending on the type of filler. The bulk density of the granular filler composition is preferably 0.5 g / cm ³ to 2.0 g / cm ³ . In particular, when the filler is a mineral (natural mineral), the bulk density of the granular filler composition is preferably in such a range. By increasing the bulk density, the supply speed and supply stability of the granular filler composition are increased when melt-kneading with a resin (particularly a thermoplastic resin).

In one embodiment, the granular filler composition is substantially free of the thermoplastic resin component as a binder component. If a granular filler composition containing no thermoplastic resin component is used, the restrictions on its use due to the thermoplastic resin binder are eliminated, and it can be used in a wide range of resin compositions having a high processing temperature represented by engineering plastics. It can be applied to various types of thermoplastic resins. The content ratio of the thermoplastic resin in the granular filler composition is preferably 5% by weight or less, more preferably 1% by weight or less, still more preferably 0.5% by weight or less, and particularly preferably 0. It is 1% by weight or less.

A-1. Filler The content ratio of the filler in the granular filler composition of the present invention is preferably 90 parts by weight or more, more preferably 95 parts by weight or more, still more preferably 95 parts by weight or more, based on 100 parts by weight of the total amount of the granular filler composition. Is more than 97 parts by weight.

As the filler, any suitable filler can be used depending on the properties required for the filler-containing resin composition and / or the molded product obtained from the filler-containing resin composition.

The characteristics / effects that can be imparted by the above fillers include, for example, increase in weight or weight reduction, reinforcement (high rigidity, high elastic modulus, high strength), dimensional stability, molding cycle (crystallization rate), and degree of crystallization. , Thermal conductivity, conductivity, magnetism, piezoelectricity, vibration damping, sound insulation, sliding property, heat insulating property, electromagnetic wave absorption, light reflectivity, light scattering property, heat ray radiation property, flame retardancy, radiation protection, Examples include UV protection, dehumidification, dehydration, deodorization, gas absorption, gas barrier, antiblocking, oil absorption, antibacterial property, biodecomposition promoting property, improvement of biodegree (improvement of ratio of natural substance-derived component amount), and the like.

For example, for the purpose of increasing the amount, calcium carbonate, talc, silica and clay are suitable. For reinforcement purposes, wallastonite, potassium titanate, zonotrite, gypsum fiber, aluminum borate, fibrous magnesium compound (MOS), aramid fiber, various fiber systems, carbon fiber (carbon fiber), glass fiber (glass fiber), Talk, mica, glass flakes, polyoxybenzoyl whisker and the like are suitable. For the purpose of imparting antibacterial properties, catechin, silver ion-supported zeolite, copper phthalocyanine, etc. are suitable. For the purpose of imparting gas barrier properties, synthetic mica-based materials, clay / synthetic mica nanofillers, and the like are suitable. For the purpose of weight reduction, balloon systems such as silica balloons, glass balloons, senospheres, pearlite, and shirasu balloons are suitable. For the purpose of imparting conductivity, carbon black, graphite, carbon fiber, metal powder, metal fiber, and metal foil are suitable. For the purpose of imparting magnetism, various magnetic materials, various ferritic stainless steels, magnetic iron oxide, samarium (Sm-Co), Nd-Fe-B, and the like are suitable. Alumina, AlN, BN, BeO, etc. are suitable for the purpose of imparting thermal conductivity. For the purpose of imparting piezoelectricity, barium titanate, lead zirconate titanate (PZT), and the like are suitable. For the purpose of imparting vibration damping properties, mica, graphite, potassium titanate, zonotrite, carbon fiber, ferrite and the like are suitable. For the purpose of imparting sound insulation, iron powder, lead powder, barium sulfate, etc. are suitable. For the purpose of imparting slidability, graphite, hexagonal BN, molybdenum sulfide, Teflon powder, talc, high molecular weight polyethylene, etc. are suitable. For the purpose of imparting electromagnetic wave absorption, electromagnetic wave absorbing ferrite, graphite, charcoal powder, carbon microcoil (CMC), carbon nanotube (CNT), PZT, etc. are suitable. For the purpose of imparting light reflection and light scattering, titanium oxide, glass beads, calcium carbonate, aluminum powder, mica, and the like are suitable. For the purpose of imparting heat ray radiation, magnesium oxide, hydrotalcite, MOS, alumina, charcoal powder and the like are suitable. For the purpose of flame retardancy, antimony oxide, aluminum hydroxide, magnesium hydroxide, zinc borate, red phosphorus, zinc carbonate, hydrotalcite, dosonite, brominated flame retardant, phosphorus flame retardant and the like are suitable. For the purpose of radiation protection, lead powder, barium sulfate, etc. are suitable. For the purpose of "ultraviolet protection", titanium oxide, zinc oxide, iron oxide, etc. are suitable. For the purpose of dehumidification and dehydration, calcium oxide, magnesium oxide, etc. are suitable. Zeolites, etc. are suitable for the purpose of deodorization and gas absorption. For the purpose of anti-blocking (preventing crimping of the film), silica, calcium carbonate, talc, spherical fine particles (silicone and acrylic beads) and the like are suitable. For the purpose of oil absorption (absorption of printing ink, quick-drying property, etc.), marimo-like calcium carbonate, marimo-like zonotrite, and the like are suitable. For the purpose of water absorption, a polymer gel for water absorption, calcium oxide, magnesium oxide, etc. are suitable. Cellulose-based materials (wood flour, wood fiber, sawdust, wood chips, newspaper, paper, flax, hemp, straw, rice husks, kenaf, jute, sisal, peanut husks, soybean hulls, etc. Etc.), starch, natural rubber, etc. are suitable.

The size of the filler can be any suitable size. The particle size of the filler is, for example, 10 nm to 100 μm. The size of the filler can be determined by the laser diffraction method.

A-2. Swellable clay mineral The swellable clay mineral is a swellable clay mineral. As described above, the swellable clay mineral is at least one selected from the group consisting of the smectite group and the vermiculite group. The smectite group is a clay mineral classified as a smectite group, and examples thereof include montmorillonite, biderite, nontronite, saponite, hectorite, saponite, stepnsite, sine holderite, and volcon scoreite. The vermiculite group is a clay mineral classified as a vermiculite group, and examples thereof include 38-sided vermiculite and 28-sided vermiculite. Clay minerals classified into the smectite group or vermiculite group have remarkable swelling properties. Among them, bentonite containing smectite as the main component absorbs a large amount of water and swells several to several tens of times in volume, and only a few percent of bentonite is submerged in water. Just by including, it becomes jelly-like. The water dispersion system of the swellable clay mineral becomes a sticky and highly viscous paste due to the infinite expansion of the clay particles, and the structure can be maintained. In the present invention, a granular filler composition can be obtained by utilizing the thickening and structural sustainability of this swellable clay mineral.

The particle size of the swellable clay mineral as a raw material powder can be micron to submicron. The number average primary particle size of the swellable clay mineral is, for example, 0.1 μm to 20 μm (preferably 0.5 μm to 10 μm). The particle size can be determined by a laser diffraction method.

The content ratio of the swellable clay mineral may be any appropriate ratio depending on the size, shape, water absorption, oil absorption property, bulk specific gravity and the like of the filler. The content ratio of the swellable clay mineral is preferably 0.1 part by weight to 10 parts by weight, more preferably 0.2 parts by weight to 6 parts by weight, based on 100 parts by weight of the granular filler composition. It is preferably 0.3 parts by weight to 5 parts by weight, and more preferably 0.5 parts by weight to 3 parts by weight. Within such a range, it is possible to obtain a granular filler composition in which the effect of the granular filler composition as a binder is preferably exhibited and the dispersibility of the filler is excellent.

A-3. Dispersant As described above, the dispersant is at least one selected from the group consisting of polyhydric alcohol fatty acid esters, fatty acid amides, polyglycerin fatty acid esters, condensed hydroxy fatty acids and alcohol esters of condensed hydroxy fatty acids. Among them, at least one selected from the group consisting of polyglycerin fatty acid ester, condensed hydroxy fatty acid and alcohol ester of condensed hydroxy fatty acid is particularly preferably used.

The dispersant is a compound composed of a hydrophobic group and a hydrophilic group. The hydrophilic / hydrophobic balance can be controlled by adjusting the degree of esterification of the compound serving as a dispersant, the type of fatty acid (presence or absence of hydroxyl group, saturated or unsaturated fatty acid, alkyl chain length), and the degree of polymerization. .. The hydrophilic / hydrophobic balance can be any appropriate balance depending on the type of the filler, the type of the resin to be combined with the granular filler composition, and the like.

The polyhydric alcohol fatty acid ester is an ester compound composed of a polyhydric alcohol and a fatty acid. The polyhydric alcohol fatty acid ester can be obtained by subjecting the polyhydric alcohol to an esterification reaction with a fatty acid.

The polyhydric alcohol may be, for example, an alcan polyol such as pentaerythritol or glycerin; a polyalcan polyol which is a polymer of the alcan polyol; a saccharide such as sucrose; a sugar derivative typified by a sugar alcohol such as sorbitol or mannitol. Can be mentioned. These alcohols may be used alone or in combination of two or more. As the fatty acid, any suitable fatty acid can be used. In one embodiment, a fatty acid having 8 or more carbon atoms (preferably 8 to 24 carbon atoms, more preferably 10 to 22 carbon atoms) is used. Specific examples of the fatty acid include capric acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitreic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, nonadecanic acid, araquinic acid, gadreic acid and eikosazienoic acid. , Arachidonic acid, behenic acid, erucic acid, docosadienoic acid, lignoseric acid, isostearic acid, ricinoleic acid, 12-hydroxystearic acid, 9-hydroxystearic acid, 10-hydroxystearic acid, hydrogenated castor oil fatty acid (12-hydroxy) In addition to stearic acid, fatty acids containing a small amount of stearic acid and palmitic acid) and the like can be mentioned. Of these, palmitic acid and stearic acid are preferable. As the fatty acid, only one kind may be used, or two or more kinds may be used in combination.

The fatty acid amide is a compound having a structure in which a fatty acid and ammonia or a primary / secondary amine are dehydrated and condensed. The fatty acid amide is not particularly limited, but specifically, saturated fatty acid monoamides such as lauric acid amide, palmitic acid amide, stearic acid amide, and behenic acid amide, oleic acid amide, erucic acid amide, ricinolic acid amide and the like. Substitution of unsaturated fatty acid monoamides, N-stearyl stearyl amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stealic acid amide, N-stearyl erucate amide, N-oleyl palmitate amide, etc. Amides, methylol stearate amides, methylol behenic acid amides and other methylol amides, methylene bisstearic acid amides, ethylene biscapric acid amides, ethylene bislauric acid amides, ethylene bisstearic acid amides, ethylene bisisostearic acid amides, ethylene bis Hydroxystearic acid amide, ethylene bisbechenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbechenic acid amide, hexamethylene bishydroxystearic acid amide, N, N'-dystearyl adipic acid amide, N, N'-di Saturated fatty acid bisamides such as stearyl sevacinic acid amides, unsaturated aliphatic bisamides such as ethylene bisoleic acid amides, hexamethylene bisoleic acid amides, N, N'-diorail adipic acid amides, m-xylylene bisstearic acid. Examples include aromatic bisamides such as amides. These fatty acid amides may be used alone or in combination of two or more. Among these, those having a melting temperature in the range of about 70 ° C to 120 ° C are particularly preferable.

The polyglycerin fatty acid ester is an ester compound composed of polyglycerin and a fatty acid.

As the polyglycerin, any suitable polyglycerin can be used. Specific examples of the polyglycerin include diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin, eikosaglycerin, tetracontaglycerin and the like. Of these, diglycerin, triglycerin, pentaglycerin or decaglycerin are preferable. Only one type of polyglycerin may be used, or two or more types may be used in combination.

As the fatty acid, any suitable fatty acid can be used. In one embodiment, fatty acids having 8 or more carbon atoms (preferably 8 to 24, more preferably 10 to 22) are used. Specific examples of the fatty acid include capric acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitreic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, nonadecanic acid, araquinic acid, gadreic acid and eikosazienoic acid. , Arachidonic acid, behenic acid, erucic acid, docosadienoic acid, lignoseric acid, isostearic acid, ricinoleic acid, 12-hydroxystearic acid, 9-hydroxystearic acid, 10-hydroxystearic acid, hydrogenated castor oil fatty acid (12-hydroxy) In addition to stearic acid, fatty acids containing a small amount of stearic acid and palmitic acid) and the like can be mentioned. Of these, palmitic acid and stearic acid are preferable. As the fatty acid, only one kind may be used, or two or more kinds may be used in combination.

Specific examples of the polyglycerin fatty acid ester include diglycerin luminic acid ester, diglycerin stearate ester, diglycerin oleic acid ester, decaglycerin oleic acid ester, decaglycerin stearate ester, decaglycerin oleic acid ester and the like. Can be mentioned. These may be used alone or in combination of two or more.

The fatty acid esterification rate of the polyglycerin fatty acid ester is preferably 35% or more, more preferably 50% to 70%. Within such a range, a filler granulated product having excellent production stability can be obtained. Further, the filler granulated product is excellent in dispersibility in a resin (particularly, a thermoplastic resin). The esterification rate (%) is expressed by the formula: esterification rate (%) = (number of mols of constituent fatty acids / number of hydroxyl groups of polyglycerin) × 100.

The polyglycerin fatty acid ester can be obtained by any suitable method. For example, polyglycerin and fatty acid are produced in the presence of a catalyst (eg, phosphoric acid, p-toluenesulfonic acid, caustic soda) or in the absence of a catalyst at 100 ° C. to 300 ° C. (preferably 120 ° C. to 260 ° C.). Can be obtained by reacting while removing from the system. The reaction is preferably carried out in the presence of an inert gas. Further, it may be carried out in an azeotropic solvent such as toluene or xylene.

The condensed hydroxy fatty acid can be obtained by dehydrating and condensing the hydroxy fatty acid. The condensed hydroxy fatty acid can be obtained by dehydration condensation by adding an alkaline catalyst such as caustic soda to the hydroxy fatty acid and removing the reaction water under heating.

The condensed hydroxy fatty acid is a condensed product of hydroxy fatty acid, and the degree of condensation thereof is preferably 2 or more, more preferably 4 or more. The upper limit of the degree of condensation of the condensed hydroxy fatty acid is, for example, 20. The degree of condensation can be calculated from the acid value of the raw material hydroxy fatty acid and the acid value after the condensation reaction.

The hydroxy fatty acid is a fatty acid having one or more hydroxyl groups in the molecule. Specific examples of hydroxy fatty acids include, for example, ricinolic acid, 12-hydroxystearic acid, savinic acid, 2-hydroxytetradecanoic acid, iprolic acid, 2-hydroxyhexadecanoic acid, yarapinolic acid, uniperic acid, ambrettoric acid, allurit. Acids, 2-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, camlorene acid, ferronic acid, celebronic acid and the like can be mentioned. The hydroxy fatty acid may be used alone or in combination of two or more.

The alcohol ester of the condensed hydroxy fatty acid can be obtained by subjecting the condensed hydroxy fatty acid to an alcohol in an esterification reaction. The alcohol ester of the condensed hydroxy fatty acid is, for example, a mixture of the condensed hydroxy fatty acid and an alcohol, an alkaline catalyst such as caustic soda or an acid catalyst such as phosphoric acid is added to the obtained mixture, and the reaction water is removed under heating. Can be obtained. The progress of esterification during this reaction can be confirmed by measuring the acid value, saponification value, hydroxyl value and the like. As described above, the degree of condensation of the condensed hydroxy fatty acid used here is preferably 2 or more, and more preferably 4 or more.

Examples of the alcohol include monohydric alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; and dihydric alcohols such as ethylene glycol and propylene glycol. Moreover, you may use a polyhydric alcohol as the said alcohol. Examples of the polyhydric alcohol include alcan polyols such as pentaerythritol and glycerin; polyalcan polyols which are polymers of the alcan polyols; sugars such as sucrose; sugar derivatives typified by sugar alcohols such as sorbitol and mannitol. Can be mentioned. These alcohols may be used alone or in combination of two or more.

Specific examples of the condensed hydroxy fatty acid and its alcohol ester include, for example, condensed ricinoleic acid obtained by dehydrating and condensing ricinoleic acid, condensed 12 hydroxystearic acid obtained by dehydrating and condensing 12 hydroxystearic acid, condensed ricinoleic acid and hexa of the glycerin 6 polymer. Condensed ricinoleic acid hexaglycerin ester, which is an ester of glycerin, condensed ricinoleic acid tetraglycerin ester, which is an ester of tetraglycerin of condensed lysinoreic acid and glycerin tetrapolymer, condensed 12 hydroxystearic, which is an ester of condensed 12 hydroxystearic acid and propylene glycol. Examples thereof include acid propylene glycol ester, condensed linoleic acid propylene glycol ester which is an ester of condensed ricinoleic acid and propylene glycol, and the like. These may be used alone or in combination of two or more.

Commercially available products may be used as the polyglycerin fatty acid ester, the condensed hydroxy fatty acid, and the alcohol ester of the condensed hydroxy fatty acid. Examples of commercially available products are "Thirabazole P-4", "Thirabazole VR-01", "Thirabazole VR-08" (polyglycerin fatty acid ester), and "Thirabazole H-818" (condensed hydroxy fatty acid) manufactured by Taiyo Kagaku Co., Ltd. Alcohol ester), etc.

The weight average molecular weight of the dispersant is preferably 800 or more, more preferably 800 to 4000. Within such a range, a filler granulated product having excellent granulation property, thermal stability and dispersibility can be obtained. The weight average molecular weight can be measured by the ultimate viscosity method.

The content ratio of the dispersant is preferably 0.1 part by weight to 10 parts by weight, more preferably 1 part by weight to 8 parts by weight, based on 100 parts by weight of the total amount of the granular filler composition. More preferably, it is 1 part by weight to 5 parts by weight. Within such a range, a granular filler composition having excellent productivity and dispersibility can be obtained.
That is, if the above-mentioned dispersant is used, the viscosity of the mixture when granulating the granular filler composition can be lowered, so that the productivity can be increased and the granulation can be easily performed. Further, when blended in a thermoplastic resin, the dispersant can greatly improve the dispersibility of the filler.

A-4. Other Ingredients The granular filler composition may further comprise any suitable other ingredient (additive), if desired. Additives include, for example, antioxidants, light stabilizers, foaming agents, UV absorbers, foaming agents, blocking inhibitors, heat stabilizers, impact modifiers, antibacterial agents, compatibilizers, plasticizers, and tackifiers. Examples thereof include agents, processing aids, lubricants, coupling agents, flame retardants, oxygen scavengers, colorants and the like. Additives can be added in the form of liquids, powders, pellets, granules, masterbatches and the like during filler granulation or in the resin compounding process. In one embodiment, the additive can be granulated with a semi-wet granulator and blended into the granular filler composition.

B. Method for Producing Granular Filler Composition The above-mentioned granular filler composition can be produced by any suitable method. The granular filler composition can be obtained, for example, by subjecting a mixture containing the filler, the swelling clay mineral and the dispersant to a semi-wet granulation method.

In one embodiment, the method for producing the granular filler composition is to granulate a mixture obtained through the mixing step of mixing the polymer, the swelling clay mineral, and the dispersant, and the mixing step. It includes a granulation step of obtaining a granulation precursor and a drying step of drying the granulation precursor.

In the semi-wet granulation method, water may be further mixed. The water to be added is not particularly limited, and for example, tap water, distilled water, ion-exchanged water, hard water, soft water and the like can be used.

The mixing amount of the water is usually 1 part by weight to 30 parts by weight, preferably 3 parts by weight to 25 parts by weight, and more preferably 5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the filler in the granular filler composition. Is.

In the mixing step, it is preferable to mix the components at room temperature and homogenize them using any suitable mixer. Examples of the mixer include a Henschel mixer, a powder kneader (KDH, KDA, CKD, CPM) (Dalton), a Spartan mixer (SPM) (Dalton), an SP granulator (SPG) (Dalton), and the like. Can be mentioned.

The mixing time in the mixing step can be any appropriate mixing time depending on the type of component, the type of mixer, the component mixing ratio, and the like. In the mixing step, the mixing time is set so that each component is uniformly dispersed. With a high-speed stirrer such as a Henschel mixer or a Spartan mixer, the processing time can be 1 to 10 minutes. On the other hand, in the case of a powder kneader, a processing time of several minutes to 60 minutes may be required.

In the granulation step, the compression granulation method is preferably adopted. Further, in the granulation step, a semi-wet granulation method can be preferably adopted. Examples of the compression granulation method / semi-wet granulation method include a disc pelleter method, a tabletting method, and a briquetting method. From the viewpoint of the balance between productivity and the quality of the obtained granular filler composition, the disc pelleter method is preferably adopted.

The disc pelleter type granulator has, as a basic structure, one or two discs having a large number of holes of 2 mm to 30 mm, and a roller for pumping raw materials into the holes of the discs. The raw material supplied between the disc and the roller or between the two discs is press-fitted into the hole of the disc as the roller rotates, and a columnar extrusion is formed. Here, the disk hole is provided with a taper so that compressive stress is applied from the outer periphery of the die hole in the process of the filler mixture passing through the hole. The length of this tapered hole is called the effective length. The extruded granulated precursor can be cut on the back surface of the disk with a cutter or the like to obtain a pellet-shaped granular filler composition. The length of the granulation precursor (resulting in the filler granulation) can be adjusted by the distance between the back surface of the disc and the cutter and the rotation speed of the rollers.

More specific examples of the disc pelleter method include a roller disc die method, a roller ring die method, a double die method, and a flat die method. As a commercially available disc pelleter type granulator, for example, a disc pelleter F series manufactured by Dalton Co., Ltd. can be mentioned.

Any suitable method can be adopted as the drying method in the drying step. After the drying step, a granular filler composition from which fine powder has been removed can be obtained by a vibrating sieve or the like. Any suitable drying equipment is used in the drying process. For example, a vibration-flow dryer is preferable because it can efficiently dry in a short time. For example, a vibration-flow dryer VDF series manufactured by Dalton can be mentioned.

C. Melt compound of resin and granular filler composition In one embodiment, a melt compound of the above granular filler composition and resin is provided. As the resin, a thermoplastic resin is preferably used.

The thermoplastic resin is not particularly limited, and is, for example, high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), polypropylene (PP), polyvinyl chloride (PVC), and polyvinylidene chloride. , Polystyrene (PS), Polyvinyl acetate (PVAc), Polyurethane (PUR), Fluorine resin, ABS resin (Acrylonitrile butadiene styrene resin), AS resin, Acrylic resin (PMMA) and other general-purpose resins, Polyamide (PA), Nylon , Polyacetal (POM), Polycarbonate (PC), Modified polyphenylene ether (m-PPE, Modified PPE, PPO), Polyesters (PET, PBT, etc.), Engineering plastics such as cyclic polyolefin (COP), Polyphenylene sulfide (PPS) ), Polytetrafluoroethylene (PTFE), Polysulfone (PSF), Polyethersulfone (PES), Acrylic polyarylate (PAR), Liquid crystal polymer (LCP) Polyether ether ketone (PEEK), Thermoplastic polyimide (PI) , Polyamideimide (PAI) and other super engineering plastics can be exemplified.

Moreover, you may use a biodegradable resin as the said resin. Examples of the biodegradable resin include homopolymers or copolymers of aliphatic polyester resins (for example, polycaprolactone, polylactic acid, polyethylene succinate, polybutylene succinate adipate, polyhydroxyvariate), and homopolymers thereof. Alternatively, a modified copolymer, etc.), an aliphatic / aromatic polyester resin (for example, an aliphatic carboxylic acid or hydroxy acid, an aromatic dicarboxylic acid and a block polymer such as 1,3-propanediol, or a random polymer), or Examples thereof include polyvinyl alcohol-based resins (for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyrate, ethylene / vinyl alcohol copolymer, etc.). Moreover, natural rubber and the like can be mentioned as a biodegradable resin derived from nature.

Any suitable method can be adopted as a method for producing the molten compound. For example, a kneader, a Banbury mixer, a roll, a single-screw or two-screw or more multi-screw extruder can be used. Preferably, a twin-screw extruder is used. The melt-kneaded composition is pelletized.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, parts and% are based on the weight standard.

[Example 1]
15 parts by weight of clean water and 1 part by weight of a dispersant (polyglycerin condensed hydroxy fatty acid ester; manufactured by Taiyo Kagaku Co., Ltd., trade name "tyrabazole H818";"C-1" in the table) are put into a 1 L plastic container. The mixture A was obtained by stirring at room temperature for 20 minutes using a stirring blade. Next, in a powder kneader (manufactured by Dalton, trade name "KDHJ-10"; treatment amount: 6 L), a filler (mica powder; manufactured by Chuzhou Grea Minerals Co., trade name "GM-4"; average particle size: 18 μm; 80 parts by weight of “A-1” in the table) and 5 parts by weight of swellable clay mineral (Bentnite; manufactured by Big Chemie Japan, trade name “CLOISITE116”; “B-1” in the table). The mixture A was put into the powder kneader while stirring the stirring blade at a rotation speed of 30 rpm. Then, stirring treatment was carried out for 6 minutes to obtain a mixture B.
The mixture B was put into a disc pelleter (manufactured by Dalton, trade name "disc pelleter F-5 / 11-175; capacity: 5 L") to obtain a pered-like granulated precursor. At this time, the hole diameter of the die was 3 mmφ, the thickness of the die plate was 15 mm, the effective length of the die hole was 10 mm, and the rotation speed of the roller of the dispenser was 108 rpm.
The obtained granulated precursor was dried at 160 ° C. for 6 hours using a hot air circulation type dryer to obtain a granular filler composition MB-1.

[Examples 2 to 9, Comparative Examples 1 to 3]
Granular filler composition MB-2 in the same manner as in Example 1 except that the filler, swelling clay mineral and dispersant shown in Table 1 and water were used in the blending amount (part by weight) shown in Table 1. -MB-9 and MB-C1 to MB-C3 were obtained.
The specific contents of each component used in Examples 1 to 9 and Comparative Examples 1 to 3 are as shown in Table 2.

<Evaluation>
The granular filler compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were subjected to the following evaluation. The results are shown in Table 3.
(1) Granulation property The obtained granular filler composition was confirmed, and the granulation property was evaluated according to the following criteria.
〇: Granulated products with a diameter of 3 mmφ can be obtained.
Δ: Although it is in the form of a granulated product of a filler, it is liable to collapse due to insufficient binding force.
X: The filler is clogged in the die, or the filler has no binding property and does not become a granular material.
(2) Granulation rate The production rate (kg / Hr) of the granular filler composition per hour was calculated.
(3) Bulk Density The bulk density of the granular filler composition (unit: kg) by measuring the weight of the dried filler granules using a 1 liter box, accurately measuring the volume of 1 liter. / L) was calculated.
(4) Measurement of Collapse Strength The decay stress (unit: kg) of the granular filler composition after drying was measured using a Kiya-type hardness tester (manufactured by Shiro Sangyo Co., Ltd., trade name “WPF1600-B”). The measured value was the average value of 20 granular filler compositions.
(5) Moisture content An infrared moisture meter (FD-660 manufactured by Kett Science Institute) was used to measure the water content (unit:% by weight) remaining in the granular filler composition.
(6) Pellet size 20 filler granules were taken out, and the average value of the length and diameter of the granules was measured using a caliper.
(7) Dispersibility of filler A twin-screw extruder (7) 20 parts by weight of a granular filler composition and 80 parts by weight of a thermoplastic resin (homopolypropylene; manufactured by Nippon Polypro Co., Ltd., trade name "Novatec MA1B", MFR 21 g / 10 min) It was put into a product of Toshiba Machinery Co., Ltd., trade name "TEM37SS", L / D = 48) and continuously melt-kneaded to produce pellets of a thermoplastic resin composition. The granular filler composition MB and the thermoplastic resin were independently and quantitatively charged into the twin-screw extruder from the hopper position at the most upstream portion of the extruder via a heavy-duty feeder. The cylinder temperature of the extruder was set to 180 ° C. after the middle stage of the extruder. The rotation speed of the main screw of the twin-screw extruder was set to 200 rpm. The melt-kneaded resin composition was extruded into a strand shape and cooled in a water-cooled bath to obtain pellets having a length of about 3 mm.
The pellets of the resin composition are rolled by a hot press to obtain a sheet having a thickness of about 0.5 mm. Through the sheet, the residual filler agglomerates were visually observed and evaluated according to the following criteria.
AA: Good dispersibility in which almost no agglomerates of the filler are observed A: A state in which a small amount of agglomerates of a relatively small filler remains BB: A state in which a large amount of agglomerates of a relatively small filler remains B: Agglomerates of a filler Large state (order of dispersed state: AA>A>BB> B (good left))

表３に示す通り、ＭＢ－１～ＭＢ－９では、安定したペレット形状、高い造粒速度、適切な硬度のペレット状の粒状フィラー組成物を得ることができる。一方、ＭＢ－Ｃ１はペレット状の粒状フィラー組成物が得られるが、熱可塑性樹脂と溶融混練した場合に、フィラーもしくは膨潤性粘土鉱物の凝集物が観察され、分散性が不十分である。ＭＢ－Ｃ２、ＭＢ－Ｃ３では、安定した形状でペレット状の粒状フィラー組成物を得ることができない。

As shown in Table 3, in MB-1 to MB-9, a pellet-shaped granular filler composition having a stable pellet shape, a high granulation rate, and an appropriate hardness can be obtained. On the other hand, in MB-C1, a pellet-shaped granular filler composition can be obtained, but when melt-kneaded with a thermoplastic resin, agglomerates of a filler or a swelling clay mineral are observed, and the dispersibility is insufficient. With MB-C2 and MB-C3, it is not possible to obtain a pellet-shaped granular filler composition with a stable shape.

[Examples 10 to 12, Comparative Examples 4 and 5]
Filler granulation MB-4 (or powder filler (A-1)) and thermoplastic resin are used in the blending amounts shown in Table 4, and a twin-screw extruder (manufactured by Toshiba Machinery Co., Ltd., trade name "TEM37SS", L / It was put into D = 48) and continuously melt-kneaded to produce pellets of a thermoplastic resin composition.
The thermoplastic resin used in Examples 10 to 12 and Comparative Examples 4 and 5 is polycarbonate (PC; manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name “Novalex 7022PJ”; MVR (300 ° C., 1.2 kg load): 11 cm. ^3/10 min), polyethylene terephthalate (PET; manufactured by Mitsubishi Engineer Plastics, trade name "PBK1").
The granular filler composition MB-4 (or powder filler (A-1)) and the thermoplastic resin are independently and quantitatively transferred to the twin-screw extruder via a heavy-duty feeder, and the uppermost stream portion of the extruder. It was thrown in from the hopper position of. The cylinder temperature of the extruder was set to 250 ° C. after the middle stage of the extruder. Further, the rotation speed of the main screw of the twin-screw extruder was set to 150 rpm. The melt-kneaded resin composition was extruded into a strand shape and cooled in a water-cooled bath to obtain pellets having a length of about 3 mm.
<Evaluation>
The pellets of the thermoplastic resin compositions obtained in Examples 10 to 12 and Comparative Examples 4 and 5 were subjected to the following evaluation. The results are shown in Table 4.
(A) Discharge rate of resin composition (unit: kg / Hr)
The amount of the compound resin composition discharged per hour.
(B) Extruder load (unit:%)
It is a display value of the actual power load% (ratio to the allowable maximum motor load) of the twin-screw extruder.
(C) Molten resin temperature at the die portion (unit: ° C.)
The temperature of the resin composition extruded from the die was measured with a contact thermocouple.
(D) MFR (unit: g / 10min)
The melt mass flow rate (MFR) was measured using a "melt indexer" manufactured by Toyo Seiki Seisakusho Co., Ltd. in accordance with JIS K7210, and the fluidity was evaluated. The measurement conditions are 270 ° C. and a 2.16 kg load.
(E) Dispersibility of filler The pellets of the resin composition are rolled by a hot press to obtain a sheet having a thickness of about 0.5 mm. The sheet was watermarked and evaluated according to the criteria of "(7) Dispersibility of filler" described above.

実施例１０、１１、１２ではいずれも安定に樹脂組成物を得ることができた。
実施例１０と比較例４の対比から、本発明の粒状フィラー組成物を使用することで、溶融混練時における押出機の負荷を低下させることができ、樹脂温度を低減できることがわかる。実施例１１に示すように、本発明の本発明の粒状フィラー組成物を使用することで、樹脂組成物の生産性を大きく改善することができ、同時に樹脂中のフィラー良分散性を同時に満足することができる溶融コンパウンドが可能となることがわかる。比較例５は粉体フィラー（Ａ－１）を使用した例であるが、吐出速度３０［ｋｇ／Ｈｒ］においてマイカ粉末Ａ－１がホッパー内でブリッジを生じ、押出機スクリューへの食い込み不良が生じ、安定に生産することができなかった。

In Examples 10, 11 and 12, the resin composition could be stably obtained.
From the comparison between Example 10 and Comparative Example 4, it can be seen that the load of the extruder at the time of melt-kneading can be reduced and the resin temperature can be reduced by using the granular filler composition of the present invention. As shown in Example 11, by using the granular filler composition of the present invention of the present invention, the productivity of the resin composition can be greatly improved, and at the same time, the good dispersibility of the filler in the resin is simultaneously satisfied. It can be seen that a molten compound that can be made is possible. Comparative Example 5 is an example in which the powder filler (A-1) is used, but the mica powder A-1 forms a bridge in the hopper at a discharge rate of 30 [kg / Hr], resulting in poor penetration into the extruder screw. It occurred and could not be produced stably.

Claims (7)

Contains fillers, swelling clay minerals, and dispersants,
The swelling clay mineral is at least one selected from the group consisting of smectite group and vermiculite group.
The dispersant is at least one selected from the group consisting of polyhydric alcohol fatty acid esters, fatty acid amides, polyglycerin fatty acid esters, condensed hydroxy fatty acids and alcohol esters of condensed hydroxy fatty acids.
Granular filler composition. The granular filler composition according to claim 1, wherein the content ratio of the swellable clay mineral is 0.1 part by weight to 10 parts by weight with respect to 100 parts by weight of the granular filler composition. The granular filler composition according to claim 1 or 2, wherein the content ratio of the dispersant is 0.1 part by weight to 10 parts by weight with respect to 100 parts by weight of the granular filler composition. The granular filler composition according to any one of claims 1 to 3, wherein the dispersant is at least one selected from the group consisting of polyglycerin fatty acid ester, condensed hydroxy fatty acid and alcohol ester of condensed hydroxy fatty acid. A mixing step of mixing a filler, a swelling clay mineral, and a dispersant,
A granulation step of granulating the mixture obtained through the mixing step to obtain a granulation precursor, and a granulation step.
A drying step of drying the granulated precursor.
A method for producing a granular filler composition. The method for producing a granular filler composition according to claim 5, which comprises granulating by a semi-wet granulation method in the granulation step. The method for producing a granular filler composition according to claim 5 or 6, which comprises performing granulation by a disc pelleter method in the granulation step.