Filler Granules

Abstract

To provide a filler granulated substance containing a filler subjected to hydrophobic surface modification (surface treatment) which can improve supply stability and supply accuracy of a filler when a resin composition is prepared, and can stably obtain a resin composition with high productivity.SOLUTION: A filler granulated substance contains a surface-treated filler and a binder, wherein the surface-treated filler is constituted by subjecting a filler before treatment to surface treatment by at least one selected from the group consisting of a silane coupling agent, a titanate coupling agent and silicone oil, and a content ratio of the surface-treated filler is 40-99.9 pts.wt. with respect to 100 pts.wt. of the total amount of the surface-treated filler and the binder.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a filler granulate.

Background Art

[0002] Conventionally, in order to improve various properties of a resin composition, a filler may be added to the resin composition. Further, among fillers, fillers having a hydrophobic surface modification on the surface thereof are known, and such fillers are advantageous in that they have high dispersibility in a resin.

[0003] Fillers are often powders. Powdery fillers generally have a low bulk density and poor fluidity during transfer, so there are many handling problems such as transportation, storage, packaging, supply stability to processing machines, etc., and problems to be solved in terms of working environment and safety to the human body. As a method for solving such problems, there is a method of semi-wet mixing a powdery filler with an aqueous polymer (an aqueous solution or an aqueous dispersion of a polymer), binding the powdery filler using the aqueous polymer as a binder, and granulating (hereinafter, also referred to as a semi-wet granulation method) (for example, Patent Document 1). However, when a filler having a hydrophobic surface modification is used, in the semi-wet granulation method, there arises a problem that granulation becomes difficult due to the water-repellent action on the filler surface.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention has been made to solve the above problems, and an object thereof is to provide a filler granulate containing a hydrophobically surface-modified (surface-treated) filler, which can improve the supply stability and supply accuracy of the filler when preparing a resin composition, and enables the resin composition to be stably obtained with high productivity.

Means for Solving the Problems

[0006] The filler granulate of the present invention contains a surface-treated filler and a binder, the surface-treated filler is constituted by surface-treating a filler before treatment with at least one selected from the group consisting of a silane coupling agent, a titanate coupling agent, and silicone oil, and the content ratio of the surface-treated filler is 40 parts by weight to 99.9 parts by weight with respect to 100 parts by weight of the total amount of the surface-treated filler and the binder. In one embodiment, the filler before treatment is at least one selected from the group consisting of a silicon-based inorganic compound, a metal hydroxide, a silicate compound, and a metal oxide. In one embodiment, the binder is constituted by at least one selected from the group consisting of a polyolefin-based resin, a polyvinyl alcohol-based resin, a polyvinyl pyrrolidone-based resin, a polyester-based resin, a polyamide-based resin, an acrylic-based resin, a urethane-based resin, an epoxy-based resin, a polysaccharide, and a swelling clay mineral. In one embodiment, the filler granulate further contains a dispersant. In one embodiment, the content ratio of the dispersant is 0.1 part by weight to 50 parts by weight with respect to 100 parts by weight of the total amount of the surface-treated filler and the binder. In one embodiment, the dispersant is at least one selected from the group consisting of a polyhydric alcohol fatty acid ester, a fatty acid amide, a polyglycerin fatty acid ester, a condensed hydroxy fatty acid, and an alcohol ester of a condensed hydroxy fatty acid. According to another aspect of the present invention, there is provided a method for manufacturing a filler granulate. This manufacturing method includes a mixing step of mixing the surface-treated filler and the binder, a granulation step of granulating the mixture obtained through the mixing step to obtain a granulate precursor, and a drying step of drying the granulate precursor. In one embodiment, the manufacturing method further includes a pretreatment step of mixing the surface-treated filler and an aqueous alcohol solution before the mixing step. In one embodiment, the alcohol concentration of the aqueous alcohol solution is 20% by weight or more. In one embodiment, in the granulation step, granulation is performed by a semi-wet granulation method. In one embodiment, in the granulation step, granulation is performed by a disk pelletizer method. According to still another aspect of the present invention, there is provided the use of the filler granulate as a raw material for a thermoplastic resin compound.

Advantages of the Invention

[0007] According to the present invention, there is provided a filler granulate containing a filler with a hydrophobic surface modification (surface treatment), which can improve the supply stability and supply accuracy of the filler when preparing a resin composition, and enables the stable obtaining of a resin composition with high productivity.

Brief Description of the Drawings

[0008]

Figure 1

Embodiments for Carrying Out the Invention

[0009] A. Overview of filler granulates The filler granulate of the present invention contains a surface-treated filler and a binder. The surface-treated filler is formed by surface-treating a pre-treatment filler with at least one selected from the group consisting of a silane coupling agent, a titanate coupling agent, and silicone oil. The content ratio of the surface-treated filler is 40 to 99.9 parts by weight with respect to 100 parts by weight of the total amount of the surface-treated filler and the binder. Typically, the pre-treatment filler and the surface-treated filler are in powder form. The filler granulate is formed by binding the surface-treated filler with a binder.

[0010] The filler granulate of the present invention is used in the production of a filler-containing resin composition and can be added and used during the melt-kneading of the resin composition. In this way, by using the filler granulate of the present invention, a filler-containing resin composition having functions derived from the filler can be obtained. Since the filler granulate of the present invention has a configuration in which the surface-treated filler is granulated by a binder in advance, if the filler-containing resin composition is prepared using the filler granulate, the productivity of the resin composition can be improved. Specifically, since the filler granulate is extremely excellent in the charging stability to a device such as an extruder, using the filler granulate can significantly improve the productivity (compound processing speed per hour) of the filler-containing resin composition. In addition, it can significantly improve the contamination of the working environment by dust, improve the labor safety and health environment of workers, and further significantly shorten the time for equipment switching and cleaning.

[0011] In addition, since the surface of the surface-treated filler is hydrophobic (water-repellent), it is inherently difficult to granulate (especially granulation by the semi-wet granulation method). However, in the present invention, even a surface-treated filler is advantageous in that it can preferably form granulated products. Such effects can be obtained (or made prominent) by, for example, a combination of (1) use of a specific binder, (2) use of an amphiphilic dispersant, (3) pretreatment of the hydrophobically surface-modified filler, (4) optimization of the mechanical mixing method of the hydrophobically surface-modified filler with the binder and the dispersant, etc. Further, by appropriately selecting the binder, efficient granulation of the surface-treated filler, good filler dispersibility when compounded with a thermoplastic resin, and thermal stability capable of withstanding the melt-kneading temperature can be obtained (details will be described later).

[0012] In one embodiment, the filler granulated product further contains a dispersant. In one embodiment, the dispersant can be a compound having amphiphilicity. By adding such a dispersant, the compatibility between the binder and the surface-treated filler can be improved. As a result, a granulated product excellent in production efficiency can be produced while containing a large amount of the surface-treated filler, and a filler granulated product excellent in quality stability (shape stability, uniformity of pellet hardness, low fine powder incorporation) can be obtained. The filler granulated product containing the dispersant has excellent filler dispersibility in the filler-containing resin composition obtained by using the filler granulated product, despite containing a high concentration of the surface-treated filler.

[0013] In one embodiment, the filler granulated product is produced by the semi-wet granulation method. According to the semi-wet granulation method, the above effects become prominent. In one embodiment, while adding an aqueous alcohol solution, the materials for forming the filler granulated product are mixed. Details will be described later.

[0014] The filler granulated product can have any suitable shape. Typically, the filler granulated product is cylindrical (pellet-shaped).

[0015] When the above filler granulate is cylindrical, the diameter of the above filler granulate is, for example, 2 mm to 5 mm. Also, the length (height) of the filler granulate is, for example, 1 mm to 5 mm. With such a shape, it is possible to obtain a filler granulate that can be preferably combined and used with a predetermined resin. The diameter of the filler granulate can be adjusted by the diameter of the die hole of the disk plate during granulation, and the length can be adjusted by the distance between the disk plate and the cutter. By matching the filler granulate to the pellet size of the resin used in combination, the handleability is improved, and the dispersibility of the filler in the melt compound also becomes better.

[0016] The breaking stress of the above filler granulate in a wooden hardness tester is preferably 0.05 kg to 10 kg, more preferably 0.5 kg to 7 kg, and even more preferably 1.0 kg to 5 kg. Within such a range, it is excellent in handleability and filler (surface-treated filler) dispersibility. Here, the breaking stress indicates the average collapse stress measured for 20 or more (preferably 25 or more) grains.

[0017] The moisture content of the above filler granulate can be any appropriate moisture content. The moisture content of the above filler granulate is preferably 10% by weight or less, more preferably 5% by weight or less, even more preferably 3% by weight or less, particularly preferably 1% by weight or less, and most preferably 0.5% by weight or less. The moisture content of the filler granulate is measured using an infrared moisture meter as described below.

[0018] The bulk density of the filler granulate can be any appropriate bulk density according to the type of the filler (surface-treated filler). When the filler is a mineral (natural mineral), the bulk density of the filler granulate is preferably 0.1 kg / L to 2.0 kg / L, more preferably 0.3 kg / L to 2.0 kg / L, and even more preferably 0.5 kg / L to 1.0 kg / L. By increasing the bulk density, the supply rate and supply stability of the filler granulate are enhanced when performing melt kneading with the resin. The bulk density is calculated by allowing the powder to naturally fall into a liter measure until it is full, accurately measuring the volume of 1 liter, and measuring its weight (unit: kg / L).

[0019] A-1. Surface-treated filler The surface-treated filler can be formed by surface-treating the filler before treatment (simply referred to as the filler) by any appropriate method using the surface treatment agent (i.e., silane coupling agent, titanate coupling agent, or silicone oil). In one embodiment, one end of the compound constituting the surface treatment agent chemically reacts with the hydroxyl group on the filler surface, and the other end forms an oriented monolayer facing outward, whereby the filler surface is surface-modified to obtain a surface-treated filler. The method for surface-treating the filler is not particularly limited, and a method known to those skilled in the art can be adopted. However, in order to obtain an excellent hydrophobic effect, a method of directly applying the surface treatment agent to the powder is preferred. Also, commercially available products may be used as the surface-treated filler.

[0020] In one embodiment, the surface of the surface-treated filler can be hydrophobic. In this specification, the surface being hydrophobic means that when a water droplet is placed still on the surface of the powder spread flat, the contact angle of the water droplet is 90 degrees or more.

[0021] The contact angle of the water droplets measured by the above method is preferably from 90 degrees to 120 degrees, more preferably from 95 degrees to 110 degrees. Within such a range, a filler granulated product excellent in filler dispersibility when compounded into a thermoplastic resin can be obtained.

[0022] As the above filler, any appropriate filler can be used according to the properties required for the filler-containing resin composition and / or the molded article obtained from the filler-containing resin composition.

[0023] Examples of the properties and effects that can be imparted by the above filler include, for example, weight increase or weight reduction, reinforcement (increase in rigidity, elastic modulus, and strength), dimensional stability, molding cycle (crystallization rate), degree of crystallinity, thermal conductivity, electrical conductivity, magnetism, piezoelectricity, vibration damping, sound insulation, slidability, heat insulation, electromagnetic wave absorption, light reflection, light scattering, heat ray radiation, flame retardancy, radiation protection, ultraviolet protection, dehumidification, dehydration, deodorization, gas absorption, gas barrier, anti-blocking, oil absorption, antibacterial property, biodegradation promotion, improvement of biocompatibility (improvement of the ratio of components derived from natural products), and the like.

[0024] Examples of the above filler include silicon-based inorganic compounds such as silica, quartz, glass, and silicon; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; silicate compounds such as talc, mica, aluminosilicate, and kaolin; metal oxides such as zinc oxide, tin oxide, aluminum oxide, magnesium oxide, iron oxide, titanium oxide, and chromium oxide; carbonates such as calcium carbonate and magnesium carbonate, sulfates such as gypsum and barium sulfate, and carbons such as graphite, carbon nanotubes, carbon black, and carbon fibers. In one embodiment, the above filler is at least one selected from the group consisting of silicon-based inorganic compounds, metal hydroxides, silicate compounds, and metal oxides. These fillers are advantageous in that the surface treatment effect by the above surface treatment agent is particularly high.

[0025] As the above silane coupling agent, any suitable coupling agent can be used. Preferably, a compound having the structure of the following formula (1) can be used as the silane coupling agent. R-(CH 2 )n-Si-(X) 3 ···(1) In formula (1), R represents a functional organic substituent, Si represents a silicon atom, and X represents a hydrolyzable group. In the above formula (1), examples of R include hydrogen, vinyl group, epoxy group, styryl group, methacryl group, acrylic group, amino group, ureido group, mercapto group, and isocyanate group. Also, examples of X include alkoxy groups (represented by methoxy group and ethoxy group), halogen, amine, and acryloxy group. X gives a reactive silanol group by hydrolysis.

[0026] Specific examples of the silane coupling agent include linear alkyltriethoxysilanes having 2 to 24 carbon atoms, vinyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, tris-(trimethoxysilylpropyl) isocyanate, 3-mercaptopropyltrimethoxysilane, and the like.

[0027] When the above surface-treated filler is hydrophobic surface-treated silica, a coupling agent in which X is chlorine in the above formula (1) is preferably used. Examples of such coupling agents include so-called hydrophobic fumed silica surface-treated with dimethyldichlorosilane, trimethylchlorosilane, trichlorooctylsilane, etc. These can be obtained as commercial products from Nippon Aerosil Co., Ltd., Tokuyama Corporation, and Asahi Kasei Wacker Silicone Co., Ltd.

[0028] As the titanate coupling agent, any suitable coupling agent can be used. Examples of the titanate coupling agent include alkoxide-based, chelate-based, and acylate-based titanate coupling agents. Specific examples of the titanate coupling agent include, for example, tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetraoctyl titanate, tetra-tert-butyl titanate, tetrastearyl titanate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethyl acetoacetate, titanium dodecylbenzene sulfonate compound, titanium phosphate compound, titanium octylene glycolate, titanium ethyl acetoacetate, titanium lactate ammonium salt, titanium lactate, titanium ethanolamine, titanium octylene glycolate, titanium aminoethylaminoethanolate, titanium isostearate, and the like.

[0029] As the silicone oil, any suitable silicone oil can be used. Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic and methacrylic-modified silicone oil, α-methylstyrene-modified silicone oil, and the like.

[0030] As described above, the method for obtaining the surface-treated filler is not particularly limited, and a method known to those skilled in the art can be adopted. In one embodiment, a method of directly applying the surface treatment agent to the filler before treatment is preferably adopted. According to this method, a surface-treated filler having high hydrophobicity can be obtained. A commercially available product may be used as the surface-treated filler.

[0031] The bulk density of the surface-treated filler is preferably from 0.01 kg / L to 1 kg / L, more preferably from 0.05 kg / L to 0.8 kg / L, and still more preferably from 0.1 kg / L to 0.5 kg / L. In the filler granulate of the present invention, although it contains a filler having a low bulk density and being in powder form, it is advantageous in that the supply stability and supply accuracy can be improved. By using the filler granulate, it becomes possible to stably obtain a filler-containing resin composition with high productivity. The size of the surface-treated filler can be any appropriate size. The number average particle diameter of the surface-treated filler is, for example, from 10 nm to 100 μm. The size of the surface-treated filler can be determined by the laser diffraction method.

[0032] As described above, the content ratio of the surface-treated filler is from 40 parts by weight to 99.9 parts by weight with respect to 100 parts by weight of the total amount of the surface-treated filler and the binder. Within such a range, a filler-containing resin composition to which the characteristics derived from the filler are efficiently imparted can be obtained. The content ratio of the surface-treated filler is preferably from 50 parts by weight to 95 parts by weight, more preferably from 60 parts by weight to 90 parts by weight, and still more preferably from 70 parts by weight to 90 parts by weight with respect to 100 parts by weight of the total amount of the surface-treated filler and the binder. In one embodiment, the content ratio of the surface-treated filler is from 80 parts by weight to 90 parts by weight with respect to 100 parts by weight of the filler granulate.

[0033] The volume content ratio of the surface-treated filler in the filler granulate is preferably from 20% by volume to 90% by volume, more preferably from 30% by volume to 80% by volume, and still more preferably from 40% by volume to 70% by volume.

[0034] A-2. Binder In one embodiment, the binder can be constituted by any appropriate resin. The binder is used to join powdery fillers together to obtain a granulate having appropriate disintegration stress, and can be a single component or a combination of a plurality of components (preferably resins). Examples of the resin constituting the binder include polyolefin resins, polyvinyl alcohol resins, polyalkylene glycol resins, polyvinylpyrrolidone resins, polyester resins, polyamide resins, acrylic resins, polyurethane resins, epoxy resins, etc. Among them, polyolefin resins, polyvinylpyrrolidone resins, polyester resins, polyamide resins or polyurethane resins are preferable, and polyvinylpyrrolidone resins are particularly preferable. These are excellent in affinity with the surface-treated filler and heat resistance. In another embodiment, polysaccharides are used as the binder. In still another embodiment, swellable clay minerals (for example, smectite, vermiculite, etc.) are used as the binder. The binder may be used alone or in combination of two or more. In one embodiment, the binder is composed of at least one selected from the group consisting of polyolefin resins, polyvinyl alcohol resins, polyvinylpyrrolidone resins, polyester resins, polyamide resins, acrylic resins, urethane resins, epoxy resins, polysaccharides and swellable clay minerals. The binder composed of these resins is excellent in affinity with the surface-treated filler and also has heat resistance capable of withstanding melt-kneading with the thermoplastic resin.

[0035] In one embodiment, a polyvinylpyrrolidone resin is used as the resin constituting the binder. Since the polyvinylpyrrolidone resin has amphiphilic properties, it is excellent in miscibility with the surface-treated filler, and it is easy to produce filler granules by the semi-wet method. Also, since it has a preferable affinity for various thermoplastic resins, it has high dispersibility of the filler with respect to the thermoplastic resin and can exhibit excellent effects as a binder for filler granules.

[0036] In one embodiment, a filler granule is produced using a polymer liquid (polymer solution, polymer dispersion) containing a binder. Since the polymer liquid can efficiently and uniformly coat the surface of the surface-treated filler, it is possible to obtain a filler granule with less powder loss, high disintegration hardness, and high bulk specific gravity. Furthermore, the dispersibility of the filler in the filler-containing resin composition can be greatly improved.

[0037] As the above binder, commercially available products may be used. Examples of commercially available products include ChemPearl (registered trademark) manufactured by Mitsui Chemicals, HYPOD (registered trademark) of The Dow Chemical Company, AQUACER (registered trademark) manufactured by BYK-Chemie Japan, Zycen, Sepolusion (registered trademark) manufactured by Sumitomo Seika Chemicals, Michem (registered trademark) manufactured by Michelman Japan, Bondic (registered trademark) of DIC, Michem (registered trademark) manufactured by Michelman Japan, Bondic (registered trademark) of DIC, Saivinol, Saiden Glue (registered trademark) manufactured by Saiden Chemical, etc. Other preferred examples include ethylene-vinyl alcohol copolymer (EVOH; Eval (registered trademark) manufactured by Kuraray), butanediol-vinyl alcohol copolymer (BVOH; Nichigo G Polymer (registered trademark) manufactured by Mitsubishi Chemical). Also, an aqueous sulfopolyester dispersion sold under the name of Eastman AQ (registered trademark) manufactured by Eastman Chemical, and a salt of hexane-1,6-diamine and adipic acid (AH salt) sold by Ascend Performance, which forms an aqueous polymer dispersion when diluted with water, etc. can be mentioned.

[0038] The content ratio of the above binder can be any appropriate ratio according to the size, shape, water absorbency, oil absorbency, bulk density, etc. of the above surface-treated filler. The content ratio of the above binder is preferably 0.1 to 60 parts by weight, preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, and still more preferably 3 to 20 parts by weight with respect to 100 parts by weight of the total amount of the above surface-treated filler and binder. Within such a range, the binding force to the surface-treated filler is preferably exhibited, and a filler granule having excellent handleability can be obtained.

[0039] A-3. Dispersant As the above dispersant, a surfactant is preferably used. The hydrophilic / hydrophobic balance in the dispersant (surfactant) can be controlled by adjusting the degree of esterification of the compound serving as the dispersant, the type of fatty acid (presence or absence of a hydroxyl group, saturated or unsaturated fatty acid, alkyl chain length), and the degree of polymerization. By using a dispersant, the productivity (discharge rate) of the filler granule can be improved, and furthermore, the cleanability of the processing machine can be enhanced.

[0040] In addition, if a filler granule containing a dispersant is used to perform melt-kneading of a resin composition to produce a filler-containing resin composition, the surfactant action of the dispersant can enhance the filler dispersibility.

[0041] Examples of the above dispersant include fatty acids, fatty acid metal salts, fatty acid sulfonates, fatty acid amides, acrylamides, polyhydric alcohol fatty acid esters, polyglycerin fatty acid esters, etc. The dispersant may be used alone or in combination of two or more.

[0042] In one embodiment, 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.

[0043] The above-mentioned polyhydric alcohol fatty acid ester is an ester compound composed of a polyhydric alcohol and a fatty acid. As the polyhydric alcohol fatty acid ester, for example, esters of polyhydric alcohols such as pentaerythritol and glycerin and fatty acids having 8 or more carbon atoms (preferably 8 to 24 carbon atoms, more preferably 10 to 22 carbon atoms) are used.

[0044] The above-mentioned fatty acid amide is a compound having a structure formed by dehydration condensation of a fatty acid and ammonia or a primary or secondary amine. Examples of the above-mentioned fatty acid amide include saturated fatty acid monoamides such as lauric acid amide, palmitic acid amide, stearic acid amide, and behenic acid amide.

[0045] The above-mentioned polyglycerol fatty acid ester is an ester compound composed of polyglycerol and a fatty acid. Examples of the polyglycerol fatty acid ester include diglycerol palmitate, diglycerol stearate, diglycerol oleate, decaglycerol palmitate, decaglycerol stearate, decaglycerol oleate, and the like.

[0046] For the above-mentioned polyglycerol fatty acid ester, condensed hydroxy fatty acid, and alcohol ester of condensed hydroxy fatty acid, commercially available products may be used. Examples of commercially available products include "Tirabazole P-4", "Tirabazole VR-01", "Tirabazole VR-08" (polyglycerol fatty acid ester), "Tirabazole H-818" (alcohol ester of condensed hydroxy fatty acid), etc. manufactured by Sun Chemical Corporation. These may be used alone or in combination of two or more.

[0047] The content ratio of the above dispersant can be any appropriate ratio according to the size, shape, water absorbency, oil absorbency, bulk density, etc. of the above surface-treated filler. The content ratio of the above dispersant is preferably 0.1 parts by weight to 50 parts by weight, more preferably 0.1 parts by weight to 30 parts by weight, still more preferably 0.5 parts by weight to 15 parts by weight, and most preferably 3 parts by weight to 15 parts by weight based on 100 parts by weight of the total amount of the above surface-treated filler and binder.

[0048] A-4. Other Components The above filler granulate can further contain any appropriate other components (additives) as required. Examples of additives include antioxidants, light stabilizers, foaming agents, ultraviolet absorbers, foaming agents, antiblocking agents, heat stabilizers, impact modifiers, antibacterial agents, compatibilizers, plasticizers, tackifiers, processing aids, lubricants, coupling agents, flame retardants, deoxidizers, colorants, etc. The additives can be compounded in the form of liquids, powders, pellets, granules, or in the form of masterbatches, etc. during filler granulation or in the process of resin compounding. In one embodiment, the above additives can be blended into a polymer solution and granulated by a semi-wet granulation machine and then compounded into the filler granulate.

[0049] B. Method for manufacturing filler granulates The above filler granulate can be manufactured by any appropriate method. The above filler granulate can be obtained, for example, by subjecting a mixture containing the above surface-treated filler, the above binder, and the above dispersant added as required to a semi-wet granulation method.

[0050] In one embodiment, the method for manufacturing the filler granulate includes a mixing step of mixing a surface-treated filler and a binder, a granulation step of granulating the mixture obtained through the mixing step to obtain a granulate precursor, and a drying step of drying the granulate precursor. In one embodiment, in the mixing step, the binder is added as an aqueous liquid (aqueous solution or aqueous dispersion) containing the binder. Further, in one embodiment, a dispersant is further added in the mixing step. In one embodiment, an aqueous alcohol solution is added in the mixing step. By including the aqueous alcohol solution, the compatibility between the surface-treated filler and the binder can be improved, and a powder mixture that can be preferably granulated can be obtained.

[0051] In one embodiment, the method for manufacturing the filler granulate includes a pretreatment step of mixing the surface-treated filler and the aqueous alcohol solution before the mixing step. By this operation, the hydrophilicity of the surface-treated filler can be enhanced, the compatibility between the binder and the surface-treated filler can be improved, and the granulation characteristics of the powder mixture can be further enhanced. When obtaining the powder mixture in this way, it is preferable to use mixing equipment with excellent stirring and mixing ability, which will be described later.

[0052] The alcohol concentration of the aqueous alcohol solution is preferably 20% by weight or more, more preferably 40% by weight or more, and still more preferably 50% by weight or more. The content of the aqueous alcohol solution is preferably 50 to 200 parts by weight, more preferably 80 to 150 parts by weight, based on 100 parts by weight of the surface-treated filler. Examples of the alcohol include methanol, ethanol, isopropyl alcohol, and the like. When the aqueous alcohol solution is used, the binder (or the aqueous liquid containing the binder) and the dispersant added as necessary can be introduced into the aqueous alcohol solution.

[0053] When the aqueous liquid containing the binder is an aqueous solution (homogeneous system), the content ratio of the binder in the aqueous liquid containing the binder is preferably 1 part by weight to 70 parts by weight, more preferably 3 parts by weight to 50 parts by weight, and still more preferably 5 parts by weight to 30 parts by weight with respect to 100 parts by weight of the aqueous liquid. Within such a range, when mixing the aqueous liquid and the surface-treated filler, the viscosity is preferably adjusted, and a mixed liquid excellent in the dispersibility of the binder can be obtained. By using such a mixed liquid, a surface-treated filler granulated product preferably formed by binding the surface-treated filler can be stably obtained.

[0054] When the aqueous liquid containing the binder is an aqueous dispersion (heterogeneous system), the solid content concentration of the binder in the aqueous liquid containing the binder is preferably 1 wt% to 70 wt%, more preferably 3 wt% to 60 wt%, and still more preferably 5 wt% to 50 wt%. Within such a range, when mixing the aqueous liquid and the surface-treated filler, the viscosity is preferably adjusted, and a mixed liquid excellent in the dispersibility of the binder can be obtained. By using such a mixed liquid, a surface-treated filler granulated product preferably formed by binding the surface-treated filler can be stably obtained.

[0055] The mixing ratio of the aqueous liquid containing the binder is preferably 1 part by weight to 300 parts by weight, more preferably 5 parts by weight to 200 parts by weight, and still more preferably 10 parts by weight to 100 parts by weight with respect to 100 parts by weight of the surface-treated filler. Due to the surface hydrophobicity of the surface-treated filler, it is preferable that the mixing ratio of the aqueous liquid containing the binder is larger than that in the case of using an untreated filler.

[0056] In the mixing step, other components (for example, the above additives), a solvent (preferably water), etc. may be further mixed. In one embodiment, by adding these components, the mixing of the aqueous liquid containing the binder and the surface-treated filler is optimized. The water to be added is not particularly limited, and for example, tap water, distilled water, ion-exchanged water, hard water, soft water, etc. can be used.

[0057] In the mixing process, it is preferable to blend the components at room temperature and homogenize them using any suitable mixer. Examples of mixers include Henschel mixers, kneaders for powders (KDH, KDA, CKD, CPM) (Dalton), Spartan mixers (SPM) (Dalton), SP granulators (SPG) (Dalton), and the like.

[0058] The mixing time in the mixing process can be any appropriate mixing time according to the type of components, the type of mixer, the component blending ratio, etc. Preferably, the mixing time is set so that the surface of the surface-treated filler is sufficiently and uniformly coated with the binder. In high-speed stirrers such as Henschel mixers and Spartan mixers, the treatment time can be 1 to 10 minutes. On the other hand, in the case of a kneader for powders, a treatment time of several minutes to 60 minutes may be required.

[0059] In the granulation process, the compression granulation method is preferably adopted. Also, in the granulation process, the semi-wet granulation method may be preferably adopted. Examples of the compression granulation method / semi-wet granulation method include the disk pelletizer method, the tabletting method, the briquetting method, and the like. From the viewpoint of the balance between productivity and the quality of the obtained filler granules, the disk pelletizer method is preferably adopted.

[0060] The granulator of the disk pelleter type has, as its basic structure, one or two disks with a large number of holes of 2 mm to 30 mm in diameter, and a roller for pumping the raw material into the holes of the disk. The raw material supplied between the disk and the roller or between two disks is pressed into the holes of the disk as the roller rotates, and a cylindrical extrudate is formed. Here, the disk holes are provided with a taper, and in the process of the above mixture passing through the holes, a mechanism is provided in which a compressive stress is applied from the outer periphery of the die holes. The length of this tapered hole is called the effective length. The extruded granule precursor can be cut by a cutter or the like on the back surface of the disk to obtain a pellet-shaped filler granule. The length of the granule precursor (and as a result, the filler granule) can be adjusted by the distance between the back surface of the disk and the cutter and the rotation speed of the roller. The distance between the back surface of the disk and the cutter is usually in the range of 1 mm to 30 mm, preferably in the range of 2 mm to 20 mm, and more preferably in the range of 3 mm to 10 mm.

[0061] More specifically, examples of the disk pelleter type include the roller-disk die method, the roller-ring die method, the double die method, the flat die method, and the like. Examples of commercially available granulators of the disk pelleter type include the disk pelleter F series manufactured by Dalton.

[0062] As the drying method in the drying process, any appropriate method can be adopted. After the drying process, by performing treatment with a vibrating sieve or the like, a filler granule from which fine powder has been removed can be obtained. In the drying process, any appropriate drying equipment is used. For example, a vibrating fluidized bed dryer is preferable because it can perform efficient drying in a short time. Examples include the vibrating fluidized bed dryer VDF series manufactured by Dalton.

[0063] C. Melt compound of resin and filler granulates In one embodiment, the filler granulate can be used as a raw material for a thermoplastic resin compound. Further, a melt compound of the filler granulate and other thermoplastic resins is provided. Any thermoplastic resin can be used as the other thermoplastic resin.

[0064] As a method for producing the melt compound, any suitable method can be adopted. For example, a kneader, a Banbury mixer, rolls, a single-screw or multi-screw extruder with two or more axes can be used. Preferably, a twin-screw extruder is used. The composition obtained by melt-kneading is pelletized.

[0065] Specific examples of the above-mentioned any thermoplastic resin include, for example, general-purpose resins such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polyurethane (PUR), fluorine-based resins, ABS resin (acrylonitrile-butadiene-styrene resin), AS resin, acrylic resin (PMMA), etc., polyamide (PA), polyacetal (POM), polycarbonate (PC), polyphenylene ether, 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), amorphous polyarylate (PAR), liquid crystal polymer (LCP), polyetherimide (PEI), polyetheretherketone (PEEK), thermoplastic polyimide (TPI), polyamideimide (PAI), etc. super engineering plastics, and is at least one selected from the group consisting of. In addition, a biodegradable polymer may be used as any of the above thermoplastic resins. Examples of the biodegradable polymer include aliphatic polyester resins (e.g., homopolymers or copolymers such as polycaprolactone, polylactic acid, polyethylene succinate, polybutylene succinate adipate, polyhydroxyvalerate, and modified products of these homopolymers or copolymers), aliphatic-aromatic polyester resins (e.g., block polymers or random polymers such as aliphatic carboxylic acids or hydroxy acids, aromatic dicarboxylic acids, and 1,3-propanediol), polyvinyl alcohol-based resins (e.g., polyvinyl alcohol, polyvinyl acetate, polyvinyl butyrate, ethylene-vinyl alcohol copolymers, etc.).

[0066] In the melt compound of the above thermoplastic resin and the above surface-treated filler granulate, since the filler granulate is excellent in the charging ability and stability to a melt kneading apparatus such as an extruder, the productivity of the resin composition can be remarkably improved, and the filler dispersibility in the resin is also excellent. In addition, it greatly contributes to the improvement of the working environment and the labor safety and health environment of workers.

Examples

[0067] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples in any way. Note that parts and % are based on weight unless otherwise specified.

[0068] [Example 1] (Pretreatment) Into a Henschel mixer (manufactured by Nippon Coke & Engineering Co., Ltd., trade name "5FM5C / I"; processing volume: 5 L), 100 parts by weight of a surface-treated filler (surface-treated fumed silica treated with dimethyldichlorosilane, manufactured by Nippon Aerosil Co., Ltd., trade name "Aerosil R972V", BET specific surface area 130 m 2 / g, in the table, "A-1") and 100 parts of a 57% aqueous ethanol solution were charged and stirred and mixed at a rotation speed of 1,000 revolutions for 2 minutes. (Mixing step) Thereafter, 100 parts by weight of a dispersion of a binder (a polyolefin dispersion (aqueous PE dispersion), manufactured by Mitsui Chemicals, Inc., trade name "Chemipar A100", polyolefin solid content concentration: 40% by weight, average particle diameter of polyolefin particles 4 μm, in the table, "B-1") was added, and stirring was further performed at a rotation speed of 1,000 rpm for 2 minutes to obtain a mixture. This mixture was put into a disk pelletizer (manufactured by Dalton, trade name "Disk Pelletizer F-5 / 11-175") to obtain a pellet-shaped granule precursor. At this time, the pore 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, the rotation speed of the roller of the pelletizer was 108 rpm, and the distance between the back surface of the disk and the cutter was 5 mm. (Drying process) The obtained granule precursor was dried at 140 °C for 4 hours using a hot air circulation dryer to obtain a filler granule (SMFG-1). An external appearance photograph of the obtained filler granule (SMFG-1) is shown in Fig. 1.

[0069] [Examples 2 to 8, Comparative Examples 1 to 2] Filler granules were obtained in the same manner as in Example 1, except that the surface-treated filler, binder, dispersant, and other components (water, aqueous alcohol solution) shown in Table 1 were used in the blending amounts shown in Table 1. The specific details of each component used in the examples and comparative examples are as shown in Table 2. In Examples 4, 5, 7, and 8, no pretreatment with an aqueous alcohol solution was performed, and the surface-treated filler was added in the mixing step. In Example 5, 10 parts by weight of water was used in the mixing step. In Examples 3 to 8, a dispersant was added in the mixing step.

[0070] [Table 1]

[0071] [Table 2]

[0072] <Evaluation> The filler granulates obtained in the examples and comparative examples were subjected to the following evaluations. The results are shown in Table 3. (1) Granulation property The obtained filler granulates were checked, and the granulation property was evaluated according to the following criteria. 〇: Granulates with a diameter of 3 mmφ can be obtained. △: It forms the shape of filler granulates, but the binding force is insufficient and it is prone to collapse. ×: The filler clogs the die, or there is no binding property of the filler and it does not form granules. (2) Granulation speed The production speed (kg / Hr) of the filler granulates per hour was calculated. (3) Bulk density The dried filler granulates were allowed to fall naturally into a 1-liter graduated cylinder until it was full, and then accurately weighed with a volume of 1 liter to measure the weight, thereby calculating the bulk density (unit: kg / L) of the filler granulates. (4) Pellet size Twenty filler granulates were taken out, and the length and diameter of the granules were measured using vernier calipers, and the average value was calculated. (5) Moisture content The moisture content (unit: weight%) remaining in the filler granulates was measured using an infrared moisture meter (FD-660 manufactured by Kett Science Laboratory Co., Ltd.). (6) Measurement of disintegration strength Using a wooden hardness tester (manufactured by Shiro Sangyo Co., Ltd., product name "WPF1600-B"), the disintegration stress (unit: kg) of the dried filler granulates was measured. The measured value was the average value of 25 filler granulates. (7) Measurement of fine powder amount 1 kg of the filler granulates was weighed and sieved through a 12-mesh sieve to measure the mass ratio (unit: weight%) of the fine powder amount. (8) Filler concentration 1 to 3 g of the filler granulate was collected, held in a crucible at 600 °C for 3 hours in an electric furnace, and the filler concentration (wt%) in the filler granulate was calculated from the ash weight.

[0073]

Table 3

[0074] As shown in Table 3, with SMFG-1 to SMFG-8, pellet-shaped filler granulates with a stable pellet shape, high granulation speed, and appropriate hardness can be obtained. On the other hand, in Comparative Example 1 (SMFG-C1) and Comparative Example 2 (SMFG-C4), since no binder is included, pellet-shaped filler granulates cannot be obtained, or they easily disintegrate after drying.

[0075] [Example 9] 90 parts by weight of a hydrogenated styrene-based thermoplastic elastomer (SEBS, manufactured by Asahi Kasei Corporation, trade name "Tuftec H1052") and 10 parts by weight of a filler granulate (SMFG-1) were put into a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., trade name "TEM18SS", L / D = 48), and continuous melt-kneading was performed to produce pellets of a resin composition of SEBS and a surface-treated filler (A-1). SEBS and the filler granulate (SMFG-1) were pre-mixed in advance and quantitatively put into the twin-screw extruder from the hopper position at the most upstream part of the extruder through a feeder. The cylinder temperature of the extruder was set to 200 °C from the middle part of the extruder and later. The rotational speed of the main screw of the twin-screw extruder was 100 rpm, and the discharge speed was 5 kg / Hr. The melt-kneaded resin composition was extruded in a strand shape and cooled in a water-cooling bath to form pellets with a length of about 3 mm. The resulting resin composition was excellent in the supply stability of the surface-treated filler (A-1) to the extruder, excellent in melt-kneading dispersibility, and excellent in strand take-up stability.

[0076] [Comparative Example 3] Using powdery silica (shown as A-1 in Table 2) without using the filler granulate (SMFG-1), melt-kneading was carried out in the same manner as in Example 8 to attempt to produce pellets. However, in Comparative Example 3, a silica bridge occurred at the chute opening, so continuous production could not be carried out, and the working environment deteriorated due to dust.

[0077] [Example 10] 30 parts by weight of homopolypropylene (h-PP, manufactured by Japan Polypropylene Corporation, trade name "Novatec MA1B") and 70 parts by weight of the filler granulate (SMFG-4) were charged into a twin-screw extruder in the same manner as in Example 9, and continuous melt-kneading was carried out to produce pellets of a resin composition of h-PP and the surface-treated filler (A-2). h-PP and the filler granulate (SMFG-4) were premixed in advance and quantitatively charged into the twin-screw extruder from the hopper position at the uppermost stream part of the extruder through a feeder. The cylinder temperature of the extruder was set to 200 °C from the middle part and downstream of the extruder. The rotational speed of the main screw of the twin-screw extruder was 100 rpm, and the discharge rate was 5 kg / Hr. The melt-kneaded resin composition was extruded in a strand shape and cooled in a water-cooled bath to obtain pellets with a length of about 3 mm. The resulting resin composition was excellent in the supply stability of the surface-treated filler (A-2) to the extruder, excellent in melt-kneading dispersibility, and excellent in strand take-up stability.

[0078] [Comparative Example 4] Attempting to produce pellets by melt-kneading in the same manner as in Example 10 using surface-treated magnesium hydroxide powder (shown as A-2 in Table 2) without using the filler granulate (SMFG-4), in Comparative Example 4, a bridge of magnesium hydroxide powder (A-2) occurred at the chute opening, so continuous production could not be carried out.

[0079] [Evaluation] The pellets of the resin compositions obtained in the examples and comparative examples were subjected to the following evaluations. The results are shown in Table 4. (a) Feed characteristics of the filler granulate (or surface-treated filler) The continuous feeding status of the surface treatment filler raw material into the extruder was checked, and the granulation property was evaluated according to the following criteria. 〇: It can be supplied stably. ×: Bridging may occur in the supply of the surface treatment filler powder raw material, and the feed is unstable. (b) Dispersibility The dispersibility in the melt-kneading of the resin and the thermoplastic polymer granulate was evaluated according to the following criteria based on the feel of the surface of the strand of the melt mixture. 〇: The surface is smooth and the dispersibility is good. ×: The surface is rough and the dispersibility is poor.

[0080]

Table 4

Claims

1. A filler granule comprising a surface-treated filler and a binder, wherein the surface-treated filler is formed by surface-treating a pre-treatment filler with at least one selected from the group consisting of a silane coupling agent, a titanate coupling agent, and silicone oil, the content ratio of the surface-treated filler is 40 to 99.9 parts by weight with respect to 100 parts by weight of the total amount of the surface-treated filler and the binder, the filler granule is formed by mixing the surface-treated filler and the binder after a process of mixing the surface-treated filler and an aqueous alcohol solution, and the alcohol concentration of the aqueous alcohol solution is 40% by weight or more. Filler granule.

2. The filler granule according to claim 1, wherein the pre-treatment filler is at least one selected from the group consisting of a silicon-based inorganic compound, a metal hydroxide, a silicate compound, and a metal oxide.

3. The filler granule according to claim 1 or 2, wherein the binder is composed of at least one selected from the group consisting of a polyolefin resin, a polyvinyl alcohol resin, a polyvinyl pyrrolidone resin, a polyester resin, a polyamide resin, an acrylic resin, a urethane resin, an epoxy resin, a polysaccharide, and a swelling clay mineral.

4. The filler granule according to any one of claims 1 to 3, further comprising a dispersant.

5. The filler granule according to claim 4, wherein the content ratio of the dispersant is 0.1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the surface-treated filler and the binder.

6. The filler granule according to claim 4 or 5, wherein the dispersant is at least one selected from the group consisting of a polyhydric alcohol fatty acid ester, a fatty acid amide, a polyglycerin fatty acid ester, a condensed hydroxy fatty acid, and an alcohol ester of a condensed hydroxy fatty acid.

7. A pre-treatment step of mixing the surface-treated filler and an aqueous alcohol solution, a mixing step of mixing the surface-treated filler and the binder, a granulation step of granulating the mixture obtained through the mixing step to obtain a granule precursor, and a drying step of drying the granule precursor, and the alcohol concentration of the aqueous alcohol solution is 40% by weight or more. A method for producing the filler granule according to any one of claims 1 to 6.

8. The method for producing a filler granulated product according to claim 7, including granulating by a semi-wet granulation method in the granulation step.

9. The method for producing a filler granulated product according to claim 7 or 8, including granulating by a disk pelletizer method in the granulation step.

10. Use of the filler granulated product according to any one of claims 1 to 6 as a raw material for a thermoplastic resin compound.

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