JP4785027B2 - Manufacturing method of resin composition and resin product using resin composition manufactured by the manufacturing method - Google Patents

Description

  The present invention relates to a method for producing a resin composition. More specifically, the present invention has excellent mechanical properties as compared with a resin composition containing a conventional filler, and is high when a flame retardant is used as a filler. The present invention relates to a method for producing a flame retardant resin composition and a resin product using the resin composition produced by the production method.

  In general, resin molded products are required to have various properties such as weather resistance, coloring, hardness, and flame retardancy, and the above properties are imparted by blending various fillers. However, when various fillers are blended in the resin, there is a problem that the mechanical properties and molding processability of the obtained molded product are lowered.

  In particular, in terms of flame retardancy, inorganic fillers such as magnesium hydroxide and aluminum hydroxide, which are non-halogen flame retardants, have been frequently used in consideration of the environment. However, the non-halogen flame retardant described above is difficult to express the desired flame retardancy unless blended in a large amount as compared with the halogen flame retardant, and the mechanical properties, molding processability, etc. of the molded product are reduced. large.

In recent years, attempts have been made to reduce the particle size of fillers to be blended and to improve dispersibility in order to prevent deterioration of mechanical properties due to blending fillers with resins. For example, a method for obtaining a filler having a small particle diameter by wet grinding pulverized zinc hydroxystannate, magnesium hydroxide, and the like has been studied. (Patent Document 1 and Patent Document 2).
JP-A-10-297920 JP 2002-167219 A

  However, as described in Patent Documents 1 and 2, the filler produced by the wet pulverization and then drying method easily causes secondary aggregation in the air even when the particle size is reduced during pulverization. It became clear that. Furthermore, the secondary agglomerated filler has a strong cohesive force, so the dispersibility in the resin is poor, and as a result, the mechanical properties and molding processability of the resin composition are similar to those of the filler having a large particle size. It became clear that it was difficult to improve.

  The present invention solves all the above-mentioned problems and has excellent mechanical properties and molding processability by dispersing a filler having a small particle size in a resin without agglomeration, and further uses a flame retardant as a filler. In some cases, an object is to obtain a resin composition having high flame retardancy.

  The inventors of the present invention have various methods for reducing the particle size of the filler compounded in the resin composition to submicron or nano-order and uniformly dispersing the filler in the resin composition without agglomerating. The present invention has been studied and completed.

That is, in the present invention,
(1) Step (a) of obtaining a slurry in which the average particle size of the dispersed filler is 0.4 μm or less by pulverizing while mixing the filler with a solvent, and substantially evaporating the solvent in the slurry. A step (a) of mixing the slurry with a base resin,
In the step (a), a dispersant is added to the slurry,
In the step (a), the dispersant contains a polyoxyalkylene compound represented by the following general formula (A) and a maleic acid derivative (B) as essential monomers, and has a mass average molecular weight of 500 to 100,000. A method for producing a resin composition comprising blending a copolymer (C) into the slurry.
(A): R1-O (AO) n-R2
(However, AO is an oxyalkylene group having 2 to 4 carbon atoms which essentially contains a oxyalkylene group having 4 carbon atoms, R1 is an alkenyl group having 2 to 5 carbon atoms, R2 is an alkyl group having 1 to 24 carbon atoms, n is an average added mole number of oxyalkylene and is 1 to 100)
(2) The method for producing a resin composition according to (1), wherein a nonionic dispersant having a fatty acid is added to the slurry in the step (a).
(3) The filler is at least one selected from the group consisting of metal hydrate, zinc stannate, zinc borate, antimony trioxide, melamine cyanurate, zinc oxide, titanium oxide, and calcium carbonate. The manufacturing method of the resin composition as described in (1) or (2) characterized.
(4) A resin product using the resin composition produced by the production method according to any one of (1) to (3).
Is provided.

  According to the method for producing a resin composition of the present invention, it is possible to uniformly disperse a filler having a remarkably reduced particle size in a resin composition without agglomeration. In addition, when a flame retardant is used as a filler, it is possible to obtain a resin composition having high flame resistance.

  In addition, the resin product using the resin composition of the present invention has excellent mechanical properties and abrasion resistance because the filler having a significantly reduced particle size is uniformly dispersed in the resin composition. Furthermore, when a flame retardant is used as a filler, it is a resin product having high flame retardancy.

First, the manufacturing method of the resin composition of this invention is demonstrated in detail.
The manufacturing method of the resin composition of this invention consists of a process (a) and a process (a).
Step (a) in the present invention is a step of obtaining a slurry in which the particle size of the dispersed filler is 0.4 μm or less by mixing the filler with a solvent.

  As a method of mixing and dispersing the filler and the solvent in the step (a), it is preferable to use a medium stirring wet pulverizer (hereinafter referred to as a bead mill). The bead mill is filled with beads in a container, and the beads are moved by rotating the agitator disk or pin, and the raw material is fed here and crushed and dispersed by grinding with beads. is there.

In the present invention, a filler mixed with a solvent is fed into the container filled with the beads. Then, by rotating the agitator disk or pin, a shearing force is generated between the beads, and the filler is mixed and dispersed in the solvent while being finely pulverized.

  In the present invention, a conventionally known bead mill can be used. For example, Agitator Mill LMZ (trade name, manufactured by Ashizawa Co., Ltd.), SUPER APEX MILL (trade name, manufactured by Kotobuki Giken Co., Ltd.) is preferably used. Can be used.

  In the present invention, metals, glass, ceramics and the like can be suitably used as the beads to be used. The use of ceramic is particularly preferable. The filling amount of beads to be used is preferably 90% or less, more preferably 70 to 80% with respect to the container. If the filling amount is small, the dispersion efficiency decreases, and if it is too large, the stirred slurry may generate heat or decrease the dispersion efficiency. The bead diameter of the beads to be used is preferably 0.05 to 1 mm, more preferably 0.1 to 0.5 mm. If the particle diameter is too large, there is a possibility that the dispersion efficiency is lowered or the particles in the slurry are destroyed and the viscosity is increased, and if it is too small, the impact force is lost and the dispersion efficiency may be lowered.

  In the present invention, the rotational speed of the agitator disk or pin is preferably 5 to 15 m / sec. More preferably, it is 8.5-12.5 m / sec. If the rotational speed is too high, the stirred slurry generates a large amount of heat, and the particles may be broken to increase the viscosity. If it is too slow, the dispersion efficiency may be reduced.

  The filler used in the present invention is not particularly limited as long as it is usually used as a filler for a resin. For example, various inorganic fillers and organic fillers conventionally used can be used. it can.

  Examples of inorganic fillers include carbon, clay, tin oxide, magnesium oxide, molybdenum oxide, antimony trioxide, quartz, talc, calcium carbonate, magnesium carbonate, zinc borate, white carbon, zinc stannate, zinc oxide, titanium oxide, etc. In addition, metal hydrates such as aluminum hydroxide, magnesium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, orthoaluminum silicate, and hydrotalcite can be used.

  Examples of the organic filler include melamine cyanurate, resin, rubber and the like. Of these, the use of metal hydrate, zinc stannate, zinc borate, antimony trioxide, melamine cyanurate, zinc oxide, titanium oxide and calcium carbonate is preferred. These materials may be used alone or in combination of two or more.

  These fillers have a particle size of 10 μm or less, preferably 5 μm or less, before the step (a) is performed. Moreover, the thing which has not surface-treated is preferable.

  The average particle diameter of the filler mixed and dispersed in the solvent in the step (a) can be adjusted by the bead diameter of the beads to be used, the pulverization time, and the like. In the present invention, the average particle diameter of the filler is preferably 0.4 μm or less, more preferably 0.2 μm or less, and still more preferably 0.1 μm or less. If the particle size is too large, the mechanical properties may be deteriorated or the desired flame retardancy may not be obtained.

  The measurement of the average particle diameter of the filler in the present invention is not particularly limited by the method usually used for the measurement of fine particles. For example, it is measured using a scattering type particle size measuring device (microtrack) by laser diffraction. Is possible.

  The solvent to be used is not particularly limited as long as the filler can be mixed and dispersed in the bead mill, and examples thereof include water, alcohol, and process oil. Of these, water is preferred.

  In the present invention, it is preferable to add a dispersant in the step (a). By adding the dispersant, in the step (a), it is possible to reduce the slurry viscosity and further improve the efficiency of fine pulverization and dispersion of the filler. In the step (a), the dispersed filler can be dispersed in the resin without reaggregation.

  As the dispersant, commonly used anionic dispersants and nonionic dispersants can be used as appropriate, but polyoxyalkylene compounds and maleic acid derivatives represented by the general formula (A) (R1-O (AO) n-R2) A copolymer (C) containing (B) as an essential monomer and having a mass average molecular weight of 500 to 100,000 (hereinafter also simply referred to as copolymer (C)) reduces the viscosity of the slurry. From the viewpoint of suppressing reaggregation of particles.

  The copolymer (C) of the present invention contains a polyoxyalkylene compound represented by the general formula (A) (R1-O (AO) n-R2) and a maleic acid derivative (B) as essential monomers, And a mass average molecular weight is 500-100,000. The copolymer (C) is adsorbed on the surface of the filler and has the effect of stabilizing the dispersed filler in the solvent due to the protective colloid effect and electric charge, and improves the dispersibility in the resin in the resin. effective.

In the copolymer (C) of the present invention, the essential monomer polyoxyalkylene compound represented by the general formula (A) is represented by the following formula.
(A): R1-O (AO) n-R2
Here, AO is an oxyalkylene group having 2 to 4 carbon atoms that essentially contains an oxyalkylene group having 4 carbon atoms, R1 is an alkenyl group having 2 to 5 carbon atoms, R2 is an alkyl group having 1 to 24 carbon atoms, n is an average added mole number of oxyalkylene and is 1 to 100.

  Examples of the oxyalkylene group having 2 to 4 carbon atoms include oxyethylene group, oxypropylene group, 1,2-oxybutylene group, 2,3-oxybutylene group, oxytetramethylene group and the like. An oxypropylene group, a 1,2-oxybutylene group, a 2,3-oxybutylene group, and an oxytetramethylene group are preferable, and a 1,2-oxybutylene group is more preferable.

  Although the said oxyalkylene group may be individual or may contain 2 or more types, it contains a C4 oxyalkylene group as an essential. Among them, the content of oxybutylene groups is preferably 10 mol% or more, and more preferably 30 mol% or more. Moreover, it is preferable that content of an oxyethylene group is 50 mol% or less.

  The average added mole number n of the oxyalkylene group is 1-100. When n exceeds 100, the viscosity of the compound becomes high and handling becomes difficult, which is not preferable. The addition form of the oxyalkylene group may be random addition or block addition.

Examples of the alkenyl group having 2 to 5 carbon atoms represented by R1 include vinyl group, allyl group, methallyl group, 2,3-dimethyl-1-propenyl group, 3-methyl-1-butenyl group, preferably allyl Group and methallyl group.

  R2 is a hydrocarbon group having 1 to 24 carbon atoms. Examples of the hydrocarbon group are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl. Group, isopentyl group, neopentyl group, hexyl group, 2-ethylhexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isotridecyl group, tetradecyl group, hexadecyl group, octadecyl group , Isostearyl group, oleyl group, octyldodecyl group, docosyl group, decyltetradecyl group, benzyl group, cresyl group, butylphenyl group, dibutylphenyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group, dioctylphenyl group, There are dinonylphenyl groups, but it is preferable Is a hexyl group, 2-ethylhexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isotridecyl group, tetradecyl group, hexadecyl group, octadecyl group, isostearyl group, oleyl group , Octyldodecyl group, docosyl group, decyltetradecyl group, benzyl group, cresyl group, butylphenyl group, dibutylphenyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group, dioctylphenyl group, dinonylphenyl group, etc. These are hydrocarbon groups of several 6 to 24, and these may be used alone or in combination of two or more.

  Another essential monomer of the copolymer is a maleic acid derivative (B). Examples of maleic acid derivatives include maleic acid and maleic anhydride. Of these, maleic anhydride is preferred.

  The composition ratio of the essential monomers (A) and (B) in the copolymer is (A) :( B) = 3: 7-7: 3, preferably 4: 6-6: 4, in molar ratio. It is.

  In addition to the essential monomers (A) and (B), a copolymerizable monomer can be copolymerized. Examples of the copolymerizable monomer include α-olefins such as styrene, vinyl acetate, acrylonitrile, and isobutylene, acrylic acid esters such as methyl acrylate, and methacrylic acid esters such as methyl methacrylate. Those having extremely low water solubility such as styrene are preferred.

  Moreover, the molecular weight of a copolymer (C) is 500-100000 by mass mean molecular weight, Preferably it is 2000-80000, More preferably, it is 5000-50000.

  Examples of the anionic dispersant in the present invention include aliphatic monocarboxylates, polyoxyethylene alkyl ether carboxylates, N-acyl sarcosine salts, N-acyl glutamates, dialkyl sulfosuccinates, alkane sulfonates, Alpha olefin sulfonate, linear alkyl benzene sulfonate, alkyl (branched) benzene sulfonate, naphthalene sulfonate-formaldehyde condensate, alkyl naphthalene sulfonate, N-methyl-N-acyl taurate, alkyl sulfate Examples thereof include salts, polyoxyethylene alkyl ether sulfates, fat and oil sulfate esters, alkyl phosphates, polyoxyethylene alkyl ether phosphates, and polyoxyethylene alkyl phenyl ether phosphates.

  Nonionic dispersants in the present invention include glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene glycol, fatty acid polyethylene glycol, fatty acid poly Examples thereof include oxyethylene sorbitan and fatty acid alkanolamide. The fatty acid is preferably a saturated or unsaturated fatty acid having 8 or more carbon atoms, such as octanoic acid, decanoic acid, dodecanoic acid, myristic acid, behenic acid, palmitic acid, isostearic acid, stearic acid, oleic acid. , Isononanoic acid, arachidic acid, coconut oil fatty acid, beef tallow fatty acid, soybean oil fatty acid, palm oil fatty acid, hardened oil fatty acid and the like.

  In the present invention, the step (A) is not particularly limited as long as the solvent of the slurry obtained in the step (A) is mixed with the base resin without substantially volatilizing. As a process that can be used in the process (A), for example, the slurry obtained in the process (A) is directly used as a base resin by supplying the slurry to the extruder (single screw, biaxial) using a supply pump or the like. A kneading method or the like can be used.

  In the step (a) of the present invention, the solvent contained in the slurry can be removed after the base resin and the slurry are mixed and the filler is uniformly dispersed in the base resin. As a method for removing the solvent, for example, when an extruder is used, there is a method in which a deaeration device is provided near the outlet of the extruder to perform deaeration. In particular, when water or alcohol is used as the solvent, it is preferable to use a deaerator. This is because if the water or alcohol contained in the slurry remains excessively in the resin composition, the obtained resin composition may foam. An example of a kneading apparatus in step (a) of the present invention is shown in FIG.

  The base resin used in the present invention is not particularly limited. For example, polyethylene, ethylene / α-olefin copolymer, polypropylene, propylene / α-olefin copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid ester Copolymers, ethylene / methacrylic acid ester copolymers, ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, ionomers, polyamides, polyurethanes, polyesters, polystyrenes and other thermoplastic resins and thermoplastic elastomers, Examples thereof include styrene butadiene rubber, butadiene rubber, isoprene rubber, acrylonitrile butadiene rubber, ethylene propylene rubber, ethylene propylene terpolymer, butyl rubber, acrylic rubber, and silicone rubber. Of these, the use of an ethylene / vinyl acetate copolymer is preferred.

  In this invention, 5-60 mass parts is preferable, and, as for the compounding quantity of the filler with respect to 100 mass parts of base resins, More preferably, it is 10-50 mass parts.

  The resin composition of the present invention is prepared by a step (a) of obtaining a filler dispersed in a solvent and a step (a) of kneading it with a base resin.

The resin composition of the present invention prepared in the above two steps exhibits excellent mechanical properties because the contained fine particle size filler is uniformly dispersed in the resin without re-aggregation. It becomes possible. This is considered to be because the reinforcing effect of the resin strength was increased by the dispersion of the fine filler having a particle diameter of 0.4 μm or less in the resin composition. Moreover, when a flame retardant is used as a filler, the resin composition of the present invention can exhibit excellent flame retardancy in addition to improvement of mechanical properties. This is presumably because the specific surface area of the filler increased and the decomposition reaction was more likely to occur by making the filler finer with a particle size of 0.4 μm or less.

In the present invention, the means for measuring the particle diameter of the filler in the resin composition is not particularly limited. For example, a method of measuring a plurality of TEM photographs and calculating the particle diameter from the images can be used.

  Moreover, it becomes possible to provide a resin composite material having a wide application range by blending the resin composition obtained in the steps (a) and (a) as a master batch with another resin.

  As the resin that can be used as the resin composite material of the present invention, both thermoplastic and thermosetting can be used, and there is no particular limitation. When a thermoplastic resin, thermoplastic elastomer, or rubber is used as the resin, the resin composition of the present invention is used together with the resin in a melt kneading apparatus that is usually used such as an extruder (single screw or twin screw), a Banbury mixer, a kneader, or a roll. It is possible to manufacture by supplying a product and melt-kneading together. When a thermosetting resin is used, for example, before curing, a resin composition obtained by kneading a slurry in a thermoplastic resin or thermoplastic elastomer in advance is added to the thermosetting resin, and then a normal curing process is performed. It is possible to manufacture by doing.

  The resin composition obtained by the production method of the present invention includes various materials (a flame retardant, a flame retardant aid, a filler, an antioxidant, a metal deactivator, an ultraviolet absorber, a crosslinking agent, a crosslinking aid, It is also possible to add pigments).

  Moreover, you may bridge | crosslink the resin composition of this invention as needed. As a method for crosslinking, an electron beam irradiation crosslinking method or a chemical crosslinking method can be employed. In the case of the electron beam crosslinking method, the resin composition of the present invention is molded and then crosslinked by irradiating an electron beam by a conventional method. In the case of the chemical cross-linking method, an organic peroxide is blended in the resin composition as a cross-linking agent, and after forming, the cross-linking is performed by a heat treatment by a conventional method.

  The shape of the resin product of the present invention is not limited, and examples thereof include a power plug, a connector, a sleeve, a box, a tape base material, a tube, and a sheet. Moreover, it can use suitably also as coating | covering materials, such as an electric wire, a cable, and an optical fiber.

  The resin product of the present invention can be molded from the resin composition of the present invention by a molding method such as ordinary extrusion molding or injection molding.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
Magnesium hydroxide (trade name: Kisuma 5, manufactured by Kyowa Chemical Co., Ltd.) is immersed in distilled water and stirred to prepare a slurry with a powder amount of 20% by mass. As a dispersant, general formula R1-O (AO) a copolymer containing a polyoxyalkylene compound represented by n-R2 and a maleic acid derivative as essential monomers and having a mass average molecular weight of 21,000 (trade name: Marialim AKM0531, Nippon Oil & Fat Co., Ltd.) (Made) was added so that it might become 5 mass% with respect to magnesium hydroxide.

  Next, this slurry was put into a medium stirring type wet pulverizer (LMZ2, manufactured by Ashizawa Co., Ltd.), and a pulverized and dispersed magnesium hydroxide slurry was prepared using φ0.3 mm zirconia beads.

  As a result of measuring the average particle size of the magnesium hydroxide in this slurry with a laser diffraction / scattering particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size was 0.30 μm.

  The slurry was injected from the middle of the twin-screw extruder using a pump, and an ethylene / vinyl acetate copolymer (trade name: Everflex V523, manufactured by Mitsui DuPont Polychemical Co., Ltd.) supplied from a hopper is shown in Table 1. The resin composition of the present invention was prepared by melt-kneading with the following composition.

Example 2
Magnesium hydroxide (trade name: 250, manufactured by Kamishima Chemical Co., Ltd.) is immersed in distilled water and stirred to prepare a slurry having a powder amount of 20% by mass. As a dispersant, general formula R1-O ( AO) a copolymer containing a polyoxyalkylene compound represented by n-R2 and a maleic acid derivative as essential monomers and having a mass average molecular weight of 20,000 (trade name: Marialim AFB1521, manufactured by NOF Corporation) ) Was added so that it might become 10 mass% with respect to magnesium hydroxide.

  Next, this slurry was put into a medium stirring type wet pulverizer (LMZ2, manufactured by Ashizawa Co., Ltd.), and a pulverized and dispersed magnesium hydroxide slurry was prepared using φ0.1 mm zirconia beads.

  As a result of measuring the average particle size of the magnesium hydroxide in this slurry with a laser diffraction / scattering particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size was 0.15 μm.

  The slurry was injected from the middle of the twin-screw extruder using a pump, and an ethylene / vinyl acetate copolymer (trade name: Everflex V523, manufactured by Mitsui DuPont Polychemical Co., Ltd.) supplied from a hopper is shown in Table 1. The resin composition of the present invention was prepared by melt-kneading with the following composition.

Example 3
Magnesium hydroxide (trade name: 250, manufactured by Kamishima Chemical Co., Ltd.) is immersed in distilled water and stirred to prepare a slurry with a powder amount of 20% by mass. As a dispersant, sodium polyacrylate (product) Name: Polystar A1060, manufactured by NOF Corporation was added so as to be 5% by mass with respect to magnesium hydroxide.

  Next, this slurry was put into a medium stirring type wet pulverizer (SAM1, manufactured by Kotobuki Giken Co., Ltd.), and pulverized and dispersed using φ0.1 mm zirconia beads. (AO) a copolymer containing a polyoxyalkylene compound represented by n-R2 and maleic anhydride or maleic acid as essential monomers and having a mass average molecular weight of 20,000 (trade name: Marialim AFB1521, Nippon Oil & Fats 5% by mass with respect to magnesium hydroxide, and polyoxyethylene sorbitan monolaurate (trade name: Nissan Nonion LT221, manufactured by NOF Corporation) with 5% by mass with respect to magnesium hydroxide. It added so that a slurry might be created.

  As a result of measuring the average particle size of the magnesium hydroxide in this slurry with a laser diffraction / scattering particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size was 0.15 μm.

  The slurry was injected from the middle of the twin-screw extruder using a pump, and an ethylene / vinyl acetate copolymer (trade name: Everflex V523, manufactured by Mitsui DuPont Polychemical Co., Ltd.) supplied from a hopper is shown in Table 1. The resin composition of the present invention was prepared by melt-kneading with the following composition.

Example 4
Magnesium hydroxide (trade name: 250, manufactured by Kamishima Chemical Co., Ltd.) is immersed in ion-exchanged water and stirred to prepare a slurry having a powder amount of 20% by mass. As a dispersant, general formula R1-O (AO) a copolymer containing a polyoxyalkylene compound represented by n-R2 and a maleic acid derivative as essential monomers and having a mass average molecular weight of 21,000 (trade name: Marialim AKM0531, Nippon Oil & Fat Co., Ltd.) (Made) was added so that it might become 5 mass% with respect to magnesium hydroxide.

  Next, this slurry was put into a medium stirring type wet pulverizer (SAM1, manufactured by Kotobuki Giken Co., Ltd.), and a pulverized and dispersed magnesium hydroxide slurry was prepared using φ0.1 mm zirconia beads.

  As a result of measuring the average particle size of the magnesium hydroxide in this slurry with a laser diffraction / scattering particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size was 0.135 μm.

  The slurry is injected from the middle of the twin-screw extruder using a pump, and ethylene / vinyl acetate copolymer (trade name: Everflex EV450, manufactured by Mitsui DuPont Polychemical Co., Ltd.) supplied from the hopper is shown in Table 1. The resin composition of the present invention was prepared by melt-kneading with the following composition.

Example 5
Magnesium hydroxide (trade name: Kisuma 5, manufactured by Kyowa Chemical Co., Ltd.) is immersed in ion-exchanged water and stirred to prepare a slurry having a powder amount of 20% by mass. As a dispersant, general formula R1- A copolymer containing a polyoxyalkylene compound represented by O (AO) n-R2 and a maleic acid derivative as essential monomers and having a mass average molecular weight of 21,000 (trade name: Marialim AKM0531, Nippon Oil & Fats Co., Ltd. )) Was added to 5 mass% with respect to magnesium hydroxide.

  Next, this slurry was put into a medium stirring type wet pulverizer (SAM1, manufactured by Kotobuki Giken Co., Ltd.), and a pulverized and dispersed magnesium hydroxide slurry was prepared using φ0.1 mm zirconia beads.

  As a result of measuring the average particle size of the magnesium hydroxide in this slurry with a laser diffraction / scattering particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size was 0.248 μm.

  The slurry was injected from the middle of the twin-screw extruder using a pump, and an ethylene / vinyl acetate copolymer (trade name: Everflex V523, manufactured by Mitsui DuPont Polychemical Co., Ltd.) supplied from a hopper is shown in Table 1. The resin composition of the present invention was prepared by melt-kneading with the following composition.

Comparative Example 1
Magnesium hydroxide (trade name: Kisuma 5, manufactured by Kyowa Chemical Co., Ltd.) is immersed in distilled water and stirred to prepare a slurry with a powder amount of 20% by mass. As a dispersant, general formula R1-O (AO) a copolymer containing a polyoxyalkylene compound represented by n-R2 and a maleic acid derivative as essential monomers and having a mass average molecular weight of 21,000 (trade name: Marialim AKM0531, Nippon Oil & Fat Co., Ltd.) (Made) was added so that it might become 5 mass% with respect to magnesium hydroxide.

  As a result of measuring the average particle size of the magnesium hydroxide in this slurry with a laser diffraction / scattering particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size was 0.80 μm.

  The slurry was injected from the middle of the twin-screw extruder using a pump, and an ethylene / vinyl acetate copolymer (trade name: Everflex V523, manufactured by Mitsui DuPont Polychemical Co., Ltd.) supplied from a hopper and Table 2 A resin composition having the same specific gravity as that of the resin composition prepared in Example 1 was prepared by melt kneading with the composition of

Comparative Examples 2 and 3
Using a twin screw extruder, magnesium hydroxide (trade name: 250, manufactured by Kamishima Chemical Co., Ltd.) and ethylene / vinyl acetate copolymer (trade name: EVAFLEX V523, manufactured by Mitsui DuPont Polychemical Co., Ltd.) Were melt-kneaded with the formulation shown in Table 2 to prepare a resin composition.

Comparative Example 4
Magnesium hydroxide (trade name: 250, manufactured by Kamishima Chemical Co., Ltd.) is immersed in ion-exchanged water and stirred to prepare a slurry having a powder amount of 20% by mass. As a dispersant, general formula R1-O (AO) a copolymer containing a polyoxyalkylene compound represented by n-R2 and a maleic acid derivative as essential monomers and having a mass average molecular weight of 21,000 (trade name: Marialim AKM0531, Nippon Oil & Fat Co., Ltd.) (Made) was added so that it might become 5 mass% with respect to magnesium hydroxide.

  As a result of measuring the average particle size of the magnesium hydroxide in this slurry with a laser diffraction / scattering particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size was 3.298 μm.

The slurry was injected from the middle of the twin-screw extruder using a pump, and an ethylene / vinyl acetate copolymer (trade name: EVAFLEX EV450, manufactured by Mitsui DuPont Polychemical Co., Ltd.) supplied from the hopper and Table 2 A resin composition was prepared by melt-kneading with the following composition.

Comparative Example 5
Magnesium hydroxide (trade name: Kisuma 5, manufactured by Kyowa Chemical Co., Ltd.) is immersed in ion-exchanged water and stirred to prepare a slurry having a powder amount of 20% by mass. As a dispersant, general formula R1- A copolymer containing a polyoxyalkylene compound represented by O (AO) n-R2 and a maleic acid derivative as essential monomers and having a mass average molecular weight of 21,000 (trade name: Marialim AKM0531, Nippon Oil & Fats Co., Ltd. )) Was added to 5 mass% with respect to magnesium hydroxide.

  As a result of measuring the average particle size of the magnesium hydroxide in this slurry with a laser diffraction / scattering particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size was 0.525 μm.

  The slurry was injected from the middle of the twin-screw extruder using a pump, and an ethylene / vinyl acetate copolymer (trade name: Everflex V523, manufactured by Mitsui DuPont Polychemical Co., Ltd.) supplied from a hopper and Table 2 A resin composition was prepared by melt-kneading with the following composition.

Comparative Example 6
Various evaluations were performed using only an ethylene / vinyl acetate copolymer (trade name: Everflex EV450, manufactured by Mitsui DuPont Polychemical Co., Ltd.).

Comparative Example 7
Various evaluations were performed using only an ethylene / vinyl acetate copolymer (trade name: Everflex V523, manufactured by Mitsui DuPont Polychemical Co., Ltd.).

The following evaluation was performed about the created resin composition.

○ Mechanical properties (tensile strength, elongation)
A press sheet having a thickness of 1 mm was prepared and punched with a JIS K7113 No. 2 dumbbell. Measured with

○ Flame resistance (oxygen index)
A press sheet having a thickness of 3 mm was prepared, and the oxygen index was measured according to JIS K7201.

○ Appearance / A press sheet having a color thickness of 1 mm was prepared, and the appearance and color were observed.

Abrasion resistance For Examples 4 and 5 and Comparative Examples 4 to 7, electric wires were prepared by coating each composition with a thickness of 0.2 mm on a 0.8 mm conductor. Each of the obtained electric wires was evaluated for wear resistance by a blade reciprocating tester specified in JASO D611. The number of abrasions until the conductor was exposed was measured at a blade tip diameter of 0.45 mm and a load of 2.45 N.

Table 1 shows the blending amounts of the resin compositions of Examples and Comparative Examples, the particle diameter of the filler, and the characteristics of the obtained compositions.
As is clear from Table 1, Examples 1-5 all show good values, while Comparative Examples 1-5 add the filler to the resin without performing step (a). Moreover, since the average particle diameter of the filler is too large, the mechanical properties and wear resistance are inferior, and the color is also white. Further, Comparative Examples 6 and 7 to which no filler was added resulted in inferior mechanical properties and wear resistance.

  As described above, according to the method for producing a resin composition of the present invention, it is possible to uniformly disperse a filler having a remarkably reduced particle diameter in a resin composition without agglomeration. It is possible to obtain a resin composition having characteristics, molding processability and abrasion resistance, and having high flame retardancy when a flame retardant is used as a filler.

  In addition, the resin product using the resin composition of the present invention has excellent mechanical properties and abrasion resistance because the filler having a significantly reduced particle size is uniformly dispersed in the resin composition. Furthermore, when a flame retardant is used as a filler, it is a resin product having high flame retardancy.

It is an example of the kneading apparatus of a process (I).

Explanation of symbols

1: Extruder 2: Base resin inlet 3: Slurry supply pump 4: Deaerator

Claims (4)

Step (a) of obtaining a slurry having an average particle size of the dispersed filler of 0.4 μm or less by pulverizing while mixing the filler with a solvent, and without substantially volatilizing the solvent in the slurry, Including the step (a) of mixing the slurry with the base resin,
In the step (a), a dispersant is added to the slurry,
In the step (a), the dispersant contains a polyoxyalkylene compound represented by the following general formula (A) and a maleic acid derivative (B) as essential monomers, and has a mass average molecular weight of 500 to 100,000. A method for producing a resin composition comprising blending a copolymer (C) into the slurry.
(A): R1-O (AO) n-R2
(However, AO is an oxyalkylene group having 2 to 4 carbon atoms which essentially contains a oxyalkylene group having 4 carbon atoms, R1 is an alkenyl group having 2 to 5 carbon atoms, R2 is an alkyl group having 1 to 24 carbon atoms, n is an average added mole number of oxyalkylene and is 1 to 100)   The method for producing a resin composition according to claim 1, wherein a nonionic dispersant having a fatty acid is added to the slurry in the step (a).   The filler is at least one selected from the group consisting of metal hydrate, zinc stannate, zinc borate, antimony trioxide, melamine cyanurate, zinc oxide, titanium oxide, and calcium carbonate. The manufacturing method of the resin composition of Claim 1 or 2.   The resin product which uses the resin composition manufactured by the manufacturing method of any one of Claims 1-3.

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